JP2001520277A - Injection molded articles made from long chain branched syndiotactic monovinylidene aromatic polymers - Google Patents

Abstract

  (57) [Summary] The present invention relates to injection molded articles made from long chain branched syndiotactic monovinylidene aromatic polymers. Long chain branches can be formed during polymerization by polymerizing in the presence of small amounts of bifunctional monomers.

Description

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates to syndiotactic monovinylidene aromatic polymers and injection molded articles made therefrom. Syndiotactic monovinylidene aromatic polymers such as syndiotactic polystyrene (SPS) are useful polymers having high melting points and crystallization rates and excellent thermal and chemical resistance. However, in some applications, such as electronic connectors and automotive parts, the melt flow rate or crystallization rate is insufficient when injection molded to obtain the desired properties. Syndiotactic copolymers having excellent thermal and chemical resistance have also been developed. U.S. Pat. No. 5,520,402 to Funaki et al. Utilizes a bifunctional monomer to form a syndiotactic copolymer with styrene, but the polymer crosslinks well at elevated temperatures to form a thermoset product. Cannot be formed and melt processed to produce injection molded articles. Injection molded articles are disclosed in U.S. Patent Nos. A5034441, 5326813, 54441.
26, 5418275 and EP 312976, 733675 and 736364 can be prepared from linear syndiotactic monovinylidene aromatic polymers. However, the melt flow rate and crystallization rate of linear syndiotactic monovinylidene aromatic polymers are sometimes too slow to have desirable properties, such as low molded in stress,
Injection molded articles, especially thin walled injection molded articles, having sufficient and uniform crystallinity cannot be produced. Therefore, it would be useful to obtain injection molded articles from syndiotactic monovinylidene aromatic polymers having fast melt flows and crystallization rates and good thermal and chemical resistance. The present invention relates to injection molded articles made from compositions comprising long chain branched syndiotactic monovinylidene aromatic polymers. Long chain branches can be formed during polymerization by polymerizing in the presence of small amounts of bifunctional monomers. The injection molded articles of the present invention have low molding stress, low pressure for filling, and have a more uniform and high level of crystallinity, which is produced from linear syndiotactic monovinylidene aromatic polymer Improved heating performance and mechanical properties, such as high temperature creep, are manifest themselves when compared to those provided. In one aspect, the invention is an injection molded article made from a composition comprising a long chain branched syndiotactic monovinylidene aromatic (LCB-SVA) polymer.

As used herein, the term “syndiotactic” refers to more than 90% syndiotactic, preferably more than 95% syndiotactic of racemic triad as measured by ¹³ C nuclear magnetic resonance spectroscopy. Having a stereoregular structure of Monovinylidene aromatic polymers are homopolymers and copolymers of vinyl aromatic monomers, that is, monomers whose chemical structure has both unsaturated and aromatic moieties. Preferred vinyl aromatic monomers, wherein H ₂ C = CR-Ar (wherein, R is an alkyl group having a hydrogen or 1-4 carbon atoms, and A
r is an aromatic group of 6-10 carbon atoms). Examples of these vinyl aromatic monomers include styrene, alpha-methylstyrene, ortho-methylstyrene, meta-methylstyrene, para-methylstyrene, vinyltoluene, para-t-
Butylstyrene, vinylnaphthalene, brominated styrene, especially p-vinyltoluene and ring-brominated or dibrominated styrene. Brominated styrene is particularly useful for making ignition resistant syndiotactic monovinylidene aromatic polymers. Alternatively, ignition resistant LCB-SVA polymers can be produced by brominating LCB-SVAp. Representative examples of syndiotactic copolymers include styrene-p-methylstyrene, styrene-pt-butylstyrene, and styrene-toluene copolymer. Syndiotactic monovinylidene aromatic polymers and the monomers making them are well known to those skilled in the art and are described, for example, in US Pat. No. 4,680,353.
No. 4,959,435, 4950724 and 4774301. Syndiotactic polystyrene is the currently preferred syndiotactic monovinylidene aromatic polymer. Long chain branching can be achieved by polymerizing vinyl aromatic monomers in the presence of small amounts of polyfunctional monomers under conditions sufficient to produce a syndiotactic monovinylidene aromatic polymer. A polyfunctional monomer is any compound having more than one olefinic functionality that can react with a vinyl aromatic monomer under polymerization conditions. Typically, the multifunctional monomer comprises a 2-4 olefinic functionality and has the formula

