Preparation of multiphase homo- or copolymers of...

Details Preparation of multiphase homo- or copolymers of... Preparation of multiphase homo- or copolymers of...

1997-05-02

2001-03-06

Lipman, Bernard (Department: 1713)

Synthetic resins or natural rubbers -- part of the class 520 ser

Synthetic resins

Polymers from only ethylenic monomers or processes of...

C526S116000, C526S119000, C526S160000, C526S348200, C526S348300, C526S348400, C526S348500, C526S348600, C526S351000, C526S352000, C526S943000

Reexamination Certificate

active

06197900

ABSTRACT:

The present invention relates to a process for the preparation of multiphase homo- or copolymers of C
2
-C
10
-alk-1-enes.
The present invention furthermore relates to the use of the homo- or copolymers, obtained by the novel process, for the production of films, fibers or moldings.
Multiphase homo- or copolymers of C
2
-C
10
-alk-1-enes are usually prepared by a multistage polymerization process, the polymer obtained in a first reaction zone initially being transferred to a second reaction zone, where a mixture of one or more C
2
-C
10
-alk-1-enes is polymerized with it. In this way, a mixture of two different polymers forms in the second reaction zone. Under certain circumstances, the mixture obtained from the second polymerization zone may furthermore be introduced into one or more further reaction zones, where other C
2
-C
10
-alk-1-enes are polymerized with it. (DE-A 40 04 087, DE-A 40 19 453).
The conventional processes are relatively complicated in terms of process engineering since, on the one hand, the reactor conditions in the individual reaction zones must be matched with one another and, on the other hand, the transfer of polymers from one reaction zone to the other is associated with certain difficulties with regard to regulations. Moreover, such multistage processes always require a very expensive apparatus, entailing considerable capital costs.
It is an object of the present invention to remedy the disadvantages described and to provide a process for the preparation of multiphase homo- or copolymers of C
2
-C
10
-alk-1-enes which is less complicated in terms of process engineering.
We have found that this object is achieved by a process for the preparation of multiphase homo- or copolymers of C
2
-C
10
-alk-1-enes, wherein polymerization is carried out in the presence of two different catalyst systems in one reaction zone, one of the catalyst systems containing, as active components, a metallocene complex of the general formula (I) or (II)
where
M
1
is a metal of group IVb, Vb or VIb of the Periodic Table,
R
1
and R
2
are identical or different and are each hydrogen, C
1
-C
10
-alkyl, C
1
-C
10
-alkoxy, C
6
-C
10
-aryl, C
6
-C
10
-aryloxy, C
2
-C
10
-alkenyl, C
7
-C
40
-arylalkyl, C
7
-C
40
-alkylaryl, C
8
-C
40
-arylalkenyl or halogen,
R
3
and R
4
are identical or different and are each hydrogen, halogen, C
1
-C
10
-alkyl which may be halogenated, C
6
-C
10
-aryl or an —NR
2
10
, —SR
10
, —OSiR
3
10
, —SiR
3
10
or —PR
2
10
radical, where R
10
is halogen, C
1
-C
10
-alkyl or C
6
-C
10
-aryl,
R
5
and R
6
are identical or different and have the meanings stated for R
3
and R
4
, with the proviso that R
5
and R
6
are not hydrogen,
R
7
is
═BR
11
, ═AlR
11
, —Ge—, —Sn—, —O—, —S—, ═SO, ═SO
2
, ═NR
11
, ═CO, ═PR
11
or ═P—(O)R
11
,
where
R
11
, R
12
and R
13
are identical or different and are each hydrogen, halogen, C
1
-C
10
-alkyl, C
1
-C
10
-fluoroalkyl, C
6
-C
10
-aryl, C
6
-C
10
-fluoroaryl, C
1
-C
10
-alkoxy, C
2
-C
10
-alkenyl, C
7
-C
40
-arylalkyl, C
8
-C
40
-arylalkenyl or C
7
-C
40
-alkylaryl, or R
11
and R
12
or R
11
and R
13
each form a ring together with the atoms linking them,
M
2
is silicon, germanium or tin,
R
8
and R
9
are identical or different and have the meanings stated for R
11
and
m and n are identical or different and are each zero, 1 or 2, m plus n being zero, 1 or 2,
and an oligomeric aluminum oxide compound.
Alkyl is straight-chain or branched alkyl, halogen (halogenated) is fluorine, chlorine, bromine or iodine, preferably fluorine or chlorine.
The novel process is used for the preparation of multiphase homo- or copolymers of C
2
-C
10
-alk-1-enes, in particular of C
2
-C
6
-alk-1-enes. Particularly preferred C
2
-C
6
