CA2109079A1 - Blends of copoly (arylene sulfide) and polyamide - Google Patents
Blends of copoly (arylene sulfide) and polyamideInfo
- Publication number
- CA2109079A1 CA2109079A1 CA 2109079 CA2109079A CA2109079A1 CA 2109079 A1 CA2109079 A1 CA 2109079A1 CA 2109079 CA2109079 CA 2109079 CA 2109079 A CA2109079 A CA 2109079A CA 2109079 A1 CA2109079 A1 CA 2109079A1
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- Prior art keywords
- copoly
- weight
- range
- poly
- admixture
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-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L81/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
- C08L81/02—Polythioethers; Polythioether-ethers
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
A composition comprising an admixture of (A) a copoly (arylene sulfide) corresponding to the structure [(-A-S-)1-x(-A-S-S-)x]n wherein (A) is a divalent substituted or unsubstituted aromatic radical, x is in the range of 0.5 to 0.001 and n is at least 25, and (B) a polyamide corresponding to general structure (I) or to general structure (II).
Description
2 PCr/~JS9~1~)3671 ~90~9 i BLENDS OF COPOLY(ARYLENE SULFIDE) AND
.
The invention relates to blends of a copoly(arylene sulfide) and a polyamideq ~ Poly(arylene sulfide) resins are thermoplastic polymeric materials with good thermal stability, unusual : insolubility, resistance to chemical environments and in~erent flame resistance. Poly(arylene sulfide) resins additionally h~ve ~ood electrical insulative properties which make them ideal f~r electrical and electronic applica~ions. Their:exGellent resistance to chemical degradation makes them ideal for use in chemical environments which in~olve organic solvents ~nd strong mineral acids, such as~;coatings for pipes, tanks, pumps and l5~ ~;oth~r equipment. These polymers can be prepared by reacting ~;
p-dichloro-benæene with~sodium sulfide in a polar organic sol~ént to produce poly~pheny~ene sul~ide) and the by-product sodium chloride~in accordance with U~.S. 2,513~188 and~U.S.~2,538,941. ~An improvement on:this procedure 2;0~ involv~s ~ddin~ M-haloamides as:catalysts.
Recently:copoly(arylene sulfides) have been discovered.
Thes~ polymers can be described as having repeating units correspondin~ to t~e:~tructure :::
[ ( A--S ) l_X (--A--S--S~) x ] n wh rein x is in th~ range of 0.5 to 0~001, A is a divalent : : aromatic radical and n is at least 200 and- is preferably in the range of 500 ~o 5,000.
It has:now bee~ disco~ered that the rate at which the copoly(arylene sulfide) crystallizes can be increased by : :
:
WOg~/19682 P~T/US92/03671 ~39~79 blending a polyamide with the copoly(arylene sulfide). This `~
blend can be broadly described as an admixture of ::
(A~ from 99.5 to 50 weight percent, based on the weight of the admixture, of a copoly(arylene sulfide) corresponding ~o the structure -~:
[ (--A--S~ x (--A--S--S--) x ~ n ~:~
wherein A is a divalent substituted or unsubstitu~ed aromatic radical, x is in the range of 0.5 to 0.001 and n is at least 25, and ~B) from 0.5 to 50 weight percent, based on the weight of the admixture, of two particular types of ~-polyamides.
:~ .
: The copoly(arylene sulfide) polymers useful in this invention are identical to the copoly(aryiene sulfide) ::
polymers disclosed in U.5. 4,786,713 and U.S~ 4,855,3g3, : hereln incorporated by reference, PXGept that the minimum ~alue of n of the copoly(arylene sulfide) polymers useful in this invention is lower than the minimum value of n for the cop~ly(arylene sulf~de) p~lymers which is disclosed in these references. The copoly(arylene sulfide) polymers useful in this in~ention are therefore inherent in the disclosure of hese references because as the molecular weight builds up toward the miminum value of n of at least ~00 which is disclosed in these references the molecular weight passes through a molecular.weight associated wi~h the lower minimum : ~alue of n o~ 25 o~ the cop~ly(arylene sulfide) pol~m~rs of this invention. The copoly(arylene sulfide) polymers use~ul i~ this invention can be prepared by those skilled in the art by following the teachings of these references and controlling the stoichiometery, time, temperature and other variables of the reaction to achiefe a molecular weight associated with a value of n which is at least 25.
