Polyphenylene sulfide resin composition

A polyphenylene sulfide resin composition improved in the impact strength, toughness, high temperature resistance and solvent resistance properties is disclosed. The composition comprises PA0 (A) 60-99.5% by weight of a thermally cured polyphenylene sulfide material having a melt viscosity of 500-30,000 poises and which has been derived, by thermally curing, from a polyphenylene sulfide having a melt viscosity of 400 poises of higher and containing 0.05-5 mol % of amino groups on the basis of the phenylene sulfide repeating units, and PA0 (B) 40-0.5% by weight of a modified polyethylene material comprising at least one polyethylene onto which at least one unsaturated carboxylic acid and/or derivative thereof is graft-copolymerized in a proportion of 0.1-10% by weight of the total weight of said modified polyethylene material.

BACKGROUND OF THE INVENTION 
1. Field of the Invention 
This invention relates to a resin composition comprising a specified class 
of polyphenylene sulfides containing amino groups and a modified 
polyethylene on to which at least one unsaturated carboxylic acid and/or 
derivative thereof is graft-polymerized and, more particularly, to such a 
composition exhibiting excellent impact, toughness, high-temperature 
resistance and solvent resistance properties. 
2. Prior Art 
Polyphenylene sulfide resins are known as a class of highly functional 
resins exhibiting excellent high-temperature resistance, fire retardance, 
chemical resistance, moldability, shapability and electrical 
characteristics and the like, and recently are used widely in applications 
including the production of electrical and electronic parts, automotive 
parts, etc. 
Polyphenylene sulfide resins may be substantially improved in their 
properties such as strength, rigidity, high-temperature resistance, 
toughness, dimensional stability, etc., by incorporating them with fibrous 
reinforcements, such as glass fibers or carbon fibers, or inorganic 
fillers, such as talc, clay or mica. Generally, polyphenylene sulfide 
resins, however, suffer from a serious drawback that they exhibit poor 
ductility properties and are brittle as compared with other known 
engineering plastics such as nylons, polycarbonates, polybutylene 
terephthalate, polyacetals and the like. Therefore, polyphenylene sulfide 
resins have been excluded from using in a certain, relatively wide range 
of applications. 
Upto the date, it has been established to improve the toughness or impact 
strength properties of polyphenylene sulfide by blending with a flexible 
polymer. For example, Japanese Patent Public Disclosure (IOKAI) No. 
59-207921 discloses a method in which a polyphenylene sulfide material is 
blended with an epoxy resin and a modified .alpha.-olefin copolymeric 
elastomer having an unsaturated carboxylic acid or anhydride or a 
derivative thereof graft-copolymerized thereon. Further, methods 
comprising blending a polyphenylene sulfide material with an 
ethylene-glycidyl methacrylate copolymer are known, for example, in 
Japanese Patent Public Disclosures Nos. 58-1547 and 59-152953. However, 
the backbones of the ordinary polyphenylene sulfide molecules lack any 
effectively reactive site. Therefore, even if a significantly reactive 
olefin copolymer is added to such an ordinary polyphenylene sulfide 
material, the added copolymer may exhibit only a poor adhesion or bonding 
at the interface between the additive and the polyphenylene sulfide 
material, resulting an unacceptable improvement in the impact resistance. 
Furthermore, there may be serious difficulties that the resulting blend 
shows deteriorated high-temperature resistance and solvent resistance 
properties. 
On the other hand, various polyphenylene sulfide compositions have been 
proposed, which comprise polyphenylene sulfide materials that have been 
treated with techniques to improve the adhesion or bonding at the 
interface between the polyphenylene sulfide and a flexible polymer 
additive. Examples of the compositions of this type which may be mentioned 
include a composition comprising a polyphenylene sulfide that has been 
treated with an acid and washed, in combination with a modified olefin 
copolymer having an unsaturated carboxylic acid or anhydride 
graft-copolymerized thereon, see Japanese Patent Public Disclosure No. 
62-169854; and a composition comprising a polyphenylene sulfide in 
combination with an olefin copolymer formed of an .alpha.-olefin and a 
glycidyl ester of .alpha.,.beta.-unsaturated carboxylic acid, see Japanese 
Patent Public Disclosure No. 62-153343. However, the impact resistance 
properties of polyphenylene sulfide cannot be acceptably improved even 
with these compositions. 
