DE1442722A1 - Polymerization catalyst - Google Patents

Description

PATENT LAWYERS · - ^. "".

D R.-l N QH Fl NCKE L. JUM '

DIPL-INQ. H.BOHR
DIPL.-INQ. S. STAEQER

Folder 188? O Br.R / fcU
Case P 15740 / I6060

Description

for the patent application of Imperial Chemical Industries Limited, London SW 1

concerning »" polymerization catalyst ¹ *

Registration priorities in Great Britain

Mr. 23557/61 * ^ 3244/61 and 18138/62 voa June 29, 1961, -

46. 9/11/1962 and 6/6/1962 will be claimed

The present invention relates to polymerization catalysts.

In British Patent 8j50424 there is a method ssur production of polymerization catalysts is described in the case of the eln-a compound of a transition metal of the groups τι / b.i. ;; VX of the Periodic Sy.'stenis with one the group H-Sl * onthaitendon connection is handled.

ß ^ genstanrii of the present invention is new silicon to propose containing polymerization catalysts, which compared to the previously known silicon-containing Polymerization catalysts have certain advantages.

BATH ORIGINAL ./.

809812/1119

These catalysts are for the polymerization of ethylene Useful- Another object is to propose a process for polymerizing ethylene using it such catalysts.

Geraäss the present invention catalysts for Äthylenpolymerisatlon are proposed in such a way that they are prepared by mixing at least one organic silicon compound which contains the group H-Si », in which the residual valences are denoted by -R, H-Si £, -Si ^ , -OR or -OSi ^ groups are saturated, where R is an alkyl, cycloalkyl, aralkyl or aryl group and the residual valencies of these groups are also saturated, with
a.) a higher halide (as explained below) of a transition metal from groups IV to VI of the periodic table and

b “) a crystalline material made of aluminum, titanium and Chlorine, whereby the titanium is almost completely in the three valuable condition and the Al-, Ti- and Cl-Atorae present in amounts of essentially Iej5i 12 or in crystalline latices are linked together. It also describes a process for polymerizing ethylene using the catalysts of the present invention * suggested. Presumably the catalysts are made of the present invention as a result of one

BATH 8 0 9 8 12/1119

chemical conversion between the mixed Components.

The term "higher halide" is understood to mean a halide of a transition metal in which the transition metal has the highest valence which the metal has in binary combination with that halogen; Furthermore, it should be understood that it is a common bond of easily detectable and clear chemical compounds rather than, for example, molecules only formed in the discharge tube. Particularly for use as constituent a.) Halides suitable in the present invention are titanium tetrachloride and vanadium tetrachloride or mixtures of the two.

Silicon compounds useful in the present invention are tritnothylsilane, triethylsilane, diphenylmethylsilane, Isophenylsilane and dimethylphenylsilane. Siloxanes are just if useful. Particularly suitable for use in the present invention are hydropolysiloxanes of the formula

H
I.
Si-O-

Jl

where η is an integer from 2 to about 100 or higher, i3t and R is an alkyl, cycloalkyl, AraIky1 or aryl group means. An example of such a hydropolysiloxane let Methyl hydrogen silicone oil.

BATH ORIGINAL

809812/1119

The used in this invention trivalent titanium chloride material forms the subject of British Patent Specification 877 050. It is usually described as ⁿ Altie ⁿ designates "Conveniently, there will be prepared by heating aluminum» aluminum with titanium tetrachloride and, after completion of the reaction by separating the unreacted titanium tetrachloride »chloride of the reaction product, for example by distillation. Its more catalytic! Properties are improved by milling, preferably dry milling in the ball mill, before use. Optional catfish, this product can be produced by reacting aluminum with titanium tetrahalide in a ball mill. -

The. Ratios of the components of the catalysts of the present invention Invention can vary widely »i.e. the Mo! Ratio of component a.) To component b.) can be between 100ι1 and Ii100 | to complete however To achieve exploitation of the present invention is that the above molar ratio between 4s 1 and 1: 4 is most suitable. The ratio of the organosilicon compound to the total transition metal compound (i.e. moles of constituent a.) + moles of constituent b.)) can also vary start, lies However, preferably between 0.1: 1 and 5s1 *

The manufacture of the catalysts of the present invention is best done by mixing the ingredients along with a hydrocarbon diluent. oxygen and moisture, have an inhibiting effect

809812/1119

BATH ORIGINAL

on the invention-specific catalysts * it is therefore necessary » Air and water are sometimes rigorous in the manufacture of the catalysts and in their use in polymerizing them to exclude

The polymerization using the catalysts of the invention can be carried out at atmospheric pressures, but preferably at higher pressures up to about 100 atmospheres or higher; However, the temperature can vary greatly * is zweekmässig between 50 and 200 ⁰ C, preferably between 70 and 95 ° C. Most conveniently, the process is carried out in an inert hydrocarbon diluent. The pre-formed catalysts or the separate catalyst components are introduced into the reaction vessel, which is then charged with ethylene at a suitable pressure. Optionally, additional amounts of any catalyst component or monomer or diluent may be added from time to time during the polymerization. The polymer thus formed is generally obtained in the form of an easy-to-handle sludge. Detrimental catalyst residues can be separated from the polymers containing them by known methods for removing transition metal catalysts. The catalysts are preferably decomposed first by treating the polymeric material with a dry alcohol such as methanol or carbonate, which can be followed by a further washing with alcohol or hydrocarbon or a treatment with an aqueous acid or alkali. Certain complex agents »such as acetylacetone 809812/1119 \ ^BM > ™ ™"

When changing from dry alcohol, direct treatment with water is cursed, as soluble catalyst residues are precipitated * which can then be effectively removed by dissolving the polymer.