The diiodoaromatic compounds which can be utilized to prepare the copoly(arylene sulfide) useful in this 5 invention, include unsubstituted or substituted aromatics which have two iodine substituents. Preferred diiodoaromatic compounds are the diiodobenzenes, --diiodonaphthalenes and diiodobiphenyls which may be un~ubstituted or substituted. More preferably the : I0 diiodoaromatic compounds suitabla for the present invention " ~
:: : include p-~iiodoben2ene, m-diiodobenzene, p,p'-diiodobiphenyl, p,p'-diiodobiphenyl, p,p'-diiododiphenyl ether and ~,6-diiodonaphthalene. Most pr ferably the diiodo ~-compound is p-dii~dobenzene.
15 :~ The polyamides useful in this invention and the method of their preparation:~are~ well known in the art. One :polyamide useful in this invention corresponds to the ~-~
: structure (CHz) ~ R-~
25 ; ~ wherein a is~n integer in:the range of 4 to 12 and i5 preferably 4, ~R corresponds to the structure :; : (-~H2-)b 30 ; . wherein b is an in~eger in the range o~ 4 to 13 and is preferably : ~ 6 :~
:: :
WO~2/196~2 PCT/US92/03671 c~ 19 4 or to the structure . _ . .
--( CH2 ) -- \ / ( CH2 ) c c- c wherein c is 0, l, 2 or 3 and is preferably 0 -~-~
and n is at least 2S, preferably 50. ~.
Examples Qf these polyamides include ~5 ~ poly(hexamethylene~adipamide, p~ly(hexamethylene -:~
sebac~amide), poly(hexamethylene dodecane diamide), poly(tridecane biassylamide), and poly(hexamethylene terephthalamide. In the preferred embodiment wherein a is 4 : and b is 6 the polyamide is often called p~ly(hexamethylene 20~:;adipamide3. In the preferred embodiment wherein a is 4 and :~
is:0 the polyamide is often called poly~cyclohexylene adlpamide)~
Another polyamide useful in this invention corresponds ; ~ ~
to the structure (CH2) wherein~
d~is an integer in the range of 5 to ll, : : :
~ and is preferably 5, :; ;
m~is at least 50 and preferably is at least ~5.
Examples o~ these polyamides include poly~e-:~ - h : caprolactam); poly(enantholactam), poly(w-undecanaamide)~
: poly(capryllactum), and poly(w-pelar~onamide) 7 In the :: .
21 ~t~û7~
preferred embodiment where d is 5 the polyamide is often called poly(e-caprolactam).
The blends of this invention can be prepared by known :.
techniques for blending polymers. For example, the polymers can be coextruded in convention twin screw extrusion equipment. Also, polymers of both polymers may be admixed and the admixed powders extruded in a single screw extruder.
Preferably, an admixture of powdered polym~r is prepared and the admixture powder is extruded in a single screw extruder.
~he amount of copoly(arylene sulfide) is in the range ~--of 99.5 to 50 weight percent, preferably ~8 to 75 weight percent, based on the weight of the admix~ure. The amount of polyamide is in the range of 0.5 to 50 weight percent, preferably 2 to 25 weight percent, ~ased on the weight of the:a~mixture.~
The compositions of this invention can be used f~r preparation of various shaped articles such as pellets, fib~rs and molded articles. The polymer can be prepared ~ into these shaped articles by conventional processes, such ;~ 20 as injection molding, melt spinning, and melt extrusion.
: The compositions of this invention can additionaIly contain:fillers, nuc:leating agents and~ reinforcing materials in~the form~o:f fibers,- minerals, powders or mats. For examp:le,:the omposi~tions can contain glass fibers, aluminum 25~ oxide, calcium oxide,~silicon dioxid ,~Titanium dioxide, ~: copper, kaolin~ and the like.
:The compositions of this inven~ion are normaIly solid in the sense that at typical room temperatures and pressures the compositions are in a solid state as compared to a liquid:state. The soIid character of the composition results from ~oth polymers having a~sufficiently high molecular weight to be~a solid.
The enhanced rate of crystallization of the composition of this inventi~n is extremely significantO High rates of crystallizatîon enables crystalline-shaped articles, such as W092/~96X2 ~C~/US92/03671 21~Y(~79 molded parts, extruded fibers or drawn film, to be more easily prepared because processing time is saved, thereby increasing production efficiency.
