DE1795620A1 - High molecular weight polymer products - Google Patents

Description

Cologne, June I5th, 1997 I Ke / IM

51, Poro Buonaparte, Malland / Italy

High molecular weight polymer products

(Addition to patent ...

(Patent application P 15 2o 289.8-44)

The invention relates to high molecular weight polymer products consisting of essentially linear and saturated Macromolecules are made up of polymer chains with randomly distributed monomer units on a lot, and that

I. Units derived from ethylene

II. Units derived from an olefin which contains an internal double bond and corresponds to ^{the general formula R 1} - CH = CH - R ^11,

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In which R and R are the same or different and denote alkyl radicals having 1 to 6 carbon atoms, aryl radicals or alkylaryl radicals, and

III. Units derived from one or more alpha-olefins of the general formula R-CH-CK ₀ , in which R is an alkyl radical with 1 to 6 carbon atoms

As examples of alpha-olefins which are used to prepare the terpolymers of the invention may earth v /, may be mentioned: propylene, butene-1, 3-methylbutene-1, pentene-1, 4-methylpentene-l and hexene -1.

As examples of olefins with an internal double bond » polymerized according to the invention with ethylene c © can be mentioned: butene-2, pentene-2, Trimethylethylene, hexene-2, heptene-2, 2-methylheptene-3, 2,7-diraethylocten-4, propenylbenzene and 5-phenylpentene-ß

Also mixtures of the two cis and trans isomers of one given olefin with internal double bond or the two isomers in pure form can be used for the purpose of the invention can be used.

The catalysts which are used for the preparation of the polymer products according to the invention can be made from Transition metals of IV, V, and VI. Group of the Periodic Table and Organometallic Compounds of Metals of groups Ia, II and Ha of the Periodic Table are produced, at least one of the Catalyst components is halogenated. Preferably, catalytic systems are used in the liquid phase in which the copolymerization reaction takes place, colloidally distributed or completely dissolved are.

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Examples of transition metals that can be used to manufacture the catalysts are: TiCl ₂ ^ ₃ TiI ^, TiCl, (produced by reducing TiCIh with hydrogen, aluminum or aluminum-alkyl), VCl ^, VOCl-, , Vanadium triacetylacetonate, vnadyl diacetylacetonate, ethyl orthovanadate, chrornyl chloride and chromium triacetylacetonate.

Suitable metal organ! see connections are for example

Al (O ₅ H ₇ J ₂ Br,

wise Al (C ₂ H ₅ ) ₃ , AlXfyH ^ C _{57 5}

Be (C ₂ H ₅ ) 2 / Li (C ₄ H ₉ ), / Al (C ₂ H ₅ ) XgZ ₂ Y, where X is halogen and Y is an electron donor, for example a tertiary or non-secondary amine, an "onium" Salt or an alkali halide are id.

Particularly good results are obtained when certain vanadium compounds are used as the transition metal compound be used. The preferred catalytic systems v / earth from vanadium tetrachloride or vanadium oxytrichloride and alurainium trialkylene or from vanadium triacetyl acetonate and dialkyl aluminum monohalides. Instead of vanadium diacetylacetonate you can Vanadyl diacetylacetonate, vajiadium chloracetylaeetonate or alkyl o-vanadates with satisfactory results be used.

can Copol '/ polymerization in a fairly wide temperature range from -8o ° to + loo ° C, vorzugsvieifio zviisehen -5o ° C and +50 ⁰ C are performed i'i.d both in the presence of an inert LÖEuncfc-: NITL .els, for example sv; iron of an aliphatic or aromatic hydrocarbon, as well as in the absence of T.ö; angsmittel.

Ui: i Copcl.v:>γ; ό of as close a composition as possible to erbsIti:?;, It is usefulHifißniif- :, the Wengen ratio 209832/0883

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between the olefins, which copolymerizes in the liquid phase should be kept constant during the copolymerization reaction. To achieve this, It can be advantageous to carry out the copolymerization continuously by adding the mixture to the polymerizing monomers fed continuously and withdrawn or circulated at a sufficiently high throughput rate.

