CN102653582A - Rubber modified polystyrene resin for electroplating - Google Patents
Rubber modified polystyrene resin for electroplating Download PDFInfo
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Abstract
The invention relates to rubber modified polystyrene resin for electroplating, which mainly comprises the following components in percentage by weight: 10 to 35 percent of nitrile ethylene monomer unit (m-1), 10 to 30 percent of conjugated dienes monomer unit (m-2), 45 to 75 percent of styrene monomer unit (m-3) and 0 to 20 percent of other copolymerization ethylene monomer unit (m-4), wherein the monomer unit (m-1), the monomer unit (m-2), the monomer unit (m-3) and the monomer unit (m-4) are totally 100 percent; moreover, the 100 percent of rubber modified polystyrene resin compound also comprises 20 to 40 weight percent of insoluble acetone; the rubber modified polystyrene resin compound comprises rubber particles (d-1) with occlusion particle structures and rubber particles (d-2) without the occlusion particle structures; the average grafting thickness of the rubber particles (d-1) is 100 to 280 dusts; a ratio of the sectional area of the rubber particles (d-1) to that of the rubber particles (d-2) is 1.1 to 14; and the average particle size of the rubber particles (d-1) is 0.35 to 0.8 mu m.
Description
Technical field
The present invention relates to a kind of modified polystyrene resin, particularly have good plating working properties and the good rubber modified polystyrene of rerum natura is a resin about a kind of.
Background technology
Rubber modified polystyrene is a resin owing to have good processing forming and physical strength, therefore on purposes such as electrical appliance, vehicle portion article, general cargo, often is used to the various goods of moulding.Wherein, acrylonitrile-butadiene-styrene (ABS) based copolymer (ABS resin) is after moulding, owing to have good plating processibility, therefore, in the galvanized occasion of needs, Automobile Products for example often are used to make in light weight and to have the various goods of metal appearance.
ABS resin moulding article normally earlier with acidic etching liquid etching moulding article, make moulding article surface form fine hole, hole when pre-electroplating treatment, electroplate afterwards again.Because the moulding article surface after the etching has hole, fine hole, therefore, when the moulding article are covered the last layer metal level by plating, can have good adherence between metal level and moulding article surface, make the metal level difficult drop-off.
Yet existing ABS resin moulding article are when electroplating, and following problem is run into by regular meeting:
(1) electroforming article outward appearance has what is called " pin hole " bad order of (pin hole), have a strong impact on former should have attractive in appearance of electroforming article.
(2) etching of ABS resin is not good, and the adherence between electrolytic coating and moulding article surface is not enough, comes off easily.
(3) through after etching, the electroplating processes, the intensity of ABS resin moulding article significantly reduces, and its range of application is restricted.
For improving the problems referred to above, one of method is to improve the shock strength of ABS resin, makes its moulding article after etching, plating, still can have enough shock strengths.TW322488 Taiwan patent announcement discloses a kind of styrene-series resin compositions of modified rubber; This resin combination has good shock strength, gloss homogeneity and thermostability; But this resin combination is applied to electroplate last time; Though find to have good shock strength, the pin hole bad order is serious, the plating adherence is also not good.Therefore, the ABS that has good physical properties and plating character simultaneously is a resin, is still problem to be solved.
Summary of the invention
Main purpose of the present invention is to provide a kind of and has good plating working properties, and the good rubber modified polystyrene of rerum natura is a resin.
For satisfying aforementioned goal of the invention; The present invention is that a kind of rubber modified polystyrene of electroplating usefulness is a resin; Contain nitrilation vinyl monomer unit (m-1) 10～35 weight %; Conjugate diene monomeric unit (m-2) 10～30 weight %; Styrenic monomers unit (m-3) 45～75 weight % and other copolymerizable vinyl monomer unit (m-4) 0～20 weight %, and this monomeric unit (m-1), this monomeric unit (m-2), this monomeric unit (m-3) and this monomeric unit (m-4) add up to 100 weight %; Again,
Based on this rubber modified polystyrene is resin 100 weight %, and this rubber modified polystyrene is insoluble part of acetone that resin contains 20～40 weight %; Wherein,
This rubber modified polystyrene is that resin is observed with transmission electron microscope, comprises rubber particles (d-1) with occlusion particle (occlusion) structure and the rubber particles (d-2) that does not have the occlusion particle configuration;
This average grafting thickness with rubber particles (d-1) of occlusion particle configuration is 100～280 dusts
This ratio with rubber particles (d-1) cross-sectional area of occlusion particle configuration and rubber particles (d-2) cross-sectional area that this does not have the occlusion particle configuration is 1.1～14;
This median size with rubber particles (d-1) of occlusion particle configuration is 0.35～0.8 μ m.
The rubber modified polystyrene of electroplating usefulness as previously mentioned is a resin; Wherein, to be selected from acrylic ester monomeric unit, methacrylate ester monomeric unit and maleimide be the group that monomeric unit is formed in these other copolymerizable vinyl monomer unit (m-4).
The rubber modified polystyrene of electroplating usefulness as previously mentioned is a resin; Wherein, these other copolymerizable vinyl monomer unit (m-4) is selected from the group that MMA MONOMER unit, Butyl Acrylate Monomer unit and N-phenylmaleimide monomeric unit are formed.
Below one by one each composition of the present invention is done detailed explanation:
Above-mentioned nitrilation vinyl monomer unit (m-1), conjugate diene monomeric unit (m-2), styrenic monomers unit (m-3), other copolymerizable vinyl monomer unit (m-4); After referring to nitrilation vinyl monomer, conjugate diene monomer, styrenic monomers, other copolymerizable vinyl monomer copolymerizations respectively, be the tectonic element in the resin in this rubber modified polystyrene.