Further, various polyphenylene sulfide compositions has been proposed, 
which comprise polyphenylene sulfide materials that have been modified 
with techniques to improve the adhesion or bonding at the interface 
between the polyphenylene sulfide and a flexible polymer additive. An 
example which may be mentioned is a composition comprising an amino and/or 
amide-containing polyphenylene sulfide and a thermoplastic elastomer, see 
Japanese Patent Public Disclosure No. 61-207462. By this approach, the 
adhesion or bonding at the interface between the polyphenylene sulfide and 
the thermoplastic elastomer may be improved only to an extent that is 
unsatisfactory in practice. 
SUMMARY OF THE INVENTION 
An object of primary importance of the invention is to provide a 
polyphenylene sulfide resin composition that is significantly improved in 
the impact resistance and toughness properties and is substantially freed 
from the problems and difficulties experienced with the above-discussed 
prior art. 
Accordingly, the present invention relates to a resin composition 
comprising a thermally cured, specific polyphenylene sulfide material 
modified by inclusion of amino groups in the molecule and which has a 
viscosity in a specified range before curing and another specified 
viscosity after curing, in conjunction with a modified polyethylene 
material on to which 0.5-10% by weight of at least one unsaturated 
carboxylic acid and/or derivative thereof is graft-copolymerized. In the 
composition, the modified polyethylene material exhibits an enhanced 
adhesion or bonding at the interface between the polyphenylene sulfide and 
polyethylene materials and permits formation of a homogeneous dispersion. 
Accordingly, the invention provides a polyphenylene sulfide resin 
composition which comprises 
(A) 60-99.5% by weight of a thermally cured polyphenylene sulfide material 
having a melt viscosity of 500-30,000 poises and which has been derived, 
by thermally curing, from a polyphenylene sulfide having a melt viscosity 
of 400 poises or higher and containing 0.05-5 mol % of amino groups on the 
basis of the phenylene sulfide repeating units, and 
(B) 40-0.5% by weight of a modified polyethylene material comprising at 
least one polyethylene onto which at least one unsaturated carboxylic acid 
and/or derivative thereof is graft-copolymerized in a proportion of 
0.1-10% by weight of the total weight of said modified polyethylene 
material. 
DETAILED DESCRIPTION OF THE INVENTION 
The invention will be described in more detail. 
Preferably, the amino-containing polyphenylene sulfide material which is 
used in the present invention has an amino-group content of 0.05-5 mol % 
and, particularly, of 0.1-3 mol %. If the amino-group content is less than 
0.05 mol %, there is little advantage achieved by the inclusion of amino 
groups. If the amino-group content is greater than 5 mol %, then the 
advantageous effect by the inclusion of amino groups is undesirably offset 
by deterioration of the mechanical strength properties. 
The amino-containing polyphenylene sulfide material which is used in the 
invention should have a melt viscosity of not less than 400 poises, 
preferably not less than 500 poises before curing, as measured in a KOHKA 
type flow tester at 300.degree. C. using an orifice of a 0.5 mm diameter 
and a 2 mm length under a load of 10 kg, and should have a melt viscosity 
in the range of from 500 to 30,000 poises, preferably from 1,000 to 20,000 
poises after curing as measured similarly. If the polyphenylene sulfide 
material has a melt viscosity of less than 400 poises before curing or a 
melt viscosity less than 500 poises after curing, the intended improvement 
in the toughness properties of the composition is achieved only to an 
unsatisfactory extent. If the cured polyphenylene sulfide material has a 
melt viscosity of greater than 30,000 poises, then the moldability of the 
composition becomes unacceptably deteriorated. 
The method for preparing the amino-containing polyphenylene sulfide 
materials to be used in the present invention is not limited to any 
specific one. However, a preferred example of the methods for this purpose 
comprises conducting a polymerization by reacting an alkali metal sulfide 
with a dihalobenzene in an organic amide solvent in the presence of an 
amino-containing aromatic halide compound. Especially, it is preferred 
that the amino groups are introduced at ends of the molecule of 
polyphenylene sulfide. 
Examples of the alkali metal sulfides which may be used include lithium, 
sodium, potassium, rubidium and cesium sulfide and mixtures thereof. These 
may be in hydrated form. The alkali metal sulfide may be prepared by 
reacting an alkali metal hydrosulfide with an alkali metal base. The 
alkali metal sulfide may be formed in situ prior to introduction of the 
dihalobenzene reactant into the polymerization system, or may be prepared 
out the polymerization system before use. 
