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WO1983004038A1 - Composition de polyester - Google Patents

Composition de polyester Download PDF

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Publication number
WO1983004038A1
WO1983004038A1 PCT/US1983/000707 US8300707W WO8304038A1 WO 1983004038 A1 WO1983004038 A1 WO 1983004038A1 US 8300707 W US8300707 W US 8300707W WO 8304038 A1 WO8304038 A1 WO 8304038A1
Authority
WO
WIPO (PCT)
Prior art keywords
composition
copolymer
alpha
olefin
sodium
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/US1983/000707
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English (en)
Inventor
Jeffrey T. Books
Michael E. Kucsma
Jesse D. Jones
Robert B. Whitehead
Edwin D. Hornbaker
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Ethyl Corp
Original Assignee
Ethyl Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from US06/397,624 external-priority patent/US4385144A/en
Application filed by Ethyl Corp filed Critical Ethyl Corp
Priority to JP58502187A priority Critical patent/JPS59500917A/ja
Publication of WO1983004038A1 publication Critical patent/WO1983004038A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/098—Metal salts of carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/15—Heterocyclic compounds having oxygen in the ring
    • C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
    • C08K5/1515—Three-membered rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
    • 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

Definitions

  • PET polyethylene tere- phthalate
  • relatively high mold temper ⁇ atures e.g. 120°-140°C.
  • Any attempt to use a lower mold temperature e.g., 100°C. or lower, results in the injected material being unmoldable as, for one thing, the molded article sticks in the mold and often can only be removed with great difficulty.
  • the molder is forced to select more expensive materials such as polybutylene terephthalate (PBT) , inasmuch as this poly (alkylene terephthalate) is easily moldable even when using mold temperatures as low as 60°C.
  • PBT polybutylene terephthalate
  • the time necessary for cool ⁇ ing the injection molded article to a temperature at which it can be removed from the mold is considerably shorter than the cooling time necessary before the PET article can be removed from an initially hotter mold. Since this shorter cool-down period of PBT results in a shorter process cycle time and a higher rate of article production, economic justification exists for its use despite its higher unit cost.
  • a welcome contribution to the art would be a
  • PET composition which can be injection molded at relative-
  • thermoplastic injection moldable composition which comprises an intimate admixture
  • a mold releasability improver selected from (i) a thermoplastic polymer of a vinyl aromatic compound, (ii) at least one mono- epoxyalkane having from 10 to 50 carbon atoms in the molecule, or (iii) an alpha- olefin-acrylic acid copolymer resin in which the alpha-olefin repeating unit is one or more acyclic hydrocarbon alpha-olefins containing at least two but no more than eight carbon atoms in the repeating unit; an
  • compositions may be molded at rela- tively low mold temperatures (e.g., in the range of 50°C. to 100°C.) without excessive sticking being encountered.
  • compositions of this invention may be injection molded at even higher mold temperatures (e.g., 100 to 150°C).
  • the compositions may additionally contain reinforcing amounts of a reinforcing filler, e.g., glass fibers either alone or in combination with particulate mineral fillers.
  • a reinforcing filler e.g., glass fibers either alone or in combination with particulate mineral fillers.
  • Other additives may also be used in the composition such as flame retardants, impact modifiers, and the like.
  • compositions of this invention containing the monoepoxyalkane mold releasability improver is the highly desirable color characteristics which they possess. More particularly they exhibit a neutr to creme white color even without use of any colorizing agents.
  • the compositions can be used for molding part having attractive appearance and coloration even though a colorizing agent is not employed therein.
  • the color characteristics of the blend are also of advantage in that the quantity of colorants used will be significantly less as compared to blends havin a less neutral coloration.
  • the polyethylene terephthalate used herein is preferably homopolymeric PET although crystallizable PET copolymers may also be used.
  • Exemplary of useful PET co ⁇ polymers are those copolymers in which the copolymer contai at least 80 mol percent of repeating units derived from terephthalic acid and ethylene glycol with the remainder (20 mol percent or less) being derived from other well known acid and/or glycol components.
