CN1172130A - Phenylethylene resin composition - Google Patents
Phenylethylene resin composition Download PDFInfo
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- CN1172130A CN1172130A CN 97104249 CN97104249A CN1172130A CN 1172130 A CN1172130 A CN 1172130A CN 97104249 CN97104249 CN 97104249 CN 97104249 A CN97104249 A CN 97104249A CN 1172130 A CN1172130 A CN 1172130A
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Abstract
The present invention discloses a kind of styrene series resin composite, including: (I) 100 weight portions of styrene series resin, including 10-100 wt% of rubber-like graft copolymer A, of which each 100 weight portions is made up by using 40-90 weight portions of rubber and 10-60 portions of monomer mixture through graft polymerization, said monomer mixture is formed from styrene series monomer, acrylonitrile series monomer and other required monomer which can be copolymerized, and 0-90 wt% of styrene series copolymer B; (II) 0.2-10.0 weight portions of heavy benzoate compound. Said composite can provide the resin product possessing good linear bonding strength, low water content and low paint-absorptivity.
Description
The invention relates to a kind of novel styrene resin composite.Specific it, the invention relates to and a kind ofly in phenylethylene resin series, add an amount of benzoic acid ester compounds, and then promote joint line intensity, low-water-content and the low styrene resin composite of inhaling character such as lacquer property of this resin.
Phenylethylene resin series generally is meant with rubber like graft copolymer and is scattered in styrene based copolymer and the impact resistant resin composition that makes.In practical application, be make phenylethylene resin series experience various machine-shaping methods and provide desire the moulding commodity.This machine-shaping method comprises the time processing as ejection formation and extrusion moulding etc., and the secondary processing of vacuum forming, application and plating etc.Wherein, with regard to regard to the product of secondary processing such as application, plating, the stress that the moulding product bear in the joint line place is the highest, breaks so often be easy to the generation of joint line place.In addition, for the moulding product, if the suction of resin lacquer property height then easily absorbs lacquer in the joint line place, this will make product be easy to break.In addition, if the water ratio height of resin then is easy to moulding product surface and produces " silver bar " (silver streak), also influence product appearance.Therefore, have high joint line intensity, the low phenylethylene resin series of inhaling lacquer property and low-water-content be for industry required.
Known improvement phenylethylene resin series after application is inhaled the method for lacquer property, as the announcement of the 2nd～No. 284906 institute of Japanese kokai publication hei, is that the acrylonitrile content with the raising resin is a solution.Just, this method will cause the flavescence of resin background color, and the tool water ratio increases and shortcoming such as viscosity increased in addition.Japanese Patent Publication is for the 60th～No. 28311 to contain 32～37 weight % vinyl cyanide in the graft copolymer side chain that is grafted on the rubbery polymer, in with graft copolymer blended vinylbenzene and acrylonitrile copolymer matrix in contain 20～37 weight % vinyl cyanide, and the phenylethylene resin series that in the free state multipolymer, contains 22～35 weight % vinyl cyanide, though the resin of the good coating of tool can be provided, but the close outstanding property of the application of this resin, particularly absorptive improvement, still imperfect.In addition, be known in the phenylethylene resin series crystalline polymers such as adding polymeric amide, inhale the lacquer property, but the gained synthetic resin is still had shortcomings such as dimensional stability and processing forming be not good with modified resin.In fact, previous prior art teaching or advise the scheme of moulding product joint line intensity such as any enhancement application, plating not.And so far, industry still is devoted to the research and development of the phenylethylene resin series of tool advantageous property combination.
The development that the present invention promptly does at the demand.Particular words it, main purpose of the present invention is intended to provide a novel styrene resin composite, it can exempt the shortcoming of above-mentioned known phenylethylene resin series, and provide moulding product joint line intensity good, inhale the desirable product that the lacquer property is low and water ratio is low.
The technical scheme that the present invention takes for the above-mentioned purpose of realization is summarised as: a kind of styrene resin composite, be in per 100 parts of heavy benzol vinylites, to add 0.2～10.0 part of heavy benzol formic acid ester compound, and provide have good moulding product joint line intensity, low-water-content and the low lacquer property of inhaling, and still keep the novel styrene resin composite of the original rerum natura equilibrated of phenylethylene resin series.
It is to comprise that the present invention has good moulding product joint line intensity, low-water-content and the low styrene resin composite of inhaling lacquer property:
(I) 100 parts of heavy benzol vinylites, it comprises
10～100 weight % rubber like graft copolymer A, per 100 parts heavily this graft copolymer be to get by the heavy monomer mixture graft polymerizations of 40～90 parts of heavy rubber and 10～60 parts, this monomer mixture is made up of styrenic monomers, acrylic monomer and other copolymerizable monomer of optionally selecting for use; And
0～90 weight % styrene based copolymer B;
(II) 0.2～10.0 part of heavy benzol formic acid ester compound.
Composition of the present invention is applicable to any shaping operation method.
According to rubber like graft copolymer of the present invention, its per 100 parts of reclosing graft copolymer A are got by the heavy monomer mixture graft polymerizations of 40～90 parts of heavy rubber and 10～60 parts, this graft polymerization procedure can be independent bulk, solution, suspension or emulsion polymerization method, also can be the combination of these polymerizations, as combinations such as emulsification-bulk or bulk-suspension polymerizations.Rubber like graft copolymer A of the present invention preferably makes with emulsion polymerization method, block polymerization or solution polymerization process, and is wherein good especially with emulsion polymerization method.
