CN102140148B - Preparation method for butyl rubber - Google Patents
Preparation method for butyl rubber Download PDFInfo
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- CN102140148B CN102140148B CN2010191140041A CN201019114004A CN102140148B CN 102140148 B CN102140148 B CN 102140148B CN 2010191140041 A CN2010191140041 A CN 2010191140041A CN 201019114004 A CN201019114004 A CN 201019114004A CN 102140148 B CN102140148 B CN 102140148B
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Abstract
The invention relates to a preparation method for butyl rubber; isobutene and isoprene monomers are contacted for cationic polymerization reaction in the temperature of minus 32 DEG C to minus 40 DEG C in the presence of aliphatic series hydrocarbon thinning agent and catalytic systems, wherein the addition amount of isobutene is 50 to 60% of the total volume; the addition amount of isoprene is 1 to 1.05% of the mass of isobutene; the rest is aliphatic series hydrocarbon thinning agent according to the volume; a catalystic system is di-isooctyl phosphate group dialkyl group single metallocene-titanium solution and equimolar tris(pentafluorophenyl)boron; the content of tris(pentafluorophenyl) boron in the catalysis system is 0.067% of the mass of isobutene; the polymerization method can complete the polymerization of butyl rubber in hexane or pentane in a higher temperature and can be combined with a method for producing halogenated butyl rubber and leaves out steps of resolving; and therefore, the preparation method has good application prospect.
Description
Technical field
The present invention relates to the preparation method of the synthetic butyl rubber of a kind of cationic polymerization.
Background technology
It is thinner that methyl chloride is all adopted in almost global butyl rubber production.Methyl chloride can cause the injury of liver, kidney, neural system and cns.Seeking the research of alternative reaction medium in the butyl rubber is extensively paid attention to.The method of in varsol (like hexane), making butyl rubber becomes an important directions of butyl rubber research and development.
In addition as known in the art, because polyreaction is the height heat release, in full-scale plant, must reaction mixture be cooled to quite low temperature.Like USP 2844569 and 2772255 descriptions, service temperature is at-90 ℃～-100 ℃, and production cost is big, and the polymkeric substance viscosity is high, operational difficulty.Though relevant novel reactor design and/or new catalystsystem development all have certain progress in this area, this requires to exist always.
Therefore need a kind of iso-butylene or iso-butylene and isoprene of being applicable to carry out the novel method of cationoid polymerisation, this method will allow polyreaction under harsh temperatures state not too, in varsol (like hexane), carry out.If it also will be useful especially that novel method can easily adapt to already present production unit.
In USP 3361725, adopt alkyl aluminum halide and dihalide aluminum alkyls mixture as catalyst composition, operation can be carried out at comparatively high temps (57 ℃～-87 ℃), and the reaction times was at 50～100 minutes.This method alkyl aluminum halide reactive behavior is lower.
In Chinese patent 99123627.0; Adopt alkyl aluminum halide, a small amount of dihalide aluminum alkyls and be selected from least a in water, aikyiaiurnirsoxan beta and composition thereof on a small quantity as catalyst composition; Operation can be carried out at comparatively high temps (57 ℃～-87 ℃), can prepare weight-average molecular weight at least about 400000 butyl polymer.There is certain risk in water at normal temperatures with in the aikyl aluminum halide reaction process, and the catalyst composition that forms simultaneously is a multiphase mixture, instability, the not easy-to-use polymerization in homogeneous phase that is used for.
In Chinese patent 99808778.5, adopt luxuriant titanium of trimethylammonium list and triphenyl-boron catalystsystem, be lower than under the normal atmosphere, be about-32 ℃, carry out cationic polymerization and can synthesize the butyl rubber of weight-average molecular weight about 600,000.But because catalyzer is insoluble to hexane, the pentane that solution polymerization is generally adopted, polyreaction can only be carried out in toluene, brings certain difficulty for the aftertreatment desolventizing.
Summary of the invention
The purpose of this invention is to provide a kind ofly, in hexane or pentane, just can accomplish butyl rubber polymeric method at higher temperature (below 32 ℃).Also can combine, save the dissolved step with the method for production halogenated butyl rubber.
The preparation method of a kind of butyl rubber of the present invention is accomplished by the following step:
Let iso-butylene and isoprene monomer in-32 ℃～-40 ℃ TR; Cationic polymerization is carried out in contact in the presence of aliphatic hydrocarbon thinner and a kind of catalystsystem, and this catalystsystem is the equimolar luxuriant titanium of di (isooctyl) phosphate base dialkyl group list and three (pentafluorophenyl group) boron.
The amount that adds iso-butylene is 50～60% of a TV, adds isoprene for adding 1～1.05% of iso-butylene quality; By volume surplus is the aliphatic hydrocarbon thinner, and the aliphatic hydrocarbon thinner is pentane or hexane; The content of three (pentafluorophenyl group) boron is 0.067% of iso-butylene quality in the catalystsystem that adds; Reaction times is 20 minutes.Reaction finishes back adding ethanol termination reaction and coagulates rubber, dry for standby.Being used for di (isooctyl) phosphate base dialkyl group list cyclopentadiene titanium compound of the present invention can obtain through following method: the reaction flask of handling to anhydrous and oxygen-free under the room temperature adds the luxuriant titanium of trialkyl-single, hexane, forms the solution of 2 mol.Mole of phosphoric acid di-isooctyl hexane solution (concentration 2 mol) such as dropping after dropwising, reacted 2 hours under stirring state, and it is subsequent use to form the luxuriant titanium solution of di (isooctyl) phosphate base dialkyl group list.Equimolar above-mentioned di (isooctyl) phosphate base dialkyl group list cyclopentadiene titanium compound and three (pentafluorophenyl group) boron react in hexane, form desired catalystsystem.
