FOAMABLE THERMOPLASTIC COMPOSITIONS, THERMOPLASTIC FOAMS AND METHODS OF MAKING SAME

COMPOSITIONS THERMOPLASTIQUES EXPANSIBLES, MOUSSES THERMOPLASTIQUES ET LEURS PROCEDES DE FABRICATION

English Abstract

Low-density, thermoplastic foams comprising: (a) thermoplastic polymer cells comprising cell walls comprising polyethylene furanoate, wherein at least about 50% by volume of the cells are closed cells; and (b) at least HFO-1234ze(E) contained in said closed cells.

French Abstract

Mousses thermoplastiques à faible densité comprenant : (a) des cellules polymères thermoplastiques comprenant des parois cellulaires comprenant du polyéthylène furanoate, au moins environ 50 % en volume des cellules étant des cellules fermées ; et (b) au moins de l'HFO-1234ze(E) contenu dans lesdites cellules fermées.

Claims

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What is claimed is:
1. A low-density, thermoplastic foam comprising:
(a) thermoplastic polymer cells comprising cell walls comprising polyethylene
furanoate, wherein at least about 50% by volume of the cells are closed cells;
and
(b) at least HF0-1234ze(E) contained in said closed cells.
2. The foam of claim 1 wherein the density of the foam is
from about 0.05 to
less than 0.2 g/cc.
3. The foam of claim 2 wherein the tensile strength of the
foam is from about
1.5 to about 3.5 Mpa.
4. The foam of claim 2 wherein the compressive strength of
the foam is from
about 0.65 to about 1.5 Mpa.
5. The foam of claim 3 wherein the compressive strength of
the foam is from
about 0.65 to about 1.5 Mpa.
6. The foam of claim 2 wherein the foam has a density of
from about 0.05 to
less than 0.1 g/cc.
7. The foam of claim 5 wherein the foam has a density of
from about 0.05 to
less than 0.1 g/cc.
8. The foam of claim 2 wherein ethylene furanoate moieties
are at least 50%
by weight of said thermoplastic polymer.
9. The foam of claim 2 wherein said cell walls consist
essentially of
polyethylene furanoate.
10. The foam of claim 2 wherein said cell walls consist
essentially of
polyethylene furanoate having a molecular weight of at least about 90,000.
11. The foam of claim 2 wherein ethylene furanoate moieties
are at least 85%
by weight of said thermoplastic polymer.
12. The foam of claim 2 wherein at least about 75% of the
cells are closed
cells.
13. A thermoplastic foam cornprising:
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(a) thermoplastic polymer cells comprising cell walls comprising polyethylene
furanoate having a crystallinity of at least 10%, wherein at least about 50%
by volume of
the cells are closed cells and wherein said thermoplastic polymer contains no
tannin
moieties or tannin moieties in an amount of less than 20% by weight; and
(b) gas in said closed cells comprising one or more HFOs having three or four
carbon atoms and/or one or more HFCOs having three or four carbon atoms
contained
in the closed cells.
14. The foam of claim 13 wherein said gas in said closed cells comprising
one
or more of 1234ze(E), 1336mzz(E), 1336nizz(Z), 1224yd(E), 1224yd(Z),
1233zd(E),
1234yf, and combinations of two or more of these.
15. The foam of claim 14 wherein at least about 75% of the cells are closed
cells.
16. The foam of claim 13 wherein said gas in said closed cells comprises at
least 60% by weight of 1234ze(E) and wherein said cell walls consist
essentially of
polyethylene furanoate having a molecular weight of at least about 90,000.
17. The foam of claim 13 wherein said gas in said closed cells consists
essentially of 1234ze(E).
18. A wind energy turbine blade and/or nacelle, or an automobile car wall,
or
an aircraft or aerospace vessel comprising the foam of any one of claims 1 -
17.
19. A foamable composition comprising:
(a) thermoplastic polymer comprising polyethylene furanoate containing no
tannin moieties or tannin moieties in an amount of less than 20% by weight;
and
(b) a blowing agent comprising one or more HFOs having three or four carbon
atoms and/or one or more HFCOs having three or four carbon atoms.
20. The foamable composition of claim 19 wherein said blowing agent
comprises from about 5% to about 95% of said one or more HFOs having three or
four
carbon atoms and/or one or more HFCOs having three or four carbon atoms.
21. The foamable composition of claim 19 wherein said polyethylene
furanoate has a molecular weight of from about 25,000 to about at least about
180,000
and has a crystallinity of from 30% to 60% by volume.
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22. The foamable composition of claim 19 wherein said polyethylene
furanoate has a molecular weight of from about 80,000 to about at least about
130,000
and has a crystallinity of from 30% to 60% by volume.
23. The foamable composition of claim 20 wherein said polyethylene
furanoate has a molecular weight of from about 80,000 to about at least about
130,000
and has a crystallinity of from 30% to 60% by volume.
24. The foamable composition of claim 23 wherein said polyethylene
furanoate has a molecular weight of from about 90,000 to about at least about
120,000
and has a crystallinity of from 30% to 60% by volume and wherein said blowing
agent
comprises at least about 60% by weight of 1234ze(E).
25. A foamable composition comprising:
(a) thermoplastic polymer comprising polyethylene furanoate; and
(b) a blowing agent comprising one or more HFOs having three or four carbon
atorns and/or one or more HFCOs having three or four carbon atoms, provided
said
blowing agent does not comprise 1336mzz.
26. The foamable composition of claim 25 wherein said blowing agent
comprises from about 5% to about 95% of said one or more HFOs having three or
four
carbon atoms and/or one or more HFCOs having three or four carbon atoms.
27. The foamable composition of claim 25 wherein said polyethylene
furanoate has a molecular weight of from about 25,000 to about at least about
180,000
and has a crystallinity of from 30% to 60% by volume.
28. The foamable composition of claim 25 wherein said polyethylene
furanoate has a molecular weight of from about 80,000 to about at least about
130,000
and has a crystallinity of from 30% to 60% by volume.
29. The foamable composition of claim 26 wherein said polyethylene
furanoate has a molecular weight of from about 80,000 to about at least about
130,000
and has a crystallinity of from 30% to 60% by volume.
30. The foamable composition of claim 29 wherein said polyethylene
furanoate has a molecular weight of from about 90,000 to about at least about
120,000
and has a crystallinity of from 30% to 60% by volume and wherein said blowing
agent
comprises at least about 60% by weight of 1234ze(E).
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Description

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FOAMABLE THERMOPLASTIC COMPOSITIONS, THERMOPLASTIC FOAMS AND
METHODS OF MAKING SAME
CROSS REFERENCE
This application is related to and incorporates by reference each of: US
Provisional
Application 63/233,720, filed August 16, 2021; US Provisional Application
63/252,110, filed
October 4, 2021; and US Provisional Application 63/278,497, filed November 12,
2021.
FIELD OF THE INVENTION
This invention relates to foamable thermoplastic compositions, thermoplastic
foams,
foaming methods, and systems and articles made from same.
BACKGROUND
While foams are used in a wide variety of applications, developing a foam that
has
excellent performance properties and is cost-effective to produce is a
derisible but difficult goal
to achieve. It is even more difficult to achieve this goal while at the same
time developing a
foam that is environmentally friendly. Producing environmentally friendly
foams is especially
difficult because they comprise both a blowing agent component and a resin
component forming
the foam structure, and each of these components has an impact on foam
performance and on
environmental properties. Environmental considerations include not only the
recyclability and
sustainability of the polymeric resin that forms the structure of the foam but
also the low
environmental impact of blowing agents used to form the foam, such as the
Global Warming
Potential (GWP) and Ozone Depletion Potential (ODP) of the blowing agent. It
is therefore a
major challenge to develop a foam that simultaneously has excellent
performance and can be
produced cost-effectively from an environmentally friend blowing agent and an
environmentally
friendly resin.
Foams based on certain thermoplastic resins, including polyester resins, have
been
investigated for potential advantage from the perspective of being recyclable
and/or sustainably-
sourced. However, difficulties have been encountered in connection with the
development of
such materials. For example, it has been a challenge to develop polyester
resins that are truly
recyclable, can be produced from sustainable sources, and which are compatible
with blowing
agents that are able, in combination with the thermoplastic, to produce foams
with good
performance properties. In many applications the performance properties that
are considered
highly desirable include the production of high-quality closed cell foams that
are low density
(and therefore have a low weight in use) and, at the same time, have
relatively high mechanical
integrity and strength.
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With respect to the selection of thermoplastic resin, EP 3,231,836
acknowledges that
while there has been interest in thermoplastic resins, in particularly
polyester-based resins, this
interest has encountered difficulty in development, including difficulty in
identifying suitable
foaming grades of such resins. Moreover, while EP 3,231,836 notes that certain
polyethylene
terephthalate (PET) resins, including recycled versions of PET, can be melt-
extruded with a
suitable physical and/or chemical blowing agent to yield closed-cell foams
with the potential for
low density and good mechanical properties, it is not disclosed that any such
resins are at once
are able to produce foams with good environmental properties and good
performance
properties, and are also able to be formed from sustainable sources. The '836
application
identifies several possible polyester resins to be used in the formation of
open-celled foams,
including polyethylene terephthalate, poly butylene terephthalate, poly
cyclohexane
terephthalate, polyethylene naphthalate, polyethylene furanoate or a mixture
of two or more of
these. While the use of polyester materials to make foams that have
essentially no closed cells,
as required by EP '836, may be beneficial for some applications, a
disadvantage of such
structures is that, in general, open cell foams will exhibit relatively poor
mechanical strength
properties.
While plastics based on 2,5-furandicarboxylic-acid-based polyester have been
noted to
have some potential advantages in certain applications, such as having good
gas barrier
properties, there has also been a recognition of substantial problems with
forming foam
materials from such plastic materials. For example, CN108410000 teaches that
2,5-
furandicarboxylic-acid-based polyesters have foaming performance that is very
poor and
processing conditions that are extremely unfavorable. These problems are said
to be
addressed by using a glassy (i.e., amorphous) polymer sheet and then exposing
the sheet to a
special, relatively complex and cumbersome dual blowing agent process.
The process described in CN108410000 suffers from several disadvantages,
including
requiring an undesirably long processing time to produce the specialized,
treated preform and
the use of a relatively complicated dual blowing agent process. This process
is also highly
disadvantageous in that it is not readily adaptable for use in connection with
currently used
commercial extrusion equipment, thus having an undesirably high new capital
cost requirement
to implement.
CN 108484959 also recognizes that 2,5-furandicarboxylic-acid-based polyesters
(such
as PEF) have poor foamability and attempts to address this significant problem
by forming a
high melt viscosity polymer by blend-reacting 2,5-furandicarboxylic acid
ethylene glycol ester
with a multifunctional monomer selected from alcohols, esters, alkanes,
carboxylic acids and
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anhydrides. Foaming properties of this material are said to be improved
relative to PEF, but no
information on the foaming process is provided.
US 2020/0308363 and US 2020/0308396 each disclose the production of amorphous
polyester copolymers that comprise starting with a recycled polyester, of
which only PET is
exemplified, as the main component and then proceeding through a series of
processing steps
to achieve an amorphous co-polymer, that is, as copolymer having no
crystallinity. These
publications indicate that it is not possible to readily form low density
polyester foams from
crystalline or semi-crystalline polymers and indicates that this problem can
be solved by forming
amorphous copolyester polymer material and using such amorphous material to
form the foam.
The synthesis of poly(ethylene furanoate) (PEE) using ethylene glycol and 2,5-
furandicarboxylic
acid is mentioned but is not exemplified. Essentially amorphous (i.e., no
crystallinity as per 0
J/G AH before foaming) ternary copolymers formed from PET, polytrimethylene
furanoate and
polycarbonate are said to have been foamed using CO2 as the blowing agent. No
foam
properties are disclosed. A wide variety of different classes of blowing agent
are mentioned for
use with amorphous polymers generally, including CO2, HF0-1233zd,
cyclopentane, acetone
and methanol.
US 9790342 discloses foams formed from the polyphenolic tannin, which may be
combined with a large number of possible monomers, and among the list of
monomers is 2,5-
furandicarboxylic acid. The foams are said to be partially open cell and
partially closed cell, with
open cell content being less than 50%. Numerous potential blowing agents are
disclosed,
including the halogenated olefin HF0-1336mmz.
With respect to blowing agents, the use generally of halogenated olefin
blowing agents,
including hydrofluoroolefins (HF0s) and hydrochlorofluorolefins (HCF0s), for
several specific
thermoplastic foams is known, as disclosed for example in US 2009/0305876,
which is assigned
to the assignee of the present invention, and which is incorporated herein by
reference. While
the '876 application discloses the use of HFO and HFCO blowing agents with
various
thermoplastic materials to form foams, including PET, there is no disclosure
or suggestion to
use any of such blowing agents with any other type of polyester resin.
Applicants have overcome the problem of forming a high performance foam that
is also
has favorable environmental features (i.e., high sustainability and low
atmospheric impact) and
in so doing have come to appreciate that these problems can be overcome and
that one or
more unexpected advantages can be achieved by the formation of thermoplastic
foams, and in
particular extruded thermoplastic foams, using a polyester resin as disclosed
herein in
combination with a blowing agent comprising one of more hydrohaloolefin as
disclosed herein.
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SUMMARY
As described above, a continuing need exists for polymeric materials, and
particularly
polymeric foams, that are sustainable and environmentally friendly, and
simultaneously a
continuing need exists for such polymeric foams that at once are able to
provide low density and
high strength. Such a combination of properties is especially important in
many applications
which require a foam that has a low weight for a given volume (i.e., has low
density) but are
required to provide strength in use. One example of such a use is in
connection with the
construction of wind turbine blades, where both light weight and high strength
are important,
and in such applications sustainability and environment friendliness are also
both very
important. As outlined above, for example, prior efforts to address this need
have encountered
a myriad of technical problems and deficiencies, and a fully acceptable
solution has heretofore
not been achieved.
The present invention satisfies one or more of the above noted needs and
overcomes
prior technical problems and includes low-density, thermoplastic foam
comprising:
(a) thermoplastic polymer cells comprising cell walls comprising polyethylene
furanoate
having a crystallinity of at least 15%, wherein at least 25% of said cells are
closed cells; and
(b) one or more HFOs having three or four carbon atoms and/or one or more
HFC0s
having three or four carbon atoms contained in the closed cells.
For the purposes of convenience, foams in accordance with this paragraph are
referred to
herein as Foam 1A.
The present invention includes low-density, thermoplastic foam comprising:
(a) thermoplastic polymer cells comprising cell walls comprising polyethylene
furanoate
having a crystallinity of at least 15%, wherein at least 25% by volume of said
cells are closed
cells; and
(b) one or more HFOs having three or four carbon atoms and/or one or more
HFC0s
having three or four carbon atoms contained in the closed cells, provided that
1336mzz is not
contained in the closed cells.
For the purposes of convenience, foams in accordance with this paragraph are
referred to
herein as Foam 1B.
The present invention includes low-density, thermoplastic foam comprising:
(a) thermoplastic polymer cells comprising cell walls comprising polyethylene
furanoate
having a crystallinity of at least 15%, wherein at least 25% by volume of said
cells are closed
cells; and
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(b) one or more HFOs having three or four carbon atoms and/or one or more
HFC0s
having three or four carbon atoms contained in the closed cells, provided that
1233zd is not
contained in the closed cells.
For the purposes of convenience, foams in accordance with this paragraph are
referred to
herein as Foam 1C.
The present invention includes low-density, thermoplastic foam comprising:
(a) thermoplastic polymer cells comprising cell walls comprising polyethylene
furanoate
having a crystallinity of at least 15%, wherein at least 15% by volume of said
cells are closed
cells and wherein ethylene furanoate moieties are at least 85% by weight of
the thermoplastic
polymer; and
(b) one or more HFOs having three or four carbon atoms and/or one or more
HFC0s
having three or four carbon atoms contained in the closed cells.
For the purposes of convenience, foams in accordance with this paragraph are
referred to
herein as Foam 1D.
Reference will be made at various locations herein to a numbered foam (e.g.,
Foam 1) or to group of numbered foams that have been defined herein, and such
reference means each of such numbered systems, including each system having a
number within the group, including any suffixed numbered system. For example,
reference to Foam 1 includes a separate reference to each of Foams 1A, 1B, 1C
and
1D, and reference to Foams 1 ¨2 is understood to include a separate reference
to
each of Foams 1A, 1B, 1C, 1D, 2A, 2B, 20, 2D, 2E and 2F. Further, this
convention is
used throughout the present specification for other defined materials,
including
Blowing Agents.
The present invention includes low-density, thermoplastic foam comprising:
(a) thermoplastic polymer cells comprising cell walls comprising polyethylene
furanoate
wherein at least 25% of said cells are closed cells; and
(b) 1234ze(E) contained in the closed cells.
For the purposes of convenience, foams in accordance with this paragraph are
referred to
herein as Foam 2A.
The present invention includes low-density, thermoplastic foam comprising:
(a) thermoplastic polymer cells comprising cell walls comprising polyethylene
furanoate
having a crystallinity of at least 15%, wherein at least 25% of said cells are
closed cells; and
(b) 1234ze(E) contained in the closed cells.
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For the purposes of convenience, foams in accordance with this paragraph are
referred to
herein as Foam 2B.
The present invention includes low-density, thermoplastic foam comprising:
(a) thermoplastic polymer cells comprising cell walls comprising polyethylene
furanoate
having a crystallinity of at least 35%, wherein at least 50% of said cells are
closed cells; and
(b) gas in said closed cell, wherein said gas comprises 1234ze(E).
For the purposes of convenience, foams in accordance with this paragraph are
referred to
herein as Foam 2C.
The present invention includes low-density, thermoplastic foam comprising:
(a) thermoplastic polymer cells comprising cell walls comprising polyethylene
furanoate
having a crystallinity of at least 35%, wherein at least 50% of said cells are
closed cells; and
(b) gas in said closed cell, wherein said gas comprises from about 25% by
weight to
100% by weight of 1234ze(E). For the purposes of convenience, foams in
accordance with this
paragraph are referred to herein as Foam 2D.
The present invention includes low-density, thermoplastic foam comprising:
(a) thermoplastic polymer cells comprising cell walls comprising polyethylene
furanoate
having a crystallinity of at least 35%, wherein at least 50% of said cells are
closed cells; and
(b) gas in said closed cell, wherein said gas comprises 1234ze(E) and at least
one co-
blowing agent. For the purposes of convenience, foams in accordance with this
paragraph are
referred to herein as Foam 2E.
The present invention includes low-density, thermoplastic foam comprising:
(a) thermoplastic polymer cells comprising cell walls comprising polyethylene
furanoate
having a crystallinity of at least 35%, wherein at least 50% of said cells are
closed cells; and
(b) gas in said closed cell, wherein said gas consists essentially of
1234ze(E). For the
purposes of convenience, foams in accordance with this paragraph are referred
to herein as
Foam 2F.
The present invention includes low-density, thermoplastic foam comprising:
(a) thermoplastic polymer cells comprising cell walls comprising polyethylene
furanoate
having a crystallinity of at least 15% wherein at least about 50% by volume of
the cells are
closed cells and wherein ethylene furanoate moieties are at least 85% by
weight of the
thermoplastic polymer; and
(b) one or more HFOs having three or four carbon atoms and/or one or more
HFC0s
having three or four carbon atoms contained in the closed cells.
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For the purposes of convenience, foams in accordance with this paragraph are
referred to
herein as Foam 3A.
The present invention includes low-density, thermoplastic foam comprising:
(a) thermoplastic polymer cells comprising cell walls comprising polyethylene
furanoate
that has a crystallinity of at least 15% and a molecular weight of from about
25,000 to about
170,000, wherein at least about 25% by volume of the cells are closed cells;
and
(b) one or more HFOs having three or four carbon atoms and/or one or more
HFC0s
having three or four carbon atoms contained in the closed cells.
For the purposes of convenience, foams in accordance with this paragraph are
referred to
herein as Foam 3B.
The present invention includes low-density, thermoplastic foam comprising:
(a) thermoplastic polymer cells comprising cell walls comprising polyethylene
furanoate
having a crystallinity of at least 15% and a molecular weight of from about
80,000 to about
170,000, wherein at least about 25% by volume of the cells are closed cells;
and
(b) one or more HFOs having three or four carbon atoms and/or one or more
HFC0s
having three or four carbon atoms contained in the closed cells.
For the purposes of convenience, foams in accordance with this paragraph are
referred to
herein as Foam 3C.
The present invention includes low-density, thermoplastic foam comprising:
(a) thermoplastic polymer cells comprising cell walls comprising polyethylene
furanoate
having a crystallinity of at least 25% and a molecular weight of from about
80,000 to about
170,000, wherein from about 35% by volume to about 90% by volume of the cells
are closed
cells; and
(b) one or more HFOs having three or four carbon atoms and/or one or more
HFC0s
having three or four carbon atoms contained in the closed cells.
For the purposes of convenience, foams in accordance with this paragraph are
referred to
herein as Foam 3D.
The present invention includes low-density, thermoplastic foam comprising:
(a) thermoplastic polymer cells comprising cell walls comprising polyethylene
furanoate
having a crystallinity of from about 35% to about 65% and a molecular weight
of from about
80,000 to about 170,000, wherein from about 35% by volume to about 90% by
volume of the
cells are closed cells; and
(b) one or more HFOs having three or four carbon atoms and/or one or more
HFC0s
having three or four carbon atoms contained in the closed cells.
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For the purposes of convenience, foams in accordance with this paragraph are
referred to
herein as Foam 3E.
The present invention includes low-density, closed-cell thermoplastic foam
comprising:
(a) closed thermoplastic cells comprising cell walls comprising polyethylene
furanoate;
and
(b) a blowing agent contained in said closed cells, wherein said foam has a
relative foam
density (RFD) of about 0.1 or less and a foam density of less than 0.3 g/cc.
For the purposes of
convenience, foams in accordance with this paragraph are referred to herein as
Foam 4A.
As used herein, the term "relative foam density," and its abbreviation "RFD"
mean the
density of the foam divided by the density of the polymer used to form the
foam.
The present invention includes low-density, closed-cell thermoplastic foam
comprising:
(a) closed thermoplastic cells comprising cell walls consisting essentially of
polyethylene
furanoate that has been treated with a chain extender; and
(b) a blowing agent contained in said closed cells,
wherein said foam has an RFD of about 0.1 or less and a density of less than
0.3 g/cc. For the
purposes of convenience, foams in accordance with this paragraph are referred
to herein as
Foam 4B.
The present invention includes low-density, closed-cell thermoplastic foam
comprising:
(a) thermoplastic polymer cells comprising cell walls forming closed cells,
wherein said
thermoplastic comprises polyethylene furanoate-based polymer having a
crystallinity of at least
about 15% and a molecular weight of greater than 25,000; and
(b) blowing agent contained in said closed cells, said blowing agent
comprising
1234ze(E). For the purposes of convenience, foams in accordance with this
paragraph are
referred to herein as Foam 5A.
The present invention includes low-density, closed-cell thermoplastic foam
comprising:
(a) thermoplastic polymer cells comprising cell walls forming closed cells,
wherein said
thermoplastic comprises polyethylene furanoate-based polymer having a
crystallinity of at least
about 25% and a molecular weight of from about 25,000 to about 170,000; and
(b) blowing agents contained in said closed cells, said blowing agent
comprising
1234ze(E). For the purposes of convenience, foams in accordance with this
paragraph are
referred to herein as Foam 5B.
The present invention includes low-density, closed-cell thermoplastic foam
comprising:
(a) closed thermoplastic cells comprising cell walls consisting essentially of
polyethylene
furanoate; and
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(b) trans-1234ze contained in said closed cells,
wherein said foam has a density of less than 0.3 g/cc. For the purposes of
convenience, foams
in accordance with this paragraph are referred to herein as Foam 6A.
The present invention includes closed-cell thermoplastic foam comprising:
(a) closed thermoplastic cells comprising cells walls consisting essentially
of
polyethylene furanoate wherein at least about 50% by volume of the cells are
closed cells; and
(b) 1234ze(E) contained in said closed cells. For the purposes of convenience,
foams in
accordance with this paragraph are referred to herein as Foam 6B.
The present invention includes closed-cell thermoplastic foam comprising:
(a) closed thermoplastic cells comprising cells walls consisting essentially
of
polyethylene furanoate wherein at least about 75% by volume of the cells are
closed cells; and
(b) 1234ze(E) contained in said closed cells. For the purposes of convenience,
foams in
accordance with this paragraph are referred to herein as Foam 6C.
The present invention includes closed-cell thermoplastic foam comprising:
(a) closed thermoplastic cells comprising cells walls consisting essentially
of
polyethylene furanoate wherein at least about 90% by volume of the cells are
closed cells; and
(b) 1234ze(E) contained in said closed cells. For the purposes of convenience,
foams in
accordance with this paragraph are referred to herein as Foam 6D.
The present invention also provides the foamable compositions, foaming methods
and
additional foams as described hereinafter.
BRIEF DESCRIPTION OF THE DRAWING
Figure 1 is a schematic representation of an extrusion system and process
according to
one embodiment of the invention and according to the examples herein.
Figure 2 is an SEM of the foam of Example 4.
DEFINITIONS
1234ze means 1,1,1,3-tetrafluoropropene, without limitation as to isomeric
form.
Trans1234ze and 1234ze(E) each means trans1,3,3,3-tetrafluoropropene.
Cis1234ze and 1234ze(Z) each means cis1,3,3,3-tetrafluoropropene.
1234yf means 2,3,3,3-tetrafluoropropene.
1233zd means 1-chloro-3,3,3-trifluoropropene, without limitation as to
isomeric form.
Trans1233zd and 1233zd(E) each means trans1-chloro-3,3,3-trifluoropropene.
1224yd means 1-chloro-2,3,3,3-tetrafluoropropane, without limitation as to
isomeric form.
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cis1224yd and 1224yd(Z) means cis1-chloro-2,3,3,3-tetrafluoropropane.
1336mzz means 1,1,1,4,4,4-hexafluorobutene, without limitation as to isomeric
form.
Trans1336mzz and 1336mzz(E) each means trans1,1,1,4,4,4-hexafluorobutene.
Cis1336mzz and 1336mzz(Z) each means cis1,1,1,4,4,4-hexafluorobutene.
Closed cell foam means that a substantial volume percentage of the cells in
the foam are
closed, for example, about 20% by volume or more.
Crystallinity means the degree of crystallinity of a polymer measured by
differential scanning
calorimetry (DSC) according to ASTM D3418 and ASTM E1356.
Ethylene furanoate moiety means the following structure:
o'N-/r
n
FDCA means 2,5-furandicarboxylic acid and has the following structure:
0 0
0
HO'TOH
FDME means dimethyl 2,5-furandicarboxylate and has the following structure:
0
0
MEG means monoethylene glycol and has the following structure:
OH
HO
Moiety as used herein means a distinct repeating unit in a polymer. For
clarity, a copolymer
having two repeating units A and B present in a 1:1 ratio would have 50 molar
% A moieties and
50 molar % of B moieties.
Other Moiety as used herein means a moiety that is not ethylene furanoate and
not formed
from tannin.
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Methylal means dimethoxymethane ((CH30)2CH2).
PEF homopolymer means a polymer consisting of ethylene furanoate moieties. For
avoidance
of doubt, the PEF homopolymer may include impurity levels of materials that
may be present.
PEF copolymer means a polymer having at least 50% by weight of ethylene
furanoate moieties
and some amount a moiety other than ethylene furanoate moieties.
PEF means poly (ethylene furanoate) and encompasses and is intended to reflect
a description
of PEF homopolymer and PEF coploymer.
SSP means solid-state polymerization.
PMDA means pyromellitic dianhydride having the following structure:
o 0
ci 0
0 0
Relative foam density and its abbreviation "RFD" mean the density of the foam
divided by the
density of the polymer used to form the foam.
Tannin moiety as used herein means a polymeric repeating unit corresponding to
the tannin
used to form the polymer, including as disclosed in US Patent No. 9,890,342.
DETAILED DESCRIPTION
Poly (ethylene furanoate)
The present invention relates to foams and foam articles that comprise cell
walls that
comprise PEF.
The PEF which forms the cells walls of the foams and foam articles of the
present
invention can be PEF homopolymer or PEF copolymer_
PEF homopolymer is a known material that is known to be formed by either:(a)
esterification and polycondensation of FDCA with MEG; or (b)
transesterification and
polycondensation of FDME with MEG as illustrated below for example:
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1. Esterification
0 0
(a) 2. Polycondensation
Ho' \\ // -OH
Catalyst
-H20
2,5-Furandicarboxylic acid (FDCA) 0
n
1. Transesterification -
0 0 (b) + 2. Polycondensation
HO
eo-
Catalyst
- Me0H
Dimethyl 2,5-Furandicarboxylate (FDME)
A detailed description of such known esterification and polycondensation
synthesis methods is provided in GB Patent 621971 (Drewitt, J. G. N., and
Lincocoln,
J., entitled "Improvements in Polymers"), which is incorporated herein by
reference. A
detailed description of such known transesterification and polycondensation
synthesis
methods is provided in Gandini, A., Silvestre, A. J. D., Nato, C. P., Sousa,
A. F., and
Gomes, M. (2009), The furan counterpart of poly(ethylene terephthalate): an
alternative material based on renewable resources.", J. Polym. Sci. Polym.
Chem. 47,
295-298. doi: 10.1002/pola.23130, which is incorporated herein by reference.
Foams
The foams of the present invention are formed from either PEF homopolymers,
PEF copolymers, or a combination/mixture of these.
The foams may be formed in preferred embodiments from PEF homopolymer in
which the polymer has at least 99.5% by weight, or at least 99.9% of by
weight, of
ethylene furanoate moieties.
It is contemplated that the foams may be formed in preferred embodiments from
PEF copolymer in which the polymer, including PEF copolymer that has from
about
60% to about 99% by weight of ethylene furanoate moieties, or from about 70%
to about
99% by weight of ethylene furanoate moieties, or from about 80% to about 99%
by weight
of ethylene furanoate moieties, or from about 90% to about 99% by weight of
ethylene
furanoate moieties or from about 95% to about 99.5% by weight of ethylene
furanoate
moieties.
For those embodiments of the present invention involving PEF copolymers, it is

