CN101255203B - Method for restraining gelatin during preparation of conjugated diolefin and monovinyl aromatic hydrocarbons random polymers - Google Patents
Method for restraining gelatin during preparation of conjugated diolefin and monovinyl aromatic hydrocarbons random polymers Download PDFInfo
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- CN101255203B CN101255203B CN2007100641354A CN200710064135A CN101255203B CN 101255203 B CN101255203 B CN 101255203B CN 2007100641354 A CN2007100641354 A CN 2007100641354A CN 200710064135 A CN200710064135 A CN 200710064135A CN 101255203 B CN101255203 B CN 101255203B
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Abstract
The invention relates to a method for depressing gel coagulating in preparation process of conjugated diene and single-ethene arene random copolymer using alpha-alkene or mixture thereof as gel depressor. The said method not only can effectively depress the formation of gel and the raw material of gel depressor is easy to obtain and the price thereof is low, especially adapted for large scale industry.
Description
Technical field
The present invention relates to alpha-olefin or its mixture is the method that suppresses gel in the preparation technology of conjugated diolefine and ethene aromatic hydrocarbons random copolymers of gel inhibitor, more particularly, relate to alpha-olefin or its mixture be gel inhibitor contain intermingle with the method that suppresses gel among the preparation technology of conjugated diolefine and single ethene aromatic hydrocarbons random copolymers at lithium series anionic.
Background technology
Currently be applicable to that the production of the conjugated-diolefin/uni-vinyl-arene copolymer of tread rubber of automobile tires can adopt continuous processing or batch technology.But no matter be continuous processing or batch technology, need an inhibition that subject matter is the reactor inner gel that solves.Gelatin phenomenon is a problem of puzzlement conjugated-diolefin/uni-vinyl-arene anionic copolymerization technology always.In reactor since the back-mixing of material and a part of swelling macromole be deposited on reactor wall, stir on wall, the heat transfer wall, make " activity " macromole be stranded in the reactor for a long time.These " activity " macromole constantly contact with the monomer that adds continuously, molecular chain increases thereupon and then forms insoluble super large molecule, be that last whole reactor has been full of insoluble jello, cause the obstruction of reactor, thereby the periodic duty of termination reaction device prematurely is called as " polymerization poisoning ".The removing of gel means that one is driven again, debugs and the normal again problem of moving.Therefore, the formation of gel has a strong impact on the homogeneity of polymkeric substance, quality product and production efficiency, has hindered the development of this polymerization technique.
US4 mentions that continuous polymerization technique adopts a kind of piston flow tubular polymerization reactor with stirring in 311,803.Its reactor divides two sections: the polymerization reaction zone that (1) band stirs keeps higher transformation efficiency at this section; (2) piston flow section is finished polyreaction or linked reaction at this.And in this patent, also mentioned employing chain-transfer agent 1 (1,2-Bd) be gel inhibitor, the chain-transfer agent 1 that this method adopts, 2-Bd is a high purity, the production cost height, price is very expensive; And complex technical process can not be used for large-scale industrial production.
US 4,091, mentioned employing solution continuous processing synthesis of conjugate diolefine/monovinylarene copolymer technology gel inhibition method in 198, this method is gel inhibitor with the silicon halide, and need be used with tert-pentyl potassium, silicon halide is the coupling agent that a kind of quilt extensively uses, so pressing down of it coagulated mechanism in fact in reaction coupling taking place in earlier stage, make big " activity " molecular inactivation that is trapped in the reactor, thereby play the effect of coagulating that presses down.This gel inhibition method only is fit to the multipolymer of preparation coupling type, has limited the use range of this gel inhibition system.
US 4,136, mentioned in 244 that adopting weak chain-transfer agent such as toluene, chlorobenzene is the method that gel inhibitor synthesizes solution polymerized butadiene styrene rubber, this method adopts continuous polymerization technique, with cyclic ethers (THF) as structure regulator, there is the recovery problem in the last handling process in this gel inhibitor, has increased production cost greatly.
Summary of the invention
Based on above-mentioned prior art situation, the present inventor has carried out research extensively and profoundly in the styrene-butadiene rubber(SBR) field, in the hope of developing a kind of be used to the prepare conjugated diolefine of low-gel content and the gel inhibitor of monovinylarene copolymer.Found that and adopt alpha-olefin or its mixture to can be used as a kind of gel inhibitor of novel cheapness, this novel inexpensive gel inhibitor can suppress the formation of gel effectively, and the synthetic polymeric articles is not had adverse influence.The present invention just is being based on this discovery and is being accomplished.
