Note: Descriptions are shown in the official language in which they were submitted.
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THERMOPLASTIC POLYURETHANE ELASTOMERS (TPUs)
PREPARED WITH POLYTRIMETHYLENE CARBONATE SOFT SEGMENT
FIELD OF THE INVENTION
The present invention relates to thermoplastic
polyurethane elastomers (hereafter TPUs). More
particularly, the present invention relates to a new
class of TPUs prepared with poly(trimethylene carbonate)
diol (PTMC diol) as the soft segment. The TPUs prepared
using PTMC diols were extended with glycols, preferably
lower functionality glycols, including, for example, 1,3-
propanediol and 1,4-butanediol.
BACKGROUND OF THE INVENTION
TPUs are of technical importance because they offer a
combination of high-quality mechanical properties with
the known advantages of inexpensive thermoplastic
processability. Much variation in mechanical properties
can be achieved by the use of different chemical
components. A survey of TPUs, their properties and
applications are discussed, for example in Polyurethane
Handbook, Gunter Oertel, Ed., Hanser Publishers, Munich,
1985, pp. 405-417.
TPUs are built up from linear polyols, usually
polyesters or polyethers, organic diisocyanates and
short-chain diols (chain extenders). The overall
properties of the TPU will depend upon the type of
polyol, its molecular weight, the structure of the
isocyanate and of the chain extender, and the ratio of
soft and hard segments.
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Polyurethanes may be either thermoplastic or
thermoset, depending on the degree of crosslinking
present. Both thermoset and thermoplastic polyurethanes
can be formed by a "one-shot" reaction between isocyanate
and polyol or by a "pre-polymer" system, wherein a
curative is added to the partially reacted polyol-
isocyanate complex to complete the polyurethane reaction.
Thermoplastic urethanes do not have primary crosslinking
while thermoset polyurethanes have a varying degree of
crosslinking, depending upon the functionality of the
reactants.
Thermoplastic polyurethanes are commonly based on
methylene diisocyanate (MDI) or toluene diisocyanate
(TDI) and include both polyester and polyether grades of
polyols. For adjustment of the properties, the polyols,
chain extenders, and diisocyanate components can be
varied within relatively wide molar ratios.
For improvement of the processing behaviour,
particularly in the case of products for processing by
extrusion, increased stability and an adjustable melt
flow are of great interest. This depends on the chemical
and morphological structure of the TPUs. The structure
necessary for an improved processing behaviour is
conventionally obtained by the use of mixtures of chain
extenders, e.g. 1,4-butanediol/1,6-hexanediol. As a
result of this the arrangement of the rigid segments is
so greatly distorted that, not only is the melt flow
improved, but, simultaneously, the thermomechanical
properties, e.g. tensile strength and resistance to
thermal distortion, are often impaired.
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The known TPUs and blends containing TPUs all suffer
some drawbacks in one or more properties, including
mechanical properties, colour stability to heat and
light, clarity, heat distortion properties, and phase
separation. Attempts to improve one property, such as
hardness, often lead to degeneration of another property.
Thus, problems exist in achieving hardness and
related mechanical properties, stable colour, clarity and
higher heat distortion temperatures in TPUs and blends
containing TPUs. There is a need in the art to discover
new formulations of TPUs that provide a broader range of
mechanical and thermal properties without the
degeneration of existing properties.
The present invention is useful in overcoming one or
more problems with known thermoplastic materials by
providing a new class of TPUs which provide new
possibilities for mechanical and thermal properties in
TPU formulations, including improvements in clarity,
hardness, higher elasticity modulus, and improved
softening temperature and coefficient of thermal
expansion.
SUMMARY OF THE INVENTION
The present invention provides a new class of TPUs
with improved properties and is based on poly(1,3-
propanediol carbonate) diol (PTMC diol), with a hard
segment comprising the portion of an isocyanate that
reacts with a glycol plus the glycol blended into the
TPU, and a diisocyanate to cure the system. The
elastomers are somewhat harder than corresponding TPUs
based on polyols known in the art. The PTMC TPUs
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exhibited good physico-mechanical properties, including
somewhat higher elasticity modulus than a control TPU.
The abrasion resistance and compression set was also very
good, comparable to that of polyether TPUs. The
softening temperature and the coefficient of thermal
expansion was found to be improved over that of a
control. In addition, using the PTMC polyol, it was
possible to improve the clarity of the TPUs and in some
examples even obtain completely clear material.
In accordance with the foregoing, the present
invention comprises a thermoplastic polyurethane
elastomer (TPU) composition which comprises:
a) a poly(trimethylene carbonate) diol (PTMC diol) as
the soft segment;
b) a diisocyanate; and
c) at least one glycol (sometimes referred to as a chain
extender) which reacts with the diisocyanate to form
the hard segment which comprises from 10% to 55% by
weight of the composition wherein the hard segment is
defined as the sum portion of diisocyanate that
reacts with the glycol plus the unreacted glycol.
BRIEF DESCRIPTION OF THE DRAWINGS
The present invention will now be described by way of
example with reference to the accompanying drawings, in
which:
Figure 1 is a graph showing the viscosity of
polycarbonate polyols;
Figure 2 is a bar graph showing stress at 100% strain
of TPUs based on 1,4-butanediol (1,4 - BD);
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Figure 3 is a bar graph showing stress at 300% strain
of TPUs based on 1,4 - BD;
Figure 4 is a bar graph showing the tensile strength
retention of TPUs based on 1,3-propanediol (1,3 - PDO);
Figure 5 is a bar graph showing weight change after a
two-week immersion in water at 70°C;
Figure 6 is a bar graph showing tensile strength,
originally, and after a two-week immersion in water at
70°C; and
Figure 7 is a bar graph showing chemical resistance
after a one-week immersion.
