CN1189508A - Anionic copolymerization of conjugated dienes and vinyl arenes in presence of alkyl ethers of tetrahydropyranyl methanol - Google Patents
Anionic copolymerization of conjugated dienes and vinyl arenes in presence of alkyl ethers of tetrahydropyranyl methanol Download PDFInfo
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Abstract
A method for preparing polymer by copolymerization comprises (A) 50-100 wt.% of at least a diolefin monomer; (B) 0-50 wt.% of at least a olefinic unsaturated monomer; copolymerizing in the inertia solvent and catalytic system. The catalytic system comprises (a) an anion initiator composed of at least a lithium derivant; (b) a modifier belonging to amylene oxide ether.
Description
The present invention relates to conjugated diolefine in the presence of the particular modification agent, say so (being total to) polymerization process in the presence of the alkyl oxide of tetrahydropyrans methyl alcohol more specifically.
In inert solvent and in the presence of catalyzer based on lithium, (being total to) polymerization of conjugated diolefine produces the polymkeric substance such as polyhutadiene and relevant multipolymer (particularly with vinylbenzene), they contain have an appointment 90% 1, the 4-microtexture and about 10% 1, the 2-microtexture.
1, diene polymer that 2-microtexture content is bigger and multipolymer have broad sense for the special applications such as tire, moulded rubber goods, coating and analogous products.
In order to improve 1, the content of 2-structure, (being total to) polymerization is generally carried out in the presence of so-called " properties-correcting agent ", and properties-correcting agent promptly can change 1, the material of 2-microtexture content.
What belong to properties-correcting agent is the tetrahydrofuran (THF) (THF) that adds in polymerization process usually in the inert solvent.But this can produce the problem of recovery and circulating solvent.
US-A-4,429,091 have narrated a kind of properties-correcting agent of mainly being made up of tetrahydrofuran base alkane (ring-type and/or line style).Obtained comparing with this properties-correcting agent with 1 of the higher percentage composition of THF, 2-microtexture.
US-A-5,231,153 have narrated the synthetic method that obtains elastomer polymer with tetrahydrofurfuryl ether copolymerization of styrene and isoprene.
US-A-4,367,325 disclose and use methoxyl group alkyl tetrahydro furans and other ether to produce the method that contents of ethylene is at least irregular phenylethylene-butadienecopolymer of 70%.US-A-4, the method for 367,325 narrations is insulation method fully, it adopts about 2 hours polymerization time.
Have now found that a kind of catalyst system for preparing conjugated diene homopolymers and multipolymer, it can overcome above-mentioned shortcoming, effective production high yield and high-content 1, and the polymkeric substance of 2-microtexture, and also at high temperature carry out.
Thus, the present invention relates to a kind of preparation method of polymkeric substance, this method with following (A) and (B) is carried out polymerization:
(A) at least a diene monomers of 50-100% (weight) preferably is selected from isoprene and 1,3-butadiene, more preferably 1,3-butadiene;
(B) at least a ethylenically unsaturated monomer of 0-50% (weight), preferred vinyl aromatic hydrocarbons, more preferably vinylbenzene,
Polymerization is to carry out in inert solvent and comprising in the presence of following (a) and the catalyst system (b):
(a) at least a anionic initiator of mainly forming by the lithium derivative;
(b) at least a properties-correcting agent that belongs to ethers;
Aforesaid method is characterised in that properties-correcting agent (b) is selected from the ethers of general formula (I):
In the formula:
A) 1-2 R equals-CH
2-O-R
1, other R equals-H;
B) R
1Be C
1-10Alkyl, preferred C
1-5Alkyl, preferred alkyl is selected from methyl and ethyl.
Especially effectively properties-correcting agent is to have general formula (I) and wherein have only a R etc.-CH
2-O-R
1And be positioned on the 2-position of amylene oxide ring, other R equals-properties-correcting agent (R of H
1Be selected from methyl and ethyl, more preferably-CH
3).In other words, most preferred properties-correcting agent is 2-methoxymethyl tetrahydropyrans.
Properties-correcting agent of the present invention is very effective because even at high temperature they still can make the polymkeric substance that obtains have high contents of ethylene, and thereby very short polymerization time arranged.They are still very effective when using low ratio properties-correcting agent/lithium.
