DE1934905A1 - Process for the production of thermoplastic masses - Google Patents

Description

1934805

CHEMISCHE WERKE HÜLS AG 4370 Mari, July 9, 1969

- Patent Department - 2068 / J

Our mark O.Z. 2394

Process for the production of thermoplastic masses

The invention relates to a method for producing thermoplastic Masses under polymerization of ole fi ns according to the low pressure process.

It is known that natural or synthetic bituminous compounds are used for the production of roofing felt, road surfaces or cable casting compounds. If compatibility is given, it does not appear to be ruled out to produce such compositions by mixing various thermoplastic, rubber-like, oily or otherwise amorphous substances. The production of such mixtures can, however, be very difficult and expensive due to the relatively high viscosities and the stickiness of some of the starting materials. We must the substances to temperatures of about 100 ⁰ C or höhar "heat where they often discolored and partially break down? The commercial form of many of these materials can also be a nuisance, namely blocks of around 25 kg that have to be crushed first.

There is therefore interest in a process that makes it possible, for example, starting from oC-olefins , to arrive directly at compounds of the type mentioned.

This object is achieved according to the invention in that one the polymerization in the presence of higher molecular weight hydrocarbons executes and this in the processing of the poly-

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merisates left in the product.

The claimed method is accordingly in essentially a modification of the olefin medium pressure polymerization according to Ziegler.

Propylene, butene-1, βκβη-1, methylpentene-1, etc. are suitable as of-olefin. Any desired mixtures, for example W of propylene and butene-1, can also be used, as well as mixtures which, in addition to one or more of the c ^ -olefins mentioned contain a shorter-chain olefin (ethylene) or longer-chain olefins (octene-1) or a diene (dicyclopentadiene). Finally, it is also possible to use mixtures which contain olefins with non-terminal double bonds, for example 2-butene. This makes it possible to use cheap C ^ cuts from petroleum cracking processes which contain, for example, about 50% butene-1, 40 % butene-2 and 10 % butane. So you can also work in the presence of saturated hydrocarbons. Preference is given to 1-butene or gas mixtures containing it.

Suitable higher molecular weight hydrocarbons are paraffins, in particular those with a viscosity of 200 to 5000 cP, preferably 2000 cP to 3000 cP / 20 ° C., including heating oils ι also paraffin wax «, especially with a Melting point from 30 to 100 C, preferably from 40 to 80 G; furthermore all kinds of bitumen, e.g. bitumen 300, bitumen 200, blown bitumens such as bitumen .75 / 30, synthetic bitumens, especially with a softening point of 20 to 175 C, preferably 25 to 75 C; also raw bitumina and distillation residues from petroleum distillation as well as Versataittbitümina with a lower pour point, and finally oily, low-sugar products atactic olefin polymers with a viscosity of 200 to 100 OpO cP / 20 ° C, as you would during polymerization

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of 1-butene, isobutene, 2-butene, 4-methylpentene-1, propene or dodecene and their mixtures, for example on Friedel-Crafts catalysts such as AlCl ₃ , FeCl ₃ , SbCl ₅ , SnCl ₄ , TiCl ₄ , ZnCl- , BF ₃ or BF.-etherate. Bitumen is preferred; the bitumen can also be blown. All of these higher molecular weight hydrocarbons should be as free as possible from active oxygen and sulfur compounds. Therefore, if necessary, these compounds are removed beforehand, expediently by adsorption on aluminum oxide or active silica or by hydrogenation on tungsten and molybdenum sulfide contacts.