  • Representative acid components are phthalic acid, isophthalic acid, naphthalene 1,4- or 2,6-dicarboxylic acid, diphenyl-4,4 *-dicarboxylic acid, diphenyl ether-4,4'-dicarboxylic acid, adipic acid, sebacic acid as well as their halogenated (preferably brominated) counterparts.
  • the glycol components may be diethylene glycol, neopentyl glycol, cyclohexanedimethanol, 2,2-bis (4-hydroxyphenyl) propane, 1,3-propanediol, 1,4- butanediol, dibromoneopentyl glycol, the bis(2-hydroxyethyl) ether of tetrabromobisphenol A, tetrabromo-p-xylylene glycol and the like.
  • the polyethylene terephthalates used herein can be virgin PET or reclaimed PET.
  • the PET used in the compositions of this invention is injection moldable and thus generally can have an intrinsic viscosity (I.V.) as low as 0.3 and preferably between about 0.4 and 1.2, more preferably between about 0.5 and 1.0, as measured at Z5"C. in a solvent consisting of 60 percent by weight phenol and 40 percent by weight of tetrachloroethane.
  • I.V. intrinsic viscosity
  • polyethylene terephalates in whic the I.V. is in the range of 0.4 to 0.9 are most preferred.
  • the vinyl aromatic polymers utilized in the compo sitions of this invention are characterized by containing at least about 55% and preferably at least about 70% by weight of units of the formula:
  • R is a hydrogen or an alkyl group of one to four carbon atoms
  • Ph is a substituted or unsubstituted phenyl group which, when substituted, may contain up to about four alkyl groups (preferably containing no more than about four carbon atoms each) , up to about four chlorine atoms, up to about two aryl substituents (prefer ⁇ ably containing no more than about ten carbon atoms each) , with the total number of such substituents preferably being four or less.
  • each substituent may differ from the others even when selected from the same class (e.g., methyl and ethyl, phenyl and tolyl, etc.).
  • the remainder of the polymer units are units derived from at least one of the following monomers: alpha-olefins of from two to eight carbon atoms, butadiene, vinyl naphthalenes, acrylonitrile, methacrylo- nitrile, maleic anhydride, malei ide, vinyl acetate, and like olefinic monomers copolymerizable with vinyl aromatic monomers such as styrene.
  • the vinyl aromatic polymer may be a homopolymer, copolymer, block polymer or graft poly ⁇ mer, and is formed from such vinyl aromatic monomers as styrene, ring-substituted methyl- or polymethylstyrenes, ring-substituted ethyl- or polyethylstyrenes, ring- substituted propyl- or polypropylstyrenes, ring-substituted butyl- or polybutylstyrenes, ring-substituted mixed poly-
  • alkylstyrenes wherein the alkyl groups dxffer from eacn other, ring-substituted chloro- or polychlorostyrenes, rin substituted alkyl- or polyalkyl chloro- or polychloro ⁇ styrenes in which the alkyl grou (s) contain(s) from one t four carbon atoms, alpha-methyl-styrene, ring-substituted methyl- or polymethyl-alpha-methyl-styrenes, ring-substitu ethyl- or polyethyl-alpha-methyl-styrenes, propyl- or poly propyl-alpha-methyl-styrenes, butyl- or polybutyl-alpha- ethyl-styrenes, ring-substituted mixed polyalky1-alpha- methyl-styrenes wherein the alkyl groups differ from each other,
  • Homopoly ers and copolymers of simple styrenic monomers are preferred from the standpoints of cost and availability.
  • simple styrenic monomers e.g., styrene, p_- ethylstyrene, 2,4-dimethylstyrene, alpha- ethy1styrene, £-chlorostyrene, etc.
  • the vinyl aromatic polymers may be unmodified (i.e., devoid of a rubbery component) or they may be a rubber-modified polymer formed by blending the polymer, and preferably by grafting, the styrenic monomer and the co onomer(s) , if used — with an elasto eric sub ⁇ stance such as polybutadiene, ' butadiene-styrene copolymers, isobutylene isoprene copolymers, ethylene-propylene copolymers, ethylene-propylene diene oncmer terpolymers (EPDM), a d the like.