The rubber like graft copolymer A that makes with emulsion polymerization method be with 40～90 parts of weights (dry weight) butadiene-based rubber emulsion and 10～60 parts heavy monomer mixture graft polymerizations and weight average particle diameter is 0.05～0.8 micron a rubber like graft copolymer A emulsion, again through condense, dehydration, drying and other steps and powder shape rubber like graft copolymer A.The graft copolymer (being referred to as the emulsification graft copolymer) that should make with emulsion polymerization method generally is to contain 15～85 weight % rubber, preferable 45～80 weight % that contain.This butadiene-based rubber emulsion then contain 60～100 weight % conjugate diene monomers and 0～40 weight % unit polymerization of unsaturated monomers and homopolymer or multipolymer.This conjugate diene monomer is the following general formula of tool:
Wherein R is H, CH
3Or Cl, and this unit unsaturated monomer can be styrenic monomers, acrylic monomer or (methyl) acrylic ester monomer.Illustrate, the contained polymkeric substance of this butadiene-based rubber emulsion can be, but is not limited to, butadiene-styrene copolymer, perbutan, divinyl-methylmethacrylate copolymer, and isoprene-butyl acrylate copolymer etc.This butadiene-based rubber emulsion, remove the polymer emulsion can directly become 0.05～0.8 micron of weight average particle diameter by above-mentioned monomer polymerization, in addition can be via earlier with the small particle size rubber latex of synthetic 0.05～0.18 micron of monomer pre-polymerization, obtain the rubber latex of 0.2～0.8 micron of particle diameter with rubber hypertrophy method commonly used again.The loose method of this rubber comprises as adding organic acid, metal-salt or containing the chemical loose method that carboxylic acid group's polymer coagulant (as butyl acrylate-Sipacril 2739OF) waits, with the loose method of churned mechanically machinery, reaches freezing loose method etc.This emulsification graft copolymer can have the unimodal formula size distribution of 0.05～0.8 micron of the flat footpath of weight particle diameter, or the double-peak type size distribution of 0.05～0.18 micron and 0.2～0.8 micron.
Carrying out the preparation of rubber like graft copolymer A with bulk or solution polymerization process, is earlier diene series rubber to be dissolved in monomer mixture and/or the solvent, makes it carry out graft polymerization reaction again and gets.In between the reaction period, can optionally add chain-transfer agent, with the controlling polymers molecular weight as uncle-dodecyl mercaptans.This graft polymerization reaction can carry out in one or more reactive tank, is preferably in carrying out with in the still type reactive tank of strong mixer.Can be in order to the solvent that carries out this bulk or solution graft copolymerization polyreaction, but be not limited to toluene, dimethylbenzene, ethylbenzene, methylethylketone, ethyl acetate etc.Above-mentioned diene series rubber, preferable is polyhutadiene, polyisoprene and sovprene.Wherein, polyhutadiene has the branch of high-cis and low cis.Typical case's high-cis divinyl is to contain cis/vinyl weight composition of 94～98%/1～50%, and all the other are transconfiguration, and tool 20～120 mooney viscosities and 100,000～800,000 molecular weight.Typical case's low-cis-polybutadiene then contains cis/vinyl weight composition of 20～40%/1～20%, and all the other are transconfiguration, and tool 20～120 mooney viscosities.Also be suitable for the rubber for preparing rubber like graft copolymer A of the present invention with bulk or solution polymerization process acrylic-nitrile rubber, styrene/butadiene rubbers (being SBR) or its mixture are arranged.Wherein, styrene/butadiene rubbers can be vinylbenzene and divinyl Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock, triblock copolymer, random copolymers or starlike (star type) multipolymer, and preferable vinylbenzene is 5: 95 to 80: 20 with the content ratio of divinyl, and the preferred molecular weight scope is 50,000～600,000.Above-mentionedly be applicable to that rubber of the present invention is preferable with divinyl rubber and styrene/butadiene rubbers, wherein again with divinyl rubber for better.
Of the present invention with bulk or solution polymerization and rubber like graft copolymer A (being called for short bulk or solution graft copolymerization thing), be to have 0.6～10 micron weight average particle diameter, be preferably 1.0～7.0 microns, and contain 4～25 weight % rubber, be preferably 4～15 weight %.
Rubber like graft copolymer A of the present invention removes and can use above-mentioned emulsification graft copolymer or bulk or solution graft copolymerization beyond the region of objective existence separately, also can merge to use this two, to form following bimodal or three peak formula size distribution:
Double-peak type: 0.2～0.8 micron median size (emulsification), with
0.6～10.0 microns median sizes (bulk or solution), or,
0.05～0.18 micron median size (emulsification), with
0.6～10.0 microns median sizes (bulk or solution).
Three peak formulas: 0.05～0.18 micron median size (emulsification),
0.2～0.8 micron median size (emulsification), with
0.6～10.0 microns median sizes (bulk or solution).
The weight average particle diameter of above-mentioned rubber particles is with perosmic anhydride (OsO
4) with after the resin dyeing, take a picture with transmission electron microscope again, get shine in the photograph about 1000 of rubber dispersed particle, survey its particle diameter, try to achieve with following formula again:
Wherein, Di is a particle diameter, and Ni is the rubber particles number of tool particle diameter Di.