The concrete example of aforementioned nitrilation vinyl monomer has: vinyl cyanide, Alpha-Methyl vinyl cyanide etc. wherein, are preferable with vinyl cyanide.Promptly forming rubber modified polystyrene of the present invention after the aforementioned concrete example polymerization of nitrilation vinyl monomer respectively is the concrete example of the nitrilation vinyl monomer unit (m-1) in the resin.Rubber modified polystyrene of the present invention is that resin contains nitrilation vinyl monomer unit (m-1) 10～35 weight %, is preferably 15～30 weight %, is more preferred from 18～27 weight %.When nitrilation vinyl monomer unit (m-1) was lower than 10 weight %, the shock strength of polystyrene resin was not enough; When nitrilation vinyl monomer unit (m-1) was higher than 35 weight %, the form and aspect of polystyrene resin were not good.
The monomeric concrete example of aforementioned conjugate diene has: 1,3-butadiene, isoprene, 1,3-pentadiene, 1,3-hexadiene, 2,4-hexadiene, 2; 3-dimethyl--1,3-butadiene, 2-ethyl-1,3-butadiene etc., in addition; The various difference shape conjugated diene compounds of carbon number between 4～7 also can use, wherein, and with 1,3-butadiene, isoprene, 1; The 3-pentadiene is preferable, is more preferred from 1,3-butadiene, and each concrete example can use separately or two or more mixing is used.Promptly form the concrete example that rubber modified polystyrene of the present invention is a conjugate diene monomeric unit (m-2) in the resin respectively after the monomeric aforementioned concrete example polymerization of conjugate diene.Rubber modified polystyrene of the present invention is that resin contains conjugate diene monomeric unit (m-2) 10～30 weight %, is preferably 12～25 weight %, is more preferred from 14～20 weight %.When conjugate diene monomeric unit (m-2) was lower than 10 weight %, the shock strength of polystyrene resin was not enough; When being higher than 30 weight %, the plating character of polystyrene resin is not good.
The concrete example of aforementioned styrenic monomers has: vinylbenzene, alpha-methyl styrene, p-methylstyrene, Vinyl toluene (vinyl toluene), vinyl naphthalene, vinyl ethylbenzene; Vinyl-dimethyl benzene etc.; Wherein, With vinylbenzene, alpha-methyl styrene, p-methylstyrene is preferable, is more preferred from vinylbenzene, and each concrete example can use separately or two or more mixing is used.Promptly forming rubber modified polystyrene of the present invention after the aforementioned concrete example polymerization of styrenic monomers respectively is the concrete example of the styrenic monomers unit (m-3) in the resin.Rubber modified polystyrene of the present invention is that resin contains styrenic monomers unit (m-3) 45～75 weight %, is preferably 50～72 weight %, is more preferred from 55～68 weight %.When styrenic monomers unit (m-3) was lower than 45 weight %, the processing forming of polystyrene resin was not good, and when being higher than 75 weight %, the shock strength of polystyrene resin is not enough, and the plating adherence is not good.
Aforementioned other copolymerizable vinyl monomers refer to have vinyl; And can with the monomer of nitrilation vinyl monomer, conjugate diene monomer or styrenic monomers copolymerization, object lesson as: acrylic ester monomer, methacrylate ester monomer, maleimide are monomer etc.
The monomeric concrete example of aforementioned acrylic ester has: methyl acrylate, ethyl propenoate, isopropyl acrylate, Bing Xisuandingzhi, polyethyleneglycol diacrylate etc., and wherein, preferable with Bing Xisuandingzhi.
The monomeric concrete example of aforementioned methacrylate ester has: TEB 3K, Jia Jibingxisuanyizhi, propyl methacrylate, NSC 20956, methylacrylic acid benzene methyl, N-Hexyl methacrylate, cyclohexyl methacrylate, methylacrylic acid dodecyl ester, 2-hydroxyethyl methacrylate, GMA, dimethylaminoethyl methacrylate, ethylene dimethacrylate (ethylene dimethacrylate), dimethacrylate peopentyl ester (neopentyl dimethacrylate) etc.; Wherein, preferable with TEB 3K, NSC 20956.
Maleimide is that monomeric concrete example has: maleimide, N-methyl maleimide, N-phenylmaleimide etc.
Except that the aforesaid propylene acid esters is that monomer, methacrylate ester monomer, maleimide are the monomer, the concrete example of the vinyl monomer that other are copolymerizable also can be acrylic monomer (as: vinylformic acid, methylacrylic acid), Maleic Acid, Anhydrous, anhydrous methyl-maleic acid, anhydrous methylfumaric acid, fumaric acid (fumaric acid), methylene-succinic acid unsaturated carboxylic acid based compounds such as (itaconic acid) with and esterification be monomer (for example dimethyl fumarate, dibutyl itaconate) etc.
Each concrete example of above-mentioned other copolymerizable vinyl monomers can use separately or two or more mixing is used.Promptly forming rubber modified polystyrene of the present invention after the aforementioned concrete example polymerization of the vinyl monomer that other are copolymerizable respectively is the concrete example of other copolymerizable vinyl monomer unit (m-4) in the resin.
Rubber modified polystyrene of the present invention be resin during fabrication; Aforementioned other the copolymerizable vinyl monomers of alternative adding; And make other copolymerizable vinyl monomer unit (m-4) content be lower than 20 weight %, in order to avoid influence rerum naturas such as plating character that rubber modified polystyrene is a resin and shock strength.For the purpose of simplified illustration; In the part content of following explanation; Rubber modified polystyrene is that resin only comprises monomeric unit (m-1), monomeric unit (m-2) and monomeric unit monomeric units such as (m-3), but also can further contain other copolymerizable vinyl monomer unit (m-4) in case of necessity.
Rubber modified polystyrene of the present invention is a resin, and preferable tying up to conjugate diene monomeric unit (m-2) is that the unitary rubber-like conjugate diene polymers of main composition exists down, copolymerization nitrilation vinyl monomer and styrenic monomers and get.Polymerization methods can be the polymerization methods of bulk/solution polymerization, emulsion polymerization or bulk-conventions such as outstanding turbid polymerization.
