CN103917594B - The manufacture method of the styrene resin composite that contains high branching type Superhigh Molecular Polymer and composition thereof - Google Patents
The manufacture method of the styrene resin composite that contains high branching type Superhigh Molecular Polymer and composition thereof Download PDFInfo
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Abstract
The invention provides and suppressed gelation, the styrene resin composite and the manufacture method thereof that comprise high branching type ultrahigh molecular weight copolymer and linear polymer. it is for manufacturing the method for the styrene resin composite that contains high branching type ultrahigh molecular weight copolymer and linear polymer, taking styrene in necessary mono-vinyl compound, add and in average 1 molecule, there is vinyl more than 2 in weight basis, there is the solvent soluble polyfunctional vinyl copolymer 50ppm～5000ppm of branched structure, carry out polymerisation, the high branching type ultrahigh molecular weight copolymer that acquisition comprises this solvent soluble polyfunctional vinyl copolymer and this mono-vinyl compound generation polymerization generation, the styrene resin composite of the linear polymer that this mono-vinyl compound generation polymerization generates.
Description
Technical field
The present invention relates to the manufacture method of styrene resin composite and obtain by this manufacture methodThe styrene resin composite obtaining, described styrene resin composite comprises following mixingThing: add to mix and contain cinnamic ethylene unsaturated monomer and have multiple in a partThe solvent soluble polyfunctional vinyl copolymer of two keys, makes it to carry out polymerization and the high score that obtainsProp up the mixture of type super high molecular weight composition and wire composition.
Background technology
Phenylethylene resin series is due to cheapness, and the aspect such as transparency, heat resistance, mechanical strength is excellentDifferent, and formability is good, therefore extensive in multiple fields such as electric product, household suppliesUse. These formed products by injection molded or by sheet material through vacuum, pressure forming, enter oneStep, by extruder, for being called as the tubular of parison, is held in mould Zhi Houcong by resin extruded under the armInside is blown into the means such as the blow molding of compressed air etc. and obtains. In addition, in order to obtain light weightAnd there is the formed body of heat-proof quality, also used the technology such as foaming and molding. Styrene resinFoaming body has multiple features such as light weight, thermal insulation, resiliency, from use heat insulation material with houseThe polystyrene foam that material is representative is to being thermoformed into dish, bowl etc., as the sheet material of packaging for foodstuffShape polystyrene paper, or make the direct impregnation of resin by being suspended the particle state that polymerization obtainsThe aliphatic hydrocarbons such as pentane, the technology such as pearl foaming that adds thermosetting container by steam etc. is widely used.In these manufacturing process, particularly have melting calender line sheet forming, blow molding,Requiring of the raw material that the strain curability of the manufacturing process such as foaming and molding during to melting is high is high.
In above-mentioned manufacturing process, the problem when using the low resin material of strain curability,Can enumerate, in sheet forming, when the finely processed products such as food containers are carried out to secondary operations,Because of the sagging of heat tracing melting, goods easily produce uneven thickness, in addition due to calenderingCrackle, the breakage etc. of the goods that property deficiency causes become easy generation; In blow molding, in typeWhen base is shaped, if strain curability is low, not only produce contracting base, be shaped and become difficulty, andAnd the product strength causing due to uneven thickness is inhomogeneous large; Further because in foaming and moldingImprove heat-insulating property, institute is so that bubble microminiaturization, the independent of foaming body become the phenomenon such as difficult.In foaming and molding, in order to improve the ratio of separated foam, do not deposit at wall when making to rollIn part as thin as a wafer, be suitable for the material that can roll, because the little material of strain curability, to thinThe resistance of the calendering in wall region is little, so if once produce thin part, be absorbed in into oneStep is rolled in the vicious circle of thin-walled property more, the final to such an extent as to fracture of wall. Strain is solidThe material that voltinism is large, the viscosity rise in the region of being rolled, the calendering of the part to thin-walled propertyResistance also uprises than heavy section, so can not be absorbed in above-mentioned vicious circle, with uniform thicknessCalendering become possibility.
As the means that improve the melting characteristic such as tension force, strain curability under molten condition, withTo make the method that styrene resin composite contains super high molecular weight composition be effective toward known.
The method of the resin combination that contains super high molecular weight composition as acquisition, known to necessarilyIt is the styrene of more than 2,000,000 compositions that scope contains the molecular weight of recording in patent documentation 1Based polymer composition. But, as the method that obtains said composition, although proposed lowTemperature is lower uses the means of polymerisation in bulk, polymerisation in solution to carry out polymerization, generates super high molecular weight composition,Or mix and adjust by other approach such as anionic polymerisation, emulsion polymerisation under molten conditionThe method of whole super high molecular weight composition, but the method exists, productivity is poor, other approach of blendingThe problems such as cost uprises in the situation of the composition of polymerization.
For fear of the problems referred to above, propose for example to contain within the specific limits and be recorded in patent literary compositionOffer the benzene that contains more than 1,000,000 molecular weight constituent of polyfunctional vinyl compound unit in 2Ethylene-based polymers etc., in order to contain branching type super high molecular weight composition, add to vinyl monomerAdd the aromatic series polyfunctional vinyl chemical combination of minute quantity taking divinyl aromatic compound as representativeThing carries out polymerization. But, if these means are applied to continuous bulk polymerization, continue long-termIn the situation of reaction, stop at the mobile of border film that be called as of the wall that is present in polymer reactorRegion in, exist gelation to carry out such problem, for fear of the problems referred to above, many officialsThe addition of energy aromatic ethenyl compound is restricted, and is difficult to generate the super of desirable amountHigh molecular weight components. Further, while being suspended polymerization, almost there is no unreacted because complete to be polymerized toThe such feature of monomer, so if be untouchedly suitable for unchangeably proposed multifunctional vinylationCompound, when polymerization finishes, group enters polyfunctional vinyl compound in polymer chain sourceSide chain vinyl is more than 90% region quick response at conversion ratio, and significantly macromolecule quantizes, instituteWith the control difficulty of molecular weight, molecular weight distribution.
