Syndio-isoblock polymer and process for its preparation

Details Syndio-isoblock polymer and process for its preparation Syndio-isoblock polymer and process for its preparation

1993-11-01

2001-05-01

Wu, David W. (Department: 1713)

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

Synthetic resins

Polymers from only ethylenic monomers or processes of...

C502S117000, C502S152000, C526S160000, C526S351000, C526S943000, C556S007000, C556S009000, C556S011000, C556S012000, C556S013000, C556S043000, C556S053000

Reexamination Certificate

active

06225425

ABSTRACT:

The invention relates to a syndio-isoblock polymer having long isotactic and syndiotactic sequences and to a process for its preparation.
It is known that polypropylene exists in various structural isomers:
(a) highly isotactic polypropylene in whose molecular chains almost all of the tertiary carbon atoms have the same configuration,
(b) isotactic stereoblock PP in whose molecular chains isotactic blocks of opposite configuration alternte with each other in a regualr manner,
(c) syndiotactic polypropylene in whose molecular chains every second tertiary cartona tom has the same configuration,
(d) atactic polypropylene in whose molecular chains the tertiary carbon atoms have a random configuration
(e) atactic-isotactic stereoblock PP in whose molecular chains isotactic and atactic blocks alternate iwht each other,
and
(f) isoblocks PP whose molecular chains contain isotactic blocks which are spearated form one anotehr by a tertiary carbona tom having, in each case, the opposite configuration relative to the isotactic blocks.
A process for the preparation of isotactic stereoblock polymers is known in which propylene is polymerized using a metallocene of a metal form group IVb, Vb or VIb of the Periodic Table (cf. U.S. Pat. No. 4,522,982. This metallocene is a mono-, di- or tricyclopentadienyl or substituted cyclopentadienyl metal compound, in particular of titanium.
The cocatalyst used is an aluminoxane.
However, in dilute solution the titanocenes which are preferably used are insufficiently heat-stable for use in an industrial process. Moreover, in this process, products having a relatively long urn of isotactic sequences (n greater than 6) are only obtained at very low temperatures (−60° C.). Finally, the cocatalysts must be used in relatively high concentrations to achieve an adequate catalyst yield, with the consequence that the catalysts residues contained int he polymer product must be removed in a separate purification step.
Furthermore, it is known that stereoblock polymers of 1-olefins having long isotactic sequences can be obtained at industrially appropriate polymerization temperatures by means of a catalyst which is composed of a metallocene compound containing cyclopentadienyl radicals which are substituted by chiral groups, and an aluminoxane (cf. EP 269,987).
Moreover, it is known that stereoblock polymers of 1-olefins having a broad uni- or multi-modal molecular weight distribution can be obtained if the polymerization of the 1-olefins is carried out using a catalyst which is composed of a bridged chiral metallocene and an alumin-oxane (cf. EP 269,986). These polymers are particularly suitable for the preparation of transparent films.
It is also known that the use of a catalyst based on bis-cyclopentadienyl compounds of zirconium and an aluminoxane in the polymerization of propylene gives only atactic polymer (cf. EP 69,951).
Moreover, using soluble stereoridgid chiral zirconium compounds, it is possible to prepare highly isotactic polypropylene (cf. EP 185,918).
Finally, isoblock polymers have been proposed.
A plymerization process has been found in which a polymer having a regular molecular structure and a high molecular weight is obtaned at industrially appropriate process temperatures in a high yield.
The present invention accordingly provides a syndio-isoblock polymer of a 1-olefin of the formula RCH═CHR′ in which R and R′ are identical or different and are an alkyl radical having 1 to 14 carbona toms or R and R′, with the carbon atoms joining them. form a rign, and the siad polymer has molecular chains in which syndiotactic and isotactic sequences are present and the sequence length is 3 to 50 monomer units.