In this invention the crystallization rate of the composition of the invention is measured by the difference in the ~SC transitions of Tcc - Tch, often referred to by those skilled in the art as the quantity "delta". If two polymers were blended together one would expect the delta value of the blend to be the linear weighted a~eragel of the two component polymers. This relationship can be expressed : by the equation , deltablend - deltal x weight fractionl + delta2 x weight -~
fraction2 Thus, for example, where equal weights of the 5:~: copoly(arylene sulfide) and another polymer are employed, ::~
~ . ~
the resul~ant deltablend would:be expected to be the average of deltal and delta2.:
: The transitions~Tcc and Tch are defined by heating the polymer sample in~a Differential Scanning Calorimeter ~DSC) 20~ instrument: at a scan rate of 20C~min. the Tcc is determined by heating the polymer to a molten state, usually : 300C and then cooling at 200c~min. The peak of the exotherm observed is~defined as the Tcc~ The Tch is .
determined by heating a sample of polymer to the melt again ~: ::25 and quenching the sample snto a metal block cooled in dry ; ice. The thus produced glassy sample is then heated from room temperature up~to a~melt. The peak of the exotherm obs rved in this heating sequence is defined as the Tch.
As will be recognized by those skilled in the art, there are numerous cases where either Tcc or Tch will be: ~: missing in the DSC trace because o~ the polymer system crystallization rate;being so slow~ This is normally a result of higher disulfide levels in the polymer. In such ,.
, WO92/~96g~ PCT/US92/~3671 21~87~
cases, delta becomes undefined and the means of comparison become the transition that does remain, such as Tch. Thus, comparing Tch's of the components and the final blend is also a valid means of assessing the expected transition vs. ;.
the one actually observed for the blend. The equation used for compari.son is the same as above except substituting Tcc for delta.
In the examples given below, differential scanning calorimetry (DSC~ is performed using a Du Pont 951 Thermoanalyzer instrument and employing a scanning rate of 20C~min.
Example 1 This example illustrates the slow crystallization rate of copoly(phenylene sulfide).
lS Copoly(phenylene-sulfide) was prepared according to the procedure described in U.S. Patent No. 4,786~713. The : copoly(phenylene sulfide) had a melt viscosity of about ~ 74,000 poise at 320C at a shear rate of 2~, sec-1. The :~ ~ ~al~ue of x for the copoly~phenylene sulfide) was estimated : to b,e about 0.094 based on elemental analysis. The polym~r : had~a glass transition temperature of about 94C as measured : by Differential Scanning Calorimetry. The glass transition temp,erature were determined as follows: ~he sample was first heated from room temperature to 330 at a heating rage 2~ of ~0C~min (first heating cycle). The sample was held at 330C ~or one minute and subsequently quenched to room temperature at 320OC~mln. In the second reheat cycle, it was heated at 20Oc~min to 330C, held for one minute at 330C, and then cooled at 200C~min. The temperaturç of crystallization, Tch, was obtained from the exothermic peak temperature during the second reheat cycle. The temperature of cryst~ zation upon cooling, Tcc was obtained during the cooling scan from the melt. The copc,ly~phenylene sulfide) has a melting polnt of 265C as measured by 1st cycle , W092/196~2 PCT/US92/03671 ~ 9 ~,3 r~ ~3 heating scan on DSC. The copoly(phenylene sulfide) did not show any significant crystallization exotherm during second heating scan or subsequent cooling scan from the melt, thus establishing that the copoly(phenylene sulfide) has a very : 5 slow crystallizing material.
:`
Exam~le 2 : This example illustrates the enhanced rate of crystallizati~n of the cvmpositions of this inventio~ :
composed ~f copoly(phenylene sulfide) and poly(hexamethylene adipamide).
Powder of the copoly(phenylene sulfide) prepared in Example l~was admixed with powdered poly(hexamethylene adipamide), to make a blend containing 80% by weight copoly(phenylene sulfide~ and 20% by weight o~
I5 poly(hPxamethylene adipamide). The admixture was dried at 90~ for 12 hours in a for~ed air-circulated oven. The polymer admixture was extruded thru an extruder. The temperature at th~ end of the die was kept at about 300C
and;~he rpm of the screw was about 90. The ex~ruded 2~0 material was analyzed by DSC for thermal transitions. The blended material had:a Tch (temperature of crystallizati~n during seco~d heating)~::of about 112C. DSC experiment was performed as follows~. The sample was:first heated from room : temperature to 330C at:a heating rate of 20C~min (first 5~ heating cycle)~ The sampIe was held at 330C for one minute and subse~uen~ly ~uenched to room temperature at 320~C~min.
