CN1560125A - Coating-resistant thermoplastic resin composition - Google Patents
Coating-resistant thermoplastic resin composition Download PDFInfo
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- CN1560125A CN1560125A CNA200410063292XA CN200410063292A CN1560125A CN 1560125 A CN1560125 A CN 1560125A CN A200410063292X A CNA200410063292X A CN A200410063292XA CN 200410063292 A CN200410063292 A CN 200410063292A CN 1560125 A CN1560125 A CN 1560125A
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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
- 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
- C08L51/04—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 grafted on to rubbers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/02—Polymerisation in bulk
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/18—Suspension polymerisation
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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
- 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
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/08—Copolymers of styrene
- C08L25/12—Copolymers of styrene with unsaturated nitriles
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2300/00—Characterised by the use of unspecified polymers
- C08J2300/22—Thermoplastic resins
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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Abstract
The invention relates to a thermoplastic resin composition with coating resistance property, in particular to a resin composition consisting of 90 to 65 weight percents of copolymer B besides 10 to 35 weight percents of rubber polymer A. The invention is characterized in that the composition has to satisfy the conditions as follow: (1) the average content of ethylene cyanide in the copolymer B is 25 to 35 weight percents; and (2) the content of polymer consisting of ethylene cyanide which is higher 2% than average content of ethylene cyanide in the copolymer B is 3 to 20 weight percents of the copolymer B.
Description
The application is to be March 12, application number in 1997 the dividing an application for the application for a patent for invention of " coating-resistant thermoplastic resin composition and manufacture method " that be 97109541.8 denomination of invention the applying date.
Technical field
Tone stability and the good thermoplastic resin composite of shaping processability when the invention relates to balance shock-resistance, anti-coating, fusion.
Background technology
The vinyl cyanide compound is carried out the resin combination that graft copolymerization becomes rubber polymer with aromatic ethylene compound.Known have acronitrile-butadiene-styrene (ABS resin), owing to have good shaping processability aspect mechanical characteristics, obtains utilizing in extensive fields.In automobile, motorcycle field,, at this moment be to carry out application mostly particularly because the advantage of light weight not only is used for inside components, and is used for exterior member.
Say that generally by increasing the content of vinyl cyanide in the ABS resin, it is known improving anti-coating, existing up till now countless research all is the method for improving coating according to the ratio of vinyl cyanide in the research ABS resin.For example, open in the flat 6-16896 communique the spy and to propose a kind of method, stipulated that rubber contains the difference of the vinyl cyanide content in the vinyl cyanide content and vinyl cyanide multipolymer in the graft copolymer and the ratio of two kinds of multipolymers.Yet the tone stability of this method during for coating and fusion is all undesirable.
Open in the flat 7-11099 communique the spy and to propose a kind of composition, vinyl cyanide content is in specified range in the rubber graft copolymer for containing to have the vinyl cyanide multipolymer of specific vinyl cyanide content.Yet, tone poor stability when problem is fusion.
Therefore, the purpose of this invention is to provide a kind of when balance shock-resistance, anti-coating, fusion aspect tone stability and the shaping processability, all good coating-resistant thermoplastic resin composition.
Present inventors are in order to reach this purpose.Carried out big quantity research, found that, by making up specific vinyl cyanide content and containing the vinyl cyanide multipolymer of combination distribution and contain rubber graft copolymer, obtained a kind of when balance shock-resistance, anti-coating, fusion all good resin combination aspect tone stability and the shaping processability, and finished the present invention.
Summary of the invention
Be the coating-resistant thermoplastic resin composition of feature by meeting the following conditions simultaneously, realized the invention described above purpose.Promptly, weight is by 5-40 (weight) % rubber polymer (A), in the resin combination that other multipolymer (B) except that rubber polymer of 95-60 (weight) % forms, the average vinyl cyanide content that has (1) multipolymer (B) is 25-35 (weight) %, (2) vinyl cyanide in multipolymer (B) is formed in the distribution, have the above multipolymer of forming (B), in multipolymer (B), have 3-20 (weight) % than average vinyl cyanide content high by 2 (weight) %.
