CN1086524A - Phenylethylene resin composition for extrusion moulding - Google Patents
Phenylethylene resin composition for extrusion moulding Download PDFInfo
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- CN1086524A CN1086524A CN 92112708 CN92112708A CN1086524A CN 1086524 A CN1086524 A CN 1086524A CN 92112708 CN92112708 CN 92112708 CN 92112708 A CN92112708 A CN 92112708A CN 1086524 A CN1086524 A CN 1086524A
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Abstract
Phenylethylene resin composition for extrusion moulding of the present invention is by total phenylethylene resin series 100 weight parts that styrenic graft copolymer (A) 15～100 weight % and styrenic (B) 85～0 weight % form, with 2,2 '-oxalamide-two-[ethyl-3-(3,5-di-t-butyl-4-hydroxyphenyl) propionic ester] 0.01～3.0 weight part constitutes.Have excellent outward appearance and shock strength by the resulting extrusion molding article of styrene resin composite of the present invention, and when making heat product, also be difficult for causing the phenomenon of uneven thickness by extrusion molding article.
Description
The invention relates to a kind of styrene resin composite that extrusion moulding is used that is suitable for, be meant a kind of styrene resin composite also suitable when extrusion molding article is used for thermoforming especially.
In the past, contain the phenylethylene resin series of graft rubber particle such as ABS resin (acrylonitrile-butadiene-styrene resin), MBS(methyl methacrylate-butadiene-styrene resin), AMBS resin (vinyl cyanide-methyl methacrylate-butadiene-styrene resin), AES resin (vinyl cyanide-EPDM-styrene resin) etc. mainly be used in injection moulding, a part then is used in extrusion moulding, and the usefulness of the back thermoforming of the extrusion moulding of being used in is also arranged.
Above-mentioned phenylethylene resin series uses does not have any problem when injection moulding, if just use when extrusion moulding, but produce problem in the practicality through regular meeting; For example: it is used when the extrusion moulding, and its finished surface can generate streak or loft, perhaps produces phenomenons such as gloss uneven, and causes the disappearance of finished product bad order; Also have, cylinder can be contaminated during manufacturing, and cause operations for forming often to be forced to interrupt; In addition, aforementioned base materials is if add man-hour with injection molding method, although have sufficient shock strength, but the shock strength of extrusion molding article is still poor, and, more can produce difference in thickness clearly when extrusion molding article further during thermoforming, cause outward appearance and intensity not good.
The purpose of this invention is to provide a kind ofly when being used in extrusion moulding, the outward appearance and the shock strength of extrusion molding article are superior, and the phenylethylene resin composition for extrusion moulding of nonstaining property in fact.
A time purpose of the present invention provides a kind of when extruding finished product and make heat product, is difficult for taking place difference in thickness, and obtains the styrene resin composite of outward appearance and excellent strength goods.
The present invention is characterized in: total phenylethylene resin series 100 weight parts that form by polystyrene graft copolymerization compound (A) 15～100 weight % and styrenic (B) 85～0 weight %, with 2,2 '-oxalamide is two-(ethyl-3-(3,5-di-t-butyl-4-hydroxyphenyl) propionic ester) and the styrene resin composite that constituted of (hereinafter to be referred as PCC) 0.01～3.0 weight part.
Being used for styrenic graft copolymer of the present invention (A) means: make to contain cinnamic polymerization of vinyl monomer in the presence of rubbery polymer, so that make produced styrenic contain the polymkeric substance that grafting becomes the rubber-like particle.
Rubbery polymer uses with diene monomer and is the polymkeric substance of monomer component below second-order transition temperature after the polymerization-20 ℃; Aforementioned diene monomer has divinyl, isoprene, ethylidene norbornene etc.; And representative rubbery polymer is as the butadiene-based polymkeric substance of polyhutadiene, butadiene-styrene copolymer, perbutan, butadiene-acrylic acid butyl ester multipolymer, butadiene-acrylonitrile-divinyl benzene copolymer etc., or ethylene-propylene-ethylidene norbornene multipolymer etc., be good especially with the butadiene-based polymkeric substance.