The new type gel inhibitor that an aspect of of the present present invention provides a kind of cheapness and has been easy to get, this gel inhibitor not only can suppress the formation of gel effectively, and have that raw material is easy to get, cheap characteristics.
It is the method that suppresses gel in the preparation technology of conjugated diolefine and single ethene aromatic hydrocarbons random copolymers of gel inhibitor with alpha-olefin or its mixture that another aspect of the present invention provides a kind of.
In a specific embodiments of the present invention, described random copolymerization technology is the lithium series anionic solution polymerization, preferably includes following steps:
Adopting organolithium under inert gas environment is initiator, and Lewis base is an additive, adds described gel inhibitor and reaction monomers, carries out conjugated diene and monovinylarene copolymerization in solvent.
There is no particular limitation for the adding mode of the gel inhibitor among the present invention, can be according to the adding mode of the conventional gel inhibitor in its yoke diene polymerization technology, for example before polymerization causes with relevant polymer raw, for example reaction monomers adds in the polymerization reactor together.
Implement best mode of the present invention
In polyreaction of the present invention, operable conjugated diene is meant any diolefinic monomer that has conjugated double bond in its molecule, as C
4～C
12Conjugated diene monomer, preferred C
4～C
8Conjugated diene monomer, its specific examples comprise 1,3-butadiene, isoprene, 1,3-pentadiene, 1, the 1,3-pentadiene of 3-hexadiene, replacement or the 1,3-butadiene of replacement, and as 2,3-dimethyl-1,3-butadiene, 1-phenyl-1,3-butadiene.Conjugated diene monomer can use separately, also can mix use.Preferably select 1,3-butadiene for use, because this monomeric rate of polymerization height.
In polyreaction of the present invention, operable mono vinyl arenes monomer is meant the aromatic monomer that has a vinyl substituted base on its aromatic ring, as contains C
8～C
20Monovinylarene, preferred C
8-C
12Monovinylarene, its specific examples comprises vinylbenzene, methyl substituted vinylbenzene, vinylbenzene that butyl replaces or their combination, as-vinyl toluene, p-methylstyrene or right-t-butyl styrene, or have substituent styrene derivatives on the vinyl, as alpha-methyl styrene.Mono vinyl arenes monomer can use separately, also can mix use.Consider from obtaining the complexity aspect, preferably use vinylbenzene and p-methylstyrene better, most preferably use vinylbenzene.
In polyreaction of the present invention, the consumption of conjugated diene monomer is a 25-95% weight based on the monomer total amount, preferred 50-90% weight; Correspondingly, the consumption of mono vinyl arenes monomer is a 5-75% weight based on the monomer total amount, preferred 10-50% weight.
In the present invention, the solvent that is suitable in the described solution polymerization can be any solvent that is suitable in the lithium series anionic polymerization technique of conjugated diene.Being preferably the mixture of hexanaphthene and normal hexane, both weight ratios are preferably 80: 20～and 90: 10.Preferably making monomer concentration as the consumption of solvent (for example mixture of hexanaphthene and normal hexane) is 2～70g total monomer/100ml solvent, preferred 5-50g total monomer/100ml solvent, most preferably 10-25g total monomer/100ml solvent.
According to the present invention, the preferred gel inhibitor that uses is meant C
4～C
10Straight or branched (preferred straight chain) alpha-olefin, its concrete preferred embodiment comprises 1-butylene, 1-amylene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene; Or C
4～C
10The mixture of alpha-olefin.More preferably C
6～C
10Alpha-olefin, its concrete preferred embodiment comprises the 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene; Or C
6～C
10The mixture of alpha-olefin.Described mixture can be the mixture of their any ratio.
In polyreaction of the present invention, there is no particular limitation for the add-on of described gel inhibitor, as long as it does not produce tangible disadvantageous effect to polyreaction.Take all factors into consideration gel and suppress effect and economic factors, be preferably 0.12～4.9g/100g solvent, reach best gel and suppress more preferably 0.12～2.45g/100g solvent of effect as the alpha-olefin of gel inhibitor or the add-on of its mixture.
