CA2031940A1 - Composition and process for making poly(arylene sulfide) resins reinforced with glass fibers - Google Patents

Abstract

Abstract Continuous glass fiber reinforced composites are made by pultruding the fibers with mixtures of certain silanes and thermoplastic resin in which the silanes have adsorbed onto the thermoplastic resin.

Description

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IMPRnVED COMPOSITION AND PROCESS FOR MAKING
POLY(ARYLENE SULFIDE) RESINS REINFORCED WITH GLASS FIBERS
B kRround of the Inventlon Tlle present invention relates to fiber reinforced thermoplastic msterials.
The production of thermoplastic msterial of poly(arylene sulfide) resins reinforced with unidirectional glass fibers by pultrusion has been disclosed. See, for example, U.S. Patent 4,680,224.
At least one fiber strand of continuous filaments is contacted with a poly(arylene sulfide) resin in the form of a powder or a slurr~. The impregnated strand or strands are then pulled through a temperature controlled die for producing a composite which can have the foro of, for exsmple, a tape, a rod or a sheet.
The glass fiber reinforced pre-preg tapes produced ln this manner are useful for such applications as structural members, aircraft psrts, doctor blades, and the like.
For some applications the continuous fiber reinforced thermoplastic pre-preg tape will be more useful with improved transverse tensile strength and improved hydrolytic stabilit~. For example, doctor blades used to process aqueous-based materials require materials of construction that have good hydrolytic stability and good transverse tenslle strength. Llkewise, structural members sub~ected to multi-directional high loads require materlals of construction ~ith, among other properties, good transverse tensile strength. Gocd transverse tensile strength also helps to eliminate continuous fiber composite microcracking, mitigates the propagation of ~icrocrecking under loaded conditions and improves resistsnca to fatique.

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Propertie~ such 8S tran~verse tenslle strength and hydrolytlc stabllity in thermoplflstic materlal of poly(arylene sulfide) relnforced with glAss flber~ have been lmproved by use of sllanes. ~hen the allanes are mlxed wlth the poly(arylene sulfide) prior to applicAtlon on the 81BSS flber it is import~nt that the silanes are mAintsined at conslstent concentratlons ln the polytarylene sulfide)s durlng treatment of the glas~ fibers and that coating of the glass flbers be unlform.

Summary of the Invention It i9 fln ob~ect of thls invention to provide a method for preparing a thermoplastlc resln and silane mixture suitable for use ln preparing glass reinforced thermoplflstic composites. It is also an ob~ect to provide this mixture, whlch wlll ~e useful in ma~lng thermoplastlc composltes wlth lmproved properties.
It ls an ob~ect of thls invention to provlde a method for producing continuous fiber relnforced thermoplastic material in whlch the flbers are treated with a sllane and thermoplastic mlxture.

Bri0f Description of the DrswinR
Figure 1 lllustrates sll~ne adsorption on poly(phenylene sulfide) as a function of time.

Detailed Description In accordance wlth thls lnvention mixtures of polysulflde organosllanes and poly(arylene sulfides) are aged to allow adsorption of the silanes onto ths poly(arylene sulfides) and these mi%tures are provided.
In accordance with another embodlment of the present lnvention an aged mixture of at least one polysulfide organosilane and poly(arylene sulfide) is used in a method of mflking glass reinforced composites.
In accordance with yet another embodiment of the pre~ent invention, glass flber reinforced poly(arylene sulfide) pre-preg tapes are prepared by passing slngle end glass rovlng through a slurry -:

