CN1345895A - Transparent phonylethylene resin composition - Google Patents
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- CN1345895A CN1345895A CN 00129533 CN00129533A CN1345895A CN 1345895 A CN1345895 A CN 1345895A CN 00129533 CN00129533 CN 00129533 CN 00129533 A CN00129533 A CN 00129533A CN 1345895 A CN1345895 A CN 1345895A
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Abstract
The present invention discloses a transparent styrene series resin composition composed of (by weight portion) 100 portions of transparent styrene series resin and 0.01-5 portions of esters compound of pentaerythritol, in which the molecular weight of dichloromethane soluble substance being in the transparent styrene series resin is less than 350, and it contains no monomer and solvent content, and is below 2.0 wt% of all soluble components. By adding esters compound of pentaerythritol and controlling specific molecular weight in the transparent styrene series resin it can make the transparent styrene series resin composition possesses good transparency and processability, at the same time do not produce die pollution when it is formed.
Description
The invention relates to a kind of transparent phonylethylene resin composition, especially refer to a kind of ester compound that in phenylethylene resin series, adds tetramethylolmethane, and styrene is a lower molecular weight content specific in the resin, obtain the transparency and processibility is good, can not produce the transparent phonylethylene resin composition of mold fouling during moulding simultaneously.
Phenylethylene resin series is a kind of material with good strength and processing forming, especially transparent phenylethylene resin series more can be used in the transparent food container, especially transparent phenylethylene resin series more can be used in the transparent food container, household supplies such as packing material, family's electrical article, and on the shell of OA machine, but because present phenylethylene resin series is in processing, its processing conditions is for the thin meatization of finished product and the tight day by day lotus of demand of maximization, therefore, for under the prerequisite that does not undermine rerum natura, improve the processibility of synthetic resin, be to have the dealer in phenylethylene resin series, to add a spot of lubricant in known skill, auxiliary when being used as machine-shaping is used the processing fluidity that improves the moulding product; And the processing aids that is generally used in phenylethylene resin series for example is: the metallic salt of lipid acid, wherein, the amine of calcium stearate, Zinic stearas, lipid acid (as the ethene bis-stearamides) truly has the effect of improvement for processibility.
As once addressing in the special fair 2-52923 application for a patent for invention case of Japan, when phenylethylene resin series is made, in reactive tank, add the ethene stearic bicine diester amine aqueous solution of 1～8 weight part, can improve the processibility of resin; And address in the Japanese kokai publication sho 63-33455 application for a patent for invention case, it is mixing to add calcium stearate or Zinic stearas in phenylethylene resin series, in the time of can improving resin forming from mould; In addition, day disclosure is speciallyyed permit in the flat 7-82439 application for a patent for invention case and is narrated, in phenylethylene resin series, add butyl stearate (butyl stearate) and a spot of triglyceride (triglyceride), can improve resin flow and shock-resistance; Yet add additives such as lubricant or parting agent in transparent phenylethylene resin series, reach from mould though can improve the processibility of resin, aforementioned additive can cause the transparent variation of resin, and can't obtain having the phenylethylene resin series of good transparency; Some additive also can cause situations such as mold fouling when ejection formation, especially when the ejection formation of high temperature, thin meatization problem with even more serious; The present invention i.e. desire solves the existing shortcoming of above-mentioned prior art.
Therefore, the objective of the invention is is providing a kind of transparency, processibility good, and can not produce the transparent phonylethylene resin composition of mold fouling phenomenon during moulding.
And transparent phonylethylene resin composition of the present invention be by:
＜I〉the transparent styrene resin of 100 weight parts; And
＜II〉ester compound of tetramethylolmethane of 0.01～5 weight part forms;
Wherein, the molecular weight of methylene dichloride solvend accounts for below the 2.0 whole solvable part weight % less than 350 low-molecular weight polymer content in the transparent phenylethylene resin series.
Transparent styrene resin of the present invention is meant to have the transparency, generally speaking, is meant and further processes painted preceding light penetration rate as yet 60% above person.
Transparent styrene resin of the present invention can be divided into two types, and promptly rubber-modified transparent styrene resin reaches the transparent styrene resin that does not contain rubber.The transparent styrene resin that does not wherein contain rubber is meant to contain the above phenylethylene resin series of styrenic monomers 30 weight %, that is, styrenic monomers 100～30 weight %, and other copolymerizable monomer 0～70 weight % institute constitutors.There is no particular restriction for above-mentioned other copolymerizable monomers, as long as can and reach transparent person with the styrenic monomers copolymerization.
The copolymerizable monomer object lesson that the present invention does not contain the transparent styrene resin of rubber can be: (methyl) acrylic ester monomer, the acrylic monomer, maleimide is a monomer, (methyl) acrylic acid series, Maleic Acid, Anhydrous and glycolmethacrylate, wherein, (methyl) acrylic ester monomer can be: methyl acrylate, ethyl propenoate, butyl acrylate, methyl methacrylate, Jia Jibingxisuanyizhi, propyl methacrylate, butyl methacrylate, the methacrylic acid benzene methyl, N-Hexyl methacrylate, cyclohexyl methacrylate, lauryl methacrylate, methacrylic acid 2-hydroxyl ethyl ester, glycidyl methacrylate, and Dimethylaminoethyl Methacrylate etc., wherein be best with the methyl methacrylate.
And the acrylic monomer can be: vinyl cyanide or Alpha-Methyl vinyl cyanide wherein, are best with the vinyl cyanide.
Maleimide is that monomer can be selected from: N-methyl maleimide, N-sec.-propyl maleimide, the N-butyl maleimide, N-hexyl maleimide, N-octyl group maleimide, N-dodecyl maleimide, N-cyclohexyl maleimide, N-phenylmaleimide, N-2,3-tolyl maleimide, N-2,4-tolyl maleimide, N-2,3-ethylbenzene base maleimide, N-2,4-ethylbenzene base maleimide, N-2,3-butylbenzene base maleimide, N-2,4-butylbenzene base maleimide, N-2,6-tolyl maleimide, N-2,3-chloro-phenyl-maleimide, N-2,4-chloro-phenyl-maleimide, N-2,3-bromophenyl Malaysia imide, N-2,4-bromophenyl Malaysia imide wherein, is best with the N-phenylmaleimide.
And the object lesson that does not contain the transparent styrene resin of rubber has: polystyrene, polystyrene-acrylic copolymer, polystyrene-(methyl) acrylate based copolymer, polystyrene-N-displacement maleimide system-acrylic copolymer, polystyrene-N-displacement maleimide based copolymer, polystyrene-(methyl) acrylic ester-N-displacement maleimide based copolymer, polystyrene-N-displacement maleimide system-acrylic-(methyl) acrylate based copolymer etc.
Another type of transparent styrene resin of the present invention: rubber-modified transparent styrene resin is preferably the transparent styrene resin through the diene series rubber modification.It can be rubber and the mixture that does not contain the transparent styrene resin of rubber, or rubber and styrenic monomers and other copolymerizable monomer are carried out graft polymerization and the person, aforementioned rubber for example is: divinyl, butadiene-styrene is cumulative or disorderly row or segmented copolymer etc.With regard to graft polymerization and the transparent styrene resin of modified rubber for, what it was preferable constitutes: the rubber particles disperse phase (A) that is formed by rubbery polymer, and monomer adds up to 100 weight parts by styrenic monomers 12～70 weight parts, (methyl) acrylic ester monomer 20～80 weight parts, acrylic monomer 0～20 weight part, and the multipolymer external phase (B) that other copolymerizable monomer 0～40 weight parts are formed is formed.