The amino-containing polyphenylene sulfide material should preferably 
comprises at least 70 mol % and more preferably at least 90 mol % of 
structural unit represented by: 
##STR1## 
The polyphenylene sulfide material may comprise less than 30 mol %, 
preferably less than 10 mol %, of one or more comonomer. 
______________________________________ 
##STR2## m-phenylene sulfide, 
##STR3## o-phenylene sulfide, 
##STR4## phenylene sulfide sulfone, 
##STR5## phenylene sulfide ketone, 
##STR6## phenylene sulfide ether, 
##STR7## diphenylene sulfide. 
______________________________________ 
The amino-containing aromatic halide reactants which may be used in the 
synthesis of the amino-containing polyphenylene sulfide material according 
to the invention are of the general formula: 
##STR8## 
where X is a halogen, Y is hydrogen, --NH.sub.2 or a halogen, each R is a 
hydrocarbyl group containing 1-12 carbon atoms, and n is an integer of 
0-4. 
Typical examples of the halide reactants include m-fluoroaniline, 
m-chloroaniline, 3,5-dichloroaniline, 3,5-diaminochlorobenzene, 
2-amino-4-chlorotoluene, 2-amino-6-chlorotoluene, 4-amino-2-chlorotoluene, 
3-chloro-m-phenylenediamine, m-bromoaniline, 3,5-dibromoaniline and 
m-iodoaniline and mixtures thereof. Especially preferred is 
3,5-diaminochlorobenzene. 
Examples of the dihalobenzene reactants include p-dichlorobenzene, 
p-dibromobenzene, p-diiodobenzene, m-dichlorobenzene, m-dibromobenzene, 
m-diiodobenzene, 1-chloro-4-bromobenzene and the like. 
The molar ratio of the alkali metal sulfide reactant to the total of the 
dihalobenzene and amino-containing aromatic halide reactants is preferably 
in the range of from 1.00:0.90 to 1.00:1.10. 
As the polymerization medium, a polar solvent, in particular an organic 
amide solvent that is aprotic and is stable against alkali at raised 
temperatures is preferred. Typical examples of suitable organic amide 
solvents include N,N-dimethyl acetamide, N,N-dimethyl formamide, 
hexamethyl phosphoramide, N-methyl-.epsilon.-caprolactam, 
N-ethyl-2-pyrrolidone, N-methyl-2-pyrrolidone, 
1,3-dimethylimidazolidinone, dimethyl-sulfoxide, sulfolane, 
tetramethylurea and the like and mixtures thereof. 
The organic amide solvent may be used in an amount of 150-3500%, preferably 
250-1500%, by weight of the weight of polymer to be produced by the 
polymerization. 
The polymerization is effected with stirring at a temperature of 
200.degree.-300.degree. C., preferably 220.degree.-280.degree. C., for a 
period of 0.5-30 hours, preferably 1-15 hours. 
The polymerization degree of the product polymer produced by the above 
method may be enhance by heating the product polymer in an 
oxygen-containing atmosphere, e.g. air or by adding, for example, a 
peroxide to the polymer and then heating the mixture so as to cure the 
polymer. Such a thermal curing treatment may be effected, for example, at 
temperatures in the range of 200.degree.-280.degree. C. for 1-12 hours. 
Especially, in order to obtain a composition of excellent impact resistance 
and toughness properties, preferably, the amino-containing polyphenylene 
sulfide is cured by heating it in a nonoxidizing, inert gas at a 
temperature in the range of about 200.degree.--about 280.degree. C. for a 
period of 1-24 hours. Examples of the nonoxidizing, inert gases which may 
be used include helium, argon, nitrogen, carbon dioxide, steam and the 
like and mixtures thereof. For an economical operation, nitrogen is 
preferably used. 
The modified polyethylene material used in the invention is a polyethylene 
on to which 0.1-10% by weight of an unsaturated carboxylic acid and/or 
derivative is graft-copolymerized. 
The term "polyethylene" as used herein is intended to refer at lease one, 
such as high density polyethylene, low density polyethylene, linear low 
density polyethylene and the like, with high density polyethylene most 
preferred. 