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contalning sn sged mlxture of the poly(srylene sulflde) 0atrix msterlal snd a polysulfide orgsnosllAne.
The sllane and thermoplsstlc composltlons of thi~ invention are useful for improving the process for ~sklng glsss reinforced thermoplastic composites. When silAnes snd thermoplastic resins Are mlxed ln a Ylurry bath for pultrusion of glsss reinforcing flbers the concentration of sllflna in the slurry must be kept consistent over time nnd throughout the slurry mlx. This has been done by constsnt monltoring and adJustment of feeds to the slurry bsth. To svold inconsistencies ln sllane concentration and to eliminste the necessity of frequent monitoring and feed sd~ustment during the pultrustion process, this invention provide~ for sging a polysulfide silAne and thermoplsstic mixture before introduction of the mixture into the slurry bath. This surprisingly gives continued even distribution of ths silAne throughout the thermoplsstic matrlx msterial, thus permitting improved contact of the silsne and thermoplsstic mixture with the glass reinforcing materisl.
Exsmples of poly(arylene sulfide) resins contemplated as useful in making the compositions of this invention include those described in U.S Patent No. 3,354,129 issued to Edmonds snd ~ill on November 21, 1967, and those described in U.S. Patent No. 3,919,177, issued to Campbell on November 11, 1977, the disclosures of which are hereby incorporated by reference. The presently preferred poly-ar is polytphenylene sulflde).
The term poly(arylene sulfide) includes homopolymers And the normally solid arylene sulfide copolymer~, terpolymers and the llke having melting or softening point~ of at least about 150C, and more preferably from About 200C to about 400C. Other examplas of poly(srylene sulfide) materials are polyt4,4-biphenylene sulfide), polyl2,4-tolylene sulfide), snd a copolymer from p-dichlorobenzene, 2,4-dichlorotoluene and sodium sulfide and the like.
The term poly(phenylene sulfide) include~ homopolymers ~nd copolymers contalning ortho-, meta- and/or psra-phenylene linkages on aryl groups in the polymer chain. Also included are sryl-substituted derviatives of thesa msterials. A1YO included are poly(arylene sulfide . . . : ~.. . .

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sulfone), polytarylene sulfide ketone) snd poly(arylene sulfide diketone).
The orgsnosilanes contemplated ss useful in making the compositions of this invention include aromatic polysulfide silsnes withln the formula:

R~ O O---R~ (I) R7 / i - (R3)x ~ ~ (R~)y - S ~\ R~
R,---o ~ [S]n ~ ~---R~
The number of sulfur atoms (S) linking the two aromstic groups is determlned by the vslue of n which represents a positive integer and rsnges from 1 to 30. A subgenus within the scope of this invention is represented by formula I wherein n ranges from 1 to 10. The preferred value for n is from 1 to S.
Each of R~ snd R2 is H or an 81kyl group having froo 1 to 30 carbon stom~. Each of R~, R~, R7, R~, R~, and Rl, is an alkyl group having from 1 to 30 carbon atoms. The alkyl groups sssociated with R~, R2, R " R " R7, R " R~ snd R " csn be linear (e.g. n-propyl) or branched (e.g. tert-butgl). ExAmples of alkgl groups withln the scope ~f this invention include, but are not limited to, the following:

- CH, - CH2CH, --CH2CH2jCH, --CH2CH2CH2CH, .. . . : :

... .

.. ' ,.

