CN103570874A - Method for terminating copolymerization between conjugated diene and vinyl aromatic hydrocarbon - Google Patents
Method for terminating copolymerization between conjugated diene and vinyl aromatic hydrocarbon Download PDFInfo
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Abstract
The invention discloses a method for terminating copolymerization between conjugated diene and vinyl aromatic hydrocarbon. The method comprises the following steps: (a) polymerizing monovinyl aromatic hydrocarbon and conjugated diene until the monovinyl aromatic hydrocarbon and the conjugated diene are basically and completely converted in a reactive inert solvent in the presence of an organic lithium initiator; and (b) adding a terminating agent and an optional anti-aging agent, wherein the terminating agent is selected from R3SiX (I) shown as a formula (I), each R is independently C1-C8 alkyl, C3-C8 naphthenic base, C3-C8 naphthenic base-C1-C8 alkyl, C1-C8 alkyl-C3-C8 naphthenic base, C6-C10 aryl, C6-C10 aryl-C1-C8 alkyl or C1-C8 alkyl-C6-C10 aryl, preferentially C1-C6 alkyl, cyclopentyl, cyclohexyl, phenyl, naphthyl, cresyl, benzyl or phenethyl; X is halogen, preferentially chlorine or bromine, more preferentially chlorine.
Description
Technical field
The present invention relates to a kind of method that stops the copolyreaction of conjugated diene and vinyl-arene.Particularly, the present invention relates to a kind of copolyreaction that stops conjugated diene-vinyl-arene, especially prepare the method for the copolyreaction of butylbenzene copolymer, wherein in the polymerization later stage, adopt a kind of terminator of novel texture.
Background technology
The copolyreaction of existing conjugated diene and vinyl-arene mainly adopts anionic solution polymerization method.Take hexanaphthene as solvent, and lithium alkylide or rare earth are catalyzer, by the multipolymer of anionic solution polymerization method synthesis of conjugate diolefine and vinyl-arene.By the copolymerization product of conjugated diene and vinyl aromatic (co) hydrocarbon reaction gained, mainly contained at present that to take vinylbenzene, divinyl, isoprene be monomer, hexanaphthene is solvent, styrene analog thermoplastic elastomer prepared by lithium alkylide initiator system (as SBS, SEBS, K resin) and synthetic rubber (as SSBR, SIBR) etc.Thermoplastic elastomer has the characteristic of plastics and rubber concurrently, is described as " third generation synthetic rubber ".In thermoplastic elastomer, SBS occupies an important position, and is that output is maximum in the world at present, and a kind of thermoplastic elastomer with fastest developing speed accounts for the 45-50% of each analog thermoplastic elastomer total quantity consumed.External SBS is mainly used in shoemaking, pitch, tackiness agent and polymer modification.But, in anionoid polymerization process, there is a distinctive phenomenon: in the situation that there is no terminator, polyreaction can ad infinitum go on.For the needs of actual use procedure, in Industrial processes, need to add in due course terminator to stop polyreaction, thereby obtain the polymkeric substance with specified molecular weight.Prior art generally adopts water or alcohols material as polyreaction terminator, but water and alcohols terminator are polar material, bad with nonpolar polymers soln consistency, easily cause and stop not exclusively, make the polymkeric substance that contains a certain amount of macromolecule in product, even cause product gel content higher.
Chinese patent application CN1919881A discloses a kind of termination containing the method for the polyreaction of conjugated diene polymer, wherein adopt 2,6-di-tert-butyl-4-methy phenol (being called for short 264) and four (β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester (being called for short 1010) phenolic type antioxidant is as the terminator containing conjugate diene polymerization reaction, but adopt the add-on that needs in this way strictly to control terminator, in actual production process, application is comparatively difficult.
Summary of the invention
The shortcoming that the terminator adopting for existing conjugated diene and vinyl-arene copolyreaction exists, the inventor has carried out extensive research, discovery can synthesize a kind of monovinylarene-conjugated diene copolymer of low-gel content, especially butylbenzene copolymer by method of the present invention.Utilize the present invention in the industrial production of conjugated diene and vinyl-arene copolymerization, can reach the best effect that stops.
Therefore, the object of the present invention is to provide a kind of method that stops the copolyreaction of conjugated diene and vinyl-arene, the multipolymer obtaining by described method has low-gel content.
