CN102485762A - Colourless butylbenzene segmented copolymer with low gel content and preparation method thereof - Google Patents
Colourless butylbenzene segmented copolymer with low gel content and preparation method thereof Download PDFInfo
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- CN102485762A CN102485762A CN200910236299XA CN200910236299A CN102485762A CN 102485762 A CN102485762 A CN 102485762A CN 200910236299X A CN200910236299X A CN 200910236299XA CN 200910236299 A CN200910236299 A CN 200910236299A CN 102485762 A CN102485762 A CN 102485762A
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Abstract
The invention relates to a butylbenzene segmented copolymer synthesized by an organic lithium initiator and a preparation method thereof. The method is characterized by comprising steps of: carrying out a butadiene-styrene anionic polymerisation in an inertia solvent by employing the organic lithium as the initiator; and subsequently carrying out a carboxylic acid termination reaction and a neutralization reaction. The prepared butylbenzene segmented copolymer has the following performances: (1) a combined styrene content of 10-60% and a vinyl content of 6-18% in a monomer unit; (2) a number-average molecular weight scope of 5*10<4>-30*10<4>; (3) Mooney viscosity of ML1+4 equal to 20-200 at 100 DEG C; (4) chrominance lower than 15APHA in a 5% toluene solution; and (5) insoluble substance content lower than 100 ppm in the 5% toluene solution. The butylbenzene segmented copolymer of the present invention can be applied to plastic modification, especially modification of ABS and HIPS.
Description
The present invention relates to butadiene-styrene block copolymer of a kind of colourless, tasteless, low-gel content and preparation method thereof, more specifically, relate to a kind of modifying plastics with butadiene-styrene block copolymer and preparation method thereof.This multipolymer in toluene solution lighter color, gel content is low, rubber is tasteless.
Mention in the prior art that lithium is under the initiator system there to be as follows the decoloring method of resinous polymer: disclose a kind of decoloring method that adopts hydrogenation catalyst preparation hydrorubber polymkeric substance like USP 4595749; Treatment process is from the hydrorubber polymkeric substance, to remove remaining metal catalyst ion; Concrete oxygenant and the di-carboxylic acid of using, wherein di-carboxylic acid adopts lower aliphatic alcohols (C
4Below) or toluene as solvent, also can use polymer solvent as solvent, the hydrorubber polymkeric substance that makes is colourless.But when adopting lower aliphatic alcohols as solvent, polymer solvent reclaims and will be difficult to from solvent totally pure impurity removal, will have a negative impact to subsequently polymerization, and also there are influences such as solubleness, polymeric chain transfer in toluene as the dissolution with solvents di-carboxylic acid.Yet most of resin type multipolymer like USP 3639517,4091053 described employing organic lithium initiator preparations; And like the conjugated diene polymer rubber of USP 3254062 said preparations when resin is carried out toughening modifying; This resin or rubber all are unfavorable for the color and luster requirement, and resin or modified resin will be unfavorable for being applied to the food grade wrapping material and other pool of checking colors has in the field such as high-grade electric appliance casing of requirement.Thereby must study the decolouring of resin or rubber, make the rubber of preparation can be applicable to modifying plastics, the particularly modification of ABS and HIPS.
The method that is usually used in improving the resinous polymer appearance luster in the industry is after polyreaction is accomplished, in polymers soln, to add entry and carbonic acid gas termination reaction; Make the remaining polymkeric substance carbon lithium key torpescence that becomes; If yet must handle carbon dioxide impurities in the gas phase after the excessive then reaction of the dioxide gas completion, otherwise influence polyreaction.USP 4403074 also discloses a kind of method that reduces impact resins shape multipolymer mist degree in addition; Mention in the treatment process with binary organic acid and carry out termination reaction; Make the reactive polymer metals ion become dicarboxylate, thereby prepare impact resins multipolymer colourless, transparent, no mist degree.The preferred hexanodioic acid of binary organic acid, solubleness is little in the hexanodioic acid water at normal temperature, and solubleness is also very little in the toluene solvant, adopts the toluene solvant requirement big, will not influence polyreaction if do not reclaim, and recovery will increase energy consumption.But all not mentioning in the treatment process that these industry are used always adopts acid that the polymkeric substance glue is carried out neutralization reaction.
USP 6184341 also discloses the decoloring method of a kind of vinyl-arene, conjugated diene block copolymer resin, has adopted termination reaction and neutralization reaction in the treatment process, but terminator is a propylene oxide, and neutralizing agent is C
2-4The monobasic organic acid.Polymer macromolecule one end that this method makes will have the polarity hydroxyl, become the high fatty alcohol polymkeric substance, if in method for preparing rubber, use propylene oxide, with the polyreaction that influences ABS and HIPS; The neutralization of rudimentary monobasic organic acid in being applied to rubber preparation test is relatively poor, does not reach the mentioned requirement less than 15APHA of the present invention such as chromaticity index, thereby should not adopt propylene oxide termination, C
2-4In the monobasic organic acid with the preparation lighter color butadiene-styrene block copolymer.
