Note: Descriptions are shown in the official language in which they were submitted.
POLYESTER RESINS CONTAINING
DIENE OLIGOMERS
BACKGROUND OF THE INVENTION
This in~ention relates to polyester resins
which have been modified with diene oligomers.
It is well ~nown that polyester re~ins can be
modified with dicyclopentadiene. See, for ~ample U.S.
Patents 3,347~806 and 4,029,848. According to U.S.
Patents 4,148,765 and 4,233,43~, it is also known to
prepare polyester resin containing dicyclopentadiene
wherein maleic acid esters of dicyclopentadiene are
prepared and incorporated into the polyester reslns.
SUMMARY OF THE INVENTION
It has now been found that greater amounts of
hydxocarbon over that known in the prior art can be
incorporated into polyester resins while maintaining
resin performance properties equal to or superior to
conventional general purpose polyester resins or the
kno~m polyester resins containing dicyclopentadiene.
The advantage of thi5 invention is thus that lower cost
resins can be prepared with about ~he same performance
properties. This result is achieved by uslng oligomers
of C4-Cs dienes.
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The resins of this invention are prepared by
reacting
A) an alpha, beta ethylenically unsatura-ted
dicarboxylic anhydride containing 0-40
mole percent of saturated or unsaturated
poly basic acids or anhydrides which are
other than the said anhydride,
B) about 0.2 to about 3.0 moles of water
per mole of unsaturated anhydride,
C) about 0.1 -to about 1.2 moles of diene
oligomer per mole of unsaturated an-
hydride, and
D) about 0.4 to about 1.3 moles of a polyol,
o~ an alkylene o~ide, or mixtures thereof
per mole of unsaturated anhydride.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The polyols used to prepare the resins of
this invention are those which are reactive with acids
and/or anhydrides and may include, for example, e~ly
lene glycol, propylene glycol, diethylene glycol,
dipropylene glycol, 1,4 butanediol, 1,6-hexanediol,
pentaerythritol, triethylene glycol, trimethylol propane,
glycerol, or mixtures thereof. Preferably, the polyols
used in this invention are glycols such as ethylene
glycol, propylene glycol, and/or dipropylene glycol
and/or diethylene glycol.
If desired, in some circ~nstances the use of
a polyol can be eliminated and an alkylene oxide used
in place thereof. The technique of preparing polyester
resins from anhydrid~s and alkylene oxides is known
from U.S. patents 3,374,208 ar~d 2,822,350. In general,
the technique involves using at least 90% of a dicarbox-
ylic acid anhydride and adding an alkylene oxide having
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2-4 carbon atoms such as ethylene oxide, propylene
oxide, butylene oxide, or mixtures thereof.
In general, the dielle oligomers used herein
are prepared by heating and reacting a hydrocarbon
stream containing one or more of the following hydrocar-
bons: dicyclopentadiene, cyclopentadiene, piperylene,
isoprene, butadiene, methyl cyclopentadiene, cyclopenta-
diene-piperylene codimers, cyclopentadiene isoprene
codimers.
A preferred aspect of this invention is the
diene oligomers made by heating and reacting crude, low
purity or high purity dicyclopentadiene streams.
The oligomers are commercially available or
may be prepared by the method set forth in the prepara~
tions below:
For the purposes of this inventon, a crude
dicyclopentadiene stream is one con-taining ~bout 5 to
50 percent by weight dicyclopentadiene, a low purity
stream is one containing about 50 to 95% dicyclopenta-
diene, and a high purity stream is one containinggreater than 95% by weight dicyclopentadiene. The
hydrocarbon mixtures are heated to 150-200C under a
pressure of 100-200 psig and in an inert gas such as
nitrogen or helium for a period of time ranging from 30
minutes to 4 hours. The resultant products are be-
lieved to be mainly complex dlmers, trimers, tetramers
and pentamers.
Saturated polybasic acids useful to prepare
these resins includ~, for example, or-thophthalic anhydride
.~ or acid, terephthalic acid, isophthalic acid, trimellitic
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--4-
anhydride, adipic acid, sebacic acid, succinic acid,
and the like acids or anhydrides or low molecular
weight esters thereof.