The modified polyethylene material used in the invention has a content of 
unsaturated carboxylic acid and/or derivative ranging from 0.1 to 10%, 
preferably from 1 to 5%, by weight. If the content is less than 0.1 wt. %, 
the advantageous effect achieved by modification with the acid component 
is not significant. On the other hand, if the content is greater than 10 
wt. %, then the mechanical strength properties become seriously 
deteriorated. 
Examples of the unsaturated carboxylic acids and/or derivatives thereof 
which may be used include acrylic, methacrylic, maleic, fumaric, itaconic 
and citraconic acids and derivatives thereof. Such an acid or derivative 
will be referred to as "monomer" hereinafter. 
Examples of acid derivatives include anhydrides, esters, amides, imides and 
metal salts. Particular examples include maleic, citraconic and itaconic 
anhydrides; methyl-, ethyl- and butyl-acrylates and methacrylates; 
glycidyl acrylate; mono- and di-ethyl malates; mono- and di-methyl 
fumarates; mono- and di-ethyl itaconates; acryl and methacryl amides; 
maleic mono- and di-amides; maleic-N-monoethyl amide, maleic-N,N-diethyl 
amide, maleic-N-monobutyl amide, maleic-N,N-dibutyl amide, fumaric mono- 
and di-amides, fumaric-N-monoethyl amide, fumaric-N,N-diethyl amide, 
fumaric-N-monobutyl amide, fumaric-N,N-dibutyl amide, maleimide, N-butyl 
maleimide, N-phenyl maleimide, sodium acrylate and methacrylate, potassium 
acrylate and methacrylate, and the like. These monomers may be used singly 
or in combination. Maleic anhydride is most preferred. 
An example of the techniques for graft-copolymerizing the monomer acid on 
to a polyethylene substrate is a process comprising mixing the 
polyethylene substrate with the monomer and a radical generator, for 
example, a peroxide and subjecting the mixture to melt-extrusion operation 
under copolymerization conditions. An alternative process is to suspend or 
dissolve a polyethylene substrate in an appropriate solvent and add a 
monomer and a radical generator to the suspension or solution, which is 
then heated so as to cause the graft-polymerization to proceed. 
The peroxides used for modification in the melt-extrusion process are 
preferably organic peroxides. Any known organic peroxide may be used. 
Examples of the peroxides include: 
2,5-dimethyl-2,5-di(tert.-butyl peroxy)hexyne-3; 
2,5-dimethyl-2,5-di(tert.-butyl peroxy)hexane; 
2,2-bis(tert.-butyl peroxy)-p-diiso-propyl benzene dicumyl peroxide; 
di(tert.-butyl peroxide; 
tert.-butyl peroxy benzoate; 
1,1-bis(tart.-butyl peroxy)-3,3,5-trimethyl cyclohexane; 
2,4-dichlorobenzoyl peroxide; 
benzoyl peroxide; 
p-chlorobenzoyl peroxide; 
azobisisobutyronitrile; and the like. 
Preferably, 2,5-dimethyl-2,5-di(tert.-butyl peroxy)hexane or 
2,5-dimethyl-2,5-di(tert.-butyl peroxy)hexyne-3 is used. 
The amount of organic peroxide added ranges from 0.005% to 2%, preferably 
from 0.1% to 1%, by weight of the weight of polyethylene substrate. 
The present resin composition comprises 60-99.5%, preferably 80-97% by 
weight of the cured, amino-containing polyphenylene sulfide material; and 
40-0.5%, preferably 20-3%, by weight of the modified polyethylene material 
having 0.5-10 wt. % of an unsaturated carboxylic acid and/or derivative 
thereof graft-copolymerized thereonto. If the modified polyethylene 
material is used in a proportion of less than 0.5% by weight, the intended 
improvement cannot be achieved satisfactorily. If the modified 
polyethylene material is in a proportion exceeding 40% by weight, then the 
desirable high-temperature resistance, chemical resistance and rigidity 
properties possessed by the polyphenylene sulfide are seriously damaged 
and the moldability of the composition tends to largely decline. 