In view of above-mentioned prior art situation; Contriver of the present invention is to being that research has extensively and profoundly been carried out in the decolouring of polymkeric substance under the initiator system at lithium; The result finds the content through alkalimetal ion in the control butadiene-styrene block copolymer; Concrete operations are metals ions that employing metals ion that alcohol acid stops, neutralization reaction removes butadiene-styrene block copolymer basic metal spike and impurity consumption initiator etc. form; Make alkalimetal ion in the polymer treatment process, remove, thereby prepare the used butadiene-styrene block copolymer of a kind of suitable modifying plastics, this multipolymer has excellent properties colourless, low-gel content; Termination reaction and neutralization reaction can be carried out simultaneously, also can proceed step by step.
The purpose of this invention is to provide a kind of butadiene-styrene block copolymer of colourless, low-gel content, this multipolymer is suitable for the requirement of modifying plastics, particularly is suitable for the modification of ABS and HIPS.
Another object of the present invention provides a kind of method for preparing above-mentioned multipolymer.
Another object of the present invention provides a kind of decoloring method of butadiene-styrene block copolymer.
One aspect of the present invention provides a kind of butadiene-styrene block copolymer of colourless, low-gel content, it is characterized in that the combined styrene content in the monomeric unit is 10-60% weight, and contents of ethylene is a 6-18% weight; The number-average molecular weight scope of polymkeric substance is 5 * 10
4-30 * 10
4Mooney viscosity ML under 100 ℃
1+4Be 20-200; The colourity of said butadiene-styrene block copolymer in 5% toluene solution is lower than 15APHA; And the insolubles content of said butadiene-styrene block copolymer in 5% toluene solution is lower than 100ppm.
The present invention provides a kind of method for preparing the butadiene-styrene block copolymer of colourless, low-gel content on the other hand, comprises the steps:
1) inert solvent, divinyl and styrene monomer and the optional structure regulator that uses are joined in the reactor drum; Add the alkali alkyl compound initiator of significant quantity then, in the presence of said initiator, carry out divinyl and cinnamic solution polymerization;
2) treat that the solution polymerization transformation efficiency reaches 99% after, add a certain amount of terminator an alkali metal salt spike carried out termination reaction, wherein terminator is alcohol acid or alcohol acid/water; And add a certain amount of neutralizing agent alkalimetal oxide and/or alkali metal hydroxide etc. in the polymers soln are carried out neutralization reaction, wherein neutralizing agent is an alcohol acid;
3) in polymers soln, add anti-aging agent.
According to the present invention, combined styrene content is 10-60% weight in the monomeric unit of butadiene-styrene block copolymer, preferred 15-30% weight; Correspondingly, be 40-90% weight in conjunction with butadiene content, preferred 70-85% weight; And contents of ethylene is a 6-18% weight, preferred 8-14% weight.
According to the present invention, the number-average molecular weight of butadiene-styrene block copolymer is 5 * 10
4-30 * 10
4, preferred 10 * 10
4-20 * 10
4
According to the present invention, the mooney viscosity ML of butadiene-styrene block copolymer under 100 ℃
1+4Be 20-200, preferred 50-150.If mooney viscosity ML
1+4Be lower than the lower limit of above-mentioned scope, then said polymkeric substance possibly adhere to finishing apparatus by cold flow, is unfavorable for its use; If mooney viscosity ML
1+4The upper limit that is higher than above-mentioned scope, then the frangible slagging of polymkeric substance is unfavorable for its processing and utilization.
The colourity of butadiene-styrene block copolymer of the present invention in 5% toluene solution is lower than 15APHA, preferably is lower than 10APHA; Insolubles content in 5% toluene solution is lower than 100ppm, preferably is lower than 50ppm.
Operable inert solvent for example is nonpolar aromatic hydrocarbons in the preparation of butadiene-styrene block copolymer of the present invention, like benzene,toluene,xylene, ethylbenzene; Aliphatic hydrocrbon is like pentane, hexane, heptane, octane; Cycloaliphates is like pentamethylene, hexanaphthene, methylcyclohexane; Or aliphatic hydrocrbon and alicyclic mixture, like hexane and hexanaphthene mixture or raffinate oil.Generally speaking, the inert solvent consumption is the 300-5000g inert solvent based on the 100g monomer.
