CN103917594A - Method for producing styrene-based resin composition comprising highly branched ultra-high-molecular-weight polymer, and composition - Google Patents
Method for producing styrene-based resin composition comprising highly branched ultra-high-molecular-weight polymer, and composition Download PDFInfo
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Abstract
Provided is a styrene-based resin composition with which gelling is controlled and which is formed from a highly branched ultra-high-molecular-weight copolymer and a linear polymer; also provided is a method for producing the same. By means of the method for producing a styrene-based resin composition comprising a highly branched super-high-molecular-weight copolymer and a linear polymer, a styrene-based resin composition is obtained that comprises the following: a highly branched ultra-high-molecular-weight copolymer which is produced by adding 50 to 5,000 ppm by weight standard of a solvent-soluble polyfunctional vinyl copolymer, having an average of two or more vinyl groups per 1 molecule and having a branch structure, to a monovinyl compound whose essential ingredient is styrene to promote polymerization and thereby polymerize the solvent-soluble multifunctional vinyl copolymer and the monovinyl compound; and a linear polymer that is produced by polymerization of the monovinyl compound.
Description
Technical field
The styrene resin composite that the present invention relates to the manufacture method of styrene resin composite and obtain by this manufacture method, described styrene resin composite comprises following mixture: add to mix and contain cinnamic ethylene unsaturated monomer and in a part, have the solvent soluble polyfunctional vinyl multipolymer of multiple pairs of keys, make it to carry out polymerization and the high branching type ultra-high molecular weight composition that obtains and the mixture of wire composition.
Background technology
Phenylethylene resin series is due to cheapness, and the aspect excellence such as transparency, thermotolerance, physical strength, and plasticity is good, therefore in multiple fields such as electric product, household supplies, is widely used.These molding by injection molded or by sheet material through vacuum, pressure forming, further by extrusion machine, hold under the arm in mould for being called as the tubular of parison resin extruded, be blown into afterwards the means such as blow molding of pressurized air etc. from inside and obtain.In addition, in order to obtain light weight and to there is the molding of heat-proof quality, the technology such as foaming and molding have also been used.The foam of styrene resin has multiple features such as light weight, thermal insulation, resiliency, from taking house with lagging material as the polystyrene foam of representative is to being thermoformed into dish, bowl etc., as the sheet polystyrene paper of food product pack, or making the aliphatic hydrocrbons such as the direct impregnation pentane of resin by being suspended the particle state that polymerization obtains, the technology such as pearl foaming that adds thermosetting container by steam etc. is widely used.In these manufacturing process, requiring of the raw material that strain solidified nature while particularly having the manufacturing process such as the sheet forming, blow molding, foaming and molding of melting calender line to melting is high is high.
In above-mentioned manufacturing process, problem when using the low resin material of strain solidified nature, can enumerate, in sheet forming, when the finely processed products such as food product containers are carried out to secondary processing, because of the sagging of heat tracing melting, goods easily produce uneven thickness, and crackle, the breakage etc. of the goods that cause due to calenderability deficiency in addition become easy generation; In blow molding, in the time that parison is shaped, if strain solidified nature is low, not only produce contracting base, be shaped and become difficulty, and the product strength causing due to uneven thickness inhomogeneous greatly; Further because improve heat-insulating property in foaming and molding, institute is so that bubble microminiaturization, the independent of foam become the phenomenon such as difficult.In foaming and molding, in order to improve the ratio of separated foam, there is not part as thin as a wafer at wall when making to roll, be suitable for the material that can roll, because the material that strain solidified nature is little, the resistance of the calendering to thin-walled property region is little, so if once produce thin part, be absorbed in further in the vicious cycle of being rolled thin-walled property more final the to such an extent as to fracture of wall.The material that strain solidified nature is large, the viscosity rise in the region of being rolled, the resistance of the calendering of the part to thin-walled property also uprises than heavy section, so can not be absorbed in above-mentioned vicious cycle, becomes possibility with the calendering of uniform thickness.
As the means that improve the melting characteristic such as tension force, strain solidified nature under molten state, in the past known to make the method that styrene resin composite contains ultra-high molecular weight composition be effective.
The method of the resin combination that contains ultra-high molecular weight composition as acquisition, the known molecular weight that contains within the specific limits record in patent documentation 1 is the styrenic polymer composition of more than 2,000,000 compositions.But, as the method that obtains said composition, carry out polymerization although proposed to use at low temperatures the means of mass polymerization, solution polymerization, generate ultra-high molecular weight composition, or under molten state, mix the method for having carried out the ultra-high molecular weight composition of adjusting by other approach such as anionoid polymerization, letex polymerization, but the method exists that productivity is poor, the problems such as cost uprises in the situation of the composition of other approach polymerizations of blending.
For fear of the problems referred to above, propose for example to contain within the specific limits styrenic that contains more than 1,000,000 molecular weight constituent of polyfunctional vinyl compound unit being recorded in patent documentation 2 etc., in order to contain branching type ultra-high molecular weight composition, add the aromatic series polyfunctional vinyl compound of minute quantity taking divinyl aromatic compound as representative to vinyl monomer and carry out polymerization.But, if these means are applied to continuous bulk polymerization, continue in the situation of long-term reaction, in the mobile region stopping that being called as border film of wall that is present in polymerization reactor, exist gelation to carry out such problem, for fear of the problems referred to above, the addition of multifunctional aromatic ethenyl compound is restricted, and is difficult to generate the ultra-high molecular weight composition of desirable amount.Also have, while being suspended polymerization, be polymerized to because complete the feature that does not almost have unreacted monomer such, if be suitable for unchangeably proposed multifunctional vinyl compound so untouched, when polymerization finishes, the side chain vinyl that group enters polyfunctional vinyl compound in polymer chain source is more than 90% region quick response at transformation efficiency, and significantly polymer quantizes, so the control difficulty of molecular weight, molecular weight distribution.