The polymerization is carried out in a manner known per se with the aid of Ziegler catalysts, which preferably have a low stereospecificity. Mixed catalysts made from compounds of titanium, vanadium, zirconium, niobium such as titanium tetrachloride, vanadium tetrachloride, vanadium oxychloride on the one hand and aluminum compounds on the other hand, e.g. aluminum trialkyls, aluminum dialkyl hydrides and aluminum alkyl halides such as aluminum triethyl, aluminum tributyl, aluminum di-iaobutyl-tripro-aluminum chloride, diethylaluminum chloride, are suitable for this purpose. Ethyl aluminum sesquichloride. Even with mixtures of titanium tetrachloride with vanadium tetrachloride or vanadium oxychloride as heavy metal components, poly-O-C-olefins with low crystallinity are obtained in good yield. As a result of the excellent compatibility of polybutene-1 and its copolymers, polybutene-containing products can also be produced with contacts of higher stereospecificity, for example with TiCl ₃ or 3TiCl ₃ «AlCl ₃ and C ₂ Hc) ₃ or Al (C ₂ Hc) ₂ Cl will.

The mixed catalyst constituents are used in a manner known per se in a heavy metal: aluminum molar ratio of 1: 0.3 to 1:12, preferably 1: 0.5 to 1: 4, in particular 1: 1 to 1: 2. The catalyst concentration, based on the total batch, is about 0.1 % to 5 %, preferably

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0.2 to 2.5 %.

A temperature range of 20 to 200 ° C, in particular from 50 to 150 ° C.

It is possible to carry out the polymerization alone in the presence of the higher molecular weight hydrocarbon. But you can also use additional solvents such as propane, butane, pentane or hexane in amounts of 5 to 100 %, based on the higher molecular weight hydrocarbons, for example, in the case of high viscosity feedstocks, such as higher viscosity bitumen, in particular the blown and synthetic bitumen, which To lower viscosity through the added monomers and low-boiling saturated hydrocarbons, which can easily be removed again after the polymerization. In the polymerization of butene-1, the inexpensive C ₄ ~ cuts, which contain approx. 50% butene-1, approx. 40 % butene-2 and approx. 10 % butane, have proven particularly useful. The butene-2 is practically inert towards the Ziegler catalysts and reduces the viscosity of the polymerization batch when the butane is used as the solvent.

It is expedient to keep a pressure during the polymerization P from 1 to 20, preferably 2 to 5 at.

You can use the submitted higher molecular weight hydrocarbon generally in a wide proportion with polymer Mistake. The tolerance limits depend, for example, on Art and crystallinity of the polymer and the type and molecular weight of the higher molecular weight hydrocarbon.

The products containing paraffin oil, for example, show one , very good compatibility of the oil with the poly-of-olefin »' In these products, the oil content does not exude. Even with diethyl ether, it is difficult to extract. In contrast, products with particularly good compatibility are obtained in the polymerization of 1-butene. Polypropylene

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containing products are only compatible if the polypropylene content is more than 60 % soluble in boiling heptane. The compatibility can be significantly improved by copolymerizing propene with other olefins, for example Athens, butene-1, 4-methylpentene-1. . .

In order to be able to achieve the desired effect of improving the quality, e.g. increasing the softening point of the bitumen to about 20O ⁰ C, a higher concentration is required for products with a low crystalline content of the poly-olefin component, e.g. 40 to 80 %, in particular 50 to 60% than for products with a higher crystalline content. With these products, the same effect can be achieved with less effort.

That too has the same influence as the crystalline part Molecular weight of the poly-of-olefin. Since, however, higher crystalline and also higher molecular weight poly-tff-olefins are poorer Compatibility, the crystallinity and the molecular weight are limited. They are from product see below Product different. With the very well tolerated polybutene are still polymers with molecular weights above 1,000,000 useful, also with the butene copolymers. With polypropylene the tolerance limit of the higher crystalline polymers is around 100,000 molecular weights.

According to a particular embodiment of the invention, a suitable ole-olefin or an olefin mixture containing it can first be converted into an oil with the aid of a Friedel-Crafts catalyst subsequent polymerization to Ziegler ₀ .for which the. same olefin or Olsflngemisch used kmnn.g werä®si "as

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higher molecular weight hydrocarbons are used. ',

The polymerization products are worked up by after the polymerization comes into contact with water or an alcohol as methanol decomposes, the polymerization product on a suitable flameproof separating device and that Washes the product with water or methanol. The laundry can open . the separation device. Then relax ™ and dried or distilled, if higher-boiling solution, medium are used. The expansion is carried out before the separation if a pressureless separation device is used will.