In polymerization process, adopt structure regulator to regulate vinyl structure content usually.With regard to the present invention, in polymerization process, can not add structure regulator, also can add the conventional any structure regulator that uses in the anionoid polymerization solution polymerized rubber system.Above-mentioned said structure regulator for example is selected from and contains oxygen, nitrogenous, sulfur-bearing, contains one or more the mixture in the Phosphorus polar compound, preferred ether compound, tertiary amine compounds or its mixture.Ether compound comprises for example cyclic ether compounds, like THF, 1, and 4-dioxy hexanaphthene; The aliphatic monoether compounds is like ether, dibutyl ether; Aliphatic series polyether compounds is suc as formula R
1OCH
2CH
2OR
2Shown compound (R wherein
1And R
2Be C
1-4Alkyl, and R
1And R
2Can be identical also can be inequality, preferred R
1And R
2Different), like glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol methyl ether, ethylene glycol dibutyl ether, or formula R
1OCH
2CH
2OCH
2CH
2OR
2Shown compound (R wherein
1And R
2Be C
1-4Alkyl, and R
1And R
2Can be identical also can be inequality, preferred R
1And R
2Different), like diglyme, diethyl carbitol, glycol ether methyl ethyl ether, diethylene glycol dibutyl ether; Aromatic oxide compounds such as phenyl ether, methyl-phenoxide, crown ether.Tertiary amine compounds for example comprises triethylamine, tripropyl amine, Tributylamine and other aminated compounds, like N, and N, N ', N '-Tetramethyl Ethylene Diamine (TMEDA), N, N-Diethyl Aniline, pyridine, quinoline, two piperidines ethane (DPE).Phosphorous compounds comprises for example HMPA (HMPA) etc.Preferably, structure regulator is THF (THF), glycol dimethyl ether (1G), diglyme (2G), N, N, N ', N '-Tetramethyl Ethylene Diamine.The structure regulator consumption is the conventional equivalent that those skilled in the art can confirm in the polymerization process, and preferable amount is the structure regulator that every mole of lithium atom adds 0.01-10mol.Preferred construction regulator amount ranges is following: every mole of lithium atom need add THF 0.1-5mol when selecting THF as structure regulator for use; Every mole of lithium atom need add 1G 0.02-0.5mol when selecting 1G as structure regulator for use; Every mole of lithium atom need add 2G 0.01-0.5mol when selecting 2G as structure regulator for use; Every mole of lithium atom need add TMEDA 0.01-0.5mol when selecting TMEDA as structure regulator for use.
Used alkali alkyl compound initiator is an organic lithium initiator in the butadiene-styrene block copolymer preparation of the present invention, like organic single lithium initiator, organic dilithium initiator, organic multi-lithium initiator.The organic single-lithium initiator representes that with RLi wherein R is the C of straight or branched
1-C
20Alkyl; C
3-C
20Naphthenic base; C
6-C
20Aryl.The specific examples of organic single-lithium can comprise for example lithium methide, lithium ethide, propyl lithium, sec.-propyl lithium, tert-butyl lithium, allyl group lithium, n-Butyl Lithium, s-butyl lithium, isobutyl-lithium, n-pentyl lithium, cyclohexyl lithium, 4-heptyl cyclohexyl lithium, 4-cyclohexyl butyllithium, 4-butyl cyclohexyl lithium, phenyl lithium, 4-aminomethyl phenyl lithium, trityl group lithium, 2-naphthyl lithium etc., preferred n-Butyl Lithium or s-butyl lithium.The specific examples of organic dilithium initiator comprises like two lithium methane, 1,4-two lithium butane, 1,10-two lithium decane, 1,20-two lithium eicosanes, 1; 4-two lithium hexanaphthenes, 1,4-two lithiums-2-butylene, 1,8-two lithiums-3-decene, 1,2-two lithiums-1; 8-phenylbenzene octane, 1,4-two lithium benzene, 1,4-two lithium naphthalenes, 9; 10-two lithium anthracenes, 1,2-two lithiums-1,2-diphenylethlene.Organic multi-lithium initiator (this paper representes with symbol PLi) is in inert solvent, to react prepared by many vinyl-arenes and aforementioned organic single-lithium initiator, the organic pair of lithium and the organic many lithiums mixture that wherein exist organic single-lithium and many vinyl-arenes (following represent with MVA) reaction to generate.In reaction process, can add conjugated diene monomer as additive,, improve the solubility property of organic multi-lithium initiator in inert solvent, obtain the homogeneous multi-lithium initiator so that on organic single-lithium, two lithium and multi-lithium initiator, form the polymkeric substance galianconism.Conjugated diene monomer consumption as additive is that every mole of organic single-lithium initiator need add conjugated diene monomer 2-15mol, preferred 5-10mol.Said conjugated diene monomer is preferably 1,3-butadiene or isoprene.In order to improve the preparation speed of organic multi-lithium initiator, in preparation multi-lithium initiator process, can add a small amount of ethers, as speed regulator, its consumption is THF/ organic single-lithium 0-1.0 (mol ratio) such as THF.Used MVA is preferred 1 in the preparation of the organic multi-lithium initiator of the present invention, 2-Vinylstyrene, 1,3-Vinylstyrene, 1,4-Vinylstyrene, divinyl benzol mixture, or technical grade Vinylstyrene.The consumption of MVA is that every mole of organic single-lithium need add MVA 0.05-1.00mol, preferred 0.05-0.5mol.What temperature of reaction was suitable when organic multi-lithium initiator prepared is 0-70 ℃, preferred 0-50 ℃.Used inert solvent means hexanaphthene, raffinates oil or the mixed solvent of hexanaphthene and normal hexane in the preparation of organic multi-lithium initiator, and wherein the content of normal hexane in mixed solvent is 5～30 weight %.