The preferable method for making of styrenic graft copolymer (A) is to make: after rubbery polymer is dissolved in and contains cinnamic vinyl monomer, again in stirring polymerization (hereinafter to be referred as rubber solutions graft polymerization method) down, above-mentioned rubber solutions graft polymerization method is block polymerization or the solution polymerization under mat stirs, and have the polymerization of the process that forms rubber particles, and bulk or solution polymerization process, the outstanding turbid polymerization of batch-wise bulk etc. of continous way are arranged; But with regard to viewpoints such as the homogeneity of quality, form and aspect, be good with the bulk or the solution polymerization process of continous way.
Aforementioned rubbery polymer in order to rubber liquid graft polymerization method has: high-cis polybutadiene, contain 1, the 2-vinyl is in conjunction with the butadiene-based polymkeric substance of the low-cis-polybutadiene of about 7～35 weight %, styrene butadiene Random copolymer RCP, styrene-butadiene block copolymer or ethylene-propylene-ethylidene norbornene multipolymer etc., and aforementioned polymer is good with the butadiene-based polymkeric substance especially.
Above-mentioned rubbery polymer and the ratio that contains cinnamic vinyl monomer, the containing ratio that should make rubbery polymer in the resulting graft copolymer is 5～30 weight %.
Formed by polymers grafted in the aforementioned rubber polymer, just constitute in the styrenic graft copolymer (A) in order to the monomer of grafted styrenic and form, be vinylbenzene 40 weight % above (but be good with 50～90 weight %), the hard propenyl monomer 60 weight % that vinyl cyanide and/or methyl methacrylate constituted following (being good with 50～10 weight % especially), other vinyl monomer then are advisable with 0～30 weight %; The vinyl cyanide in the propenyl monomer in the above-mentioned hard propenyl monomer and the ratio of methyl methacrylate are vinyl cyanide 0～100 weight %, methyl methacrylate 0～100 weight %; And with regard to hardness and viewpoint attractive in appearance, the scope of above-mentioned methyl methacrylate is advisable with 10～80 weight %; Moreover what spendable herein other vinyl monomers were representative is: alpha-methyl styrene, p-methylstyrene, tribromo-benzene ethene, phenyl maleimide, maleic anhydride, dimethyl fumarate, methacrylic acid, methyl acrylate, N-vinyl pyrrolidone, dimethyl itaconate, hydroxyethyl methylacrylate, Vinylstyrene, dimethacrylate ethyl etc.
Vinyl monomer among the present invention means: vinylbenzene and the undersaturated compound of olefinic that can be free-radical polymerized; Above-mentioned in rubber liquid graft polymerization method manufacturing and styrenic graft copolymer in, comprise the rubber-like particle and the free styrenic of the rubber-like particle that is grafted with styrenic and part.
The median size of above-mentioned rubber-like particle is advisable with 0.5～5.0 μ m from improving the shock strength of extrusion molding article; And be incorporated into the styrenic of rubber-like particle, and the amount (i.e. Tong Cheng percentage of grafting) that is contained in the styrenic in the rubber-like particle, with the rubbery polymer is that benchmark is preferably usually: 50～300 weight % are good with 80～200 weight % especially.
The molecular-weight average of above-mentioned free styrenic (Weight) is preferably 80,000～400,000, and with 100,000～350,000 for better; And rubber-like size of particles selected should be complied with the glossy degree that requires and done appropriate selection, for example: when extruding finished product and wish for high gloss, if the particle diameter of its rubber-like particle is advisable with 0.5～1.3 μ m, and when extruding finished product and wishing for low gloss, serves as appropriate with 1.3～5.0 then.
Polystyrene graftomer (A) also has other preferable manufacture method, it can add in the emulsive rubbery polymer and contains cinnamic monomer, perhaps one side is added a polymeric method (hereinafter to be referred as emulsification graft polymerization method), and the block polymerization of emulsification, the outstanding turbid polymerization of emulsification also are contained in the aforementioned emulsification graft polymerization method certainly.
Be used in the rubbery polymer in the emulsification graft polymerization method, can use the polymkeric substance that contains diene monomers, as: the butadiene-based polymkeric substance of polyhutadiene, perbutan, divinyl-divinyl benzene copolymer, butadiene-acrylic acid butyl ester multipolymer etc., or ethylene-propylene-ethylidene norbornene multipolymer etc., butadiene-based polymkeric substance, be good especially with the butadienecopolymer that contains polyhutadiene and vinylbenzene below the 10 weight % and/or vinyl cyanide; Above-mentioned rubbery polymer is to make with the ratio that contains cinnamic vinyl monomer: the containing ratio of rubbery polymer is 35～85 weight % in the resultant graft copolymer, is good with the ratio of 50～80 weight % especially wherein.