contemplated that those skilled in the art will be able, in view of the
teachings
contained herein, to select the type and amount of co-polymeric materials to
be used
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within each of the ranges described herein to achieve the desired
enhancement/modification of the polymer without undue experimentation.
For those embodiments of the present invention involving the use of PEF
homopolymer or PEF copolymer, it is contemplated that such material may be
formed
with a wide variety of molecular weights and physical properties within the
scope of the
present invention. In preferred embodiments, the foams, including each of
Foams 1 ¨
6, are formed from PEF having the ranges of characteristics identified in
Table 1
below, which are measured as described in the Examples hereof:
TABLE 1
Broad Range Intermediate Narrow
Range
Range
Polymer property
Molecular weight 25,000¨ 150,000 45,000¨ 130,000 55,000¨
120,000
Glass Transition 75 ¨ 100 75 ¨ 95 75 ¨ 95
Temperature, Tg, C
Melting Temperature, 180 ¨250 190 - 240 200 ¨230
C
Decomposition 300 - 420 320 - 400 330 ¨ 380
Temperature, Td, C
Crystallinity, % 25 - 75 30 ¨ 60 40 ¨ 50
In general, it is contemplated that those skilled in the art will be able to
formulate PEF polymers
within the range of properties described above without undue experimentation
in view of the
teachings contained herein. In preferred embodiments, however, PEF in general
and PEF
homopolymer in particular having these properties is achieved using one or
more of the
synthesis methods described above, in combination with a variety of known
supplemental
processing techniques, including by treatment with chain extenders, such as
PMDA, and/or SSP
processing. It is believed that, in view of the disclosures contained herein,
including the polymer
synthesis described in the Examples below, a person skilled in the art will be
able to produce
PEF polymers within the range of characteristics described in the table above
and elsewhere
herein.
An example of the process for chain extension treatment of polyesters is
provided in the
article "Recycled poly(ethylene terephthalate) chain extension by a reactive
extrusion process,"
Firas Awaja, Fugen Daver, Edward Kosior, 16 August 2004, available at
https:fidoL omj 0. 002/pen 20155, which is incorporated herein by reference.
As explained in
US 1009/0264545, which is incorporated herein by reference, chain extenders
generally are
typically compounds that are at least di-functional with respect to reactive
groups which can
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react with end groups or functional groups in the polyester to extend the
length of the polymer
chains. In certain cases, as disclosed herein, such a treatment can
advantageously increases
the average molecular weight of the polyester to improve its melt strength
and/or other
important properties. The degree of chain extension achieved is related, at
least in part, to the
structure and functionalities of the compounds used. Various compounds are
useful as chain
extenders. Non-limiting examples of chain extenders include trimellitic
anhydride, pyromellitic
dianhydride (PMDA), trimellitic acid, haloformyl derivatives thereof, or
compounds containing
multi-functional epoxy (e.g., glycidyl), or oxazoline functional groups.
Nanocomposite material
such as finely dispersed nanoclay may optionally be used for controlling
viscosity.
Commercial chain extenders include CESA-Extend from Clariant, Joncryl from
BASF, or
Lotader from Arkema. The amount of chain extender can vary depending on the
type and
molecular weight of the polyester components. The amount of chain extender
used to treat the
polymer can vary widely, and in preferred embodiments ranges from about 0.1 to
about 5 wt. %,
or preferably from about 0.1 to about 1.5 wt. %. Examples of chain extenders
are also described
in U.S. Pat. No. 4,219,527, which is incorporated herein by reference.
An example of the process for SSP processing of poly(ethylene furanoate) is
provided in
the article "Solid-State Polymerization of Poly(ethylene furanoate) Biobased
Polyester, I: Effect
of Catalyst Type on Molecular Weight Increase,'
Nejib Kasmi, Mustapha Majdoub, George Z. Papageorgiou, Dimitris S. Achilias,
and Dimitrios N.
Bikiaris, which is incorporated herein by reference.
The REF thermoplastic polymers which are especially advantageous for making
foamable compositions and foams of the present invention are identified in the
following
Thermoplastic Polymer Table (Table 2), wherein all numerical values in the
table are
understood to be preceded by the word "about."
TABLE 2- THERMOPLASTIC POLYMER TABLE
Thermoplastic Ethylene Tannin Other MW,
Crystallinity,
Polymer (TPP) furanoate moieties, moieties, Kg/mol %
Number moieties, wt% wt% wt%
TPPlA 100 0 0 25 ¨ 180 25 ¨
100
TPP113 100 0 0 25 - 75 30 ¨
60
TPP1C 100 0 0 80 ¨ 130 30 ¨ 60
TPP1D 100 0 0 90 ¨ 120 35 ¨ 50
TPME 100 0 0 90 ¨ 110 35 ¨ 45
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Thermoplastic Ethylene Tannin Other MW,
Crystallinity,
Polymer (TPP) furanoate moieties, moieties, Kg/m ol %
Number moieties, wt% wt% wt%
TPP2A 85 to <100 >0 to < 15 0 25 ¨ 180 25 ¨
100
TPP2B 85 to <100 >0 to < 15 0 25 ¨ 75 30 ¨
60
TPP2C 85 to <100 >0 to < 15 0 80 ¨ 130 30 ¨ 60
TPP2D 85 to<100 >Oto< 15 0 90 ¨ 120 35 ¨ 50
TPP2E 85 to <100 >0 to < 15 0 90 ¨ 110 35 ¨ 45
TPP3A 5 to 95 0 5 to 95 25 ¨ 180 25 ¨
100
TPP3B 5 to 95 0 5 to 95 25 ¨ 75 30 ¨
60
TPP3C 5 to 95 0 5 to 95 80 ¨ 130 30 ¨ 60
TPP3D 5 to 95 0 5 to 95 90 ¨ 120 35 ¨ 50
TPP3E 5 to 95 0 5 to 95 90 ¨ 110 35 ¨ 45
TPP4A 5 to 95 >0 - < 15 5 to 95 25 ¨ 180 25 ¨
100
TPP4B 5 to 95 >0 - < 15 5 to 95 25 ¨ 75 30 ¨
60
TPP4C 5 to 95 ->0 - <- 15 5 to 95 80 ¨ 130 30 ¨
60
TPP4D 5 to 95 >0 - < 15 5 to 95 90 ¨ 120 35 ¨
50
TPP4E 5 to 95 >0 - < 15 5 to 95 90 ¨ 110 35 ¨
45
TPP5A 10 0 90 25 ¨ 180 25 ¨
100
TPP5B 10 0 90 25 ¨ 75 30 ¨ 60
TPP5C 10 0 90 80 ¨ 130 30 ¨ 60
TPP5D 10 0 90 90 ¨ 120 35 ¨ 50
TPP5E 10 0 90 90 ¨ 110 35 ¨ 45
TPP6A 90 0 10 25 ¨ 180 25 ¨
100
TPP6B 90 0 10 25 ¨ 75 30 ¨ 60
TPP6C 90 0 10 80 ¨ 130 30 ¨ 60
TPP6D 90 0 10 90 ¨ 120 35 ¨ 50
TPP6E 90 0 10 90 ¨ 110 35 ¨ 45
For the purposes of definition of terms used herein, it is to be noted that
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reference will be made at various locations herein to the thermoplastic
polymers
identified in the first column in each of rows in the TPP table above, and
reference to
each of these numbers is a reference to a thermoplastic polymer as defined in
the
corresponding columns of that row. Reference to a group of TPPs that have been
defined in the table above by reference to a TPP number means separately and
individually each such numbered TPP, including each TPP having the indicated
number, including any such number that has a suffix. So for example, reference
to
TPP1 is a separate and independent reference to TPP1A, TPP1B, TPP1C, TPP1D
and TPP1E. Reference to TPP1 ¨ TPP2 is a separate and independent reference to
TPP1A, TPP1B, TPP1C, TPP1D, TTP1E, TPP2A, TPP2B, TPP2C, TPP2D and
TPP1E. This use convention is used for the Foamable Composition Table and the
Foam Table below as well.
Blowing Agent
As explained in detail herein, the present invention includes, but is not
limited to,
applicant's discovery that a select group of blowing agents are capable of
providing foamable
PEF foamable compositions and PEF foams having a difficult-to-achieve and
surprising
combination of physical properties, including low density as well as good
mechanical strength
properties.
The blowing agent used in accordance with the present invention preferably
comprises
one or more hydrohaloolefins having three or four carbon atoms For the
purposes of
convenience, a blowing agent in accordance with this paragraph is sometimes
referred to herein
as Blowing Agent 1.
The blowing agent used in accordance with of the present invention preferably
comprises one or more of 1234ze, 1234yf, 1336mzz, 1233zd and 1224ydf (referred
to
hereinafter for convenience as Blowing Agent 2), or comprises one or more of
trans1234ze,
1336mzz, trans1233zd and cis1224yd (referred to hereinafter for convenience as
Blowing
Agent 3) ; or comprises one or more of trans1234ze, trans1336mzz, trans1233zd
and
cis1224yd (referred to hereinafter for convenience as Blowing Agent 4); or
comprises one or
more of trans1234ze and trans1336mzz (referred to hereinafter for convenience
as Blowing
Agent 5); or comprises trans1234ze (referred to hereinafter for convenience as
Blowing Agent
6) ; or comprises trans1336mzz (referred to hereinafter for convenience as
Blowing Agent 7);
or comprises cis1336mzz (referred to hereinafter for convenience as Blowing
Agent 8); or
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comprises 1234yf(referred to hereinafter for convenience as Blowing Agent 9);
or comprises
1224yd (referred to hereinafter for convenience as Blowing Agent 10); or
comprises
trans1233zd(referred to hereinafter for convenience as Blowing Agent 11).
It is thus contemplated that the blowing agent of the present invention,
including each of
Blowing Agents 1 ¨ 11, can include, in addition to each of the above-
identified blowing agent(s),
co-blowing agent including in one or more of the optional potential co-blowing
agents as
described below. In preferred embodiments, the present foamable compositions,
foams, and
foaming methods include a blowing agent as described according described
herein, wherein
the indicated blowing agent (including the compound or group of compound(s)
specifically
identified in each of Blowing Agent 1 ¨ 11) is present in an amount, based
upon the total weight
of all blowing agent present, of at least about 50% by weight, or preferably
at least about 60%
by weight, preferably at least about 70% by weight, or preferably at least
about 80% by weight,
or preferably at least about 90% by weight, or preferably at least about 95%
by weight, or
preferably at least about 99% by weight, based on the total of all blowing
agent components.
The blowing agent used in accordance with of the present invention also
preferably
consists essentially of one or more of 1234ze, 1234yf, 1336rnzz, 1233zd and
1224ydf (referred
to hereinafter for convenience as Blowing Agent 12); or consists essentially
of one or more of
trans1234ze, 1336mzz, trans1233zd and cis1224yd (referred to hereinafter for
convenience as
Blowing Agent 13); or consists essentially of one or more of trans1234ze,
trans1336mzz,
trans1233zd and cis1224yd (referred to hereinafter for convenience as Blowing
Agent 14); or
consists essentially of one or more of trans1234ze and trans1336mzz (referred
to hereinafter for
convenience as Blowing Agent 15); or consists essentially of trans1234ze
(referred to
hereinafter for convenience as Blowing Agent 16); or consists essentially of
trans1336mzz
(referred to hereinafter for convenience as Blowing Agent 17); or consists
essentially of
cis1336mzz (referred to hereinafter for convenience as Blowing Agent 18); or
consists
essentially of 1234yf (referred to hereinafter for convenience as Blowing
Agent 19); or consists
essentially of 1224yd (referred to hereinafter for convenience as Blowing
Agent 20); or
consists essentially of trans1233zd (referred to hereinafter for convenience
as Blowing Agent
21).
It is contemplated and understood that blowing agent of the present invention,
including
each of Blowing Agents 1 ¨21, can include one or more co-blowing agents which
are not
included in the indicated selection, provided that such co-blowing agent in
the amount used
does not interfere with or negate the ability to achieve relatively low-
density foams as described
herein, including each of Foams 1 ¨ 6, and preferably further does not
interfere with or negate
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the ability to achieve foam with mechanical strengths properties as described
herein. It is
contemplated, therefore, that given the teachings contained herein a person of
skill in the art will
be able to select, by way of example, one or more of the following potential
co-blowing agents
for use with a particular application without undue experimentation: one or
more saturated
hydrocarbons or hydrofluorocarbons (HFCs), particularly C4-06 hydrocarbons or
C1-C4 HFCs,
that are known in the art. Examples of such HFC co-blowing agents include, but
are not limited
to, one or a combination of difluoromethane (HFC-32), fluoroethane (HFC-161),
difluoroethane
(HFC-152), trifluoroethane (HFC-143), tetrafluoroethane (HFC-134),
pentafluoroethane (HFC-
125), pentafluoropropane (HFC-245), hexafluoropropane (HFC-236),
heptafluoropropane (H FO-
227ea), pentafluorobutane (HFC-365), hexafluorobutane (HFC-356) and all
isomers of all such
HFC's. With respect to hydrocarbons, the present blowing agent compositions
also may include
in certain preferred embodiments, for example, iso, normal and/or cyclopentane
and butane
and/or isobutane. Other materials, such as water, CO2, CFCs (such as
trichlorofluoromethane
(CFC-11) and dichlorodifluoromethane (CFC-12)), hydrochlorocarbons (HCCs such
as
dichloroethylene (preferably trans-dichloroethylene), ethyl chloride and
chloropropane), HCFCs,
C1-05 alcohols (such as, for example, ethanol and/or propanol and/or butanol),
C1-C4
aldehydes, C1-C4 ketones, C1-C4 ethers (including ethers (such as dimethyl
ether and diethyl
ether), diethers (such as dimethoxy methane and diethoxy methane)), and methyl
formate,
organic acids (such as but not limited to formic acid), including combinations
of any of these
may be included, although such components are not necessarily preferred in
many
embodiments due to negative environmental impact.
The blowing agent used in accordance with the present invention also
preferably
consists of one or more of 1234ze, 1234yf, 1336mzz, 1233zd and 1224ydf
(referred to
hereinafter for convenience as Blowing Agent 22); or consists of one or more
of trans1234ze,
1336mzz, trans1233zd and c1s1224yd (referred to hereinafter for convenience as
Blowing
Agent 23); or consists of one or more of trans1234ze, trans1336mzz,
trans1233zd and
cis1224yd (referred to hereinafter for convenience as Blowing Agent 24); or
consists of one or
more of trans1234ze and trans1336mzz (referred to hereinafter for convenience
as Blowing
Agent 25); or consists of trans1234ze (referred to hereinafter for convenience
as Blowing
Agent 26); or consists of trans1336mzz (referred to hereinafter for
convenience as Blowing
Agent 27); or consists of cis1336mzz (referred to hereinafter for convenience
as Blowing
Agent 28); or consists of 1234yf (referred to hereinafter for convenience as
Blowing Agent 29);
or consists of 1224yd (referred to hereinafter for convenience as Blowing
Agent 30): or
consists of trans1233zd (referred to hereinafter for convenience as Blowing
Agent 31).
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Foams and Foaming Process
The foams of the present invention may generally be formed from a foamable
composition of the present invention. In general, the foamable compositions of
the present
invention may be formed by combining a PEF polymer with a blowing agent of the
present
invention, including each of Blowing Agents 1 ¨ 31.
Foamable compositions that are included within the present invention and which
provide
particular advantage in connection with forming the foams of the present
invention, are
described in the following Foamable Composition Table (Table 3), in which all
numerical values
in the table are understood to be preceded by the word "about" and in which
the following terms
used in the table have the following meanings:
CBAG1 means co-blowing agent selected from the group consisting of 1336mzz(Z),

1336mzzm(E), 1224yd(Z), 1233zd(E), 1234yf and combinations of two or more of
these.
CBAG2 means co-blowing agent selected from the group consisting of water, CO2,
Cl ¨
06 hydrocarbons (HCs) HCFCs, Cl ¨ C5 HFCs, C2 ¨ C4 hydrohaloolefins, C1-05
alcohols, C1-
C4 aldehydes, C1-C4 ketones, C1-C4 ethers, Cl ¨ C4 esters, organic acids and
combinations
of two or more of these.
CCBAG3 means co-blowing agent selected from the group consisting of water,
002,
isobutane, n-butane, isopentane, cyclopentane, cyclohexane, trans-
dichloroethylene, ethanol,
propanol, butanol, acetone, dimethyl ether, diethyl ether, dimethoxy methane,
diethoxy
methane, methyl formate, difluoromethane (HFC-32), fluoroethane (HFC-161), 1,1-

difluoroethane (HFC-152a), trifluoroethane (HFC-143), 1,1,1,2-
tetrafluoroethane (HFC-134a),
pentafluoroethane (HFC-125), pentafluoropropane (HFC-245), hexafluoropropane
(HFC-236),
heptafluoropropane (HFC-227ea), pentafluorobutane (HFC-365), hexafluorobutane
(HFC-356),
and combinations of any two or more of these.
NR means not required.
TABLE 3- FOAMABLE COMPOSITION TABLE
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Foamable Foamable Composition Components
Composition
Number
Blowing Agent(s) and Amounts, wt% of All Blowing Agents
Polymer, Blowing Agent 1 Wt% BA! Co Blowing Agent(s)
Wt% CB
TPP No. (BA!) (CB)
FC1A1 TPPlA 1234ze(E) 100 NR 0
FC1B1 TPP1B 1234ze(E) 100 NR 0
FC1C1 TPP1C 1234ze(E) 100 NR 0
FC1D1 TPP1D 1234ze(E) 100 NR 0
FC1E1 TPPlE 1234ze(E) 100 NR 0
FC1A2 TPP2A 1234ze(E) 100 NR 0
FC1B2 TPP2B 1234ze(E) 100 NR 0
FC1C2 TPP2C 1234ze(E) 100 NR 0
FC1D2 TPP2D 1234ze(E) 100 NR 0
FC1E2 TPP2E 1234ze(E) 100 NR 0
FC1A3 TPP3A 1234ze(E) 100 NR 0
FC1B3 TPP3B 1234ze(E) 100 NR 0
FClC3 TPP3C 1234ze(E) 100 NR 0
FC1D3 TPP3D 1234ze(E) 100 NR 0
FC1E3 TPP3E 1234ze(E) 100 NR 0
FC1A4 TPP4A 1234ze(E) 100 NR 0
FC1B4 TPP4B 1234ze(E) 100 NR 0
FC1C4 TPP4C 1234ze(E) 100 NR 0
FC1D4 TPP4D 1234ze(E) 100 NR 0
FC1E4 TPP4E 1234ze(E) 100 NR 0
FC1A5 TPP5A 1234ze(E) 100 NR 0
FC1B5 TPP5B 1234ze(E) 100 NR 0
FC1C5 TPP5C 1234ze(E) 100 NR 0
FC1D5 TPP5D 1234ze(E) 100 NR 0
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Foamable Foamable Composition Components
Composition
Number
Blowing Agent(s) and Amounts, wt% of All Blowing Agents
Polymer, Blowing Agent 1 Wt% BA! Co Blowing Agent(s)
Wt% CB
TPP No. (BA!) (CB)
FC1E5 TPP5E 1234ze(E) 100 NR 0
FC1A6 TPP6A 1234ze(E) 100 NR 0
FC1B6 TPP6B 1234ze(E) 100 NR 0
FC1C6 TPP6C 1234ze(E) 100 NR 0
FC106 TPP6D 1234ze(E) 100 NR 0
FC1E6 TPP6E 1234ze(E) 100 NR 0
FC2A1 TPPlA 1234ze(E) 5 - 95 CBAG1 5 -
95
FC2B1 TPP1B 1234ze(E) 5 - 95 CBAG1 5 -
95
FC2C1 TPP1C 1234ze(E) 5 - 95 CBAG1 5 -
95
FC2D1 TPP1D 1234ze(E) 5 - 95 CBAG1 5 -
95
FC2E1 TPPlE 1234ze(E) 5 - 95 CBAG1 5 -
95
FC2A2 TPP2A 1234ze(E) 5 - 95 CBAG1 5 -
95
FC2B2 TPP2B 1234ze(E) 5 - 95 CBAG1 5 -
95
FC2C2 TPP2C 1234ze(E) 5-95 CBAG1 5 -
95
FC2D2 TPP2D 1234ze(E) 5 - 95 CBAG1 5 -
95
FC2E2 TPP2E 1234ze(E) 5 - 95 CBAG1 5 -
95
FC2A3 TPP3A 1234ze(E) 5 - 95 CBAG1 5 -
95
FC2B3 TPP3B 1234ze(E) 5 - 95 CBAG1 5 -
95
FC2C3 TPP3C 1234ze(E) 5 - 95 CBAG1 5 -
95
FC2D3 TPP3D 1234ze(E) 5 - 95 CBAG1 5 -
95
FC2E3 TPP3E 1234ze(E) 5 - 95 CBAG1 5 -
95
FC2A4 TPP4A 1234ze(E) 5 - 95 CBAG1 5 -
95
FC2B4 TPP4B 1234ze(E) 5 - 95 CBAG1 5 -
95
FC2C4 TPP4C 1234ze(E) 5 - 95 CBAG1 5 -
95
21
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Foamable Foamable Composition Components
Composition
Number
Blowing Agent(s) and Amounts, wt% of All Blowing Agents
Polymer, Blowing Agent 1 Wt% BA! Co Blowing Agent(s)
Wt% CB
TPP No. (BA!) (CB)
FC2D4 TPP4D 1234ze(E) 5 - 95 CBAG1 5 -
95
FC2E4 TPP4E 1234ze(E) 5 - 95 CBAG1 5 -
95
FC2A5 TPP5A 1234ze(E) 5 - 95 CBAG1 5 -
95
FC2B5 TPP5B 1234ze(E) 5 - 95 CBAG1 5 -
95
FC2C5 TPP5C 1234ze(E) 5 - 95 CBAG1 5 -
95
FC2D5 TPP5D 1234ze(E) 5 - 95 CBAG1 5 -
95
FC2E5 TPP5E 1234ze(E) 5 - 95 CBAG1 5 -
95
FC2A6 TPP6A 1234ze(E) 5 - 95 CBAG1 5 -
95
FC2B6 TPP6B 1234ze(E) 5 - 95 CBAG1 5 -
95
FC2C6 TPP6C 1234ze(E) 5 - 95 CBAG1 5 -
95
FC2D6 TPP6D 1234ze(E) 5 - 95 CBAG1 5 -
95
FC2E6 TPP6E 1234ze(E) 5 - 95 CBAG1 5 -
95
FC3A1 TPPlA 1234ze(E) 5 - 95 CBAG2 5 -
95
FC3B1 TPP1B 1234ze(E) 5-95 CBAG2 5 -
95
FC3C1 TPP1C 1234ze(E) 5 - 95 CBAG2 5 -
95
FC3D1 TPP1D 1234ze(E) 5 - 95 CBAG2 5 -
95
FC3E1 TPPlE 1234ze(E) 5 - 95 CBAG2 5 -
95
FC3A2 TPP2A 1234ze(E) 5 - 95 CBAG2 5 -
95
FC3B2 TPP2B 1234ze(E) 5 - 95 CBAG2 5 -
95
FC3C2 TPP2C 1234ze(E) 5 - 95 CBAG2 5 -
95
FC3D2 TPP2D 1234ze(E) 5 - 95 CBAG2 5 -
95
FC3E2 TPP2E 1234ze(E) 5 - 95 CBAG2 5 -
95
FC3A3 TPP3A 1234ze(E) 5 - 95 CBAG2 5 -
95
FC3B3 TPP3B 1234ze(E) 5 - 95 CBAG2 5 -
95
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Foamable Foamable Composition Components
Composition
Number
Blowing Agent(s) and Amounts, wt% of All Blowing Agents
Polymer, Blowing Agent 1 Wt% BA! Co Blowing Agent(s)
Wt% CB
TPP No. (BA!) (CB)
FC3C3 TPP3C 1234ze(E) 5 - 95 CBAG2 5 -
95
FC3D3 TPP3D 1234ze(E) 5 - 95 CBAG2 5 -
95
FC3E3 TPP3E 1234ze(E) 5 - 95 CBAG2 5 -
95
FC3A4 TPP4A 1234ze(E) 5 - 95 CBAG2 5 -
95
FC3B4 TPP4B 1234ze(E) 5 - 95 CBAG2 5 -
95
FC3C4 TPP4C 1234ze(E) 5 - 95 CBAG2 5 -
95
FC3D4 TPP4D 1234ze(E) 5 - 95 CBAG2 5 -
95
FC3E4 TPP4E 1234ze(E) 5 - 95 CBAG2 5 -
95
FC3A5 TPP5A 1234ze(E) 5 - 95 CBAG2 5 -
95
FC3B5 TPP5B 1234ze(E) 5 - 95 CBAG2 5 -
95
FC3C5 TPP5C 1234ze(E) 5 - 95 CBAG2 5 -
95
FC3D5 TPP5D 1234ze(E) 5 - 95 CBAG2 5 -
95
FC3E5 TPP5E 1234ze(E) 5 - 95 CBAG2 5 -
95
FC3A6 TPP6A 1234ze(E) 5 - 95 CBAG2 5 -
95
FC3B6 TPP6B 1234ze(E) 5 - 95 CBAG2 5 -
95
FC3C6 TPP6C 1234ze(E) 5 - 95 CBAG2 5 -
95
FC3D6 TPP6D 1234ze(E) 5 - 95 CBAG2 5 -
95
FC3E6 TPP6E 1234ze(E) 5 - 95 CBAG2 5 -
95
FC4A1 TPPlA 1234ze(E) 5 - 95 CBAG3 5 -
95
FC4B1 TPP1B 1234ze(E) 5 - 95 CBAG3 5 -
95
FC4C1 TPP1C 1234ze(E) 5 - 95 CBAG3 5 -
95
FC4D1 TPP1D 1234ze(E) 5 - 95 CBAG3 5 -
95
FC4E1 TPP1E 1234ze(E) 5 - 95 CBAG3 5 -
95
FC4A2 TPP2A 1234ze(E) 5 - 95 CBAG3 5 -
95
23
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Foamable Foamable Composition Components
Composition
Number
Blowing Agent(s) and Amounts, wt% of All Blowing Agents
Polymer, Blowing Agent 1 Wt% BA! Co Blowing Agent(s)
Wt% CB
TPP No. (BA!) (CB)
FC4B2 TPP2B 1234ze(E) 5 - 95 CBAG3 5 -
95
FC4C2 TPP2C 1234ze(E) 5 - 95 CBAG3 5 -
95
FC4D2 TPP2D 1234ze(E) 5 - 95 CBAG3 5 -
95
FC4E2 TPP2E 1234ze(E) 5 - 95 CBAG3 5 -
95
FC4A3 TPP3A 1234ze(E) 5 - 95 CBAG3 5 -
95
FC4B3 TPP3B 1234ze(E) 5 - 95 CBAG3 5 -
95
FC4C3 TPP3C 1234ze(E) 5 - 95 CBAG3 5 -
95
FC4D3 TPP3D 1234ze(E) 5 - 95 CBAG3 5 -
95
FC4E3 TPP3E 1234ze(E) 5 - 95 CBAG3 5 -
95
FC4A4 TPP4A 1234ze(E) 5 - 95 CBAG3 5 -
95
FC4B4 TPP4B 1234ze(E) 5 - 95 CBAG3 5 -
95
FC4C4 TPP4C 1234ze(E) 5 - 95 CBAG3 5 -
95
FC4D4 TPP4D 1234ze(E) 5 - 95 CBAG3 5 -
95
FC4E4 TPP4E 1234ze(E) 5 - 95 CBAG3 5 -
95
FC4A5 TPP5A 1234ze(E) 5 - 95 CBAG3 5 -
95
FC4B5 TPP5B 1234ze(E) 5 - 95 CBAG3 5 -
95
FC4C5 TPP5C 1234ze(E) 5 - 95 CBAG3 5 -
95
FC4D5 TPP5D 1234ze(E) 5 - 95 CBAG3 5 -
95
FC4E5 TPP5E 1234ze(E) 5 - 95 CBAG3 5 -
95
FC4A6 TPP6A 1234ze(E) 5 - 95 CBAG3 5 -
95
FC4B6 TPP6B 1234ze(E) 5 - 95 CBAG3 5 -
95
FC4C6 TPP6C 1234ze(E) 5 - 95 CBAG3 5 -
95
FC4D6 TPP6D 1234ze(E) 5 - 95 CBAG3 5 -
95
FC4E6 TPP6E 1234ze(E) 5 - 95 CBAG3 5 -
95
24
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Foamable Foamable Composition Components
Composition
Number
Blowing Agent(s) and Amounts, wt% of All Blowing Agents
Polymer, Blowing Agent 1 Wt% BA! Co Blowing Agent(s)
Wt% CB
TPP No. (BA!) (CB)
FC5A1 TPPlA 1234ze(E) 5 - 95 cyclopentane 5 -
95
FC5B1 TPP1B 1234ze(E) 5 - 95 cyclopentane 5 -
95
FC5C1 TPP1C 1234ze(E) 5 - 95 cyclopentane 5 -
95
FC5D1 TPP1D 1234ze(E) 5 - 95 cyclopentane 5 -
95
FC5E1 TPPlE 1234ze(E) 5 - 95 cyclopentane 5 -
95
FC5A2 TPP2A 1234ze(E) 5 - 95 cyclopentane 5 -
95
FC5B2 TPP2B 1234ze(E) 5 - 95 cyclopentane 5 -
95
FC5C2 TPP2C 1234ze(E) 5 - 95 cyclopentane 5 -
95
FC5D2 TPP2D 1234ze(E) 5 - 95 cyclopentane 5 -
95
FC5E2 TPP2E 1234ze(E) 5 - 95 cyclopentane 5 -
95
FC5A3 TPP3A 1234ze(E) 5 - 95 cyclopentane 5 -
95
FC5B3 TPP3B 1234ze(E) 5 - 95 cyclopentane 5 -
95
FC5C3 TPP3C 1234ze(E) 5 - 95 cyclopentane 5 -
95
FC5D3 TPP3D 1234ze(E) 5 - 95 cyclopentane 5 -
95
FC5E3 TPP3E 1234ze(E) 5 - 95 cyclopentane 5 -
95
FC5A4 TPP4A 1234ze(E) 5 - 95 cyclopentane 5 -
95
FC5B4 TPP4B 1234ze(E) 5 - 95 cyclopentane 5 -
95
FC5C4 TPP4C 1234ze(E) 5 - 95 cyclopentane 5 -
95
FC5D4 TPP4D 1234ze(E) 5 - 95 cyclopentane 5 -
95
FC5E4 TPP4E 1234ze(E) 5 - 95 cyclopentane 5 -
95
FC5A5 TPP5A 1234ze(E) 5 - 95 cyclopentane 5 -
95
FC5B5 TPP5B 1234ze(E) 5 - 95 cyclopentane 5 -
95
FC5C5 TPP5C 1234ze(E) 5 - 95 cyclopentane 5 -
95
FC5D5 TPP5D 1234ze(E) 5 - 95 cyclopentane 5 -
95
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Foamable Foamable Composition Components
Composition
Number
Blowing Agent(s) and Amounts, wt% of All Blowing Agents
Polymer, Blowing Agent 1 Wt% BA! Co Blowing Agent(s)
Wt% CB
TPP No. (BA!) (CB)
FC5E5 TPP5E 1234ze(E) 5 - 95 cyclopentane 5 -
95
FC5A6 TPP6A 1234ze(E) 5 - 95 cyclopentane 5 -
95
FC5B6 TPP6B 1234ze(E) 5 - 95 cyclopentane 5 -
95
FC5C6 TPP6C 1234ze(E) 5 - 95 cyclopentane 5 -
95
FC5D6 TPP6D 1234ze(E) 5 - 95 cyclopentane 5 -
95
FC5E6 TPP6E 1234ze(E) 5 - 95 cyclopentane 5 -
95
FC6A1 TPPlA 1234ze(E) 5 - 95 HFC-134a 5 -
95
FC6B1 TPP1B 1234ze(E) 5 - 95 HFC-134a 5 -
95
FC6C1 TPP1 C 1234ze(E) 5-95 1-1FC-134a 5 -
95
FC6D1 TPP1D 1234ze(E) 5 - 95 HFC-134a 5 -
95
FC6E1 TPPlE 1234ze(E) 5 - 95 HFC-134a 5 -
95
FC6A2 TPP2A 1234ze(E) 5 - 95 HFC-134a 5 -
95
FC6B2 TPP2B 1234ze(E) 5 - 95 HFC-134a 5 -
95
FC6C2 TPP2C 1234ze(E) 5-95 HFC-134a 5 -
95
FC6D2 TPP2D 1234ze(E) 5 - 95 HFC-134a 5 -
95
FC6E2 TPP2E 1234ze(E) 5 - 95 HFC-134a 5 -
95
FC6A3 TPP3A 1234ze(E) 5 - 95 HiFC-134a 5 -
95
FC6B3 TPP3B 1234ze(E) 5 - 95 HFC-134a 5 -
95
FC6C3 TPP3C 1234ze(E) 5 - 95 HFC-134a 5 -
95
FC6D3 TPP3D 1234ze(E) 5 - 95 HFC-134a 5 -
95
FC6E3 TPP3E 1234ze(E) 5 - 95 HFC-134a 5 -
95
FC6A4 TPP4A 1234ze(E) 5 - 95 HFC-134a 5 -
95
FC6B4 TPP4B 1234ze(E) 5 - 95 HFC-134a 5 -
95
FC6C4 TPP4C 1234ze(E) 5 - 95 HFC-134a 5 -
95
26
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Foamable Foamable Composition Components
Composition
Number
Blowing Agent(s) and Amounts, wt% of All Blowing Agents
Polymer, Blowing Agent 1 Wt% BA! Co Blowing Agent(s)
Wt% CB
TPP No. (BA!) (CB)
FC6D4 TPP4D 1234ze(E) 5 - 95 HFC-134a 5 -
95
FC6E4 TPP4E 1234ze(E) 5 - 95 HFC-134a 5 -
95
FC6A5 TPP5A 1234ze(E) 5 - 95 HFC-134a 5 -
95
FC6B5 TPP5B 1234ze(E) 5 - 95 HFC-134a 5 -
95
FC6C5 TPP5C 1234ze(E) 5 - 95 HF'C-134a 5 -
95
FC6D5 TPP5D 1234ze(E) 5 - 95 HFC-134a 5 -
95
FC6E5 TPP5E 1234ze(E) 5 - 95 HFC-134a 5 -
95
FC6A6 TPP6A 1234ze(E) 5 - 95 HFC-134a 5 -
95
FC6B6 TPP6B 1234ze(E) 5-95 ITFC-134a 5 -
95
FC6C6 TPP6C 1234ze(E) 5 - 95 HFC-134a 5 -
95
FC6D6 TPP6D 1234ze(E) 5 - 95 HFC-134a 5 -
95
FC6E6 TPP6E 1234ze(E) 5 - 95 HFC-134a 5 -
95
FC7A1 TPPlA 1234ze(E) 5 - 95 CO2 5 -
95
FC7B1 TPP1B 1234ze(E) 5 - 95 CO2 5 -
95
FC7C1 TPP1C 1234ze(E) 5 - 95 CO2 5 -
95
FC7D1 TPP1D 1234ze(E) 5 - 95 CO2 5 -
95
FC7E1 TPPlE 1234ze(E) 5 - 95 CO2 5 -
95
FC7A2 TPP2A 1234ze(E) 5 - 95 CO2 5 -
95
FC7B2 TPP2B 1234ze(E) 5 - 95 CO2 5 -
95
FC7C2 TPP2C 1234ze(E) 5 - 95 CO2 5 -
95
FC7D2 TPP2D 1234ze(E) 5 - 95 CO2 5 -
95
FC7E2 TPP2E 1234ze(E) 5 - 95 CO2 5 -
95
FC7A3 TPP3A 1234ze(E) 5 - 95 CO2 5 -
95
FC7B3 TPP3B 1234ze(E) 5 - 95 CO2 5 -
95
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Foamable Foamable Composition Components
Composition
Number
Blowing Agent(s) and Amounts, wt% of All Blowing Agents
Polymer, Blowing Agent 1 Wt% BA! Co Blowing Agent(s)
Wt% CB
TPP No. (BA!) (CB)
FC7C3 TPP3C 1234ze(E) 5 - 95 CO2 5 -
95
FC7D3 TPP3D 1234ze(E) 5 - 95 CO2 5 -
95
FC7E3 TPP3E 1234ze(E) 5 - 95 CO2 5 -
95
FC7A4 TPP4A 1234ze(E) 5 - 95 CO2 5 -
95
FC7B4 TPP4B 1234ze(E) 5 - 95 CO2 5 -
95
FC7C4 TPP4C 1234ze(E) 5 - 95 CO2 5 -
95
FC7D4 TPP4D 1234ze(E) 5 - 95 CO2 5 -
95
FC7E4 TPP4E 1234ze(E) 5 - 95 CO2 5 -
95
FC7A5 TPP5A 1 234ze(E) 5 - 95 CO2 5 -
95
FC7B5 TPP5B 1234ze(E) 5 - 95 CO2 5 -
95
FC7C5 TPP5C 1234ze(E) 5 - 95 CO2 5 -
95
FC7D5 TPP5D 1234ze(E) 5 - 95 CO2 5 -
95
FC7E5 TPP5E 1234ze(E) 5 - 95 CO2 5 -
95
FC7A6 TPP6A 1234ze(E) 5 - 95 CO2 5 -
95
FC7B6 TPP6B 1234ze(E) 5 - 95 CO2 5 -
95
FC7C6 TPP6C 1234ze(E) 5 - 95 CO2 5 -
95
FC7D6 TPP6D 1234ze(E) 5 - 95 CO2 5 -
95
FC7E6 TPP6E 1234ze(E) 5 - 95 CO2 5 -
95
FC8A1 TPPlA 1234ze(E) 5 - 95 1233zd(E) 5 -
95
FC8B1 TPP1B 1234ze(E) 5 - 95 1233zd(E) 5 -
95
FC8C1 TPP1C 1234ze(E) 5-95 1233zd(E) 5-
95
FC8D1 TPP1D 1234ze(E) 5-95 1233zd(E) 5-
95
FC8E1 TPP1E 1234ze(E) 5 - 95 1233zd(E) 5 -
95
FC8A2 TPP2A 1234ze(E) 5 - 95 1233zd(E) 5 -
95
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Foamable Foamable Composition Components
Composition
Number
Blowing Agent(s) and Amounts, wt% of All Blowing Agents
Polymer, Blowing Agent 1 Wt% BA! Co Blowing Agent(s)
Wt% CB
TPP No. (BA!) (CB)
FC8B2 TPP2B 1234ze(E) 5 - 95 1233zd(E) 5 -
95
FC8C2 TPP2C 1234ze(E) 5 - 95 1233zd(E) 5 -
95
FC8D2 TPP2D 1234ze(E) 5 - 95 1233zd(E) 5 -
95
FC8E2 TPP2E 1234ze(E) 5 - 95 1233zd(E) 5 -
95
FC8A3 TPP3A 1234ze(E) 5 - 95 1233zd(E) 5 -
95
FC8B3 TPP3B 1234ze(E) 5 - 95 1233zd(E) 5 -
95
FC8C3 TPP3C 1234ze(E) 5 - 95 1233zd(E) 5 -
95
FC8D3 TPP3D 1234ze(E) 5 - 95 1233zd(E) 5 -
95
FC8E3 TPP3E 1234ze(E) 5 - 95 1233zd(E) 5 -
95
FC8A4 TPP4A 1234ze(E) 5 - 95 1233zd(E) 5 -
95
FC8B4 TPP4B 1234ze(E) 5 - 95 1233zd(E) 5 -
95
FC8C4 TPP4C 1234ze(E) 5 - 95 1233zd(E) 5 -
95
FC8D4 TPP4D 1234ze(E) 5 - 95 1233zd(E) 5 -
95
FC8E4 TPP4E 1234ze(E) 5 - 95 1233zd(E) 5 -
95
FC8A5 TPP5A 1234ze(E) 5 - 95 1233zd(E) 5 -
95
FC8B5 TPP5B 1234ze(E) 5 - 95 1233zd(E) 5 -
95
FC8C5 TPP5C 1234ze(E) 5 - 95 1233zd(E) 5 -
95
FC8D5 TPP5D 1234ze(E) 5 - 95 1233zd(E) 5 -
95
FC8E5 TPP5E 1234ze(E) 5 - 95 1233zd(E) 5 -
95
FC8A6 TPP6A 1234ze(E) 5 - 95 1233zd(E) 5 -
95
FC8B6 TPP6B 1234ze(E) 5 - 95 1233zd(E) 5 -
95
FC8C6 TPP6C 1234ze(E) 5 - 95 1233zd(E) 5 -
95
FC8D6 TPP6D 1234ze(E) 5 - 95 1233zd(E) 5 -
95
FC8E6 TPP6E 1234ze(E) 5 - 95 1233zd(E) 5 -
95
29
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Foam Forming Methods
It is contemplated that any one or more of a variety of known techniques for
forming a thermoplastic foam can be used in view of the disclosures contained
herein to
form a foam of the present invention, including each of Foams 1 ¨ 6 and each
of foams
Fl ¨ F8, and all such techniques and all foams formed thereby or within the
broad
scope of the present invention. For clarity, it will be noted that definition
of the foams in
the Table below all begin with only the letter F, in contrast to the foams
defined by the
paragraphs in the summary above, which begin with the capitalized word Foam.
In general, the forming step involves first introducing into a PEF polymer of
the
present invention, including each of TPP1 ¨ TPP6, a blowing agent of the
present
invention, including each of Blowing Agents 1 ¨ 31, to form a foamable PEF
composition comprising PEF and blowing agent. One example of a preferred
method
for forming a foamable PEF composition of the present invention is to
plasticize the
PEF, preferably comprising heating the PEF to its melt temperature, preferably
above
its melt temperature, and thereafter exposing the PEF melt to the blowing
agent under
conditions effective to incorporate (preferably by solubilizing) the desired
amount of
blowing agent into the polymer melt.
In preferred embodiments, the foaming methods of the present invention
comprise providing a foamable composition of the present invention, including
each of
FC1 ¨ FC8 and foaming the provided foamable composition. In preferred
embodiments, the foaming methods of the present invention comprising providing
a
foamable composition of the present invention, including each of FC1 ¨ FC8,
and
extruding the provided foamable composition to form a foam of the present
invention,
including each of Foams 1 ¨ 6 and each of foams Fl ¨ F8.
Foaming processes of the present invention can include batch, semi-batch,
continuous processes, and combinations of two or more of these. Batch
processes
generally involve preparation of at least one portion of the foamable polymer
composition, including each of FC1 ¨ FC8, in a storable state and then using
that
portion of foamable polymer composition at some future point in time to
prepare a foam.
Semi-batch process involves preparing at least a portion of a foamable polymer
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composition, including each of FC1 ¨ FC8, and intermittently expanding that
foamable
polymer composition into a foam including each of Foams 1 ¨6 and each of foams
Fl ¨
F8, all in a single process. For example, U.S. Pat. No. 4,323,528, herein
incorporated
by reference, discloses a process for making thermoplastic foams via an
accumulating
extrusion process. The present invention thus includes processes that
comprises: 1)
mixing PEF thermoplastic polymer, including each of TPP1 ¨ TP P6, and a
blowing
agent of the present invention, including each of Blowing Agents 1 ¨ 31, under

