MARINE FOAM

MOUSSE MARINE

English Abstract

The invention generally pertains to the use of polyurethane foam blown by at least one blowing agent having a boiling point at atmospheric pressure of between ~5°C to ~50°C, including miscible blends thereof, which passes all United States Coast Guard Title 33, Part 183 specifications wherein the buoyant force of the froth polyurethane or polyisocyanurate foam is not reduced more than 5% after exposure to being immersed in a fully saturated gasoline vapor atmosphere, in reference fuel B, in reference oil No. 2, and in a 5% solution of Na3PO4.

French Abstract

De manière générale, l'invention se rapporte à l'utilisation de mousse de polyuréthane soufflée par au moins un agent de soufflage ayant un point d'ébullition à une pression atmosphérique compris entre ~ 5 °C et ~ 50 °C, comprenant des mélanges miscibles de celui-ci, ce qui permet d'adopter toutes les réglementations de la Partie 183, du Titre 33 des Gardes-Côtes des États-Unis, la force de flottaison de l'écume de mousse de polyisocyanurate ou de polyuréthanne n'étant pas réduite de plus de 5 % après exposition et devant être immergée dans une atmosphère de vapeur d'essence totalement saturée, dans le carburant B de référence, dans l'huile No. 2 de référence, et dans une solution de 5 % de Na3PO4.

Claims

CLAIMS
We Claim:
1. A two component polyurethane foam blown by at least one hydrofluorocarbon
blowing agent having a
boiling point at atmospheric pressure of between -5°C to -50°C
and miscible blends thereof, the two
component polyurethane foam synthesized from two sets of pressurized reactants
which comprise an A-
side and a B-side:
the B-side comprising a polyol blend:
25-45 wt% of at least one polyether polyol in the polyol blend present in a
major
amount;
10-30 wt% of at least one phthalic anhydride based aromatic polyester polyol
present
in a minor amount in the polyol blend, the at least one phthalic anhydride
based aromatic polyester polyol comprising at least 35% of the polyol blend;
30-62.5 wt% of at least one other additive selected from the group comprising
at least
one flame retardant and at least one plasticizer;
1-5 wt% of at least one surfactant;
1-5 wt% of at least one catalyst;
0.5-3 wt% of water; and
the at least one hydrofluorocarbon blowing agent having a boiling point at
atmospheric pressure of between -5°C to -50°C and miscible
blends
thereof;
the A-side comprising:
a poly- or diisocyanate; and
the at least one hydrofluorocarbon blowing agent having a boiling point at
atmospheric pressure of between -5°C to -50°C and miscible
blends
thereof.
- 20 -

2. The polyurethane foam of claim 1, wherein the at least one phthalic
anhydride based aromatic polyester
is
<IMG>
wherein
R1 is selected from the group consisting of an alkylene group
of from 2
to 10 carbon atoms, ¨CH2-R3-CH2¨, and ¨(R4O)m-R4¨ ;
R2and R5 are independently ¨[OH2CH2O]x¨,
¨[CH2OH(OH3)O]x¨, ¨[CH2CH2CH(CH3)O]x¨ or a random
combination thereof;
R3 is selected from the group consisting of
<IMG>
each R4 is independently an alkylene group of from 2 to 4 carbon
atoms; and
x, m, and n are independently from 1-200.
3. The polyurethane foam of claim 2, wherein the at least one phthalic
anhydride based aromatic polyester
polyol is
<IMG>
and further wherein
a hydroxyl number in mg KOH/g is between 230 and 250 inclusive;
a viscosity value at 25 °C is between 2,000 and 4,500 cP inclusive;
an equivalent average weight is approximately 234; and
an average molecular weight is approximately 468.
-21 -

4. The polyurethane foam of claim 2, wherein the at least one polyether polyol
is
<IMG>
and further wherein
a hydroxyl number in mg KOH/g is approximately 600;
a viscosity value at 25 °C is approximately 380 cP;
an average molecular weight is approximately 280; and
n' is an index from 1-200.
5. The polyurethane foam of claim 4, wherein the at least one other additive
is selected from the group
comprising
<IMG>
6. The polyurethane foam of claim 5, wherein the at least one catalyst is at
least two catalysts selected from
the group comprising
<IMG>
7. The polyurethane foam of claim 6, wherein the water is added in an amount
of approximately 1% by
weight.
8. The polyurethane foam of claim 7, wherein the at least one blowing agent
has a boiling point at
atmospheric pressure of between -10°C to -40°C.
9. The polyurethane foam of claim 8, wherein the at least one blowing agent is
1,1,1,3,3-
pentafluoropropane.
- 22 -

10. A process of synthesizing a two-component polyurethane foam blown by at
least one hydrofluorocarbon
blowing agent having a boiling point at atmospheric pressure of between
~5°C to ~50°C, and miscible
blends thereof, the two-component polyurethane foam synthesized from two sets
of pressurized reactants
which comprise an A-side and a B-side:
the B-side comprising a polyol blend:
25-45 wt% of at least one polyether polyol in the polyol blend present in a
major
amount;
10-30 wt% of at least one phthalic anhydride based aromatic polyester polyol
present
in a minor amount in the polyol blend;
30-62.5 wt% of at least one other additive selected from the group comprising
at least
one flame retardant and at least one plasticizer;
1-5 wt% of at least one surfactant;
1-5 wt% of at least one catalyst;
0.5-3 wt% of water; and
the at least one hydrofluorocarbon blowing agent having a boiling point at
atmospheric pressure of between ~5°C to ~50°C and miscible
blends
thereof;
the A-side comprising:
a poly- or diisocyanate; and
the at least one hydrofluorocarbon blowing agent having a boiling point at
atmospheric pressure of between ~5°C to ~50°C and miscible
blends
thereof;
the process comprising the step of adding at least one phthalic anhydride
based aromatic polyester polyol
comprising at least 35% of the polyol blend, the ortho substitution on the
phenyl ring
providing additional thermal, hydrolytic and chemical stability to a
polyurethane without the
added amount of the at least one phthalic anhydride based aromatic polyester
polyol.
- 23 -

11. The process of claim 10, wherein the at least one phthalic anhydride based
aromatic polyester polyol is
<IMG>
wherein
R1 is selected from the group consisting of an alkylene group
of from 2
to 10 carbon atoms, ¨CH2-R3-CH2¨, and ¨(R4O)m-R4¨;
R2and R5 are independently ¨[CH2CH2O]x¨,
¨[CH2CH(CH3)O]x¨, ¨[CH2CH2CH(CH3)O]x¨, or a random
combination thereof;
R3 is selected from the group consisting of
<IMG>
each R4 is independently an alkylene group of from 2 to 4 carbon
atoms; and
x, m, and n are independently from 1-200.
12. The process of claim 11, wherein the at least one phthalic anhydride based
aromatic polyester polyol is
<IMG>
and further wherein
a hydroxyl number in mg KOH/g is between 230 and 250 inclusive;
a viscosity value at 25 °C is between 2,000 and 4,500 cP inclusive;
an equivalent average weight is approximately 234; and
an average molecular weight is approximately 468.
- 24 -

13. The process of claim 11, wherein the at least one polyether polyol is
<IMG>
and further wherein
a hydroxyl number in mg KOH/g is approximately 600;
a viscosity value at 25 °C is approximately 380 cP;
an average molecular weight is approximately 280; and
n' is an index from 1-200.
14. The process of claim 13, wherein the at least one other additive is
selected from the group comprising
<IMG>
15. The process of claim 14, wherein the at least one catalyst is at least two
catalysts selected from the group
comprising
<IMG>
16. The process of claim 15, wherein the water is added in an amount of
approximately 1% by weight.
17. The process of claim 16, wherein the at least one blowing agent has a
boiling point at atmospheric
pressure of between ¨10°C to ¨40°C.
18. The process of claim 17, wherein the at least one blowing agent is
1,1,1,3,3-pentafluoropropane.
- 25 -

