DE1769072A1 - Process for the continuous compounding of isoolefin polymers - Google Patents

Description

Appropriate for continuous compounding of isoolefin polymers.

The invention relates to a process for continuous compounding of isoolefin polymers, namely homopolymers of C4 to C6 isoolefins, copolymers of C4 to C6 isoolefins with C to C C @ multiolefins and copolymers of C4- to C8-iscolerines with a vinylaromatic hydrocarbon, which thereby is characterized because # a slurry of the polymer in one of one C1 to C3 alkyl halide, non-solvent, liquid reaction diluent at a temperature above the boiling point of the diluent with a Bringing C5 to C10 inert hydrogen solvent into contact with the diluent to evaporate and to dissolve the polymer in the solvent, whereupon the Polymer by @ inarbe @ th an @onlenwasserstoffmaterials, such as z. @. a paraffin wax, a mineral lubricating oil or mixtures thereof in this solution with these additives compounded, the solution containing the modified polymer cci a temperature above the boiling point of the solvent with an i, yüi ü bi 1ibii Io: idut, W'sri Cii cdf. \ Jn iii tCrüliInD bling; that has a higher boiling point than the solvent nat to evaporate the solvent and a second suspension of the polymer to form in the second nonsolvent, and then the modified polymer from this world Au @ schlämm @@ wins.

To obtain high yields of polymers such as polyisoolefins or copolymers of isoolefins with multiolefins and / or vinyl aromatic hydrocarbons to achieve, such polymers are technically produced in a diluent, that does not dissolve the resulting polymer or mixed polymer, such as C1 - to C3-alkyl halides with boiling points below that of water. When polymerizing from C4 - to C8 - Isoolefins such as isobutylene, 2-methyl-1-butene and 3-methyl-1-butene or the like. With smaller amounts of C4 to C1d multiolefins, such as isoprene, butadiene, dimethylbutadiene, Piperylene, dimethylallyl, alloocymes, cyclopentadiene, myrcene, vinylfulvene or the like and / or monoolefin compounds containing a cyclic core, such as styrene, a-methylstyrene, p-methylstyrene, p-chlorostyrene, dichlorostyrene, dihydronaphthalene, Indene etc. are temperatures below 0 °, usually below -50 ° up to applied around -2000.

The polymer or mixed polymer formed in the reaction zone falls in the form of a slurry in the alkyl halide used as a diluent at. This slurry is then poured into a flash drum in the usual manner introduced, where they are used for the purpose of removing volatile substances with steam and for the purpose of Reslurrying the polymer or interpolymer in an aqueous suspension comes into contact with hot water. The polymeric product is then after one of the usual processes by filtration, extrusion with degassing, drying or the like. Won. The polymer or mixed polymer obtained in this way has a Staudinger molecular -weight from about 2,000 to 1,000,000, usually from about 5,000 to 500,000, preferably from about 10,000 to 3,000,000.

Although the highest yields of polymer or mixed polymer with a narrow molecular range can then be achieved when the polymeric product is in shape a slurry, it must in many cases the resulting, dried polymers then in a solvent, e.B. in one inert hydrocarbon, to be dissolved to ensure homogeneous mixing of the polymer or copolymers with pigments, oils, waxes, asphalt, resins, plasticizers and the like. To facilitate. If a polymer or mixed polymer is to be produced by halogenation, Nitration, sulfonation or the like. Are chemically converted, so can These reactions are also best carried out when the polymeric material is in one Solvent is dissolved. However, all known methods of solution are such polymeric substances time-consuming and costly. The solution time varies depending on the Oil molecular weight of the polymer or mixed polymer between a few minutes and several hours or longer, provided that it is appropriately effective Sihr, kneading or homogenizing devices can be used. The present invention solves the problem of creating a cheap, continuous process with which the undissolved polymeric substances obtained in high yields into dissolved polymers transformed werrien. This results in a chemical conversion or a subsequent one Mixing with pigments, vulcanizing agents, oils, waxes, plasticizers, fillers materials, asphalt, resins, thickeners or the like. Much easier.

The method consists in slamming it in a diluent Polymers or copolymers of low temperature, especially those from the reaction zone outflowing slurry, at a higher temperature with a solvent, e.g. with a C5 to C10, advantageously a C6 to C8 hydrocarbon, the one has a higher boiling point than the diluent, under such conditions in Is brought into contact, in which the diluent evaporates and at least a greater part of the polymer is dissolved in the solvent. The resulting Diluent vapors are condensed and in liquid form in recycled the reaction zone. The resulting polymeric solution can then optionally brought into contact with a chemical agent capable of converting the same or with a solid material, e.g. with fillers, pigments or vulcanizing agents be mixed in rubber-like copolymers, in particular in butyl rubber.

The resulting polymer solution is then in each case with a higher as the solvent-boiling medium brought into contact under such conditions, under which the solvent evaporates. The solvent vapors produced here are condensed and returned in liquid form to the flash evaporation zone. If the higher-boiling medium is an oil, wax or asphalt or the like, then that is it End product a mixture of unchanged or chemically modified polymers in such a medium. However, the invention provides that the unchanged Polymers, the chemically converted polymer or the polymer mixture not only in the high-boiling media described above, but also in a non-dissolving, liquid medium whose boiling point is above that of the solvent, such as. B. in alcohols, ethers, ketones etc. or preferably in an aqueous medium such conditions can be obtained under which the solvent evaporates and an excellent slurry of separated particles of the modified or unmodified polymeric material forms in the nonsolvent medium.

According to one embodiment of this invention, after the polymerization or copolymerization in the presence of a Cl used as a diluent - Until the C3 alkyl halide has been completed, the slurry of the polymer Substance in a flash evaporation zone with a solvent for the polymer used a C5 to C10 hydrocarbon with a boiling point above that of the alkyl halide diluent is brought into contact, the temperature so far elevated that sufficient alkyl halide diluent is distilled off to substantially achieve dissolution of all of the copolymer in the hydrocarbon solvent. The resulting diluent vapors are returned to the reaction zone, and the polymeric product is prior to vulcanization with at least one 'solid Mixed fabric. The processed, polymer-containing solution is then heated for that long and / or contacted with hot water until substantially all of it Solvent is removed. The solvent vapors are in a flash zone recycled and the resulting, solvent-free mixture is, if necessary, then dried and then vulcanized.

In a preferably used embodiment of this invention describes a process for the production of butyl rubber in aqueous suspension, that consists in that a coming from the reaction zone butyl rubber, which is in a C1- to C3-alkyl halide serving as a diluent at an over the boiling point of the diluent was slurried, in a flash zone with a sufficient amount of one as a solvent serving, higher than the diluent boiling C5 to C10 hydrocarbons, sufficient to dissolve all of the butyl rubber in the solvent Amount of diluent to volatilize, is brought into contact. Afterward the resulting diluent vapors are condensed in liquid form The present diluents are returned to the reaction zone and the resulting diluents Butyl rubber solution mixed with a solid. The resulting mixture will with an aqueous medium boiling higher than the solvent under conditions brought in ßeriihrurg, among which are: Solvent evaporates and becomes forms a suspension of processed butyl rubber in water. The educated Solvent vapors are condensed in liquid form (le Solution with LeL returned to the flash evaporation zone. The resulting The suspension of processed butyl rubber can then be filtered, with degassing extruded, dried or subjected to a similar treatment so that from this the processed butyl rubber can be obtained in anhydrous form.

According to one embodiment of this invention, the polymeric material at a temperature of about -100 to 0 ° in the diluent used C1 to C3 alkyl halide (expediently the one that flows out of the reaction vessel Slurry) and then slurried at a higher, preferably between about 0 and 1000 with a solvent, e.g. with a C5 bis C10 hydrocarbon that evaporates and reaches a temperature of around 100 and 2500 was overheated, brought into contact under conditions conducive to the diluent volatilized and the polymeric material dissolves in the solvent. Will on this Way the solvent evaporates up to about 500 above its boiling point, so amounts to the required exchange area of the evaporator is only about 1/6 or 1/8 of the area a solvent exchanger, because in the first case the heat transfer coefficient are much higher.