Further, be suspended polymerization although disclose in patent documentation 3 to utilize, use polyfunctional polyClose initator, styrenic is contained have the super high molecular weight composition of branched structureMethod also discloses and has used multifunctional polymerization initator in patent documentation 4, makes styrene poly-The method that compound contains the super high molecular weight composition with branched structure, but in the method, benzeneEthylene-based polymer entirety easily macromolecule quantizes, if for fear of this situation, uses simultaneouslyChain-transferring agent equimolecular quantity conditioning agent, it is insufficient that effect easily becomes. In addition, patent documentation 5In recorded by use multifunctional aromatic ethenyl compound and chain-transferring agent simultaneously, controlThe method of the degree of polymerization of phenylethylene resin series, but not only exist and the feelings that use Multifunctional initiatorThe problem of the same neutralization effect of condition, and exist as chain-transferring agent, if use thio-alcohol,, due to the problem of distinctive foul smell, exist the scope of application to be restricted such problem.
Prior art document
Patent documentation
Patent documentation 1: examined patent publication 62-61231 communique
Patent documentation 2: Unexamined Patent 2-170806 communique
Patent documentation 3: Unexamined Patent 7-278218 communique
Patent documentation 4: Unexamined Patent 8-59721 communique
Patent documentation 5: JP 2002-241413 communique
Summary of the invention
The object of this invention is to provide efficiency and manufacture well the method for styrene resin compositeAnd utilize melting characteristic excellence that the method obtains contain high branching type super high molecular weight materialStyrene resin composite, wherein this styrene resin composite possesses becoming at sheet materialThe shapings such as shape, foaming and molding, blow molding add the processing method of man-hour requirement melting calender lineOptimal melting characteristic, gel-free shape thing, contain high branching type super high molecular weight composition and lineShape composition.
That is, the present invention relates to the manufacture method of phenylethylene resin series polymer, contain height for manufacturingThe side of the styrene resin composite of branching type super high molecular weight co-polymer and linear polymerMethod, this composition of styrene resin comprises by taking styrene as necessary mono-vinyl chemical combinationIn thing, add to mix and in average 1 molecule, there is vinyl more than 2, tool in weight basisThere is the solvent soluble polyfunctional vinyl copolymer 50ppm～5000ppm of branched structure and enterRow polymerization, this solvent soluble polyfunctional vinyl copolymer and this mono-vinyl compound occurThe line that the high branching type ultrahigh molecular weight copolymer that polymerization generates and this vinyl monomer polymerization produceShaped polymer.
In above-mentioned manufacture method, as solvent soluble polyfunctional vinyl copolymer, preferablyEnumerate and make divinyl compound and mono-vinyl compound polymerization that can copolymerization and obtain, andIn construction unit, contain with following formula (a1) with 0.05～0.50 scope as molar fraction meterThe side chain vinyl in the divinyl compound source representing, the inertia in weight average molecular weight halfPolyfunctional vinyl copolymerization in the scope that footpath (nm) and the ratio of above-mentioned molar fraction are 1～100Thing.
(in formula, R1Represent to derive from the alkyl of divinyl compound. )
In addition, the polystyrene tree that the present invention relates to contain high branching type ultrahigh molecular weight copolymerOil/fat composition, is characterized in that, it contains the weight average molecule that utilizes above-mentioned manufacture method and obtainAmount is 1,000, more than 000 high branching type ultrahigh molecular weight copolymer 2.0～20.0 % by weight,Weight average molecular weight is 100,000～500,000 wire styrenic 80.0～98.0% by weight, weight average molecular weight is 200,000～800,000.
Specific embodiments
Below, explain the present invention. As the polymerization using in the present invention, preferablyUse so-called continuous bulk polymerization method: add mix comprise cinnamic mono-vinyl compound andSolvent soluble polyfunctional vinyl copolymer, solvent as required, polymerization catalyst, chainTransfer agent etc., continuously monomer class is sent into possess series connection and/or be arranged in parallel 1 aboveReactor and remove the equipment of the volatile ingredient removing step of unreacted monomer etc., periodically entersThe polymerization of enforcement. As the pattern of reactor, exemplified with the tank reactor of complete mixed type,Have piston fluidity tower reactor, carry out polymerization while discharge a part of polymer fluidCircular form reactor etc. Putting in order of these reactors is not particularly limited, but in continuous lifeIn product in order to suppress the generation of gelling material, at solvent soluble polyfunctional vinyl copolymer beUnder unreacted state, the state that does not occur high concentration be detained in the film of the border of reactor wallBe important, as the first reactor, preferably select the tank reactor of complete mixed type.
In addition, as polymerization of the present invention, also preferably use what is called to be suspended polymerization: to addAdd to mix and comprise cinnamic mono-vinyl compound, the copolymerization of solvent soluble polyfunctional vinylAfter thing, polymerization catalyst, chain-transferring agent etc. as required, it is suspended in water, entersRow polymerization. In order to make decentralized stabilization, organic to being dissolved with polyvinyl alcohol, methylcellulose etc.Be dispersant, or tricalcium phosphate, magnesium sulfate etc. inorganic be dispersant, neopelexIn water Deng anionic surfactant, drop into monomer class, under agitation make it to disperse,In the scope of 100～150 DEG C, carry out polymerization. If it is rear directly at aqueous dispersion shape to consider that reaction finishesConstant under state, make it the situation of depressing the aliphatic hydrocarbon foamed gas such as impregnation pentane adding, excellentFinal polymerisation conversion when choosing reaction finishes is more than 99%. If less than 99%, twoIn the situation more than boiling point that temperature when inferior shaping is remaining monomer, follow significant stench.
