U.S. patent number RE31,436 [Application Number 05/814,066] was granted by the patent office on 1983-11-01 for thermosetting polyester composition containing normally solid carboxy-containing diene polymer.
This patent grant is currently assigned to Phillips Petroleum Company. Invention is credited to Aubrey South, Jr..
United States Patent |
RE31,436 |
South, Jr. |
November 1, 1983 |
**Please see images for:
( Certificate of Correction ) ** |
Thermosetting polyester composition containing normally solid
carboxy-containing diene polymer
Abstract
A thermosettable composition suitable for preparing reinforced
plastic articles is prepared by combining an unsaturated polyester,
a normally solid carboxy-containing polymer of a conjugated diene,
a vinyl monomer, a catalyst and a reinforcing agent or filler.
Preferably the composition is prepared utilizing a mixer giving
moderate shear such as a twin-rotor mixer. The resulting
composition when cured exhibits high impact strength and good
surface finish.
Inventors: |
South, Jr.; Aubrey
(Bartlesville, OK) |
Assignee: |
Phillips Petroleum Company
(Bartlesville, OK)
|
Family
ID: |
27102198 |
Appl.
No.: |
05/814,066 |
Filed: |
July 8, 1977 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
|
Reissue of: |
679284 |
Apr 22, 1976 |
04020036 |
Apr 26, 1977 |
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Current U.S.
Class: |
523/514; 523/521;
523/523 |
Current CPC
Class: |
C08F
279/02 (20130101); C08K 7/02 (20130101); C08L
67/06 (20130101); C08L 67/06 (20130101); C08L
53/02 (20130101); C08K 7/02 (20130101); C08L
67/06 (20130101); C08L 67/06 (20130101); C08L
2666/08 (20130101) |
Current International
Class: |
C08L
67/06 (20060101); C08F 279/00 (20060101); C08F
279/02 (20060101); C08K 7/00 (20060101); C08K
7/02 (20060101); C08L 67/00 (20060101); C08L
067/06 () |
Field of
Search: |
;260/4R,862
;524/513,426,399,436,394,433,505 ;525/171 ;523/514,521,523 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
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979128 |
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Dec 1975 |
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CA |
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1953062 |
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May 1970 |
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DE |
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2225736 |
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Jan 1973 |
|
DE |
|
5833 |
|
Sep 1975 |
|
FR |
|
49-54489 |
|
May 1974 |
|
JP |
|
50-114490 |
|
Sep 1975 |
|
JP |
|
51-52488 |
|
May 1976 |
|
JP |
|
1276198 |
|
Jun 1972 |
|
GB |
|
1396894 |
|
Jun 1975 |
|
GB |
|
1396895 |
|
Jun 1975 |
|
GB |
|
Primary Examiner: Jacobs; Lewis T.
Claims
What is claimed is:
1. A .Iadd.cured thermoset article produced by subjecting to heat a
thermosetting .Iaddend.composition comprising:
a. an unsaturated polyester prepared by reacting an unsaturated
dicarboxylic acid and a polyol;
b. .Iadd.a diene component consisting essentially of .Iaddend.a
normally solid carboxy-containing polymer of a conjugated diene
having a weight average molecular weight within the range of
.[.30,000.]. .Iadd.50,000 .Iaddend.to .[.400,000.]. .Iadd.250,000
and wherein said carboxy-containing polymer has a polymerized
conjugated diene content of from 55 to 100 weight
percent.Iaddend.;
c. a vinyl monomer;
d. a catalyst; and
e. .[.at least one of.]. a .Iadd.fibrous .Iaddend.reinforcing agent
.[.or a filler.]..
2. .[.A composition.]. .Iadd.An article .Iaddend.according to claim
1 wherein said polymer of a conjugated diene has .[.a weight
average molecular weight within the range of 50,000 to 250,000
and.]. an inherent viscosity within the range of 0.6 to 2.
3. .[.A composition.]. .Iadd.An article .Iaddend.according to claim
1 wherein said polymer of a conjugated diene is a copolymer of
butadiene and styrene.
4. .[.A composition.]. .Iadd.An article .Iaddend.according to claim
1 wherein said polyester is prepared by reacting fumaric acid and
propylene glycol.
5. .[.A composition.]. .Iadd.An article .Iaddend.according to claim
1 wherein said vinyl monomer is styrene.
6. .[.A composition.]. .Iadd.An article .Iaddend.according to claim
1 wherein a ratio of (a) to (b) is within the range of 5:1 to 1:1
and wherein said vinyl monomer is present in an amount within the
range of 30 to 200 parts by weight per 100 parts by weight of (a)
plus (b).