Be used to polymers grafted (just in the aforementioned rubbery polymer, constitute in the styrenic graft copolymer monomer in order to the grafted styrenic) form, be more than the vinylbenzene 40 weight %, be preferably 50～90 weight %, below the hard propenyl monomer 60 weight % that vinyl cyanide and/or methyl methacrylate constituted, be preferably 50～10 weight %, other vinyl monomer is preferably 0～30 weight %; The vinyl cyanide in the above-mentioned hard propenyl monomer and the ratio of methyl methacrylate are vinyl cyanide 0～100 weight %, methyl methacrylate 0～100 weight %; With regard to the viewpoint of rerum natura and price, vinyl cyanide should be in the scope of 70～100 weight %; Representative the having of spendable herein other vinyl monomers: p-methylstyrene, tribromo-benzene ethene, phenyl maleimide, methyl acrylate, glycidyl methacrylate and Vinylstyrene etc.
In the styrenic graft copolymer that emulsification graft polymerization method is produced, comprise: be grafted with styrenic the rubber-like particle and the part the rubber-like particle, with the free styrenic; The median size of above-mentioned rubber-like particle is good from improving the shock strength of extrusion molding article with 0.05～0.4 μ m; Be incorporated into the styrenic of rubber-like particle, and the polymerization scale of construction (percentage of grafting just) that is contained in the polystyrene in the rubber-like particle, be normally 20～100 weight % of benchmark with the rubbery polymer, be good with 25～70 weight % especially wherein; And free styrenic molecular-weight average is preferably 40,000～300,000, is good with 50,000～250,000 especially wherein.
In the aforementioned rubber-like particle when the particle of 0.05～0.1 μ m be that the particle diameter of 0～85 weight %, 0.1～0.2 μ m is the particle diameter of 0～40 weight %, 0.2～0.4 μ m when being 15～100 weight %, rather good from the outward appearance transitivity.
Take out the process of styrenic graft copolymer from the phenylethene grafted copolymer of emulsification shape, use condensing agent to condense usually; Above-mentioned condensing agent is normally: the acids of sulfuric acid, acetic acid as the calcium salt of calcium chloride, as the magnesium salts of magnesium chloride, sal epsom, as aluminium salt of Tai-Ace S 150 etc., is good with magnesium salts wherein.
The graft copolymer that styrenic graft copolymer (A) is come out by the manufacturing of rubber solutions graft polymerization method, with by the prepared graft copolymer of emulsification graft polymerization method the two with suitable proportion and usefulness, from outward appearance, the shock strength of extrusion molding article and prevent aspects such as heat product uneven thickness and Yan Youjia; That is styrenic graft copolymer (G1) is to contain rubbery polymer 5～30 weight % and the average rubber particle diameter is 0.5～5.0 μ m according to the formation ， And that bulk or solution polymerization process carry out rubber particles; In addition, styrenic graft copolymer (G2) contains rubbery polymer 35～85 weight % according to the obtained ， And of emulsion polymerization, and its average rubber particle diameter is 0.05～0.4 μ m; And with respect to the as above polymeric total of both rubber-like, the ratio of the rubbery polymer in aforementioned (G1) is that 3～80 weight %(are good with 5～70 weight % especially wherein).
Employed styrenic (B) is the thermoplastic styrene polymkeric substance of vinylbenzene containing ratio more than 50 weight % among the present invention, for example: polystyrene, styrene-acrylonitrile copolymer, styrene-methylmethacrylate copolymer, styrene-acrylonitrile-methylmethacrylate copolymer, vinylbenzene-phenyl maleimide multipolymer, styrene-acrylonitrile-phenyl maleimide multipolymer, styrene-acrylonitrile-diethylbenzene multipolymer, styrene-maleic anhydride copolymer, make styrene-maleic anhydride copolymer and aniline reaction and multipolymer that imidization forms etc.; Wherein become hard propenyl monomer 50～10 weight % that vinylbenzene 50～90 weight %, vinyl cyanide and/or methyl methacrylates are constituted by set of monomers, other vinyl monomer 0～30 weight % is good; The usage ratio of vinyl cyanide in the hard propenyl monomer and methyl methacrylate is the scope of vinyl cyanide 0～100 weight %, methyl methacrylate 0～100 weight % herein; When the hardness of paying attention to finished product and when attractive in appearance, this methyl methacrylate is good with the scope of 10～90 weight %.
