DE1805672C3 - Process for the production of olefin copolymers - Google Patents

Description

COR

I! ο

-R ¹ COOR ² aryl

other

—CR- ¹

denotes, where R and R ^{2 are} hydrogen atoms or alkyl, haloalkyl, aryl, haloaryl or alkaryl radicals; R ^{1 is} an alkylene structure; R ^{3 is} an alkyl, haloalkyl, arylhaloaryl, aralkyl or alkaryl radical and Z is a hydrogen or halogen atom or an alkyl, haloalkyl, aryl or haloaryl radical and Z ^! and Z ^{2 represents} halogen atoms or alkyl, haloalkyl, aryl or haloaryl radicals.

These coordination catalysts are for the polymerization of ethylene and at least one other α-olefin and for the production of copolymers suitable from ethylene, propylene and a non-conjugated diene.

The catalyst systems described are effective for the production of olefin polymers, however, they have a relatively short lifespan and there is therefore a need for enhancement the effectiveness, d. H. after increasing the amount of polymer, soft a given amount of catalyst can generate. In the case of catalysts containing vanadium, it was also necessary that polymers produced with it were washed or otherwise cleaned to remove vanadium residues to remove, as such residues reduce the electrical resistance and the Stability against heat oxidation and discoloration of the polymers.

The invention relates to a process for the production of olefin copolymers from ethylene and at least one other - / - olefin, from other -i-olefins than ethylene from one another or from Ethylene. Propylene and a non-conjugated diene through copolymerization of the monomers in one Diluent with the aid of a catalyst system which (a) a vanadium compound in a concentration from 0.001 to 1 mole liter of the diluent, (b | a dialkyl aluminum halide and or an alkyl aluminum dihalide in an amount corresponding to an atomic ratio of Al: V in the vanadium compound from 3: 1 to 250: 1 and (c) an organic, oxidizing halogen compound in an amount of 1 to 2000 moles per gram of vanadium contains in the vanadium compound, in which

'' s one the polymerization with the help of a catalyst system executes, which also (dl a hydrocarbon-soluble activator, the (1) isoprenylaluminum. (2) a trialkyl aluminum of less than

Il carbon atoms. (3) a Lewis base which is a UIk ¹ I ", Ke [OiI. Amide, or A mi π and contains fewer than three carbon atoms, or 14) a compound of the formula

R ⁵

Al-A

is. in the A an acetylacetonate residue or a residue Jer formula

- OR ⁷

NR ⁴ R ⁷

O
- CjCR ⁷

or —N

means, where each of the symbols R ⁴ , R ⁵ . R ⁶ and R ', which can be the same or different, represent an alkyl group with 1 to 8 carbon atoms and R ^y denotes an alkylene radical with 4 or 5 carbon atoms, in an amount of from 0.1 to 10.0% per atom of vanadium in the vanadium compound.

Each of the Bf components of the catalyst system can be a single compound or a mixture of compounds.

Isoprenylaluminum is *, a polymer made from isoprene and triisobutylaluminum, which can be prepared according to Example 1 of US Pat. No. 3,146,136.

All components of the catalyst are preferably hydrocarbon-soluble at least to such an extent that as is necessary in order to obtain the essential proportions of the components given here receive and can use the catalyst in solution polymerizations. The catalyst can also be used in dispersion polymerizations. In this catalyst system the ratio is of dialkyl aluminum halide and or alkyl aluminum dihalide to vanadium atoms

. 10-200
preferably j—.

The catalyst system used in the present invention can be used as a modification of a coordination catalyst based on vanadium, which is a dialkyl aluminum halide and or Contains alkyl aluminum dihalide and an oxidant; the modification is that an activator which is so reactive that the alkyl aluminum halide present in the polymerization reaction mixture during the Polymcrisationsreaktioii preferably instead of with the oxidant with the Activator reacts. The catalyst system used according to the invention provides in comparison with the same Catalyst system that does not contain an activator, higher vanadium outputs.

