CA1087777A - Tough thermoplastic polyester compositions - Google Patents
Tough thermoplastic polyester compositionsInfo
- Publication number
- CA1087777A CA1087777A CA253,144A CA253144A CA1087777A CA 1087777 A CA1087777 A CA 1087777A CA 253144 A CA253144 A CA 253144A CA 1087777 A CA1087777 A CA 1087777A
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- Canada
- Prior art keywords
- carbon atoms
- percent
- random copolymer
- taken
- class consisting
- Prior art date
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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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
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
Abstract
ABSTRACT OF THE DISCLOSURE
Toughened multi-phase thermoplastic composition consisting essentially of one phase containing 60 to 99 percent by weight of a polyester including polycarbonate matrix resin of inherent viscosity of at least 0.35 deciliter/gram, and 1 to 40 percent by weight of at least one other phase containing particles of at least one random copolymer having a particle size in the range of 0.01 to 3.0 microns and being adhered to the polyester, the at least one random copolymer having a tensile modulus in the range of 1.0 to 50,000 p.s.i., the ratio of the tensile modulus of the polyester matrix resin to tensile modulus of said at least one polymer being greater than 10 to 1. Said at least one polymer is either a branched or straight chain polymer. The toughened compositions are useful for making molded and extruded parts. Such parts possess greater ductility, less reduction in toughness from scratches and molded-in notches and reduced susceptibility to catastrophic failure when compared to known melt fabricated materials.
Toughened multi-phase thermoplastic composition consisting essentially of one phase containing 60 to 99 percent by weight of a polyester including polycarbonate matrix resin of inherent viscosity of at least 0.35 deciliter/gram, and 1 to 40 percent by weight of at least one other phase containing particles of at least one random copolymer having a particle size in the range of 0.01 to 3.0 microns and being adhered to the polyester, the at least one random copolymer having a tensile modulus in the range of 1.0 to 50,000 p.s.i., the ratio of the tensile modulus of the polyester matrix resin to tensile modulus of said at least one polymer being greater than 10 to 1. Said at least one polymer is either a branched or straight chain polymer. The toughened compositions are useful for making molded and extruded parts. Such parts possess greater ductility, less reduction in toughness from scratches and molded-in notches and reduced susceptibility to catastrophic failure when compared to known melt fabricated materials.
Description
10~'7777 - BACKGROUND OF THE INVENTION
Field of the Invention mis invention relates to thermoplastic composi-tions, and more particularly to polyester including poly-carbonate compositions having improved ductility or toughness, and to the processes for preparing such compositions.
Description of the Prior Art Unmodified thermoplastic polyesters are frequently regarded as "tough". For ~xample~ some polyesters have good elongation; high energy to break, as demonstrated in tensile tests; high tensile impact strength and high energy absorption as demonstrated in falling dart tests, e.g., the Gardner impact test.
In one aspect of-toughness the polyester materials are quite erratic; namely~ resistance to crack propagation.
mis deficiency is reflected in notch sensitivity, brittle breaks and occasional catastrophic failure of molded or extruded parts. The tendency of some poly- -esters to break in a brittle rather than ductile fashion is a significant limitation of utility. A resin may be characterized in its tendency toward ductility by the notched Izod test ASTM D-2~6-56. With the normal notch radius of 10 mils~ polyethylene terephthalate and polybutylene terephthalate will have notched Izod values of about 0.3 to 1 ft. lb./inch of notch. Polyesters known as polycarbonates may have values in the range of 10 to 1~ ft. lbs./inch of notch in 1/~ inch sections, but the value falls off rapidly when the notch radius is decreased or thicker samples are used.
Field of the Invention mis invention relates to thermoplastic composi-tions, and more particularly to polyester including poly-carbonate compositions having improved ductility or toughness, and to the processes for preparing such compositions.
Description of the Prior Art Unmodified thermoplastic polyesters are frequently regarded as "tough". For ~xample~ some polyesters have good elongation; high energy to break, as demonstrated in tensile tests; high tensile impact strength and high energy absorption as demonstrated in falling dart tests, e.g., the Gardner impact test.
In one aspect of-toughness the polyester materials are quite erratic; namely~ resistance to crack propagation.
mis deficiency is reflected in notch sensitivity, brittle breaks and occasional catastrophic failure of molded or extruded parts. The tendency of some poly- -esters to break in a brittle rather than ductile fashion is a significant limitation of utility. A resin may be characterized in its tendency toward ductility by the notched Izod test ASTM D-2~6-56. With the normal notch radius of 10 mils~ polyethylene terephthalate and polybutylene terephthalate will have notched Izod values of about 0.3 to 1 ft. lb./inch of notch. Polyesters known as polycarbonates may have values in the range of 10 to 1~ ft. lbs./inch of notch in 1/~ inch sections, but the value falls off rapidly when the notch radius is decreased or thicker samples are used.
-2 10t~7 777 There is much prior art concerned with improving the impact strength of polyester~. A variety of additives have been added to polyesters with some improvement in toughness being obtained. British Patent 1,208,585 of A.J.
Di~kætra et al., published October 14, 1970, discloses that a notched Izod of 4.3 ft. lbs./~nch can be achieved with the addition of 25 percent by weight terpolymer to the polyester.
British Patent 1,208,585 fails to recognize that combination of properties necessary to achieve high toughness. For example, particle size ranges from 0.5 to 10 microns; if the size is too small the improvement in impact strength may be reduced. In additlon, the material which causes the adherence iæ not present in the phase with the at least one polymer, Cope U.S. Patent 3,435,093 discloses blends of polyethylene terephthalate and an ionic hydrocarbon copolymer of ~-olefins of the formula R-CH-CH2 where R is hydrogen or an alkyl radi-cal of 1 to 3 carbon atoms and ~,~-ethylenically unsaturated carboxylic acids containing 3 to 5 carbon atoms, the carboxylic acid groups of the ionic copolymer being O to 100 percent neutralized by metal cations. Cope states that improvement in toughness is achieved by the blends. Cope, however, did not recogni~e that improved toughness of poly-ester compositions can be achieved provided that at least one polymer present has a small particle size, a tensile modulus of 50,000 or lesæ and the ratio of the tensile modulus of the polyester to the tensile modulus o~ said polymer is greater than 10 to 1.
Gander et al. U.S. Patent 4,020,126, issued
Di~kætra et al., published October 14, 1970, discloses that a notched Izod of 4.3 ft. lbs./~nch can be achieved with the addition of 25 percent by weight terpolymer to the polyester.
British Patent 1,208,585 fails to recognize that combination of properties necessary to achieve high toughness. For example, particle size ranges from 0.5 to 10 microns; if the size is too small the improvement in impact strength may be reduced. In additlon, the material which causes the adherence iæ not present in the phase with the at least one polymer, Cope U.S. Patent 3,435,093 discloses blends of polyethylene terephthalate and an ionic hydrocarbon copolymer of ~-olefins of the formula R-CH-CH2 where R is hydrogen or an alkyl radi-cal of 1 to 3 carbon atoms and ~,~-ethylenically unsaturated carboxylic acids containing 3 to 5 carbon atoms, the carboxylic acid groups of the ionic copolymer being O to 100 percent neutralized by metal cations. Cope states that improvement in toughness is achieved by the blends. Cope, however, did not recogni~e that improved toughness of poly-ester compositions can be achieved provided that at least one polymer present has a small particle size, a tensile modulus of 50,000 or lesæ and the ratio of the tensile modulus of the polyester to the tensile modulus o~ said polymer is greater than 10 to 1.
Gander et al. U.S. Patent 4,020,126, issued
3--., .
'~
l~W~7 April 26, 1977, discloses a polyethylene terephthalate/
terpolymer blend, the terpolymer being present in 1 to 5 percent by weight and comprising at least 65 percent by weight ethylene with (a) at least 5 percent by weight of vinyl ester of a 1 to 6 carbon atom saturated monobasic aliphatic carboxylic acid and (b) 0.5 to 10 percent by weight of acrylic or methacrylic acid. It is disclosed that polyethylene terephthalate blended with the terpolymer is tough. It is not tau~ht that improved toughness can be achieved in polyesters if the particle size, tensile modulus of the at least one polymer and the ratio of tensile modulus of the at least one polymer and the polyester matrix ;-resin are maintained within certain ranges.
French Patent 2,194,741 of X.P. Perry et al., published March 1, 1974, relates to blends of polyesters ;
melting above 100C. with 1.5 to 90 percent by weight of a copolyether ester. Impact strength is said to be improved.
The copolyether esters are block copolymers rather than random copolymers. There is no teaching that tensile modulus, ratios of tensile modulus and particle size of the pol~mer additive are necessary to provide improved toughness.
Polycarbonates are known to be among the tougher materials used for molded and extruded parts.
Kim U.S. Patent 3,334,154 is an example. It has been found, however, that when polycarbonates have been tested for toughness using the notched Izod test as indicated above the toughness is a funct~on of the notch radius.
This disadvantage is substantially eliminated when at least one polymer according to this invention is present ~ A
'.~
los7m . with the polycar~onate.
S~R~ OF THE INVENTION
According to this invention~ there is proYided a toughened multi-phase thermoplàstic composition consist-ing essentially of one phase containing 60 to 99 percent by weight o~ a matrix resin taken frQm the class consist-ing of (a) polyester matrix resin having an inherent viscosity in the range of abou~ 0.4 to 4.0 deciliters/
gram~ said polyester being prepared from an aramatic di-.
carboxylic acid having from ~ to 14 carbon atoms and at least one glycol taken from the class consisting of a glycol of the formula HO(CH2)nOH where n is an integer of 2 to 10, neopentyl glycol and cyclohexane dimethanol, a portion of the moles of acid being replaceable by at least one acid taken from the group consisting of at least one different aromatic dicarboxylic acid having from B to 14 carbon atoms in an amount up to 50 mole percent, and an aliphatic dicarboxylic acid having from 2 to 12 carbon atoms in an amount up to 20 mole percent; and (b) polycarbonate matrix resin ha~ing an inherent viscosity in the range of about 0.35 to 0.75 deciliter/
gram, said polycarbonate possessing recurring str~cttral units of the formula:
~ .
. !~A--~ ~
where A is a divalent aromatic radical o~ a dihydric -phenol; and 1 to ~0 percent.by weight of at least ~ne other phase containing particles of at least one random ~p~lymer taken from t~e class consisting Or branched and s~r2ight chain polymers, said at least one random copolymer.ha~ing 108777 7 .
a particle size in the range of 0.01 to 3.0-microns, being adhered to the matrix resin, and ha~ing a tensile modulus in the range of about 1.0 to 50,000 p.s.i., the ratio of the tensile modulus Or the matrix resin to tensile modulus o~ said at least one random copolymer being greater than 10 to 1.
me term "consisting essentially of" means that in addition to the required matrix resin and the at least one random copolymer, other components can be present in the toughened composition provided that the basic and essential characteristics of the toughened composition are not materially affected thereby.
The term "branched and straight chain polymers' means that the polymers are not crosslinked to a degree which will increase their modulus to greater than 50,000 p.s.i. or decrease their melt ~low to a level which pre-vents effective dispersion.
According to another aspect of this invention, there is provided a process for the preparation of a toughened multi-phase thermoplastic composition which comprises, in a closed system, (A) admixing (1) 60 to 99 percent by weight of a matrix resin taken from the class consisting of (a) polyester matrix resin and (b) polycarbonate as defined above~ and (2) 1 to 40 percent - ~ by weight of at least one random copolymer at a tempera-ture in the range of about 5 to 100C. above the melting point of said matrix resin and (B) shearing to disperse the at least one random copolymer in said matrix to a particle size in the range of 0.01 to 3.0 microns, said at least one random copolymer being adhered to said matrix losm7 and having a tensile modulus in the range of 1.0 ~o 50~000 p.s.i.~ the ratio of the tensile moduius of said matrix to tensile modulus of said at least one random c.opolymer being greater than 10 to 1.
DETAILED DESCRIPTION OF THE INVENTION
. me resins that function as the matrix resin of the toughened compositions of this invention are well known in the art. The matrix resins can be o~ the polyester types as described above having an inherent viscosit~ in the range of about 0.4 to 4.0 deciliters/
gram~ the polycarbonate types also as described above having an inherent viscosity in.the range of about 0.35 to 0.75 deciliter/gram and mixtures of said resins.
The term "polyester resins" includes, in general, linear saturated condensation products of glycols and dicarboxylic acids, or reactive derivatives thereof.
Preferably, they will comprise condensation products of aromatic dicarboxylic acids having ~ to 14 carbon atoms and at least one glycol of the formula HO(CH2)nOH where n is an integer of 2 to 10, neopentyl glycol, and cyclo-hexane dimethanol. Up to 50 mole percent of the aromatic dicarboxylic acids can be replaced by at least one different ar~matic dicarboxylic acid having from B to 1~ carbon atoms, and/or up to 20 mole percent can be replaced by an aliphatic dicarboxylic acid having from 2 to 12 carbon atoms.
The preferred polyesters are well ~nown as film and fiber ~ormers, and they are provided by methods outlined in Whinfield et al. U. S. Patent 2,465~319 and Pengilly U. S. Patent 3~0~7,539. The preferred polyesters will comprise polyethylene terephthalate;
poly(l,4-butylene) terephthalate; and l,~-cyclohexylene dimethylene terephthalate/isophthalate copolymer and other linear homopolymer esters deriYed from aromatic dicarboxylic acids, including isophthalic, bibenzoic, naphthalene-dicarboxylic including the 1,5-; 2,6-; and 2,7-naphthalenedicarboxylic acids; 4,4'-diphenylenedi-carboxylic acid; bis(p-carboxyphenyl) methane; ethylene-bis-p-benzoic acid; 1,4-tetramethylene bis(p-oxybenzoic) acid; ethylene bis(p-oxybenzoic) acid; 1,3-trimethylene bis(p-oxybenzoic) acid; and l,~-tetramethylene bis(p-oxybenzoic acid, and glycols of the general formula ~O(CH2)nOH where n is an integer from 2 to 10, e.g., ethylene glycol; 1,3-trimethylene glycol; 1,4-tetra-methylene glycol; l,6-hexamethylene glycol; l,~-octa-methylene glycol; 1,10-decamethylene glycol; 2~2- -dimethyl-1,3-propane diol; 1,3-propylene glycol; 1,~-butylene glycol; neopentyl glycol and cyclohexa~e di-methanol. Up to 20 mole percent, as indicated above, of one or more aliphatic acids, including adipic, sebacic, azelaic, dodecanedioic acid or 1,4-cyclohexanedicarboxylic ~ acid can be present. It is understood that the polyesters may include minor quantities of ethers incidentally formed as by-products from the glycols employed in the preparation of the polymeric ester.
The inherent viscosity of the polyesters and polycarbonates is measured at a concentration of 0.32 g./100 ml. in trifluoroacetic acid (25)/methylene chloride (75) at 25 + 0.10C. It is computed by the formula-losm7 natural log elution time of solution elution of solvent Inherent Viscosity = C
where C is the concentration expressed in grams of polymer per 100 milliliters of solution. The viscometer used is a calibrated Ostwald-Cannon-Finske viscometer No. 50 (Ace Glass Co.).
The term "polycarbonate resin" as used herein is meant to embrace within its scope carbonate polymers of dihydric phenols as well as carbonate copolymers of such dihydric phenols with glycols, such as ethylene glycol or propylene glycol, for example dibasic acids, such as, for example, isophthalic or terephthalic acid;
and hydroxyl or acid-terminated polyesters, such as, for example, the hydroxyl or acid-terminated polyester of neopentyl glycol and adipic acid. Such polycarbonate resins may be prepared by reacting a dihydric phenol with a carbonate precursor such as phosgene, a halo-formate or a carbonate ester. Generally speaking, the resulting carbonate polymers may be typified as possessing recurring structural units of the formula:
r 0l ~ O-A-O- ~
where A is a divalent aromatic radical of the dihydric phenol, preferably bisphenol A, employed in the polymer pro-ducing reaction. Preferably, the polycarbonate resins have inherent viscosities (as measured in p-dioxane in deciliters per gram at 30C.) ranging from about 0.35 to about 0.75.