DETAILED DESCRIPTION OF THE PRESENT INVENTION
In the present invention a new class of thermoplastic
polyurethanes (TPUs) was prepared using poly(trimethylene
carbonate) diol as the soft segment, a hard segment
containing a glycol, preferably a short chain glycol, and
a diisocyanate. A suitable poly(trimethylene carbonate)
glycol was prepared by a process described below and the
specimen used in the Examples of the present invention
was characterized by a molecular weight of about 2000.
Thermoplastic polyurethane elastomers based on the PTMC
diol were evaluated for their properties.
Both aromatic and cycloaliphatic TPUs based on PTMC
diols were prepared and evaluated. 4, 4'-Diphenylmethane
diisocyanate (MDI) was utilized to prepare aromatic and
methylene-bis(4-cyclohexyl isocyanate)(H12MDI) to prepare
aliphatic TPUs. The elastomers were prepared using the
one shot procedure. In Examples 2, 3, 5, and 10, 1,3-PDO
and 1,4-BD were used as chain extenders and the hard
segment concentration was varied in the Examples from 22
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to 35%. For comparison, TPUs based on a commercial
poly(1,6 - hexanediol carbonate) glycol (Desmophen C-200,
commercially available from Bayer Co.), and
representative of polyols used in the art, were prepared
S and evaluated.
The physico-mechanical properties (hardness, stress-
strain properties, tear resistance, compression set,
resilience and abrasion resistance) of TPUs were measured
according to ASTM standard methods. The solvent
resistance (paraffin oil, ethylene glycol, and diluted
acid/bases) was determined by measuring the weight change
upon immersion. Water resistance was evaluated by
measuring the retention of stress-strain properties and
the weight change upon immersion in water at 70°C.
The morphology of the elastomers was studied by
thermal analysis including differential scanning
calorimetry (DSC), thermo-mechanical analysis (TMA), and
dynamic-mechanical analysis(DMA), as well as Fourier
transform infra-red analysis (FTIR). The elastomer
transparency was also measured by determining the light
transmission (%) in the visible range of 474 to 630
nanometers.
Due to the rigid nature of the PTMC diol, the
elastomers exhibited relatively high Tg (around 0°C).
Their hardness was somewhat higher than that of the
corresponding TPUs based on, for example, Desmophen C-
200, poly(tetramethyleneoxide)(PTMO) 2000 or caprolactone
polyols (See Tables 17 & 18).
The PTMC 2000 TPUs exhibited good physico-mechanical
properties. Their elasticity modulus was higher than
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Desmophen C-200 TPUs. The abrasion resistance and
compression set of PTMC 2000 TPUs was very good,
comparable to that of polyether TPUs.
The heat stability of PTMC 2000 TPUs, as indicated by
the properties at elevated temperature, the softening
temperature, and the coefficient of thermal expansion was
found to be improved over that of Desmophen C-200 TPUs.
By using PTMC 2000 it is possible to improve the clarity
of TPUs and to even obtain completely clear material with
H12MDI .
The resistance of PTMC 2000 TPUs to oil was excellent
and the resistance to other media such as diluted
inorganic acids, bases, and ethylene glycol was excellent
as well.
Poly(trimethylene carbonate) polyols
Although higher functionality polyols can generally
be used to prepare thermoset systems, the TPUs of the
present invention utilize in the examples a PTMC diol
prepared in a specific manner, a glycol, and a
diisocyanate. The PTMC diols were prepared as described
in our copending Application No. PCT/EPO1/02323. The
PTMC diols described therein are characterized by
improvements in clarity with virtually all end groups
being hydroxypropyl groups, with no measurable allyl
groups .
In order to produce poly(trimethylene carbonate)
characterized by these desirable properties, trimethylene
carbonate is reacted with a polyhydric alcohol in the
presence of a catalyst, preferably under nitrogen The
polyhydric alcohol can be a diol or triol or higher
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polyhydric alcohol, such as, for example, propanediol and
trimethylolpropane, individually, or mixtures thereof.
The poly(trimethylene carbonate) can be prepared
without a catalyst. However, the catalyst provides the
S advantage of shorter reaction times. Suitable catalysts
are selected from salts of Group IA or Group IIA of the
Periodic Table. Good results were obtained using sodium
acetate. The Group IA or IIA catalysts are effective in
small amounts, ranging from less than 1 ppm to greater
than 10,000, although one would typically expect to use
an amount in the range of 5 to 1000 ppm, preferably about
10 to 100 ppm, and most preferably about 10-40 ppm.
The poly(trimethylene carbonate) is preferably
produced without a solvent, although a solvent could be
used .
The poly(trimethylene carbonate) is produced at a
temperature in the range of 50-160°C. A preferred range
is 100-150°C, and more preferably 110-130°C. Pressure is
not critical, and actually almost any pressure could be
used, but good results were obtained using ambient
pressure.
The poly(trimethylene carbonate) will have properties
that are determined by several factors, the most
important factors being the amount and identity of
any initiating alcohol(s), catalysts and catalyst
amounts, and the process conditions. A manufacturer may
vary the determining factors to predictably produce the
molecular weight, polydispersity, and other
characteristics needed for the intended application.
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In the present invention, to prepare a new class of
TPUs that provides new formulation options, good results
were obtained using a PTMC diol prepared as described and
having a molecular weight below about 10,000, preferably
from 1000 to 3000. The TPUs in the Examples herein were
prepared with a PTMC diol having a molecular weight of
2000.