conditions to form a foamable PEF composition; 2) extruding the foamable PEF
composition, including each of FC1 ¨ FC8, into a holding zone maintained at a
temperature and pressure which does not allow the foamable composition to
foam,
where the holding zone preferably comprises a die defining an orifice opening
into a
zone of lower pressure at which the foamable polymer composition, including
each of
FC1 ¨ FC8, foams and an openable gate closing the die orifice; 3) periodically
opening
the gate while substantially concurrently applying mechanical pressure by
means of a
movable ram on the foamable polymer composition, including each of FC1 ¨ FC8,
to
eject it from the holding zone through the die orifice into the zone of lower
pressure, and
4) allowing the ejected foamable polymer composition to expand, under the
influence of
the blowing agent, to form the foam, including each of Foams 1 ¨ 6 and each of
foams
Fl ¨ F8.
The present invention also can use continuous processes for forming the foam.
By way of example such a continuous process involves forming a foamable PEF
composition, including each of FC1 ¨ FC8, and then expanding that foamable PEF

composition without substantial interruption. For example, a foamable PEF
composition,
including each of FC1 ¨ FC8, may be prepared in an extruder by heating the
selected
PEF polymer resin, including each of TPP1 ¨ TPP6, to form a PEF melt,
incorporating
into the PEF melt a blowing agent of the present invention, including each of
Blowing
Agents 1 ¨ 31, preferably by solubilizing the blowing agent into the PEF melt,
at an
initial pressure to form a foamable PEF composition comprising a substantially

homogeneous combination of PEF and blowing agent, including each of FC1 ¨ FC8,
and then extruding that foamable PEF composition through a die into a zone at
a
selected foaming pressure and allowing the foamable PEF composition to expand
into a
31
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foam, including each of Foams 1 ¨6 and each of foams Fl ¨ F8 described below,
under
the influence of the blowing agent. Optionally, the foamable PEF composition
which
comprises the PEF polymer, including each of FC1 ¨ FC8, and the incorporated
blowing
agent, including each of Blowing Agents 1 ¨ 31, may be cooled prior to
extruding the
composition through the die to enhance certain desired properties of the
resulting foam,
including each of Foams 1 ¨ 6 and each of foams Fl ¨ F8.
The methods can be carried out, by way of example, using extrusion equipment
of the general type disclosed in Figure 1. In particular, the extrusion
apparatus can
include a raw material feed hopper 10 for holding the PEF polymer 15 of the
present
invention, including each of TPP1 ¨ TPP6, and one or more optional components
(which may be added with the PEF in the hopper or optionally elsewhere in the
process
depending on the particular needs of the user). The feed materials 15,
excluding the
blowing agent, can be charged to the hopper and delivered to the screw
extruder 10.
The extruder 20 can include thermocouples (not shown) located at three points
along
the length thereof and a pressure sensor (not shown) at the discharge end 20A
of the
extruder. A mixer section 30 can be located at the discharge end 20A of the
extruder
for receiving blowing agent components of the present invention, including
each of
Blowing Agents 1 ¨ 31, via one or more metering pumps 40A and 40B and mixing
those
blowing agents into the PEF melt in the mixer section. Sensors (not shown) can
be
included for monitoring the temperature and pressure of the mixer section 30.
The
mixer section 30 can then discharge the foamable composition melt of the
present
invention, including each of FC1 ¨ FC8, into a pair of melt coolers 50
oriented in series,
with temperature sensors (not shown) located in each cooler to monitor the
melt
temperature. The melt is then extruded through a die 60, which also had
temperature
and pressure sensors (not shown) for monitoring the pressure and temperature
at the
die. The die pressure and temperature can be varied, according to the needs of
each
particular extrusion application to produce a foam 70 of the present
invention, including
each of including each of Foams 1 ¨ 6 and each of foams Fl ¨ F8 described
below. The
foam can then be carried away from the extrusion equipment by a conveyor belt
80.
The foamable polymer compositions of the present invention, including each of
FC1 ¨ FC8, may optionally contain additional additives such as nucleating
agents, cell-
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controlling agents, glass and carbon fibers, dyes, pigments, fillers,
antioxidants,
extrusion aids, stabilizing agents, antistatic agents, fire retardants, IR
attenuating agents and thermally insulating additives. Nucleating agents
include, among
others, materials such as talc, calcium carbonate, sodium benzoate, and
chemical blowing agents such azodicarbonamide or sodium bicarbonate and citric
acid.
IR attenuating agents and thermally insulating additives can include carbon
black,
graphite, silicon dioxide, metal flake or powder, among others. Flame
retardants can
include, among others, brominated materials such as hexabromocyclodecane and
polybrominated biphenyl ether. Each of the above-noted additional optional
additives
can be introduced into the foam at various times and that various locations in
the
process according to known techniques, and all such additives and methods of
addition
or within the broad scope of the present invention.
Foams
In preferred embodiments, the foams of the present invention are formed in a
commercial extrusion apparatus and have the properties as indicated in the
following Table 4, with the values being measured as described in the Examples

hereof:
TABLE 4
Broad First Second First Second
Range Intermediate Intermediate Narrow Narrow
Range Range Range Range
Foam property
Foam density, 0.05¨ .06 ¨ 0.14 .06 ¨ 0.14 0.06¨
0.06 ¨
g/cc (ISO 845)
.16 0.11
0.11
Compressive 0.5 ¨ 0.6 ¨ 1.5 0.9 ¨ 2.3 0.6 ¨ 0.9
¨ 1.7
Strength
2.5 1.1
(perpendicular to
the plane) (ISO
844), Mpa
Tensile strength 1.0¨ 1.2 ¨ 3.7 1.8 ¨ 5.6 1.2¨ 1.8
¨ 4.7
perpendicular to
6.2 3.1
the plane (ASTM
C297), Mpa
Average Cell Size, 10¨ 20 ¨ 150 20 ¨ 150 20 - 100 20 -
100
(SEM)
200
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Foams that are included within the present invention and which provide
particular
advantage are described in the following Table 5, and in which all numerical
values in
the table are understood to be preceded by the word "about" and in which the
designation NR means "not required."
TABLE 5 ¨ FOAM TABLE
Foam Properties
% Density, Compressive Tensile
Strength,
Foamable Closed gicc3 Strength, ((ASTM C297),
Foam Composition, Cell (ISO 844), megapascal
Number No. megapascal
FlAlA FC1A1 >25 NR NR NR
FIB1A FC1B1 >25 NR NR NR
F1C1A FC1C1 >25 NR NR NR
Fl DIA FC1D1 >25 NR NR NR
FIE lA FC1E1 >25 NR NR NR
F1A2A FC1A2 >25 NR NR NR
F1B2A FC1B2 >25 NR NR NR
Fl C2A FC1C2 >25 NR NR NR
F1D2A FC1D2 >25 NR NR NR
F1E2A FC1E2 >25 NR NR NR
F1A3A FC1A3 >25 NR NR NR
F1B3A FC1B3 >25 NR NR NR
Fl C3A FC1C3 >25 NR NR NR
F1D3A FC1D3 >25 NR NR NR
FIE3A FC1E3 >25 NR NR NR
F1A4A FC1A4 >25 NR NR NR
Fl B4A FC1B4 >25 NR NR NR
Fl C4A FC1C4 >25 NR NR NR
F1D4A FC1D4 >25 NR NR NR
F1E4A FC1E4 >25 NR NR NR
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Foam Properties
% Density, Compressive Tensile
Strength,
Foamable Closed g/cc3 Strength, ((ASTM C297),
Foam Composition, Cell (ISO 844), megapascal
Number No. megapascal
F1A5A FC1A5 >25 NR NR NR
F1B5A FC1B5 >25 NR NR NR
F1C5A FC1C5 >25 NR NR NR
F1D5A FC1D5 >25 NR NR NR
F1E5A FC1E5 >25 NR NR NR
F1A6A FC1A6 >25 NR NR NR
F1B6A FC1B6 >25 NR NR NR
F1C6A FC1C6 >25 NR NR NR
F1D6A FC1D6 >25 NR NR NR
Fl E6A FC1E6 >25 NR NR NR
F2A1A FC2A1 >25 NR NR NR
F2B1A FC2B1 >25 NR NR NR
F2C1A FC2C1 >25 NR NR NR
F2D1A FC2D1 >25 NR NR NR
F2E1A FC2E1 >25 NR NR NR
F2A2A FC2A2 >25 NR NR NR
F2B2A FC2B2 >25 NR NR NR
F2C2A FC2C2 >25 KR NR NR
F2D2A FC2D2 >25 NR KR NR
F2E2A FC2E2 >25 NR NR NR
F2A3A FC2A3 >25 NR NR NR
F2B3A FC2B3 >25 NR NR NR
F2C3A FC2C3 >25 NR NR NR
F2D3A FC2D3 >25 NR NR NR
F2E3A FC2E3 >25 NR NR NR
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Foam Properties
% Density, Compressive Tensile
Strength,
Foamable Closed g/cc3 Strength, ((ASTM C297),
Foam Composition, Cell (ISO 844), megapascal
Number No. megapascal
F2A4A FC2A4 >25 NR NR NR
F2B4A FC2B4 >25 NR NR NR
F2C4A FC2C4 >25 NR NR NR
F2D4A FC2D4 >25 NR NR NR
F2E4A FC2E4 >25 NR NR NR
F2A5A FC2A5 >25 NR NR NR
F2B5A FC2B5 >25 NR NR NR
F2C5A FC2C5 >25 NR NR NR
F2D5A FC2D5 >25 NR NR NR
F2E5A FC2E5 >25 NR NR NR
F2A6A FC2A6 >25 NR NR NR
F2B6A FC2B6 >25 NR NR NR
F2C6A FC2C6 >25 NR NR NR
F2D6A FC2D6 >25 NR NR NR
F2E6A FC2E6 >25 NR NR NR
F3A1A FC3A1 >25 NR NR NR
F3B1A FC3B1 >25 NR NR NR
F3C1A FC3C1 >25 KR NR NR
F3D1A FC3D1 >25 NR NR NR
F3E1A FC3E1 >25 NR NR NR
F3A2A FC3A2 >25 NR NR NR
F3B2A FC3B2 >25 NR NR NR
F3C2A FC3C2 >25 NR NR NR
F3D2A FC3D2 >25 NR NR NR
F3E2A FC3E2 >25 NR NR NR
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Foam Properties
% Density, Compressive Tensile
Strength,
Foamable Closed g/cc3 Strength, ((ASTM C297),
Foam Composition, Cell (ISO 844), megapascal
Number No. megapascal
F3A3A FC3A3 >25 NR NR NR
F3B3A FC3B3 >25 NR NR NR
F3C3A FC3C3 >25 NR NR NR
F3D3A FC3D3 >25 NR NR NR
F3E3A FC3E3 >25 NR NR NR
F3A4A FC3A4 >25 NR NR NR
F3B4A FC3B4 >25 NR NR NR
F3C4A FC3C4 >25 NR NR NR
F3D4A FC3D4 >25 NR NR NR
F3E4A FC3E4 >25 NR NR NR
F3A5A FC3A5 >25 NR NR NR
F3B5A FC3B5 >25 NR NR NR
F3C5A FC3C5 >25 NR NR NR
F3D5A FC3D5 >25 NR NR NR
F3E5A FC3E5 >25 NR NR NR
F3A6A FC3A6 >25 NR NR NR
F3B6A FC3B6 >25 NR NR NR
F3C6A FC3C6 >25 KR NR NR
F3D6A FC3D6 >25 NR KR NR
F3E6A FC3E6 >25 NR NR NR
F4A1A FC4A1 >25 R NR NR
F4B1A FC4B1 >25 NR NR NR
F4C1A FC4C1 >25 NR NR NR
F4D1A FC4D1 >25 NR NR NR
F4E1A FC4E1 >25 NR NR NR
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Foam Properties
% Density, Compressive Tensile
Strength,
Foamable Closed g/cc3 Strength, ((ASTM C297),
Foam Composition, Cell (ISO 844), megapascal
Number No. megapascal
F4A2A FC4A2 >25 NR NR NR
F4B2A FC4B2 >25 NR NR NR
F4C2A FC4C2 >25 NR NR NR
F4D2A FC4D2 >25 NR NR NR
F4E2A FC4E2 >25 NR NR NR
F4A3A FC4A3 >25 NR NR NR
F4B3A FC4B3 >25 NR NR NR
FC4C3A FC4C3 >25 NR NR NR
F4D3A FC4D3 >25 NR NR NR
F4E3A FC4E3 >25 NR NR NR
F4A4A FC4A4 >25 NR NR NR
F4B4A FC4B4 >25 NR NR NR
F4C4A FC4C4 >25 NR NR NR
F4D4A FC4D4 >25 NR NR NR
F4E4A FC4E4 >25 NR NR NR
F4A5A FC4A5 >25 NR NR NR
F4B5A FC4B5 >25 NR NR NR
F4C5A FC4C5 >25 KR NR NR
F4D5A FC4D5 >25 NR NR NR
F4E5A FC4E5 >25 NR NR NR
F4A6A FC4A6 >25 NR NR NR
F4B6A FC4B6 >25 NR NR NR
F4C6A FC4C6 >25 NR NR NR
F4D6A FC4D6 >25 NR NR NR
F4E6A FC4E6 >25 NR NR NR
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Foam Properties
% Density, Compressive Tensile
Strength,
Foamable Closed g/cc3 Strength, ((ASTM C297),
Foam Composition, Cell (ISO 844), megapascal
Number No. megapascal
F5A1A FC5A1 >25 NR NR NR
F5B1A FC5B1 >25 NR NR NR
F5C1A FC5C1 >25 NR NR NR
F5D1A FC5D1 >25 NR NR NR
F5E1A FC5E1 >25 NR NR NR
F5A2A FC5A2 >25 NR NR NR
F5B2A FC5B2 >25 NR NR NR
F5C2A FC5C2 >25 NR NR NR
F5D2A FC5D2 >25 NR NR NR
F5E2A FC5E2 >25 NR NR NR
F5A3A FC5A3 >25 NR NR NR
F5B3A FC5B3 >25 NR NR NR
F5C3A FC5C3 >25 NR NR NR
F5D3A FC5D3 >25 NR NR NR
F5E3A FC5E3 >25 NR NR NR
F5A4A FC5A4 >25 NR NR NR
F5B4A FC5B4 >25 NR NR NR
F5C4A FC5C4 >25 KR NR NR
F5D4A FC5D4 >25 NR NR NR
F5E4A FC5E4 >25 NR NR NR
F5A5A FC5A5 >25 NR NR NR
F5B5A FC5B5 >25 NR NR NR
F5C5A FC5C5 >25 NR NR NR
F5D5A FC5D5 >25 NR NR NR
F5E5A FC5E5 >25 NR NR NR
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Foam Properties
% Density, Compressive Tensile
Strength,
Foamable Closed g/cc3 Strength, ((ASTM C297),
Foam Composition, Cell (ISO 844), megapascal
Number No. megapascal
F5A6A FC5A6 >25 NR NR NR
F5B6A FC5B6 >25 NR NR NR
F5C6A FC5C6 >25 NR NR NR
F5D6A FC5D6 >25 NR NR NR
F5E6A FC5E6 >25 NR NR NR
F6A1A FC6A1 >25 NR NR NR
F6B1A FC6B1 >25 NR NR NR
F6C1A FC6C1 >25 NR NR NR
F6D1A FC6D1 >25 NR NR NR
F6E1A FC6E1 >25 NR NR NR
F6A2A FC6A2 >25 NR NR NR
F6B2A FC6B2 >25 NR NR NR
F6C2A FC6C2 >25 NR NR NR
F6D2A FC6D2 >25 NR NR NR
F6E2A FC6E2 >25 NR NR NR
F6A3A FC6A3 >25 NR NR NR
F6B3A FC6B3 >25 NR NR NR
F6C3A FC6C3 >25 KR NR NR
F6D3A FC6D3 >25 NR NR NR
F6E3A FC6E3 >25 NR NR NR
F6B4A FC6B4 >25 NR NR NR
F6C4A FC6C4 >25 NR NR NR
F6D4A FC6D4 >25 NR NR NR
F6E4A FC6E4 >25 NR NR NR
F6A5A FC6A5 >25 NR NR NR
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Foam Properties
% Density, Compressive Tensile
Strength,
Foamable Closed g/cc3 Strength, ((ASTM C297),
Foam Composition, Cell (ISO 844), megapascal
Number No. megapascal
F6B5A FC6B5 >25 NR NR NR
F6C5A FC6C5 >25 NR NR NR
F6D5A FC6D5 >25 NR NR NR
F6E5A FC6E5 >25 NR NR NR
F6A6A FC6A6 >25 NR NR NR
F6B6A FC6B6 >25 NR NR NR
F6C6A FC6C6 >25 NR NR NR
F6D6A FC6D6 >25 NR NR NR
F6E6A FC6E6 >25 NR NR NR
F7A1A FC7A1 >25 NR NR NR
F7B1A FC7B1 >25 NR NR NR
F7C1A FC7C1 >25 NR NR NR
F7D1A FC7D1 >25 NR NR NR
F7E1A FC7E1 >25 NR NR NR
F7A2A FC7A2 >25 NR NR NR
F7B2 FC7B2 >25 NR NR NR
F7C2A FC7C2 >25 NR NR NR
F7D2A FC7D2 >25 NR NR NR
F7E2A FC7E2 >25 NR NR NR
F7A3A FC7A3 >25 NR NR NR
F7B3A FC7B3 >25 NR NR NR
F7C3A FC7C3 >25 NR NR NR
F7D3A FC7D3 >25 NR NR NR
F7E3A FC7E3 >25 NR NR NR
F7A4A FC7A4 >25 NR NR NR
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Foam Properties
% Density, Compressive Tensile
Strength,
Foamable Closed g/cc3 Strength, ((ASTM C297),
Foam Composition, Cell (ISO 844), megapascal
Number No. megapascal
F7B4A FC7B4 >25 NR NR NR
F7C4A FC7C4 >25 NR NR NR
F7D4A FC7D4 >25 NR NR NR
F7E4A FC7E4 >25 NR NR NR
F7A5A FC7A5 >25 NR NR NR
F7B5A FC7B5 >25 NR NR NR
F7C5A FC7C5 >25 NR NR NR
F7D5A FC7D5 >25 NR NR NR
F7E5A FC7E5 >25 NR NR NR
F7A6A FC7A6 >25 NR NR NR
F7B6A FC7B6 >25 NR NR NR
F7C6A FC7C6 >25 NR NR NR
F7D6A FC7D6 >25 NR NR NR
F7E6A FC7E6 >25 NR NR NR
F8A1A FC8A1 >25 NR NR NR
F8B1A FC8B1 >25 NR NR NR
F8C1A FC8C1 >25 NR NR NR
F8D1A FC8D1 >25 NR NR NR
F8E1A FC8E1 >25 NR NR NR
F8A2A FC8A2 >25 NR NR NR
F8B2A FC8B2 >25 NR NR NR
F8C2A FC8C2 >25 NR NR NR
F8D2A FC8D2 >25 NR NR NR
F8E2A FC8E2 >25 NR NR NR
F8A3A FC8A3 >25 NR NR NR
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Foam Properties
% Density, Compressive Tensile
Strength,
Foamable Closed g/cc3 Strength, ((ASTM C297),
Foam Composition, Cell (ISO 844), megapascal
Number No. megapascal
F8B3A FC8B3 >25 NR NR NR
F8C3A FC8C3 >25 NR NR NR
F8D3A FC8D3 >25 NR NR NR
F8E3A FC8E3 >25 NR NR NR
F8A4A FC8A4 >25 NR NR NR
F8B4A FC8B4 >25 NR NR NR
F8C4A FC8C4 >25 NR NR NR
F8D4A FC8D4 >25 NR NR NR
F8E4A FC8E4 >25 NR NR NR
F8A5A FC8A5 >25 NR NR NR
F8B5A FC8B5 >25 NR NR NR
F8C5A FC8C5 >25 NR NR NR
F8D5A FC8D5 >25 NR NR NR
F8E5A FC8E5 >25 NR NR NR
F8A6A FC8A6 >25 NR NR NR
F8B6A FC8B6 >25 NR NR NR
F8C6A FC8C6 >25 NR NR NR
F8D6A FC8D6 >25 KR NR NR
F8E6A FC8E6 >25 NR NR NR
F1A1B FC1A1 NR <0.16 NR NR
F1B1B FC1B1 NR <0.16 NR NR
F1C1B FC1C1 NR <0.16 NR NR
F1D1B FC1D1 NR <0.16 NR NR
F1E1B FC1E1 NR <0.16 NR NR
F1A2B FC1A2 NR <0.16 NR NR
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Foam Properties
% Density, Compressive Tensile
Strength,
Foamable Closed g/cc3 Strength, ((ASTM C297),
Foam Composition, Cell (ISO 844), megapascal
Number No. megapascal
F1B2B FC1132 NR <0.16 NR NR
F1C2B FC1C2 NR <0.16 NR NR
F1D2B FC1D2 NR <0.16 NR NR
F1E2B FC1E2 NR <0.16 NR NR
F1A3B FC1A3 NR <0.16 NR NR
F1B3B FC1B3 NR <0.16 NR NR
F1C3B FC1C3 NR <0.16 NR NR
F1D3B FC1D3 NR <0.16 NR NR
F1E3B FC1E3 NR <0.16 NR NR
Fl A4B FC1A4 NR <0.16 NR NR
F1B4B FC1B4 NR <0.16 NR NR
F1C4B FC1C4 NR <0.16 NR NR
F1D4B FC1D4 NR <0.16 NR NR
F1E4B FC1E4 NR <0.16 NR NR
Fl A5B FC1A5 NR <0.16 NR NR
F1B5B FC1B5 NR <0.16 NR NR
F1C5B FC1C5 NR <0.16 NR NR
F1D5B FC1D5 NR <0.16 NR NR
F1E5B FC1E5 NR <0.16 NR NR
F1A6B FC1A6 NR <0.16 NR NR
F1B6B FC1B6 NR <0.16 NR NR
F1C6B FC1C6 NR <0.16 NR NR
F1D6B FC1D6 NR <0.16 NR NR
F1E6B FC1E6 NR <0.16 NR NR
F2A1B FC2A1 NR <0.16 NR NR
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Foam Properties
% Density, Compressive Tensile
Strength,
Foamable Closed g/cc3 Strength, ((ASTM C297),
Foam Composition, Cell (ISO 844), megapascal
Number No. megapascal
F2B1B FC2B1 NR <0.16 NR NR
F2C1B FC2C1 NR <0.16 NR NR
F2D1B FC2D1 NR <0.16 NR NR
F2E1B FC2E1 NR <0.16 NR NR
F2A2B FC2A2 NR <0.16 NR NR
F2B2B FC2B2 NR <0.16 NR NR
F2C2B FC2C2 NR <0.16 NR NR
F2D2B FC2D2 NR <0.16 NR NR
F2E2B FC2E2 NR <0.16 NR NR
F2A3B FC2A3 NR <0.16 NR NR
F2B3B FC2B3 NR <0.16 NR NR
F2C3B FC2C3 NR <0.16 NR NR
F2D3B FC2D3 NR <0.16 NR NR
F2E3B FC2E3 NR <0.16 NR NR
F2A4B FC2A4 NR <0.16 NR NR
F2B4B FC2B4 NR <0.16 NR NR
F2C4B FC2C4 NR <0.16 NR NR
F2D4B FC2D4 NR <0.16 NR NR
F2E4B FC2E4 NR <0.16 NR NR
F2A5B FC2A5 NR <0.16 NR NR
F2B5B FC2B5 NR <0.16 NR NR
F2C5B FC2C5 NR <0.16 NR NR
F2D5B FC2D5 NR <0.16 NR NR
F2E5B FC2E5 NR <0.16 NR NR
F2A6B FC2A6 NR <0.16 NR NR
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Foam Properties
% Density, Compressive Tensile
Strength,
Foamable Closed g/cc3 Strength, ((ASTM C297),
Foam Composition, Cell (ISO 844), megapascal
Number No. megapascal
F2B6B FC2B6 NR <0.16 NR NR
F2C6B FC2C6 NR <0.16 NR NR
F2D6B FC2D6 NR <0.16 NR NR
F2E6B FC2E6 NR <0.16 NR NR
F3A1B FC3A1 NR <0.16 NR NR
F3B1B FC3B1 NR <0.16 NR NR
F3C1B FC3C1 NR <0.16 NR NR
F3D1B FC3D1 NR <0.16 NR NR
F3E1B FC3E1 NR <0.16 NR NR
F3A2B FC3A2 NR <0.16 NR NR
F3B2B FC3B2 NR <0.16 NR NR
F3C2B FC3C2 NR <0.16 NR NR
F3D2B FC3D2 NR <0.16 NR NR
F3E2B FC3E2 NR <0.16 NR NR
F3A3B FC3A3 NR <0.16 NR NR
F3B3B FC3B3 NR <0.16 NR NR
F3C3B FC3C3 NR <0.16 NR NR
F3D3B FC3D3 NR <0.16 NR NR
F3E3B FC3E3 NR <0.16 NR NR
F3A4B FC3A4 NR <0.16 NR NR
F3B4B FC3B4 NR <0.16 NR NR
F3C4B FC3C4 NR <0.16 NR NR
F3D4B FC3D4 NR <0.16 NR NR
F3E4B FC3E4 NR <0.16 NR NR
F3A5B FC3A5 NR <0.16 NR NR
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Foam Properties
% Density, Compressive Tensile
Strength,
Foamable Closed g/cc3 Strength, ((ASTM C297),
Foam Composition, Cell (ISO 844), megapascal
Number No. megapascal
F3B5B FC3B5 NR <0.16 NR NR
F3C5B FC3C5 NR <0.16 NR NR
F3D5B FC3D5 NR <0.16 NR NR
F3E5B FC3E5 NR <0.16 NR NR
F3A6B FC3A6 NR <0.16 NR NR
F3B6B FC3B6 NR <0.16 NR NR
F3C6B FC3C6 NR <0.16 NR NR
F3D6B FC3D6 NR <0.16 NR NR
F3E6B FC3E6 NR <0.16 NR NR
F4A1B FC4A1 NR <0.16 NR NR
F4B1B FC4B1 NR <0.16 NR NR
F4C1B FC4C1 NR <0.16 NR NR
F4D1B FC4D1 NR <0.16 NR NR
F4E1B FC4E1 NR <0.16 NR NR
F4A2B FC4A2 NR <0.16 NR NR
F4B2B FC4B2 NR <0.16 NR NR
F4C2B FC4C2 NR <0.16 NR NR
F4D2B FC4D2 NR <0.16 NR NR
F4E2B FC4E2 NR <0.16 NR NR
F4A3B FC4A3 NR <0.16 NR NR
F4B3B FC4B3 NR <0.16 NR NR
F4C3B FC4C3 NR <0.16 NR NR
F4D3B FC4D3 NR <0.16 NR NR
F4E3B FC4E3 NR <0.16 NR NR
F4A4B FC4A4 NR <0.16 NR NR
47
CA 03228700 2024- 2- 12 SUBSTITUTE SHEET (RULE 26)