According to the present invention, described object realizes by a kind of method that stops the copolyreaction of conjugated diene and vinyl-arene, and described method comprises:
(a), under the existence of organic lithium initiator, monovinylarene and conjugated diene are polymerized to substantially in reaction-inert solvent and transform completely;
(b) add terminator and optional anti-aging agent,
Wherein said terminator is selected from those shown in formula (I),
R
3SiX(I)
Wherein,
Each R is C independently of each other
1-C
8alkyl, C
3-C
8cycloalkyl, C
3-C
8cycloalkyl-C
1-C
8alkyl, C
1-C
8alkyl-C
3-C
8cycloalkyl, C
6-C
10aryl, C
6-C
10aryl-C
1-C
8alkyl or C
1-C
8alkyl-C
6-C
10aryl, preferably C
1-C
6alkyl, cyclopentyl, cyclohexyl, phenyl, naphthyl, tolyl, benzyl or styroyl;
X is halogen, preferably chlorine or bromine, more preferably chlorine.
Embodiment
In the description of this invention below, except separately clearly stating, the numerical value in the application all can be considered by word " approximately " to be modified.But the inventor has as far as possible accurately reported the numerical value in embodiment, although these numerical value inevitably comprise certain error.
In this application, unless clearly got rid of, concrete or preferred embodiment of the present invention can combine.In addition, every key element of the embodiment of the present application is the concrete preferred selection of the upper technical characterictic corresponding with it.If described upper technical characterictic can combine with other upper feature, the described key element of embodiment, described concrete preferred selection, also can combine with described other upper feature.These combinations should be regarded as a part for the original record content of the application.
An aspect of of the present present invention provides a kind of method that stops the copolyreaction of conjugated diene and vinyl-arene, comprising:
(a), under the existence of organic lithium initiator, monovinylarene and conjugated diene are polymerized to substantially in reaction-inert solvent and transform completely;
(b) add terminator and optional anti-aging agent,
Wherein said terminator is selected from those shown in formula (I),
R
3SiX(I)
Wherein,
Each R is C independently of each other
1-C
8alkyl, C
3-C
8cycloalkyl, C
3-C
8cycloalkyl-C
1-C
8alkyl, C
1-C
8alkyl-C
3-C
8cycloalkyl, C
6-C
10aryl, C
6-C
10aryl-C
1-C
8alkyl or C
1-C
8alkyl-C
6-C
10aryl, preferably C
1-C
6alkyl, cyclopentyl, cyclohexyl, phenyl, naphthyl, tolyl, benzyl or styroyl;
X is halogen, preferably chlorine or bromine, more preferably chlorine.
Organic lithium initiator for step (a) for example can be organic single-lithium initiator, organic dilithium initiator or organic multi-lithium initiator.
Organic single-lithium initiator for example can represent with RLi, the C that wherein R is straight or branched
1-C
20alkyl; C
3-C
20cycloalkyl; C
6-C
20aryl.The specific examples of organic single-lithium can comprise such as lithium methide, lithium ethide, propyl lithium, isopropyl lithium, tert-butyl 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., preferably n-Butyl Lithium or s-butyl lithium.The specific examples of organic dilithium initiator comprises as two lithium methane, Isosorbide-5-Nitrae-bis-lithium butane, 1,10-bis-lithium decane, 1,20-bis-lithium eicosanes, 1,4-bis-lithium hexanaphthenes, 1,2-bis-lithium-1,8-phenyl octane, 1,4-bis-lithium benzene, Isosorbide-5-Nitrae-bis-lithium naphthalene, 9,10-bis-lithium anthracenes.Organic multi-lithium initiator (representing with symbol PLi herein) for example can react prepared by many vinyl-arenes and aforementioned organic single-lithium initiator in inert solvent, wherein exists organic single-lithium to react organic pair of lithium and the organic many lithiums mixture generating with many vinyl-arenes (representing with MVA below).In reaction process, can add conjugated diene monomer as additive, so that form polymkeric substance galianconism on organic single-lithium, two lithium and multi-lithium initiator, improve the solubility property of organic multi-lithium initiator in inert solvent, obtain the multi-lithium initiator of homogeneous phase.Conjugated diene monomer consumption as additive is that every mole of organic single-lithium initiator need add conjugated diene monomer 2-15mol, preferably 5-10mol.Described conjugated diene monomer is preferably 1,3-butadiene, isoprene.In order to improve the preparation speed of organic multi-lithium initiator, in preparing multi-lithium initiator process, can add a small amount of ethers, such as THF is as speed regulator, its consumption is THF/ organic single-lithium 0-1.0 (mol ratio).In the preparation of the organic multi-lithium initiator of the present invention, MVA used preferably 1,2-Vinylstyrene, 1,3-Vinylstyrene, Isosorbide-5-Nitrae-Vinylstyrene, divinyl benzol mixture, or technical grade Vinylstyrene.The consumption of MVA is that every mole of organic single-lithium need add MVA0.05-1.00mol, preferably 0.05-0.5mol.That when prepared by organic multi-lithium initiator, temperature of reaction is suitable is 0-70 ℃, preferably 0-50 ℃.
According to the preferred embodiments of the invention, in step (a), use organic single-lithium initiator, particularly n-Butyl Lithium.