Glycol f Chain Extender)
The glycol component may be selected from aliphatic,
alicyclic, aralkyl, and aromatic glycols. As would be
known to those skilled in the art, higher functionality
alcohols could be useful in many applications. In the
present invention, however, good results were obtained
using lower functionality glycols. Examples of glycols
employed include, but are not limited to, ethylene
glycol; propylene glycol; 1,3-propanediol; 2-methyl - 1,3
- propanediol; 2,4-dimethyl-2-ethylhexane-1,3-diol; 2,2-
dimethyl-1,3-propanediol; 2-ethyl-2-butyl-1,3-
propanediol; 2-ethyl-2-isobutyl-1,3-propanediol; 1,3-
butanediol; 1,4-butanediol; 1,5-pentanediol; 1,6-
hexanediol; 2,2,4-trimethyl-1,6-hexanediol;
thiodiethanol; 1,2-cyclohexanedimethanol; 1,3-
cyclohexanedimethanol; 1,4-cyclohexanedimethanol;
2,2,4,4-tetramethyl-1,3-cyclobutanediol; and p-
xylylenediol, or mixtures thereof. Additional examples
of suitable glycols include hydroxyalkyl derivatives of
hydroquinone, i.e. bis 2- hydroxyethyl ether (HQEE), and
hydroxyalkyl derivatives of resorcinol and bisphenol A.
The glycol is preferably selected from 1,3-propanediol
and 1,4-butanediol, or mixtures thereof. Examples 2, 3,
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and 10 demonstrate the use of 1,3 - propanediol and 1,4
- butanediol.
The hard segment concentration is the sum of the
portion of isocyanate that reacts with the glycol plus
5 the unreacted glycol. The glycol hard segment is blended
into the TPU in an amount which corresponds to 10 to 55%
hard segment concentration, preferably from 20 to 40%
hard segment concentration.
Isocyanate
Isocyanates useful for curing polyurethane elastomers
generally include aliphatic, aromatic or cycloaliphatic
polyisocyanates. For the preparation of the TPUs of the
present invention diisocyanates were employed. Suitable
diisocyanates are aliphatic, aromatic or cycloaliphatic
diisocyanates. An example of an aliphatic diisocyanate
is hexamethylene diisocyanate. Examples of
cycloaliphatic diisocyanates include isophorone
diisocyanate, 1,4-cyclohexane diisocyanate, 1-methyl-2,4-
and -2,6-cyclohexane diisocyanate, as well as the
corresponding isomer mixtures, 4,4'-, 2,4'- and 2,2'-
dicyclohexyl-methane diisocyanate, as well as the
corresponding isomer mixtures. Examples of aromatic
diisocyanates include 2,4-toluene diisocyanate, mixtures
of 2,4- and 2,6-toluene diisocyanate, 4,4'-, 2,4'- and
2,2'-diphenylmethane diisocyanate, mixtures of 2,4'- and
4,4'-diphenylmethane diisocyanate, urethane-modified
liquid 4,4'- and/or 2,4'-diphenylmethane diisocyanates,
4,4'-diisocyanatodiphenylethane-(1,2) and 1,5-naphthalene
diisocyanate. Other examples of suitable diisocyanates
include, but are not limited to, diphenylene-4-4'-
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diisocyanate, 3,3'-dimethoxy-4-4'-diphenylene
diisocyanate, methylene-bis-(4-cyclohexylisocyanate),
tetramethylene diisocyanate, decamethylene diisocyanate,
ethylene diisocyanate, ethylidene diisocyanate,
S propylene-1,2-diisocyanate, cyclohexylene-1,2-
diisocyanate, m-phenylene diisocyanate, p-phenylene
diisocyanate, 3,3'-dimethyl-4,4'-biphenylene
diisocyanate, 3,3'-dimethoxy-4,4'-biphenylene
diisocyanate, 3,3'-diphenyl-4,4'-biphenylene
diisocyanate, 4,4'-biphenylene diisocyanate, 3,3'-
dichloro-4,4'-biphenylene diisocyanate, furfurylidene
diisocyanate, xylylene diisocyanate, diphenyl propane-
4,4'-diisocyanate, bis-(2-isocyanatoethyl) fumarate,
naphthalene diisocyanate, and combinations thereof.
Additional diisocyanate compounds might include, for
example: 1,4'-dicyclohexylmethane diisocyanate, 3-
isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate,
cyclohexylene-1,4-diisocyanate, 4,4'-methylenebis(phenyl
isocyanate), 2,2-diphenylpropane-4,4'-diisocyanate, p-
phenylene diisocyanate, m-phenylene diisocyanate, xylene
diisocyanate, 1,4-naphthalene diisocyanate, 4,4'-diphenyl
diisocyanate, azobenzene-4,4'-diisocyanate, m- or p-
tetramethylxylene diisocyanate and 1-chlorobenzene-2,4-
diisocyanate, 1,6-hexamethylene diisocyanate, 4,6'-
xylylene diisocyanate, 2,2,4-(2,4,4-)trimethylhexa-
methylene diisocyanate, 3,3'-dimethyldiphenyl 4,4'-
diisocyanate, 3,3'-dimethyl-diphenylmethane 4,4'-
diisocyanate, and the like.
The preferred diisocyanates employed in the Examples
to demonstrate the benefits of the present invention were
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4, 4' - diphenylmethane diisocyanate (MDI) and methylene
- bis(4-cyclohexyl isocyanate) (H12MDI).
Catal3rsts
Where a catalyst is utilized, suitable catalysts are
those which accelerate the reaction between the NCO
groups of the diisocyanates and the hydroxyl groups of
the structural components. Examples include tertiary
amines and organic metal compounds known in the art and
described, for example, in US-A-6022939. Suitable
compounds include, for example, triethylamine,
dimethylcyclohexylamine, N-methylmorpholine, N,N'-
dimethylpiperazine, 2-(dimethylaminoethoxy)ethanol and
diazabicyclo(2,2,2)octane, and mixtures thereof, as well
as organic metal compounds such as titanic acid esters,
iron compounds, and tin compounds, examples of which
include tin diacetate, tin dioctoate, tin dilaurate and
the tin dialkyl salts of aliphatic carboxylic acids, such
as dibutyltin diacetate and dibutyltin dilaurate, or
mixtures thereof. The catalysts are usually used in
quantities of 0.0005 to 0.5 parts per 100 parts of
polyhydroxy compound.