In the preparation process of butadiene-styrene block copolymer of the present invention, the organic lithium initiator consumption depends on the size of design number-average molecular weight, and its significant quantity (in lithium atom) is that those skilled in the art can confirm.General organic lithium initiator consumption (in lithium atom) need add 0.33-2.0mmol with every 100g monomer.Organic lithium initiator can once add, and also can add several times.
Butadiene-styrene block copolymer solution polymerization temperature of the present invention is the anionic polymerisation temperature that common organolithium causes, and for example the optimal temperature of polyreaction is 0-150 ℃.From economy and inhibition side reaction angle, the preferred polymeric temperature of reaction is 30-100 ℃.
The butadiene-styrene block copolymer of, low-gel content colourless in order to prepare; Butadiene-styrene block copolymer of the present invention must add terminator and carry out termination reaction before last handling process; So that remaining carbon-basic metal spike loses activity in the polymers soln; Make polymkeric substance carbon-basic metal key become an alkali metal salt, thereby make remaining polymkeric substance carbon-basic metal key torpescence that becomes.The selected terminator of the polymers soln that the present invention makes is alcohol acid or alcohol acid/water, and the object lesson of said alcohol acid has Hydrocerol A, lactic acid, oxysuccinic acid, tartrate etc. and composition thereof, optimization citric acid, lactic acid and composition thereof.According to the present invention; Terminator can directly join in the polymers soln; Or join in the polymers soln, or earlier alcohol acid is dissolved in inert solvent such as hexanaphthene/hexane mixed solvent, hexanaphthene, hexane, raffinates oil, in the toluene, joins in the polymers soln then with aqueous solution form.When alcohol acid used with aqueous solution form, water itself also can play terminator.In termination reaction of the present invention, the amount ranges of alcohol acid is 0.02-2.00 weight part/100 parts by weight polymer, preferred 0.04-1.00 weight part/100 parts by weight polymer.If the aftertreatment of polymkeric substance glue adopts direct devolatilization dry technology to remove the inert solvent in the polymkeric substance, then alcohol acid can directly join in the polymers soln, perhaps alcohol acid is dissolved in the inert solvent to add afterwards; If the aftertreatment of polymkeric substance glue is adopted similar fashion such as water vapour cohesion from solvent, to precipitate and separated out rubber sample, the form that then alcohol acid can the aqueous solution joins carries out termination reaction in the polymers soln.
The butadiene-styrene block copolymer of, low-gel content colourless in order to prepare; Butadiene-styrene block copolymer of the present invention must add neutralizing agent and carry out neutralization reaction before last handling process; Make in the polymers soln dissolved alkaline matter such as alkalimetal oxide, oxyhydroxide etc. be neutralized; Become an alkali metal salt, in last handling process, remove along with aqueous phase dissolved.Operable neutralizing agent is an alcohol acid according to the present invention, and its object lesson has Hydrocerol A, lactic acid, oxysuccinic acid, tartrate and composition thereof etc.According to the present invention; Neutralizing agent can directly join in the polymers soln; Or join in the polymers soln with the form of the aqueous solution; Or earlier alcohol acid is dissolved in inert solvent such as hexanaphthene/hexane mixed solvent, hexanaphthene, hexane, raffinates oil, in the toluene etc., joins in the polymers soln then.In neutralization reaction of the present invention, the amount ranges of alcohol acid is 0.02-2.00 weight part/100 parts by weight polymer, preferred 0.04-1.00 weight part/100 parts by weight polymer.If the aftertreatment of polymkeric substance glue adopts direct devolatilization dry technology to remove the inert solvent in the polymkeric substance, then alcohol acid can directly join in the polymers soln, also can after alcohol acid being dissolved in the inert solvent, add; If the aftertreatment of polymkeric substance glue is adopted similar fashion such as water vapour cohesion from solvent, to precipitate and separated out rubber sample, the form that then alcohol acid can the aqueous solution joins carries out neutralization reaction in the polymers soln.