2 ~ 3 ~ 3 CH~CHCH~

THCH
CH~
CHCH~CH~
1H, CH, - CH~
CH~

CH2 - (CH2), - CH~

CH~CH2CH~f - CH~
fH2 CH~
1H, - CH2(CH2)~ - CH~

fH~ ~(CH2),--CH, --CH2--(CH2) ~ CN--C~ CH, (CH2), - CH~
fH, fH (CH~)~, CH--CH, CH, 1H, 6 ~ ~ C~

A subgenus within the scope of thls lnventlon ls represented by formula I wherein eflch of R~ and R2 i5 H or sn fllkyl group havlng from l to lO cflrbon atoms flnd each of R~, R " R7, R " R~ ~nd R~ i8 Bn alkyl group having from l to lO carbon fltoms. Preferably, each of Rl and R~ ls H or an alkyl group hav~ng from l to 5 cflrbon fltomS and each of R~, R~, R7, R~, R~ and Rlo i8 sn alkyl group hflvlng fro~ l to 5 carbon atoms. In an embodlment of thls Lnventlon each of Rl and R2 reprssents a methyl group (-CH,) snd each of R~, R~, R7, R " R, and Rl, represents an ethyl group (-CH~CHl).
Each of the letters x and y represents elther l or 0. When x = O, R~ ls absent from formula I and the Sl bond extends to a carbon member of the correspondlng aromatic rlng. When x = l, R~ ls as defined below. In fl slmllar manner when y = O, R~ ls flbsent from formulA I and the Si bond extends to a carbon member of the correspondlng aromstlc rlng. When y = l, R~ ls as deflned below.
Each of R, and R~, when present (l.e. when x = l, y = l), 1s fln fllkylene group hflvlng from 1 to 30 cflrbon 8toms. The fllkylene group can be llnear or branched. Examples of fllkylene groups wlthln the scopa of thls ln~entlon lnclude, but are not llmlted to, the followlng:

~HI----CHsCR2CH2 ~HlcH2cH2cH2--:

:~, 7 2 ~

--CHCH~
CH, CU, CH2CH, --CH~fHCH2 .' CH, CH, - CH~(CH2).CH2 fH2CH, ---CH2(CH,~2 - C - CH2CH, -CH~

- CH~(CH2)27CH~ -CH2(CH2)~CH, - CH2(CH2)lf - (CH2)~CH~ -CH~(CH2),CH, A subgenus within the scope of thls lnventlon i~ represented by formula I wherein each of R~ and R~ (when present) 1~ sn alkylene group having from 1 to 10 carbon atom~. Preferably, each of Rl and R4 (when present) is an alkylene group having from 1 to 5 carbon atoss. In an embodiment of this invention each of R~ and R4 i8 present (i.e. x a 1 and y - 1) and represents an ethylene group (l.e. -CH2CH,-).

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R, and R~ tor Sl when x = O) cfln be bonded to any avallsble carbon stom of the correspondlng aromatlc rlng, wlth the understandlng that they cannot both be bonded to the same rlng atom or to the rin8 atom to which the sulfur 15 bonded. The pvsltion of Rl wlth respect to the sulfur substltuent can be ortho, meta or para. The posltlon of R, (or Sl when x = O) wlth reSpQct to the sulfur substltuent can be ortho, meta or para. In a slmllar manner Rl and R~ tox Sl when y = O) can be bonded to any avallAble carbon atom of the correspondlng aromatic rlng, with the understandlng that they cannot both be bonded to the sane rlng atom or to the rlng atom to which the sulfur is bonded. The position of R~ wlth respect to thc sulfur substituent can be ortho, meta or para.
The position of 2~ (or Sl when y = O) wlth respect to the sulfur substituent can be ortho, meta or para. Examples of various orlentations within the scope of this lnvention lnclude, but are not limited to, the followlng:

R, R~ (II) R~ ~ S]n ~

Rl R2 (III) R3 ~ S]n ~

;. : :
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R3 R~ R~ (IV) RI~lS]n~R~ (V) The preferred silane compounds of this invention are defined by the following chemical formula:

(VI) CH,CH2{~ ~ H2CH, CH,CI32 }Si--CH2CH2 ,~ /~CHICH,--S$ ~CH2CH, CH,CHi~ ~[SIn~O--CH2CH~

where n is an inte8er from 1 to 5. Included are all positional lsomers of the above. Examples include, but Are not llmlt~d to9 the followlng:

(VII) CH~CH2---O CH~ CH~ / O---CHlCH~
CH,CH2--o 3 si--CH2CH2 ~ S--S--S ~ CH~CH2--Si ) CH2CH, CH~CH2--) H2CH3 ~o 2~

(VIII) CH,CH2~
CH~GH2---C~ l CH25Hs CH~ / O--CH2CH~
CH,CH2--0 / ~ S ~ CH2CH2--Si--O------CH CH, CH~

(IX) CH,CH2 - O CM~
CH,CH2-- ~Si--CH2cH2~ S S- S--S S~ O~H2CHI
CH~CH2 - O
CH2CH2--S~ ) CH2CH, \0--CH2CH, The compo91tlon can cont8in more th8n one sil8n6 withln the scope of formulas I through IX. 8y w8y of non-llmiting e~ample the poly(8rylene sulflde) compo5itlon c8n contaln the compound8 VII, VIII
and IX above. In one embodlment of thls inventlon the poly(arylene sulfide) composltlon contain~ two or more 9il8ne9 deflned by (X) CH~CH~---O O---CHICH3 \ CH~ CH~ /
CH~CH~ O---Sl - CH~CH2 . I ~ CH2CHA - Sl---O---CH2CH~
CH3CH2---O ~ 1 In ~ \ o---cH2cH3 :