The polymer products prepared according to the invention are high molecular weight solids which consist of linear macromolecules. They can either be completely amorphous or show reduced crystallinity of the kind characteristic of linear polyethylene. For example, amorphous products are obtained in the production of ethylene-propylene-ois-butene-2-terpolymers if the molar content of the ethylene does not exceed 75%. The obtained according to the invention! Amorphous polymers made up of three components can be completely extracted with boiling n-heptane. Only part of the crude polymer is extracted with boiling ethyl ether. The molar content of monomers in the fraction which can be extracted with boiling ether does not differ significantly from that of the fraction which is insoluble in boiling ethyl ether but extractable with boiling n-heptane, and from that of the crude polymers. This is the confirmation that each macromolecule actually consists of monomer units derived from the polymerization of all monomers used, ie the products obtained according to the invention actually consist of terpolymers, tetrapolymers, etc. and not of mixtures of homopolymers or copolymers.

The formation tlioöcr particular polymer products gemäsc the Erfinrrnig w: r * also having regard to the US Patent 2 77 ^r) 577 can not be foreseen, as is well known, 20 9832/0883

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Olefiiiu with internal double bond neither with catalysts dor the type described above, nor with other catalysts form dioodolecular polymers- only by carrying out the copolymerization of the olefins containing internal double bonds with ethylene it is possible to obtain high molecular weight polymer products containing units resulting from the polymerization derive these olefins with an internal double bond.

This is likely due to the fact that the Carbon atoms of ethylene that have no substituents except for the hydrogen atoms, which are of small steric size, to the two carbon atoms of the double bond have bound and are in the growing chain between two from the olefin with an internal double bond inserting the monaural units coming from it, considerably reduce the steric hindrances responsible for direct attachment of a Unit of the olefin with an internal double bond to another unit of the same type is impossible.

Since alpha-olefins as well as olefins with an internal double bond an alkyl group as a substituent on a carbon atom of the double bond, even if this bond is only to one of the carbon atoms of the double bond is bound, it was to be expected that, for the steric reasons mentioned above, the copolymerization would be terminated or at least only the binary copolymerization of ethylene with the olefin containing the inner double bond and the alpha-olefin could.

The tendency towards the formation of amorphous products of ola stomeric character is stronger in these copolymers with three or more components than in binary

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Copolymers due to their simultaneous presence of three (or more) different monomer units, which are known to cause greater disorder in the cause linear macromolecules.

The polymer products according to the invention are suitable as elastomers, if they consist of completely amorphous materials, or as plastics (fibers, foils or other consumer goods) if they consist of crystalline substances.

example 1

The reaction apparatus consists of a 500 ml glass cylinder with gas inlet and outlet pipes, mechanical stirrer and thermometer pocket. The gas introduction pipe is guided to the bottom of the vessel and \ ends in a frit. |

The air is displaced from the vessel with anhydrous nitrogen. The reaction apparatus is then cooled to -3o ° C. 100 ml of anhydrous n-Heplan \ are introduced. This solvent is saturated at -35o ° C by adding a mixture containing cis-butene-2 (marked with * ¹ C), propylene and ethylene in a molar ratio of *

J5: ^: J5 contains, in an amount of 50 normal liters / yy Std. Is passed through.

Meanwhile the catalyst is made under nitrogen at -j5o ° C by adding a solution of 9 millimoles Aluminum tri-n-hexyl in 20 ml anhydrous n-hepta; i is mixed with a solution of 3.6 millimoles of vanadium tetra chloride in 2o ml of anhydrous n-heptane. The analyzer is introduced into the reaction apparatus immediately after its preparation. The mixture of Ethylene, propylene and butene-2 are continuously added an amount of 50 normal liters' hour. fed.

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V,

One hour after the addition of the ketal V ^ r-te .-. · 3, the reaction is terminated by adding 2 ·> ml of methanol are treated one after the other with aqueous hydrochloric acid and V / oBser. It is then fully coagulated with an excess CINP ". Ao.eton-I'iethanol-Gemj sehes. After drying in vacuo as the product to be 'Λ, 2 g of a white solid of rubbery Aur.sch." Ι obtained. Be the j X-ray examination ervioist Li oh the product as amorphous.