Work-up can also be carried out in a simple manner by adding a metal oxide or a metal hydroxide, e.g. lime, and optionally subsequent filtration take place. Working up can continue to take place with steam.

The products produced according to the invention are distinguished by excellent and new properties. When a larger amount of 1-butene is polymerized in a smaller L · amount of a polybutene oil, a viscous compound is obtained which is suitable as a sealing compound, as an additive to road paving compounds and for the production of roofing felt. If a small amount of 1-butene is polymerized in a larger amount of a polybutene oil, a highly viscous oil is obtained which is suitable as an additive to roller oils and as a viscosity improver for lubricating oils. If butene is polymerized in the same amount of a butene oil, a highly viscous compound is obtained which is suitable as a cable potting compound.

The properties of the products produced according to the invention are, however, also very surprising. For example, a polymerization product according to the invention consists of equal parts of bitumen (softening point 40 ^QG ) and amorphous

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Polybutene (which in the absence of bitumen polymerized a softening point of 105 ⁰ C would have) a softening point of 200 ° C.

Therefore, the new products are ideally suited as sealing compounds, Cable casting compounds, road paving compounds or as an additive for road paving compounds and as a viscosity improver for lubricating oils.

example 1

6.6 parts by weight of a paraffin wax with a melting point of 60 ⁰ C are melted in a 40! -Druckkessel with a stirrer at 70 ⁰ C. 10 parts by weight of 1-butene and 2 parts by weight of propene and then 0.026 part by weight of titanium tetrachloride, 0.012 part by weight of vanadiurooxychloride and 0.031 part by weight of aluminum triethyl (as a 20% solution in butane) are added under nitrogen. The polymerization takes place at 90 ^° C. with stirring within 16 hours. The contact is then decomposed under the action of an Ultra-Turrax stirrer with 5 parts by weight of methanol and the solid is separated off on a suitable separating device, for example a suction filter. The product washed with a further 5 parts by weight of methanol is dried. 11.8 parts by weight of a colorless product with a ^ _re ^^ t of 0.5, which is well suited for the production of cable potting compounds, are obtained.

Example 2

4.5 parts by weight of a highly viscous mineral oil with a viscosity of 200 cSt at 50 ° C. are placed in a pressure-resistant 40 l polymerization kettle. A contact of 0.026 parts by weight of TiCl ₄ * 0.031 parts by weight of Al (C ₂ H ₅ ) ₃ (as a 2096 solution in butene) is added. Then be

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polymerized at 90 ° C 12 parts by weight of a mixture of 56 % butene-1, 36% butene-2 and 8 % butane. After a polymerisation time of 20 hours, the contact is decomposed with 5 parts by weight of methanol. The polymerization batch is pumped around for one hour at 90 ° C. using a Reaktron device. The contact is then washed out in a countercurrent washer with 25 parts by weight of water. The polybutene-containing product is separated off, largely freed from the unconverted 1-butene, 2-butene and butane by letting down the pressure and dried. 10.6 parts by weight of a polybutene-containing product with a τ? - Value of 0.4, which is 62.2% soluble in boiling ether. The oil used does not exude even after long periods of storage.

Example 3

2 parts by weight of bitumen B 200 with a softening point of 40 ° C. are placed in a 40 liter stirred tank and heated to 50 ° C. 12 parts by weight of a C ^ cut with 54 % butene-1, 23% trans-butene-2, 13% cis-butene-2, 8% n-butane and 2 % ieo-butane are added. 0.2 part by weight of titanium tetrachloride and then 0.18 part by weight of aluminum triethyl (in 0.9 part by weight of butane) are pressed into the kettle via a lock with dry, oxygen-free nitrogen. The polymerization is carried out at 50 ° C. with stirring. After decomposition with 2.5 parts by weight of methanol, outgassing of the unreacted butene or butane and separation of the methanol, 3.8 parts by weight of a product are obtained which has a softening point of about 220.degree.