In the present invention, be more than 99% in order to make final polymerisation conversion, preferably to relativelyIn raw material charge weight, the peroxide that to have added 1 hour half life temperature be the scope of 130 ± 10 DEG CThe material solution that compound series catalysts 200ppm forms above carries out below 120 DEG C of reaction temperaturesAfter being polymerized to more than 50%, to exceed 5 DEG C of above reactions of half life temperature of above-mentioned catalystTemperature, carries out above polymerization in 3 hours. By using this condition, can not extend terrifically poly-Closing the time, is more than 99% and can easily make final polymerisation conversion. In the reaction of back segmentTemperature is that in 1 hour situation below half life temperature, polymerization time extends terrifically, makes rawProducing property significantly reduces.
Be more than 99% in order to make final conversion ratio, cause as used organic peroxideAgent, exemplified with tert-butyl hydroperoxide acetate, tert butyl peroxy benzoate, 2,2-bis--(t-butyl peroxy) butane, dicumyl peroxide etc.
In the present invention, solvent soluble polyfunctional vinyl copolymer can be dissolved in single etheneUnder the state of based compound class, polymer solvent etc., as required, in continuous bulk polymerization situationDescend multiple reactors midway, the interpolation midway of polymerisation in the time being suspended polymerization.
What use in the present invention (also claims below taking styrene as necessary mono-vinyl compoundFor styrenic monomers) can be that styrene is 100%, can be also comprise styrene andThe mixture of other mono-vinyl compound. As other mono-vinyl compound, can liftGo out to have can with the material of styrene copolymerized olefinic double bond: the aromatic series second such as p-methyl styreneAlkene monomer class; The acrylic monomers such as acrylic acid, methacrylic acid; Acrylonitrile, metering systemThe vinyl cyanide monomer such as nitrile; The acrylic monomer such as butyl acrylate, methyl methacrylate orThe α such as anhydrous maleic acid, fumaric acid, β-ethylene unsaturated carboxylic acid class; Phenyl maleimide,The imide series monomer classes such as N-cyclohexylmaleimide. Can use these single ethene in addition simultaneouslyBased compound is one kind or two or more. Therefore, due to styrene and other mono-vinyl chemical combinationThe ratio of thing is that 20～100 % by mole of styrene, other mono-vinyl compound are 0～80% by mole bring into play the characteristic of styrene resin composite, so preferably.
The solvent soluble polyfunctional vinyl copolymer using in the present invention (is also referred to as belowPolyfunctional vinyl copolymer) for by carrying out copolymerization with styrenic monomers, produce to branchThe material of the phenylethylene resin series of the super high molecular weight being branched.
The polyfunctional vinyl copolymer using in the present invention can be according to No. 2004-123873, JPIn communique, JP 2005-213443 communique, WO2009/110453 etc., disclosed method obtains. Specifically, use divinyl compound and the mono-vinyl chemical combination more than at least oneThing, makes it copolymerization, obtains and has being total to of reactive side chain vinyl of representing with formula (a1)Polymers. Further, as above-mentioned patent documentation is recorded, can use and on end, be imported into etheneThe material of other terminal groups beyond base, particularly because of as phenoxy group methyl acrylate classIn molecule, there is the compound of unsaturated bond and gone back except (a1) by terminal-modified materialCan be used as crosslinking points and act on, so preferably. Now, because the unsaturated bond that contains endConstruction unit (a2) also has vinyl, so with the total of the construction unit of formula (a1)Molar fraction (a3) has shown the amount of overall vinyl.
In order to obtain polyfunctional vinyl copolymer, as used divinyl compound,Exemplified with the divinyl aromatic compound class taking divinylbenzene as representative with ethylene glycol bisthioglycolateAliphatic, ester ring type (methyl) esters of acrylic acid etc. that (methyl) acrylate is representative.
In addition, as mono-vinyl compound as used herein, can enumerate and comprise as the aforementioned benzeneThe mono-vinyl compound of the single-ethenyl aromatic compound of ethene etc.
As the manufacture method of polyfunctional vinyl copolymer, can be by being for example selected from LouisAcid catalyst, be selected under the existence of co-catalyst of ester compounds, make to be selected from divinyl fragranceCompounds of group, single-ethenyl aromatic compound and other mono-vinyl compounds two or moreCompound carry out cationic copolymerization and obtain. In addition, use (methyl) acrylic esterIn the situation of divinyl, mono-vinyl compound, because cationoid reaction does not carry out, soCan, under the existence of the free radical catalysts such as peroxide, obtain by radical polymerization.
The use amount of divinyl compound and mono-vinyl compound, to produce in the present inventionThe mode of the composition of the polyfunctional vinyl copolymer using and determining, but preferably use all single10～90 % by mole, more preferably 30～90 % by mole of body, be more preferably 50～90 % by moleDivinyl compound. Preferably use 90～10 % by mole of whole monomers, more preferably 70～10 % by mole, be more preferably the mono-vinyl compound of 50～10 % by mole. At this, as 2-Phenoxy group ethylacrylic acid methyl esters such in cationic polymerization, rise as terminal-modified doseThe material of effect does not calculate as monomer.