Aforesaid rubbery polymer is preferably by styrenic monomers 5～50 weight %, and diene monomer 95～50 weight % constitute; Above-mentioned rubbery copolymer is in the presence of organic solvent, use organolithium compound to be used as initiator, and with styrenic monomers, diene monomer, and proper amount of solvent is carried out the segmented copolymer that anionic polymerisation forms, the Mooney of above-mentioned multipolymer (Mooney) viscosity (ML
1+4) be 20～80, the viscosity of the styrene monomer solution of 25 ℃ 5 weight % is 3～60cps, and 1 in the diolefin series unit, the 2-vinyl structure accounts for more than the 8 weight %, the content of polystyrene block accounts for 5～35 weight % of rubbery copolymer, the structure of above-mentioned rubbery copolymer can be: all be homopolymer block (block) structure, part disorderly row's block structure, form part cumulative block (taper-block) structure, linear configuration and a difference structure etc., its representative construction can be: 1. shape block copolymer:
(1)(A-B)
n
(2)
(3)
In the following formula, A is for being the polymer block of main composition with polystyrene, and B is for being the polymer block of main composition with diene, and the boundary of A block and B block not necessarily needs clear and definite differentiation, n=1 or 1 above integer.2. difference shape segmented copolymer:
(1)
(2)
(3)
(4)
In the following formula, A, B are with the 1st explanation, and X is coupler residue (for example: silicon tetrachloride, tin tetrachloride etc.), or is polyfunctional organolithium compound residue, and n and m are 1～10 integer.3. the mixture of aforementioned the 1st and the 2nd 's arbitrary form.
In addition, forming a part cumulative block structure and can be vinylbenzene incremental block structure, perhaps is divinyl incremental block structure, and the object lesson of above-mentioned incremental block structure is as follows:
D-D/S-S (S-D/S)
n-S
D-S-D/S-S D/S-(S-D/S)
n
D-S-D/S-S-D X-[(S-D/S)
n]
m+1
S-D-D/S-S X-[(D/S-S)
n]
m+1
D/S-S-D-S X-[(S-D/S)
n-S]
m+1
S-D/S-S X-[(D/S-S)
n-D/S]
m+1
(S-D/S)
n D-D/S-S-S-D/S-D
Wherein, S is a polystyrene block, D is that polydiene is a block, D/S is the cumulative vinylbenzene of vinylbenzene or diolefin series component content-diolefin series copolymerization block, X is multi-functional initiator base or multi-functional coupler base, m, n are 1～10 integer, are to be the best with D-D/S-S or D-S-D/S-S, D-D/S-S-S-D/S-D in the above-mentioned object lesson.For the present invention, be more suitable with incremental block structure.
Aforementioned styrenic monomers can be: vinylbenzene, alpha-methyl styrene, p-methylstyrene ,-vinyl toluene, neighbour-vinyl toluene, ethyl styrene, 2,4-dimethyl styrene, right-t-butyl styrene, Alpha-Methyl-p-methylstyrene, bromo-vinylbenzene, two bromo-vinylbenzene, 2,4,6 tribromo-benzene ethene etc., above-mentioned styrenic monomers can use separately or several merge use.
And diene monomer is to be selected from: 1,3-butadiene, 2-methyl isophthalic acid, 3-divinyl, 2-methyl isophthalic acid, 3-isoprene, 2,3-two-methyl isophthalic acid, 3-divinyl, 1,3-isoprene, 1,3-hexadiene etc., above-claimed cpd can be used alone or two or more mixing is used, wherein, and again with 1,3-divinyl or 1,3-isoprene are preferable.
The employed organolithium compound catalyst of aforementioned rubbery copolymer is the compound that contains an above lithium atom in the molecule, and it can be selected from: one or more mix lithium ethide, just-amyl group lithium, sec.-propyl lithium, just-butyllithium, secondary butyllithium, hexyl lithium, cyclohexyl lithium, phenyl lithium, phenmethyl lithium, naphthyl lithium, tert-butyl lithium, trimethylene two lithiums, tetramethylene two lithiums, the two lithiums of divinyl and the two lithiums of isoprene etc. and use.
The rate of polymerization, 1 of aforementioned rubbery copolymer when polymerization, the 2-contents of ethylene, and the reactivity of diene monomer and styrenic monomers random row state when, can change agent by polar compound or random row (random) and adjust, above-mentioned polar compound or random rowization agent are to be selected from: the potassium or the sodium salt of ethers, amine (amine), thioether amine, alkylbenzene, sulphur (sulfon) acids, trialkylphosphine oxide.
In addition, multipolymer external phase of the present invention (B) is by (methyl) acrylic ester monomer of the styrenic monomers of 12～70 weight parts, 20～80 weight parts, the acrylic monomer of 0～20 weight part, and other copolymerizable monomer of 0～40 weight part form, wherein, the object lesson of styrenic monomers is the styrenic monomers of rubbery copolymer as described above, no longer repeats to enumerate explanation at this.
And aforementioned (methyl) acrylic ester monomer is to comprise: methyl acrylic ester and esters of acrylic acid, wherein, methyl acrylic ester can be for example: methyl methacrylate, Jia Jibingxisuanyizhi, butyl methacrylate etc., and esters of acrylic acid for example is: methyl acrylate, ethyl propenoate, n-butyl acrylate, vinylformic acid 2-methyl amyl ester, vinylformic acid 2-ethyl pentyl group ester, Octyl acrylate etc., wherein, be preferable with methyl methacrylate and methyl acrylate again.And acrylic monomer of the present invention can be: vinyl cyanide, Alpha-Methyl vinyl cyanide etc.
The copolymerizable monomer of multipolymer external phase of the present invention (B) is 0～40 weight part, there is no particular restriction for the monomer whose kind, can adjust content ratio, the flexion rate of each copolymerization monomer according to need, it is transparent in necessary that last resin combination is reached, and the concrete example of above-mentioned copolymerizable monomer has: the unsaturated fatty acids of methylene-succinic acid, toxilic acid, fumaric acid, butenoic acid, styracin etc.; N-methyl maleimide, N-ethyl maleimide, N-butyl maleimide, N-octyl group maleimide, N-sec.-propyl maleimide, N-phenylmaleimide, N-be right-maleimide of bromo-phenyl maleimide, N-neighbour-chloro-phenyl maleimide, N-cyclohexyl maleimide etc.; The unsaturated carboxylic acid anhydrides class of maleic anhydride, itaconic anhydride, citraconic anhydride; The unsaturated compound class of amino-containeds such as allyl amine, (methyl) vinylformic acid amido ethyl ester, (methyl) vinylformic acid amido propyl ester; The acrylamide based compound of acrylamide, N methacrylamide etc.
The weight average molecular weight of multipolymer external phase (B) and without particular limitation is generally 50,000～300 in the resin combination of the present invention, 000, be preferably 60,000～200,000, be more preferred from 70,000～150,000, when weight average molecular weight is lower than at 50,000 o'clock, the impact strength of resin combination is poor, is higher than at 300,000 o'clock and work as weight average molecular weight, the flowability of resin combination can descend, and the poor in processability and the transparency are poor; In addition, the weight average particle diameter of the rubber particles of resin combination of the present invention does not also have special restriction, generally at 0.1～2.0 μ m, be preferably 0.1～1.5 μ m, be more preferred from 0.2～1.0 μ m, when the weight average particle diameter of rubber particles during less than 0.1 μ m, the impact strength decreased of resin combination, if weight average particle diameter is greater than 2.0 μ m, then the transparency of resin combination is poor.The weight average particle diameter of above-mentioned rubber particles is the picture that is taken with the ultrathin sectioning of infiltration type electron microscope, in this photo minimum 300 more than the particle, and record weight average particle diameter with following formula.
Ni is the number of the rubber particles of particle diameter Di in the following formula.
Gel content in the resin combination of the present invention, that is the insoluble part content of toluene/acetone (weight ratio 1/1) there is no particular restriction, be generally 2～40 weight %, be preferably 8～35 weight %, be more preferred from 12～30 weight %.In addition, there is no particular restriction for the swelling index in the resin combination of the present invention, is generally 2～25, is preferably 3～20, is more preferred from 5～15.