Instead of 2 parts by weight of bitumen B 200, 2 parts by weight of blown bitumen 75/30 Ep (R and K) 75 ° one, according to the information in Example 3, 4.0 Ge

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* '- CS:

parts of a product with a softening point of approx. 215 C. Softening points will be at the same level when using bitumen 300 and scrap bitumen 500.

If the polymerization is carried out without the addition of bitumen, so a largely atakic polybutene is obtained with a softening point of 115 C.

Example 4

20 parts by weight of a C. cut with 52 % 1-butene, 24 % trans-butene-2, 16 % cis-2-butene and 8 % butane are placed in a 40 l stirred tank. 0.1 part by weight of aluminum chloride - anhydrous - is added via a lock * The polymerization proceeds with cooling at 10 ° C. After polymerization, the aluminum chloride is in a counter ^ - current scrubber separated washed with water, the washed ^ polybutene and he removed in a DÜnnschidiuardampf at 10 mm Pig and 120 ⁰ C of low boilers. A polybutene oil which has a viscosity of 685 cP at 20 ° C. is obtained in a yield of 75 % (based on butene-1 and butene-2).

5 parts by weight of this polybutene oil are placed in a pressure-tight polymerization kettle. A contact of 0.015 part by weight of titanium tetrachloride and 0.057 part by weight of a 20% strength solution of aluminum triethyl in butane is added. Within half an hour, 10 parts by weight of butene-1 (99 5 & Lg) were run in at 120 ° C. After a further polymerization time of 5 hours at 120.degree. C., the contact is decomposed with 4 parts by weight of methanol and worked up as described in Example 2. 9.8 parts by weight of a product with a ^ _{re (} q "" ^{value of} 0.3, 63.4 % soluble in boiling ether) are obtained.

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Example 5

20 parts by weight of bitumen 300, 18 parts by weight of propene, 15 parts by weight of Athens, 0.3 parts by weight of dicyclopentadiene O, 3 parts by weight of vanadium oxychloride and 2.0 parts by weight of ethylaluminum sesquichloride are continuously run every hour at 50 ° C. into a pressure-resistant 300 l stirred tank vessel with level control Kettle, the polymer solution or suspension is continuously fed through a shut-off device controlled by the stand into a second container, in which the product is freed from chlorine-containing impurities and unreacted monomers with superheated steam and then with nitrogen. Per hour is obtained 46 parts by weight of a product having a softening point of 200 ° C _r which is suitable as an additive to pavement materials and for the production of roofing felts.

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Claims (1)

1934805 OZ 2394 9.7.1969 Claims 1. Process for the production of thermoplastic masses under Polymerization of olefins by the low pressure process, characterized in that the polymerization in the presence of higher molecular weight hydrocarbons executes and leaves this in the work-up of the polymer in the product. 2. The method according to claim 1, characterized by that / that paraffin oil is used as a higher molecular weight hydrocarbon. 3. The method according to claim 1, characterized in that is called a higher molecular weight hydrocarbon paraffin wax used. 4. The method according to claim 1, characterized in that bitumen is used as a higher molecular weight hydrocarbon, 5. The method according to claim 1, characterized in that an oily olefin polymer is used as the higher molecular weight hydrocarbon. 0 09883/20 51 - 12 - OZ 2394 July 9, 1969 6. The method according to claim 1 to 5, characterized by ,, that propylene is used as the oC-olefin. 7 "Method according to claims 1 to 5, characterized in that butene-1 is used as the olefin. 8. The method according to claim 1 to 7, because you r c h g e k e η η ζ e i c h net that one uses a mixture as o ^ -olefin which is also shorter or shorter longer chain Q ^ olefins, isoolefins and / or olefins with a non-terminal double bond. 9. The method according to claim 1 to 8, dad u r eh e k en η ζ ei c h η e t that the polymerization is carried out in the presence of dienes. 009883/2051