The catalyst system described is particularly useful for the production of olctinmischpolymeriuatcn from ethylene and other - (- olefins or for Manufacture of copolymers from ethylene. Propylene and a non-conjugate diene. It is particularly useful for making polymers from ethylene propylene dicyclopentadiene.

Ethylene Propylene Methylennnrburnen, Äthylen Propylen Alhylidenenitrhiti new uiui Ethylen Propylen 1.4-1 lexadien.Aather also Ethylen Propylen-Poly kidney can be produced with similar advantages,
The catalysts are coordination catalysts based on vanadium, e.g. B. those described in US Pat. No. 3,301,834, which by adding an activator and adjusting the proportions of vanadium, aluminum, oxy-

IQ dans and activator have been modified within the above ranges. Preferred vanadium components for the catalyst are VCl ₄ , VOCl ₃ and vanadium trisacetylacetonate; however, any of those vanadium compounds known to be useful as components of coordination catalysts for the polymerization of α-olefins can be used. These include addition complexes of vanadium halides with ligands containing oxygen and nitrogen, chelate complexes of vanadium with 1,3-diketone compounds and alkyl vanadate esters. All of these connections are known.

Among the dialkyl aluminum halides or alkyl aluminum dihalides and mixtures thereof, the chlorides are the preferred halides; however, the bromides and iodides can also be used will; Fluorides can be used in mixtures with other halides. To be favoured Alkyl aluminum halides in which the alkyl groups contain 1 to 8 carbon atoms.

The polymerization can be carried out batchwise or continuously in solution or dispersion and some of the catalyst coated materials can be admixed or separated before use can be added to the polymerization reaction vessel. For convenience, the ingredients usually added separately in the form of solutions to the polymerization medium. These ways of working belong to the known state of the art.

One of the important advantages of this invention is the high catalyst performance achieved. The catalyst performance is measured here in grams of polymer that are formed per gram-mole of vanadium used. In the manufacture of ethylene »propylene 1.4-hexadiene polymers become catalytic converters in 30 minutes of more than 500,000 and often more than 1 million. The performance of this Catalysts is usually at least twice that of the same catalyst without an activator and often many times larger.

Suitable oxidants are trabromocarbon. 2 - bromo - 2 - methylpropionyl bromide, N - bromopyridium nium tribromide. Bromoacetyl bromide. Chloroacctyl chloride. Trichloroacetyl chloride, trichloroacetic anhy drid. 2.2.2 - Trichloro - N - phenylacctamide. 2.2.2 - trichlor-N.N-diphenylacctamide.

QSCCl, RSCCl ₃ Q-CHBr CH ₂ Br QCHX

O
(HCIXCl

C)

NQ.

OO
CCl ₃ -C-NR ⁴

CClj

ClX CCU

ArCX, or ArCX ₂

where / ι is greater than 1, R is as defined above, Q is an aryl radical, such as a phenyl or naphthyl ^{radical, R 4 is} an alkyl radical, Ar is an aryl radical other than the phenyl radical (z. B. a naphthyl radical) or a haloaryl radical and X represents a halogen atom such as Cl, Br or J. Further examples of oxidants are

CCI ₂ = CCI-CCI ₂ -CCi ₂ -CCI = CCI ₂ C ₆ H ₅ HgCX ₃
Cl CN, 0

35

40

45

CH

CH,

CCl ₃

CH ₃ I CH ₃ CCl ₃

CCl ₃

Cl ₃ -CC = CH ₂ CH ₃

Br

Cl ₃ C

Cl

Cl Cl I CCl ₃

Cl

Cl

\ Cl Cl CCl ₃ / Cl Cl / I. \ ν T Cl

CCl,

CCl,

CHCl ₂

Br

CHCl,

Cl

CHBr,

α- / "V s-m

CIC- -CCl

I ί

Cl ₂ C CCl ₂

Cl ₁ C-CCl ₂ -CCl,

CCl, - CH-CCl, (CCl., I ₂ C -CCI ₂

CCl ₂ CTICCI ₂ Mr.