In the step of the inventive method (a), organic lithium initiator consumption depends on the size of design number-average molecular weight, and its significant quantity (calculating with lithium atom) is that those skilled in the art can determine.General organic lithium initiator consumption (calculating with lithium atom) need to add 0.5-2.5mmol with every 100g monomer.Organic lithium initiator can once add, and also can add several times.
In the methods of the invention, polymeric reaction temperature is the anionic polymerisation temperature that common organolithium causes, and for example the optimal temperature of polyreaction is 0-130 ℃.From economy and inhibition side reaction angle, preferred polymeric temperature of reaction is 30-110 ℃, more preferably 50-100 ℃.Polymerization pressure is 0.005-1MPa gauge pressure, is preferably 0.1-0.3MPa gauge pressure.Polymerization reaction time is 0.2-2 hour.
Conjugated diene of the present invention can be C
4-C
12conjugated diolefine, preferably C
4-C
8conjugated diolefine.Example is isoprene, 1,3-butadiene, 2,3-methyl isophthalic acid, 3-divinyl, 1,3-pentadiene, 3-butyl-1,3-octadiene, 2-phenyl-1,3-butadiene, 1,3-hexadiene or its arbitrary combination, more preferably 1,3-butadiene.
Monovinylarene of the present invention can be the monovinylarene containing 8-20 carbon atom conventionally; Be preferably vinylbenzene, especially C
1-C
4the vinylbenzene that alkyl replaces or their arbitrary combination.Aforementioned term " C
1-C
4the vinylbenzene that alkyl replaces " in the C that mentions
1-C
4alkyl refers to the straight or branched alkyl with 1-4 carbon atom, for example methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl and the tertiary butyl.In preferred embodiments, aforementioned C
1-C
4the vinylbenzene that alkyl replaces be between vinyl toluene, p-methylstyrene, p-tert-butylstyrene, alpha-methyl styrene or its arbitrary combination.
In the methods of the invention, the gross weight of monomer of take is benchmark, and conjugated diene consumption is that 50-85 % by weight and monovinylarene consumption are 15-50 % by weight, and preferably conjugated diene consumption is that 55-75 % by weight and monovinylarene consumption are 25-45 % by weight.
Operable reaction-inert solvent is for example nonpolar aromatic hydrocarbons in the methods of the invention, as benzene,toluene,xylene, ethylbenzene; Aliphatic hydrocrbon, as pentane, hexane, heptane, octane; Alicyclic hydrocarbon, as pentamethylene, hexanaphthene, methylcyclohexane; Or aliphatic hydrocrbon and alicyclic mixture, as hexane and hexanaphthene mixture or raffinate oil.Generally speaking, reaction-inert solvent consumption is 300-5000g reaction-inert solvent based on 100g monomer.
According to the preferred embodiments of the invention, in step (a), first add solvent and monovinylarene; After replacing with rare gas element, add conjugated diene, finally add organic lithium initiator; Certainly also can first add solvent, then with rare gas element, replace, then monovinylarene and conjugated diene be added simultaneously, then add organic lithium initiator.Rare gas element can be conventional those in this area, as nitrogen, argon gas or helium etc.
According to embodiments more of the present invention, for example, in the preparation process of segmented copolymer, without adding structure regulator as activator, thereby simplified polymerization process, be particularly conducive to the carrying out of solvent recuperation process.Certainly, in the methods of the invention, particularly for the polyreaction of preparing random copolymers, add structure regulator and be also fine.Said structure regulator can be conventional use any in anionoid polymerization solution polymerized rubber system, for example be selected from containing oxygen, nitrogenous, sulfur-bearing, containing one or more the mixture in Phosphorus polar compound, preferably ether compound, tertiary amine compounds or its mixture.Ether compound for example comprises tetrahydrofuran (THF), 1,4-dioxy hexanaphthene, ether, dibutyl ether, glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol methyl ether, ethylene glycol dibutyl ether, diglyme, diethyl carbitol, glycol ether methyl ethyl ether, diethylene glycol dibutyl ether, triglyme, tetraethylene glycol dimethyl ether, phenyl ether, methyl-phenoxide, crown ether, triethylamine, tripropyl amine, Tributylamine, N, N, N ', N '-Tetramethyl Ethylene Diamine (TMEDA), N, N-Diethyl Aniline, pyridine, quinoline, dipiperidinoethane (DPE), HMPA (HMPA) etc.Preferred structure conditioning agent is tetrahydrofuran (THF), glycol dimethyl ether, diglyme and N, N, N ', N '-Tetramethyl Ethylene Diamine (TMEDA).