The composition according to the invention may be prepared by various known 
methods. The starting material amino-containing polyphenylene sulfide is 
thermally cured before use. The cured polyphenylene sulfide may be mixed 
with the modified polyethylene material having the acid and/or derivative 
graft-polymerized thereonto, in a mixer, such as tumbler mixer, Henschel 
mixer, ball mill, ribbon blender and the like. The mixture in powder or 
pelletized form may be fed into a melt-mixing or blending machine to give 
a resin composition according to the invention. Alternatively, the cured 
polyphenylene sulfide and modified polyethylene materials may be fed to a 
melt-mixing or blending machine and combined into a composition according 
to the invention. Melt-blending may be effected at a temperature of 
250.degree.-350.degree. C. in a suitable machine, such as kneader, Banbury 
mixer, extruder or the like. For ease of operation, an extruder may be 
desirably employed for this purpose. 
Provided that the object of the invention is not significantly spoiled, any 
conventional fibrous or powdery filler may be incorporated in the present 
resin composition; for example, fibers of glass, carbon, silica, alumina, 
silicon carbide, zirconia, calcium titanate, and calcium sulfate; fibers 
of aramide and wholly aromatic polyester, powders or particulates of 
wollastonite, calcium carbonate, magnesium carbonate, talc, mica, clay, 
silica, alumina, kaolin, zeolites, gypsum, calcium silicate, magnesium 
silicate, calcium sulfate, titanium oxide, magnesium oxide, carbon black, 
graphite, iron oxides, zinc oxide, copper oxide, glass, quartz and quartz 
glass; glass beads; and glass balloons. These fillers may be used a 
mixture thereof. If desired, the fillers may be treated with, for example, 
a silane or titanate coupling agent before use. 
Glass fibers, for example, chopped strands of a fiber length 1.5-12 mm and 
a fiber diameter 3-24 .mu.m, milled fibers of a fiber diameter 3-8 .mu.m, 
glass flakes and powder of less than 325 mesh size may be mentioned as 
suitable examples. 
In addition, provided that the object of the invention is not significantly 
spoiled, the present composition may include additives, such as releasing 
agent, lubricant, heat stabilizer, antioxidant, UV absorber, nucleating 
agent, blowing agent, rust-proofing agent, ion-trapping agent, 
flame-retardant, flame-proofing aid, colorant (e.g. dye or pigment), 
antistatic agent or the like; wax; and a minor proportion of other 
polymer. These may be present singly or in combination. 
Examples of the other polymers which may be optionally incorporated 
includes various thermoplastic elastomer, such as olefin-, styrene-, 
urethane-, ester-, fluoride-, amide- and acrylate-based elastomers; 
rubbery polymers, such as polybutadiene, polyisoprene, polychloroprene, 
polybutene, styrene-butadiene rubber and hydrogenates thereof, 
acrylonitrile-butadiene rubber, ethylene-propylene copolymer and 
ethylene-propylene-ethylidene-norbornene copolymer; polyamides, such as 
nylon-6, -6/6, -4/6, -6/10, -11 and -12; polyesters, such as polyethylene 
terephthalate, polybutylene terephthalate and polyarylates; polystyrene, 
poly .alpha.-methylstyrene, polyvinyl acetate, polyvinyl chloride, 
polyacrylates, polymethacrylates, polyacrylonitrile, polyurethanes, 
polyacetals, polyphenylene oxides, polycarbonates, polysulfones, polyether 
sulfones, polyaryl sulfones, polyphenylene sulfide sulfones, polyphenylene 
sulfide ketones, polyether ketones, polyether ether ketones, polyamide 
imides, polyimides, silicone resins, phenoxy resins, fluorine resins and 
the like. Also may be mentioned as example, a class of resins which, when 
molten, form an anisotropic melt phase and may be melt-processed. The 
above-listed optional additive polymers may be used in a variety of forms, 
for example, as a homopolymer or as a random or block graft copolymer. 
They may be used singly or in any suitable combination and may be modified 
before use, if desired. 
Incorporation of the additives into the present composition may be effected 
in any suitable manner. For example, the additives may be added to 
component (A) and/or (B) before or during the composition is prepared. 
Alternatively, the additive may be incorporated into the composition after 
the composition is formulated from components (A) and (B), in particular 
when the composition is molten before use.

EXAMPLE 
The invention will be further illustrated with reference to the following 
Examples by which the scope of the invention is not restricted. 