Furthermore, the invention provides a process for the preparation of the abovementioned syndio-isoblock polyers by polymerization of a 1-olefin of the formula RCH═CHR′ in which R and R′ have the abovementioned meaning, at a temeprature of −60 to 100°C., a pressure of 0.5 to 100 bar, in solution, suspension or in the gas phase, in the presence of a catalyst which is composed of a metallocene and an aluminoxane, wherein the metallocene is a compound of the formula I
in which
M
1
is titanium, zicrconioum, hafnium, vandadium, niobium or tantalum,
R
1
and R
2
are identical or differenct and are a hydrogen atom, a halogen atom, 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 or C
8
-C
40
-arylalkenyl,
R
3
, R
4
, R
5
, R
6
, R
7
and R
8
are identical or different and are a hydrogen atom, C
1
-C
10
alkenyl, C
7
-C
40
-arylalkyl, C
7
-C
40
-alkylaryl or C
8
-C
40
-arylalkenyl,
R
3
R
4
, R
5
R
6
, R
7
and R
8
are identical or different and are a hydrogen atom, 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 a halogen atom,
R
9
is
=BR
10
, =AlR
10
, —Ge—, —Sn—, —O—, —S—, =SO, =SO
2
, =NR
10
, =CO, =PR
10
or =P (O)R
10
, where R
10
, R
11
, R
12
, R
13
and R
14
are identical or different and are a hydrogen atom, a halogen atom, a C
1
-C
10
-alkyl, C
1
-C
10
-fluoroalkyl, C
6
-C
10
-fluoroaryl, C
6
-C
10
-aryl, C
1
-C
10
-alkoxy, C
2
-C
10
-alkenyl, C
7
-C
40
-arylalkyl, C
8
-C
40
-aryl-alkenyl, or C
7
-C
40
-alkylaryl, or R
10
and R
11
, or R
10
and R
12
, together in each case with the atoms joining them, form a ring, and
M
2
is silicon, germanium or tin.
The catalyst to be used in the process according to the invention is composed of an aluminoxane, and a metallocene of the formula I
In formula I, M
1
is a metalfrom the group which includes titanium, zirconium, hafnium, vanadium, niobium and tentalum, preferably zirconium or hafnium.
R
1
and R
2
are identical or different and are a hydrogen atom, C
1
-C
10
-, preferably C
1
-C
3
-alkyl, C
1
-C
10
-, preferably C
1
-C
3
-alkoxy, C
6
-C
10
-, preferably C
6
-C
8
-aryl, C
6
-C
10
-, preferably C
6
-C
8
-aryloxy, C
2
-C
10
-, preferably C
2
-C
4
-alkenyl, C
7
-C
40
-, preferably C
7
-C
10
-arylalkyl, C
7
-C
40
-, preferably C
7
-C
12
-alkylaryl, C
8
-C
40
-, preferably C
8
-C
12
-arylalkeny or a halogen atom, preferably chlorine.
R
4
R
5
, R
6
, R
7
adn R
8
are identical or different and are a hydrogen atom, C
1
-C
10
-, preferably C
1
-C
3
-alkyl, particularly preferably methyl (in the case of R
3
) and H (in the cases of R
4
, R
5
, R
6
, R
7
and R
8
).
R
9
is a one- or multi-membered bridge and is
=BR
10
, =AiR
10
, —Ge—, —Sn—, —O—, —S—, =SO, =SO
2
, =NR
10
, =CO, =PR
10
or =P(O)R
10
, while R
10
, R
11
, R
12
, R
13
and R
14
are identical or different and ar e a hydrogen atom, a halogen atom, preferably chlorine, C
1
-C
10
-, preferably C
1
-C
3
-alkyl, in particular methyl or ethyl, C
1
-C
10
-fluoroalkyl, preferably a CF
3
group, C
6
-C
10
-fluoroaryl, preferably pentafluorophenyl, C
6
-C
10
-, preferably C
6
-C
8
-aryl, C
1
-C
10
-, preferably C
1
-C
4
-alkoxy, in particular methoxy, C
2
-C
10
-, preferably C
2
-C
4
-alkenyl, C
7
-C
40
-, preferably C
7
-C
10
-aryl-alkyl, C
8
-C
40
-, preferably C
8
-C
12
-arylalkenyl or C
7
-C
40
-, preferably C
7
-C
12
-alkylaryl, or R
10
and R
11
, or R
10
and R
12
, together in each case with the atoms joining them, form a ring.
M
2
is silicon, germanium or tin, preferably silicon or germanium.
R
9
is preferably ═CR
10
R
11
, ═SiR
10
R
11
, ═Ger
10
R
11
, —O—, —S—, ═SO, ═PR
10
or ═P(O)R
10
.
the metallocense described above can be prepared by the following general reaction scheme:
Preference is given to the use of metallocense such as dimethylmethylene-(9-fluorenyl)-3-methyl-(cyclo-pentadienyl)zircomium dichloride and (dimethylmethylene)-(9-fluorenyl)-3-methyl-(cyclopentadienyl)hafnium dichloride.
The cocatalyst is an aluminoxane of the formula II
in the case of the linear type and/or of the formula III
in the case of the cyclic type. In t

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