CA2063492A1 - Polyester resin blends - Google Patents
Polyester resin blendsInfo
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- CA2063492A1 CA2063492A1 CA 2063492 CA2063492A CA2063492A1 CA 2063492 A1 CA2063492 A1 CA 2063492A1 CA 2063492 CA2063492 CA 2063492 CA 2063492 A CA2063492 A CA 2063492A CA 2063492 A1 CA2063492 A1 CA 2063492A1
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Abstract
ABSTRACT
This invention relates to thermoplastic molding compositions, comprising:
(a) a polyester resin derived from a cyclohexanedimethanol and a hexacarbocyclic dicarboxylic acid; and (b) a poly(arylene sulfide) resin preferably a poly(phenylene sulfide) resin, and, preferably, (c) a mineral reinforcing agent.
The compositions of the present invention have improved notched impact strength and certain other properties.
This invention relates to thermoplastic molding compositions, comprising:
(a) a polyester resin derived from a cyclohexanedimethanol and a hexacarbocyclic dicarboxylic acid; and (b) a poly(arylene sulfide) resin preferably a poly(phenylene sulfide) resin, and, preferably, (c) a mineral reinforcing agent.
The compositions of the present invention have improved notched impact strength and certain other properties.
Description
POLYESTER RESIN BLENDS
Keith N. Gray This invention relates to thermoplastic molding compositions that have improved physical properties.
More particularly, the invention pertains to reinforced compositions, preferably glass reinforced compositions, containing a poly(arylene sulfide) resin, preferably polyphenylene sulfide (PPS) resin; and (b) a polyester resin derived from a cyclohexane dimethanol and a carbocylic dicarboxylic acid or ester.
8ACKGROUND OF THE INVF~TION
High molecular weight polyesters and particularly linear polyesters derived from 1,4-cyclohexanedi-methanol have been available for a number of years.
These are described inter a_ in Kilber et al~
U.S. Pat. No. 2,901,466. This patent discloses that such polyesters are particularly advantageous as film and fiber-formers. The compositions disclosed herein are also used for injection molding, extrusion and other plastic forming operations.
20634g~
Keith N. Gray This invention relates to thermoplastic molding compositions that have improved physical properties.
More particularly, the invention pertains to reinforced compositions, preferably glass reinforced compositions, containing a poly(arylene sulfide) resin, preferably polyphenylene sulfide (PPS) resin; and (b) a polyester resin derived from a cyclohexane dimethanol and a carbocylic dicarboxylic acid or ester.
8ACKGROUND OF THE INVF~TION
High molecular weight polyesters and particularly linear polyesters derived from 1,4-cyclohexanedi-methanol have been available for a number of years.
These are described inter a_ in Kilber et al~
U.S. Pat. No. 2,901,466. This patent discloses that such polyesters are particularly advantageous as film and fiber-formers. The compositions disclosed herein are also used for injection molding, extrusion and other plastic forming operations.
20634g~
Poly(arylene sulfide) resins, e.g., poly(phenylene sulfide)(PPS), have become well known in the art for their thermal resistance, chemical resistance and an excellent balance of physical properties for use in preparing a variety of compositions useful in preparing articles by injection molding or compression molding techniques.
It has now been unexpectedly discovered that reinforced mixtures, preferably glass reinforced mixtures, of poly(cyclohéxane-dimethylene arylates) and poly(arylene sulfide) resin, particularly a PPS resin, exhibit an improvement in impact strength and other improved physical properties.
DETAILED DESCRIPTION OF THE INVENTION
The polyesters utilized in the process of the present invention are derived from cyclohexanedimethanol and are prepared by condensing either the cis- or trans-isomer (or a mixture thereof) of, for example, 1,4-cyclohexanedimethanol with a carbocyclic dicarboxylic acid or ester so as to produce a polyester having recurring units having the following formula I:
~CH2-CH2 R 1l wherein the substituted cyclohexane ring is selected 206349~
It has now been unexpectedly discovered that reinforced mixtures, preferably glass reinforced mixtures, of poly(cyclohéxane-dimethylene arylates) and poly(arylene sulfide) resin, particularly a PPS resin, exhibit an improvement in impact strength and other improved physical properties.
DETAILED DESCRIPTION OF THE INVENTION
The polyesters utilized in the process of the present invention are derived from cyclohexanedimethanol and are prepared by condensing either the cis- or trans-isomer (or a mixture thereof) of, for example, 1,4-cyclohexanedimethanol with a carbocyclic dicarboxylic acid or ester so as to produce a polyester having recurring units having the following formula I:
~CH2-CH2 R 1l wherein the substituted cyclohexane ring is selected 206349~
from the group consisting of the cis- and trans-isomers thereof and R represents an organic radical containing from 6 to 20 carbon atoms which is the decarboxylated residue derived from a carbocyclic d;carboxylic acid or ester.