19. A two-component polyurethane foam blown by at least one hydrofluoroolefin
blowing agent having a
boiling point at atmospheric pressure of between -5°C to -50°C
and miscible blends thereof, the two-
component polyurethane foam synthesized from two sets of pressurized reactants
which comprises an A-
side and a B-side:
the B-side comprising a polyol blend:
25-45 wt% of at least one polyether polyol in the polyol blend present in a
major
amount;
10-30 wt% of at least one phthalic anhydride based aromatic polyester polyol
present
in a minor amount in the polyol blend, the at least one phthalic anhydride
based aromatic polyester polyol comprising at least 35% of the polyol blend;
30-63 wt% of at least one other additive selected from the group comprising at
least
one flame retardant and at least one plasticizer;
1-5 wt% of at least one surfactant;
1-5 wt% of at least two catalysts, one of which is a tin-based catalyst;
essentially no water; and
the least one hydrofluoroolefin blowing agent having a boiling point at
atmospheric
pressure of between -5°C to -50°C and miscible blends thereof;
the A-side comprising:
a poly- or diisocyanate; and
the least one hydrofluoroolefin blowing agent having a boiling point at
atmospheric
pressure of between -5°C to -50°C and miscible blends thereof.
20. The polyurethane foam of claim 19, wherein the at least one phthalic
anhydride based aromatic polyester
polyol is
<IMG>
wherein
- 26 -

is selected from the group consisting of an alkylene group of from 2
to 10 carbon atoms, -CH2-R3-CH2-, and -(R4O)m-R4- ;
R2 and R5 are independently -[CH2CH2O]x-,
-[CH2CH(CH3)O]x-, -[CH2CH2CH(CH3)O]x-, or a random
combination thereof;
R3 is selected from the group consisting of
<IMG>
each R4 is independently an alkylene group of from 2 to 4 carbon
atoms; and
x, m, and n are independently from 1-200.
21. The polyurethane foam of claim 20, wherein the at least one phthalic
anhydride based aromatic polyester
polyol is
<IMG>
and further wherein
a hydroxyl number in mg KOH/g is between 230 and 250 inclusive;
a viscosity value at 25 °C is between 2,000 and 4,500 cP inclusive;
an equivalent average weight is approximately 234; and
an average molecular weight is approximately 468.
22. The polyurethane foam of claim 20, wherein the at least one polyether
polyol is
<IMG>
and further wherein
-27-

a hydroxyl number in mg KOH/g is approximately 600;
a viscosity value at 25 °C is approximately 380 cP;
an average molecular weight is approximately 280; and
n' is an index from 1-200.
23. The polyurethane foam of claim 22, wherein the at least one other additive
is selected from the group
comprising
<IMG>
24. The polyurethane foam of claim 23, wherein the at least two catalysts
comprise
<IMG>
and at least one of
<IMG>
25. The polyurethane foam of claim 24, wherein the at least one blowing agent
has a boiling point at
atmospheric pressure of between -10°C to -40°C.
26. The polyurethane foam of claim 25, wherein the at least one blowing agent
is 1,1,1,4,4,4 hexafluoro-2-
butene.
27. A process of synthesizing a two-component polyurethane foam blown by at
least one hydrofluoroolefin
blowing agent having a boiling point at atmospheric pressure of between -
5°C to -50°C, and miscible
blends thereof, the two-component polyurethane foam synthesized from two sets
of pressurized reactants
which comprises an A-side and a B-side:
the B-side polyol blend comprising:
25-45 wt% of at least one polyether polyol in the polyol blend present in a
major
amount;
- 28 -

10-30 wt% of at least one phthalic anhydride based aromatic polyester polyol
present
in a minor amount in the polyol blend;
25-45 wt% of at least one plasticizer;
5-20 wt% of at least one flame retardant;
1-5 wt% of at least two catalysts, one of which is a tin-based catalyst;
no added water; and
the at least one hydrofluoroolefin blowing agent having a boiling point at
atmospheric
pressure of between ~5°C to ~50°C, and miscible blends thereof;
the A-side comprising:
a poly- or diisocyanate; and
the at least one hydrofluoroolefin blowing agent having a boiling point at
atmospheric
pressure of between ~5°C to ~50°C, and miscible blends thereof;
the process comprising the step of adding at least one phthalic anhydride
based aromatic polyester polyol
comprising at least 35% of the polyol blend, the ortho substitution on the
phenyl ring
providing additional thermal, hydrolytic and chemical stability to a
polyurethane without the
added amount of the at least one phthalic anhydride based aromatic polyester
polyol.
28. The process of claim 27, wherein the at least one phthalic anhydride based
aromatic polyester polyol is
<IMG>
wherein
R1 is selected from the group consisting of an alkylene group
of from 2
to 10 carbon atoms, ¨CH2-R3-CH2¨, and ¨(R40)m-R4¨ ;
R2 and R5 are independently ¨[CH2CH2O]x¨,
¨[CH2CH(CH3)O]x-, ¨[CH2CH2CH(CH3)O]x¨, or a random
combination thereof;
R3 is selected from the group consisting of
- 29 -

<IMG>
each R4 is independently an alkylene group of from 2 to 4 carbon
atoms; and
x, m, and n are independently from 1-200.
29. The process of claim 28, wherein the at least one phthalic anhydride based
aromatic polyester polyol is
<IMG>
and further wherein
a hydroxyl number in mg KOH/g is between 230 and 250 inclusive;
a viscosity value at 25 °C is between 2,000 and 4,500 cP inclusive;
an equivalent average weight is approximately 234; and
an average molecular weight is approximately 468.
30. The process of claim 28, wherein the at least one polyether polyol is
<IMG>
and further wherein
a hydroxyl number in mg KOH/g is approximately 600;
a viscosity value at 25 °C is approximately 380 cP;
an average molecular weight is approximately 280; and
n' is an index from 1-200.
31. The process of claim 30, wherein the at least one other additive is
selected from the group comprising
- 30 -

<IMG>
32. The process of claim 31, wherein the at least two catalysts comprise
<IMG>
33. The process of claim 32, wherein the at least one blowing agent has a
boiling point at atmospheric
pressure of between ¨10°C to ¨4°C.
34. The process of claim 33, wherein the at least one blowing agent is
1,1,1,4,4,4 hexafluoro-2-butene.
- 31 -

Description

CA 02988976 2017-12-08
WO 2016/201293 PCMJS2016/036977
Marine Foam
Technical Field
[0001] The invention described herein pertains generally to a composition and
a method involving the use of
polyurethane or polyisocyanurate foam blown by a blowing agent having a
boiling point at atmospheric
pressure of between -5 C to -50 C, which passes all United States Coast Guard
Title 33, Part 183
specifications wherein the buoyant force of the froth polyurethane or
polyisocyanurate foam is not reduced
more than 5% after exposure to being immersed in a fully saturated gasoline
vapor atmosphere at an
elevated temperature, as well as being tested at room temperature in reference
fuel B, in reference oil No. 2,
and in a 5% solution of Na3PO4 for defined periods of time.
Background of the Invention
[0002] United States Coast Guard Title 33, Part 183 specifications are
difficult to meet with existing
polyurethane or polyisocyanurate foams when it comes to buoyancy after
exposure to fully saturated
gasoline vapor atmosphere, in reference fuel B, in reference oil No. 2, and in
a 5% solution of Na3PO4.
[0003] Without being held to any one theory or mode of operation, it is
believed that at least part of the
issue focuses on the need to increase the thermal, hydrolytic and chemical
stability of the foam,
necessitating an increase in the phthalic anhydride containing polyols and a
decrease in (or elimination of)
the sucrose polyester polyol which is typically present in many foams so as to
enable the foam to meet the
ASTM E-84 test standards regarding the surface burning characteristics of
building materials.
Summary of the Invention
[0004] In accordance with one aspect of the present invention, there is
provided a frothable foam which a
polyurethane or polyisocyanurate foam is blown by at least one HFC blowing
agent having a boiling point at
atmospheric pressure of between -5 C to -50 C, including miscible blends
thereof, which passes all United
States Coast Guard Title 33, Part 183 specifications wherein the buoyant force
of the foam is not reduced
more than 5% after exposure to each of the following conditions, namely:
being immersed in a fully saturated gasoline vapor atmosphere for 30 days at a
minimum
temperature of 38 C;
being immersed for 24 hours at 23 C plus or minus 2 C in reference fuel B;
being immersed for 30 days at 23 C plus or minus 2 C in reference fuel B;
being immersed for 24 hours at 23 C plus or minus 2 C in reference oil No. 2;
being immersed for 30 days at 23 C plus or minus 2 C in reference oil No. 2;
being immersed for 24 hours at 23 C plus or minus 2 C in a 5% solution of
Na3PO4; and
being immersed for 30 days at 23 C plus or minus 2 C in a 5% solution of
Na3PO4.
- 1 -