The resulting alkyl halide vapors are preferably condensed and returned in liquid form to the reaction zone for additional slurry. The resulting polymer or mixed polymer solution is then used in any way, e.g. steam by stripping off non-converted olefins with solvent treated. The olefin-free solution is then treated with a chemical agent, that is able to modify the polymer or copolymers, brought into contact.

The polymer or mixed polymer solution can, however, also contain smaller Quantities of such substances or additives, such as oils, pigments, waxes, asphalts, resins, Plasticizers etc. be mixed. The so modified, in the solvent dissolved polymers or mixed polymers and the additives can then with a higher boiling point Solvent or non-solvent medium, such as an aqueous one, higher than the solvent boiling medium, can be brought into contact under conditions under which the solvent evaporates and the resulting solvent vapors are superheated and recycled in vapor form to dissolve additional polymeric material. However, the polymeric material can also be dissolved while it is well dissolved in the solvent be mixed with substances such as oils, waxes, asphalt, resins or plasticizers, these substances serve as a higher-boiling medium to remove the solvent easily Addition of other, higher-boiling solvents or non-solvents, such as Remove water.

Rubber-like copolymers suitable for the present invention from isoolefins and eultiolefins are preferably rubber-like copolymers from 1 or more C4 to C8 isoolefins and 1 or more C4 to C14 multiolefin hydrocarbons, such as diolefins, triolefins or other olefin hydrocarbons that are more than contain an olefin double bond. Some of these rubbery interpolymers are marked by the fact that they have a medium to high molecular weight and a have a relatively low number of unsaturated copolymerization groups and using known vulcanization or curing processes that for vulcanization types of butyl rubber suitable at least partially at elevated temperatures can react with sulfur to an elastic product.

To the above-mentioned class of isoolefins and copolymers Multiolefins include, for example, miscpolymers, which are a larger amount, preferably about 85 to 99.5% by weight of an isoolefin having about 4 to 7 carbon atoms, such as isobutylene, 2-methyl-1-butene, 3-methyl-l-butene, 4-methyl-l-pentene, 2-ethyl-1-butene, 4-ethyl-1-pentene or the like. Or a mixture of such olefins, and a small amount, preferably about 0.5 to 15% by weight of a multiolefin with about 4 to 14, preferably with 4 to 6 carbon atoms, or two or three or contain more of the following multiols: (1) acyclic or open-chain conjugated diolefins such as 1,3-butadiene, isoprene, 2,4-dimethyl-1,3-butadiene, piperylene, 3-methyl-1,3-pentadiene, hexadiene, 2-neopentyl-l, 3-butadiene, etc.

(2) Both conjugated and non-conjugated alicyclic diolefins, such as cyclopentadiene, methyl cyclopentadiene, dicyclopentadiene, cyclohexadiene, 1-vinyl-3-cyclohexane, 1-vinyl-1-cyclohexene, 1-vinyl-1-cyclopentene, 1-vinyl-2-cyclobutene, dimethyldicyclopentadiene etc., as well as monocyclic diolefin terpenes such as dipentene, terpinene, terpinolene, Phellandrene, Sylvestren etc ..

(3) cyclic triolefins, such as 2,6-dimethyl-4-methylene-2, 5-heptadiene, 2-methyl-1,3, 5-hexatriene and other conjugated triolefins, as well as myrcene, ocimene, Alloocimen and others.

(4) Alicyclic triolefins such as powders, 6,6-dimethylfulvene, 6,6-methylethylfulvene, 6-ethylfulvene, 6,6-diphenylfulvene, 6-phenylfulvene and other fulvenes of the formula in which R represents a hydrogen, an alkyl, cycloalkyl, aryl, aralkyl or alkaryl radical; as well as other alicyclic triolefins such as 1,3,3-trimethyl-6-vinyl-2, 4-cyclohexadiene, cycloheptatriene etc. and (5) higher multiolefins such as 6,6-vinylmethyl-fullvene (a tetraolefin) and 6,6- Diisoporpenylfulvene (a pentaolefin) or the like.

There can also be similar mixed pole @ the small amounts, e.g. about 0.05 up to 5.0%, preferably 0.2 to 1.0% crosslinking agents, such as divinylbenzene, disinylnaphthalene, Dimethylallyl, etc. can be used.

A particularly suitable rubber-like copolymer butyl rubber is made from isoolefins and multiolefins. Many processes for manufacturing of butyl rubber are found in both patent and general technical literature described. These processes generally describe interpolymerization the above monomers at a temperature between about 0 and 200 °, preferably between about -20 and -130 ° in the presence of a Friedel-Crafts catalyst, such as an aluminum halide (e.g. 3 aluminum chloride), titanium tetrachloride, boron trifluoride, uranium chloride, aluminum octoxychloride etc. The polymerization is usually carried out in an inert diluent. The interpolymer contains about 90 to 99.5% by weight of the isoolefin and about 0.5 Up to 10% by weight of the multiolefin results in rubber-like products with Staudinger molecular weights between about 20,000 and 300,000, i.e. with determined by viscosity measurements, average molecular weights from about 200,000 up to 2,000,000 or 3,000,000. The iodine numbers (Wijs) of the resulting rubbery polymers are generally about 0.5 to 50, preferably about 1.0 to 20 centigrams / gram.

Other suitable copolymers of isoolefins and multiolefins, processed according to the invention with advantage and chemically altered are mixed polymers, which are composed of about 50 to 100 parts by weight of a C4 -to C14 multiolefins, such as a conjugated C4 - to C10 diolefin and from about 100 parts by weight of a C4 to C8 isoolefin, such as isobutylene or 2-methyl-1-butene, have been manufactured. These copolymers are used in the manufacture of rubber, Kitten etc. used. They generally have iodine numbers between about 30 and 100 (wijs).

Another class of interpolymers made from isoolefins and multiolefins are the mixed polymerization products from about 100 to 800 parts by weight of one C4 to C14 multiolefins and about 100 parts by weight of a C4 to C8 isoolefin. These copolymers generally have iodine numbers between about 100 and 175 and are suitable for rubber cement and as an additive for mineral lubricating oils.

According to the invention, tripolymers of isoolefins, multiolefins are also used and monoolefin compounds with an aromatic nucleus such as styrene, α-methylstyrene, p-methylstyrene, indene, dihydronaphthalene, p-chlorostyrene, dichlorostyrene, mixtures thereof etc. treated. The monoolefin compound is (based on the total conversion monomers) used in smaller amounts, preferably in such amounts that in the resulting Copolymers about 0.05 to 10.0, advantageously about 0.5 to 5.0 weight % of the aromatic monoolefin compound are bound.

The alkyl halide serving as a diluent is according to the invention a non-reactive Cl - to C-alkyl halide, which under the polymerization conditions not the monomer and the catalyst, but the rubbery polymer dissolves and does not enter into any complications with the catalyst. Suitable diluents are: methyl chloride, methylene chloride, ethyl chloride, Ethylene chloride, M ethyl fluoride, ethyl fluoride, ethylene fluoride, 1-fluoro-2-fluoroethane, 1-fluoro-2-2'-difluoro -ethane, perfluoropropane, etc. While the alkyl chlorides preferably have 1 or 2 carbon atoms contain, the alkyl fluorides preferably have 1 to 3 carbon atoms. Preference is given to using ethyl chloride, methyl fluoride and from economic ones Reasons in particular methyl chloride.

Suitable hydrocarbon solvents are: C5 to C10, advantageously C5 to C9> especially C6 to C8 hydrocarbons, e.g. N- or iso-paraffins such as hexane, heptane, octane, isohexane, isooctane; Naphthens such as cyclohexane and methylcyclohexane; aromatic hydrocarbons such as benzene, toluene and xylenes; Saturated hydrocarbon fractions such as unprocessed petrol, petrol, directly distilled white petrol; very light Fractions of cracked gas oils or kerosene; mixtures thereof etc .. Preferred solvents are saturated hydrocarbons such as heptane, hexane, isooctane, cyclohexane, hydrogenated Raw and hydrogenated gasolines.

The new process not only facilitates the chemical conversion of the polymeric substance in solution, but also a rapid and uniform one Mixing large amounts of these polymeric substances with liquids such as oils, waxes and asphaltene, since the polymeric substances are dissolved in solvents. Through the the polymeric solution was added to such under the above conditions High-boiling materials will not only mix evenly, but at the same time also achieved the removal of the solvent.