Preparation
The TPUs of the present invention were prepared by
the one shot method. In the examples hard segments were
included in the PTMC polyurethanes at concentrations
ranging from about 10 to 55%, preferably 20 to 40% by
weight.
The isocyanate index, ratio of isocyanate to hydroxyl
equivalent, depends on the isocyanate and glycol (often
called the chain extender) employed. In the case of
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thermoset elastomers in general the index may be anywhere
from 0.105 to 600, or more. The isocyanate index in the
present invention could be from 0.8 to 1.04, depending on
the formulation, but is preferably close to about 1.02.
The polyol and glycol (chain extender) were heated at
a temperature from 70 to 150°C, preferably 95 to 140°C,
and in specific examples 100 to 135°C. Somewhat higher
temperatures could be used, but, as is known in the art,
are generally not recommended in order to avoid side
reactions. The diisocyanate was preheated at the mixing
temperature, added to the mixture of polyol and chain
extender and all components were mixed vigorously for 5
to 10 seconds. The mixture was then poured in a
preheated Teflon-coated mould (<150°C). Gelation was
determined by string formation, which generally occurred
within about 10-20 seconds, and when that occurred the
mould was placed in a Carver press and the resin was
compression-moulded at elevated pressure and moderately
elevated temperature. The pressure is preferably from
137.9 to 206.8 Mpa (20,000 to 30,000 psi), and a
suitable temperature is from 100°C to 140°C. Suitable
pressures can be well above or below this range, as would
be known to those skilled in the art. Afterwards the
polyurethane sheet was post-cured in an oven at from 90
to 150°C, preferably 100 to 140°C, for a time that may be
from several hours to several days, depending upon the
temperature.
The following examples will serve to illustrate
specific embodiments of the present invention disclosed
herein. These examples are intended only as a means of
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illustration and should not be construed as limiting the
scope of the present invention in any way. Those skilled
in the art will recognize many variations that may be
made without departing from the spirit of the disclosed
present invention.
Experimental
The materials utilized in the Examples are shown in
Table 1. The isocyanates were used as received from the
suppliers. The NCO% concentration was checked by
titration by the di-n-butylamine method of ASTM D1638-74.
The hydroxyl number of the polyols was determined by
using the standard phthalic anhydride esterification
method (ASTM D4273).
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CA 02404753 2002-09-25
WO 01/72867 PCT/EPO1/03496
0 0 0
U U U
v ~'
U U U
N N w N
~ i
~
c' p ~~17 P~0
J~ c p
11
0 0 0 0 0 0 0
u1 0 0 o 0 0 0
I~ Lf1O 00 Lf1 In N
W o 0 o M ~r N M
ao a~o ,--i
tr r''
w
a~
0 0 0
U U
.-1 r-I
w
Ol b1 ~
W
f~ -r-i
-r-I
~ U .-,
'~-'~
1~ 1~ N 'O
r-1
(~ (~ 1J
.~,~',~ r1
r-IJ-1 O
~
, ~:
,~ ,f,'
N ~ ,~ v O
v U
'd
U
(2,' Id O O r1
U -r-1 -r-I U1
O U7
r1 ''O ''O -rl
-r-I -r-I
11 (lS td C'.,O r-I
O O d~
;
O ~ _
>C
b ~1 S-1 N N 'O d'
d'
H ~ ~ .~ O
O N
M M l0
U .-1 r-1 ,~-I ~ r-I
r-I r-I
~ ~ ~ W CO
O O O N N
U as w w ,-i ~ g
O
PO U
l0 N ~,
01 r1 r1
1 i
a0 r1
O
N ~D LI
O
d' d~ m
N
N N zi N
~
0 0
~
0 o x rd ~
a~
b o o W O 5r ~
,~
wi N N ~1A U '~
, 'ti
m
ri U U
~
l~ O ,~,' fd M d~ r1 U1
,'~', U1
Ul
~ w
A A U ~ ,~ A A
A
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WO 01/72867 PCT/EPO1/03496
Example 1
In Example 1 the viscosity of the polyols was tested.
The viscosity of PTMC 2000 at room temperature was found
to be much higher than that of Desmophen C-200, which is
due to the higher concentration of stiff carbonate groups
in PTMC 2000 (Table 2, Figure 1). The viscosity was
significantly decreased by temperature. Due to the
shorter hydrocarbon sequence (three CHz groups) the glass
transition temperature of PTMC 2000 was found to be -
28.5°C, significantly higher than that of Desmophen C-
200, which has six CHZ groups (-58.3°C).