In the second reheat cycle, it was heated at 20C~min to : 330C~ held for`one minute at 330C, and then cooled at :~
:20~c~min. The temperature of crystallization, Tch, was obtained from the~exothermic peak temperature~:;during the second r heat cycle. The temperature of crystallizati~n upon cooling, Tcc was obtained during the c~oling scan ~rom the melt. Tcc for the blend was about 222C. These data illustrate that the ompositions of this inve~tivn exhibits :
WO92/19682 PCT/US92/03~71 ~lo!~n7~ ;
an enhanced rate of crystallization composed to that of only ~.
copoly(phenylene sulfide).
xamPle 3 This example illustrates the faster crystallization rate of the composition of this invention.
Example 2 was repeated except that the amount of poly(hexamethylene adipamide) was 5~ by weight. The melt blended material h~d a Tch of 130.3C and Tcc of 202.5C.
The crystallization rate is much higher as compared to 100%
copoly(phenylene sulfide~ of Example l.
Example 4 This example illustrates the faster Grystallization rate of the composition of this invention.
Example 2: is repeated except that ~he amount of poly(hexamethylene adipamide) is reduced to 1% ~y weight.
The melt blended material had a Tch of 134C and tcc of 208C. These data establish that the compositio~ of the : ~ invention exhibits an enhanced rate of crysta1liza~ion : compared to~100% copoly(phenylene sulfide) of Example l.
2~0 ~Exam~Ie 5 : This example illustrates the faster crystallizati~n ;rate of the composition of this invention.
: :Example 2 i5 repeated @xcept that the amount o~
: : poly~(hexamethy-ene adipamide) is reduced ~o 0.5% by weight.
The melt blended material had a Tch of 167C and Tcc of 153.4C. These data establishes that the composition ~f ;this invention exhibit an enhanced rate of crystallization compared to 100% copoly(phenylene sulfide) of Example l.
210g~79 Exam~le 6 This example illustrates the faster crystallization rate of the composition of this invention comprises copoly(phenylene sulfide) and poly(e-caprolactam).
Five weight ~ poly(e-caprolactam) was melt blended with .
95 weight % of the copoly(phenylene sulfide~ used in Example 1. DSC transitions showed a Tch of 123C and Tcc of lg5.7C. These data establish a much faster rate of : : crystallization of the composition of the invention than ~:: 10 that for 100% copoly(phenylene sulfide) of Example 1.
:~ ., Example 7 This example illustrates the faster rate of crystallization;of the composition of this invention.
~ : 5 wt ~ of poly(w-undecaneamide) was melt blended with : : lS 95 wt % of copoly(phenylene sulfide). The procedure was the : ~ same as in Example 2.~ DSC transitions showed a Tch : (temperature of crystalli~ation upon heating) of lll~C and Tcc (temperature of crystallization upon cooling) of 206C.
~ This again illustrates faster crystallization behavior of :~ ~ 20 copoly~(phenylene sul~ide) in the blend.
: :
:~::: :
'~
.
The invention relates to blends of a copoly(arylene sulfide) and a polyamideq ~ Poly(arylene sulfide) resins are thermoplastic polymeric materials with good thermal stability, unusual : insolubility, resistance to chemical environments and in~erent flame resistance. Poly(arylene sulfide) resins additionally h~ve ~ood electrical insulative properties which make them ideal f~r electrical and electronic applica~ions. Their:exGellent resistance to chemical degradation makes them ideal for use in chemical environments which in~olve organic solvents ~nd strong mineral acids, such as~;coatings for pipes, tanks, pumps and l5~ ~;oth~r equipment. These polymers can be prepared by reacting ~;
p-dichloro-benæene with~sodium sulfide in a polar organic sol~ént to produce poly~pheny~ene sul~ide) and the by-product sodium chloride~in accordance with U~.S. 2,513~188 and~U.S.~2,538,941. ~An improvement on:this procedure 2;0~ involv~s ~ddin~ M-haloamides as:catalysts.
Recently:copoly(arylene sulfides) have been discovered.
Thes~ polymers can be described as having repeating units correspondin~ to t~e:~tructure :::
[ ( A--S ) l_X (--A--S--S~) x ] n wh rein x is in th~ range of 0.5 to 0~001, A is a divalent : : aromatic radical and n is at least 200 and- is preferably in the range of 500 ~o 5,000.