When rubber modified polystyrene of the present invention is that resin is when adopting bulk/solution polymerization; Usually can earlier aforementioned conjugate diene polymers be dissolved in styrenic monomers or be dissolved in styrenic monomers and the formed mixture of a part of nitrilation vinyl monomer (or being dissolved in styrenic monomers, solvent and the formed mixture of a part of nitrilation vinyl monomer), add all the other monomers mixing again and carry out polyreaction.In the reaction process; The nitrilation vinyl monomer and the styrenic monomers copolymerization of a part form not grafted nitrilation ethene system-styrene based copolymer; The nitrilation vinyl monomer and the styrenic monomers of another part then graft on the conjugate diene polymers; Form rubber particles, and be scattered in aforementioned not grafted nitrilation ethene system-styrene based copolymer.
When rubber modified polystyrene of the present invention is resin employing emulsion polymerization, normally nitrilation vinyl monomer and styrenic monomers are added in the emulsion of conjugate diene polymers, carry out graft copolymerization.In the reaction process; Most of nitrilation vinyl monomer and styrenic monomers can graft on the conjugate diene polymers emulsified particle in the emulsion; Form rubber particles, few part nitrilation vinyl monomer and styrenic monomers then can form not grafted nitrilation ethene system-polystyrene co-polymer.Can be behind the emulsion polymerization via the engineering of condensing, wash, dewater of convention; And mix extrusion with nitrilation ethene system-styrene based copolymer of making separately; The rubber particles of emulsification graft copolymerization gained is scattered in nitrilation ethene system-styrene based copolymer, is resin to obtain rubber modified polystyrene.
The present invention's rubber modified polystyrene is that resin system contains two kinds of heteroid rubber particles, a kind of rubber particles (d-1) for having the occlusion particle configuration, another kind of rubber particles (d-2) for not having the occlusion particle configuration.Wherein, Rubber particles (d-1) with occlusion particle (occlusion) structure means in the rubber particles inner packet and is covered with granular nitrilation ethene system-styrene based copolymer, and the particle diameter of this granular nitrilation ethene system-styrene based copolymer is more than or equal to 0.05 μ m person; The rubber particles (d-2) that does not have an occlusion particle configuration means that rubber particles inside do not contain granular nitrilation ethene system-styrene based copolymer, or the particle diameter of contained granular nitrilation ethene system-styrene based copolymer is less than 0.05 μ m person.
Observe with transmission electron microscope, the ratio of cross-sectional area summation and the cross-sectional area summation of the rubber particles (d-2) that does not have the occlusion particle configuration with rubber particles (d-1) of occlusion particle configuration is 1.1～14, is preferably 2.5～9.When aforementioned cross-sectional area ratio less than 1 the time, the plating outward appearance of rubber modified polystyrene based resin molded articles, to electroplate adherence not good; Greater than 14 o'clock, the moulding article shock strength after the plating was not enough or the plating adherence is not good.Have the occlusion particle configuration rubber particles (d-1) can by block/or solution polymerization, emulsion polymerization or bulk-modes such as outstanding turbid polymerization make, wherein, again with block/or the solution polymerization mode be preferable.Preferable can the making of rubber particles (d-2) that does not have the occlusion particle configuration by the emulsion polymerization mode.Rubber modified polystyrene of the present invention is that resin can mix two kinds of resins and gets; First kind of resin contains the rubber particles (d-1) with occlusion particle configuration; Second kind of resin contains the rubber particles (d-2) with occlusion particle configuration; The suitable blending ratio of two kinds of resins of adjustment can be with the ratio control of cross-sectional area in aforementioned range.
The present invention does not have the rubber particles (d-2) of occlusion particle configuration; Its preferable median size is that 0.15～0.5 μ m can add interfacial agent, chain-transfer agent, initiator, nitrilation vinyl monomer and styrenic monomers etc. in the conjugate diene polymers emulsion, carries out the emulsification graft copolymerization and gets.The conjugate diene polymers emulsion can be monomeric homopolymer of above-mentioned conjugate diene or multipolymer; For example; The emulsion of polyhutadiene, TR 301, sovprene, BS, perbutan, divinyl-methylmethacrylate copolymer, isoprene-butyl acrylate copolymer etc. or its mixture is preferably polyhutadiene emulsion or BS emulsion.Can be become weight average particle diameter during manufacturing by the monomer polymerization of aforementioned polymer is the conjugate diene polymers particle of 0.15～0.5 μ m; Or aggregate into the low particle size emulsion that weight average particle diameter is 0.05～0.12 μ m earlier, again with the loose method of rubber of convention will aforementioned 0.05～0.12 μ m the loose one-tenth of small particle size particle median size be the conjugate diene polymers particle of 0.15～0.5 μ m.The loose method of aforementioned rubber can be the loose method of additive, freezing loose method or the loose method of churned mechanically machinery.Can add acidic substance such as acetic anhydride, hydrogenchloride, sulfuric acid in the loose method of additive; Or salt-base substances such as sodium-chlor, Repone K, calcium chloride, magnesium chloride, or (methyl) acrylic acid series-(methyl) propenoate based copolymer (for example methylacrylic acid-butyl acrylate copolymer) etc. contains the polymer coagulant of acidic group.