In the present invention, (A) is diene series rubber as the rubber polymer that is used to contain rubber graft copolymer (I), acrylic rubber, ethene is rubber etc., can enumerate polyhutadiene as specific examples, poly-(butadiene-styrene), poly-(butadiene-acrylonitrile), poly-isoprene, poly-(butadiene-acrylic acid butyl ester), poly-(butadiene-acrylic acid methyl esters), poly-(divinyl-methyl methacrylate), poly-(butyl acrylate-methyl methacrylate), poly-(butadiene-acrylic acid ethyl ester), ethylene-propylene rubber, ethylene-propylene-elastoprene, poly-(ethene-iso-butylene), poly-(ethylene-methyl acrylate) etc.These rubber polymers can use a kind or use mixture more than 2 kinds.In these rubber polymers, consider, preferably use polyhutadiene, poly-(butadiene-styrene), poly-(butadiene-acrylonitrile), ethylene-propylene rubber with regard to shock-resistance.
In the present invention, specific examples as the cyaniding second diene monomer (a) that is used for containing rubber graft copolymer (I), vinyl cyanide based copolymer (II) and vinyl cyanide based copolymer (III), two alkene nitriles and methacrylonitrile etc. can have been enumerated, available mixture more than a kind or 2 kinds.Wherein consider that with regard to anti-coating aspect vinyl cyanide is good especially.
As the aromatic vinyl that is used for containing rubber graft copolymer (I), vinyl cyanide based copolymer (II) and vinyl cyanide based copolymer (III) is the specific examples of monomer (b).Vinylbenzene, alpha-methyl styrene, o-methyl styrene, p-methylstyrene, right-t-butyl styrene and halogenated styrenes etc. can have been enumerated.Can use a kind or 2 kinds with mixture on.Wherein consider preferably to use vinylbenzene, alpha-methyl styrene with regard to shaping processability, vinylbenzene is better.
In the present invention, as being used for containing rubber graft copolymer (I) but the specific examples of other vinyl monomer (c) of copolymerization, can enumerate the unsaturated carboxylic acid of vinylformic acid, methacrylic acid etc.; (methyl) esters of acrylic acid of methyl acrylate, methyl methacrylate, butyl acrylate etc.; (methyl) acrylic amide of acrylamide, Methacrylamide, N methacrylamide etc.; The maleimide of maleimide, N-methyl maleimide, N-benzene maleimide etc.; Unsaturated carboxylic acid anhydrides such as maleic anhydride, citraconic anhydride, aconitic anhydride etc. are wherein considered the most handy methyl methacrylate, N-benzene maleimide with regard to shaping processability.
Among the present invention, rubber polymer (A) is necessary for 5-40 (weight) %, removes in addition, and other multipolymer (B) must be 95-60 (weight) %.When rubber polymer (A) less than 5 (weight) %, the shock-resistance of resulting coating-resistant thermoplastic resin composition is not enough, when surpassing 40 (weight) %, because the shaping processability of the coating-resistant thermoplastic resin composition that obtains is too poor and undesirable.Wherein consider that from balance shock-resistance and shaping processability aspect preferably rubber polymer (A) is for 10-35 (weight) %, except that rubber polymer, other multipolymer (B) is 90-65%.
The average vinyl cyanide content of multipolymer among the present invention (B) must be 25-35 (weight) %.When average vinyl cyanide contained quantity not sufficient 25 (weight) %, the anti-coating of the coating-resistant thermoplastic resin composition that obtains was not enough, and when surpassing 35 (weight) %, the tone stability during fusion is too poor and undesirable.Wherein, average vinyl cyanide content 28-33 (weight) %, the tone stability during from anti-being coated with property of balance and fusion is considered best.
Vinyl cyanide at multipolymer (B) among the present invention is formed in the distribution, has the above multipolymer of forming than average vinyl cyanide content high by 2 (weight) %, must be 3-20 (weight) % in multipolymer (B).During less than 3 (weight) %, the anti-coating of the coating-resistant thermoplastic resin composition that obtains is not enough, and when surpassing 20 (weight) %, the tone stability during fusion is because too poor and undesirable.Tone stability during wherein from anti-coating of balance and fusion considers to be preferably 5-18 (weight) %.
The content that is used to contain the rubber polymer (A) of rubber graft copolymer (I) among the present invention does not have particular restriction, but is thought of as 10-80 (weight) % with regard to shock-resistance, preferably 40-70 (weight) %.In containing rubber graft copolymer (I), though be that the content of monomer (a) does not have particular restriction, be thought of as 5-50 (weight) % with regard to shaping processability to vinyl cyanide, be preferably 10-40 (weight) %.In containing rubber graft copolymer (I), though to aromatic vinyl is that the content of monomer (b) does not have particular restriction, but be thought of as 10-80 (weight) % with regard to shaping processability, 20-70 (weight) % preferably, in containing rubber graft copolymer (I), but the content of other vinyl monomer (c) of copolymerization though there is not particular restriction, is thought of as 5-50 (weight) % with regard to shaping processability.