Further, although disclose in patent documentation 3 to utilize and be suspended polymerization, use multifunctional polymerization initiator, styrenic is contained have the method for the ultra-high molecular weight composition of branched structure, in patent documentation 4, also disclose and used multifunctional polymerization initiator, styrene polymer is contained have the method for the ultra-high molecular weight composition of branched structure, but in the method, styrenic entirety easily polymer quantizes, if for fear of this situation, use chain-transfer agent equimolecular quantity conditioning agent, it is insufficient that effect easily becomes simultaneously.In addition, in patent documentation 5, record by use multifunctional aromatic ethenyl compound and chain-transfer agent simultaneously, control the method for the polymerization degree of phenylethylene resin series, but not only there is the problem of the neutralization effect same with the situation that uses Multifunctional initiator, and exist as chain-transfer agent, if use thio-alcohol, due to the problem of distinctive foul smell, exists use range 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 manufactures well the method for styrene resin composite and utilizes the styrene resin composite that contains high branching type ultra-high molecular weight material of the melting characteristic excellence of the method acquisition, wherein this styrene resin composite possesses the optimal melting characteristic of working method, the gel-free shape thing to add man-hour requirement melting calender line in shapings such as sheet forming, foaming and molding, blow moldings, contains high branching type ultra-high molecular weight composition and wire composition.
, the present invention relates to the manufacture method of phenylethylene resin series polymkeric substance, for manufacturing the method for the styrene resin composite that contains high branching type ultra-high molecular weight co-polymer and linear polymer, this composition of styrene resin comprises by having vinyl more than 2 with weight basis to adding in necessary mono-vinyl compound taking vinylbenzene to mix in average 1 molecule, there is the solvent soluble polyfunctional vinyl multipolymer 50ppm～5000ppm of branched structure and carry out polymerization, the linear polymer that the high branching type ultrahigh molecular weight copolymer that this solvent soluble polyfunctional vinyl multipolymer and this mono-vinyl compound generation polymerization generate and this vinyl monomer polymerization produce.
In above-mentioned manufacture method, as solvent soluble polyfunctional vinyl multipolymer, preferably enumerate and make divinyl compound and mono-vinyl compound polymerization that can copolymerization and obtain, and the side chain vinyl that contains with 0.05～0.50 scope the divinyl compound source representing with following formula (a1) as molar fraction meter in structural unit, the polyfunctional vinyl multipolymer in the scope that the radius of inertia (nm) in weight-average molecular weight and the ratio of above-mentioned molar fraction are 1～100.
(in formula, R
1represent to derive from the alkyl of divinyl compound.)
In addition, the present invention relates to the styrene resin composite that contains high branching type ultrahigh molecular weight copolymer, it is characterized in that, it contains the weight-average molecular weight of utilizing above-mentioned manufacture method and obtain is 1,000, more than 000 high branching type ultrahigh molecular weight copolymer 2.0～20.0 % by weight, weight-average molecular weight are 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 process using in the present invention, preferably use so-called continuous bulk polymerization method: add mixing and comprise cinnamic mono-vinyl compound and solvent soluble polyfunctional vinyl multipolymer, solvent as required, polymerizing catalyst, chain-transfer agent etc., continuously monomer class is sent into the equipment that possesses series connection and/or be arranged in parallel 1 above reactor and remove the volatile component removing step of unreacted monomer etc., periodically made it polymerization.As the pattern of reactor, exemplified with the tank reactor of complete mixed type, have piston fluidity tower reactor, carry out polymerization while discharge circular form reactor of a part of polymer fluid etc.Putting in order of these reactors is not particularly limited, but in producing continuously in order to suppress the generation of gelling material, be under unreacted state at solvent soluble polyfunctional vinyl multipolymer, the state that does not occur high density be detained in the film of the border of reactor wall is important, as the first reactor, preferably select the tank reactor of complete mixed type.
In addition, as polymerization process of the present invention, also preferably use what is called to be suspended polymerization: after adding and mixing and comprise cinnamic mono-vinyl compound, solvent soluble polyfunctional vinyl multipolymer, polymerizing catalyst, chain-transfer agent etc. as required, it is suspended in water, carries out polymerization.In order to make decentralized stabilization, to being dissolved with the organic system such as polyvinyl alcohol, methylcellulose gum dispersion agent, or tricalcium phosphate, magnesium sulfate etc. inorganic be to drop into monomer class in the anionic surfactant's such as dispersion agent, Sodium dodecylbenzene sulfonate water, under agitation make it to disperse, in the scope of 100～150 DEG C, carry out polymerization.If it is rear directly constant under water-dispersion state to consider that reaction finishes, make it the situation of depressing the aliphatic hydrocarbon foamed gas such as impregnation pentane adding, final polymerisation conversion when preferred reaction finishes is more than 99%.If less than 99%, more than the boiling point that temperature in the time of post forming is remaining monomer, follow significant stench.
In the present invention, be more than 99% in order to make final polymerisation conversion, preferably to respect to raw material Intake Quantity, the material solution that the superoxide series catalysts 200ppm that to have added 1 hour half life temperature be the scope of 130 ± 10 DEG C forms is above after 120 DEG C of temperature of reaction are polymerized to more than 50% below, to exceed 5 DEG C of above temperature of reaction of half life temperature of above-mentioned catalyzer, carry out above polymerization in 3 hours.By using this condition, can not extend terrifically polymerization time, be more than 99% and can easily make final polymerisation conversion.In the case of the temperature of reaction of back segment be 1 hour below half life temperature, polymerization time extends terrifically, and productivity is significantly reduced.