As mentioned above, the polymkeric substance that makes with properties-correcting agent of the present invention generally is an elastomerics, and it can be produced with lithium initiator by at least a diene is initial.The diene monomers that can use is the diene with 4-12, preferred 4-8 carbon atom.Above-mentioned diene is conjugated diolefine normally, and the most frequently used is isoprene and divinyl.Other operable diene has 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 3-butyl-1, and 3-octadiene, 2-phenyl-1,3-butadiene etc., they can use or mix use separately.
Also can use the mixture that contains one or more above-mentioned diene in the methods of the invention with the low molecular weight hydrocarbon dilution.These mixtures (being referred to as the low liquid stream of diene content) can be obtained from many refinery liquid streams (for example petroleum naphtha or gas oil cracking), they also can be the suitable mixtures of preparation, and propane, propylene, Trimethylmethane, normal butane, 1-butylene, iso-butylene, anti--2-butylene, suitable-2-butylene, tetrahydrobenzene, ethene, propylene etc. can be arranged with the representative instance of diene blended low molecular weight hydrocarbon.
Except that preparation diene homopolymer, properties-correcting agent of the present invention also can be used for preparing the multipolymer of one or more diene that high-vinyl-content is arranged, and for example prepares high-vinyl-content isoprene/butadiene multipolymer.
In addition, properties-correcting agent of the present invention can be used for preparing high-vinyl-content diene monomers and can with the elastocopolymer or the terpolymer of at least a ethylenically unsaturated monomer of diene monomers copolymerization.The representative instance of above-mentioned ethylenically unsaturated monomer is to have one or more CH
2The vinylidene monomer of=CH-chain end group, vinyl-arene (for example vinylbenzene, alpha-methyl styrene, bromostyrene, chlorostyrene, fluorostyrene etc.), alpha-olefin (such as ethene, propylene, 1-butylene).
At least a. the elastocopolymer of saturated diene and at least a ethylenically unsaturated monomer copolymerization contains the diene monomers of 50-99% (weight) and other ethylenically unsaturated monomer of 1-50% (weight) usually.
The multipolymer of diene monomers and vinyl aromatic monomer has many-sided application, and typical example is styrene butadiene rubbers (SBR), and it is by 50-95% (weight) diene monomers and 5
The vinyl aromatic monomer of 50% (weight) is formed.
When preparing multipolymer with diene, vinyl aromatic monomer is the most widely used ethylenically unsaturated monomer of a class.The selection of these vinyl aromatic (co) hydrocarbon compounds obviously be will with the diene monomers copolymerization.In the presence of the initiator of forming by alkyl or aryl lithium derivative, can any vinyl aromatic (co) hydrocarbon compound of polymeric all be operable.The vinyl aromatic (co) hydrocarbon compound contains the 8-20 carbon atom usually, preferred 8-14 carbon atom.Preferred vinyl aromatic (co) hydrocarbon compound is a vinylbenzene.Except that vinylbenzene, the representative instance of vinyl aromatic (co) hydrocarbon compound is 1-vinyl naphthalene, 2-vinyl naphthalene, 3-vinyl toluene, 4-propylstyrene, 4-phenylcyclohexane ethene, 4-dodecyl vinylbenzene, 2-ethyl-4-benzyl vinylbenzene, 4-(phenyl butyl) vinylbenzene.
The relative quantity of conjugated diolefine and mono-vinyl derivative can change in the scope of broad.When the preparation elastomeric polymer, the ratio of diene and vinyl aromatic (co) hydrocarbon compound should make it produce elastocopolymer.Diene/vinyl aromatic monomer ratio that just can not obtain elastomeric polymer above it is unclear or obvious limit, but elastocopolymer generally contains the diene of at least 50 weight parts.When producing elastomerics by the inventive method, the weight ratio of diene and vinyl aromatic (co) hydrocarbon compound is normally in 50: 50 to 95: 5 scope.Obviously also can use the mixture of diene mixture and vinyl aromatic (co) hydrocarbon compound.
(being total to) polymerization of the inventive method can be carried out in hydrocarbon solvent, and hydrocarbon solvent can be aromatic hydrocarbons, paraffinic hydrocarbons or naphthenic hydrocarbon.The common per molecule of these solvents contains 4-10 carbon atom, is liquid under polymerizing condition.The representative instance of solvent has butane, pentane, octane-iso, hexanaphthene, normal hexane, benzene,toluene,xylene, ethylbenzene etc., and they can use separately or use with its mixture.