Unsaturated dicarboxylic acids anhydrides
useful to prepare these resins are maleic anhydride,
citraconic anhydride, and mixtures thereof.
Useful unsaturated dicarboxylic acids that
can be used are maleic, teraconic, itaconic, fumaric
and mixtures thereof.
The polyesters of this invention are prepared
by reacting in an inert atmosphere about 1 mole of an
~, ~ ethylenically unsaturated dicarboxylic acid anhy-
dride with 0.2 moles to about 3.0 moles of water,
preferably 0.1 to 1.1 moles of water, about 0.1 moles
to 1.2 moles of hydrocarbon oligomer per mole of anhy-
dride and preferably 0.4 to 0.7 moles of oligomer and
about 0.5 to 1.3 moles of a polyol, preferably 0.7 to
0.9 moles.
If desired, the polyesters of this invention
can also include abouk 0.1 to 0.4 moles of a saturated
or unsaturated acid per mole of anhydride and pre-
ferably 0.1 to 0.3 moles.
The addition order may vary; for example: a)
all components could be added at the same time, b) the
water and acid anhydride could be reacted from several
minutes to several hours before adding the hydrocarbon
oligomer which in turn could be reacted from several
minutes to several hours before adding a polyol, c)
small amounts of polyol m~y be added with the water,
O acid anhydride and the oligomer and brouqht to th~
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-5-
desired amount toward the end of the process, d) water
may be added to a mixture of anhydride and oligomer and
reacted before adding a polyol.
The initial reaction temperatures can range
from 50C to 200C (prPferably 70C-140C) until a
substantial portion of the hydrocarbon oligomer has
been reacted.
After this initial reac-tion, the mass is
heated -to about 160C to about 250C and preferably
190C to 205C. Water is remo~ed with a condensing
system and the reaction allowed to proceed to an acid
number of about 10 to about 45.
The p~lyesters of this invention may also be
prepared by using reaction conditions and stoichiometry
so ~hat the mono glycolate of maleic acids or bis-
maleate of a glycol are formed prior to addition of the
hydrocarbon oligomer. In this case water is not re-
quired to facilitate oligomer maleate formation.
Still another approach is to isolate the
2~ desired intermediate mixture
O O
HO - C C - OR
HC = CH
O o
., .,
RO - C C - OR
HC = CH
where R is a hydrocarbon oligomer before
proceeding with the polyester reaction.
- C-29,332 -5-
--6--
If desired an acid catalyst, such as boron
trifluoride, sulfuric acid, toluene sulfonic acid, and
the lik~ can be used to catalyze ester formation of an
acid and the hydrocarbon oligomer.
The resin is recovered and blended with an
ethylenically unsaturated monomer copolymerizable with
the unsaturated polyester polymers to form a blend
wherein the weight ratio of polyester to monomer is in
the range from about 4:1 to about 1:2. Such ethy-
lenically unsaturated monomers are well known and
include: styrene, methyl styrene, chlorostyrene, vinyl
toluene, divinyl benzene, vinyl acetate, methacrylic
acid, methyl methacrylate, diallyl phthalate, dicyclopen-
tadiene alkenoates and halogenated dicyclopentadiene
alkenoates, and lik~ unsaturated monomeLs or mixtures
thereof.
These polyester blends with lmsaturated
monomers should contain about 20 to about ;70 percent by
weight and preferably 30-50 percent by weight of the
monomers based on the weight of the polyester. A small
amount of an inhibitor such as tertiaxy butyl catechol,
hydroquinone, or the like may be added to this mixture.
The final blend is a crosslinka~le polyester
composition which is useful to make laminates, castings
or coatings.
The laminates of this invention are made by
mixing into the crosslinkable composition free radical
forming catalysts in known amounts and adding this
mixture to a suitable fibrous reinforcement such as
asbestos fi~ers, carbon fibers, fibrous glass, or
inorganic fibers.
