DE1495795A1 - Copolymerization of alpha olefins with aryl alkenes - Google Patents

Description

FAüliWl.KKE ΐ: θί Ci ¹ ST AG. formerly Meiscer Lucius & rriiniiv-Akt c-iizeichen: P Ik 95 795.0 - Fw hhO3 Date: May 19, 19o9

Copolymerization of OL olefins with aryl alkenes

It is known that one C ^ olefins with organometallic Mixed catalysts, which have found their way into technology as "Ziegler catalysts", at low pressure and can convert lower temperature into high molecular weight polymers and copolymers. ·

It is also known that Q ^ olefins with vinyl aromatics, e.g. styrene, can copolymerize (cf. Belgian patents No. 5 ^ 7.218 and No. 538.782).

Furthermore, in US Pat. No. 2,842,531, a method for the preparation of copolymers from phenylalkenes and ethylenically unsaturated monomers. The products obtained thereafter, however, have a rather poor transparency and tend to be troublesome Stress corrosion cracking. In addition, considerable amounts of comonoraere must be used *.

The same disadvantages also apply to the process of US Pat. No. 2,091,6OI, which involves the manufacture of a Copolymer of equal parts of styrene and 1-allyl-U-chlorobenzene concerns and also for the method of the German patent specification 1.073 ·· 20 ^.

A process has now been found for the production of copolymers from 0 £ -01efinen and aryl alkenes, optionally as Block copolymerization, in the presence of catalyst combinations

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nations made of TiCl. or TiCl and Al (c, _, H _) _ and / or Al (C H.) Cl and / or Al (C Tl _r ) Cl "boi temperatures between 30 and 150 ° C., preferably 0-80 ° C. and pressures between 1-10 atü, characterized in that 99-85 Gev.- ^r b OC-olefins of the general formula CHy = CH-U, where R = H, alkyl, aryl or alkaryl, with 1-15 wt .- ^ Aryl alkenes of the formula

CH ₃ - (CH ₂ ) _n - CH - (CH ₂ ) _m - CH = CH ₂

Ar

copolymerized by the low pressure process, wherein in the general formula η = 0 - 12, m = 1 - 12 and Ar denotes an aromatic nucleus, and so does the aromatic nucleus condensed, unsubstituted or singly or multiply by the groups alkyl, cycloalkyl, alkoxy, aryloxy, halogen and Dialkylamino can be substituted.

In the process according to the invention, OC -olefins of the general formula CH = CHR, where R = H, alkyl, aryl or alkaryl radicals having 1-15 carbon atoms, are preferably used for the copolymerization. As an example its ethylene, propylene, Duten-1, 3-Methylbutene-1, Penten-1, ^ -Phenylbutene-1, Hexen-1 and Styrene named.

Components with which the O ^ -olefins can be copolymerized are, in particular, 4-phenylpentene- 1, k- phenylhexene-1, 4-phenylheptene-1, 5-phenylhexene-1, 5-phenylheptene-1, 4-p- Tolylpentene-i, 12-Phenyltridecen-1 listed. The phenyl nuclei can in each case preferably be substituted by methyl, ethyl or chlorine groups.

The copolymers prepared according to the invention contain 99 - 85 wt .- ^ C ^ olefins and correspondingly 1-15 wt .- ^

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Ary 1 alkenes. They show unervarte one legally f; orin {e tendency to Sp ''.! I nungsrißkorros ion, bositzen { 'never o;':!. Ni see Ed gonschafteri and work great J ^m thftrmoplas vorformon tisdien state. Furthermore, these products are marked by the installation of Phenylgruppon and are readily prepared by JR recordings i denti Vi grace.

Polion made from the polymer, thin-walled press-J) IaIt ¹ U or spray-zgtissar t ike I have a slightly cutaneous transparency compared to those made from the propylene homopolymer, so that the copolymers can be used everywhere where it is particularly important a high degree of clarity of the finished products arrives.

The contacts suitable for producing the copolymers by the process according to the invention are the organometallic mixed catalysts normally used for the low-pressure polymerization of ^ -olefins. Combinations of TiCl, with Al (CH) and / or Al (CH _r ) Cl and / or Al (C ^ ll) Cl are particularly advantageously used. The catalyst system is prepared by mixing 0.1-20 parts, preferably 2-k parts, of the reducing organo-alurainium compound with one part of the TiCli in an inert solvent, for example an aliphatic hydrocarbon. It is also possible to use prefabricated TiCl ", which has been produced from TiCl by reduction with hydrogen at high temperatures or with aluminum powder.

The catalyst mixture that results directly from the implementation the combination mentioned at temperatures from -20 to +100 C, but preferably from -10 to + ^ 0 C, result, can be used as such without further purification, with the usual activation during the polymerization the above-mentioned organoaluminum compounds takes place.