Employed conjugate diene polymers emulsion dry weight is preferably 50～85 weight parts in the above-mentioned emulsification graft copolymerization; Nitrilation vinyl monomer and styrenic monomers are 15～50 weight parts; Weight with respect to nitrilation vinyl monomer and styrenic monomers adds up to 100 weight %, and the used initiator addition of polymerization is preferably 0.01～5 weight %, is more preferred from 0.1～3 weight %; And, can add a spot of chain-transfer agent in order suitably to control the molecular weight of graft copolymer.Aforementioned initiator can be superoxide or azo cpd.Suitable superoxide initiator is for example: water-soluble initiators such as alkali metal peroxide, persulphate, perborate, peracetate, percarbonate, hydrogen peroxide, or two tributyl superoxide (di-tert-butyl-peroxide), BPO (benzoyl peroxide), the two dodecanoyl (1auroyl peroxide) of peroxo-, the two stearyls (o1eyl peroxide) of peroxo-, hydrogen phosphide cumene (cumene hydroperoxide), tributyl hydrogen peroxide (tert-butyl hydroperoxide).Suitable azo cpd is for example: Diisopropyl azodicarboxylate (2; 2 '-azodi (isobutyronitrile)), AMBN (2; 2 '-azodi (2-methylbutyronitrile)), azo two cyclohexanenitriles (1,1 '-azodi (hexahydrobenzonitrile)) etc.Aforementioned chain-transfer agent can be mercaptan, halogenide, terpenes or other have the compound of chain transfer character, for example n-dodecyl mercaptan, the 3rd (dodecyl) mercaptan, α-Jia Jibenyixierjuwu etc.Aforementioned initiator and chain-transfer agent all can use one or more to mix respectively separately and use.
Above-mentioned emulsification graft copolymerization can be stirred down in the environment of 20～100 ℃ of temperature and the existence of normal pressure rare gas element and carried out, and also can rare gas element be forced into 0～100psig.Reaction times is generally 2～10 hours, is preferably 4～9 hours.
After the emulsification graft copolymerization is accomplished; Can in emulsion, add condensing agent condenses; And remove through the washing engineering that impurity, dehydration engineering reduce water cut, dry engineering is removed residual water-content and made the powdered resin that contains the rubber particles (d-2) with occlusion particle configuration, and be thermoplastic resin fusion such as the resin extrusion of mixing further optionally with this powdered resin and nitrilation ethene system-styrene based copolymer, other rubber modified polystyrenes.When observing with transmission electron microscope, the median size that does not have the rubber particles (d-2) of occlusion particle configuration is preferable with 0.05～0.5 μ m.The present invention is in mixing by the prepared rubber particles (d-2) that does not have the occlusion particle configuration of different ingredients in case of necessity.
The contained rubber particles with occlusion particle configuration (d-1) in the resin of the present invention, its median size is 0.35～0.8 μ m, is preferably 0.4～0.7 μ m.When median size during less than 0.35 μ m, the rubber modified polystyrene based resin molded articles shock strength after the plating is not enough; When median size during greater than 0.8 μ m, the plating outward appearance of rubber modified polystyrene based resin molded articles, to electroplate adherence not good.In addition; Average grafting thickness with rubber particles (d-1) of occlusion particle configuration is 100～280 dusts
when being lower than 100 dusts, and the plating adherence of rubber modified polystyrene based resin molded articles is not good; During greater than 280 dusts, melting viscosity is too high, and rubber modified polystyrene is the processibility variation of resin.
Rubber particles (d-1) with occlusion particle configuration can be made by bulk/solution polymerization, emulsion polymerization or bulk-modes such as outstanding turbid polymerization, wherein, is preferable with bulk/solution polymerization mode again.The emulsion polymerization embodiment is identical with the emulsification graft copolymerization of the above-mentioned rubber particles (d-2) that does not have an occlusion particle configuration; But during polymerization before adding initiator; Need in the conjugate diene emulsion, to add a part of nitrilation vinyl monomer and/or styrenic monomers; Make conjugate diene polymers absorb a part of nitrilation vinyl monomer and/or styrenic monomers earlier, be beneficial to form the occlusion particle configuration.Bulk/solution polymerization then can be implemented in the following manner: nitrilation vinyl monomer and 0～30 parts by weight of styrene that conjugate diene polymers 4～27 weight parts are dissolved in 63～96 weight parts are the formed solution of monomer, and under the agitation as appropriate situation, react.When the transformation efficiency of polyreaction reaches 40～90 weight %; Remove fugitive constituents such as unreacted monomer and solvent via the devolatilization engineering; Can make a rubber modified polystyrene is resin; It contains the rubber particles with occlusion particle configuration (d-1) of median size 0.35～0.8 μ m, and the average grafting thickness of this rubber particles (d-1) is 100～280 dusts.The concrete example of aforementioned conjugate diene polymers has: the mixture of polyhutadiene, TR 301, sovprene, BS, perbutan, divinyl-methylmethacrylate copolymer, isoprene-butyl acrylate copolymer etc. or several aforementioned concrete examples is preferably polyhutadiene, styrene/butadiene copolymers or its mixture.
Above-mentioned bulk/solution polymerization can use flow reactor to implement; Flow reactor can be columnar flow (plug flow) formula reactor drum, complete mixing reactor (CSTR) or contain the pipe reactor etc. of silent oscillation electric hybrid module; Wherein, be preferable with column flow reactor, complete mixing reactor.Previous reaction device quantity can be one or more, also can be also with different types of reactor drum more than 2 kinds or 2 kinds.Spendable initiator for example during bulk/solution polymerization: acyl peroxide class (diacyl peroxides), peroxyesters (peroxyesters), ketal peroxide class (peroxyketals), peroxycarbonates class (peroxy (di) carbonates), azo compound etc.
In order to obtain the rubber particles (d-1) that the present invention has the occlusion particle configuration; In above-mentioned bulk/solution polymerization; Need to cooperate the rubber content in the polymeric solution; Select suitable initiator, and suitably controlled polymerization temperature, reactor drum stirring velocity, reaction residence time etc., so that prepared rubber particles (d-1) median size with occlusion particle configuration is that 0.35～0.8 μ m and average grafting thickness are 100～280 dusts.Generally speaking, the superoxide initiator has preferable grafting efficiency than azo compound, can be in order to promote grafting thickness; Polymerization temperature is lower, the reaction residence time, the occlusion particle configuration of gained rubber particles was comparatively careful when longer; When the reactor drum stirring velocity was very fast, the median size of gained rubber particles was less; When rubber content was higher, viscosity was higher relatively, under the same process condition, had less median size usually.Correlation technique personage can adjust aforementioned condition, to make the rubber particles (d-1) that the present invention has the occlusion particle configuration.The present invention is in mixing by the prepared rubber particles (d-1) with occlusion particle configuration of different ingredients in case of necessity.