7. .[.A composition.]. .Iadd.An article .Iaddend.according to claim
1 wherein said catalyst is a peroxide .Iadd.and said composition
contains in addition a lubricant and a thickener. .Iaddend.
8. .[.A composition.]. .Iadd.An article .Iaddend.according to claim
1 .[.containing.]. .Iadd.wherein said fibrous reinforcing agent is
composed of .Iaddend.glass fibers and .Iadd.wherein said
composition contains in addition .Iaddend.calcium carbonate.
9. .[.A composition.]. .Iadd.An article .Iaddend.according to claim
1 wherein said unsaturated polyester is produced by reacting
fumaric acid and propylene glycol, said normally solid
carboxy-containing polymer is a copolymer of butadiene and styrene
characterized by a vinyl addition of 5 to 76 percent and having
0.01 to 5 weight percent carboxyl content, said vinyl monomer is
styrene, a ratio of (a) to (b) being within the range of 5:1 to
1:1, said vinyl monomer is present in an amount within the range of
30 to 200 parts by weight per 100 parts by weight of (a) plus (b),
said catalyst is tertiary butyl perbenzoate present in an amount
within the range of 1-5 parts by weight per 100 parts by weight of
(a) plus (b).Iadd., said fibrous reinforcing agent is composed of
glass fibers present in an amount within the range of 40 to 200
parts by weight per 100 parts by weight of (a) plus (b)
.Iaddend.and wherein said composition contains calcium carbonate
filler in an amount within the range of 200 to 800 parts by weight
of filler per 100 parts .[.per.]. .Iadd.by .Iaddend.weight of (a)
plus (b), .[.glass fiber reinforcing agent in an amount within the
range of 40 to 200 parts by weight per 100 parts by weight of (a)
plus (b),.]. 1 to 15 parts by weight of zinc stearate per 100 parts
by weight of (a) plus (b) and 1 to 10 parts by weight of magnesium
hydroxide per 100 parts by weight of (a) plus (b). .[.10. A cured
article produced by subjecting the composition of claim 9 to
heat..]. .[.11. A cured article produced by subjecting the
composition of
claim 1 to heat..]. 12. A method of forming thermosetting
compositions suitable for preparing reinforced plastic articles
comprising milling together under conditions of moderate shear:
a. an unsaturated polyester prepared by reacting an unsaturated
dicarboxylic acid and a polyol;
b. a normally solid carboxy-containing polymer of a conjugated
diene having a weight average molecular weight within the range of
30,000 to 400,000;
c. a vinyl monomer;
d. a catalyst; and
e. .[.at least one of.]. a .Iadd.fibrous .Iaddend.reinforcing agent
.[.or a
filler.].. 13. A method according to claim 12 wherein said milling
is done
with a twin-rotor mixer using sigma blades. 14. A method according
to claim 13 wherein said unsaturated polyester is produced by
reacting fumaric acid and propylene glycol, said normally solid
carboxy-containing polymer is a copolymer of butadiene and styrene
characterized by a vinyl unsaturation of 5 to 76 percent and having
0.01 to 5 weight percent carboxyl content, said vinyl monomer is
styrene, a ratio of (a) to (b) is within the range of 5:1 to 1:1,
said vinyl monomer is present in an amount within the range of 30
to 200 parts by weight per .[.110.]. .Iadd.100 .Iaddend.parts by
weight of (a) plus (b), said catalyst is tertiary butyl
perbenzoate.Iadd., said fibrous reinforcing agent is composed of
glass fibers present in an amount within the range of 40 to 200
parts by weight per 100 parts by weight of (a) plus (b)
.Iaddend.and wherein said composition contains calcium carbonate
filler in an amount within the range of 200 to 800 parts by weight
of filler per 100 parts .[.per.]. .Iadd.by .Iaddend.weight of (a)
plus (b), .[.glass fiber reinforcing agent in an amount within the
range of 40 to 200 parts by weight of (a) plus (b),.]. 1 to 15
parts by weight of a lubricant per 100 parts by weight of (a) plus
(b) and 1 to 10 parts by weight of an oxide or hydroxide of a
group II metal. 15. A method according to claim 13 wherein said
shear
produces a temperature rise of 2.degree. to 30.degree. C. 16. A
method according to claim 12 wherein the resulting composition is
subjected to curing conditions of 100.degree. C. to 200.degree. C.