The dihydric phenols which may be employed to provide such aromatic carbonate polymers are mononuclear or polynuclear aromatic compounds, containing as functional _g _ - losm7 groups, two hydroxyl radicals, each of which is attached directly to a carbon atom of an aromatic'nucleus.
Typical dihydric phen~ls are 2,2 ~is-(4-hydroxyphenyl)-pr'opane; hydroquinone;resorcino~ 2,2 bis-(4-hydroxy-phenyl)-pentane; 2,~' dihydroxydiphenyl methane; bis-(2-hydroxyphenyl)-methane; bis(~-hydroxyphenyl)-methane;
bis-(4-hydroxy-5-nitrophenyl)-methane; 1,1 bis-(4-hydroxyphenyl)-ethane; 3,3 bis-(4-hydroxyphenyl)-pentane; 2,2' dihydroxydiphenyl; 2,6 dihydroxy naphthal-ene; bis-(~-hydroxyphenyl)-sulfone; 2,2' dihydroxydiphenyl sulfone; 4~' dihydroxydiphenyl ether; and ~4' dihydroxy-2,5-diethoxydiphenyl ether. A ~ariety of additional dihydric phenols which may be employed to provide such carbonate polymers are disclosed in Goldberg U. S. Patent 2~999,~35. It is~ of course, possible to employ two or more different dihydric phenols or~ as stated above, a dihydric phenol in combination with a glycol, a hydroxy or acid-terminated polyester, or a dibasic acid in the event a carbonate copolymer rather than a homopolymer is desired.
As great as 99 percent by weight of the composition can be composed of matrix resin; however, preferred compositions contain from 60 to 99 percent, and more narrowly ~0 to 95 percent, by weight of matrix resin.
The composition is toughened by the combination of at least one random copolymer with the matrix resin.
The term "at least one random copolymer" means one or more copolymers, and optionally one or more homopolymers, which coexist in single discrete particles haYing a los~m . -particle size ranging from 0.01 to 3 microns, preferably0.02 to 1 micron, within the matrix, so that either the mixture of polymers or at least one of the copolymers in the mixture meets the following criteria.
(a) sites which adhere to the matrix resin;
(b) tensile modulus, as added, in the range of about 1.0 to 50,000 p.s.i., preferably about 5 to 20,000 p.s.i., the ratio Or tensile modulus of the matrix resin to tensile modulus of said at least one random copolymer being greater than 10 to 1, preferably greater than 20 to 1.
The matrix resin is the continuous phase in the composition and the at least one random copolymer,some-times referred to as polymer, performs the function of a soft dispersed phase which is adhered to the matrix resin.
The polymer may be elastomeric, but it has been found that thermoplastic polymers which are not elastomeric are also effective in the compositions.
me polymers are branched or straight chain and are of such composition that crosslinking other than by reaction with the matrix resin is not necessary to their function and excessive crosslinking may, in fact, be harmful.
Branched and straight chain polymers userul as - the soft phase of the composition are represented by the formula:
A(a~ B(b)-c(c)-D(d)-E(e)-F(r)-G(g)-H(h) deriYed in any order~ e.g., random, ~rom monomers A to 0 H where A is ethylene;
B is C0;
los7m C is an unsaturatPd monomer taken from the class consisting of ~ ethylenically unsaturated carboxylic acids having from 3 to ~ carbon atoms, and deri~atives thereof taken from the class consistin~ of monoesters of alcohols of l-to 29 carbon atoms and the dicsrboxylic acids and anhydrides of the dicarboxylic acids and the metal salts of the monocarboxylic, di- -- carboxylic acids and the monoester of the di-carboxylic acid having from 0 to 100 percent of the carboxylic acid groups ionized by - - neutralization with metal ions and dicarboxylic acids and monoesters of the dicarbo~ylic acid neutralized by amine-ended caprolactam oligomers -~
having a DP of 6 to 24;
D is an unsaturated epoxide of ~ to 11 carbon atoms;
E is the residue derived by the loss of nit-rogen from .an aromatic sulfonyl azide substituted by carboxylic acids ta~en from.the class consisting of monocarboxylic and dicarboxylic acids having from 7 to 12 ca.bon atoms and deri~atiYes thereof taken fron the class consisting of monoesters of alcohols of 1 to 29 carbon atoms and the dicarboxylic acids and anhydrides o. the dicarboxylic acids and the metal salts of the monocarboxyiic, dicarboxylic acids ar.d the monoester of the dicarboxylic acid having from 0 to 100 percent Or the carboxylic acid groups ionized by neutralization with.me~al - losm7 ions;
F is an unsatursted mono~er taken f~om the class consisting of.acrylate esters haYing from 4 to 22 carbon atoms, vinyl esters of acids ha~ing from 1 to 20 carbon atoms (substantially no residual acid), vinyl ethers of 3 to 20 carbon atoms, and Yinyl a~d Yinylidene halides,and nitriles ha~ing fr~m 3 to 6 carbon atoms;
G is an unsaturated monomer ha~ing pendant hydro-carbon chains of 1 to 12 carbon atoms capable of being grafted with monomers having at least one reactive group of the type defined in C, D and E, and pendant aromatic groups which may -have 1 to 6 substituent groups having a total Or 1~ carbon atoms; and H is an unsaturated monomer taken from the class . ~
consisting of branched, straight chain and :
cyclic compounds ha~ing from ~ to 1~ carbon atoms and at least one additional nonconjugated `-unsaturated carbon-carbon bond capable Or being ; grafted with a monomer ha~ing at least one reacti~e group of the type defined in C, D and E.
The aforementioned monomers may be present in the polymer in the following mole fraction:
(a) 0 to 0.95;
(b) 0 to 0.3;
(c) 0 to 0.5;
(d) 0 to 0.5;
. (e) 0 to 0.5;
3 (f ) O to 0 .99;
lOB777~7 .
(g) O to 0.99; and (h) O to 0.99 so that the total of all components is a mole fraction of 1Ø
Preferably (a) to (h) are present in the following mole fraction:
(a) O to 0.9;
(b) O to 0.2~ most preferably 0.1 to 0.2;
(c) 0.0002 to 0.2~ most preferably 0.002 to 0.05;
(d) 0.005 to 0.2, most preferably 0.01 to 0.1;
(e) 0.0002 to 0.1, most preferably 0.002 to 0.01;
(f) O to O.~;
(g) O to 0.9~; and (h) O to O.gg I . , .
At least one of B, C, D and ~ is present in all polymeric systems. When A is present, in addition to at least one of B, C, D and E being present, at least one of F~ G and H is al~o present. ~ mixture of two or more polymers can be used with the proviso that at least one o~ B, C, D and E is present in at least one of the co-polymers.
The copolymeric component o~ the toughened - composition may be prepared by standard copolymerization reaction or by a grafting reaction. Thus B, C, D and E
may ~e copolymerized with A, F, G and H and C, D and E
may be added by a grafting reaction.`
- 108~7 Illustrative of monomers C to H of the above for~uIa are.
C is maleic acid, maleic anhydride, maleic acid monoethyl ester, metal salts of acid monoethyl ester, f~maric acid, fumaric acid monoethyl ester, itaconic acid, vinyl benzoic acid, vinyl phthalic acid~ metal salts of fumaric acid monoethyl ester, monoesters of maleic, fumaric~ itaconic acids with R
where R is up to 29 carbon atoms~ e.g., methyl~
propyl, isopropyl, butyl, isobutyl, hexyl, cyclohexyl, octyl, 2-ethyl hexyl~ decyl, stearyl, methoxy ethyl, ethox~ ethyl, hydroxy ethyl, etc.
D is glycidyl ~ethacrylate, glycidyl acry~ate, --allyi glycidyl ether, Yinyl glycidyl ether, glycidyl itaconate, etc.; ~
is phthalic anhydride sulfonyl azide, methyl ester and monooctadecyl ester of phthalic - 20 anhydride sul~onyl azide, benzoic acid sulfonyl azide, naphthoic acid sulfonyl azide, naphthoic diacid sulfonyl azide, R-monoesters (and metal salts thereof) o~ phthalic acid and naphthoic diacid sulfonyl azide, where R is up to 2 carbon atoms, etc.;
F is methyl methacryiate, methyl, ethyl and butyl acrylatej vinyl acetate, methyl vinyl ether, zinc methacrylate, acrylonitrile, ~ - esters ~ of acrylic, methacrylic acids, R - vinyl 3 ethers, ~inyl ~enzoate, vinyl naphthoate, --1~--`` 10877~7 , , ~inyl esters o~ R-acids, where R is up to l~
. carbon ato~s, vinyl chloride~ Yinylidene fluoride, etc.;
G is styrene, propylene, isobutylene, vinyl naphthalene, ~inyl pyridine, vinyl pyrrolidone~
mono-, di-~ trichloro styrene, R'-styrene where R' is 1 to lO carbon atoms, ~utene, hexene~
octene, decene,.etc.; and - H is hexadiene, norbornadiene, butadiene, iso-prene~ di~inyl, allyl styrene, etc.
Useful.copolymers for toughening polyester or polycarbonate compositions are the following alternating or prImarily random copolymers:
zinc salt of ethylene/iscbutyl acryla e/methacrylic acid; ethylene/methyl acrylate/monoethyl ester of maleic anhydride and 0 to 100 percent neutralized zinc, sodium, calcium, lithium, antimony, and potassiu~ salts thereof;
. . .
ethylene/methyl acrylate/mixture of ethylene/isobutylacrylate/~ethacrylic acid and ethylene/methyl acrylate/
monoethyl ester of maleic anhydride and zinc salts thereof;
ethylene/methyl acrylate/methacrylic acid and zinc salts thereof; ethylene/vinyl acetat~/methacrylic âcid and zinc salts thereof; ethylene/methyl methacrylate/methacrylic acid and zinc salts thereo~; ethylene~viny~ acetate/
carbon monoxide; mixtures of ethylene/~inyl acetate/
carbon monoxide and a zinc salt of ethylene/isobutyl acrylate/methacrylic acid; mixtures of ethylene/~inyl acetate and a zinc salt of ethylene/isobutyl acrylate/
methacrylic acid; mixtures of ethylene/isobutyl acrylâte 3 and a zinc salt of ethylene/isobutyl acrylate/methacrylic acid; mixtures of ethylene/acrylic acid and ethylene/
vinyl acetate; ethylene/isobutyl acrylate/carbon monoxide;
ethylene/stearyl methacrylate/carbon monoxide; ethylene/
n-butyl acrylate¢carbon monoxide; ethylene/2-ethyl hexyl methacrylate/carbon monoxide; ethylene/methyl ~inyl ether/
carbon monoxide; ethylene/vinyl acetate/maleic anhydride;
ethylene/~inyl acetate monoethyl ester of maleic anhydride; ethylene/vinyl acetate/glycidyl methacrylate;
ethylene/propylene/1,4 hex~diene-g-maleic anhydride;
mIxtures of ethylene/propylene/1,4 hexadiene and ethylene/
maleic anhydride; ethylene/propylene/norbornadiene/
1~4 hex~diene-g-benzoic acid sulfonyl azide; ethylene/
propylene/l,~ hexadiene-g-phthalic anhydride sulfonyl azide; mixtures of ethylenè/propylene/l,~ hexadiene and ethylene/propylene/l,~ hexadiene-g-malei~ ~nhydride;
ethylene/propylene/1,4 hexadiene-g-maIeic ~nhydride neutralized with amine ended oligomer of ~aprolactam;
ethylene/propylene/1,4 hexadiene/malei~ anhy~ride neutralized wi~h zinc rosinate; ethylene/propylene/
1,~ hexadiene-g-fumaric acid; ethylene/propylene/
1,4 hexadiene/norbornadiene-g-maleic anhydride; ethylene/
propylene/l,~ he~adiene/norbornadiene-g-~onoethyl ester of maleic anhydride; ethylene/propylene/l,~ hexadiene/
norbornadiene-g-f~maric acid; ethylene/p~opylene/
1~4 hexadiene/glycidyl methacrylate; ethylene/propylene/
1,4 hexadiene/norbornadiene-g-phthalic ~n~ydride sulfonyl ~zide; mixtures of ethylene/propylene/~,4 hexadiene and ~hylene/monoethyl ester of malèic a~hyd~i~-e;-mixtures o~ eth~lenejpropylene/1,4 hexadiene -ar~ ~$~yl~ne ~ utyl 3 hydrogen m~leate; mixtures of ethyle~ r~pyl~ne/
1,4 hexadiene and ethylene/maleic anhydride, mixtures of butadiene/acrylonitrile and styrene/maleic anhydride;
mix~ures of styrene/~tadiene and ethylene/maleic an~ydride; isobutylene/isoprene-g-phthalic anhydride sulfonyl azide; poly(isobutylene)-g-phthalic anhydride sulfonyl azide; mixtures of ethylene/propylene/l,~-hexadiene/
n~rbornadiene and styrene/maleic anhydride; isoprene/
phthalic anhydride; mixtures Or natural rubber and ethylene/monoethyl ester of maleic anhydride; butyl acrylate/monoethyl ester of fumaric acid; ethyl acrylate/
fumaric acid; epichlorohydrin/ethylene oxide; mixtures of ethylene/propylene and ethylene/.monoethyl ester of ma~eic anhydride; ethylene/propylene-g-?hthalic anhydride sulfonyl azide; ethylene/propylene/5-ethylidine-2-norbornene-g-fumaric acid~ ethylene/pro?ylene/dicyclo-pentadiene-g-monoethyl ester of maleic acid, ethylene/
propylene/~-propenyl-2-norbornene-g-~aleic anhydride, ethylene/propylene/tetrahydroindene-g-f~aric acid, ethylene/propylene/1,4-hexadiene/5-ethylidine-2-norbornene-g-fumaric acid, ethylene/vinyl acetate/C0/
glycidyl methacrylate, ethylene/vinyl acetate/C0/
glycidyl acrylate, ethylene/methyl acrylate/glycidyl methacrylate, ethylene/methyl acrylate/glycidyl acrylate~
me improvement in ductility of a c~position characterized by a higher notched I~od value is approximately proportional to the concentration o~
adherent sites in the polymeric component as well as to the melt viscosity which is a measure of the molecular weight, and molecular weight distribution within the limits of effectiYe dispersion. ~ere high concentrations losm7 .
of adherent sites are utilized, it is generally possiole to mix two polymers together, i.e.~ one as the source of adherent sites, and the other as a diluent. Mixing may be accomplished by combining the polymers with the matrix resin separately or in combination with the proviso that the polymer containing the adherent sites must not be combined with the matrix resin prior to combination of any other polymers. In ethylene/propylene/diene polymers molecular weights equivalent to melt flow of 0.5 to ~00 g./10 mins. and more by ASTM D 123~ but at 2gOC. and a total load of 2160 g. are effective. In the ~ariety of polymers employed a melt flow range of more than 0.1 to 000 may be employed but a range of 0.5 to 100 is preferred.
While not being limited to any theory, it is believed that the soft phase polymer only has to adhere with the matrix resin at the interface or surface of the two phases. The mechanism of adhesion is not fully understood and may be achieved by bonds which vary in energy from hydrogen bonding to covalent bonding.
The notched Izod test further characterizes the composition with regard to its ductility. Expressed in ft. lb./inch o~ notch, notched Izo~ ~alues in the dry as molded condition for preferred polymers are at least the values represented by the formula:
0.2 C
B ~ 2.0 ~ 0.5 (C2-10)~
B ~ 12.0 where B is the notched Izod of the polyester or polycarbonate matrix polymer~ Cl is 2 to 10 percent by weight of the at least 108m7 one polymer~ and C2 is 10 to 30 per-- cent by weight of the at leagt one polymer. B ~ 12.0 applies between 30 and 40 percent.