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However, the catalyst conversion products are expediently freed from undesired reaction products which can reduce the activity of the catalyst by washing with inert, aliphatic hydrocarbons. Similarly, one can subject the catalyst mixtures to aging by being 80 ° for example, 1-3 hours at elevated temperatures, for example - 150 ^O C heated. Naturally, atmospheric oxygen and moisture must be kept completely away during the preparation of the catalyst, as well as later during the polymerization. This is achieved by allowing all reactions to take place under the purest, dry nitrogen or under noble gas. The aliphatic, alicyclic or aromatic hydrocarbons customary for the Ziegler low-pressure process, such as, for example, n-heptane, η-hexane, cyclohexane, cyclopentane, toluene; In addition, chlorobenzene, anisole or well-purified mineral oil fractions can also be used.

As mentioned, the reduced titanium compound is expediently activated subsequently during the polymerization with A1 (C “H_) _, Al (C ₀ Hj ₀ Cl or Al (C ₀ H _1. ), -Cl _{1 _} of the polymerization mixture is about 0.1 to 100 mmol TiCl ~ / l, preferably 5-25 mmol TiCl "/ l Disper- . '■ I"

J'j

solvent.

The copolymerization of the οζ, -olefins and arylalkenes is carried out as a block copolymerization or as an ordinary copolymerization in suspension by dispersing the monomers one or more times one after the other or together with the dispersion of the polymerization catalyst in an aliphatic, alicyclic or aromatic hydrocarbon, e.g. n-heptane , η-hexane, cyclohexane, cyclopentane, toluene, chlorobenzene, anisole or well-purified mineral oil fractions in the boiling range 160 - 250 C / are added. The polymerization

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BATH ORIGINAL

but can also be used in mixtures of monomers, even without Solvent.

The polymerization is carried out at temperatures between 30 and 15Ο C, preferably 4θ - 80 ° C. carried out. It can be at normal pressure or under slightly elevated pressure, preferably 1-10 atmospheres. The polymerization time is usually 0.5 to 15 hours, preferably 2 to 8 hours, until the desired degree of polymerization is reached. Thereafter the polymerization is terminated by adding an alcohol, e.g. isopropanol, n ^ butanol etc., or a ketone, e.g. acetone. After washing with water, the polymer powder is filtered off, several times with gasoline, methanol and acetone washed and finally dried. The dispersant can also be used in the customary way by steam distillation removed.

The copolymers obtained by the process according to the invention can be processed into molded bodies by the methods customary for olefin polymers.

The following examples serve to illustrate the present invention without, however, wishing to restrict it. · · '·

example 1

a) Catalyst production

In 1.5 1 of a rinsed with ultrapure nitrogen, of water, Oxygen, sulfur and olefins-free petroleum fractions from the boiling range 180 - 200 ° C are 490 ml (= 2.2 mol) Ethyl aluminum sesquichloride dissolved, and a solution of 220 ml (= 2 mol) of titanium tetrachloride in 3OO ml of the petroleum fraction from the boiling range 180 - 200 ° C in 3 hours

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O C added dropwise. The resulting, deep red dispersion is Stirred for 2 hours at 0 ° C. and heated at 110 ° C. for 5 hours with further stirring. After cooling to room temperature the resulting precipitate is allowed to settle and the supernatant clear solution is siphoned off. You wash it Contact with the petroleum fraction described above with stirring about 10 times and remove the dispersant each time again by siphoning. The titration of the washing solution hydrolyzed with water finally gives a content of 5 in atom Cl / l contact dispersion.

b) Copolymerization of 4-phenylpentene-1 with propylene (Mixed polymerisation in suspension)

Man, under nitrogen k 7 ml (= O ^ mmol) of diethylaluminum monochloride in 2 1 derfoben mentioned, heated to 50 C petroleum fraction having a boiling range 180-200 ° C. Then 8.8 g (= 60 mmoles) of U-phenylpentene-1 are added to the solution and, after a further 10 minutes , k ml (= 20 mmoles of TiCl “) of the contact described under 1a) are added for 2 hours. Then propylene is added to the extent that it is consumed, while maintaining 10 $> exhaust gas. With a ^ water bath, the temperature in the 'polymerization vessel is kept at 50 C. After 5 hours, the polymerization is stopped by adding 50 ml of n-butanol, the polymerization mixture is stirred for 30 minutes at 50 C and five times with 500 ml of 50 C warm oxygen - Washed in free water. Fine, colorless polymer powder is filtered off, washed three times with n-hexane, five times each time with methanol and acetone and finally dried at 70 ° C. in a vacuum. 220 g of a crystalline polymer powder with a melting point of 165 ° C. and a * γ spec / c value of 8.5 ^ (measured in 0.1 l ^ b

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Solution of decahydronaphthalene at 135 ° C). The space-time yield is 23.1 g / l.h, of which 95.2% is crystalline Modification. Let by distilling off the mother liquor 11g of amorphous and oily constituents are isolated.