CA 02988976 2017-12-08
WO 2016/201293 PCT/1JS2016/036977
[0005] The polyurethane or polyisocyanurate foam comprises:
35-75 wt.% of a polyol blend which comprises:
25-45 wt.% of at least one polyether polyol in the polyol blend present in a
major
amount;
10-30 wt.% of at least one phthalic anhydride based aromatic polyester polyol
present in a minor amount in the polyol blend, the at least one phthalic
anhydride based aromatic polyester polyol comprising at least 35% of the
polyol blend;
30-65 wt.% of at least one other additive comprising at least one plasticizer
and at least one
flame retardant
1-5 wt.% of at least one surfactant;
1-5 wt.% of at least one catalyst;
0.5-3 wt.% of water; and
the weight percentages combining to total 100%.
[0006] In a generic sense, the at least one phthalic anhydride based aromatic
polyester polyol is
00
0 0
H-R2-0-R1 ,
wherein
is selected from the group consisting of an alkylene group of from 2
to 10 carbon atoms, ¨CH2-R3-CH2¨, and ¨(R40)m-R4¨ ;
R2 and R5 are independently ¨[CH2CH20]2¨,
¨[CH2CH(CH3)0],¨, ¨[CH2CH2CH(CH3)0]õ¨, or a random
combination thereof;
R3 is selected from the group
consisting of
cH3 02H5 CH2OH
-C- -C- -C- and ¨T-
1
cH, CH2OH CH2OH CH2OH OH .
- 2 -

each R4 is independently an alkylene group of from 2 to 4 carbon
atoms; and
x, m, and n are independently from 1-200.
[0007] In a more preferred embodiment, the at least one phthalic anhydride
based aromatic polyester
polyol preferably is
0 0
.0
rl
and further wherein
a hydroxyl number in mg KOH/g is between 230-250 inclusive;
a viscosity value at 25 C is between 2,000 - 4,500 cP inclusive;
an equivalent average weight is approximately 234; and
an average molecular weight is approximately 468.
[0008] The at least one polyether polyol preferably is
(11`
3
and further wherein
a hydroxyl number in mg KOH/g is approximately 600;
a viscosity value at 25 C is approximately 380 cP;
an average molecular weight is approximately 280: and
n' is an index from 1-200.
[0009] The at least one other additive preferably is selected from the group
comprising
Br j.1
B 0
,c_on
O-P-0
and
(Lr.C1 Br CH,
CH, Br 0
[0010] The at least one catalyst preferably is at least two catalysts
CH3
H3C,, /CH3
COK
N-CH2CH2-N-CH2CH2-N\CH and N3
3
H3C/
FI,C/
[0011] The water is added in an amount of approximately 1% by weight and
preferably the at least one
HFC blowing agent has a boiling point at atmospheric pressure of between -10 C
to -40 C. The at least
-3-
CA 2988976 2019-02-28

1
one HFC blowing agent is typically 1,1,1,3,3-pentafluoropropane, optionally
combined with a second
blowing agent.
-3a-
CA 2988976 2019-02-28

[0012] A process to achieve the above is also described involving the
synthesizing a polyurethane or
polyisocyanurate foam blown by at least one HFC blowing agent having a boiling
point at atmospheric
pressure of between -5 C to -50 C, which passes all United States Coast Guard
Title 33, Part 183
specifications.
[0012a] In a first aspect, this document discloses a two component
polyurethane foam blown by at least
one hydrofluorocarbon blowing agent having a boiling point at atmospheric
pressure of between -5 C to
-50 C and miscible blends thereof, the two component polyurethane foam
synthesized from two sets of
pressurized reactants which comprise an A-side and a B-side: the B-side
comprising a polyol blend: 25-
45 wt% of at least one polyether polyol in the polyol blend present in a major
amount; 10-30 wt% of at
least one phthalic anhydride based aromatic polyester polyol present in a
minor amount in the polyol
blend, the at least one phthalic anhydride based aromatic polyester polyol
comprising at least 35% of the
polyol blend; 30-62.5 wt% of at least one other additive selected from the
group comprising at least one
flame retardant and at least one plasticizer; 1-5 wt% of at least one
surfactant; 1-5 wt% of at least one
catalyst; 0.5-3 wt% of water; and the at least one hydrofluorocarbon blowing
agent having a boiling point
at atmospheric pressure of between -5 C to -50 C and miscible blends thereof;
the A-side comprising: a
poly- or diisocyanate; and the at least one hydrofluorocarbon blowing agent
having a boiling point at
atmospheric pressure of between -5 C to -50 C and miscible blends thereof.
[0012b] In a second aspect, this document discloses a process of synthesizing
a two-component
polyurethane foam blown by at least one hydrofluorocarbon blowing agent having
a boiling point at
atmospheric pressure of between -5 C to -50 C, and miscible blends thereof,
the two-component
polyurethane foam synthesized from two sets of pressurized reactants which
comprise an A-side and a B-
side: the B-side comprising a polyol blend: 25-45 wt% of at least one
polyether polyol in the polyol blend
present in a major amount; 10-30 wt% of at least one phthalic anhydride based
aromatic polyester polyol
present in a minor amount in the polyol blend; 30-62.5 wt% of at least one
other additive selected from
the group comprising at least one flame retardant and at least one
plasticizer; 1-5 wt% of at least one
surfactant; 1-5 wt% of at least one catalyst; 0.5-3 wt% of water; and the at
least one hydrofluorocarbon
blowing agent having a boiling point at atmospheric pressure of between -5 C
to -50 C and miscible
blends thereof; the A-side comprising: a poly- or diisocyanate; and the at
least one hydrofluorocarbon
blowing agent having a boiling point at atmospheric pressure of between -5 C
to -50 C and miscible
blends thereof; the process comprising the step of adding at least one
phthalic anhydride based aromatic
polyester polyol comprising at least 35% of the polyol blend, the ortho
substitution on the phenyl ring
providing additional thermal, hydrolytic and chemical stability to a
polyurethane without the added amount
of the at least one phthalic anhydride based aromatic polyester polyol.
[0012c] In a third aspect, this document discloses a two-component
polyurethane foam blown by at least
one hydrofluoroolefin blowing agent having a boiling point at atmospheric
pressure of between -5 C to
-50 C and miscible blends thereof, the two-component polyurethane foam
synthesized from two sets of
-4-
CA 2988976 2019-07-18