It has:now bee~ disco~ered that the rate at which the copoly(arylene sulfide) crystallizes can be increased by : :
:
WOg~/19682 P~T/US92/03671 ~39~79 blending a polyamide with the copoly(arylene sulfide). This `~
blend can be broadly described as an admixture of ::
(A~ from 99.5 to 50 weight percent, based on the weight of the admixture, of a copoly(arylene sulfide) corresponding ~o the structure -~:
[ (--A--S~ x (--A--S--S--) x ~ n ~:~
wherein A is a divalent substituted or unsubstitu~ed aromatic radical, x is in the range of 0.5 to 0.001 and n is at least 25, and ~B) from 0.5 to 50 weight percent, based on the weight of the admixture, of two particular types of ~-polyamides.
:~ .
: The copoly(arylene sulfide) polymers useful in this invention are identical to the copoly(aryiene sulfide) ::
polymers disclosed in U.5. 4,786,713 and U.S~ 4,855,3g3, : hereln incorporated by reference, PXGept that the minimum ~alue of n of the copoly(arylene sulfide) polymers useful in this invention is lower than the minimum value of n for the cop~ly(arylene sulf~de) p~lymers which is disclosed in these references. The copoly(arylene sulfide) polymers useful in this in~ention are therefore inherent in the disclosure of hese references because as the molecular weight builds up toward the miminum value of n of at least ~00 which is disclosed in these references the molecular weight passes through a molecular.weight associated wi~h the lower minimum : ~alue of n o~ 25 o~ the cop~ly(arylene sulfide) pol~m~rs of this invention. The copoly(arylene sulfide) polymers use~ul i~ this invention can be prepared by those skilled in the art by following the teachings of these references and controlling the stoichiometery, time, temperature and other variables of the reaction to achiefe a molecular weight associated with a value of n which is at least 25.
The diiodoaromatic compounds which can be utilized to prepare the copoly(arylene sulfide) useful in this 5 invention, include unsubstituted or substituted aromatics which have two iodine substituents. Preferred diiodoaromatic compounds are the diiodobenzenes, --diiodonaphthalenes and diiodobiphenyls which may be un~ubstituted or substituted. More preferably the : I0 diiodoaromatic compounds suitabla for the present invention " ~
:: : include p-~iiodoben2ene, m-diiodobenzene, p,p'-diiodobiphenyl, p,p'-diiodobiphenyl, p,p'-diiododiphenyl ether and ~,6-diiodonaphthalene. Most pr ferably the diiodo ~-compound is p-dii~dobenzene.
15 :~ The polyamides useful in this invention and the method of their preparation:~are~ well known in the art. One :polyamide useful in this invention corresponds to the ~-~
: structure (CHz) ~ R-~
25 ; ~ wherein a is~n integer in:the range of 4 to 12 and i5 preferably 4, ~R corresponds to the structure :; : (-~H2-)b 30 ; . wherein b is an in~eger in the range o~ 4 to 13 and is preferably : ~ 6 :~
:: :
WO~2/196~2 PCT/US92/03671 c~ 19 4 or to the structure . _ . .
--( CH2 ) -- \ / ( CH2 ) c c- c wherein c is 0, l, 2 or 3 and is preferably 0 -~-~
and n is at least 2S, preferably 50. ~.
Examples Qf these polyamides include ~5 ~ poly(hexamethylene~adipamide, p~ly(hexamethylene -:~
sebac~amide), poly(hexamethylene dodecane diamide), poly(tridecane biassylamide), and poly(hexamethylene terephthalamide. In the preferred embodiment wherein a is 4 : and b is 6 the polyamide is often called p~ly(hexamethylene 20~:;adipamide3. In the preferred embodiment wherein a is 4 and :~
is:0 the polyamide is often called poly~cyclohexylene adlpamide)~
Another polyamide useful in this invention corresponds ; ~ ~
to the structure (CH2) wherein~
d~is an integer in the range of 5 to ll, : : :
~ and is preferably 5, :; ;
m~is at least 50 and preferably is at least ~5.
Examples o~ these polyamides include poly~e-:~ - h : caprolactam); poly(enantholactam), poly(w-undecanaamide)~
: poly(capryllactum), and poly(w-pelar~onamide) 7 In the :: .
21 ~t~û7~
preferred embodiment where d is 5 the polyamide is often called poly(e-caprolactam).