Preparation 1 
Synthesis of amino-containing polyphenylene sulfide 
A 15 liter-capacity autoclave was charged with 5 liters of 
N-methyl-2-pyrrolidone (referred to as NMP hereinafter) and heated to a 
temperature of 120.degree. C. To the heated autoclave, 1,866 g of Na.sub.2 
S.2.8H.sub.2 O was introduced. The mixture was heated slowly to 
205.degree. C. over a period of about 2 hours with stirring so as to 
distill 407 g of water off the autoclave. After the reaction system was 
cooled down to 140.degree. C., 2080 g of p-dichlorobenzene was added. The 
autoclave was sealed and the reaction mixture was heated to 225.degree. C. 
and allowed to polymerize for 3 hours at this temperature. Then the 
temperature of the reaction was raised up to 250.degree. C. When 
250.degree. C. was attained, a solution of 3,5-diaminochlorobenzene 20.2 g 
(corresponding to about 1 mol % of the p-chlorobenzene used hereinabove) 
in 50 ml NMP was injected into the reaction system, which was allowed to 
be polymerized at 250.degree. C. for a further period of 3 hours. 
Upon completion of the polymerization, the reaction system was cooled to 
room temperature. A sample of the resulting slurry mixture was taken and 
filtered to give a filtrate. The proportion of unconverted 
3,5-diaminochlorobenzene remaining in the filtrate was determined using a 
gas chromatograph apparatus (GC-12A manufactured by Shimadzu Seisakusho 
Ltd.). It was found that 38% of the 3,5-diaminochlorobenzene was 
converted. 
The slurry from the above polymerization was poured into a mass of water so 
as to precipitate the product polymer, which was then filtered off, washed 
with pure water, and hot-vacuum dried overnight. The thus isolated PPS had 
a melt viscosity of 500 poises as measured in a KOHKA type flow tester at 
300.degree. C. using an orifice of a 0.5 mm diameter and a 2 mm length 
under a load of 10 kg. 
The polymer was thermally cured at 235.degree. C. for a further period of 2 
hours in air to give a cured polymer product having an increased melt 
viscosity of 8,000 poises as measured by the above-specified method. The 
thus resulting cured, amino-containing polyphenylene sulfide material will 
be referred to as PPS-I. 
Preparation 2 
Curing of PPS under a non-oxidizing inert atmosphere 
The procedure of Preparation 1 was repeated to give an uncured PPS, which 
was then heated to 230.degree. C. for 10 hours under a nitrogen 
atmosphere. The thus thermally cured amino-containing polyphenylene 
sulfide had a melt viscosity of 1,500 poises. This product will be 
referred to as PPS-II. 
Preparation 3 
Synthesis of amino-containing polyphenylene sulfide 
The general procedure of the preceding Preparation 1 as repeated except 
that 2009 g p-dichlorobenzene and 19.0 g 3,5-diaminochlorobenzene 
(corresponding to about 1 mol % of the p-dichlorobenzene used herein) were 
used in Preparation 3 and that the temperature of the reaction mixture was 
slowly raised to 250.degree. C. over a period of one hour and 20 minutes 
and allowed to polymerize at 250.degree. C. for a further 3 hours so as to 
give an amino-containing polyphenylene sulfide having a melt viscosity of 
110 poises. The proportion of unconverted 3,5-diaminochlorobenzene 
remaining in the filtrate was determined by gas chromatography technique 
using Shimadzu GC-12A. It was found that 36% of the supplied 
3,5-diaminochlorobenzene was converted. This polymer was thermally cured 
in air at 235.degree. C. for a further 2 hours to attain an increased melt 
viscosity of 8,000 poises. The thus resulting cured, amino-containing 
polyphenylene sulfide material will be referred to as PPS-III. 
Preparation 4 
Synthesis of polyphenylene sulfide free of amino groups 
The general procedure of Preparation 1 was repeated except that 2080 g 
p-dichlorobenzene was used with omitting the amino-containing aromatic 
halide, i.e. 3,5-diaminochlorobenzene. 
The resulting polymer had a melt viscosity of 550 poises. Then the polymer 
was thermally cured in air at 235.degree. C. for 2 hours to attain an 
increased melt viscosity of 8000 poises. The thus resulting cured 
polyphenylene sulfide material will be referred to as PPS-IV. 
Preparation 5 
Synthesis of amino-containing polyphenylene sulfide 
An amino-containing polyphenylene sulfide resin was prepared by repeating 
the general procedure of the preceding Preparation 1 except that 2080 g 
p-dichlorobenzene and 18.4 g 2-chloroaniline (corresponding to about 1 mol 
% of the p-dichlorobenzene) were employed in this Preparation 5, and that 
the temperature of the reaction mixture was slowly raised to 250.degree. 