In polymerization process structure regulator consumption be those skilled in the art can be definite conventional amount used, preferable amount is the structure regulator that every mole of lithium atom adds 0.1-100mol.Preferred structure regulator amount ranges is as follows: while selecting THF as structure regulator, every mole of lithium atom need add THF0.4-80mol; While selecting glycol dimethyl ether as structure regulator, every mole of lithium atom need add glycol dimethyl ether 0.05-40mol; While selecting diglyme as structure regulator, every mole of lithium atom need add diglyme 0.01-20mol; While selecting TMEDA as structure regulator, every mole of lithium atom need add TMEDA0.01-20mol.
In the step (a) of the inventive method, substantially completely transform and refer to that monomer conversion reaches more than 95%, preferably more than 97%.
In order to prepare the monovinylarene-conjugated diene copolymer of low-gel content, before aftertreatment monovinylarene-conjugated diene copolymer, must add terminator termination reaction.
Terminator described in the inventive method is selected from those shown in formula (I),
R
3SiX(I)
Wherein,
Each R is C independently of each other
1-C
8alkyl, C
3-C
8cycloalkyl, C
3-C
8cycloalkyl-C
1-C
8alkyl, C
1-C
8alkyl-C
3-C
8cycloalkyl, C
6-C
10aryl, C
6-C
10aryl-C
1-C
8alkyl or C
1-C
8alkyl-C
6-C
10aryl, preferably C
1-C
6alkyl, cyclopentyl, cyclohexyl, phenyl, naphthyl, tolyl, benzyl or styroyl;
X is halogen, preferably chlorine or bromine, more preferably chlorine.
In a preferred embodiment of the invention, at least two R in formula (I) are C
1-C
8alkyl.In another preferred embodiment of the present invention, three R in formula (I) are C
1-C
8alkyl.
For term halogen herein, for example comprise fluorine, chlorine, bromine and iodine.
For term C herein
1-C
8alkyl refers to saturated straight chain or the branched hydrocarbyl radical with 1-8 carbon atom, for example C
1-C
6alkyl, as methyl, ethyl, propyl group, 1-methylethyl, butyl, 1-methyl-propyl, 2-methyl-propyl, 1, 1-dimethyl ethyl, amyl group, 1-methyl butyl, 2-methyl butyl, 3-methyl butyl, 2, 2-dimethyl propyl, 1-ethyl propyl, 1, 1-dimethyl propyl, 1, 2-dimethyl propyl, hexyl, 1-methyl amyl, 2-methyl amyl, 3-methyl amyl, 4-methyl amyl, 1, 1-dimethylbutyl, 1, 2-dimethylbutyl, 1, 3-dimethylbutyl, 2, 2-dimethylbutyl, 2, 3-dimethylbutyl, 3, 3-dimethylbutyl, 1-ethyl-butyl, 2-ethyl-butyl, 1, 1, 2-trimethylammonium propyl group, 1, 2, 2-trimethylammonium propyl group, 1-ethyl-1-methyl-propyl and 1-Ethyl-2-Methyl propyl group.
For term C herein
3-C
8cycloalkyl for example comprises cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, suberyl and ring octyl group.
For term C herein
6-C
10aryl for example comprises phenyl (C
6h
5-) and naphthyl (C
10h
7-).
For term C herein
6-C
10aryl-C
1-C
8alkyl for example comprises benzyl and styroyl.
For term C herein
1-C
8alkyl-C
6-C
10aryl for example comprises tolyl.
According to a preferred embodiment of the invention, the terminator for step (b) can be selected from benzyl dimethyl chlorosilane, normal-butyl dimethylchlorosilane, three n-butyl chloride silane, ethyl dimethylchlorosilane, chlorotriethyl silane, trimethylchlorosilane, phenyldimethylchlorosilane, tri-phenyl chloride, cyclohexyl dimethylchlorosilane, cyclopentyl dimethylchlorosilane, n-propyl dimethylchlorosilane and tolyl dimethylchlorosilane.
The amount of terminator can be the conventional amount used of this area.Those skilled in the art can be according to the various factors in polymerization system, as the impurity existing, as the amount of water is specifically selected.It is 1.05-2.0:1 that the consumption of common terminator makes the mol ratio of terminator and organic lithium initiator (lithium atom of take calculating), preferably 1.1-1.5:1.
According to a preferred embodiment of the invention, its be additionally included in step (a) and (b) between add coupling agent to carry out the step of linked reaction.
The inventive method can also, after described polyreaction completes substantially, add the coupling agent of 2-4 functionality to carry out linked reaction.The mol ratio of coupling agent and organic lithium initiator (calculating with lithium atom) can be 0.03-0.30, preferably 0.1-0.2.Can use in the method for the invention the conventional coupling agent in this area, coupling agent is preferably selected from silicon tetrachloride, tin tetrachloride, Vinylstyrene, dimethyl adipate, dimethyldichlorosilane(DMCS) and METHYL TRICHLORO SILANE.Coupling agent conventionally joins in inert solvent and is mixed with dilute solution, joins in polymers soln after polyreaction completes, and fully stirs and makes it disperse and react completely.