According to one embodiment of the invention, polyisoolefins and especially polyisobutylene with a Staudinger molecular weight of about 5,000 to 30,000, preferably from about 10,000 to 25,000, most preferably in the form of a slurry made in a diluent, the diluent being a hydrocarbon -Solvent replaced and the latter is volatilized, while the polyisoolefin with a higher boiling Medium, e.g. B. is mixed homogeneously with a mineral lubricating oil. Same procedure is preferred for the addition of copolymers of isoolefins in smaller amounts with about 10 to 40% by weight, based on the mixed polymer of an aromatic Vinyl hydrocarbon, such as styrene, is applied to mineral lubricating oils. In both In some cases, the polymer or mixed polymer serves as a valuable viscosity improver and is advantageously added to a lubricating oil prepared according to that described above Process in concentrated form in a relatively small amount of lubricating oil was dispersed.

Adhesive strips and adhesive plasters can also be made from polyisoolefins or Copolymers of isoolefins and an aromatic vinyl hydrocarbon with a molecular weight according to Staudinger of about 10,000 to 1,000,000, according to the invention are dissolved in C5 to C10 hydrocarbons. Mixtures, about 15 to 40% by weight of polymers or copolymers with molecular weights consist of about 30,000 to 120,000 and about 60 to 85% by weight of paraffin wax, can also be prepared according to the invention in that the polymerization diluent by a C5 - to C1O hydrocarbon and the latter by the higher-boiling one Paraffin wax is replaced.

Such mixtures of polymers and wax are used with a wax layer coated paper and cardboard boxes, used like milk cartons, where any leakage as a result of ringing cracks occurring at low temperatures can be avoided got to. Also high molecular weight homopolymers and mixed polymers with molecular weights according to Staudinger from about 100,000 to 1,000,000 can refer to the above-described Way to be mixed with wax. The amounts of wax are generally around 90 to 99.5, with the homopolymer or mixed polymer making up the remainder.

It also falls within the scope of the present invention, e.g. 0.05 to 5.0, preferably about 0.5 to 3.0 parts by weight of polyisoolefins or copolymers of isoolefins and a minor amount of about 10 to 40% by weight aromatic Vinyl hydrocarbons of about 95 to 99.95 weight, preferably about Mixing 97 to 99.5% by weight of asphalt. The inclusion of such small amounts of homopolymers or, in particular, of mixed polymers makes the asphalt lower Temperature more brittle and at higher temperature r z The new process facilitates also the throaty and even addition of oils and pigments in high yield rubber-like copolymers obtained from isoolefins and multiolefins, such as Butyl rubber, as the mixed polymers are dissolved in the solvents.

The new process also facilitates continuous production and processing of extremely high molecular weight butyl rubber. Manufactured according to the invention Butyl rubber can be produced rapidly and continuously and as a viscous, 10 to 20 weight goat solution in a hydrocarbon solvent, as a z. B. about 20 to 30% by weight of solids contained tender rubber cement than with oil stretched rubber mixtures or as mixtures of butyl rubber and one therein dispersed suitable filler or pigment are shipped and stored. In the case of the addition of fillers and pigments and / or an oil dispersion makes the new process a time consuming and costly discontinuous one Kneading butyl rubber with a pigment filler or oil in a Banbury mixer or superfluous on a rubber roller. The one with pigments, fillers and / or Oiling processed butyl rubber is a more homogeneous blend of superior quality, that for tires, hoses, insulating materials, vulcanizing bags, made of rubber manufactured window covers, etc. is used.

While it was previously difficult to get very high molecular weight butyl rubber with plasticizers such as oils, tars, waxes, organic phosphates or resins to stretch will after the new process involves stretching with oil reaches Ti to any extent because the butyl rubber is in solution. Through this higher Proportion of plasticizing oil, technical and economic advantages are achieved. For example werder. reduced production costs by stretching with oil, because 01 is much cheaper than butyl rubber.

Furthermore, compared to high molecular weight butyl rubber itself, by stretching the oil, the grinding resistance is greatly increased. So far took place the stretching with oil of high molecular weight butyl rubber (i.e. of one by viscosity measurements certain average molecular weight of over about 800,000) Hot grinding, which reduces the molecular weight of the butyl rubber to a lower level Molecular weight has been depressed. If, according to the invention, the oil is added before removal of the solvent used for the butyl rubber, this degradation becomes decreased.

Similar advantages arise with the addition of pigments, sulfur, Zinc oxide, amines or accelerators in those intended for the alkyl halide Flash evaporation drum. Suitable pigments are: carbon black, silica, hydrated Silicas such as Hi-Sil 202, clays, etc., retackifiers such as urea-aldehyde resins, Phenol aldehyde resins (e.g. a Re.orcinol formaldehyde resin) or phenol dialcohol resins Or the like. Are also advantageously the butyl rubber dissolved according to the invention added.

The production of a butyl rubber latex is also more advantageous. The one dissolved in the hydrocarbon in the flaghide alkyl halide drum Butyl rubber can be emulsified after an inversion process, with the solution of rubbery butyl polymer, an emulsifier and water to form an emulsion of water-in-polymer is added, which is then followed by further Addition of water is converted into an emulsion of polymer-in-water. According to the invention usable Emulsifiers can be nonionic, anionic, or cationic. The most suitable Nonionic emulsifiers are the polyoxyalkenated alkyl phenols or alcohols of the formula R (OCHR1CHR1) nOH in which R is an alkyl, aryl, alkaryl or aralkyl radical represents, R1 is an alkyl radical or hydrogen and n is an integer of about Means 4 to 10 or higher. The alkene oxide units should be at least about 40 «Make up the total molecular weight of the compound. These connections will by condensation of an alkylphenol or alcohol with a lower alkylene oxide, like ethylene oxide or propylene oxide, won. Among those that can be used according to the invention Anionic emulsifiers include substances like sodium lauryl sulfate, the sodium salt the sulfonates of polyoxyethylated alkylphenols, sodium oleyl taurate, fatty acid soaps of alkali metals etc.

Cationic emulsifiers particularly suitable for the present invention are: alkyldimethyl benzyl ammonium chloride, diisobutylphenoxy ethoxyethyldimethylbenzyl ammonium chloride, Dimethylphenoxy-ethoxyethyldimethylbenzyl-ammonium chloride, etc. The amount of emulsifier is generally from about 0.2 to 15.0, based on the polymer, preferably from about 0.5 to 5.0 weight.

A particularly advantageous emulsifying combination is a mixture of Eat about 0.5 to 5.0 weight parts each, potassium ol, hydrolyzed polyvinyl alcohol and a polyoxyethylated alkylphenol, which under the name Triton-I-l00 is distributed.

Before the butyl rubber solution is homogenized into a latex this by heating or flash evaporation a sufficient amount the hydrocarbon solvent to a polymer content of about 15 to 50, most conveniently from about 20 to 30 weight percent concentrated. By concentrating may occur during the subsequent wiping of the emulsion Difficulties minimized.

The butyl rubber solution can also be mixed with the emulsifying agents, as mentioned above, and it is for this reason that they are added preferably in one remote from the alkyl halide flash drum Zone.

The resulting mixture of butyl rubber in a hydrocarbon solvent is dissolved, water and emulsifying agents are then used to obtain a crude emulsion pumped in a conventional mixer or dispersator, e.g. of the impeller type. the The raw emulsion is then put into a highly efficient mixing machine, e.g. a colloid mill or placed in an ultrasonic mixer. The emulsion is then used for recovery a fine emulsion with the desired consistency either for a few stops the homogenizing system is rounded or in a row in about 2 to 10 homogenizing systems directed.

The emulsion emerging from the last homogenizer is in a device for volatilizing the hydrocarbon, x. B. in about 1 to 5 evaporators, known as turba film evaporators, are pumped to the hydrocarbon solvent and remove some water. This gives you a latex of the desired one Concentration. This latex contains about 30 to 70, preferably about 40 to 60 % By weight (e.g. 50% by weight) of butyl rubber. In order to achieve a maximum The abovementioned evaporators generally have an evaporation capacity at temperatures operated from about 38 to 1040 and under a pressure of about 0.07 to 1.4 kg / dm2 (abs.). The latex obtained is stored in stirred tanks kept that with the heating and cooling devices necessary for the different seasons of the year are provided. At least part of the butyl rubber latex can also be used for processing Carbon black or another filler used before vulcanization is added will. This addition facilitates the subsequent addition of carbon black and the Total dispersion of the carbon black improved.