In the present invention, used additive can be Lewis base in the polymerization process.Various Lewis base compounds can be selected for use, preferably select for use ether compound, tertiary amine compound and arbitrary combination thereof as polar additive and structure regulator, can select tetrahydrofuran (THF), tetrahydropyrans or 1,4-dioxane for use as cyclic ether compounds; Aliphatic monoether can be selected Anaesthetie Ether or dibutyl ether for use; The optional spent glycol dme of aliphatic series polyether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, diglyme, diethyl carbitol or diethylene glycol dibutyl ether; Aromatic oxide can be selected diphenyl ether, methyl-phenoxide or similar ether for use; Tertiary amine compound can be selected triethylamine, tripropyl amine, Tributylamine or other tertiary amine compound such as N for use, N, N ', N '-Tetramethyl Ethylene Diamine, N, N-Diethyl Aniline, pyridine or quinoline etc., the consumption of additive makes that preferably the weight ratio of itself and organic lithium initiator is 30: 1～1: 1, preferred 20: 1～10: 1.
In the present invention, used organic lithium initiator preferably uses organic single-lithium for commonly used those in anionoid polymerization field in the polymerization process, those shown in the formula RLi for example, and wherein R is the C of straight or branched
2-C
6Alkyl, cyclohexyl or C
6-C
10Aryl as lithium ethide, propyl lithium, sec.-propyl lithium, n-Butyl Lithium, s-butyl lithium, amyl group lithium, hexyl lithium, cyclohexyl lithium, phenyl lithium, aminomethyl phenyl lithium, naphthyl lithium etc., but is preferably selected n-Butyl Lithium or s-butyl lithium for use.The consumption of initiator depends on the size of design molecular weight in the polymerization process.General initiator amount is that every 100g monomer need add 0.3～2.5mmol.Initiator can once add or gradation (for example being divided into twice) adds polymerization reaction system.
In polyreaction of the present invention, operable rare gas element is commonly used those in this area, as nitrogen, argon gas or chlorine etc.
In polyreaction of the present invention, coupling agent is the material of nonessential interpolation, operable coupling agent is many vinyl compounds, halogenide, ether, aldehyde, ketone, ester etc., as Vinylstyrene, tetrem thiazolinyl silane, tetrachloromethane, silicon tetrachloride, tin tetrachloride, dimethyl terephthalate (DMT) etc.Coupling agent is Vinylstyrene, silicon tetrachloride or tin tetrachloride etc. preferably.It is 0.1～2 that the consumption of coupling agent preferably makes the mol ratio of coupling agent and organic lithium initiator.
In the preparation method of conjugated diene of the present invention and uni-vinyl-arene copolymer rubber, operable terminator is water or alcohols, as being methyl alcohol, ethanol, Virahol etc., preferably selects Virahol for use.It is 0.1～1 that the consumption of terminator preferably makes the mol ratio of terminator and organic lithium initiator.
In the present invention, operable anti-aging agent can be normally used phenols or amine, be preferably 2,6 ditertiary butyl p cresol (abbreviation antioxidant 264), tert-butyl catechol, 2,2 '-methylene radical-two (4-methyl-6-tert butyl phenol) (abbreviation antioxidant 2246) etc.The add-on of anti-aging agent is 0.5～2% weight based on polymkeric substance generally.
In the present invention, polymeric reaction temperature is generally 0～150 ℃, and preferred 20～110 ℃, most preferably 30～90 ℃.
In the present invention, polymerization pressure is generally 0.1～0.8MPa, preferred 0.1～0.4MPa, and 0.1～0.25MPa most preferably, pressure described herein is gauge pressure.
Adopt gel inhibition method of the present invention that the synthetic polymeric articles is not had adverse influence, can obtain number-average molecular weight is 50000～600000, and molecular weight distributing index is 1.3～2.5 rubber product.
The lithium series anionic solution polymerization process of conjugated diene is well known in the art, and for example can be referring to patent US4,311,803, US4,091,198.More than NM operating parameters and concrete steps about this polymerization technique can be with reference to the lithium series anionic solution copolymerization technology of the conjugated diene and the monovinylarene of routine.
The new type gel inhibitor of the application of the invention can suppress the formation of gel effectively.In addition, gel inhibitor of the present invention has raw material and is easy to get, and the characteristics of cost cheapness, is particularly suitable for being applied to large-scale industrial production.This gel inhibitor and gel inhibition method are suitable for the intermittence or the continuous processing of the lithium series anionic solution polymerization of conjugated diene and monovinylarene copolymerization.
Unless otherwise, all per-cents used herein and ratio are all by weight.
The publication that this paper quotes is incorporated herein by reference for all purposes.
Embodiment
Describe the present invention in detail by embodiment and Comparative Examples below, but scope of the present invention is not limited to these embodiment.
The molecular weight of polymkeric substance and molecular weight distribution are tested with gel permeation chromatograph (mobile phase solvent is THF for day island proper Tianjin LC-10Atvp of company series, normal temperature mensuration) in an embodiment.