In the polymerization that properties-correcting agent of the present invention also can be used for causing with the lithium catalyst system.
When using properties-correcting agent of the present invention to carry out solution polymerization, the contained amount of monomer of reaction mixture is 5-50% (weight).Reaction mixture obviously comprises organic solvent, monomer, lithium initiator and properties-correcting agent.In a preferred specific embodiments, reaction mixture contains the monomer that can reach 30% (weight).
The lithium initiator that uses in the inventive method comprises its simple function and polyfunctional derivative.
The lithium initiator amount of using in the inventive method can be different, is decided by the molecular weight of wanting the polymeric monomer and will obtaining.But conventional lithium initiator consumption is 0.01-0.2phm (part/hundred parts of monomers), preferred 0.01-0.1phm lithium, more preferably 0.025-0.07phm lithium.
The selection of lithium initiator can be according to desired degree of branching and elasticity, feed type etc.About used feed type, if the diene concentration in the liquid stream is low, the multifunctional initiator of then preferential selection.In fact be present in the diene liquid stream of non-purifying any possible impurity can both with carbon-lithium key reaction, make the initiator inactivation.
Operable multifunctional initiator is that those can be with the initiator of the monofunctional compound prepared in reaction of many vinyl phosphonics or many vinyl silanes and lithium, and this reaction is preferably in inert diluent (for example hydrocarbon) and carry out in the presence of polar organic compound.Reaction between organolithium compound and the many vinyl silanes (or many vinyl phosphonics) can cause sedimentary formation, can add the solubilization monomer when needing, and makes its dissolving, for example adds conjugated diolefine or vinyl aromatic (co) hydrocarbon compound.In addition, above-mentioned reaction can be carried out in the presence of a spot of solubilization monomer.
The representative instance of single organolithium derivative is lithium ethide, sec.-propyl lithium, n-Butyl Lithium, s-butyl lithium, tert-butyl lithium, uncle's octyl group lithium, NSC 62789 base lithium, phenyl lithium, 2-naphthyl lithium, 4-butyl phenyl lithium, 4-tolyl lithium, cyclohexyl lithium.
The representative instance of many vinyl silanes is tetrem thiazolinyl silane, methyl trivinyl silane, diethyl divinyl silane, two dodecyl divinyl silane, cyclohexyl trivinyl silane, phenyl trivinyl silane, benzyl trivinyl silane.
The representative instance of many vinyl phosphonics is trivinyl phosphine, methyl divinyl phosphine, dodecyl divinyl phosphine, diethylamino phenyl thiazolinyl phosphine, ring octyl group divinyl phosphine.
Other multifunctional polymerization initiator can be from single organolithium derivative, reacts with many vinyl aromatic (co)s hydrocarbon compound and conjugated diolefine or mono vinyl aromatic compound or the two to prepare.Normally add these components in the presence of as the hydrocarbon of thinner or hydrocarbon mixture and polar organic compound during in beginning.In addition, multifunctional polymerization initiator can prepare with two-step approach, at first with single organolithium derivative and conjugated diolefine or mono vinyl aromatic compound reaction, and then adds many vinyl aromatic (co)s hydrocarbon compound.Can use any above-mentioned diene or mono vinyl aromatic compound.
Typical many vinyl aromatic (co)s hydrocarbon compound comprises 1,2-Vinylstyrene, 1,3-Vinylstyrene, 1,4-Vinylstyrene, 1,2,4-trivinylbenzene, 1,3-divinyl naphthalene, 1,8-divinyl naphthalene, 1,3,5-trivinyl naphthalene, 2,4-divinyl biphenyl, 3,5,4 '-trivinyl biphenyl, a di isopropenylbenzene, to di isopropenylbenzene.Preferably contain the divinyl aromatic hydrocarbons of 18 carbon atoms at the most, particularly adjacent, or to Vinylstyrene, they can use or mix use separately.
In addition, can use specific organolithium compound, and though be simple function or polyfunctional.These compounds can formula R
1(Li)
xRepresentative, R in the formula
1Represent the alkyl of 1-20 carbon atom, x is the integer of 1-4.Typical organolithium compound is lithium methide, lithium ethide, sec.-propyl lithium, n-Butyl Lithium, s-butyl lithium, tert-butyl lithium, uncle's octyl group lithium, positive decyl lithium, phenyl lithium, 1-naphthyl lithium, 4-fourth phenyl lithium, cyclohexyl lithium, 4-butyl cyclohexyl lithium, two lithium methane, 1,4-two lithium butane, 1,10-two lithium decane, 1,4-two lithium hexanaphthenes.