[0003]

Embedded image

(Wherein R is a vinyl group or a group containing 2-20 carbon atoms including a terminal vinyl group, and the group containing 2-20 carbon atoms is an alkyl, alkenyl, cyclo Can be alkyl or aromatic, the cycloalkyl group contains at least 5 carbon atoms and the aromatic group contains at least 6 carbon atoms, and n is 1-
An integer of 3 and the R group is meta or para with respect to the vinyl group of the formula, and when n is greater than 1, R may be the same or different. Preferably, R is a vinyl group. Preferably, the multifunctional monomer comprises two terminal vinyl groups when n is equal to one. Typically, these monomers include bifunctional vinyl aromatic monomers such as di-vinyl-benzene or di-styryl-ethane. The amount of the polyfunctional monomer is determined by the weight average molecular weight (Mw) of the polymer to be produced.
And typically will be 10 pp based on the amount of vinyl aromatic monomer.
m, preferably from 50 ppm, more preferably from 75 ppm, and most preferably from 100 ppm to 1000 ppm, preferably 800 pp
m, more preferably up to 500 ppm, and most preferably 650 pp
m. The polyfunctional monomer can be introduced during the polymerization by any method that allows the polyfunctional monomer to react with the vinyl aromatic monomer during the polymerization to produce an LCB-SVA polymer. For example, the polyfunctional monomer can be first dissolved in the vinyl aromatic monomer prior to polymerization or can be separately introduced into the polymerization reactor before or during the polymerization. In addition, the polyfunctional monomer can be dissolved in the inert solvent used in the polymerization, such as toluene or ethylbenzene.

[0005] Any method of polymerization that produces a syndiotactic monovinylidene aromatic polymer can be achieved using the LCB-SVA of the present invention as long as the polyfunctional monomer is also present during the polymerization.
Can be used to produce polymers. Representative polymerization methods for making syndiotactic monovinylidene aromatic polymers are well known to those skilled in the art and are described in U.S. Patent Nos. A4680353, 5066741, 5206197, and 5294685. Typically, the weight average molecular weight (Mw) of the LCB-SVA polymer is 5000
From 0, preferably from 100,000, more preferably from 125,000, and most preferably from 150,000 to 3,000,000, preferably 10,000
00, more preferably up to 500,000, and most preferably 3500
Up to 00. Branched syndiotactic monovinylidene aromatic polymers comprise an extension of a syndiotactic monovinylidene aromatic polymer chain attached to a polymer backbone. The long chain branched syndiotactic monovinylidene aromatic polymers generally comprise a chain extension of at least 10 monomer repeat units, preferably at least 100, more preferably at least 300, and most preferably at least 500 monomer repeat units. Typically, the injection molded articles of the present invention have LCB-S without the presence of other polymers.
Manufactured from a composition of VAp. However, injection molded articles can be made from compositions comprising the LCB-SVA polymer and other components, including other polymers. The amount of LCB-SBA polymer included in the composition for making the injection molded article depends on the end application in which the benefits may be obtained in slightly lesser quantities in some cases. In general,
At least 5% by weight of the LCB-SVA polymer is used in compositions for making injection molded articles, generally at least 20%, preferably at least 40%, more preferably at least 70% and most preferably 100%. Other polymers included in these compositions include linear SPS, polystyrene, polyphenylene oxide, polyolefins such as polypropylene, polyethylene, poly (4-methylpentene), ethylene-propylene copolymer, ethylene-butene-propylene copolymer, nylon, For example, but not limited to, nylon-6, nylon-6,6, polyester, such as poly (ethylene terephthalate), poly (butylene terephthalate), and copolymers or blends thereof. Antioxidants, impact modifiers, ignition resistors, coupling agents such as maleated polymers (including maleic anhydride-modified polyphenylene oxide or maleic anhydride-modified syndiotactic monovinylidene aromatic polymer), wetting of the base fabric Other substances or additives including strength improving binders, flame retardants (including brominated polystyrene, brominated syndiotactic monovinylidene aromatic polymers, brominated aromatic compounds, antimony trioxide and polytetrafluoroethylene) The thing is LC
It can be added to B-SVA polymer compositions, or injection molded articles made therefrom.