Be more than 99% in order to make final transformation efficiency, as used organic peroxide evocating agent, exemplified with tert-butyl hydroperoxide acetic ester, tert butyl peroxy benzoate, 2,2-bis--(t-butyl peroxy) butane, dicumyl peroxide etc.
In the present invention, solvent soluble polyfunctional vinyl multipolymer can be dissolved under the state of mono-vinyl compounds, polymer solvent etc., as required, in continuous bulk polymerization situation multiple reactors midway, the interpolation midway of polyreaction in the time being suspended polymerization.
What use in the present invention (is also referred to as styrenic monomers) taking vinylbenzene as necessary mono-vinyl compound and can is vinylbenzene below as 100%, can be also the mixture that comprises vinylbenzene and other mono-vinyl compound.As other mono-vinyl compound, can enumerate have can with the material of styrene copolymerized olefinic double bond: the aromatic vinyls such as p-vinyl toluene are monomer class; The Acrylic Acid Monomer such as vinylformic acid, methacrylic acid; The vinyl cyanide monomer such as vinyl cyanide, methacrylonitrile; The α such as the acrylic monomer such as butyl acrylate, methyl methacrylate or Maleic Acid, Anhydrous, fumaric acid, β-ethylene unsaturated carboxylic acid class; The imide series such as phenyl maleimide, N-cyclohexylmaleimide monomer class.Can use these mono-vinyl compounds in addition one kind or two or more simultaneously.Therefore, because the ratio of the mono-vinyl compound of vinylbenzene and other is that 20～100 % by mole of vinylbenzene, other mono-vinyl compound are 0～80 % by mole of characteristic of bringing into play styrene resin composite, so preferably.
The solvent soluble polyfunctional vinyl multipolymer (being also referred to as below polyfunctional vinyl multipolymer) using in the present invention, for by carrying out copolymerization with styrenic monomers, produces the material of the phenylethylene resin series of the ultra-high molecular weight being branched branch.
The polyfunctional vinyl multipolymer using in the present invention can obtain according to disclosed method in JP 2004-123873 communique, JP 2005-213443 communique, WO2009/110453 etc.Specifically, use divinyl compound and the mono-vinyl compound more than at least one, make it copolymerization, obtain the multipolymer with the reactive side chain vinyl representing with formula (a1).Further, as above-mentioned patent documentation is recorded, can use the material that is imported into vinyl other terminal group in addition on end, particularly because the compound in the molecule as phenoxy group methyl acrylate class with unsaturated link(age) also be can be used as cross-linking set effect except (a1) by terminal-modified material, so preferably.Now, because the structural unit of the unsaturated link(age) that contains end (a2) also has vinyl, so shown the amount of overall vinyl with the molar fraction (a3) of the total of the structural unit of formula (a1).
In order to obtain polyfunctional vinyl multipolymer, as used divinyl compound, exemplified with the divinyl aromatics class taking Vinylstyrene as representative and the aliphatics taking ethylene glycol bisthioglycolate (methyl) acrylate as representative, ester ring type (methyl) esters of acrylic acid etc.
In addition, as mono-vinyl compound as used herein, can enumerate the mono-vinyl compound of the single-ethenyl aromatic compound that comprises as the aforementioned vinylbenzene etc.
As the manufacture method of polyfunctional vinyl multipolymer, can, by being for example selected from lewis acid catalyst, being selected under the existence of promotor of ester cpds, make the two or more compound that is selected from divinyl aromatics, single-ethenyl aromatic compound and other mono-vinyl compounds carry out cationic copolymerization and obtain.In addition, in the divinyl of use (methyl) acrylic ester, the situation of mono-vinyl compound, because cationoid reaction does not carry out, so can, under the existence of the free radical catalysts such as superoxide, obtain by radical polymerization.
The usage quantity of divinyl compound and mono-vinyl compound, with produce the polyfunctional vinyl multipolymer using in the present invention composition mode and determine, but preferably use 10～90 % by mole, more preferably 30～90 % by mole of whole monomers, be more preferably the divinyl compound of 50～90 % by mole.Preferably use 90～10 % by mole, more preferably 70～10 % by mole of whole monomers, be more preferably the mono-vinyl compound of 50～10 % by mole.At this, as 2-phenoxy group ethylacrylic acid methyl esters in cationoid polymerisation, the material working as terminal-modified dose does not calculate as monomer.
As the lewis acid catalyst using in the manufacture of polyfunctional vinyl multipolymer, for comprising the compound of metal ion (acid) and ligand (alkali), can be not particularly limited and use if can accept the material of electron pair.From the control of molecular weight and molecualr weight distribution and the viewpoint of polymerization activity, most preferably use ether (diethyl ether, the dme etc.) complex compound of boron trifluoride.Lewis acid catalyst, with respect to 1 mole of whole monomer, uses in the scope of 0.001～10 mole, but more preferably 0.001～0.01 mole.If it is not the usage quantity of lewis acid catalyst is excessive, because polymerization velocity becomes too fast, so the control of molecular weight distribution becomes difficulty, therefore preferred.
As promotor, can enumerate and be selected from the more than a kind of ester cpds.Wherein, from the viewpoint of the molecular weight distribution control of polymerization velocity and multipolymer, preferably use the ester cpds of carbon number 4～30.From the viewpoint easily obtaining, preferably use ethyl acetate, propyl acetate and butylacetate.Promotor, with respect to 1 mole of monomeric compound, uses in 0.001～10 molar range, but more preferably 0.01～1 mole.If the usage quantity of promotor is excessive, polymerization velocity reduces, and the productive rate of multipolymer declines.On the other hand, if the usage quantity of promotor is too small, the elective reduction of polyreaction, except producing the increase of molecular weight distribution, outside the generation of gel etc., the control of polyreaction also becomes difficulty.