Properties-correcting agent of the present invention can be introduced reaction zone in any way, and for example, properties-correcting agent can or add in the zone of convergency respectively with the organo-metallic initiator.
The amount of properties-correcting agent can be different, depend on desired polymkeric substance contents of ethylene.For example, if require the polymkeric substance of low vinyl content, then use the properties-correcting agent of about 0.1 molar weight of every mole metal initiator.If require the polymkeric substance of high-vinyl-content, then use relatively large properties-correcting agent.Yet the modification dosage that every mole metal initiator uses is that groundless is higher than 40 moles.Preferably every mole of lithium is used the properties-correcting agent of 0.2-10 mole, preferred 0.5-5 mole.
Compare with the properties-correcting agent of prior art, the efficient of properties-correcting agent of the present invention when hanging down consumption is amazing.
The brainstrust of this area knows that when comparing use ether properties-correcting agent with high ether/lithium, ether properties-correcting agent can make the polymerizing catalyst inactivation, has consequently changed molecular weight distribution curve and molecular weight values itself.Therefore, importantly, use the littler properties-correcting agent of modification dosage that usage quantity is used than known technology when reaching identical (being total to) polymkeric substance contents of ethylene, promptly lower ether/lithium ratio is such as using properties-correcting agent of the present invention.
Polymerization temperature can change in-20 ℃ to 150 ℃ wide region.In most of the cases preferentially select 10 ℃-125 ℃ temperature.Polymerization can be carried out under isothermal or adiabatic condition.Must be noted that at high temperature the statistics and convergence of diene and vinyl-arene is incomplete when using prior art properties-correcting agent; And on the other hand, properties-correcting agent of the present invention even at high temperature also allow diene and vinyl aromatic (co) hydrocarbon compound random polymerization preferably.
With regard to pressure, can keep under polymerizing condition is that the pressure of liquid phase is normally enough basically.
Polymerization can proceed to the monomer enough time of polymeric almost completely that makes.In other words, polymerization is carried out with the high-transformation rate.
Polymerization available standards method stops, and for example uses non-coupling terminator, such as water, acid, lower alcohol; Or use coupling agent.
The representative instance of coupling agent comprises many vinyl-arenes, polyepoxide, polyisocyanates, multi-imide, many aldehyde, many ketone, polyhalogenide, polynary acid anhydride, polynary ester (polyvalent alcohol and monocarboxylic ester), dibasic ester (ester of monohydroxy-alcohol and di-carboxylic acid).
Can reclaim with ordinary method by the polymkeric substance that the inventive method makes with solution polymerization technique.In many cases, preferable methods is to destroy residual carbon-lithium key, reclaims the polymkeric substance that produces then.Adding antioxidant in polymeric solution makes it not be harmful to oxygen that to contact also be favourable with the protection polydiene.The polymkeric substance that produces can be precipitated out from polymeric solution, and adding lower alcohol (for example Virahol) can make residual lithium inactivation.The recovery of polymkeric substance can be used ordinary method, such as decant, filtration, centrifugal.The used vapour stripping is to remove volatile residue.
Used properties-correcting agent can be used for intermittent type or continous way production in the inventive method, is still under quite high temperature effectively.
In intermittence type polymerization, properties-correcting agent of the present invention provides the possibility of using wide temperature range, therefore allows the increase of monomer concentration, also makes this method that economic output is arranged.
In the continous way polymerization, higher temperature has made it kinetics faster, and consequently flow is big, the residence time is shorter, and therefore the output of less expensive arranged.
The following examples will be to the invention provides better explanation.
Embodiment
The preparation of THPA-m (methyl THP trtrahydropyranyl ether)
The solution of impouring 60-70mmol (7-8g) 2-methylol tetrahydropyrans in the 100-200ml methylene dichloride in churned mechanically 1 liter of flask is housed, add the 28 gram 50%NaOH aqueous solution and 6-7g bromination triethyl hexadecyldimethyl benzyl ammoniums again, add 100-150mmol methyl-sulfate (12-18g) then, it was at room temperature stirred 8-10 hour.