The preferred polyester resins may be derived from the reaction of a mixture of the cis-and trans-isomers of 1,4-cyclohexanedimethanol with a mixture of iso- and terephthalic acids. These polyesters have recurring units of the formula II:
CH2 - CH2 l O-CH2-CH CH-CH2-0-C~C-These polyesters can be produced by well known methods in the art such as those set forth in U.S. 2,901,466. The poly (1,4-cyclohexanedimethanol terephthalate) is commercially available. Of course, it is understood that the polyester resins of this invention can be prepared by condensing 1,4-cyclohexanedimethanol and minor amounts of other bifunctional glycols with the carbocyclic dicarboxylic acid. These other bifunctional glycols include the polymethylene glycols containing from 2 to 10 or more carbon atoms such as ethylene glycol, butylene glycol, etc. Preferred polyesters will contain cyclohexane dimethanol units in which the ratio of the trans-/cis-isomer moities is greater than approximately 70%.
The term "carbocyclic" is used herein in its art recognized sense, that is, it refers to any organic compound whose carbon skeleton is in the form of a closed ring. Obviously, not all the atoms in the closed ring have to be carbon, although the term incorporates both aliphatic and aromatic compounds in which all the atoms are carbon. The preferred number of carbon atoms in the carbocyclic functionality employed in the present invention will generally range between 3 and about 15, with the more preferred number of carbon atoms being 6. In the most preferred embodiment of this invention, the carbocyclic dicarboxylic acid or ester is a hexacarbocyclic dicarboxylic acid or ester.
Examples of hexacarbocyclic dicarboxylic acids or esters wherein the carboxy radicals are attached in para relationship to a hexacarbocyclic residue indicated by R in formula (I) include terephthalic acid, trans-hexahydroterephthalic acid, 4,4'-sulfonyldibenzoic acid, 4,4' diphenic acid, 4,4'-benzophenone dicarboxylic acid, 1,2-di(p-carboxyphenyl)ethane, 1,2-di(p-carboxyphenyl)ethene, 1,2-di(p-carboxyphenoxy)-ethane, 4,4'-dicarboxydiphenyl ether, etc. and mixtures of these. All of these acids contain at least one hexacarbocyclic nucleus. Fused rings can also be present such as in 1,4-, 1,5 or 2,6-napthalenedicarboxylic acid. The hexacarbocyclic dicarboxylic acids or esters are preferably those containing a trans cyclohexane nucleus or an aromatic nucleus containing from one to two benzene rings of which at least one has the usual benzenoid unsaturation. Of course, either fused or attached rings can be present. All of the compounds named in this paragraph come within the scope of this preferred group. The preferred dicarboxylic acid is terephthalic acld.
These polyesters, which are alternatively refered to herein as "PCT Resins" should have an intrinsic viscosity between 0.40 and 2.0 dl./g.
measured in a 60/40 phenoltetrachloroethane solution or a similar solvent at 25-30C. Especially preferred polyesters will have an intrinsic viscosity in the range of 0.5 and 1.2 dl./g.
Any crystallizable poly(arylene sulfide)(PAS) can be employed in this invention, including copolymers, mixtures and blends. Usually, the PAS will contain repeat units of the formula [Ar-S]
wherein Ar is a divalent aromatic radical. Preferred divalent aromatic radicals can be independently selected from the group consisting of phenylene, ~ 6- 8CV-4986 biphenylene or naphthylene. Usually the poly(arylene sulfide) will comprise a poly(phenylene sulfide~ which has at least about 90 percent by weight of the repeat units with the formula ~ S _ Examples of methods for obtaining this polymer include a method which comprises polymerizing p dichlorobenzene in the presence of sulfur and sodium carbonate, a method which comprises polymerizing p-dichlorobenzene in a basic solvent in the presence ofsodium sulfide, or sodium hydrosulfide and sodium hydroxide or hydrogen sulfide and sodium hydroxide, and a method comprising self-condensation of p-chlorothiophenol.
PPS may also be prepared by reacting p-dichlorobenzene with sodium sulfide in a polar organic solvent to produce PPS and sodium chloride as a by-product.
The invention encompasses the use of either or both of linear and branched poly (arylene sulfides).