Gel content adopts and dissolves the filtration method mensuration of weighing in an embodiment, and this testing method is:
Accurately weighing sample glue 10 grams are after drying prepared according to 5% weight of toluene solution, treat that sample glue dissolves fully after, behind 360 order stainless (steel) wire suction filtrations, dry weighing, record the gel content in the sample.
Embodiment 1
Test takes the batchwise polymerization method to carry out in 10 liters of polymeric kettles, under the high pure nitrogen protection, adds mixed solvent (hexanaphthene and normal hexane, weight ratio are 88: 12) 4810g, vinylbenzene 225g, additive THF11.4g successively in still, and paradigmatic system is through high-purity N
2After the displacement deoxidation, add 1,3-butadiene 624g, press down and coagulate agent 1-hexene 5.9g, n-Butyl Lithium 0.73g carries out copolyreaction then.The polymerization kick off temperature is 50 ℃, and reaction pressure is 0.1-0.3MPa.When polymerization temperature reaches 80 ℃, add the second step initiator n-Butyl Lithium 0.30g, transformation efficiency reaches at 100% o'clock, adds tin tetrachloride 0.33g again in polymeric kettle, proceeds linked reaction.After linked reaction finishes, adding terminator Virahol 0.5g and antioxidant 2246 once more is 10g, carries out termination reaction, after glue condenses through water vapor, after two-shipper (promptly the dehydration extruding drying machine and the extruding drying machine that expands are as follows) drying, obtain the solution polymerized butadiene styrene rubber product.The molecular weight, molecular weight distribution and the gel content data that record in the sample see Table 1.
Embodiment 2
Test takes the batchwise polymerization method to carry out in 10 liters of polymeric kettles, under the high pure nitrogen protection, adds mixed solvent (hexanaphthene and normal hexane, weight ratio are 88: 12) 4810g, vinylbenzene 225g, additive THF 11.4g successively in still, and paradigmatic system is through high-purity N
2After the displacement deoxidation, add 1,3-butadiene 624g, press down and coagulate agent 1-hexene 59g, n-Butyl Lithium 0.73g, carry out copolyreaction then.The polymerization kick off temperature is 50 ℃, and reaction pressure is 0.1-0.3MPa.When polymerization temperature reaches 80 ℃, add the second step initiator n-Butyl Lithium 0.30g, transformation efficiency reaches at 100% o'clock, adds tin tetrachloride 0.33g again in polymeric kettle, proceeds linked reaction.After linked reaction finished, adding terminator Virahol 0.5g and antioxidant 2246 once more was 10g, carries out termination reaction, and glue obtains the solution polymerized butadiene styrene rubber product after condensing through water vapor after the two-shipper drying.The molecular weight, molecular weight distribution and the gel content data that record in the sample see Table 1.
Embodiment 3
Test takes the batchwise polymerization method to carry out in 10 liters of polymeric kettles, under the high pure nitrogen protection, adds mixed solvent (hexanaphthene and normal hexane, weight ratio are 88: 12) 4810g, vinylbenzene 225g, additive THF 11.4g successively in still, and paradigmatic system is through high-purity N
2After the displacement deoxidation, add 1,3-butadiene 624g, press down and coagulate agent 1-hexene 118g, n-Butyl Lithium 0.73g, carry out copolyreaction then.The polymerization kick off temperature is 50 ℃, and reaction pressure is 0.1-0.3MPa.When polymerization temperature reaches 80 ℃, add the second step initiator n-Butyl Lithium 0.30g, transformation efficiency reaches at 100% o'clock, adds tin tetrachloride 0.33g again in polymeric kettle, proceeds linked reaction.After linked reaction finished, adding terminator Virahol 0.5g and antioxidant 2246 once more was 10g, carries out termination reaction, and glue obtains the solution polymerized butadiene styrene rubber product after condensing through water vapor after the two-shipper drying.The molecular weight, molecular weight distribution and the gel content data that record in the sample see Table 1.
Embodiment 4
Test takes the batchwise polymerization method to carry out in 10 liters of polymeric kettles, under the high pure nitrogen protection, adds mixed solvent (hexanaphthene and normal hexane, weight ratio are 88: 12) 4810g, vinylbenzene 225g, additive THF11.4g successively in still, and paradigmatic system is through high-purity N
2After the displacement deoxidation, add 1,3-butadiene 624g, press down and coagulate agent 1-octene 118g, n-Butyl Lithium 0.73g carries out copolyreaction then.The polymerization kick off temperature is 50 ℃, and reaction pressure is 0.1-0.3MPa.When polymerization temperature reaches 80 ℃, add the second step initiator n-Butyl Lithium 0.30g.Transformation efficiency reaches at 100% o'clock, adds tin tetrachloride 0.33g again in polymeric kettle, proceeds linked reaction.After linked reaction finished, adding terminator Virahol 0.5g and antioxidant 2246 once more was 10g, carries out termination reaction, and glue obtains the solution polymerized butadiene styrene rubber product after condensing through water vapor after the two-shipper drying.The molecular weight, molecular weight distribution and the gel content data that record in the sample see Table 1.