The blends of this invention can be prepared by known :.
techniques for blending polymers. For example, the polymers can be coextruded in convention twin screw extrusion equipment. Also, polymers of both polymers may be admixed and the admixed powders extruded in a single screw extruder.
Preferably, an admixture of powdered polym~r is prepared and the admixture powder is extruded in a single screw extruder.
~he amount of copoly(arylene sulfide) is in the range ~--of 99.5 to 50 weight percent, preferably ~8 to 75 weight percent, based on the weight of the admix~ure. The amount of polyamide is in the range of 0.5 to 50 weight percent, preferably 2 to 25 weight percent, ~ased on the weight of the:a~mixture.~
The compositions of this invention can be used f~r preparation of various shaped articles such as pellets, fib~rs and molded articles. The polymer can be prepared ~ into these shaped articles by conventional processes, such ;~ 20 as injection molding, melt spinning, and melt extrusion.
: The compositions of this invention can additionaIly contain:fillers, nuc:leating agents and~ reinforcing materials in~the form~o:f fibers,- minerals, powders or mats. For examp:le,:the omposi~tions can contain glass fibers, aluminum 25~ oxide, calcium oxide,~silicon dioxid ,~Titanium dioxide, ~: copper, kaolin~ and the like.
:The compositions of this inven~ion are normaIly solid in the sense that at typical room temperatures and pressures the compositions are in a solid state as compared to a liquid:state. The soIid character of the composition results from ~oth polymers having a~sufficiently high molecular weight to be~a solid.
The enhanced rate of crystallization of the composition of this inventi~n is extremely significantO High rates of crystallizatîon enables crystalline-shaped articles, such as W092/~96X2 ~C~/US92/03671 21~Y(~79 molded parts, extruded fibers or drawn film, to be more easily prepared because processing time is saved, thereby increasing production efficiency.
In this invention the crystallization rate of the composition of the invention is measured by the difference in the ~SC transitions of Tcc - Tch, often referred to by those skilled in the art as the quantity "delta". If two polymers were blended together one would expect the delta value of the blend to be the linear weighted a~eragel of the two component polymers. This relationship can be expressed : by the equation , deltablend - deltal x weight fractionl + delta2 x weight -~
fraction2 Thus, for example, where equal weights of the 5:~: copoly(arylene sulfide) and another polymer are employed, ::~
~ . ~
the resul~ant deltablend would:be expected to be the average of deltal and delta2.:
: The transitions~Tcc and Tch are defined by heating the polymer sample in~a Differential Scanning Calorimeter ~DSC) 20~ instrument: at a scan rate of 20C~min. the Tcc is determined by heating the polymer to a molten state, usually : 300C and then cooling at 200c~min. The peak of the exotherm observed is~defined as the Tcc~ The Tch is .
determined by heating a sample of polymer to the melt again ~: ::25 and quenching the sample snto a metal block cooled in dry ; ice. The thus produced glassy sample is then heated from room temperature up~to a~melt. The peak of the exotherm obs rved in this heating sequence is defined as the Tch.
As will be recognized by those skilled in the art, there are numerous cases where either Tcc or Tch will be: ~: missing in the DSC trace because o~ the polymer system crystallization rate;being so slow~ This is normally a result of higher disulfide levels in the polymer. In such ,.
, WO92/~96g~ PCT/US92/~3671 21~87~
cases, delta becomes undefined and the means of comparison become the transition that does remain, such as Tch. Thus, comparing Tch's of the components and the final blend is also a valid means of assessing the expected transition vs. ;.
the one actually observed for the blend. The equation used for compari.son is the same as above except substituting Tcc for delta.
In the examples given below, differential scanning calorimetry (DSC~ is performed using a Du Pont 951 Thermoanalyzer instrument and employing a scanning rate of 20C~min.