According to the present invention, termination reaction and neutralization reaction can separately be carried out, and also can carry out simultaneously.If carry out simultaneously; Then polyreaction directly joins termination reaction and the required alcohol acid of neutralization reaction in the polymers soln after accomplishing; Or join in the polymers soln with the form of the aqueous solution; Or earlier alcohol acid is dissolved in inert solvent such as hexanaphthene/hexane mixed solvent, hexanaphthene, hexane, raffinates oil, in the toluene etc., joins in the polymers soln then.
Adopting preparation method proposed by the invention to carry out pickling, to stop the prepared butadiene-styrene block copolymer of neutralization procedure colourless, tasteless and gel content is low, is that modifying plastics is with the glue kind, particularly prepare the desirable modified adhesive kind of highly anti-impact ABS and HIPS.
In addition, the thermo oxidative aging performance of butadiene-styrene block copolymer of the present invention obviously is superior to non-acid wash and stops the neutral polymkeric substance after adding anti-anti-aging agent, and resulting polymers has good heat resistanceheat resistant oxidative stability.Operable anti-aging agent comprises Irganox 1520 (Switzerland vapour Bagong department) according to the present invention, four [3-(3; The 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester (promptly 1010)/tricresyl phosphite (2; The 4-di-tert-butyl-phenyl) ester (promptly 168) compound anti-aging agent (wherein 168 content is not higher than 50% weight), 3-(3; The 5-di-tert-butyl-hydroxy phenyl) propionic acid stearyl (promptly 1076)/tricresyl phosphite (2, the 4-di-tert-butyl-phenyl) ester (promptly 168) compound anti-aging agent (wherein 168 content is not higher than 50% weight)., descend the generation adverse consequences under certain condition after adding anti-aging agent such as Irganox 1520 and be two keys of preventing in the molecular chain and oxygen etc. and contact, such as reactions such as crosslinked, degraded, the gel content of increase rubber in toluene solution such as heat effect.According to the present invention, the consumption of anti-aging agent is a 0.05-0.5% weight based on dried glue weight.At last, polymers soln can precipitate from solvent through similar fashion such as alcoholization deposition, spinning, filtration, decant, water vapour cohesions separates out, and also can adopt the stripping mode that the volatile organic compounds separated from solvent in the polymkeric substance is gone out.
The mooney viscosity ML of butadiene-styrene block copolymer of the present invention
1+4Record with day SMV-300 type instrument of island proper Tianjin company; Combined styrene content, vinyl structure, cis-1,4 structure, anti-form-1 in the polymer monomers unit, 4 structural contents are tested with U.S. Perkin-Elmer type IR; Gel content in the toluene solution is with 360 order stainless (steel) wires, and toluene is made solvent, dissolved separating 24 hours, concentration 5% weight, a dissolving method test.Polymkeric substance toluene solution colourity adopts toluene as solvent, and 5% weight solution is put into tube comparison tubes and standard platinum-cobalt liquor compare test.The molecular weight of polymkeric substance and the GPC-10A type gel permeation chromatograph test (solvent: THF that distributes and use day island proper Tianjin company thereof; Flow velocity: 1.0ml/min; Room temperature; GPC post: Water-HR4 * 2+HT5).
Below in conjunction with embodiment and Comparative Examples the present invention is described further, like no specified otherwise, all content percentage ratios and umber all by weight, these embodiment and Comparative Examples only play illustration purpose, do not limit protection scope of the present invention.
Embodiment 1
With refining nitrogen 5L stainless steel polymeric kettle is replaced repeatedly repeatedly.In nitrogen atmosphere, in still, add respectively 143g through drying and the vinylbenzene, 2500g of eliminating impurity through drying and the hexanaphthene, 333g of eliminating impurity through drying and eliminate divinyl, 10ml n-Butyl Lithium (the 0.39M cyclohexane solution of impurity; Down together); Under 50-55 ℃, carry out polyreaction; Accomplish through 20 minutes afterreactions; Add 0.4g Hydrocerol A (the 0.1M aqueous solution) immediately and carry out termination reaction and neutralization reaction; After last question response is accomplished the anti-aging agent Irganox 1520 (production of Switzerland vapour Bagong department) of 1.2g is joined in the glue behind the mixing, obtain the butadiene-styrene block copolymer product after 10 minutes through the roller drying in 120 ℃ of mills of the product after the water vapour coagulative precipitation.The gained sample is tested, and its number-average molecular weight is 15.2 ten thousand, and weight-average molecular weight is 17.2 ten thousand, and mooney viscosity is that the gel content in 125,5% toluene solutions is that the colourity of 0.0025%, 5% toluene solution is 5APHA.