Embodiment 5
Test takes the batchwise polymerization method to carry out in 10 liters of polymeric kettles, under the high pure nitrogen protection, adds mixed solvent (hexanaphthene and normal hexane, weight ratio are 88: 12) 4810g, vinylbenzene 225g, additive THF 11.4g successively in still, and paradigmatic system is through high-purity N
2After the displacement deoxidation, add 1,3-butadiene 624g, press down and coagulate agent 1-butylene 118g, n-Butyl Lithium 0.73g, carry out copolyreaction then.The polymerization kick off temperature is 50 ℃, and reaction pressure is 0.1-0.3MPa.When polymerization temperature reaches 80 ℃, add the second step initiator n-Butyl Lithium 0.30g, transformation efficiency reaches at 100% o'clock, adds tin tetrachloride 0.33g again in polymeric kettle, proceeds linked reaction.After linked reaction finished, adding terminator Virahol 0.5g and antioxidant 2246 once more was 10g, carries out termination reaction, and glue obtains the solution polymerized butadiene styrene rubber product after condensing through water vapor after the two-shipper drying.The molecular weight, molecular weight distribution and the gel content data that record in the sample see Table 1.
Embodiment 6
Test takes the batchwise polymerization method to carry out in 10 liters of polymeric kettles, under the high pure nitrogen protection, adds mixed solvent (hexanaphthene and normal hexane, weight ratio are 88: 12) 4810g, vinylbenzene 225g, additive THF 11.4g successively in still, and paradigmatic system is through high-purity N
2After the displacement deoxidation, add 1,3-butadiene 624g, press down and coagulate agent 1-decene 118g, n-Butyl Lithium 0.73g, carry out copolyreaction then.The polymerization kick off temperature is 50 ℃, and reaction pressure is 0.1-0.3MPa.When polymerization temperature reaches 80 ℃, add the second step initiator n-Butyl Lithium 0.30g, transformation efficiency reaches at 100% o'clock, adds tin tetrachloride 0.33g again in polymeric kettle, proceeds linked reaction.After linked reaction finished, adding terminator Virahol 0.5g and antioxidant 2246 once more was 10g, carries out termination reaction, and glue obtains the solution polymerized butadiene styrene rubber product after condensing through water vapor after the two-shipper drying.The molecular weight, molecular weight distribution and the gel content data that record in the sample see Table 1.
Embodiment 7
The gel inhibitor that adopts in the present embodiment is the alpha-olefin mixture, and it consists of:
Content weight content (%)
1-hexene 60
1-octene 20
1-decene 20.
Test takes the batchwise polymerization method to carry out in 10 liters of polymeric kettles, under the high pure nitrogen protection, adds mixed solvent (hexanaphthene and normal hexane, weight ratio are 88: 12) 4810g, vinylbenzene 225g, additive THF 11.4g successively in still, and paradigmatic system is through high-purity N
2After the displacement deoxidation, add 1,3-butadiene 624g, press down and coagulate agent (above-mentioned alpha-olefin mixture) 118g, n-Butyl Lithium 0.73g, carry out copolyreaction then.The polymerization kick off temperature is 50 ℃, and reaction pressure is 0.1-0.3MPa.When polymerization temperature reaches 80 ℃, add the second step initiator n-Butyl Lithium 0.30g, transformation efficiency reaches at 100% o'clock, adds tin tetrachloride 0.33g again in polymeric kettle, proceeds linked reaction.After linked reaction finished, adding terminator Virahol 0.5g and antioxidant 2246 once more was 10g, carries out termination reaction, and glue obtains the solution polymerized butadiene styrene rubber product after condensing through water vapor after the two-shipper drying.The molecular weight, molecular weight distribution and the gel content data that record in the sample see Table 1.
