DE1570600C - Process for the copolymerization of alpha olefins with omega halogen alpha olefins - Google Patents

Description

3 4

The preparation of the inventive co- an alcohol, for. B. isopropanol, n-butanol, or polymerization-suitable mixed catalyst can be a ketone, such as acetone. After washing with water, for example, the polymer powder is filtered off, more alkali metal halide, diethylaluminum monochloride and times with gasoline, methanol and acetone washed TiCl ₃ , that z. B. by reducing the TiCl ₄ to 5 and finally dried. The dispersant can be inorganic by means of aluminum metal or also by the usual route by means of steam-hydrogen or by organic means. distillation can be removed.

organoaluminum compounds, such as A1 (C ₂ H _S ) ₃ , The ge-Al (C ₂ H ^) ₂ Cl, Al ₂ (C ₂ Hs) ₃ Cl ₃ , Al (C ₂ H ₅ ) Cl ₂ The copolymers obtained can, according to the Mehat, be mixed in an inert solvent in the polymerization io methods, as are customary for olefin polymers. The ratio of aluminum to z. B. after injection molding or extrusion blown alkali halide can be between 4: 1 and 1: 2; process, are processed to moldings, but preferably one works at a ratio of 2: 1 to 1: 1. The following examples serve to illustrate. The ratio of aluminum to the present invention, but excluding titanium, can be between 10: 1 and 1: 1; However, if you want to restrict preference, you choose a ratio of 3: 1 to
1.5: 1 /.,. ;

The catalyst concentration in the Polymerisa- Example 1

tion solution carries 0.1 to 100 mmol TiCl ₃ / l dispersion _a ) catalyst position

lubricant, preferably 5 to 25 mmol TiCl ₃ / l Disper- 20. . ■

greed. In 1.51 of a flushed with pure nitrogen

The catalyst combination used according to the invention freed from water, oxygen, sulfur and olefins has in the copolymerization of "oils" petroleum fraction boiling from 180 to 200 ° C are finen with ω-halo-α-olefins compared to the known 490 ml (= 2.2 Mole) ethylaluminum sesquichloride ge process various benefits. The addition of 25 dissolves and a solution of 220 ml (= 2 mol) of titanium alkali halides to the catalyst mixture vertetrachloride in 30 ml of the above-mentioned petroleum fraction is avoided, primary reactions between the ω-halos are added dropwise at 0 ° C. in 3 hours. The resulting, gen-α-olefins and the aluminum organyls. Furthermore, deep red dispersion is nachkann 2 hours at 0 ⁰ C is stirred with their wide variety of "olefins, and further stirring for 5 hours at individually or in combination with co-halogen -« - olefins 30 110 ° C heated. After cooling to room temperature, copolymerize and not only, as in the Belgian one, the resulting _{TiCl 3} precipitate is allowed to settle in patent specification 622 213, ethylene or others and the supernatant, clear solution is siphoned off. One α-olefins only together with ethylene. On the other hand, the contact washes .the contact about ten times with stirring is achieved with the higher space-time ratio used according to the invention with the petroleum fraction and catalyst combinations described above. The titration of the increase in stereospecificity hydrolyzed with water than when using washing solution finally results in a content of conventional catalysts or catalyst combinations of 5 mAtom Cl / 1 contact dispersion, combinations with the addition of pyridine. For this reason, one is able to work with lower catalyst 40 b) copolymerization of 5-chloropentene-1 with per-concentrations than has been the case up to now. pylene (interpolymerization) process that has become known was possible. Man,.

in this way polymer solutions can be obtained, which are due to 4.7 ml (= 40 mmol) under pure nitrogen

its low content of ash-forming substances diethyl aluminum monochloride and 3.0 g (= 40 mmol)

and because of the significantly lower amorphous poly- 45 KCl in 21 absolute heptane and heated to 50 ° C.

Have merizat parts processed more easily. Then 5.2 g (= 50 mmol) of 5-chloropentene-1 are added

The inventive copolymerization of the "oils" and, after a further 10 minutes, 25 ml (= 20 mmol

fine with ω-halo-a-olefins can be used as a block or TiCl ₃ ) of the contact described under 1, a); to.

Ordinary copolymerization with random distribution. Propylene is then passed into the for 5 hours

division of the components in suspension by 50 degrees as it is consumed, with a quantity

be performed by mixing the monomers once. 10% exhaust gas is complied with,

or several times in a row, separately or together. After 5 hours the polymerization is through

the dispersion of the polymerization catalyst is stopped by adding 50 ml of n-butanol, 30 minutes

an aliphatic, alicyclic or aromatic stirred up to 50 ° C and five times with 500 ml 50 ° C

Hydrocarbon, e.g. B. n-heptane, η-hexane, cyclo- 55 warm, oxygen-free water. Man

hexane, cyclopentane, toluene, chlorobenzene, anisole filtered from the fine, colorless polymer powder,

or well-purified mineral oil fractions. then washes with η-hexane, five times each time