It has been found generally th~t dry as molded notched I~od values of at least ~ ft. ~bs./inch are readily achie~ed at lower concentration values than is achie~ed by prior art materials.
me melt flow of the thermoplastic composition is in the range of about 0.01 to 200 grams per minute by ASTM D-123~ at 2~0C. and 2160 g. load. Since the viscosity is highly shear sensitive the compositions o~
the invention are well suited for extrusion applications.
It is apparent from the above description that a ~ariety of polymers are effective in toughening matrix resins and a substantially large number of combina-tions are useful. It is therefore not surprising t~at the limits of effecti~eness of some components of the compositions depend on the other co~ponents. For example, the lower limit of conceneration Or an ef~e~tive adhering site,-e.g., maleic anhydride, will probably be lower than a less effective adhering site, e.g., methacrylic acid. Similarly, the balance between hydroxyl and carboxyl end groups in a matrix may influence the comparati~e effectiveness of different adhere~t si~es Qf the at least one polymer. ?olymers or polymeric ~ixt~res in the lower modulus range tend to be more e~ecti~e th~n those pol~ers or polymeric mixtures in the h~her modulus ran~e and may be useful at lowèr con~antrati~s 3 of adherent site. The equation describing t~a relation-.
losm7 ship between notched Izod and concentration of polymer is applicable only for ?oly~ers with an opti~ ccmbina-tion of adherence, modulus, and particle size. It is also understood that the ~lxtures described herein are effective only tYhen ~he components of the mixture co-exist in the same discrete particles in the matrix resin. Howe~er, more than one such polymeric mixture can be present in the toughened ther~oplastic composition.
- The compositions of the inYention may be modi-fied by one or more conventional additives such asstabilizers and i~hibitors of oxida~ive, thermal~ and ultraviolet light degradation; lubricants and mold release agents, colorants including dyes and pigments, fibrous and particulate fil~ers and reinforce~ents, nucleating agents, flame retardants, etc.
The stabilizers can be incorporated into the composition at any stage in the preparation ~f the thermoplastic composition. Preferably the stabilizers are included early to preclude the initiation of degradation before the com~osition c~n be protected.
Such stabilizers must be compatible with the composition.
Viscosity stabilizers such as polycarbodiimides may be used.
The oxidative and ther~al stabilizers useful in the materials o~ the present ln~ention include those used in addition polymers generally. They ir.clude, for example, hindered phenols, hydroquinones~ sec~ndary amines and varieties of substituted members of those groups and combinations thereof.
losm7 The ultraviolet light stabilizers~ e.g., up to 2.0 percent, based on the weight o~ matrix resin, can also be those used in addition polymers generally.
Examples of ultraYiolet light stabilizers include various substituted resorcinols, salicylates, benzotriazoles~
benzophenones, and the like.
Suitable lubricants and mold release agents, e.g.~ up to 1.0 percent, based on the weight of the composition, are stearic acid~ stearic alcohol, stear~mides;
organic dyes such as nigrosine, etc.; pigments~ e.g., titanium dioxide, cadmium sulfide, cadmium sulfide selenide, phthalocyanines, ultramarine blue, carbon black~ etc.; up to 50 percent, based on the weight of the composit-ion, of fibrous and particulate fillers and rein-forcements, e.g.~ carbon fibers, glass fibers, amorphous silica, asbestos, calcium silica~e, aluminum silicate, magnesium carbonate-, ksolin, chalk, powdered quartz, mica~ feldspar, etc.; nucleating agents, e.g., talc~
calcium fluoride, sodium fluoride, alumina, and finely divided polytetrafluoroethylene, etc.;
Flame retardants including 1 to 10 weight per-- cent of multi~alent metal oxides such as the oxides and mixed oxides of iron~ tin~ antimony~ zinc~ copper~
magnesium, and lead in combination with 3 to 20 weight percent of halogenated aromatic and cycloaliphatic compounds such as hexabromobenzene~ ~echlorane Plu~
(sold by Hooker Chemical Company)~ decabromobiphenyl ether~ hexabromodiphenylcarbonate~ derivatives of halogenated bisphenol A such as tètrabromobisphenol-A
diacetate, etc. Weights are based on the weight o~
composition.
The colorants (dyes and pigments) can be present in an amount of up to about 5.0 percent by weight, based on the weight of the composition.
me toughened compositions of this invention can be prepared by melt blending, in a closed system, a matrix resin and at least one polymer into a uniform mix-ture in a multi-screw extruder such as a NERNE~ P~LEIDERER*
extruder having generally 2-5 kneading blocks and at least one reverse pitch to generate high shear, or other conventional plasticating devices such as a BRABENDER*, BANBURY* mill, or the like. Alternatively, the blends may be made by coprecipitation from solutlon, blending or by dry mixing together of the components followed by melt fabrication of the dry mixture by extrusion.
The compositions described in the examples are prepared with a WERNER PFLEIDERER twin screw extruder. m e constituents are dry blended and extruded under vacuum 5 to 100C. above the melting point of the matrix resin, preferably 310C. or below. The extrudate, which is opaque at temperatures less than 20C. above the melting point, denoting a two phase system~ is cooled in a water bath, cut, vacuum dried and molded into test pieces. Of course, many process variations are possible.
It may be desirable to form a concentrate Or the toughened thermoplastic composition. This is accomplished by admixing the matrix resin in higher concentrations based on the weight of total composition, e.g., up to about 50 percent by weight, with the at least one random * denotes trade mark ~ ~
, i 108m7 copolymer. Additional matrix resin is admixed with the composition to yield the desired concent~ate, such as a toughened composition containing 1 to 20 percent by we~ght of at least one random copolymer.
It may be useful to increase the molecular weight of the toughened thermoplastic composition during the preparation of the composition. By way of illustration, an admixture of low molecular weight matrix resin and at least one random copolymer is prepared in a plasticating device as described above and the molecular weight is increased either in the melt or at an elevated temperature below the melting point (solid phase) of the matrix resin. By way of illustration, after melt blending the composition is either (1) held in the melt at a temperature about 10 to 40C. above the melting point at a pressure of about 1 to 25 mm Hg absolute for up to one hour~ or (2) in the solid phase~ after cutting, ~uenching and drying, at an elevated temperature at least 15C. below the melt temperature of the matrix resin in a~ inert gas stream for at least two hours.
The toughened thermoplastic co-~positions c2n be made into a wide range of useful articles by con~enti~nal molding methods employed in the ~abrication of thermo-plastic articlest i.e., as molded parts, extruded shapes, e.g., tubing, films~ sheets, fibers and oriented fibers, la~inates and wire coating. "Molding" means forming an article by deforming the blend in the heated plastic state~
The compositions of this invention are characteri~ed by an outstanding combination ~f properties~
108m7 foremost of which is outstanding toughness properties in view of the quantity of at least one random copolymer present with the matrix resin. The unusually high toughness pro-vides greater ductility, less sensitivity to scratches and molded in notches, and vastly reduced susceptibility to catastrophic failure when compared with previously known compositions in molded parts. Injection molded parts often are of varying thicknesses and may have scratches, molded-in notches of varying radii, and molded in stresses. In addition, orientation effects may cause varied ductility throughout a molded part.
The maintenance of high uniform values of notches Izod toughness throughout such molded parts characterizes the improved compositions resistance to brittle breaks.
The compositions are of sufficient toughness that the effect of minor changes in processing conditions will not cause significant variations in toughness from lot to lot quantities of composition.
EXAMPLES OF THE INVENTION
The following examples illustrate the invention wherein the percentages are by weight unless indicated.
The toughened polyester and polycarbonate compositions are prepared as follows: `
The matrix resin and polymer(s) in dry form are mixed after weighing in the proper proportions by tumbling in a polyethylene bag. The mixture is then blended in a 28 mm Werner Pfleiderer extruder in which the hopper is blanketed with nitrogen and the vacuum port maintained at about 25 to 30 inches vacuum.
Extruder barrel temperatures are set at about 1087 m the melting point of the matrix resin (+ 10C., level condition) yielding melt temperatures in the range of 5 to about 100C. above the melting point of the matrix.
The beading exiting the extruder is water quenched, cut and vacuum dried overnight at 120C. prior to molding. Test bars, 1/2 x 5 x 1/8 inch are molded in 3 oz. and 6 oz. injection molding machines at melt temperatures 10 to 30C. above the melting point of the matrix resin. The mold temperature is about 90 C.
with fast injection and a 20/20 or 20/30 molding cycle (seconds ram forward/second hold). With some composi-tions containing polyethylene terephthalate, mold temperatures up to 140C. are used to ensure crystalliza-tion. The molded bars are tested using the following test procedures in the dry-as-molded state:
Notched Izod toughness: at each end ASTM D-256-56 Tensile Strength: ASTM D-638-58T
Elongation: ASTM D-638-58T
Flexural Modulus: ASTM D-790-58T
Tensile Modulus of the matrices: ASTM D-638-58T (dry) Tensile Modulus of the polymers: ASTM D-882 (50% RH) Melt Flow: ASTM D-1238-73 Particle Size: Electron micrographs of microtomed or fractured surfaces.
Information relating to the matrix resin and polymers used in conjunction with the matrix resin are set forth in Tables l-A and l-B, respectively. The acronyms used hereinafter are set forth in Table 2.
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~2 .087777 TA3LE OF ~CRO~m:S
E ethylene IBA isobutyl acrylate MAA methacrylic acid MA methyl acrylate monoeth~l ester of maleic anhydride VA vinyl acetate CO carbon monoxide GMA glycidyl methacrylate FA fumaric acid p p~opylene -g- graft !
E~AMPLES 1 to 1~
These Examples prepared according to the procedure described abo~e are set forth in Table 3.
Control A is molded of a commercially a~ailable comparati~ely high molecular weight polyethylene terephthalate. Examples 1 and 2 show the increase in ductility characterized by a sharp increase in notched Izod with up to 30 weight percent addition of polymer.
Similar effects are illustrated with two additional polymers in polybutylene terephthalate, Examples 3 and 4.
Example 5 prepared with Control B, which has substantially lower inherent viscosity than Control A, illustrates, by comparison with Example 2, the general fact that lower molecular weight materials are more difficult to toughen than ~igh molecular weight materials.
Example 6, made in a different sample lot of Matrix 3, illustrates, similarly to Examples 3 and 4, substantial toughening by a soft polymer with effective adherent sites.
Examples 7 to 10 illustràte toughening Of ~olybutylene terephthalate of lower molecular weight ~os7~m than that used in Examples 3 and ~ using several different polymers.
Examples 11 and 12 illustrate toughening of a polyester copolymer. The same toughener is used to improve the toughness of a polycarbonate polymer, Example 13 in comparison with Control F. The improvement in ductility characterized by higher notched Izod than the control with a 2 mil notch is of particular significance in this Example.
Examples 1~ through 16 illustrate toughening of glass reinforced material in comparison ~nth Control G.
- Example 17 illustrates toughening o~ mineral filled material in comparison with Control H. Example 1 illustrates toughening of glass reinforced, flame retarded polyester in comp~rison with Control I. The degree of flame retardance of Example 1~ is demonstrated by tests which yield a V-0 rating in 1/16 inch sections by Underwriters Laboratory specific2tion test UL 94.
Examples 14 to 1~ were prepared by compounding the rein~orcing and fl~me retardant additives with the toughened polyester on a two inch single screw extruder fitted with a Yacuum port.
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~I N ~ h ~ h a 10~7 This Example describes extruding and stretching a composition Or 1,4-polybutylene glycol terephthalate (Matrix 4) and a copolymer of ethylene/methyl acrylate/
glycidyl methacrylate (Polymer ~).
A composition Or ~7 weight percent of Matrix 4 and 13 weight percent Or Polymer ~ is melt extruded into the form of a film. me composition is extruded at a temperature in the range of 260C. (initial end of barrel) to 2~5C. (at the die end of the barrel) in a Sterling extruder through an ~ inch (20.32 centimeters) wide Johnson-die maintained at a temperature of about 29~C.
me molten film is extruded onto the surface of a rotating (at about 15 feet `(4.572 meters) per minute) ~uench drum maintained at a temperature Or about 42C.
Full wire electrostatic pinning is used to insure uniform quenching of the cast film which is 10 mils (250 microns) in thickness. Sheets, ~ inches by 4 inchas (10.16 centimeters by 10.16 centimeters) cut from the roll of cast film are stretched simultaneously (in a T. M. Long Co. stretcher~ 3x in mutually perpendicular directions at a temperature of about 600C., and thereafter heat set in frames at 200C. in an oven.
me cast film stretches uniformly in all directions.
The following physical properties are measured on the cast film and the stretched rilm.
Tensile strength (p.s.i. ) - ASTM test D-~g2 Tensile modulus (p.s.i.) - ASTM test D-~2 Elongation at break (percent) - ASTM test D-~2 ~33-1087~7 , Pneumatic ball impact resistance test (kilogram-centimeter/mil) - ASTM test D-3099 Tear initiation test (grams/mil) - ASTM test D-1004 ~
Tear propagation test (grams/mil) - ASTM test D-1922 Density (~radient tube method) (grams/ccj - ASTM
test D-1505 Oxygen transmission rate (cc-mil~00 sq. in.-24 hrs.
atmosphere) - AS~I test D-143~.
A control film which is extruded from 100 per-cent Matrix 4 is cast in the same manner as that described abo~e for the above composition. me above physical properties are measured on the control cast Matrix 4 film, the cast film from the composition, and the stretched film of the composition. The physical properties are given in Table 4. It is found that the control,film of cast 100 percent Matrix 4 can not be stretched under the conditions employed with the composition of this Example.
A sample of the cast film from the composition is thermoformed, after being preheated for about 10 seconds in an oven heated to about 210C., into the shape of a dish 1.5 inches (3.~1 centimeters) deep by 5 inches (12.7 centimeters) in diameter. The male portion of the dish mold is heated to about 200C. and the female portion is at about 160C.
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l~W~7 April 26, 1977, discloses a polyethylene terephthalate/
terpolymer blend, the terpolymer being present in 1 to 5 percent by weight and comprising at least 65 percent by weight ethylene with (a) at least 5 percent by weight of vinyl ester of a 1 to 6 carbon atom saturated monobasic aliphatic carboxylic acid and (b) 0.5 to 10 percent by weight of acrylic or methacrylic acid. It is disclosed that polyethylene terephthalate blended with the terpolymer is tough. It is not tau~ht that improved toughness can be achieved in polyesters if the particle size, tensile modulus of the at least one polymer and the ratio of tensile modulus of the at least one polymer and the polyester matrix ;-resin are maintained within certain ranges.
French Patent 2,194,741 of X.P. Perry et al., published March 1, 1974, relates to blends of polyesters ;
melting above 100C. with 1.5 to 90 percent by weight of a copolyether ester. Impact strength is said to be improved.
The copolyether esters are block copolymers rather than random copolymers. There is no teaching that tensile modulus, ratios of tensile modulus and particle size of the pol~mer additive are necessary to provide improved toughness.
Polycarbonates are known to be among the tougher materials used for molded and extruded parts.
Kim U.S. Patent 3,334,154 is an example. It has been found, however, that when polycarbonates have been tested for toughness using the notched Izod test as indicated above the toughness is a funct~on of the notch radius.
This disadvantage is substantially eliminated when at least one polymer according to this invention is present ~ A
'.~
los7m . with the polycar~onate.