Table 2
Viscosity of the Polycarbonate Polyols
Viscosity mPa.s (cps
Temperature (°C) PTMC 2000 Desmophen c-200
100 1750 400
87 490
84 2500
77 660
70 5450 750
60 8600
57 1430
50 14600 1860
40 69500 5250
36 >100000
24 10900
Example 2
In Example 2 the compatibility of the chain extenders
with the polyols was examined. The compatibility of PTMC
2000 with chain extenders (1,4 - BD and 1,3 - PDO) was
studied by mixing components at specified ratios at
different temperatures. Visual observation of the
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mixtures was recorded. Different o concentrations of
chain extenders were examined in the control polyol and
the PTMC 2000 at room temperature, 70°C, and 90°C. PTMC
2000 was compatible with 1,4 - butanediol (1,4 - BD) and
S 1,3 - propanediol (1,3 - PDO) from room temperature to
90°C (Table 3). In this evaluation the weight ratio of
polyol to chain extender corresponds to elastomers with
hard segment concentrations of 22 to 350. The
compatibility of Desmophen C-200 with chain extenders at
room temperature was limited. The results are shown in
Table 3:
Table 3
The Compatibility of Polycarbonate Diols with the Chain
Extenders
H. S. 22 25 28 35
Temperature RT 70 90 RT 70 90 RT 70 90 RT 70 90
(C)
1,3-PDO
PTMC 2000 C C C C C C C C C C C C
Desmophen PC C C PC C C PC C C NC C C
C-200
1,4-BD
PTMC 2000 C C C C C C C C C C C C
Desmophen PC C C PC C C PC C C NC C C
C-200
C = Compatible; PC = Partially Compatible;
NC = No Compatibility
Example 3
In Example 3 TPUs were prepared by the one-shot
method at hard segment concentrations of 22, 25, 28, and
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35%. Prior to elastomer preparation polyols and chain
extenders were vacuum dried at 70°C for at least 24
hours. The diisocyanates were used as received from the
suppliers. The NCO% was checked by titration by the di-
n-butylamine method ( ASTM D1638-74). The isocyanate
index (isocyanate to hydroxyl equivalent ratio) was 1.02.
Polyol and chain extender were weighed in a plastic cup
and heated at 100°C or 135°C. Benzoyl chloride was added
to the mixture of polyol and chain extender.
Diisocyanate, which was previously heated at the mixing
temperature, was added to the mixture of polyol and chain
extender and all components were mixed vigorously for 5-
10 seconds. The mixture was then poured into a Teflon-
coated mould, which was preheated at 105°C or 135°C.
When gelation occurred (as determined by string
formation), the mould was placed in a Carver press and
the resin was compression-moulded at 165.5 Mpa (24,000
psi) at 105°C or 135°C. Afterwards, the polyurethane
sheet was post-cured in an oven at 105°C or 135°C for 24
hours (or 135°C for 20 hours and 150°C for 4 hours).
Post-curing is not always necessary. The curing and
postcuring conditions in the preparation of aromatic TPUs
are shown in Table 4 and for the aliphatic TPUs in Tables
13 and 14. The polyurethane elastomers were tested one
week after preparation.
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Table 4
Curing and Post-Curing Conditions
in the Preparation of MDI-TPUs
PTMC 2000 Desmophen C
200
Mixing Conditions 135°C for 10 sec. 105°C for 5
2 drops Benzoyl Chloride sec.
(1,4-BD)
4 drops Benzoyl Chloride
(1,3-PBD)
Curing Conditions 135°C for 1 hr 105°C for 1 hr
(pressed at 165.5 MPa (24000 (pressed at
psi) 165.5 MPa
(24000 lbs) )
Post-curing 135°C for 20 hrs (1,4-BD) 105°C for 24
Conditions 135°C for 20 hrs hrs
150°C for 4 hrs (1,3-PDO)
S Example 4
In Example 4, the formulations and properties of MDI-
based TPUs based on PTMC 2000 and Desmophen C-2000
extended with 1,3 - PDO were tested.
The data are shown in Tables 5 and 6. Increasing the
hard segment concentration from 22 to 35% resulted in the
hardness of PTMC 2000 TPUs increasing from 73 to 91 Shore
A. The hardness of Desmophen C-200 TPUs was somewhat
lower at the same hard segment concentration. In
general, the tensile strength, elasticity modulus and Die
C tear resistance of TPUs increased with the hard segment
concentration as expected. The abrasion resistance of
PTMC 2000 elastomers was very good, better than that
obtained for Desmophen C-200. This could possibly be due
to the reinforcing effect of hydrogen bonds in PTMC 2000
19
CA 02404753 2002-09-25
WO 01/72867 PCT/EPO1/03496
polyurethanes, which contain a high proportion of
carbonate groups capable of forming hydrogen bonds. The
abrasion resistance of PTMC 2000 TPUs was similar to or
even better than that of PTMO 2000 and TONE
polycaprolactone TPUs. Some examples of PTMO 2000 TPUs
have abrasion resistance indices of, for example, 13 and
20. See Tables 6-A, 17, and 18, which contain data
regarding properties of TPUs based on commercial polyols.
PTMC TPUs demonstrated relatively low compression set
(4 to 7%), lower than that of Desmophen C-200 TPUs (14.3
to 23.50). It is interesting to note that the resilience
of 1,3 - PDO extended polycarbonate TPUs increased with
increase of the hard segment concentration.
CA 02404753 2002-09-25
WO 01/72867 PCT/EPO1/03496
0
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21
CA 02404753 2002-09-25
WO 01/72867 PCT/EPO1/03496
0
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22
CA 02404753 2002-09-25
WO 01/72867 PCT/EPO1/03496
ui
a~
0
0
o ., o o W
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d~ N N
In lf1 N N
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23
CA 02404753 2002-09-25
WO 01/72867 PCT/EPO1/03496
Example 5
In Example 5 PTMC TPUs were prepared with 1,4 -BD
chain extender at a hardness range from 22 to 35% and
examined for various properties. Data are shown in
Tables 7 and 8. The strength properties (tensile
strength, 100°s and 300% elasticity modulus, Young's
modulus and toughness) and Die C tear strength of PTMC
2000 and Desmophen C-200 TPUs changed quite uniformly
with increase in the hard segment concentration. The
tensile strength of the PTMC-TPUs was found to be
somewhat lower compared to Desmophen C-200, but modulus
values were somewhat higher in the former case (Figures 2
& 3). The properties such as elongation at break,
modulus, and resilience indicate that 1,4 - BD extended
TPUs are more flexible than those extended with 1,3 -
PDO. It was found repeatedly that the resilience of PTMC
TPUs increased with increase of hard segment
concentration.