Preferred activators are trialkylaluminum compounds with fewer than 31 carbon atoms and compounds of the general formula defined above

AlOR ⁷

R "

where R ⁵ . R ⁶ and R ^{7 are} alkyl of I to S carbon atoms. The compounds triethylaluminium. Triisobutyl aluminum. Isoprenyl aluminum, tridecyl aluminum,

(C ₂ Hs) ₂ -AlOC ₂ H ₅ and (C ₂ H ₅ ) ₂ AlO (iC ₃ H ₇ )

are particularly preferred because they are excellent in appearance, readily available, and excellent in handling characteristics exhibit. Other representative activators are, for example

(C ₄ Hg) ₂ Al- N (C ₂ Hj) ₂

(C ₂ H ₅ J ₃ N

Pyridine

(C ₂ H ₅ ) ₂ O

Diethyl aluminum acetylacctonate or amines, such as alk \ l- and arylamines. where each * «primary, secondary or teriiäi can be. Representative · Amines are Aniline. Dimethyhiniline. Athvlamin. Prop \ lamin. Bu-Ivlaniin and the Trihcxvlaminc. DimethvHither. Diethyl ether and tetrahydrofuran are useful ethers, / u useful ketones include .acetone. Methyl ethyl ketone. Methyl isobutene> lketone. Cyclopentanone and cyclohexiinone.

In any given I all a Lewis base can be examined for its usefulness as an activator to determine in the method of the invention by adding a molar fraction of the Lewis base to be tested two molar parts of benzotrichloride and a 0.1 molar solution of diisohutylaluminium chloride. the 5 Moltcile of the latter compound contains \ ermischl will. The test solvent is preferably the solvent to be used in the polymerization. If the mixture does not turn brown within 30 minutes, the compound is suitable as an activator ingredient in the catalyst solution according to the invention. Ordinary room temperatures are used.

The activator mcngc used depends on each Usually depends on the amount and type of oxidant used. and both as well as the amount of the Dialky aluminum halide and or alkyl aluminum dihalide depend on the vanadium mcigc present. The amount of activator required increases usually in proportion to the amount of oxidant. Amount of vanadium and the Vcrweil / cit. With the help of the above A skilled chemist can use the tests described here to obtain the minimum required ratios in a given case Easy to find out about activator Usually, activator to oxidant ratios are sufficient from 0.25: 1 to 2: 1.

The activator is used in the catalyst in an amount of about 0.1 to 150 Moltcikhen. respect to the vanadium in the catalyst, and preferably existing ■ used in an amount of 1 to 50 parts of Part v ^y vanadium. An amount less than this is ineffective in obtaining significantly improved vanadium performances, and an amount greater than this tends to lower the performances and add to the cost of the catalyst. Suitable diluents are, for example, hexane. Heptane. Benzene. Toluene. Chlorobenzene. Cycle hexane. Tetrachlorethylene and trifluoroethane.

so B e i s ρ i e 1 e 1 to 8

and comparative experiments A to I.

The advantages of the method of the invention can easily be taken from the table in which the performance of some of the preferred catalyst systems with those of the corresponding three-component systems. in which the activator is missing can be compared. In each case, the polymerif> o based monomers ethylene propylene 1,4-Hexadicn, which are practically used in proportions of 60 35 5 and the polymerization was carried out at 25 ° C. All parts, percentages and proportions, Unless otherwise indicated, those specified here are parts by weight and percentages by weight and proportions by weight.