In addition, as the catalyzer using in the time manufacturing polyfunctional vinyl multipolymer by radical polymerization, exemplified with the superoxide or 1 of the simple functions such as the azo-compound as taking Diisopropyl azodicarboxylate as representative, dibenzoyl peroxide, t-butyl peroxy benzoic ether, multi-functional superoxide more than such 2 functionalities of two (tert-butyl hydroperoxide) hexanaphthenes of 1-, can use it separately or use two or more simultaneously.
The polyfunctional vinyl multipolymer using in the present invention can obtain by manufacture method described above, but the not polymerization of a part of the vinyl of the divinyl compound that need to use as monomer and residual.Therefore, on average in 1 molecule, there are more than at least 2 preferably 3 above vinyl.This vinyl exists mainly as the structural unit representing with above formula (a1).Therefore, there is not polymerization and residual by a part for vinyl, can suppress crosslinking reaction, give solvent soluble.At this, so-called solvent soluble refers to and dissolves in toluene, dimethylbenzene, tetrahydrofuran (THF) (THF), ethylene dichloride or chloroform, more than saying specifically dissolve 5g in these solvents 100g in the time of 25 DEG C, do not produce gel.On the other hand, a part for divinyl compound, because the reaction of two vinyl is cross-linked or branch is necessary, can become the multipolymer with branched structure thus.So, for a part for divinyl compound, make one of 2 vinyl to react, not polymerization and residual, for other a part, reacts 2 vinyl, can obtain thus the polyfunctional vinyl multipolymer using in the present invention.The such a polymerization process that obtains polyfunctional vinyl multipolymer, is known as mentioned above, can be so that mode as above and manufacturing.
The weight-average molecular weight (Mw) of polyfunctional vinyl multipolymer is preferably 1,000～100,000, and more preferably 5,000～70,000.Be less than 1000 situation, the situation of divinyl aromatic compound or multifunctional (methyl) esters of acrylic acid is same with using, in successive polymerization, suppressing the effect that gelation carries out reduces, also become difficulty in the control that is suspended the molecular weight distribution in high conversion region in polymerization, can not obtain sufficient effect, therefore not preferred.
The unit that is imported into the vinyl that contains divinyl compound source of polyfunctional vinyl multipolymer has the structural unit representing with above-mentioned formula (a1), but the molar fraction of this structural unit (a1) is 0.05～0.50.Be less than in the situation of 0.05 mole, be difficult to obtain high branching type ultrahigh molecular weight copolymer, therefore not preferred.On the other hand, exceed in the situation of 0.50 mole, the molecular weight of high branching type ultrahigh molecular weight copolymer excessively increases, and gelation becomes easy generation, therefore not preferred.In addition, as mentioned above, because by thering is the compound of unsaturated link(age) in molecule and the terminal-modified material structural unit except representing with formula (a1), the structural unit (a2) of the unsaturated link(age) that contains end also has vinyl, so the molar fraction (a3) that both add up to can be 0.05～0.50.
In addition, the scope that the ratio of the radius of inertia (nm) in preferred its weight-average molecular weight of polyfunctional vinyl multipolymer and the molar fraction of said structure unit (a1) or the molar fraction (a3) of above-mentioned total is 1～100.In order not follow, the branching type ultra-high molecular weight composition gelation for giving strain solidified nature is modulated to more preferably 10～80 scope.Above-mentioned ratio exceedes in 100 situation, and gelation is not carried out, but is difficult to obtain high branching type ultrahigh molecular weight copolymer, therefore not preferred.On the other hand, be less than in 1 situation, the molecular weight of high branching type ultrahigh molecular weight copolymer excessively increases, and gelation easily occurs, therefore not preferred.At this, the radius of inertia is the value of utilizing the method for recording in embodiment to measure.In addition, polyfunctional vinyl multipolymer is the polymkeric substance with the distribution of molecular weight aspect, certainly, because this radius of inertia also has distribution, so the mean value of the radius of inertia as a whole of the radius of inertia in employing weight-average molecular weight.
Index in this defined expression radius of inertia with the content of two keys, the ratio that is the molar fraction of structure unit (a1) or the molar fraction (a3) of above-mentioned total can be said as in the time forming branching type ultra-high molecular weight composition, represent that the polyfunctional vinyl multipolymer that becomes core in much scopes, has the index of the reflecting point of what degree in polymeric reaction solution.If this is than too small, near reflecting point is positioned at, becomes and easily cause gelation, in addition, if this is than excessive, the polymer of branching type composition quantizes to become difficulty.
Fit rate as polyfunctional vinyl multipolymer with respect to styrenic monomers, in weight basis, preferably 50ppm～5000ppm, more preferably 100ppm～3000ppm.The fit rate of polyfunctional vinyl multipolymer is less than in the situation of 50ppm, is difficult to obtain sufficient effect of the present invention, therefore not preferred.On the other hand, exceed in the situation of 5000ppm, have the possibility that produces gel.
By making aforementioned multifunctional vinyl compound multipolymer and styrenic monomers polymerization, obtain the mixture as the high branching type ultrahigh molecular weight copolymer (also referred to as high branching type multipolymer) of the multipolymer of polyfunctional vinyl multipolymer and styrenic monomers and the linear polymer that only generated by styrenic monomers, i.e. styrene resin composite of the present invention.As styrenic monomers, use in the situation of monomer of more than two kinds, linear polymer becomes multipolymer.
The weight-average molecular weight (Mw) of the styrene resin composite obtaining by the present invention is preferably 200,000～800,000.Mw less than 200,000, the shock strength after processing is insufficient, and Mw exceedes 800,000, viscosity rise, it is insufficient that processibility becomes.