  • EPDM ethylene-propylene diene oncmer terpolymers
  • the rubber-modified polymers should contain no more than about 15% and preferably no more than about 12% by weight of the rubber based on the weight of the rubber-modified vinyl aromatic polymer.
  • vinyl aromatic polymers use of crystal polystyrene (i.e., unmodified polystyrene) , rubber-modified polystyrene (often referred to as high-impact polystyrene) , and styrene-maleic anhydride copolymers (rubber-free) is particularly preferred.
  • compositions ofthis invention preferably have an amount of the vinyl aromatic polymer of (b) within the range of from 0.5 to 12 parts per hundred parts of PET and an amount of the sodium salt of (c) within the range of from 0.05 to 5 parts per hundred parts of PET. Most pre ⁇ ferably, the amounts of these components used fall within the range of from 2 to 8 parts of vinyl aromatic polymer and from 0.1 to 3 parts of the sodium salt per hundred part of PET.-
  • Synergistic effect is noted for example by the use of sodium salts of substantially saturated aliphatic monocarboxylic acids, such as sodium pal itate (sodium hexadecanoate) , sodium stearate, sodium behenate, sodium ontanate, sodium tetracosanoate and the like. While less preferable use may be made of the sodium salts of the cor ⁇ responding mildly unsaturated aliphatic mono carboxylic acids such as sodium oleate, sodium ricinoleate, sodium linoleate, sodium palmitoleate, sodium vaccenate, sodium erucate and the like. Of the foregoing salts, sodium stearate is most preferred.
  • a highly preferred combination for use in this invention is the combination of a polystyrene or a styrene copolymer such as a styrene-maleic anhydride copolymer either or both of which may be in crystal or rubber-modifie form and a sodium salt of a monocarboxylic acid having 16 or more carbon atoms in the molecule, most preferably a salt of an alkanoi ⁇ acid, such as sodium eicosanate, sodium stearate, or the like.
  • Sodium stearate can be purchased from several sources; for example, it is available as Sodium Stearate T-l produced by Witco Chemical Corporation, Organic Division, New York, New York 10017.
  • the onoepoxyalkanes utilized in the compositions of this invention have from 10 to 50 carbon atoms (prefer ⁇ ably from 10 to 30 carbon atoms) in the molecule and may be utilized individually or as mixtures.
  • a few illustrative examples of monoepoxyalkanes suitable for use in this invention are: 3,4-e ⁇ oxypentacosane; 9,10.-epoxytriacontane; 7,8-epoxytetracontane; 2,3-epoxy- 5,7,7-trimethyloctane, and the like.
  • 1,2-epoxyalkanes include but are not limited to, the following: 1,2-epoxydecane; 1,2-epoxyundecane; 1,2-epoxydodecane; 1,2-epoxytridecane; 1,2-epoxytetradecane; 1,2-epoxypentadecane; 1,2- epoxyhexadecane; 1,2-epoxyheptadecane; 1,2-epoxyoctadecane; 1,2-epoxynonadecane; 1,2-epoxyeicosane; 1,2-epoxyhen- eicosane; 1,2-epoxydocosane; 1,2-epoxytricosane; 1,2- epoxytetracosane; 1,2-epoxypentacosane; 1,2-epoxyhexacosane;
  • 1,2-epoxyalkanes are available commercially under the following product designations:
  • Vikolox 20 (1,2-epoxyeicosane) .
  • mixtures include, but are not limited to, mixtures of 1,2-epoxyalkanes comprising 1,2-epoxyalkanes from the C., (i,2-epoxyundecane) to the C, . (1,2-epoxytetra- decane) range; from the C, ⁇ (1 ,2-epoxypentadecane) to the
  • C-g (1,2-epoxyoctadecane) range from the C 2Q (1,2- epoxyeicosane) to the C 24 (1,2-epoxytetracosane) range; and from the C 24 (1,2-e ⁇ oxytetracosane) ' to the C, Q (1,2- epoxytriacontane) range.
