DE1520177A1 - Process for the copolymerization of olefins - Google Patents

Description

ΚΥ0ΪΪΑ HAKKO LOGYQ CO., Ltd. Tokjro / Japan

Process for Miechpolyaerisation rpn olefins.

The invention relates to the synthesis of οInas Miachpoly · * - riaata aua ewei species Ton 01afin «ii. The aim of the foundation is to create one. Procedure * .for dia frala and spawned Heretell-UQg aiaas Miechpolyeeriaata old ai * ar favünacfaten ZüiwuMetiattg in aeganwaxt tinaa Eataljraatora ron Ziaglartjp, dar dorcli ain oauartigea HarataXluQgevad becomes a £ * n.

eafaat dar aosABAanta tieglertypkatalysator al «

ponenta «in · organic · connection of metals of Qruppan X, II and III and all other components a connection of transition-EtstaXlan in groups IV to VIII of the periodic fyatava. Xiaar of the & Ά most frequently used Ziaglertyp catalytic converters. a system of trialkylaluminium and titantate caciaorld, since "waiting for the polymerisation and Miechpolyeerieation of various olinins is used.

isfboi der Miec-kpolymerisation »ου * a» i Arteis 009814/1715 ORIGINAL BATHROOM

Olefinmonoraeren in the presence of a Ziegler catalyst, if one of the monomers a "reaction rate as a Konozneres" (hereinafter referred to as H.R.R. for short) shows the essential is lower than that of the other, the copolymer obtained also has a lower content of dec. ereteren. E.g. has in the interpolymerization of propylene with isoprene, the interpolymer obtained is of a lower propylene grade, since the M.R.R. of propylene is far lower than that of isoprene. Therefore a-uij to obtain a copolymer that has a higher Has propylene content, the feed ratio, the propylene in all, mean are much higher. In such conditions it is kau «possible to get a copolymer with a certain Zueanimensetsung see below.

On the basis of extensive investigations, the invention makes it possible for the first time to avoid this disadvantage, which occurs in conventional processes, and also to prevent free synthesis. Copolymers of a desired composition, through the use of a catalyst of the regulator type, which is produced according to a process that differs from the known processes. the above-mentioned weight will be overcome and a copolymer will be obtained with a desired high content of one monomer, without the conversion ratio of this monomer as a starting material being made higher. Examples manner ee is easy rcöglich in Mischpolycerisation of Propylan »it isoprene, a Synt he ao a KischpolyBtirisats

0098U / 1715 BAD

of a »high propylene content without daa fUh * imgev * rhKltnie of propylene is courtly thought of.

Furthermore, catalysts which are different in their polymerization activity can be obtained by the conditions

\ be changed when the catalytic converters are distributed, so it should

! Böglich is the M.fi.H. to change at will. Therefore,.

even if two kinds of olefins are used at a given feed ratio, copolymers of a desired one Composition can be obtained freely by synthesis using the catalysts prepared under different conditions.

In general, the catalyst is used for copolymerization is used by two Olafioen, according to the traditional methods, s * B. by mixing trialkylaluminum with titanium chloride either in Qegaawart from both alefineα or in one atmosphere inar-

UkQu harg «at« llt. ~ ->;'' ^: '' - "

The erfiEdUB "afemäs" e feature is that the learning the Ejitalymatora and the Kleeht "olymeriaatlon" differ from the Usual procedure in such a way that it is first presented Catalyst is produced in the presence of only one olefin and then the other olefin is added to initiate the interpolymerization initiate. In this falla there is the presence of a small crowd daa the latter 01 * fin «not disadvantageous for achieving the goal of the invention * in particular if a catalyst» which is produced according to the arfisdungägöiSiiaBen '/ experienced un <$ AIu-

.-. '0 0-9 8 U7 17 iS'

contains minima and titanium in such a ratio that a high polymerization reactivity to propylene is used in the admixture polymerization for propylene with another olefin is, the effect of the copolymerization is significantly improved and results in a copolymer with a high ^ ropylene content.

■ ♦
The above-mentioned copolymer is a copolymer due to the fact that in the case of fractional precipitation it shows a precipitation point which is different from that of the homopolymer and the composition of which can be analyzed with the aid of an infrared absorption spectrum.

A copolymer can therefore easily be produced by synthesis which has a desired composition if the catalyst according to the invention is used and the feed ratio where two olefin acids are selected in a suitable manner.

mrdca Beiepi ·! «for di * Xrfi & dung g« g «b * tt.

Example 1 (Miechpolyaerieation »on propylene with isoprene) Reaction conditions

P / I (mono delivery ratio of propylene to isoprene)! 1/1 temperature: 0 ⁰ C

Brück: Outside air pressure Solvents: a-hexane, loo al

_k Catalyst composition Al / Ti (colar ratio / on aluminum

009814/1715 ^ original

to titanium): 15o "provided that Ti o.,. oo24 mol

amounts to Order of addition Al —— ^ Ti

In a reaction vessel, η-hexane and propylene were added.