In solvable part of the methylene dichloride of the phenylethylene resin series that the present invention is transparent, molecular weight accounts for below the 2.0 whole solvable part weight % less than 350 low-molecular weight polymers, is preferably below the 1.0 weight %, is more preferred from below the 0.6 weight %; When molecular weight, is easy to generate the phenomenon of mold fouling, and causes the flaw of product during greater than 2.0 weight % less than the content of 350 low-molecular weight polymer during phenylethylene resin series machine-shaping; The solvable part molecular weight of the methylene dichloride of this so-called phenylethylene resin series is less than 350 low-molecular weight polymer, be to refer to phenylethylene resin series is added in the solvent of methylene dichloride, wherein soluble part (solvable part) is measured molecular weight wherein with GC-mass (gas chromatograph-mass spectrograph) and is lower than low-molecular weight polymer content (with the conversion of vinylbenzene standard area) 350 below.
The ester compound of contained tetramethylolmethane is the ester compound that tetramethylolmethane and carboxylic acid cpd reaction form in the transparent phonylethylene resin composition of the present invention, wherein, carboxylic acid cpd can be: lauric acid (claims dodecylic acid again, lauric acid), palmitinic acid (claims hexadecanoic acid again, palmitic acid), stearic acid (claims octadecanoic acid again, stearic acid), arachidonic acid (arachidonic acid), mountain Yu acid (claims docosoic acid again, behenic acid), wood resin acid (lignoceric acid), cerinic acid (claims carboceric acid again, cerotic acid), montanic acid (claims montanic acid again, montanic acid), oleic acid (claims octadecenic acid again, oleic acid), elaidic acid (elaidic acid), sinapinic acid (erucicacid), linolic acid (linoleic acid), linolenic acid (linolenic acid), oxalic acid (claims oxalic acid again, oxalic acid), propanedioic acid (malonic acid), Succinic Acid (succinic acid), pentanedioic acid (glutaric acid), hexanodioic acid (adipic acid), pimelic acid (pimelic acid), suberic acid (suberic acid), nonane diacid (azelaic acid), sebacic acid (sebacic acid), nonane dicarboxylic acid (nonane dicarboxylic acid), decane dicarboxylic acid (decane dicarboxylicacid), undecane diacid (undecane dicarboxylic acid), dodecane dicarboxylic acid (dodecanedicarboxylic acid), docosandioic acid (eicosane dicarboxylic acid), maleic acid (maleic acid), FUMARIC ACID TECH GRADE (fumaric acid), maleic acid (citraconic acid), methylfumaric acid (mesaconic acid), methyne divinyl (itconic acid), cyclopropane-carboxylic acid (cycloproane dicarboxylic acid), cyclobutane-carboxylic acid (cyclobutane dicarboxylicacid), cyclopentadecane carboxylic acid (cyclopentadiane dicarboxylic acid), dextrocamphoric acid (camphoracid), six hydrogen o-benzoic acids (hexahydrophthalic acid), phthalic acid (phthalic acid), four phthalic acids (terephthalic acid), isophthalic acid (isophthalic acid), naphthalic acid (naphthalic acid), phenylbenzene-o, o '-dicarboxylic acid (diphenyl-o, o '-dicarboxyl acid) etc.
And the concrete example of the ester compound of the tetramethylolmethane of transparent phonylethylene resin composition of the present invention has: tetramethylolmethane tristearate (pentaerythritol tristearate), tetramethylolmethane hexanedioyl stearate (pentaerythritol adipate stearate), tetramethylolmethane succinyl stearate (pentaerythritol succinate stearate), pentaerythritol tetrastearate (pentaerythritoltetrastearate), and tetramethylolmethane cinnamic acid in April ester (pentaerythritol tetralaurate), wherein, be preferable with pentaerythritol tetrastearate; The manufacturing of the ester compound of above-mentioned tetramethylolmethane can be used the catalyst of esterification procedure especially according to the esterification response procedures, for example: organo-tin compound, and the usage quantity of alcohols and carboxylic acid cpd in the reaction, decide according to different kinds and stoichiometry.
The addition of the ester compound of tetramethylolmethane of the present invention is 0.01～5 weight part with respect to 100 weight part transparent styrene resins, be preferably 0.02～3 weight part, be more preferred from 0.05～1.5 weight part, when addition during less than 0.01 weight part, the forming process of phenylethylene resin series is poor, and is poor from mould, and when addition during greater than 5 weight parts, be easy to generate mold fouling, the thermotolerance of resin combination and the transparency be variation all.
The ester compound addition manner of tetramethylolmethane of the present invention is also without particular limitation, and it can add when the phenylethylene resin series polymerization, or adds after polymerization, or adds with forcing machine or static(al) mixing tank mode.
The method for making of transparent styrene resin of the present invention can be emulsification, outstanding turbid, block (or solution) polymerization, and perhaps the polymerization of above several combinations is preferably emulsification or bulk (or solution) polymerization, is more preferred from bulk or solution polymerization process.
One of manufacture method of the transparent styrene resin that the present invention is rubber-modified, be in the presence of rubbery copolymer, with styrenic monomers, (methyl) acrylic monomer, acrylic monomer and add other copolymerizable monomer in case of necessity and criticize formula or continous way bulk or solution graft copolymerization polyreaction; If with the continuous solution polymerization is example, at first above-mentioned rubbery copolymer and monomer are added appropriate solvent formation raw material mixing solutions, the aforementioned base materials mixing solutions can dissolve in tradition has the dissolving tank of high shear stress, high stirring velocity, this dissolving tank can use: have ribbon spiral formula paddle, propeller type paddle or other can produce paddle of high shear stress etc., under time enough, above-mentioned rubbery copolymer can be dissolved into fully the state of rubber solutions, conveniently to carry out with the operation of pump delivery to reactor; With aforementioned base materials solution or monomer solution respectively successive feed in first reactor and/or second reactor and/or its follow-up reactor, and cooperate need first and/or second and/or its follow-up reactor add under chain transfer agent, the initiator and carry out graft polymerization reaction.
Above-mentioned reactive tank can be continuously stirring formula reactive tank (CSTR), or embolism streaming reactive tank (Plugflow reactor), or same a kind of or different types of combination of static(al) hybrid (static) reactor; Its temperature of reaction is controlled at 70～230 ℃, and final monomer conversion can reach 30～95%, but is preferable with 50～90%.
Transparent styrene resin of the present invention is when polymerization, spendable solvent species has: aromatic hydrocarbons, ketone, ester class, and wherein, best aromatic hydrocarbons for example is: toluene, ethylbenzene and dimethylbenzene, and ketone best be butanone, the ester class is good with vinyl acetic monomer then; In addition, the present invention also can use the part of aliphatic hydrocarbons such as hexane, hexanaphthene, normal heptane as solvent.
Transparent phonylethylene resin composition of the present invention in the mill, spendable initiator has: dibenzoyl peroxide (benzoyl peroxide), peroxidation diisopropyl benzene (dicumyl peroxide), surpass oxidation dibenzoyl (di benzoyl superoxide), tert-butyl peroxide (t-butylperoxide), t-butyl hydroperoxide (t-butyl hydroxy peroxide), hydrogen peroxide isopropyl benzene (cumene hydroperoxide), tert-butyl peroxide benzoate (t-butyl peroxybenzoate), two-2-peroxidation second hexyl, two carbonic ethers (di-2-ethylhexyl peroxy dicarbonate), tert-butyl peroxide sec.-propyl carbonic ether (tert-butyl peroxy isopropyl carbonate, be called for short BPIC), cyclohexanone peroxide (cycolhexanoe peroxide), 2,2-azo-two-isopropyl cyanide (2,2-azo-bis-isobutyronitrile), 1,1-azo-two-1-hexanaphthene carbonyl nitrile (1,1-azo-bis-1-cyclohexane carbonitrile), 2,2-azo-two-2-methylbutyronitrile (2,2-azo-bis-2-methylbutyronitrile), azo-two-isopropyl cyanide (azo-bis-isobutyronitrile), 1,1-diperoxy tertiary butyl hexanaphthene (1,1-di-butyl peroxy cyclohexane, be called for short TX-22), 1,1-two-tert-butyl peroxide-3,3,5-trimethyl-cyclohexane (1,1-di-t-butylperoxy-3,3,5-trimethyl cyclohexane, be called for short TX-29A), 2,5-dimethyl-2,5-pair-(2-ethyl peroxidation hexanoyl) hexane [2,5-dimethyl-2,5-bis-(2-ethylhexanoxy peroxy) hexanel], 4-(t-butylperoxy carbonyl)-3-hexyl-6-[7-(tert-butyl peroxide carbonyl) heptyl] hexanaphthene 4-(t-butyl peroxy carbonyl)-3-hexyl-6-[7-(t-butyl peroxy carbonyl) heptyl] cyclohexane}, two-tertiary butyl diperoxy nonane diacid (di-t-butyl-diperoxyazelate), 2,5-dimethyl-2, two (the benzoyl peroxide)-hexanes [2 of 5-, 5-dimethyl-2,5-bis-(benzoyl peroxy) hexane], two-tert-butyl peroxide-six hydrogen-terephthalate (di-t-butyl peroxy-hexahydro-terephthalate, be called for short BPHTP), 2,2-two (4,4-two-tert-butyl peroxide) cyclohexyl propane [2,2-bis-(4,4-di-t-butylperoxy) cyclohexanyl propane] etc.