24
CA 02404753 2002-09-25
WO 01/72867 PCT/EPO1/03496
0 0 0 0 0
0
0 0 0 0
.
. o
M tf1 O N
IW f'1
If1 dl 10 dl
dl N
r1 I~ dl l0
L~ M
l17 01 r1 '-'
N r1
M OJ N I~
1 Lf1 ll1 N r-1
01 dl
N
W VI lf1 O L~ r1 dl
O OD r1
U1 01 M Lfl l0 r1 N
r1 ri 01
\
_ _ _
0 0 .-.
o
0 0 ., 0 0
0
1 o 0
d' ov oo dl
ao
r1 01 r~ d0
00
r-I O1 M r1 r
M dl
\ N dl r M M
ao
p ao fa ~- o -- ...
~ ~ --
0 N N I~ '-' '-'
1 ~ r-I M t11 L~
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[I~ r1 O L~ O l~ M
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_ _
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N dl
~I . . . O
~
M N O M N
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M d~
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1D '-'
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1 M d~ r1 M
r1 01 r1
M
l0 r1 O 01 N
O
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r~ H
(~4"~ .-. .-,
,-.
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0 0 .-. 0
.-. 0
U1 . . o o ~r
.
V' M d'
ri r1
h M LI1 10
~ p O ~
ri r1 d' N
dl Lfl
N A v o ~
N N Lf1
~ t l
~
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O ~ " 0 M
dl r-I
N
~-I a1 41 M N O I~
00
(1~ Cl~ L~ r1 l0 r1 d' V'
M Lrl M
r1
U G
-r-I
G w
rd
tll tll
Ra ~ L~
I O U
0 ,!~ c~ c0 t0 w
td td
U ~ x
~ ~ ~ ~
aP a~
-r-I
rt
1W n b rt ~n N
Ch ~ ?a N U
~-1
("., r-I 'l F.,'
J-1 1.1
1~N ~ cJ~ J.1 to
Cl~
(a~-I 'L~ ~I JJ
d~ dP
~ O o o N m N
U
U1 O ~ O -rl U
o W
-rl r-1 U7 .(~,
M U1 N
U1 N J-1 U7 ~i N N
~ N -rl
W r-I (d W p; -ri
U7 W ~'., C~
F'.N W C', ~'a 1-1 ?a -ri
N N b1
.(", O ~ t~ U1
S-I ~-I
~
~ ~
u ~ H ~
1 H
CA 02404753 2002-09-25
WO 01/72867 PCT/EPO1/03496
Example 6
In Example 6 the heat resistance of the elastomers
was evaluated by measuring the stress-strain properties
at 70°C. The retention of the tensile strength was found
to be somewhat higher for PTMC 2000/1,3 - PDO/MDI TPUs
than for Desmophen C-200/1,3 - PDO/MDI TPU (See Figure
4). The elongation at break of PTMC 2000 increased
significantly upon heating and the elasticity modulus
decreased (See Table 5). The heat resistance of
Desmophen C-200/1,4 - BD/MDI TPUs was poor (See Table 8).
The coefficient of thermal expansion, as measured by TMA
was found to be lower for PTMC TPUs than for Desmophen C-
200 (See Table 9). The softening temperature of the TPUs
as measured by TMA was in the range of 160 to 209°C for
PTMC 2000 and 160 to 175°C for the corresponding
Desmophen C-200 polyurethanes. The softening temperature
of Desmophen C-200 was not affected significantly by the
chain extender.
26
CA 02404753 2002-09-25
WO 01/72867 PCT/EPO1/03496
0
0
0 0 0
0 0 .-. o .-. 00
.-. ,~
0 0 0 0 0 . o o .
r1 00 d~ N l0 l!1 01
01 tn
10 Q1 . ~
M
M OD M N OD 4D M ~O
l0 N
10 r1 OD O1 N a0 M '-'
Ln '~
u1 V O r1 M O '-' d~
10 a0 d~
M N .~ ~. .~ M ~.
.-. ~.,~
01 L~
01 N L~ l~ ri dl 01
01 O O
O M 00 ri N O1 r1 M
~
A O OD d~ Lf1 N ri ri M r1 M
N I M
d~ t
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O
O O
O .-. ~. O O
0 0 .-. o .-. .-. o
o r .-. .
O o 0 o ao . 0 0 0 o ao
W OD d~ In 01 M
L(1 d~
ri N Ln M 01 L
N 00 l~ O ~ l0 O
O In d~ N
M r1
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r1 ~ ll1 r1
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O 10 O M i-1 I~ Ll1
00 00
L~ d~ L~ 00 O 01 N N
N
A l~ M 00 OD r1 r1 10 N h d~
d' I~ V' 00
r1
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N O O O O
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L~ L~ N O r1 L~
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h ~ . . h . . . ~p N
~
1D 00 N L~ r1 ri 01 cft
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r~ M O 6~ r1 N d~ M M
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M
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0
L~ r1 'd~ d~ d0 d~
N tf1
. N tmn u~ h
N O N d~ 10 Lf1
r1
N M N 01 O tf1 01 N
N r1
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M L~ "
N N .r ~ ~. pp
~.