[0006] Impact modifiers that can be used in the LCB-SVA polymer composition include block or graft copolymers of vinyl aromatic and butadiene or isoprene monomers, substantially random interpolymers of alpha-olefin monomers and vinyl aromatic monomers, and Contains polyolefin elastomer. As used herein, the term "interpolymer" refers to a polymer made by the polymerization of at least two different monomers. The generic term interpolymer therefore includes polymers made from two different monomers and copolymers commonly used to refer to polymers made from more than two different monomers. When the present invention describes a polymer or interpolymer as consisting of or containing a monomer, it means that the polymer or interpolymer polymerizes or contains therein units derived from this monomer. . For example, if the monomer is ethylene _CH 2 = CH _2, a derivative of the unit, when formulated into _polymers, -CH 2 -CH ₂ - is. The vinyl aromatic monomer contained in the substantially random interpolymer of the alpha-olefin and vinyl aromatic monomer interpolymer is the vinyl aromatic monomer described above as a monomer useful for making the syndiotactic monovinylidene aromatic polymer. Group monomer. The aliphatic alpha-olefin monomer contained in the interpolymer is 2-1.
It includes aliphatic and cycloaliphatic alpha-olefins having 8 carbon atoms, and preferably alpha-olefins having 2-8 carbon atoms. Most preferably, the aliphatic alpha-olefin comprises ethylene or propylene, preferably ethylene, and optionally one or more other alpha-olefins having 3-8 carbon atoms, such as ethylene and propylene, or ethylene and propylene. Octene, or also ethylene and propylene and octene.

[0007] The interpolymer is preferably a pseudo-random linear or substantially linear, more preferably linear, interpolymer of an aliphatic alpha-olefin and a vinyl aromatic monomer. These pseudorandom linear interpolymers are described in EP A 0 416 815. Substantially random interpolymers can be modified by typical grafting, hydrogenation, functionalization or other reactions well known to those skilled in the art, provided that their impact or ductility modifying function is not substantially affected. . Polymers are easily sulfonated or chlorinated according to established techniques to provide functionalized derivatives. Pseudo-random interpolymers can be prepared as described in EP A0416815. Preferred operating conditions for these polymerization reactions are pressures from atmospheric to 3000 atm and temperatures from 30-200 ° C. Examples of suitable catalysts and methods for producing pseudo-random interpolymers are described in European Patents A 416 815, 468 651, 514 828, 52 732, WO 93/23412, U.S. Patents A 5347024, 547093, 5
No. 6,248,78, 5556928, and U.S. Pat.
7475, 5096867, 5064802, 5132380 and 518919
No. 2. Elastomeric polyolefin impact modifiers are described, for example, in US Pat.
Any elastomeric polyolefin such as those described in No. 18. Elastomeric polyolefins include any polymer consisting of one or more _C2-20 alpha-olefins in polymerized form having a Tg of 25C or less, preferably 0C or less. Examples of polymer types from which the elastomeric polyolefins of the present invention are selected include homo- and copolymers of alpha-olefins, such as ethylene / propylene, ethylene / 1-butene, ethylene / 1-hexene or ethylene / 1-octene copolymer, And terpolymers of ethylene, propylene and comonomers such as hexadiene or ethylidene norbornene. Grafted derivatives of the aforementioned rubbery polymers, for example polystyrene-, maleic anhydride-
, Polymethyl methacrylate- or styrene / methyl methacrylate copolymer grafted elastomeric polyolefins can also be used.