In order to the monomer mixture of preparation rubber like graft copolymer A of the present invention, be to contain styrenic monomers, acrylic monomer and other copolymerizable monomer of optionally selecting for use.This monomer mixture is preferably and contains 50～90 weight % styrenic monomers, 10～50 weight % acrylic monomers and 0～40 other copolymerizable monomer of weight %.Wherein, this styrenic monomers can be vinylbenzene or is substituted vinylbenzene, this be substituted vinylbenzene can be alpha-methyl styrene, p-methylstyrene, right-chloro-styrene, neighbour-chloro-styrene ,-chloro-styrene, right-t-butyl styrene, 2,5-dichlorostyrene, 3,4-dichlorostyrene, 2,4,6-tribromo-benzene ethene, 2,5-Dowspray 9 or Vinylstyrene etc.Preferable styrenic monomers is vinylbenzene or alpha-methyl styrene.This acrylic monomer can be the vinyl cyanide that is substituted of vinyl cyanide or methacrylonitrile, is preferable with vinyl cyanide.These other copolymerizable monomer then can be (methyl) acrylic ester monomer, maleimide is monomer, vinylformic acid, Maleic Acid, Anhydrous and glycolmethacrylate.Should have by the monomeric example of (methyl) acrylic ester, but be not limited to, methyl acrylate, butyl acrylate, ethyl propenoate, methyl methacrylate, Jia Jibingxisuanyizhi, propyl methacrylate, butyl methacrylate, cyclohexyl methacrylate, Dimethylaminoethyl Methacrylate, methacrylic acid dodecane ester, methacrylic acid 2-hydroxyl ethyl ester, glycidyl methacrylate, methacrylic ester benzene methyl, and methacrylic acid glycol ester are preferably methyl methacrylate.This maleimide is that monomeric example has, but be not limited to, N-methyl maleimide, N-sec.-propyl maleimide, the N-butyl maleimide, N-hexyl maleimide, N-octyl group maleimide, N-dodecyl maleimide, N-cyclohexyl maleimide, N-phenylmaleimide, N-2,3-tolyl maleimide, N-2,4-tolyl maleimide, N-2,3-ethylbenzene base maleimide, N-2,4-ethylbenzene base maleimide, N-2,3-butylbenzene base maleimide, N-2,4-butylbenzene base maleimide, N-2,6-tolyl maleimide, N-2,3-chloro-phenyl-maleimide, N-2,4-chloro-phenyl-maleimide, N-2,3-bromophenyl Malaysia imide, N-2,4-bromophenyl Malaysia imide is preferably N-phenylmaleimide.
According to styrene based copolymer B of the present invention, its per 100 parts of heavy benzol vinyl copolymers are to be got by 45～90 parts of heavy benzol vinyl monomers, 10～50 parts heavy acrylic monomers and 0～40 part of other copolymerizable monomer polymerization of weight.Wherein, this styrenic monomers, acrylic monomer and other copolymerizable monomer are all as in order to the definien of institute in the monomer mixture for preparing rubber like graft copolymer A of the present invention.This styrene based copolymer B can get via the above-mentioned monomer of bulk, solution, suspension or emulsion polymerization, is preferably bulk and solution polymerization.This styrene based copolymer B has 60,000 to 140,000 weight average molecular weight, and 30,000 to 70,000 number molecular-weight average.Molecular weight is too high, can cause inhaling the lacquer phenomenon, crosses the low shock-resistance that then diminishes.
Benzoic ether (benzoate) compound that is applicable to styrene resin composite of the present invention can be, but be not limited to, propylene glycol dibenzoate (dipropylene glycol dibenzoate), neopentyl glycol dibenzoate (neopentyl glycol dibenzoate), glycerol three benzoic ethers (glycerol tribenzoate), isoamyl tetrol four benzoic ethers (pentaerythritoltetrabenzoate), polypropylene glycol dibenzoate (polypropylene glycol dibenzoate), and composition thereof.This benzoic acid ester compounds is preferable with 0.2～10 part of weight of per 100 parts of heavy benzol vinylites in the storage of styrene resin composite of the present invention, is more preferred from 0.5～5 part of weight.Too high benzoic acid ester compounds content will impair the softening temperature and the shock-resistance of resin itself, and low excessively benzoic ether content then can't provide suction lacquer property, the water ratio desiring to ask to make up with joint line intensity.
Can be via general fusion method, use as fusion devices such as simple helix or duplex forcing machine, fusion cylinder or inner blenders, the above-mentioned rubber like graft copolymer A of fusion, styrene based copolymer B and benzoic acid ester compounds, water ratio of the present invention is low, the low and good styrene resin composite of moulding product joint line intensity of suction lacquer property and get.
Styrene resin composite of the present invention can contain other materials according to need in addition.For example: antioxidant, plasticizer, processing aid, lubricant, UV light absorber, ultra-violet stabilizer, charged preventor, weighting agent, reinforcer, colorant, incombustible agent, difficult combustion auxiliary agent, thermo-stabilizer, thermo-color prevent agent, coupler or other additives etc.These additives can be in polyreaction, after the polyreaction, condense preceding or extrude in the process of mixing and add.