pressurized reactants which comprises an A-side and a B-side: the B-side
comprising a polyol blend: 25-
45 wt% of at least one polyether polyol in the polyol blend present in a major
amount; 10-30 wt% of at
least one phthalic anhydride based aromatic polyester polyol present in a
minor amount in the polyol
blend. the at least one phthalic anhydride based aromatic polyester polyol
comprising at least 35% of the
polyol blend; 30-63 wt% of at least one other additive selected from the group
comprising at least one
flame retardant and at least one plasticizer; 1-5 wt% of at least one
surfactant; 1-5 wt% of at least two
catalysts, one of which is a tin-based catalyst; essentially no water; and the
least one hydrofluoroolefin
blowing agent having a boiling point at atmospheric pressure of between -5 C
to -50 C and miscible
blends thereof; the A-side comprising: a poly- or diisocyanate; and the least
one hydrofluoroolefin blowing
agent having a boiling point at atmospheric pressure of between -5 C to -50 C
and miscible blends
thereof.
[0012d] In a fourth aspect, this document discloses a process of synthesizing
a two-component
polyurethane foam blown by at least one hydrofluoroolefin blowing agent having
a boiling point at
atmospheric pressure of between -5 C to -50 C, and miscible blends thereof,
the two-component
polyurethane foam synthesized from two sets of pressurized reactants which
comprises an A-side and a
B-side: the B-side polyol blend comprising: 25-45 wt% of at least one
polyether polyol in the polyol blend
present in a major amount; 10-30 wt% of at least one phthalic anhydride based
aromatic polyester polyol
present in a minor amount in the polyol blend; 25-45 wt% of at least one
plasticizer; 5-20 wt% of at least
one flame retardant; 1-5 wt% of at least two catalysts, one of which is a tin-
based catalyst; no added
water; and the at least one hydrofluoroolefin blowing agent having a boiling
point at atmospheric pressure
of between -5 C to -50 C, and miscible blends thereof; the A-side comprising:
a poly- or diisocyanate;
and the at least one hydrofluoroolefin blowing agent having a boiling point at
atmospheric pressure of
between -5 C to -50 C, and miscible blends thereof; the process comprising the
step of adding at least
one phthalic anhydride based aromatic polyester polyol comprising at least 35%
of the polyol blend, the
ortho substitution on the phenyl ring providing additional thermal, hydrolytic
and chemical stability to a
polyurethane without the added amount of the at least one phthalic anhydride
based aromatic polyester
polyol.
[0013] In accordance with another aspect of the present invention, there is
provided a frothable foam
which a polyurethane or polyisocyanurate foam is blown by at least one HFO
blowing agent having a
boiling point at atmospheric pressure of between -5 C to -50 C, including
miscible blends thereof, which
passes all United States Coast Guard Title 33, Part 183 specifications wherein
the buoyant force of the
foam is not reduced more than 5% after exposure to each of the following
conditions, namely:
being immersed in a fully saturated gasoline vapor atmosphere for 30 days at a
minimum
temperature of 38 C;
being immersed for 24 hours at 23 C plus or minus 2 C in reference fuel B;
being immersed for 30 days at 23 C plus or minus 2 C in reference fuel B;
-4a-
CA 2988976 2019-07-18

being immersed for 24 hours at 23 C plus or minus 2 C in reference oil No. 2;
being immersed for 30 days at 23 C plus or minus 2 C in reference oil No. 2;
being immersed for 24 hours at 23 C plus or minus 2 C in a 5% solution of
Na3PO4; and
being immersed for 30 days at 23 C plus or minus 2 C in a 5% solution of
Na3PO4.
[0014] The polyurethane or polyisocyanurate foam comprises:
35-75 wt.% of a polyol blend which comprises:
25-45 wt.% of at least one polyether polyol in the polyol blend present in a
major
amount;
10-30 wt.% of at least one phthalic anhydride based aromatic polyester polyol
present in a minor amount in the polyol blend, the at least one phthalic
anhydride
based aromatic polyester polyol comprising at least 35% of the polyol blend;
30-65 wt.% of at least one other additive comprising at least one plasticizer
and at
least one flame retardant;
1-5 wt.% of at least one surfactant;
1-5 wt.% of at least two catalysts, at least one of which is tin-based;
essentially no water; and
the weight percentages combining to total 100%.
-4b-
CA 2988976 2019-07-18

[0015] In a generic sense, the at least one phthalic anhydride based aromatic
polyester polyol is
00
0
H _____________________ R2-0¨R1 R1-0¨R5¨H
wherein
R1 is selected from the group consisting of an alkylene group
of from 2
to 10 carbon atoms, ¨CH2-1V-CH2¨, and ¨(R40)m-R4¨ ;
R2and R5 are independently ¨[CH2CH20])r-,
¨[CH2CH(C1-13)0],¨. ¨[CH2CH2CH(CH3)0]x--, or a random
combination thereof;
R3 is selected from the group consisting of
CH2OH
721-15
1 CI H3
¨C¨ ¨C¨ ¨C¨ and ¨C---
1
CH, CH2OH CH2OH CH2OH OH .
each R4 is independently an alkylene group of from 2 to 4 carbon
atoms; and
x, m, and n are independently from 1-200.
[0016] In a more preferred embodiment the at least one phthalic anhydride
based aromatic polyester
polyol preferably is
C>
n
and further wherein
a hydroxyl number in mg KOH/g is between 230-250 inclusive;
a viscosity value at 25 C is between 2000, - 4,500 cP inclusive;
an equivalent average weight is approximately 234; and
an average molecular weight is approximately 468.
[0017] The at least one polyether polypi preferably is
-5
CA 2988976 2019-02-28

0H20,2-00,H6-
and further wherein
a hydroxyl number in mg KOH/g is approximately 600;
a viscosity value at 25 C is approximately 380 cP;
an average molecular weight is approximately 280; and
n' is an index from 1-200.
[0018] The at least one other additive is preferably selected from the group
comprising
Br 0
CH3 0 c,,,
0-7-0
and
, CH3
CH, Br 0
[0019] The at least two catalysts comprise
(ri2),c1-6
cH3(cF12)11¨S¨Sn¨S¨(CH21,CH,
(CF12)30H3
and at least one of
0
H3GO
\I,1 N"0
K`
FI,C/
and
[0020] The at least one HFO blowing agent preferably has a boiling point at
atmospheric pressure of
between -10 C to -40 C and is 1,1,1,4,4,4 hexafluoro-2-butene, optionally
combined with a second
blowing agent.
[0021] A process to achieve the above is also described involving the
synthesizing a polyurethane or
polyisocyanurate foam blown by at least one HFO blowing agent having a boiling
point at atmospheric
pressure of between -5 C to -50 C, which passes all United States Coast Guard
Title 33, Part 183
specifications.
[0022] The above and other aspects of the invention are achieved by using low
pressure, high boiling
point blowing agents, either neat or as a miscible blend or azeotrope with
other blowing agents,
recognizing that the invention encompasses future blowing agents having
characteristics defined herein,
particularly higher boiling points.
[0023] These and other objects of this invention will be evident when viewed
in light of the detailed
description and appended claims.
-6 -
CA 2988976 2019-02-28

Detailed Description of the Invention
[0024] The best mode for carrying out the invention will now be described for
the purposes of illustrating
the best mode known to the applicant at the time of the filing of this patent
application. The examples and
-6a -
CA 2988976 2019-02-28

figures are illustrative only and not meant to limit the invention, which is
measured by the scope and spirit
of the claims.
[0025] The invention relates to improved polyurethane and polyisocyanurate
foams, which employ at
least an effective amount of a low pressure, higher boiling point blowing
agent(s) including miscible
blends thereof.
[0026] As used in this application, a non-limiting exemplary definition for
the term "polyurethane" or
"PUR", which includes mixtures of polyurethanes, means a class of reaction
polymers in which a urethane
linkage is produced by reacting an isocyanate group, -NCO with a hydroxyl
(alcohol) group, -OH.
Polyurethanes are produced by the polyaddition reaction of a polyisocyanate
with a polyalcohol (polyol) in
the presence of a catalyst and other additives. In this case, a polyisocyanate
is a molecule with two or
more isocyanate functional groups, R-(N=C=O)n a 2 and a polyol is a molecule
with two or more hydroxyl
functional groups, IT-(OH)n 2. The reaction product is a polymer containing
the urethane linkage,
-RNHCOOR'-. Isocyanates will react with any molecule that contains an active
hydrogen. Importantly,
isocyanates react with water to form a urea linkage and carbon dioxide gas.
Commercially,
polyurethanes are produced by reacting a liquid isocyanate with a liquid blend
of polyols, catalyst, and
other additives. The isocyanate is commonly referred to in North America as
the "A-side" or just the "iso".
The blend of polyols and other additives is commonly referred to as the "B-
side" or as the "poly". In
Europe the definitions for the contents of the "A" and "B" compositions are
reversed.
[0027] As used in this application, a non-limiting exemplary definition for
the term "isocyanate", which
includes mixtures of isocyanates, means a moiety which contains an -N=C=O
arrangement of chemical
elements. Molecules that contain two isocyanate groups are called
diisocyanates. Isocyanates can be
classed as aromatic, such as diphenylmethane diisocyanate ("MDI") or toluene
diisocyanate ("TDI"); or
aliphatic, such as hexamethylene diisocyanate ("HDI"). An example of a
polymeric isocyanate is
polymeric diphenylmethane diisocyanate, which is a blend of molecules with two-
, three-, and four- or
more isocyanate groups, with an average functionality of 2.7. Isocyanates can
be further modified by
partially reacting them with a polyol to form a prepolymer. Important
characteristics of isocyanates are
their molecular backbone, % -N=C=O content, functionality, and viscosity. Any
organic polyisocyanate
can be employed in the polyurethane or polyisocyanurate foam synthesis
inclusive of aliphatic and
aromatic polyisocyanates. Suitable organic polyisocyanates include aliphatic,
cycloaliphatic, arylaliphatic,
aromatic, and heterocyclic isocyanates which are well known in the field of
polyurethane chemistry.
Representative organic polyisocyanates correspond to the formula:
R(NCO)z
wherein R is a polyvalent organic radical which is either aliphatic,
arylalkyl, aromatic or mixtures thereof,
and z is an integer which corresponds to the valence of R and is at least two.
Representative of the
organic polyisocyanates contemplated herein includes, for example, the
aromatic diisocyanates such as
-7-
CA 2988976 2019-02-28