[0008] The LCB-SVA polymer composition may also include an inorganic reinforcing agent. Suitable reinforcing agents include any mineral, glass, ceramic, polymeric or carbon reinforcing fillers such as glass fibers, mica, talc, carbon fibers, wollastonite, graphite, silica, magnesium carbonate, alumina, metal fibers, kaolin, Includes silicon carbide and glass flake. These materials have a length to diameter ratio (L / D) greater than 5.
). The preferred particle diameter is 0.1 microm-1mm. Preferred tougheners are 0.1-10 mm long and 5-10 mm.
Glass fiber with L / D of 0, glass roving or chopped glass fiber. Three of these suitable glass fibers are available from Owens Corning Fiberglass under the name OCF-187A or 497, or under the name 3540.
Available from PPG. Suitable fillers reduce the linear coefficient of thermal expansion of the resulting material, add dyes or pigments thereto, reduce the flame spreadability of the composition, or reduce the physical properties of other compositions. Includes non-polymeric materials designed to denature. Suitable fillers are mica, talc, chalk, titanium dioxide,
Includes clay, alumina, silica, glass microparticles, wollastonite, calcium carbonate, magnesium sulfate, barium sulfate, calcium oxysulfate, tin oxide, metal powder, glass powder, and various pigments. Preferred fillers are in the form of microparticles having a (L / D) of less than 5. The amount of reinforcing agent or filler used is preferably 10-
50 parts by weight. Preferred fillers are talcs having a number average diameter of less than 1 micron, such as MP available from Mineral Technologies.
Wollastonite having a number average diameter of less than 10-52, as well as 5 microns, such as G
LS Minerals, Inc. Jilin 2000 available from
It is.

[0009] The toughening agent can include a coating on the surface of the sizing agent or a similar coating, and can, among other functions, promote adhesion between the toughening agent of the composition and the remaining components, particularly the matrix. Suitable sizing agents are amines, aminosilanes,
It contains epoxy and aminophosphine functional groups and contains up to 30 non-hydrogen atoms. Preferred are aminosilane coupling agents and their C _1-4 alkoxy substituted derivatives, especially 3-aminopropyltrimethoxysilane. The LCB-SVA polymer composition also includes a lubricant such as stearic acid, behenic acid, zinc stearate, calcium stearate, magnesium stearate, ethylene bis-stearamide, pentaerythritol tetrastearate, organic phosphate, mineral oil, trimellitate, polyethylene glycol, Silicone oil, epoxidized soybean oil, tricresyl phosphate, polyethylene glycol dimethyl ether, dioctyl adipate, di-n-butyl phthalate, palmityl palmitate, butylene glycol montanate (Wax OP), pentaerythritol tetramontanate (TPET 141) , Aluminum mono-stearate, aluminum di-stearate, montanic acid wax, montanic acid ester wax, polar polyester It may include other additives comprising ethylene wax, and a non-polar polyethylene wax. Other additives include polyarylene ethers such as U.S. Patent Nos. A3306874, 3308875, 3257357 and 32.
No. 57358. A preferred polyarylene ether is poly (2,6-dimethyl-1,4-phenylene) ether. Polyphenylene ethers are usually prepared by an oxidative coupling reaction of the corresponding bisphenol compound. Preferred polyarylene ethers are polyarylene ethers functionalized with polar groups, which are a well-known group of compounds prepared by contacting a polyarylene ether with a reactant containing a polar group. The reaction is
It is usually carried out at elevated temperatures, preferably at the melting temperature of the polyarylene ether, under conditions to obtain a uniform blend of the functionalized reactants. The preferred temperature is 150-300 ° C.

[0010] Suitable polar groups include acid anhydrides, acid halides, acid amides, sulfones, oxazolines, epoxies, isocyanates and amino groups. Preferred polar group containing reactants are compounds having up to 20 carbons that include reactive unsaturation, eg, ethylenic or aliphatic ring unsaturation, with the desired polar group functionality. A particularly preferred reactant containing a polar group is a dicarboxylic anhydride, most preferably maleic anhydride. Typically, the polar group functionalizing reagent used is 0.01-20%, preferably 0.5-15%, most preferably 1-10%, based on the weight of the polyarylene ether. is there. The reaction can be carried out, if desired, in the presence of a free radical generator such as an organic peroxide or hydroperoxide agent. The preparation of polyarylene ethers functionalized with polar groups has already been described in U.S. Pat. Nos. 3,375,228, 4,771,096 and 4,654,405. Polar group-modified polyarylene ethers advantageously serve as compatibilizers to improve the adhesion between the toughener and the syndiotactic monovinylidene aromatic polymer. Accordingly, their use is particularly desirable when fillers or reinforcing agents are further utilized. The amount of polyarylene ether used in the resin blend of the present invention is 1
Based on 00 parts of glass and polyarylene ether, preferably 0.1-50
Parts by weight, preferably 0.2-10 parts by weight. The polar group-modified polyarylene ether will be in the form of a coating applied to the outer surface of the toughener to provide added compatibility between the toughener and the polymer matrix. The polar group-modified polyarylene ether used as such is
Similarly, it can be added to additional amounts of the polyarylene ether or polar group-modified polyarylene ether incorporated into the blend. The surface coating is suitably applied to the toughening agent by contact with a solution or emulsion of a polyarylene ether functionalized with polar groups. Suitable solvents for dissolving polyarylene ethers functionalized with polar groups for use in preparing oil-in-water or water-in-oil emulsions or for forming solutions are methylene chloride, trichloromethane , Trichloroethylene and trichloroethane. Preferably, the polyarylene ethers functionalized with polar groups in the solution or the emulsion have 0
. It is 1-20% by weight, preferably 0.5-5% by weight. After coating the reinforcement with either a solution or an emulsion, the liquid medium is removed, for example, by evaporation, devolatilization or vacuum drying. The resulting surface coating is desirably 0.001-10% by weight of the uncoated stiffener weight.