The molecular-weight average of this styrenic (B) is preferably 60,000～400,000, is good with 80,000～300,000 especially; The containing ratio of the rubbery polymer that is contained in total again phenylethylene resin series is preferably 4～30 weight %, is good with 10～25 weight % especially.
Styrenic graft copolymer (A) in total phenylethylene resin series used in the present invention is that the former is that 15～100 weight %, the latter are in the scope of 85～0 weight % with the ratio that cooperates of styrene polymer (B); As if styrenic graft copolymer (A) is below the 15 weight %, then the shock strength deficiency of extrusion molding article.
Being used for PCC function of the present invention is that employed cylinder pollutes in the time of can preventing extrusion moulding, can eliminate the streak on extrusion molding article surface simultaneously; The generation of this kind effect is not know in the past, and is very mysterious phenomenon, and this actuation gear is not being understood at present yet.
The usage quantity of above-mentioned PCC is preferably 0.01～3.0 weight part with respect to total phenylethylene resin series, is good with 0.02～1.5 weight part especially; When the usage quantity of PCC is lower than 0.01 weight part, can't produce aforementioned effect, and if usage quantity is when being higher than 3.0 weight parts, then increase economically unfavorable on foot; The addition means of aforementioned PCC can be sneaked into after the phenylethylene resin series polymerization, and it is without particular limitation also can to add ， And in the polymerization stage of each composition.
Styrene resin composite of the present invention can be used to be used in all purposes that extrusion moulding is used, as is used for: sheet material, film, tubing, special-shaped extrusion pin etc., and be specially adapted to sheet material and film; And aforementioned sheet material, film more can be used in thermoforming, and for example: vacuum forming, extrusion forming, the purposes of above-mentioned heat product for example has: the door nexine of container class, freezer and internal layer case, suitcase, leather trunk etc.
Can add the material that uses other according to need with respect to styrene resin composite of the present invention, have as this kind examples of substances: antioxidant, lubricant, UV light absorber, ultraviolet tranquilizer, charged preventor, weighting agent, reinforcer, tinting material, fire retardant, flame retardant, thermal stabilizer, coupler or other additives etc., wherein:
It is that antioxidant, thioether are materials such as antioxidant, phosphorous antioxidant, sequestrant that antioxidant should use usually as phenol; Representative person has and phenol is antioxidant: (3,5-dual-tert-butyl-4-hydroxyphenyl) tetramethylolmethane four (3-(3 two (the 3-(3-tertiary butyl-5-methyl-4-hydroxyphenyl) propionic esters of propionic acid stearyl, triethylene glycol),, 5-dual-tert-butyl-4-hydroxyphenyl) the 2-tertiary butyl-6-(3-tertiary butyl-2-hydroxyl-6-methylbenzene methyl propionic ester))-4-aminomethyl phenyl acrylate, 2,2 '-methylene-bis (4-methyl-6-tert butyl phenol) and 2,2 '-sulphur two (4-methyl-6-tert butyl phenol) etc.
Thioether is the representative person of antioxidant as the two octadecyl esters of the two propionic acid of sulphur, the two palm esters of the two propionic acid of sulphur, tetramethylolmethane four (β-dodecane methyl-sulphur propionic ester), two octadecyl thioethers etc.
Phosphorous antioxidant is that phosphorous acid ester is an antioxidant, representative person is as: three (nonyl phenyl) phosphorous acid ester, phosphorous acid tridecyl ester, ring-type neopentane tetralyl two (octadecyl phosphorous acid ester), 4,4 '-butylidene two (3-methyl-6-tert butyl phenyl-double tridecyl phosphorous acid ester), three (2, the 4-tert-butyl-phenyl) phosphorous acid ester or four (2, the 4-tert-butyl-phenyl)-4,4 '-biphenylene phosphonic acid ester, 9,10-dihydro-9-oxy-10-phospho phenanthrene-10-oxide compound etc.