Virgin PPS is isolated as an off-white powder and is a linear material of modest molecular weight, ie.
approximately 15,000 - 20,000. This material is produced by the Toso Susteel Company under the tradename SUSTEEL 160.
206349~
_7- 8CV-4986 The composition of the present invention will also optionally include, as a third component of the com-posisition, at least one a mineral reinforcing agent, preferably a glass reinforcing agent. Suitable mineral reinforcing agents for use in the present invention include fillers such as talc, mica, wollastinite, asbestos and clay. Other suitable mineral reinforcing agents include fibrous materials such as ceramic fila-ments, carbon fibers, glass flake and milled glass.
The preferred mineral reinforcing agent is fibrous (filamentous) glass. Filamentous glass, is well known to those skilled in the art and is widely available from a number of manufacturers. For compositions ultimately to be employed for electrical uses, it is preferred to use fibrous glass filaments comprised of lime-aluminum borosilicate glass that is relatively soda free. This is known as "E" glass. However, other glasses are userul where electrical properties are not so important, e.g., the low soda glass known as "C"
glass. The filaments are made by standard processes, e.g., by steam or air blowing, flame blowing and mechanical pulling. The preferred filaments for plastic reinforcements are made by mechanical pulling.
The filament diameters range from about 0.00012 to 0.00075 inch, but this is not critical to the present invention. The length of the glass filaments is also -~- 8CV-498 not critical to the invention. However, in preparing the molding compositions, it is convenient to use the filamentous glass in the form of chopped strands of from about one-eighth to about two inches long. In articles molded from the compositions, on the other hand, even shorter lengths will be encountered because, during compounding considerable fragmentation will occur. This is desirable, however, because the best properties are exhibited by thermoplastic injection molded articles in which the filament lengths lie between about 0.0005 to 0.250 inch.
It should be unders~ood that the composition obtained according to this invention may contain one or more conventional additives such as, for example, antioxidants, carbon black, agents, plasticizers, rubbery impact modifiers, lubricity promoters, color stabilizers, ultraviolet absorbers, X-ray opacifiers, dyes, pigments, fillers, mold release agents, nucleants, and the like. The composition of the present invention can also contain standard halogenated flame retardant compounds, particularly brominated flame retardant compounds, with or without sodium antimonate. Examples of suitable flame retardant compounds for use in the present invention include brominated polystyrene, brominated epoxides, tetra-bromo bisphenol-A based polymers and the like.
2~3~92 When such flame retardant additives are utilized, the composition may also optionally contain an effec~ive amount of a drip inhibitor. Suitable non-dripping agents are well known and widely available. They include fumed and collidal silicas and polytetrafluoroethylene resins. Especially preferred are the polytetrafluoroethylene resins, most preferably TEFLON~6 from E.I. DuPont.
Representative phenol derivatives useful as stabilizers include 3,5-di-tert-butyl-hydroxy hydro-cinnamic triester with 1~3, 5-tris-(2-hydroxyethyl-s--triazine-2,4,6-(lH, 3H, 5H) trione; 4,4'-bis--(2,6-ditertiary-butylphenol); 1,3,5-trimethyl-2,4,6--tris-(3,5-ditertiary-butyl-4-hydroxylbenzyl)benzene and 4,4'-butylidene-bis (6-tertiary-butyl-m-cresol).
Mixtures of hindered phenols with esters or thiodipropionic, mercaptides and phosphite esters are particularly useful. Additional stabilization to ultraviolet light can be obtained by compounding with various UV absorbers such as substituted benzophenones and/or benzotriazoles.
Particularly useful stabilizers are hindered phenols which include phenols of the formula ~ R3 2063~92 wherein R3 and R4 are hydrocarbon groups having from one to about 20 carbon atoms, and Rs is a hydrogen atom or a hydrocarbon group having from one to about 20 carbon atoms, and bisphenol of the formula A ~ (CH2)n ~ A
wherein R6, R7 and R8 are each a hydrogen atom or a hydrocarbon group having from one to about 20 carbon atoms, one of the two A's on each ring is a hydroxyl group and the other A on each ring is a hydrogen atom or a hydrocarbon group having from one to about 20 carbon atoms; and n is an integer of from 0 to about 20.
The compositions of the present invention will preferably contain (a) from about 5% to about 95%
by weight, and prefereably from about 40% to about 80%
by weight of a resin derived from a cyclohexane--dimethanol and a carbocylic dicarboxylic acid and (b) from about 5 % to about 95% by weight and preferably from about 20% to about 60% by weight of a poly(arylene sulfide) resin, said weight percentages being based on the total weight of (a) and (b).