Though to percentage of grafting, also first viscosity of grafting composition multipolymer does not have particular restriction, consider that with regard to shock-resistance percentage of grafting is 10-80 (weight) %, the multipolymer reducing viscosity of grafting composition is 0.2-0.8dl/g.
It is that monomer (a) is 15-35 (weight) % that vinyl cyanide based copolymer (II) among the present invention contains vinyl cyanide, and aromatic vinyl is that monomer (b) is 85-65 (weight) %.When vinyl cyanide is monomer (a) less than 15 (weight) %, the anti-coating of the coating-resistant thermoplastic resin composition of the vinyl cyanide based copolymer that use obtains is bad, when surpassing 35 (weight) %, tone stability all significantly reduces and undesirable when using the shaping processability of coating-resistant thermoplastic resin composition of the vinyl cyanide based copolymer that obtains and fusion.When aromatic vinyl is monomer (b) less than 65 (weight) %, tone stability significantly reduces during the fusion of the coating-resistant thermoplastic resin composition that obtains, when surpassing 85 (weight) %, the anti-coating of the coating-resistant thermoplastic resin composition that obtains, undesirable owing to significantly reduce.Particularly containing vinyl cyanide is that monomer (a) is 20-30 (weight) %, aromatic vinyl be monomer (b) for the vinyl cyanide multipolymer (II) of the scope of 80-70 (weight) % for well.
Vinyl cyanide based copolymer (III) among the present invention is that the vinyl cyanide that contains 30-50 (weight) % is monomer (a), and the aromatic vinyl of 70-50 (weight) % is monomer (b).When vinyl cyanide is monomer (a) less than 30 (weight) %, bad with the anti-coating of the coating-resistant thermoplastic resin composition of the vinyl cyanide multipolymer of gained, when surpassing 50 (weight) % because fusion tone stability reduces also undesirable.The vinyl cyanide that preferably contains 33-45 (weight) % is monomer (a), and the aromatic vinyl of 67-55 (weight) % scope is the vinyl cyanide multipolymer (III) of monomer (b).
In the composition of vinyl cyanide in multipolymer (B) distributes, has the above multipolymer of forming than average vinyl cyanide content high by 2 (weight) %, must be 3-20 (weight) % of multipolymer (B), but the concrete grammar as it has, in form distributing with the above ratio of forming that has of 50-90 weight part than average vinyl cyanide content high by 2 (weight) %, it is the following vinyl cyanide multipolymer (II) of 2 (weight) %, with the 5-45 weight part, has the above ratio of forming than average vinyl cyanide high by 2 (weight) %, vinyl cyanide based copolymer (III) for 25-40 (weight) % carries out the blended method.
The composition of vinyl cyanide distributes, and adds hexanaphthene in the butanone solution of vinyl cyanide based copolymer, and sedimentary respectively vinyl cyanide multipolymer is carried out drying, behind the gravimetry, measures vinyl cyanide content with infrared spectrophotometer.Average vinyl cyanide content does not carry out fractionation precipitation, but tries to achieve all with the infrared light photometer.
About the manufacture method that contains rubber graft copolymer (I) of the present invention, there is not particular restriction, can pass through emulsion polymerization method, mass polymerization, solution polymerization process, and the polymerization that they combine made, wherein, consider that with regard to rubber size and control percentage of grafting emulsion polymerization method is good especially.
As the polymerization process of vinyl cyanide multipolymer (II) among the present invention, though there is not particular restriction, consider that the composition that makes vinyl cyanide distributes accurately, use mass polymerization, solution polymerization process is good especially.
As the polymerization process of vinyl cyanide based copolymer (III) among the present invention,, consider that the composition that makes vinyl cyanide distributes accurately, uses the water system suspension polymerization best though there is not particular restriction.
As the suspension stabilizer that uses in the above-mentioned polymerization, can use clay, barium sulfate, magnesium hydroxide etc. inorganic is the organic system suspension stabilizer etc. of suspension stabilizer, polyvinyl alcohol, carboxymethyl cellulose, polyacrylamide, methyl methacrylate/acrylic acid amides multipolymer etc., can utilize azo polymerization initiator, hydroperoxide series initiators to carry out polymerization.