The present invention i @ d @ the accompanying drawings further bes i-Figure I is a representation of a flow scheme in which a typical Process for the production, processing and recovery of polymerization products according to the invention from isoolefins or a mixture of isoolefins with multiolefins or aromatic Vinyl hydrocarbons is shown.

The plant contains a polymerization kettle I, which is equipped with one of Shaft 7 carried stirrer is provided.

The boiler is surrounded by a heat-insulating jacket, which at the same time serves as a cooling jacket. The boiler is also equipped with an inlet line 5 for charging, a catalyst inlet line 6 and a finished product outlet line 7 are provided.

A polymerizable mixture of about 70 to 99.5% by weight of one C4 to C8 isoolefins, such as at least about 98, preferably at least about 99% purity isobutylene and about 0.5 to 30 weight percent of one C4 to C10 conjugated multiolefins, such as at least about 90, preferably Isoprene present at least in about 95% or even higher purity with about 1 to 5 volumes of a C1 - to C3 -alkyl halide, such as methyl chloride, are continuously introduced into the reaction vessel through line 5.

At the same time a solution of a Friedel Craftstalysators, what for one expediently in a C1 - to C3-alkyl halide, preferably in methyl chloride dissolved aluminum halide used, introduced through line 6 into the boiler 1. In the reactor the concentration of the aluminum halide catalyst is determined by a corresponding regulation of the amount of the recycled through line 8 in line 5 Alkyl halide diluent to about 0.01-0.50, advantageously about 0.02 to 0.30, preferably to about 0.05 to 0.2 weight, based on the entire monomer feed and diluent in the reaction vessel. The degree of conversion of monomers into rubbery interpolymer is determined by Control the above feed to catalyst ratio to about 50 to 90, preferably kept to about 70 to 80 ffi. The quality of the polymer product is controlled by setting the polymerization temperature to about -18 to -184, advantageously to about -73 to -129, preferably to about -84 to -107 ° (e.g. at -93 °). The reaction can either be under pressure or in vacuo take place under atmospheric conditions, advantageously a pressure 2. between about 0.7 and about 17.5 kg / cm2 is adhered to.

The pressure is adjusted to be around 0.14 to 3.5 kg / mc2 is above the pressure prevailing in flash evaporation drum 53.

After completion of the reaction, a slurry of about 10 to 25, preferably about 15 to 20 weight percent butyl rubber in the alkyl halide withdrawn from the reaction vessel through line 7 and into the flash evaporation drum 53, which is equipped with an agitator 16. The flash evaporation drum 53 becomes sufficient on one to evaporate the alkyl halide diluent high temperatures and expediently at around 0.14 to 3.5 kg / cm below the the pressure prevailing in reactor 1 is maintained. Depending on the alkyl-6alogenide used the flash drum 53, e.g., at a temperature between about -18 and 1210, preferably between about 38 and 71u and generally operated at a pressure of about atmospheric at 14 kg / cm2. Good results were achieved at about 540 and about 0.35 kg / cm2 in flash drum 53.

At the same time, a liquid hydrocarbon that is higher than the alkyl halide serving as diluent boils, through line 9 in the flash evaporation drum 53 is injected. The hydrocarbon solvent can be about 0 to 500, advantageously about 20 to 300, preferably about 50 to Contains 200 parts of water per million, so most appropriately just enough water, to deactivate the catalyst. But it can also be a small amount of an oxidized Hydrocarbon, such as an alcohol (e.g. isopropanol) or water with either mixed with the solvent or injected into the flash evaporation tube 53 to prevent "post-polymerization". As mentioned above, it is desirably a lower pressure in the flash drum than in that Apply reaction kettle. This will get the butyl polymer slurry in the alkyl halide from the reaction kettle to the flash drum. The latter can be achieved by any suitable heat exchanger, such as by heating slits in the lower part of the flash evaporation drum (not shown) or through the circulation heat exchanger (shown in the figure) from the outlet line 10, the pump 11, line 12, the heat exchanger 13 and the inlet line 14 consists.

Temperature and pressure are like this in the flash evaporation drum adjusted so that a sufficient amount of the alkyl halide flashes through line 15, to at increased speed dliösy of the butyl rubber copolymers in the Effect hydrocarbon solvent. In general, about 80 up to 100% of the alkyl halide removed. The butyl rubber dissolved in the hydrocarbon is withdrawn through line 18. The butyl rubber solution is then either direct injected through line 19 into hydrocarbon flash drum 20, or if the butyl copolymer is to be extended with oil, dispersed into a latex or mixed with a pigment. The solution is expediently withdrawn through line 21. Then it can be stretched with oil, made into a latex and / or with a pigment filler or vulcanizing agent dispersed and finally through line 22 in line 19 will be introduced.

The butyl rubber mixed polymer can, however, also after deduction through Line 17 extended with oil and / or dispersed with a pigment or filler and finally injected into line 19 through line 22. The stretching oil can also with advantage directly in the flash evaporation drum 53 (not shown) introduced and the mixture of butyl rubber polymer and Ü1 then from stripped of hydrocarbon solvent. In any case it is easy Extending oils in rubbery copolymers of isoolefins and multiolefins and therein lies one of the most important advantages of this invention.

The butyl rubber solution flowing from line 18 through line 19 in the flash evaporation drum 20 contains about 5 to 10 weight P solute rubbery polymer. While the butyl rubber solution through line 19 in the flash drum 20 enters, it is through atomizer 24 at a Temperature from about 66 to 121 °, e.g. B. at 820 and under a pressure of about 0.07 up to 3.5 kg / cm2, e.g. B. atomized at 1.05 kg / cm2 by means of steam. The flash evaporation drum 20 is provided with a water inlet line 23 and with an agitator 25; The latter facilitates the preparation of a water slurry of the butyl rubber polymer. The flash drum is preferably also at a temperature of about 66 to 121 ° and a pressure between atmospheric up to about 3.5 kg / cm2 operated. The vaporized hydrocarbon, e.g. B. heptane, hexane, etc. is withdrawn through line 26 and as described more fully below won. According to another preferred embodiment to be used, is also Low pressure steam through line 27 into the hydrocarbon flash drum 20 blown in.

The resulting slurry of butyl rubber in water contains about 1 to 5, e.g. 2, G @ polymer and comes out of the flash drum 20 line 28 in the vacuum stripper 29, which is also with an agitator 30, a Line 31 for the steam kept at low pressure and a head line 32 to remove the product obtained under vacuum and with a steam jet. The scraper is preferably at about 49 to 71 °, e.g. at 60 ° and at a pressure of about 0.14 to 0.42 kg / cm2 (e.g. at 0.28 kg / cm2) and is used to remove the last traces of hydrocarbon from the butyl rubber slurry in water and recycling them through lines 32 and 33 to the flash drum 20. The butyl rubber slurry in water is then withdrawn through line 34 and by means of the pump 35 through the line 36 for the purpose of carrying out the various known final treatment stages of butyl rubber, such as filtering, drying, extrusion etc., carefully controlling the conditions necessary for the finishing treatment be pumped on.

When producing high molecular weight bityl rubber there is a reduction the molecular weight loss of the rubbery end polymer, e.g. by achieves that the resulting polymer less or preferably not at all is ground and the final compression either does not take place or the compression, the squeegee, the pressure and the shear rate in the extruder are so strong be reduced so that the shear stresses from a normal value of about 8.4-33.5 mkg / sec per kg per hour to a value of less than about 5 mkg / sec per kg per hour. Furthermore, the average determined by viscosity measurements Molecular weight of the resulting polymer thereby to about 900,000 to 2,000,000 be kept that the temperature during the final treatment to below about 149, preferably below about 1210 (e.g. 1040). The remaining the above-mentioned finishing steps are carried out in the usual way.

The hexane or other hydrocarbon solvents are used in accordance with the invention from flash drum 20 through line 26 into condenser 44 and from there passed into the separator 45. The separator 45 becomes the heavier one Layer of water withdrawn through line 46. Residual alkyl halide vapors, if any are removed through line 47. The rest of the product, the consists essentially of pure hydrocarbon solvent and per million contains about 50 to 200 parts of water (e.g. 100 parts of water per million) is through Line 48 via pump 49 and through line 9 into the alkyl halide flash drum 53 rounded. The hydrocarbon contains about 20 or more parts of water each Million, it has the merit of deactivating the catalyst as mentioned above.