Transparent phonylethylene resin composition of the present invention in the mill, spendable chain transfer agent for example is:
1) mercaptan (mercaptan) class: methyl mercaptan, n-butyl mercaptan, cyclohexyl mercaptan, just-lauryl mercaptan, stearic acid-base mercaptan (stearyl mercaptan), uncle-lauryl mercaptan (t-dodeylmercaptan is called for short TDM), just-propyl group mercaptan, n-octyl mercaptan, uncle-octyl mercaptan, uncle-nonyl mercaptan etc.
2) alkanamine (alkyl amines) class: single ethylamine, diethylamide, triethylamine, single isopropylamine, two single propyl group amine, monobutyl amine, di-n-butyl amine, three-n-butylamine etc.
Other are for example: pentaphenylethane (pentaphenylethane), α-Jia Jibenyixierjuwu (α-methyl styrene dimer), terpinylene (terpinolene).
After the aforementioned polyreaction, from reactor, take out, low-volatiles such as unreacted monomer, solvent are removed, after polymer recovery, can make the transparent styrene resin through the devolatilization device.
The ester compound of tetramethylolmethane of the present invention also can be after the phenylethylene resin series polymerization be finished, mixing with phenylethylene resin series, by Bradley Bender plastometer, Banbury, kneading-mixing machine, roller press, and mixed milling machine mixing-mixing making as one of one or two forcing machines etc.Usually these forcing machines of mat etc. mix-mixing after, the extrudate that will extrude out is again cooled off, granulation, above-mentioned mixing generally be under 160-280 ℃, to carry out, and be good with 180-250 ℃ temperature, the order of respectively allocating composition of aforementioned mixing-mixing is also without particular limitation.
In the scope of the effect that does not significantly undermine resin combination of the present invention, adjustable other compositions, these other compositions are for example: the additive of tinting material, weighting agent, incombustible agent, difficult combustion auxiliary agent (ANTIMONY TRIOXIDE SB 203 99.8 PCT etc.), photostabilizer, thermo-stabilizer, plasticizer, lubricant, parting agent, tackifier, charged preventor, antioxidant, conductive agent etc.; Above-mentioned additive can be for example: the ester of mineral oil, for example butyl stearate is that plasticizer, polyester are that organopolysiloxane, higher fatty acid and metal-salt thereof, the bulky amine of plasticizer, for example polydimethylsiloxane is antioxidant, glass fibre etc., and it can use or mix use separately; Above-mentioned ester be the usage quantity of plasticizer or mineral oil be based on 100 parts by weight resin constituents generally at 0～5 weight %, be preferably 0.05～2 weight %, and the usage quantity of organopolysiloxane is preferably 0.002～0.2 weight % generally at 0～0.5 weight %.
[physical property measurement]
One, the transparency (mist degree, Haze):, and comply with the thick test piece of resin combination ejection formation 3mm
The ASTM D-1003 standard test transparency, when the high more expression transparency of Haze value poor more.
Two, penetration coefficient (Transmittance): according to ASTM-1003 regulation test thickness 3mm test piece,
Unit represents with %.
Three, processibility (Spiral flow): transparent phonylethylene resin composition is in the ISIOOEN of Toshiba emission forming machine, in 60 ℃ of 220 ℃ of die temperatures of cylinder temperature, ejaculation pressure 600kg/cm
2, use eddy flow mould (2mmt) to be shaped, and assess its flowability with length of flow.
Four, (Melt index, MI): the back gets with the test of ASTM D-1238 method melting index.
Five, forming mold pollutes: behind continuously shaped 50 moulds under 280 ℃, observe the influence of pollutent to the moulding product.
◎: the expression mould does not pollute.
△: the expression mould has pollution slightly.
*: the expression mold fouling is serious.
Six, the solvable part molecular weight of the methylene dichloride of phenylethylene resin series is less than the survey method of 350 low-molecular weight polymer content (weight %): with styrene-series resin compositions, after the dichloromethane solvent dissolving, separate through heart whizzer far away, getting the upper strata analyzes with gas chromatograph-mass spectrograph (GC-MASS) for solvable part, when on the gas chromatograph with mass spectrograph localized molecules amount be lower than below 350 low-molecular weight polymer for example: trimer or dipolymer, and convert with vinylbenzene standard area; Above-mentioned low-molecular weight polymer for example is: AMS, MMS, AS, MSS, SSS, MS etc., wherein A is an acrylonitrile monemer, M is (methyl) methacrylate monomer, and S is a styrene monomer, and gas phase analyzer is the numbering 5890A of Hewlett Packard (Hewlett-Packard) company.
[embodiment]
Embodiment 1
The use capacity is that the continuous polymerization unit that four series connection of complete mixed type reactive tank of 40 liters are constituted is made transparent phonylethylene resin composition, with rubbery copolymer 8.4 weight parts (phenylethylene/butadiene content=25/75 weight %, 1,2-contents of ethylene=15.4%, the cumulative segmented copolymer of Mooney viscosity 45), with vinylbenzene 23.4 weight parts, methyl methacrylate 38.2 weight parts, ethylbenzene 30 weight parts, lauryl mercaptan 0.08 weight part, pentaerythritol tetrastearate 0.045 weight part, and dibenzoyl peroxide 0.08 weight part forms feedstock solution, use pump to be supplied to continuously and carry out polymerization in the reactive tank with the flow of 35kg/hr, the temperature of first reactive tank is 109 ℃, the temperature of second reactive tank is 114 ℃, the temperature of the 3rd reactive tank is 130 ℃, the temperature of the 4th reactive tank is 140 ℃, and the total polymerization turnover ratio is 60%.Be supplied to the devolatilization device by reactive tank continuously through polymeric solution after the polymerization, the vacuum tightness of controlling its devolatilization is at 200Torr, the volatile matter of unreacted monomer and organic solvent etc. is separated, then via extrusion machine with resin pelletization.
Contain vinylbenzene structure monomer 36 weight parts, methyl methacrylate 64 weight parts in the external phase of its composition, the pentaerythritol tetrastearate content of transparent phonylethylene resin composition is 0.1 weight part (based on the transparent styrene resin of 100 weight parts), the weight average particle diameter of disperse phase rubber particles is 0.42 μ m, and molecular weight was lower than 350 low-molecular weight polymer content and accounts for 0.62 whole solvable part weight % during methylene dichloride was solvable part.