And the representative person of sequestrant is: the sodium salt of phenyl phenacyl ketone, ethylene dinitrilotetra-acetic acid etc.
The addition of aforementioned antioxidant is generally with respect to total phenylethylene resin series and adds up to 0.03～1.6 weight %.
The representative person of lubricant is as the compound of metallic soaps such as calcium stearate, Magnesium Stearate, lithium stearate, ethylene distearyl acid amides, methylene distearyl acid amides, palmitic amide, butyl stearate, stearic acid palm ester, polyethylene glycol mono stearate, behenic acid, stearic acid etc., polyethylene wax, montanin wax, carnauba wax, petroleum wax etc.; The addition of above-mentioned lubricant is with respect to 0.03～5.0 weight % of the common total of total vinylite.
The representative person of UV light absorber is: benzene And three azole compounds, benzophenone based compound, and the representative person of ultraviolet tranquilizer is: the resistance amine compound; The addition of aforementioned substances is with respect to total phenylethylene resin series 0.02～2.0 weight % of total amount usually.
The representative person of charged preventor is as the low molecule based compound of tertiary amine based compound, quaternary ammonium salt based compound etc., or the polymeric amide polyethers, as the macromolecular material of the permanent charged preventor of demonstration of epichlorohydrin polymkeric substance.
Weighting agent representative person is as lime carbonate, silicon-dioxide, mica.
The representative person of reinforcer is as: glass fibre, carbon fiber, various brilliant silk class.
Tinting material representative person is as titanium oxide, ferric oxide, carbon black, phthalocyanine pigment.
The representative person of fire retardant or flame retardant is as decabrominated dipheny base ether, tetrabromo-bisphenol, brominated Polystyrene oligomerisation compound, brominated epoxy resin, hexabromocyclododecane, chlorinatedpolyethylene, triphenylphosphate, red phosphorus, weisspiessglanz, aluminium hydroxide, magnesium hydroxide, zinc borate, melamine, silica oil, polytetrafluorethylepowder powder, expansile graphite etc.
The representative person of tranquilizer is as dibutyl tin maleate, alkaline magnalium hydroxyl carbonate etc.
The representative person of coupler is as silane system, phthalate, germanic acid ester based compound.
In styrene resin composite of the present invention for modification, can suitably use the additive of polymer system, the representative person of above-mentioned polymer system additive can give an example as: be the various acrylic acid polymer (being called as processing aid) that improve the extrusion moulding processibility or chlorinated polyethylene resin, polymethylmethacrylate, polycarbonate resin, polyamide resin, poly-terephthalic acid butene esters, olefin polymer, polystyrene thermoplastic elastomer, low-molecular-weight styrene-maleic anhydride copolymer, silica oil, various phase solvations etc.
The median size of the rubber-like particle among the aforementioned the present invention of being recorded in is meant: the thin slice that uses resin combination is taken pictures with the penetrating type electron microscope and is tried to achieve the area of rubber particles, gets the mean value of its area again and gets.
And the molecular-weight average of styrenic of the present invention etc. is meant: the weight average molecular weight that the polystyrene conversion of trying to achieve with gel permeation chromatography is come out.
＜embodiment 〉
Below be described in more detail the present invention according to embodiment, and the % of following Production Example, embodiment and comparative example record and part as long as do not have and specify all is benchmark with weight.
＜Production Example 1〉is by rubber solutions graft polymerization manufactured graftomer
(company of Asahi Chemical Industry makes, commodity are by name: A Sha Pulan 700A) the 11% raw material mixed solution that is constituted mixes with the speed of 24kg/hr by vinylbenzene 67%, vinyl cyanide 22%, polyhutadiene; And ethylene distearyl acid amides 8.0g/hr, benzoyl peroxide and tert-dodecyl mercaptan and aftermentioned reclaim liquid and close and become and feed feeding, with the axe type polymerization tank (volume of a polymerization tank is 45 liters) of supply all the people present polyphone and attached agitator.