[0011] Other additives useful in LCB-SVA polymer compositions are nucleating agents that can be cooled from the melt to reduce the time required to initiate crystallization of the syndiotactic monovinylidene aromatic polymer. The nucleating agent leads to a large degree of crystallinity in the molding resin and also to a more constant level of crystallization under various molding conditions. Higher levels of crystallization are desirable to achieve increased chemical resistance. Further, the morphology of the crystals can be varied as desired. Examples of suitable nucleating agents for use in the present invention include magnesium aluminum hydroxide, calcium carbonate, mica, wollastonite, titanium dioxide, silica, sodium sulfate, lithium chloride, sodium benzoate, aluminum benzoate, talc, And monolayers of metal salts, especially aluminum or sodium salts of organic or phosphonic acids. Especially preferred compounds are aluminum salts and sodium salts, and C _1-10 alkyl-substituted benzoic acid derivatives of benzoic acid. The most highly preferred nucleating agent is aluminum tris (p-tert-butyl) benzoate. The amount of nucleating agent used must be sufficient to cause nucleation and onset of crystallization of the syndiotactic vinyl aromatic polymer in a short time relative to the composition lacking the nucleating agent. The preferred amount is 0.5-5 parts by weight.

[0012] Other additives may also be included in the compositions of the present invention and include additives such as flame retardants, pigments, and antioxidants, which are Ciba Geigy Corpo.
IRGANOX ™ 1010, 555, 142 available from Ration
5 and 1076, IRGAFOS ™ 168, CGL-415 and GALV
IINOXYL ™; SEENOX ™ 41 available from Witco
2S; ULTR available from GE Specialty Chemicals
ANOX ™ 626 and 815; M available from Adeka Argus
ARK PEP ™ 36; T. A available from Vanderbilt
GERITE (TM) WHITE, MA and DPPD, METHYL ZIMA
TE, VANOX ™ MTI and 12; Uniroyal Chemical
NAUGARD ™ 445 and XL-1 available from America; America
n CYANOX ™ STDP and 277 available from Cyanamid
7; RONOTEC ™ 201 (Vitamin E) available from Roche;
MIXXIM CD-12 and CD-16 available from Fairmount;
Ethanox ™ 398, DHT-4a, SA available from Ethyl
YTEX ™ 8010, 120, BT93 and 102; Hoechst C
Hostanox ™ PAR 24, 03 and ZnCS1 available from Elanese; cesium benzoate; sodium hydroxide; SANDOSTAB ™ PEPQ available from Sandoz; t-butylhydroquinone;
SANTOVAR ™ A available from nsanto; phenothiazine; pyridoxine; copper stearate; cobalt stearate; Mooney Chem.
MOLYBDENUM TENCEM ™ available from icals; ruthenium (III) acetyl ascentate; boric acid; citric acid; Adeka A
MARK ™ 6000 available from rgus; antimony oxide; 2,6-
Di-t-butyl-4-methylphenol; stearyl-β- (3,5-di-te
tert-butyl-4-hydroxyphenol) propionate; and triethylene glycol-bis-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate; tris (2,4-tert-butylphenyl) phosphonate Phyte and 4,4'-butylidenebis (3-methyl-6-tert-butylphenyl-di-tridecyl) -phosphite; trisnonylphenyl phosphite; carbon black; P available from Ferro Corporation.
YROCHEK ™ PB68; decabromodiphenyl oxide; anti-blocking agents such as fine particles of alumina, silica, aluminosilicate, calcium carbonate, calcium phosphate and silicon resins; light stabilizers such as sterically hindered amine-containing compounds or benzotriazole-containing compounds; Agents such as organopolysiloxanes or mineral oils;
Foaming agents; extrusion aids; stabilizers such as bis (2,4-di-tertbutylphenyl) pentaerythritol and trisnonylphenyl phosphite.