As the lewis acid catalyst using in the manufacture of polyfunctional vinyl copolymer, forThe compound that comprises metal ion (acid) and ligand (alkali), if can accept dupletMaterial can be not particularly limited and use. From the control of molecular weight and molecualr weight distribution and poly-Close active viewpoint, most preferably use the ether (diethyl ether, dimethyl ether etc.) of boron trifluorideComplex compound. Lewis acid catalyst is with respect to 1 mole of whole monomer, at 0.001～10 moleScope in use, but more preferably 0.001～0.01 mole. If lewis acid catalystUse amount is excessive, because polymerization speed becomes too fast, so the control of molecular weight distribution becomesDifficulty, therefore not preferred.
As co-catalyst, can enumerate and be selected from the more than a kind of ester compounds. Wherein from polymerization speedThe viewpoint of degree and the molecular weight distribution control of copolymer, is preferably used the ester of carbon number 4～30Compound. From the viewpoint easily obtaining, preferably use ethyl acetate, propyl acetate and secondAcid butyl ester. Co-catalyst is with respect to 1 mole of monomeric compound, in 0.001～10 molar rangeInterior use, but more preferably 0.01～1 mole. If the use amount of co-catalyst is excessive, poly-Sum velocity reduces, and the productive rate of copolymer declines. On the other hand, if the use amount of co-catalystToo small, the elective reduction of polymerisation, except producing the increase of molecular weight distribution, gelGeneration etc. outside, the control of polymerisation also becomes difficulty.
In addition, as using in the time manufacturing polyfunctional vinyl copolymer by radical polymerizationCatalyst, azo-compound, diphenyl peroxide exemplified with picture taking azodiisobutyronitrile as representativeThe peroxide or 1 of the simple functions such as formyl, t-butyl peroxy benzoic ether, the two (tert-butyl groups of 1-Peroxidating) more than such 2 functionalities of cyclohexane multi-functional peroxide, can be by itUse separately or use two or more simultaneously.
The polyfunctional vinyl copolymer using in the present invention can be by manufacture method described aboveAnd obtaining, a but part for the vinyl of the divinyl compound that need to use as monomerNot polymerization and residual. Therefore, on average in 1 molecule, there are more than at least 2 preferably 3Above vinyl. This vinyl is deposited mainly as the construction unit representing with above formula (a1). Therefore, there is not polymerization and residual by a part for vinyl, can suppress cross-linking reaction,Give solvent soluble. At this, so-called solvent soluble refer to dissolve in toluene, dimethylbenzene,Oxolane (THF), dichloroethanes or chloroform, say in the time of 25 DEG C molten at these specificallyMore than dissolving 5g in agent 100g, do not produce gel. On the other hand, divinyl compoundA part, because the reaction of two vinyl is cross-linked or branch is necessary, can become and have thusThe copolymer of branched structure. So, for a part for divinyl compound, make 2 secondOne of thiazolinyl reacts, and not polymerization and residual, for other a part, makes 2Individual vinyl reacts, and can obtain thus the polyfunctional vinyl copolymerization using in the present inventionThing. The such a polymerization that obtains polyfunctional vinyl copolymer is known as mentioned above, can be so that mode as above and manufacturing.
The weight average molecular weight (Mw) of polyfunctional vinyl copolymer is preferably 1,000～100,000,More preferably 5,000～70,000. Be less than 1000 situation, with use aromatic diethylene baseThe situation of compound or multifunctional (methyl) esters of acrylic acid is same, suppresses solidifying in continuous polymerizationThe effect that gel is carried out reduces, being suspended the molecular weight distribution in high conversion region in polymerizationControl also become difficulty, can not obtain sufficient effect, therefore not preferred.
Be imported into the vinyl that contains divinyl compound source of polyfunctional vinyl copolymerUnit there is the construction unit representing with above-mentioned formula (a1), but this construction unit (a1)Molar fraction is 0.05～0.50. Be less than in the situation of 0.05 mole, be difficult to obtain high branchType ultrahigh molecular weight copolymer, therefore not preferred. On the other hand, exceed the situation of 0.50 moleUnder, the molecular weight of high branching type ultrahigh molecular weight copolymer excessively increases, and it is easy that gelation becomesOccur, therefore not preferred. In addition, as mentioned above, because by thering is unsaturated bond in moleculeCompound and the terminal-modified material construction unit except representing with formula (a1) contains endThe construction unit (a2) of unsaturated bond of end also has vinyl, thus both add up to moleMark (a3) can be 0.05～0.50.
In addition, the radius of inertia (nm) in preferred its weight average molecular weight of polyfunctional vinyl copolymerRatio with the molar fraction of said structure unit (a1) or the molar fraction (a3) of above-mentioned totalIt is 1～100 scope. In order not follow, the branching type superelevation for giving strain curability is dividedSon is measured composition gelation and is modulated more preferably 10～80 scope. Above-mentioned ratio exceedesIn 100 situation, gelation is not carried out, but is difficult to obtain the copolymerization of high branching type super high molecular weightThing, therefore not preferred. On the other hand, be less than in 1 situation high branching type super high molecular weightThe molecular weight of copolymer excessively increases, and gelation easily occurs, therefore not preferred. At this, be used toProperty radius is the value of utilizing the method for recording in embodiment to measure. In addition, polyfunctional vinylCopolymer is the polymer with the distribution of molecular weight aspect, certainly, because this radius of inertia is alsoThere is distribution, so the radius of inertia as a whole of the radius of inertia in employing weight average molecular weightMean value.
Index in this defined expression radius of inertia with the content of two keys, i.e. structural units(a1) ratio of molar fraction or the molar fraction of above-mentioned total (a3) can be said as formingWhen branching type super high molecular weight composition, represent that the polyfunctional vinyl copolymer that becomes core is in polymerizationIn reaction solution, in much scopes, there is the index of the reflecting point of what degree. If this is than mistakeLittle, near reflecting point is positioned at, becomes and easily cause gelation, in addition, if this ratioExcessive, the macromolecule of branching type composition quantizes to become difficulty.