The polymerization can also take place at temperatures above 95 C in such a way that the polymer produced is soluble in the hydrocarbon medium.

When using the inventive catalysts, Misshpolyeere of _; Kthyls can be produced with other α-elements, for example JPropylene. . ^; i: ^ ..

The advantages of Organositieiu-mverbindungen as Redüktiohsmittei in olefin polymerization in comparison with others Components such as aluminum and tin halides exist in their non-toxicity and the fact that they are not T. are spontaneously flammable. Those used in this invention Polysiloxanes also have a relatively higher stability to heat as well as to reaction heat, like oxygen and water.

The catalysts of the present invention have a greater level of activity than known _s Orgäriösiiibtiimkömponenfcen containing catalysts.

The following examples explain the present; Invention, but without restricting them in any way.

809812/1119

example 1

40 Milllaol methylhydropolysiloxane (IUCH ₅ , n ~ 40), 10 Mllllaol TlQi ₄ and 10 Mllllmol "Altie", which had previously been dry-ground in a ball mill, were put together in 500 .mu.m of a dry petroleum fraction with a boiling point between 180 and 220 ⁰ C, from which all the dissolved qase had been removed, mixed. The mixture was added to the petroleum fraction in a rotary autoclave with a capacity of 5 liters, from which oxygen was blown through it

was removed with oxygen-free nitrogen / The pressure in the autoclave was gebrächt to 26 atmospheres Xthyleh and the temperature raised to 90 ⁰ C. The polymerization started immediately, the temperature was adjusted to 90 to 95 ° C by suitable cooling. After 5 hours the. The polymerization is stopped, the polymer sludge is removed from the autoclave and treated with n-butanol to decompose the catalyst. The polymer was separated off by filtration, washed with acetone and dried at 60 ° C. in vacuo. 556 β pure white fine-grained polymer were obtained.

Examples 2 to 15

Examples 2 to 15 are compiled in the table below The procedure used in each example is the same as that described in Example 1.

BATH ORIGINAL

8 0 9.8 1 2 1 1 1 1 9

Tabel

Bel-
game Slliciura
fade ~.
manure
Trash "Altio"
Milll-,
aol Higher -
Halogen
nid milli-
mol Thinner
potential
withJtel duration
Hours. Temp.
⁰ C the end
prey
S. 2 (CH ₅ HSlO) _n
OK. 10 VCl ₄
10 oil
fracti
on (Sdp.
180-220
* C) 5 90 522 3 (CII ₃ HSlO) _n
.12 12th TiCl ₄
12th ff 90 706 '4 (CH ₅ HaIo) _n
10 10 TiCl ₄
10 ti 5 90 536 5 ' (CH ^ HSiO) _n
20th 15th TiCl ₄
10 • » 5 90 798 6th (CH ₅ HSiO) _n
20th 15th TiCl ₄
15th «■ 15th 90 7th (CH ₅ HSiO) _n
20th 15th TlCl ₄
15th toluene 5 90 213 8th (CH ₅ HSiO) _n
20th 15th TiCl ₄
15th Petrol
ether _n
80-100 ° C 5 90 202 pressure
AtJBO -
spherai 25th 25th 25th 25th 7th 2β 26th

BATH

809812/1119

Table (continued)

f - '' ■
at
game SilicliM-
connect
manure
Millieol "Attic"
MiUl-
BOl Higher -
Halöge
nid MiUi-
mol Thinning
tion
middle pressure
Atmosphere
sphä
ren duration
hours Temp.
° c the end
beu
te
G !
9 (CH ₃ HSiO) _n
40 10 TiCl ₄
10 Oil-
frafcti-
ön 250
ecm 1 2 90 1"'· 1
ί
t
i
10
i (C ₆ H ₅ ) ^ SiH
20th 15th TiCl ₄
15th oil
fracti
on (Sdp.
180-220
* c) 7th 5 90 322 11 4o iH
8th TiCl ₄
10 η 25th 5 90 860 ί
12th (CH ₃ ISiO) _n
16 12th TiCl ₄
12th « 13th > 55 29 I ^ (C ₆ H ₅ HSiO) _n
20th 15th TiCl ₄
15th It 27 5 91-93 630 lh (C ₆ H ₅ CH ₃ BSi
20th ) ₂ o
15th TiCl ₄ ,
15th ti 27 5 90-95 1200 15th (CgH ^ -JiSij
20th _ °
15th TiCl ₄
15th η 27 5 92-9 * 416

809812/1119

Elderly 1 16 ~. .