Manufacture method for coating-resistant thermoplastic resin composition of the present invention does not have particular restriction.Can use screw mixer, V-Mixer, disk mixer etc. during cooperation.In addition, combination treatment can adopt the extrusion machine of single shaft extrusion machine, double-shafted extruder etc., Pa Beili mixing tank, mixing roller, pressurization mixing machine etc.
In continuous bulk polymerization process, under agitation preferably will contain rubber graft copolymer (I) and, be added continuously in the vinyl cyanide multipolymer (II) of the state of dissolving with the vinyl cyanide multipolymer (III) of suspension polymerization manufactured, can improve tone better.
Particularly, removing in the monomer operation of vinyl cyanide based copolymer (II), for remaining monomer is the following vinyl cyanide based copolymer (II) of 10 (weight) %, slurries that will make by emulsion polymerization latex or the dried particles shape vinyl cyanide based copolymer (III) that contains rubber graft copolymer (I) and utilize suspension polymerization to make that moisture cake is dehydrated in advance, use single shaft extrusion machine or double-shafted extruder to infeed continuously in the double-shafted extruder that has ventilating pit, when melting mixing, remove monomer simultaneously, make coating-resistant thermoplastic resin composition, see ideal from tone.
Can cooperate other composition as required in the present invention, as 2,6-two-tertiary butyl-4-sylvan, 4, the phenol of 4 '-butylidene-two (3-methyl-6-tert-butylphenol) etc. is antioxidant; The phosphorous acid ester of three (mixing, list and hexichol) phosphorous acid ester, hexichol isodecyl phosphorous acid ester etc. is an antioxidant; The sulphur of dilauryl thiodipropionic acid ester, myristyl thiodipropionic acid ester, distearyl thiodipropionic acid ester etc. is antioxidant; The benzotriazole UV absorbers of 2-hydroxyl-4-octyloxy benzophenone, 2-(2-hydroxy-5-methyl phenyl) benzotriazole etc.; Two (2,2,6,6-tetramethyl-)-inorganic filling material such as various additives of fire retardant of lubricant such as hard esteramides of antistatic agent, pentaerythritol tetrastearate, ethylene of photostabilizers such as 4-piperidines, hydroxyalkyl amine, sulfonate etc., metal base and tetrabromo-bisphenol, ten bromine phenol oxide compounds, TBA epoxy oligomer, TBA polycarbonate oligomer, ANTIMONY TRIOXIDE SB 203 99.8 PCT etc., flame retardant etc., tinting material, glass fibre, carbon fiber etc.
Wherein, best aspect coating, the 0.1-5 weight part of pentaerythritol tetrastearate is for well.Improve the coating poor effect during less than 0.1 weight part, when surpassing 5 weight parts, degenerate also undesirable owing to plasticity.
Because coating-resistant thermoplastic resin composition of the present invention is splendid aspect tone stability and the shaping processability when balance shock-resistance, anti-coating, fusion, so can be used for various shaping processing such as reaction-injection moulding, sheet material shaping, extrusion molding, blowing, compression molding, vacuum forming, their processed goods is applicable to application, vacuum evaporation, plating etc.
As the coating that is suitable for coating-resistant thermoplastic resin composition of the present invention especially, acrylic acid series coating and polyurethane coating are arranged.Said acrylic acid series coating is with vinylformic acid or its ester class, and the multipolymer of methacrylic acid or its ester class and other vinyl compound is filmed as formation and is the coating of main component.In addition, said polyurethane series coating is to combine urethane or be coated with the coating that generates urethane bonds in the membrane process in formation in resin matrix having.
In order to be described more specifically the present invention, below enumerate embodiment and comparative example describes, still, these embodiment do not constitute qualification to the present invention.In reference example, embodiment, the comparative example be divided into weight part, % is weight %.Also have, gained contains each rerum natura numerical value of rubber graft copolymer (I), vinyl cyanide based copolymer (II), vinyl cyanide based copolymer (III), multipolymer (B) and coating-resistant thermoplastic resin composition, tries to achieve with following testing method.
Percentage of grafting: acetone joined contain in the rubber graft copolymer (I) (weight M), refluxed 3 hours, this solution centrifugal was separated 40 minutes, filter insoluble composition, should insoluble composition 60 ℃ of following vacuum-dryings 5 hours, measure its weight (N).Obtain percentage of grafting with following formula.But L is the rubber polymer content (%) that contains in the rubber graft copolymer (I) in the formula.
Percentage of grafting (%)=100 * (N-M * L/100)/(M * L/100)
Reducing viscosity: use the Ubbelohde viscometer, measuring temperature is 30 ℃, utilizes test portion concentration to measure for the butanone solution of 0.4g/dl.