Rubber modified polystyrene based on 100 weight % is a resin; Rubber modified polystyrene of the present invention is that the acetone of resin is 20～40 weight % for insoluble part; When insoluble part of acetone is lower than 20 weight %; Rubber modified polystyrene is that the shock strength of resin is not good, and plating character is not good when insoluble part of acetone is higher than 20 weight %.The present invention can suitably adjust the rubber particles of creating conditions, having the occlusion particle configuration (d-1) of the rubber particles (d-1) with occlusion particle configuration and not have the ratio of the rubber particles (d-2) of occlusion particle configuration according to aforesaid method; Make the gained resin except that the condition that satisfies above-mentioned grafting thickness, particle diameter and cross-sectional area ratio, also making acetone simultaneously is 20～40 weight % for insoluble part.
Rubber modified polystyrene of the present invention is a resin; Can further add various additives in case of necessity; Like inhibitor, lubricant, UV light absorber, UV stabilizer, charged preventor, tinting material etc., the interpolation time can in rubber modified polystyrene be the polymerization stage of resin add or polymerization after add with the extrusion type that mixes.Rubber modified polystyrene based on 100 weight parts is a resin, and the aforementioned additive consumption is generally below 6 weight parts.Except aforementioned additive; Also can optionally add other additives; As: incombustible agent, impact modifying agent (for example Zylox (silicone rubber), (methyl) acrylic ester-butadiene-based-styrene based copolymer (MBS) etc.) etc.; Rubber modified polystyrene based on 100 weight parts is a resin, and additive amount such as incombustible agent, impact modifying agent are generally below 20 weight parts.
Embodiment
The present invention will be described further with regard to following examples, but will be appreciated that, following embodiment is merely the usefulness that illustrates, and should not be interpreted as the restriction that the present invention is implemented.
The obtained rubber modified polystyrene of the embodiment of the invention and comparative example is that the analysis transitivity evaluation method of resin is following.
One, nitrilation vinyl monomer unit (m-1), conjugate diene monomeric unit (m-2), styrenic monomers unit (m-3), other copolymerizable vinyl monomer unit (m-4) content analysis
Rubber modified polystyrene is the monomeric unit (m-1)～(m-4) in the resin, measures with the fourier-transform infrared line spectrometer (Fourier Transform Infrared Spectrometer) of Nicolet corporate system, model Nexus 470.
Two, acetone is analyzed for insoluble part
17.5m1 adding the 0.5g rubber modified polystyrene in the acetone is resin; Sway 6hr (hour); Add again toluene 17.5ml continue to sway to the next day, then isolate insoluble part, then dry with insoluble part with centrifugation; The insoluble part weight of scale, and to converse rubber modified polystyrene be the insoluble part of content (unit: weight %) of acetone in the resin.
Three, the average grafting thickness that has the rubber particles (d-1) of occlusion particle configuration is analyzed
With rubber modified polystyrene be resin with acetone solution, and removed solvable part the separation with centrifugation.The gained rubber particles is scattered in the epoxy resin solid host; Make host and rubber particles thorough mixing; The stiffening agent thorough mixing that adds the epoxy resin solid again, and the heating make its sclerosis, be finely disseminated test film in the resin to obtain rubber particles at epoxy.
The gained test film is with perosmic anhydride (OsO
4) dyeing, make the section of 90nm thickness with slicing machine, take a picture with 60,000 times transmission electron microscope again.After the perosmic anhydride dyeing, the conjugated diene monomer units part of rubber particles is dyed black with epoxy resin, and the outer grafting part of rubber particles then can not be colored and be white.With the rubber particles with occlusion particle configuration (d-1) that shines in the photograph more than 25; With image processing software (the analysis software of Soft Imaging System company; Version 3 .00) area of the outer grafting part of analytical calculation rubber particles is that the rubber particles girth after the outer grafting part of A, deduction is L, and the grafting thickness (t) of this rubber particles is t=(A/L).Try to achieve the average grafting thickness (unit: dust) of rubber particles again with occlusion particle configuration according to following calculating formula (I).
Calculating formula (I) as previously mentioned, wherein, D
iBe the diameter of i rubber particles, its value for aforementioned image software 1 °, 2 °, 3 ° ..., analyze the maximum diameter of this rubber particles on 180 ° the direction respectively, get the numerical value of arithmetic mean gained then; N is the sampling sum that has the rubber particles (d-1) of occlusion particle configuration in the analytic process, n>=25.
Four, rubber particles (d-1) cross-sectional area that has the occlusion particle configuration is analyzed with rubber particles (d-2) the cross-sectional area ratio that does not have the occlusion particle configuration
With rubber modified polystyrene is that resin dyes with perosmic anhydride, makes the section of 90nm thickness with slicing machine, takes a picture with 10,000 times transmission electron microscope again.With above-mentioned image software respectively rubber particles (d-1) cross-sectional area of analytical calculation with occlusion particle configuration be A
(d-1)With the rubber particles that does not have the occlusion particle configuration (d-2) cross-sectional area be A
(d-2), calculating its ratio then is A
(d-1)/ A
(d-2)
Five, the median size analysis that has the rubber particles (d-1) of occlusion particle configuration
With rubber modified polystyrene is that resin dyes with perosmic anhydride, makes the section of 90nm thickness with slicing machine, takes a picture with 10,000 times transmission electron microscope again.With about 200～1000 of the rubber particles that has the occlusion particle configuration in the photo (d-1), measure its particle diameter with above-mentioned image software respectively, following again column count formula (II) is tried to achieve median size (unit: μ m).