The injection molded articles of the present invention can be manufactured by various methods, including direct injection molding, gas assisted injection molding, co-injection molding, reciprocating screw injection molding, multi-station reciprocating screw injection molding, multi-station screw / Includes RAM injection molding and blow molding. Typically, the injection molded articles of the present invention are about 0.1-10 mm thick, more preferably 0.5-5 mm thick. The injection molded articles of the present invention can also be coated or laminated with other materials to add additional properties to the injection molded article. The injection molded articles of the present invention can be used for electronic connectors, electrical connectors, electrical components, parts under the hood of cars, lighting parts, air induction parts of cars, refrigerant system parts of cars, and battery seals. The following examples are provided to illustrate the invention. The examples are not intended to limit the scope of the invention, and they should not be construed as such. Amounts are by weight or parts by weight, unless otherwise indicated.

EXAMPLES Preparation of LCB-SVA All reactions are performed under an inert atmosphere in a dry box. Reactants, toluene and styrene monomers are purified and handled using standard inert atmosphere techniques. Di-styryl-ethane (DSE) is disclosed in H. J. Li et al. Po
lymer Sci. Part A, Polymer Chem. 32 (199
4) Manufactured according to the procedure described in 2023. 10% methylalumoxane in toluene solution, 1 mol of triisobutylaluminum in toluene, and pentamethylcyclopentadienyl in toluene
A 0.03 molar solution of titanium trimethoxide is mixed in a dry box in a volumetric flask in a ratio of 75: 25: 1, and the final concentration of the catalyst solution is 0.1% based on titanium.
003 mol. 4.54 g of styrene are placed in four ampoules. A 1% solution of di-styryl-ethane (DSE) in toluene is added at the ppm levels shown below. The ampoule is then sealed and equilibrated for 10 minutes at a polymerization temperature of 70 ° C. The polymerization is 17
Begin by adding the catalyst solution at a 5000: 1 styrene to titanium molar ratio. The polymerization is stopped after 1 hour by adding excess methanol. The polymerization is isolated and dried, and the molecular weight is determined by high temperature size exclusion chromatography. The results are shown below.

[0015]

[Table 1]

The significant increase in Mz due to di-styryl-ethane is due to long chain branching in the SPS polymer. Large scale reactions are performed in a 5 inch Teledyne kneader mixer described in U.S. Pat. No. 5,254,647. A solution of 1.3% by weight of di-styryl-ethane in toluene was added to the styrene monomer in the amounts shown in Table 2,
It is then fed to the reactor at 17.5 kg / h, with an average residence time of 18 minutes. The polymerization is carried out at a temperature of 55-67.5 ° C. A catalyst solution of methylaluminoxane, triisobutylaluminum and octahydrofluorenyltitanium trimethoxide catalyst is fed to the reactor at a styrene to titanium molar ratio of 80000: 1 to 100000: 1. The product is a fine white powder with 36-50% conversion. Samples are collected under nitrogen and stopped by the addition of excess methanol. Sample 2
Dry in a vacuum oven at 220 ° C., 5 mmHg, swept with nitrogen for hours. The weight average molecular weight (Mw) of the polymer is measured by high temperature size exclusion chromatography. Table 2 shows the results.

[0017]

[Table 2]

[0018] A significant increase in Mz by di-styryl-ethane is indicative of long chain branching. The above sample in powder form is converted to pellets using a 0.5 inch single screw extruder. The molecular weight of the pellet is summarized below.