Average vinyl cyanide containing ratio: the heating test portion, make the film of 40 μ m, try to achieve with infrared spectrophotometer with pressing machine.
Vinyl cyanide is formed distribution: the 2g test portion is dissolved in the 80ml butanone, add hexanaphthene again, the vinyl cyanide based copolymer that is settled out is carried out vacuum-drying, measure its weight, utilize the ratio of the absorbancy of infrared spectroscopic analysis to try to achieve the vinyl cyanide content of vinyl cyanide based copolymer.Equally, make the graphic representation of accumulating weight % and vinyl cyanide content, obtain the ratio above than average vinyl cyanide amount high by 2 (weight) %.
Lzod impact strength: coating-resistant thermoplastic resin composition is carried out reaction-injection moulding,, measure 1/2 inch lzod impact strength that has recess according to ASTM D 256.
Tone stability during fusion: during with the coating-resistant thermoplastic resin composition reaction-injection moulding, 230 ℃ are detained after 30 minutes down in forming mill, according to the Japanese electric look industry of JIS K 7103 usefulness (strain) system colour examining colour-difference-metre, measure the xanthochromia degree (YI) of gained molding.
Anti-coating: with the coating-resistant thermoplastic resin composition reaction-injection moulding, spraying acrylic acid series coating solution (rattan changes into coating ア Network ラ リ イ Application #66 E/ シ Application Na ア Network ラ リ イ Application I type シ Application Na-=50/50 weight ratio of (strain) system) on the gained molding, drying is 30 minutes under 70 ℃, estimates the outward appearance of application face.During polyurethane series coating, be coated with Japanese プ イ Application ト strain system Block ラ Star シ コ ホ ワ イ ト (ア Application ダ-コ-ト: Pu BlushWhite Base ミ De Le コ-ト: Pu Blush White Coctail #1, ト Star プ コ-ト: Pu Pearl Chear, stiffening agent: Polyuremighty lacHardenner, シ Application Na-: Polyuremightylac), drying is 30 minutes under 70 ℃, estimates the density of filming of application face.
Mobile: as, to measure the fusion flow velocity of 220 ℃ of 10kg loads according to ISO 1133.
In order to be described more specifically the present invention, below describe, but the present invention is not limited in these embodiment with embodiment and comparative example, if do not have special indicated words at this, % is that weight %, part are weight part.
Embodiment
Reference example 1 (containing the manufacturing of rubber graft copolymer (I))
In the reaction vessel of crossing with nitrogen replacement, the 120 fens pure water of packing into, 0.5 part glucose, 0.5 part of trisodium phosphate, 0.005 part of ferrous sulfate and 50 parts of (calculating) polyhutadiene latex (rubber size 0.3 μ m with solids component, gel content 85%), stir on the limit, and the limit is raised to 65 ℃ with reactor temperature.When internal temperature reaches 65 ℃, begin as polymerization, in 5 hours, drip by monomer (40 parts of vinylbenzene, 10 parts of vinyl cyanide) and 0.3 part of mixture that uncle-lauryl mercaptan forms continuously.Carry out simultaneously, in 7 hours, drip continuously by withered rare, the 2.5 parts of potassium oleates of 0.25 part of hydroperoxide and 25 parts of aqueous solution that pure water forms, question response end.Solidify the gained graft copolymer latex with sulfuric acid, with in the caustic alkali and after, washing, filtration, drying obtain containing rubber graft copolymer (I).This rubber polymer content that contains rubber graft copolymer (I) is 50%, and percentage of grafting is 45%, and the resinous principle reducing viscosity is 0.68dl/g.
Reference example 2 (manufacturing of vinyl cyanide multipolymer (II) A)
Use is by 2 grooves and the preheating machine of pattern shown in the table 1, and remove the continuous bulk polymerization device that uniset constitutes, with 135kg/ hour, in the 1st polymerization tank, infeed continuously by 25 parts of vinyl cyanide, 75 parts of vinylbenzene and 0.15 part of monomer mixture that the n-octyl mercaptan forms, carry out continuous bulk polymerization.The percent polymerization of controlling the 1st polymerization tank is between the 58-61%, and the percent polymerization of the polymkeric substance that the 2nd polymerization tank goes out moves between 90-91%.Polymerization reaction mixture, utilize the single shaft extruder type to remove uniset, reclaim unreacted monomer by the venting port reduction vaporization, by vinyl cyanide multipolymer (II) A of record in the end acquisition table 3 that removes uniset, it is the average vinyl cyanide content of co-polymer (II) A and the ratio (%) above than average vinyl cyanide content high by 2 (weight) % that the gained vinyl cyanide has been shown in the table 3.