The alkyl halide flowing through line 15 is obtained by that the vapors optionally in a first stage compressor 54 to a final pressure from about 2.8 to 4.2 kg / cm, the alkyl halide optionally through Introduction of the same through line 55 into the drying plant working with alumina 56 is dried and the alkyl halodi optionally again in a compressor 57 of the second stage is compressed to a pressure of about 10.5 to 12.25 kg / cm2 will. The alkyl halide flash evaporation drum 53 can, however, also under a so high pressure must be maintained that the alkyl halide vapors easily pass through cooling water can be condensed in direct heat exchange, so that the compressor 54 or 57 becomes superfluous. Albeit in this case the pressure in the alkyl halide flash drum 53 lower than that in the reactor by at least about 0.14 to 3.5 kg / cm2 Pressure is, the pressure in the flash evaporation drum is at least at least about 0.91 to 14 kg / cm2, e.g. set to about 3.5 kg / cm2.

In the latter case, the alkyl halide can through line 15, the Branch 50, the condenser 51, the line 52, the line 55, the drying system 56, line 58, second stage compressor 37, and through line 38 in the fractionation column 37 are passed. Some of the condensed in the condenser 51 Alkyl halide vapors may enter flash vaporization drum 53 through line 61 be recycled to the alkyl halide content of the overhead stream from line 15 to increase escaping vapors. The alkyl halide can, however, also by conduction 15, junction 50, condenser 51, line 59, junction 58, compressor 57 of the second stage and pass through line 38 in Fraktionizrkolonne 37 or else can only be passed through lines 60 and 38 into fractionation column 37.

In either case, the resulting alkyl halide stream is by conduction 38 introduced into fractionation column 57. The fractionation column 37 can with a Be provided with boilers and contain about 30 to 100, e.g. 50 plates. Your reflux ratio is preferably about 5/1 to 15/1, for example about 10/1 or 12/1.

The overhead product contains about 5 to 20, e.g., 10 weight percent of the column feed and consists essentially of pure alkyl halide, such as methyl chloride. After this this overhead product with the desired amount of the catalyst used Line 40 exiting aluminum halides was mixed, the former passes through the head line 99 into the catalyst inlet line 6 leading into reactor 1 Residue from the fractionation column 37 is through the line 42 entered into a second fractionation column 41. The latter contains about 10 to 30, e.g. 20 plates and operates with a reflux ratio of about 0.5 / 1 to 2/1 (e.g. from 1.5 / 1).

The bulk of the diluent alkyl halide is then withdrawn through the head line 8 from the fractionation column 41 and with fresh monomers entering through line 5 are mixed and introduced into kettle 1. The alkyl halide emerging from fractionation column 41 through line 8 contains about 4 to 8% by weight of unsaturated C4 compounds, such as isobutylene. The residue from fractionation column 41 is then passed through line 43 into one with 30 to 70 plates provided stripping column (not shown), in which a small amount of methyl chloride and unsaturated C4 compounds is recovered, which is recycled in line 8. The residue from the stripping column is now free of methyl chloride, but contains further amounts of C4 hydrocarbons, which, like the unreacted Isoolefin (e.g. isobutylene) and multiolefin (e.g. isoprene) monomers to the removed in the usual way. The unreacted isoolefin and multiolefin become then (after additional fractionation for the purpose of splitting the stream into the respective Material) through the usual extraction systems for isobutylene or for isoprene won.

Figure 2 shows another system that can be used according to the invention and details of the procedure are shown. The system contains at least 2 (e.g. 2 to 5) Polymerization kettles, namely kettles 1 and 66, both with on shaft 3 and 70 seated agitators 2 and 68 are provided. The polymerization process and recovery of the polymer is carried out in a manner similar to that described above was described, only are in the recovery of the polymer by evaporation of the Diluent a superheated C5 - to C10 hydrocarbon or mixture of such Hydrocarbons in vapor form through line 9, 78 and 7 in the Flash evaporation drum 53 blown in.

More precisely, liquid hexane flows through line 9 to the valve 72 pass, through valve 74 in the evaporator and superheater 76, in which hexane evaporates and is overheated to 1490. This superheated steam is then passed through line 78 passed into junction 7, where it flows in with the stream emerging from the reactor Comes into contact with this current and enters the flash evaporation drum 53, in which the hexane vapor condenses and gives off so much heat that the methyl chloride evaporated.

The latter is, as described below, as the top product withdrawn through line 15.

The temperature and pressure in flash evaporation drum 53 are, as in the procedure previously described, adjusted so that a sufficient amount the methyl chloride used as a diluent is flash evaporated through line 15, a high-speed solution of the butyl rubber polymer in the hydrocarbon solvent such as hexane. In general about 70 to 100% (e.g. 85 ") of the methyl chloride is removed. The one dissolved in hexane Butyl rubber is then withdrawn through line 18.

The butyl rubber solution can be drawn off through line 17 or 21 and while it is in solution, according to the invention with pigments, fillers, Oils, waxes, asphalt, resins, plasticizers or the like mixed or chemically modified and finally introduced through line 22 into line 19.

In any case, the solution of the invention is made of butyl rubber polymer or another polymer or mixed polymer that is mixed with pigments, oils, waxes, Asphaltene, resins, plasticizers or the like has been mixed or chemically converted, then introduced into the hydrocarbon flash drum 20 through line 19.

This solution generally contains about 2 to 20, preferably about 5 to 15% by weight (e.g. 10% by weight) of solute rubbery Mixed polymer. The evaporation and removal of the hydrocarbon takes place after the description given by the method of Figure 1, only that which is obtained Hydrocarbon solvent through line 48 by means of pump 49 and through Line 9, past valve 72, through valve 74 into the evaporator and superheater 76 repatriated. The hexane vapor is superheated in superheater 76 by 600, i.e. to brought to a temperature of about 1490 and passed through line 78 and junction 7 in the alkyl halide plasma vaporization drum 53 was introduced.

The recovery of the alkyl halide used as a diluent and the preparation of the catalyst solutions are carried out according to the description of the corresponding procedure for Figure 1.

While the reactor 1, as mentioned above, is in operation, the Reactor 66 shut down and cleaned. More precisely, a part (e.g., 20 % By weight) of the total hexane vapors passed through valve 72 into condenser 80, in which the vapors condense, but at a temperature of about 38 to 660, e.g. at 540. The liquid, hot hexane then passes through a pipe 82, past the closed valve 84, through the open valve 86 into the reactor 66, where the hexane dissolves the butyl rubber occluding on the walls of the reactor and the same leads through line 88 into line 7, which leads into the upper part of the Alkyl halide flash evaporation drum 53 opens. After about 20 to 50 hours (e.g. 35 hours) the walls of reactor 1 become so through polymer deposits occluded or soiled that it is desirable to prevent the polymerization in Continue reactor 66 and shut down reactor 1 for cleaning. Valves 86, 90, 92, 94 and 104 are then used to start reactor 66 closed and valves 84, 96, 98, 100 and 102 opened. Reactor 1 will then turned off and with hot hexane flowing out of line 82 through valve 84 washed, the dissolved rubber through valve 100 in line 88 which opens into line 7 and passes through this into the alkyl halide flash drum 53.

As mentioned above, the new method is particularly suitable Butyl rubber with 01 stretch.