Examples 1 to 4 and comparative experiments A to E in the table were carried out according to that in example 10

309 651/227

805

operation described below continuously accomplished. Examples 5 to 5 and the comparison tests f- to i were as follows! accomplished:

Polymerization grade gaseous ethylene and propylene before use through molecular sieves of porous grains with a diameter of 1.59 mm and an effective Hydrate pore diameters of 5 Λ! Naff iumaluminosilicate, see USA patent 8882 243 and 2 882 244. The liquid 1.4-Hcxadiene tKMi polymerization quality (predominantly trans-) tff was by indicator silica gel and then by neutral aminotropic aluminum oxide for chromatoiraphic Purposes passed under a nitrogen atmosphere and then through to use Protected in a nitrogen atmosphere, in the dark stored via indicator cicelic acid rule. The hexane solvent was purged with nitrogen and prior to the Use slowly through molecular sieves made of pofous grains with a diameter of 1.59 mm: o • nd an effective pore diameter of 5 µsec hydrated sodium aluminum silicate directed.

Ethylene and propylene were introduced at rates of 1 l and 2 l / minute above the surface tiner 500 milliliter batch of hexane, which was moved at 25 C in a 1 l 4-neck glass flask in "means of a polytetrafluoroethylene stirrer was. After about 5 to 10 minutes, it was assumed that the solvent to the monomers \ o was saturated. which were then continuously fed with derlelbcn speed. a 5-MiIIiliter content of I.4-hexadiene was introduced by syringe Then the coordination catalyst ingredients are added one after the other at intervals of 1 minute or less between the individual additions from syringes. Diethylaluminum chloride (Comparative Experiment F and Example 5). were the first constituent that was added as a normal solution (I gAtom aluminum liter) in heptane.

In Examples 5, 6 and 7, _{Eth 2} AlOAth was added next (as a normal solution in heptane), the oxidant was added (without solvent), and then VCl _{4 was} added (as a 0.01 molar solution in tetrachlorethylene).

In comparative experiment I and example 8, after the addition of i-BuA1Cl _2, hexachloropropene was added (without solvent); then VCl _{4 was} added (as a 0.01 molar solution in tetrachlorethylene), and at the same time the activator (as an O.lnormal solution in heptane) was added at a rate of 2.1 milliequivalents hour.

All polymerizations were carried out at 25 ° C. In Example 5 and Comparative Experiment F was the catalyst performance subtracted from the dry weight of a 25 ml sample at the time indicated was decided. In Examples 6 to 8 and Comparative Experiments G to I, the catalyst performance was determined from the weight of the polymer, which due to precipitation at the indicated time- 65 * point was isolated. In all of those cases where polymer was isolated, the polymer composition was determined spectroscopically.

985 (XX) ld ld 881 (XX) ld r ι Gebi Gebi Gebi Polymer Polymer Polymer 135 (KK) C. C. C. 635 (XK) 37. U no C. no LU
O < I. j < UU LO Γ I C. C. C. OEt! C. ke; '5
Yes! no < SJ LU

i.

rl rl η ~ ι ι-, .7,

so so

-α

■ χ)

-α

SlJ SIj SI.

-ο

CQ

2JOCp-O = W

Sp SD ^ j SO SIj SIj SO Sl

ω si ~ ϊ U ύ U ο S

■ 3 ~ ^ ₁ -3 τ; τ τ ί:

JC

■ <

ii Oil
054 ο 04 O 043 043 043 5 O ^ ο ο O ο O ο ο C. iidium I Van

^ i

U O

η Γ * ϊ ττ; -% - ■ ~, —J,

UUUÖUÖUC OOOOOOOC

CQ U

j =

χ:

BO ti

ο.

CQ>

3 W)

JC
υ

4>

DQ>

t> ei

> CO

> C

Fortseizuna

Comparative experiment F
Example 5

Comparative experiment C

Example 6

Comparative experiment H

Example 7

Comparative experiment I
Example 8

Vanadium ver
binding

Viinadium concentration ")

Organo-aluminum-j _Λ | γ compound I.