Optionally, the composition of the present invention may also contain from about 2% to about 100% by weight add-on and preferably from about 10% to about 70% by 2063~92 weight add-on of a mineral reinforcing agen~, based on the total weight of the polyester resin and the poly(arylene sulfide) resin.
The components of the composition of the present invention can be intimately blended in a number of procedures. In one way, the various additives to the polyester resin are put into an extrusion compounder with the dry polyester resin and the blend is heated at an elevated temperature, e.g., 560-600F., and extruded to produce molding pellets. The additives are mixed with the powdered or granular polyester and the mixture can be heated and directly formed into molded items using machines which compound and mold.
DESCRIPTION OF THE PREFERRED EMBODIMENT
The following examples are presented to more fully and clearly illus~rate the present invention.
They are presented as illustrative of the invention and are not to be construed as limiting the invention thereto. In the examples all parts and percentages are on a weight basis unless otherwise specified.
The following Example 1 illustrates a compo-sition following outside the scope of the instant invention in that it does not contain any poly(arylene sulfide) resin. Example 6 is also outside of the scope of the present invention in that it doesn't contain any of the specified polyester resin. These examples are ~063~9~
presented for comparative purposes only.
In all the examples, the compositions were pre-pared by melt blending the polyester resins and the indicated additional components as set forth in Table I
below using a 2.5 inch single screw extruder at approximately 570F. The resulting polymeric composition was formed, by injection molding, into test specimens of the size described in the corresponding ASTM methods. The notched izod and other properties of the compositions were tested with the results of these tests set forth in Table II below.
The following ASTM methods were used in determining the physical characteristics of the com-positions:
Flexural Strength ASTM D790 Tensile Properties ASTM D638 Izod Impact Strength ASTM D256 Shrinkage ASTM D955 TABLE I
FORMULATIONS
PCT 69.00 55.20 41.40 27.60 13.80 ---PPS --- 13.80 27.60 41.40 55.20 69.00 STAB 1 0.5 0.5 0.5 0.5 0.5 0.5 STAB 2 0.5 0.5 0.5 0.5 0.5 0.5 GLASS 30.00 30.00 30.00 30.00 30.00 30.00 PROPERTIES
MELT VISCOSITY 4,481 5,605 6,319 7,645 9,498 11,373 (POISE)@ 295C
HDT (F) 454 476 478 490 498 496 @ 264 psi NOTCHED IMPACT
(FT. LBS./IN.) 1.5 1.4 1.3 1.2 1.1 1.3 UNNOTCHED IMPACT
(FT. LBS./IN.) 9.616.2 14.1 10.2 6.9 9.5 TENSILE
ELONGATION (%) 7.7 8.7 9.0 8.8 7.7 8.6 STRENGTH (kpsi) 14.7 15.9 17.2 18.0 18.6 20.1 FLEXURAL
STRENGTH (kpsi) 23.1 22.9 25.0 25.3 26.7 27.3 MODULUS (kpsi) 897 996 975 1080 1110 1320 SHRINK (WITH/AGAINST FLOW) (MILS/IN.) 2 5/ 2 4/ 1 6/ 1 5 1 3 1 2 SPIRAL FLOW(IN.)8.69.2 9.6 10.7 NM NM
Tensile elongation was measured by cross head displacement on 2.5 by 0.5 inch Type 5 tensile bars.
Spiral flow was measured at 90 mil channel thickness for the spiral flow, at a melt temperature of 305 C.
PCT stands for poly(l,4-cyclohexane dimethanol), which is sold under the trademmark Eastman 3879 by the Eastman Kodak Company.
PPS stands for poly(phenylen~ sulfide, SUSTEEL 160, manufactured by Toso Susteel.
STAB 1 stands for tetrakis methylene (3,5-di-t-butyl-4-hydroxyhydrocinnamate) which is manufactured by Geigy Chemical Corporation under the trademark Irganox~ 1010.
STAB 2 stands for bis(2,4-di-t-butylphenyl) pentaerythritol diphosphate which is manufactured by G.E. Specialty Chemicals under the trademark ULTRANOX
626.
The glass utilized was 1/8" chopped strand glass fibers.
NM indicates not measured for those particular formulations.
2063~92 The above data indicates that physical properties of glass reinforced PCT/PPS blends are improved over glass filled blends of PCT or PPS alone. For example, it is surprising that the unnotched impact strength of various PCT/PPS blends is improved over the glass reinforced PCT or PPS compositions. The improvement in spiral flow upon addition of PPS to the glass filled PCT is especially surprising in view of the increased melt viscosity. Such improvement is clearly unexpected and is synergistic in nature.