Example 1 This example illustrates the slow crystallization rate of copoly(phenylene sulfide).
lS Copoly(phenylene-sulfide) was prepared according to the procedure described in U.S. Patent No. 4,786~713. The : copoly(phenylene sulfide) had a melt viscosity of about ~ 74,000 poise at 320C at a shear rate of 2~, sec-1. The :~ ~ ~al~ue of x for the copoly~phenylene sulfide) was estimated : to b,e about 0.094 based on elemental analysis. The polym~r : had~a glass transition temperature of about 94C as measured : by Differential Scanning Calorimetry. The glass transition temp,erature were determined as follows: ~he sample was first heated from room temperature to 330 at a heating rage 2~ of ~0C~min (first heating cycle). The sample was held at 330C ~or one minute and subsequently quenched to room temperature at 320OC~mln. In the second reheat cycle, it was heated at 20Oc~min to 330C, held for one minute at 330C, and then cooled at 200C~min. The temperaturç of crystallization, Tch, was obtained from the exothermic peak temperature during the second reheat cycle. The temperature of cryst~ zation upon cooling, Tcc was obtained during the cooling scan from the melt. The copc,ly~phenylene sulfide) has a melting polnt of 265C as measured by 1st cycle , W092/196~2 PCT/US92/03671 ~ 9 ~,3 r~ ~3 heating scan on DSC. The copoly(phenylene sulfide) did not show any significant crystallization exotherm during second heating scan or subsequent cooling scan from the melt, thus establishing that the copoly(phenylene sulfide) has a very : 5 slow crystallizing material.
:`
Exam~le 2 : This example illustrates the enhanced rate of crystallizati~n of the cvmpositions of this inventio~ :
composed ~f copoly(phenylene sulfide) and poly(hexamethylene adipamide).
Powder of the copoly(phenylene sulfide) prepared in Example l~was admixed with powdered poly(hexamethylene adipamide), to make a blend containing 80% by weight copoly(phenylene sulfide~ and 20% by weight o~
I5 poly(hPxamethylene adipamide). The admixture was dried at 90~ for 12 hours in a for~ed air-circulated oven. The polymer admixture was extruded thru an extruder. The temperature at th~ end of the die was kept at about 300C
and;~he rpm of the screw was about 90. The ex~ruded 2~0 material was analyzed by DSC for thermal transitions. The blended material had:a Tch (temperature of crystallizati~n during seco~d heating)~::of about 112C. DSC experiment was performed as follows~. The sample was:first heated from room : temperature to 330C at:a heating rate of 20C~min (first 5~ heating cycle)~ The sampIe was held at 330C for one minute and subse~uen~ly ~uenched to room temperature at 320~C~min.
In the second reheat cycle, it was heated at 20C~min to : 330C~ held for`one minute at 330C, and then cooled at :~
:20~c~min. The temperature of crystallization, Tch, was obtained from the~exothermic peak temperature~:;during the second r heat cycle. The temperature of crystallizati~n upon cooling, Tcc was obtained during the c~oling scan ~rom the melt. Tcc for the blend was about 222C. These data illustrate that the ompositions of this inve~tivn exhibits :
WO92/19682 PCT/US92/03~71 ~lo!~n7~ ;
an enhanced rate of crystallization composed to that of only ~.
copoly(phenylene sulfide).
xamPle 3 This example illustrates the faster crystallization rate of the composition of this invention.
Example 2 was repeated except that the amount of poly(hexamethylene adipamide) was 5~ by weight. The melt blended material h~d a Tch of 130.3C and Tcc of 202.5C.
The crystallization rate is much higher as compared to 100%
copoly(phenylene sulfide~ of Example l.
Example 4 This example illustrates the faster Grystallization rate of the composition of this invention.
Example 2: is repeated except that ~he amount of poly(hexamethylene adipamide) is reduced to 1% ~y weight.
The melt blended material had a Tch of 134C and tcc of 208C. These data establish that the compositio~ of the : ~ invention exhibits an enhanced rate of crysta1liza~ion : compared to~100% copoly(phenylene sulfide) of Example l.
2~0 ~Exam~Ie 5 : This example illustrates the faster crystallizati~n ;rate of the composition of this invention.
: :Example 2 i5 repeated @xcept that the amount o~
: : poly~(hexamethy-ene adipamide) is reduced ~o 0.5% by weight.
The melt blended material had a Tch of 167C and Tcc of 153.4C. These data establishes that the composition ~f ;this invention exhibit an enhanced rate of crystallization compared to 100% copoly(phenylene sulfide) of Example l.
210g~79 Exam~le 6 This example illustrates the faster crystallization rate of the composition of this invention comprises copoly(phenylene sulfide) and poly(e-caprolactam).
Five weight ~ poly(e-caprolactam) was melt blended with .
95 weight % of the copoly(phenylene sulfide~ used in Example 1. DSC transitions showed a Tch of 123C and Tcc of lg5.7C. These data establish a much faster rate of : : crystallization of the composition of the invention than ~:: 10 that for 100% copoly(phenylene sulfide) of Example 1.