In the situation that adding coupling agent, the consumption of described terminator make terminator with the molar ratio of the organic lithium initiator calculating with lithium atom as can be 0.2-2.0:1, preferred 0.25-1.5:1.
According to the present invention, terminator can directly join in polymers soln, or first terminator is dissolved in to above-mentioned reaction-inert solvent, as hexanaphthene/hexanes mixtures, hexanaphthene, hexane, raffinate oil, in toluene, then join in polymeric solution.
According to the present invention, after adding terminator, can optionally add anti-aging agent.Being applicable to anti-aging agent of the present invention can be the normally used phenols in this area or amine, such as, but not limited to, 2,6-ditertbutylparacresol (antioxidant 264), tert-butyl catechol, 2,2 '-methylene radical-bis-(4-methyl-6-tert-butylphenol) (antioxidant 2246).
According to the preferred embodiments of the invention, the add-on of described anti-aging agent can be generally the 0.5-2% of polymer weight, preferably 0.6-1.0%.
Finally, polymers soln can, by similar fashion Precipitations from solvent such as alcoholization precipitation, centrifugation, filtration, decant, water vapour cohesions, also can adopt stripping mode that the volatile organic compounds separated from solvent in polymkeric substance is gone out.
The inventive method can be used for the copolyreaction that random copolymers or segmented copolymer, the especially butadiene-styrene block copolymer of monovinylarene-conjugated diene are prepared in termination.
The gel content of the multipolymer obtaining by terminating method of the present invention is low.When by terminating method of the present invention during for the preparation of thermoplastic elastomer, gained thermoplastic elastomer has low-gel content and excellent physical and mechanical properties, is suitable as tackiness agent.
Finally, the invention still further relates to terminator as herein defined in the copolyreaction that stops conjugated diene-vinyl-arene, especially prepare butylbenzene copolymer, particularly prepare the purposes in the copolyreaction of butadiene-styrene block copolymer.
Below, with non-limiting example, further illustrate the present invention.But it should be noted, it is limitation of the present invention that these embodiment should not be considered as.
Embodiment
In present specification, unless expressly stated otherwise,, all parts and per-cent are all based on weight.
experiment
Conjugated diene unit medium vinyl structure, cis-1,4 structures, anti-form-1, the Switzerland AVANCE DRX400MHz of Bruker company nuclear magnetic resonance spectrometer for 4 structural contents, sample dissolves and is mixed with 2～3% (w/v) solution with deuterochloroform at normal temperatures, take TMS as zero calibration, under room temperature, test;
360 order stainless (steel) wires for gel content in toluene solution, toluene is made solvent, dissolved solution 24 hours, concentration 5% weight, a dissolving method test.
The molecular weight of polymkeric substance and distribution (M thereof
w/ M
n) and the GPC-10A type gel permeation chromatograph test (solvent: THF of Japanese Shimadzu company for coupling efficiency; Flow velocity: 1.0ml/min; Room temperature; GPC post: Water-HR4 * 2+HT5).
embodiment 1
Before polymerization, by 5A molecular sieve for mixed solvent (hexanaphthene and normal hexane, weight ratio is 88:12) (
purchased from Dalian Kang Yu Chemical Co., Ltd., at 500 ℃, dry 5 hours in advance) soak 1 week.Under high pure nitrogen protection, in 300 liters of polymeric kettles, add mixed solvent 105Kg, vinylbenzene 6Kg successively, paradigmatic system is through high-purity N
2after displacement deoxidation, add divinyl 14Kg, stir after 10 minutes, add n-butyllithium solution 2000ml (concentration of n-Butyl Lithium is 0.2mol/L) to carry out polyreaction.Polymerization kick off temperature is 50 ℃, and reaction pressure is 0.1MPa.While reacting 15 minutes, reach 85 ℃ of peak temperature, reaction pressure is 0.28MPa.Peak temperature samples survey transformation efficiency and reaches 100% after 5 minutes, reaction pressure is 0.15MPa, to adding 180ml silicon tetrachloride solution in reactor, (concentration is 0.4mol/L, solvent is that weight ratio is the hexanaphthene of 88:12 and the mixture of normal hexane) carry out coupling, after coupling 15 minutes, in polymeric kettle, add trimethylchlorosilane 12g, carry out termination reaction.Stir and after 5 minutes, add anti-aging agent 2,6 ditertiary butyl p cresol 160g.