A 5 liter autoclave was evacuated and purged with nitrogen in the usual manner. 1.5 liters of degassed high-boiling paraffine fraction with the trade name ^rt Sihai * ol ⁿ ""'. was then added. The catalyst components were then. nents (10 Milllraol TiCi ₁ ^, 10 Milllmol "Altls" and 8 "0 MilllmQl degassed Mefchy! hydrogen! licon oil with the molecular weight of approx was placed a Briiclc of about 14 kg / cm and then heated to 95 ° C. the polymerization was stopped 4.8 hours long time wavy at 94 · to 96 ⁰ C and 28 kg / cm performed. After 3 hours the Kthylenzufuhr was to to observe the amount of the pressure drop, measured as 6.44 kg / cm. at the end of the polymerization, the autoclave was cooled rapidly and ethylene vented. the polymeric slurry was treated with butanol, filtered, washed with petroleum ether (boiling point 60 to 80 ⁰ C) , pressed with acetone and dried in vacuo. 36O g of polymer were obtained, corresponding to a conversion of 640 mol of monomer / mol of titanium.

Bet game 17

Example 16 was repeated with the modification that 80 millimoles of diphenylmethylsilane were used as the organosilicon component were used. The polymerization was continued for 5 1/4 hours and the amount of pressure drop was not measured;

BATH 809812/1119

the other conditions were the same as in the example. 100 g of polymer were obtained, corresponding to a conversion of 135 moles of monomer / mole of titanium. The melt viscosity of the material was 2.6 × 10 poise units.

In these examples, moles of organosilicon compound are calculated as terms of equivalents, assuming the H-Si1 bonds in each molecule in the reaction centers. Thus, the equivalent weights of the disiloxanes of the formula R ₃ HSi-O-SiR ₂ H are taken as their half molecular weights and the equivalent weights of the hydropolysiloxanes are taken as the "molecular weight * of their repeating unit -RHS10-.

Patent claims: BATH ORIGINAL

809812/1119

Claims (1)

Patent-proof 1.) a catalyst for the Äthy! Copolymerization, characterized in that it _f sfirdi prepared dm'ch won mixing at least one organic Siliciuaverblndufig ^ containing the group H-Si ^ »wherein the residual valences, with -H, H-Si ^ ₉ -OR or -O-Si groups are separated, where R represents an alkyl, cycloalkyl, aralkyl or aryl group and the rest of these groups are also substituted with a ») a higher halide of a transition metal from the Groups IF to VI of the Periodic System * and b.) A crystalline material made of aluminum, titanium and Chlorine »whereby the titanium is almost completely in a trivalent state and the Al, Ti« and Cl atoms present in amounts of essentially 1: 3s12 or in crystalline latices are linked together. S.) Catalyst according to claim I _3, characterized in that the higher halide is titanium tetra chloride or vanadium tetrachloride. 3 «) catalyst according to claim 1, characterized in that that a sera made of titanium tetra chloride and vanadium tetrachloride is incorporated. ORIGINAL 809812/1119 4.) Catalyst according to claim 1 »3 or 3» characterized in that the organic oil compound TrimethyLailan, j » _t TrISthylsilan, Diphenylmethylsilan, Ifriphenylsilan or Dime thy lptienylsi lan is used. 5.) Catalyst according to claim 1, 2 or 2, characterized in that the organosilicon compound is a siloxane is applied. 6.) Catalyst according to claim 1 »2 or 3 # characterized * that the organosilicon compound is a hydropolysyl oxane of the formula -Si-O- I. R. is used, where η is an integer from 2 to about 100 is and R is an alkyl, cycloalkyl, araikyl or Represents aryl group. 7 ·) Catalyst according to claim 6, characterized in that R is a methyl group. 8.) Catalyst according to claim 1 to 7 * characterized in that component b.) Before the implementation » Preferably dry grinding is done in a ball mill. BATH ORIGINAL 809812 ^ 1119 9 ») Catalyst according to claims 1 to 8, characterized in that the Mo! Ratio of constituent a.) To constituent b.) Is between 4 * 1 and Is4. . 10.) Catalyst according to claim 1 to 9 * characterized in that etags is the molar ratio of the organosilicon compound ztsr Qesamtübergangsme ta llverb indang between 0.1: 1 and 5s 1 is. 11.) Catalyst according to claim 1 to 10, characterized in that it is in the presence of a hydrocarbon diluent will be produced. 12.) Process for the polymerization of ethylene »characterized in that ethylene is brought into contact with a catalyst according to claims 1 to 11. 13 '} Method according to claim 12, characterized in that this is carried out in the presence of a hydrocarbon diluent oil. 14.) The method according to claim 12 or 13, characterized. zeldtmett that the polymerization is carried out under superatmospheric pressure up to about 100 atmospheres. 15 «) Method according to claim 10 to 14, characterized in that it is marked that the polymerization temperature is between 70 and 95 ° C. 809812/1119