  • examples of mixtures of 1,2- epoxyalkanes include, but are not limited to, the following:
  • At least one or more monoepoxyalkanes having from 10 to 50 carbon atoms in the molecule may be utilized in the compositions of this invention, processing considerations and availability make it convenient to use one or more 1,2-epoxyalkanes within the range of 12 to 30 carbon atoms.
  • compositions of this invention preferably have an amount of at least one monoepoxyalkane within the range of from 0.5 to 12 and most preferably from 2 to 8 parts per hundred parts of PET.
  • Preferred compositions of this invention preferably have, in addition to at least one monoepoxyalkane, an amount of a synergistic adjuvant within the range of from 0.05 to 5 and most preferably from 0.1 to 3 parts per hundred parts of PET.
  • compositions of this invention utilizing the combination of a synergistic adjuvant and at least one monoepoxyalkane exhibit a more significant enhancement of PET moldability.
  • alkali metal salts of aliphatic monocarboxylic acids alkali metal salts of aromatic carboxylic acids, alkali metal salts of carbonic acid, ionomer resins having alkali metal cations, and the like.
  • the sodium and potassium salts are preferred. Examples include, but are not limited to, the following: the sodium and potassium salts of
  • 2.8 such as that available from E. I. du Pont de Nemours & Co. , Wilmington, Delaware, under the product designation Surlyn 1605, and the like. While less preferable, use may be made of the sodium or potassium salts of mildly un- saturated aliphatic monocarboxylic acids, such as the salts of oleic acid, ricinoleic acid, linoleic acid, palmitoleic acid, vaccenic acid, erucic acid and the like.
  • mildly un- saturated aliphatic monocarboxylic acids such as the salts of oleic acid, ricinoleic acid, linoleic acid, palmitoleic acid, vaccenic acid, erucic acid and the like.
  • Preferred salts are sodium formate, sodium acetate, sodium stearate, potassium stearate, lithium stearate, sodium benzoate, sodium methacrylate , sodium carbonate and an ionomer resin (sodium salt) with a melt flow index of 2.8 such as that available from E. I. du Pont de Nemours & Company under the product designation Surlyn 1605.
  • Preferred monoepoxyalkane-adjuvant combinations for use in this invention are the combinations of a 1,2- epoxyalkane or a mixture of 1,2-epoxyalkanes and ionomer resins (sodium salts) with a melt flow index of 2.8 such as that available fr ⁇ ti E. I. du Pont de Nemours & Co.
  • Surlyn 1605 or an alkali metal salt of an aliphatic monocarboxylic acid or an alkali metal salt of an aromatic carboxylic acid or an alkali metal salt of a carbonic acid. It is most preferred to use the potassium or sodium salts of these acids.
  • the alpha-olefin-acrylic acid copolymers resins used as component (b) of this invention can be a random or a graft copolymer.
  • the alpha-olefin repeating units those which are derived, at least in part, from the monomer ethylene are preferred.
  • alpha olefin-acrylic acid copolymers are: propylene; 1-butene; ethylene and propylene; ethylene, propylene and 1,5- hexadiene; ethylene, propylene and ethylidene norbornene; ethylene and 1-butene; ethylene and 1-octene; and ethylene and 4-methyl-l-pentene.
  • the acrylic acid repeating unit in the case where the alpha-olefin-acrylic acid copolymer is a graft copolymer, can either be the "backbone" portion of the copolymer or the "graft" portion of the copolymer.
  • the copolymerized acrylic acid can be present in an amount sufficient to give the copolymer an Acid Number within the range of from 25 to 140, measured as the milligrams KOH per gram of copolymer needed to titrate the copolymer to neutralization.
  • PET which contains neither the alpha-olefin- acrylic acid copolymer and the adjuvant, when injection molded undergoes severe sticking in the mold. It also has been demonstrated that the use of the adjuvant alone results in severe sticking. Surprisingly, the addition of the alpha-olefin-acrylic acid copolymers of this invention to the PET-adjuvant composition results in an enhancement of moldability characteristics, i.e., sticking is reduced.