Obviously, other modifications and variations of the present invention are possible in light of the above teachings. It is therefore to be understood that changes may be made in the particular embodi-ments of the invention described which are within thefull intended scope of the invention as defined by the appended claims.
The preferred polyester resins may be derived from the reaction of a mixture of the cis-and trans-isomers of 1,4-cyclohexanedimethanol with a mixture of iso- and terephthalic acids. These polyesters have recurring units of the formula II:
CH2 - CH2 l O-CH2-CH CH-CH2-0-C~C-These polyesters can be produced by well known methods in the art such as those set forth in U.S. 2,901,466. The poly (1,4-cyclohexanedimethanol terephthalate) is commercially available. Of course, it is understood that the polyester resins of this invention can be prepared by condensing 1,4-cyclohexanedimethanol and minor amounts of other bifunctional glycols with the carbocyclic dicarboxylic acid. These other bifunctional glycols include the polymethylene glycols containing from 2 to 10 or more carbon atoms such as ethylene glycol, butylene glycol, etc. Preferred polyesters will contain cyclohexane dimethanol units in which the ratio of the trans-/cis-isomer moities is greater than approximately 70%.
The term "carbocyclic" is used herein in its art recognized sense, that is, it refers to any organic compound whose carbon skeleton is in the form of a closed ring. Obviously, not all the atoms in the closed ring have to be carbon, although the term incorporates both aliphatic and aromatic compounds in which all the atoms are carbon. The preferred number of carbon atoms in the carbocyclic functionality employed in the present invention will generally range between 3 and about 15, with the more preferred number of carbon atoms being 6. In the most preferred embodiment of this invention, the carbocyclic dicarboxylic acid or ester is a hexacarbocyclic dicarboxylic acid or ester.
Examples of hexacarbocyclic dicarboxylic acids or esters wherein the carboxy radicals are attached in para relationship to a hexacarbocyclic residue indicated by R in formula (I) include terephthalic acid, trans-hexahydroterephthalic acid, 4,4'-sulfonyldibenzoic acid, 4,4' diphenic acid, 4,4'-benzophenone dicarboxylic acid, 1,2-di(p-carboxyphenyl)ethane, 1,2-di(p-carboxyphenyl)ethene, 1,2-di(p-carboxyphenoxy)-ethane, 4,4'-dicarboxydiphenyl ether, etc. and mixtures of these. All of these acids contain at least one hexacarbocyclic nucleus. Fused rings can also be present such as in 1,4-, 1,5 or 2,6-napthalenedicarboxylic acid. The hexacarbocyclic dicarboxylic acids or esters are preferably those containing a trans cyclohexane nucleus or an aromatic nucleus containing from one to two benzene rings of which at least one has the usual benzenoid unsaturation. Of course, either fused or attached rings can be present. All of the compounds named in this paragraph come within the scope of this preferred group. The preferred dicarboxylic acid is terephthalic acld.
These polyesters, which are alternatively refered to herein as "PCT Resins" should have an intrinsic viscosity between 0.40 and 2.0 dl./g.
measured in a 60/40 phenoltetrachloroethane solution or a similar solvent at 25-30C. Especially preferred polyesters will have an intrinsic viscosity in the range of 0.5 and 1.2 dl./g.
Any crystallizable poly(arylene sulfide)(PAS) can be employed in this invention, including copolymers, mixtures and blends. Usually, the PAS will contain repeat units of the formula [Ar-S]
wherein Ar is a divalent aromatic radical. Preferred divalent aromatic radicals can be independently selected from the group consisting of phenylene, ~ 6- 8CV-4986 biphenylene or naphthylene. Usually the poly(arylene sulfide) will comprise a poly(phenylene sulfide~ which has at least about 90 percent by weight of the repeat units with the formula ~ S _ Examples of methods for obtaining this polymer include a method which comprises polymerizing p dichlorobenzene in the presence of sulfur and sodium carbonate, a method which comprises polymerizing p-dichlorobenzene in a basic solvent in the presence ofsodium sulfide, or sodium hydrosulfide and sodium hydroxide or hydrogen sulfide and sodium hydroxide, and a method comprising self-condensation of p-chlorothiophenol.
PPS may also be prepared by reacting p-dichlorobenzene with sodium sulfide in a polar organic solvent to produce PPS and sodium chloride as a by-product.
The invention encompasses the use of either or both of linear and branched poly (arylene sulfides).