VCl ₄
VCl ₄

VCl ₄
VCl ₄

VCl ₄

VCl ₄

VO ₄
VCI ₄

0.02
0.02

0.02
0.02

0.02

0.02

0.05
0.05

AIh ₁ AlCl "

the same

1-BuAlCl ₂ 'ι desül.

I 400

desul. 1250

200

desizl. : 200

destil. ■ 200

200

64 64

Ox) dans

Oxy- j dans V) ■

Activator

Activator V ^J )

Power')

the same

desul.

Cl, C

desul.

c, ci _h

Notes: ") Concentration of the vanadium compound in ml 1 diluent.

") Atomic ratio of aluminum (in the OrgaimulummiiimverbiMdiingi.: U Vanadium.

^c ) Molar ratio of oxide / vanadium.

^J) molar ratio of activator ai vanadium

*) Grams of polymer | e (one mole of vanadium

^f ) Diisobutylaluminium chloride.

*) Diethylaluminum ethoxide.

*) Diithylaluminum chloride

') Trialkylaluminum.

J) isobutyl aluminum dichloride.

1000 i no

1000 I EuAlOEt 150

250: no

250: Et, AIOEt 100

125: no

no polymer forms

960,000

568 (X) O

200 (KX)

Response time (min.)

18.5

IS.5

30th

30th

30th

125 ; Et ₂ AlOEt 100 no 1 3Θ5 0 (X) ! 30th 200 i no - Polymer formed I 60 200 ! Et, Al 84 1,660,000 60

805 672

Example 9

To 1000 ml of cyclohexane, which is made with ethylene propylene monomers had been presaturated in a reaction vessel under atmospheric pressure (conditions: 20 ° C; the flow velocities were that same as in example 1), were given in sequence:

a) 5 mmol of diisobutylaluminum chloride (0.1 molar in tetrachlorethylene).

b) 0.10 g (1.075 mmol) aniline (as a 10% solution in tetrachlorethylene).

c) 5 ml 1,4-hexadiene,

d) 0.4 ml (2.83 mmol) benzotrichloride,

e) 0.025 mmol of VCl ₄ (0.025 molar in cyclohexane).

The molar ratio b: e was accordingly 43: 1, the molar ratio d: e 113: 1.

The polymerization started slowly and became faster over time. At the end of 3 minutes it was wrong; this speed was ^{maintained at 20 °} C. for 51 minutes. A yellow color formed during the polymerization which turned to black after 51 minutes. A total of 31.6 g of polymer was then isolated by precipitation with acidified (e.g. aqueous HCl) acetone MeOT (1: 1). The catalyst performance in this discontinuous operation was 1.26 million. The resulting ethylene terpolymer had an inherent viscosity of 2.20 and contained 4.02% 1,4-hexadiene and 49% propylene.

Example 10

Hexane was purged thoroughly with nitrogen and then through towers with molecular sieve packing under nitrogen pressure sent to remove the last traces of water or similar catalyst poisons, before the hexane was metered into a reaction vessel under atmospheric pressure. Diisobutyl aluminum chloride and diethylaluminum ethoxide (from triethylaluminum and absolute ethanol in equimolar amounts Quantities prepared) was in a molar ratio of 3: 1 to hexane and a total aluminum concentration of 0.1 mol in a feed tank. Vanadium oxytrichloride was found to be 0.002 molar Solution in hexane, benzotrichloride as a 0.05 molar solution in hexane and 1,4-Hcxadicn (97% trans) as 2 molar solution in hexane prepared in separate feed tanks. These solutions and hexane were added to a well-stirred reaction vessel with a capacity of 500 ml. The total feed of liquid was 75 ° ml hour. This was 0.04 millimoles / VOCl, hour. GmMoI combined Aluminum connections hour. 0.8 mmol of benzotrichloride hour and 44 millimoles of 1.4 Hcxadicn'hour fed. Ethylene and propylene were made