Embodiment
Comparative Examples 1:
Be equipped with in the reaction flask of whisking appliance through the anhydrous and oxygen-free processing to 200 milliliters of tops, add 9 milliliters of iso-butylenes of-32 ℃, add 0.0645 milligram of isoprene, 6 milliliters of toluene subsequently; Polymkeric substance is cooled to-32 ℃, adds 1.5 milliliters of trimethylammoniums (1,2 in order; 3; 4,5-methyl) cyclopentadienyltitanium toluene solution (concentration 0.042 mol), 1.5 milliliter of three (pentafluorophenyl group) boron toluene solution (concentration 0.042 mol), the reaction beginning.React after 20 minutes,, have a large amount of white polymer to separate out with 20 milliliters of ethanol termination reactions.Polymkeric substance vacuum-drying, yield are 98%.Mn=72800, Mw=116500, the isoprene mole fraction is 1.0 in the rubber.
Embodiment 1:
In 50 milliliters of reaction flasks that anhydrous and oxygen-free is handled, add the luxuriant titanium of 3.1505 gram trimethylammonium lists under the room temperature, 10 milliliters of hexanes form the solution of 2 mol.Under stirring state, drip di (isooctyl) phosphate hexane solution (6.4201 gram di (isooctyl) phosphates add hexane and are made into 10 ml solns), have great amount of bubbles to produce, after dropwising, reacted 2 hours, generate catalyst solution I.Through evaporating solvent, post separates purifies, and obtains faint yellow product di (isooctyl) phosphate base dimethyl-cyclopentadienyltitanium 453.6224 grams, productive rate 98%, molecular formula C
33H
45PO
4Ti, molecular weight 5.Ultimate analysis: C (wt%), measured value (theoretical value): 67.81 (67..82); H (wt%), measured value (theoretical value): 7.71 (7.68).
In 50 milliliters of reaction flasks that anhydrous and oxygen-free is handled, add three (pentafluorophenyl group) boron, 0.0323 gram under the room temperature, add 4.7 milliliters of hexane dilutions, drip 1.3 milliliters of (0.063 mmole) catalyst solution I.After dropwising, form catalyst solution II, subsequent use.
Be equipped with in the reaction flask of whisking appliance through the anhydrous and oxygen-free processing to 200 milliliters of tops; 9 milliliters of iso-butylenes that add-32 ℃ add 0.0645 milligram of isoprene, 3 milliliters of hexanes subsequently, and polymkeric substance is cooled to-32 ℃; Add 6.0 milliliters of catalyst solution II in order, the reaction beginning.React after 20 minutes,, have a large amount of white polymer to separate out with 20 milliliters of ethanol termination reactions.Polymkeric substance vacuum-drying, yield are 98%.Mn=70300, Mw=121500, the isoprene unit mole fraction is 1.0 in the rubber.
Embodiment 2:
Repeat the method for embodiment 1, different is that polymeric reaction temperature is-40 ℃.Polymer yield is 99%.Mn=132300, Mw=215650, the isoprene unit mole fraction is 1.0 in the rubber.
Embodiment 3:
Repeat the method for embodiment 1, different is that solvent is a pentane, and 0.0677 gram isoprene directly adds without solvent cut.Polymer yield is 98%.Mn=70310, Mw=121606, the isoprene unit mole fraction is 1.0 in the rubber.
Embodiment 4:
Repeat the method for embodiment 2, different is that solvent is a pentane, and 0.0677 gram isoprene directly adds without solvent cut.Polymer yield is 99%.Mn=133100, Mw=216840, the isoprene unit mole fraction is 1.0 in the rubber.
Claims (3)
1. the preparation method of a butyl rubber is characterized in that: iso-butylene and isoprene monomer are in-32 ℃～-40 ℃ TR, and cationic polymerization is carried out in contact in the presence of aliphatic hydrocarbon thinner and catalystsystem;
The amount that adds iso-butylene is 50～60% of a TV, and the amount that adds isoprene is for adding 1～1.05% of iso-butylene quality, and by volume surplus adds the aliphatic hydrocarbon thinner;
Catalystsystem is the luxuriant titanium of di (isooctyl) phosphate base dialkyl group list and equimolar three (pentafluorophenyl group) boron;
The content of three (pentafluorophenyl group) boron is 0.067% of iso-butylene quality in the catalystsystem.
2. the preparation method of a kind of butyl rubber according to claim 1 is characterized in that:
Described catalystsystem obtains through following method:
In the reaction flask that anhydrous and oxygen-free is handled, add the luxuriant titanium hexane solution of a certain amount of trialkyl-single under the room temperature; Mole of phosphoric acid di-isooctyl hexane solutions such as dropping under agitation; It is subsequent use to form the luxuriant titanium solution of di (isooctyl) phosphate base dialkyl group list; The equimolar above-mentioned luxuriant titanium of di (isooctyl) phosphate base dialkyl group list and three (pentafluorophenyl group) boron react in hexane, form desired catalystsystem.
3. the preparation method of a kind of butyl rubber according to claim 1, it is characterized in that: described aliphatic hydrocarbon thinner is pentane or hexane.
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