Embodiment 2
The use capacity is that the continuous polymerization unit that four series connection of complete mixed type reactive tank of 40 liters are constituted is made transparent phonylethylene resin composition, with rubbery copolymer 8.4 weight parts (phenylethylene/butadiene content=25/75 weight %, 1,2-contents of ethylene=15.4%, the cumulative segmented copolymer of Mooney viscosity 45), with vinylbenzene 23.4 weight parts, methyl methacrylate 38.2 weight parts, ethylbenzene 30 weight parts, lauryl mercaptan 0.09 weight part, pentaerythritol tetrastearate 0.14 weight part, and dibenzoyl peroxide 0.09 weight part forms feedstock solution, use pump to be supplied to continuously and carry out polymerization in the reactive tank with the flow of 35kg/hr, the temperature of first reactive tank is 103 ℃, the temperature of second reactive tank is 107 ℃, the temperature of the 3rd reactive tank is 122 ℃, the temperature of the 4th reactive tank is 132 ℃, and the total polymerization transformation efficiency is 60%.Be supplied to the devolatilization device by reactive tank continuously through polymeric solution after the polymerization, the vacuum tightness of controlling its devolatilization is at 130Torr, the volatile matter of unreacted monomer and organic solvent etc. is separated, then via extrusion machine with resin pelletization.
Contain vinylbenzene structure monomer 36 weight parts, methyl methacrylate 64 weight parts in the external phase of its composition, the pentaerythritol tetrastearate content of transparent phonylethylene resin composition is 0.3 weight part (based on the transparent styrene resin of 100 weight parts), the weight average particle diameter of disperse phase rubber particles is 0.41 μ m, and molecular weight was lower than 350 low-molecular weight polymer content and accounts for 0.43 whole solvable part weight % during methylene dichloride was solvable part.
Embodiment 3
The use capacity is that the continuous polymerization unit that four series connection of complete mixed type reactive tank of 40 liters are constituted is made transparent phonylethylene resin composition, with rubbery copolymer 8.4 weight parts (phenylethylene/butadiene content=25/75 weight %, 1,2 contents of ethylene=15.4%, the cumulative segmented copolymer of Mooney viscosity 45), with vinylbenzene 22.8 weight parts, methyl methacrylate 37.0 weight parts, vinyl cyanide 1.8 weight parts, ethylbenzene 30 weight parts, lauryl mercaptan 0.1 weight part, pentaerythritol tetrastearate 0.32 weight part, and dibenzoyl peroxide 0.1 weight part forms feedstock solution, use pump to be supplied to reactive tank continuously and carry out polymerization with the flow of 35kg/hr, the temperature of first reactive tank is 102 ℃, the temperature of second reactive tank is 106 ℃, the temperature of the 3rd reactive tank is 117 ℃, the temperature of the 4th reactive tank is 127 ℃, and the total polymerization transformation efficiency is 60%.Be supplied to the devolatilization device by reactive tank continuously through polymeric solution after the polymerization, the vacuum tightness of controlling its devolatilization is at 80Torr, the volatile matter of unreacted monomer and organic solvent etc. is separated, then via extrusion machine with resin pelletization.
Contain vinylbenzene structure monomer 34 weight parts, methyl methacrylate 63 weight parts, vinyl cyanide 3 weight parts in the external phase of its composition, the pentaerythritol tetrastearate content of transparent phonylethylene resin composition is 0.7 weight part (based on the transparent styrene resin of 100 weight parts), the weight average particle diameter of disperse phase rubber particles is 0.35 μ m, and molecular weight was lower than 350 low-molecular weight polymer content and accounts for 0.22 whole solvable part weight % during methylene dichloride was solvable part.
Embodiment 4
The use capacity is that the continuous polymerization unit that four series connection of complete mixed type reactive tank of 40 liters are constituted is made transparent phonylethylene resin composition, with rubbery copolymer 8.4 weight parts (phenylethylene/butadiene content=25/75 weight %, 1,2 contents of ethylene=15.4%, the cumulative segmented copolymer of Mooney viscosity 45), with vinylbenzene 22.8 weight parts, methyl methacrylate 37.0 weight parts, vinyl cyanide 1.8 weight parts, ethylbenzene 30 weight parts, lauryl mercaptan 0.1 weight part, pentaerythritol tetrastearate 0.91 weight part, and dibenzoyl peroxide 0.1 weight part forms feedstock solution, use pump to be supplied to continuously and carry out polymerization in the reactive tank with the flow of 35kg/hr, the temperature of first reactive tank is 102 ℃, the temperature of second reactive tank is 106 ℃, the temperature of the 3rd reactive tank is 117 ℃, the temperature of the 4th reactive tank is 127 ℃, and the total polymerization transformation efficiency is 60%.Be supplied to the devolatilization device by reactive tank continuously through polymeric solution after the polymerization, the vacuum tightness of controlling its devolatilization is at 80Torr, the volatile matter of unreacted monomer and organic solvent etc. is separated, then via extrusion machine with resin pelletization.
Contain vinylbenzene structure monomer 34 weight parts, methyl methacrylate 63 weight parts, vinyl cyanide 3 weight parts in the external phase of its composition, the pentaerythritol tetrastearate content of transparent phonylethylene resin composition is 2.0 weight parts (based on the transparent styrene resins of 100 weight parts), the weight average particle diameter of disperse phase rubber particles is 0.35 μ m, and molecular weight was lower than 350 low-molecular weight polymer content and accounts for 0.21 whole solvable part weight % during methylene dichloride was solvable part.
Embodiment 5
The use capacity is that the continuous polymerization unit that four series connection of complete mixed type reactive tank of 40 liters are constituted is made transparent phonylethylene resin composition, with rubbery copolymer 8.4 weight parts (phenylethylene/butadiene content=25/75 weight %, 1,2-contents of ethylene=15.4%, the cumulative segmented copolymer of Mooney viscosity 45), with vinylbenzene 22.8 weight parts, methyl methacrylate 37.0 weight parts, vinyl cyanide 1.8 weight parts, ethylbenzene 30 weight parts, lauryl mercaptan 0.1 weight part, and dibenzoyl peroxide 0.1 weight part forms feedstock solution, use pump to be supplied to continuously and carry out polymerization in the reactive tank with the flow of 35kg/hr, the temperature of first reactive tank is 102 ℃, the temperature of second reactive tank is 106 ℃, the temperature of the 3rd reactive tank is 117 ℃, the temperature of the 4th reactive tank is 127 ℃, and the total polymerization transformation efficiency is 60%.Be supplied to the devolatilization device by reactive tank continuously through polymeric solution after the polymerization, the vacuum tightness of controlling its devolatilization is at 80Torr, the volatile matter of unreacted monomer and organic solvent etc. is separated, then via extrusion machine with the Resin adhesive granulation.After afterwards the pentaerythritol tetrastearate of above-mentioned phenylethylene resin series 100 weight parts and 0.3 weight part being mixed, through the mixing extruding pelletization of forcing machine.
Contain vinylbenzene structure monomer 34 weight parts, methyl methacrylate 63 weight parts, vinyl cyanide 3 weight parts in the external phase of its composition, the pentaerythritol tetrastearate content of transparent phonylethylene resin composition is 0.3 weight part (based on the transparent styrene resin of 100 weight parts), the weight average particle diameter of disperse phase rubber particles is 0.33 μ m, and molecular weight was lower than 350 low-molecular weight polymer content and accounts for 0.24 whole solvable part weight % during methylene dichloride was solvable part.Comparative example 1
The use capacity is that the continuous polymerization unit that four series connection of complete mixed type reactive tank of 40 liters are constituted is made transparent phonylethylene resin composition, with rubbery copolymer 8.4 weight parts (phenylethylene/butadiene content=25/75 weight %, 1,2-contents of ethylene=15.4%, the cumulative segmented copolymer of Mooney viscosity 45), with vinylbenzene 22.8 weight parts, methyl methacrylate 37.0 weight parts, vinyl cyanide 1.8 weight parts, ethylbenzene 30 weight parts, lauryl mercaptan 0.06 weight part, pentaerythritol tetrastearate 0.48 weight part, and dibenzoyl peroxide 0.05 weight part forms feedstock solution, use pump to be supplied to continuously and carry out polymerization in the reactive tank with the flow of 35kg/hr, the temperature of first reactive tank is 114 ℃, the temperature of second reactive tank is 120 ℃, the temperature of the 3rd reactive tank is 135 ℃, the temperature of the 4th reactive tank is 155 ℃, and the total polymerization transformation efficiency is 64%.Be supplied to the devolatilization device by reactive tank continuously through polymeric solution after the polymerization, the vacuum tightness of controlling its devolatilization is at 250 Torr, the volatile matter of unreacted monomer and organic solvent etc. is separated, then via extrusion machine with the Resin adhesive granulation.