Embodiment 2
With refining nitrogen 5L stainless steel polymeric kettle is replaced repeatedly repeatedly.In nitrogen atmosphere, in still, add respectively 143g through drying and the vinylbenzene, 2500g of eliminating impurity through drying and the hexanaphthene, 333g of eliminating impurity through drying and eliminate divinyl, 0.25g THF, the 10ml n-Butyl Lithium of impurity; Under 50-55 ℃, carry out polyreaction; Accomplish through 15 minutes afterreactions; Add 0.4g Hydrocerol A (the 0.1M aqueous solution) immediately and carry out termination reaction and neutralization reaction; After last question response is accomplished the anti-aging agent Irganox 1520 (production of Switzerland vapour Bagong department) of 1.2g is joined in the glue behind the mixing, obtain the butadiene-styrene block copolymer product after 10 minutes through the roller drying in 120 ℃ of mills of the product after the water vapour coagulative precipitation.The gained sample is tested, and its number-average molecular weight is 15.0 ten thousand, and weight-average molecular weight is 16.9 ten thousand, and mooney viscosity is that the gel content in 120,5% toluene solutions is that the colourity of 0.0030%, 5% toluene solution is 7APHA.
Embodiment 3
With refining nitrogen 5L stainless steel polymeric kettle is replaced repeatedly repeatedly.In nitrogen atmosphere, in still, add respectively 72g through drying and the vinylbenzene, 2500g of eliminating impurity through drying and the hexanaphthene, 404g of eliminating impurity through drying and eliminate divinyl, the 15ml n-Butyl Lithium of impurity; Under 50-55 ℃, carry out polyreaction; Accomplish through 20 minutes afterreactions; The mixture (being the 0.05M aqueous solution) that adds 0.2g Hydrocerol A and 0.2g lactic acid immediately carries out termination reaction and neutralization reaction; After last question response is accomplished the anti-aging agent Irganox 1520 (production of Switzerland vapour Bagong department) of 1.2g is joined in the glue behind the mixing, obtain the butadiene-styrene block copolymer product after 10 minutes through the roller drying in 120 ℃ of mills of the product after the water vapour coagulative precipitation.The gained sample is tested, and its number-average molecular weight is 9.2 ten thousand, and weight-average molecular weight is 10.4 ten thousand, and mooney viscosity is that the gel content in 55,5% toluene solutions is that the colourity of 0.0020%, 5% toluene solution is less than 5APHA.
Embodiment 4
With refining nitrogen 5L stainless steel polymeric kettle is replaced repeatedly repeatedly.In nitrogen atmosphere, in still, add respectively 72g through drying and the vinylbenzene, 2500g of eliminating impurity through drying and the hexanaphthene, 404g of eliminating impurity through drying and eliminate divinyl, the 15ml n-Butyl Lithium of impurity; Under 50-55 ℃, carry out polyreaction; Accomplish through 20 minutes afterreactions; Add 0.2g lactic acid (the 0.1M aqueous solution) immediately and carry out termination reaction; Stop after 10 minutes; Add 0.2g lactic acid (the 0.1M aqueous solution) again and carry out neutralization reaction, treat at last after neutralization reaction is accomplished the anti-aging agent Irganox 1520 (production of Switzerland vapour Bagong department) of 1.2g to be joined in the glue behind the mixing, obtain the butadiene-styrene block copolymer product after 10 minutes through the roller drying in 120 ℃ of mills of the product after the water vapour coagulative precipitation.The gained sample is tested, and its number-average molecular weight is 9.2 ten thousand, and weight-average molecular weight is 10.3 ten thousand, and mooney viscosity is that the gel content in 52,5% toluene solutions is that the colourity of 0.0010%, 5% toluene solution is less than 5APHA.
Embodiment 5
With refining nitrogen 5L stainless steel polymeric kettle is replaced repeatedly repeatedly.In nitrogen atmosphere, in still, add respectively 143g through drying and the vinylbenzene, 2500g of eliminating impurity through drying and the hexanaphthene/hexane mixed solvent (82/18 weight ratio), 333g of eliminating impurity through drying and eliminate divinyl, 0.25g THF, the 10ml n-Butyl Lithium of impurity; Under 50-55 ℃, carry out polyreaction; Accomplish through 15 minutes afterreactions; Add 0.4g tartrate (the 0.1M aqueous solution) immediately and carry out termination reaction and neutralization reaction; After last question response is accomplished the anti-aging agent Irganox 1520 (production of Switzerland vapour Bagong department) of 1.2g is joined in the glue behind the mixing, obtain the butadiene-styrene block copolymer product after 10 minutes through the roller drying in 120 ℃ of mills of the product after the water vapour coagulative precipitation.The gained sample is tested, and its number-average molecular weight is 14.9 ten thousand, and weight-average molecular weight is 16.8 ten thousand, and mooney viscosity is that the gel content in 119,5% toluene solutions is that the colourity of 0.0025%, 5% toluene solution is 10APHA.