Be applicable to that examples of antioxidants of the present invention has, but be not limited to that phenol is that antioxidant, thioether are materials such as antioxidant, phosphorous antioxidant and chelating.Wherein: phenol is that the addition of antioxidant is good with 0.005～2.0 weight %, its representative instance has: octadecyl-3-(3,5-two-tertiary butyl-4-hydroxyphenyl)-propionic ester, triethylene glycol-two (3-(the 3-tertiary butyl-5-methyl-4-hydroxyphenyl) propionic ester), four (stretch methyl-3-(3,5-two-tertiary butyl-4-hydroxyphenyl) methane propionic ester), the 2-tertiary butyl-6-(the 3-tertiary butyl-2-hydroxyl-6-methylbenzene methyl)-4-aminomethyl phenyl acrylate, 2,2 '-stretch methyl-two (4-methyl-6-tert butyl phenol), 2,2 '-thiobis (4-methyl-6-tert butyl phenol), 2,2 '-sulfo--two stretches ethyl-two (3-(3,5-two-uncle tributyl-4-hydroxyphenyl) propionic esters).Thioether is that the addition of antioxidant is good with 0.005～2.0 weight %, and its representative instance has: distearyl thiodipropionic acid ester, two palmityl thiodipropionic acid esters, five tetrahydroxybutanes-four-(β-ten dimethyl-sulphur propionic ester), two octadecyl thioethers etc.It is antioxidant or phosphoric acid ester antioxidant that phosphorous antioxidant can be phosphorous acid ester, its addition is good with 0.015～2.0 weight %, representative instance has: three (nonyl phenyl) phosphorous acid ester, dodecyl phosphorous acid 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, four (2, the 4-tert-butyl-phenyl)-4,4 '-stretch xenyl phosphoric acid ester, 9,10-dihydro-9-oxy-10-phosphoric acid phenanthrene-10-oxygen support etc.The addition of chelating is good with 0.001～2.0 weight %, and its representative instance has: the sodium salt of phenyl phenacyl ketone and diethylamine four acetic acid etc.The total addition level of above-mentioned antioxidant is generally 0.03～2.0 weight % of styrene resin composite.
The example that is applicable to lubricant of the present invention has, but be not limited to, metallic soaps such as calcium stearate, Magnesium Stearate, lithium stearate, stretch ethyl distearyl acid amides, stretch methyl distearyl acid amides, compounds such as palmitic amide, butyl stearate, stearic acid palm ester, poly-propionic acid alcohol tristearate, behenic acid, stearic acid, and polyethylene wax, octocosoic acid wax, carnauba wax (Carnuba wax), petroleum wax etc.The addition of lubricant is generally 0.03～5.0 weight % of total styrene resin composite.
Can in the present composition, add processing aid, with extrusion moulding and the hot formability that improves resin as methyl methacrylate system.
The use of UV light absorber and ultra-violet stabilizer, then can improve resin the irradiation of thermotolerance, UV resistant the rerum natura deterioration of the variable color that produces or resin.Wherein, the UV light absorber that is suitable for has, but be not limited to, benzotriazole based compound, benzophenone based compound, cyanogen acrylic acid series compound, and the ultra-violet stabilizer that is suitable for has, but is not limited to, the retardance amine compound, to merge use retardance amine is that ultra-violet stabilizer and cyanogen acrylic acid series UV light absorber are good, for example: the Uvinul 4050H of BASF AG (0.02～1.0 weight %)/Uvinul 3035 (0.02～1.0 weight %).The total addition level of above-mentioned substance is generally 0.02～20 weight % of styrene resin composite.
Being suitable for to the example of charged preventor of the present invention has, but be not limited to, the low molecule based compound of tertiary amine based compound, quarternary ammonium salt based compound etc., or polymeric amide polyethers, epichlorohydrin polymer etc. are the macromolecular material of permanent charged preventing property.
Be suitable for to the representative instance of weighting agent of the present invention and include, but not limited to lime carbonate, tripoli and mica etc.
The representative instance that is applicable to the reinforcer of the present composition has: glass fibre, carbon fiber and various brilliant silk (whisker) class.The representative instance of colorant has: titanium oxide, ferric oxide, graphite and phthalocyanine pigment etc.The representative instance of incombustible agent or difficult combustion auxiliary agent has: decabrominated dipheny base ether, tetrabromo-bisphenol, brominated Polystyrene oligopolymer, brominated epoxy resin, hexabromocyclododecane, chlorinatedpolyethylene, triphenyl phosphoric acid, red phosphorus, weisspiessglanz, aluminium hydroxide, magnesium hydroxide, zinc borate, trimeric cyanamide, isocyanide amine salt, silica powder, polytetrafluorethylepowder powder and expansile graphite etc.The representative instance of stablizer has: dibutyl tin maleate, alkali magnalium hydroxyl carbonate etc.And thermo-color prevents that agent from can be low-molecular-weight vinylbenzene-Maleic Acid, Anhydrous multipolymer, and its addition is generally 0.1～1.0 weight % of styrene resin composite of the present invention.The representative instance of coupler is: silane system, phthalate and germanic acid ester based compound etc.