Fit rate as polyfunctional vinyl copolymer with respect to styrenic monomers, with weightBenchmark meter, preferably 50ppm～5000ppm, more preferably 100ppm～3000ppm. Multifunctional secondThe fit rate of thiazolinyl copolymer is less than in the situation of 50ppm, is difficult to obtain of the present invention sufficientEffect, therefore not preferred. On the other hand, exceed in the situation of 5000ppm, exist to produce and coagulateThe possibility of glue.
By making aforementioned multifunctional vinyl compound copolymer and styrenic monomers polymerization, obtainAs the high branching type superelevation of the copolymer of polyfunctional vinyl copolymer and styrenic monomersMolecular weight copolymer (also referred to as high branching type copolymer) and only being generated by styrenic monomersThe mixture of linear polymer, i.e. styrene resin composite of the present invention. As styreneBe monomer, use in the situation of monomer of more than two kinds, linear polymer becomes copolymer.
The weight average molecular weight (Mw) of the styrene resin composite obtaining by the present invention is preferredBe 200,000～800,000. Mw less than 200,000, the impact strength after processing is insufficient, MwExceed 800,000, viscosity rise, it is insufficient that processability becomes.
In styrene resin composite as above, comprise high branched copolymers and wirePolymer, but by making it the styrene resin composite for showing Mw as above, heightThe Mw of branched copolymers becomes more than 1,000,000 super high molecular weights, and linear polymer becomes 10Ten thousand～500,000. Therefore, preferably Mw is more than 1,000,000 high branch ultrahigh molecular weight copolymerThe ratio that is 100,000～500,000 wire styrenic with Mw is 2:98～20:80.These ratio, can be by adjusting polyfunctional vinyl copolymer with respect to styrenic monomersMixing ratio and polymerizing condition, control.
About the manufacture of styrene resin composite, from the viewpoint of the control of polymerisation,As required, can use the polymerization initiator such as polymer solvent, organic peroxide or analiphatic sulphurThe chain-transferring agents such as alcohol.
Polymer solvent, in continuous bulk polymerization, uses in order to reduce the viscosity of reactant, doesFor this organic solvent, can enumerate toluene, ethylbenzene, dimethylbenzene, acetonitrile, benzene, chlorobenzene, dichloroBenzene, methyl phenyl ethers anisole, cyano group benzene, dimethyl formamide, DMA, MethylethylKetone etc.
Particularly in continuous bulk polymerization, in the interpolation of wanting to make polyfunctional vinyl copolymerIn quantitative change situation how, from suppressing the viewpoint of gelation, also preferably with an organic solvent.Thus, the addition of the polyfunctional vinyl copolymer shown in can making previously increases tremendously,Be difficult to produce gel.
The use amount of organic solvent is not particularly limited, but goes out from controlling the such viewpoint of gelationSending out, preferably with respect to total amount 100 weight portions of monomer component, is 1～50 weight portion conventionally,More preferably in the scope of 5～30 weight portions. Exceed in the situation of 50 weight portions, productivity is remarkableReduce, the molecular weight of chain phenylethylene resin series excessively reduces, therefore not preferred.
As polymerization initiator, preferably radical polymerization initiator, can enumerate known conventional exampleAs 1,1-bis-(t-butylperoxy) cyclohexane, 2,2-bis-(t-butylperoxy) butane,The ketal peroxide classes such as 2,2-bis-(4,4-, bis--butyl peroxy cyclohexyl) propane; Isopropylbenzene hydrogenThe hydroperoxide type such as peroxide, tert-butyl hydroperoxide; Di-t-butyl peroxide, mistakeOxidation dicumyl, two-dialkyl peroxide classes such as tertiary hexyl peroxide; Benzoyl peroxide,The diacyl peroxide classes such as diacyl peroxide; Tert butyl peroxy benzoate, two-The peroxyesters such as t-butyl peroxy isophthalic acid ester, t-butylperoxy propyl group monocarbonate; N,N'-azodiisobutyronitrile, N, N'-azo two (cyclohexane-1-formonitrile HCN), N, N'-azo is two(2-methylbutyronitrile), N, N'-azo two (2,4-methyl pentane nitrile), N, N'-azoTwo [2-(methylol) propionitrile] etc., can use these a kind or be used in combination two or more.
So that the molecular weight of styrene resin composite can not become excessive mode and add chainTransfer agent, can use the simple function chain-transferring agent that has 1 chain and shift base, have multiple chains and turnMove the Polyfunctional chain transfer agent of base. As simple function chain-transferring agent, can enumerate alkyl sulfide alcohols,Mercaptoacetate class etc.
As Polyfunctional chain transfer agent, can enumerate by thioglycolic acid or 3-mercaptopropionic acid and esterChange ethylene glycol, neopentyl glycol, trimethylolpropane, pentaerythrite, dipentaerythritol, three seasonsThe material of the polyalcohol hydroxyls such as penta tetrol, D-sorbite.
Embodiment
Below use embodiment further to specifically describe the present invention. The assay method using asDescribed in lower.
(GPC determination method) is by high speed liquid chromatograph (TosohCorporation systemHLC-8220GPC), RI detector, tsk gel GMH × 1 × 2, solvents tetrahydrofurane, streamThe mean molecule quantity of bioassay standard polystyrene conversion when speed 1.0ml/ minute, 40 DEG C of temperature.