S~R~ OF THE INVENTION
According to this invention~ there is proYided a toughened multi-phase thermoplàstic composition consist-ing essentially of one phase containing 60 to 99 percent by weight o~ a matrix resin taken frQm the class consist-ing of (a) polyester matrix resin having an inherent viscosity in the range of abou~ 0.4 to 4.0 deciliters/
gram~ said polyester being prepared from an aramatic di-.
carboxylic acid having from ~ to 14 carbon atoms and at least one glycol taken from the class consisting of a glycol of the formula HO(CH2)nOH where n is an integer of 2 to 10, neopentyl glycol and cyclohexane dimethanol, a portion of the moles of acid being replaceable by at least one acid taken from the group consisting of at least one different aromatic dicarboxylic acid having from B to 14 carbon atoms in an amount up to 50 mole percent, and an aliphatic dicarboxylic acid having from 2 to 12 carbon atoms in an amount up to 20 mole percent; and (b) polycarbonate matrix resin ha~ing an inherent viscosity in the range of about 0.35 to 0.75 deciliter/
gram, said polycarbonate possessing recurring str~cttral units of the formula:
~ .
. !~A--~ ~
where A is a divalent aromatic radical o~ a dihydric -phenol; and 1 to ~0 percent.by weight of at least ~ne other phase containing particles of at least one random ~p~lymer taken from t~e class consisting Or branched and s~r2ight chain polymers, said at least one random copolymer.ha~ing 108777 7 .
a particle size in the range of 0.01 to 3.0-microns, being adhered to the matrix resin, and ha~ing a tensile modulus in the range of about 1.0 to 50,000 p.s.i., the ratio of the tensile modulus Or the matrix resin to tensile modulus o~ said at least one random copolymer being greater than 10 to 1.
me term "consisting essentially of" means that in addition to the required matrix resin and the at least one random copolymer, other components can be present in the toughened composition provided that the basic and essential characteristics of the toughened composition are not materially affected thereby.
The term "branched and straight chain polymers' means that the polymers are not crosslinked to a degree which will increase their modulus to greater than 50,000 p.s.i. or decrease their melt ~low to a level which pre-vents effective dispersion.
According to another aspect of this invention, there is provided a process for the preparation of a toughened multi-phase thermoplastic composition which comprises, in a closed system, (A) admixing (1) 60 to 99 percent by weight of a matrix resin taken from the class consisting of (a) polyester matrix resin and (b) polycarbonate as defined above~ and (2) 1 to 40 percent - ~ by weight of at least one random copolymer at a tempera-ture in the range of about 5 to 100C. above the melting point of said matrix resin and (B) shearing to disperse the at least one random copolymer in said matrix to a particle size in the range of 0.01 to 3.0 microns, said at least one random copolymer being adhered to said matrix losm7 and having a tensile modulus in the range of 1.0 ~o 50~000 p.s.i.~ the ratio of the tensile moduius of said matrix to tensile modulus of said at least one random c.opolymer being greater than 10 to 1.
DETAILED DESCRIPTION OF THE INVENTION
. me resins that function as the matrix resin of the toughened compositions of this invention are well known in the art. The matrix resins can be o~ the polyester types as described above having an inherent viscosit~ in the range of about 0.4 to 4.0 deciliters/
gram~ the polycarbonate types also as described above having an inherent viscosity in.the range of about 0.35 to 0.75 deciliter/gram and mixtures of said resins.
The term "polyester resins" includes, in general, linear saturated condensation products of glycols and dicarboxylic acids, or reactive derivatives thereof.
Preferably, they will comprise condensation products of aromatic dicarboxylic acids having ~ to 14 carbon atoms and at least one glycol of the formula HO(CH2)nOH where n is an integer of 2 to 10, neopentyl glycol, and cyclo-hexane dimethanol. Up to 50 mole percent of the aromatic dicarboxylic acids can be replaced by at least one different ar~matic dicarboxylic acid having from B to 1~ carbon atoms, and/or up to 20 mole percent can be replaced by an aliphatic dicarboxylic acid having from 2 to 12 carbon atoms.
The preferred polyesters are well ~nown as film and fiber ~ormers, and they are provided by methods outlined in Whinfield et al. U. S. Patent 2,465~319 and Pengilly U. S. Patent 3~0~7,539. The preferred polyesters will comprise polyethylene terephthalate;
poly(l,4-butylene) terephthalate; and l,~-cyclohexylene dimethylene terephthalate/isophthalate copolymer and other linear homopolymer esters deriYed from aromatic dicarboxylic acids, including isophthalic, bibenzoic, naphthalene-dicarboxylic including the 1,5-; 2,6-; and 2,7-naphthalenedicarboxylic acids; 4,4'-diphenylenedi-carboxylic acid; bis(p-carboxyphenyl) methane; ethylene-bis-p-benzoic acid; 1,4-tetramethylene bis(p-oxybenzoic) acid; ethylene bis(p-oxybenzoic) acid; 1,3-trimethylene bis(p-oxybenzoic) acid; and l,~-tetramethylene bis(p-oxybenzoic acid, and glycols of the general formula ~O(CH2)nOH where n is an integer from 2 to 10, e.g., ethylene glycol; 1,3-trimethylene glycol; 1,4-tetra-methylene glycol; l,6-hexamethylene glycol; l,~-octa-methylene glycol; 1,10-decamethylene glycol; 2~2- -dimethyl-1,3-propane diol; 1,3-propylene glycol; 1,~-butylene glycol; neopentyl glycol and cyclohexa~e di-methanol. Up to 20 mole percent, as indicated above, of one or more aliphatic acids, including adipic, sebacic, azelaic, dodecanedioic acid or 1,4-cyclohexanedicarboxylic ~ acid can be present. It is understood that the polyesters may include minor quantities of ethers incidentally formed as by-products from the glycols employed in the preparation of the polymeric ester.
The inherent viscosity of the polyesters and polycarbonates is measured at a concentration of 0.32 g./100 ml. in trifluoroacetic acid (25)/methylene chloride (75) at 25 + 0.10C. It is computed by the formula-losm7 natural log elution time of solution elution of solvent Inherent Viscosity = C
where C is the concentration expressed in grams of polymer per 100 milliliters of solution. The viscometer used is a calibrated Ostwald-Cannon-Finske viscometer No. 50 (Ace Glass Co.).
The term "polycarbonate resin" as used herein is meant to embrace within its scope carbonate polymers of dihydric phenols as well as carbonate copolymers of such dihydric phenols with glycols, such as ethylene glycol or propylene glycol, for example dibasic acids, such as, for example, isophthalic or terephthalic acid;
and hydroxyl or acid-terminated polyesters, such as, for example, the hydroxyl or acid-terminated polyester of neopentyl glycol and adipic acid. Such polycarbonate resins may be prepared by reacting a dihydric phenol with a carbonate precursor such as phosgene, a halo-formate or a carbonate ester. Generally speaking, the resulting carbonate polymers may be typified as possessing recurring structural units of the formula:
r 0l ~ O-A-O- ~
where A is a divalent aromatic radical of the dihydric phenol, preferably bisphenol A, employed in the polymer pro-ducing reaction. Preferably, the polycarbonate resins have inherent viscosities (as measured in p-dioxane in deciliters per gram at 30C.) ranging from about 0.35 to about 0.75.
The dihydric phenols which may be employed to provide such aromatic carbonate polymers are mononuclear or polynuclear aromatic compounds, containing as functional _g _ - losm7 groups, two hydroxyl radicals, each of which is attached directly to a carbon atom of an aromatic'nucleus.
Typical dihydric phen~ls are 2,2 ~is-(4-hydroxyphenyl)-pr'opane; hydroquinone;resorcino~ 2,2 bis-(4-hydroxy-phenyl)-pentane; 2,~' dihydroxydiphenyl methane; bis-(2-hydroxyphenyl)-methane; bis(~-hydroxyphenyl)-methane;
bis-(4-hydroxy-5-nitrophenyl)-methane; 1,1 bis-(4-hydroxyphenyl)-ethane; 3,3 bis-(4-hydroxyphenyl)-pentane; 2,2' dihydroxydiphenyl; 2,6 dihydroxy naphthal-ene; bis-(~-hydroxyphenyl)-sulfone; 2,2' dihydroxydiphenyl sulfone; 4~' dihydroxydiphenyl ether; and ~4' dihydroxy-2,5-diethoxydiphenyl ether. A ~ariety of additional dihydric phenols which may be employed to provide such carbonate polymers are disclosed in Goldberg U. S. Patent 2~999,~35. It is~ of course, possible to employ two or more different dihydric phenols or~ as stated above, a dihydric phenol in combination with a glycol, a hydroxy or acid-terminated polyester, or a dibasic acid in the event a carbonate copolymer rather than a homopolymer is desired.
As great as 99 percent by weight of the composition can be composed of matrix resin; however, preferred compositions contain from 60 to 99 percent, and more narrowly ~0 to 95 percent, by weight of matrix resin.
The composition is toughened by the combination of at least one random copolymer with the matrix resin.
The term "at least one random copolymer" means one or more copolymers, and optionally one or more homopolymers, which coexist in single discrete particles haYing a los~m . -particle size ranging from 0.01 to 3 microns, preferably0.02 to 1 micron, within the matrix, so that either the mixture of polymers or at least one of the copolymers in the mixture meets the following criteria.
(a) sites which adhere to the matrix resin;
(b) tensile modulus, as added, in the range of about 1.0 to 50,000 p.s.i., preferably about 5 to 20,000 p.s.i., the ratio Or tensile modulus of the matrix resin to tensile modulus of said at least one random copolymer being greater than 10 to 1, preferably greater than 20 to 1.
The matrix resin is the continuous phase in the composition and the at least one random copolymer,some-times referred to as polymer, performs the function of a soft dispersed phase which is adhered to the matrix resin.
The polymer may be elastomeric, but it has been found that thermoplastic polymers which are not elastomeric are also effective in the compositions.
me polymers are branched or straight chain and are of such composition that crosslinking other than by reaction with the matrix resin is not necessary to their function and excessive crosslinking may, in fact, be harmful.
Branched and straight chain polymers userul as - the soft phase of the composition are represented by the formula:
A(a~ B(b)-c(c)-D(d)-E(e)-F(r)-G(g)-H(h) deriYed in any order~ e.g., random, ~rom monomers A to 0 H where A is ethylene;
B is C0;
los7m C is an unsaturatPd monomer taken from the class consisting of ~ ethylenically unsaturated carboxylic acids having from 3 to ~ carbon atoms, and deri~atives thereof taken from the class consistin~ of monoesters of alcohols of l-to 29 carbon atoms and the dicsrboxylic acids and anhydrides of the dicarboxylic acids and the metal salts of the monocarboxylic, di- -- carboxylic acids and the monoester of the di-carboxylic acid having from 0 to 100 percent of the carboxylic acid groups ionized by - - neutralization with metal ions and dicarboxylic acids and monoesters of the dicarbo~ylic acid neutralized by amine-ended caprolactam oligomers -~
having a DP of 6 to 24;
D is an unsaturated epoxide of ~ to 11 carbon atoms;
E is the residue derived by the loss of nit-rogen from .an aromatic sulfonyl azide substituted by carboxylic acids ta~en from.the class consisting of monocarboxylic and dicarboxylic acids having from 7 to 12 ca.bon atoms and deri~atiYes thereof taken fron the class consisting of monoesters of alcohols of 1 to 29 carbon atoms and the dicarboxylic acids and anhydrides o. the dicarboxylic acids and the metal salts of the monocarboxyiic, dicarboxylic acids ar.d the monoester of the dicarboxylic acid having from 0 to 100 percent Or the carboxylic acid groups ionized by neutralization with.me~al - losm7 ions;
F is an unsatursted mono~er taken f~om the class consisting of.acrylate esters haYing from 4 to 22 carbon atoms, vinyl esters of acids ha~ing from 1 to 20 carbon atoms (substantially no residual acid), vinyl ethers of 3 to 20 carbon atoms, and Yinyl a~d Yinylidene halides,and nitriles ha~ing fr~m 3 to 6 carbon atoms;
G is an unsaturated monomer ha~ing pendant hydro-carbon chains of 1 to 12 carbon atoms capable of being grafted with monomers having at least one reactive group of the type defined in C, D and E, and pendant aromatic groups which may -have 1 to 6 substituent groups having a total Or 1~ carbon atoms; and H is an unsaturated monomer taken from the class . ~
consisting of branched, straight chain and :
cyclic compounds ha~ing from ~ to 1~ carbon atoms and at least one additional nonconjugated `-unsaturated carbon-carbon bond capable Or being ; grafted with a monomer ha~ing at least one reacti~e group of the type defined in C, D and E.
The aforementioned monomers may be present in the polymer in the following mole fraction:
(a) 0 to 0.95;
(b) 0 to 0.3;
(c) 0 to 0.5;
(d) 0 to 0.5;
. (e) 0 to 0.5;
3 (f ) O to 0 .99;
lOB777~7 .
(g) O to 0.99; and (h) O to 0.99 so that the total of all components is a mole fraction of 1Ø
Preferably (a) to (h) are present in the following mole fraction:
(a) O to 0.9;
(b) O to 0.2~ most preferably 0.1 to 0.2;
(c) 0.0002 to 0.2~ most preferably 0.002 to 0.05;
(d) 0.005 to 0.2, most preferably 0.01 to 0.1;
(e) 0.0002 to 0.1, most preferably 0.002 to 0.01;
(f) O to O.~;
(g) O to 0.9~; and (h) O to O.gg I . , .
At least one of B, C, D and ~ is present in all polymeric systems. When A is present, in addition to at least one of B, C, D and E being present, at least one of F~ G and H is al~o present. ~ mixture of two or more polymers can be used with the proviso that at least one o~ B, C, D and E is present in at least one of the co-polymers.
The copolymeric component o~ the toughened - composition may be prepared by standard copolymerization reaction or by a grafting reaction. Thus B, C, D and E
may ~e copolymerized with A, F, G and H and C, D and E
may be added by a grafting reaction.`
- 108~7 Illustrative of monomers C to H of the above for~uIa are.
C is maleic acid, maleic anhydride, maleic acid monoethyl ester, metal salts of acid monoethyl ester, f~maric acid, fumaric acid monoethyl ester, itaconic acid, vinyl benzoic acid, vinyl phthalic acid~ metal salts of fumaric acid monoethyl ester, monoesters of maleic, fumaric~ itaconic acids with R
where R is up to 29 carbon atoms~ e.g., methyl~
propyl, isopropyl, butyl, isobutyl, hexyl, cyclohexyl, octyl, 2-ethyl hexyl~ decyl, stearyl, methoxy ethyl, ethox~ ethyl, hydroxy ethyl, etc.
D is glycidyl ~ethacrylate, glycidyl acry~ate, --allyi glycidyl ether, Yinyl glycidyl ether, glycidyl itaconate, etc.; ~
is phthalic anhydride sulfonyl azide, methyl ester and monooctadecyl ester of phthalic - 20 anhydride sul~onyl azide, benzoic acid sulfonyl azide, naphthoic acid sulfonyl azide, naphthoic diacid sulfonyl azide, R-monoesters (and metal salts thereof) o~ phthalic acid and naphthoic diacid sulfonyl azide, where R is up to 2 carbon atoms, etc.;
F is methyl methacryiate, methyl, ethyl and butyl acrylatej vinyl acetate, methyl vinyl ether, zinc methacrylate, acrylonitrile, ~ - esters ~ of acrylic, methacrylic acids, R - vinyl 3 ethers, ~inyl ~enzoate, vinyl naphthoate, --1~--`` 10877~7 , , ~inyl esters o~ R-acids, where R is up to l~
. carbon ato~s, vinyl chloride~ Yinylidene fluoride, etc.;
G is styrene, propylene, isobutylene, vinyl naphthalene, ~inyl pyridine, vinyl pyrrolidone~
mono-, di-~ trichloro styrene, R'-styrene where R' is 1 to lO carbon atoms, ~utene, hexene~
octene, decene,.etc.; and - H is hexadiene, norbornadiene, butadiene, iso-prene~ di~inyl, allyl styrene, etc.