Embodiment 8
Test takes the batchwise polymerization method to carry out in 10 liters of polymeric kettles, under the high pure nitrogen protection, adds mixed solvent (hexanaphthene and normal hexane, weight ratio are 88: 12) 4810g, vinylbenzene 225g, additive THF11.4g successively in still, and paradigmatic system is through high-purity N
2After the displacement deoxidation, add 1,3-butadiene 624g, press down and coagulate agent 1-hexene 236g, n-Butyl Lithium 0.73g carries out copolyreaction then.The polymerization kick off temperature is 50 ℃, and reaction pressure is 0.1-0.3MPa.When polymerization temperature reaches 80 ℃, add the second step initiator n-Butyl Lithium 0.30g, transformation efficiency reaches at 100% o'clock, adds tin tetrachloride 0.33g again in polymeric kettle, proceeds linked reaction.After linked reaction finished, adding terminator Virahol 0.5g and antioxidant 2246 once more was 10g, carries out termination reaction, and glue obtains the solution polymerized butadiene styrene rubber product after condensing through water vapor after the two-shipper drying.The molecular weight, molecular weight distribution and the gel content data that record in the sample see Table 1.
Embodiment 9
Test takes the batchwise polymerization method to carry out in 10 liters of polymeric kettles, under the high pure nitrogen protection, adds mixed solvent (hexanaphthene and normal hexane, weight ratio are 88: 12) 4810g, vinylbenzene 225g, additive THF11.4g successively in still, and paradigmatic system is through high-purity N
2After the displacement deoxidation, add 1,3-butadiene 624g, press down and coagulate agent 1-hexene 118g, n-Butyl Lithium 0.42g carries out copolyreaction then.The polymerization kick off temperature is 50 ℃, and reaction pressure is 0.1-0.3MPa.When polymerization temperature reaches 80 ℃, add the second step initiator n-Butyl Lithium 0.2g, after transformation efficiency reaches 100%, adding terminator Virahol 0.5g and antioxidant 2246 once more is 10g, carry out termination reaction, glue obtains the solution polymerized butadiene styrene rubber product after condensing through water vapor after the two-shipper drying.The molecular weight, molecular weight distribution and the gel content data that record in the sample see Table 1.
Comparative Examples 1
Test takes the batchwise polymerization method to carry out in 10 liters of polymeric kettles, under the high pure nitrogen protection, adds mixed solvent (hexanaphthene and normal hexane, weight ratio are 88: 12) 4810g, vinylbenzene 225g, additive THF 11.4g successively in still, and paradigmatic system is through high-purity N
2After the displacement deoxidation, add 1,3-butadiene 624g, press down and coagulate agent 1,2-Bd 5.5g (with 1, the pure content meter of 2-Bd), n-Butyl Lithium 0.73g carry out copolyreaction then.The polymerization kick off temperature is 50 ℃, and reaction pressure is 0.1-0.3MPa.When polymerization temperature reaches 80 ℃, add the second step initiator n-Butyl Lithium 0.30g.Transformation efficiency reaches at 100% o'clock, adds tin tetrachloride 0.33g again in polymeric kettle, proceeds linked reaction.After linked reaction finished, adding terminator Virahol 0.5g and antioxidant 2246 once more was 10g, carries out termination reaction, and glue obtains the solution polymerized butadiene styrene rubber product after condensing through water vapor after the two-shipper drying.The molecular weight, molecular weight distribution and the gel content data that record in the sample see Table 1.
Comparative Examples 2
Test takes the batchwise polymerization method to carry out in 10 liters of polymeric kettles, under the high pure nitrogen protection, adds mixed solvent (hexanaphthene and normal hexane, weight ratio are 88: 12) 4810g, vinylbenzene 225g, additive THF 11.4g successively in still, and paradigmatic system is through high-purity N
2After the displacement deoxidation, add 1,3-butadiene 624g, a small amount of agent 1-hexene 2.95g, n-Butyl Lithium 0.73g with fixed attention of pressing down of the present invention, carry out copolyreaction then.The polymerization kick off temperature is 50 ℃, and reaction pressure is 0.1-0.3MPa.When polymerization temperature reaches 80 ℃, add the second step initiator n-Butyl Lithium 0.30g, transformation efficiency reaches at 100% o'clock, adds tin tetrachloride 0.33g again in polymeric kettle, proceeds linked reaction.After linked reaction finished, adding terminator Virahol 0.5g and antioxidant 2246 once more was 10g, carries out termination reaction, and glue obtains the solution polymerized butadiene styrene rubber product after condensing through water vapor after the two-shipper drying.The molecular weight, molecular weight distribution and the gel content data that record in the sample see Table 1.