Calculating formula (II) as previously mentioned, wherein, n
jRepresent rubber particles directly to be D
jThe rubber particles number, wherein, D
jAccount form and aforementioned have the D in the average grafting thickness analysis method of rubber particles (d-1) of occlusion particle configuration
iAccount form is identical.
Six, shock strength evaluation (Izod)
Rubber modified polystyrene is the test piece that resin penetrates ASTM D-256 defined, and tests (unit: Kg-cm/cm) according to the regulation of ASTMD-256.
Seven, electroplate the adherence evaluation
(a) electroplating processes
Prepare test piece: the test piece of ejection formation 150mm * 70mm * 3mm.
The test piece pre-treatment:
Hydroxide is received in containing in test piece, dipping 20 minutes in 67 ℃ of aqueous solution of sodium phosphate, yellow soda ash, X 2073, carries out skimming treatment, washes then 4 minutes.
Etch processes: through the test piece of aforementioned pre-treatment in 67 ℃ of following etchings 30 minutes.The etching aqueous solution consists of Cr
2O
3180g/l, H
2SO
4(proportion=1.84) 350ml/l.Etching after washing 4 minutes.
Pickling is handled: through the test piece of aforementioned etch processes, under 35 ℃, be soaked in 3.0% hydrochloric acid soln 1.5 minutes.
Sensitization is handled: through the test piece of aforementioned pickling processing, to consist of SnCl
23.5g/100ml, 35 ℃ of solution soaking of HCl10～20ml/100ml handled 2 minutes, washed 4 minutes; Again to consist of PdCl
20.25～0.5g/l, HCl 0.25～1ml/l, H
3BO
335 ℃ of solution soaking of 20g/l were handled 3.5 minutes, washed 4 minutes.
Electroplating processes: the test piece after aforementioned sensitization is handled, with 3A/dm
2Current density form the copper electrolytic coating in the thick copper of test piece electroplating surface 50 μ m; Inferior with test piece with 3～5A/dm
2Current density on the copper electrolytic coating, electroplate the thick nickel of 7 μ m and form the nickel electrolytic coating; Again with test piece with 15A/dm
2Current density on the nickel electrolytic coating, electroplate the thick chromium of 2 μ m and form the chromium electrolytic coating.
The plating aftertreatment: the test piece after aforementioned electroplating processes, to consist of NaHSO
3The solution soaking of 20g/l was handled 4 minutes, washed 8 minutes.
(b) adherence evaluation
Utilize blade that test piece is cut in the square scope of 2cm * 2cm and be divided into each parallel and vertical line grid square 100 lattice of 11, its spacing is 0.2mm.
The use viscosity adhesive tape of 45g/mm (3M#595 or other have the adhesive tape of suitable stickiness) at least sticks in the test piece of drawing lattice; And with this adhesive tape of finger press; Confirm that adhesive tape sticks in the test piece surface; Paste the back and tear adhesive tape rapidly, and observe electrolytic coating with 20 times of reading lenses and peel off the lattice number with vertical direction.
Electroplating the adherence judgement criteria is:
Zero: peel off lattice number≤10 lattice
△: 10 lattice＜peel off lattice number≤20 lattice
*: 20 lattice＜peel off lattice number≤30 lattice
* *: 30 lattice＜peel off lattice number
Eight, pin hole (Pin hole) is estimated
Use " upper quadrant blown film single screw extruder ", be that resin extrudes with rubber modified polystyrene, and be processed as the film of thickness 0.005 ± 0.0025inch.Get the film of 10cm * 10cm area and inspect foreign matter, and according to the standards evaluation.
| Foreign matter diameter R (mm) | Foreign matter mark (branch) |
| R≤0.05 | 0 |
| 0.05＜R≤0.15 | 1 |
| 0.15＜R≤0.25 | 2 |
| 0.25＜R≤0.3 | 4 |
| 0.30＜R≤0.4 | 9 |
| 0.40＜R | 21 |
The pin hole evaluation result:
Zero: foreign matter mark≤3 minute
△: foreign matter mark≤9 minute
*: foreign matter mark≤18 minute
* *: foreign matter mark≤30 minutes
Synthetic example 1: manufacturing example (I) with rubber particles (d-1) of occlusion particle configuration
With vinylbenzene 103.2 weight parts, rubber-like phenylethylene/butadiene co-polymer 15 weight parts (phenylethylene/butadiene content=25 weight %/75 weight %; Mw=13 ten thousand), ethylbenzene 45.4 weight parts, vinyl cyanide 31.4 weight parts, n-butyl acrylate 3.9 weight parts, lauryl mercaptan 0.08 weight part, 3-(3; The 5-di-tert-butyl-hydroxy phenyl) propionic acid octadecane alcohol ester 0.063 weight part and N; N '-ethylene bis stearamide 0.063 weight part is mixed into mixture; Vinylbenzene 100 weight parts, 1; Two (t-butyl peroxy acyl) hexanaphthene 3.0 weight parts of 4-and BPO 1.8 weight parts form initiator solution; Use pumping with mixture with 61kg/ hour flow, initiator solution flow with 1.3kg/ hour, be supplied to continuously in the first reactor drum continuous polymerization unit and react, the polymers soln that has reacted gets into second reactor drum, the 3rd reactor drum and the 4th reactor drum more in regular turn and reacts.Above-mentioned first, second, third, fourth reactor drum is docile and obedient the preface tandem arrangement; Wherein, the first, second, third and the 4th reactor drum is the column flow reactor of 100 liters of capacity.75～90 ℃ of the first reactor reaction temperature, stirring rod rotating speed 110rpm, 95～105 ℃ of the second reactor reaction temperature; Stirring rod rotating speed 80rpm; 110～125 ℃ of the 3rd reactor reaction temperature, stirring rod rotating speed 60rpm, 135～150 ℃ of the 4th reactor reaction temperature; Stirring rod rotating speed 5rpm, last polymkeric substance solid is 62.5%.After the reaction completion, remove unreacted monomer and solvent confession recovery use through devolatilization equipment, after die head extruded bar, warp cooled off, granulate equipment again, and can obtain rubber modified polystyrene is resin (I).With the electron microscope observation rubber modified polystyrene is resin (I), can be observed the rubber particles (d-1) with occlusion particle configuration.