whereln the aver8ge value of n for the mixture i~ about 2 to about 4 and preferably about 2.8.
Presently preferred is a 9il8ne h8ving the formula above whereln Rl and R2 8re -CH~; wherein R~ 8nd R~ 8re -CHsC8~-; whereln Rs~
R~ R7~ R~ R~ 8nd R~o are ~CHaCH3; wherein x = 1 and y = 1; whereln the 8verage value of n 19 about 2.8. Thl9 material i9 commerclally , . . ~ .. . . . ~ , ., - - :

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svailable from Union Carbide Corporstion under the product name Ucarsll RC-2 or flS ~-9194.
The fiber relnforced pultruded thermoplastics produced ln accordance wlth this ~nvention sre basically comprised of poly(arylene sulfide) resin, glsss reinforcing material, and at least one polysulfide organosi18ne.
The presently preferred composltion of mstter comprises substantially linear poly(phenylene sulfide) having a melt flow within the range of about 1 to sbout 800 grams per 10 minutes, unidirection811y aligned continuous gl8ss fiber reinforcements, a silane content of from about 0.01 to about 5.0 weight percent based on weight of the glass or, more preferably, from about 0.05 to flbout 0.5 weight percent based on weight of the glass, and demonstrates improved transverse tensile strength.
The welght ratlo of the poly(arylene sulfide) to the polysulfide organosilane in the sil~ne and thermoplastic mixture of this invention is greater thsn about 2 to 1 and less than about 5,000 to 1.
The scope of this inventlon encompa ses 8 broad range and requires only that an amount of silsne sufficient to increase the transverse tensile strength or to improve the hydrolytic stsbility of the resulting composition be used.
The ~ilane and thermoplastic mixtures presently preferred have been sged sufficiently to 811OW enough adsorption of the polysulflde silsne onto the poly(arylene sulfide) to significantly reduce the need for constant monitoring 8nd feed sd~usting in a thermoplastic pultrusion process.
The poly(arylene sulfide) resin is present in the pultruded composite in an amount in the range of from about 20X to about 90% by weight of the composition, preferably in the range of from about 25% to about 60% by weight, and most preferably in the range of from about 25%
to sbout 35% by weight.
The glass reinforcing material i9 present in the pultruded composlte in an amount in the range of from about 80% to about lOX by weight of the total compos~tion, preferably from ~bout 40X to about 75%
by weight, and most preferably from about 65% to about 75% by weixht.

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Continuous un~directionslly sllgned glAss flbers arranged in single end rovings are contemplated as a suitnble reinforcement materisl. The glsss flber~ sre ~vAi~sble commercially. Example3 include Certainteed 70C ~ized E glass and CertflintQed 70D-ll, with the latter be~n8 presently preferred. However, fiber contemplated a~ useful in this invention i9 not limited to s~ngle end roving, but msy Al-~O be a conventionfll or assembled roving. Also, these exflmples are not to be construed as constraints on the d~amoter of flber contemplated a8 useful in this inventlon.
It is also within the scope of this inventlon to make 8 glas~
reinforced thermoplastic composite by pultruding a woven glAss fabric through a slurry of the polysulfide sllane And thermoplastic mixture.
Dlluents contemplated as useful lnclude but flre not limited to WAter, slcohols and mixtures thereof.
The diluent is typically wster or 8n aqueous mixture containlng one or more ~lcohols. In Addltion to diluent, the thermoplastic snd resin mi~ture msy contain Additives such as acid to ad~ust the pH of the mixture, lubrlcants, surfsctsnts and wetting agents.
The inventive method for producing tbe unldirectionsl fiber reinforced thermoplAstic mAteriAl comprise~ the following steps:
tl) preparing A slurry or emulsion comprising a tbermoplAstic resin, one or more of the chosen silanes snd opt~onslly other addltive~
as needed;
(2) allowing the thermoplastic resin/silane mlxture to aBe long enough to signiflcAntly increAse adsorption of the ~ilsne onto the thermoplastic resin;
(3) passing the continuous glass fibers through the slurry of step (1);
(4) passing the trested and impregnated 81AS~ fibers through an oven;