Two keys (a2) in (two key sizing technique) construction unit (a1), terminal-modified dose of sourceAnd the molar fraction of both totals (a3) is for being used NEC's JNM-LA600 type processed nuclear-magnetismResonance light-dividing device, analyzes by 13C-NMR and 1H-NMR, determines structure. As solvent,Use chloroform-d1, use the resonance line of tetramethylsilane as internal standard.
(radius of inertia) passes through film after sample being adjusted into 0.5% tetrahydrofuran solutionFilter filters, and uses GPC multi-angle light scattering method to measure filtrate. Further,After being adjusted into 0.2% tetrahydrofuran solution, places 1 day by sample. ,, use tetrahydrochysene furan thereafterThe dilution of muttering is the solution of 4 kinds of concentration (0.02,0.05,0.10,0.12 % by weight), usesThese solution, carry out dn/dc mensuration, are calculated the radius of inertia of sample by the dn/dc value obtaining.
(confirmation of gelling material) used injection molding machine, is configured as 180mm × 180mm × 3mmFlat board, by visual, confirm the wire from door section that produces in the time containing gelling materialHaving or not of vestige.
Synthesis example 1
(polyfunctional vinyl copolymer α)
By divinylbenzene 3.1 moles (399.4g), EST 0.7 mole (95.1g),2.3 moles of styrene 0.3 mole (31.6g), 2-phenoxy group ethyl-methyl acrylate(463.5g), toluene 974.3g drops in the reactor of 3.0L, adds 42.6g in the time of 50 DEG CBoron trifluoride diethyl ether complex compound, make it to react 6.5 hours. Make by sodium bicarbonate solutionAfter polymerisation stops, washing oil reservoir 3 times by pure water, in the time of room temperature by reaction mixtureDrop in a large amount of methyl alcohol, polymer is separated out. By methyl alcohol by the washing of obtained polymer,Filter, be dried, weigh, obtain polyfunctional vinyl copolymer α 372.5g. This multifunctional secondThe weight average molecular weight Mw of thiazolinyl copolymer α is 8000, contains divinyl compound sourceThe molar fraction of the structural units (a1) of vinyl is 0.44, the 2-phenoxy group ethyl first of endTwo keys (a2) in base acrylate source are 0.03, combine the molar fraction (a3) of both totalsBe 0.47. In addition, the radius of inertia (r) of the copolymer in weight average molecular weight 8000 is 6.4nm.Compared with being 15nm with the radius of inertia of the molecular weight 8000 of straight chain type, in known synthesis examplePolyfunctional vinyl copolymer has branched structure. In addition, calculate the radius of inertia (r) with moleThe ratio (r/a3) of mark (a3) is 13.6.
Synthesis example 2
(polyfunctional vinyl copolymer β)
By divinylbenzene 2.6 moles (332.0g), EST 1.5 moles (198.0g),3.1 moles of styrene 1.1 moles (109.6g), 2-phenoxy group ethyl-methyl acrylate(630.4g), toluene 886.0g drops in the reactor of 3.0L, adds 35.5g in the time of 50 DEG CBoron trifluoride etherate, make it to react 5.0 hours. Make to gather by sodium bicarbonate solutionClose reaction stop after, wash oil reservoir 3 times by pure water, in the time of room temperature, reaction mixture is thrownEnter in a large amount of methyl alcohol, polymer is separated out. By methyl alcohol by the washing of obtained polymer,Filter, be dried, weigh, obtain polyfunctional vinyl copolymer β 564.0g. This multifunctional secondThe Mw of thiazolinyl copolymer β is 5000, the knot of the vinyl that contains divinyl compound sourceThe molar fraction of structure unit (a1) is 0.25, the 2-phenoxy group ethyl-methyl acrylate of endTwo keys (a2) in source are 0.02, and the molar fraction (a3) that combines both totals is 0.27.In addition, the radius of inertia of the copolymer in weight average molecular weight is 8.1nm. Molecule with straight chain typeThe radius of inertia in amount 5000 is that 12nm compares, the polyfunctional vinyl in known synthesis exampleCopolymer has branched structure.
Synthesis example 3
(polyfunctional vinyl copolymer γ)
By divinylbenzene 1.2 moles (159.8g), EST 0.7 mole (95.3g),3.1 moles of styrene 2.1 moles (223.2g), 2-phenoxy group ethyl-methyl acrylate(632.0g), toluene 1082.5g drops in the reactor of 3.0L, adds 56.8g in the time of 50 DEG CBoron trifluoride diethyl ether complex compound, make it to react 6.0 hours. Make by sodium bicarbonate solutionAfter polymerisation stops, washing oil reservoir 3 times by pure water, in the time of room temperature by reaction mixtureDrop in a large amount of methyl alcohol, polymer is separated out. By methyl alcohol by the polymer washing obtaining,Filter, be dried, weigh, obtain polyfunctional vinyl copolymer γ 340.8g. This multifunctional secondThe Mw of thiazolinyl copolymer γ is 5000, the vinyl that contains divinyl aromatic compound sourceThe molar fraction of construction unit (a1) be 0.13, the 2-phenoxy group ethyl-methyl propylene of endTwo keys (a2) in acid esters source are 0.01, combine both molar fractions (a3) of total is 0.14.In addition, the radius of inertia of the copolymer in weight average molecular weight is 10.6nm. Molecule with straight chain typeThe radius of inertia in amount 5000 is that 12nm compares, the polyfunctional vinyl in known synthesis exampleCopolymer has branched structure.
Polyfunctional vinyl copolymer in above-mentioned synthesis example 1～3 all dissolves in toluene, diformazanBenzene, oxolane, dichloroethanes and chloroform.