ίο at a speed of 2.1 and 3.5JMoI Introduced into the reaction solution for an hour. When the polymer production in the reaction vessel a had reached steady value, the outflowing liquid wedge was collected with aqueous HCl solution and finally washed with water, bcvo- the polymer was isolated by evaporation of the solvent. The polymer yield was 39.4 g hour, and the polymer contained 40% propylene and 3.3% 1,4-hexadiene. The inherent viscosity of the polymer (0.1 g of polymer in 100 ml of perchlorethylene at 30X) was 1.97. The performance of the catalyst was 985,000. Without the activator, the dirobutyl aluminum chloride had to have a vanadium oxychloride ratio of up to can be increased to 160 to obtain a high molecular weight polymer with about the same composition as to obtain the polymer described above and the performance was only 135,000.

Example 11

The procedure of Example 10 was used, a total of 1.7161 liquid hours being introduced into a reaction vessel with a volume of about 800 ml. This resulted in 80 millimoles of 1,4-hexadiene. 6. OmMoI of mixed aluminum compounds as a 0.05 molar solution in hexane. 2 mmol of benzal chloride as a 0.025 molar solution in hexane. 0.04 mmol vanadium acetylacetonate as a 0.001 molar solution in hexane. 1.47MoI ethylene and 2.34 mol propylene / hour fed. In the steady state, the polymer yield was 25.5 g / hour. The isolated polymer contained 30% Pr> pylene, and 4.0% hexadiene, and had an inherent viscosity (0.1 ε polymer in 100 ml of perchlorethylene at 30 ^p C) prior to 2:35. The performance of the catalyst was 638,000. Without the ethoxide, no polymer was formed.

Claims (3)

Patent claims: 1. Process for the production of olefin copolymers from ethylene and at least one other n-olefin, from other n-olefins than Ethylene with one another or from ethylene, propylene and a non-conjugated diene through copolymerization of the monomers in a diluent with the aid of a catalyst system which (a) a vanadium compound in a concentration from 0.001 to 1 mole / liter of the diluent, (b) a dialkyl aluminum halide and or an alkyl aluminum dihalide in an amount corresponding to an atomic ratio of Al: V in the vanadium compound from 3: 1 to 250: 1 and (c) an organic, oxidizing agent Halogen compound in an amount of 1 to 2000 moles per gram of vanadium in the vanadium compound contains, characterized in that the polymerization using a Performs catalyst system, which also (d) a hydrocarbon-soluble activator, the (1) isoprenyl aluminum, (2) a trialkyl aluminum having fewer than 31 carbon atoms, (3) a Lewis base, which is an ether, ketone, amide, or amine and has fewer than 19 carbon atoms contains, or (4) a compound of the formula R ⁵ Al-A R ⁶ is. in which A is an acetylacetonate radical or a radical of the formula - OR ⁷ -NR ⁴ R ⁷
O Il. . - OCR ⁷ or - NR ⁹ denotes, where each of the symbols R ⁴ , R ⁵ , R ⁶ and R ⁷ , which can be identical or different, denotes an alkyl group having 1 to 8 carbon atoms and R ⁹ denotes an alkylene radical having 4 or 5 carbon atoms, in an amount from 0.1 to 150 moles per gram of vanadium in the vanadium compound. 2. The method according to claim 1, characterized in that triethyl aluminum or triisobutyl aluminum can be used as an activator. 3. The method according to claim 1, characterized in that diethyl aluminum ethoxide or diethyl aluminum isopropoxide can be used as an activator. From British patent specification 1 020 808 it is known that ethylene, alone or in combination with other olefins, can be polymerized in a diluent in the presence of a coordination catalyst comprising a vanadium compound soluble in the organic diluent, an organoaluminum compound such as an alkyl aluminum halide, and a Oxydans, such as a halogenated compound of the formula C (X) ₃ Y, in which X is halogen, usually chlorine or bromine, and Y is a group such as