Be modification styrene-series resin compositions of the present invention, can suitably use the polymkeric substance additive, the rubber-modified phenylethylene resin series (for example acrylonitrile-butadiene-styrene resin) that for example adopts emulsion polymerization method mode in addition to make, rubber (for example EPDM) beyond the butadiene-based rubber, through the AES of butyl acrylate rubber modification resin, phenylethylene resin series such as AAS resin, Maleic Acid, Anhydrous-styrol copolymer, vinylbenzene-maleimide copolymer, the maleimide amine content surpasses styrene-acrylonitrile-Maleic Acid, Anhydrous multipolymer of 40 weight %, styrene-acrylonitrile-Maleic Acid, Anhydrous multipolymer through the aniline imidization, no grafted bridge formation rubber (as acrylonitrile-butadiene rubber), ethylene chloride resin, the poly-phenyl ether of stretching, polymethylmethacrylate, polycarbonate resin, polyamide resin, poly-terephthalic acid butene esters, the polystyrene thermoplastic elastomer, and various phase solvations etc., its usage quantity is 3～200 parts of weights of per 100 parts of styrene resin composites heavily of the present invention.
Further describe the present invention in detail with following embodiment and physical property measurement.The composition unless specifically stated otherwise of following composition, otherwise all represent with weight part.
Following examples only are in order to detailed description the present invention, but scope of the present invention is not exceeded with these embodiment.
＜preparation example 〉
＜preparation example 1〉rubber like graft copolymer A-1
The composition umber
1,3-butadiene 95.0
Vinyl cyanide 5.0
Potassium persulfate solution (1%) 15.0
Trisodium phosphate 3.0
Potassium oleate 1.5
Distilled water 140.0
Uncle-lauryl mercaptan 0.2
Make above-mentioned the prescription in 65 ℃ of reactions 12 hours, the synthetic rubber latex of 0.1 micron of about 40%, the weight average particle diameter of transformation efficiency 94%, solids content.
In addition, the polymer coagulant that contains the carboxylic acid group in addition with following composition manufacturing:
The composition umber
N-ethyl propenoate 85
Vinylformic acid 15
Uncle-lauryl mercaptan 0.3
Potassium oleate 2.0
Dioctyl sodium sulphosuccinate 1.0
Isopropyl benzene hydrogen peroxidase 10 .4
Sodium formaldehyde sulphoxylate 0.3
Distilled water 200
Make above-mentioned the prescription in 75 ℃ of reactions 5 hours, transformation efficiency is about 95%, pH value 6.0 contains carboxylic acid group's polymer coagulant.
Then, contain loose 100 parts of (dry weight) above-mentioned synthetic rubber latex of polymer coagulant of carboxylic acid group with 3 parts (dry weights), the pH value of gained enlarged rubber emulsion is 8.5, and weight average particle diameter is 0.31 micron.
Again this enlarged rubber emulsion is carried out graft polymerization reaction with following prescription, and makes rubber like graft copolymer A-1:
The composition umber
Enlarged rubber emulsion (0.31 micron) (dry weight) 100.0
Vinylbenzene 25.0
Vinyl cyanide 8.3
Potassium oleate 1.2
Uncle-lauryl mercaptan 0.2
Isopropyl benzene hydrogen peroxidase 10 .5
Copperas solution (0.2%) 3.0
Formaldehyde sodium sulfoxylate solution (10%) 3.0
Ethylene dinitrilotetra-acetic acid solution (0.25%) 20.0
Distilled water 200.0
With calcium chloride (CaCl
2) the gained grafting rubbers emulsion of condensing, make rubber like graft copolymer A-1, its rubber content 75 weight %, 0.31 micron of weight average particle diameter.
＜preparation example 2〉rubber like graft copolymer A-2
Make in＜preparation example 1〉the synthetic rubber latex (0.1 micron of rubber weight average particle diameter) that makes directly and the graft polymerization reaction that carries out of following table prescription, make rubber like graft copolymer A-2.
The composition umber
Synthetic rubber latex (0.1 micron) (dry weight) 100.0
Vinylbenzene 32.4
Vinyl cyanide 12.6
Potassium oleate 1.6
Uncle-lauryl mercaptan 0.27
Isopropyl benzene hydrogen peroxidase 10 .67
Copperas solution (0.2%) 4.0
Formaldehyde sodium sulfoxylate solution (10%) 4.0
Ethylene dinitrilotetra-acetic acid solution (0.25%) 27.0
Distilled water 200.0
With calcium chloride (CaCl
2) the gained grafting rubbers emulsion of condensing, make rubber like graft copolymer, A-2,, its rubber content 69 weight %, 0.1 micron of weight average particle diameter.
＜preparation example 3〉rubber like graft copolymer A-3
With 0.1 part of uncle-lauryl mercaptan and 0.07 part of benzoyl peroxide as initiator, (company of Asahi Chemical Industry produces with 6.6 parts of polyhutadiene, trade(brand)name Asadene 55AS) is dissolved in fully in 74.4 parts of vinylbenzene, 25.6 parts of vinyl cyanide and the 30 parts of ethylbenzene, to form feedstock solution.Afterwards, it is that temperature of reaction is 100 ℃ in 45 liters first reactor that feedstock solution is sent into volume continuously, and configuration is provided with the screw mixer of refrigeration cycle pipe in the reactor, and stir speed (S.S.) is 300rpm.To take out continuously and send in regular turn in second reactor through the mixture behind first reactor reaction, the device of this second reactor is identical with first reactor, the transformation efficiency of mixture of waiting reaches at 60% o'clock, the mixture taking-up is sent in the devolatilization device, remove unreacted monomer and volatile matter, and then it is extruded granulation, make rubber like graft copolymer A-3, its rubber content 11 weight %, weight average particle diameter is 1.1 microns.