Virgin PPS is isolated as an off-white powder and is a linear material of modest molecular weight, ie.
approximately 15,000 - 20,000. This material is produced by the Toso Susteel Company under the tradename SUSTEEL 160.
206349~
_7- 8CV-4986 The composition of the present invention will also optionally include, as a third component of the com-posisition, at least one a mineral reinforcing agent, preferably a glass reinforcing agent. Suitable mineral reinforcing agents for use in the present invention include fillers such as talc, mica, wollastinite, asbestos and clay. Other suitable mineral reinforcing agents include fibrous materials such as ceramic fila-ments, carbon fibers, glass flake and milled glass.
The preferred mineral reinforcing agent is fibrous (filamentous) glass. Filamentous glass, is well known to those skilled in the art and is widely available from a number of manufacturers. For compositions ultimately to be employed for electrical uses, it is preferred to use fibrous glass filaments comprised of lime-aluminum borosilicate glass that is relatively soda free. This is known as "E" glass. However, other glasses are userul where electrical properties are not so important, e.g., the low soda glass known as "C"
glass. The filaments are made by standard processes, e.g., by steam or air blowing, flame blowing and mechanical pulling. The preferred filaments for plastic reinforcements are made by mechanical pulling.
The filament diameters range from about 0.00012 to 0.00075 inch, but this is not critical to the present invention. The length of the glass filaments is also -~- 8CV-498 not critical to the invention. However, in preparing the molding compositions, it is convenient to use the filamentous glass in the form of chopped strands of from about one-eighth to about two inches long. In articles molded from the compositions, on the other hand, even shorter lengths will be encountered because, during compounding considerable fragmentation will occur. This is desirable, however, because the best properties are exhibited by thermoplastic injection molded articles in which the filament lengths lie between about 0.0005 to 0.250 inch.
It should be unders~ood that the composition obtained according to this invention may contain one or more conventional additives such as, for example, antioxidants, carbon black, agents, plasticizers, rubbery impact modifiers, lubricity promoters, color stabilizers, ultraviolet absorbers, X-ray opacifiers, dyes, pigments, fillers, mold release agents, nucleants, and the like. The composition of the present invention can also contain standard halogenated flame retardant compounds, particularly brominated flame retardant compounds, with or without sodium antimonate. Examples of suitable flame retardant compounds for use in the present invention include brominated polystyrene, brominated epoxides, tetra-bromo bisphenol-A based polymers and the like.
2~3~92 When such flame retardant additives are utilized, the composition may also optionally contain an effec~ive amount of a drip inhibitor. Suitable non-dripping agents are well known and widely available. They include fumed and collidal silicas and polytetrafluoroethylene resins. Especially preferred are the polytetrafluoroethylene resins, most preferably TEFLON~6 from E.I. DuPont.
Representative phenol derivatives useful as stabilizers include 3,5-di-tert-butyl-hydroxy hydro-cinnamic triester with 1~3, 5-tris-(2-hydroxyethyl-s--triazine-2,4,6-(lH, 3H, 5H) trione; 4,4'-bis--(2,6-ditertiary-butylphenol); 1,3,5-trimethyl-2,4,6--tris-(3,5-ditertiary-butyl-4-hydroxylbenzyl)benzene and 4,4'-butylidene-bis (6-tertiary-butyl-m-cresol).
Mixtures of hindered phenols with esters or thiodipropionic, mercaptides and phosphite esters are particularly useful. Additional stabilization to ultraviolet light can be obtained by compounding with various UV absorbers such as substituted benzophenones and/or benzotriazoles.
Particularly useful stabilizers are hindered phenols which include phenols of the formula ~ R3 2063~92 wherein R3 and R4 are hydrocarbon groups having from one to about 20 carbon atoms, and Rs is a hydrogen atom or a hydrocarbon group having from one to about 20 carbon atoms, and bisphenol of the formula A ~ (CH2)n ~ A
wherein R6, R7 and R8 are each a hydrogen atom or a hydrocarbon group having from one to about 20 carbon atoms, one of the two A's on each ring is a hydroxyl group and the other A on each ring is a hydrogen atom or a hydrocarbon group having from one to about 20 carbon atoms; and n is an integer of from 0 to about 20.
The compositions of the present invention will preferably contain (a) from about 5% to about 95%
by weight, and prefereably from about 40% to about 80%
by weight of a resin derived from a cyclohexane--dimethanol and a carbocylic dicarboxylic acid and (b) from about 5 % to about 95% by weight and preferably from about 20% to about 60% by weight of a poly(arylene sulfide) resin, said weight percentages being based on the total weight of (a) and (b).