for a time within the range of 1 to 15 minutes. .Iadd. 17. A
composition consisting essentially of:
a. an unsaturated polyester prepared by reacting an unsaturated
dicarboxylic acid and a polyol;
b. a normally solid carboxy-containing polymer of a conjugated
diene having a weight average molecular weight within the range of
30,000 to 400,000 and wherein said carboxy-containing polymer has a
polymerized conjugated diene content of from 55 to 100 weight
percent;
c. a vinyl monomer;
d. a catalyst;
e. a fibrous reinforcing agent;
f. a lubricant selected from aluminum stearate, barium stearate,
clacium stearate, magnesium stearate of zinc stearate;
g. a thickener selected from oxides and hydroxides of magnesium,
calcium, strontium, barium and zinc; and
h. a filler. .Iaddend. .Iadd. 18. A composition according to claim
17 wherein said unsaturated polyester is prepared by reacting
fumaric acid and propylene glycol, said normally solid
carboxy-containing polymer is a copolymer of butadiene and styrene
characterized by a vinyl unsaturation of 5 to 76 percent and having
0.01 to 5 weight percent carboxyl content, said vinyl monomer is
styrene, a ratio of (a) to (b) is within the range of 5:1 to 1:1,
said vinyl monomer is present in an amount within the range of 30
to 200 parts by weight per 100 parts by weight of (a) plus (b),
said catalyst is tertiary butyl perbenzoate present in an amount
within the range of 1-5 parts by weight per 100 parts by weight of
(a) plus (b), said fibrous reinforcing agent is composed of glass
fibers present in an amount within the range of 40 to 200 parts by
weight per 100 parts by weight of (a) plus (b), said lubricant is
zinc stearate present in an amount within the range of 1-15 parts
by weight per 100 parts by weight of (a) plus (b), said thickener
is magnesium hydroxide present in an amount within the range of
1-10 parts by weight per 100 parts by weight of (a) plus (b) and
said filler is calcium carbonate present in an amount within the
range of 200 to 800 parts by weight per 100 parts by weight of (a)
plus (b). .Iaddend.
Description
BACKGROUND OF THE INVENTION
This invention relates to unsaturated polyester compositions
containing a polymer of a conjugated diene.
It is known in the art to produce unsaturated polyester
compositions containing rubber. However, it has been found that
such compositions tend to exhibit separation when combined with a
reinforcing agent or filler, thus impairing the physical
properties, particularly impact strength.
Liquid or semi-solid rubbers which can simply be mixed with
polyesters to produce thermosetting compositions are also well
known and a broad spectrum of low molecular weight liquid or
semi-solid rubbers are suggested in the art for use in such
compositions. However, low molecular weight rubber compositions
tend to give very poor surface finish in systems containing a
reinforcing agent or filler.
SUMMARY OF THE INVENTION
It is an object of this invention to provide a thermosetting
polyester composition having good impact strength and good surface
characteristics;
It is a further object of this invention to provide a molded
article having improved pigmentability.
It is still a further object of this invention to provide a cured
thermoset article; and it is yet a further object of this invention
to provide a method for producing a polyester composition
containing a normally solid polymer of a conjugated diene capable
of giving high strength articles having good surface
characteristics.
In accordance with this invention there is provided a composition
comprising an unsaturated polyester and a normally solid
carboxy-containing polymer of a conjugated diene in a composition
also containing a vinyl monomer, a catalyst and a reinforcing agent
or filler.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
This invention concerns thermosetting composition comprising an
unsaturated polyester, a normally solid carboxy-containing a
polymer of a conjugated diene, a vinyl monomer, a catalyst and one
or more reinforcing agents or fillers.
The unsaturated polyesters are prepared by reacting an unsaturated
dicarboxylic acid having 4 to 12 carbon atoms such as maleic,
fumaric, itaconic, citraconic, mesaconic (or anhydrides or acid
halides thereof), cis-2-dodecenedioc acid and mixtures thereof with
one or more polyols. Representative polyols that can be used
include alkylene glycols having 2-10 carbon atoms, dialkylene
glycols having 4-18 carbon atoms, glycerol, pentaerythritol,
trimethylolpropane, trimethylpentanediol, trimethylpropanediol and
hydrogenated bisphenol-A.
Up to one-half or more on a molar ratio of the unsaturated acid can
be replaced by one or more saturated polycarboxylic acids having
from 2-12 carbon atoms to modify the degree of unsaturation and
reactivity of the polyester. Illustrative of these are oxalic acid,
malonic acid, succinic acid, methylsuccinic acid, glutaric acid,
adipic acid, suberic acid, sebacic acid, the phthalic acids,
naphthalene dicarboxylic acid, cyclohexane dicarboxylic acid,
citric acid and the like and mixtures thereof.
