Note: Descriptions are shown in the official language in which they were submitted.
2~09~
--1--
POLYPHENYLENE SULFIDE RESIN CO~lPOSITION
BAC~GROU~D 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, polybu~ylene
terephthalate, polyacetals and the like. Therefore,
polyphenylene sulfide resins have been excluded from
usin~ in a certain, relatively wi.de range of applications.
Upto the date, it has been establis}led to im~rove
the toughness or impact strengtll properties of polyphellylene
sulfide by blending Witll a flexible pol~mer. ~or example,
Japanese Patent Public Disclosure (I~OI~Al) No. a9-207921
discloses a method in ~YhiCh a polyphenylelle sulfide ma~erial
i.s blended with an epoxy resin and a modified ~-olefin
2~0~0~
--2--
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 poly-
phenylene sulfide materials that have been treated withtechniques 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
~-olefin and a glycidyl ester of ~,~-unsaturated carboxylic
acid, see Japanese Patent Public Disclosure No. 62-153343.
However, the impact resistance properties of polyphenylene
sulfide cannot be acceptably improved even Wit}l these
compositions.
Further, various polyphenylene sulfide compositions
has been proposed, which comprise polyphenylene sulfide
materials that have been modified ~vith techni4ues to
20~9~7
--3--
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 compris-
ing an amino and/or amide-containing polyphenylene sulfide
and a thermoplastic elastomer, see Japanese Patent Public
Disclosure No. 61-207462. ~y 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.
10 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-copolymeri~ed. 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 dlspersion.
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 - S mol% of
amino groups on the basis of the phenylene sulfide repeating
units, and
3f~
~4-
(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,
o-f 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 inventi.on 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 300C 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,
25 preferably from 1,000 to 20,000 poi.ses after curing as
measured simi.larly. If the polyphenylene sulride material
has a melt viscosity of less than 400 poises before curing
or a melt viscosity less than 500 poises af-ter curing,
the intended improvement in the toughness properties of
the composition is achieved only to an unsa-tisfactory
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. Ilowever, a
preferred example of the methods for this purpose comprises
2~60~07
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:
~ S -
The polyphenylene sulfide material may comprise less
than 30 mol%, preferably less than 10 mol%, of one or more
comonomer.
-6- 2~0907
~- S -
m-phenylene sulfide,
S
o-phenylene sulfide,
S ~ SO2 - phenylene sulfide sulfone,
~ S ~ CO - phenylene sulfide ketone,
5 ~ S ~ O - phenylene sulfide ether,
0~ S - dlphenylene 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 ~ormula:
NH2
X ~ (~)n
where X is a halogen, Y is hydrogen, -NH2 or a halogen, each
R is a hydrocarbyl group containing 1 - 12 carbon atoms, and
n is an integer of O - 4.
.
.. . .. .
~7~ 2~907
Typical examples of the halide reactants include
m-fluoroaniline, m-chloroaniline, 3,5-dichloroaniline1
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 agains~ 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-E-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 welght
of polymer to be produced by the polymerization.
The polymerization is effected with stirring at
a temperature of 200 - 300C, preferablY 220 - 280C, for
a period of 0.5 - 30 hours, preferablY l - 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 - 280C for 1 - 12 hours.
-8- 2~6~07
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 - about 280C 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 pre*erred.
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-me~hyl
fumarates; mono- and di-ethyl itaconates; acryl and
_9_
methacryl amides; maleic m.ono- and di-amides; maleic-N-
rnonoethyl amide, maleic-N,N-diethyl amide, maleic-N-
monobutyl amide, maleic-N,N-dibutyl amide, fumaric mono-
and di-amides, fumaric-~-monoethyl amide, fumaric-N,N-
S diethyl amide, fumaric-N-monobutyl amide, fumaric-~,N-
dibutyl amide, maleimide, N-butyl maleimide, N--phenyl
maleimide, sodium acrylate and methacrylate, potassium
acrylate and methacrylate, and the like. Tllese monorners
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 copolymeri%ation 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. Exampl.es of the
peroxides include:
2,5-dimethy]-2,5-di(tert.-bIl~y:I. pcroxy)hexyrIe-3;
2,5-dimethyl-2,5-di(tert.-buI;y:l peroxy)hexaIle;
2,2-bis(tert.-butyl peroxy)-p-diiso-propyl ben%ene
dicumyl peroxide;
di(tert.-butyl peroxide;
tert.-butyl peroxy benzoate;
1,1-bis(tart.-butyl peroxy)-3,3,5--trimethyl cyclohexane;
2,4-dich]orobenzoyl peroxi.de;
benzoyl peroxide;
p-chlorobenzoyl peroxide;
a%obisisobutyroni.trile; and the li.ke.
Preferably, 2,5-dime~hyl-2,5-di(~ert.-butyl
peroxy)hexane or 2,5-di.mei;hyl-2,5-di.(tert~-butyl
peroxy)hexyne-3 i.s used.
2~09~
--10--
The amount of organic peroxide added ranges from
O.G05% 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 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 polyphen~lene 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 - 350C in a suitable machine, such
as kneader, Banbury mixer, extruder or the like. ~or ease
of operation, an extruder may be desirably employed for
3s 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;
~06~3~
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 ~m, milled
fibers of a fiber diameter 3 - 8 ~m, glass flakes and powder
of less than 325 mesh size may be mentioned as suitable
examples.