Reference example 3 (manufacturing of vinyl cyanide multipolymer (II) B)
Use by style shown in the table 2 by 1 groove and preheating machine and remove the continuous bulk polymerization device that uniset is formed, in polymerization tank, infeed continuously by 25 parts of vinyl cyanide, 75 parts of vinylbenzene and 0.18 part of monomer mixture that the n-octyl mercaptan forms with 135kg/ hour speed, carry out continuous bulk polymerization.The polymer polymerizing rate that polymerization tank is gone out is controlled between the 74-76%, after polymerization reaction mixture is used the preheating of single shaft extruder type preheating machine, remove uniset with double-shafted extruder again, reclaim unreacted monomer by the venting port reduction vaporization, by vinyl cyanide based copolymer (II) B that forms of record in the end acquisition table 3 that removes uniset.The average vinyl cyanide content of gained vinyl cyanide based copolymer (II) B and the ratio (%) above than average vinyl cyanide content high by 2 (weight) % are shown in table 3.
Reference example 4 (manufacturing of vinyl cyanide based copolymer (II) C)
Use is by 1 groove of style shown in the table 2 and preheating machine, and remove the continuous bulk polymerization device that uniset is formed, speed during with 135kg/ infeeds in polymerization tank continuously by 28 parts of vinyl cyanide, 72 parts of vinylbenzene and 0.18 part of monomer mixture that the n-octyl mercaptan forms, carry out continuous bulk polymerization, the percent polymerization that polymerization tank is gone out polymkeric substance is controlled at 74-76%, after polymerization reaction mixture is used the preheating of single shaft extruder type preheating machine, utilize double-shafted extruder type demonomerization machine, reclaim unreacted monomer by the venting port reduction vaporization, obtain vinyl cyanide based copolymer (II) C that record is formed the table 3 from the end that removes uniset.The average vinyl cyanide content of gained vinyl cyanide based copolymer (II) C and the ratio (%) above than average vinyl cyanide content high by 2 (weight) % are shown in table 3.
Reference example 5 (manufacturing of vinyl cyanide based copolymer (III) a)
20 liters of capacity, have in the stainless steel autoclave of plate washer and the pull-up paddle of Fa Ede, pack into and be dissolved with the solution of 0.05 part of methyl methacrylate/acrylamide copolymer (special public clear 45-24151 communique record) in 165 parts of ion exchanged waters, stir with 400rpm, will replace in the system with nitrogen.Then, limit stirring reaction system, add by 31 parts of vinyl cyanide, 69 parts of vinylbenzene, 0.3 part of uncle's dodecyl mercaptans and 0.52 part 2 on the limit, the mixing solutions of 2 '-Diisopropyl azodicarboxylate is warmed up to 60 ℃, the beginning polymerization, by polymerization begin in 100 minutes, to be warmed up to 65 ℃, afterwards, in 50 minutes, be warmed up to 100 ℃, polymerization finishes.After, press usual method, cool off reactive system, isolating polymer, washing, drying, obtain vinyl cyanide based copolymer (III) a.The average vinyl cyanide content of gained vinyl cyanide multipolymer (III) a and the ratio (%) above than average vinyl cyanide content high by 2 (weight) % are shown in table 3.
Reference example 6 (manufacturing of vinyl cyanide based copolymer (III) b)
Except vinyl cyanide being become 37 parts, vinylbenzene becomes 63 especially, and other and reference example 5 the same manufacturings obtain vinyl cyanide based copolymer (III) b that table 3 is put down in writing.
The manufacturing of reference example 7 (vinyl cyanide based copolymer (III) c))
Except vinyl cyanide being become 20 parts, vinylbenzene becomes 80 especially, and other and reference example 5 the same manufacturings obtain vinyl cyanide based copolymer (III) c that table 3 is put down in writing.
The manufacturing of reference example 8 (vinyl cyanide based copolymer (III) d))
Except vinyl cyanide being become 37 parts, vinylbenzene becomes 63 especially, and other and reference example 5 the same manufacturings obtain vinyl cyanide based copolymer (III) d that table 3 is put down in writing.