The temperature of reaction of aforementioned polymerization tank remains in respectively: 110 ℃ of 97 ℃ of first polymerization tanks, 100 ℃ of second polymerization tanks, 106 ℃ of trimerization grooves and the 4th polymerization tanks; And the toluene in the reaction solution remains in 16% ratio, when the 4th polymerization tank internal reaction liquid inclines when, makes it pass through a devolatilization device removing volatile matter, and obtains granular graftomer; On the other hand, the volatile matter of being removed is condensing as reclaiming liquid with condenser, re-uses and mix with the aforementioned base materials blended liquid phase continuously; Adjust speed of response with this method by the amount of benzoyl peroxide, or adjust melt flow index by the amount of tert-dodecyl mercaptan, and make graft copolymer (composition with vinylbenzene 67%, vinyl cyanide 22%, polyhutadiene 11% with the speed of about 24kg/hr, the melt flow index of above-mentioned polymkeric substance is 0.9, and the average rubber particle diameter is 1.1 μ m, below is considered as G-1).
The aforementioned flow index that dissolves is to measure (g/10min of unit) according to ASTM D-1238conditionG.
The manufacturing of＜Production Example 2〉polyhutadiene emulsion adhesive
100 parts of divinyl
90 parts of deionized waters
2.7 parts of potassium stearates
The homogenizing potassium rosinate is 2.7 parts
1.6 parts of Potassium Persulphates
0.33 part of Dodecyl Mercaptan
According to above-mentioned prescription, under 60 ℃ of stirrings, carry out reaction in 60 hours, under reduced pressure remove at last after the remaining divinyl, make the polyhutadiene latex (below be considered as E-1) of concentration 50% by the water that adds concentration adjustment usefulness.
＜Production Example 3〉is by emulsification graft polymerization manufactured graft copolymer
E-1(solid composition) 60 part
30 parts of vinylbenzene
12 parts of vinyl cyanide
0.22 part of cumene hydroperoxide
1.5 parts of potassium oleates
0.3 part of trisodium phosphate
Dextran 10 .5 part
0.1 part in ferrous sulfate
100 parts in water (containing the water among the E-1)
According to above-mentioned prescription, under 85 ℃ of stirrings, carry out reaction in 5.5 hours, make the graft copolymer latex.
Then, after the heating of aforementioned graft copolymer latex, the aqueous solution of sal epsom 5% that adds necessary amount is to condensing, and filters after it is condensed, dry and obtain graft copolymer powder (below be considered as G-2); Consisting of of aforementioned graft copolymerization zoarium: polyhutadiene 60%, vinylbenzene 29%, vinyl cyanide 11%, its average rubber particle diameter are 0.31 μ m.
The manufacturing of＜Production Example 4〉styrenic
Mix with the speed of 12kg/hr raw material vinylbenzene 73%, vinyl cyanide 27%, again with ethylene distearyl acid amides 3.0g/hr and benzoyl peroxide and tert-dodecyl mercaptan with aftermentioned reclaims liquid and as hello feeding, remain in 108 ℃, 45 liters of volumes and with in the axe type polymerization tank of agitator with temperature in being supplied to, and make the toluene ratio in the reaction solution remain on 15%, and percent polymerization remain on 55%.
After reaction solution is removed volatile component by the devolatilization device, can obtain the particle of styrene-acrylonitrile copolymer; On the other hand, the volatile component of being removed re-used with condensing the mixing with the aforementioned base materials mixed solution continuously as recovery Ye ， And of condenser; Adjusting speed of response with this method by the amount of benzoyl peroxide, or adjust the amount of tert-dodecyl mercaptan, is 1 styrene-acrylonitrile copolymer (vinylbenzene 73%, vinyl cyanide 27% below are considered as S-1) and make melt flow index with the speed of about 12kg/hr.
The manufacturing of＜Production Example 5〉styrenic
Except that the raw material mixed solution consists of vinylbenzene 60%, vinyl cyanide 22%, methyl methacrylate 18%, all the other are with the method for Production Example 4, and making melt flow index with the speed of about 12kg/hr is styrene-acrylonitrile-methylmethacrylate copolymer (vinylbenzene 60%, vinyl cyanide 22%, methyl methacrylate 18% below are considered as S-2) of 1.0.