WO 2023/023085
PCT/US2022/040504
Foam Properties
% Density, Compressive Tensile
Strength,
Foamable Closed g/cc3 Strength, ((ASTM C297),
Foam Composition, Cell (ISO 844), megapascal
Number No. megapascal
F4B4B FC4B4 NR <0.16 NR NR
F4C4B FC4C4 NR <0.16 NR NR
F4D4B FC4D4 NR <0.16 NR NR
F4E4B FC4E4 NR <0.16 NR NR
F4A5B FC4A5 NR <0.16 NR NR
F4B5B FC4B5 NR <0.16 NR NR
F4C5B FC4C5 NR <0.16 NR NR
F4D5B FC4D5 NR <0.16 NR NR
F4E5B FC4E5 NR <0.16 NR NR
F4A6B FC4A6 NR <0.16 NR NR
F4B6B FC4B6 NR <0.16 NR NR
F4C6B FC4C6 NR <0.16 NR NR
F4D6B FC4D6 NR <0.16 NR NR
F4E6B FC4E6 NR <0.16 NR NR
F5A1B FC5A1 NR <0.16 NR NR
F5B1B FC5B1 NR <0.16 NR NR
F5C1B FC5C1 NR <0.16 NR NR
F5D1B FC5D1 NR <0.16 NR NR
F5E1B FC5E1 NR <0.16 NR NR
F5A2B FC5A2 NR <0.16 NR NR
F5B2B FC5B2 NR <0.16 NR NR
F5C2B FC5C2 NR <0.16 NR NR
F5D2B FC5D2 NR <0.16 NR NR
F5E2B FC5E2 NR <0.16 NR NR
F5A3B FC5A3 NR <0.16 NR NR
48
CA 03228700 2024- 2- 12 SUBSTITUTE SHEET (RULE 26)

WO 2023/023085
PCT/US2022/040504
Foam Properties
% Density, Compressive Tensile
Strength,
Foamable Closed g/cc3 Strength, ((ASTM C297),
Foam Composition, Cell (ISO 844), megapascal
Number No. megapascal
F5B3B FC5B3 NR <0.16 NR NR
F5C3B FC5C3 NR <0.16 NR NR
F5D3B FC5D3 NR <0.16 NR NR
F5E3B FC5E3 NR <0.16 NR NR
F5A4B FC5A4 NR <0.16 NR NR
F5B4B FC5B4 NR <0.16 NR NR
F5C4B FC5C4 NR <0.16 NR NR
F5D4B FC5D4 NR <0.16 NR NR
F5E4B FC5E4 NR <0.16 NR NR
F5A5B FC5A5 NR <0.16 NR NR
F5B5B FC5B5 NR <0.16 NR NR
F5C5B FC5C5 NR <0.16 NR NR
F5D5B FC5D5 NR <0.16 NR NR
F5E5B FC5E5 NR <0.16 NR NR
F5A6B FC5A6 NR <0.16 NR NR
F5B6B FC5B6 NR <0.16 NR NR
F5C6B FC5C6 NR <0.16 NR NR
F5D6B FC5D6 NR <0.16 NR NR
F5E6B FC5E6 NR <0.16 NR NR
F6A1B FC6A1 NR <0.16 NR NR
F6B1B FC6B1 NR <0.16 NR NR
F6C1B FC6C1 NR <0.16 NR NR
F6D1B FC6D1 NR <0.16 NR NR
F6E1B FC6E1 NR <0.16 NR NR
F6A2B FC6A2 NR <0.16 NR NR
49
CA 03228700 2024- 2- 12 SUBSTITUTE SHEET (RULE 26)

WO 2023/023085
PCT/US2022/040504
Foam Properties
% Density, Compressive Tensile
Strength,
Foamable Closed g/cc3 Strength, ((ASTM C297),
Foam Composition, Cell (ISO 844), megapascal
Number No. megapascal
F6B2B FC6B2 NR <0.16 NR NR
F6C2B FC6C2 NR <0.16 NR NR
F6D2B FC6D2 NR <0.16 NR NR
F6E2B FC6E2 NR <0.16 NR NR
F6A3B FC6A3 NR <0.16 NR NR
F6B3B FC6B3 NR <0.16 NR NR
F6C3B FC6C3 NR <0.16 NR NR
F6D3B FC6D3 NR <0.16 NR NR
F6E3B FC6E3 NR <0.16 NR NR
F6B4B FC6B4 NR <0.16 NR NR
F6C4B FC6C4 NR <0.16 NR NR
F6D4B FC6D4 NR <0.16 NR NR
F6E4B FC6E4 NR <0.16 NR NR
F6A5B FC6A5 NR <0.16 NR NR
F6B5B FC6B5 NR <0.16 NR NR
F6C5B FC6C5 NR <0.16 NR NR
F6D5B FC6D5 NR <0.16 NR NR
F6E5B FC6E5 NR <0.16 NR NR
F6A6B FC6A6 NR <0.16 NR NR
F6B6B FC6B6 NR <0.16 NR NR
F6C6B FC6C6 NR <0.16 NR NR
F6D6B FC6D6 NR <0.16 NR NR
F6E6B FC6E6 NR <0.16 NR NR
F7A1B FC7A1 NR <0.16 NR NR
F7B1B FC7B1 NR <0.16 NR NR
CA 03228700 2024- 2- 12 SUBSTITUTE SHEET (RULE 26)

WO 2023/023085
PCT/US2022/040504
Foam Properties
% Density, Compressive Tensile
Strength,
Foamable Closed g/cc3 Strength, ((ASTM C297),
Foam Composition, Cell (ISO 844), megapascal
Number No. megapascal
F7C1B FC7C1 NR <0.16 NR NR
F7D1B FC7D1 NR <0.16 NR NR
F7E1B FC7E1 NR <0.16 NR NR
F7A2B FC7A2 NR <0.16 NR NR
F7B2B FC7B2 NR <0.16 NR NR
F7C2B FC7C2 NR <0.16 NR NR
F7D2B FC7D2 NR <0.16 NR NR
F7E2B FC7E2 NR <0.16 NR NR
F7A3B FC7A3 NR <0.16 NR NR
F7B3B FC7B3 NR <0.16 NR NR
F7C3B FC7C3 NR <0.16 NR NR
F7D3B FC7D3 NR <0.16 NR NR
F7E3B FC7E3 NR <0.16 NR NR
F7A4B FC7A4 NR <0.16 NR NR
F7B4B FC7B4 NR <0.16 NR NR
F7C4B FC7C4 NR <0.16 NR NR
F7D4B FC7D4 NR <0.16 NR NR
F7E4B FC7E4 NR <0.16 NR NR
F7A5B FC7A5 NR <0.16 NR NR
F7B5B FC7B5 NR <0.16 NR NR
F7C5B FC7C5 NR <0.16 NR NR
F7D5B FC7D5 NR <0.16 NR NR
F7E5B FC7E5 NR <0.16 NR NR
F7A6B FC7A6 NR <0.16 NR NR
F7B6B FC7B6 NR <0.16 NR NR
51
CA 03228700 2024- 2- 12 SUBSTITUTE SHEET (RULE 26)

WO 2023/023085
PCT/US2022/040504
Foam Properties
% Density, Compressive Tensile
Strength,
Foamable Closed g/cc3 Strength, ((ASTM C297),
Foam Composition, Cell (ISO 844), megapascal
Number No. megapascal
F7C6B FC7C6 NR <0.16 NR NR
F7D6B FC7D6 NR <0.16 NR NR
F7E6B FC7E6 NR <0.16 NR NR
F8A1B FC8A1 NR <0.16 NR NR
F8B1B FC8B1 NR <0.16 NR NR
F8C1B FC8C1 NR <0.16 NR NR
F8D1B FC8D1 NR <0.16 NR NR
F8E1B FC8E1 NR <0.16 NR NR
F8A2B FC8A2 NR <0.16 NR NR
F8132B FC8B2 NR <0.16 NR NR
F8C2B FC8C2 NR <0.16 NR NR
F8D2B FC8D2 NR <0.16 NR NR
F8E2B FC8E2 NR <0.16 NR NR
F8A3B FC8A3 NR <0.16 NR NR
F8B3B FC8B3 NR <0.16 NR NR
F8C3B FC8C3 NR <0.16 NR NR
F8D3B FC8D3 NR <0.16 NR NR
F8E3B FC8E3 NR <0.16 NR NR
F8A4B FC8A4 NR <0.16 NR NR
F8B4B FC8B4 NR <0.16 NR NR
F8C4B FC8C4 NR <0.16 NR NR
F8D4B FC8D4 NR <0.16 NR NR
F8E4B FC8E4 NR <0.16 NR NR
F8A5B FC8A5 NR <0.16 NR NR
F8B5B FC8B5 NR <0.16 NR NR
52
CA 03228700 2024- 2- 12 SUBSTITUTE SHEET (RULE 26)

WO 2023/023085
PCT/US2022/040504
Foam Properties
Density, Compressive Tensile
Strength,
Foamable Closed g/cc3 Strength, ((ASTM C297),
Foam Composition, Cell (ISO 844), megapascal
Number No. megapascal
F8C5B FC8C5 NR <0.16 NR NR
F8D5B FC8D5 NR <0.16 NR NR
F8E5B FC8E5 NR <0.16 NR NR
F8A6B FC8A6 NR <0.16 NR NR
F8B6B FC8B6 NR <0.16 NR NR
F8C6B FC8C6 NR <0.16 NR NR
F8D6B FC8D6 NR <0.16 NR NR
F8E6B FC8E6 NR <0.16 NR NR
F1A1C FC1A1 NR 0.05 - 0.16 NR NR
F1B1C FC1B1 NR 0.05 - 0.16 NR NR
F1C1C FC1C1 NR 0.05 - 0.16 NR NR
F1D1C FC1D1 NR 0.05 - 0.16 NR NR
F1E1C FC1E1 NR 0.05 - 0.16 NR NR
F1A2C FC1A2 NR 0.05 - 0.16 NR NR
Fl B2C FC1B2 NR 0.05 - 0.16 NR NR
F1C2C FC1C2 NR 0.05 - 0.16 NR NR
F1D2C FC1D2 NR 0.05 - 0.16 NR NR
F1E2C FC1E2 NR 0.05 - 0.16 NR NR
F1A3C FC1A3 NR 0.05 - 0.16 NR NR
F1B3C FC1B3 NR 0.05 - 0.16 NR NR
F1C3C FC1C3 NR 0.05 - 0.16 NR NR
F1D3C FC1D3 NR 0.05 - 0.16 NR NR
F1E3C FC1E3 NR 0.05 - 0.16 NR NR
F1A4C FC1A4 NR 0.05 - 0.16 NR NR
F1B4C FC1B4 NR 0.05 - 0.16 NR NR
53
CA 03228700 2024- 2- 12 SUBSTITUTE SHEET (RULE 26)

WO 2023/023085
PCT/US2022/040504
Foam Properties
Density, Compressive Tensile
Strength,
Foamable Closed g/cc3 Strength, ((ASTM C297),
Foam Composition, Cell (ISO 844), megapascal
Number No. megapascal
F1C4C FC1C4 NR 0.05 - 0.16 NR NR
F1D4C FC1D4 NR 0.05 - 0.16 NR NR
F1E4C FC1E4 NR 0.05 - 0.16 NR NR
F1A5C FC1A5 NR 0.05 - 0.16 NR NR
F1B5C FC1B5 NR 0.05 - 0.16 NR NR
F1C5C FC1C5 NR 0.05 - 0.16 NR NR
F1D5C FC1D5 NR 0.05 - 0.16 NR NR
F1E5C FC1E5 NR 0.05 - 0.16 NR NR
F1A6C FC1A6 NR 0.05 - 0.16 NR NR
Fl B6C FC1B6 NR 0.05 - 0.16 NR NR
F1C6C FC1C6 NR 0.05 - 0.16 NR NR
F1D6C FC1D6 NR 0.05 - 0.16 NR NR
F1E6C FC1E6 NR 0.05 - 0.16 NR NR
F2A1C FC2A1 NR 0.05 - 0.16 NR NR
F2B1C FC2B1 NR 0.05 - 0.16 NR NR
F2C1C FC2C1 NR 0.05 - 0.16 NR NR
F2D1C FC2D1 NR 0.05 - 0.16 NR NR
F2E1C FC2E1 NR 0.05 - 0.16 NR NR
F2A2C FC2A2 NR 0.05 - 0.16 NR NR
F2B2C FC2B2 NR 0.05 - 0.16 NR NR
F2C2C FC2C2 NR 0.05 - 0.16 NR NR
F2D2C FC2D2 NR 0.05 - 0.16 NR NR
F2E2C FC2E2 NR 0.05 - 0.16 NR NR
F2A3C FC2A3 NR 0.05 - 0.16 NR NR
F2B3C FC2B3 NR 0.05 - 0.16 NR NR
54
CA 03228700 2024- 2- 12 SUBSTITUTE SHEET (RULE 26)

WO 2023/023085
PCT/US2022/040504
Foam Properties
Density, Compressive Tensile
Strength,
Foamable Closed g/cc3 Strength, ((ASTM C297),
Foam Composition, Cell (ISO 844), megapascal
Number No. megapascal
F2C3C FC2C3 NR 0.05 - 0.16 NR NR
F2D3C FC2D3 NR 0.05 - 0.16 NR NR
F2E3C FC2E3 NR 0.05 - 0.16 NR NR
F2A4C FC2A4 NR 0.05 - 0.16 NR NR
F2B4C FC2B4 NR 0.05 - 0.16 NR NR
F2C4C FC2C4 NR 0.05 - 0.16 NR NR
F2D4C FC2D4 NR 0.05 - 0.16 NR NR
F2E4C FC2E4 NR 0.05 - 0.16 NR NR
F2A5C FC2A5 NR 0.05 - 0.16 NR NR
F2B5C FC2B5 NR 0.05 - 0.16 NR NR
F2C5C FC2C5 NR 0.05 - 0.16 NR NR
F2D5C FC2D5 NR 0.05 - 0.16 NR NR
F2E5C FC2E5 NR 0.05 - 0.16 NR NR
F2A6C FC2A6 NR 0.05 - 0.16 NR NR
F2B6C FC2B6 NR 0.05 - 0.16 NR NR
F2C6C FC2C6 NR 0.05 - 0.16 NR NR
F2D6C FC2D6 NR 0.05 - 0.16 NR NR
F2E6C FC2E6 NR 0.05 - 0.16 NR NR
F3A1C FC3A1 NR 0.05 - 0.16 NR NR
F3B1C FC3B1 NR 0.05 - 0.16 NR NR
F3C1C FC3C1 NR 0.05 - 0.16 NR NR
F3D1C FC3D1 NR 0.05 - 0.16 NR NR
F3E1C FC3E1 NR 0.05 - 0.16 NR NR
F3A2C FC3A2 NR 0.05 - 0.16 NR NR
F3B2C FC3B2 NR 0.05 - 0.16 NR NR
CA 03228700 2024- 2- 12 SUBSTITUTE SHEET (RULE 26)

WO 2023/023085
PCT/US2022/040504
Foam Properties
Density, Compressive Tensile
Strength,
Foamable Closed g/cc3 Strength, ((ASTM C297),
Foam Composition, Cell (ISO 844), megapascal
Number No. megapascal
F3C2C FC3C2 NR 0.05 - 0.16 NR NR
F3D2C FC3D2 NR 0.05 - 0.16 NR NR
F3E2C FC3E2 NR 0.05 - 0.16 NR NR
F3A3C FC3A3 NR 0.05 - 0.16 NR NR
F3B3C FC3B3 NR 0.05 - 0.16 NR NR
F3C3C FC3C3 NR 0.05 - 0.16 NR NR
F3D3C FC3D3 NR 0.05 - 0.16 NR NR
F3E3C FC3E3 NR 0.05 - 0.16 NR NR
F3A4C FC3A4 NR 0.05 - 0.16 NR NR
F3B4C FC3B4 NR 0.05 - 0.16 NR NR
F3C4C FC3C4 NR 0.05 - 0.16 NR NR
F3D4C FC3D4 NR 0.05 - 0.16 NR NR
F3E4C FC3E4 NR 0.05 - 0.16 NR NR
F3A5C FC3A5 NR 0.05 - 0.16 NR NR
F3B5C FC3B5 NR 0.05 - 0.16 NR NR
F3C5C FC3C5 NR 0.05 - 0.16 NR NR
F3D5C FC3D5 NR 0.05 - 0.16 NR NR
F3E5C FC3E5 NR 0.05 - 0.16 NR NR
F3A6C FC3A6 NR 0.05 - 0.16 NR NR
F3B6C FC3B6 NR 0.05 - 0.16 NR NR
F3C6C FC3C6 NR 0.05 - 0.16 NR NR
F3D6C FC3D6 NR 0.05 - 0.16 NR NR
F3E6C FC3E6 NR 0.05 - 0.16 NR NR
F4A1C FC4A1 NR 0.05 - 0.16 NR NR
F4B1C FC4B1 NR 0.05 - 0.16 NR NR
56
CA 03228700 2024- 2- 12 SUBSTITUTE SHEET (RULE 26)

WO 2023/023085
PCT/US2022/040504
Foam Properties
Density, Compressive Tensile
Strength,
Foamable Closed g/cc3 Strength, ((ASTM C297),
Foam Composition, Cell (ISO 844), megapascal
Number No. megapascal
F4C1C FC4C1 NR 0.05 - 0.16 NR NR
F4D1C FC4D1 NR 0.05 - 0.16 NR NR
F4E1C FC4E1 NR 0.05 - 0.16 NR NR
F4A2C FC4A2 NR 0.05 - 0.16 NR NR
F4B2C FC4B2 NR 0.05 - 0.16 NR NR
F4C2C FC4C2 NR 0.05 - 0.16 NR NR
F4D2C FC4D2 NR 0.05 - 0.16 NR NR
F4E2C FC4E2 NR 0.05 - 0.16 NR NR
F4A3C FC4A3 NR 0.05 - 0.16 NR NR
F4B3C FC4B3 NR 0.05 - 0.16 NR NR
F4C3C FC4C3 NR 0.05 - 0.16 NR NR
F4D3C FC4D3 NR 0.05 - 0.16 NR NR
F4E3C FC4E3 NR 0.05 - 0.16 NR NR
F4A4C FC4A4 NR 0.05 - 0.16 NR NR
F4B4C FC4B4 NR 0.05 - 0.16 NR NR
F4C4C FC4C4 NR 0.05 - 0.16 NR NR
F4D4C FC4D4 NR 0.05 - 0.16 NR NR
F4E4C FC4E4 NR 0.05 - 0.16 NR NR
F4A5C FC4A5 NR 0.05 - 0.16 NR NR
F4B5C FC4B5 NR 0.05 - 0.16 NR NR
F4C5C FC4C5 NR 0.05 - 0.16 NR NR
F4D5C FC4D5 NR 0.05 - 0.16 NR NR
F4E5C FC4E5 NR 0.05 - 0.16 NR NR
F4A6C FC4A6 NR 0.05 - 0.16 NR NR
F4B6C FC4B6 NR 0.05 - 0.16 NR NR
57
CA 03228700 2024- 2- 12 SUBSTITUTE SHEET (RULE 26)

WO 2023/023085
PCT/US2022/040504
Foam Properties
Density, Compressive Tensile
Strength,
Foamable Closed g/cc3 Strength, ((ASTM C297),
Foam Composition, Cell (ISO 844), megapascal
Number No. megapascal
F4C6C FC4C6 NR 0.05 - 0.16 NR NR
F4D6C FC4D6 NR 0.05 - 0.16 NR NR
F4E6C FC4E6 NR 0.05 - 0.16 NR NR
F5A1C FC5A1 NR 0.05 - 0.16 NR NR
F5B1C FC5B1 NR 0.05 - 0.16 NR NR
F5C1C FC5C1 NR 0.05 - 0.16 NR NR
F5D1C FC5D1 NR 0.05 - 0.16 NR NR
F5E1C FC5E1 NR 0.05 - 0.16 NR NR
F5A2C FC5A2 NR 0.05 - 0.16 NR NR
F5B2C FC5B2 NR 0.05 - 0.16 NR NR
F5C2C FC5C2 NR 0.05 - 0.16 NR NR
F5D2C FC5D2 NR 0.05 - 0.16 NR NR
F5E2C FC5E2 NR 0.05 - 0.16 NR NR
F5A3C FC5A3 NR 0.05 - 0.16 NR NR
F5B3C FC5B3 NR 0.05 - 0.16 NR NR
F5C3C FC5C3 NR 0.05 - 0.16 NR NR
F5D3C FC5D3 NR 0.05 - 0.16 NR NR
F5E3C FC5E3 NR 0.05 - 0.16 NR NR
F5A4C FC5A4 NR 0.05 - 0.16 NR NR
F5B4C FC5B4 NR 0.05 - 0.16 NR NR
F5C4C FC5C4 NR 0.05 - 0.16 NR NR
F5D4C FC5D4 NR 0.05 - 0.16 NR NR
F5E4C FC5E4 NR 0.05 - 0.16 NR NR
F5A5C FC5A5 NR 0.05 - 0.16 NR NR
F5B5C FC5B5 NR 0.05 - 0.16 NR NR
58
CA 03228700 2024- 2- 12 SUBSTITUTE SHEET (RULE 26)

WO 2023/023085
PCT/US2022/040504
Foam Properties
Density, Compressive Tensile
Strength,
Foamable Closed g/cc3 Strength, ((ASTM C297),
Foam Composition, Cell (ISO 844), megapascal
Number No. megapascal
F5C5C FC5C5 NR 0.05 - 0.16 NR NR
F5D5C FC5D5 NR 0.05 - 0.16 NR NR
F5E5C FC5E5 NR 0.05 - 0.16 NR NR
F5A6C FC5A6 NR 0.05 - 0.16 NR NR
F5B6C FC5B6 NR 0.05 - 0.16 NR NR
F5C6C FC5C6 NR 0.05 - 0.16 NR NR
F5D6C FC5D6 NR 0.05 - 0.16 NR NR
F5E6C FC5E6 NR 0.05 - 0.16 NR NR
F6A1C FC6A1 NR 0.05 - 0.16 NR NR
F6B1C FC6B1 NR 0.05 - 0.16 NR NR
F6C1C FC6C1 NR 0.05 - 0.16 NR NR
F6D1C FC6D1 NR 0.05 - 0.16 NR NR
F6E1C FC6E1 NR 0.05 - 0.16 NR NR
F6A2C FC6A2 NR 0.05 - 0.16 NR NR
F6B2C FC6B2 NR 0.05 - 0.16 NR NR
F6C2C FC6C2 NR 0.05 - 0.16 NR NR
F6D2C FC6D2 NR 0.05 - 0.16 NR NR
F6E2C FC6E2 NR 0.05 - 0.16 NR NR
F6A3C FC6A3 NR 0.05 - 0.16 NR NR
F6B3C FC6B3 NR 0.05 - 0.16 NR NR
F6C3C FC6C3 NR 0.05 - 0.16 NR NR
F6D3C FC6D3 NR 0.05 - 0.16 NR NR
F6E3C FC6E3 NR 0.05 - 0.16 NR NR
F6B4C FC6B4 NR 0.05 - 0.16 NR NR
F6C4C FC6C4 NR 0.05 - 0.16 NR NR
59
CA 03228700 2024- 2- 12 SUBSTITUTE SHEET (RULE 26)

WO 2023/023085
PCT/US2022/040504
Foam Properties
Density, Compressive Tensile
Strength,
Foamable Closed g/cc3 Strength, ((ASTM C297),
Foam Composition, Cell (ISO 844), megapascal
Number No. megapascal
F6D4C FC6D4 NR 0.05 - 0.16 NR NR
F6E4C FC6E4 NR 0.05 - 0.16 NR NR
F6A5C FC6A5 NR 0.05 - 0.16 NR NR
F6B5C FC6B5 NR 0.05 - 0.16 NR NR
F6C5C FC6C5 NR 0.05 - 0.16 NR NR
F6D5C FC6D5 NR 0.05 - 0.16 NR NR
F6E5C FC6E5 NR 0.05 - 0.16 NR NR
F6A6C FC6A6 NR 0.05 - 0.16 NR NR
F6B6C FC6B6 NR 0.05 - 0.16 NR NR
F6C6C FC6C6 NR 0.05 - 0.16 NR NR
F6D6C FC6D6 NR 0.05 - 0.16 NR NR
F6E6C FC6E6 NR 0.05 - 0.16 NR NR
F7A1C FC7A1 NR 0.05 - 0.16 NR NR
F7B1C FC7B1 NR 0.05 - 0.16 NR NR
F7C1C FC7C1 NR 0.05 - 0.16 NR NR
F7D1C FC7D1 NR 0.05 - 0.16 NR NR
F7E1C FC7E1 NR 0.05 - 0.16 NR NR
F7A2C FC7A2 NR 0.05 - 0.16 NR NR
F7B2C FC7B2 NR 0.05 - 0.16 NR NR
F7C2C FC7C2 NR 0.05 - 0.16 NR NR
F7D2C FC7D2 NR 0.05 - 0.16 NR NR
F7E2C FC7E2 NR 0.05 - 0.16 NR NR
F7A3C FC7A3 NR 0.05 - 0.16 NR NR
F7B3C FC7B3 NR 0.05 - 0.16 NR NR
F7C3C FC7C3 NR 0.05 - 0.16 NR NR
CA 03228700 2024- 2- 12 SUBSTITUTE SHEET (RULE 26)

WO 2023/023085
PCT/US2022/040504
Foam Properties
Density, Compressive Tensile
Strength,
Foamable Closed g/cc3 Strength, ((ASTM C297),
Foam Composition, Cell (ISO 844), megapascal
Number No. megapascal
F7D3C FC7D3 NR 0.05 - 0.16 NR NR
F7E3C FC7E3 NR 0.05 - 0.16 NR NR
F7A4C FC7A4 NR 0.05 - 0.16 NR NR
F7B4C FC7B4 NR 0.05 - 0.16 NR NR
F7C4C FC7C4 NR 0.05 - 0.16 NR NR
F7D4C FC7D4 NR 0.05 - 0.16 NR NR
F7E4C FC7E4 NR 0.05 - 0.16 NR NR
F7A5C FC7A5 NR 0.05 - 0.16 NR NR
F7B5C FC7B5 NR 0.05 - 0.16 NR NR
F7C5C FC7C5 NR 0.05 - 0.16 NR NR
F7D5C FC7D5 NR 0.05 - 0.16 NR NR
F7E5C FC7E5 NR 0.05 - 0.16 NR NR
F7A6C FC7A6 NR 0.05 - 0.16 NR NR
F7B6C FC7B6 NR 0.05 - 0.16 NR NR
F7C6C FC7C6 NR 0.05 - 0.16 NR NR
F7D6C FC7D6 NR 0.05 - 0.16 NR NR
F7E6C FC7E6 NR 0.05 - 0.16 NR NR
F8A1C FC8A1 NR 0.05 - 0.16 NR NR
F8B1C FC8B1 NR 0.05 - 0.16 NR NR
F8C1C FC8C1 NR 0.05 - 0.16 NR NR
F8D1C FC8D1 NR 0.05 - 0.16 NR NR
F8E1C FC8E1 NR 0.05 - 0.16 NR NR
F8A2C FC8A2 NR 0.05 - 0.16 NR NR
F8B2C FC8B2 NR 0.05 - 0.16 NR NR
F8C2C FC8C2 NR 0.05 - 0.16 NR NR
61
CA 03228700 2024- 2- 12 SUBSTITUTE SHEET (RULE 26)

WO 2023/023085
PCT/US2022/040504
Foam Properties
Density, Compressive Tensile
Strength,
Foamable Closed g/cc3 Strength, ((ASTM C297),
Foam Composition, Cell (ISO 844), megapascal
Number No. megapascal
F8D2C FC8D2 NR 0.05 - 0.16 NR NR
F8E2C FC8E2 NR 0.05 - 0.16 NR NR
F8A3C FC8A3 NR 0.05 - 0.16 NR NR
F8B3C FC8B3 NR 0.05 - 0.16 NR NR
F8C3C FC8C3 NR 0.05 - 0.16 NR NR
F8D3C FC8D3 NR 0.05 - 0.16 NR NR
F8E3C FC8E3 NR 0.05 - 0.16 NR NR
F8A4C FC8A4 NR 0.05 - 0.16 NR NR
F8B4C FC8B4 NR 0.05 - 0.16 NR NR
F8C4C FC8C4 NR 0.05 - 0.16 NR NR
F8D4C FC8D4 NR 0.05 - 0.16 NR NR
F8E4C FC8E4 NR 0.05 - 0.16 NR NR
F8A5C FC8A5 NR 0.05 - 0.16 NR NR
F8B5C FC8B5 NR 0.05 - 0.16 NR NR
F8C5C FC8C5 NR 0.05 - 0.16 NR NR
F8D5C FC8D5 NR 0.05 - 0.16 NR NR
F8E5C FC8E5 NR 0.05 - 0.16 NR NR
F8A6C FC8A6 NR 0.05 - 0.16 NR NR
F8B6C FC8B6 NR 0.05 - 0.16 NR NR
F8C6C FC8C6 NR 0.05 - 0.16 NR NR
F8D6C FC8D6 NR 0.05 - 0.16 NR NR
F8E6C FC8E6 NR 0.05 - 0.16 NR NR
FlAID FC1A1 NR NR 0.6 - 2.5 1.0 - 6.2
F1B1D FC1B1 NR NR 0.6 - 2.5 1.0 - 6.2
F1C11) FC1C1 NR NR 0.6 - 2.5 1.0 - 6.2
62
CA 03228700 2024- 2- 12 SUBSTITUTE SHEET (RULE 26)