Embodiment 1-3
With vinyl cyanide multipolymer (III) a-b and the pentaerythritol tetrastearate that obtains among vinyl cyanide based copolymer (II) A-C, the reference example 5-6 that obtains among rubber graft copolymer (I), the reference example 2-4 that contain that obtains in the reference example 1, press proportioning shown in the table 4, mix the back, use Φ 40mm single shaft extrusion machine melting mixing with enjoying Xi Er (ヘ Application シ エ Le) mixing tank, obtain coating-resistant thermoplastic resin composition.Measure the average vinyl cyanide content of rubber polymer content, the multipolymer (B) of gained coating-resistant thermoplastic resin composition, the ratio (%) above, 1/2 inch than average vinyl cyanide content high by 2 (weight) % of multipolymer (B), the lzod impact strength, the xanthochromia degree (YI) that have recess, coating and fusion flow velocity are shown in Table 4.
Embodiment 4
The same with reference example 3, use continuous bulk polymerization, obtain vinyl cyanide based copolymer (II) B of record in the table 3.By the end that the removes uniset 1/3 long bobbin that is connected in series, by double-shafted extruder type feeder with heating unit, speed during with 20kg/, that makes in the example 1 for reference contains rubber graft copolymer (I) powder, vinyl cyanide multipolymer (III) b that makes in speed during with the 7kg/ example 6 for reference and the speed during with 1kg/ are for pentaerythritol tetrastearate, vinyl cyanide based copolymer (II) B of speed during with 73kg/, in removing uniset, behind the melting mixing, reclaim unreacted monomer by the venting port reduction vaporization, thread by the cutting knife cutting spues obtains the coating-resistant thermoplastic resin composition particle.Measure the average vinyl cyanide content of rubber polymer content, the multipolymer (B) of gained coating-resistant thermoplastic resin composition, the ratio (%) above, 1/2 inch than average vinyl cyanide content high by 2 (weight) % of multipolymer (B), have lzod impact strength, xanthochromia degree (Y1), coating and the fusion flow velocity of recess, be shown in table 4.
Comparative example 1-8
With the vinyl cyanide based copolymer III that obtains among vinyl cyanide based copolymer (II) A-C, the reference example 5-8 that obtains among rubber graft copolymer (I), the reference example 2-4 that contains that obtains in the reference example 1) a-d, and pentaerythritol tetrastearate, by cooperating ratio in the table 4, after enjoying the mixing of Xi Er mixing tank, carry out melting mixing with Φ 40mm extrusion machine, obtain coating-resistant thermoplastic resin composition.Measure the rubber polymer content of gained coating-resistant thermoplastic resin composition, the average vinyl cyanide content of multipolymer (B), the ratio (%) above than average vinyl cyanide content high by 2 (weight) % of multipolymer (B), 1/2 inch, lzod impact strength, xanthochromia degree (Y1), coating and the fusion flow velocity of band recess are shown in table 4.
By embodiment 1-4 as can be known, the coating-resistant thermoplastic resin composition in the specialized range of the present invention, capitally balance the stability and the shaping processability of tone when shock-resistance, anti-coating, fusion.
Yet, comparative example 1-8, the average vinyl cyanide content of rubber polymer content, multipolymer (B) and the ratio (%) above than average vinyl cyanide content high by 2 (weight) % of multipolymer (B), owing to exceed the scope of the present invention's regulation, so the coating of comparative example 1,7 degenerates, the tone stability and the coating of comparative example 4 are very poor, and the impact strength of comparative example 6 is very low, the xanthochromia degree of comparative example 2,3,5,8 is very big, and tone stability is very poor.
According to embodiment and comparative example as can be known, coating-resistant thermoplastic resin composition of the present invention, capitally balance the stability and the shaping processability of tone when shock-resistance, anti-coating, fusion.This is by the vinyl cyanide based copolymer that will have specific vinyl cyanide content and composition distribution, contains rubber graft copolymer and the combination of pentaerythritol tetrastearate as required, just is achieved.
Anti-application dress thermoplastic resin composition of the present invention, it is characterized in that to have specific vinyl cyanide content and form the vinyl cyanide based copolymer that distributes, contain rubber graft copolymer and pentaerythritol tetrastearate effectively makes up, so capitally balance shock-resistance, tone stability and shaping processability when anti-coating, fusion.
Coating-resistant thermoplastic resin composition of the present invention effectively utilizes these features, can be for various shapings processing, and particularly be suitable for and make the resin material that acrylic acid series coating and polyurethane series coating are used for automobile, motorcycle exterior member.