I l!1 l0 N O 01
LI7 M l~ N N
O
d~ N l!1 . M p~ - In d~
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l0 N OD lD O I~ M I ~ dW f1
N In L~ O
~'
r1 r
1
U ~n
N
~
fy' -ri -ri -r1 -r1 -ri N
-r1 -r1 -ri r1
-ri
U7 W U1 U1 W W !A '-' ,"j,'
W UJ N
R~ CL t~ W L~ C4 R~
G-1 i~ C~
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v
rtl ~U ~6 ~d ro t0 a~ bi
~ ra ~0 ~
w w a' w w w w a
w w
I ~ ~ ~ ~ ~ ~ ~ ~ ~ x ~w
~ ~ ~
0 0
0
~
a
_
_
l~ U1 fI5 1J fn ((j N
(~ ftf U
W d'1 ~ ~-I L~ Cl1 ~ ~-I U
S-I S-I N
Fi r1 1.1 1=,' ri J..I t=i
J..I 1.1 -H N
J-1N ~ Ul J-tN ~ U1 fn ~ r--I
~ -r-I
rt ~.I ' as rt ~-I 'd as 1.y1 U
aP a~a
O o o ~ >~ O o o m N
N
U1 O ~ ut W O ~ p o -~ U U
o o m u~
N -.~ V v N -~ r-I V m m
u~ O
U N 1~ UI -~ N t~ m N S-1 N N
N
~n a~ r1 rt - r1 c0 . ~n fx -~ o
m m s~ m ~ ~1
v -~I C7~ 1a -~I 0~ O~ ~ O
b~ m m ~n ~n .~
.~
t~ N N p ~,' N Vi p ~". U Sa -rip
N N Cf1 N 01 ~-I
f:' O ~ G O '~ ~.1 rt m
~I S-1 S-I ~
~
?.1 O N r1 O O N r-I O l~ N N
1~ J-~ J~ O
O
~I F W ~ cn N W ~ tn w ~ H r~
~n En E-~ p
x ~ I
27
CA 02404753 2002-09-25
WO 01/72867 PCT/EPO1/03496
Examp~ a 7
In Example 7 morphology was examined. The glass
transition temperature of PTMC TPUs was about 0°C and
shifted about 10°C when measured by DMA. The relatively
high Tg defines these polyurethanes more as elastoplastic
materials with very good elasticity above room
temperature. The glass transition temperature of
Desmophen C-200 TPUs was about 30 degrees lower. An
insight into the morphology was also obtained by FTIR
spectroscopy. The FTIR spectra of the elastomers
exhibited the bands typical for polycarbonate aromatic
polyurethanes: -NH, (free and bonded) at 3300-3400 cm-1;
CH2 at 2900-2970 cm-1; C=O in carbonate and bonded
urethane group at 1740 - 1759 cm-1; C=O free urethane
group at 1706 cm-1; aromatic group at 1600 cm-1 and
-C-O-C- in ether group at 1033 cm-1. The ratio of
absorbance 1705 cm-1/1745 cm-1 increased with an increase
of the hard segment concentration indicating probably an
increase in the proportion of unbonded urethane groups.
This ratio was found to be higher with the PTMC TPUs.
The hydrogen bonds in the polycarbonate polyurethanes are
formed between urethane groups, and by bridging carbonate
and urethane groups.
28
CA 02404753 2002-09-25
WO 01/72867 PCT/EPO1/03496
Table 9
Some Morphological Properties of TPUs
Tg(DMA) Tg(DSC) Tm(TMA) Coef. Of Thermal Exp.
(C) (C) (C) (mm~a1 C)
SPM-22 13.96 -1.12 159.86 123.00
SPM-25 9.88 0.36 201.97 87.20
SPM-28 11.89 0.19 206.67 231.00
SPM-35 9.71 2.88 208.64 149.00
DPM-22 -28.34 -29.76 175.01 426.00
DPM-25 -30.00 -31.54 161.10 281.00
DPM-28 -31.60 -31.80 169.47 224.00
DPM-35 -28.53 -30.32 162.02 219.00
Example 8
In Example 8 the water resistance of the formulations
with PDO/MDI was examined. The water resistance was
evaluated by measuring the weight gain and change in
stress-strain properties upon immersion in water at 70°C
for two weeks. The results are shown in Tables 10 and 11
and in Figures 5 and 6. The weight gain of PTMC TPUs was
1.2 to 1.6%, and less (0.8 to 10) for Desmophen C-200.
These results correlate well with the change in tensile
strength, which was 8 to 57o for PTMC 2000(depending on
the hard segment concentration) and 3.6 to 33.50 for
Desmophen C-200. The better water resistance of
Desmophen C-200 is due to the more hydrophobic structure
( six -CHZ groups ) .
The relative transparency was measured by determining
the light transmission (o) in the visible range of 474 to
630 nanometers. The degree of transparency decreased
with increase of the hard segment concentration. PTMC
2000 TPUs exhibited significantly higher transparency at
different hard segment concentrations as compared to
29
CA 02404753 2002-09-25
WO 01/72867 PCT/EPO1/03496
Desmophen C-200. This could be due to the less ordered
structure of PTMC backbone or the higher degree of phase
mixing of flexible and hard segments.
CA 02404753 2002-09-25
WO 01/72867 PCT/EPO1/03496
H
\
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31
CA 02404753 2002-09-25
WO 01/72867 PCT/EPO1/03496
0 0
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32
CA 02404753 2002-09-25
WO 01/72867 PCT/EPO1/03496
Example 9
In Example 9 the chemical resistance of TPUs was
measured in various media including oil (100% neutral
paraffinic oil), Fisher Brand 19, ethylene glycol, dilute
acids (10°s HZSOQ and 10% HCl) and sodium hydroxide.
Results are shown in Table 12 and in Figure 7. The
weight gain in hydraulic oil was low while in inorganic
acids, it was higher, especially with PTMC TPUs. The
weight gain in sodium hydroxide was relatively low except
for Desmophen C-200 at 35% hard segment concentration.
Unexpectedly, the weight gain in ethylene glycol was much
lower with PTMC than with Desmophen C-200 TPUs. Overall
the resistance of TPU in this media was good. For
reference the resistance of TPUs based on
poly(oxytetramethylene) glycols is shown in Table 12 -A.