(5) giving the composite final shaping in a heated die.
Alternatively, after Allowing the thermoplastic re3in/silane mixture to Age (step 2), the mixture could be dried, then used in a second slurry for step (3).

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Preferflbly the oven wlll mAintsln the temperature of the polytaryleno sulflde) At least as high as the ~eltlng point of the poly(a~ylenè sulflde~.
The slurry or emulslon ls prepared by any suitable procedure.
One method 19 to mlx the silane and suxfactAnt, add the ~llane/surfactant mlxture to the water and then add the poly(srylene sulflde) powder. AgltAtlon of the components durlng the preparatlon and aglng of the mlxture ls advsntageous. Any sultabla temperature, usually 20-50C, may be used durlng aglng of the ~lxture and for the bath temperature.
Havlng a mlxture of the thermoplsstlc resin snd sllans in which the sllane ls substsntislly complately adsorbed onto the thermoplastic prlor to use of the mlxture as a slurry for pultruslon allows for running the pultrusion process without frequent monitorlng of the slurry bath for consistency of the concentration of silsne in the slurry.
Adsorptlon slgniflcantly lncreases during the flrst approxlmAtely 20 hours and exhibits a slower sdsorpt~on rate from about 20 hours to about 35 hours of aging. ThereAfter the increB3e in sdsorption is slgnificantly slowed. After about 48 hours of aging, thera does not appear to be any Appreclsble incresse in the smount of sllane adsorbed onto tha thermoplAstlc resin. Presently preferred is from about 1 hour to about 100 hours of aglng. ~ore preferred is from about 6 hours to about 75 hours; most preferred ls from sbout 12 hours to ~bout 48 hours.
The rate of adsorption of the sllane onto the poly(arylene sulfide) depends upon such factors as bath temperAture~ silane concentratlon, poly(arylene sulflde) surface area, and Agitstion.
Commerlcsl ob~ectlves ln production of flber reinforced thermoplastic materiAls msy not re4uire maxlmu- adsorption of the polysulflde sllane onto the poly(arylene sulfide) because of the benefits obtainable with use of shorter aging perlods.

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Example I
Thls ex~mple demonstrstes the dlfference ln behavlor of the polysulflde sll~nes whlch sre used ln thls lnventlon and an epoxy sllane in sn aqueous bath with polyphenylene sulfida (PPS). An air ~illed PPS
with a mean pflrticle size of 17 microns was combined with aqueous solutions of the silAnes (0.5 welght percent silane b~sed on the PPS
weight). The mlxtures, about 3000 g, COntAining 15 weight percent PPS
were stirred with magnetic stirring bars at 28C. At various time intervals 8 100 mL sample of each slurry was collected and anAlyzed.
Each sample slurry WAS centrifuged and the liquld removed for analysls of the silicon content by lnductively coupled plAsms. The PPS solid was collected by filtering on a Buchner funnel, wsshed with w~ter, dried for a minimum of 15 minutes at 110C, and analyzed for silicon content by neutron actlvation. Calculations involving Ucarsil RC-2 assume that the molecular weight ls 652 g/mole, the alkyl groups on the aromatlc rings are methyl, and that there are 2.8 sulfur atoms per molecule.
The results of the control run uslng Ucarsll TC-100 epoxy silane ~3-glycidoxypropyltrimethoxysilane) from Unlon Carbldo are summarlzed ln Table I. The TC-100 remalns predomlnantly in the aqueous solution during the test and very little slllcon wss detected on the PPS
over the time period of the test. Flgure l ~hows the concentration of sillcon on the PPS during the test.
In sharp contrast wlth the above results wlth TC-100, the run wlth the Ucarsll RC-2 polysulflde sllane from Unlon Carblde (Table II) shows that the RC-2 silane adheres to the PPS. About 83 weight percent of the RC-2 initislly present ln the solution was found on the PPS sfter about 24 hours and sbout 88 weight percent of the RC-2 was on the PPS
after 48 hours. The silicon levels in the llquld phase are believed to be low due to difficulties in asperating the relatively insoluble silane to the plasma torch wlth the existing equipment. The results of thls run are also shown ln Flgure 1 with the upper line representlng the calculated maximum possible level of silicon on PPS. These curves in Figure 1 clearly show the dlfference ln behavior between the epoxy sllane and the polysulfide sllane in an aqueous mixtur~ wlth PPS.