In styrene resin composite as above, comprise high branched copolymers and linear polymer, but by making it the styrene resin composite for showing Mw as above, the Mw of high branched copolymers becomes more than 1,000,000 ultra-high molecular weights, and linear polymer becomes 100,000～500,000.Therefore, preferably Mw is that more than 1,000,000 high branch ultrahigh molecular weight copolymer and Mw are that the ratio of 100,000～500,000 wire styrenic is 2:98～20:80.These ratio, can, by adjusting mixing ratio and the polymerizing condition of polyfunctional vinyl multipolymer with respect to styrenic monomers, control.
About the manufacture of styrene resin composite, from the viewpoint of the control of polyreaction, as required, can use the chain-transfer agent such as the polymerization starter such as polymer solvent, organo-peroxide or aliphatics mercaptan.
Polymer solvent is in continuous bulk polymerization, use in order to reduce the viscosity of reactant, as this organic solvent, can enumerate toluene, ethylbenzene, dimethylbenzene, acetonitrile, benzene, chlorobenzene, dichlorobenzene, methyl-phenoxide, cyano group benzene, dimethyl formamide, N,N-dimethylacetamide, methyl ethyl ketone etc.
Particularly in continuous bulk polymerization, in the case of wanting to make the interpolation quantitative change how of polyfunctional vinyl multipolymer, from suppressing the viewpoint of gelation, also preferably with an organic solvent.Thus, the addition of the polyfunctional vinyl multipolymer shown in can making previously increases tremendously, is difficult to produce gel.
The usage quantity of organic solvent is not particularly limited, but from controlling the such viewpoint of gelation, preferably with respect to total amount 100 weight parts of monomer component, is 1～50 weight part, more preferably in the scope of 5～30 weight parts conventionally.Exceed in the situation of 50 weight parts, productivity significantly reduces, and the molecular weight of chain phenylethylene resin series excessively reduces, therefore not preferred.
As polymerization starter, preferably radical polymerization initiator, can enumerate known conventional for example 1,1-bis-(t-butylperoxy) hexanaphthene, 2,2-bis-(t-butylperoxy) butane, 2, the ketal peroxide classes such as 2-bis-(4,4-, bis--butyl peroxy cyclohexyl) propane; The hydroperoxide type such as cumene hydroperoxide, tert-butyl hydroperoxide; Di-t-butyl peroxide, dicumyl peroxide, two-dialkyl peroxide classes such as tertiary hexyl superoxide; The diacyl peroxide such as benzoyl peroxide, diacyl peroxide class; The peroxyesters such as tert butyl peroxy benzoate, two-t-butyl peroxy isophthalic acid ester, t-butylperoxy propyl group monocarbonate; N, N'-Diisopropyl azodicarboxylate, N, N'-azo two (hexanaphthene-1-formonitrile HCN), N, N'-azo two (2-methylbutyronitrile), N, N'-azo two (2,4-methyl pentane nitrile), N, N'-azos two [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 chain-transfer agent, can use the simple function chain-transfer agent that there is 1 chain and shift base, the Polyfunctional chain transfer agent with multiple chains transfer bases.As simple function chain-transfer agent, can enumerate alkyl sulfide alcohols, mercaptoacetate class etc.
As Polyfunctional chain transfer agent, can enumerate by the material of the polyvalent alcohol hydroxyls such as thioglycolic acid or 3-thiohydracrylic acid and esterification ethylene glycol, neopentyl glycol, TriMethylolPropane(TMP), tetramethylolmethane, Dipentaerythritol, tripentaerythritol, Sorbitol Powder.
Embodiment
Below use embodiment further to specifically describe the present invention.The measuring method using is as described below.
(GPC assay method) molecular-weight average of bioassay standard polystyrene conversion during by Liquid Chromatograph (Tosoh Corporation HLC-8220GPC processed), RI detector, tsk gel GMH × 1 × 2, solvents tetrahydrofurane, flow velocity 1.0ml/ minute, 40 DEG C of temperature.
(two key quantitative method) structural unit (a1), two keys (a2) in terminal-modified dose of source and the molar fraction (a3) of both totals are for being used NEC JNM-LA600 type processed nucleus magnetic resonance light-dividing device, analyze by 13C-NMR and 1H-NMR, determine structure.As solvent, use chloroform-d1, use the resonance line of tetramethylsilane as internal standard.
(radius of inertia) filters by film filter after sample being adjusted into 0.5% tetrahydrofuran solution, uses GPC multi-angle light scattering method to measure filtrate.Further, sample being adjusted into 0.2% tetrahydrofuran solution places 1 day afterwards.Thereafter, using tetrahydrofuran (THF) dilution is the solution of 4 kinds of concentration (0.02,0.05,0.10,0.12 % by weight), uses these solution, carries out dn/dc mensuration, is calculated the radius of inertia of sample by the dn/dc value obtaining.
(confirmation of gelling material) used injection molding machine, is configured as the flat board of 180mm × 180mm × 3mm, by visual, confirms having or not of the linear trace from door section that produces in the time containing gelling material.
Synthesis example 1
(polyfunctional vinyl multipolymer α)
Divinylbenzene 3.1 moles of (399.4g), EST 0.7 mole of (95.1g), vinylbenzene 0.3 mole of (31.6g), 2-phenoxy group ethyl-methyl acrylate 2.3 moles of (463.5g), toluene 974.3g are dropped in the reactor of 3.0L, the boron trifluoride diethyl ether complex compound that adds 42.6g in the time of 50 DEG C, makes it to react 6.5 hours.Make after polyreaction stops, washing oil reservoir 3 times by pure water by sodium hydrogen carbonate solution, in the time of room temperature, reaction mixture is dropped in a large amount of methyl alcohol, polymkeric substance is separated out.By obtained polymkeric substance washing, filtration, dry, weighing, obtain polyfunctional vinyl multipolymer α 372.5g by methyl alcohol.The weight-average molecular weight Mw of this polyfunctional vinyl multipolymer α is 8000, and the molar fraction (a3) that the molar fraction of the structure unit (a1) of the vinyl that contains divinyl compound source is 0.44, two keys (a2) in the 2-phenoxy group ethyl-methyl acrylate source of end are 0.03, combine both totals is 0.47.In addition, the radius of inertia (r) of the multipolymer 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, the polyfunctional vinyl multipolymer in known synthesis example has branched structure.In addition, calculating the radius of inertia (r) is 13.6 with the ratio (r/a3) of molar fraction (a3).