Add 2-3ml ethanol and make reaction terminating, and mixture was stirred several hours.
Extract organic phase subsequently, then evaporate to dryness in rotatory evaporator.Steam unreacted alcohol, use silica gel chromatography with hexanaphthene/ether purification reaction mixture.
The polymerization of divinyl
Conventional steps (seeing Morton, anionoid polymerization: principle and practice, AcademicPress, New York, 1983) is used in experiment, uses lithium catalyst.
Model experiment is as follows: the properties-correcting agent (being generally 0.6-0.7mmol) and the 0.05-0.07 gram n-Butyl Lithium that add 700 gram solvents (hexanaphthene), 15 gram divinyl, requirement in 1 liter of reactor.
Used temperature is shown in the embodiment, and almost keeps constant in polymerization process, and this is because the high dilution of used reactor and big thermal capacity cause.
Reaction proceeds to transform fully and (is generally 80 ℃, 10 minutes; Or 25 ℃, 2-3 hour), add water (1-2mmol) then and make the active centre inactivation.(BHT 0.15phr), removes with stripping and to desolvate to add oxidation inhibitor in the polyhutadiene that obtains.In addition, make the polymkeric substance aggegation by adding non-solvent (ethanol).Polymkeric substance is with the used ether/lithium ratio of gpc analysis, with IR assay determination microtexture.
Carrying out test for data in the presence of the properties-correcting agent of properties-correcting agent of the present invention and prior art is shown in Table 1.
In table 1 (and the table that relates to copolymerization in succession), abbreviation THPA-m represents 2-methoxymethyl tetrahydropyrans, and (substituting group is at 2-position, R
1=-CH
3Formula I compound); THPA-et represents 2-ethoxyl methyl tetrahydropyrans, and (substituting group is at 2-position, R
1=-CH
2CH
3Formula I compound); THFA-m represents 2-methoxymethyl tetrahydrofuran (THF) (also claiming the methyl tetrahydrofurfuryl ether); THFA-et refers to 2-ethoxyl methyl tetrahydrofuran (THF), is also referred to as ethyl tetrahydrofurfuryl ether.Cited tetrahydrofuran derivatives is a usefulness as a comparison, because they are used for US-A-5, in 231, the 153 described methods.
Provided the contents of ethylene of the polyhutadiene of polymerization temperature, properties-correcting agent/lithium mol ratio and generation in the table.Contents of ethylene is meant the per-cent of all two keys that exist in ethylene double bond (1,2) and the polymer backbone.
Table 1
Butadiene homopolymerization
| Embodiment number | Ether | Temperature (℃) | Vinyl % (1,2/ total vinyl) | Ether/lithium ratio |
| ????1 | ??THPA-m | ????25 | ????74.7 | ????0.7 |
| A1 relatively | ??THFA-m | ????25 | ????73.4 | ????0.7 |
| ????2 | ??THPA-et | ????25 | ????80.5 | ????1.1 |
| A2 relatively | ??THFA-et | ????25 | ????79 | ????1.1 |
| ????3 | ??THPA-m | ????50 | ????64.2 | ????0.7 |
| A3 relatively | ??THFA-m | ????50 | ????58.4 | ????0.7 |
| ????4 | ??THPA-et | ????50 | ????58.3 | ????1 |
| A4 relatively | ??THFA-et | ????50 | ????56.9 | ????1 |
| ????5 | ??THPA-m | ????80 | ????46.6 | ????0.7 |
| ????5b | ??THPA-m | ????80 | ????50.5 | ????2 |
| A5 relatively | ??THFA-m | ????80 | ????37.5 | ????0.7 |
| ????6 | ??THPA-et | ????80 | ????40.5 | ????1 |
| A6 relatively | ??THFA-et | ????80 | ????40.2 | ????1 |
The data of table 1 show that in the time of 25 ℃, the performance of THPA-m performance of the present invention is substantially equal to the performance of THFA-m; And when high temperature, (see it is highly significant) from the viewpoint of industry, under identical properties-correcting agent/lithium ratio, THPA-m exists than THFA-m can make polyhutadiene have significantly high contents of ethylene down.
On the other hand, THPA-et can not get having better result down than THFA-et under identical ether/lithium ratio.
Synthesizing of polyisoprene
Polymerization is carried out in polymerization as above-mentioned divinyl.The results are shown in table 1a.