Glue, after water vapor cohesion, obtains butadiene-styrene block copolymer product after mill is dry.Record product performance data in Table 1.
comparative example 1
Before polymerization, by 5A molecular sieve for mixed solvent (hexanaphthene and normal hexane, weight ratio is 88:12) (
purchased from Dalian Kang Yu Chemical Co., Ltd., at 500 ℃, dry 5 hours in advance) soak 1 week.Under high pure nitrogen protection, in 300 liters of polymeric kettles, add mixed solvent 105Kg, vinylbenzene 6Kg successively, paradigmatic system is through high-purity N
2after displacement deoxidation, add divinyl 14Kg, stir after 10 minutes, add n-butyllithium solution 2000ml (concentration of n-Butyl Lithium is 0.2mol/L) to carry out polyreaction.Polymerization kick off temperature is 50 ℃, and reaction pressure is 0.1MPa.While reacting 15 minutes, reach 85 ℃ of peak temperature, reaction pressure is 0.28MPa.Peak temperature samples survey transformation efficiency and reaches 100% after 5 minutes, reaction pressure is 0.15MPa, to adding 180ml silicon tetrachloride solution in reactor, (concentration is 0.4mol/L, solvent is that weight ratio is the hexanaphthene of 88:12 and the mixture of normal hexane) carry out coupling, after coupling 15 minutes, in polymeric kettle, add water 2.0g, carry out termination reaction.Stir and after 5 minutes, add anti-aging agent 2,6 ditertiary butyl p cresol 160g.
Glue, after water vapor cohesion, obtains butadiene-styrene block copolymer product after mill is dry.Record product performance data in Table 1.
embodiment 2
Before polymerization, by 5A molecular sieve for mixed solvent (hexanaphthene and normal hexane, weight ratio is 88:12) (
purchased from Dalian Kang Yu Chemical Co., Ltd., at 500 ℃, dry 5 hours in advance) soak 1 week.Under high pure nitrogen protection, 195kg mixed solvent is added in 500 liters of polymeric kettles and with high pure nitrogen deoxygenation and processed, first in backward polymeric kettle, add 11kg vinylbenzene, 26kg divinyl afterwards, then by chuck, reactor is heated to 50 ℃.Add n-butyllithium solution 3700ml (concentration of n-Butyl Lithium is 0.2mol/L) to carry out polyreaction.Polymerization kick off temperature is 50 ℃, and reaction pressure is 0.1MPa.While reacting 15 minutes, reach 90 ℃ of peak temperature, reaction pressure is 0.3MPa.Peak temperature samples survey transformation efficiency and reaches 100% after 5 minutes, reaction pressure is 0.16MPa, to adding 330ml silicon tetrachloride solution in reactor, (concentration is 0.4mol/L, solvent is that weight ratio is the hexanaphthene of 88:12 and the mixture of normal hexane) carry out coupling, after coupling 15 minutes, in polymeric kettle, add 22g trimethylchlorosilane to carry out termination reaction.Stir and after 5 minutes, add anti-aging agent 2,6 ditertiary butyl p cresol 296g.
Glue, after water vapor cohesion, obtains butadiene-styrene block copolymer after mill is dry.Record product performance data in Table 1.
comparative example 2
Before polymerization, by 5A molecular sieve for mixed solvent (hexanaphthene and normal hexane, weight ratio is 88:12) (
purchased from Dalian Kang Yu Chemical Co., Ltd., at 500 ℃, dry 5 hours in advance) soak 1 week.Under high pure nitrogen protection, 195kg mixed solvent is added in 500 liters of polymeric kettles and with high pure nitrogen deoxygenation and processed, first in backward polymeric kettle, add 11kg vinylbenzene, 26kg divinyl afterwards, then by chuck, reactor is heated to 50 ℃.Add n-butyllithium solution 3700ml (concentration of n-Butyl Lithium is 0.2mol/L) to carry out polyreaction.Polymerization kick off temperature is 50 ℃, and reaction pressure is 0.1MPa.While reacting 15 minutes, reach 90 ℃ of peak temperature, reaction pressure is 0.3MPa.Peak temperature samples survey transformation efficiency and reaches 100% after 5 minutes, reaction pressure is 0.16MPa, to adding 330ml silicon tetrachloride solution in reactor, (concentration is 0.4mol/L, solvent is that weight ratio is the hexanaphthene of 88:12 and the mixture of normal hexane) carry out coupling, after coupling 15 minutes, in polymeric kettle, add 3.6g water to carry out termination reaction.Stir and after 5 minutes, add anti-aging agent 2,6 ditertiary butyl p cresol 296g.