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--7--
Examples of these catalysts are benzoyl
peroxide, tertiary butyl peroxide, methylethyl ketone
peroxide and the like. It is frequently of value to
add accelerators and promoters such as cobalt naphthenate,
dimethyl aniline, and the like.
The polyester resin is rolled, sprayed or
impregnated into the fibrous reinforcemen~ such as
fibrous glass and cured in a manner well known in th~
art. When fibrous glass is used, it can be in any orm
such as chopped strands, filaments, glass ribbons,
glass yarns, or reinforcing mats.
The polyester r~sins may ~e compounded with
solvents-, pigments, or other resinous products and
cured to form useful coatings in a kno~n manner.
The following examples and pr~parations are
presented to illustrate but not limit the invention.
PREPARATION 1
160Q gms of crude dicyclopentadiene (83%
DCPD, 16% codimers, 1% lights) were charged to a Parr
reactor and pressurized to 200 psig with nitrogen. The
temperature controller was set at 185C. The total
time in the temperature range of 160C to 185C was 2
hours and 38 minutes.
The product was a slurry at room temperature
and believed to contain unreacted DCPD, trime~, -tetramer
and some heavier components with an average molecular
weight about equal to the trimer (198).
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L3
--8--
PREPARATION 2
The procedure of Preparation 1 i5 repeated
using 1600 yrams of a technical grade dicyclopentadiene
(97% DCPD). The product produced is similar to Prepa-
ration 1.
Example 1
To a reactor equipped with a thermowell,
temperature control, stirrer, inert gas sparge, partial
condenser and full condenser was charged 392 gms (4.0
moles) of maleic anhydride. The maleic anhydride was
heated to a melt temperature of 70C at which point
about 3/4 of a total charge of 50.4 gms ~2.8 moles) of
water was added to the reactor. After 2 minutes, 1/~
of the total charge of 514.8 gms (2.4 moles~ of the
15 cyclopentadiene oligomer similar to Preparation 2 was
added~ After 20 minutes the solution temperature was
107C due to exotherm. At this point ano~her 1~4 of
the oligomer was added along with the remaining portion
of the water. The temperature controller was set at
20 120C and the rest of the oligomer added over a 30
minute time period. After an additional 38 minutes
reaction time, 193.7 ~ms (3.12 moïes~ of eth~lene
glycol was added to the reactor. The temperature
controller was set at 160C, the condenser system
engaged and the nitrogen gas sparge started. After 2
hours the reactor temperature control was set at 200C.
The polyester was cooked to a final acid number of 27.
100 ppm hydroguinone was added when the temperature was
reduced to 160C. The percent hydrocarbon content was
calculated to be 46.6% by weight.
Example 2
To a reactor described in Example 1 with the
same addition order and approximately the same tempera-
ture conditions were added the follo~ing components:
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_9_
313.6 gms (3.2 moles) maleic anhydride,
125.6 gms (O.8 moles) of a mixture of
dimethyl esters of adipic acid,
glutaric acid and succinic acid with
an average molecular weight of 157,
514.8 gms (2.4 moles) cyclopentadiene
oligomer,
50.4 gms (2.8 moles) water,
193.7 gms (3.12 moles) ethylene glycol.
The dibasic esters and ethylene glycol were
added to the reactor immediately prior to the 160C
heat cycle. The resin was cooked to an acid number of
13. The resin was cooled to 160C and 100 ppm hydro
quinone added. When blended with 43% styrene the r~sin
had a gel time of 7.7 min., a cure time of 14.7 minut~s
and a maximum ~xotherm of 146C when cured at 180aF
wi~h 1% benzoyl peroxide.
Control 1
The ollowing components were used to pxepare
a dicyclopentadiene polye~ter:
784 ~ms ~8.9 mol s) maleic anhydride,
653.7 gms (4.8 moles) 96 9% C10 hydro-
carbon DCPD concentrate,
100.8 gms (5.6 moles) water,
387.5 ~ms (6.24 moles) ethylene glycol.