Table 1a
| Test | Ether | Temperature (℃) | 3,4 unit % | Ether/lithium ratio |
| ????IPR/1 | ??THPA-m | ????80℃ | ????31 | ????0.95 |
| IPR/2 relatively | ??THFA-m | ????80℃ | ????18 | ????0.95 |
Data in the table show, under the situation of polyisoprene, use ether of the present invention (with respect to the ether of prior art) also to make 3, and the unitary content of 4-increases.
Synthesizing of styrene-butadiene copolymer
The synthesis step of butadiene-styrene copolymer is similar to butadiene homopolymerization, and except adding second kind of monomer before adding butyllithium, comprises that sample thief is the GC that initial monomer forms and analyzes.After adding initiator, get other sample of low-conversion (10-15% is the highest) simultaneously, also measure the variation that monomer is formed with GC.After transforming fully, repeat above-mentioned same steps as of homopolymer being carried out GPC and IR analysis.Test data is shown in table 2.
The copolymerization of table 2 Butadiene
| Embodiment number | Ether | Temperature (℃) | Vinylbenzene % | Vinyl % | Ether/lithium ratio |
| ????7 | ??THPA-m | ????25 | ????26.9 | ????67.6 | ????0.7 |
| A7 (comparison) | ??THFA-m | ????25 | ????29.7 | ????66.1 | ????0.7 |
| ????8 | ??THPA-m | ????50 | ????24.9 | ????55.6 | ????0.7 |
| A8 (comparison) | ??THFA-m | ????50 | ????24.4 | ????48.8 | ????0.7 |
| ????9 | ??THPA-m | ????80 | ????26.2 | ????40 | ????0.7 |
| A9 (comparison) | ??THFA-m | ????80 | ????24.5 | ????33.2 | ????0.7 |
The data of table 2 show that THPA-m has higher efficient than THFA-m at various temperatures, particularly when 50 ℃ and 80 ℃.Particularly importantly, the multipolymer in 80 ℃ of preparations in the presence of THPA-m has 40% contents of ethylene, and is 33.2% with the content that contrast properties-correcting agent obtains.
The evaluation of copolymerization efficient is (to see H.Catalgiz-Giz, A.T.Giz, " polymer materialization (Macromol.Chem.Phys.) " with Kelen-Tudos type computing method, 195,855,1994) prove conclusively and with Digital Computing and (to see M.Dube, R.Amin Sahayel, A.Penlidis, K.F.Q ' Driscoll, P.M.Reilly, J.Pol.Sci.Polym.Chem.29,703,1991), measure reactivity ratio (table 3) with pinpoint accuracy.
(kbb is the homopolymerization kinetic constant to value r1=kbb/kbs shown in the table 3, kbs is the conversion to the vinylbenzene lithium (Cross-over) kinetic constant from the divinyl lithium), r2=kss/ksb (kss is a vinylbenzene homopolymerization kinetic constant, and ksb is the conversion kinetic constant to the divinyl lithium from the vinylbenzene lithium).
In the ideal copolymerization, r1 and r2 approach 1.In fact as pointed in the scientific literature, during r1=r2=1, what obtain is the ideal statistical copolymer.
Table 3 copolymerization efficient
| Embodiment number | Ether | Temperature (℃) | ????r1 | ????r2 | Ether/lithium ratio |
| ????10 | ??THPA-m | ????25 | ????0.7 | ????1.25 | ????0.7 |
| A10 relatively | ??THFA-m | ????25 | ????0.9 | ????1.15 | ????0.7 |
| ????11 | ??THPA-m | ????50 | ????1.15 | ????0.6 | ????0.7 |
| A11 relatively | ??THFA-m | ????50 | ????1.18 | ????0.35 | ????0.7 |
| ????12 | ??THPA-m | ????80 | ????1.41 | ????0.12 | ????0.7 |
| A12 relatively | ??THFA-m | ????80 | ????2.18 | ????0.14 | ????0.7 |
Very important data in the table 3 are embodiment 12 and A12 (comparison) test.The r1 value that properties-correcting agent of the present invention (embodiment 12) can obtain under 80 ℃ equals 1.41, and the analog value of the methyltetrahydro ether of glycosyl of prior art is 2.18.This explanation (as shown in table 4), according to the present invention, the copolymerization at high temperature of vinylbenzene and divinyl produces the multipolymer with big vinylbenzene statistical distribution.