The form of table 1 coincidence arrangement
The form of table 2 poly-unit
| Whipped form | Complete mixed type with screw-blade |
| Temperature (℃) | ????135 |
| Pressure (kg/cm 2G) | ????0.9 |
| Refrigerating unit | Condenser with water jacket and monomer vapor evaporation backflow usefulness |
Table 3 vinyl cyanide based copolymer (II) and vinyl cyanide based copolymer (III)
| Vinyl cyanide based copolymer (II) | Vinyl cyanide based copolymer (III) | |||||||
| Reference example NO | ??2 | ??3 | ????4 | ??5 | ??6 | ??7 | ??8 | |
| ????????????NO | ??A | ??B | ????C | ??a | ??b | ??c | ??d | |
| Vinyl cyanide | ??％ | ??25 | ??25 | ????28 | ??31 | ??37 | ??20 | ??37 |
| Vinylbenzene | ??％ | ??75 | ??75 | ????72 | ??69 | ??63 | ??80 | ??63 |
| The ratio above than average vinyl cyanide content high by 2 (weight) % | ??％ | ??1.5 | ??0 | ????0 | ??26 | ??38 | ??30 | ??45 |
Table 4 coating-resistant thermoplastic resin composition
*Suction * the suction of 1: zero nothing
*2: zero nothings are peeled off △ and are partly peeled off * roughly peel off
Claims (1)
1. coating-resistant thermoplastic resin composition, by the rubber polymer A of 10-35 weight %, except that rubber polymer, the resin combination that the multipolymer B of 90-65 weight % forms is characterized in that it must satisfy the condition of following (1) and (2),
(1) the average vinyl cyanide content of multipolymer B is 25-35 weight %,
(2) form distribution with regard to the vinyl cyanide of multipolymer B, have the 3-20% weight that accounts for multipolymer B than the amount of the multipolymer of forming more than high 2% weight of average vinyl cyanide content.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP55814/1996 | 1996-03-13 | ||
| JP5581496 | 1996-03-13 |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB971095418A Division CN1205262C (en) | 1996-03-13 | 1997-03-12 | Paint-resistant thermoplastic resin composition and process for producing same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1560125A true CN1560125A (en) | 2005-01-05 |
Family
ID=13009411
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA200410063292XA Pending CN1560125A (en) | 1996-03-13 | 1997-03-12 | Coating-resistant thermoplastic resin composition |
| CNB971095418A Expired - Lifetime CN1205262C (en) | 1996-03-13 | 1997-03-12 | Paint-resistant thermoplastic resin composition and process for producing same |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB971095418A Expired - Lifetime CN1205262C (en) | 1996-03-13 | 1997-03-12 | Paint-resistant thermoplastic resin composition and process for producing same |
Country Status (4)
| Country | Link |
|---|---|
| KR (1) | KR100492806B1 (en) |
| CN (2) | CN1560125A (en) |
| MY (1) | MY128484A (en) |
| TW (1) | TW467938B (en) |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6026424B2 (en) * | 1978-10-18 | 1985-06-24 | ジェイエスアール株式会社 | Impact resistant resin composition |
| JPH0616896Y2 (en) * | 1989-09-25 | 1994-05-02 | 信越化学工業株式会社 | Heating furnace equipment |
| JPH0711099Y2 (en) * | 1989-12-22 | 1995-03-15 | 株式会社コシハラ | Endless winch |
| KR950013178B1 (en) * | 1992-04-13 | 1995-10-25 | 주식회사엘지화학 | Polyolefin composition having excellent painting and coating |
| KR0171620B1 (en) * | 1993-06-14 | 1999-03-30 | 채오병 | The composition of antistatic styrenic thermoplastic materials |
| JPH0711099A (en) * | 1993-06-28 | 1995-01-13 | Asahi Chem Ind Co Ltd | Resin composition excellent in coating property and plating property |
-
1997
- 1997-03-05 TW TW086102655A patent/TW467938B/en not_active IP Right Cessation
- 1997-03-10 KR KR1019970007886A patent/KR100492806B1/en not_active IP Right Cessation
- 1997-03-11 MY MYPI97001023A patent/MY128484A/en unknown
- 1997-03-12 CN CNA200410063292XA patent/CN1560125A/en active Pending
- 1997-03-12 CN CNB971095418A patent/CN1205262C/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| KR100492806B1 (en) | 2005-10-13 |
| MY128484A (en) | 2007-02-28 |
| TW467938B (en) | 2001-12-11 |
| CN1205262C (en) | 2005-06-08 |
| CN1169445A (en) | 1998-01-07 |
| KR970065631A (en) | 1997-10-13 |
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