  • sodium stearate is highly pre ⁇ ferred.
  • other alkali metal salts of substantially saturated aliphatic monocarboxylic acids will likewise perform.
  • Exemplary of such monocarboxylic acid salts are sodium acetate, potassiu acetate, sodium propionate, potassium propionate, sodium hexoate, sodium octoate, sodium decanoate, sodium laurate, potassium laurate, sodium tetradecanoate, sodium hexa- decanoate and the like.
  • a preferred class of adjuvants comprises the alkali metal salts of sub ⁇ stantially saturated aliphatic monocarboxylic acids having from 12 to 36 carbon atoms in the molecule and of these, the alkali metal salts of the acids containing from 16 to 30 carbon atoms in the molecule are especially preferred.
  • Potassium myristate, sodium palmitate, sodium stearate, potassium stearate', sodium behenate and sodium montanate serve as examples of such materials.
  • the potassium salts and especially the sodium salts of the above-described acids are most preferred, however, the lithium, cesium and rubidium salts, while not as available and economical, should perform satisfactorily with the alpha-olefin-acrylic acid copolymer to achieve the moldability enhancement sought.
  • compositions preferably have an amount of the alpha-olefin-acrylic acid copolymer resin within the range of from 0.5 to 12 parts per hundred parts of PET and an amount of the adjuvant within the range of from 0.05 to 5 parts per hundred parts of PET. Most preferably, the amounts of these components used fall, per hundred parts of PET, within the range of from 2 to 8 parts of the alpha- olefin-acrylic acid copolymer resin and from 0.1 to 3 parts of the adjuvant.
  • the composition of this invention may also be utilized in the composition of this invention.
  • the composition additionally contains a reinforcing filler.
  • This filler depending on its nature, can increase the strength and impact qualities of the EET composition.
  • the use of a reinforcing filler is often required by most present day commercial usage of injection molded PET.
  • any reinforce ⁇ ment can be used, e.g., fibers, whiskers, or platelets of metals, e.g., aluminum, iron or nickel, and the like, and non-metals, e.g., ceramics, carbon filaments, silicates, asbestos, titanate whiskers, quartz, glass- flakes and fibe and the like.
  • the filler will comprise from 10 to 160 parts per hundred of the unreinforced polyethylene terephthalate resin. Amounts of filler, especially glass fibers, in the range of from 3 ' 0 to 140 parts per hundred of the unrein ⁇ forced PET are preferred as such compositions have parti- cularly desirable properties. From the standpoint of ease in injection molding usage, reinforced compositions of this invention, especially those using glass fibers, preferably contain a filler constituent in an amount within the range from 30 to 90 parts per hundred parts by weight of the un- reinforced polyethylene terephthalate resin.
  • the preferred reinforcing fillers are glass. It is most preferred to use fibrous glass filaments of lime-aluminum borosilicate glass that are relatively soda free. This is known as "E" glass.
  • E glass lime-aluminum borosilicate glass
  • flame retardants may be added if the end use of the product requires the product to be possibly subjected to ignition sources.
  • Flame-retarding additives which can be used for the compositions according to the invention comprise a large number of chemical compounds which are well known to. those skilled in the art. In general, they contain chemical elements which are used because of their flame-retarding capacity, for example, bromine, chlorine, antimony, phosphorus and nitrogen.
  • the flame- retarding additives are bromine and/or chlorine contain- ing organic compounds (optionally used together with auxiliary compounds, such as antimony trioxide, zinc borate, etc.) or elementary phosphorus or phosphorus compounds such as ammonium polyphosphate, various bromine and/or chlorine containing organic phosphate esters, hexaphenoxyphosphazene and the like.
  • auxiliary compounds such as antimony trioxide, zinc borate, etc.
  • elementary phosphorus or phosphorus compounds such as ammonium polyphosphate, various bromine and/or chlorine containing organic phosphate esters, hexaphenoxyphosphazene and the like.