The proportion of polyhydric alcohols having more than two hydroxy
groups such as glycerol, pentaerythritol, etc. and the proportion
of polycarboxylic acids having more than two carboxy groups such as
citric acid is preferably less than about 5 mole percent each based
on total amount of polyol and polycarboxylic acid respectively so
that a polyester is obtained with maximum esterification of the
hydroxy and carboxy groups without being so viscous that difficulty
would be experienced during subsequent compounding.
The carboxy-containing solid polymers of conjugated dienes of this
invention are known polymers. Carboxy terminated polymers, for
example, are described in U.S. Pat. Nos. 3,135,716 (Uraneck et al,
June 1964) and 3,242,129 (Wilder, March 1966), the disclosures of
which are hereby incorporated by reference. The resulting polymers
generally have a carboxyl content in the range of about 0.01 to 5
weight percent. The polymers of conjugated dienes for use in this
invention are normally solid and generally have a weight average
molecular weight of 30,000 to 400,000 or higher, preferably 50,000
to 250,000. In terms of inherent viscosity, the ranges encompassed
are from about 0.4 to 3, more preferably from about 0.6 to 2.
Inherent viscosity is determined using 0.1 gram per 100 ml of
toluene at 25.degree. C.
The diene addition in the polymers of conjugated dienes can be in
the 1, 2 mode or the 1, 4 mode or combinations thereof. The
unsaturation microstructure of the polymers is generally in the
range of from about 5 to 76 percent vinyl, from about 5 to 60
percent trans and from about 15 to 50 percent cis unsaturation.
The polymers of this invention include the homopolymers and
copolymers of the conjugated dienes. Also included are copolymers
of the conjugated dienes and a monovinyl-substituted aromatic
hydrocarbon containing from about 8-18 carbon atoms per molecule.
Examples of the monovinyl-substituted aromatic monomer include:
styrene, 3-methylstyrene, 4-n-propylstyrene, 4-cyclohexylstyrene,
4-docecylstyrene .[..]. .Iadd.dodecylstyrene
2-ethyl-4-benzylstyrene, 4-(4-phenyl-n-butyl)sytrene,
1-vinylnaphthalene, 2-vinylnaphthalene, t-butylstyrene and the
like. The monovinyl-substituted aromatic hydrocarbon can contain
alkyl, cycloalkyl, and aryl substituents, and combinations thereof
such as alkylaryl in which the total number of carbon atoms in the
combined substituents is generally not greater than 12. Styrene is
presently preferred because of its availability and effectiveness.
The polymerized conjugated diene content of these .[.copolymers.].
.Iadd.polymers .Iaddend.ranges from about 20 to 100 weight percent,
more preferably from about 55 to 100 weight percent.
Although the presently preferred conjugated diene is 1,3-butadiene,
it is within the scope of the carboxy-containing polymers of this
invention to use conjugated dienes containing from 4-12 carbon
atoms per molecule, more preferably from 4-8 carbon atoms per
molecule. Examples of such compounds include 1,3-butadiene,
isoprene, 2,3-dimethyl-1,3-butadiene, piperylene,
3-butyl-1,3-octadiene, 1-phenyl-1,3-butadiene, and the like and
mixtures thereof.
The conjugated diene-monovinyl-substituted aromatic hydrocarbon
copolymers can be of random or block configuration or combinations
thereof. Block polymers are presently preferred.
The polymers of conjugated dienes of this invention can be prepared
according to previously cited patents and by free radical
polymerization in solution, suspension or emulsion processes. For
example, polymerization can be initiated with carboxy-containing
compounds such as azobis-cyanopentanoic acid,
di(.beta.-carboxypropionyl)peroxide (succinic acid peroxide) and
the like. Chain transfer agents such as thioglycolic acid and the
like are used to regulate the molecular weight of the polymer
produced in such processes.
It is within the scope of preparing the carboxy-containing polymers
of conjugated dienes to react polymers such as hydroxy terminated
polymers with an anhydride of an unsaturated dicaboxylic acid such
as maleic anhydride, citraconic anhydride, .[..]. .Iadd.anhydride
.Iaddend.itaconic anhydride, chloromaleic anhydride and the like to
produce polymers with attached groups terminated with a carboxy
group. Other carboxy containing diene polymers can be prepared in
emulsion systems incorporating reactive unsaturated carboxylic acid
monomers.
Also diene polymers can be modified with peroxide and unsaturated
reactive carboxylic acids or thio .[.containing .].
.Iadd.containing .Iaddend.carboxylic acids to give carboxy
containing polymers.
The ratio of unsaturated polyester to carboxy-containing polymer of
a conjugated diene generally ranges from about 15:1 to 0.5:1,
preferably from about 5:1 to 1:1.