WO 2023/023085
PCT/US2022/040504
Foam Properties
% Density, Compressive Tensile
Strength,
Foamable Closed g/cc3 Strength, ((ASTM C297),
Foam Composition, Cell (ISO 844), megapascal
Number No. megapascal
F1D1D FC1D1 NR NR 0.6 - 2.5 1.0 - 6.2
F1E1D FC1E1 NR NR 0.6 - 2.5 1.0 - 6.2
F1A2D FC1A2 NR NR 0.6 - 2.5 1.0 - 6.2
F1B2D FC1B2 NR NR 0.6 - 2.5 1.0 - 6.2
Fl C2D FC1C2 NR NR 0.6 - 2.5 1.0 - 6.2
F1D2D FC1D2 NR NR 0.6 - 2.5 1.0 - 6.2
F1E20 FC1E2 NR NR 0.6 - 2.5 1.0 - 6.2
F1A3D FC1A3 NR NR 0.6 - 2.5 1.0 - 6.2
F1B3D FC1B3 NR NR 0.6 - 2.5 1.0 - 6.2
Fl C3D FC1C3 NR NR 0.6 - 2.5 1.0 - 6.2
F1D30 FC1D3 NR NR 0.6 - 2.5 1.0 - 6.2
F1E30 FC1E3 NR NR 0.6 - 2.5 1.0 - 6.2
F1A40 FC1A4 NR NR 0.6 - 2.5 1.0 - 6.2
F1B4D FC1B4 NR NR 0.6 - 2.5 1.0 - 6.2
Fl C4D FC1C4 NR NR 0.6 - 2.5 1.0 - 6.2
F1D40 FC1D4 NR NR 0.6 - 2.5 1.0 - 6.2
F1E40 FC1E4 NR NR 0.6 - 2.5 1.0 - 6.2
F1A5D FC1A5 NR NR 0.6 - 2.5 1.0 - 6.2
F1B5D FC1B5 NR NR 0.6 - 2.5 1.0 - 6.2
F1050 FC1C5 NR NR 0.6 - 2.5 1.0 - 6.2
F1D5D FC1D5 NR NR 0.6 - 2.5 1.0 - 6.2
F1E5D FC1E5 NR NR 0.6 - 2.5 1.0 - 6.2
F1A6D FC1A6 NR NR 0.6 - 2.5 1.0 - 6.2
F1B6D FC1B6 NR NR 0.6 - 2.5 1.0 - 6.2
F1C6D FC1C6 NR NR 0.6 - 2.5 1.0 - 6.2
63
CA 03228700 2024- 2- 12 SUBSTITUTE SHEET (RULE 26)

WO 2023/023085
PCT/US2022/040504
Foam Properties
% Density, Compressive Tensile
Strength,
Foamable Closed g/cc3 Strength, ((ASTM C297),
Foam Composition, Cell (ISO 844), megapascal
Number No. megapascal
F1D6D FC1D6 NR NR 0.6 - 2.5 1.0 - 6.2
F1E6D FC1E6 NR NR 0.6 - 2.5 1.0 - 6.2
F2A1D FC2A1 NR NR 0.6 - 2.5 1.0 - 6.2
F2B1D FC2B1 NR NR 0.6 - 2.5 1.0 - 6.2
F2C1D FC2C1 NR NR 0.6 - 2.5 1.0 - 6.2
F2D1D FC2D1 NR NR 0.6 - 2.5 1.0 - 6.2
F2E1D FC2E1 NR NR 0.6 - 2.5 1.0 - 6.2
F2A20 FC2A2 NR NR 0.6 - 2.5 1.0 - 6.2
F2B20 FC2B2 NR NR 0.6 - 2.5 1.0 - 6.2
F2C20 FC2C2 NR NR 0.6 - 2.5 1.0 - 6.2
F2D20 FC2D2 NR NR 0.6 - 2.5 1.0 - 6.2
F2E20 FC2E2 NR NR 0.6 - 2.5 1.0 - 6.2
F2A30 FC2A3 NR NR 0.6 - 2.5 1.0 - 6.2
F2B3D FC2B3 NR NR 0.6 - 2.5 1.0 - 6.2
F2C30 FC2C3 NR NR 0.6 - 2.5 1.0 - 6.2
F2D30 FC2D3 NR NR 0.6 - 2.5 1.0 - 6.2
F2E30 FC2E3 NR NR 0.6 - 2.5 1.0 - 6.2
F2A4D FC2A4 NR NR 0.6 - 2.5 1.0 - 6.2
F2B4D FC2B4 NR NR 0.6 - 2.5 1.0 - 6.2
F2C4D FC2C4 NR NR 0.6 - 2.5 1.0 - 6.2
F2D41) FC2D4 NR NR 0.6 - 2.5 1.0 - 6.2
F2E41) FC2E4 NR NR 0.6 - 2.5 1.0 - 6.2
F2A51) FC2A5 NR NR 0.6 - 2.5 1.0 - 6.2
F2B51) FC2B5 NR NR 0.6 - 2.5 1.0 - 6.2
F2C51) FC2C5 NR NR 0.6 - 2.5 1.0 - 6.2
64
CA 03228700 2024- 2- 12 SUBSTITUTE SHEET (RULE 26)

WO 2023/023085
PCT/US2022/040504
Foam Properties
% Density, Compressive Tensile
Strength,
Foamable Closed g/cc3 Strength, ((ASTM C297),
Foam Composition, Cell (ISO 844), megapascal
Number No. megapascal
F2D5D FC2D5 NR NR 0.6 - 2.5 1.0 - 6.2
F2E5D FC2E5 NR NR 0.6 - 2.5 1.0 - 6.2
F2A6D FC2A6 NR NR 0.6 - 2.5 1.0 - 6.2
F2B6D FC2B6 NR NR 0.6 - 2.5 1.0 - 6.2
F2C60 FC2C6 NR NR 0.6 - 2.5 1.0 - 6.2
F2D6D FC2D6 NR NR 0.6 - 2.5 1.0 - 6.2
F2E6D FC2E6 NR NR 0.6 - 2.5 1.0 - 6.2
F3A1D FC3A1 NR NR 0.6 - 2.5 1.0 - 6.2
F3B1D FC3B1 NR NR 0.6 - 2.5 1.0 - 6.2
F3C1D FC3C1 NR NR 0.6 - 2.5 1.0 - 6.2
F3D1D FC3D1 NR NR 0.6 - 2.5 1.0 - 6.2
F3E1D FC3E1 NR NR 0.6 - 2.5 1.0 - 6.2
F3A20 FC3A2 NR NR 0.6 - 2.5 1.0 - 6.2
F3B2D FC3B2 NR NR 0.6 - 2.5 1.0 - 6.2
F3C20 FC3C2 NR NR 0.6 - 2.5 1.0 - 6.2
F3D20 FC3D2 NR NR 0.6 - 2.5 1.0 - 6.2
F3E20 FC3E2 NR NR 0.6 - 2.5 1.0 - 6.2
F3A3D FC3A3 NR NR 0.6 - 2.5 1.0 - 6.2
F3B3D FC3B3 NR NR 0.6 - 2.5 1.0 - 6.2
F3C30 FC3C3 NR NR 0.6 - 2.5 1.0 - 6.2
F3D31) FC3D3 NR NR 0.6 - 2.5 1.0 - 6.2
F3E31) FC3E3 NR NR 0.6 - 2.5 1.0 - 6.2
F3A41) FC3A4 NR NR 0.6 - 2.5 1.0 - 6.2
F3B41) FC3B4 NR NR 0.6 - 2.5 1.0 - 6.2
F3C41) FC3C4 NR NR 0.6 - 2.5 1.0 - 6.2
CA 03228700 2024- 2- 12 SUBSTITUTE SHEET (RULE 26)

WO 2023/023085
PCT/US2022/040504
Foam Properties
% Density, Compressive Tensile
Strength,
Foamable Closed g/cc3 Strength, ((ASTM C297),
Foam Composition, Cell (ISO 844), megapascal
Number No. megapascal
F3D40 FC3D4 NR NR 0.6 - 2.5 1.0 - 6.2
F3E40 FC3E4 NR NR 0.6 - 2.5 1.0 - 6.2
F3A5D FC3A5 NR NR 0.6 - 2.5 1.0 - 6.2
F3B5D FC3B5 NR NR 0.6 - 2.5 1.0 - 6.2
F3C5D FC3C5 NR NR 0.6 - 2.5 1.0 - 6.2
F3D5D FC3D5 NR NR 0.6 - 2.5 1.0 - 6.2
F3E5D FC3E5 NR NR 0.6 - 2.5 1.0 - 6.2
F3A60 FC3A6 NR NR 0.6 - 2.5 1.0 - 6.2
F3B60 FC3B6 NR NR 0.6 - 2.5 1.0 - 6.2
F3C60 FC3C6 NR NR 0.6 - 2.5 1.0 - 6.2
F3D60 FC3D6 NR NR 0.6 - 2.5 1.0 - 6.2
F3E60 FC3E6 NR NR 0.6 - 2.5 1.0 - 6.2
F4A1D FC4A1 NR NR 0.6 - 2.5 1.0 - 6.2
F4B1D FC4B1 NR NR 0.6 - 2.5 1.0 - 6.2
F4C1D FC4C1 NR NR 0.6 - 2.5 1.0 - 6.2
F4D1D FC4D1 NR NR 0.6 - 2.5 1.0 - 6.2
F4E1D FC4E1 NR NR 0.6 - 2.5 1.0 - 6.2
F4A2D FC4A2 NR NR 0.6 - 2.5 1.0 - 6.2
F4B2D FC4B2 NR NR 0.6 - 2.5 1.0 - 6.2
F4C20 FC4C2 NR NR 0.6 - 2.5 1.0 - 6.2
F4D21) FC4D2 NR NR 0.6 - 2.5 1.0 - 6.2
F4E21) FC4E2 NR NR 0.6 - 2.5 1.0 - 6.2
F4A31) FC4A3 NR NR 0.6 - 2.5 1.0 - 6.2
F4B31) FC4B3 NR NR 0.6 - 2.5 1.0 - 6.2
FC4C3D FC4C3 NR NR 0.6 - 2.5 1.0 - 6.2
66
CA 03228700 2024- 2- 12 SUBSTITUTE SHEET (RULE 26)

WO 2023/023085
PCT/US2022/040504
Foam Properties
% Density, Compressive Tensile
Strength,
Foamable Closed g/cc3 Strength, ((ASTM C297),
Foam Composition, Cell (ISO 844), megapascal
Number No. megapascal
F4D30 FC4D3 NR NR 0.6 - 2.5 1.0 - 6.2
F4E30 FC4E3 NR NR 0.6 - 2.5 1.0 - 6.2
F4A4D FC4A4 NR NR 0.6 - 2.5 1.0 - 6.2
F4B4D FC4B4 NR NR 0.6 - 2.5 1.0 - 6.2
F4C40 FC4C4 NR NR 0.6 - 2.5 1.0 - 6.2
F4D4D FC4D4 NR NR 0.6 - 2.5 1.0 - 6.2
F4E4D FC4E4 NR NR 0.6 - 2.5 1.0 - 6.2
F4A50 FC4A5 NR NR 0.6 - 2.5 1.0 - 6.2
F4B50 FC4B5 NR NR 0.6 - 2.5 1.0 - 6.2
F4C5D FC4C5 NR NR 0.6 - 2.5 1.0 - 6.2
F4D5D FC4D5 NR NR 0.6 - 2.5 1.0 - 6.2
F4E50 FC4E5 NR NR 0.6 - 2.5 1.0 - 6.2
F4A60 FC4A6 NR NR 0.6 - 2.5 1.0 - 6.2
F4B6D FC4B6 NR NR 0.6 - 2.5 1.0 - 6.2
F4C60 FC4C6 NR NR 0.6 - 2.5 1.0 - 6.2
F4D60 FC4D6 NR NR 0.6 - 2.5 1.0 - 6.2
F4E60 FC4E6 NR NR 0.6 - 2.5 1.0 - 6.2
F5A1D FC5A1 NR NR 0.6 - 2.5 1.0 - 6.2
F5B1D FC5B1 NR NR 0.6 - 2.5 1.0 - 6.2
F5C1D FC5C1 NR NR 0.6 - 2.5 1.0 - 6.2
F5D1D FC5D1 NR NR 0.6 - 2.5 1.0 - 6.2
F5E1D FC5E1 NR NR 0.6 - 2.5 1.0 - 6.2
F5A21) FC5A2 NR NR 0.6 - 2.5 1.0 - 6.2
F5B21) FC5B2 NR NR 0.6 - 2.5 1.0 - 6.2
F5C21) FC5C2 NR NR 0.6 - 2.5 1.0 - 6.2
67
CA 03228700 2024- 2- 12 SUBSTITUTE SHEET (RULE 26)

WO 2023/023085
PCT/US2022/040504
Foam Properties
% Density, Compressive Tensile
Strength,
Foamable Closed g/cc3 Strength, ((ASTM C297),
Foam Composition, Cell (ISO 844), megapascal
Number No. megapascal
F5D20 FC5D2 NR NR 0.6 - 2.5 1.0 - 6.2
F5E2D FC5E2 NR NR 0.6 - 2.5 1.0 - 6.2
F5A3D FC5A3 NR NR 0.6 - 2.5 1.0 - 6.2
F5B3D FC5B3 NR NR 0.6 - 2.5 1.0 - 6.2
F5C30 FC5C3 NR NR 0.6 - 2.5 1.0 - 6.2
F5D3D FC5D3 NR NR 0.6 - 2.5 1.0 - 6.2
F5E3D FC5E3 NR NR 0.6 - 2.5 1.0 - 6.2
F5A4D FC5A4 NR NR 0.6 - 2.5 1.0 - 6.2
F5B40 FC5B4 NR NR 0.6 - 2.5 1.0 - 6.2
F5C40 FC5C4 NR NR 0.6 - 2.5 1.0 - 6.2
F5D4D FC5D4 NR NR 0.6 - 2.5 1.0 - 6.2
F5E4D FC5E4 NR NR 0.6 - 2.5 1.0 - 6.2
F5A5D FC5A5 NR NR 0.6 - 2.5 1.0 - 6.2
F5B5D FC5B5 NR NR 0.6 - 2.5 1.0 - 6.2
F5C50 FC5C5 NR NR 0.6 - 2.5 1.0 - 6.2
F5D5D FC5D5 NR NR 0.6 - 2.5 1.0 - 6.2
F5E50 FC5E5 NR NR 0.6 - 2.5 1.0 - 6.2
F5A6D FC5A6 NR NR 0.6 - 2.5 1.0 - 6.2
F5B6D FC5B6 NR NR 0.6 - 2.5 1.0 - 6.2
F5C60 FC5C6 NR NR 0.6 - 2.5 1.0 - 6.2
F5D6D FC5D6 NR NR 0.6 - 2.5 1.0 - 6.2
F5E61) FC5E6 NR NR 0.6 - 2.5 1.0 - 6.2
F6A1D FC6A1 NR NR 0.6 - 2.5 1.0 - 6.2
F6B1D FC6B1 NR NR 0.6 - 2.5 1.0 - 6.2
F6C1D FC6C1 NR NR 0.6 - 2.5 1.0 - 6.2
68
CA 03228700 2024- 2- 12 SUBSTITUTE SHEET (RULE 26)

WO 2023/023085
PCT/US2022/040504
Foam Properties
% Density, Compressive Tensile
Strength,
Foamable Closed g/cc3 Strength, ((ASTM C297),
Foam Composition, Cell (ISO 844), megapascal
Number No. megapascal
F6D1D FC6D1 NR NR 0.6 - 2.5 1.0 - 6.2
F6E1D FC6E1 NR NR 0.6 - 2.5 1.0 - 6.2
F6A2D FC6A2 NR NR 0.6 - 2.5 1.0 - 6.2
F6B2D FC6B2 NR NR 0.6 - 2.5 1.0 - 6.2
F6C20 FC6C2 NR NR 0.6 - 2.5 1.0 - 6.2
F6D2D FC6D2 NR NR 0.6 - 2.5 1.0 - 6.2
F6E2D FC6E2 NR NR 0.6 - 2.5 1.0 - 6.2
F6A30 FC6A3 NR NR 0.6 - 2.5 1.0 - 6.2
F6B30 FC6B3 NR NR 0.6 - 2.5 1.0 - 6.2
F6C30 FC6C3 NR NR 0.6 - 2.5 1.0 - 6.2
F6D30 FC6D3 NR NR 0.6 - 2.5 1.0 - 6.2
F6E30 FC6E3 NR NR 0.6 - 2.5 1.0 - 6.2
F6B40 FC6B4 NR NR 0.6 - 2.5 1.0 - 6.2
F6C4D FC6C4 NR NR 0.6 - 2.5 1.0 - 6.2
F6D40 FC6D4 NR NR 0.6 - 2.5 1.0 - 6.2
F6E40 FC6E4 NR NR 0.6 - 2.5 1.0 - 6.2
F6A5D FC6A5 NR NR 0.6 - 2.5 1.0 - 6.2
F6B5D FC6B5 NR NR 0.6 - 2.5 1.0 - 6.2
F6C5D FC6C5 NR NR 0.6 - 2.5 1.0 - 6.2
F6D50 FC6D5 NR NR 0.6 - 2.5 1.0 - 6.2
F6E51) FC6E5 NR NR 0.6 - 2.5 1.0 - 6.2
F6A61) FC6A6 NR NR 0.6 - 2.5 1.0 - 6.2
F6B61) FC6B6 NR NR 0.6 - 2.5 1.0 - 6.2
F6C61) FC6C6 NR NR 0.6 - 2.5 1.0 - 6.2
F6D61) FC6D6 NR NR 0.6 - 2.5 1.0 - 6.2
69
CA 03228700 2024- 2- 12 SUBSTITUTE SHEET (RULE 26)

WO 2023/023085
PCT/US2022/040504
Foam Properties
% Density, Compressive Tensile
Strength,
Foamable Closed g/cc3 Strength, ((ASTM C297),
Foam Composition, Cell (ISO 844), megapascal
Number No. megapascal
F6E60 FC6E6 NR NR 0.6 - 2.5 1.0 - 6.2
F7A1D FC7A1 NR NR 0.6 - 2.5 1.0 - 6.2
F7B1D FC7B1 NR NR 0.6 - 2.5 1.0 - 6.2
F7C1D FC7C1 NR NR 0.6 - 2.5 1.0 - 6.2
F7D1D FC7D1 NR NR 0.6 - 2.5 1.0 - 6.2
F7E1D FC7E1 NR NR 0.6 - 2.5 1.0 - 6.2
F7A2D FC7A2 NR NR 0.6 - 2.5 1.0 - 6.2
F7B20 FC7B2 NR NR 0.6 - 2.5 1.0 - 6.2
F7C20 FC7C2 NR NR 0.6 - 2.5 1.0 - 6.2
F7D20 FC7D2 NR NR 0.6 - 2.5 1.0 - 6.2
F7E2D FC7E2 NR NR 0.6 - 2.5 1.0 - 6.2
F7A3D FC7A3 NR NR 0.6 - 2.5 1.0 - 6.2
F7B30 FC7B3 NR NR 0.6 - 2.5 1.0 - 6.2
F7C3D FC7C3 NR NR 0.6 - 2.5 1.0 - 6.2
F7D30 FC7D3 NR NR 0.6 - 2.5 1.0 - 6.2
F7E30 FC7E3 NR NR 0.6 - 2.5 1.0 - 6.2
F7A40 FC7A4 NR NR 0.6 - 2.5 1.0 - 6.2
F7B4D FC7B4 NR NR 0.6 - 2.5 1.0 - 6.2
F7C4D FC7C4 NR NR 0.6 - 2.5 1.0 - 6.2
F7D40 FC7D4 NR NR 0.6 - 2.5 1.0 - 6.2
F7E40 FC7E4 NR NR 0.6 - 2.5 1.0 - 6.2
F7A50 FC7A5 NR NR 0.6 - 2.5 1.0 - 6.2
F7B5D FC7B5 NR NR 0.6 - 2.5 1.0 - 6.2
F7C5D FC7C5 NR NR 0.6 - 2.5 1.0 - 6.2
F7D50 FC7D5 NR NR 0.6 - 2.5 1.0 - 6.2
CA 03228700 2024- 2- 12 SUBSTITUTE SHEET (RULE 26)

WO 2023/023085
PCT/US2022/040504
Foam Properties
% Density, Compressive Tensile
Strength,
Foamable Closed g/cc3 Strength, ((ASTM C297),
Foam Composition, Cell (ISO 844), megapascal
Number No. megapascal
F7E50 FC7E5 NR NR 0.6 - 2.5 1.0 - 6.2
F7A60 FC7A6 NR NR 0.6 - 2.5 1.0 - 6.2
F7B6D FC7B6 NR NR 0.6 - 2.5 1.0 - 6.2
F7C6D FC7C6 NR NR 0.6 - 2.5 1.0 - 6.2
F7D60 FC7D6 NR NR 0.6 - 2.5 1.0 - 6.2
F7E6D FC7E6 NR NR 0.6 - 2.5 1.0 - 6.2
F8A1D FC8A1 NR NR 0.6 - 2.5 1.0 - 6.2
F8B1D FC8B1 NR NR 0.6 - 2.5 1.0 - 6.2
F8C1D FC8C1 NR NR 0.6 - 2.5 1.0 - 6.2
F8D1B FC8D1 NR NR 0.6 - 2.5 1.0 - 6.2
F8E1D FC8E1 NR NR 0.6 - 2.5 1.0 - 6.2
F8A2B FC8A2 NR NR 0.6 - 2.5 1.0 - 6.2
F8B20 FC8B2 NR NR 0.6 - 2.5 1.0 - 6.2
F8C2D FC8C2 NR NR 0.6 - 2.5 1.0 - 6.2
F8D2D FC8D2 NR NR 0.6 - 2.5 1.0 - 6.2
F8E20 FC8E2 NR NR 0.6 - 2.5 1.0 - 6.2
F8A30 FC8A3 NR NR 0.6 - 2.5 1.0 - 6.2
F8B3D FC8B3 NR NR 0.6 - 2.5 1.0 - 6.2
F8C3D FC8C3 NR NR 0.6 - 2.5 1.0 - 6.2
F8D30 FC8D3 NR NR 0.6 - 2.5 1.0 - 6.2
F8E31) FC8E3 NR NR 0.6 - 2.5 1.0 - 6.2
F8A41) FC8A4 NR NR 0.6 - 2.5 1.0 - 6.2
F8B41) FC8B4 NR NR 0.6 - 2.5 1.0 - 6.2
F8C41) FC8C4 NR NR 0.6 - 2.5 1.0 - 6.2
F8D41) FC8D4 NR NR 0.6 - 2.5 1.0 - 6.2
71
CA 03228700 2024- 2- 12 SUBSTITUTE SHEET (RULE 26)

WO 2023/023085
PCT/US2022/040504
Foam Properties
Density, Compressive Tensile
Strength,
Foamable Closed g/cc3 Strength, ((ASTM C297),
Foam Composition, Cell (ISO 844), megapascal
Number No. megapascal
F8E40 FC8E4 NR NR 0.6 - 2.5 1.0 - 6.2
F8A5D FC8A5 NR NR 0.6 - 2.5 1.0 - 6.2
F8B5D FC8B5 NR NR 0.6 - 2.5 1.0 - 6.2
F8C5D FC8C5 NR NR 0.6 - 2.5 1.0 - 6.2
F8D5D FC8D5 NR NR 0.6 - 2.5 1.0 - 6.2
F8E5D FC8E5 NR NR 0.6 - 2.5 1.0 - 6.2
F8A6D FC8A6 NR NR 0.6 - 2.5 1.0 - 6.2
F8B60 FC8B6 NR NR 0.6 - 2.5 1.0 - 6.2
F8C60 FC8C6 NR NR 0.6 - 2.5 1.0 - 6.2
F8D60 FC8D6 NR NR 0.6 - 2.5 1.0 - 6.2
F8E6D FC8E6 NR NR 0.6 - 2.5 1.0 - 6.2
FlAlE FCIA1 >25% 0.05 - 0.1 0.6 - 2.5 1.0 - 6.2
BlE FC1B1 NR NR 0.6 - 2.5 1.0 - 6.2
F1C1E FC1C1 NR NR 0.6 - 2.5 1.0 - 6.2
F1D1E FC1D1 NR NR 0.6 - 2.5 1.0 - 6.2
FlElE FC1E1 NR NR 0.6 - 2.5 1.0 - 6.2
F1A2E FC1A2 NR NR 0.6 - 2.5 1.0 - 6.2
ELME FC1132 NR NR 0.6 - 2.5 1.0 - 6.2
F1C2E FC1C2 NR NR 0.6 - 2.5 1.0 - 6.2
F1D2E FC1D2 NR NR 0.6 - 2.5 1.0 - 6.2
F1E2E FC1E2 NR NR 0.6 - 2.5 1.0 - 6.2
F1A3E FC1A3 NR NR 0.6 - 2.5 1.0 - 6.2
F1B3E FC1B3 NR NR 0.6 - 2.5 1.0 - 6.2
F1C3E FC1C3 NR NR 0.6 - 2.5 1.0 - 6.2
F1D3E FC1D3 NR NR 0.6 - 2.5 1.0 - 6.2
72
CA 03228700 2024- 2- 12 SUBSTITUTE SHEET (RULE 26)

WO 2023/023085
PCT/US2022/040504
Foam Properties
% Density, Compressive Tensile
Strength,
Foamable Closed g/cc3 Strength, ((ASTM C297),
Foam Composition, Cell (ISO 844), megapascal
Number No. megapascal
F1E3E FC1E3 NR NR 0.6 - 2.5 1.0 - 6.2
F1A4E FC1A4 NR NR 0.6 - 2.5 1.0 - 6.2
F1B4E FC1B4 NR NR 0.6 - 2.5 1.0 - 6.2
F1C4E FC1C4 NR NR 0.6 - 2.5 1.0 - 6.2
F1D4E FC1D4 NR NR 0.6 - 2.5 1.0 - 6.2
F1E4E FC1E4 NR NR 0.6 - 2.5 1.0 - 6.2
F1A5E FC1A5 NR NR 0.6 - 2.5 1.0 - 6.2
FlBSE FC1B5 NR NR 0.6 - 2.5 1.0 - 6.2
F1C5E FC1C5 NR NR 0.6 - 2.5 1.0 - 6.2
F1D5E FC1D5 NR NR 0.6 - 2.5 1.0 - 6.2
F1E5E FC1E5 NR NR 0.6 - 2.5 1.0 - 6.2
F1A6E FC1A6 NR NR 0.6 - 2.5 1.0 - 6.2
F1B6E FC1B6 NR NR 0.6 - 2.5 1.0 - 6.2
F1C6E FC1C6 NR NR 0.6 - 2.5 1.0 - 6.2
F1D6E FC1D6 NR NR 0.6 - 2.5 1.0 - 6.2
F1E6E FC1E6 NR NR 0.6 - 2.5 1.0 - 6.2
F2A1E FC2A1 NR NR 0.6 - 2.5 1.0 - 6.2
F2B1E FC2B1 NR NR 0.6 - 2.5 1.0 - 6.2
F2C1E FC2C1 NR NR 0.6 - 2.5 1.0 - 6.2
F2D1E FC2D1 NR NR 0.6 - 2.5 1.0 - 6.2
F2E1E FC2E1 NR NR 0.6 - 2.5 1.0 - 6.2
F2A2E FC2A2 NR NR 0.6 - 2.5 1.0 - 6.2
F2B2E FC2B2 NR NR 0.6 - 2.5 1.0 - 6.2
F2C2E FC2C2 NR NR 0.6 - 2.5 1.0 - 6.2
F2D2E FC2D2 NR NR 0.6 - 2.5 1.0 - 6.2
73
CA 03228700 2024- 2- 12 SUBSTITUTE SHEET (RULE 26)

WO 2023/023085
PCT/US2022/040504
Foam Properties
% Density, Compressive Tensile
Strength,
Foamable Closed g/cc3 Strength, ((ASTM C297),
Foam Composition, Cell (ISO 844), megapascal
Number No. megapascal
F2E2E FC2E2 NR NR 0.6 - 2.5 1.0 - 6.2
F2A3E FC2A3 NR NR 0.6 - 2.5 1.0 - 6.2
F2B3E FC2B3 NR NR 0.6 - 2.5 1.0 - 6.2
F2C3E FC2C3 NR NR 0.6 - 2.5 1.0 - 6.2
F2D3E FC2D3 NR NR 0.6 - 2.5 1.0 - 6.2
F2E3E FC2E3 NR NR 0.6 - 2.5 1.0 - 6.2
F2A4E FC2A4 NR NR 0.6 - 2.5 1.0 - 6.2
F2B4E FC2B4 NR NR 0.6 - 2.5 1.0 - 6.2
F2C4E FC2C4 NR NR 0.6 - 2.5 1.0 - 6.2
F2D4E FC2D4 NR NR 0.6 - 2.5 1.0 - 6.2
F2E4E FC2E4 NR NR 0.6 - 2.5 1.0 - 6.2
F2A5E FC2A5 NR NR 0.6 - 2.5 1.0 - 6.2
F2B5E FC2B5 NR NR 0.6 - 2.5 1.0 - 6.2
F2C5E FC2C5 NR NR 0.6 - 2.5 1.0 - 6.2
F2D5E FC2D5 NR NR 0.6 - 2.5 1.0 - 6.2
F2E5E FC2E5 NR NR 0.6 - 2.5 1.0 - 6.2
F2A6E FC2A6 NR NR 0.6 - 2.5 1.0 - 6.2
F2B6E FC2B6 NR NR 0.6 - 2.5 1.0 - 6.2
F2C6E FC2C6 NR NR 0.6 - 2.5 1.0 - 6.2
F2D6E FC2D6 NR NR 0.6 - 2.5 1.0 - 6.2
F2E6E FC2E6 NR NR 0.6 - 2.5 1.0 - 6.2
F3A1E FC3A1 NR NR 0.6 - 2.5 1.0 - 6.2
F3B1E FC3B1 NR NR 0.6 - 2.5 1.0 - 6.2
F3C1E FC3C1 NR NR 0.6 - 2.5 1.0 - 6.2
F3D1E FC3D1 NR NR 0.6 - 2.5 1.0 - 6.2
74
CA 03228700 2024- 2- 12 SUBSTITUTE SHEET (RULE 26)

WO 2023/023085
PCT/US2022/040504
Foam Properties
% Density, Compressive Tensile
Strength,
Foamable Closed g/cc3 Strength, ((ASTM C297),
Foam Composition, Cell (ISO 844), megapascal
Number No. megapascal
F3E1E FC3E1 NR NR 0.6 - 2.5 1.0 - 6.2
F3A2E FC3A2 NR NR 0.6 - 2.5 1.0 - 6.2
F3B2E FC3B2 NR NR 0.6 - 2.5 1.0 - 6.2
F3C2E FC3C2 NR NR 0.6 - 2.5 1.0 - 6.2
F3D2E FC3D2 NR NR 0.6 - 2.5 1.0 - 6.2
F3E2E FC3E2 NR NR 0.6 - 2.5 1.0 - 6.2
F3A3E FC3A3 NR NR 0.6 - 2.5 1.0 - 6.2
F3B3E FC3B3 NR NR 0.6 - 2.5 1.0 - 6.2
F3C3E FC3C3 NR NR 0.6 - 2.5 1.0 - 6.2
F3D3E FC3D3 NR NR 0.6 - 2.5 1.0 - 6.2
F3E3E FC3E3 NR NR 0.6 - 2.5 1.0 - 6.2
F3A4E FC3A4 NR NR 0.6 - 2.5 1.0 - 6.2
F3B4E FC3B4 NR NR 0.6 - 2.5 1.0 - 6.2
F3C4E FC3C4 NR NR 0.6 - 2.5 1.0 - 6.2
F3D4E FC3D4 NR NR 0.6 - 2.5 1.0 - 6.2
F3E4E FC3E4 NR NR 0.6 - 2.5 1.0 - 6.2
F3A5E FC3A5 NR NR 0.6 - 2.5 1.0 - 6.2
F3B5E FC3B5 NR NR 0.6 - 2.5 1.0 - 6.2
F3C5E FC3C5 NR NR 0.6 - 2.5 1.0 - 6.2
F3D5E FC3D5 NR NR 0.6 - 2.5 1.0 - 6.2
F3E5E FC3E5 NR NR 0.6 - 2.5 1.0 - 6.2
F3A6E FC3A6 NR NR 0.6 - 2.5 1.0 - 6.2
F3B6E FC3B6 NR NR 0.6 - 2.5 1.0 - 6.2
F3C6E FC3C6 NR NR 0.6 - 2.5 1.0 - 6.2
F3D6E FC3D6 NR NR 0.6 - 2.5 1.0 - 6.2
CA 03228700 2024- 2- 12 SUBSTITUTE SHEET (RULE 26)