Comparative Examples 1
With refining nitrogen 5L stainless steel polymeric kettle is replaced repeatedly repeatedly.In nitrogen atmosphere, in still, add respectively 143g through drying and the vinylbenzene, 2500g of eliminating impurity through drying and the hexanaphthene, 333g of eliminating impurity through drying and eliminate divinyl, the 10ml n-Butyl Lithium of impurity; Under 50-55 ℃, carry out polyreaction; Accomplish through 20 minutes afterreactions; Add the 0.4g Virahol immediately and carry out termination reaction; Treat at last after termination reaction is accomplished the anti-aging agent Irganox 1520 (production of Switzerland vapour Bagong department) of 1.2g to be joined in the glue behind the mixing, obtain the butadiene-styrene block copolymer product after 10 minutes through the roller drying in 120 ℃ of mills of the product after the water vapour coagulative precipitation.The gained sample is tested, and its number-average molecular weight is 15.0 ten thousand, and weight-average molecular weight is 16.9 ten thousand, and mooney viscosity is that the gel content in 128,5% toluene solutions is that the colourity of 0.0075%, 5% toluene solution is 20APHA.
Comparative Examples 2
With refining nitrogen 5L stainless steel polymeric kettle is replaced repeatedly repeatedly.In nitrogen atmosphere, in still, add respectively 72g through drying and the vinylbenzene, 2500g of eliminating impurity through drying and the hexanaphthene/hexane mixed solvent (82/18 weight ratio), 404g of eliminating impurity through drying and eliminate divinyl, 0.25g THF, the 15ml n-Butyl Lithium of impurity; Under 50-55 ℃, carry out polyreaction; Accomplish through 15 minutes afterreactions; Add the 0.4g Virahol immediately and carry out termination reaction; After last question response is accomplished the anti-aging agent Irganox 1520 (production of Switzerland vapour Bagong department) of 1.2g is joined in the glue behind the mixing, obtain the butadiene-styrene block copolymer product after 10 minutes through the roller drying in 120 ℃ of mills of the product after the water vapour coagulative precipitation.The gained sample is tested, and its number-average molecular weight is 9.3 ten thousand, and weight-average molecular weight is 10.6 ten thousand, and mooney viscosity is that the gel content in 55,5% toluene solutions is that the colourity of 0.0125%, 5% toluene solution is 30APHA.
Comparative Examples 3
With refining nitrogen 5L stainless steel polymeric kettle is replaced repeatedly repeatedly.In nitrogen atmosphere, in still, add respectively 143g through drying and the vinylbenzene, 2500g of eliminating impurity through drying and the hexanaphthene, 333g of eliminating impurity through drying and eliminate divinyl, the 10ml n-Butyl Lithium of impurity; Under 50-55 ℃, carry out polyreaction; Accomplish through 20 minutes afterreactions; Disposable immediately adding 0.4g hexanodioic acid (0.01M toluene solution) stops/neutralization reaction; Treat at last after termination reaction is accomplished the anti-aging agent Irganox 1520 (production of Switzerland vapour Bagong department) of 1.2g to be joined in the glue behind the mixing, obtain the butadiene-styrene block copolymer product after 10 minutes through the roller drying in 120 ℃ of mills of the product after the water vapour coagulative precipitation.The gained sample is tested, and its number-average molecular weight is 15.3 ten thousand, and weight-average molecular weight is 17.6 ten thousand, and mooney viscosity is that the gel content in 120,5% toluene solutions is that the colourity of 0.0105%, 5% toluene solution is 20APHA.
Comparative Examples 4
With refining nitrogen 5L stainless steel polymeric kettle is replaced repeatedly repeatedly.In nitrogen atmosphere, in still, add respectively 143g through drying and the vinylbenzene, 2500g of eliminating impurity through drying and the hexanaphthene/hexane mixed solvent (82/18 weight ratio), 333g of eliminating impurity through drying and eliminate divinyl, 0.25g THF, the 10ml n-Butyl Lithium of impurity; Under 50-55 ℃, carry out polyreaction; Accomplish through 15 minutes afterreactions; Disposable immediately adding 0.4g propionic acid (the 0.1M aqueous solution) stops/neutralization reaction; After last question response is accomplished the anti-aging agent Irganox 1520 (production of Switzerland vapour Bagong department) of 1.2g is joined in the glue behind the mixing, obtain the butadiene-styrene block copolymer product after 10 minutes through the roller drying in 120 ℃ of mills of the product after the water vapour coagulative precipitation.The gained sample is tested, and its number-average molecular weight is 14.8 ten thousand, and weight-average molecular weight is 16.7 ten thousand, and mooney viscosity is that the gel content in 118,5% toluene solutions is that the colourity of 0.0130%, 5% toluene solution is 25APHA.
Embodiment 6-10
The preparation method of embodiment 1-5 is applied to embodiment 6-10, processes the batten of 2mm thickness after the polymer rubber drying of embodiment 6-10, batten heats once more in 120 ℃ of ageing ovens and carried out thermo-oxidative ageing 20 minutes, and polymer performance is listed in the table 1.