Representative vinyl monomers include styrene, vinyltoluene,
divinylbenzene, 2-vinylpyridine, diallyl phthalate, triallyl
isocyanurate, .alpha.-methylstyrene, alkyl acrylates and alkyl
methacrylates in which the carbon atoms in the alkyl groups range
from 1 to about 6 and the like and mixtures thereof. The presently
preferred vinyl monomer is styrene because of its availability,
reactivity, cost and desirable properties. Total vinyl monomer from
all sources is 15 to 300, preferably 30 to 200 parts by weight
vinyl monomer per 100 parts by weight polyester plus polymer of a
conjugated diene.
The catalysts used in this invention are conventional free radical
polymerization initiators selected from among organic peroxides and
hydroperoxides such as benzoyl peroxide, dicumyl peroxide, methyl
ethyl ketone peroxide, lauryl peroxide, cyclohexanone peroxide,
t-butyl perbenzoate, t-butyl hydroperoxide, t-butylbenzene
hydroperoxide, cumene hydroperoxide, t-butyl peroctoate and the
like. In addition, azo compounds such as azobis-isobutyronitrile
can be employed. A presently preferred catalyst is t-butyl
perbenzoate. The catalyst is generally used in the range from about
0.1 to 10 parts by weight per 100 parts by weight polyester plus
carboxy-containing polymer of a conjugated diene, more preferably
from about 1-5 parts by weight catalyst.
The reinforcing agents used in this invention comprise fibers
selected from among glass, asbestos, carbon, graphite, metal,
synthetic polymers such as polyamides, polyester, polyolefins and
the like and natural fibers such as cotton, jute, hemp, sisal,
flax, wood, paper and the like. A presently preferred fiber is
glass. The fibers can be used in the form of mats, fabrics,
threads, chopped fiber and the like. The quantity of reinforcing
agent is generally used in the range from about 20 to 300 parts by
weight per 100 parts by weight polyester plus carboxy-containing
polymer of a conjugated diene, more preferably from about 40 to 200
parts by weight reinforcing agent.
Desirably, from about 0.2 to 20 parts by weight, preferably from
about 1 to 10 parts by weight per 100 parts by weight of polyester
plus carboxy-containing polymer of a conjugated diene of an oxide
or hydroxide of a Group II metal are added to the compositions of
this invention. Exemplary of such compounds are the oxides and
hydroxides of magnesium, calcium, strontium, barium and zinc. The
compounds provide a thickening function.
In addition to the previously named components of the compositions
of this invention other optional additives can be used. These
include fillers, pigments, colorants, lubricants, stabilizers,
silane coupling agents and the like. Fillers include calcium
carbonate, calcium silicate, talc, clay, alumina, aluminum
hydroxide, antimony trioxide, silica, mica, barium sulfate, calcium
sulfate, and the like and mixtures thereof. Presently preferred
fillers include calcium carbonate, clay and talc because of
availability and cost. The quantity of filler, when used, is
generally used in the range of from about 50 to 1000 parts by
weight per 100 parts by weight polyester plus carboxy-containing
polymer of a conjugated diene, more preferably from about 200 to
800 parts by weight filler.
A lubricant such as aluminum, barium, calcium, magnesium or zinc
stearate and the like in the range of from about 0.2 to 20 parts by
weight, more preferably from about 1 to 15 parts by weight per 100
parts by weight carboxy-containing polymer of a conjugated diene
plus polyester can be used to impart mold release properties to the
compositions.
A stabilizer such as a barium or cadmium soap, a tin compound such
as tin octanoate, a phosphite such as dimethyl phosphite,
tris(nonylphenyl)phosphite, alkyl phenols such as BHT, quinones,
amines, and the like can be employed in an amount ranging from
about 0.02 to 5 parts by weight per 100 parts by weight polyester
plus carboxy-containing polymer of a conjugated diene.
Conventional colorants and pigments such as TiO.sub.2, carbon
black, phthalocyanine pigments and the like, and mixtures thereof,
are employed as desired in amounts sufficient to give the desired
color to the final molded product. The compositions of this
invention possess outstanding pigmentability and smoothness. The
ingredients are incorporated by a milling technique which involves
moderate shear. This can be accomplished by means of twin-rotor
mixtures designed to give moderate shear to the paste-like
ingredients. It is essential to provide some shear and because of
the viscosity of the materials being mixed, proper mixing cannot be
obtained simply by stirring or by using a conventional impeller
mixer. On the other hand, high intensity mixing which would
generate excessive heat and activate the catalyst must be avoided
also. Sheet molding compounding line mixing equipment can also be
used. This mixing under sufficient shear to achieve good dispersion
of the ingredients without heat buildup sufficient to activate the
catalyst insures a good blend and is necessitated by the fact that
the polymer of the conjugated diene is a normally solid material as
opposed to a liquid or semi-solid. Shear which gives a heat
build-up of 1-50, preferably 2.degree.-30.degree. C. is
satisfactory.