The adiabatic copolymerization of phenylethylene/butadiene
Under nitrogen protection, 1125 gram divinyl and 375 are restrained in the reactor of 20 liters of vinylbenzene addings.To wherein adding 0.91 gram (7mmol) THPA-m; In comparative example, add 0.805 gram (7mmol) THFA-m.When initial temperature reaches 26 ℃, add 0.704 gram (11mmol) butyllithium.
Because the monomer of high density is arranged, and temperature rises to 87 ℃ by 26 ℃.Test-results (at properties-correcting agent of the present invention and relatively carry out in the presence of the properties-correcting agent (THFA-m and ethylene glycol bisthioglycolate uncle butyl ether-be abbreviated as EGBE)) is shown in Table 4.The 3rd hurdle is depicted as the percentage ratio of styrene comprise vinylbenzene total amount in the block in the table 4.Styrene block one speech is meant the segment more than 10 styrene units, analyzes according to the ozone analytical method.
Table 4
| Properties-correcting agent | Vinyl % | Vinylbenzene in the block piece/total vinylbenzene | Ether/lithium ratio |
| ??THPA-m | ????50 | ????0.9％ | ????0.7 |
| ??THFA-m | ????44.4 | ????4.8％ | ????0.7 |
| ????EGBE | ????45 | ????30％ | ????0.7 |
Result in the table 4 shows, identical ether/lithium than the time, properties-correcting agent of the present invention can provide the styrene/butadiene copolymers of high-vinyl unit content with respect to the properties-correcting agent of prior art.In addition, block styrene % is significantly less than the block styrene % that obtains with prior art properties-correcting agent.
Claims (9)
1. one kind by polymerization (A) with (B) prepare the method for polymkeric substance:
(A) at least a diene monomers of 50-100% (weight);
(B) at least a ethylenically unsaturated monomer of 0-50% (weight); Above-mentioned polymerization is carried out in the presence of catalyst system in inert solvent, and this catalyst system comprises:
(a) at least a anionic initiator of mainly forming by the lithium derivative;
(b) at least a properties-correcting agent that belongs to ethers;
The method is characterized in that ether (b) is selected from the have general formula ethers of (I)
In the formula:
A) 1-2 R equals-CH
2-O-R
1, other R equals-H;
B) R
1Be C
1-10Alkyl, preferred C
1-5Alkyl, preferred alkyl is selected from methyl and ethyl.
2. the method for claim 1 is characterized in that, diene monomers (A) is selected from isoprene and 1,3-butadiene.
3. the method for claim 2 is characterized in that, diene monomers (A) is a 1,3-butadiene.
4. the method for claim 1 is characterized in that, ethylenically unsaturated monomer (B) is selected from the vinyl aromatic (co) hydrocarbon compound.
5. the method for claim 4 is characterized in that, vinyl aromatic (co) hydrocarbon compound (B) is a vinylbenzene.
6. the method for claim 1 is characterized in that, has only a R to equal-CH
2-O-R
1, other 4 R equal-H.
7. the method for claim 1 is characterized in that ,-CH
2-O-R
1Base is positioned on the alpha-position of Sauerstoffatom of tetrahydropyrans.
8. the method for claim 7 is characterized in that, R
1Be selected from-CH
3With-CH
2CH
3
9. the method for claim 8 is characterized in that, R
1Be-CH
3
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97113179A CN1189508A (en) | 1997-01-30 | 1997-05-30 | Anionic copolymerization of conjugated dienes and vinyl arenes in presence of alkyl ethers of tetrahydropyranyl methanol |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IT000171A/97 | 1997-01-30 | ||
| CN97113179A CN1189508A (en) | 1997-01-30 | 1997-05-30 | Anionic copolymerization of conjugated dienes and vinyl arenes in presence of alkyl ethers of tetrahydropyranyl methanol |
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| Publication Number | Publication Date |
|---|---|
| CN1189508A true CN1189508A (en) | 1998-08-05 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN97113179A Pending CN1189508A (en) | 1997-01-30 | 1997-05-30 | Anionic copolymerization of conjugated dienes and vinyl arenes in presence of alkyl ethers of tetrahydropyranyl methanol |
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| Country | Link |
|---|---|
| CN (1) | CN1189508A (en) |
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1997
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