2,4-toluene diisocyanate, 2,6-toluene diisocyanate, mixtures of 2,4- and 2,6-
toluene diisocyanate, crude
toluene diisocyanate, methylene diphenyl diisocyanate, crude methylene
diphenyl diisocyanate and the
like; the
-7a-
CA 2988976 2019-02-28

CA 02988976 2017-12-08
WO 2016/201293 PCT/US2016/036977
aromatic triisocyanates such as 4,4',4"-triphenylmethane triisocyanate, 2,4,6-
toluene triisocyanates; the
aromatic tetraisocyanates such as 4,4'-dimethyldiphenylmethane-2,2'5,5'-
tetraisocyanate, and the like;
arylalkyl polyisocyanates such as xylylene diisocyanate; aliphatic
polyisocyanate such as hexamethylene-
1,6-diisocyanate, lysine diisocyanate methylester and the like; and mixtures
thereof. Other organic
polyisocyanates include polymethylene polyphenylisocyanate, hydrogenated
methylene diphenyl isocyanate,
m-phenylene diisocyanate, naphthylene-1,5-diisocyanate, 1-methoxyphenylene-2,4-
diisocyanate, 4,4'-
biphenylene diisocyanate, 3,3'-dimethoxy-4,4'-biphenyl diisocyanate, 3,3'-
dimethy1-4,4'-biphenyl
diisocyanate, and 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate; Typical
aliphatic polyisocyanates are
alkylene diisocyanates such as trimethylene diisocyanate, tetramethylene
diisocyanate, and hexamethylene
diisocyanate, isophorene diisocyanate, 4,4'-methylenebis(cyclohexyl
isocyanate), and the like; typical
aromatic polyisocyanates include m-, and p-phenylene diisocyanate,
polymethylene polyphenyl isocyanate,
2,4- and 2,6-toluenediisocyanate, dianisidine diisocyanate, bitoylene
isocyanate, naphthylene 1,4-
diisocyanate, bis(4-isocyanatophenyl)methene, bis(2-methyl-4-
isocyanatophenyl)methane, and the like.
[0028] As used in this application, a non-limiting exemplary definition for
the term "polyol", which includes
mixtures of polyols, can be any polyol which reacts in a known fashion with an
isocyanate in preparing a
polyurethane or polyisocyanurate foam. In one sense, polyol means a moiety
which contains more than one
hydroxyl group. Molecules that contain two hydroxyl groups are called diols,
those with three hydroxyl
groups are called triols, et cetera. Polyols are polymers in their own right.
They are formed by base-
catalyzed addition of propylene oxide ("PO"), ethylene oxide ("E0") onto a
hydroxyl or amine containing
initiator, or by polyesterification of a di-acid, such as adipic acid, with
glycols, such as ethylene glycol ("EG")
or dipropylene glycol ("DPG"). Polyols extended with PO or EO are polyether
polyols. Polyols formed by
polyesterification are polyester polyols. The choice of initiator, extender,
and molecular weight of the polyol
greatly affect its physical state, and the physical properties of the
polyurethane polymer. Important
characteristics of polyols are their molecular backbone, initiator, molecular
weight, % primary hydroxyl
groups, functionality, and viscosity. Useful polyols comprise one or more of a
sucrose containing polyol;
phenol, a phenol formaldehyde containing polyol; a glucose containing polyol;
a sorbitol containing polyol; a
methylglucoside containing polyol; an aromatic polyester polyol; polyols
derived from natural products (e.g.
soy beans), glycerol; ethylene glycol; diethylene glycol; propylene glycol;
graft copolymers of polyether
polyols with a vinyl polymer; a copolymer of a polyether polyol with a
polyurea; one or more of (a) condensed
with one or more of (b) as illustrated by (a) glycerine, ethylene glycol,
diethylene glycol, trimethylolpropane,
ethylene diamine, pentaerythritol, soy oil, lecithin, tall oil, palm oil,
castor oil; and (b) ethylene oxide,
propylene oxide. a mixture of ethylene oxide and propylene oxide; or
combinations thereof.
- 8 -

[0029] As used in this application, the Poly-G 37-600 polyether polyol will
mean and have the following
characteristics.
Hydroxyl Number, mg KOH/g 600
Water, % by wt., max. 0.08
rl Viscosity at 77 F (25 C), cP 380
Molecular Weight (average) 280
Specific Gravity at 77 F (25 C), 1.051
[0030] As used in this application, one of the preferred phthalic anhydride
based polyester polyols is and
has the following physical characteristics.
Hydroxyl Number, 230-250 (mg KOH/g)
Water, max. 0.15% by wt.
Acid Number, max . 0.6- 1.0 mg KOH/g
0 0
Viscosity at 77 F (25 C), 2,000 - 4,500 cP
0 Equivalent Weight
(average) 234
n Molecular Weight (average) 468
Color, Gardner 4
Specific Gravity @ 25 C, 1.19
[0031] As used in this application, the terephthalic anhydride based polyester
polyol will mean and
having the following characteristics.
Hydroxyl Number, 335-365 (mg KOH/g)
Water, max. 0.15% by wt.
0 0 Acid No. 0.5-2.0 mg
KOH/g
HOO C> I Viscosity @ 25 C 2500-3500 cP
Specific Gravity @25 C, 1.233
n
Functionality 2.20
Equivalent Weight 160.3
[0032] As used in this application, a more generic non-limiting exemplary
definition for the term phthalic
anhydride based polyester polyol is
00
0 0
H-R2-0-R1
wherein
is selected from the group consisting of an alkylene group of from 2
to 10 carbon atoms, ¨CH2-R3-CH?¨, and ¨(R40)m-R4;
R2 and R5 are independently ¨[CH2CH201x¨,
¨[CH2CH(CH3)0]x¨, ¨[CH2CH2CH(CH3)0]x--, or a random
combination thereof;
-9 -
CA 2988976 2019-02-28