The curing can be done at a temperature known in the art for the
particular catalyst utilized. Generally a temperature of
100.degree. to 200.degree. C. and a time of 1 to 15 minutes in a
press is sufficient.
EXAMPLE
Thermosetting compositions were prepared using a variety of
butadiene rubbers, some being carboxy-terminated and a commercially
available unsaturated polyester resin (3702-5, Koppers Co.). The
polyester was essentially a 0.9:1 mole ratio fumaric acid/propylene
glycol resin with some maleic acid units as indicated by nuclear
magnetic resonance analysis.
Each composition was prepared by mixing a solution of the rubber
dissolved in styrene with about 1/4 of the calcium carbonate filler
in a Baker-Perkins sigma mixer for 5 minutes. The remaining calcium
carbonate was then added and mixed an additional 5 minutes. A
mixture of the polyester resin dissolved in styrene, magnesium
hydroxide thickener, zinc stearate mold release agent and t-butyl
perbenzoate catalyst which had been premixed was then added and
mixed for 15 minutes. The chopped fiber glass reinforcing agent was
added in 2 increments to the mixture and mixing was continued an
additional 10 minutes. Plaques, measuring 6 inches .times.6
inches.times.0.15 inches (15.2.times.15.2.times.0.38 cm), were
compression molded from each composition for 5 minutes at
300.degree. F. (149.degree. C.) and 7,000 psig (48.3 MPa gage).
Each plaque was then evaluated to determine its physical
properties. The nature and quantity of each component used and
physical properties determined are presented in Tables I and II.
Microstructure of the polymers of conjugated dienes in Table I was
normalized in consideration of styrene content. All of the
ingredients in Table II are in parts by weight.
The physical properties were determined in accordance with the test
procedures as follows:
Flexural modulus and flexural strength, ASTM D790.
Tensile and elongation, ASTM D256.
Shrinkage, ASTM D955.
Gloss, ASTM D523.
Average roughness, height in microns, was measured by a Bendix
Profilometer, Type QBA, LX-6 tracer, FT Skidmount.
Reverse impact, height in inches, was determined by dropping a 0.6
lb. (277 g) dart with rounded tip on a plaque. Failure is indicated
in inches at which a crack or cracks appear on the reverse
side.
Carboxy content was determined by calculation based on the
molecular weight and amount of CO.sub.2 coupling agent used. The
carboxy content of polymer G was also determined by titration with
sodium methoxide using thymol blue indicator and the results
correlated well with the calculated value.
Molecular weight was determined by .[.gas.]. .Iadd.gel
.Iaddend.permeation chromotography using THF as the solvent.
TABLE 1 ______________________________________ Polymer of
Conjugated Diene Characteristics Micro- struc- ture % Buta-
Molecular Vinyl/ diene Weight Wt. % Trans/ Sty- Inherent Wt. No.
Polymer CO.sub.2 H Cis rene Viscosity Avg. Avg.
______________________________________ A.sup.(a) 0 9/53/38 75/25
0.95 83,000 68,000 B.sup.(b) 0 11/55/34 52/48 1.12 101,000 57,000
C.sup.(c) 0 10/45/45 60/40 0.77 160,000 120,000 D.sup.(d) 0 --
70/30 1.12 128,000 113,000 E.sup.(e) 0.035 -- 70/30 1.21 154,000
125,000 F.sup.(f) 0 -- 70/30 1.77 256,000 209,000 G.sup.(g) 0.26
61/17/22 100/0 0.36 23,800 18,100 H.sup.(h) 0.02 11/47/42 71/29
1.52 177,000 119,000 I.sup.(i) 0.025 75/8/17 71/29 1.11 172,000
130,000 J.sup.(j) -- -- -- -- -- --
______________________________________ .sup.(a) Solprene 1205 block
copolymer. .sup.(b) Solprene 410 block copolymer. .sup.(c) Solprene
414 radial block copolymer. .sup.(d) Linear styrenebutadiene block
copolymer. .sup.(e) Butadienestyrene carboxyterminated block
copolymer containing less than 10% styrenebutadiene X
butadienestyrene linear block copolymer where X is a coupling
agent, the coupled polymer being produced as the carboxyterminated
polymer is formed. .sup.(f) Linear styrenebutadiene-styrene block
copolymer. .sup.(g) CO.sub.2 H terminated polybutadiene. .sup.(h) A
mixture of polymers consisting of about 48 wt. % styrenebutadiene
block polymer of about a wt. average molecular weight of 100,000
containing the CO.sub.2 H end groups, about 46 wt. %
styrenebutadiene X butadienestyrene linear block copolymer of about
200,000 wt. average molecular weight and about 6 wt. % polystyrene
of about 6,000 wt. average molecular weight (CO.sub.2 H
terminated). .sup.(i) Block copolymer, CO.sub.2 H terminated, 30%
coupled similar to polymer H. .sup.(j) Commercially available
polyvinyl acetate based product for use i polyester formulations
from Union Carbide.