Glue, after water vapor cohesion, obtains butadiene-styrene block copolymer after mill is dry.Record product performance data in Table 1.
embodiment 3
Under high pure nitrogen protection, to adding mixed solvent (hexanaphthene and normal hexane, weight ratio is 88:12, pre-treatment is with embodiment 1) 3497g, vinylbenzene 200g in 10 liters of polymeric kettles, paradigmatic system is through high-purity N successively
2after displacement deoxidation, add divinyl 466g, stir after 10 minutes, add n-butyllithium solution 68ml (concentration of n-Butyl Lithium is 0.2mol/L) to carry out polyreaction.Polymerization kick off temperature is 50 ℃, and reaction pressure is 0.1MPa.While reacting 15 minutes, reach 80 ℃ of peak temperature, reaction pressure is 0.25MPa.Peak temperature samples survey transformation efficiency and reaches 100% after 5 minutes, reaction pressure is 0.13MPa, to adding 6ml silicon tetrachloride solution in polymeric kettle, (concentration is 0.4mol/L, solvent is that weight ratio is the hexanaphthene of 88:12 and the mixture of normal hexane) carry out coupling, coupling, after 15 minutes, adds trimethylchlorosilane 0.4g to carry out termination reaction, after termination reaction 10 minutes, from polymeric kettle, discharge glue, in glue, add anti-aging agent 2,6 ditertiary butyl p cresol 5.3g.
Glue, after water vapor cohesion, obtains butadiene-styrene block copolymer product after mill is dry.Record product performance data in Table 1.
comparative example 3
Under high pure nitrogen protection, to adding mixed solvent (hexanaphthene and normal hexane, weight ratio is 88:12, pre-treatment is with embodiment 1) 3497g, vinylbenzene 200g in 10 liters of polymeric kettles, paradigmatic system is through high-purity N successively
2after displacement deoxidation, add divinyl 466g, stir after 10 minutes, add n-butyllithium solution 68ml (concentration of n-Butyl Lithium is 0.2mol/L) to carry out polyreaction.Polymerization kick off temperature is 50 ℃, and reaction pressure is 0.1MPa.While reacting 15 minutes, reach 80 ℃ of peak temperature, reaction pressure is 0.25MPa.Peak temperature samples survey transformation efficiency and reaches 100% after 5 minutes, reaction pressure is 0.13MPa, to adding 6ml silicon tetrachloride solution in polymeric kettle, (concentration is 0.4mol/L, solvent is that weight ratio is the hexanaphthene of 88:12 and the mixture of normal hexane) carry out coupling, coupling, after 15 minutes, adds water 0.07g to carry out termination reaction, after termination reaction 10 minutes, from polymeric kettle, discharge glue, in glue, add anti-aging agent 2,6 ditertiary butyl p cresol 5.3g.
Glue, after water vapor cohesion, obtains butadiene-styrene block copolymer product after mill is dry.Record product performance data in Table 1.
Table 1 product performance data
| Embodiment/comparative example | Embodiment 1 | Comparative example 1 | Embodiment 2 | Comparative example 2 | Embodiment 3 | Comparative example 3 |
| M n(ten thousand) | 5.6 | 5.6 | 5.7 | 5.8 | 5.5 | 5.6 |
| M w(ten thousand) | 5.7 | 5.7 | 5.8 | 5.9 | 5.6 | 5.7 |
| M w/M n | 1.018 | 1.018 | 1.018 | 1.017 | 1.018 | 1.018 |
| CE，% | 74 | 75 | 74 | 74 | 76 | 75 |
| St% | 31 | 30 | 30 | 30 | 29 | 30 |
| Bv% | 12.4 | 12.8 | 12.5 | 12.4 | 12.6 | 12.5 |
| Ct% | 55.4 | 55.3 | 53.7 | 53.7 | 55.1 | 55.2 |
| Cc% | 32.2 | 31.9 | 33.8 | 33.9 | 32.3 | 32.3 |
| Gel, ppm | 11 | 28 | 12 | 31 | 9 | 20 |
Note:
M
nfor basic number-average molecular weight; M
wfor basic weight-average molecular weight; CE is coupling efficiency; Bv% is 1,2-structural content; Cc% is cis-Isosorbide-5-Nitrae structural content; Ct% is trans-Isosorbide-5-Nitrae structural content.
As can be seen from the above table: the SBS multipolymer of being prepared by the present invention has extremely low gel content.
Although the present invention is described with regard to some embodiment, the present invention is not limited to disclosed specific embodiments or embodiment, but wishes to cover the purport of the present invention that defined by appended claims and the whole improved forms in scope.