Comparative Examples 3
Test takes the batchwise polymerization method to carry out in 10 liters of polymeric kettles, under the high pure nitrogen protection, adds mixed solvent (hexanaphthene and normal hexane, weight ratio are 88: 12) 4810g, vinylbenzene 225g, additive THF 11.4g successively in still, and paradigmatic system is through high-purity N
2After the displacement deoxidation, add 1,3-butadiene 624g, a large amount of agent 1-hexene 472g, n-Butyl Lithium 0.73g with fixed attention of pressing down of the present invention, carry out copolyreaction then.The polymerization kick off temperature is 50 ℃, and reaction pressure is 0.1-0.3MPa.When polymerization temperature reaches 80 ℃, add the second step initiator n-Butyl Lithium 0.30g, transformation efficiency reaches at 100% o'clock, adds tin tetrachloride 0.33g again in polymeric kettle, proceeds linked reaction.After linked reaction finished, adding terminator Virahol 0.5g and antioxidant 2246 once more was 10g, carries out termination reaction, and glue obtains the solution polymerized butadiene styrene rubber product after condensing through water vapor after the two-shipper drying.The molecular weight, molecular weight distribution and the gel content data that record in the sample see Table 1.
Comparative Examples 4
Test takes the batchwise polymerization method to carry out in 10 liters of polymeric kettles, under the high pure nitrogen protection, adds mixed solvent (hexanaphthene and normal hexane, weight ratio are 88: 12) 4810g, vinylbenzene 225g, additive THF 11.4g successively in still, and paradigmatic system is through high-purity N
2After the displacement deoxidation, add 1,3-butadiene 624g, n-Butyl Lithium 0.73g carries out copolyreaction then under the condition of not adding gel inhibitor.The polymerization kick off temperature is 50 ℃, and reaction pressure is 0.1-0.3MPa.When polymerization temperature reaches 80 ℃, add the second step initiator n-Butyl Lithium 0.30g, transformation efficiency reaches at 100% o'clock, adds tin tetrachloride 0.33g again in polymeric kettle, proceeds linked reaction.After linked reaction finished, adding terminator Virahol 0.5g and antioxidant 2246 once more was 10g, carries out termination reaction, and glue obtains the solution polymerized butadiene styrene rubber product after condensing through water vapor after the two-shipper drying.The molecular weight, molecular weight distribution and the gel content data that record in the sample see Table 1
Table 1
| Sequence number | Mn (ten thousand) | Mw/Mn | Gel content (ppm) | Gel form |
| Embodiment 1 | 10 | 1.83 | 190 | Disperse microparticle |
| Embodiment 2 | 12 | 1.77 | 75 | Disperse microparticle |
| Embodiment 3 | 13 | 1.74 | 37 | Disperse microparticle |
| Embodiment 4 | 12 | 1.75 | 30 | Disperse microparticle |
| Embodiment 5 | 12 | 1.81 | 85 | Disperse microparticle |
| Embodiment 6 | 13 | 1.73 | 42 | Disperse microparticle |
| Embodiment 7 | 11 | 1.79 | 33 | Disperse microparticle |
| Embodiment 8 | 11 | 1.82 | 35 | Disperse microparticle |
| Embodiment 9 | 11 | 1.75 | 37 | Disperse microparticle |
| Comparative Examples 1 | 12 | 1.83 | 45 | Disperse microparticle |
| Comparative Examples 2 | 11 | 1.87 | 3752 | Block gel |
| Sequence number | Mn (ten thousand) | Mw/Mn | Gel content (ppm) | Gel form |
| Comparative Examples 3 | 12 | 1.77 | 37 | Disperse microparticle |
| Comparative Examples 4 | 11 | 1.74 | 8826 | Block gel |
Annotate: Mn (ten thousand) is a number-average molecular weight; Mw/Mn is a molecular weight distributing index;
Gel content (ppm) is for recording the gel weight content in the sample;
Gel form is obtained by visual observations.
Claims (24)
1. suppress the method for gel in the random copolymerization technology of conjugated diolefine and monovinylarene, wherein said random copolymerization is the lithium series anionic solution polymerization, it is characterized in that adopting C in described polymerization technique
4-C
10The straight or branched alpha-olefin or its mixture as gel inhibitor, the content of described gel inhibitor is the 0.12-4.9g/100g solvent.
2. according to the process of claim 1 wherein that described gel inhibitor is C
6-C
10Alpha-olefin or its mixture.
3. according to the process of claim 1 wherein that described alpha-olefin is selected from 1-butylene, 1-amylene, 1-hexene, 1-heptene, 1-octene, 1-nonene and 1-decene.