[0019]

[Table 3]

The melt strength is determined by S.I. K. Goyal's "Plastics Engineeri
ng "51 (2) 25, 1995, and the test conditions were 1 in / min plunger speed, 50 ft / min winder speed and 27
9 ° C. The melt flow rate is measured according to ASTM D1238 and the test conditions are a 1.2 kg load and 300 ° C. 300,000 Mw linear SPS
Polymer is used as a control. The results are summarized below.

[0021]

[Table 4]

The LCB-SPS sample has a higher melt strength and a higher melt flow rate than the linear SPS control sample.

Example 1 Preparation of LCB-SPS and Injection Molded Articles Therefrom The polymerization reaction was performed in a 5 inch Teledyne kneader mixer with an average residence time of 18 minutes, followed by a 500 L tank reactor with an average residence time of 10 hours. Done. The operation of these devices is described in U.S. Pat. No. 5,254,647. The styrene monomer was 250 ppm of a 3.3% solution of di-styryl-ethane in toluene.
And fed to the reactor at 17.5 kg / h. The polymerization is carried out at a temperature of 55 ° C. A catalyst solution of methylaluminoxane, triisobutylaluminum and octahydrofluorenyltitanium trimethoxide is also fed to the reactor at a styrene to titanium molar ratio of 80000: 1. After polymerization, the polymer, as described above,
Devolatize and pelletize. The molecular weight of the polymer was measured by high temperature size exclusion chromatography and the results are shown below.

[0024]

[Table 5]

A 300,000 Mw linear SPS polymer is used as a control. The LCB-SPS and control polymer are formulated with 30% glass fibers, antioxidants, nucleating agents, and release agents. The composition was prepared using the following conditions:
Extrude with a mm co-rotating twin screw extruder.

[0026]

[Table 6]

The resulting pellets are injection molded on a 100 ton injection molding machine into standard tensile bar samples. The set points of the machine used to form the tension bar are as follows.

[0028]

[Table 7]

The glass-filled LCB-SPS composition comprises a corresponding glass-filled linear SPS composition (
It has a higher strain temperature (461 ° F.) than 373 ° F.). Other lots of LCB-SPS polymer are made in the same manner as above. The molecular weight of the polymer was measured by high temperature size exclusion chromatography and the results are as follows.

[0030]

[Table 8]

A 300,000 Mw linear SPS polymer is used as a control. LCB-SPS and control polymer, 30% glass fiber, antioxidant,
Formulated with a package of nucleating agent, release agent, and flame retardant. The mixture is extruded on a 40 mm co-rotating twin screw extruder using the same conditions as above. The resulting pellets are injection molded into standard tensile bar samples using a 100 ton injection molding machine using the same injection molding conditions as above. The formulated pellets are then melted and the viscosity is measured using the capillary method.

[0032]

[Table 9]

The glass-filled ignition-resistant LCB-SPS composition has a viscosity that is 12-20% lower than the corresponding linear SPS over a shear rate of 100-10000 sec ⁻¹ . Bending creep was fitted with a high-temperature oven with dry _{N 2} environment Rheomet
rics RSA II solids analyzer. The sample consisted of an injection molded bar, 12.7 mm wide, 3.2 mm thick and at least 60 m long
m. It has a constant 48 mm span using a three-point bending fixture. Set oven at 250 ° C. and equilibrate for 10 minutes. A compressive force of 1 g is applied to the sample to make it constant at 1.58 × 10 ⁶ Pa. The resulting creep strain is recorded as over 600 s, resulting in 500 strain measurements during the experiment.

[0034]

[Table 10]