Details of the polymerization and properties of the copolymers are listed in the table below.

Example 2

a) Catalyst production

90 ml (= 2.2 mol) of ethylaluminum sesquichloride are dissolved in 1.5 l of a petroleum fraction, free of water, oxygen, sulfur and olefins and boiling from 180 - 200 ° C, which has been flushed with pure nitrogen and a solution of 220 ml (= 2 Mol) titanium tetrachloride in 3OO ml of the petroleum fraction from the boiling range 180 - 200 ^O C ^ 5 hours at 0 ° C was added dropwise. The resulting, deep red dispersion is stirred for 2 hours at 0 ^° C. and heated at 110 ° C. for 5 hours with further stirring.

b) Copolymerization of * 4-phenylhexene-1 with propylene (Mixed polymerisation in suspension)

Under nitrogen, 5.6 ml (= ^ O mmol) of aluminum triethyl and 28.4 ml (= 20 mmol of TiCl_) of the catalyst described under 2a are added to 2 liters of a petroleum fraction with a boiling point of 180-200 ° C. and heated to 50 with stirring C. Then 35 g (= 220 mmol) of ^ -phenylhexene-1 are added to the dispersion and propylene is introduced for 2 hours to the extent that it is connected. The amount dos propylene measures, it is believed with a rotameter and about 10 h ^r exhaust gas.

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Working up is carried out as in Example ib). 138 g of a crystalline polymer powder with a melting point of 162.5 ° C. and a Vspec / c value of 9.18 (measured in 0.1 # solution of decahydronaphthalene at 135 ° C.) are obtained. The space-time yield is 3.5 g / lh, of which 99.7 # crystalline modification. The product has a ball indentation hardness of (10 sec / 60 sec) 695/656 Kp / cm ^2. Polypropylene, comparable to polypropylene, has such a viscosity of 6 ^ ^{0/570 Kp / cm 2} .

Example 3

Copolymerization of 4-phenylpentene-1 with propylene (block copolymerization <Period copolymerization>)

Under nitrogen, 5.6 ml (= kO mmol) of aluminum triethyl and 28.4 ml (= 20 mmol of TiCl ₃ ) of the catalyst described under 2a) are added to 2 l of the above-mentioned petroleum fraction with a boiling point of 180-200 ° C. and the mixture is heated with stirring to 50 ° C. Propylene is now passed in for 30 minutes in the same proportion as it is consumed, while observing $ 10 off-gas. The propylene supply is then stopped and nitrogen is passed in until all unused propylene has been removed from the polymerization vessel (about 10 minutes). 8.8 g (-3 & 60 mmol) of 4-phenylpentene-1 are now added under a nitrogen atmosphere and 1 Then the nitrogen supply is stopped and propylene is passed in again for half an hour, the propylene is then again expelled with nitrogen, 8.8 g (6θ mmol) of 4-phenylpentene-1 are added, and the mixture is kept under nitrogen for one hour and then polymerizes for a further 2 hours, with enough propylene being passed in that about 10 $ escape as exhaust gas. The work-up of the polymer is carried out as under 1b) spec / c-Vert

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from 7.00 (measured in 0.1% solution of decahydronaphthalene), The space-time yield is 2.8 g / l.h, of which 96.8 # are crystalline Modification. 8 g of amorphous and low molecular weight, oily polymers can be isolated from the mother layer.

Example k

Copolymerization of 4-phenylpentene-i with ethylene

Under nitrogen, 5.6 ml (= kO mmol) of alurainium triethyl and 28, k ml (= 20 mmol of TiCl “) of the catalyst described under 2a) are added to the above-mentioned petroleum fraction with a boiling point of 180-200 C and heated with stirring 50 ° C. Then 8.8 g (a ^ 60 mmol) of 4-phenylpentene-1 are added to the solution and 15 l / h of ethylene and 10 l / h of nitrogen are passed in for 5 hours. The work-up is carried out as under 1b). 95 g of a crystalline polymer powder with a melting point of 128 ° C. and a spec / c value of 10.8 (measured in a 0.1 solution of decahydronaphthalene) are obtained. The space-time yield is 9.5 g / lh. The product has a density of 0.9 ^ 75 g / cm. The polymer contains 2.3 wt .- ^ U-phenylpentene-1.

Example 5-9

Copolymerization of other aryl alkenes with propylene

The polymerization is carried out according to example 2b) and the work-up according to the example 1 b). Details of the polymerization and properties of the polymers are summarized in the table.