Contain vinylbenzene structure monomer 34 weight parts, methyl methacrylate 63 weight parts, vinyl cyanide 3 weight parts in the external phase of its composition, the pentaerythritol tetrastearate content of transparent phonylethylene resin composition is 1.0 weight parts (based on the transparent styrene resins of 100 weight parts), the weight average particle diameter of disperse phase rubber particles is 0.45 μ m, and molecular weight was lower than 350 low-molecular weight polymer content and accounts for 2.2 whole solvable part weight % during methylene dichloride was solvable part.Comparative example 2
The use capacity is that the continuous polymerization unit that four series connection of complete mixed type reactive tank of 40 liters are constituted is made transparent phonylethylene resin composition, with rubbery copolymer 8.4 weight parts (phenylethylene/butadiene content=25/75 weight %, 1,2-contents of ethylene=15.4%, the cumulative segmented copolymer of Mooney viscosity 45), with vinylbenzene 22.8 weight parts, methyl methacrylate 37.0 weight parts, vinyl cyanide 1.8 weight parts, ethylbenzene 30 weight parts, lauryl mercaptan 0.1 weight part, and dibenzoyl peroxide 0.1 weight part forms feedstock solution, use pump to be supplied to continuously and carry out polymerization in the reactive tank with the flow of 35kg/hr, the temperature of first reactive tank is 102 ℃, the temperature of second reactive tank is 106 ℃, the temperature of the 3rd reactive tank is 117 ℃, the temperature of the 4th reactive tank is 127 ℃, and the total polymerization transformation efficiency is 60%.Be supplied to the devolatilization device by reactive tank continuously through polymeric solution after the polymerization, the vacuum tightness of controlling its devolatilization is at 80Torr, the volatile matter of unreacted monomer and organic solvent etc. is separated, then via extrusion machine with the Resin adhesive granulation.
Contain vinylbenzene structure monomer 34 weight parts, methyl methacrylate 63 weight parts, vinyl cyanide 3 weight parts in the external phase of its composition, the pentaerythritol tetrastearate content of transparent phonylethylene resin composition is 1.0 weight parts (based on the transparent styrene resins of 100 weight parts), the weight average particle diameter of disperse phase rubber particles is 0.37 μ m, and the content that molecular weight was lower than 350 low-molecular weight polymer during methylene dichloride was solvable part accounts for 0.25 whole solvable part weight %.Release is poor during the resin combination ejection formation of gained.Comparative example 3
The use capacity is that the continuous polymerization unit that four series connection of complete mixed type reactive tank of 40 liters are constituted is made transparent phonylethylene resin composition, with rubbery copolymer 8.4 weight parts (phenylethylene/butadiene content=25/75 weight %, 1,2-contents of ethylene=15.4%, the cumulative segmented copolymer of Mooney viscosity 45), with vinylbenzene 22.8 weight parts, methyl methacrylate 37.0 weight parts, vinyl cyanide 1.8 weight parts, ethylbenzene 30 weight parts, lauryl mercaptan 0.09 weight part, and dibenzoyl peroxide 0.1 weight part forms feedstock solution, use pump to be supplied to continuously and carry out polymerization in the reactive tank with the flow of 35kg/hr, the temperature of first reactive tank is 102 ℃, the temperature of second reactive tank is 106 ℃, the temperature of the 3rd reactive tank is 117 ℃, the temperature of the 4th reactive tank is 127 ℃, and the total polymerization transformation efficiency is 60%.Be supplied to the devolatilization device by reactive tank continuously through polymeric solution after the polymerization, the vacuum tightness of controlling its devolatilization is at 80Torr, the volatile matter of unreacted monomer and organic solvent etc. is separated, then via extrusion machine with the Resin adhesive granulation.After afterwards the pentaerythritol tetrastearate of above-mentioned phenylethylene resin series 100 weight parts and 6 weight parts being mixed, through the mixing extruding pelletization of forcing machine.
Contain vinylbenzene structure monomer 34 weight parts, methyl methacrylate 63 weight parts, vinyl cyanide 3 weight parts in the external phase of its composition, the pentaerythritol tetrastearate content of transparent phonylethylene resin composition is 6.0 weight parts (based on the transparent styrene resins of 100 weight parts), the weight average particle diameter of disperse phase rubber particles is 0.4 μ m, and molecular weight was lower than 350 low-molecular weight polymer content and accounts for 0.24 whole solvable part weight % during methylene dichloride was solvable part.Comparative example 4
The use capacity is that the continuous polymerization unit that four series connection of complete mixed type reactive tank of 40 liters are constituted is made transparent phonylethylene resin composition, with rubbery copolymer 8.4 weight parts (phenylethylene/butadiene content=25/75 weight %, 1,2-contents of ethylene=15.4%, the cumulative segmented copolymer of Mooney viscosity 45), with vinylbenzene 22.8 weight parts, methyl methacrylate 37.0 weight parts, vinyl cyanide 1.8 weight parts, ethylbenzene 30 weight parts, lauryl mercaptan 0.09 weight part, and dibenzoyl peroxide 0.09 weight part forms feedstock solution, use pump to be supplied to continuously and carry out polymerization in the reactive tank with the flow of 35kg/hr, the temperature of first reactive tank is 103 ℃, the temperature of second reactive tank is 107 ℃, the temperature of the 3rd reactive tank is 123 ℃, the temperature of the 4th reactive tank is 131 ℃, and the total polymerization transformation efficiency is 60%.Be supplied to the devolatilization device by reactive tank continuously through polymeric solution after the polymerization, the vacuum tightness of controlling its devolatilization is at 130Torr, the volatile matter of unreacted monomer and organic solvent etc. is separated, then via extrusion machine with the Resin adhesive granulation.The methyl stearate of above-mentioned phenylethylene resin series 100 weight parts and 2 weight parts is mixed after by the mixing extruding pelletization of forcing machine.
Contain vinylbenzene structure monomer 34 weight parts, methyl methacrylate 63 weight parts, vinyl cyanide 3 weight parts in the external phase of its composition, the content of the methyl stearate of transparent phonylethylene resin composition is 2.0 weight parts (based on the transparent styrene resins of 100 weight parts), the weight average particle diameter of disperse phase rubber particles is 0.4 μ m, and molecular weight was lower than 350 low-molecular weight polymer content and accounts for 0.43 whole solvable part weight % during methylene dichloride was solvable part.Comparative example 5
The use capacity is that the continuous polymerization unit that four series connection of complete mixed type reactive tank of 40 liters are constituted is made transparent phonylethylene resin composition, with rubbery copolymer 8.4 weight parts (phenylethylene/butadiene content=25/75 weight %, 1,2-contents of ethylene=15.4%, the cumulative segmented copolymer of Mooney viscosity 45), with vinylbenzene 22.8 weight parts, methyl methacrylate 37.0 weight parts, vinyl cyanide 1.8 weight parts, ethylbenzene 30 weight parts, lauryl mercaptan 0.08 weight part, and dibenzoyl peroxide 0.08 weight part forms feedstock solution, use pump to be supplied to continuously and carry out polymerization in the reactive tank with the flow of 35kg/hr, the temperature of first reactive tank is 104 ℃, the temperature of second reactive tank is 109 ℃, the temperature of the 3rd reactive tank is 125 ℃, the temperature of the 4th reactive tank is 135 ℃, and the total polymerization transformation efficiency is 60%.Be supplied to the devolatilization device by reactive tank continuously through polymeric solution after the polymerization, the vacuum tightness of controlling its devolatilization is at 200 Torr, the volatile matter of unreacted monomer and organic solvent etc. is separated, then via extrusion machine with the Resin adhesive granulation.The butyl stearate of above-mentioned phenylethylene resin series 100 weight parts and 2 weight parts mixes after by the mixing extruding pelletization of forcing machine.