So far, the oil stretching of butyl rubber took place in that the A hydrocarbon oil is added to uncured, undissolved butyl polymers and the resultant mixture is kneaded on a roll or in a Banbury mixer, etc. became. The present invention now enables rapid and homogeneous mixing of butyl rubber with hydrocarbon oils or other extenders or plasticizers facilitated because the same of the butyl rubber solution in the flash drum 53 added or fed from line 17 or 21. Because the butyl rubber is in solution, a similar one, stretched or softened with oil, is formed Butyl rubber. A kneading device is no longer necessary. Are the butyl rubber and the extender mixed homogeneously by a suitable simple mixing device, so the hydrocarbon solvent can be volatilized by a hot, aqueous medium will. A mixture of butyl rubber and extender oil remains, which is more homogeneous is than the products manufactured by the previously known processes. As a stretching oil a hydrocarbon plasticizing oil is most suitably used, the has the following properties: Normal range He prefers ~~~~~~~~~~~~~~~~ Specific gravity range 0.8496-1.0 0.8871-0.9659 Flash point, Co (open-shell method) 148-370> 176 pour point, Co -10-15 -9.5-1.1 SSU at 380 50-10,000 300-1000 Iodine number (Wijs) 0-50 0-20 (centigrams / gram) The amount of extension oil z. B. a naphtha oil or even better a paraffin oil, depends on the molecular weight of the butyl rubber polymer. For example, every 100 parts by weight becomes one Butyl rubber polymers, its average, determined by viscosity measurements Molecular weight ranges from about 250,000 to about 20,000,000, generally about 1 to 75 (preferably 5 to 50) parts by weight of oil are used.

While it was previously difficult to get very high molecular weight butyl rubber with plasticizers such as oils, tars, waxes, organic phosphates or resins to stretch quickly becomes any desired degree of such under the new process Oil stretching achieved because the butyl rubber is in solution. Because of the higher proportion Plasticizing oil has advantages both technical and economic Kind of scored. For example, the oil-stretching of the rubber lowers the production cost as oil is much cheaper than rubber. Furthermore, compared to unstretched high molecular weight butyl rubber, by stretching the same with oil the grinding resistance increases significantly. So far, the Ö1 stretch has taken place of high molecular weight butyl rubber (with, for example, a viscosity measurement certain average molecular weight of more than about 800,000) often by Hot grinding, resulting in large losses in the molecular weight of the rubber. By an addition of oil prior to the grinding according to the invention eliminates these losses avoided.

By introducing fillers, pigments, sulfur, zinc oxide, Accelerators, ultra accelerators, waxes, calcium oxide, magnesium oxide, anti-oxidants, Metal salts, etc. in the alkyl halide flash drum become similar Benefits achieved. Suitable pigments are: carbon black, silica, hydrogenated silica such as Hi-Sil 202, Tone etc. Additional solid substances that can be used for this are: Iron oxides, lead oxides, clays, Metal silicates or the like. Also Tackifying resins such as urea-aldehyde resins, phenol-aldehyde type resins (e.g. resorcinol formaldehyde resin), phenol dialcohol resins or the like are used to advantage in the following amounts with butyl rubber, which is based on that set out above Was solved way, processed according to the invention. 100 parts by weight in solution Butyl rubber polymer are advantageously used for vulcanization with about 10 to about 150 or 200, preferably from about 20 or 40 to about 100 parts by weight a filler such as carbon black, silica, hydrogenated silica, alumina, magnesium oxide, Calcium oxide, clays, their mixtures, etc. processed according to the invention. The processed Charge most expediently still contains about 2 to 30, preferably about 5 to 20 parts by weight of a basic metal compound such as a divalent metal oxide (e.g. zinc oxide), amounts corresponding to the vulcanization (i.e. about 2 to 10 parts by weight) Sulfur and about 0.5 to 2.0 parts by weight of an ultra accelerator such as alkylthiuram sulfide, e.g. tetramethylthiuram disulfide, etrabutylthiuram disulfide or other derivatives of Thiocarbamic acid, such as alkyl thiocarbamates (e.g. ellurdiethyldithiocarbamate, zinc dimethyldithiocarbamate) etc. The alkyl groups in the above ultra-accelerators should be preferred Contain 1 to 5 carbon atoms.

The dissolved rubber can be used to advantage during processing also about 0 to 5, preferably 0.5 to 3.0 parts by weight of a mold release agent, such as stearic acid, can be added. Other vulcanizing agents are organic compounds, in which a nitroso or an oximo or oximino group to an aromatic Core and / or is bonded to a tertiary carbon atom. Preferred vulcanizing agents of this type are quinoid compounds, such as or, in particular, p-quinone dioxime, or in particular p-dinitrosobenzene and derivatives of these substances.

The above mixtures are advantageously about 5 minutes to about 2 hours (e.g. 10 to 60 minutes) at about 93 to 177 ° or about 0.5 to 20 Cured at about 177 to 232 ° in minutes. The higher the vulcanization temperature, the shorter the time and vice versa. In special cases it proves to be advantageous if the mixtures mentioned also include vulcanizing agents such as benzothiazyl sulphide, Mercaptobenzothiazole, polyarylguanidines, hexamethylenetetramine or diamine, titanium dioxide, contain blue-coloring or other colored pigments that essentially as described with regard to the addition of other fillers, pigments and vulcanizing agents, can be added.

The production of a butyl rubber latex has also proven itself the new process as advantageous.

Butyl rubber in the alkyl halide flash drum 53 has been dissolved in a hydrocarbon or from lines 17 or 21 can be processed into an emulsion using an inversion process.

The rubber-like butyl polymer solution becomes the result of the addition an emulsifier and water into a water-in-polymer emulsion and these then converted into a polymer-in-water emulsion by adding more water. The emulsifiers to be used according to the invention can be nonionic or anionic or cationic type. The most suitable nonionic emulsifying agents are the polyoxyalkenated alkylphenols or alcohols of the formula R (OCHRlCHRl nOH in R is an alkyl, aryl, alkaryl radical, Rl is an alkyl radical or hydrogen and n is an integer from about 4 to 10 or higher.

The alkene oxide units should be at least about 40 ffi of the total molecular weight make the connection.

These compounds are produced by condensation of an alkylphenol or an alcohol with a lower alkylene oxide, such as ethylene oxide or propylene oxide, manufactured. Anionic emulsifiers to be used according to the invention are substances such as sodium lauryl sulfate, the sodium salt of the sulfonates of polyoxyethylated alkylphenols, Sodium oleyl taurate, fatty acid soaps of alkali metals, etc.

Cationic emulsifying agents particularly suitable for the present purpose are: alkyldimethylbenzylammonium chloride, diisobutylphenoxy-ethoxyethyldimethylbenzyl-ammonium chloride, Dimethylphenoxy-ethoxyethyl, dimethylbenzyl-ammonium chloride, etc .. The amount of emulsifier is generally about 0.2 to 15.0, based on the polymer, preferably about 0.5 to 5.0 weight.

A particularly advantageous emulsifying combination consists of one Mixture of about 0.5 to 10 parts each of potassium oil, hydrolyzed polyvinyl alcohol and a poly (hydroxyethylated) alkylphenol sold under the name Triton-X-100 is distributed.

The butyl rubber solution becomes a latex before homogenization by heating or flashing a sufficient amount of hydrocarbon -Solvents more advantageous (if necessary) to a polymer content of about 15 to 20, preferably from about 20 to 30% by weight concentrated. Through the concentration any foaming difficulties that may arise during the subsequent emulsion stripping process greatly reduced. Preferably the butyl rubber solution is also added prior to mixing concentrated with the emulsifying agents as mentioned above. In this case it takes place their addition preferably in a zone adjoining line 17 or 21 (not shown) and not in the alkyl halide flash drum 53.

The resulting mixture of dissolved butyl rubber, water and emulsifying agents is then in a conventional mixing device for the purpose of obtaining a raw emulsion or an impeller dispersator? pumped. This raw emulsion is then converted into a highly effective mixing machine, e.g. in a colloid mill or in an ultrasonic mixer (e.g. a Rapisonic Homogenizer). The emulsion is then either several times Recirculated or fed one after the other into about 2 to 10 homogenizing machines, to obtain a fine emulsion of the desired persistence. The ones from the The emulsion coming to the last homogenization stage is poured into a device for volatilization of the solvent, preferably in about 1 to 5 evaporators known as Turba film pumped. In this the hydrocarbon and some water are removed and a Obtained latex product of the desired concentration. This latex generally contains about 30 to 70, preferably about 40 to 60 weight percent (e.g. 50 weight percent) butyl rubber. The above-mentioned evaporators are used to achieve maximum evaporation capacity at a temperature of about 38 to 1040 and a pressure of about 0.08 to 1.4 kg / cm2 operated. The latex obtained is advantageously stored in stirred tanks kept with a warming required for the different seasons and cooling device are provided. The butyl rubber latex can also at least a part of the carbon black or other filler with which this is before vulcanization to be processed, are added. With this addition, the subsequent The introduction of carbon black is facilitated and a better carbon black dispersion is achieved overall.