The polymer performance of table 1. embodiment 6-10
Comparative Examples 5-8
The preparation method of Comparative Examples 1-4 is applied to ratio 5-8, processes the batten of 2mm thickness after the polymer rubber drying of Comparative Examples 5-8, batten heats once more in 120 ℃ of ageing ovens and carried out thermo-oxidative ageing 20 minutes, and polymer performance is listed in the table 2.
The polymer performance of table 2. Comparative Examples 5-8
Claims (16)
1. a butadiene-styrene block copolymer is characterized in that the combined styrene content in the monomeric unit is 10-60% weight, preferred 15-30% weight; Contents of ethylene is a 6-18% weight, preferred 8-14% weight; The number-average molecular weight scope of polymkeric substance is 5 * 10
4-30 * 10
4, preferred 10 * 10
4-20 * 10
4Mooney viscosity ML under 100 ℃
1+4Be 20-200, preferred 50-150; The colourity of said butadiene-styrene block copolymer in 5% toluene solution is lower than 15APHA, preferably is lower than 10APHA; And the insolubles content of said butadiene-styrene block copolymer in 5% toluene solution be lower than 100ppm, preferably is lower than 50ppm.
2. a method for preparing according to the butadiene-styrene block copolymer described in the claim 1 comprises the steps:
1) inert solvent, divinyl and vinylbenzene and the optional structure regulator that uses are joined in the reactor drum, add the alkali alkyl compound initiator of significant quantity then, in the presence of said initiator, carry out solution polymerization;
2) treat that the solution polymerization transformation efficiency reaches 99% after, add a certain amount of terminator an alkali metal salt spike carried out termination reaction, wherein terminator is alcohol acid or alcohol acid/water; And add a certain amount of neutralizing agent alkalimetal oxide and/or alkali metal hydroxide etc. in the polymers soln are carried out neutralization reaction, wherein neutralizing agent is an alcohol acid;
3) in polymers soln, add anti-aging agent.
3. method according to claim 2 is characterized in that said alkali alkyl compound initiator is the organic lithium initiator that is selected from organic single-lithium initiator, organic dilithium initiator and organic multi-lithium initiator.
4. method according to claim 3 is characterized in that described organic single-lithium initiator is a n-Butyl Lithium.
5. method according to claim 3; It is characterized in that described organic multi-lithium initiator is in inert solvent, under 0-70 ℃ temperature, to react prepared by many vinyl-arenes and organic single-lithium initiator, the mol ratio of wherein said many vinyl-arenes and organic single-lithium is 0.05-1.00.
6. method according to claim 5; It is characterized in that the further mol ratio that adds conjugated diene and said conjugated diene and organic single-lithium is 5-10 in described organic multi-lithium initiator preparation; Wherein said conjugated diene is selected from 1,3-butadiene and isoprene.
7. method according to claim 5 is characterized in that the said many vinyl-arenes in described organic multi-lithium initiator preparation are Vinylstyrene.
8. method according to claim 2 is characterized in that used inert solvent is selected from nonpolar aromatic hydrocarbons, aliphatic hydrocrbon, cycloaliphates and aliphatic hydrocrbon and alicyclic mixture.
9. method according to claim 2 is characterized in that said structure regulator is selected from ether compound, tertiary amine compounds and composition thereof.
10. method according to claim 9 is characterized in that said ether compound is THF, glycol dimethyl ether or diglyme; Said tertiary amine compounds is N, N, N ', N '-Tetramethyl Ethylene Diamine.
11. method according to claim 2 is characterized in that said solution polymerization temperature is 0-150 ℃, is preferably 30-100 ℃.
12. method according to claim 2 is characterized in that termination reaction and neutralization reaction proceed step by step, perhaps termination reaction and neutralization reaction are carried out simultaneously.
13. method according to claim 2, the alcohol acid consumption is 0.02-2.00 weight part/100 parts by weight polymer when it is characterized in that termination reaction, is preferably 0.04-1.00 weight part/100 parts by weight polymer.
14. method according to claim 2, the alcohol acid consumption is 0.02-2.00 weight part/100 parts by weight polymer when it is characterized in that neutralization reaction, is preferably 0.04-1.00 weight part/100 parts by weight polymer.
15. method according to claim 2 is characterized in that alcohol acid directly uses or uses with the aqueous solution or the solution form in inert solvent.
16. method according to claim 2 is characterized in that alcohol acid is Hydrocerol A, oxysuccinic acid, tartrate, lactic acid or its mixture, optimization citric acid, lactic acid or the mixture of the two.
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| CN104098719A (en) * | 2013-04-09 | 2014-10-15 | 中国石油化工股份有限公司 | Reactive polymer in-kettle termination method capable of preventing generation of gel in kettle |
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