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Copolymerization of aryl alkenes and propylene at 50 C. (catalyst concentration: 10 mmol TiCl_ / l, [__ batch: 2 l) - *

At- Cat.d. Polymer- Propy- Arylalken 'mmol Poly- Krist .Krist in Gew. #' ^ Red density Krist.

game division lon-

game type 'feed

merging time
hours

Ge aryl velvet alkenes
poly- im
meri krist.
sats polymers

g / cm-

M.p.

cn
o 6

a mixed poly

merization shot

a mixed pole. "

a block copol. "

a mixed pole.

a mixed pole.

α mixed pole

2a mixed pole. Deficit

a mixed pole. "

4-phenylpene-60 5 220 95.2 th-1

4-phenyl-220 2 138 99.7 hexene-1

4-phenyl-120 5 240 96.8 pentene-1

4-phenyl-200 2 154 92.5 "nepten-1

12-phenyl- 100 2 i40 90.1 tridocon-t1

4-phonyl-240 2 I38 93.6 ponton-1

4-phenyl-60 5 180 98.0 pentcy-1

4-phonyl-240 5 150 92.3 ponton-1

1.6 8.5 ** 0.9020 I65

1.5 9.18 0.9039 162.5

2.0 7.00 0.9026 166 1.3 9.49 0.9018 164

1.1 8.70 0.9011 161 3.7 9.9 ^ 0.9038 160

4.0 7.72 0.9030 163

11.1 7.90 0.9015 162

• 1) The compounds were checked by elemental analysis and IR spectroscopy .

2) The determination of the wt .- ^ of the aryl alkenes in the copolymer was carried out with the aid of troscopy. The products were each transferred three times from xylene and after each of these

IH-Spek- Opera-

10 hours in the Soxhlet

extracted.

Claims (8)

1. Process for the preparation of copolymers from C ^ olefins and aryl alkenes, optionally as block copolymerization, in the presence of catalyst combinations made from TiCl. or TiCl and Al (C ₂ H ₅ ) and / or Al (C ₂ H ₅ ) ₂ Cl and / or Al ₂ (C ₃ H ) Cl ₃ at temperatures between 30 and 150 C and pressures between 1-10 atu , characterized in that 99-85 wt .- ^ OC-olefins of the general formula CH ₂ SCH-R, where R = H, alkyl, aryl or alkaryl, with 1-15 wt .- ^ aryl alkenes of the formula CH ₃ - (CHg) _n - CH - (CH ₂ ) _m - CH = Ar copolymerized by the low-pressure process, where in the general formula η a 0 - 12, ms 1 -.12 and Ar denote an aromatic nucleus, and the aromatic nucleus is also condensed, unsubstituted or singly or multiply by the groups alkyl, cycloalkyl, Alkoxy, aryloxy, halogen and dialkyjamino can be substituted. -m ν / 2. The method according to claim 1, characterized in that Ο (* olefins ethylene or propylene are used. 3. The method according to claim 1, characterized in that the arylalkene is ^ -phenylpentene-1. k » Process according to claim 1, characterized in that the arylalkene is lt-phenylhexene-1. 5. The method according to claim 1, characterized in that the Arylalkene-1-phenylheptene-1. ^ ⁷ ^ ^{1 Ab6} * * ^{i; r} ' ^{SaU 3 d: !! i} 9098A6 / 1150 6. The method according to claim 1, characterized in that the '' arylalkene is 12-phenyltridecene-1. 7. copolymers consisting of 99-85 wt .- ^, based on the copolymer of 4CH_-CH_ · ^ -f -Grundbausteinen or CHp-CII ■) -Grundbaus te inen and from 1-15 wt .- ^, based on the copolymer, to (CH ₃ - (CH ₂ ) -CH- (CH ₂ ) -CH-CH ₂ } - Grundbau-Ar stones (η = 0 - 12, zn = 1 - 12, Ar = phenyl nucleus) with "^ red-lferten, measured in 0.1% solution of decahydronaphthalene at 135 ° C, from 7.0 to .9.5. 8. Copolymers consisting of 99 - 85 wt .- $, based on the copolymer of {· CH ₃ -CH ₂₎ - basic construction teiim or -fCH "-CH) -Grundbausteinen and from 1 - 15 wt .- $, based on the copolymer, at (CH ₃ - (CH ₃ J _n -CH- (CH ₃ ) _m «CH-CH ₂ ^ -Grundbau- "Ar stones (n = 0 - 12, in = 1 - 12, Ar = phenyl nucleus) with / ^ red values, measured in a 0.1 solution of decahydronaphthalene at 135 ° C, from 7.0 to 9 »5» produced by the method according to claim 1. 909846/1150 copy