The heat and charge schedule was e~actly as
described in Example 1 ~xcapt that a C10 hydrocarbon
was used in place o~ the CPD ollgomer. The resin was
inhibited with 100 ppm hydroquinone. The final acid
~0 number was 25. The percent hydrocarbon conten-t was
calculated to be 36.3%.
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--10--
Control 2
Using the same reactor equipment, a general
purpose polyester resin was prepared using known pro-
cedures from
0.4 moles maleic anhydride,
O r 6 moles phthaiic anhydride,
1.08 moles propylene glycol.
The finai acid number was about 30. It was
inhibited with 100 ppm hydroquinone.
The followiny results were obtained from the
resins of E~ample 1, Controls 1 and 2 when ~hey were
cured with styrene.
TABLE I
- PROPERTIES
30% StYrene Example 1 Control 1 Control 2
Viscosity, cps 1260 172~ -
180F SPI gel
gel time**, ~min.~ 5~6 3.4
cure time, (min.3 7.5 5 r 6
2 0 max . exotherm 212C 222C
43% Styrene
Viscosit~, cps 127 161 105*
180F SPI Gel
gel time**, (min.) 5.3 3.0 7.3*
cure time. (min.) 7.5 5.0 10.~*
max. exotherm 227~C 240C 204C*
* with 44% styre~e
** cured with 1% benzoyl peroxide.
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Example 3 (DLN-585122~26)
A reactor equipped as in Example 1 was
charged with 392 gms (4.0 moles) of maleic anhydride
and brought to a melt temperature of 70C. 3/4 of the
total 50.4 gms ~2.8 moles) of water to be used was
added. This was immediately followed with about l/4,
of a total of 475.2 g~s (about 2.4 mo~es) to ~e used,
of an oligomer commercially available from the C.X.I.
Corporation. The oligomer was believed to be prepared
from a hydrocarbon cracking by-product stream and it
contains primarily cyclopentadiene, or its dimer DCPD,
piperylene, and isoprene. A slight exotherm to 111C
was observed. The remaining water and oligomer were
added over the next 30 minute period. After 2 hours at
120C-135C, 193.7 gms (3.12 moles) of ethylene glycol
was added, the controller set at 1~0C, the nitrogen
sparge, partial condenser, and full condenser were
engaged. After 1 1/2 hours the temperature was set at
205C where it stayed until an acid number of 34 was
attained. Since about 14% of the hydrocarbon did not
react, 12.4 sms of ethylene glycol was added 2 hours
and 15 minutes before the end of the cook to aleviate
sublimation. 100 ppm hydroquinone was added during
cool down.
The resin was blended with 30% styrene. The
room temperature solution viscosity was about 8000 cps
The density was 1.0991. When catalyzed with 0.5%
cobalt naphthenate 6% and 1.5% M~X peroxide the resin
had a room tempexature gel time of 3.5 minu~ces; a cure
30 time of 9.6 minutes; and a max.imum exotherm of 184C.
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-12-
Example 4
The resins of Example 1 and Controls 1 and 2
were mixed with 30% by weight of styrene and 1% benzoyl
peroxide, cast into molds from whicn test specimens
having the dimensions 1" x 3" x 1/8" were cut. The
strips were then weighted and immersed in toluene for 3
days at 45C and the gain in weight recorded. The
results are shown in Table II.
T~LI~ II
Toluene Resistance
(% wt increase)
Ex~mple 1 Control 1 Control 2
Toluene 0.90 0.33 failed*
* indicates the strip fell apart.
The above data indicates that the resin con-
taining the oligimer had outstanding solvent resistance.
Test strips were prepared as in Example 4 and
placed in an oven at 210C with periodic weighting to
determine weight loss. The results are set ~orth in
Table III.
TABLE III
Weight Loss in Percent
by Weight at 210C
E~ample 1 Control 1
252 days 0.74 0.47
10 days 1.41 1.56
25 days 2.40 2.76
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-13-
The data in Table III shows that Example 1 is
substantially bet-ter than the con~rol in weight loss.
The Control 2 resin is known to have a 25 to 50% weight
loss under the same conditions.
C-29,332 -13-