Synthetic example 2: manufacturing example (II) with rubber particles (d-1) of occlusion particle configuration
Identical with synthetic routine 1, but change rubber-like phenylethylene/butadiene co-polymer into 21.9 weight parts, and n-butyl acrylate changes into and not adding; 1, two (t-butyl peroxy acyl) hexanaphthenes of 4-change 3.2 weight parts into, and the first reactive tank stirring rod rotating speed changes 120rpm into; The second reactive tank stirring rod rotating speed changes 100rpm into, and all the other conditions are constant, and last polymkeric substance solid is 61.2%; After devolatilization program, extrusion adhesive tape, cooling and granulation, can obtain rubber modified styrene series resin (II).With the electron microscope observation rubber modified polystyrene is resin (II), can be observed the rubber particles (d-1) with occlusion particle configuration.
Synthetic example 3: manufacturing example (III) with rubber particles (d-1) of occlusion particle configuration
Identical with synthetic routine 1, but change rubber-like phenylethylene/butadiene co-polymer into 24.3 weight parts, and n-butyl acrylate changes into and not adding; 1, two (t-butyl peroxy acyl) hexanaphthenes of 4-change 3.2 weight parts into, and the first reactive tank stirring rod rotating speed changes 120rpm into; The second reactive tank stirring rod rotating speed changes 120rpm into, and all the other conditions are constant, and last polymkeric substance solid is 60.3%; After devolatilization program, extrusion adhesive tape, cooling and granulation, can obtain rubber modified styrene series resin (III).With the electron microscope observation rubber modified polystyrene is resin (III), can be observed the rubber particles (d-1) with occlusion particle configuration.
Synthetic example 4: manufacturing example (IV) with rubber particles (d-1) of occlusion particle configuration
Identical with synthetic routine 1, but change rubber-like phenylethylene/butadiene co-polymer into 17.9 weight parts, and BPO 1.8 weight parts change Diisopropyl azodicarboxylate 1.2 weight parts into; The first reactive tank stirring rod rotating speed changes 120rpm into; The first reactor reaction temperature is adjusted into 75～85 ℃, and all the other conditions are constant, and last polymkeric substance solid is 62.4%; After devolatilization program, extrusion adhesive tape, cooling and granulation, can obtain rubber modified styrene series resin (IV).With the electron microscope observation rubber modified polystyrene is resin (IV), can be observed the rubber particles (d-1) with occlusion particle configuration.
Synthetic example 5: manufacturing example (V) with rubber particles (d-1) of occlusion particle configuration
Identical with synthetic routine 1, but change rubber-like phenylethylene/butadiene co-polymer into 16.7 weight parts, and n-butyl acrylate 3.9 weight parts change TEB 3K 5 weight parts into; 1, two (t-butyl peroxy acyl) hexanaphthenes of 4-change 3.2 weight parts into, and the first reactive tank stirring rod rotating speed changes 120rpm into; All the other conditions are with synthetic example 1; Last polymkeric substance solid is 62.8%, after devolatilization program, extrusion adhesive tape, cooling and granulation, can obtain rubber modified styrene series resin (V).With the electron microscope observation rubber modified polystyrene is resin (V), can be observed the rubber particles (d-1) with occlusion particle configuration.
Synthetic example 6: manufacturing example (VI) with rubber particles (d-1) of occlusion particle configuration
Identical with synthetic routine 1; But change rubber-like phenylethylene/butadiene co-polymer into 16.7 weight parts, n-butyl acrylate 3.9 weight parts change n-butyl acrylate 3.9 weight parts+N-phenylmaleimide 0.4 weight part, 1 into; Two (t-butyl peroxy acyl) hexanaphthenes of 4-change 3.2 weight parts into; The first reactive tank stirring rod rotating speed changes 120rpm into, and all the other conditions are with synthetic example 1, and last polymkeric substance solid is 62.4%; After devolatilization program, extrusion adhesive tape, cooling and granulation, can obtain rubber modified styrene series resin (VI).With the electron microscope observation rubber modified polystyrene is resin (VI), can be observed the rubber particles (d-1) with occlusion particle configuration.
Synthetic example 7: the manufacturing example that does not have the rubber particles (d-2) of occlusion particle configuration
| Composition | Weight part |
| 1,3-butadiene | 95.0 |
| Vinyl cyanide | 5.0 |
| Potassium persulfate solution | 15.0 |
| Sodium pyrosulfate | 3.0 |
| Potassium oleate | 1.5 |
| Zero(ppm) water | 140.0 |
| The 3rd-lauryl mercaptan | 0.2 |
65 ℃ of down reactions 12 hours, obtain transformation efficiency and be 94%, solids content is about 40%, weight average particle diameter is the conjugate diene polymers emulsion of 0.1 μ m according to above prescription.
In addition, the polymer coagulant that contains the carboxylic acid group with the following ingredients manufacturing.
| Composition | Weight part |
| The n-ethyl propenoate | 85 |
| Vinylformic acid | 15 |
| The 3rd-lauryl mercaptan | 0.3 |
| Potassium oleate | 2.0 |
| Dioctyl sodium sulphosuccinate | 1.0 |
| The isopropyl benzene hydrogen peroxide | 0.4 |
| Rongalite | 0.3 |
| Zero(ppm) water | 200 |
75 ℃ of down reactions 5 hours, obtain transformation efficiency and be 95%, the polymer coagulant that contains the carboxylic acid group of pH value 6.0 according to above prescription.