Claims (17)
1. a method that stops the copolyreaction of monovinylarene-conjugated diene, comprising:
(a), under the existence of organic lithium initiator, make monovinylarene and conjugated diene in reaction-inert solvent, be polymerized to transformation efficiency and reach more than 95%;
(b) add terminator and optional anti-aging agent,
Wherein said terminator is selected from those shown in formula (I),
R
3SiX(I)
Wherein,
Each R is C independently of each other
1-C
8alkyl, C
3-C
8cycloalkyl, C
3-C
8cycloalkyl-C
1-C
8alkyl, C
1-C
8alkyl-C
3-C
8cycloalkyl, C
6-C
10aryl, C
6-C
10aryl-C
1-C
8alkyl or C
1-C
8alkyl-C
6-C
10aryl, preferably C
1-C
6alkyl, cyclopentyl, cyclohexyl, phenyl, naphthyl, tolyl, benzyl or styroyl;
X is halogen, preferably chlorine or bromine, more preferably chlorine.
2. according to the process of claim 1 wherein that at least two R in formula (I) are C
1-C
8alkyl, preferably three R are C
1-C
8alkyl.
3. according to the process of claim 1 wherein that described terminator is selected from benzyl dimethyl chlorosilane, normal-butyl dimethylchlorosilane, three n-butyl chloride silane, ethyl dimethylchlorosilane, chlorotriethyl silane, trimethylchlorosilane, phenyldimethylchlorosilane, tri-phenyl chloride, cyclohexyl dimethylchlorosilane, cyclopentyl dimethylchlorosilane, n-propyl dimethylchlorosilane and tolyl dimethylchlorosilane.
4. according to the method for any one in claim 1-3, wherein said organic lithium initiator is organic single-lithium initiator, organic dilithium initiator or organic multi-lithium initiator, preferably n-Butyl Lithium.
5. according to the method for any one in claim 1-4, wherein, in step (a), transformation efficiency reaches more than 97%.
6. according to the method for any one in claim 1-5, wherein reaction-inert solvent used is selected from nonpolar aromatic hydrocarbons, aliphatic hydrocrbon, alicyclic hydrocarbon and aliphatic hydrocrbon and alicyclic mixture, preferably C6 alkane or its mixture, more preferably hexanaphthene or normal hexane, or the mixture of hexanaphthene and normal hexane.
7. according to the method for any one in claim 1-6, wherein conjugated diene is C
4-C
12conjugated diolefine, is preferably isoprene, 1,3-butadiene, 2,3-methyl isophthalic acid, 3-divinyl, 1,3-pentadiene, 3-butyl-1,3-octadiene, 2-phenyl-1,3-butadiene, 1,3-hexadiene or its arbitrary combination, more preferably 1,3-butadiene.
8. according to the method for any one in claim 1-7, wherein monovinylarene is the monovinylarene containing 8-20 carbon atom; Be preferably vinylbenzene, C
1-C
4vinylbenzene or their arbitrary combination, wherein C that alkyl replaces
1-C
4the vinylbenzene that alkyl replaces is preferably a vinyl toluene, p-methylstyrene, p-tert-butylstyrene, alpha-methyl styrene or its arbitrary combination.
9. according to the method for any one in claim 1-8, wherein, in step (a), first add reaction-inert solvent and monovinylarene, after replacing with rare gas element, add conjugated diene, finally add organic lithium initiator; Or first add solvent, then with rare gas element, replace, then monovinylarene and conjugated diene are added simultaneously, then add organic lithium initiator.
10. according to the method for any one in claim 1-9, it is 1.05-2.0:1 with take the mol ratio of the organic lithium initiator that lithium atom calculates that the consumption of described terminator makes terminator, preferably 1.1-1.5:1.
11. according to the method for any one in claim 1-9, its be additionally included in step (a) and (b) between add coupling agent to carry out the step of linked reaction.
12. according to the method for claim 11, and wherein said coupling agent is selected from silicon tetrachloride, tin tetrachloride, Vinylstyrene, dimethyl adipate, dimethyldichlorosilane(DMCS) and METHYL TRICHLORO SILANE.
13. according to the method for claim 11 or 12, and the mol ratio of the organic lithium initiator that wherein said coupling agent and the lithium atom of take calculate is 0.03-0.30, preferably 0.1-0.20.
14. according to the method for any one in claim 11-13, and it is 0.2-2.0:1 with take the mol ratio of the organic lithium initiator that lithium atom calculates that the consumption of described terminator makes terminator, preferably 0.25-1.5:1.
15. according to the method for any one in claim 1-14, and described anti-aging agent is phenols or amines antioxidants, preferably, and 2,6 ditertiary butyl p cresol, tert-butyl catechol, 2,2 '-methylene radical-bis-(4-methyl-6-tert-butylphenol).
16. according to the method for any one in claim 1-15, and wherein said method is for stopping preparing the copolyreaction of random copolymers or segmented copolymer, the especially butadiene-styrene block copolymer of monovinylarene-conjugated diene.
17. terminators as defined in any one in claim 1-3, stopping the copolyreaction of conjugated diene-vinyl-arene, are especially prepared butylbenzene copolymer, particularly prepare the purposes in the copolyreaction of butadiene-styrene block copolymer.
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