WO 2023/023085
PCT/US2022/040504
Foam Properties
% Density, Compressive Tensile
Strength,
Foamable Closed g/cc3 Strength, ((ASTM C297),
Foam Composition, Cell (ISO 844), megapascal
Number No. megapascal
F3E6E FC3E6 NR NR 0.6 - 2.5 1.0 - 6.2
F4A1E FC4A1 NR NR 0.6 - 2.5 1.0 - 6.2
F4B1E FC4B1 NR NR 0.6 - 2.5 1.0 - 6.2
F4C1E FC4C1 NR NR 0.6 - 2.5 1.0 - 6.2
F4D1E FC4D1 NR NR 0.6 - 2.5 1.0 - 6.2
F4E1E FC4E1 NR NR 0.6 - 2.5 1.0 - 6.2
F4A2E FC4A2 NR NR 0.6 - 2.5 1.0 - 6.2
F4B2E FC4B2 NR NR 0.6 - 2.5 1.0 - 6.2
F4C2E FC4C2 NR NR 0.6 - 2.5 1.0 - 6.2
F4D2E FC4D2 NR NR 0.6 - 2.5 1.0 - 6.2
F4E2E FC4E2 NR NR 0.6 - 2.5 1.0 - 6.2
F4A3E FC4A3 NR NR 0.6 - 2.5 1.0 - 6.2
F4B3E FC4B3 NR NR 0.6 - 2.5 1.0 - 6.2
F4C3E FC4C3 NR NR 0.6 - 2.5 1.0 - 6.2
F4D3E FC4D3 NR NR 0.6 - 2.5 1.0 - 6.2
F4E3E FC4E3 NR NR 0.6 - 2.5 1.0 - 6.2
F4A4E FC4A4 NR NR 0.6 - 2.5 1.0 - 6.2
F4B4E FC4B4 NR NR 0.6 - 2.5 1.0 - 6.2
F4C4E FC4C4 NR NR 0.6 - 2.5 1.0 - 6.2
F4D4E FC4D4 NR NR 0.6 - 2.5 1.0 - 6.2
F4E4E FC4E4 NR NR 0.6 - 2.5 1.0 - 6.2
F4A5E FC4A5 NR NR 0.6 - 2.5 1.0 - 6.2
F4B5E FC4B5 NR NR 0.6 - 2.5 1.0 - 6.2
F4C5E FC4C5 NR NR 0.6 - 2.5 1.0 - 6.2
F4D5E FC4D5 NR NR 0.6 - 2.5 1.0 - 6.2
76
CA 03228700 2024- 2- 12 SUBSTITUTE SHEET (RULE 26)

WO 2023/023085
PCT/US2022/040504
Foam Properties
% Density, Compressive Tensile
Strength,
Foamable Closed g/cc3 Strength, ((ASTM C297),
Foam Composition, Cell (ISO 844), megapascal
Number No. megapascal
F4E5E FC4E5 NR NR 0.6 - 2.5 1.0 - 6.2
F4A6E FC4A6 NR NR 0.6 - 2.5 1.0 - 6.2
F4B6E FC4B6 NR NR 0.6 - 2.5 1.0 - 6.2
F4C6E FC4C6 NR NR 0.6 - 2.5 1.0 - 6.2
F4D6E FC4D6 NR NR 0.6 - 2.5 1.0 - 6.2
F4E6E FC4E6 NR NR 0.6 - 2.5 1.0 - 6.2
F5A1E FC5A1 NR NR 0.6 - 2.5 1.0 - 6.2
F5B1E FC5B1 NR NR 0.6 - 2.5 1.0 - 6.2
F5C1E FC5C1 NR NR 0.6 - 2.5 1.0 - 6.2
F5D1E FC5D1 NR NR 0.6 - 2.5 1.0 - 6.2
F5E1E FC5E1 NR NR 0.6 - 2.5 1.0 - 6.2
F5A2E FC5A2 NR NR 0.6 - 2.5 1.0 - 6.2
F5B2E FC5B2 NR NR 0.6 - 2.5 1.0 - 6.2
F5C2E FC5C2 NR NR 0.6 - 2.5 1.0 - 6.2
F5D2E FC5D2 NR NR 0.6 - 2.5 1.0 - 6.2
F5E2E FC5E2 NR NR 0.6 - 2.5 1.0 - 6.2
F5A3E FC5A3 NR NR 0.6 - 2.5 1.0 - 6.2
F5B3E FC5B3 NR NR 0.6 - 2.5 1.0 - 6.2
F5C3E FC5C3 NR NR 0.6 - 2.5 1.0 - 6.2
F5D3E FC5D3 NR NR 0.6 - 2.5 1.0 - 6.2
F5E3E FC5E3 NR NR 0.6 - 2.5 1.0 - 6.2
F5A4E FC5A4 NR NR 0.6 - 2.5 1.0 - 6.2
F5B4E FC5B4 NR NR 0.6 - 2.5 1.0 - 6.2
F5C4E FC5C4 NR NR 0.6 - 2.5 1.0 - 6.2
F5D4E FC5D4 NR NR 0.6 - 2.5 1.0 - 6.2
77
CA 03228700 2024- 2- 12 SUBSTITUTE SHEET (RULE 26)

WO 2023/023085
PCT/US2022/040504
Foam Properties
% Density, Compressive Tensile
Strength,
Foamable Closed g/cc3 Strength, ((ASTM C297),
Foam Composition, Cell (ISO 844), megapascal
Number No. megapascal
F5E4E FC5E4 NR NR 0.6 - 2.5 1.0 - 6.2
F5A5E FC5A5 NR NR 0.6 - 2.5 1.0 - 6.2
F5B5B FC5E5 NR NR 0.6 - 2.5 1.0 - 6.2
F5C5E FC5C5 NR NR 0.6 - 2.5 1.0 - 6.2
F5D5E FC5D5 NR NR 0.6 - 2.5 1.0 - 6.2
F5E5E FC5E5 NR NR 0.6 - 2.5 1.0 - 6.2
F5A6E FC5A6 NR NR 0.6 - 2.5 1.0 - 6.2
F5B6E FC5B6 NR NR 0.6 - 2.5 1.0 - 6.2
F5C6E FC5C6 NR NR 0.6 - 2.5 1.0 - 6.2
F5D6E FC5D6 NR NR 0.6 - 2.5 1.0 - 6.2
F5E6E FC5E6 NR NR 0.6 - 2.5 1.0 - 6.2
F6A1E FC6A1 NR NR 0.6 - 2.5 1.0 - 6.2
F6B1E FC6B1 NR NR 0.6 - 2.5 1.0 - 6.2
F6C1E FC6C1 NR NR 0.6 - 2.5 1.0 - 6.2
F6D1E FC6D1 NR NR 0.6 - 2.5 1.0 - 6.2
F6E1E FC6E1 NR NR 0.6 - 2.5 1.0 - 6.2
F6A2E FC6A2 NR NR 0.6 - 2.5 1.0 - 6.2
F6B2E FC6E2 NR NR 0.6 - 2.5 1.0 - 6.2
F6C2E FC6C2 NR NR 0.6 - 2.5 1.0 - 6.2
F6D2E FC6D2 NR NR 0.6 - 2.5 1.0 - 6.2
F6E2E FC6E2 NR NR 0.6 - 2.5 1.0 - 6.2
F6A3E FC6A3 NR NR 0.6 - 2.5 1.0 - 6.2
F6B3E FC6B3 NR NR 0.6 - 2.5 1.0 - 6.2
F6C3E FC6C3 NR NR 0.6 - 2.5 1.0 - 6.2
F6D3E FC6D3 NR NR 0.6 - 2.5 1.0 - 6.2
78
CA 03228700 2024- 2- 12 SUBSTITUTE SHEET (RULE 26)

WO 2023/023085
PCT/US2022/040504
Foam Properties
% Density, Compressive Tensile
Strength,
Foamable Closed g/cc3 Strength, ((ASTM C297),
Foam Composition, Cell (ISO 844), megapascal
Number No. megapascal
F6E3E FC6E3 NR NR 0.6 - 2.5 1.0 - 6.2
F6A4E FC6A4 NR NR 0.6 - 2.5 1.0 - 6.2
F6B4E FC6B4 NR NR 0.6 - 2.5 1.0 - 6.2
F6C4E FC6C4 NR NR 0.6 - 2.5 1.0 - 6.2
F6D4E FC6D4 NR NR 0.6 - 2.5 1.0 - 6.2
F6E4E FC6E4 NR NR 0.6 - 2.5 1.0 - 6.2
F6A5E FC6A5 NR NR 0.6 - 2.5 1.0 - 6.2
F6B5E FC6B5 NR NR 0.6 - 2.5 1.0 - 6.2
F6C5E FC6C5 NR NR 0.6 - 2.5 1.0 - 6.2
F6D5E FC6D5 NR NR 0.6 - 2.5 1.0 - 6.2
F6E5E FC6E5 NR NR 0.6 - 2.5 1.0 - 6.2
F6A6E FC6A6 NR NR 0.6 - 2.5 1.0 - 6.2
F6B6E FC6B6 NR NR 0.6 - 2.5 1.0 - 6.2
F6C6E FC6C6 NR NR 0.6 - 2.5 1.0 - 6.2
F6D6E FC6D6 NR NR 0.6 - 2.5 1.0 - 6.2
F6E6E FC6E6 NR NR 0.6 - 2.5 1.0 - 6.2
F7A1E FC7A1 NR NR 0.6 - 2.5 1.0 - 6.2
F7B1E FC7B1 NR NR 0.6 - 2.5 1.0 - 6.2
F7C1E FC7C1 NR NR 0.6 - 2.5 1.0 - 6.2
F7D1E FC7D1 NR NR 0.6 - 2.5 1.0 - 6.2
F7E1E FC7E1 NR NR 0.6 - 2.5 1.0 - 6.2
F7A2E FC7A2 NR NR 0.6 - 2.5 1.0 - 6.2
F7B2E FC7B2 NR NR 0.6 - 2.5 1.0 - 6.2
F7C2E FC7C2 NR NR 0.6 - 2.5 1.0 - 6.2
F7D2E FC7D2 NR NR 0.6 - 2.5 1.0 - 6.2
79
CA 03228700 2024- 2- 12 SUBSTITUTE SHEET (RULE 26)

WO 2023/023085
PCT/US2022/040504
Foam Properties
% Density, Compressive Tensile
Strength,
Foamable Closed g/cc3 Strength, ((ASTM C297),
Foam Composition, Cell (ISO 844), megapascal
Number No. megapascal
F7E2E FC7E2 NR NR 0.6 - 2.5 1.0 - 6.2
F7A3E FC7A3 NR NR 0.6 - 2.5 1.0 - 6.2
F7B3E FC7B3 NR NR 0.6 - 2.5 1.0 - 6.2
F7C3E FC7C3 NR NR 0.6 - 2.5 1.0 - 6.2
F7D3E FC7D3 NR NR 0.6 - 2.5 1.0 - 6.2
F7E3E FC7E3 NR NR 0.6 - 2.5 1.0 - 6.2
F7A4E FC7A4 NR NR 0.6 - 2.5 1.0 - 6.2
F7B4E FC7B4 NR NR 0.6 - 2.5 1.0 - 6.2
F7C4E FC7C4 NR NR 0.6 - 2.5 1.0 - 6.2
F7D4E FC7D4 NR NR 0.6 - 2.5 1.0 - 6.2
F7E4E FC7E4 NR NR 0.6 - 2.5 1.0 - 6.2
F7A5E FC7A5 NR NR 0.6 - 2.5 1.0 - 6.2
F7B5E FC7B5 NR NR 0.6 - 2.5 1.0 - 6.2
F7C5E FC7C5 NR NR 0.6 - 2.5 1.0 - 6.2
F7D5E FC7D5 NR NR 0.6 - 2.5 1.0 - 6.2
F7E5E FC7E5 NR NR 0.6 - 2.5 1.0 - 6.2
F7A6E FC7A6 NR NR 0.6 - 2.5 1.0 - 6.2
F7B6E FC7B6 NR NR 0.6 - 2.5 1.0 - 6.2
F7C6E FC7C6 NR NR 0.6 - 2.5 1.0 - 6.2
F7D6E FC7D6 NR NR 0.6 - 2.5 1.0 - 6.2
F7E6E FC7E6 NR NR 0.6 - 2.5 1.0 - 6.2
F8A1E FC8A1 NR NR 0.6 - 2.5 1.0 - 6.2
F8B1E FC8B1 NR NR 0.6 - 2.5 1.0 - 6.2
F8C1E FC8C1 NR NR 0.6 - 2.5 1.0 - 6.2
F8D1E FC8D1 NR NR 0.6 - 2.5 1.0 - 6.2
CA 03228700 2024- 2- 12 SUBSTITUTE SHEET (RULE 26)

WO 2023/023085
PCT/US2022/040504
Foam Properties
% Density, Compressive Tensile
Strength,
Foamable Closed g/cc3 Strength, ((ASTM C297),
Foam Composition, Cell (ISO 844), megapascal
Number No. megapascal
F8E1E FC8E1 NR NR 0.6 - 2.5 1.0 - 6.2
F8A2E FC8A2 NR NR 0.6 - 2.5 1.0 - 6.2
F8B2E FC8B2 NR NR 0.6 - 2.5 1.0 - 6.2
F8C2E FC8C2 NR NR 0.6 - 2.5 1.0 - 6.2
F8D2E FC8D2 NR NR 0.6 - 2.5 1.0 - 6.2
F8E2E FC8E2 NR NR 0.6 - 2.5 1.0 - 6.2
F8A3E FC8A3 NR NR 0.6 - 2.5 1.0 - 6.2
F8B3E FC8B3 NR NR 0.6 - 2.5 1.0 - 6.2
F8C3E FC8C3 NR NR 0.6 - 2.5 1.0 - 6.2
F8D3E FC8D3 NR NR 0.6 - 2.5 1.0 - 6.2
F8E3E FC8E3 NR NR 0.6 - 2.5 1.0 - 6.2
F8A4E FC8A4 NR NR 0.6 - 2.5 1.0 - 6.2
F8B4E FC8B4 NR NR 0.6 - 2.5 1.0 - 6.2
F8C4E FC8C4 NR NR 0.6 - 2.5 1.0 - 6.2
F8D4E FC8D4 NR NR 0.6 - 2.5 1.0 - 6.2
F8E4E FC8E4 NR NR 0.6 - 2.5 1.0 - 6.2
F8A5E FC8A5 NR NR 0.6 - 2.5 1.0 - 6.2
F8B5E FC8B5 NR NR 0.6 - 2.5 1.0 - 6.2
F8C5E FC8C5 NR NR 0.6 - 2.5 1.0 - 6.2
F8D5E FC8D5 NR NR 0.6 - 2.5 1.0 - 6.2
F8E5E FC8E5 NR NR 0.6 - 2.5 1.0 - 6.2
F8A6E FC8A6 NR NR 0.6 - 2.5 1.0 - 6.2
F8B6E FC8B6 NR NR 0.6 - 2.5 1.0 - 6.2
F8C6E FC8C6 NR NR 0.6 - 2.5 1.0 - 6.2
F8D6E FC8D6 NR NR 0.6 - 2.5 1.0 - 6.2
81
CA 03228700 2024- 2- 12 SUBSTITUTE SHEET (RULE 26)

WO 2023/023085
PCT/US2022/040504
Foam Properties
Density, Compressive Tensile
Strength,
Foamable Closed g/cc3 Strength, ((ASTM C297),
Foam Composition, Cell (ISO 844), megapascal
Number No. megapascal
F8E6E FC8E6 NR NR 0.6 ¨ 2.5 1.0 ¨ 6.2
The foams of the present invention have wide utility. The present foams,
including each of
Foams 1 ¨ 6 and foams Fl ¨ F8, have unexpected advantage in applications
requiring low
density and/or good compression and/or tensile and/or shear properties, and/or
long-term
stability, and/or sustainable sourcing, and/or being made from recycled
material and being
recyclable. In particular, the present foams, including each of Foams 1 ¨6 and
each of foams
Fl ¨ F8, have unexpected advantage in: wind energy applications (wind turbine
blades (shear
webs, shells, cores, and root); marine applications (hulls, decks,
superstructures, bulkheads,
stringers, and interiors); industrial low weight applications; automotive and
transport applications
(interior and exterior of cars, trucks, trains, aircraft, and spacecraft).
EXAMPLES
Example 1A ¨ PEF PREPARATION AT MW 114,000 WITH PMDA CHAIN EXTENDER
AND SSP
A bio-based polyethylene furanoate homopolymer was prepared by esterification
and
polycondensation of 2,5-furandicarboxylic acid with mono ethylene glycol
according to known
methods to produce PEF homopolymer, which is then treated according to
techniques
corresponding to the techniques described in detail in Examples 47, 49 and 51
below, with the
chain extender PM DA at 0.6% by weight and then subject to solid state
polymerization
according to known techniques to produce a PEF homopolymer. The PEF polymer
was tested
and found to have the following characteristicsl:
Molecular Weight ¨ 114,000
Molecular weight as determined and referenced herein refers to molecular
weight determination by diffusion
ordered nuclear magnetic resonance spectroscopy (DOSY NM R) as per the
description contained in "Application of
1H DOSY NM R in Measurement of Polystyrene Molecular Weights," VNU Journal of
Science: Natural Sciences and
Technology, Vol. 36, No. 2 (2020) 16-21 June 2020, Nam et al., with final
fitting performed by two functions:
log D = Cr log M log A (as per Grubb's Group, Macromolecules 2012, 45, 9595-
9603) R2=0.977 and
log D = a log M + 3 [log (M)]2 + A (R2=0.998) with a final fit of the data as
follows: a: 0.4816276533; 13: -
0.064669629A: -21.74524435. Decomposition temperature was determined by
thernnogravinnetric analysis (TGA)
based on ASTM E1131. Density of the polymer was measured in accordance with
ASTM D71). The remaining
properties, including crystallinity, were determined in accordance ASTM D3418
and ASTM E1356.
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Density (g/cc) ¨ 1.43
Glass Transition Temperature - 86 C
Melt Temperature - 214 C
Decomposition Temperature ¨ 347 C
Crystallinity - 46%
The PEF polymer so produced is referred to in these Examples as PEX1.
Example 1B ¨ CLOSED CELL PEF FOAMS FROM PEX1 OVER A RANGE OF
RELATIVE DENSITIES AND BLOWING AGENTS
The present invention includes the advantages formation of PEF foams having a
high
volume percentage of closed cells over a range of relative foam densities
(RFDs) and using a
range of blowing agents. Although applicant is not bound by any theory of
operation, it is
believed that one or more of the advantageous foam properties of the present
invention arise, at
least in part, as a result of the ability to form foams with high closed cell
content. In particular,
the following Table El B illustrates the volume percent closed cells for
several foams made by
applicant:
TABLE El B ¨ FOAM CLOSED CELL CONTENT
FOAM COMPONENTS FOAM PROPERTIES DETAILED EXAMPLE
Polymer Blowing RFD Volume %
Agent Closed Cells*
PEX1 1243ze(E) 0.078 91 Example 4B
PEX1 1243ze(E) 0.036 92 Example 6
PEX1 1336mzz(Z) 0.14 76 Example 26B
PEX1 1336mzz(Z) 0.13 67 Example 26B
PEX1 1233zd(E) 0.15 46
PEX1 isopentane 0.13 40 Example C2
*Volume % closed cells is determined herein by ASTM D6226.
Comparative Example 1 ¨ PEF FOAM PREPARATION USING PEX1 AND CO2 AS
BLOWING AGENT
1 gram of PEX1 in a glass container was loaded into a 60 cc autoclave and then
dried
under vacuum for six (6) hours at 130 C. The dried polymer was then cooled to
room
temperature and placed in a glass container inside an autoclave. About 0.25
moles (11 grams)
of CO2 blowing agent was then pumped into the autoclave containing the dried
polymer, and
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then the autoclave was heated to bring the polymer to a melt state at a
temperature of about
240 C and a pressure above about 610 psig. The polymer/CO2blowing agent was
maintained
in this melt state for about 1 hour and the temperature and pressure of the
melt/blowing agent
was then reduced over a period of about 5¨ 15 minutes to about 190 C and 610
psig
(hereinafter referred to for convenience as pre-foaming temperature and pre-
foaming pressure,
respectively), and then maintained at about this temperature and pressure for
a period of about
30 minutes to allow the amount of blowing agent incorporated into the melt
under such
conditions to reach equilibrium. The temperature and pressure in the autoclave
were then
reduced rapidly (over a period of about 10 seconds for the pressure reduction
and about 1 ¨ 10
minutes for the temperature reduction using chilled water)) to ambient
conditions (approximately
22 C and 1 atmosphere) and foaming occurred. The foam thus produced was tested
to
determine the following properties:
= compressive strength ("CS") (measured perpendicular to the plane (that
was in direct
contact with the blowing agent) in accordance with ISO 844)
= compressive modulus ("CM") (measured perpendicular to the plane (that was in
direct contact with the blowing agent) in accordance with ISO 844)
= tensile strength ("TS") (measured perpendicular to the plane (that was in
direct contact
with the blowing agent) in accordance with ASTM 0297)
= tensile modulus ("TM") (measured perpendicular to the plane (that was in
direct contact
with the blowing agent) in accordance with ASTM C297)
= relative foam density ("RFD").
As used herein, RFD is the density of the foam produced divided by the density
of the starting
polymer. Density is measured in these Examples using a method which
corresponds generally
to ASTM D71, except that hexane is used for displacement instead of water.
The foam produced in this Comparative Example 1 was tested and found to have
the
properties as reported in Table Cl below:
TABLE Cl
RFD 0.25
TS, Megapascal (Mpa) 0.74
CS, Mpa 0.5
TM, Mpa 32
CM, Mpa 8
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As reported above, the foam made using CO2 under the reported conditions had
an RFD
of 0.25, that is, a density that was only 25% of the density of the starting
polymer. This is a
foam density that is too high for many important applications.
Examples 2 ¨ 4 - PEF FOAM PREPARATION USING PEX1 AND
trans-1234ze, trans-1233zd and trans-1336mzz as BLOWING AGENT
Comparative Example 1 was repeated, except the CO2 blowing agent was replaced,
on
a molar equivalent basis in a separate run with each of trans-1234ze, trans-
1233zd and trans-
1336mzz, with the pre-foaming pressure for each run being maintained within a
similar pre-
foaming pressure (not more than about 50 psig greater than the 610 psig pre-
foaming pressure
used in Comparative Example 1). The foams thus produced were observed to be
good, high-
quality foam, and were then tested and found to have the properties reported
in Table E2-4
below:
TABLE E2-4
Ex Blowing RFD Avg. RELATIVE MECHANICAL PROPERTIES*
Agent Cell
Size, um
RTS RTM RCS RCM
2 trans- 0.1 108 1 1 1 1
1233zd
3 trans- 0.13 65 2.48 5.31 1.81 2.98
1336mzz
4A trans- 0.07 80 6.08 7.18 1.07 1.92
1234ze
k-For convenience and unless otherwise indicated in these Examples, the
comparative strength
and modulus results in the Examples hereof are reported based on trans-1233zd
as the base-
line value of 1 and are identified as RTS, RCS, RTM and RCM. Thus, for
example, the tensile
strength using trans-1234z blowing agent in Example 4 is 6.08 times greater
than the tensile
strength measured in Example 2. Tensile properties were determined based on
ASTM C297
and compressive properties were determined based on ASTM C365 and ASTM
D1621/1S0
844.
As can be seen from the results reported in Table E2 ¨4 above, each of the HFO
compounds tested as blowing agents produced a foam that had a dramatically and
unexpectedly improved density compared to CO2, that is, in each case the
density of the foam
produced with the tested HFO resulted in density value that is at least about
1.9 times less than
the density of the CO2 blown foam. Furthermore, from among the foams produced,
the trans-
1234ze produced a foam that was more than 3.5 times less than the density of
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foam, and the use of the trans-1234ze also unexpectedly produced a foam that
was
dramatically superior to even the other HFO blowing agents in terms of the
important tensile
properties, with the 1234ze foam being at least 2.7 times better in tensile
strength than the
1233zd foam.
The foam formed with 1234ze(E) in Example 4A produced a high-quality, low-
density
foam with an excellent uniform distribution of cells, as illustrated in Figure
2. Figure 2 is an
SEM micrograph of a thin slice of the foam produced, thus showing cell walls
having
been removed from the side of the cell facing the viewer, allowing visibility
into the cell,
and showing that well-formed closed cells comprise the foam.
Example 5 - PEF FOAM PREPARATION USING PEX1 AND cis1224yd as BLOWING
AGENT
Comparative Example 1 was repeated, except the CO2 blowing agent was replaced
in
the process with cis1224yd and the process conditions were modified in a
manner to produce a
foam having within an amount of moles of blowing agent in the foam that is
within 15% of the
moles of blowing agent in Comparative Example 1. In particular, the foam thus
produced using
cis1224yd according to this Example was observed to be an acceptable foam and
to have an
RFD that was within about 15 relative percent of the RFD produced using CO2 in
Comparative
Example 1, and therefore the foam of this example had a density that is too
high for many
important applications. However, for applications for which it is acceptable
to have such a
density, the foam produced in this Example was tested compared to CO2 and was
found to be
dramatically superior in the strength and modulus properties, as reported in
Table E5 below:
TABLE E5
Ex Blowing RFD Avg. RELATIVE MECHANICAL PROPERTIES*
Agent Cell
Size,
Pm
RTS RTM RCS RCM
C1CO2 0.25 189 1 1 1 1
3 Cis1224yd 0.22 128 1.61 2.02 1.68 2.38
*The relative mechanical properties reported in this Table E5 are compared to
the properties
from the foam produced with CO2 as the blowing agent in Comparative Example 1.
As can be seen from TABLE E5 above, on an equivalent molar blowing agent basis
(i.e.,
within 15%), the foams made using cis1224yd were surprisingly superior to the
foam made
using CO2 based on each of the physical strength and modulus properties
tested. For example,
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the foam made with ci51224yd produced a foam with both tensile and compressive
modulus
that is twice the value produced using CO2, while at the same time having
compressive and
tensile strengths that are more than 60% better than CO2. This result is
unexpected.
Example 6- PEF FOAM PREPARATION USING PEX1 AND trans-1234ze as
BLOWING AGENT
Comparative Example 1 was repeated, except: (1) the CO2 blowing agent was
replaced
with trans-1234ze and with an increase in molar amount of the trans-1234ze (by
about 2.5 more
moles than Comparative Example 1) to raise the pre-foaming pressure to 1590
psig. The foam
thus produced was observed to be a good, high-quality foam, and was then
tested and found to
have the properties reported in Table E6 below (with the value of the
mechanical properties
again being reported as a ratio of the values for 1233zd in Example 2 as
baseline of 1):
TABLE E6
Example Blowing RFD Vol% Avg. RELATIVE MECHANICAL PROPERTIES
Agent Closed Cell
Cells Size
(pm)
RTS RTM RCS
RCM
6 trans- 0.04 92.1 22 4.3 3.02 0.7
0.52
1234ze
12
Example 7 - PEF FOAM PREPARATION USING PEX1 AND cis-1336mzz as
BLOWING AGENT
Comparative Example 1 was repeated, except: (1) the CO2 blowing agent was
replaced
with cis1336mzz and with a decrease in molar amount of the cis-1336mzz (using
about 0.33
times the moles than Comparative Example 1) to decrease the pre-foaming
pressure to 190
psig. The foam thus produced was observed to be a good, high-quality foam, and
was then
tested and found to have the properties as reported in Table E7 below (with
the value of the
mechanical properties being reported as a ratio of the values for 1233zd in
Example 2 as
baseline of 1):
TABLE E7
Example Blowing RFD Avg. RELATIVE MECHANICAL PROPERTIES
Agent Cell
Size,
RTS RTM RCS RCM
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7 cis1336nnzz 0.11 177 5.87 6.46 0.79 1.21
Example 8 - PEF FOAM PREPARATION USING PEX1 AND trans-1336mzz as
BLOWING AGENT
Comparative Example 1 was repeated, except: (1) the CO2 blowing agent was
replaced,
on a molar equivalent basis with trans-1336ze; and (2) the pre-foaming
pressure was decreased
to 170 psig. The foam thus produced was observed to be a good, high-quality
foam, and was
then tested and found to have the properties as reported in Table E8 below
(with the value of
the mechanical properties again being reported as a ratio of the values for
1233zd in Example 2
as baseline of 1):
TABLE E8
Example Blowing RFD Avg. RELATIVE MECHANICAL PROPERTIES
Agent Cell
Size,
(pm)
RTS RTM RCS RCM
8 trans 0.12 130 6.52 5.32 2.55 2.65
1336mzz
Example 9¨ PEF PREPARATION AT MW 56,000 WITH PMDA CHAIN EXTENDER
AND SSP
A bio-based polyethylene furanoate homopolymer was prepared by esterification
and
polycondensation of 2,5-furandicarboxylic acid with mono ethylene glycol
according to known
methods to produce PEF homopolymer, which is then treated according to known
techniques
with the chain extender PMDA at 0.6% by weight and then subject to solid state
polymerization
according to known techniques to produce a PEF homopolymer. The PEF polymer
was tested
and found to have the following characteristics:
Molecular Weight ¨ 56,000
Density, g/cc ¨ 1.43
Glass Transition Temperature - 91 C
Melt Temperature - 222 C
Decomposition Temperature ¨ 347 C
Crystallinity - 46%
The PEF polymer so produced is referred to in these Examples as PEX9.
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Examples 10 and 11 - PEF FOAM PREPARATION USING PEX9 and 1234yf and
trans-1234ze as BLOWING AGENT
PEX9 was processed in two runs in an autoclave according to essentially the
same
procedure described in Comparative Example 1 except that 1234yf and
trans1234ze
(respectively Example 10 and Example 11) were each used as the blowing agent
and except as
noted below. The polymer/blowing agent was then heated (without pre-drying the
polymer) to a
melt state at a temperature of about 240 C and a pressure of about 2380 psig
in the case of
1234yf as the blowing agent and of about 2250 psig in the case of trans1234ze
as the blowing
agent, and then the polymer/blowing agent was maintained in this melt state
for about 1 hour.
The temperature and pressure of the melt were then reduced over a period of
about 5¨ 15
minutes to about 190 C and about 1580 psig for trans1234ze and 1720 psig for
1234yf, and
then maintained at about this temperature and pressure for a period of about
30 minutes to
dissolve the blowing agent in the polymer, and then the temperature and
pressure of the
polymer were reduced rapidly as described in Comparative Example 1 to ambient
conditions
(approximately 22 C and 1 atmosphere). The foams thus produced were observed
to be good,
high-quality foam, and were then tested and have the properties identified
below in Table El 0-
11:
TABLE El 0-11
Example Blowing Agent RFD Avg. Cell
Size,
(pm)
10 1234yf 0.19 73
11 trans1234ze 0.09 45
Example 12 - PEF FOAM PREPARATION USING PEX9 and using trans1234ze as
BLOWING AGENT
PEX9 was processed in an autoclave according to essentially the same procedure
describe in Comparative Example 1 except that: (1) trans-1234ze was used as
the blowing
agent and in an increased molar amount (using about 2.6 times the moles used
in Comparative
Example 1) to produce a pre-foaming pressure was about 1590 psig; and
depressurization to
ambient occurred over about 2 seconds. The foam thus produced was observed to
be good,
high-quality foam, and was tested and found to have an RFD of 0.05 , an
average cell size of 41
(pm) and about 92%.
Example 13¨ PEF PREPARATION AT MW 25,000 WITH SSP
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A bio-based polyethylene furanoate homopolymer was prepared by esterification
and
polycondensation of 2,5-furandicarboxylic acid with mono ethylene glycol
according to known
methods to produce PEF homopolymer, which is then subject to solid state
polymerization
according to known techniques to produce a PEF homopolymer. The PEF polymer
was tested
and found to have the following characteristics:
Molecular Weight ¨ 25,000
Glass Transition Temperature - 89 C
Melt Temperature - 217 C
Decomposition Temperature ¨ 347 C
Crystallinity - 41%
The PEF polymer so produced is referred to in these Examples as PEX13.
Example 14¨ PEF FOAM PREPARATION USING PEX13 AND trans-1234ze as
BLOWING AGENT
Comparative Example 1 was repeated, except: (1) PEX13 was used instead of
PEX1;
(2) the CO2 blowing agent was replaced with trans-1234ze (at an increased in
molar amount of
about 2.8 times the moles used in Comparative Example 1,) to produce a pre-
foaming pressure
of about 1718 psig and the pre-foaming temperature was about 200 C. The foam
thus
produced was observed to be a good, high-quality foam, and was then tested and
found to have
an RFD of 0.26, which is too high for many important applications, and an
average cell size of
69 (pm).
Example 15¨ PEF FOAM PREPARATION USING PEX13 AND trans-1233zd as
BLOWING AGENT
Comparative Example 1 was repeated, except: (1) PEX13 was used instead of
PEX1;
(2) the CO2 blowing agent was replaced, on a molar equivalent basis (i.e.,
within 15%) with
trans-1233zd; and (3) the pre-foaming pressure was about 645 psig. The foam
thus produced
was observed to be good, high-quality foam, and was then tested and found to
have an RFD of
0.24 and an average cell size of 136 (pm).
Examples 16-20 ¨PEF FOAM PREPARATION USING PEF WITH MW OF 25,000 ¨
125,000
Comparative Example 1 is repeated, except that the conditions and materials
are altered
as indicted below in Table E16 through Table E20, using blowing agents shown
in the table on a
molar equivalent (i.e., within 15%) basis (with all values understood to be
"about" the indicated
value).
TABLE E16
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Example Thermoplastic Blowing Foam Properties**
Properties* Agent
WT% MW RFD Strength Modulus Vol% Closed
PEF Cells
16A 50 25,000 1234ze(E) <0.2 A A 50
16B 60 25,000 1234yf <0.2 A A 50
16C 70 25,000 1233zd(E) <0.2 A A 50
16D 80 25,000 1336mzz(E) <0.2 A A 50
16E 90 25,000 1336mzz(Z) <0.2 A A 50
16F 100 25,000 1224yd(Z) <0.2 A A 50
16G 50 25,000 1234ze(E) <0.2 A A 75
16H 60 25,000 1234yf <0.2 A A 75
161 70 25,000 1233zd(E) <0.2 A A 75
16J 80 25,000 1336mzz(E) <0.2 A A 75
16K 90 25,000 1336mzz(Z) <0.2 A A 75
16L 100 25,000 1224yd(Z) <0.2 A A 75
16M 50 25,000 1234ze(E) <0.2 A A 90
16N 60 25,000 1234yf <0.2 A A 90
160 70 25,000 1233zd(E) <0.2 A A 90
16P 80 25,000 1336mzz(E) <0.2 A A 90
16Q 90 25,000 1336mzz(Z) <0.2 A A 90
16R 100 25,000 1224yd(Z) <0.2 A A 90
16S 50 25,000 1234ze(E) <0.2 A A 100
16T 60 25,000 1234yf <0.2 A A 100
16U 70 25,000 1233zd(E) <0.2 A A 100
16V 80 25,000 1336mzz(E) <0.2 A A 100
16W 90 25,000 1336mzz(Z) <0.2 A A 100
16X 100 25,000 1224yd(Z) <0.2 A A 100
* WT% PEE moieties in the polymer
**A - acceptable
TABLE E17
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Example Thermoplastic Blowing Foam Properties**
Properties Agent
WT% MW RFD Strength Modulus Vol% Closed
PEF* Cells
17A 50 50,000 1234ze(E) <0.2 A A 50
17B 60 50,000 1234yf <0.2 A A 50
17C 70 50,000 1233zd(E) <0.2 A A 50
17D 80 50,000 1336mzz(E) <0.2 A A 50
17E 90 50,000 1336mzz(Z) <0.2 A A 50
17F 100 50,000 1224yd(Z) <0.2 A A 50
17G 50 50,000 1234ze(E) <0.2 A A 75
17H 60 50,000 1234yf <0.2 A A 75
171 70 50,000 1233zd(E) <0.2 A A 75
17J 80 50,000 1336mzz(E) <0.2 A A 75
17K 90 50,000 1336mzz(Z) <0.2 A A 75
17L 100 50,000 1224yd(Z) <0.2 A A 75
17M 50 50,000 1234ze(E) <0.2 A A 90
17N 60 50,000 1234yf <0.2 A A 90
170 70 50,000 1233zd(E) <0.2 A A 90
17P 80 50,000 1336mzz(E) <0.2 A A 90
17Q 90 50,000 1336mzz(Z) <0.2 A A 90
17R 100 50,000 1224yd(Z) <0.2 A A 90
17S 50 50,000 1234ze(E) <0.2 A A 100
17T 60 50,000 1234yf <0.2 A A 100
17U 70 50,000 1233zd(E) <0.2 A A 100
17V 80 50,000 1336mzz(E) <0.2 A A 100
17W 90 50,000 1336mzz(Z) <0.2 A A 100
17X 100 50,000 1224yd(Z) <0.2 A A 100
* WT% PEE moieties in the polymer
**A - acceptable
TABLE E18
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Example Thermoplastic Blowing Foam Properties**
Properties Agent
WT% MW RFD Strength Modulus Vol% Closed
PEF* Cells
18A 50 75,000 1234ze(E) <0.2 A A 50
18B 60 75,000 1234yf <0.2 A A 50
18C 70 75,000 1233zd(E) <0.2 A A 50
18D 80 75,000 1336mzz(E) <0.2 A A 50
18E 90 75,000 1336mzz(Z) <0.2 A A 50
18F 100 75,000 1224yd(Z) <0.2 A A 50
18G 50 75,000 1234ze(E) <0.2 A A 75
18H 60 75,000 1234yf <0.2 A A 75
181 70 75,000 1233zd(E) <0.2 A A 75
18J 80 75,000 1336mzz(E) <0.2 A A 75
18K 90 75,000 1336mzz(Z) <0.2 A A 75
18L 100 75,000 1224yd(Z) <0.2 A A 75
18M 50 75,000 1234ze(E) <0.2 A A 90
18N 60 75,000 1234yf <0.2 A A 90
180 70 75,000 1233zd(E) <0.2 A A 90
18P 80 75,000 1336mzz(E) <0.2 A A 90
18Q 90 75,000 1336mzz(Z) <0.2 A A 90
18R 100 75,000 1224yd(Z) <0.2 A A 90
18S 50 75,000 1234ze(E) <0.2 A A 100
18T 60 75,000 1234yf <0.2 A A 100
18U 70 75,000 1233zd(E) <0.2 A A 100
18V 80 75,000 1336mzz(E) <0.2 A A 100
18W 90 75,000 1336mzz(Z) <0.2 A A 100
18X 100 75,000 1224yd(Z) <0.2 A A 100
* WT% PEE moieties in the polymer
**A - acceptable
TABLE E19
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Example Thermoplastic Blowing Foam Properties**
Properties Agent
WT% MW RFD Strength Modulus Vol% Closed
PEF* Cells
19A 50 100,000 1234ze(E) <0.2 A A 50
19B 60 100,000 1234yf <0.2 A A 50
19C 70 100,000 1233zd(E) <0.2 A A 50
19D 80 100,000 1336mzz(E) <0.2 A A 50
19F 90 100,000 1336mzz(Z) <0.2 A A 50
19F 100 100,000 1224yd(Z) <0.2 A A 50
19G 50 100,000 1234ze(E) <0.2 A A 75
19H 60 100,000 1234yf <0.2 A A 75
191 70 100,000 1233zd(E) <0.2 A A 75
19J 80 100,000 1336mzz(E) <0.2 A A 75
19K 90 100,000 1336mzz(Z) <0.2 A A 75
19L 100 100,000 1224yd(Z) <0.2 A A 75
19M 50 100,000 1234ze(E) <0.2 A A 90
19N 60 100,000 1234yf <0.2 A A 90
190 70 100,000 1233zd(E) <0.2 A A 90
19P 80 100,000 1336mzz(E) <0.2 A A 90
19Q 90 100,000 1336mzz(Z) <0.2 A A 90
19R 100 100,000 1224yd(Z) <0.2 A A 90
19S 50 100,000 1234ze(E) <0.2 A A 100
19T 60 100,000 1234yf <0.2 A A 100
19U 70 100,000 1233zd(E) <0.2 A A 100
19V 80 100,000 1336mzz(E) <0.2 A A 100
19W 90 100,000 1336mzz(Z) <0.2 A A 100
19X 100 100,000 1224yd(Z) <0.2 A A 100
* WT% PEE moieties in the polymer
**A - acceptable
TABLE E20
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Example Thermoplastic Blowing Foam Properties**
Properties Agent
WT% MW RFD Strength Modulus Vol% Closed
PEF* Cells
20A 50 125,000 1234ze(E) <0.2 A A 50
20B 60 125,000 1234yf <0.2 A A 50
20C 70 125,000 1233zd(E) <0.2 A A 50
20D 80 125,000 1336mzz(E) <0.2 A A 50
20E 90 125,000 1336mzz(Z) <0.2 A A 50
20F 100 125,000 1224yd(Z) <0.2 A A 50
20G 50 125,000 1234ze(E) <0.2 A A 75
20H 60 125,000 1234yf <0.2 A A 75
201 70 125,000 1233zd(E) <0.2 A A 75
20J 80 125,000 1336mzz(E) <0.2 A A 75
20K 90 125,000 1336mzz(Z) <0.2 A A 75
20L 100 125,000 1224yd(Z) <0.2 A A 75
20M 50 125,000 1234ze(E) <0.2 A A 90
20N 60 125,000 1234yf <0.2 A A 90
200 70 125,000 1233zd(E) <0.2 A A 90
20P 80 125,000 1336mzz(E) <0.2 A A 90
20Q 90 125,000 1336mzz(Z) <0.2 A A 90
20R 100 125,000 1224yd(Z) <0.2 A A 90
20S 50 125,000 1234ze(E) <0.2 A A 100
201 60 125,000 1234yf <0.2 A A 100
20U 70 125,000 1233zd(E) <0.2 A A 100
20V 80 125,000 1336mzz(E) <0.2 A A 100
20W 90 125,000 1336mzz(Z) <0.2 A A 100
20X 100 125,000 1224yd(Z) <0.2 A A 100
In each case in Tables E16 ¨ E20 above, the thermoplastic polymer used to make
the foam had
characteristics (measured in accordance with same procedures as identified
above in
Comparative Example 1) within the ranges indicated below:
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Glass Transition Temperature ¨ 75 - 95 C
Melt Temperature ¨ 190 - 240 C
Decomposition Temperature ¨ 320 - 400 C
Crystallinity ¨ 30 - 60%
All foams thus produced according to these examples are observed to be foams
of
acceptable quality.
Examples 21 -22 PEF FOAM PREPARATION USING PEX1 AND BLOWING AGENT
CONSISTING OF trans-1234ze AND CO-BLOWING AGENTS
Example 4 is repeated in a series of runs, except that in each run the blowing
agent
consisting of 0.25 moles of trans1234ze used in Example 4 is replaced by a
combination
consisting of about 0.125 moles of trans1234ze and 0.125 moles of a co-blowing
agent. The
blowing agent combinations used in each of Examples 21 ¨ 22 are shown in Table
E21-22, with
the relative mechanical property results being presented in this table based
on the result from
Example 4 as the base line of 1.
TABLE E21-22
Ex Co-Blowing Foaming RFD
RELATIVE MECHANICAL PROPERTIES (Based on
Agent (50 Pressure,
Example 4 Results with 1234ze with no co-blowing
mole% with psig agent as the base of 1)