Synthesis example 2
(polyfunctional vinyl multipolymer β)
Divinylbenzene 2.6 moles of (332.0g), EST 1.5 moles of (198.0g), vinylbenzene 1.1 moles of (109.6g), 2-phenoxy group ethyl-methyl acrylate 3.1 moles of (630.4g), toluene 886.0g are dropped in the reactor of 3.0L, the boron trifluoride ethyl ether complex that adds 35.5g in the time of 50 DEG C, makes it to react 5.0 hours.Make after polyreaction stops, washing oil reservoir 3 times by pure water by sodium hydrogen carbonate solution, in the time of room temperature, reaction mixture is dropped in a large amount of methyl alcohol, polymkeric substance is separated out.By obtained polymkeric substance washing, filtration, dry, weighing, obtain polyfunctional vinyl multipolymer β 564.0g by methyl alcohol.The Mw of this polyfunctional vinyl multipolymer β is 5000, the molar fraction of the structural unit (a1) of the vinyl that contains divinyl compound source is 0.25, two keys (a2) in the 2-phenoxy group ethyl-methyl acrylate source of end are 0.02, and the molar fraction (a3) that combines both totals is 0.27.In addition, the radius of inertia of the multipolymer in weight-average molecular weight is 8.1nm.Compared with being 12nm with the radius of inertia in the molecular weight 5000 of straight chain type, the polyfunctional vinyl multipolymer in known synthesis example has branched structure.
Synthesis example 3
(polyfunctional vinyl multipolymer γ)
Divinylbenzene 1.2 moles of (159.8g), EST 0.7 mole of (95.3g), vinylbenzene 2.1 moles of (223.2g), 2-phenoxy group ethyl-methyl acrylate 3.1 moles of (632.0g), toluene 1082.5g are dropped in the reactor of 3.0L, the boron trifluoride diethyl ether complex compound that adds 56.8g in the time of 50 DEG C, makes it to react 6.0 hours.Make after polyreaction stops, washing oil reservoir 3 times by pure water by sodium hydrogen carbonate solution, in the time of room temperature, reaction mixture is dropped in a large amount of methyl alcohol, polymkeric substance is separated out.By the polymkeric substance washing obtaining, filtration, dry, weighing, obtain polyfunctional vinyl multipolymer γ 340.8g by methyl alcohol.The Mw of this polyfunctional vinyl multipolymer γ is 5000, and the molar fraction of the structural unit (a1) of the vinyl that contains divinyl aromatics source is 0.13, two keys (a2) in the 2-phenoxy group ethyl-methyl acrylate source of end are 0.01, combine both molar fractions (a3) of total is 0.14.In addition, the radius of inertia of the multipolymer in weight-average molecular weight is 10.6nm.Compared with being 12nm with the radius of inertia in the molecular weight 5000 of straight chain type, the polyfunctional vinyl multipolymer in known synthesis example has branched structure.
Polyfunctional vinyl multipolymer in above-mentioned synthesis example 1～3 all dissolves in toluene, dimethylbenzene, tetrahydrofuran (THF), ethylene dichloride and chloroform.
Embodiment 1
Equably after benzene mixed ethene 85 weight parts, ethylbenzene 15 weight parts, polyfunctional vinyl multipolymer (α) 0.06 weight part, within 15L/ hour, to send into continuously continuous bulk polymerization equipment, described mass polymerization equipment have 2 tank reactors that are connected in series, in keep static mixer internal volume 15L tower reactor and there is preheater and the volatile component of the flashing chamber type of vacuum tank is removed device, tank reactor has the complete Combination of internal volume 30L, and static mixer has piston fluidity.Be that 140 DEG C, the inlet portion of the 3rd reactor are that 140 DEG C, export department are after the mode of 160 DEG C periodically improves temperature so that the first reactor is 130 DEG C, the second reactor, be transferred to the preheater that is heated to 220 DEG C, be dropped in by pressure be adjusted into 8 holders preheater under vacuum tank, remove thus unreacted monomer, solvent, utilize toothed gear pump from vacuum tank on one side afterwards, be thread shape by resin drawing, shear on one side, obtain thus styrene resin composite.After arriving and keeping the constant steady state of this steady state, the resin combination after 24 hours, 72 hours, 144 hours is implemented to the evaluation of molecular weight, gelling material, be the results are shown in table 1.
Embodiment 2
Except replacing the polyfunctional vinyl multipolymer (α) in embodiment 1, use outside polyfunctional vinyl multipolymer (β), operation similarly to Example 1, obtains polystyrene resin polymkeric substance.The molecular weight of each time, the evaluation result of gelling material in table 1, are shown.
Embodiment 3
Except replacing the polyfunctional vinyl multipolymer (α) in embodiment 1, use outside polyfunctional vinyl multipolymer (γ), operation similarly to Example 1, obtains polystyrene resin polymkeric substance.The molecular weight of each time, the evaluation result of gelling material in table 1, are shown.