Before the addition of isoprene, that is, in the presence of propylene alone, triethylaluminum (AlBt-.) As aluminum and titanium tatrachloride (TiCl.) As titanium were added dropwise to the reaction vessel to produce a so-called Ziegler-type catalyst in the presence of propylene alone. This means that the catalyst was initially treated with propylene alone. After the addition of the catalyst, the contents of the reaction vessel were stirred for a given period of time and then a given amount of isoprene was added to the reaction vessel. Klsehpolyeerieation was initiated with the addition of roa isoprene * Ksieh de " during the receipt of α" α a "al * something during a time" | M "orden 3d al η-butanol this time, xm the Beak interruption su. In addition, 150 al methanol were added to the mixture to cause the polymerization product to settle, which was then filtered and separated with the aid of a glass filter.

The composition of the copolymer obtained was as follows: Mixed polymer composition:

BAD OfUGiNAL

0Q98U / 171 5

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15201Ϊ7

Catalyst manufacture

Example ($ .n presence of Propylene alone)

Comparison (in the presence of both propylene and isoprene)

Isoprene 49 %

97 %

Propylene 51 %

3 *

Therefore, by using the catalyst according to the invention, it was possible to obtain a copolymer whose propylene content is far higher than that obtained by the conventional process.

Example 2

The copolymers were prepared under the same reaction conditions as in Example 1, with the exception that the uses * catalyst in its molar ratio of aluminum EU Titan (AVTi) has been changed · The results are shown in the table below

Mixed polymerisation

Catalyst made in the presence of propylene alone

1.25

l, 5o

Comparison (in the presence of both propylene and Isoprene)

P (*) I (*) P (56) K *) 1 99 2 98 9 91 - - ^ ₉ 51 3 97

009814 / 171S

QRiGlHAl.

-7- B «1« pi »1 p (copolymerization of propylene with butadiene)

Pie reaction was carried out in the same manner as in Example 1 below carried out under the following conditions:

P / B (monomer feed ratio from propylene to butadiene): 1/1 Temperature: 0 ⁰ C. . ' Pressure: outside air pressure λ

Solvent: η-hexane, 100 ml

Catalyst composition: * Al (CpH ₅ ), + TiCl ^. Composition of the Miechpolymerisate obtained

Catalyst advice Propylene content (mol ^) In the presence of both olefins 21 Id Presence of propylene alone hk

As can be seen, the use of an old propylene alone results in |

Catalyst produced a mixed polymer sate with higher a Pro pylene content than if the catalyst was made from both olefins

Example V (high polymerisation of propylene or ethylene)

The Beaktion was else in the same "as in B _e iepiel one carried out under the following conditions:

. 0 0 9 8 1 A / 17 1 5 bad original

P / E (monomer feed ratio of propylene to ethylene): 1/1 temperature; O ⁰ C

Pressure: outside air pressure

Solvent: η-hexane, 100 ml

Catalyst composition: Al (C _? H _c ), + VC1,.

Composition of the copolymer obtained

Catalyst production propylene content (KoI %)

In the presence of both olefins · 35

In the presence of propylene alone 43

As can be seen, the catalyst prepared in the presence of propylene alone gives a. Copolymer with a higher one Prcpylengenalt than in the case in which the catalyst is in the presence Clay is made of both olefins.

As stated above, the ability of the conventional changes Process Cla presence of both monomers) Catalysts for the formation of copolymers slightly, even if the AlAi ratio (molar ratio) is changed, during the experience according to the dsm according to the invention, i.e., in the present Catalysts made by ropyl®n alone the η copolymers obtained in the event of a change? of the Al / Ti ratio changed greatly. As a result of this effect of the Catalysts according to the invention can be copolymers of

47 171 5 -

BATH ORIGINAL

A desired äusamsüirisstv> »; ~ <g easily by iJynthesis Appropriate choice of the contributory factor v-lafin monomaric (z.3 ,, P / I, in example H - »rrAeUn,

_fJS -, ... _{r #} ,, ...- SAD ORIGINAL

Claims (1)

-ΐο- 620177 P ά be η ta η β ρ ruc 7i>rfaiu'jn to the copolymer Lon y> n ,, / ;: ί ■ · '· ■ ίΐι from ϋ .- · *: 1: ι.>-; ί "ΐΒ» propylene and isoprene) in "ι4 £ βιϊάλϊϊ, -; ·. ■ · β Kutalysut-.a-ri τ · : _,; to bildon π 2I "(jlor type inabesondere oei sin Jr. Kowbin ^ inn, ϊγ at 1 x *! S üchwle · r Li ;, a copolymer, ladui ·" ■ ^ -jkennxe ivhnet that ixiiVBt the catalyst using vm /-.-7β"1 Artsa / η Katallen with a 2.ur Homopolymerleahion ^ rsgi ^ neten Molir yerhaltnic (κ, Β. Al / Ti-Verhiiltaie) in the presence of the eia-ja. Olefin «hjrgeef slit is, daa in de & copolymer obtained by einera hohon He just should be present, and then the copolymerization untor ZuifjÄti d * e other olefins 2UR Education atm Kiechpolymarisata from the g "winechten iu-samnsneetaung durcbg-jfüiu ^ t is.