trans-1234ze)
RTS RTM RCS
RCM
21 Cyclopentane 485 0.05 0.14 0.1 0.26
0.0045
22 tran51233zd 608 0.1 0.34 0.21 0.53
0.37
As can be seen from the results reported in Table E21 ¨ 22 above, in each case
the
replacement of 0.125 moles of trans-1234ze (50 mole% of the total blowing
agent used) with an
equivalent molar amount of the indicated co-blowing agent causes highly
detrimental and
substantial reduction in the tensile properties of the foam. By way of
example, the tensile
modulus of the foam blowing with cyclopentane co-blowing agent is only about
3% of the tensile
modulus achieved by trans1234ze alone, and every mechanical property measured
in Example
21 is 20% or less than the value achieved by Example 4.
Comparative Example 2¨ PEF FOAM PREPARATION USING PEX1 AND HFC-134a
AS BLOWING AGENT
1 gram of PEX1 in a glass container was loaded into an autoclave and then
dried for
under vacuum for six (6) hours at 130 C. The dried polymer was then cooled to
room
temperature and placed in a glass container inside an autoclave. About 0.25
moles (25.3
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grams) of R-134a blowing agent was then pumped into the autoclave containing
the dried
polymer, and then the autoclave was heated to bring the polymer to a melt
state at a
temperature of about 240 C and a pressure above about 570 psig. The
polymer/R134a blowing
agent was maintained in this melt state for about 1 hour and the temperature
and pressure of
the melt/blowing agent was then reduced over a period of about 5 ¨ 15 minutes
to about 190 C
and 570 psig (hereinafter referred to for convenience as pre-foaming
temperature and pre-
foaming pressure, respectively), and then maintained at about this temperature
and pressure for
a period of about 30 minutes to allow the amount of blowing agent incorporated
into the melt
under such conditions to reach equilibrium. The temperature and pressure in
the autoclave
were then reduced rapidly (over a period of about 10 seconds for the pressure
reduction and
about 1 ¨ 10 minutes for the temperature reduction using chilled water)) to
ambient conditions
(approximately 22 C and 1 atmosphere) and foaming occurred. The foam thus
produced had a
relatively acceptable foam structure and was tested to determine relative foam
density (RFD)
and strength and modulus properties. The RFD of the foam was 0.12.
Example 23- PEF FOAM PREPARATION USING PEX1 AND trans-1336mzz as
BLOWING AGENT
Comparative Example 2 was repeated, except: (i) the HFC-134a blowing agent was
replaced in the process with trans1336mmzz in two separate runs; and (ii) the
process
conditions were modified in a manner to produce a foam having a density
similar to the density
of the foam produced in Comparative Example 2. In particular, the foams thus
produced using
trans1336mzz according to this Example were observed to be acceptable foams
and had RFD
values that were within about 15% of the RFD produced using HFC-134a in
Comparative
Example 2. The foams produced were tested to determine various properties,
including
strength and modulus properties, and were found to be dramatically superior to
the foam made
with HFC-134a in each of the measured properties, as reported in Table E23
below:
TABLE E23
Ex Blowing RFD Avg. RELATIVE MECHANICAL PROPERTIES*
Agent Cell
Size,
Pm
RTS RTM RCS RCM
C2 134a 0.12 1 1 1 1
23A trans1336mzz 0.12 130 150 10.7 35.6 15.2
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23B trans1336mzz 0.13 65 57 10.7 25.3 16.9
*The relative mechanical properties reported in this Table E23 are compared to
the properties
from the foam produced with HFC-134a as the blowing agent in Comparative
Example 2.
As can be seen from TABLE E23 above, the foams made using trans1336mzz were
surprisingly and dramatically superior to the foam made using HFC-134a in
terms of all the
physical strength and modulus properties tested. For example, the foam made
with
trans1336mzz produced a foam with both tensile and compressive strengths that
were more
than 10 times better than the strength of foam made with HFC-134a, while at
the same time
having compressive and tensile modulus that are more 3 times better than foam
made using
HFC-134a. This result shows a dramatic and unexpected improvement in physical
properties of
the foam.
Comparative Example 3¨ PEF FOAM PREPARATION USING PEX1 AND
ISOPENTANE AS BLOWING AGENT
1 gram of PEX1 in a glass container was loaded into an autoclave and then
dried for
under vacuum for six (6) hours at 130 C. The dried polymer was then cooled to
room
temperature and placed in a glass container inside an autoclave. About 0.25
moles (27.8
grams) of isopentane blowing agent was then pumped into the autoclave
containing the dried
polymer, and then the autoclave was heated to bring the polymer to a melt
state at a
temperature of about 240 C and a pressure above about 443 psig. The
polymer/isopentane
blowing agent was maintained in this melt state for about 1 hour and the
temperature and
pressure of the melt/blowing agent was then reduced over a period of about 5 ¨
15 minutes to
about 190 C and 443 psig (hereinafter referred to for convenience as pre-
foaming temperature
and pre-foaming pressure, respectively), and then maintained at about this
temperature and
pressure for a period of about 30 minutes to allow the amount of blowing agent
incorporated into
the melt under such conditions to reach equilibrium. The temperature and
pressure in the
autoclave were then reduced rapidly (over a period of about 10 seconds for the
pressure
reduction and about 1 ¨ 10 minutes for the temperature reduction using chilled
water)) to
ambient conditions (approximately 22 C and 1 atmosphere) and foaming occurred.
The foam
thus produced had a relatively acceptable foam structure and was tested to
determine relative
foam density (RFD) and strength and modulus properties. The RFD of the foam
was 0.13.
Examples 24¨ 25- PEF FOAM PREPARATION USING PEX1 AND trans-1336mzz as
BLOWING AGENT
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Comparative Example 3 was repeated, except the isopentane blowing agent was
replaced in the process with tran51336mmzz(E). The process conditions were
modified in a
manner to produce a foam having RFD values that were within about 15% of the
RFD produced
using isopentane in Comparative Example 3. The foam produced was tested to
determine
various properties, including strength and modulus properties, and was found
to be dramatically
superior in each of the measured property, as reported in Table E24-25 below:
TABLE E24-25
Ex Blowing RFD Vol% Avg. RELATIVE MECHANICAL
Agent Closed Cell PROPERTIES*
Cells Size, pm
RTS RTM RCS RCM
C3 isopentane 0.12 40 NA 1 1 1 1
24 trans1336mzz 0.12 NA 130 1.57 17.8 1.2 7.6
25 trans1336mzz 0.13 67.3 65 0.6 1.2 1.1 0.76
AVG 0.125 97.5 1.09 9.5 1.15 4.2
*The relative mechanical properties reported in this Table E26 are compared to
the properties
from the foam produced with isopentane as the blowing agent in Comparative
Example 3.
As can be seen from TABLE E24-25 above, the foams made using trans1336mzz were