  • Suitable impact modifiers are ethylene-vinyl acetate copolymers, ethylene-acrylic acid copolymers (having some of the acid functions neutralized) , ethylene- ethacrylic acid copolymers (having some of the methacrylic acid functions neutralized) , ethylene-alkyl acrylate- methacryli ⁇ acid terpolymer (also having some of the meth ⁇ acrylic acid fnctions neutralized), ABS ,.methyl methacrylate grafted polybutadiene,methyl methacrylate.grafted poly(alkyl acrylates) , methyl methacrylate-styrene grafted rubbers, oxidized polyethylene, styrene- butadiene-styrene (S-B-S) block copolymers, styrene- butadiene multiblock copolymers, styrene-butadiene radial block copolymers, hydrogenated S-B-S block copoly
  • the customary amounts of stabilizers can be added to the ' c ⁇ pdsitions of this invention.
  • suitable stabilizers are phenols and phenol derivatives, preferably sterically hindered phenols which contain alkyl substituents with up to 6 carbon atoms in the position(s) ortho to the phenolic hydroxyl grou (s); amines, preferably secondary arylamines and their deriva ⁇ tives; phosphates and phosphites, preferably the aryl derivatives thereof; and quinones.
  • a few non-limiting examples include 4,4'-bis(2,6-di-tert-butyIphenol) ,
  • compositions of this invention there may be additionally added ultraviolet ray absorbents, lubricants antistatic agents, colorizing agents, antifungal agents, foaming agents, etc. depending upon the ultimate use of the molded product.
  • compositions of this invention can be pre- pared by blending the various components in a blender, e.g., a tumble blender or a Henschel mixer, compounding the mixtur in an extruder, e.g., a twin-screw 28 mm Werner-Pfleiderer extruder, and thereafter chopping the extrudate into pellets
  • a blender e.g., a tumble blender or a Henschel mixer
  • compounding the mixtur in an extruder e.g., a twin-screw 28 mm Werner-Pfleiderer extruder
  • chopping the extrudate into pellets
  • the resultant product is suitable for use in injection mold ing operations.
  • the compositions of this invention can be satisfactorily injection molded at mold temperatures less than 100°C. with an acceptably short cycle time and with the molded article exhibiting physical properties which are commercially attractive or which at least have commercial potential.
  • the various PET compositions of these Examples were prepared by mixing the components to form a premix, compounding the premix in a single screw extruder at temper ⁇ atures of about 500°F. to 540°F. (260°C. to 282°C), and molding the pellets into test bars on a reciprocating screw injection molding machine.
  • the injection mold was suit ⁇ ably shaped and dimensioned for providing an article having the configuration shown in the Figure of the Drawing — whic is a top plan view of the article.
  • the mold utilized was a. center gated mold having a non-moveable planar sprue side and a moveable cavity side.
  • the article formed by the mold has a plurality of runners, labeled "A", which terminate into various test pieces.
  • test piece Emanating from the center of the runner grid is a conven- tional tapered sprue.
  • Two of the test pieces are rect ⁇ angular bars and are labeled with the letter "B". These "B" bars are about 6 inches (15.24 cm) long, 1/2 inch (1.27 cm) wide and 1/4 inch (0.635 cm) thick.
  • the test piece labeled “C” in the Figure is a rectangular bar which is 2-1/2 inches (6.35 cm) long, 1/2 inch (1.27 cm) wide and 1/8 inch (0.3175 cm) thick.
  • the two "dog bone” shaped test pieces are labeled "D" and are used for the testing of tensile properties.
  • PET Polyethylene terephthalate
  • Vituf 5901 crystallin PET having an intrinsic viscosity of 0.59 measured at 25°C. in solvent consisting of 60 percent by weight phenol and 40 percent by weight of tetrachloroethane
  • Table I reports the moldability characteristics of various compositions of this invention (Examples 1-3) and of compositions not utilizing the combination of a vinyl aromatic polymer and a sodium salt pursuant to this invention (Comparative Examples 4-7) . Moldability of the compositions was evaluated by determining "the number of sticks” (i.e., the number of times the molding cycle had to be stopped and a molded specimen physically removed from the mold) in relation to the "number of shots" (i.e., the number of injections) that were made with the given PET composition. In severe cases, removal of a stuck part required prying or chiseling; in less severe cases, re ⁇ moval was possible by hand.