-alk-1-enes are ethylene, propylene, but-1-ene, pent-1-ene and hex-1-ene. The term multiphase homo- or copolymers of C
2
-C
10
-alk-1-enes is intended to mean not only three-phase and four-phase mixtures but also in particular two-phase mixtures of homo- or copolymers of these C
2
-C
10
-alk-1-enes. Examples of particularly preferred two-phase mixtures include copolymers of ethylene or of propylene with other copolymers of ethylene or of propylene, and minor amounts, ie. up to 40, in particular up to 30, % by weight of further C
2
-C
6
-alk-1-enes, for example propylene, ethylene, but-1-ene, pent-1-ene or hex-1-ene, may also be present in the copolymers. Other preferred two-phase mixtures include two different homopolymers of propylene or other C
2
-C
6
-alk-1-enes, or a homopolymer of ethylene or propylene with a copolymer of ethylene or propylene with minor amounts, ie. up to 40, in particular up to 30, % by weight of further C
2
-C
6
-alk-1-enes.
On the one hand, Ziegler-Natta catalyst systems may be used as catalyst systems in the novel process.
Ziegler-Natta catalyst systems contain, inter alia, a cocatalyst in addition to a titanium-containing solid component. A suitable cocatalyst is an aluminum compound. An electron donor compound is preferably used as a further component of the cocatalyst, in addition to this aluminum compound. The polymerization is carried out in the reactors usually used in industry for polymerization reactions, preferably in the gas phase.
For the preparation of the titanium-containing solid component, the titanium compounds used are in particular halides or alcoholates of trivalent or tetravalent titanium, the chlorides of titanium, in particular titanium tetrachloride, being preferred. The titanium-containing solid component advantageously contains a finely divided carrier, silicas and aluminas as well as aluminum silicates of the empirical formula SiO
2
.aAl
2
O
3
, where a is from 0.001 to 2, in particular from 0.01 to 0.5, having proven useful for this purpose. Further carriers include finely divided polyolefins, for example finely divided polypropylene.
Inter alia, compounds of magnesium are also used in the preparation of the titanium-containing solid component. Particularly suitable compounds of this type are magnesium halides, alkylmagnesiums and arylmagnesiums, as well as alkoxymagnesium and aryloxymagnesium compounds, magnesium chloride, magnesium bromide and di-C
1
-C
10
-alkylmagnesium compounds being preferably used. The titanium-containing solid component may also contain halogen, preferably chlorine or bromine.
The titanium-containing solid component furthermore contains electron donor compounds, for example mono- or polyfunctional carboxylic acids, carboxylic anhydrides and carboxylic esters, and ketones, ethers, alcohols, lactones and organophosphorus and organosilicon compounds. Preferably used electron donor compounds within the titanium-containing solid component are phthalic acid derivatives of the general formula III
where X
1
and Y
1
are each chlorine or C
1
-C
10
-alkoxy or together are oxygen. Particularly preferred electron donor compounds are phthalic esters where X
1
and Y
1
are each C
1
-C
8
-alkoxy, for example methoxy, ethoxy, propoxy or butoxy.
Further preferred electron donor compounds within the titanium-containing solid components include diesters of 3-membered or 4-membered, unsubstituted or substituted cycloalkane-1,2-dicarboxylic acids and monoesters of unsubstituted or substituted benzophenone-2-Carboxylic acids.
The alcohols usually used in esterification reactions, including C
1
-C
15
-alkanols, C
5
-C
7
-Cycloalkanols, which in turn may carry C
1
-C
10
-alkyl groups, and C
6
-C
10
-phenols are used as hydroxy compounds in the case of these esters.
The titanium-containing solid component can be prepared by methods known per se. Examples of these are described, inter alia, in EP-A 45 975, EP-A 45 977, EP-A 86 473, EP-A 171 200, GB-A 2 111 066 and U.S. Pat. No. 4,857,613.
The titanium-containing solid component obtainable thereby is used with cocatalysts as a Ziegler-Natta catalyst system. Suitable cocatalysts are aluminum compounds and further electron donor compounds.
Aluminum compounds which are suitable cocatalysts are trialkylaluminum as well as compounds in which an alkyl group has be

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