C. over a period of one hour and 20 minutes and then the mixture was 
allowed to polymerize at 250.degree. C. for a further 3 hours. The 
resulting amino-containing polyphenylene sulfide had a melt viscosity of 
480 poises. Analysis of the unconverted 2-chloroaniline remaining in the 
filtrate by gas chromatography (using Shimadzu GC-12A gas chromatograph 
apparatus) revealed a 2-chloroaniline conversion of 35%. 
The polymer was thermally cured in air at 235.degree. C. for a further 2 
hours to give a cured amino-containing polyphenylene sulfide having a melt 
viscosity of 8,000 poises. This cured polymer will be referred to as 
PPS-V. 
Preparation 6 
Synthesis of amino-containing polyphenylene sulfide 
An amino-containing polyphenylene sulfide resin was prepared by repeating 
the general procedure of the preceding Preparation 1 except that 1789 g 
p-dichlorobenzene, and 310 g 3,5-diaminochlorobenzene (corresponding to 
about 15 mol % of the total amount of the p-dichlorobenzene and 
3,5-diaminochlorobenzene present) were employed in this Preparation 6, and 
that the temperature of the reaction mixture was slowly raised to 
250.degree. C. over a period of one hour and 20 minutes and then the 
mixture was allowed to polymerize at 250.degree. C. for a further 3 hours. 
The resulting amino-containing polyphenylene sulfide had a melt viscosity 
that was too low to be determined by the above-specified flow tester 
method. Analysis of the unconverted 3,5-diaminochlorobenzene remaining in 
the filtrate by gas chromatography (using Shimadzu GC-12A gas 
chromatograph apparatus) revealed a 3,5-diaminochlorobenzene conversion of 
38%. 
The polymer was thermally cured in air at 235.degree. C. for a further 10 
hours to give a cured amino-containing polyphenylene sulfide having an 
increased melt viscosity of 6,600 poises. This cured polymer will be 
referred to as PPS-VI. 
Preparation 7 
Graft copolymerization of polyethylene with acid 
A high density polyethylene 97.5 weight % was premixed with maleic 
anhydride 2 weight % and 2,5-dimethyl-2,5-di(tert.-butyl peroxy)hexane 0.5 
weight %. The premix was fed to an extruder machine with a cylinder 
maintained at a temperature of 210.degree. C. During passage through the 
extruder, the premix was kneaded and allowed to react. By this procedure, 
pellets of a graft copolymerized, high density polyethylene were prepared. 
Preparation 8 
Preparation of carboxylic group-containing olefinic copolymer 
An ethylene-butene-1 copolymer (commercially available under trade mark 
TAFMER A4090) 100 parts by weight was premixed with maleic anhydride 1 
part by weight and 1,3-bis(tert.-butyl peroxy propyl) benzene 0.5 parts by 
weight. The premix was fed to an extruder machine with a cylinder 
maintained at 220.degree. C. During passage through the extruder, the 
premix was kneaded and allowed to react. By this procedure, pellets of a 
carboxylic group-containing olefinic copolymer were prepared. 
By IR spectrography, the quantity of maleic anhydride grafted on to the 
ethylene-butene-1 copolymer substrate was confirmed to be 0.75 parts by 
weight of maleic anhydride per 100 parts by weight of ethylene-butene-1 
copolymer. This graft copolymer will be referred to as "modified PO". 
Example 1 
PPS-I from Preparation 1 and the graft copolymerized polyethylene from 
Preparation 7 were mixed in relative proportions of 90% and 10% by weight 
and fed to a vent-type vacuum twin-screw extruder which had a venting 
pressure of 30 Torrs at the vent. In the extruder, the mixture was kneaded 
at 300.degree. C. to produce pellets thereof. A sample of the pellets was 
injection molded at a temperature of 300.degree. C. to prepare various 
test specimens to be subjected to tests of: 
Izod Impact Strength; notched, according to ASTM D-256 
Tensile Elongation; according to ASTM D638, at 5 mm/minute 
Heat Distortion Temperature; according to ASTM D648, with a load of 18.6 
kg/cm.sup.2 
In addition, a 1/8 inch thick test specimen prepared for the heat 
distortion temperature test was subjected to a solvent resistance test, 
where the specimen was immersed in a gasohol mixture comprising gasoline 
and methanol in a weight ratio of 80:20, at a temperature of 125.degree. 