  • the number of sticks i.e., the number of times the molding cycle had to be stopped and a molded specimen physically removed from the mold
  • the number of shots i.e., the number of injections
  • PET Polyethylene terephthalate
  • Vituf 5901 - crystalline PET having an intrinsic viscosity of 0.59 measured at 25°C. in solvent consisting of 60 percent by weight phenol and 40 percent by weight of tetrachloroethane
  • Styrene-maleic anhydride copolymer from ARCO/ Polymers; designated as Dylark 338S, a rubber- modified copolymer " containing about 4 weight percent rubber and about 13.4 weight percent maleic anhydride, the balance being styrene
  • Polyethylene Terephthalate parts 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100
  • PET Polyethylene terephthalate
  • - ⁇ •crystalline PET having an intrinsic viscosity of 0.59 measured at 25°C. in solvent consisting of 60 percent by weight phenol and 40 percent by weight of tetrachloroethane
  • KaneAce B56 MBS copolymer; from Kanegafuchi Chemical Company, designated as KaneAce B56, (believed to be a graft copolymer comprising methyl methacrylate, butadiene and styrene)
  • ABS copolymer from Borg Warner, designated as Blendex 101, (believed to be a graft copolymer comprising acrylonitrile, butadiene and styrene)
  • Styrene-methyl methacrylate copolymer from Richardson Company, designated as N.A.S. 81 (believed to contain about 20 to 30 weight percent of methyl methacrylate)
  • PET Polyethylene terephthalate
  • Vituf 5901 - crystalline PET having an intrinsic viscosity of 0.59 measured at 25°C. in solvent con- sisting of 60 percent by weight phenol and 40 percent by weight of tetrachloroethane
  • Examples 22-25 Sodium stearate; from Witco Chemical Company; T-l or. Heat Stable grade.
  • Table VI Examples 22-25
  • Table VII Examples 26-34 report the moldability characteristics of various compositions of this invention.
  • Example 25 Table VI
  • Example 34 Table VII are examples of com- positions that do not contain an adjuvant. Moldability of the compositions was evaluated in the same manner previously described.
  • PET Polyethylene terephthalate
  • Vituf 5901 - crystalline PET having an intrinsic viscosity of 0.59 measure at 25°C. in solvent consisting of 60 percent by weight phenol and 40 percent by weight of tetrachloroethan .
  • Ethylene-aerylie acid copolymer from Allied Chemical, Fiber and Plastics Company, Morr stown, New Jersey and designated A-C 540A.
  • Table XI reports the moldability characteristics of various compositions of this invention- (Examples 37-39J. This table also reports (Comparative Examples 40 & 41] on
  • the mold tempera-ture was kept at approximately 200°F. (93°C.). All parts shown in the Tables are by weight.
  • A-C 540A (ethylene-acrylic acid copolymer) - parts/100 parts PET 3.0
  • Polybond 1016 (propylene-ethylene acrylic acid copolymer) - parts/100 parts PET 3.0
  • PET Resxn parts 100 100 100 Fiberglass, parts/100 parts PET 43 43 43 AC540A, parts/100 parts PET 3 Polybond 1016, parts/100 parts PET 3 Polybond XEA-7/ parts/100 parts PET 3 Sodium Stearate, parts/100 parts PET 0,5 0.5 0.5
  • Table XII illustrate the good balance of physical properties exhibited by articles in ⁇ jection molded from compositions of this invention, as determined by the same procedures as used in Table II.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

On améliore l'aptitude au moulage par injection des térephtalates de polyéthylène par adjonction de faibles quantités de (i) un agent améliorant le démoulage des polymères thermoplastiques sélectionnés parmi un composé vinylique aromatique, un copolymère d'acide alpha-oléfine-acrylique et au moins un monoépoxyalcane et de (ii) un sel métallique de sodium ou d'alcali d'un acide monocarboxylique à chaîne longue agissant de concert avec les deux premiers agents d'amélioration et facultativement avec le dernier pour améliorer l'aptitude au moulage et au démoulage même lorsque la composition est moulée par injection à des températures aussi faibles que 93oC. Un article de test moulé est décrit, comprenant une pluralité de canaux de coulage (A) débouchant dans des différentes pièces de test (B, C, D, E).