surprisingly superior, on average, to the foam made using isopentane in terms
of the physical
strength and modulus properties tested. This result is unexpected.
Example 26- PEF FOAM PREPARATION USING PEX1 AND cis-1336mzz as
BLOWING AGENT
Comparative Example 3 was repeated, except: (i) the isopentane blowing agent
was
replaced in the process with cis1336mmzz(E); and (ii) the process conditions
were modified in a
manner to produce a foam having an RFD that was within about 18% of the RFD
produced
using isopentane in Comparative Example 3. The foam produced was tested to
determine
various properties and was found to be dramatically superior in tensile
strength and tensile
modulus, as reported in Table E26 below:
TABLE E26
Ex Blowing RFD Vol% Avg. RELATIVE MECHANICAL PROPERTIES*
Agent Closed Cell
Cells Size,
pm
RTS RCS RTM RCM
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C3 isopentane 0.13 40 NA 1 1 (.69) 1(42.4)
1(22.2)
(0.95)
26A Cis1336mzz 0.11 NA 177 1.42 0.48 1.46 0.31
26B Cis1336mzz 0.14 75.8 169 1.62 2.8 2.14 1.2
*The relative mechanical properties reported in this Table E26 are compared to
the properties
from the foam produced with isopentane as the blowing agent in Comparative
Example 3.
As can be seen from TABLE E26 above, the foam made with cis1336mzz produced a
foam with tensile strengths that were at least 40% better than foam made using
isopentane.
This result shows that dramatic and unexpected improvement in physical
properties of the foam
can be achieved according to the present invention.
Comparative Example 4¨ PEF FOAM PREPARATION USING PEX1 AND
CYCLOPENTANE AS BLOWING AGENT
1 gram of PEX1 in a glass container was loaded into an autoclave and then
dried for
under vacuum for six (6) hours at 130 C. The dried polymer was then cooled to
room
temperature and placed in a glass container inside an autoclave. About 0.25
moles (32.9
grams) of cyclopentane blowing agent was then pumped into the autoclave
containing the dried
polymer, and then the autoclave was heated to bring the polymer to a melt
state at a
temperature of about 240 C and a pressure above about 320 psig. The
polymer/cyclopentane
blowing agent combination was maintained in this melt state for about 1 hour,
and the
temperature and pressure of the melt/blowing agent were then reduced over a
period of about 5
¨ 15 minutes to about 190 C and 320 psig (hereinafter referred to for
convenience as pre-
foaming temperature and pre-foaming pressure, respectively), and then
maintained at about this
temperature and pressure for a period of about 30 minutes to allow the amount
of blowing agent
incorporated into the melt under such conditions to reach equilibrium. The
temperature and
pressure in the autoclave were then reduced rapidly (over a period of about 10
seconds for the
pressure reduction and about 1 ¨ 10 minutes for the temperature reduction
using chilled water))
to ambient conditions (approximately 22 C and 1 atmosphere) and foaming
occurred. The foam
thus produced had a relatively acceptable foam structure and was tested to
determine relative
foam density (RFD) and strength and modulus properties. The RFD of the foam
was 0.2.
Example 27- PEF FOAM PREPARATION USING PEX1 AND ci51224yd as
BLOWING AGENT
Comparative Example 4 was repeated, except: (i) the cyclopentane blowing agent
was
replaced in the process with cis1224yd; and (ii) the process conditions were
modified in a
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manner to produce a foam having and RFD value that was within about 15% of the
RFD
produced using cyclopentane in Comparative Example 4 The foam produced was
tested to
determine various properties, including strength and modulus properties, and
was found to be
dramatically superior in each of the measured property, as reported in Table
E27 below:
TABLE E27
Ex Blowing RFD Avg. RELATIVE MECHANICAL PROPERTIES*
Agent Cell
Size,
Pm
RTS RCS RTM RCM
C2 cyclopentane 0.2 1 1 1 1
27 cis1224yd 0.22 130 2.16 1.42 1.05 1.45
*The relative mechanical properties reported in this Table E26 are compared to
the properties
from the foam produced with isopentane as the blowing agent in Comparative
Example 4.
As can be seen from TABLE E27 above, the foam made using cis1224yd were
surprisingly superior to the foam made using cyclopentane in terms of all
physical strength and
modulus properties tested. For example, the foam made with cis1224yd produced
a foam with
a tensile strength more than 2 times better than the values achieved using
cyclopentane. This
result shows that dramatic and unexpected improvement in physical properties
of the foam can
be achieved according to the present invention.
Example 28¨ PEF PREPARATION AT MW ABOUT 33,000 WITH PMDA CHAIN
EXTENDER AND SSP
A bio-based polyethylene furanoate homopolymer was prepared by esterification
and
polycondensation of 2,5-furandicarboxylic acid with mono ethylene glycol
according to known
methods to produce PEF homopolymer, which is then treated according to known
techniques
with the chain extender PMDA at 0.7% by weight and then subject to solid state
polymerization
according to known techniques to produce a PEF homopolymer. The PEF polymer
was tested
and found to have the following characteristics, using the same measurement
techniques as
described in Example 1:
Molecular Weight ¨ -4=33,000
Glass Transition Temperature ¨ 90.5 C
Melt Temperature - 224 C
Decomposition Temperature ¨ 341 C
Crystallinity - 45%
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The PEF polymer so produced is referred to in these Examples as PEX28.
Comparative Example 5¨ PEF FOAM PREPARATION USING PEX28 AND CO2 AS
BLOWING AGENT
1 gram of PEX28 in a glass container was loaded into an autoclave and then
dried under
vacuum for six (6) hours at 130 C. The dried polymer was then cooled to room
temperature and
placed in a glass container inside an autoclave. About 0.25 moles (11 grams)
of CO2 blowing
agent was then pumped into the autoclave containing the dried polymer, and
then the autoclave
was heated to bring the polymer to a melt state at a temperature of about 240
C and a pressure
above about 242 psig. The polymer/CO2blowing agent was maintained in this melt
state for
about 1 hour and the temperature and pressure of the melt/blowing agent was
then reduced
over a period of about 5-15 minutes to about 180 C and 242 psig (hereinafter
referred to for
convenience as pre-foaming temperature and pre-foaming pressure,
respectively), and then
maintained at about this temperature and pressure for a period of about 30
minutes to allow the
amount of blowing agent incorporated into the melt under such conditions to
reach equilibrium.
The temperature and pressure in the autoclave were then reduced rapidly (over
a period of
about 10 seconds for the pressure reduction and about 1 ¨ 10 minutes for the
temperature
reduction using chilled water)) to ambient conditions (approximately 22 C and
1 atmosphere)
and foaming occurred. The foam thus produced had a relatively acceptable foam
structure and
was tested to determine density, strength and modulus properties using the
same procedure as
described in Comparative Example 1. The foam produced in this Comparative
Example 5 had
an RFD of 0.09.
Example 29 - 31 - PEF FOAM PREPARATION USING PEX31 AND trans1234ze as
BLOWING AGENT
Comparative Example 5 was repeated, except the CO2 blowing agent was replaced
in
the process with trans1234ze in three separate runs. The foam thus produced
using
trans1234ze according to this Example was observed to be an acceptable foam
and to have an
RFD that was within about 15 relative percent of the RFD produced using CO2 in
Comparative
Example 5. The foams produced were tested to determine various properties,
including
strength and modulus properties, and were found to be dramatically superior in
each of the
measured properties, as reported in Table E29-31 below:
TABLE E29-31
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Ex Blowing RFD Avg. RELATIVE MECHANICAL PROPERTIES*
Agent Cell
Size, pm
RTS RCS RIM RCM
C5 CO2 0.09 NA 1 1 1 1
29 trans1234ze 0.08 149 145 16.5 35.2 4
30 trans1234ze 0.08 297 144 33.5 32.67 5
31 trans1234ze 0.09 NA 81 25 17.4 5.8
As can be seen from TABLE E29-31 above the foams made using trans1234ze were
surprisingly superior to the foam made in Comparative Example 5 using CO2 for
all of the
physical strength and modulus properties tested. For example, the foam made
with
trans1234ze produced a foam with both tensile and compressive modulus that is
at least 4
times the value produced using CO2. This result is unexpected.
Examples 32 - 43 ¨ PEF FOAM PREPARATION USING PEF WITH MW OF 25,000 ¨
125,000 and Blowing Agent Comprising trans1234ze and co-blowing agents
The foams made with 1234ze(E) in Example 16 having a volume of closed cells
being
90% or greater are repeated, except that instead of using a blowing agent
consisting of
1234ze(E), a co-blowing as indicated the following table is used to replace
portions of the
1234ze(E) ranging from 5% to 45% on a molar basis, as indicated below in Table
E32-43 (with
all values understood to be "about" the indicated value).
TABLE E32-43
Example Thermoplastic Co-Blowing Foam Properties***
Properties Agent/amount
(mole% of total
blowing agent)
WT% MW RFD Strength Modulus Vol%
PEF
Closed
Cells
32A 10 25,000¨ CO2/5% - 45% <0.2 A A =>90
125,000
32B 20 25,000 ¨ CO2/5% - 45% CO2/5 /0A A =>90
125,000 -45%
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32C 30 25,000 - CO215% - 45% CO2/5%
=>90
125,000 -45%
32D 40 25,000 - CO2/5% - 45% CO2/5 /0A A
=>90
125,000 -45%
32E 50 25,000 - CO2/5% - 45% CO2/5%A A
=>90
125,000 -45%
32F 60 25,000 - CO215% - 45% CO2/5%A A
=>90
125,000 -45%
32G 70 25,000 - CO2/5% - 45% CO2/5%A A
=>90
125,000 -45%
32H 80 25,000 - CO2/5% - 45% CO2/5%A A
=>90
125,000 -45%
321 90 25,000 - CO2/5% - 45% CO2/5%A A
=>90
125,000 -45%
32J 100 25,000- CO215% - 45% CO2/5%A A
=>90
125,000 -45%
33A 10 25,000- Butane*/5% - 45% <0.2 A A
=>90
125,000
33B 20 25,000 - Butane*/5% - 45% <0.2 A A
=>90
125,000
33C 30 25,000 - Butane*/5% - 45% <0.2 A A
=>90
125,000
330 40 25,000 - Butane*/5% - 45% <0.2 A A
=>90
125,000
33E 50 25,000 - Butane*/5% - 45% <0.2 A A
=>90
125,000
33F 60 25,000 - Butane*/5% - 45% <0.2 A A
=>90
125,000
33G 70 25,000 - Butane*/5% - 45% <0.2 A A
=>90
125,000
33H 80 25,000 - Butane*/5% - 45% <0.2 A A
=>90
125,000
331 90 25,000 - Butane*/5% - 45% <0.2 A A
=>90
125,000
33J 100 25,000- Butane*/5% - 45% <0.2 A A
=>90
125,000
34A 10 25,000- Pentane**/5 /0 - <0.2 A A
=>90
125,000 45%
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34B 20 25,000 - Pentane**/5% - <0.2 A A =>90
125,000 45%
34C 30 25,000 - Pentane**/5/0- <0.2 A A =>90
125,000 45%
34D 40 25,000 - Pentane**/5% - <0.2 A A =>90
125,000 45%
34E 50 25,000 - Pentane**/5% - <0.2 A A =>90
125,000 45%
34F 60 25,000 - Pentane**/5% - <0.2 A A =>90
125,000 45%
34G 70 25,000 - Pentane**/5% - <0.2 A A =>90
125,000 45%
34H 80 25,000 - Pentane**/5% - <0.2 A A =>90
125,000 45%
341 90 25,000 - Pentane**/5% - <0.2 A A =>90
125,000 45%
34J 100 25,000- Pentane**/5% - <0.2 A A =>90
125,000 45%
35A 10 25,000- Methanol/5% - <0.2 A A =>90
125,000 45%
35B 20 25,000 - Methanol/5% - <0.2 A A =>90
125,000 45%
35C 30 25,000 - Methanol/5% - <0.2 A A =>90
125,000 45%
35D 40 25,000 - Methanol/5% - <0.2 A A =>90
125,000 45%
35E 50 25,000 - Methanol/5% - <0.2 A A =>90
125,000 45%
35F 60 25,000 - Methanol/5% - <0.2 A A =>90
125,000 45%
35G 70 25,000 - Methanol/5% - <0.2 A A =>90
125,000 45%
35H 80 25,000 - Methanol/5% - <0.2 A A =>90
125,000 45%
351 90 25,000 - Methanol/5% - <0.2 A A =>90
125,000 45%
35J 100 25,000- Methanol/5% - <0.2 A A =>90
125,000 45%
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36A 10 25,000- Ethanol/5% -
45% <0.2 A A =>90
125,000
36B 20 25,000 - Ethano115% -
45% <0.2 A A =>90
125,000
36C 30 25,000 - Ethanol/5% -
45% <0.2 A A =>90
125,000
36D 40 25,000 - Ethanol/5% -
45% <0.2 A A =>90
125,000
36E 50 25,000 - Ethanol/5% -
45% <0.2 A A =>90
125,000
36F 60 25,000 - Ethanol/5% -
45% <0.2 A A =>90
125,000
36G 70 25,000 - Ethanol/5% -
45% <0.2 A A =>90
125,000
36H 80 25,000 - Ethanol/5% -
45% <0.2 A A =>90
125,000
361 90 25,000 - Ethanol/5% -
45% <0.2 A A =>90
125,000
36J 100 25,000- Ethanol/5% -
45% <0.2 A A =>90
125,000
37A 50 25,000 - Methyl <0.2 A A =>90
125,000 formate/5% - 45%
37B 60 25,000 - Methyl <0.2 A A =>90
125,000 formate/5% - 45%
37C 70 25,000 - Methyl <0.2 A A =>90
125,000 formatel5'Yo - 45%
37D 80 25,000 - Methyl <0.2 A A =>90
125,000 formate/5% - 45%
37E 90 25,000 - Methyl <0.2 A A =>90
125,000 formate/5% - 45%
37F 100 25,000- Methyl <0.2 A A =>90
125,000 formate/5% - 45%
38A 10 25,000- Dimethyl <0.2 A A =>90
125,000 ether (DME)/5% -
45%
38B 20 25,000 - Dimethyl <0.2 A A =>90
125,000 ether (DME)/5 /0 -
45%
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38C 30 25,000 - Dimethyl <0.2 A A =>90
125,000 ether (DME)/5% -
45%
38D 40 25,000 - Dimethyl <0.2 A A =>90
125,000 ether (DME)/5% -
45%
38E 50 25,000 - Dimethyl <0.2 A A =>90
125,000 ether (DME)/5')/0 -
45%
38F 60 25,000 - DME/5% - 45% <0.2 A A =>90
125,000
38G 70 25,000 - DME /5% - 45% <0.2 A A =>90
125,000
38H 80 25,000 - DME /5% - 45% <0.2 A A =>90
125,000
381 90 25,000 - DME /5% - 45% <0.2 A A =>90
125,000
38J 100 25,000- DME /5% - 45% <0.2 A A =>90
125,000
39A 10 25,000- HFC-134a/5% - <0.2 A A =>90
125,000 45%
39B 20 25,000 - HFC-134a/5% - <0.2 A A =>90
125,000 45%
39C 30 25,000 - HFC-134a/5% - <0.2 A A =>90
125,000 45%
39D 40 25,000 - HFC-134a/5% - <0.2 A A =>90
125,000 45%
39E 50 25,000 - HFC-134a/5% - <0.2 A A =>90
125,000 45%
39F 60 25,000 - HFC-134a/5% - <0.2 A A =>90
125,000 45%
39G 70 25,000 - HFC-134a/5% - <0.2 A A =>90
125,000 45%
39H 80 25,000 - HFC-134a/5% - <0.2 A A =>90
125,000 45%
391 90 25,000 - HFC-134a/5% - <0.2 A A =>90
125,000 45%
39J 100 25,000- HFC-134a/5% - <0.2 A A =>90
125,000 45%
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40A 10 25,000- 1336mzz(E)/5 /0 - <0.2 A A =>90
125,000 45%
40B 20 25,000- 1336mzz(E)/5% - <0.2 A A =>90
125,000 45%
40C 30 25,000- 1336m2z(E)/51Y0 - <0.2 A A =>90
125,000 45%
40D 40 25,000- 1336mzz(E)/5 /0 - <0.2 A A =>90
125,000 45%
40E 50 25,000- 1336mzz(E)/5/0 - <0.2 A A =>90
125,000 45%
40F 60 25,000- 1336m2z(E)/5 /0 - <0.2 A A =>90
125,000 45%
40G 70 25,000- 1336mzz(E)/5% - <0.2 A A =>90
125,000 45%
40H 80 25,000- 1336mzz(E)/5% - <0.2 A A =>90
125,000 45%
401 90 25,000- 1336mzz(E)/5% - <0.2 A A =>90
125,000 45%
40J 100 25,000- 1336mzz(E)/5/0 - <0.2 A A =>90
125,000 45%
41A 10 25,000- 1336mzz(Z)/5% - <0.2 A A =>90
125,000 45%
41B 20 25,000- 1336mzz(Z)/5% - <0.2 A A =>90
125,000 45%
41C 30 25,000- 1336mzz(Z)/5% - <0.2 A A =>90
125,000 45%
41D 40 25,000- 1336mzz(Z)/5% - <0.2 A A =>90
125,000 45%
41E 50 25,000- 1336mzz(Z)/5% - <0.2 A A =>90
125,000 45%
41F 60 25,000- 1336mzz(Z)/5% - <0.2 A A =>90
125,000 45%
41G 70 25,000- 1336mzz(Z)/5% - <0.2 A A =>90
125,000 45%
41H 80 25,000- 1336mzz(Z)/5% - <0.2 A A =>90
125,000 45%
411 90 25,000- 1336mzz(Z)/5% - <0.2 A A =>90
125,000 45%
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41J 100 25,000¨ 1336mzz(Z)/5% - <0.2 A A =>90
125,000 45%
42A 10 25,000¨ 1233zd(E)/5/0 - <0.2 A A =>90
125,000 45%
42B 20 25,000¨ 1233zd(E)/5% - <0.2 A A =>90
125,000 45%
42C 30 25,000¨ 1233zd(E)/5 /0 - <0.2 A A =>90
125,000 45%
42D 40 25,000¨ 1233zd(E)/5/0 - <0.2 A A =>90
125,000 45%
42E 50 25,000¨ 1233zd(E)/5 /0 - <0.2 A A =>90
125,000 45%
42F 60 25,000¨ 1233zd(E)/5% - <0.2 A A =>90
125,000 45%
42G 70 25,000¨ 1233zd(E)/5% - <0.2 A A =>90
125,000 45%
42H 80 25,000¨ 1233zd(E)/5% - <0.2 A A =>90
125,000 45%
421 90 25,000¨ 1233zd(E)/5% - <0.2 A A =>90
125,000 45%
42J 100 25,000¨ 1233zd(E)/5 /0 - <0.2 A A =>90
125,000 45%
43A 10 25,000¨ 1224yd(Z)/5% - <0.2 A A =>90
125,000 45%
43B 20 25,000¨ 1224yd(Z)/5 /0 - <0.2 A A =>90
125,000 45%
43C 30 25,000¨ 1224yd(Z)/5 A, - <0.2 A A =>90
125,000 45%
43D 40 25,000¨ 1224yd(Z)/5% - <0.2 A A =>90
125,000 45%
43E 50 25,000¨ 1224yd(Z)/5/0 - <0.2 A A =>90
125,000 45%
43F 60 25,000¨ 1224yd(Z)/5% - <0.2 A A =>90
125,000 45%
43G 70 25,000¨ 1224yd(Z)/5 /0 - <0.2 A A =>90
125,000 45%
43H 80 25,000¨ 1224yd(Z)/5% - <0.2 A A =>90
125,000 45%
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431 90 25,000¨ 1224yd(Z)/5 /0 - <0.2 A A =>90
125,000 45%
43J 100 25,000¨ 1224yd(Z)/5/0 - <0.2 A A =>90
125,000 45%
* butane refers separately and independently to each of iso and normal butane
** pentane refers separately and independently to each of iso, normal, neo and
cyclo-pentane
***A - acceptable
Example 44A and 44B ¨ PEF HOMOPOLYMER PREPARATION WITH MW OF ABOUT 75
KG/MOL AND 90.8 KG/MOL WITH PM DA AND SSP
Two homopolymers of PEF were with polymer molecular weights of about 75,000
g/mol
and about 91,000 g/mol. In particular, the 75 kg/mol PEF homopolymer was
formed by
esterification and polycondensation of 350 grams of 2,5-furandicarboxylic acid
(FDCA) with 279
grams of mono-ethylene glycol (EG). The reactants were added to a 1-liter
cylindrical steel
reactor equipped with an overhead stirrer and a distillation/condensation
apparatus. After pulling
vacuum and back filling with nitrogen, 0.288 gram of titanium (IV)
isopropoxide catalyst was added
to the flask. The flask was then lowered into a 180 C salt bath and overhead
mixing was started
at 200 rpm under a nitrogen atmosphere. After 2.5 hours, the bath temperature
was increased
to 210 C. After 30 minutes at this temperature under nitrogen, vacuum was
started. After 40
minutes under vacuum, the temperature was increased to 230 C and was continued
for 1
hour. Under a stream of nitrogen, PMDA (2.73 g ¨ 0.7% by weight) was slowly
added over the
span of about 5 minutes. An additional 30 minutes of mixing at temperature
were allowed before
stopping the reaction. To perform SSP, an aliquot (30 g) of the product was
ground and heated
at 180 C under vacuum for 3 days on a rotary evaporator to produce the PEF
hornopolymer as
reported below.
For the 90.8 kg/mol MW polymer, FDCA (75 g) and EG (59.6 g) were added to a
500 mL
cylindrical steel reactor equipped with an overhead stirrer and a
distillation/condensation
apparatus. After pulling vacuum and back filling with nitrogen, 0.100 gram of
titanium (IV)
isopropoxide catalyst was added to the flask. The flask was then lowered into
a 180 C salt bath
and overhead mixing was started at 200 rpm under a nitrogen atmosphere. After
2.5 hours, the
bath temperature was increased to 210 C. After 30 minutes at this temperature
under nitrogen,
vacuum was started. After 40 min under vacuum, the temperature was increased
to 250 C and
was continued for 2 hours. Under a stream of nitrogen, PM DA (0.587 g) was
slowly added over
the span of about 5 minutes. The reaction was stopped after an additional 30
minutes of mixing
at temperature. The product was removed from the vessel. Gamma-valerolactone
was added to
dissolve the polymer that was remaining in the reactor and on the impeller.
The mixture was
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stirred for several hours at 190 C. The gamma-valerolactone was distilled from
the polymer under
vacuum resulting in a solid. To perform SSP, an aliquot (30 g) of the product
was ground and
heated at 180 C under vacuum for 3 days on a rotary evaporator to produce the
PEF
homopolymer as reported below. The polymer was then subject to solid state
polymerization
according to known techniques to produce the PEF homopolymer as reported
below.
The PEF polymers thus produced were tested using the measurement protocols as
described above and found to have the characteristics reported in Table E44
below:
TABLE E44
Example 44A (PEF44A) Example 44B (PEF44B)
Molecular Weight, g/mol 75,000 90,800
Glass Transition 90.2 92
Temperature, C
Melt Temperature, C 222 202
Decomposition 346 335
Temperature, C
Crystallinity, A 42 54
The PEF polymers produced in these examples are referred to in Table E47 above
and
hereinafter as PEF44A and PEF44B.
Examples 45A ¨ 45G - PEF FOAM PREPARATION USING PEF44A AND PEF44B
WITH TRANS1234ZE BLOWING AGENT
Three foams were made from PEF44A, and four foams were made using PEF44B as
described
herein using foaming processes that were designed using the same criteria as
described in
Example 1. The foams thus produced were tested and found to have the
properties as reported
in Table E45 below.
TABLE E45
Example¨) E45A E45B E45C E45D E45E E45F E45G
MATERIALS
Polymer (MW, PEF44A PEF44A PEF44A PEF44 B PEF44B PEF44B
PEF44B
K) (75) (75) (75) (90.8) (90.8) (90.8) (90.8)
Blowing Agent* 1234ze( 1234ze( 1234ze(E) 1234ze(E) 1234ze(E)
1234ze(E) 1234ze(E)
E) E)
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Example-) E45A E45B E45C E45D E45E E45F E45G
Blowing Agent, 0.35 0.26 0.35 0.22 0.26 0.22
0.22
(moles)
CONDITION
Melt Temp., C 240 240 240 240 240 240
240
Melt Press., 1408 948 1417 365 881 604
609
psig
Pre-foaming 190 190 190 190 190 190
190
Temp., C
Pre-foaming 1080 764 1080 548 722 508
508
Press., psig
FOAM
PROPERTIES
RFD 0.046 0.061 0.077 0.077 0.08 0.082
0.084
Avg. RFD .0535 0.08
Tensile 1.25 0.99 2.09 2.97 2.64 2.81
3.09
Strength,
megapascal
Avg. IS 1.12 2.7
Compressive 0.64 0.4 0.4 0.8 0.41 1.29
0.97
Strength,
megapascal
Avg. CS 0.52 0.78
The tensile strength and compressive strength of the PEE foams of this example
are determined
and found to be unexpectedly high. For example, even though the foam made with
CO2 in
Comparative Example 1 had a much higher density and with a polymer of higher
molecular
weight, the foams of this Example have a tensile strength that is, on average,
at least 1.5 times
the strength of the foams made with CO2 of Comparative Example 1.
Example 46A and 46B - PEF HOMOPOLYMER PREPARATION WITH MW OF
ABOUT 49 KG/MOL WITH PMDA AND SSP
A homopolymer of REF was made using the same additives and basic polymer
formation procedures as were in Example 45 to achieve polymer molecular weight
of about
49,000 g/mol. In particular, the 49 kg/mol MW REF homopolymer was formed by
esterification
and polycondensation of 75 grams of 2,5-furandicarboxylic acid (FDCA) with
59.8 grams of
mono ethylene glycol (EG). The reactants were added to a 500 mL cylindrical
steel reactor
equipped with an overhead stirrer and a distillation/condensation apparatus.
After pulling
vacuum and back filling with nitrogen, 0.067 gram of titanium (IV)
isopropoxide catalyst was
added to the flask. The flask was then lowered into a 180 C salt bath and
overhead mixing was
started at 200 rpm under a nitrogen atmosphere. After 2.5 hours, the bath
temperature was
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increased to 210 C. After 30 minutes at this temperature under nitrogen,
vacuum was started.
After 40 minutes under vacuum, the temperature was increased to 230 C and was
continued for
1 hour. Under a stream of nitrogen, 0.59 gram (0.7% by weight) of PMDA wase
slowly added
over a time of about 5 minutes. To perform SSP, an aliquot (30 g) of the
product was ground
and heated at 180 C under vacuum for 3 days on a rotary evaporator to produce
the PEF
homopolymer as reported below. The PEF homopolymer was tested using the same
measurement techniques as described in Example 1 and found to have the
characteristics
reported in Table E46 below:
TABLE E46
Example 46 (PEF45)
Molecular Weight, g/mol 49,000
Glass Transition Temperature, C 92
Melt Temperature, C 220
Decomposition Temperature, C 340
Crystallinity, % 43
The PEF polymer so produced is referred to in Table E45 and in the Examples
hereinafter as PEF45.
Examples 47A ¨ 47C: PEF FOAM PREPARATION USING PEF45 AND
TRANS1234ZE AS BLOWING AGENT
Three foams were made from PEF45 as described herein using foaming processes
that
were designed using the same criteria as described in Example 1. The foams
thus produced
were tested and found to have the properties as reported in Table E47 below:
TABLE E47
Example¨> E47A E47B E47C
MATERIALS
Polymer (MW, K) PEF45 PEF45 PEF45
(49) (49) (49)
Blowing Agent* 1234ze(E) 1234ze(E) 1234ze(E)
Blowing Agent, (moles) 0.22 0.26 0.26
CONDITION
Melt Temp., C 240 240 240
Melt Press., 680 933 925
Pre-foaming Temp., C 190 190 190
Pre-foaming Press., psig 560 746 746
FOAM
PROP
RFD 0.08 0.094 0.064
Avg. RFD 0.079
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Exam ple¨> E47A E47B E47C
Tensile Strength, 0.82 2.07 1.46
megapascal
Avg. TS 1.45
Compressive Strength, 0.81 0.73 0.33
megapascal
Avg. CS 0.62
The tensile strength and compressive strength of the PEF foams of this example
are determined
and found to be unexpectedly high. For example, even though the foam made with
CO2 in
Comparative Example 1 had a much higher density and was made from a polymer
having a
much higher molecular weight, the foams of this Example have a tensile
strength that is, on
average, about 2 times the strength of the foams made with CO2 of Comparative
Example 1.
Example 48¨ PEF HOMOPOLYMER PREPARATION WITH MW OF 33 KG/M OL
WITH PM DA AND SSP
A homopolymer of PEF was made using the same additives and basic polymer
formation procedures as were used to form the PEF homopolymer of Example 45 to
achieve
polymer molecular weight of about 30,000 kg/mol. In particular, the PEF
homopolymer was
formed by esterification and polycondensation of 2,5-furandicarboxylic acid
with mono-ethylene
glycol according to methods consistent with those described herein to produce
PEF
homopolymer, which is then treated according to known techniques with PMDA at
0.7% by
weight. The polymer then undergoes solid state polymerization consistent with
the prior
examples to produce a PEF homopolymer. The PEF polymer was tested using the
same
measurement techniques as described in Example 1 and found to have the
characteristics
reported in Table E48 below:
TABLE E48
Example 48
Designation PEF48
Molecular Weight, g/mol 33,000
Glass Transition 90.5
Temperature, C
Melt Temperature, C 224
Decomposition Temperature, 341
oc
Crystallinity, % 45
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The PEE polymer produced in this Example is referred to Table E48 above and
hereinafter as PEF48.
Examples 49A and 49B: PEF FOAM PREPARATION USING PEF48 AND
TRANS12342E AS BLOWING AGENT
Two foams were made from PEF48 using foaming processes that were designed
using
the same criteria as described in these examples. The foams thus produced were
tested and
found to have the properties as reported in Table E49 below:
TABLE E49
Example¨> E49A E49B
MATERIALS
Polymer (MW, kg/mol) PEF48 (33) PEF48 (33)
Blowing Agent* 1234ze(E) 1234ze(E)
Blowing Agent, (moles) 0.21 0.12
CONDITION
Melt Temp., C 240 240
Melt Press., 553 268
Pre-foaming Temp., C 190 190
Pre-foaming Press., psig 474 240
FOAM
PROP
RFD 0.08 0.081
Avg. RFD 0.0805
Tensile Strength, megapascal 1.45 1.44
Avg. IS 1.445
Compressive Strength, 0.33 0.67
nnegapascal
Avg. CS 0.5
The tensile strength and compressive strength of the PEE foams of this example
were tested
and found to be unexpectedly high. For example, even though the foam made with
CO2 in
Comparative Example 1 had a much higher density and was made from a polymer
having a
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much higher molecular weight, the foams of this Example have a tensile
strength that is, on
average, about 2 times the strength of the foams made with CO2 of Comparative
Example 1.
Example 50¨ PEF HOMOPOLYMER PREPARATION WITH MW OF 58 KG/MOL
WITH PMDA AND SSP
A homopolymer of PEF was made using the same additives and basic polymer
formation procedures as were used to form the PEF homopolymer of Example 45 to
achieve
polymer molecular weight of about 58,000 kg/mol. In particular, the PEF
homopolymer was
formed by esterification and polycondensation of 2,5-furandicarboxylic acid
with mono-ethylene
glycol according to methods consistent with those described herein to produce
PEF
homopolymer, which is then treated according to known techniques with PMDA at
0.7% by
weight. The polymer then undergoes solid state polymerization consistent with
the prior
examples to produce a PEF homopolymer. The PEF polymer was tested using the
same
measurement techniques as described in Example 1 and found to have the
characteristics
reported in Table E49 below:
TABLE E50
Example 50
Designation PEF50
Molecular Weight, g/mol 58,000
Glass Transition 90.6
Temperature, C
Melt Temperature, C 222
Decomposition Temperature, 347
DC
Crystallinity, % 46
The PEF polymer produced in this Example is referred to Table E50 above and
hereinafter as PEF50.
Examples 51A and 51B: PEF FOAM PREPARATION USING PEF49 AND
TRANS1233zd and TRANS1234ZE + TRANS1233zd AS BLOWING AGENT
Two foams were made from PEF50 using foaming processes that were designed
using
the same criteria as described in these examples. The foam E51B in the table
below was made
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with a 50:50 molar ratio of tran51233zd(E):1234zd(E). The foams thus produced
were tested
and found to have the properties as reported in Table E51 below:
TABLE E51
Example¨) E51A E51B
MATERIALS
Polymer (MW, kg/mol) PEF50 (58) PEF50 (58)
Blowing Agent* 1233zd(E) 1233zd(E)
+1234ze(E)
Blowing Agent, (moles) 0.4 0.29
CONDITION
Melt Temp., C 240 240
Melt Press., 725 705
FOAM
PROP.
RFD 0.182 0.150
Tensile Strength, 0.51 0.75
nnegapascal
Compressive Strength, 0.26 1.04
megapascal
As can be seen from the Table E51 above, the foam of the present invention
made using
1233zd(E) as the sole blowing agent (Example E51A) formed a foam with an RFD
of 0.182 and
had a tensile strength of 0.51 megapascals and a compressive strength of 0.26
megapascals.
The foam made by adding 1234ze(E) as a blowing agent (Example 51B) produced a
foam with
a foam with a lower density, but which unexpectedly and surprisingly is much
stronger in terms
of both tensile strength and the compressive strength. This example thus
provides further
evidence of the unexpected advantage provided by using 1234ze(E) as a blowing
agent
according to the present invention. Furthermore, even though the foam made
with CO2 in
Comparative Example 1 had a much higher density and was made from a polymer
having a
much higher molecular weight than Example 51B, the foams of Example 51B have a
comparable tensile strength and a compressive strength that is more than 2
times the
compressive strength of the foams made with CO2 of Comparative Example 1.
The following clauses provide descriptions within the scope of the present
invention.
Clause 1. A low-density, thermoplastic foam comprising:
(a) thermoplastic polymer cells comprising cell walls forming closed cells,
wherein ethylene furanoate moieties are at least 50% by weight of the
thermoplastic
polymer; and
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(b) one or more HFOs having three or four carbon atoms and/or one or more
HFC0s having three or four carbon atoms contained in the closed cells.
Clause 2. The foam of clause 1 wherein said cell walls consisting essentially
of
polyethylene furanoate that has been treated with a chain extender.
Clause 3. The foam of clause 1 wherein said cell walls consist essentially of
polyethylene furanoate having a molecular weight of greater than 25,000.
Clause 4. The foam of clause 1 wherein ethylene furanoate moieties are at
least
70% by weight of the thermoplastic polymer.
Clause 5. The foam of clause 1 wherein ethylene furanoate moieties are at
least
90% by weight of the thermoplastic polymer.
Clause 6. The foam of clause 1 wherein said foam has a relative foam density
(RFD) of about 0.2 or less.
Clause 7. The foam of clause 1 wherein said foam has a foam density of less
than 0.4 g/cc.
Clause 8. The foam of clause 1 wherein said foam has a foam density of less
than 0.2 g/cc.
Clause 9. The foam of clause 1 wherein said one or more blowing agents
contained in said closed cells comprise one or more of 1224yd, 1233zd(E),
1234yf,
1234ze(E), 1336mzz(E) and 1336mzz(Z).
Clause 10. The foam of clause 9 wherein said cell walls consist essentially of
polyethylene furanoate having a molecular weight of greater than 100,000.
Clause 11. The foam of clause 1 wherein said one or more blowing agents
contained in said closed cells comprise at least 1234ze(E).
Clause 12. The foam of clause 11 wherein said cell walls consist essentially
of
polyethylene furanoate having a molecular weight of greater than 100,000 and
wherein
said foam has a relative foam density (RFD) of about 0.2 or less.
Clause 13. The foam of clause 1 wherein said one or more blowing agents
contained in said closed cells comprise at least 1336nizz(Z).
Clause 14. The foam of clause 13 wherein said cell walls consist essentially
of
polyethylene furanoate having a molecular weight of greater than 100,000 and
wherein
said foam has a relative foam density (RFD) of about 0.2 or less.
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Clause 15. The foam of clause 1 wherein said one or more blowing agents
contained in said closed cells comprise at least 1336nizz(Z) and/or 1234ze(E).
Clause 16. The foam of clause 15 wherein said cell walls consist essentially
of
polyethylene furanoate having a molecular weight of greater than 100,000 and
wherein
said foam has a relative foam density (RFD) of about 0.2 or less.
Clause 17. A wind energy turbine blade and/or nacelle comprising a foam
according to anyone of clauses 1 ¨16.
Clause 18. An automobile car wall comprising a foam according to anyone of
clauses 1 ¨16.
Clause 19. A marine vessel comprising a foam according to anyone of clauses 1
¨ 16.
Clause 20. An aircraft or aerospace vessel comprising a foam according to
anyone of clauses 1 ¨ 16.
Clause 21. A low-density, thermoplastic foam comprising:
(a) thermoplastic polymer cells comprising cell walls forming closed cells,
wherein ethylene furanoate moieties are at least 50% by weight of the
thermoplastic
polymer; and
(b) one or more HFOs having three or four carbon atoms and/or one or more
HFC0s having three or four carbon atoms contained in the closed cells.
Clause 22. A low-density, thermoplastic foam comprising:
(a) closed thermoplastic cells comprising cell walls forming closed cells,
said cell
walls consisting essentially of polyethylene furanoate that has been treated
with a chain
extender and that has a molecular weight of greater than 25,000; and
(b) one or more HFOs having three or four carbon atoms and/or one or more
HFC0s having three or four carbon atoms contained in the closed cells.
Clause 23. A low-density, thermoplastic foam comprising:
(a) closed thermoplastic cells comprising cell walls comprising polyethylene
furanoate that has been treated with a chain extender and that has a molecular
weight
of greater than 25,000, wherein ethylene furanoate moieties are at least 70%
by weight
of the thermoplastic polymer; and
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(b) one or more HFOs having three or four carbon atoms and/or one or more
HFC0s having three or four carbon atoms contained in the closed cells.
Clause 24. A low-density, closed-cell thermoplastic foam comprising:
(a) closed thermoplastic cells comprising cell walls comprising polyethylene
furanoate that has been treated with a chain extender and that has a molecular
weight
of greater than 25,000, wherein ethylene furanoate moieties are at least 90%
of the
thermoplastic contains ethylene furanoate moieties; and
(b) one or more HFOs having three or four carbon atoms and/or one or more
HFC0s having three or four carbon atoms contained in the closed cells.
Clause 25A. A includes low-density, closed-cell thermoplastic foam comprising:
(a) closed thermoplastic cells comprising cell walls consisting essentially of

polyethylene furanoate that has been treated with a chain extender; and
(b) a blowing agent contained in said closed cells,
wherein said foam has a relative foam density (RFD) of about 0.2 or less and a
foam
density of less than 0.3 g/cc.
Clause 25B. A includes low-density, thermoplastic foam comprising:
(a) thermoplastic polymer cells comprising cell walls wherein at least about
50%
by volume of the cells are closed cells and wherein ethylene furanoate
moieties are at
least 50% by weight of the thermoplastic polymer; and
(b) one or more HFOs having three or four carbon atoms and/or one or more
HFC0s having three or four carbon atoms contained in the closed cells.
Clause 25C. A includes low-density, thermoplastic foam comprising:
(a) thermoplastic polymer cells comprising cell walls comprising polyethylene
furanoate that has been treated with a chain extender and that has a molecular
weight
of greater than 25,000, wherein ethylene furanoate moieties are at least 50%
of the
thermoplastic and wherein at least about 50% by volume of the cells are closed
cells;
and
(b) one or more HFOs having three or four carbon atoms and/or one or more
HFC0s having three or four carbon atoms contained in the closed cells.
Clause 250. A includes low-density, thermoplastic foam comprising:
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(a) thermoplastic polymer cells comprising cell walls comprising polyethylene
furanoate that has been treated with a chain extender and that has a molecular
weight
of greater than 25,000, wherein ethylene furanoate moieties are at least 50%
of the
thermoplastic and wherein at least about 75% by volume of the cells are closed
cells;
and
(b) one or more HFOs having three or four carbon atoms and/or one or more
HFC0s having three or four carbon atoms contained in the closed cells.
Clause 25E. A includes low-density, thermoplastic foam comprising:
(a) thermoplastic polymer cells comprising cell walls comprising polyethylene
furanoate that has been treated with a chain extender and that has a molecular
weight
of greater than 25,000, wherein ethylene furanoate moieties are at least 50%
of the
thermoplastic and wherein at least about 90% by volume of the cells are closed
cells;
and
(b) one or more HFOs having three or four carbon atoms and/or one or more
HFC0s having three or four carbon atoms contained in the closed cells.
Clause 26. A includes low-density, closed-cell thermoplastic foam comprising:
(a) closed thermoplastic cells comprising cell walls consisting essentially of

polyethylene furanoate that has been treated with a chain extender; and
(b) a blowing agent contained in said closed cells,
wherein said foam has an RFD of about 0.2 or less and a density of less than
0.3 g/cc.
Clause 27. A low-density, closed-cell thermoplastic foam comprising:
(a) closed thermoplastic cells comprising cell walls consisting essentially of

polyethylene furanoate that has been treated with a chain extender; and
(b) a blowing agent contained in said closed cells,
wherein said foam has a density of less than 0.25 g/cc.
Clause 28A. A low-density, closed-cell thermoplastic foam comprising:
(a) thermoplastic polymer cells comprising cell walls comprising polyethylene
furanoate that has been treated with a chain extender and that has a molecular
weight
of greater than 50,000, wherein ethylene furanoate moieties are at least 50%
of the
thermoplastic and wherein at least about 50% by volume of the cells are closed
cells;
and
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(b) one or more HFOs having three or four carbon atoms and/or one or more
HFC0s having three or four carbon atoms contained in the closed cells.
Clause 28B. A low-density, closed-cell thermoplastic foam comprising:
(a) thermoplastic polymer cells comprising cell walls comprising polyethylene
furanoate that has been treated with a chain extender and that has a molecular
weight
of greater than 50,000, wherein ethylene furanoate moieties are at least 50%
of the
thermoplastic and wherein at least about 75% by volume of the cells are closed
cells;
and
(b) one or more HFOs having three or four carbon atoms and/or one or more
HFC0s having three or four carbon atoms contained in the closed cells.
Clause 28C. A low-density, closed-cell thermoplastic foam comprising:
(a) closed thermoplastic cells comprising cell walls consisting essentially of

polyethylene furanoate that has been treated with a chain extender and that
has a
molecular weight of greater than 100,000; and
(b) a blowing agent contained in said closed cells, wherein said foam has a
density of less than 0.3 g/cc.
Clause 29 A low-density, closed-cell thermoplastic foam comprising:
(a) closed thermoplastic cells comprising cell walls consisting essentially of

polyethylene furanoate that has been treated with a chain extender; and
(b) a blowing agent contained in said closed cells and comprising one or more
HFOs having three or four carbon atoms and/or one or more HFC0s having three
or
four carbon atoms, wherein said foam has a density of less than 0.3 g/cc.
Clause 30. A low-density, closed-cell thermoplastic foam comprising:
(a) closed thermoplastic cells comprising cell walls consisting essentially of
polyethylene furanoate that has been treated with a chain extender; and
(b) a blowing agent contained said closed cells and comprising one or more
HFOs having three or four carbon atoms and/or one or more HFC0s having three
or
four carbon atoms, wherein said foam has a density of less than 0.25 g/cc.
Clause 31. A low-density, closed-cell thermoplastic foam comprising:
(a) thermoplastic polymer cells comprising cell walls forming closed cells,
wherein ethylene furanoate moieties are at least 50% by weight of the
thermoplastic
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polymer and wherein said thermoplastic comprises polyethylene furanoate-based
polymer that has been treated with a chain extender and that has a molecular
weight of
greater than 25,000; and
(b) one or more blowing agents contained in said closed cells, said blowing
agent
comprising one or more of 1224yd, 1233zd(E), 1234yf, 1234ze(E), 1336mzz(E) and
1336mzz(Z).
Clause 32. A low-density, closed-cell thermoplastic foam comprising:
(a) thermoplastic polymer cells comprising cell walls forming closed cells,
wherein ethylene furanoate moieties are at least 70% by weight of the
thermoplastic
polymer and wherein said thermoplastic comprises polyethylene furanoate-based
polymer that has been treated with a chain extender and that has a molecular
weight of
greater than 100,000; and
(b) one or more blowing agents contained in said closed cells, said blowing
agent
comprising one or more of 1224yd, 1233zd(E), 1234yf, 1234ze(E), 1336mzz(E) and
1336mzz(Z).
Clause 33. A low-density, closed-cell thermoplastic foam comprising:
(a) thermoplastic polymer cells comprising cell walls forming closed cells,
wherein ethylene furanoate moieties are at least 90% by weight of the
thermoplastic
polymer and wherein said thermoplastic comprises polyethylene furanoate-based
polymer that has been treated with a chain extender and that has a molecular
weight of
greater than 100,000; and
(b) one or more blowing agents contained in said closed cells, said blowing
agent
comprising one or more of 1224yd, 1233zd(E), 1234yf, 1234ze(E), 1336mzz(E) and

1336mzz(Z).
Clause 34. A low-density, closed-cell thermoplastic foam comprising:
(a) thermoplastic polymer cells comprising cell walls forming closed cells,
wherein ethylene furanoate moieties are at least 90% by weight of the
thermoplastic
polymer and wherein said thermoplastic comprises has a molecular weight of
greater
than 100,000; and
(b) one or more blowing agents contained in said closed cells, said blowing
agent
comprising one or more of 1234ze(E), 1336mzz(E) and 1336mzz(Z).
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Clause 35. A low-density, closed-cell thermoplastic foam comprising:
(a) thermoplastic polymer cells comprising cell walls forming closed cells,
wherein ethylene furanoate moieties are at least 90% by weight of the
thermoplastic
polymer and wherein said thermoplastic comprises has a molecular weight of
greater
than 100,000; and
(b) one or more blowing agents contained in said closed cells, said blowing
agent
consisting essentially of 1234ze(E).
Clause 36. A includes low-density, closed-cell thermoplastic foam comprising:
(a) thermoplastic polymer cells comprising cell walls forming closed cells,
wherein ethylene furanoate moieties are at least 90% by weight of the
thermoplastic
polymer and wherein said thermoplastic comprises has a molecular weight of
greater
than 100,000; and
(b) one or more blowing agents contained in said closed cells, said blowing
agent
consisting essentially of 1336mzz(E).
Clause 37. A low-density, closed-cell thermoplastic foam comprising:
(a) closed thermoplastic cells comprising cell walls consisting essentially of

polyethylene furanoate; and
(b) trans-1234ze contained in said closed cells,
wherein said foam has a density of less than 0.3 g/cc.
Clause 38. A low-density, closed-cell thermoplastic foam comprising:
(a) closed thermoplastic cells comprising cell walls consisting essentially of

polyethylene furanoate, and
(b) HF0-1234yf contained in said closed cells,
wherein said foam has a density of less than 0.3 g/cc.
Clause 39. A low-density, closed-cell thermoplastic foam comprising:
(a) closed thermoplastic cells comprising cells walls consisting essentially
of
polyethylene furanoate; and
(b) 1336mzz(E) contained in said closed cells,
wherein said foam has a density of less than 0.3 g/cc.
Clause 40. A low-density, closed-cell thermoplastic foam comprising:
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(a) closed thermoplastic cells comprising cells walls consisting essentially
of
polyethylene furanoate; and
(b) 1336mzz(Z) contained in said closed cells,
wherein said foam has a density of less than 0.3 g/cc.
Clause 41. A low-density, closed-cell thermoplastic foam comprising:
(a) closed thermoplastic cells comprising cells walls consisting essentially
of
polyethylene furanoate; and
(b) 1224yd contained in said closed cells,
wherein said foam has a density of less than 0.3 g/cc.
Clause 42. A foamable thermoplastic compositions comprising:
(a) thermoplastic material consisting essentially of polyethylene furanoate
that
has been treated with a chain extender and that has a molecular weight of
greater than 25,000, wherein at least 50% of the thermoplastic contains
ethylene furanoate moieties; and
(b) one or more HFOs having three or four carbon atoms and/or one or more
HFC0s having three or four carbon atoms.
Clause 43. A foamable thermoplastic compositions comprising:
(a) thermoplastic material consisting essentially of polyethylene furanoate
having a
molecular weight of greater than 100,000, wherein at least 50% of the
thermoplastic contains ethylene furanoate moieties;
(b) one or more HFOs having three or four carbon atoms and/or one or more
HFC0s having three or four carbon atoms.
Clause 44. A foamable thermoplastic compositions comprising:
(a) thermoplastic material consisting essentially of chain-extended
polyethylene
furanoate having a molecular weight of greater than 100,000, wherein at least
90% of the thermoplastic contains ethylene furanoate moieties; and
(b) one or more HFOs having three or four carbon atoms and/or one or more
HFC0s having three or four carbon atoms contained in said closed cells.
Clause 45. Methods for forming thermoplastic foam comprising foaming a
foamable
composition of the present invention, including each of Clauses 42 ¨ 44.
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Clause 46. Methods for forming extruded thermoplastic foam comprising
extruding
a foamable composition of the present invention, including each of Clauses 42
¨ 44.
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Representative Drawing