C. for 8 hours. The weight of the specimen was measured before and after 
the immersion test. The solvent resistance performance was rated by the 
difference of the two weights. 
The results are set forth in Table 1. 
Example 2 
PPS-II from Preparation 2 and the graft copolymerized polyethylene from 
Preparation 7 were mixed in relative proportions of 90% and 10% by weight. 
The mixture was processed and tested as in Example 1. 
The results are set forth in Table 1. 
Example 3 
PPS-I from Preparation 1, the grafted polyethylene from Preparation 7, and 
glass fibers were mixed in relative proportions of 63%, 7% and 30% by 
weight. The mixture was processed and tested as in Example 1. The results 
are set forth in Table 1. 
Example 4 
PPS-V from Preparation 5 and the grafted polyethylene from Preparation 7 
were mixed in relative proportions of 90% and 10% by weight. The mixture 
was processed and tested as in Example 1. The results are set forth in 
Table 1. 
Comparative Examples 1 and 2 
The procedure of Example 1 was repeated using either PPS-III or PPS-IV as 
an amino-containing polyphenylene sulfide material. The results are shown 
in Table 1. 
Comparative Examples 3-6 
PPS-I from Preparation 1, the grafted polyethylene from Preparation 7 and 
glass fiber were mixed in various relative proportions as given in Table 
1. Each of the mixtures was processed and tested as in Example 1. The 
results are also shown in Table 1. 
Comparative Example 7 
PPS-I from Preparation 1 and an unmodified high density polyethylene were 
mixed in relative proportions of 90% and 10% by weight. The mixture was 
processed and tested as in Example 1. The results are shown in Table 1. 
Comparative Example 8 
PPS-VI from Preparation 6 and the grafted polyethylene from Preparation 7 
were mixed in relative proportions of 90% and 10% by weight. The mixture 
was processed and tested as in Example 1. The results are shown in Table 
1. 
Comparative Example 9 
PPS-I from Preparation 1 and the modified P0 from Preparation 8 were mixed 
in relative proportions of 90% and 10% by weight. The mixture was 
subjected to the process as described in Example 1. However, during the 
melt-kneading in the vented twin-screw extruder, part of the melt was 
expelled through the vent. This made the extrusion procedure unstable. 
Further, it was found that the resulting pellets had bubbles caught 
therein. Furthermore, the moldings showed a poor appearance. The test 
results are shown in Table 1. 
As above-illustrated, according to the invention, a specially prepared 
polyphenylene sulfide material containing a specified amount of amino 
groups is formulated with a specially modified polyethylene material so as 
to provide a polyphenylene sulfide resin composition which retains the 
desired properties, such as high temperature resistance and chemical 
resistance, possessed originally by the unmodified polyphenylene sulfide 
itself and is significantly improved in the toughness properties, such as 
impact strength, and in the tensile elongation properties. 
TABLE 1 
__________________________________________________________________________ 
Composition (% by weight) Izod Heat Solvent 
Polyethylene Tensile 
impact 
distortion 
resistance 
Graft- 
Un- 
Modi- elonga- 
strength 
temperature 
(increase 
PPS copoly- 
modi- 
fied 
Glass 
tion 
(notched) 
(18.6 kg/cm.sup.2) 
in weight) 
I II 
III 
IV 
V VI 
merized 
fied 
PO fibers 
(%) (kg .multidot. cm/cm) 
(.degree.C.) 
(%) 
__________________________________________________________________________ 
Examples 
1 90 10 10 5 103 2.0 
2 90 10 12 5 102 2.0 
3 63 7 30 3 10 260 1.8 
4 90 10 8 5 103 2.0 
Com- 
parative 
Examples 
1 90 10 3 3 101 2.2 
2 90 10 3 3 101 2.2 
3 100 2 2 105 1.8 
4 70 30 2 7 260 1.7 
5 99.8 0.2 2 2 105 1.8 
6 60 impossible to knead and extrude 
7 90 10 2 2 104 2.5 
8 90 
10 1 1 100 2.2 
9 90 10 5 3 101 2.5 
__________________________________________________________________________