Contain vinylbenzene structure monomer 34 weight parts, methyl methacrylate 63 weight parts, vinyl cyanide 3 weight parts in the external phase of its composition, the butyl stearate content of transparent phonylethylene resin composition is 2.0 weight parts (based on the transparent styrene resins of 100 weight parts), the weight average particle diameter of disperse phase rubber particles is 0.41 μ m, and molecular weight was lower than 350 low-molecular weight polymer content and accounts for 0.62 whole solvable part weight % during methylene dichloride was solvable part.Comparative example 6
The use capacity is that the continuous polymerization unit that four series connection of complete mixed type reactive tank of 40 liters are constituted is made transparent phonylethylene resin composition, with rubbery copolymer 8.4 weight parts (phenylethylene/butadiene content=25/75 weight %, 1,2-contents of ethylene=15.4%, the cumulative segmented copolymer of Mooney viscosity 45), with vinylbenzene 22.8 weight parts, methyl methacrylate 37.0 weight parts, vinyl cyanide 1.8 weight parts, ethylbenzene 30 weight parts, lauryl mercaptan 0.1 weight part, and dibenzoyl peroxide 0.1 weight part forms feedstock solution, use pump to be supplied to continuously and carry out polymerization in the reactive tank with the flow of 35kg/hr, the temperature of first reactive tank is 102 ℃, the temperature of second reactive tank is 106 ℃, the temperature of the 3rd reactive tank is 117 ℃, the temperature of the 4th reactive tank is 127 ℃, and the total polymerization transformation efficiency is 60%.Be supplied to the devolatilization device by reactive tank continuously through polymeric solution after the polymerization, the vacuum tightness of controlling its devolatilization is at 80Torr, the volatile matter of unreacted monomer and organic solvent etc. is separated, then via extrusion machine with the Resin adhesive granulation.The ethene bis-stearamides of above-mentioned phenylethylene resin series 100 weight parts and 2 weight parts mixes after by the mixing extruding pelletization of forcing machine.
Contain vinylbenzene structure monomer 34 weight parts, methyl methacrylate 63 weight parts, vinyl cyanide 3 weight parts in the external phase of its composition, the ethene stearic bicine diester amine content of transparent phonylethylene resin composition is 2.0 weight parts (based on the transparent styrene resins of 100 weight parts), the weight average particle diameter of disperse phase rubber particles is 0.35 μ m, and molecular weight was lower than 350 low-molecular weight polymer content and accounts for 0.21 whole solvable part weight % during methylene dichloride was solvable part.Comparative example 7
The use capacity is that the continuous polymerization unit that four series connection of complete mixed type reactive tank of 40 liters are constituted is made transparent phonylethylene resin composition, with rubbery copolymer 8.4 weight parts (phenylethylene/butadiene content=25/75 weight %, 1,2-contents of ethylene=15.4%, the cumulative segmented copolymer of Mooney viscosity 45), with vinylbenzene 22.8 weight parts, methyl methacrylate 37.0 weight parts, vinyl cyanide 1.8 weight parts, ethylbenzene 30 weight parts, with lauryl mercaptan 0.1 weight part, Chinese wax oil 0.91 weight part, dibenzoyl peroxide 0.1 weight part forms feedstock solution, use pump to be supplied to continuously and carry out polymerization in the reactive tank with the flow of 35kg/hr, the temperature of first reactive tank is 102 ℃, the temperature of second reactive tank is 106 ℃, the temperature of the 3rd reactive tank is 117 ℃, the temperature of the 4th reactive tank is 127 ℃, and the total polymerization transformation efficiency is 60%.Be supplied to the devolatilization device by reactive tank continuously through polymeric solution after the polymerization, the vacuum tightness of controlling its devolatilization is at 80Torr, the volatile matter of unreacted monomer and organic solvent etc. is separated, then via extrusion machine with the Resin adhesive granulation.
Contain vinylbenzene structure monomer 34 weight parts, methyl methacrylate 63 weight parts, vinyl cyanide 3 weight parts in the external phase of its composition, the Chinese wax oil-contg of transparent phonylethylene resin composition is 2.0 weight parts (based on the transparent styrene resins of 100 weight parts), the weight average particle diameter of disperse phase rubber particles is 0.37 μ m, and molecular weight was lower than 350 low-molecular weight polymer content and accounts for 0.21 whole solvable part weight % during methylene dichloride was solvable part.Comparative example 8
The use capacity is that the continuous polymerization unit that four series connection of complete mixed type reactive tank of 40 liters are constituted is made transparent phonylethylene resin composition, with rubbery copolymer 8.4 weight parts (phenylethylene/butadiene content=25/75 weight %, 1,2-contents of ethylene=15.4%, the cumulative segmented copolymer of Mooney viscosity 45), with vinylbenzene 22.8 weight parts, methyl methacrylate 37.0 weight parts, vinyl cyanide 1.8 weight parts, ethylbenzene 30 weight parts, with lauryl mercaptan 0.1 weight part, dibenzoyl peroxide 0.1 weight part forms feedstock solution, use pump to be supplied to continuously and carry out polymerization in the reactive tank with the flow of 35kg/hr, the temperature of first reactive tank is 102 ℃, the temperature of second reactive tank is 106 ℃, the temperature of the 3rd reactive tank is 117 ℃, the temperature of the 4th reactive tank is 127 ℃, and the total polymerization transformation efficiency is 60%.Be supplied to the devolatilization device by reactive tank continuously through polymeric solution after the polymerization, the vacuum tightness of controlling its devolatilization is at 80Torr, the volatile matter of unreacted monomer and organic solvent etc. is separated, then via extrusion machine with the Resin adhesive granulation.After afterwards the polyethylene wax (PE Wax) of above-mentioned phenylethylene resin series 100 weight parts and 2 weight parts being mixed, through the mixing extruding pelletization of forcing machine.
Contain vinylbenzene structure monomer 34 weight parts, methyl methacrylate 63 weight parts, vinyl cyanide 3 weight parts in the external phase of its composition, the polyethylene wax content of transparent phonylethylene resin composition is 2.0 weight parts (based on the transparent styrene resins of 100 weight parts), the weight average particle diameter of disperse phase rubber particles is 0.37 μ m, and molecular weight was lower than 350 low-molecular weight polymer content and accounts for 0.22 whole solvable part weight % during methylene dichloride was solvable part.
The characteristic test of above embodiment 1～5 and comparative example 1～8 relatively sees Table one.
Embodiment 6
Use polystyrene 100 weight parts (the POLYREX PG383 of Qi Mei company) and the pentaerythritol tetrastearate of 0.6 weight part to mix the back by the mixing extruding pelletization of forcing machine, survey its methylene dichloride solvable part in the molecular weight content that is lower than 350 low-molecular weight polymer be 0.65 weight %, processibility (MI) is 3.6, the transparency (Haze) is 1.0%, penetration coefficient is 90.5%, and the release of ejection formation is good.Comparative example 9
Using polystyrene 100 weight parts (the POLYRE PG383 of Qi Mei company) to survey molecular weight in solvable part of its methylene dichloride, to be lower than 350 low-molecular weight polymer content be 0.65 weight %, processibility (MI) is 3.0, the transparency (Haze) is 0.8%, penetration coefficient is 90.8%, but the release of the ejection formation of resin is poor.