＜embodiment 1 〉
With 40 parts of 20 parts of 40 parts of G-1, G-2, S-1, PCC0.3 part and weight ratio is (3, the 5-tertiary butyl-4-hydroxyphenyl) propionic acid stearyl 17%, tricresyl phosphite (2, the 4-tert-butyl-phenyl) 0.7 part of the mixed thing (hereinafter to be referred as additive A) of ester 50%, Magnesium Stearate 33% mixes with forcing machine, utilize one to extrude the thin slice that sheet producing device makes its formation thickness 3.0mm again, the aforementioned sheet producing device of extruding is continuously in screw rod, after the single axle extrusion shaping machine of bar footpath 90mm, L/D=28 with four cooling drums.
Extrusion moulding extrude thin slice outward appearance and cylinder contaminative stable after, with visual inspection, the thin slice outward appearance does not have loft fully after 48 hours, and gloss is good and do not have inhomogeneously, the cylinder of moulding is also pollution-free.
To extrude the thin slice incision and make test film, measuring Emhorn (izod) shock strength according to ASTM D-256 is kg-Cm/Cm for 15(unit); In addition, for reference is provided, also measured for the test film that is come out by the injection moulding manufacturing, its Emhorn shock strength is 20.
＜comparative example 1 〉
Except that not using the PCC, all the other are all same with embodiment 1, and extrude the thin slice moulding equally to test.
As a result, a lot of streaks are arranged on thin slice, and gloss uneven, cylinder severe contamination, and the Emhorn shock strength of thin slice is 14, is 20 by the measured Emhorn shock strength of injection moulding.
＜embodiment 2 〉
0.7 part of 30 parts of 70 parts of S-1, G-2 and 0.2 part of PCC, additive A are mixed with forcing machine, and from then on mixture is made and is extruded thin slice with the sheet producing device of extruding that is same as embodiment 1, to test.
The thin slice outward appearance does not have streak fully, gloss is good and it is inhomogeneous not have, cylinder does not pollute yet.
The Emhorn shock strength of thin slice is 7, is 17 by the measured Emhorn shock strength of injection moulding.
＜comparative example 2 〉
Except that not using the PCC, all the other all are same as embodiment 2 uses and extrude the thin slice moulding to test.
A lot of streaks are arranged on thin slice, and gloss uneven, cylinder severe contamination, and the Emhorn shock strength of thin slice is 6, is 16 by the measured Emhorn shock strength of injection moulding.
＜embodiment 3 〉
With the forcing machine blended, from then on mixture is made and is extruded thin slice with the sheet producing device of extruding that is same as embodiment 1, to test with 0.7 part of 10 parts of 90 parts of G-1, G-2 and 0.3 part of PCC, additive A.
The thin slice outward appearance does not have streak fully, gloss is good and it is inhomogeneous not have, cylinder is also pollution-free.
The Emhorn shock strength of thin slice is 18, is 25 by the measured Emhorn shock strength of injection moulding.
＜embodiment 4 〉
0.7 part of 40 parts of 20 parts of 40 parts of G-1, G-2, S-2 and PCC0.3 part, additive A are mixed with forcing machine, make and extrude thin slice with the sheet producing device of extruding that is same as embodiment 1 from this mixture, to test.
The thin slice outward appearance does not have streak fully, gloss is good and it is inhomogeneous not have, cylinder does not pollute yet.
The Emhorn shock strength of thin slice is 15, is 22 by the measured Emhorn shock strength of injection moulding.
＜application examples 1 〉
Utilize the thin slice of extruding that embodiment 1 and 4 makes, carry out the vacuum formability evaluation by vacuum formability basic test method as follows; Result such as table 1, the thin slice vacuum formability of extruding that manufactures with embodiment 1 and 4 promotes significantly.
＜vacuum formability basic test method 〉
Tension test method according to ASTM D-638 is implemented, and the transverse section is healed little and unit elongation represents that more greatly vacuum formability is better.
| Test portion | The transverse section | Unit elongation % |
| Embodiment 1 | Do not have | 103 |
| Embodiment 4 | Do not have | 106 |
＜application examples 2 〉
Utilization is extruded thin slice by what embodiment 4 made, carry out pencil hardness test with the pencil (the famous-brand and high-quality Buddhist nun of Mitsubishi's pencil system commodity) of hardness H after, have no scar and well-tended appearance as before.
Via above explanation, test-results as can be known, the resulting extrusion molding article of styrene resin composite of the present invention has excellent outward appearance and shock strength, and can not pollute cylinder; And when extrusion molding article is made heat product, not only be difficult for causing the phenomenon of uneven thickness, also can obtain the finished product of outward appearance and excellent strength; Therefore, above-mentioned composition of the present invention has the utility value on the industry really very much.