Embodiment 1
Benzene mixed ethene 85 weight portions, ethylbenzene 15 weight portions, polyfunctional vinyl are common equablyAfter polymers (α) 0.06 weight portion, sent into continuously continuous bulk polymerization with 15L/ hour and establishStandby, described polymerisation in bulk equipment have 2 tank reactors that are connected in series, in keep quietThe tower reactor of the internal volume 15L of state mixer and there is preheater and the sudden strain of a muscle of vacuum tankThe volatile ingredient of steam room type is removed device, and tank reactor has the mixing completely of internal volume 30LProperty, static mixer has piston fluidity. So that the first reactor is 130 DEG C, the second reactionDevice is that 140 DEG C, the inlet portion of the 3rd reactor are that 140 DEG C, export department are the mode rank of 160 DEG CSection property ground is transferred to the preheater that is heated to 220 DEG C after improving temperature, is dropped in pressureBe adjusted into 8 holders preheater under vacuum tank, remove thus unreacted monomer, solvent,Utilizing gear pump from vacuum tank on one side afterwards, is thread shape by resin drawing, shear on one side,Obtain thus styrene resin composite. Arrive and keep the constant stable state of this stable stateAfterwards, to the resin combination after 24 hours, 72 hours, 144 hours implement molecular weight,The evaluation of gelling material, the results are shown in table 1.
Embodiment 2
Except replacing the polyfunctional vinyl copolymer (α) in embodiment 1, use multifunctionalOutside ethylenic copolymer (β), operation similarly to Example 1, obtains polystyrene treeLipopolymer. The molecular weight of each time, the evaluation result of gelling material in table 1, are shown.
Embodiment 3
Except replacing the polyfunctional vinyl copolymer (α) in embodiment 1, use multifunctionalOutside ethylenic copolymer (γ), operation similarly to Example 1, obtains polystyrene treeLipopolymer. The molecular weight of each time, the evaluation result of gelling material in table 1, are shown.
Embodiment 4
Except making the addition 0.06 of the polyfunctional vinyl copolymer (α) in embodiment 1Weight portion becomes outside 0.01 weight portion, and operation similarly to Example 1, obtains polystyreneResin combination. The molecular weight of each time, the evaluation result of gelling material in table 1, are shown.
Embodiment 5
Be that 70 weight portions, ethylbenzene are 30 weight portions except making styrene, many in embodiment 1Addition 0.06 weight portion of functional ethylene's base co-polymer (α) becomes outside 0.3 weight portion,Operation similarly to Example 1, obtains polystyrene resin polymer. In table 1, show eachThe molecular weight of individual time, the evaluation result of gelling material.
Embodiment 6
Except making the addition 0.06 of the polyfunctional vinyl copolymer (α) in embodiment 1Weight portion becomes 0.1 weight portion, with the styrene while, adds tertiary lauryl mercaptan (tDM)Outside 0.05 weight portion, operation similarly to Example 1, obtains polystyrene resin composite.
Comparative example 1
Except not adding polyfunctional vinyl copolymer (α), similarly to Example 1Operation, obtains wire polystyrene.
Comparative example 2
Except making the addition 0.06 of the polyfunctional vinyl copolymer (α) in embodiment 1Weight portion becomes beyond 0.001 weight portion, and operation similarly to Example 1, obtains polyphenyl secondOlefine resin composition.
Comparative example 3
Except making the addition 0.06 of the polyfunctional vinyl copolymer (α) in embodiment 1Weight portion becomes beyond 1 weight portion, and operation similarly to Example 1 obtains polystyrene treeOil/fat composition.
Comparative example 4
Except replacing the polyfunctional vinyl copolymer (α) in embodiment 1, make divinylbenzeneBe beyond 0.05 weight portion, operation similarly to Example 1, obtains polystyrene resin combinationThing. The molecular weight of each time, the evaluation result of gelling material in table 1, are shown. 24 hoursDo not observe gelling material, but within 72 hours, produced gelling material, within 144 hours, become in a large number and containThere is the state of gelling material.
Comparative example 5
Except replacing the polyfunctional vinyl copolymer (α) in embodiment 1, make divinylbenzeneBe beyond 0.025 weight portion, operation similarly to Example 1, obtains polystyrene resin groupCompound. Within 72 hours, do not observe gelling material, but confirm to produce for 144 hours gelling material.
Comparative example 6
Except replacing the polyfunctional vinyl copolymer (α) in embodiment 1, use divinylBenzene 0.05 weight portion, the ratio that makes styrene and solvent ethylbenzene is styrene 70 weight portions, secondBeyond benzene 30 weight portions, operation similarly to Example 1, obtains polystyrene resin composite.
By use amount and the polystyrene of the reaction raw materials in embodiment 1～6 and comparative example 1～6The physical property of resin combination gathers and is shown in table 1.
Embodiment 7
To be provided with 10 liters of internal volumes shell, pack even mixing into the reactor of mixerThe styrene monomer 3kg of polyfunctional vinyl copolymer (α) 0.06 weight portion and comprise workFor being suspended tricalcium phosphate 0.05 weight portion of stabilizing agent, detergent alkylate as surfactantThe water 4kg of sodium sulfonate 0.005 weight portion, under agitation makes solution be suspended. Add to this suspensionAdd with respect to styrene monomer 100 weight portions, as the t-butyl peroxy benzene first of polymerization initiatorAcid esters 0.2 weight portion, further adds the α-methylstyrenedimer as chain-transferring agent0.04 weight portion. Stir suspension on one side, in the time of 115 DEG C, heat 5 hours on one side, at 140 DEG CShi Jiare carries out polymerization for 3 hours. After polymerization finishes, add hydrochloric acid to suspension, neutralization is doneFor being suspended the tricalcium phosphate of stabilizing agent. By the resin washing of the pearl of acquisition, filter after, enterRow heated-air drying, obtains styrene resin composite.