Embodiment 7
After the pentaerythritol tetrastearate of use styrene-acrylonitrile copolymer 100 weight parts (the KIBISAN PN-117 of Qi Mei company) and 0.5 weight part mixes, by the mixing extruding pelletization of forcing machine, survey its methylene dichloride solvable part in molecular weight to be lower than 350 low-molecular weight polymer content be 1.85 weight %, processibility (MI) is 3.4, the transparency (Haze) is 1.5%, penetration coefficient is 90.6%, and the release of ejection formation is good.Comparative example 10
Use styrene-acrylonitrile copolymer 100 weight parts (the KIBISAN PN-117 of Qi Mei company), survey its methylene dichloride solvable part in molecular weight to be lower than 350 low-molecular weight polymer content be 1.85 weight %, processibility (MI) is 3.0, the transparency (Haze) is 1.4%, penetration coefficient is 90.8%, but resin ejection formed release is poor.
Experimental result by comparative example 1 is learnt, when molecular weight is higher than 2.0 weight parts less than 350 low-molecular weight polymer content in methylene dichloride in the resin combination is solvable part, resin produces mold fouling when ejection formation, and learn by the experimental result of comparative example 2, in resin, do not add the ester time-like of tetramethylolmethane, the processibility of resin is undesirable and release resin is poor, and add the ester time-like of excessive tetramethylolmethane in the resin, easily produce mold fouling and transparency and also reduce, this is by the experimental result susceptible of proof of comparative example 3; Learn by experimental results such as comparative examples 4,5,7 again, when in transparent styrene resin, adding stearic acid formyl, butyl stearate, Chinese wax oil respectively, can produce the phenomenon of mold fouling and transparency difference.Learn by comparative example 6,8 experimental results that in addition add ethene distearyl acid amides, polyethylene wax in resin, then the transparency of resin is poor.
Consult various embodiments of the present invention, the present invention adds the ester compound of the tetramethylolmethane of certain content at the transparent styrene resin, and in the control resin methylene dichloride solvable part in specific lower molecular weight content, really can make resin combination have the good transparency and processibility, when resin forming, also can not produce simultaneously the phenomenon of mold fouling, therefore, the present invention is a novelty, progress really, and has the resin combination of utility value on the industry.
Only the above only is several preferable possible embodiments of the present invention, is familiar with this technology personage such as, its according to can thinking easily of doing of the spiritual category of the present invention and modification or change, all ought to be included in the technical solution of the present invention scope.
Table one: the characteristic test comparison sheet between various embodiments of the present invention and comparative example.
Annotate: 1) Chinese wax oil: (ESSO Primol 382).
2) polyethylene wax: (Mitsui Chemicals 200P).
Claims (10)
1, a kind of transparent phonylethylene resin composition, it is characterized in that it be by:
＜I〉the transparent styrene resin of 100 weight parts; And
＜II〉ester compound of tetramethylolmethane of 0.01～5 weight part forms;
Wherein, the molecular weight of solvable part of methylene dichloride accounts for below the 2.0 whole solvable part weight % less than 350 low-molecular weight polymer content in the transparent phenylethylene resin series.
2, transparent phonylethylene resin composition according to claim 1 is characterized in that described transparent styrene resin is the transparent styrene resin through the diene series rubber modification.
3, transparent phonylethylene resin composition according to claim 1, it is characterized in that this transparent styrene resin is by the disperse phase of the rubber particles that rubbery copolymer forms (A), and monomer adds up to styrenic monomers 12～70 weight parts, (methyl) acrylic ester monomer 20～80 weight parts, acrylic monomer 0～20 weight part of 100 weight parts, and other formed multipolymer external phases of copolymerizable monomer 0～40 weight part (B) constitute.
4, transparent phonylethylene resin composition according to claim 3 is characterized in that rubbery copolymer is the multipolymer that contains styrenic monomers 5～50 weight % and diene monomer 95～50 weight %.
5, transparent phonylethylene resin composition according to claim 3 is characterized in that this rubbery copolymer is the cumulative segmented copolymer of moiety.
6, transparent phonylethylene resin composition according to claim 1, the ester compound that it is characterized in that this tetramethylolmethane are that tetramethylolmethane and carboxylic acid cpd reaction form.
7, transparent phonylethylene resin composition according to claim 6 is characterized in that this carboxylic acid cpd is to be selected from following one or more lauric acid (lauric acid), palmitinic acid (palmitic acid), stearic acid (stearic acid), arachidonic acid (arachidonic acid), mountain Yu acid (behenic acid), wood resin acid (lignoceric acid), cerinic acid (ceroticacid), montanic acid (montanic acid), oleic acid (oleic acid), elaidic acid (elaidicacid), sinapinic acid (erucic acid), linolic acid (linoleic acid), linolenic acid (linolenic acid), oxalic acid (oxalic acid), propanedioic acid (malonic acid), Succinic Acid (succinic acid), pentanedioic acid (glutaric acid), hexanodioic acid (adipic acid), pimelic acid (pimelic acid), suberic acid (suberic acid), nonane diacid (azelaic acid), sebacic acid (sebacic acid), nonane dicarboxylic acid (nonane dicarboxylic acid), decane dicarboxylic acid (decane dicarboxylic acid), undecane diacid (undecanedicarboxylic acid), dodecane dicarboxylic acid (dodecane dicarboxylic acid), docosandioic acid (eicosane dicarboxylic acid), maleic acid (maleic acid), FUMARIC ACID TECH GRADE (fumaric acid), maleic acid (citraconic acid), methylfumaric acid (mesaconic acid), methyne Succinic Acid (itconic acid), cyclopropane-carboxylic acid (cycloproane dicarboxylic acid), cyclobutane-carboxylic acid (cyclobutanedicarboxylic acid), cyclopentadecane carboxylic acid (cyclopentadiane dicarboxylic acid), dextrocamphoric acid (camphor acid), six hydrogen o-benzoic acids (hexahydrophthalic acid), phthalic acid (phthalic acid), four phthalic acids (terephthalic acid), isophthalic acid (isophthalic acid), naphthalic acid (naphthalic acid), phenylbenzene-o-o '-dicarboxylic acid (diphenyl-o-o '-dicarboxyl acid) etc.
8, transparent phonylethylene resin composition according to claim 1, the molecular weight that it is characterized in that solvable part of the methylene dichloride of this transparent styrene resin accounts for below the 1.0 whole solvable part weight % less than 350 low-molecular weight polymer content.
9, transparent phonylethylene resin composition according to claim 1 is characterized in that this transparent styrene resin is not contain rubber constituent, and is made of styrenic monomers 100～30 weight % and other copolymerizable monomer 0～70 weight %.
10, transparent phonylethylene resin composition according to claim 9 is characterized in that this transparent styrene resin is the polymkeric substance that is selected from one or more; Above-mentioned polymkeric substance can be selected from: polystyrenic polymer, polystyrene-acrylic copolymer, polystyrene-(methyl) acrylate based copolymer, polystyrene-N-displacement maleimide system-acrylic copolymer, polystyrene-N-displacement maleimide based copolymer, polystyrene-(methyl) acrylic ester-N-displacement maleimide based copolymer, polystyrene-N-displacement maleimide system-acrylic-(methyl) acrylate based copolymer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB001295330A CN1142211C (en) | 2000-09-28 | 2000-09-28 | Transparent phonylethylene resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB001295330A CN1142211C (en) | 2000-09-28 | 2000-09-28 | Transparent phonylethylene resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1345895A true CN1345895A (en) | 2002-04-24 |
| CN1142211C CN1142211C (en) | 2004-03-17 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB001295330A Expired - Lifetime CN1142211C (en) | 2000-09-28 | 2000-09-28 | Transparent phonylethylene resin composition |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1142211C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111333510A (en) * | 2020-03-05 | 2020-06-26 | 广东炜林纳新材料科技股份有限公司 | High-temperature-resistant lubricant, and preparation method and application thereof |
-
2000
- 2000-09-28 CN CNB001295330A patent/CN1142211C/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111333510A (en) * | 2020-03-05 | 2020-06-26 | 广东炜林纳新材料科技股份有限公司 | High-temperature-resistant lubricant, and preparation method and application thereof |
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| Publication number | Publication date |
|---|---|
| CN1142211C (en) | 2004-03-17 |
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