Claims (5)
1, a kind of phenylethylene resin composition for extrusion moulding, it is characterized in that, total phenylethylene resin series 100 weight parts that form by styrenic graft copolymer (A) 15～100 weight % and styrenic (B) 85～0 weight %, with 2,2 '-oxalamide is two-and [ethyl-3-(3,5-di-t-butyl-4-hydroxyphenyl) propionic ester] 0.01～30 weight part constitutes.
2, according to 1 described phenylethylene resin composition for extrusion moulding of claim the, it is characterized in that, the graft phenylethene based polymer that formation styrenic graft copolymer (A) is contained and the monomer of styrenic (B) are formed, all be by vinylbenzene 50～90 weight % with by hard propenyl monomer 50～10 weight % that vinyl cyanide and/or methyl methacrylate constituted, and other vinyl monomers 0～30 weight % is formed.
3, according to claim the 1 or 2 described phenylethylene resin composition for extrusion moulding, it is characterized in that, this styrenic graft copolymer (A) be by:
Styrenic graft copolymer (G1) is that mat bulk or solution polymerization process form rubber particles, and contains 5～30 weight % rubbery polymers that its average rubber particle diameter is 0.5～5.0 μ m; And
Styrenic graft copolymer (G2) is that the mat emulsion polymerization method makes, and for containing 35～85 weight % rubbery polymers, its average rubber particle diameter is 0.05～0.4 μ m;
The rubbery polymer that formation adds up to respect to both, rubbery polymer (G1) is the ratio of 3～80 weight %, and the total amount of the rubbery polymer in total phenylethylene resin series is 4～30 weight %.
4, according to 3 described phenylethylene resin composition for extrusion moulding of claim the, it is characterized in that, the graft phenylethene based polymer that is contained in the styrenic graft copolymer (G1) and at least a the consisting of of styrenic (B): hard propenyl monomer 50～10 weight % that vinylbenzene 50～90 weight %, vinyl cyanide and/or methyl methacrylates are constituted, other vinyl monomer 0～30 weight %, and in the hard propenyl monomer methyl methacrylate to occupy ratio be 10～80 weight %.
5, a kind of manufacture method of extrusion molding article, it is characterized in that, total phenylethylene resin series 100 weight parts that styrenic graft copolymer (A) 15～100 weight % and styrenic (B) 85～0 weight % constituted via forcing machine, and 2,2 '-oxalamide is two-(ethyl-3-(3,5-di-tert-butyl-hydroxy phenyl) propionic ester) and the styrene resin composite that constituted of 0.01～3.0 weight part carries out extrusion moulding and makes finished product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN92112708A CN1049230C (en) | 1992-11-03 | 1992-11-03 | Phenylethylene resin composition for extrusion moulding |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN92112708A CN1049230C (en) | 1992-11-03 | 1992-11-03 | Phenylethylene resin composition for extrusion moulding |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1086524A true CN1086524A (en) | 1994-05-11 |
| CN1049230C CN1049230C (en) | 2000-02-09 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN92112708A Expired - Fee Related CN1049230C (en) | 1992-11-03 | 1992-11-03 | Phenylethylene resin composition for extrusion moulding |
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| Country | Link |
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| CN (1) | CN1049230C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102241861A (en) * | 2010-05-12 | 2011-11-16 | 上海英科实业有限公司 | Flame retardant polystyrene foamed hard wood-imitating material and preparation method thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4877826A (en) * | 1988-10-05 | 1989-10-31 | The Dow Chemical Company | Weatherable styrenic polymer blend comprising polyalkylene glycol |
| JP2726918B2 (en) * | 1989-07-03 | 1998-03-11 | 三菱レイヨン株式会社 | Impact resistant thermoplastic resin composition |
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1992
- 1992-11-03 CN CN92112708A patent/CN1049230C/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102241861A (en) * | 2010-05-12 | 2011-11-16 | 上海英科实业有限公司 | Flame retardant polystyrene foamed hard wood-imitating material and preparation method thereof |
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| Publication number | Publication date |
|---|---|
| CN1049230C (en) | 2000-02-09 |
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