Testing method
Obtained product in the example is all tested with following method, to assess its rerum natura:
Joint line intensity: (referring to figure below) is that 50 millimeters * 40 millimeters * 1/8 cun and periphery are that 150 millimeters * 70 millimeters * 1/8 cun ring-type rectangular parallelepiped forming mould upper right side is established one and penetrated the pan feeding sluice gate in central authorities, when raw material is in pan feeding sluice gate feeding ring-type forming mould, can form a joint line away from pan feeding sluice gate end in the mould lower left.On molding, form the joint line place and cut out middle testing plate (70 millimeters * 10 millimeters * 1/8 cun) with a lateral junction zygonema, and the shock strength of testing its non-notch (no notch), with kilogram centimetre/centimetre expression.That is this test is according to ASTM D-256
Water content: the particles that makes placed in 100 ℃ of baking boxs go through 4 hours, carry out hot loss of weight analysis.
Emhorn shock strength (Izod): according to the test of ASTM D-256 regulation, with kilogram centimetre/centimetre expression.
Softening temperature: according to the test of ASTM D-1525 regulation, with a ℃ expression.
Suction lacquer property: in making particles, add 1.0 parts heavy black look mothers (Cabot, trade(brand)name UN-2014) and thorough mixing, get 15 centimeters * 7 centimeters * 0.3 centimeter moulding product with the ejaculator ejaculation.The moulding product are immersed methyl alcohol and methylethylketone (methyl alcohol: take out after mixing solutions methylethylketone=78: 22) is gone through 2 seconds.If moulding product surface is albinism, then represent resin tool suction lacquer property, represent with " * ": if no albinism is then represented not tool suction lacquer property of resin, represent,, then represent with " △ " if be slight albinism with " zero ".
＜embodiment 〉
Example 1
Utilize 18.7 weight %＜preparation examples 1〉prepared rubber like graft copolymer A-1 and 81.3 weight % styrene based copolymer composition-styrene resins.Wherein, this styrene based copolymer has 83,000 weight average molecular weight Mw, 41,000 number average molecular mass Mn and contain 28 weight % vinyl cyanide and 72 weight % vinylbenzene.The rubber content of styrene resin is 20 weight %.In 100 parts of styrene resins, add 2.0 parts of propylene glycol dibenzoates, form a homogeneous melt.Push this melt thing and cut into particulate state into strips, and test its rerum natura, the results are shown in table one.
Example 2
Heavily cover example 1 step, but replace 2.0 parts of propylene glycol dibenzoates with 1.0 parts of neopentyl glycol dibenzoate.
Example 3
Heavily cover example 1 step, but replace 2.0 parts of propylene glycol dibenzoates with 3.0 parts of glycerol three benzoic ethers.
Example 4
Heavily cover example 1 step, but styrene resin contains 32.0 weight % rubber like graft copolymer A, its rubber like graft copolymer A-1 and A-2 by equivalent forms.
Example 5
Heavily cover example 2 steps, but it is the rubber like graft copolymer A of 57.6 weight % that styrene resin contains the total amount that comprises 21.3 weight % rubber like graft copolymer A-1 and 36.3 weight % rubber like graft copolymer A-3, and adds 2.0 parts of neopentyl glycol dibenzoate.
Example 6
Heavily cover example 3 steps, but styrene resin contains and comprises 11.4 weight % rubber like graft copolymer A-1,17.1 the total amount of weight % rubber like graft copolymer A-2 and 25.9 weight % rubber like graft copolymer A-3 is the rubber like graft copolymer A of 54.4 weight %, and adds 2.0 parts of glycerol three benzoic ethers.
Example 7
Heavily cover example 1 step, but the contained styrene based copolymer of styrene resin is to have 121,000 weight average molecular weights and 60,000 number molecular-weight average.
Example 8
Heavily cover example 1 step, but the contained styrene based copolymer of styrene resin is to have 65,000 weight average molecular weights and 32,000 number molecular-weight average.
Comparative example 1
Heavily cover example 1 step, but do not add any benzoic acid ester compounds.
Comparative example 2
Heavily cover example 1 step, but only add 0.1 part of propylene glycol dibenzoate.
Comparative example 3
Heavily cover example 2 steps, but the consumption of neopentyl glycol dibenzoate is 15.0 parts.
(referring to back subordinate list one) shown by the result of table one example 1～6 with comparative example 1～3, the present invention adds benzoic acid ester compounds in styrene resin really can effectively promote the joint line intensity of resin, and gratifying joint line intensity, suction lacquer property and water content properties of combination are provided.In addition, by the result of comparative example 2 and 3 as can be known, too high Yu low excessively benzoic ether consumption if not shock-resistance and softening temperature are caused disadvantageous effect, is can impair joint line intensity to coat with lacquer property with suction.In addition, by the result of example 7 and 8 as can be known, the contained styrene based copolymer of styrene resin is preferably has 60,000 to 140,000 weight average molecular weights and 30,000 to 70,000 number molecular-weight average, molecular weight is higher, and product is inhaled the increase of lacquer property, molecular weight is low excessively, then can't provide satisfied and impact strength.