Optionally, the composition of the present invention may also contain from about 2% to about 100% by weight add-on and preferably from about 10% to about 70% by 2063~92 weight add-on of a mineral reinforcing agen~, based on the total weight of the polyester resin and the poly(arylene sulfide) resin.
The components of the composition of the present invention can be intimately blended in a number of procedures. In one way, the various additives to the polyester resin are put into an extrusion compounder with the dry polyester resin and the blend is heated at an elevated temperature, e.g., 560-600F., and extruded to produce molding pellets. The additives are mixed with the powdered or granular polyester and the mixture can be heated and directly formed into molded items using machines which compound and mold.
DESCRIPTION OF THE PREFERRED EMBODIMENT
The following examples are presented to more fully and clearly illus~rate the present invention.
They are presented as illustrative of the invention and are not to be construed as limiting the invention thereto. In the examples all parts and percentages are on a weight basis unless otherwise specified.
The following Example 1 illustrates a compo-sition following outside the scope of the instant invention in that it does not contain any poly(arylene sulfide) resin. Example 6 is also outside of the scope of the present invention in that it doesn't contain any of the specified polyester resin. These examples are ~063~9~
presented for comparative purposes only.
In all the examples, the compositions were pre-pared by melt blending the polyester resins and the indicated additional components as set forth in Table I
below using a 2.5 inch single screw extruder at approximately 570F. The resulting polymeric composition was formed, by injection molding, into test specimens of the size described in the corresponding ASTM methods. The notched izod and other properties of the compositions were tested with the results of these tests set forth in Table II below.
The following ASTM methods were used in determining the physical characteristics of the com-positions:
Flexural Strength ASTM D790 Tensile Properties ASTM D638 Izod Impact Strength ASTM D256 Shrinkage ASTM D955 TABLE I
FORMULATIONS
PCT 69.00 55.20 41.40 27.60 13.80 ---PPS --- 13.80 27.60 41.40 55.20 69.00 STAB 1 0.5 0.5 0.5 0.5 0.5 0.5 STAB 2 0.5 0.5 0.5 0.5 0.5 0.5 GLASS 30.00 30.00 30.00 30.00 30.00 30.00 PROPERTIES
MELT VISCOSITY 4,481 5,605 6,319 7,645 9,498 11,373 (POISE)@ 295C
HDT (F) 454 476 478 490 498 496 @ 264 psi NOTCHED IMPACT
(FT. LBS./IN.) 1.5 1.4 1.3 1.2 1.1 1.3 UNNOTCHED IMPACT
(FT. LBS./IN.) 9.616.2 14.1 10.2 6.9 9.5 TENSILE
ELONGATION (%) 7.7 8.7 9.0 8.8 7.7 8.6 STRENGTH (kpsi) 14.7 15.9 17.2 18.0 18.6 20.1 FLEXURAL
STRENGTH (kpsi) 23.1 22.9 25.0 25.3 26.7 27.3 MODULUS (kpsi) 897 996 975 1080 1110 1320 SHRINK (WITH/AGAINST FLOW) (MILS/IN.) 2 5/ 2 4/ 1 6/ 1 5 1 3 1 2 SPIRAL FLOW(IN.)8.69.2 9.6 10.7 NM NM
Tensile elongation was measured by cross head displacement on 2.5 by 0.5 inch Type 5 tensile bars.
Spiral flow was measured at 90 mil channel thickness for the spiral flow, at a melt temperature of 305 C.
PCT stands for poly(l,4-cyclohexane dimethanol), which is sold under the trademmark Eastman 3879 by the Eastman Kodak Company.
PPS stands for poly(phenylen~ sulfide, SUSTEEL 160, manufactured by Toso Susteel.
STAB 1 stands for tetrakis methylene (3,5-di-t-butyl-4-hydroxyhydrocinnamate) which is manufactured by Geigy Chemical Corporation under the trademark Irganox~ 1010.
STAB 2 stands for bis(2,4-di-t-butylphenyl) pentaerythritol diphosphate which is manufactured by G.E. Specialty Chemicals under the trademark ULTRANOX
626.
The glass utilized was 1/8" chopped strand glass fibers.
NM indicates not measured for those particular formulations.
2063~92 The above data indicates that physical properties of glass reinforced PCT/PPS blends are improved over glass filled blends of PCT or PPS alone. For example, it is surprising that the unnotched impact strength of various PCT/PPS blends is improved over the glass reinforced PCT or PPS compositions. The improvement in spiral flow upon addition of PPS to the glass filled PCT is especially surprising in view of the increased melt viscosity. Such improvement is clearly unexpected and is synergistic in nature.