Embodiment 4
Except addition 0.06 weight part that makes the polyfunctional vinyl multipolymer (α) in embodiment 1 becomes 0.01 weight part, operation similarly to Example 1, obtains polystyrene resin composite.The molecular weight of each time, the evaluation result of gelling material in table 1, are shown.
Embodiment 5
Be that 70 weight parts, ethylbenzene are 30 weight parts except making vinylbenzene, addition 0.06 weight part of the polyfunctional vinyl multipolymer (α) in embodiment 1 becomes outside 0.3 weight part, operation similarly to Example 1, obtains polystyrene resin polymkeric substance.The molecular weight of each time, the evaluation result of gelling material in table 1, are shown.
Embodiment 6
Except addition 0.06 weight part that makes the polyfunctional vinyl multipolymer (α) in embodiment 1 becomes 0.1 weight part, with the vinylbenzene while, add outside tertiary lauryl mercaptan (tDM) 0.05 weight part, operation similarly to Example 1, obtains polystyrene resin composite.
Comparative example 1
Except not adding polyfunctional vinyl multipolymer (α), operation similarly to Example 1, obtains wire polystyrene.
Comparative example 2
Except addition 0.06 weight part that makes the polyfunctional vinyl multipolymer (α) in embodiment 1 becomes 0.001 weight part, operation similarly to Example 1, obtains polystyrene resin composite.
Comparative example 3
Except addition 0.06 weight part that makes the polyfunctional vinyl multipolymer (α) in embodiment 1 becomes 1 weight part, operation similarly to Example 1, obtains polystyrene resin composite.
Comparative example 4
Except replacing the polyfunctional vinyl multipolymer (α) in embodiment 1, making divinylbenzene is beyond 0.05 weight part, and operation similarly to Example 1, obtains polystyrene resin composite.The molecular weight of each time, the evaluation result of gelling material in table 1, are shown.Within 24 hours, do not observe gelling material, but within 72 hours, produced gelling material, within 144 hours, become the state that contains in a large number gelling material.
Comparative example 5
Except replacing the polyfunctional vinyl multipolymer (α) in embodiment 1, making divinylbenzene is beyond 0.025 weight part, and operation similarly to Example 1, obtains polystyrene resin composite.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 multipolymer (α) in embodiment 1, use divinylbenzene 0.05 weight part, the ratio that makes vinylbenzene and solvent ethylbenzene is beyond vinylbenzene 70 weight parts, ethylbenzene 30 weight parts, and operation similarly to Example 1, obtains polystyrene resin composite.
The usage quantity of reaction raw materials in embodiment 1～6 and comparative example 1～6 and the physical property of polystyrene resin composite are gathered and be shown in table 1.
Embodiment 7
To being provided with the shell of 10 liters of internal volumes, packing into and evenly mixed the styrene monomer 3kg of polyfunctional vinyl multipolymer (α) 0.06 weight part and comprised as being suspended tricalcium phosphate 0.05 weight part of stablizer, water 4kg as Sodium dodecylbenzene sulfonate 0.005 weight part of tensio-active agent with the reactor of stirrer, under agitation make solution be suspended.Add with respect to styrene monomer 100 weight parts to this suspension liquid, as t-butyl peroxy benzoic ether 0.2 weight part of polymerization starter, further add α-methylstyrenedimer 0.04 weight part as chain-transfer agent.Stir suspension liquid on one side, in the time of 115 DEG C, heat 5 hours on one side, in the time of 140 DEG C, heat and within 3 hours, carry out polymerization.After polymerization finishes, add hydrochloric acid to suspension liquid, neutralization is as the tricalcium phosphate that is suspended stablizer.By the resin washing of the pearl of acquisition, filter after, carry out warm air drying, obtain styrene resin composite.
Embodiment 8
Except replacing the polyfunctional vinyl multipolymer (α) in embodiment 7, use polyfunctional vinyl multipolymer (β) in addition, operation similarly to Example 7, obtains styrene resin composite.
Embodiment 9
Except replacing the polyfunctional vinyl multipolymer (α) in embodiment 7, use polyfunctional vinyl multipolymer (γ) in addition, operation similarly to Example 7, obtains styrene resin composite.
Embodiment 10
Except addition 0.06 weight part that makes the polyfunctional vinyl multipolymer (α) in embodiment 7 becomes 0.01 weight part, operation similarly to Example 7, obtains polystyrene resin composite.
Embodiment 11
Except addition 0.06 weight part that makes the polyfunctional vinyl multipolymer (α) in embodiment 7 becomes 0.1 weight part, operation similarly to Example 7, obtains polystyrene resin composite.
Comparative example 7
Except not adding polyfunctional vinyl multipolymer (α), operation similarly to Example 7, obtains wire polystyrene.
Comparative example 8
Except addition 0.06 weight part that makes the polyfunctional vinyl multipolymer (α) in embodiment 7 becomes 0.001 weight part, operation similarly to Example 7, obtains polystyrene resin composite.
Comparative example 9
Except addition 0.06 weight part that makes the polyfunctional vinyl multipolymer (α) in embodiment 7 becomes 1 weight part, operation similarly to Example 7, obtains polystyrene resin composite.
Comparative example 10
Except replacing the polyfunctional vinyl multipolymer (α) in embodiment 7, making divinylbenzene is beyond 0.05 weight part, and operation similarly to Example 7, obtains polystyrene resin composite.
The usage quantity of reaction raw materials in embodiment 7～11 and comparative example 7～10 and the physical property of polystyrene resin composite are gathered and be shown in table 2.
In table 1～2, linking agent means polyfunctional vinyl multipolymer or divinylbenzene (DVB), and chain-transfer agent means tDM.Entirety Mw means the weight-average molecular weight of polystyrene resin composite, Mw1, more than 000,000 ratio means the ratio (% by weight) in polystyrene resin composite, Y in the evaluation of gelling material means to exist gelling material, and N means not exist gelling material.