The LCB-SPS composition also has improved creep resistance at elevated temperatures.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme court ゛ (Reference) C08L 25:08 C08L 25:08 (81) Designated country EP (AT, BE, CH, CY, DE, DK, ES, FI, FR, GB, GR, IE, IT, LU, MC, NL, PT, SE), OA (BF, BJ, CF, CG, CI, CM, GA, GN, GW, ML, MR, NE, SN, TD, TG), AP (GH, GM, KE, LS, MW, SD, SZ, UG, ZW), EA (AM, AZ, BY, KG, KZ, MD, RU, TJ, TM ), AL, AM, AT, AU, AZ, BA, BB, BG, BR, BY, CA, CH, CN, CU, CZ, DE, DK, EE, ES, FI, GB, G E, GH, GM, HR, HU, ID, IL, IS, JP, KE, KG, KP, KR, KZ, LC, LK, LR, LS, LT, LU, LV, MD, MG, MK, MN , MW, MX, NO, NZ, PL, PT, RO, RU, SD, SE, SG, SI, SK, SL, TJ, TM, TR, TT, UA, UG, UZ, VN, YU, ZW ( 72) Inventor Fan, Ibin 77566, Texas, United States Lake Jackson Dubury Drive 223 (72) Inventor Nichols, Kevin El, Michigan, USA 48642 Midland Jones Lane 3862 F-term (reference) 4F071 AA12X AA15X AA20X AA22 AA22X AA51 AB17 AB21 AB26 AB28 AC09 AE05 AE07 AE11 BC07 4F206 AA13 AA27 AB05 AB07 AB25 JA07 JF02 JQ81 4J002 AC08Y AE00Z AE03Z BB02Y BB17Y BC03W BC05Y BC08W BC09W BC11W BC11X BC13W BD15X BN14Z CH02Y BN15Z BP01 DA016 DA026 DA066 DD079 DE079 DE127 DE139 DE146 DE149 DE236 DE239 DG049 DJ006 DJ009 DJ016 DJ036 DJ046 DJ049 DJ056 DJ059 DL006 EB137 EF058 EG038 EG048 EG079 EH048 EW048 FA046 FB146 FB216 FD016 FD070 FD13XFD FD13X00 FD13X00

Claims (14)

[Claims] 1. An injection molded article made from a composition comprising a long chain branched syndiotactic monovinylidene aromatic polymer. 2. The injection molded article of claim 1, wherein the composition further comprises 10-50% by weight of glass fibers based on the total weight of the composition. 3. The injection molded article of claim 2, wherein the composition further comprises a brominated flame retardant and antimony trioxide. 4. The injection molded article of claim 2, wherein the composition further comprises an impact modifier. 5. The impact modifier is a block or graft copolymer of a vinyl aromatic monomer and a butadiene or isoprene monomer; a substantially random interpolymer of an alpha-olefin and a vinyl aromatic monomer; or a polyolefin elastomer. Item 5. The injection molded article according to Item 4. 6. The impact modifier is a styrene-butadiene-styrene copolymer, styrene-isoprene-styrene copolymer, styrene-ethylene / butadiene-styrene copolymer, styrene-ethylene / propylene-styrene copolymer, styrene-butadiene copolymer, styrene-isoprene. 6. The injection molded article of claim 5, selected from the group consisting of copolymers, butadiene-styrene-butadiene copolymers, isoprene-styrene-isoprene copolymers, hydrogenated products thereof, ethylene-styrene interpolymers and ethylene-octene copolymers. 7. The injection molded article of claim 1, wherein the composition further comprises a lubricant. 8. A lubricant comprising stearic acid, behenic acid, zinc stearate, calcium stearate, magnesium stearate, ethylene bis-stearamide, pentaerythritol tetrastearate, organic phosphate, mineral oil, trimellitate, polyethylene glycol, silicone oil, Epoxidized soybean oil, tricresyl phosphate, polyethylene glycol dimethyl ether, dioctyl adipate, di-n-butyl phthalate, butylene glycol montanate (
Wax OP), pentaerythritol tetramontanate (TPET 141)
8.) The injection molded article of claim 7, wherein the article is selected from the group consisting of: aluminum mono-stearate, aluminum di-stearate, montanic acid wax, montanic acid ester wax, polar polyethylene wax, and non-polar polyethylene wax. 9. The injection molded article of claim 1, wherein the composition further comprises a polyarylene ether. 10. The injection molded article of claim 9, wherein the polyarylene ether is a polar group functionalized polyarylene ether. 11. The injection molded article of claim 1, wherein the composition further comprises a nucleating agent. 12. The nucleating agent may be a monolayer of aluminum magnesium hydroxide, calcium carbonate, mica, wollastonite, titanium dioxide, silica, sodium sulfate, lithium chloride, sodium benzoate, aluminum benzoate, talc, organic acid and phosphonic acid. The injection molded article of claim 11, wherein the article is selected from the group consisting of aluminum and sodium salts of acids. 13. The injection molded article of claim 1, wherein the composition further comprises an antioxidant. 14. The injection molded article of claim 1, wherein the composition further comprises a flame retardant.