Obviously, other modifications and variations of the present invention are possible in light of the above teachings. It is therefore to be understood that changes may be made in the particular embodi-ments of the invention described which are within thefull intended scope of the invention as defined by the appended claims.
Claims (20)
1. A thermoplastic composition comprising:
(a) a polyester resin derived from a cyclohexanedimethanol and a carbocyclic dicarboxylic acid; and (b) a polyarylene sulfide resin.
(a) a polyester resin derived from a cyclohexanedimethanol and a carbocyclic dicarboxylic acid; and (b) a polyarylene sulfide resin.
2. The composition of Claim 1 further comprising (c) a mineral reinforcing agent.
3. The composition of Claim 2 wherein, the mineral reinforcing agent is a glass reinforcing agent.
4. The composition according of claim 3 wherein the glass reinforcing agent is glass fibers.
5. The composition of Claim 1 wherein component (a) comprises from about 5% to about 95% by weight of the total by weight of components (a) and (b).
6. The composition of Claim 5 wherein component (a) comprises from about 40% to about 80% by weight of the total by weight of components (a) and (b).
7. The composition of Claim 1 wherein component (b) comprises from about 5% to about 95% by weight of the total by weight of components (a) and (b).
8. The composition of Claim 7 wherein component (b) comprises from about 20% to about 60% by weight of the total of components (a), (b), and (c).
9. The composition of Claim 1 wherein component (c) comprises from about 2% to about 100% add-on by weight of the total by weight of components (a) and (b).
10. The composition of Claim 9 wherein component (c) comprises from about 10% to about 70% add-on by weight of the total by weight of components (a) and (b).
11. The composition as defined in Claim 1 wherein the carbocyclic acid is a hexacarbocyclic acid.
12. A composition as defined in Claim 11 wherein component (a) has repeating units of the formula:
wherein the substituted cyclohexane ring is selected from the group consisting of the cis- and trans-isomers thereof and R represents an organic radical containing from 6 to 20 carbon atoms which is the decarboxylated residue derived from a hexacarbocyclic dicarboxylic acid.
wherein the substituted cyclohexane ring is selected from the group consisting of the cis- and trans-isomers thereof and R represents an organic radical containing from 6 to 20 carbon atoms which is the decarboxylated residue derived from a hexacarbocyclic dicarboxylic acid.
13. A composition as defined in Claim 12 wherein the polyester resin has the repeating unit:
14. A composition as defined in Claim 1 wherein the polyester resin contains cyclohexane dimethanol units containing a trans-/cis-isomer ratio greater than approximately 70%.
15. A composition as defined in Claim 1 wherein said poly-(arylene sulfide) resin has repeat units of the formula [Ar-S]
wherein Ar is a divalent aromatic radical independently selected from the group consisting of phenylene, biphenylene and naphthylene.
wherein Ar is a divalent aromatic radical independently selected from the group consisting of phenylene, biphenylene and naphthylene.
16. The composition according to claim 15 wherein said poly(arylene sulfide) resin composition comprises a poly(phenylene sulfide) resin.
17. A method according to claim 16 wherein said poly(phenylene sulfide) is poly(p-phenylene sulfide).
18. The composition of claim 1 which further contains an effective stabilizing amount of at least one thermal stabilizer.
19. A thermoplastic composition comprising:
(a) a polyester resin derived from a cyclohexanedimethanol and a hexacarbocyclic dicarboxylic acid;
(b) a polyarylene sulfide resin; and (c) a glass fiber reinforcing agent.
(a) a polyester resin derived from a cyclohexanedimethanol and a hexacarbocyclic dicarboxylic acid;
(b) a polyarylene sulfide resin; and (c) a glass fiber reinforcing agent.
20. The invention as defined in any of the preceding claims including any further features of novelty disclosed.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA 2063492 CA2063492A1 (en) | 1992-03-19 | 1992-03-19 | Polyester resin blends |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA 2063492 CA2063492A1 (en) | 1992-03-19 | 1992-03-19 | Polyester resin blends |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2063492A1 true CA2063492A1 (en) | 1993-09-20 |
Family
ID=4149461
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2063492 Abandoned CA2063492A1 (en) | 1992-03-19 | 1992-03-19 | Polyester resin blends |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA2063492A1 (en) |
-
1992
- 1992-03-19 CA CA 2063492 patent/CA2063492A1/en not_active Abandoned
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