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TABLE I
Epoxy SllAne Dlstrlbution ln Aqueous Poly(phenylene sulflde) Bath Sllane Conce~tratlonSllane Conc2ntratlon T me ln Bath. hrs.ln liquld . PPmOD solld ~ ppm 0.0 (calculated) 570 0 0,0 588 11 2.~S 585 14 19.5 585 15 26.0 578 13 32.0 573 12 44.5 579 13 70.75 577 24 Determlned by lnductlvely coupled plasms.
Determined by neutron activation.

TABLE II
Pol~sulflde Sllane Distribution in_Aqueous Polv(phenylene sulfide) Bath Sllane Conc~n~rationSilane Conc~ntr~tlon Time in Bath. hrs.ln liquid ' , Pp-on solid , ppn 0.0 (calculated) 430 0 o.o 26 11 2.5 27 1100 19.25 34 1900 25.75 31 ~ 2000 32.0 30 2100 44.25 28 2100 70.75 24 2100 lDetermined by induct~vely coupled plasm~.
2Determined by neutron activation.
3Low results csused by sample precipitation.

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Example II
Thls example demonstrates the preparatlon and propert~es of unidlrectlonsl contlnuous glass flber relnforced poly(phenylene sulflda) (PPS) composltes where a polysulfide sllane ls contacted with the PPS
resln snd Aged before the prepreg operstion. Several other sllsnes were used for composite preparatlon for comparison.
All compounds were made USillg techniques disclosed in U.S.
Patent 4,680,224, modlfled to lnclude a curtain sprAyer ln the slurry bath and rolllng redlrect bars at sny polnt the glass is wet. All composites were made using Certainteed 70-C sized E glass, 20 eicron diameter, 250 yield, 1.0 weight percent of the lndicated sllans ln the slurry bath (bssed on the weight of resin in the slurry bath), and a poly(phenylene sulfide) with a melt flow of approxlmately 50-150 g/10 min. (ASTM D1238-79, Procedure B, Condition 315/5.0, modified to use a 5 minute prehest tlme rather than the 6 minute minimum stated in the test method). Technlques dlsclosed in U.S. Patent 3,919,177; U.S. Patents 4,801,664 andlor 4,414,729 were used for preparAtion of the poly(phenylene sulflde) for the test.
The slurry concentretion and amount of slurry needed for producing the composite will depend on such factors as the si~e of bath or baths, the line speed snd properties of the fiber to be impregnated.
This wss determined empirically so as to produce a slurry which would result in a composlte having 30 ~ 2 weight percent resin snd 70 ~ 2 weight percent glass.
In these exsmples, the main batb was 20.5 weight percent PPS
resln ~nd the add bath wss 30 weight percent PPS. The surfsctsnt was Neodol 91-6 at a concentration of 0.26 weig~t percent based on the PPS
wslght. Ucarsll RC-2, a polysulfide aliphatic silans from Unlon Carbide, was used in a run with prolonged contact of the PPS with the silane before the pultrusion. Several other silanes were used iD other run~ without extended contact with the PPS. Emulsions were formed when RC-2, T2905, ~nd B2494 were used. DSC-18 wa~ a solid and A-1160 was water soluble.
In the slurry formation, the appropriate amount o~ water was weighed in a large contAiner and the pH was ad~usted to spproximstely 4 ~' ~
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by uslng acetlc acld. The approprlate amount of surfactant was welghed and added to the sllane snd stlrred by hand untll the mlxture was uniform, Then, the sllane/surfActant mlxture wss added to the w~ter wlth very rlgorous contlnuous mlxlng. Aftsr ~ll of the sllane/surfactant mlxture was added to the water, less vlgorous stlrrlng was contlnued for four hours. It 19 not necessAry to stir rlgorously after the emulslon has formed.
Then the PPS resln was added to the water/sllsne/surfActant mlxture. The resultlng slurry was very thlck and was not used for 48 hours after lt had been blended ln order to allow the silane to adsorb onto the PPS resln. The mlxture was stlrred two or three tlmes dally untll use.
Whlle thls inventlon has been descrlbed ln detall for the purpose of lllustration, lt is not to be construed as llmlted thereby.
This patent ls lntended to cover all changes and modlflcatlons wlthln the spirlt and scope thereof.