R3 is selected from the group consisting of
cH3 1 1 C2 H5 C1H2OH 1
¨C¨C _________________________ ¨C¨ ¨C¨ and ¨C¨
I 1 1
CH3 CH2OH CH2OH CH2OH OH =
each R4 is independently an alkylene group of from 2 to 4 carbon
atoms; and
x, m, n and n' are independently from 1-200.
[0033] As used in this application, a non-limiting exemplary definition for
the term "polyol premix", which
includes mixtures of polyol premixes, means a polyol premix which includes a
catalyst. Useful catalysts
are primary amines, secondary amines or most typical tertiary amines. Useful
tertiary amine catalysts
non-exclusively include dicyclohexylnnethylamine; ethyldiisopropylamine;
dimethylcyclohexylamine;
dimethylisopropylamine; methylisopropylbenzylamine;
methylcyclopentylbenzylamine; isopropyl-sec-
butyl-trifluoroethylamine; diethyl-(a-phenylethyl)amine, tri-n-propylamine, or
combinations thereof. Useful
secondary amine catalysts non-exclusively include dicyclohexylamine; t-
butylisopropylamine; di-t-
butylamine; cyclohexyl-t-butylamine; di-sec-butylamine, dicyclopentylamine; di-
(
trifluoromethylethyl)amine; di-a-phenylethyl)amine; or combinations thereof.
Useful primary amine
catalysts non-exclusively include: triphenylmethylamine and 1,1-diethyl-n-
propylamine. Other useful
amines include morpholines, imidazoles, ether containing compounds, and the
like. These include
dimorpholinodiethylether; N-ethylmorpholine; N-methylmorpholine;
bis(dimethylaminoethypether;
imidazole; n-methylimidazole; 1,2-dimethylimidazol; dimorpholinodimethylether;
N,N,N',N',N",N"-
pentamethyldiethylenetriamine; N,N,N',N',N",N"-pentaethyldiethylenetriamine;
N,N,N',N',N",N"-
pentamethyldipropylenetriamine; bis(diethylaminoethyl)ether; and
bis(dimethylaminopropyl)ether. The
polyol premix composition may contain an optional silicone surfactant. The
silicone surfactant is used to
form a foam from the mixture, as well as to control surface tension that
impacts the size of the bubbles of
the foam so that a foam of a desired open or closed cell structure is
obtained. Preferably, a foam with
small bubbles or cells therein of uniform size is desired since it has the
most desirable physical properties
such as compressive strength and thermal conductivity. Also, it is critical to
have a foam with stable cells
which do not collapse prior to forming or during foam rise. The polyol premix
composition may optionally
contain a non-silicone surfactant, such as a non-silicone, non-ionic
surfactant. These may include
oxyethylated alkylphenols, oxyethylated fatty alcohols, paraffin oils, castor
oil esters, ricinoleic acid esters,
turkey red oil, groundnut oil, paraffins and fatty alcohols. A preferred non-
silicone surfactant is LK-443
which is commercially available from Air Products Corporation.
[0034] As used in this application, a non-limiting exemplary definition for
the term "polyisocyanurate" or
"PIR", which includes mixtures of polyisocyanurates, means the reaction the
reaction product of MDI and
a polyol, which typically takes place at higher temperatures compared to the
reaction temperature for the
manufacture of PUR. Without being limited to any theory of operation or
synthesis, at these elevated
temperatures and in the presence of specific catalysts, MDI will first react
with itself, producing a stiff, ring
molecule, which is a reactive intermediate (a tri-isocyanate isocyanurate
compound). Remaining MDI and
-10 -
CA 2988976 2019-02-28

1
the tri-isocyanate react with polyol to form a complex poly(urethane-
isocyanurate) polymer, which is
foamed in the presence of a suitable blowing agent. This isocyanurate polymer
has a relatively strong
molecular structure, because of the combination of strong chemical bonds, the
ring structure of
isocyanurate and high
,
-10a -
1 CA 2988976 2019-02-28

CA 02988976 2017-12-08
WO 2016/201293 PCT/1JS2016/036977
cross link density, each contributing to the greater stiffness than found in
comparable polyurethanes. The
greater bond strength also means these are more difficult to break, and as a
result a FIR foam is chemically
and thermally more stable: breakdown of isocyanurate bonds is reported to
start above 200 C, compared
with urethane at 100 to 110 C. FIR typically has an MDI/polyol ratio, also
called its index (based on
isocyanate/polyol stoichiometry to produce urethane alone), of between 200 and
500. By comparison PUR
indices are normally around 100. As the index increases material stiffness but
also brittleness also increase,
although the correlation is not linear. Depending on the product application
greater stiffness, chemical
and/or thermal stability may be desirable. As such PIR manufacturers offer
multiple products with identical
densities but different indices in an attempt to achieve optimal end use
performance.
[0035] As used in this application, a non-limiting definition for the term
"blowing agent" which includes
miscible mixtures and azeotropes of blowing agents, means a propellant or
solvent which are useful and
provide efficacy to various applications in the form of insulation
performance, pressure performance, or
solubility, without deleterious effect due to molar gas volume, flammability
migration, or GWP reduction, yet
which have a vapor pressure within defined limits as defined herein. Exemplary
and non-limiting blowing
agents include HFC-245fa (Honeywell Intl.), namely 1,1,1,3,3
pentafluoropentane or FEA-1100 (DuPont),
namely 1,1,1,4,4,4 hexafluoro-2-butene.
[0036] It is often necessary or even desirable to mitigate the global warming
potential ("GWP") of blowing
agent, aerosol, or solvent compositions. As used herein, GWP is measured
relative to that of carbon dioxide
and over a 100 year time horizon, as defined in "The Scientific Assessment of
Ozone Depletion, 2002, a
report of the World Meteorological Association's Global Ozone Research and
Monitoring Project." In certain
preferred forms, the present compositions also preferably have an Ozone
Depletion Potential ("ODP") of not
greater than 0.05, more preferably not greater than 0.02 and even more
preferably about zero. As used
herein, "ODP" is as defined in "The Scientific Assessment of Ozone Depletion,
2002, A Report of the World
Meteorological Association's Global Ozone Research and Monitoring Project."
[0037] As used herein, a non-limiting definition for the term "co-blowing
agent" which includes mixtures or
miscible blends and/or azeotropes of blowing agents, means a one or more co-
blowing agents, co-
propellants, or co-solvents which are useful and provide efficacy to various
applications in the form of
insulation performance, pressure performance, or solubility, without
deleterious effect due to molar gas
volume, flammability mitigation, or GWP reduction. These co-agents include but
are not limited to: one or
more additional components of hydrofluorocarbons, Ci to 06 hydrocarbons, Ci to
CB alcohols, ethers,
diethers, aldehydes, ketones, hydrofluoroethers, CI to 04 chlorocarbons,
methyl formate, water, carbon
dioxide, 03 to 04 hydrofluoroolefins, and 03 to 04 hydrochlorofluoroolefins.
Examples of these non-
exclusively include one or more of difluoromethane, trans-1,2-
dichloroethylene, difluoroethane, 1,1,1,2,2-
pentafluoroethane, 1,1,2,2-tetrafluoroethane, 1,1,1,2-tetrafluoroethane, 1,1,1-
trifluoroethane, 1 ,1-
difluoroethane, fluoroethane, hexafluoropropane isomers, including HFC-236fa,
pentafluoropropane isomers
of HFC-245fa, heptafluoropropane isomers, including HFC-227ea,
hexafluorobutane isomers, and
pentafluorobutane isomers including HFC-365mfc, tetrafluoropropane isomers,
and trifluoropropene isomers
- 11 -