4. according to the method for claim 3, wherein said alpha-olefin is selected from the 1-hexene, 1-heptene, 1-octene, 1-nonene and 1-decene.
5. according to the process of claim 1 wherein that the lithium series anionic solution polymerization of described conjugated diolefine and monovinylarene comprises the steps:
Adopting organolithium under inert gas environment is initiator, and Lewis base is an additive, adds described gel inhibitor and reaction monomers, carries out the copolymerization of conjugated diene and monovinylarene in solvent.
6. according to the process of claim 1 wherein that the lithium series anionic solution polymerization process of described conjugated diolefine and monovinylarene is the batchwise polymerization method.
7. according to the process of claim 1 wherein that the add-on of described gel inhibitor alpha-olefin or its mixture is the 0.12-2.45g/100g solvent.
8. according to the process of claim 1 wherein that described gel inhibitor adds with reaction monomers.
9. according to the method for claim 5, wherein said solvent is the mixture of hexanaphthene and normal hexane, and both weight ratios are 80: 20-90: 10.
10. according to the method for claim 5, wherein said organic lithium initiator is the organic single-lithium shown in the general formula R Li, and wherein R is the C of straight or branched
2-C
6Alkyl, cyclohexyl or C
6-C
10Aryl, and described organic lithium initiator consumption is that every 100g monomer adds 0.3-2.5mmol.
11. according to the method for claim 10, wherein said organic lithium initiator is lithium ethide, propyl lithium, n-Butyl Lithium, s-butyl lithium, amyl group lithium, hexyl lithium, cyclohexyl lithium, phenyl lithium, aminomethyl phenyl lithium or naphthyl lithium.
12. according to the method for claim 11, wherein said organic lithium initiator is n-Butyl Lithium or s-butyl lithium.
13. according to the method for claim 11, wherein said propyl lithium initiator is the sec.-propyl lithium.
14. according to the method for claim 5, wherein said Lewis base is selected from cyclic ether compounds, aliphatic monoether, the aliphatic series polyether, aromatic oxide, tertiary amine compound and arbitrary combination thereof, and the consumption of described Lewis base is 30 for the weight ratio of itself and organic lithium initiator: 1-1: 1.
15. according to the method for claim 5, wherein said Lewis base is selected from cyclic ether compounds, aliphatic monoether, the aliphatic series polyether, aromatic oxide, pyridine, quinoline and arbitrary combination thereof, and the consumption of described Lewis base is 30 for the weight ratio of itself and organic lithium initiator: 1-1: 1.
16. method according to claim 14, described Lewis base is selected from tetrahydrofuran (THF), tetrahydropyrans, 1,4-dioxane, Anaesthetie Ether, dibutyl ether, glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, diglyme, diethyl carbitol, diethylene glycol dibutyl ether, diphenyl ether, methyl-phenoxide, triethylamine, tripropyl amine, Tributylamine, N, N, N ', N '-Tetramethyl Ethylene Diamine, N, N-Diethyl Aniline and arbitrary combination thereof.
17. according to the process of claim 1 wherein that described conjugated diene is C
4-C
12Conjugated diene, and described conjugated diene consumption is a 25-95% weight based on monomer weight.
18. according to the method for claim 17, wherein said conjugated diene is selected from 1,3-butadiene, isoprene, 1,3-pentadiene, 1,3-hexadiene, 2,3-dimethyl-1,3-butadiene, 1-phenyl-1,3-butadiene, and arbitrary combination.
19. according to the method for claim 18, wherein said conjugated diene is a 1,3-butadiene.
20. according to the process of claim 1 wherein that described monovinylarene is meant C
8-C
20Monovinylarene, and the monovinylarene consumption is a 5-75% weight based on monomer weight.
21. according to the method for claim 20, wherein said monovinylarene is a vinylbenzene, methyl substituted vinylbenzene, vinylbenzene that butyl replaces or their combination.
22. according to the method for claim 21, wherein said monovinylarene is selected from: vinylbenzene ,-vinyl toluene, p-methylstyrene, right-t-butyl styrene, alpha-methyl styrene, and arbitrary combination.
23. according to the method for claim 5, it is 2-70g total monomer/100ml solvent that wherein said solvent load makes monomer concentration.
24. according to the process of claim 1 wherein that described polymeric reaction temperature is that 0-150 ℃ and polymerization pressure are the 0.1-0.8MPa gauge pressure.
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| CN104098719B (en) * | 2013-04-09 | 2016-03-02 | 中国石油化工股份有限公司 | Terminating method in a kind of reactive polymer still preventing generation gel in still |
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