Useful.copolymers for toughening polyester or polycarbonate compositions are the following alternating or prImarily random copolymers:
zinc salt of ethylene/iscbutyl acryla e/methacrylic acid; ethylene/methyl acrylate/monoethyl ester of maleic anhydride and 0 to 100 percent neutralized zinc, sodium, calcium, lithium, antimony, and potassiu~ salts thereof;
. . .
ethylene/methyl acrylate/mixture of ethylene/isobutylacrylate/~ethacrylic acid and ethylene/methyl acrylate/
monoethyl ester of maleic anhydride and zinc salts thereof;
ethylene/methyl acrylate/methacrylic acid and zinc salts thereof; ethylene/vinyl acetat~/methacrylic âcid and zinc salts thereof; ethylene/methyl methacrylate/methacrylic acid and zinc salts thereo~; ethylene~viny~ acetate/
carbon monoxide; mixtures of ethylene/~inyl acetate/
carbon monoxide and a zinc salt of ethylene/isobutyl acrylate/methacrylic acid; mixtures of ethylene/~inyl acetate and a zinc salt of ethylene/isobutyl acrylate/
methacrylic acid; mixtures of ethylene/isobutyl acrylâte 3 and a zinc salt of ethylene/isobutyl acrylate/methacrylic acid; mixtures of ethylene/acrylic acid and ethylene/
vinyl acetate; ethylene/isobutyl acrylate/carbon monoxide;
ethylene/stearyl methacrylate/carbon monoxide; ethylene/
n-butyl acrylate¢carbon monoxide; ethylene/2-ethyl hexyl methacrylate/carbon monoxide; ethylene/methyl ~inyl ether/
carbon monoxide; ethylene/vinyl acetate/maleic anhydride;
ethylene/~inyl acetate monoethyl ester of maleic anhydride; ethylene/vinyl acetate/glycidyl methacrylate;
ethylene/propylene/1,4 hex~diene-g-maleic anhydride;
mIxtures of ethylene/propylene/1,4 hexadiene and ethylene/
maleic anhydride; ethylene/propylene/norbornadiene/
1~4 hex~diene-g-benzoic acid sulfonyl azide; ethylene/
propylene/l,~ hexadiene-g-phthalic anhydride sulfonyl azide; mixtures of ethylenè/propylene/l,~ hexadiene and ethylene/propylene/l,~ hexadiene-g-malei~ ~nhydride;
ethylene/propylene/1,4 hexadiene-g-maIeic ~nhydride neutralized with amine ended oligomer of ~aprolactam;
ethylene/propylene/1,4 hexadiene/malei~ anhy~ride neutralized wi~h zinc rosinate; ethylene/propylene/
1,~ hexadiene-g-fumaric acid; ethylene/propylene/
1,4 hexadiene/norbornadiene-g-maleic anhydride; ethylene/
propylene/l,~ he~adiene/norbornadiene-g-~onoethyl ester of maleic anhydride; ethylene/propylene/l,~ hexadiene/
norbornadiene-g-f~maric acid; ethylene/p~opylene/
1~4 hexadiene/glycidyl methacrylate; ethylene/propylene/
1,4 hexadiene/norbornadiene-g-phthalic ~n~ydride sulfonyl ~zide; mixtures of ethylene/propylene/~,4 hexadiene and ~hylene/monoethyl ester of malèic a~hyd~i~-e;-mixtures o~ eth~lenejpropylene/1,4 hexadiene -ar~ ~$~yl~ne ~ utyl 3 hydrogen m~leate; mixtures of ethyle~ r~pyl~ne/
1,4 hexadiene and ethylene/maleic anhydride, mixtures of butadiene/acrylonitrile and styrene/maleic anhydride;
mix~ures of styrene/~tadiene and ethylene/maleic an~ydride; isobutylene/isoprene-g-phthalic anhydride sulfonyl azide; poly(isobutylene)-g-phthalic anhydride sulfonyl azide; mixtures of ethylene/propylene/l,~-hexadiene/
n~rbornadiene and styrene/maleic anhydride; isoprene/
phthalic anhydride; mixtures Or natural rubber and ethylene/monoethyl ester of maleic anhydride; butyl acrylate/monoethyl ester of fumaric acid; ethyl acrylate/
fumaric acid; epichlorohydrin/ethylene oxide; mixtures of ethylene/propylene and ethylene/.monoethyl ester of ma~eic anhydride; ethylene/propylene-g-?hthalic anhydride sulfonyl azide; ethylene/propylene/5-ethylidine-2-norbornene-g-fumaric acid~ ethylene/pro?ylene/dicyclo-pentadiene-g-monoethyl ester of maleic acid, ethylene/
propylene/~-propenyl-2-norbornene-g-~aleic anhydride, ethylene/propylene/tetrahydroindene-g-f~aric acid, ethylene/propylene/1,4-hexadiene/5-ethylidine-2-norbornene-g-fumaric acid, ethylene/vinyl acetate/C0/
glycidyl methacrylate, ethylene/vinyl acetate/C0/
glycidyl acrylate, ethylene/methyl acrylate/glycidyl methacrylate, ethylene/methyl acrylate/glycidyl acrylate~
me improvement in ductility of a c~position characterized by a higher notched I~od value is approximately proportional to the concentration o~
adherent sites in the polymeric component as well as to the melt viscosity which is a measure of the molecular weight, and molecular weight distribution within the limits of effectiYe dispersion. ~ere high concentrations losm7 .
of adherent sites are utilized, it is generally possiole to mix two polymers together, i.e.~ one as the source of adherent sites, and the other as a diluent. Mixing may be accomplished by combining the polymers with the matrix resin separately or in combination with the proviso that the polymer containing the adherent sites must not be combined with the matrix resin prior to combination of any other polymers. In ethylene/propylene/diene polymers molecular weights equivalent to melt flow of 0.5 to ~00 g./10 mins. and more by ASTM D 123~ but at 2gOC. and a total load of 2160 g. are effective. In the ~ariety of polymers employed a melt flow range of more than 0.1 to 000 may be employed but a range of 0.5 to 100 is preferred.
While not being limited to any theory, it is believed that the soft phase polymer only has to adhere with the matrix resin at the interface or surface of the two phases. The mechanism of adhesion is not fully understood and may be achieved by bonds which vary in energy from hydrogen bonding to covalent bonding.
The notched Izod test further characterizes the composition with regard to its ductility. Expressed in ft. lb./inch o~ notch, notched Izo~ ~alues in the dry as molded condition for preferred polymers are at least the values represented by the formula:
0.2 C
B ~ 2.0 ~ 0.5 (C2-10)~
B ~ 12.0 where B is the notched Izod of the polyester or polycarbonate matrix polymer~ Cl is 2 to 10 percent by weight of the at least 108m7 one polymer~ and C2 is 10 to 30 per-- cent by weight of the at leagt one polymer. B ~ 12.0 applies between 30 and 40 percent.
It has been found generally th~t dry as molded notched I~od values of at least ~ ft. ~bs./inch are readily achie~ed at lower concentration values than is achie~ed by prior art materials.
me melt flow of the thermoplastic composition is in the range of about 0.01 to 200 grams per minute by ASTM D-123~ at 2~0C. and 2160 g. load. Since the viscosity is highly shear sensitive the compositions o~
the invention are well suited for extrusion applications.
It is apparent from the above description that a ~ariety of polymers are effective in toughening matrix resins and a substantially large number of combina-tions are useful. It is therefore not surprising t~at the limits of effecti~eness of some components of the compositions depend on the other co~ponents. For example, the lower limit of conceneration Or an ef~e~tive adhering site,-e.g., maleic anhydride, will probably be lower than a less effective adhering site, e.g., methacrylic acid. Similarly, the balance between hydroxyl and carboxyl end groups in a matrix may influence the comparati~e effectiveness of different adhere~t si~es Qf the at least one polymer. ?olymers or polymeric ~ixt~res in the lower modulus range tend to be more e~ecti~e th~n those pol~ers or polymeric mixtures in the h~her modulus ran~e and may be useful at lowèr con~antrati~s 3 of adherent site. The equation describing t~a relation-.
losm7 ship between notched Izod and concentration of polymer is applicable only for ?oly~ers with an opti~ ccmbina-tion of adherence, modulus, and particle size. It is also understood that the ~lxtures described herein are effective only tYhen ~he components of the mixture co-exist in the same discrete particles in the matrix resin. Howe~er, more than one such polymeric mixture can be present in the toughened ther~oplastic composition.
- The compositions of the inYention may be modi-fied by one or more conventional additives such asstabilizers and i~hibitors of oxida~ive, thermal~ and ultraviolet light degradation; lubricants and mold release agents, colorants including dyes and pigments, fibrous and particulate fil~ers and reinforce~ents, nucleating agents, flame retardants, etc.
The stabilizers can be incorporated into the composition at any stage in the preparation ~f the thermoplastic composition. Preferably the stabilizers are included early to preclude the initiation of degradation before the com~osition c~n be protected.
Such stabilizers must be compatible with the composition.
Viscosity stabilizers such as polycarbodiimides may be used.
The oxidative and ther~al stabilizers useful in the materials o~ the present ln~ention include those used in addition polymers generally. They ir.clude, for example, hindered phenols, hydroquinones~ sec~ndary amines and varieties of substituted members of those groups and combinations thereof.
losm7 The ultraviolet light stabilizers~ e.g., up to 2.0 percent, based on the weight o~ matrix resin, can also be those used in addition polymers generally.
Examples of ultraYiolet light stabilizers include various substituted resorcinols, salicylates, benzotriazoles~
benzophenones, and the like.
Suitable lubricants and mold release agents, e.g.~ up to 1.0 percent, based on the weight of the composition, are stearic acid~ stearic alcohol, stear~mides;
organic dyes such as nigrosine, etc.; pigments~ e.g., titanium dioxide, cadmium sulfide, cadmium sulfide selenide, phthalocyanines, ultramarine blue, carbon black~ etc.; up to 50 percent, based on the weight of the composit-ion, of fibrous and particulate fillers and rein-forcements, e.g.~ carbon fibers, glass fibers, amorphous silica, asbestos, calcium silica~e, aluminum silicate, magnesium carbonate-, ksolin, chalk, powdered quartz, mica~ feldspar, etc.; nucleating agents, e.g., talc~
calcium fluoride, sodium fluoride, alumina, and finely divided polytetrafluoroethylene, etc.;
Flame retardants including 1 to 10 weight per-- cent of multi~alent metal oxides such as the oxides and mixed oxides of iron~ tin~ antimony~ zinc~ copper~
magnesium, and lead in combination with 3 to 20 weight percent of halogenated aromatic and cycloaliphatic compounds such as hexabromobenzene~ ~echlorane Plu~
(sold by Hooker Chemical Company)~ decabromobiphenyl ether~ hexabromodiphenylcarbonate~ derivatives of halogenated bisphenol A such as tètrabromobisphenol-A
diacetate, etc. Weights are based on the weight o~
composition.
The colorants (dyes and pigments) can be present in an amount of up to about 5.0 percent by weight, based on the weight of the composition.
me toughened compositions of this invention can be prepared by melt blending, in a closed system, a matrix resin and at least one polymer into a uniform mix-ture in a multi-screw extruder such as a NERNE~ P~LEIDERER*
extruder having generally 2-5 kneading blocks and at least one reverse pitch to generate high shear, or other conventional plasticating devices such as a BRABENDER*, BANBURY* mill, or the like. Alternatively, the blends may be made by coprecipitation from solutlon, blending or by dry mixing together of the components followed by melt fabrication of the dry mixture by extrusion.
The compositions described in the examples are prepared with a WERNER PFLEIDERER twin screw extruder. m e constituents are dry blended and extruded under vacuum 5 to 100C. above the melting point of the matrix resin, preferably 310C. or below. The extrudate, which is opaque at temperatures less than 20C. above the melting point, denoting a two phase system~ is cooled in a water bath, cut, vacuum dried and molded into test pieces. Of course, many process variations are possible.
It may be desirable to form a concentrate Or the toughened thermoplastic composition. This is accomplished by admixing the matrix resin in higher concentrations based on the weight of total composition, e.g., up to about 50 percent by weight, with the at least one random * denotes trade mark ~ ~
, i 108m7 copolymer. Additional matrix resin is admixed with the composition to yield the desired concent~ate, such as a toughened composition containing 1 to 20 percent by we~ght of at least one random copolymer.
It may be useful to increase the molecular weight of the toughened thermoplastic composition during the preparation of the composition. By way of illustration, an admixture of low molecular weight matrix resin and at least one random copolymer is prepared in a plasticating device as described above and the molecular weight is increased either in the melt or at an elevated temperature below the melting point (solid phase) of the matrix resin. By way of illustration, after melt blending the composition is either (1) held in the melt at a temperature about 10 to 40C. above the melting point at a pressure of about 1 to 25 mm Hg absolute for up to one hour~ or (2) in the solid phase~ after cutting, ~uenching and drying, at an elevated temperature at least 15C. below the melt temperature of the matrix resin in a~ inert gas stream for at least two hours.
The toughened thermoplastic co-~positions c2n be made into a wide range of useful articles by con~enti~nal molding methods employed in the ~abrication of thermo-plastic articlest i.e., as molded parts, extruded shapes, e.g., tubing, films~ sheets, fibers and oriented fibers, la~inates and wire coating. "Molding" means forming an article by deforming the blend in the heated plastic state~
The compositions of this invention are characteri~ed by an outstanding combination ~f properties~
108m7 foremost of which is outstanding toughness properties in view of the quantity of at least one random copolymer present with the matrix resin. The unusually high toughness pro-vides greater ductility, less sensitivity to scratches and molded in notches, and vastly reduced susceptibility to catastrophic failure when compared with previously known compositions in molded parts. Injection molded parts often are of varying thicknesses and may have scratches, molded-in notches of varying radii, and molded in stresses. In addition, orientation effects may cause varied ductility throughout a molded part.
The maintenance of high uniform values of notches Izod toughness throughout such molded parts characterizes the improved compositions resistance to brittle breaks.
The compositions are of sufficient toughness that the effect of minor changes in processing conditions will not cause significant variations in toughness from lot to lot quantities of composition.
EXAMPLES OF THE INVENTION
The following examples illustrate the invention wherein the percentages are by weight unless indicated.
The toughened polyester and polycarbonate compositions are prepared as follows: `
The matrix resin and polymer(s) in dry form are mixed after weighing in the proper proportions by tumbling in a polyethylene bag. The mixture is then blended in a 28 mm Werner Pfleiderer extruder in which the hopper is blanketed with nitrogen and the vacuum port maintained at about 25 to 30 inches vacuum.
Extruder barrel temperatures are set at about 1087 m the melting point of the matrix resin (+ 10C., level condition) yielding melt temperatures in the range of 5 to about 100C. above the melting point of the matrix.
The beading exiting the extruder is water quenched, cut and vacuum dried overnight at 120C. prior to molding. Test bars, 1/2 x 5 x 1/8 inch are molded in 3 oz. and 6 oz. injection molding machines at melt temperatures 10 to 30C. above the melting point of the matrix resin. The mold temperature is about 90 C.
with fast injection and a 20/20 or 20/30 molding cycle (seconds ram forward/second hold). With some composi-tions containing polyethylene terephthalate, mold temperatures up to 140C. are used to ensure crystalliza-tion. The molded bars are tested using the following test procedures in the dry-as-molded state:
Notched Izod toughness: at each end ASTM D-256-56 Tensile Strength: ASTM D-638-58T
Elongation: ASTM D-638-58T
Flexural Modulus: ASTM D-790-58T
Tensile Modulus of the matrices: ASTM D-638-58T (dry) Tensile Modulus of the polymers: ASTM D-882 (50% RH) Melt Flow: ASTM D-1238-73 Particle Size: Electron micrographs of microtomed or fractured surfaces.