Some embodiments of this invention are illustrated by the following Examples explained in more detail.

Example 1 According to the system in Figure 1, 2718 kg / h are 99 percent by weight Isobutylene and 99.3 kg / h of 95 percent by weight isoprene in line 5 with the from Line 8 coming recycle stream, consisting of 10,736 kg / h of methyl chloride and 946 kg recycled butylene, mixed. The combined streams are cooled to -95 ° (not shown) and pumped into the reaction vessel 1. To catalyze the polymerization 0.9 kg / h of aluminum chloride are used in 1812 kg / h as a catalyst solvent Serving, purified methyl chloride was dissolved, cooled to -90 ° and passed through the catalyst line 6 injected into jar # 1. The polymerization is carried out at -92 ° and yields 16.512 kg / h of a 14.6 percent strength by weight polymer slurry that through Line 7 emerges from vessel 1. This stream goes straight to the methyl chloride flash tank 53, which works at a temperature of 66 ° and a pressure of 3.5 kg / cm2. the The rate at which the vapors flow overhead from this flash drum exit through line 15 is 24. 375 kg / h. These vapors consist of 62 weight «From methyl chloride, 30% by weight from hexane and the remaining 8% by weight «From polymerization monomers with 4 and 5 carbon atoms. This stream of steam is passed into the line 50, cooled in the heat exchanger 51 to 320, whereby 9,787 kg / h of the vapors are condensed and through line 61 into the flash evaporation drum 53 returned to the content of methyl chloride in the coming from line 15 Increase head steam flow. The non-condensed vapors from the heat exchanger 51 are bypassed by the first stage compressor 54 and through the conduit 52 and 55 introduced into the alumina drying system 55.

At this stage of the process, this drying system 56 serves as a Protective chamber to remove the last traces of water. This drying system is also used the removal of trace amounts of polymerization poisons, such as Methyl alcohol, Dimethyl ether and all alcohols, such as isopropanol, which may cause deactivation of the catalyst can be used in the methyl chloride flash evaporation drum. After passing through the alumina drying system 56, the steam flow is at a Speed of 14,591 / h in the compressor 57 to 2 a pressure of 11.6 kg / cm2 compressed and through line 38 to fractionation column 37 for purification of the methyl chloride pumped. This column, which has 50 fractionation trays, is working with a high reflux ratio of 10 to 1 and discharges (through line 39) the top stream 1812 kg / h of highly purified methyl chloride. The one from this column Exiting bottom flow of 28,780 / h passes through line 42 into a second Fractionation column 41, which is provided with 20 fractionation trays. From this column 11,189 kg / h of methyl chloride and 946 kg / h of C4-olefins as top stream through line 8 deducted. The mentioned C4-olefins are in a purity of 94% by weight Isobutylene occurs when 362 kg / h of C4 olefins are discharged from column 41 as the bottom stream and through line 43 to a third 50 tray fractionation column (not shown) are introduced. The through line 43 from the fractionation column The residues that emerge consist of 362 kg / h of C4 olefins and 68 kg / h of C5 hydrocarbons (91 weight isoprene) and 666 kg / h hexane. The C4 and C5 hydrocarbons are, as described above, drained from the polymerization plant and introduced into the usual plants for the extraction of isobutylene or isoprene, During the 666 ks / h witches won and from line 43 (duroh corresponding, not pipe connections shown) in line 26, through the condenser 44, the settling tank 45, line 48, pump 49, and line 9 finally into the methyl chloride flash drum 3 can be returned.

A 10 percent by weight is produced in the methyl chloride flash evaporation drum 53 Butyl polymer solution in the hexane used as solvent. Is the working temperature 660 and if it is high molecular weight butyl rubber, the solution has a Staudinger molecular weight of 86,000 (i.e. one based on viscosity measurements certain average molecular weight of 1,270,000) and a viscosity from 1000 centistoke.

This flow of 22850 kg / h, which is a 10 percent by weight solution of butyl rubber, consists mainly of hexane as a solvent, but also contains 8.0 or 2.3% by weight of methyl chloride and polymerization monomers with 4 and 5 hydrocarbons. This solution, based on the hexane, per million Parts contains 125 parts of water, is fed directly through line 10, pump 11 and lines 12, 18 and 19 inserted into hexane flash drum 20, which works at a temperature of 790 and a pressure of 0.7 kg / cm2. The solution is atomized by means of steam from the atomizer 24 and 1814 l / minute return water from the finishing zone (not shown) are also by conduction 23 is pumped into the hexane flash drum 23. Under these conditions will be a 2 percent by weight butyl rubber slurry in water obtained and at the same time (in connection with the vacuum wiper 29, which works at 60 ° and 0.28 kg / cm2) all remaining methyl chloride, 4 and 5 hydrocarbon monomers and the hexane used as solvent is flashed off as a head stream. In this Example are 1943 kg / h of IVIethylchloride, 562 kg / h of C4 and monomers, 18.958 kg / h of hexane and 1359 kg / h of steam as overhead stream in line 26 flash-evaporated and condensed in the condenser 44 and cooled to 47 °. The water and the hexane are then separated in the settling tank 45. Hexane hydrocarbon phase above from the sedimentation tank 45, the fractionation system (not shown) is fed at 665 kg / h recycled hexane, as well as 9,785 kg / h condensed vapors from the line 62 (not shown), which are supplied by the cooling device 51 by the line 61 leads into the methyl chloride flash evaporation drum, combined. If the pressure in the methyl chloride flash drum increases to over 11.2 kg / cm² so no compressors are necessary to condense the as a diluent used to facilitate vaporized methyl chloride by cooling water.

Example 2: In a copper vessel with a diameter of 100 mm, which is cooled from the outside by means of liquid ethylene at atmospheric pressure to -90 ° became a rubbery butyl copolymer of isobutylene and isoprene produced using 960 cc (910 g) of methyl chloride as the diluent and the reactants from 9.3 ccm (6.2 g) isoprene and 308 ccm (200 g) Isobutylene passed.

A fine stream of catalyst solution (0.244 g AlC13 per 100 ccm methyl chloride used as a catalyst solution) was so long in the vigorous Cold cold feed sprayed up to 90% of the olefin feed in polymer were converted). For this purpose, there was a catalyst solution at a rate of 16.8 ccm / minute five minutes necessary. After all the catalyst has been added and completed After the polymerization, the cold slurry was divided into three equal parts and treated each part in different ways.

Experiment A.

The cold butyl rubber slurry was stirred into vigorously poured hot water (900) containing 1.82 g of zinc stearate as a non-tackifier and 0.45 g as an anti-oxidant, it uses phenyl-ß-naphtylamine (i.e., based based on the weight of the dry copolymer, 1 or 0.25% by weight). This were the methyl chloride and any unreacted monomers removed. The resulting white interpolymer was filtered, followed by wet Polymer crumbs received, which were later dried on a roller at 1500 for 10 minutes became.

Attempt B.

The cold butyl rubber slurry in methyl chloride was 91 g Sterling "R" (a semi-rigid furnace black, i.e. SRF carbon black) was added before the former was poured into vigorously stirred hot water (900) containing 1.82 g of zinc stearate and 0.45 g of phenyl-ß-naphthylamine.

As was found after removal of the solvent, there was something Soot suspended and floated on the water.

During the filtration through which most of the water is removed it was found that the carbon black was not bonded well to the rubber. This wet, black copolymers later dried almost completely over 10 minutes on a roller at 1500.

Experiment C.

In this experiment, the cold butyl chewing gum slurry was used in Methyl chloride treated according to the invention, i.e. it was brought into 2,000 cc of hexane, the methyl chloride being removed by heating to 0 °. At this moment 91 grams of Sterling "R" -Ru # (SRi; i) was added. This became complete and instantaneous processed into it by stirring by hand. For the purpose of evaporation as a solvent The hexane used was then placed in hot water (900) 3 which contained 1.82 g of zinc stearate and 0.45 g of phenyl-ß-naphthylamine.

Steam was added to accelerate evaporation. A stable slurry resulted which, in contrast to Experiment B, neither floating on the water, still unbound on the surface of the : Tried copolymers contained soot particles. Even the water was easier to filter off than in experiment B. The wet polymer was later dried on a roller at 150 ° for 10 minutes.