CA 02988976 2017-12-08
WO 2016/201293 PCT/US2016/036977
(HFO-1243). Specifically included are all molecules and isomers of HFO-1234,
including 1,1,1,2-
tetrafluoropropene (HF0-1234y0, and cis- and trans-1,2,3,3-tetrafluoropropene
(HF0-1234ye), HFC-1233zd,
and HFC-1225ye. Preferred co-blowing agents non-exclusively include:
hydrocarbons, methyl formate,
halogen containing compounds, especially fluorine containing compounds and
chlorine containing
compounds such as halocarbons, fluorocarbons, chlorocarbons,
fluorochlorocarbons, halogenated
hydrocarbons such as hydrofluorocarbons, hydrochlorocarbons,
hydrofluorochlorocarbons,
hydrofluoroolefins, hydrochlorofluoroolefins, 002, CO2 generating materials
such as water, and organic acids
that produce CO2 such as formic acid. Examples non-exclusively include low-
boiling, aliphatic hydrocarbons
such as ethane, propane(s), i.e. normal pentane, isopropane, isopentane and
cyclopentane; butanes(s), i.e.
normal butane and isobutane; ethers and halogenated ethers; trans 1,2-
dichloroethylene, pentafluorobutane;
pentafluoropropane; hexafluoropropane; and heptafluoropropane; 1-chloro-
1,2,2,2-tetrafluoroethane (HCFC-
124); and 1,1-dichloro-1-fluoroethane (HCFC-141b) as well as 1,1,2,2-
tetrafluoroethane (HFC-134); 1,1,1,2-
tetrafluoroethane (HFC-134a); 1-chloro 1,1-difluoroethane (HCFC-142b);
1,1,1,3,3-pentafluorobutane (HFC-
365mfc); 1,1,1,2,3,3,3-heptafluoropropane (HCF-227ea); trichlorofluoromethane
(CFC-11),
dichlorodifluoromethane (CFC-12); 1,1,1,3,3,3-hexafluoropropane (HFC-236fa);
1,1,1,2,3,3-
hexafluoropropane (HFC-236ea); difluoromethane (HFC-32); difluoroethane (HFC-
152a); trifluoropropenes,
pentafluoropropenes, chlorotrifluoropropenes, tetrafluoropropenes including
1,1,1,2-tetrafluoropropene
(HF0-1234yf), 1,1,1,2,3-pentafluoropropene (HF0-1225ye), and 1-chloro-3,3,3-
trifluoropropene (HCFC-
1233zd). Combinations of any of the aforementioned are useful. The relative
amount of any of the above
noted additional co-blowing agents, as well as any additional components
included in present compositions,
can vary widely within the general broad scope of the present invention
according to the particular
application for the composition, and all such relative amounts are considered
to be within the scope hereof.
[0038] As used herein, a non-limiting definition for the term, "effective
amount" means a quantity sufficient to
improve the result of the foaming operation when compared to a control without
the added low pressure
blowing agent.
[0039] As used herein, a non-limiting definition for the term, "higher boiling
point blowing agent" means a
blowing agent having a boiling point at atmospheric pressure of between -5 C
to -50 C, more preferably
-10 C to -40 C.
[0040] As used herein, a non-limiting definition for the term "lower pressure
blowing agent" means a blowing
agent having a vapor pressure of between -5 psig to -30 psig at approximately
room temperature, -75 F
(equivalently -34.5 kPa to -206.9 kPa at approximately room temperature, -24
C).
[0041] As used herein, a non-limiting definition for the term "approximately"
means a deviation from the
stated end points of a range of 10%.
[0042] The polymerization reaction is catalyzed by tertiary amines, such as
dimethylcyclohexylamine, and
organometallic compounds, such as dibutyltin dilaurate or bismuth octanoate.
Furthermore, catalysts can be
chosen based on whether they favor the urethane (gel) reaction, such as 1,4-
diazabicyclo[2.2.2]octane (also
-12-

CA 02988976 2017-12-08
WO 2016/201293 PCT/US2016/036977
called DABCO or TEDA), or the urea (blow) reaction, such as bis-(2-
dimethylaminoethyl)ether, or specifically
drive the isocyanate trimerization reaction, such as potassium octoate.
[0043] At its simplest level, the distinction between PIR and PUR polymers is
not large. The proportion of
MDI is higher than for PUR and instead of a polyether polyol, a polyester
derived polyol is used in the
reaction. Catalysts and additives used in PIR formulations also differ from
those used in PUR.
[0044] The foam of the invention dispenses from relatively inexpensive
pressurized, but considered low-
pressure (130-225 psi) cylinders rather than high pressure dispensing
equipment (> 1,000 psi as typically
used in impingement mixing) of the prior art. The use of cylinder dispensed
polyurethane foam does not
have upfront capital costs for equipment as would be necessary with high
pressure dispensed polyurethane
foam, which is in the order of $30,000 to $100,000 for the special handling
equipment required, including
proportioning units and spray guns.
Example #1
[0045] A typical polyurethane foam was made in by combining two polyether
polyols, e.g., poly-G 37-600
and Voranole 360 in addition one aromatic polyester polyol (Terole 352) in the
ratios illustrated in Table I.
Plasticizer, flame retardant, surfactants, catalysts & water were also added
in the ratios illustrated in Table I
to form the "B"-side cylinder. Diphenylmethane diisocyanate was used to form
the "PC-side cylinder. The
propellant HFC-245fa was employed for both the "A" and "B" cylinders in the
quantities illustrated in Table II.
Example #2
[0046] A new formulation polyurethane foam was made by combining one polyether
polyol (poly-G 37-600)
with one aromatic polyester polyol (Stepanpole PS-3524) in the ratio
illustrated in Table I. The total amounts
of polyols of Example #1 and Example #2 were adjusted to be equal.
Plasticizer, flame retardant,
surfactants, catalysts & water were also added in the ratios illustrated in
Table Ito form the "B"-side cylinder.
Diphenylmethane diisocyanate was used to form the "A"-side cylinder. The
propellant HFC-245fa was
employed for both the "A" and ''B" cylinders in the quantities illustrated in
Table II.
Example #3
[0047] A new formulation polyurethane foam was made by combining one polyether
polyol (poly-G 37-600)
with one aromatic polyester polyol (Stepanpole PS-3524) in the ratio
illustrated in Table I. The total amounts
of polyols of Example #1, #2 and #3 were adjusted to be equal. Plasticizer,
flame retardant, surfactants,
catalysts & water were also added in the ratios illustrated in Table Ito form
the "B"-side cylinder.
Diphenylmethane diisocyanate was used to form the "A"-side cylinder. The
propellant FEA-1100 was
employed for both the "A" and "B" cylinders in the quantities illustrated in
Table II noting that the catalyst
package was different due to the internal olefin propellant used in the
formulation, which also requires
essentially the absence of water due at least in part to the reactivity of the
internal olefinic bond of the
propellant or synonymously blowing agent.
- 13-

Table I
Component Formula Ex. #1 Ex. #2 Ex. #2 Ex. #3
Ex. #3
(wt.%) (wt.%) Range (wt.%) Range
(wt.%) (wt.%)
Polyether 34.2%
34.2% 25-45% 36.4% 25-45%
polyol
- 3
Polyether CH, 10.0%
polyol CH (O-CH---CH, )-OH
H:C, H H
,0
-0
H TH3
OH
HO HC-H2C
CH
H I CH3
icw.4 0-CH2-CH )T-- OH
CH
I
CH-I 0 CH, CH ), OH
0) ( 0\
HO --;( HC-H2C CH2-- CH ),OH
CH, CH,
Polyester 9.6%
polyol
411:0
Polyester 19.6% 10-
30% 19.6% 10-30%
polyol 0 0
C> _
Additive CH, CH, 30.0%
30.0% 25-45% 30.0% 25-45%
Additive 9 10.0%
10.0% 5-20% 10.0% 5-20%
Br D'=-"T'CH
OH
Br 0
Surfactant 13 8499 Tegostae proprietary
polyether 1.5% 1.5% 1-5% 1.5% 1-5%
polydimethylsiloxane copolymer foam stabilizer
Surfactant LK 443 Dabcoe proprietary non-
silicone containing 1.5% 1.5% 1-5% 1.5% 1-5%
organic surfactant having a viscosity at 25 C of 2600 cps.
20% sal. in water, and an average OH# of 36 containing
0.1-1% N-vinyl-2-pyrrolidone
Catalyst H3C\ /CH, cH3 0.5% 0.5% 1-5%
H,C/ CH2CH2--N
\CH,
Catalyst o 1.7% 1.7%
1-5% 0.8% 0.5-2%
Catalyst
0/ 0.1% 0.01-1%
/
-14 -
CA 2988976 2019-02-28

Catalyst 72)3cH3 0.1% 0.01-
1%
cH3(cF12)11¨s¨sn¨s¨(cH2)11cR3
(CI-12)3cH3
-14a
CA 2988976 2019-02-28