PCT/US1983/000707 1982-05-13 1983-05-06 Composition de polyester Ceased WO1983004038A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP58502187A JPS59500917A (ja) 1982-05-20 1983-05-06 ポリエステル組成物

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
US37800682A 1982-05-13 1982-05-13
US378,006 1982-05-13
US38004982A 1982-05-20 1982-05-20
US380,049 1982-05-20
US06/397,624 US4385144A (en) 1982-07-12 1982-07-12 Polyester composition
US397,624 1982-07-12

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WO1983004038A1 true WO1983004038A1 (fr) 1983-11-24

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0388388A3 (fr) * 1989-03-17 1991-01-02 Monsanto Company Mélanges de polyesters résistant aux chocs
WO2023005869A1 (fr) * 2021-07-29 2023-02-02 金发科技股份有限公司 Composition d'alliage polycarbonate/polyester résistant à un vieillissement thermo-oxydatif à long terme et procédé de préparation associé

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3516957A (en) * 1968-04-29 1970-06-23 Eastman Kodak Co Thermoplastic polyester composition containing organic ester mold release agent
US3673139A (en) * 1970-04-06 1972-06-27 Sandoz Ltd Process for the production of injection moulded and extrusion moulded polyester products
GB2015014A (en) * 1978-02-28 1979-09-05 Du Pont Polyethylene terephthalate resin compositions
US4215032A (en) * 1978-05-18 1980-07-29 Toyo Boseki Kabushiki Kaisha Polyester composition
US4260690A (en) * 1979-01-23 1981-04-07 Bayer Aktiengesellschaft Thermoplastic polyester moulding compositions with good toughness properties
US4276208A (en) * 1978-10-09 1981-06-30 Teijin Limited Glass fiber-reinforced thermoplastic polyester composition
US4327007A (en) * 1980-12-22 1982-04-27 Allied Chemical Corporation Polyethylene terephthalate composition containing aliphatic plasticizer and nucleating agent

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3516957A (en) * 1968-04-29 1970-06-23 Eastman Kodak Co Thermoplastic polyester composition containing organic ester mold release agent
US3673139A (en) * 1970-04-06 1972-06-27 Sandoz Ltd Process for the production of injection moulded and extrusion moulded polyester products
GB2015014A (en) * 1978-02-28 1979-09-05 Du Pont Polyethylene terephthalate resin compositions
US4215032A (en) * 1978-05-18 1980-07-29 Toyo Boseki Kabushiki Kaisha Polyester composition
US4276208A (en) * 1978-10-09 1981-06-30 Teijin Limited Glass fiber-reinforced thermoplastic polyester composition
US4260690A (en) * 1979-01-23 1981-04-07 Bayer Aktiengesellschaft Thermoplastic polyester moulding compositions with good toughness properties
US4327007A (en) * 1980-12-22 1982-04-27 Allied Chemical Corporation Polyethylene terephthalate composition containing aliphatic plasticizer and nucleating agent

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0388388A3 (fr) * 1989-03-17 1991-01-02 Monsanto Company Mélanges de polyesters résistant aux chocs
US5162416A (en) * 1989-03-17 1992-11-10 Monsanto Company Impact resistant polyester blends
WO2023005869A1 (fr) * 2021-07-29 2023-02-02 金发科技股份有限公司 Composition d'alliage polycarbonate/polyester résistant à un vieillissement thermo-oxydatif à long terme et procédé de préparation associé

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