Table 12
Chemical Resistance after One-week Immersion at Room
Temperature
Oil Ethylene
HCI 10%
H2S04
10% NaOH
10%
Glycol
Weight
change
(o)
DPM TPUs* 0.0-0.32 1.00-1.26 0.22-0.830.14-0.53 0.0-1.10
DBM TPUs* 0.0-0.28 0.90-0.92 0.22-0.440.00-0.58 0.35-0.48
SPM TPUs* 0.15-0.310.39-0.63 0.80-1.510.66-1.52 0.00-0.58
* Hard Segment Concentration was varied from 22 to 350.
33
CA 02404753 2002-09-25
WO 01/72867 PCT/EPO1/03496
Table 12-A
Resistance after One-Week Immersion of TPUs Based on
POTMG 1000/1,4 - BD/MDI, 35% Hard Segment Concentration*
Weight Increase
HZSO4, 30% 1.1
NaOH 10% 1.6
Ethylene Glycol 41.4
Oil 3.1
* Reactivity Studies and Cast Elastomers Based on Trans-
cyclohexane - 1,4-Diisocyanate and 1,4-Phenylene Diisocyanate, S.
W. Wong and K. C. Frisch, Advances in Urethane Science and
Technology, Vol. 8, page 74 (1981).
Example 10
In Example 10 TPUs based on the cycloaliphatic
diisocyanate H12MDI and PTMC 2000 were cured. The curing
conditions are shown in Tables 13 and 14. In the
designations in the first row of each table, SPH-25 to
SPH-35 corresponds to PTMC2000/1,3 -PDO/H12MDI with the
hard segment concentration from 25 to 35%. SBH-25 to
SBH-35 corresponds to PTMC2000/1,4 - BD/H12MDI with the
hard segment concentration from 25 to 35%.
The tensile strength, which increased with hard
segment concentrations, exhibited moderate values,
somewhat higher with 1,3 - PDO than with 1,4 - BD chain
extender. PTMC 2000 TPUs exhibited better properties
with 1,3 - PDO than with 1,4 - BD chain extender, with
both MDI and H12MDI. It could be noted that H12MDI TPUs
34
CA 02404753 2002-09-25
WO 01/72867 PCT/EPO1/03496
were cured at lower temperatures than MDI TPUs, due to
their lower green strength.
The glass transition temperature was determined by
differential scanning calorimetry and dynamic-mechanical
method. The DSC glass transition temperature of H12MDI
TPUs was somewhat below 0°C, lower than that of MDI based
TPUs, indicating less interaction of the flexible segment
with H12MDI. The softening temperature of H12MDI was
typically in the range of 175 to 193°C. 1,3 - PDC
extended TPUs were transparent at 25o hard segment
concentration and translucent at 28 to 35o hard segment
concentrations. 1,4 - BD extended TPUs were translucent
at 25% hard segment and hazy at higher hard segment
concentration. As a reference some properties of TPUs
based on H12MDI/PTM02000/1,4 - BD are shown in Table 13 -
A.
The weight change of SPH-TPUs upon immersion in water
at 70°C for two weeks was 1.2 to 1.73%, similar to MDI-
TPUs (See Table 15).
The resistance of H12MDI - TPUs in hydraulic oil,
ethylene glycol, 10% HCl, 10°s H2S04, and 10% NaOH, as
measured by the weight gain is shown in Table 16. The
resistance to oil was excellent (no weight increase).
The weight gain in acid, sodium hydroxide and especially
in ethylene glycol was higher.
CA 02404753 2002-09-25
WO 01/72867 PCT/EPO1/03496
0 0
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36
CA 02404753 2002-09-25
WO 01/72867 PCT/EPO1/03496
U
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37
CA 02404753 2002-09-25
WO 01/72867 PCT/EPO1/03496
0 0 .-.
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w r1x H ~ ~ xx H w ~ U1 W H H H U r.~
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38
CA 02404753 2002-09-25
WO 01/72867 PCT/EPO1/03496
Table 15
Weight change after Two-Week Immersion in Water at 70°C
Initial Weight Final Weight Weight Change
(gr) (gr)
SPH-25 0.1860 0.1882 1.20
SPH-28 0.1305 0.1327 1.72
SPH-30 0.1925 0.1952 1.42
SPH-35 0.2025 0.2087 1.73
Table 16
Chemical Resistance after One-Week Immersion
at Room Temperature
Oil H2S04
Ethylene NaOH
HCI 100
10%
Glycol 100
Weight
change
(%)
SPH TPUs*0.0 1.20-2.30 1.26-2.001.20-1.701.26-2.35
SPH TPUs*0.0 2.30-3.33 0.70-1.000.80-1.000.86-1.00
* Hard Segment Concentration was varied from 25 to 35%.
Table 17
The Effect of Hard Segment Concentration
on the Hardness of TPUs Based on PTMG 2000*
2PTMG20 3PTMG20
Hard Segment 22 33
Concentration(%)
Hardness
Shore A 70 85
Shore D 33 38
* M. Vlajic, E. Torlic, A. Sendijarevic, and V.
Sendijarevic, Polimeri, Vol. 10(3), pages 62-66, 1989.
39
CA 02404753 2002-09-25
WO 01/72867 PCT/EPO1/03496
Table 18
The Effect of Hard Segment Concentration on the Hardness
of TPUs Based on CPL 2000*
2CLP20 3CLP20 4CLP20
Hard Segment 22 32 39
Conc . ( % )
Hardness
Shore A 72 82 89
Shore D 33 39 44
* M. Vlajic, E.Torlic, A. Sendijarevic, and V.
Sendijarevic, Polimeri, Vol. 10(3), pages 62-66, 1989.