Embodiment 8
Except replacing the polyfunctional vinyl copolymer (α) in embodiment 7, use multifunctionalIn addition, operation similarly to Example 7, obtains polystyrene tree to ethylenic copolymer (β)Oil/fat composition.
Embodiment 9
Except replacing the polyfunctional vinyl copolymer (α) in embodiment 7, use multifunctionalIn addition, operation similarly to Example 7, obtains polystyrene tree to ethylenic copolymer (γ)Oil/fat composition.
Embodiment 10
Except making the addition 0.06 of the polyfunctional vinyl copolymer (α) in embodiment 7Weight portion becomes beyond 0.01 weight portion, and operation similarly to Example 7, obtains polystyreneResin combination.
Embodiment 11
Except making the addition 0.06 of the polyfunctional vinyl copolymer (α) in embodiment 7Weight portion becomes beyond 0.1 weight portion, and operation similarly to Example 7, obtains polystyreneResin combination.
Comparative example 7
Except not adding polyfunctional vinyl copolymer (α), similarly to Example 7Operation, obtains wire polystyrene.
Comparative example 8
Except making the addition 0.06 of the polyfunctional vinyl copolymer (α) in embodiment 7Weight portion becomes beyond 0.001 weight portion, and operation similarly to Example 7, obtains polyphenyl secondOlefine resin composition.
Comparative example 9
Except making the addition 0.06 of the polyfunctional vinyl copolymer (α) in embodiment 7Weight portion becomes beyond 1 weight portion, and operation similarly to Example 7 obtains polystyrene treeOil/fat composition.
Comparative example 10
Except replacing the polyfunctional vinyl copolymer (α) in embodiment 7, make divinylbenzeneBe beyond 0.05 weight portion, operation similarly to Example 7, obtains polystyrene resin combinationThing.
By the use amount of the reaction raw materials in embodiment 7～11 and comparative example 7～10 and polyphenyl secondThe physical property of olefine resin composition gathers and is shown in table 2.
In table 1～2, crosslinking agent means polyfunctional vinyl copolymer or divinylbenzene (DVB),Chain-transferring agent means tDM. Entirety Mw means the weight average molecular weight of polystyrene resin composite,Mw1, the ratio that more than 000,000 ratio means in polystyrene resin composite (weighsAmount %), the Y in the evaluation of gelling material means to exist gelling material, and N means not exist solidifyingJelly.
Table 1
Table 2
The possibility of utilizing in industry
According to the present invention, in the processing of rolling at the thin-walled of following taking foaming and molding as representative, canProduce the microgel that does not comprise the fracture of bringing out thinner wall section, further, contain and solidifying with strainProperty be that dissolve characteristic aspect excellence, when calendering of representative, the high branching type of wall thickness was super equablyThe styrene resin composite of high molecular weight copolymer and linear polymer. Further, pass throughUse utilizes the present invention and the styrene resin composite that obtains, be suppressed in sheet forming because ofWhat sagging, uneven thickness when secondary operations, gelling material caused break, the deterioration of outward appearance.In addition, the bubble can eliminate contracting base in the time of blow molding, foaming and molding time breaks, bubble is swollenSwollen, generate the variety of issues such as bubble continuously.
Claims (2)
1. the manufacture method of styrene resin composite, it contains high branching type superelevation for manufacturingThe method of the styrene resin composite of molecular weight copolymer and linear polymer, its feature existsIn, to adding with weight basis average 1 taking styrene as necessary mono-vinyl compoundIn molecule, there are 2 above, to there is branched structure multifunctional ethene of solvent soluble of vinylBase co-polymer 50ppm～5000ppm, carries out polymerisation, and it is many that acquisition comprises this solvent solubleThe high branching type supra polymer that functional ethylene's base co-polymer and this mono-vinyl compound copolymerization generateThe phenylethylene resin series of the linear polymer that amount copolymer, this mono-vinyl compound polymerization generateComposition.
2. styrene resin composite, it is that method according to claim 1 obtainsStyrene resin composite, is characterized in that, contain weight average molecular weight and be 1,000,000 withOn high branching type ultrahigh molecular weight copolymer 2.0～20.0 % by weight and weight average molecular weight be100,000～500,000 wire styrenic 80.0～98.0 % by weight, weight averageMolecular weight is 200,000～800,000.
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| TWI664199B (en) * | 2014-12-26 | 2019-07-01 | 日商日鐵化學材料股份有限公司 | Terminally modified soluble polyfunctional vinyl aromatic copolymer, method for producing the same, hardening composition, hardened material, film, hardenable composite material, laminate, metal foil with resin, varnish for circuit board material, hardening Resin composition, resin film for forming optical waveguide, and optical waveguide |
| CN106008841B (en) * | 2015-03-25 | 2020-03-31 | 株式会社Jsp | Composite resin particle and method for producing same |
| JP6865076B2 (en) * | 2016-03-28 | 2021-04-28 | Ｐｓジャパン株式会社 | Styrene-based copolymer and its production method |
| KR102494998B1 (en) * | 2016-11-01 | 2023-02-02 | 닛테츠 케미컬 앤드 머티리얼 가부시키가이샤 | Copolymer rubber, manufacturing method thereof, and crosslinked rubber composition |
| CN110945043B (en) * | 2017-07-21 | 2022-10-11 | 株式会社Jsp | Styrene-based resin and method for producing styrene-based resin |
| JP7190649B2 (en) * | 2018-04-27 | 2022-12-16 | パナソニックＩｐマネジメント株式会社 | Resin composition, prepreg, resin-coated film, resin-coated metal foil, metal-clad laminate, and wiring board |
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