Information relating to the matrix resin and polymers used in conjunction with the matrix resin are set forth in Tables l-A and l-B, respectively. The acronyms used hereinafter are set forth in Table 2.
losm7 , b ~1 c 'q , , O O O O
~-0 C: X ~
$ ~ O -~
,, O ~ ~ ~ æ
~ q a ..
c ~1 ~ 0 0 q o 1~ 0 x ' h~
I ~ ~ 1 ~ 01 0 0 0 U~
I ~ c ~ a tP~
.C o ,~ E h ~ ~ O 0 0 0 S
r~ z ~ S IJ ~ C ~ ~ 3 '~ * 0 s s a ~ ~,w ~ .C s ~ s ~ C
O D.V Cl.~ ~ O ~ O a ¦ ~¦ ¦ 0 ~ ~ C o ~q D oo ~o ~ ~ d o h E~
~ ~ 0 u~ ~ C 'X ~ ~) 10 ~ ~ ~ ~ ~r ~r ~ ~r a: ~; C ~ C ~7 s la P ,I X X X 3 x x ~
. 1 0 1~ ~ .t O ~1 s ~ ~ .q o ~ v ~ .
- 0~ ~ o ~,1 c æ ~: x ~ x æ ~ x ., O O o ~ ~ ~r Ul (O X O O O ~ O ~ X U~
.-- . .
o , .~ ~
~ -1 N ~n .
~ _~ N ~ ~ U`)~D r ~v~
- X
o O D 'O
a` , N ~ ~ ' 1` 0 0 O ,, ~ * L ,~
~ ' ~
108m7 c ~ -:t ~ 0 ' O
~ . - ~
h O O C ~
D U c !i _ .c a O ~ ' ~ O ~ ~ v -N ~ C C o )'~ P o E~ C
~ 0 ~ O ~o ~o e ~
o a ~ C ~ 0 o ~ s a ~ Q~ C ,~
I c ~ ~ ~ o 0 ~ ~ a ~q o .~ a "~ ~ C ~e ~ o7 ~; o a~ ~ 0~ ~ ~ ~ ~N~
0 ~D ~ N . ~ ~ k ~ c~ o o ~ 3 e P~ ~ --I O ~r ~rl N O ~ ID O O C~
~< ~1 ~ ~ ~ 0 ~ O ~~` O ~ N C ~ 0 ~ O ~ 00 I ~ I` U~ ~ O ~ ~ ~0 ~ ~ ~ <~ O ~ Z ~ C ~
t~ ~ ~ ~ ~ ~ O ~ 5~ U ~ 1~ 0 ~ 1`~; ~ ~ ~ ~0 X~ ~ ~
N
N ~
X
~2 .087777 TA3LE OF ~CRO~m:S
E ethylene IBA isobutyl acrylate MAA methacrylic acid MA methyl acrylate monoeth~l ester of maleic anhydride VA vinyl acetate CO carbon monoxide GMA glycidyl methacrylate FA fumaric acid p p~opylene -g- graft !
E~AMPLES 1 to 1~
These Examples prepared according to the procedure described abo~e are set forth in Table 3.
Control A is molded of a commercially a~ailable comparati~ely high molecular weight polyethylene terephthalate. Examples 1 and 2 show the increase in ductility characterized by a sharp increase in notched Izod with up to 30 weight percent addition of polymer.
Similar effects are illustrated with two additional polymers in polybutylene terephthalate, Examples 3 and 4.
Example 5 prepared with Control B, which has substantially lower inherent viscosity than Control A, illustrates, by comparison with Example 2, the general fact that lower molecular weight materials are more difficult to toughen than ~igh molecular weight materials.
Example 6, made in a different sample lot of Matrix 3, illustrates, similarly to Examples 3 and 4, substantial toughening by a soft polymer with effective adherent sites.
Examples 7 to 10 illustràte toughening Of ~olybutylene terephthalate of lower molecular weight ~os7~m than that used in Examples 3 and ~ using several different polymers.
Examples 11 and 12 illustrate toughening of a polyester copolymer. The same toughener is used to improve the toughness of a polycarbonate polymer, Example 13 in comparison with Control F. The improvement in ductility characterized by higher notched Izod than the control with a 2 mil notch is of particular significance in this Example.
Examples 1~ through 16 illustrate toughening of glass reinforced material in comparison ~nth Control G.
- Example 17 illustrates toughening o~ mineral filled material in comparison with Control H. Example 1 illustrates toughening of glass reinforced, flame retarded polyester in comp~rison with Control I. The degree of flame retardance of Example 1~ is demonstrated by tests which yield a V-0 rating in 1/16 inch sections by Underwriters Laboratory specific2tion test UL 94.
Examples 14 to 1~ were prepared by compounding the rein~orcing and fl~me retardant additives with the toughened polyester on a two inch single screw extruder fitted with a Yacuum port.
- 1087~7 h ~ ~ c ~
8 h ~ o . . .
O ~ : ' ~ P- ' ' ' 't~
. . ~ ~
~40 I o o o o o o o~
0rl 1 0 O ~ o o ~ h ~, ~ O O ~ ~ h ~t.
o 8 ~ ~ ~ ~ 0 "
N C~l N ~ l C~l C~l ~ J
O
~ O ~, .e ant . _ _ o ~_ ~ O ~ t` ~ O ~O O ~ U~ O U~
~; h ~ ~o ~ O ~ ~ r~ N N O ~1 ~ N ~
~ ~ . ' ,~
a _ ~ '~ ~
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a~ I O O O O I O O I O I ~ ~ ~ I o o 0 N ~ N N N N N ~1 ~ ~ ~ h ~d h ~h :S .
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z~ ~ ~ ~o ~ ........
-~ ~ ~ ~ ~ ~ ~ ~ o ~ ~ ~ s0 ~
h ~,0, O OI oI o o o I o I o ~ O a O C~-- H N Nr l ~I H ~1 ,1 ~0~
h :~ N o O o o ~rJ
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OX
0 ~, ~ X H --~ p ,o ~o ~1 rO t~.
~I N ~ h ~ h a 10~7 This Example describes extruding and stretching a composition Or 1,4-polybutylene glycol terephthalate (Matrix 4) and a copolymer of ethylene/methyl acrylate/
glycidyl methacrylate (Polymer ~).
A composition Or ~7 weight percent of Matrix 4 and 13 weight percent Or Polymer ~ is melt extruded into the form of a film. me composition is extruded at a temperature in the range of 260C. (initial end of barrel) to 2~5C. (at the die end of the barrel) in a Sterling extruder through an ~ inch (20.32 centimeters) wide Johnson-die maintained at a temperature of about 29~C.
me molten film is extruded onto the surface of a rotating (at about 15 feet `(4.572 meters) per minute) ~uench drum maintained at a temperature Or about 42C.
Full wire electrostatic pinning is used to insure uniform quenching of the cast film which is 10 mils (250 microns) in thickness. Sheets, ~ inches by 4 inchas (10.16 centimeters by 10.16 centimeters) cut from the roll of cast film are stretched simultaneously (in a T. M. Long Co. stretcher~ 3x in mutually perpendicular directions at a temperature of about 600C., and thereafter heat set in frames at 200C. in an oven.
me cast film stretches uniformly in all directions.
The following physical properties are measured on the cast film and the stretched rilm.
Tensile strength (p.s.i. ) - ASTM test D-~g2 Tensile modulus (p.s.i.) - ASTM test D-~2 Elongation at break (percent) - ASTM test D-~2 ~33-1087~7 , Pneumatic ball impact resistance test (kilogram-centimeter/mil) - ASTM test D-3099 Tear initiation test (grams/mil) - ASTM test D-1004 ~
Tear propagation test (grams/mil) - ASTM test D-1922 Density (~radient tube method) (grams/ccj - ASTM
test D-1505 Oxygen transmission rate (cc-mil~00 sq. in.-24 hrs.
atmosphere) - AS~I test D-143~.
A control film which is extruded from 100 per-cent Matrix 4 is cast in the same manner as that described abo~e for the above composition. me above physical properties are measured on the control cast Matrix 4 film, the cast film from the composition, and the stretched film of the composition. The physical properties are given in Table 4. It is found that the control,film of cast 100 percent Matrix 4 can not be stretched under the conditions employed with the composition of this Example.
A sample of the cast film from the composition is thermoformed, after being preheated for about 10 seconds in an oven heated to about 210C., into the shape of a dish 1.5 inches (3.~1 centimeters) deep by 5 inches (12.7 centimeters) in diameter. The male portion of the dish mold is heated to about 200C. and the female portion is at about 160C.
~34-.t N S . 1~D
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Claims (46)
1. A toughened multi-phase thermoplastic compo-sition consisting essentially of one phase containing 60 to 99 percent by weight of a matrix resin taken from the class consisting essentially of (a) polyester matrix resin having an inherent viscosity, as measured at a concentration of 0.32 g./100 ml. in trifluoroacetic acid (25%)/methylene chloride (75%) at 25°C., in the range of about 0.4 to 4.0 deciliters/gram, said polyester being prepared from an aromatic dicarboxylic acid having from 8 to 14 carbon atoms and at least one glycol taken from the class consisting of a glycol of the formula HO(CH2)nOH where n is an integer of 2 to 10, neopentyl glycol and cyclohexane dimethanol, a portion of the moles of acid being replaceable by at least one acid taken from the group consisting of at least one different aromatic dicarboxylic acid having from 8 to 14 carbon atoms in an amount up to 50 mole percent, and an aliphatic dicarboxylic acid having from 2 to 12 carbon atoms in an amount up to 20 mole percent; and (b) polycarbonate matrix resin having an inherent viscosity, as measured at a concentration of 0.32 g./100 ml. in trifluoro-acetic acid (25%)/methylene chloride (75) at 25°C., in the range of about 0.35 to 0.75 deciliter/gram, said polycarbonate possessing recurring structural units of the formula:
where A is a divalent aromatic radical of a dihydric phenol;
and 1 to 40 percent by weight of at least one other phase containing particles of at least one random copolymer taken from the class consisting of branched and straight chain polymers, said at least one random copolymer having a particle size in the range of 0.01 to 1.0 microns, being adhered to the matrix resin, and having a tensile modulus in the range of about 1.0 to 20,000 p.s.i., the ratio of the tensile modulus of the matrix resin to tensile modulus of said at least one random copolymer being greater than 10 to 1, said at least one random copolymer being represented by the formula:
A(a)-B(b)-C(c)-D(d)-E(e)-F(f)-G(g)-H(h) derived in any order from monomers A to H wherein A is ethylene;
B is CO;
C is an unsaturated monomer taken from the class consisting of .alpha.,.beta.-ethylenically unsaturated carboxylic acids having from 3 to 8 carbon atoms, and derivatives thereof taken from the class consisting of monoesters of alcohols of 1 to 29 carbon atoms and the dicarboxylic acids and anhydrides of the dicarboxylic acids and the metal salts of the monocarboxylic, dicarboxylic acids and the monoester of the dicarboxylic acid having from 0 to 100 percent of the carboxylic acid groups ionized by neutralization with metal ions and dicarboxylic acids and monoesters of the dicarboxylic acid neutralized by amine-ended caprolactam oligomers having a DP of 6 to 24;
D is an unsaturated epoxide of 4 to 11 carbon atoms;
E is the residue derived by the loss of nitrogen from an aromatic sulfonyl azide substituted by carboxylic acids taken from the class consisting of monocarboxylic and dicarboxylic acids having from 7 to 12 carbon atoms and derivatives thereof taken from the class consisting of monoesters of alcohols of 1 to 29 carbon atoms and the dicarboxylic acids and anhydrides of the dicarboxylic acids and the metal salts of the monocarboxylic, dicarboxylic acids and the monoester of the dicarboxylic acid having from 0 to 100 percent of the carboxylic acid groups ionized by neutralization with metal ions;
F is an unsaturated monomer taken from the class consisting of acrylate esters having from 4 to 22 carbon atoms, vinyl esters of acids having from 1 to 20 carbon atoms, vinyl ethers of 3 to 20 carbon atoms, vinyl and vinylidene halides, and nitriles having from 3 to 6 carbon atoms;
G is an unsaturated monomer having at least one substituent selected from the group consisting of pendant hydrocarbon chains of 1 to 12 carbon atoms and pendant aromatic groups which may have 1 to 6 substituent groups having a total of 14 carbon atoms; and H is an unsaturated monomer taken from the class consisting of branched, straight chain and cyclic compounds having from 4 to 14 carbon atoms and at least one additional unsaturated carbon-carbon bond capable of being grafted with a monomer having at least one reactive group of the type defined in C, D and E;
monomers A to H being present in the following mole fraction:
(a) 0 to 0.95, (b) 0 to 0.30, (c) 0 to 0.5, (d) 0 to 0.5, (e) 0 to 0.5, (f) 0 to 0.99, (g) 0 to 0.99, and (h) 0 to 0.99; said at least one polymer having present at least one of monomers B, C, D and E with the proviso that when monomer A is present, in addition to at least one of monomers B, C, D and E, at least one of monomers F, G and H is also present.
where A is a divalent aromatic radical of a dihydric phenol;
and 1 to 40 percent by weight of at least one other phase containing particles of at least one random copolymer taken from the class consisting of branched and straight chain polymers, said at least one random copolymer having a particle size in the range of 0.01 to 1.0 microns, being adhered to the matrix resin, and having a tensile modulus in the range of about 1.0 to 20,000 p.s.i., the ratio of the tensile modulus of the matrix resin to tensile modulus of said at least one random copolymer being greater than 10 to 1, said at least one random copolymer being represented by the formula:
A(a)-B(b)-C(c)-D(d)-E(e)-F(f)-G(g)-H(h) derived in any order from monomers A to H wherein A is ethylene;
B is CO;
C is an unsaturated monomer taken from the class consisting of .alpha.,.beta.-ethylenically unsaturated carboxylic acids having from 3 to 8 carbon atoms, and derivatives thereof taken from the class consisting of monoesters of alcohols of 1 to 29 carbon atoms and the dicarboxylic acids and anhydrides of the dicarboxylic acids and the metal salts of the monocarboxylic, dicarboxylic acids and the monoester of the dicarboxylic acid having from 0 to 100 percent of the carboxylic acid groups ionized by neutralization with metal ions and dicarboxylic acids and monoesters of the dicarboxylic acid neutralized by amine-ended caprolactam oligomers having a DP of 6 to 24;
D is an unsaturated epoxide of 4 to 11 carbon atoms;
E is the residue derived by the loss of nitrogen from an aromatic sulfonyl azide substituted by carboxylic acids taken from the class consisting of monocarboxylic and dicarboxylic acids having from 7 to 12 carbon atoms and derivatives thereof taken from the class consisting of monoesters of alcohols of 1 to 29 carbon atoms and the dicarboxylic acids and anhydrides of the dicarboxylic acids and the metal salts of the monocarboxylic, dicarboxylic acids and the monoester of the dicarboxylic acid having from 0 to 100 percent of the carboxylic acid groups ionized by neutralization with metal ions;
F is an unsaturated monomer taken from the class consisting of acrylate esters having from 4 to 22 carbon atoms, vinyl esters of acids having from 1 to 20 carbon atoms, vinyl ethers of 3 to 20 carbon atoms, vinyl and vinylidene halides, and nitriles having from 3 to 6 carbon atoms;
G is an unsaturated monomer having at least one substituent selected from the group consisting of pendant hydrocarbon chains of 1 to 12 carbon atoms and pendant aromatic groups which may have 1 to 6 substituent groups having a total of 14 carbon atoms; and H is an unsaturated monomer taken from the class consisting of branched, straight chain and cyclic compounds having from 4 to 14 carbon atoms and at least one additional unsaturated carbon-carbon bond capable of being grafted with a monomer having at least one reactive group of the type defined in C, D and E;
monomers A to H being present in the following mole fraction:
(a) 0 to 0.95, (b) 0 to 0.30, (c) 0 to 0.5, (d) 0 to 0.5, (e) 0 to 0.5, (f) 0 to 0.99, (g) 0 to 0.99, and (h) 0 to 0.99; said at least one polymer having present at least one of monomers B, C, D and E with the proviso that when monomer A is present, in addition to at least one of monomers B, C, D and E, at least one of monomers F, G and H is also present.