In addition, provided that the ob;ect 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 polybutadlene, 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, -ll and -12; polyesters, such
as polyethylene terephthalate, polybutylene terephthalate
and polyarylates; polYstyrene, poly ~-methylstyrene.
; . . ................... .. . . .
. ,: .
~o~oi~
-12-
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 Inay 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
re~erence to the following Examples by which the scope
of the invention is not restricted.
PreParation 1
Synthesis of amlno-containin~ Polyphenylene sulfide
A 15 liter-capacity autoclave was charged with 5
liters of N-methyl-2-pyrrolidone (referred to as ~MP
hereinafter) and heated to a temperature of 120C. To the
heated autoclave, 1.866 g of Na2S-2.8H20 was introduced.
The mixture was heated slowly to 205C over a period of
about 2 hours with stirring so as to dis~ill 407 g of water
off the autoclave. After the reaction system was cooled
down to 140C, 2080 g of p-dichlorobenzene was added. The
autoclave was sealed and the reaction mixture was heated
2~3~0~3r7
-13-
to 225C and allowed to polymerize for 3 hours at this
temperature. Then the temperature of the reaction was
raised up to 250C. When 250C was attained, a solution of
3,5-diaminochlorobenzene 20.2 g (corresponding to about 1
mol% of the p-chloroben~ene used hereinabove) in 50 mQ NMP
was injected into the reaction system, which was allowed to
be polymerized at 250C 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-diaminochloro-
benzene 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 300C 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 235C for a
further period of 2 hours in air to give a cured polymer
product having an lncreased 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 230C 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.
2~907
-14-
PreParation 3
Synthesis of amino-containing polyPhenylene sulfide
The general procedure of the preceding Preparation 1
was 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 250C over a period of one hour and 20
minutes and allowed to polymerize at 250C 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 235C 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-diamino-
chlorobenzene.
The resulting polYmer had a melt viscosity of
550 poises. Then the polymer was thermally cured in air at
235C 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.
PrePa-ration 5
Synthesis of amino-containinF 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,
2~0907
-15-
and that the temperature of the reaction mixture was slowly
raised to 250C over a period of one hour and 20 minutes
and then the mixture was allowed to polymerize at 250C
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 235C
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-containinF 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 250C over a period of one
hour and 20 minutes and then the mixture was allowed to
polymerize at 250C 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) revéaled a 3,5-diaminochlorobenzene conversion
of 38%.
The polymer was thermally cured in a.ir at 235C 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.
-16- 2~6~907
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 210C. During passage through the
extruder, the premix was kneaded and allowed to react.
By this procedure, pellets of a graft copolymerized, high
- 10 density polyethYlene were prepared.
PreParation 8
PreParation of carboxylic ~roup-containinF olefinic
coPolymer
An ethylene-butene-1 copolymer (commercially avail-
able under trade mark TAFMER A4090) 100 parts by weight waspremixed 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 220G. 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-l 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 "modifled P0".
ExamPle
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 300C to produce pellets thereof. A sample of
the pellets was in~ection molded at a temperature of 300C
to prepare various test specimens to be sub~ected to tests
of:
-17- 2~6~07
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/cm2
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 125C 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 lO~o 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 mi.xed in various
.
3 ~
-18-
relative proportions as given in Table 1. Each of the
mixtures was processed and tested as in Example l. I`he
results are al.so shown in Table l.
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 sho~Yn 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 ] and the modified P0 from
Preparation 8 were mixed in relative proportions of 90% and
10% by weight. The mixtllre was subjected to the process as
described in Example 1. However, during the melt-kneading
- 20 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 -I;he invel-ltion, a
specially prepared polypherlylelle suJ.f:i(le ma-(;el:ial. contaiJlirlg
a speci-fied amount of amino groups is formulated with a
specially modified polyethylene material so as to provide
a po].yphenylene su].fide resin composition which retains the
desired proper-ties, SUC}l as high temperature resistance and
chemical resis-tance, possessed originally by the unmodified
polyphenylene sul.fide itseli` and is significantly improved
in the toughness properties, such as impact strength, and
in the tensile elongation properties.
-l9- 206~907
~ sO\o o o o __ ~ ~ ~ ~o lo _ _
oQ~
u~ ? .
o~Ei _ _ _ _ X
.,_1 ~ ~_ C'~ C`l O ~ ~ ~ ~ O U~ ~ ~ O ~
~ o ~ C~ ~ o ~ ~ C~ ~ ~ o o o
m ' ~ _
s ~ e o
~ b~ S E u) u~ o u~ ~ t~) ~`1 ~ c~~ c~ ~ c,
H E ~ _ . w
Co~ ~ ~ C'~ CO ~ ~ C~ ~ C~ C~ ~ U~
E~
-- U~S~ _
~ - ~ ~ - -
E~ S- ~0 . o~ .
s ~ ~ e4~ . . _ O _
~ ~ 1~ _ __ _
o\ H N O O t-- O O O O O O
~1 ~ 0~ _ __ _ _ _ __ _
O H O _ _ O _
e ~ ~ ='~
H O ~ o O C~ O O O
~ C`l ~ ~ ~ c~l ~ ~ Ln CD t- 0~
_ saldul~x~ saldulex~ aA~ dulo~