With the conjugate diene polymers emulsion (dry weight) that the polymer coagulant that contains the carboxylic acid group (dry weight) of 3 weight parts comes loose 100 weight parts, the pH value of resulting hypertrophyization conjugate diene polymers emulsion is 8.5, and weight average particle diameter is 0.30 μ m.
Above-mentioned hypertrophyization conjugate diene polymers emulsion is carried out graft polymerization reaction according to following prescription, to make the rubber particles (d-2) that does not have the occlusion particle configuration.
| Composition | Weight part |
| Conjugate diene polymers emulsion (dry weight) | 100 |
| Vinylbenzene | 25 |
| Vinyl cyanide | 8.3 |
| Potassium oleate | 1.2 |
| The 3rd-lauryl mercaptan | 0.2 |
| The isopropyl benzene hydrogen peroxide | 0.5 |
| Copperas solution (0.2%) | 3.0 |
| Rongalite solution (10%) | 3.0 |
| Diethylamine four acetums (0.25%) | 20 |
| Zero(ppm) water | 200 |
Vinylbenzene, vinyl cyanide in the last table prescription added polymerization in the reactive system with continuous addition manner in 5 hours; After prepared conjugate diene polymers graft emulsion condenses, dewaters with calcium chloride; Be dried to again below the moisture content 2 weight %, just can make the resin (VII) that contains rubber particles (d-2) with occlusion particle configuration.With the electron microscope observation rubber modified polystyrene is resin (VII), can be observed the rubber particles (d-2) with occlusion particle configuration.
Nitrilation ethene system-styrene based copolymer: use strange U.S. manufactured, the product of model PN-127H is as resin (VIII).
Embodiment 1～6 and comparative example 1～6:
To synthesize each resin of routine gained and resin (VIII), and do according to the ratio of table 1 and mix extrusion, granulation after tube machine mixes, obtaining rubber modified polystyrene is resin, and it is analyzed the transitivity evaluation result and sees table 1.
Can be known by table 1 result: comparative example 1 is owing to have rubber particles (d-1) the grafting thickness deficiency of occlusion particle configuration, and rubber modified polystyrene is that resin can't have suitable plating adherence; Comparative example 2 is owing to rubber particles (d-1) median size with occlusion particle configuration is excessive, and rubber modified polystyrene is that resin can't have suitable plating adherence; Comparative example 3,4 since the cross-sectional area of the rubber particles (d-1) with occlusion particle configuration and the rubber particles (d-2) that does not have the occlusion particle configuration than too small; Rubber modified polystyrene is that resin can't have suitable plating adherence, and the phenomenon of pin hole bad order is arranged; Comparative example 5 is because the content ratio of conjugate diene monomeric unit (m-2) is too low, and do not contain the rubber particles (d-2) with occlusion particle configuration, and rubber modified polystyrene is that the resin shock strength is not enough; Though therefore the content ratio of comparative example 6 conjugate diene monomeric units (m-2), makes that rubber particles (d-1) median size with occlusion particle configuration is excessive than comparative example 5 height, rubber modified polystyrene is that resin can't have suitable plating adherence.
In sum; Rubber modified polystyrene of the present invention is that resin is used rubber particles (d-1) with occlusion particle configuration and the 2 kinds of rubber particles of rubber particles (d-2) that do not have the occlusion particle configuration with; And the cross-sectional area of suitably adjusting the two compares, control has the rubber particles (d-1) of occlusion particle configuration median size, grafting thickness and rubber modified polystyrene are in the resin; The ratio of each monomeric unit (m-1)～(m-4); Not only can make rubber modified polystyrene of the present invention is that resin has the excellent character of electroplating, and also has good physical properties simultaneously, can be in order to make appearance looks elegant, the good moulding article of shock strength.
Claims (6)
1. a plating is a resin with rubber modified polystyrene; It is characterized in that; Contain nitrilation vinyl monomer unit (m-1) 10～35 weight %, conjugate diene monomeric unit (m-2) 10～30 weight %, styrenic monomers unit (m-3) 45～75 weight % and other copolymerizable vinyl monomer unit (m-4) 0～20 weight %; And this monomeric unit (m-1), this monomeric unit (m-2), this monomeric unit (m-3) and this monomeric unit (m-4) add up to 100 weight %;
Again, be resin 100 weight % based on this rubber modified polystyrene, also contain insoluble part of acetone of 20～40 weight %; Wherein,
This rubber modified polystyrene is that resin is observed with transmission electron microscope, comprises rubber particles (d-1) with occlusion particle configuration and the rubber particles (d-2) that does not have the occlusion particle configuration;
The average grafting thickness of this rubber particles (d-1) is 100～280 dusts; The ratio of this rubber particles (d-1) cross-sectional area and this rubber particles (d-2) cross-sectional area is 1.1～14; The median size of this rubber particles (d-1) is 0.35～0.8 μ m.
2. plating according to claim 1 is a resin with rubber modified polystyrene, it is characterized in that, the ratio of this rubber particles (d-1) cross-sectional area and this rubber particles (d-2) cross-sectional area is 2.5～9.
3. plating according to claim 1 is a resin with rubber modified polystyrene, it is characterized in that, the median size of this rubber particles (d-1) is 0.4～0.7 μ m.
4. plating according to claim 1 is a resin with rubber modified polystyrene, it is characterized in that, this rubber particles (d-1) is by block polymerization or solution polymerization and get.
5. plating according to claim 1 is a resin with rubber modified polystyrene; It is characterized in that it is the group that monomeric unit is formed that said vinyl monomer unit (m-4) is selected from acrylic ester monomeric unit, methacrylate ester monomeric unit and maleimide.
6. plating according to claim 1 is a resin with rubber modified polystyrene; It is characterized in that said vinyl monomer unit (m-4) is selected from the group that MMA MONOMER unit, Butyl Acrylate Monomer unit and N-phenylmaleimide monomeric unit are formed.
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