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Claims (14)

THAT WHICH IS CLAIMED IS:

1. A method comprising combining (a) poly(arylene sulfide) and (b) at least one polysulfide organosilane having the formula:

wherein n is an integer from 1 to 30; wherein each of R1 and R2 is H or an alkyl group having 1 to 30 carbon atoms; wherein each of R5, R6, R7, R8, R9 and R10 is an alkyl group having from 1 to 30 carbon atoms;
wherein x is 0 or 1; wherein y is 0 or 1; and wherein each of R3 and R4 is an alkylene group having from 1 to 30 carbon atoms; and thereafter allowing said mixture to age for a time sufficient to allow adsorption of said at least one polysulfide organosilane onto said poly(arylene sulfide).

2. A method according to claim 1 wherein said mixture is aged from about 1 hour to about 100 hours.

3. A method according to claim 1 wherein said mixture is aged from about 6 hours to about 75 hours.

4. A method according to claim 1 wherein said mixture is aged from about 12 hours to about 48 hours.

5. A method according to claim 1 wherein the weight ratio of (a) to (b) is greater than about 2 to 1 and less than about 5,000 to 1.

6. A method of preparing a glass reinforced thermoplastic composite comprising:
(a) combining poly(arylene sulfide) and at least one silane within the formula:

wherein n is an integer from 1 to 30; wherein each of R1 and R2 is H or an alkyl group having 1 to 30 carbon atoms; wherein each of R5, R6, R7, R8, R9 and R10 is an alkyl group having from 1 to 30 carbon atoms;
wherein x is 0 or 1; wherein y is 0 to 1; and wherein each of R3 and R4 is an alkylene group having from 1 to 30 carbon atoms;
(b) allowing said mixture to age for a time sufficient to allow adsorption of said at least one polysulfide organosilane onto said poly(arylene sulfide);
(c) passing glass fibers through a slurry bath containing said mixture of said poly(arylene sulfide) and said at least one polysulfide organosilane, to impregnate said glass fibers; and (d) heating and shaping said impregnated glass fibers.

7. A method according to claim 6 wherein said mixture is aged from about 1 to about 100 hours.

8. A method according to claim 6 wherein said mixture is aged from about 6 hours to about 75 hours.

9. A method according to claim 6 wherein said mixture is aged from about 12 hours to about 48 hours.

10. A method according to claim 6 wherein said glass is continuous glass fiber.

11. A composition produced by the method of claim 1.

12. A composition produced by the method of claim 1 wherein the weight ratio of said poly(arylene sulfide) to said at least one polysulfide organosilane is greater than about 2 to 1 and less than about 5,000 to 1.

13. A composition produced by the method of claim 1 wherein said poly(arylene sulfide) is poly(phenylene sulfide).

14. A composition produced by the method of claim 1 wherein solid poly(arylene sulfide) is poly(phenylene sulfide sulfone).