CA 02988976 2017-12-08
WO 2016/201293 PCT/US2016/036977
Component Formula Ex. #1 Ex. #2 Ex. #2 Ex.
#3 Ex. #3
(wt.%) (wt.%) Range (wt.%) Range
(wt.%) (wt.%)
Other Water 1.0% 1.0% 0.5-3%
Totals 100% 100% 100% 100% 100%
[0048] Formulations of Example #1 and Example #2 were made using the
hydrofluorocarbon ("HFC") high
boiling point propellant 1,1,1,3,3-pentafluoropropane (HFC-245fa) while
Example #3 was made using the
hydrofluoroolefin ("HFO") internal olefin propellant 1,1,1,4,4,4 hexafluoro-2-
butene (FEA-1100) as illustrated
in Table II.
Table II
Composition Example #1
Example #2 Example #3
"A-side"
MDI 94% 94% 94%
HFC-245fa propellant 6% 6%
FEA-1100 propellant 6%
"B"-side
"B"-side blend of Table I 89% 89% 89%
HFC-245fa propellant 11% 11%
FEA-1100 propellant 11%
-15-

CA 02988976 2017-12-08
WO 2016/201293 PCT/1JS2016/036977
[0049] The examples above had the following physical characteristics.
Table Ill
Initial 3 no. 6 mo. 9 mo. 12 no.
Example #1
NB ratio 1.40 1.20 1.40 1.38 1.29
Gel (sec) 39 64 71 82 92
Tack (sec) 75 112 127 170 192
p (lbs/ft3) 2.18 2.29 2.14 2.40 2.58
CDR 1.00 1.64 1.82 2.10 2.36
R-value ('Phr"ft2/13TU"in) 6.59 6.92 5.84 4.92 5.13
% CCC 90.49 85.04 89.92 90.00 74.84
II comp. (psi) 26.27 22.00 32.55 29.34 29.08
Example #2
NB ratio 1.24 1.19 0.92 1.21 1.25
Gel (sec) 33 44 59 88 85
Tack (sec) 61 77 101 139 237
p (lbs/ft3) 1.90 2.03 2.20 2.22 2.39
CDR 1.00 1.33 1.79 2.67 2.58
R-value ("F"hr"ft2113TU"in) 7.11 NR 7.30 5.65 5.20
% CCC 85.99 NR NR 92.22 81.25
II comp. (psi) 22.17 NR 22.06 27.55 29.93
Example #3
NB ratio 1.01 1.10 0.97 1.20 1.11
Gel (sec) 35 41 56 48 28
Tack (sec) 43 67 94 74 47
p (lbs/ft3) 3.04 2.98 3.52 3.67 3.51
CDR 1.00 1.19 1.60 1.37 0.80
R-value (0Phr"ft2/13TU"in) 7.12 6.38 6.32 6.62 7.14
% CCC 93.57 95.15 91.21 82.23 91.24
II comp. (psi) 35.85 38.93 50.03 46.99 NR
[0050] One important test for flotation purposes, is the ability of any
synthesized foam to pass the U.S.
Coast Guard Title 33, Part 183 test, which employs a series of ASTM standards,
namely ASTM D471 &
ASTM D2842. The results of the testing for Example #1, Example #2 and Example
#3 are illustrated in
Table IV and the adjacent P/F columns are a shorthand notation as to whether
the composition passed or
failed the identified testing protocol.
-16-

CA 02988976 2017-12-08
WO 2016/201293 PCT/US2016/036977
Table IV
Test Requirements Ex. #1 P/F Ex. #2
P/F Ex. #3 P/F
Effects of Fluids 24 hrs. @23 C Reference Fuel "B" -5% max 0.0% P
0.0% P
Effects of Fluids 30 days @23 C Reference Fuel "B" -5% max +1.9%
P 0.0% P
Effects of Fluids 24 hrs. @ 23 C IRM 902 Oil -5% max 0.0% P 0.0%
P 0.0% P
Effects of Fluids 30 days @23 C IRM 902 Oil -5% max -2.0% P
+1.9% P -2.0% P
_
Effects of Fluids 24 hrs. @ 23 C 5% Na3PO4 -5% max 0.0% P
0.0010 P 0.0% P
Effects of Fluids 30 days 23 C 5% Na3PO4 -5% max -2.0% P
+3.8% P -2.0% P
Effects of Fluids 30 Days at 38 C gasoline vapor -5% max -13.7% F
+5.0% P +5.0% P
[0051] As illustrated above, Title 33: Navigation and Navigable Waters has
several stringent requirements,
as illustrated in Chapter I: Coast Guard, Department of Homeland Security,
Subchapter S: Boating Safety,
Part 183: Boats and Associated Equipment, Subpart F: Flotation Requirements
for Inboard Boats,
Inboard/Outdrive Boats, and Airboats.
[0052] 183.114 - Test of flotation materials.
(a) Vapor test. The flotation material must not reduce in buoyant force more
than 5% after being
immersed in a fully saturated gasoline vapor atmosphere for 30 days at a
minimum temperature of 38 C.
(b) 24-hour gasoline test. The flotation material must not reduce in buoyant
force more than 5%
after being immersed for 24 hours at 23 C plus or minus 2 C in reference fuel
B, of ASTM D 471
(incorporated by reference, see 183.5).
(c) 30-day gasoline test. The flotation material must not reduce in buoyant
force more than 5%
after being immersed for 30 days at 23 C plus or minus 2 C in reference fuel
B, of ASTM D 471
(incorporated by reference, see 183.5).
(d) 24-hour oil test. The flotation material must not reduce in buoyant force
more than 5% after
being immersed for 24 hours at 23 C plus or minus 2 C in reference oil No. 2,
of ASTM D 471 (incorporated
by reference, see 183.5).
(e) 30-day oil test. The flotation material must not reduce in buoyant force
more than 5% after
being immersed for 30 days at 23 C plus or minus 2 C in reference oil No. 2,
of ASTM D 471 (incorporated
by reference, see 183.5).
-17-

CA 02988976 2017-12-08
WO 2016/201293 PCT/1JS2016/036977
(f) 24-hour bilge cleaner test. The flotation material must not reduce in
buoyant force more than
5% after being immersed for 24 hours at 23 C plus or minus 2 C in a 5%
solution of trisodium phosphate in
water.
(q) 30-day bilge cleaner test. The flotation material must not reduce in
buoyant force more than
5% after being immersed for 30 days at 23 C plus or minus 2 C in a 5% solution
of trisodium phosphate in
water.
(h) The buoyant force reduction in paragraphs (a) through (g) of this section
is measured in
accordance with ASTM D 2842 (incorporated by reference, see 183.5).
[0053] 183.114 Flotation Performance Tests
Test 183.114 Area 183.110 Engine room bilge Engine room
(unless open to atmosphere)
(a) Vapor test X
(b) 24 hour gasoline test X
(c) 30 day gasoline lest X
(d) 24 hour oil test X
(e) 30 day oil test X
(f) 24 hour bilge cleaner test X
(g) 30 day bilge cleaner test X
[0054] What is illustrated above is that by switching to a higher percentage
of aromatic ortho-substituted
polyester polyols (i.e., phthalic anhydride based in comparison to
terephthalic anhydride based) in the foam
composition for the "B"-side in combination with the reduction and/or removal
of a large amount (preferably
totally) of a sucrose glycerine polyether polyol (illustrated by the above
Example #2 & Example #3), the foam
became clearly less subject to degradation by various solvents which would
commonly be encountered by
foams in a marine environment as compared and contrasted to Example #1. What
is surprising is that
increasing the amount of ortho-substitution in the aromatic polyester polyol
(phthalic anhydride based) on the
phthalic acid ring resulted in a much more stable composition compared to para-
substitution (terephthalic
anhydride based).
[0055] It is also evident that by changing the propellant from a HFC
(hydrofluorocarbon) to an HFO
(hydrofluoroolefin) required some changes in the catalyst package in addition
to essentially the complete
removal of water from the formulation in order to protect the internal double
bond from prematurely being
attacked in the pressurized container.
[0056] The best mode for carrying out the invention has been described for
purposes of illustrating the best
mode known to the applicant at the time. The examples are illustrative only
and not meant to limit the
invention, as measured by the scope and merit of the claims. The invention has
been described with
reference to preferred and alternate embodiments. Obviously, modifications and
alterations will occur to
-18-

CA 02988976 2017-12-08
WO 2016/201293 PCT/US2016/036977
others upon the reading and understanding of the specification. It is intended
to include all such
modifications and alterations insofar as they come within the scope of the
appended claims or the
equivalents thereof.
-19-