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, can produce the microgel that does not comprise the fracture of bringing out thinner wall section, further, contain taking strain solidified nature as representative dissolve excellence aspect characteristic, calendering time the high branching type ultrahigh molecular weight copolymer of wall thickness and the styrene resin composite of linear polymer equably.Further, the styrene resin composite that utilizes the present invention to obtain by use, what sagging, the uneven thickness while being suppressed in sheet forming because of secondary processing, 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, air bubble expansion, generate the variety of issues such as bubble continuously.
Claims (3)
1. the manufacture method of styrene resin composite, it is for manufacturing the method for the styrene resin composite that contains high branching type ultrahigh molecular weight copolymer and linear polymer, it is characterized in that, to thering is vinyl more than 2 with weight basis as necessary mono-vinyl compound adds taking vinylbenzene in average 1 molecule, there is the solvent soluble polyfunctional vinyl multipolymer 50ppm～5000ppm of branched structure, carry out polyreaction, the high branching type ultrahigh molecular weight copolymer that acquisition comprises this solvent soluble polyfunctional vinyl multipolymer and this mono-vinyl compound copolymerization generation, the styrene resin composite of the linear polymer that this mono-vinyl compound polymerization generates.
2. the manufacture method of styrene resin composite claimed in claim 1, it is characterized in that, solvent soluble polyfunctional vinyl multipolymer is that polymerization can obtain with the mono-vinyl compound of divinyl compound copolymerization, the unit that further contains with 0.05～0.50 scope the side chain vinyl that contains divinyl compound source being represented by following formula (a1) as molar fraction in structural unit, in the scope that the radius of inertia (nm) in weight-average molecular weight and the ratio of above-mentioned molar fraction are 1～100
(in formula, R
1represent to derive from the alkyl of divinyl compound).
3. styrene resin composite, it is the styrene resin composite that method according to claim 1 and 2 obtains, it is characterized in that, containing weight-average molecular weight is 1,000, more than 000 high branching type ultrahigh molecular weight copolymer 2.0～20.0 % by weight and weight-average molecular weight are 100,000～500,000 wire styrenic 80.0～98.0 % by weight, weight-average molecular weight is 200,000～800,000.
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| PCT/JP2011/075578 WO2013069077A1 (en) | 2011-11-07 | 2011-11-07 | Method for producing styrene-based resin composition comprising highly branched ultra-high-molecular-weight polymer, and composition |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104628922A (en) * | 2014-09-30 | 2015-05-20 | 青岛科技大学 | Preparation method of ultra-high molecular weight polystyrene used for selective laser sintering rapid formation |
| CN106008841A (en) * | 2015-03-25 | 2016-10-12 | 株式会社Jsp | Composite resin particles and manufacturing method thereof |
| CN109906238A (en) * | 2016-11-01 | 2019-06-18 | 日铁化学材料株式会社 | Copolymer rubber and its manufacturing method and crosslinked rubber composition |
| CN110945043A (en) * | 2017-07-21 | 2020-03-31 | 株式会社Jsp | Styrene resin and process for producing styrene resin |
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| KR102498471B1 (en) * | 2014-12-26 | 2023-02-10 | 닛테츠 케미컬 앤드 머티리얼 가부시키가이샤 | Terminal-modified soluble polyfunctional vinyl aromatic copolymer, and curable resin composition and optical waveguide produced using 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 |
| 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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| CN101641380A (en) * | 2007-03-26 | 2010-02-03 | 新日铁化学株式会社 | Soluble polyfunctional vinyl aromatic copolymer, and method for production thereof |
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| JP2684400B2 (en) * | 1989-01-09 | 1997-12-03 | 出光石油化学株式会社 | Styrene polymer and method for producing the same |
| JP4401456B2 (en) * | 1998-10-23 | 2010-01-20 | ダイセル化学工業株式会社 | Styrenic resin composition and molding sheet using the same |
| JP4338951B2 (en) * | 2002-10-01 | 2009-10-07 | 新日鐵化学株式会社 | Soluble polyfunctional vinyl aromatic copolymer and polymerization method thereof |
| JP4842024B2 (en) * | 2006-06-15 | 2011-12-21 | 新日鐵化学株式会社 | Soluble polyfunctional vinyl aromatic copolymer and method for producing the same |
| JP5658607B2 (en) * | 2010-03-31 | 2015-01-28 | 新日鉄住金化学株式会社 | Method for producing styrenic resin composition containing hyperbranched ultrahigh molecular weight substance and composition thereof |
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| CN101641380A (en) * | 2007-03-26 | 2010-02-03 | 新日铁化学株式会社 | Soluble polyfunctional vinyl aromatic copolymer, and method for production thereof |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104628922A (en) * | 2014-09-30 | 2015-05-20 | 青岛科技大学 | Preparation method of ultra-high molecular weight polystyrene used for selective laser sintering rapid formation |
| CN106008841A (en) * | 2015-03-25 | 2016-10-12 | 株式会社Jsp | Composite resin particles and manufacturing method thereof |
| CN106008841B (en) * | 2015-03-25 | 2020-03-31 | 株式会社Jsp | Composite resin particle and method for producing same |
| CN109906238A (en) * | 2016-11-01 | 2019-06-18 | 日铁化学材料株式会社 | Copolymer rubber and its manufacturing method and crosslinked rubber composition |
| CN110945043A (en) * | 2017-07-21 | 2020-03-31 | 株式会社Jsp | Styrene resin and process for producing styrene resin |
| CN110945043B (en) * | 2017-07-21 | 2022-10-11 | 株式会社Jsp | Styrene-based resin and method for producing styrene-based resin |
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| CN103917594B (en) | 2016-05-11 |
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