The polymerization can, however, also take place without a solution of methanol and acetone and finally dries

medium in the monomers themselves are carried out at 70 ° C in vacuo. ■. . .

the. 60 213 g of a crystalline polymer remain behind

The polymerization takes place at temperatures between. powder with a iyspez / c value of 6.8 (30And measured 150 ° C, vorzugsweise40bis 8O ⁰ C, O, l ° / _O performed. percent solution of decahydronaphthalene at It can at normal pressure slightly elevated 135 ⁰ C or more). The space-time yield is 22.5 g / l · h, pressure, preferably 1 to 10 atmospheres, of which 94.7% polymerizes crystalline modification. From become. The polymerization time is usually 65 mother liquor, 12 g of amorphous and low molecular, oily constituents for 0.5 to 15 hours, preferably 2 to 8 hours, can be isolated. Details until the desired degree of polymerization is achieved. the polymerization and properties of the copoly- The polymerization is terminated by adding .merisate are listed in the table. .; ..; .. ·

Example2

Copolymerization of 11-chlorundecene-1 with propylene (periodic copolymerization)

4.7 ml (= 40 mmol) of diethylaluminum monochloride and 3.0 g (= 40mmol) of KCl in 21% of absolute heptane are added under pure nitrogen and heated to 50 ° C. 25 ml (= 20 mmol of TiCl ₃ ) are then pipetted into the solution. of the contact described under 1, a) and then introduces propylene for 30 minutes as it is consumed, maintaining an amount of 10% exhaust gas. The propylene feed is then stopped and nitrogen is passed in until all of the unconsumed propylene has been removed from the polymerization vessel (about 10 minutes). 9.4 g (= 50 mmol) of 11-chlorundecene-1 are now added under a nitrogen atmosphere and kept under nitrogen for 1 hour. Propylene is then passed in for 30 minutes as it is consumed (10% exhaust gas). The propylene is then again expelled with nitrogen, 9.4 g (= 50 mmol) of 11-chloroundecene-1 are added, the mixture is kept under nitrogen for 1 hour and then polymerized for a further 2 hours, with propylene being introduced as it is consumed becomes (+ 10% exhaust gas).

The polymer is worked up as under 1, b). This gives 137 g of a crystalline polymer powder having a ^ sp / c value of 5.3 (measured in 0, l% ig ^he solution of decahydronaphthalene at 135 ° C). The space-time yield is 15.5 g / l -ih, of which 88.4% is crystalline modification. 18 g of amorphous and low molecular weight, oily constituents can be isolated from the mother liquor.

Example3

Copolymerization of 5-chloropentene-l with ethylene (mixed polymerization)

4.7 ml (= 40 mmol) of diethylaluminum monochloride and 3.0 g (= 40 mmol) of KCl in 21 absolute heptane are added under nitrogen and the mixture is heated to 50 ° C. Then 5.2 g (= 50 mmol) of 5 are added to the solution -Chlorpentene-l and after a further 10 minutes 25 ml (= 20 mmol TiCl ₃ ) of the contact described under 1, a). 20 l / h of ethylene and 5 l / h of pure nitrogen are then passed in for 5 hours. The work-up is carried out as under 1, b).

This gives 194 g of a crystalline polymer powder having a ?? sp / c value of 10.7 (measured in 0, l% ig ^he solution of decahydronaphthalene at 135 ° C). The space-time yield is 19.4 g / l - h. The copolymer has a density of φ ²⁰ = 0.9367 and contains 1.0 percent by weight of 5-chloropentene-1.

Examples 4 to 10

Copolymerization of other ω-halogen-a-olefins with propylene. The polymerization is carried out according to Example 1, b) or 3, the work-up according to Example 1, b). The details of the polymerization and properties the polymers are listed in the table.

Examples 11 and 12

The copolymerization of 5-chloropentene-1 with propylene was carried out as indicated in Example 1, b); however, instead of 40 mmol of KCl, 40 mmol of RbCl (example 11) or 40 mmol of CaCl (example 12) added. Details can be found in the table.

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Claims (2)