2. A composition according to Claim 1 wherein the tensile modulus of said at least one random copolymer is about 5.0 to 20,000 p.s.i. and the ratio of tensile modulus is greater than 20 to 1.
3. A composition according to Claim 1 wherein said at least one random copolymer is present as part of a mixture.
4. A composition according to Claim 1 wherein the ratio of tensile modulus is greater than 20 to 1.
5. A composition according to Claim 1 wherein the notched Izod in the dry as molded condition is at least the values represented by the formulae:
B + 0.2 C1 B + 2.0 + 0.5 (C2-10), B + 12.0 where B is the notched Izod of the polyester matrix resin, C1 is 2 to 10 percent by weight of the at least one random copolymer, and C2 is 10 to 30 percent by weight of the at least one random copolymer, and the notched Izod is at least B + 12.0 when the concentration of the at least one random copolymer is between 30 and 40 percent by weight.
B + 0.2 C1 B + 2.0 + 0.5 (C2-10), B + 12.0 where B is the notched Izod of the polyester matrix resin, C1 is 2 to 10 percent by weight of the at least one random copolymer, and C2 is 10 to 30 percent by weight of the at least one random copolymer, and the notched Izod is at least B + 12.0 when the concentration of the at least one random copolymer is between 30 and 40 percent by weight.
6. A composition according to Claim 1 wherein the notched Izod in the dry as molded condition is at least the values represented by the formulae:
B + 0.2 C1 B + 2.0 + 0.5 (C2-10), B + 12.0 where B is the notched Izod of the polycarbonate matrix resin, C1 is 2 to 10 percent by weight of the at least one random copolymer, and C2 is 10 to 30 percent by weight of the at least one random copolymer, and the notched Izod is at least B + 12.0 when the concentration of the at least one random copolymer is between 30 and 40 percent by weight.
B + 0.2 C1 B + 2.0 + 0.5 (C2-10), B + 12.0 where B is the notched Izod of the polycarbonate matrix resin, C1 is 2 to 10 percent by weight of the at least one random copolymer, and C2 is 10 to 30 percent by weight of the at least one random copolymer, and the notched Izod is at least B + 12.0 when the concentration of the at least one random copolymer is between 30 and 40 percent by weight.
7. A composition according to Claim 1 wherein the notched Izod value, dry as molded, is greater than 8 ft. lbs./inch when the concentration of said at least one random copolymer is from 5 to 20 percent by weight.
8. A composition according to Claim 1 wherein there is present up to 5.0 percent by weight, based on the weight of the composition, of at least one colorant.
9. A composition according to Claim 1 wherein there is present up to 50 percent by weight, based on the weight of the composition, of glass fibers.
10. A composition according to Claim 1 wherein there is present up to 50 percent by weight, based on the weight of the composition, of fibrous and particulate mineral fillers and reinforcements.
11. A composition according to Claim 1 wherein there is present up to 1.0 percent by weight, based on the weight of polyester, of a stabilizer.
12. A composition according to Claim 1 wherein there is present, based on the weight of the composition, of up to 10 percent of a polyvalent metal oxide and up to 20 percent of a halogenated organic compound taken from the group consisting of aromatic and cycloaliphatic compounds.
13. A composition according to Claim 1 wherein said at least one random copolymer has present carbon monoxide.
14. A composition according to Claim 1 wherein said at least one random copolymer has present an unsaturated monomer taken from the class consisting of .alpha.,.beta.-ethylenically unsaturated carboxylic acids having from 3 to 8 carbon atoms, and derivatives thereof taken from the class consisting of monoesters of alcohols of 1 to 29 carbon atoms and the dicar-boxylic acids and anhydrides of the dicarboxylic acids and the metal salts of the monocarboxylic, dicarboxylic acids and the monoester of the dicarboxylic acid having from 0 to 100 percent of the carboxylic acid groups ionized by neutral-ization with metal ions.
15. A composition according to Claim 1 wherein said at least one random copolymer has present an unsaturated epoxide of 4 to 11 carbon atoms.
16. A composition according to Claim 1 wherein said at least one random copolymer has present the residue derived by the loss of nitrogen from an aromatic sulfonyl azide substituted by carboxylic acids taken from the class consisting of monocarboxylic and dicarboxylic acids having from 7 to 12 carbon atoms and derivatives thereof taken from the class consisting of monoesters of alcohols of 1 to 29 carbon atoms and the dicarboxylic acids and anhydrides of the dicarboxylic acids and the metal salts of the monocarboxylic, dicarboxylic acids and the monoester of the dicarboxylic acid having from 0 to 100 percent of the carboxylic acid groups ionized by neutralization with metal ions.
17. A composition according to Claim 1 wherein said at least one random copolymer has present an unsaturated monomer taken from the class consisting of acrylate esters having from 4 to 22 carbon atoms, vinyl esters of acids having from 1 to 20 carbon atoms, vinyl ethers of 3 to 20 carbon atoms, vinyl and vinylidene halides, and nitriles having from 3 to 6 carbon atoms.
18. A composition according to Claim 1 wherein said at least one random copolymer has present an unsaturated monomer having pendant hydrocarbon chains of 1 to 12 carbon atoms capable of being grafted with monomers having at least one reactive group of the type defined in C, D and E, and pendant aromatic groups which may have 1 to 6 substituent groups having a total of 14 carbon atoms.
19. A composition according to Claim 1 wherein said at least one random copolymer has present an unsaturated monomer taken from the class consisting of branched, straight chain and cyclic compounds having from 4 to 14 carbon atoms and at least one additional nonconjugated unsaturated carbon-carbon bond capable of being grafted with a monomer having at least one reactive group of the type defined in C, D and E.
20. A composition according to Claim 4 wherein said at least one random copolymer consists essentially of polymerized ethylene, at least one polymerized .alpha.-olefin of 3 to 6 carbon atoms, and at least one polymerized unsat-urated monomer taken from the class consisting of branched, straight chain and cyclic compounds having from 4 to 14 carbon atoms and at least one additional nonconjugated unsaturated carbon-carbon bond, and grafted thereto an unsaturated monomer taken from the class consisting of ethylenically unsaturated dicarboxylic acids having from 3 to 8 carbon atoms, and derivatives thereof taken from the class consisting of monoesters of alcohols of 1 to 29 carbon atoms, anhydrides of the dicarboxylic acids, the metal salts of the dicarboxylic acids and the monoesters of said dicarboxylic acid having from 0 to 100 percent of the carboxylic groups ionized by neutralization with metal ions.
21. A composition according to Claim 20 wherein said at least one random copolymer is a copolymer of ethylene, propylene and 1,4-hexadiene having grafted thereto an unsat-urated monomer taken from the class consisting of fumaric acid, maleic acid, maleic anhydride and the monoalkyl ester of said acids in which the alkyl group of the ester has 1 to 3 carbon atoms, said at least one polymer having an after grafting melt flow rate of 0.1 to 100 g./10 minutes, ASTM D
1238 at 280°C. and a total load of 2160 grams.
1238 at 280°C. and a total load of 2160 grams.
22. A composition according to Claim 20 wherein said at least one random copolymer is a tetrapolymer of ethylene, propylene, 1,4-hexadiene and 2,5-norbornadiene having grafted thereto an unsaturated monomer taken from the class consisting of fumaric acid, maleic acid, maleic anhydride and the monoalkyl ester of said acids in which the alkyl group of the ester has 1 to 3 carbon atoms, said at least one polymer having an after grafting melt flow rate of 0.1 to 100 g./10 minutes, ASTM D 1238 at 280°C. and a total load of 2160 grams.
23. A composition according to Claim 21 wherein said matrix resin is polyethylene terephthalate.
24. A composition according to Claim 22 wherein said matrix resin is polyethylene terephthalate.
25. A composition according to Claim 21 wherein said matrix resin is polybutylene terephthalate.
26. A composition according to Claim 22 wherein said matrix resin is polybutylene terephthalate.
27 A composition according to Claim 21 wherein the matrix resin is a polycarbonate.
28. A composition according to Claim 22 wherein the matrix resin is a polycarbonate.
29. A composition according to Claim 4 wherein said at least one random copolymer is a random copolymer consisting essentially of polymerized ethylene, alkyl acrylate selected from methyl and ethyl acrylate, and from about 0.0025-0.077 mole/100 g. polymer of a mono alkyl ester of 1,4-butene-dioic acid in which the alkyl group of the ester has 1 to 6 carbon atoms, said copolymer having from about 0.64-0.80 mole of (-CO2-) units per 100 grams of copolymer, and having 0 to 100 percent of the esters of 1,4-butene-dioic acid ionized by neutralization with metal ions selected from lithium, sodium, potassium, calcium and zinc ions, said copolymer having a melt index at 190°C. and a total load of 2160 grams of about 0.3 to 100 grams/10 minutes, and when neutralized having a melt flow rate of 0.04 to 100 grams/10 minutes under condition G of ASTM D 1238.
30. A composition according to Claim 29 wherein said mono alkyl ester of 1,4-butene-dioic acid consists essentially of ethyl hydrogen maleate.
31. A composition according to Claim 30 wherein said matrix resin is polyethylene terephthalate.
32. A composition according to Claim 30 wherein said matrix resin is polybutylene terephthalate.
33. A process for the preparation of a toughened multi-phase thermoplastic composition which comprises, in a closed system, (i) admixing (1) 60 to 99 percent by weight of a matrix resin taken from the class consisting essentially of (a) polyester matrix resin having an inherent viscosity, as measured at a concentration of 0.32 g./100 ml. in trifluoro-acetic acid (25%)/methylene chloride (75%) at 25°C., in the range of about 0.4 to 4.0 deciliters/gram, said polyester being prepared from an aromatic dicarboxylic acid having from 8 to 14 carbon atoms and at least one glycol taken from the class consisting of a glycol of the formula HO(CH2)nOH where n is an integer of 2 to 10, neopentyl glycol and cyclohexane dimethanol, a portion of the moles of acid being replaceable by at least one acid taken from the group consisting of at least one different aromatic dicarboxylic acid having from 8 to 14 carbon atoms in an amount up to 50 mole percent, and an aliphatic dicarboxylic acid having from 2 to 12 carbon atoms in an amount up to 20 mole percent; and (b) polycarbonate matrix resin having an inherent viscosity, as measured at a concentration of 0.32 g./100 ml. in trifluoroacetic acid (25%)/methylene chloride (75%) at 25°C., in the range of about 0.35 to 0.75 deciliter/gram, said polycarbonate possess-ing recurring structural units of the formula:
where A is a divalent aromatic radical of a dihydric phenol;
and (2) 1 to 40 percent by weight of at least one random copolymer taken from the class consisting of branched and straight chain polymers, at a temperature in the range of about 5 to 100°C. above the melting point of said matrix resin, said at least one random copolymer being represented by the formula:
A(a)-B(b)-C(c)-D(d)-E(e)-F(f)-G(g)-H(h) derived in any order from monomers A to H wherein A is ethylene;
B is CO;
C is an unsaturated monomer taken from the class consisting of .alpha.,.beta.-ethylenically unsaturated carboxylic acids having from 3 to 8 carbon atoms, and derivatives thereof taken from the class consisting of monoesters of alcohols of 1 to 29 carbon atoms and the dicarboxylic acids and anhydrides of the dicarboxylic acids and the metal salts of the monocarboxylic, dicarboxylic acids and the monoester of the dicarboxylic acid having from 0 to 100 percent of the carboxylic acid groups ionized by neutralization with metal ions and dicarboxylic acids and monoesters of the dicarboxylic acid neutralized by amine-ended capro-lactam oligomers having a DP of 6 to 24;
D is an unsaturated epoxide of 4 to 11 carbon atoms;
E is the residue derived by the loss of nitrogen from an aromatic sulfonyl azide substituted by carboxylic acids taken from the class consisting of monocarboxylic and dicarboxylic acids having from 7 to 12 carbon atoms and derivatives thereof taken from the class consisting of monoesters of alcohols of 1 to 29 carbon atoms and the dicarboxylic acids and anhydrides of the dicarboxylic acids and the metal salts of the monocarboxylic, dicarboxylic acids and the monoester of the dicarboxylic acid having from 0 to 100 percent of the carboxylic acid groups ionized by neutralization with metal ions;
F is an unsaturated monomer taken from the class consisting of acrylate esters having from 4 to 22 carbon atoms, vinyl esters of acids having from 1 to 20 carbon atoms, vinyl ethers of 3 to 20 carbon atoms, vinyl and vinylidene halides, and nitriles having from 3 to 6 carbon atoms;
G is an unsaturated monomer having at least one substituent selected from the group consisting of pendant hydrocarbon chains of 1 to 12 carbon atoms and pendant aromatic groups which may have 1 to 6 substituent groups having a total of 14 carbon atoms; and H is an unsaturated monomer taken from the class consisting of branched, straight chain and cyclic compounds having from 4 to 14 carbon atoms and at least one additional unsaturated carbon-carbon bond capable of being grafted with a monomer having at least one reactive group of the type defined in C, D and E;
monomers A to H being present in the following mole fraction:
(a) 0 to 0.95, (b) 0 to 0.30, (c) 0 to 0.5, (d) 0 to 0.5, (e) 0 to 0.5, (f) 0 to 0.99, (g) 0 to 0.99, and (h) 0 to 0.99; said at least one polymer having present at least one of monomers B, C, D and E with the proviso that when monomer A is present, in addition to at least one of monomers B, C, D and E, at least one of monomers F, G and H is also present, and (ii) shearing to disperse said at least one random copolymer in said matrix to a particle size in the range of 0.01 to 1.0 microns, said at least one random copolymer being adhered to said matrix, and having a tensile modulus in the range of 1.0 to 20,000 p.s.i., the ratio of the tensile modulus of said matrix to tensile modulus of said at least one random copolymer being greater than 10 to 1.
where A is a divalent aromatic radical of a dihydric phenol;
and (2) 1 to 40 percent by weight of at least one random copolymer taken from the class consisting of branched and straight chain polymers, at a temperature in the range of about 5 to 100°C. above the melting point of said matrix resin, said at least one random copolymer being represented by the formula:
A(a)-B(b)-C(c)-D(d)-E(e)-F(f)-G(g)-H(h) derived in any order from monomers A to H wherein A is ethylene;
B is CO;
C is an unsaturated monomer taken from the class consisting of .alpha.,.beta.-ethylenically unsaturated carboxylic acids having from 3 to 8 carbon atoms, and derivatives thereof taken from the class consisting of monoesters of alcohols of 1 to 29 carbon atoms and the dicarboxylic acids and anhydrides of the dicarboxylic acids and the metal salts of the monocarboxylic, dicarboxylic acids and the monoester of the dicarboxylic acid having from 0 to 100 percent of the carboxylic acid groups ionized by neutralization with metal ions and dicarboxylic acids and monoesters of the dicarboxylic acid neutralized by amine-ended capro-lactam oligomers having a DP of 6 to 24;
D is an unsaturated epoxide of 4 to 11 carbon atoms;
E is the residue derived by the loss of nitrogen from an aromatic sulfonyl azide substituted by carboxylic acids taken from the class consisting of monocarboxylic and dicarboxylic acids having from 7 to 12 carbon atoms and derivatives thereof taken from the class consisting of monoesters of alcohols of 1 to 29 carbon atoms and the dicarboxylic acids and anhydrides of the dicarboxylic acids and the metal salts of the monocarboxylic, dicarboxylic acids and the monoester of the dicarboxylic acid having from 0 to 100 percent of the carboxylic acid groups ionized by neutralization with metal ions;
F is an unsaturated monomer taken from the class consisting of acrylate esters having from 4 to 22 carbon atoms, vinyl esters of acids having from 1 to 20 carbon atoms, vinyl ethers of 3 to 20 carbon atoms, vinyl and vinylidene halides, and nitriles having from 3 to 6 carbon atoms;
G is an unsaturated monomer having at least one substituent selected from the group consisting of pendant hydrocarbon chains of 1 to 12 carbon atoms and pendant aromatic groups which may have 1 to 6 substituent groups having a total of 14 carbon atoms; and H is an unsaturated monomer taken from the class consisting of branched, straight chain and cyclic compounds having from 4 to 14 carbon atoms and at least one additional unsaturated carbon-carbon bond capable of being grafted with a monomer having at least one reactive group of the type defined in C, D and E;
monomers A to H being present in the following mole fraction:
(a) 0 to 0.95, (b) 0 to 0.30, (c) 0 to 0.5, (d) 0 to 0.5, (e) 0 to 0.5, (f) 0 to 0.99, (g) 0 to 0.99, and (h) 0 to 0.99; said at least one polymer having present at least one of monomers B, C, D and E with the proviso that when monomer A is present, in addition to at least one of monomers B, C, D and E, at least one of monomers F, G and H is also present, and (ii) shearing to disperse said at least one random copolymer in said matrix to a particle size in the range of 0.01 to 1.0 microns, said at least one random copolymer being adhered to said matrix, and having a tensile modulus in the range of 1.0 to 20,000 p.s.i., the ratio of the tensile modulus of said matrix to tensile modulus of said at least one random copolymer being greater than 10 to 1.