:~ ., Example 7 This example illustrates the faster rate of crystallization;of the composition of this invention.
~ : 5 wt ~ of poly(w-undecaneamide) was melt blended with : : lS 95 wt % of copoly(phenylene sulfide). The procedure was the : ~ same as in Example 2.~ DSC transitions showed a Tch : (temperature of crystalli~ation upon heating) of lll~C and Tcc (temperature of crystallization upon cooling) of 206C.
~ This again illustrates faster crystallization behavior of :~ ~ 20 copoly~(phenylene sul~ide) in the blend.
: :
:~::: :
'~
Claims (5)
1. A composition comprising an admixture of (A) from 99.5 to 50 weight percent, based on the weight of the admixture, of a copoly(arylene sulfide) corresponding to the structure [ (-A-S)1-x(-A-S-S-)x ]n wherein A is a divalent substituted or unsubstituted aromatic radical, x is in the range of 0.5 to 0.001 and n is at least 25, and (B) from 0.5 to 50 weight percent, based on the weight of the admixture, of a polyamide corresponding to the structure wherein a is an integer in the range of 4 to 12, R corresponds to the structure (-CH2-)b wherein b is an integer in the range of 4 to 13 or to the structure wherein c is 0, 1, 2 or 3, and n is at least 25, or a polyamide corresponding to the structure wherein d is an integer in the range of 5 to 11 and m is at least 50.
2. The composition of claim 1 wherein the divalent aromatic radical is provided by diiodobenzene, diiodonaphthalene or diiodobiphenyl.
3. The composition of claim 1 wherein the divalent aromatic radical is selected from p-diiodobenzene, m-diiodobenzene, p,p'-diiodobiphenyl, p,p'-diiododiphenyl ether or 2,6-diiodonaphthalene.
4. The composition of claim 1 wherein a is an integer in the range of 4 to 8, b is an integer in the range of 4 to 8, c is 0 or 1 n is at least 25, d is an integer in the range of 5 to 11, and m is at least 50.
5. A composition comprising an admixture of (A) from 98 to 75 weight percent, based on the weight of the admixture, of a copoly(phenylene sulfide) corresponding to the structure [ (-A-S-)1-x(-A-S-S-)x ]n wherein A is a divalent phenylene radical, x is in the range of 0.5 to 0.001 and n is at least 50, and (B) from 2 to 25 weight percent, based on the weight of the admixture, of a polyamide corresponding to the structure wherein R corresponds to the structure (-CH2-)6 or to the structure and n is at least 50, or a polyamide corresponding to the structure wherein m is at least 75.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US69637891A | 1991-05-06 | 1991-05-06 | |
| US696,378 | 1991-05-06 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2109079A1 true CA2109079A1 (en) | 1992-11-07 |
Family
ID=24796816
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2109079 Abandoned CA2109079A1 (en) | 1991-05-06 | 1992-05-04 | Blends of copoly (arylene sulfide) and polyamide |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP0588885A1 (en) |
| JP (1) | JPH06507440A (en) |
| CA (1) | CA2109079A1 (en) |
| WO (1) | WO1992019682A1 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101183780B1 (en) * | 2006-08-24 | 2012-09-17 | 에스케이케미칼주식회사 | Manufacturing process for Polyarylene sulfide |
| US10494526B2 (en) | 2012-09-19 | 2019-12-03 | Sk Chemicals Co., Ltd. | Polyarylene sulfide resin composition and formed article |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4528335A (en) * | 1984-05-18 | 1985-07-09 | Phillips Petroleum Company | Polymer blends |
| JPH03229759A (en) * | 1990-02-02 | 1991-10-11 | Tosoh Corp | Polyphenylene sulfide resin composition |
-
1992
- 1992-05-04 CA CA 2109079 patent/CA2109079A1/en not_active Abandoned
- 1992-05-04 JP JP4511978A patent/JPH06507440A/en active Pending
- 1992-05-04 WO PCT/US1992/003671 patent/WO1992019682A1/en not_active Application Discontinuation
- 1992-05-04 EP EP19920912185 patent/EP0588885A1/en not_active Withdrawn
Also Published As
| Publication number | Publication date |
|---|---|
| JPH06507440A (en) | 1994-08-25 |
| EP0588885A1 (en) | 1994-03-30 |
| WO1992019682A1 (en) | 1992-11-12 |
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