1 2 combinations of TiCl3, aluminum trialkyls and / or patent claims: halogen-containing organoaluminum compounds and alkali halides, where the MoI- 1. Process for the production of copoly- ratio aluminum compound to alkali halide merizates of α-olefins with ω-halogen-α-ole-5 from 4: 1 to 1: 2 and the molar ratio of aluminum fins according to the Ziegler low pressure process, connection to titanium compound 10: 1 to 1: 1 characterized in that one should wear. 99.9 to 80 percent by weight "olefins of the general invention, both the pure aluminum mean formula CH ₂ == CH - R, where R = H, niumorganyl alkali halide complexes, which according to Alkyl, aryl or Alkyarl means, can be prepared with 0.1 to io known processes, or 20 percent by weight of tu-halogen - «- olefins of general mixtures of. organoaluminum compounds common formula. be used with alkali halides. After _, "_ _{Ru (ru} ν _r " _γ methods according to the invention are preferred CH ₂ - CH - (.CH ₂ ) ,, - CH ₂ - Λ, «-olefins of the general formula CH ₂ = CH - R, where M = I to 15, X = Cl, Br, J mean 15 where R = H, "with alkyl, aryl or alkaryl radicals can, copolymerized with catalysts which means 1 to 15 carbon atoms, with ν the specified copolymerized from combinations of TiCl ₃ , aluminum tri- ω-halo-a-olefins. As examples alkylene and / or halogen-containing organoaluminum be ethylene, propylene, butene-1, 3-methylbutene-1, niche compounds and alkali halides are pentene-1, 4-methyl-pentene-l, 4-phenylbutene-l, 5-phe- stand, with the molar ratio aluminum-2 ° nylpentene-1, hexene-1 and styrene called - preferred, bond to alkali halide of 4: 1 to 1: 2, however, ethylene and propylene are used. and the molar ratio of aluminum compound to As cu-halo-a-olefins with which the «-olefins Titanium compound should be 10: 1 to 1: 1. can be copolymerized, are preferred 2. The method according to claim 1, characterized in that it is 4-chlorobutene-1. 5-chloropentene-l, 6-chlorine drawn, that the polymerization as a block 35 xene-1, ll-chlorundecene-l, 4-bromobutene-l, 5-bromine or copolymerization with random distribution pentene-1, 6-bromohexene-1, 11-broniundecene-1 and of the monomer units. 5-iodopentene called, but especially 5-chloro 3. Process according to Claims 1 and 2, characterized in penten-1. ,
characterized in that ethylene or the copolymers prepared according to the invention are used as "olefins" propylene. "30 contain 99.9 to 80 percent by weight" olefins and 4. The method according to claims 1 to 3, characterized accordingly 0.1 to 20 percent by weight eo-halogen, that as co-halogen - «- olefins a-olefins. They generally have good mecha-4-chlorobutene-l, 5-chloropentene-l, 11-chlorunde- nische properties and can be well in thermocen-1, Deform 4-bromobutene-l, 5-bromopene-l, 11-bromoplastic state. After exchanging the undecen-1 or 5-iodopentene-1 can be used. 35 halogen in the polymer due to amines (e.g. aniline, Morpholine) can be derived from the modified Shaped bodies produced by polymers, in particular Ribbons, fibers, threads and foils, colored with acidic dyes in deep shades. These colorations 40 are characterized by special light and washing It is known that -olefins are resistant to catalysts. '. · from combinations of compounds of the elements Furthermore, the inventively produced the 4th to 8th subgroups with organometallic, halogen-containing copolymers in be compounds the I. to III. Groups of the periodic known way with oxides of polyvalent metals, Polymerize the system at low pressure and 45 z. B. magnesium or zinc oxide, or with bifunctional copolymerization can. convert nellen amines. It is also known that «-olefins with Die for the preparation of the copolymers according to the tü-halogen - «- olefins can copolymerize suitable catalysts in the process according to the invention one adds pyridine to the catalyst mixtures are mixed catalysts of TiCl ₃ and aluminum (cf. Polymer Prepints, September 1964, Vol. 5, No. 2, 50 organonium compounds , to which one additionally-p. 656) or catalyst mixtures of trisacetyl borrowed or alkali halides are added. Particularly advantageous acetonates of vanadium and monochlorodiisobutyl are combinations of TiCl ₃ with A1 (C ₂ H _S ) ₃ , aluminum or TiCl ₄ and triisobutylaluminum A1 (C ₂ H ₅ ) ₂ C1 or A1 ₂ (C ₂ H ₅ ) ₃ C1 ₃ with the addition of turns (see Belgian patent specification 622 213). These ■ alkali halides are used. With alkali halides, however, processes do not run with good space-time - for example NaF, NaCl, KF, KCl, RbF, yields can occur. RbCl, RbBr, CsF, CsCl and CsBr, preferably It has now been found that copolymers KCl can be used. Since the effect of the alkali of «-olefins with co-halogen -« - olefins after the halide in the formation of complex salts with Ziegler low-pressure process is based advantageously on the organoaluminum compounds, if you 99.9 to 80 percent by weight «-olefins 60 after the equation
of the general formula CH ₂ = CH - R, in which. R = H, alkyl, aryl or alkaryl, with 0.1, AlR C1 ₃ _ "+ MeX = Me- [AI R" Cl ₃ _ _n X]
up to 20 percent by weight ω-halogen-a-olefins of the all-,
common formula R = alkyl, η = 1 to 3, Me = alkali metal, X = Ha- £ j_j _ Qpj (QW) CH χ ⁶ 5 log, it is also possible to replace the aluminum ² ν 2 2 organic component and the alkali halide wherein η = 1 to 15, X = Cl, Br, J can mean to add the pre-formed complex, z. B. copolymerized with catalysts consisting of grain K- [A1 (C ₂ H ₅ ) ₂ CI ₂ ].