34. A process according to Claim 33 wherein the tensile modulus of said at least one random copolymer is about 5.0 to 20,000 p.s.i. and the ratio of tensile modulus is greater than 20 to 1.
35. A process according to Claim 33 wherein said at least one random copolymer is present as part of a mixture.
36. A process according to Claim 33 wherein the ratio of tensile modulus is greater than 20 to 1.
37. A process according to Claim 33 wherein the notched Izod in the dry as molded condition is at least the values represented by the formulae:
B + 0.2 C1 B + 2.0 + 0.5 (C2-10) B + 12.0 where B is the notched Izod of the matrix resin, C1 is 2 to 10 percent by weight of the at least one random copolymer, and C2 is 10 to 30 percent by weight of the at least one random copolymer, and the notched Izod is at least B + 12.0 when the concentration of the at least one random copolymer is between 30 and 40 percent by weight.
B + 0.2 C1 B + 2.0 + 0.5 (C2-10) B + 12.0 where B is the notched Izod of the matrix resin, C1 is 2 to 10 percent by weight of the at least one random copolymer, and C2 is 10 to 30 percent by weight of the at least one random copolymer, and the notched Izod is at least B + 12.0 when the concentration of the at least one random copolymer is between 30 and 40 percent by weight.
38. A process according to Claim 33 wherein the notched Izod value, dry as molded, is greater than 8 ft. lbs./
inch when the concentration of said at least one random copolymer is from 5 to 20 percent by weight.
inch when the concentration of said at least one random copolymer is from 5 to 20 percent by weight.
39. A process according to Claim 36 wherein said at least one random copolymer consists essentially of poly-merized ethylene, at least one polymerized .alpha.-olefin of 3 to 6 carbon atoms, and at least one polymerized unsaturated monomer taken from the class consisting of branched, straight chain and cyclic compounds having from 4 to 14 carbon atoms and at least one additional nonconjugated unsaturated carbon-carbon bond, and grafted thereto an unsaturated monomer taken from the class consisting of .alpha.,.beta.-ethylenically unsaturated dicarboxylic acids having from 3 to 8 carbon atoms, and derivatives thereof taken from the class consisting of mono-esters of alcohols of 1 to 29 carbon atoms, anhydrides of the dicarboxylic acids, the metal salts of the dicarboxylic acids and the monoesters of said dicarboxylic acid having from 0 to 100 percent of the carboxylic groups ionized by neutralization with metal ions.
40. A process according to Claim 39 wherein said matrix resin is polyethylene terephthalate.
41. A process according to Claim 39 wherein said matrix resin is polybutylene terephthalate.
42. A process according to Claim 36 wherein said at least one random copolymer is a random copolymer consist-ing essentially of polymerized ethylene, alkyl acrylate selected from methyl and ethyl acrylate, and from about 0.0025-0.077 mole/100 g. polymers of a mono alkyl ester of 1,4-butene-dioic acid in which the alkyl group of the ester has 1 to 6 carbon atoms, said copolymer having from about 0.64-0.80 mole of (-CO2-) units per 100 grams of copolymer, and having 0 to 100 percent of the esters of 1,4-butene-dioic acid ionized by neutralization with metal ions selected from lithium, sodium, potassium, calcium and zinc ions, said copolymer having a melt index at 190°C. and a total load of 2160 grams of about 0.3 to 100 grams/10 minutes, and when neutralized having a melt flow rate of 0.04 to 100 grams/10 minutes under condition G of ASTM D 1238.
43. A process according to Claim 42 wherein said matrix resin is polyethylene terephthalate.
44. A process according to Claim 42 wherein said matrix resin is polybutylene terephthalate.
45. A process for preparing a toughened multiphase thermoplastic composition consisting essentially of one phase containing 80 to 99 percent by weight of a matrix resin taken from the class consisting essentially of (a) polyester matrix resin having an inherent viscosity, as measured at a concentration of 0.32 g./100 ml. in trifluoroacetic acid (25%)/methylene chloride (75%) at 25°C., in the range of about 0.4 to 4.0 deciliters/gram, said polyester being prepared from an aromatic dicarboxylic acid having from 8 to 14 carbon atoms and at least one glycol taken from the class consisting of a glycol of the formula HO(CH2)nOH where n is an integer of 2 to 10, neopentyl glycol and cyclohexane dimethanol, a portion of the moles of acid being replaceable by at least one acid taken from the group consisting of at least one different aromatic dicarboxylic acid having from 8 to 14 carbon atoms in an amount up to 50 mole percent, and an aliphatic dicarboxylic acid having from 2 to 12 carbon atoms in an amount up to 20 mole percent; and (b) polycarbonate matrix resin having an inherent viscosity, as measured at a concentration of 0.32 g./100 ml. in trifluoroacetic acid (25%)/methylene chloride (75%) at 25°C., in the range of about 0.35 to 0.75 deciliter/gram, said polycarbonate possessing recurring structural units of the formula:
where A is a divalent aromatic radical of a dihydric phenol;
and 1 to 20 percent by weight of at least one other phase containing particles of at least one random copolymer taken from the class consisting of branched and straight chain polymers, said at least one random copolymer having a particle size in the range of 0.01 to 1.0 microns, being adhered to the matrix resin, and having a tensile modulus in the range of about 1.0 to 20,000 p.s.i., the ratio of the tensile modulus of the matrix resin to tensile modulus of said at least one random copolymer being greater than 10 to 1, said at lease one random copolymer being represented by the formula:
A(a)-B(b)-C(c)-D(d)-E(e)-F(f)-G(g)-H(h) derived in any order from monomers A to H wherein A is ethylene;
B is CO;
C is an unsaturated monomer taken from the class consisting of .alpha.,.beta.-ethylenically unsaturated carboxylic acids having from 3 to 8 carbon atoms, and derivatives thereof taken from the class consisting of monoesters of alcohols of 1 to 29 carbon atoms and the dicarboxylic acids and anhydrides of the dicarboxylic acids and the metal salts of the monocarboxylic, dicarbox-ylic acids and the monoester of the dicarboxylic acid having from 0 to 100 percent of the carboxylic acid groups ionized by neutralization with metal ions and dicarboxylic acids and monoesters of the dicarboxylic acid neutralized by amine-ended capro-lactam oligomers having a DP of 6 to 24;
D is an unsaturated epoxide of 4 to 11 carbon atoms;
E is the residue derived by the loss of nitrogen from an aromatic sulfonyl azide substituted by carboxylic acids taken from the class consisting of monocarboxylic and dicarboxylic acids having from 7 to 12 carbon atoms and derivatives thereof taken from the class consisting of monoesters of alcohols of 1 to 29 carbon atoms and the dicarbox-ylic acids and anhydrides of the dicarboxylic acids and the metal salts of the monocarboxylic, dicarboxy-lic acids and the monoester of the dicarboxylic acid having from 0 to 100 percent of the carboxylic acid groups ionized by neutralization with metal ions;
F is an unsaturated monomer taken from the class consisting of acrylate esters having from 4 to 22 carbon atoms, vinyl esters of acids having from 1 to 20 carbon atoms, vinyl ethers of 3 to 20 carbon atoms, vinyl and vinylidene halides, and nitriles having from 3 to 6 carbon atoms;
G is an unsaturated monomer having at least one substitutent selected from the group consisting of pendant hydrocarbon chains of 1 to 12 carbon atoms and pendant aromatic groups which may have 1 to 6 substituent groups having a total of 14 carbon atoms; and H is an unsaturated monomer taken from the class consisting of branched, straight chain and cyclic compounds having from 4 to 14 carbon atoms and at least one additional unsaturated carbon-carbon bond capable of being grafted with a monomer having at least one reactive group of the type defined in C, D
and E;
monomers A to H being present in the following mole fraction;
(a) 0 to 0.95, (b) 0 to 0.30, (c) 0 to 0.5, (d) 0 to 0.5, (e) 0 to 0.5, (f) 0 to 0.99, (g) 0 to 0.99, and (h) 0 to 0.99, said at least one polymer having present at least one of monomers B, C, D and E with the proviso that when monomer A is present, in addition to at least one of monomers B, C, D and E, at least one of monomers F, G and H is also present, which comprises initially admixing said matrix resin and up to about 40 percent by weight of the said at least one random copolymer and subsequently admixing additional matrix resin until said desired concentration is achieved.
where A is a divalent aromatic radical of a dihydric phenol;
and 1 to 20 percent by weight of at least one other phase containing particles of at least one random copolymer taken from the class consisting of branched and straight chain polymers, said at least one random copolymer having a particle size in the range of 0.01 to 1.0 microns, being adhered to the matrix resin, and having a tensile modulus in the range of about 1.0 to 20,000 p.s.i., the ratio of the tensile modulus of the matrix resin to tensile modulus of said at least one random copolymer being greater than 10 to 1, said at lease one random copolymer being represented by the formula:
A(a)-B(b)-C(c)-D(d)-E(e)-F(f)-G(g)-H(h) derived in any order from monomers A to H wherein A is ethylene;
B is CO;
C is an unsaturated monomer taken from the class consisting of .alpha.,.beta.-ethylenically unsaturated carboxylic acids having from 3 to 8 carbon atoms, and derivatives thereof taken from the class consisting of monoesters of alcohols of 1 to 29 carbon atoms and the dicarboxylic acids and anhydrides of the dicarboxylic acids and the metal salts of the monocarboxylic, dicarbox-ylic acids and the monoester of the dicarboxylic acid having from 0 to 100 percent of the carboxylic acid groups ionized by neutralization with metal ions and dicarboxylic acids and monoesters of the dicarboxylic acid neutralized by amine-ended capro-lactam oligomers having a DP of 6 to 24;
D is an unsaturated epoxide of 4 to 11 carbon atoms;
E is the residue derived by the loss of nitrogen from an aromatic sulfonyl azide substituted by carboxylic acids taken from the class consisting of monocarboxylic and dicarboxylic acids having from 7 to 12 carbon atoms and derivatives thereof taken from the class consisting of monoesters of alcohols of 1 to 29 carbon atoms and the dicarbox-ylic acids and anhydrides of the dicarboxylic acids and the metal salts of the monocarboxylic, dicarboxy-lic acids and the monoester of the dicarboxylic acid having from 0 to 100 percent of the carboxylic acid groups ionized by neutralization with metal ions;
F is an unsaturated monomer taken from the class consisting of acrylate esters having from 4 to 22 carbon atoms, vinyl esters of acids having from 1 to 20 carbon atoms, vinyl ethers of 3 to 20 carbon atoms, vinyl and vinylidene halides, and nitriles having from 3 to 6 carbon atoms;
G is an unsaturated monomer having at least one substitutent selected from the group consisting of pendant hydrocarbon chains of 1 to 12 carbon atoms and pendant aromatic groups which may have 1 to 6 substituent groups having a total of 14 carbon atoms; and H is an unsaturated monomer taken from the class consisting of branched, straight chain and cyclic compounds having from 4 to 14 carbon atoms and at least one additional unsaturated carbon-carbon bond capable of being grafted with a monomer having at least one reactive group of the type defined in C, D
and E;
monomers A to H being present in the following mole fraction;
(a) 0 to 0.95, (b) 0 to 0.30, (c) 0 to 0.5, (d) 0 to 0.5, (e) 0 to 0.5, (f) 0 to 0.99, (g) 0 to 0.99, and (h) 0 to 0.99, said at least one polymer having present at least one of monomers B, C, D and E with the proviso that when monomer A is present, in addition to at least one of monomers B, C, D and E, at least one of monomers F, G and H is also present, which comprises initially admixing said matrix resin and up to about 40 percent by weight of the said at least one random copolymer and subsequently admixing additional matrix resin until said desired concentration is achieved.
46. A composition according to Claim 1 in the form of a film.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US580,514 | 1975-05-23 | ||
| US05/580,514 US4172859A (en) | 1975-05-23 | 1975-05-23 | Tough thermoplastic polyester compositions |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1087777A true CA1087777A (en) | 1980-10-14 |
Family
ID=24321416
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA253,144A Expired CA1087777A (en) | 1975-05-23 | 1976-05-21 | Tough thermoplastic polyester compositions |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US4172859A (en) |
| JP (1) | JPS5928223B2 (en) |
| CA (1) | CA1087777A (en) |
| DE (1) | DE2622876A1 (en) |
| FR (1) | FR2311808A1 (en) |
| GB (1) | GB1552637A (en) |
| IT (1) | IT1061452B (en) |
| NL (1) | NL182891C (en) |
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| NL112074C (en) * | 1957-12-10 | 1900-01-01 | ||
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| IT963692B (en) * | 1972-08-03 | 1974-01-21 | Montedison Spa | SHOCK-RESISTANT POLYESTERS |
| JPS559435B2 (en) * | 1972-08-30 | 1980-03-10 | ||
| DE2252974C2 (en) * | 1972-10-28 | 1982-05-06 | Bayer Ag, 5090 Leverkusen | Thermoplastic molding compounds and moldings made from polycarbonate and styrene-maleic anhydride copolymer |
| DE2259565C3 (en) * | 1972-12-06 | 1985-08-22 | Bayer Ag, 5090 Leverkusen | Molding compositions based on polycarbonate and a polybutadiene graft copolymer |
-
1975
- 1975-05-23 US US05/580,514 patent/US4172859A/en not_active Expired - Lifetime
-
1976
- 1976-05-21 DE DE19762622876 patent/DE2622876A1/en active Granted
- 1976-05-21 CA CA253,144A patent/CA1087777A/en not_active Expired
- 1976-05-21 JP JP51058016A patent/JPS5928223B2/en not_active Expired
- 1976-05-21 NL NLAANVRAGE7605494,A patent/NL182891C/en not_active IP Right Cessation
- 1976-05-21 IT IT23534/76A patent/IT1061452B/en active
- 1976-05-24 GB GB21500/76A patent/GB1552637A/en not_active Expired
- 1976-05-24 FR FR7615622A patent/FR2311808A1/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS51144452A (en) | 1976-12-11 |
| NL182891C (en) | 1991-05-16 |
| DE2622876A1 (en) | 1976-12-09 |
| GB1552637A (en) | 1979-09-19 |
| FR2311808B1 (en) | 1983-01-21 |
| NL7605494A (en) | 1976-11-25 |
| JPS5928223B2 (en) | 1984-07-11 |
| IT1061452B (en) | 1983-02-28 |
| US4172859A (en) | 1979-10-30 |
| FR2311808A1 (en) | 1976-12-17 |
| DE2622876C2 (en) | 1989-01-12 |
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