Table one
| Example number | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | |||
| Phenylethylene resin series (I) | Rubber like graft copolymer (A) | Rubber like graft copolymer (A-1) rubber like graft copolymer (A-2) rubber like graft copolymer (A-3) | Weight % | ????18.7 | ????18.7 | ????18.7 | ????16 | ????21.3 |
| Weight % | ????16 | |||||||
| Weight % | ????36.3 | |||||||
| Styrene based copolymer (B) | Content weight average molecular weight (Mw) number molecular-weight average (Mn) vinyl cyanide vinylbenzene | Weight % | ????81.3 | ????81.3 | ????81.3 | ????68 | ????42.4 | |
| ??×10000 | ????8.3 | ????8.3 | ????8.3 | ????8.3 | ????8.3 | |||
| ??×10000 | ????4.1 | ????4.1 | ????4.1 | ????4.1 | ????4.1 | |||
| Weight % | ????28 | ????28 | ????28 | ????28 | ????28 | |||
| Weight % | ????72 | ????72 | ????72 | ????72 | ????72 | |||
| Benzoic acid ester compounds (II) | The propylene glycol dibenzoate | Weight part | ????2.0 | ????2.0 | ||||
| Neopentyl glycol dibenzoate | Weight part | ????1.0 | ????2.0 | |||||
| Glycerol three benzoic ethers | Weight part | ????3.0 | ||||||
| The rubber content of phenylethylene resin series | Weight % | ????20 | ????20 | ????20 | ????20 | ????20 | ||
| Joint line intensity | Kilogram centimetre/centimetre | ????30.0 | ????29.5 | ????31.1 | ????30.6 | ????30.2 | ||
| Water content | ????％ | ????0.25 | ????0.26 | ????0.22 | ????0.26 | ????0.25 | ||
| Inhale lacquer property | ????○ | ????○ | ????○ | ????○ | ????○ | |||
| Izod | Kilogram centimetre/centimetre | ????25.0 | ????26.0 | ????24.2 | ????26.2 | ????24.8 | ||
| Softening temperature | ????℃ | ????105 | ????105.5 | ????104.2 | ????104.5 | ????106.2 | ||
Table one (continuing)
| Example number | Example 6 | Example 7 | Example 8 | |||||
| Phenylethylene resin series (I) | Rubber like graft copolymer (A) | Rubber like graft copolymer (A-1) rubber like graft copolymer (A-2) rubber like graft copolymer (A-3) | Weight % | ????11.4 | ????18.7 | ????18.7 | ||
| Weight % | ????17.1 | |||||||
| Weight % | ????25.9 | |||||||
| Styrene based copolymer (B) | Content weight average molecular weight (Mw) number molecular-weight average (Mn) vinyl cyanide vinylbenzene | Weight % | ????45.6 | ????81.3 | ????81.3 | |||
| ??×10000 | ????8.3 | ????12.1 | ????6.5 | |||||
| ??×10000 | ????4.1 | ????6.0 | ????3.2 | |||||
| Weight % | ????28 | ????28 | ????28 | |||||
| Weight % | ????72 | ????72 | ????72 | |||||
| Benzoic acid ester compounds (II) | The propylene glycol dibenzoate | Weight part | ????2.0 | ????2.0 | ||||
| Neopentyl glycol dibenzoate | Weight part | |||||||
| Glycerol three benzoic ethers | Weight part | ????2.0 | ||||||
| The rubber content of phenylethylene resin series | Weight % | ????20 | ????20 | ????20 | ||||
| Joint line intensity | Kilogram centimetre/centimetre | ????31.5 | ????25.2 | ????22.6 | ||||
| Water content | ???％ | ????0.24 | ????0.25 | ????0.28 | ||||
| Inhale lacquer property | ????○ | ????△ | ????○ | |||||
| Izod | Kilogram centimetre/centimetre | ????26.6 | ????32.6 | ????18.2 | ||||
| Softening temperature | ???℃ | ????105.9 | ????106.8 | ????103.2 | ||||
Table one (continuing)
| Example number | Comparative example 1 | Comparative example 2 | Comparative example 3 | |||||
| Phenylethylene resin series (I) | Rubber like graft copolymer (A) | Rubber like graft copolymer (A-1) rubber like graft copolymer (A-2) rubber like graft copolymer (A-3) | Weight % | ????18.7 | ????18.7 | ????18.7 | ||
| Weight % | ||||||||
| Weight % | ||||||||
| Styrene based copolymer (B) | Content weight average molecular weight (Mw) number molecular-weight average (Mn) vinyl cyanide vinylbenzene | Weight % | ????81.3 | ????81.3 | ????81.3 | |||
| ??×10000 | ????8.3 | ????8.3 | ????8.3 | |||||
| ??×10000 | ????4.1 | ????4.1 | ????4.1 | |||||
| Weight % | ????28 | ????28 | ????28 | |||||
| Weight % | ????72 | ????72 | ????72 | |||||
| Benzoic acid ester compounds (II) | The propylene glycol dibenzoate | Weight part | ????0.1 | |||||
| Neopentyl glycol dibenzoate | Weight part | ????15.0 | ||||||
| Glycerol three benzoic ethers | Weight part | |||||||
| The rubber content of phenylethylene resin series | Weight % | ????20 | ????20 | ????20 | ||||
| Joint line intensity | Kilogram centimetre/centimetre | ????12.3 | ????13.6 | ????23.5 | ||||
| Water content | ????％ | ????0.45 | ????0.43 | ????0.30 | ||||
| Inhale lacquer property | ????× | ????× | ????○ | |||||
| Izod | Kilogram centimetre/centimetre | ????25.2 | ????25.0 | ????9.2 | ||||
| Softening temperature | ????℃ | ????106 | ????105.8 | ????98.2 | ||||
Claims (12)
1, a kind of styrene resin composite is characterized in that comprising:
(I) 100 parts of heavy benzol vinylites, it comprises
10～100 weight % rubber like graft copolymer A, per 100 parts heavily this graft copolymer be to get by the heavy monomer mixture graft polymerizations of 40～90 parts of heavy rubber and 10～60 parts, this monomer mixture is by styrenic monomers, acrylic monomer, reach other copolymerizable monomer of optionally selecting for use and form, and
0～90 weight % styrene based copolymer B;
(II) 0.2～10.0 part of heavy benzol formic acid ester compound.