TABLE II
__________________________________________________________________________
Run Number 1 2 3 4 5 6 7 8 9
__________________________________________________________________________
Polymer J 0 0 16 0 0 0 0 0 0 Polymer A 0 0 0 26 0 0 0 0 0 Polymer B
0 0 0 0 25 25 26 0 0 Polymer C 0 0 0 0 0 0 0 25 0 Polymer D 0 0 0 0
0 0 0 0 26 Polymer E (0.035% COOH) 0 0 0 0 0 0 0 0 0 Polymer F 0 0
0 0 0 0 0 0 0 Polymer G (0.26% COOH) 0 0 0 0 0 0 0 0 0 Polymer H
(0.02% COOH) 0 0 0 0 0 0 0 0 0 Polymer I (0.025% COOH) 0 0 0 0 0 0
0 0 0 Styrene monomer 34 34 40 51 53 53 51 56 75 Polyester resin 66
66 40 49 50 50 49 50 49 Calcium carbonate 300 300 300 370 376 376
370 376 368 Zinc stearate 3.5 3.5 3.5 4.3 4.4 4.4 4.3 4.4 4.3
Magnesium hydroxide 1.9 1.9 1.9 2.4 0 0 2.4 2.4 2.4 t-butyl
perbenzoate 0.94 0.95 0.94 1.2 1.2 1.2 1.2 1.2 1.2 1/4" glass fiber
71 71 70 87 125 125 87 88 86 Days molded after compounding 5 0 0 0
0 4 7 0 7 Flexural modulus, psi .times. 10 2,220 2,080 1,860 1,640
1,740 1,720 nd 1,720 1,310 Flexural strength, psi 15,700 13,800
10,500 12,200 10,600 10,300 nd 11,300 10,800 Tensile break psi
4,230 3,980 4,720 5,020 .[.75,790.]. 3,490 nd 6,660 4,130
.Iadd.5590.Iaddend. Elongation, % 1 2 2 2 3 2 nd 3 2 Notched Izod
impact, ft. lbs/in. 3.5 2.3 2.4 2.9 0.95 1.0 nd 2.6 2.4 Unnotched
Izod impact, ft. lbs/in. 4.4 4.1 4.4 4.0 1.9 2.8 nd 3.4 4.4 Reverse
impact, inches (0.6 lb. dart) 4 <3 3-6.sup.(a) <3 nd nd 6
<3 3.5 Shore D Hardness 92 95 90 90 nd nd nd 90 90 Average
roughness, microns 0.22 0.46 0.45 0.74 0.40 0.55 nd 1.1 0.45
Shrinkage, mil/inch 3 3 -0.2 0 -0.8 -0.3 nd -0.1 0.3 Gloss, % at
60.degree. angle nd 60 28 nd nd nd nd 19 19 Density, g/cc nd 2.1
2.0 2.0 nd nd nd 1.9 nd Remarks Control Control Control Control
Control Control Control Control Control
__________________________________________________________________________
Run Number 10 11 12 13 14 15 16 17 18
__________________________________________________________________________
Polymer J 0 0 0 0 0 0 0 0 0 Polymer A 0 0 0 0 0 0 0 0 0 Polymer B 0
0 0 0 0 13 0 0 0 Polymer C 0 0 0 0 0 0 0 0 0 Polymer D 0 0 13 0 0 0
0 0 0 Polymer E (0.035% COOH) 26 0 0 13 0 0 0 0 0 Polymer F 0 26 13
13 0 0 0 0 0 Polymer G (0.26% COOH-Low 0 0 0 0 25 13 0 0 0 MW)
Polymer H (0.02% COOH) 0 0 0 0 0 0 25 25 0 Polymer I (0.025% COOH)
0 0 0 0 0 0 0 0 25 Styrene monomer 75 75 75 75 57 75 73 78 56
Polyester resin 49 49 49 49 50 49 50 50 50 Calcium carbonate 368
368 368 368 374 368 282 376 376 Zinc stearate 4.3 4.3 4.3 4.3 4.4
4.3 4.5 4.4 4.5 Magnesium hydroxide 2.4 2.4 2.4 2.4 2.4 2.4 2.4 2.4
2.4 t-butyl perbenzoate 1.2 1.2 1.2 1.2 1.2 1.2 1.3 1.2 1.2 1/4"
glass fiber 86 86 86 86 88 86 88 88 88 Days molded after
compounding 7 7 7 7 6 7 6 0 0 Flexural modulus, psi .times. 10
1,070 1,150 1,190 1,080 1,420 1,230 1,030 1,230 1,640 Flexural
strength, psi 13,100 9,980 11,200 11,800 13,400 12,900 12,500
14,500 11,300 Tensile break psi 7,280 4,270 5,570 6,000 3,830 4,890
8,090 6,710 5,300 Elongation, % 4 2 3 3 2 3 4 3 3 Notched Izod
impact, ft. lbs/in. 2.6 2.9 3.6 3.6 3.4 3.3 2.5 2.6 4.4 Unnotched
Izod impact, ft. lbs/in. 4.1 4.1 6.5 5.2 4.5 4.9 3.9 4.5 6.6
Reverse impact, inches (0.6 lb. dart) 14 8 5 10 11 10 7 12
6-12.sup.(b) Shore D Hardness 88 90 90 89 nd 90 nd 90 90 Average
roughness, microns 0.25 0.35 0.35 0.28 1.9 1.5 0.32 0.42 0.43