The product contains Ic ·, 5 KoI-Jj butene-2, determined by radJ.c "> h <T" ii. v. ^) so analysis, and ^ o mol-1 'propylene, determined by jn'r. ^ r-ot analysis. The latter analysis allows <v \ s " to determine the absorption intensity of Ϊ" ethylgrur.j »en at 7 ^ 25 U> gkb the sum of the content: h propylene and butene? in the terpolymer results in: Since ürir content of butene-2 of the terpolymer is known from radi ochemisehen analysis, I'ropyler-c can <? B .->. By difference lt bereclmet v / ground.

The 8 terpolyniere obtained in the manner described is completely extractable iv.zt Hi: the n-heptane and has a maximum viscosity of 1.8, determined in tetrchyercnaphthalene at 133 C.

Hcif'Pl z) '"'

The apparatus described in .M i: riel 1 is vented wj- · ■ ·! \ -, i``V nitrogen au / -? Jc ° C cooled. Then i.'orden air T. "■ ·: ■■ ngsmittel loo üi3 '.;: Scurfreics n-Heptcn t'.liK.i ^f "^; n '·. which becomes saturated at -3o ° C by adding a t-cinl: -. «-> -., ■ ·· trans-butene-i ¹ (;: J ■ _ '" mayed), Pro. Oe * and.

l33. "'.-'_;'" r. '.: 5rd of I'-italy.i; ¹ '. <-v under Gtjckstoff means - ^v t. \> -: · -'- "VlIt, 1" dcin <: ii "· '' ■: ing of 9 M1113ü .. ·!

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Aluminum tri-n-hexyl in 2o ml of anhydrous n-heptane is mixed with a solution of 3.6 millimoles of vanadium tetrachloride in 2o ml of anhydrous heptane. Immediately after its preparation, the catalyst is placed in the reaction apparatus.

The mixture of ethylene, propylene and butene-2 is continuously in an amount of 5o standard l / hour. fed. One hour after the addition of the catalyst, the reaction is terminated by adding 20 ml of methanol. The product is purified and isolated in the manner described in Example 1. It weighs 4.5 S and has the shape of a white pest of rubbery Appearance. It turns out on the X-ray examination as amorphous and can be completely extracted with boiling n-heptane. It contains 2.5 moles of butene-2, determined by radiochemical analysis.

Example 3

The conditions mentioned in Example 1 are used, with the exception that the catalyst from 14 millimoles of diethyl aluminum monochloride and 2.8 millimoles of vanadium triacetylacetonate in Jo ml of anhydrous Toluene and not from aluminum tri-n-hexyl and vanadium tetrachloride.

In one hour, 1.8 g of an ethylene-propylene-3utene-2 terpolymer are obtained which contains 7 * 5 % butene-2, determined by radiochemical analysis.

The product obtained can be completely extracted with boiling n-heptane and is found on X-ray examination as amorphous.

P π tent claims ο

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Claims (2)

Claims e 1. High molecular weight polymer products, characterized in that they are composed of essentially linear and saturated Macromolecules with in the polymer chain randomly distributed monomer units of the general Formulas - CH ₀ - CH ₀ - -CH ₀ - CH - -CH - CH - d d d χ ¹ I'TJ in which R is an alkyl radical with 1 to 6 carbon atoms and R and R, which can be the same or different, denote alkyl, aryl or aralkyl radicals, and reduced crystallinity of the kind characteristic of linear polyethylene have an ethylene content above 75 mol $ or are amorphous with an ethylene content up to 75 mol $. 2. High molecular weight amorphous polymer products according to claim 1, characterized in that they are up to 75 mol # ethylene, the remainder propylene and butene-2 contain, one determined in tetrahydronaphthalene at 135 ° C Have an intrinsic viscosity of about 1.8 and are fully extractable with boiling n-heptane. 209832/0883.
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