2, composition according to claim 1 is characterized in that: this rubber like graft copolymer A gets with bulk, solution, suspension and/or emulsion polymerization method polymerization.
3, composition according to claim 2 is characterized in that: this rubber like graft copolymer A be with the emulsion polymerization method polymerization be the best.
4, composition according to claim 3 is characterized in that: this rubber like graft copolymer A is the unimodal formula size distribution with 0.05～0.8 micron of weight average particle diameter.
5, composition according to claim 3 is characterized in that: this rubber like graft copolymer A has 0.05～0.18 micron of weight average particle diameter and 0.2～0.8 micron double-peak type size distribution.
6, composition according to claim 2 is characterized in that: with bulk or solution polymerization process polymerization and must have 0.6～10 micron weight average particle diameter by this rubber like graft copolymer A.
7, composition according to claim 2 is characterized in that: this rubber like graft copolymer A is made up of the bulk or the solution graft copolymerization thing of 0.6～10 micron of the emulsification graft copolymer with 0.05～0.18 micron of weight average particle diameter and double-peak type size distribution of 0.2～0.8 micron and weight average particle diameter.
8, composition according to claim 1, it is characterized in that: should connect the monomer mixture of weighing copolymer A in order to preparation rubber-like is to contain 50～90 weight % styrenic monomers, 10～50 weight % acrylic monomers and 0～40 other copolymerizable monomer of weight %.
9, composition according to claim 1 is characterized in that: per 100 parts heavily this styrene based copolymer B be by 45～90 parts of heavy benzol vinyl monomers, 10～50 parts heavy acrylic monomers and 0～40 part of other copolymerizable monomer polymerization of weight and get.
10, composition according to claim 1 is characterized in that: this styrene based copolymer B is the number molecular-weight average with 60,000 to 140,000 weight average molecular weights and 30,000 to 70,000.
11, composition according to claim 1 is characterized in that: the consumption of this benzoic acid ester compounds is that 0.5～5 part of per 100 parts of heavy benzol vinylite are heavily for better.
12, composition according to claim 1 is characterized in that: this benzoic acid ester compounds is to be selected from the group that is made up of propylene glycol dibenzoate, neopentyl glycol dibenzoate, glycerol three benzoic ethers, isoamyl tetrol four benzoic ethers, polypropylene glycol dibenzoate and composition thereof.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 97104249 CN1172130A (en) | 1997-05-07 | 1997-05-07 | Phenylethylene resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 97104249 CN1172130A (en) | 1997-05-07 | 1997-05-07 | Phenylethylene resin composition |
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| Publication Number | Publication Date |
|---|---|
| CN1172130A true CN1172130A (en) | 1998-02-04 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 97104249 Pending CN1172130A (en) | 1997-05-07 | 1997-05-07 | Phenylethylene resin composition |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7122251B2 (en) | 2001-05-31 | 2006-10-17 | Mitsubishi Rayon Co., Ltd. | Resin composition for plating substrate and resin molding using the same, and metal plated parts |
| CN1330694C (en) * | 2000-09-21 | 2007-08-08 | 兰爱克谢斯德国有限责任公司 | Moulding material with dibenzoate additive |
| CN111868118A (en) * | 2018-12-10 | 2020-10-30 | 株式会社Lg化学 | Method for preparing thermoplastic copolymer, thermoplastic copolymer prepared therefrom, and thermoplastic resin composition comprising the same |
-
1997
- 1997-05-07 CN CN 97104249 patent/CN1172130A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1330694C (en) * | 2000-09-21 | 2007-08-08 | 兰爱克谢斯德国有限责任公司 | Moulding material with dibenzoate additive |
| US7122251B2 (en) | 2001-05-31 | 2006-10-17 | Mitsubishi Rayon Co., Ltd. | Resin composition for plating substrate and resin molding using the same, and metal plated parts |
| CN111868118A (en) * | 2018-12-10 | 2020-10-30 | 株式会社Lg化学 | Method for preparing thermoplastic copolymer, thermoplastic copolymer prepared therefrom, and thermoplastic resin composition comprising the same |
| US11603421B2 (en) | 2018-12-10 | 2023-03-14 | Lg Chem, Ltd. | Method for preparing thermoplastic copolymer, thermoplastic copolymer prepared therefrom, and thermoplastic resin composition including the same |
| CN111868118B (en) * | 2018-12-10 | 2023-06-30 | 株式会社Lg化学 | Process for producing thermoplastic copolymer, thermoplastic copolymer produced thereby and thermoplastic resin composition comprising the same |
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