Shrinkage, mil/inch 0.2 0.2 0.4 0.4 -0.2 -0.4 -0.1 -0.1 0 Gloss, %
at 60.degree. angle 56 30 24 45 nd 23 nd 82 78 Density, g/cc nd nd
nd nd nd nd nd 1.9 2.0 Remarks Invention Control Control Invention
Control Control Invention Invention Invention
__________________________________________________________________________
.sup.(a) Broke at 6 inches, did not break at 3. Rerun showed actual
value to be 4 after 6 days aging. .sup.(b) Broke at 12, did not
break at 6. Rerun showed actual value to be 9 after 4 days
aging.
Inspection of the data presented in Table II shows that polyester
compositions in the absence of a polymeric modifier as in control
runs 1 and 2 yield relatively hard, brittle molded plaques with
poor reverse impact values of about 4 inches. The composition of
control run 1 was allowed to mature 5 days at room temperature
before molding. Experience has shown such a maturation period is
desirable to obtain the maximum physical properties and this
feature is observed in the poorer properties shown in run 2.
Control run 3 shows that LP-40A (a commercial polyvinyl acetate
product) included in the composition gives a molded product having
a reverse impact value of up to about 6 inches. However, compared
with run 2, gloss is impaired and flexural strength is somewhat
decreased. The effect of adding various butadiene-styrene
copolymers is shown in control runs 4-9. The results obtained are
about the same as those obtained in control run 3. The increase in
reverse impact strength with the addition of carboxy-terminated
normally solid polymers of conjugated dienes is shown in invention
runs 10, 13, 16, 17 and 18 and such other physical properties as
flexural strength, elongation, gloss and surface roughness (when
determined) are also considered to be satisfactory. Invention run
13 shows that the carboxy-terminated polymers can be admixed with
up to about 50 weight percent of a non-carboxy rubber, such as a
linear block copolymer or a radial block copolymer and still obtain
compositions exhibiting a good balance of physical properties. The
relatively good reverse impact of control run 11 represents an
anomalous result but in any event the gloss is poor. Admixing a
linear block (i.e. ABA) polymer with a linear AB block polymer as
in the run 12 composition gives a reverse impact value about the
same as in the other control runs. Control runs 14 and 15 show that
while good reverse impact can be obtained with low molecular weight
carboxy terminated polymer, the compositions are unsatisfactory
because of high surface roughness. Invention run 16 has a reverse
impact strength of 7 at a low loading of calcium carbonate. At the
same low loading of calcium carbonate a control run made without
the normally solid carboxy-containing polymer of a conjugated diene
had a reverse impact strength of 3.5 inches.
A visual examination of the molded plaques of the invention showed
uniform pigmentation compared with a mottled appearance of the
sample using the commercial polyvinyl acetate modifier (run 3).
While this invention has been described in detail for the purpose
of illustration it is not to be construed as limited thereby but is
intended to cover all changes and modifications within the spirit
and scope thereof.
* * * * *