Hot grinding of the polymers from experiments A, B and C gave the following: The hot milling of the polymer from Experiment A was normal. However, it was very difficult to evaporate the water and produce a strip of the polymer of experiment B. The hot milling of the wet polymer from Run C of this invention was found as the lightest. This was almost immediately after the fourth squeeze gained a strip of the excess water. The dry white polymer off Experiment A weighed 186.6 g, the black polymer from Experiment B 259.4 g and the black Polymers from Experiment C 262.4 g. The two black charges showed the same Mooney viscosity at 1000 (large rotor) for 5 minutes, namely 85 each time, while the Mooney viscosity of the white polymer from Experiment A was 61.

Then in the usual manner on a roller with a roller temperature out of 500 one SRF carbon black (i.e.

91 g Sterling "R") worked into the polymer from Experiment A. The three black polymer blends were then cured on a cold roller added, whereby the following basic composition was followed: Parts by weight: Polymeric 100 sterling "R" (SRF carbon black) 50 zinc oxide 5 sulfur 2 Tuade (tetramethyltniuram disulfide) 1 From the data of the processed, non-vulcanized butyl rubber mixtures found that in polymer blend C of this invention, the carbon black disperses much better was than in the polymer mixtures A or B.

Discs (15 x 15 x 1.9) of each mixture were given for 40 minutes Vulcanized in 1520. The resulting vulcanizates had the following physical properties: Polymer made of tensile strength modulus of elasticity up to 300% elongation kg / cm tension, kg / cm2 Elongation,% Trial A 127 900 530 Trial B 132 910 550 Trial C 146 990 610 Aus The above values show that the inventive method (experiment C) to a better carbon black dispersion and vulcanizates with higher tensile strength, larger Young's modulus and elongation resulted better than the other known ones in trial A and B applied method. Example 3: A copolymer consisting of about 60 weight percent isobutylene and 40 weight percent styrene, was in the form of a slurry prepared in methyl chloride according to the invention in a hydrocarbon solvent dissolved and processed with asphalt in the dissolved state.

According to the method of the system in Figure 1, 1359 kg / h are 99.3 percent by weight Isobutylene and 906 kg / h of 99.2 percent by weight styrene in line 5 with the from Line 8 coming return stream of 10.283 kg / h of methyl chloride mixed. the combined streams are cooled to 950 and added to vessel 1. Although / the If only one reaction vessel is shown in the illustration, the process can also be performed under Use about 2 to 5 (e.g. 3) in a row - * n of the following Reactors are run through different stages, with the conversion in increased at each stage. The procedure is carried out in this way over different stages out, so the total conversion can be increased and products with higher Molecular weight can be achieved. To catalyze the copolymerization are 3.6 kg / h of aluminum chloride, which is used as a catalyst in 1812 kg / h of purified Methyl chloride are dissolved, cooled to -900 and passed through catalyst pipe 6 in Vessel 1 injected. The polymerization is carried out at 920 to give 2174 kg / h of a 15.1 weight percent interpolymer slurry supplied by conduit 7 exits from vessel 1.

This stream goes directly into the methyl chloride flash evaporation drum 53, which works at a temperature of 650 and a pressure of 3.5 kg / cm2. the Speed of the top stream from this flash evaporation drum through conduit 15 escaping vapors is 17,395 kg / h. The vapors are 76.3% by weight % from methyl chloride, 23.1% by weight from hexane and the remaining 0.6% by weight % from isobutylene and styrene monomers. Said steam flow is in line 50 led, cooled in the heat exchanger 51 to 32 °, producing 4530 kg of fumes per hour are condensed and entered through line 61 into the flash evaporation drum 53, the methyl chloride content in the overhead stream from line 15 Increase steaming. The non-condensed vapors from the heat exchanger 51 are bypassing the first stage compressor 54 and through line 52 and 55 in the clay drying system 56 initiated. Serves at this stage of the procedure this clay drying system as a protective chamber to remove the last traces of water.

In addition, 56 trace amounts of polymerization poisons, such as methyl alcohol, dimethyl ether or the like. Removed, so that such poisons, if if they are used, they are introduced into the reaction vessel in precisely controlled quantities can be.

After passing through the alumina drying system 56, the steam flow at a speed of 12865 kg / h in the compressor 57 to a pressure of 2 compressed 11.5 kg / cm2 and through line 38 into the fractionation column 37 initiated to purify the methyl chloride. This provided with 50 fractionation trays The column operates at a reflux ratio of 10 to 1 and discharges as an overhead stream in line 39 1812 kg / h of highly purified methyl chloride. The one emerging from this column Bottom stream of 11,053 kg / h is passed through line 42 into a second, with 20 fractionation trays provided precautionary column 41 initiated. This column produces 10,283 kg / h Methyl chloride and 22.65 kg / h C4 - olefins, which mainly consist of isobutylene, discharged into line 8 as an overhead stream. The exiting through line 43 Residues from fractionation column 41 consist of 22.65 kg / h C4 olefins (mainly Isobutylene), 45.35 kg / h C8 hydrocarbons (predominantly, e.g. 90% by weight % from styrene) and 680 kg / h hexane. These C4 and C8 hydrocarbons are made from withdrawn from the mixed polymerisation system and transferred to the usual extraction systems for isobutylene or for styrene, while 680 kg / h of hexane is obtained and from line 43 in line 26 (through the corresponding pipe connections, not shown) the condenser 44, optionally through the settling tank 45, the line 48, the pump 49 and line 9 finally into the methyl chloride flash evaporation drum 53 to be returned.

A 10 is produced in the methyl chloride flash evaporation drum 53 % solution of isobutylene and styrene in the hexane used as solvent. This stream, which has a speed of 21,744 / h, consists primarily of the Hexane used as a solvent, but also contains about 9.0% by weight of methyl chloride. This solution, the 2,174 kg / h copolymer and, based on the hexane, 125 parts Water per million contains is withdrawn through line 17 at 45.300 kg / h Asphalt mixed and then directly through lines 18 and 19 into the hexane flash drum 20th pumped, which works at a temperature of 73 ° and a pressure of 0.7 kg / cm2. Under these conditions, an essentially pure mixture of isobutylene-styrene polymers is obtained obtained in asphalt and at the same time (in connection with that at 60 ° and 0.35 kg / cm2 (abs.) Working vacuum stripper 29) all of the remaining methyl chloride and hexane used as solvent flashed overhead. In this example 1948 kg / h of methyl chloride and 19,026 kg / h of hexane are used as the top stream in line 26 flash evaporated, which then condensed in condenser 44 and cooled to 480 will.

The hexane is then recycled from the (not drawn) fractionation system, as well as with 4,500 kg / h condensed vapors (not shown) from line 62 leading from chiller 51 through line 61 into the methyl chloride flash drum 53 leads, mixed.

Similar results can be obtained when the inventive Procedure carried out according to the previous example, but isobutylene as sole monomer and polyisobutylene as that in the hydrocarbon solvent the substance to be dissolved is obtained.

Claims (2)

Claims: -I. Veriahren for continuous compounding of isoolefin polymers, namely nomopolymers, of C4 to C8 isoolefins, mixed polymers from C4 to isoolefins with C4 to C14 multiolefins and copolymers of C4 to C8 isoolefins with a vinyl aromatic hydrocarbon, including among others G e -k e n n z e i c h e t that one is a slurry of polymer in a a non-solvent, liquid reaction diluent consisting of a C1 to sz3 alkyl halide at a temperature above the boiling point of the diluent with a Bringing inert C to C10 hydrocarbon solvent into contact with the diluent to evaporate and to dissolve the polymer in the solvent, whereupon the polymer by mini-work of a colile wetter toffmaterials, such as e.g. a paraffin wax, a mineral lubricating oil or mixtures thereof in this solution with these additives compounded, the solution containing the modified polymer at a temperature above the boiling point of one solvent with a second non-solvent, aqueous Brings medium into contact that has a higher boiling point than the solvent, to evaporate the solvent and a second slurry of the polymer to form in the second nonsolvent, and then the modified polymer wins from this second slurry. 2. The method according to claim l, characterized in that as Hydrocarbon material incorporated asphalt.