Production of homocopolymers, co-polymers or block...

Details Production of homocopolymers, co-polymers or block... Production of homocopolymers, co-polymers or block...

1999-10-06

2001-07-17

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...

C526S172000, C526S281000, C526S282000, C502S162000, C502S257000

Reexamination Certificate

active

06262194

ABSTRACT:

Preparation of homopolymers, copolymers or block copolymers comprising cycloolefinic monomer units
The present invention relates to a process for preparing homopolymers, copolymers or block copolymers comprising cycloolefinic monomer units. The invention further relates to homopolymers, copolymers and block copolymers comprising cycloolefinic monomer units whose polymer chains have hydroxyl end groups. In addition, the invention relates to the use of a metal catalyst in the preparation of homopolymers, copolymers or block copolymers comprising cycloolefinic monomer units.
Processes for the polymerization of, in particular, strained cycloolefins such as norbornene go back to work by Andersen and Merckling who availed themselves of the method of ring-opening metathesis polymerization for this purpose (cf. U.S. Pat. No. 2,721,189). The addition homopolymerization of norbornene to give 1,2-linked, saturated polymers is achieved according to Seehof et al., J. Mol. Catal. 1992, 76, 219 using the cationic palladium complex [Pd(CH
3
CN)
4
](BF
4
)
2
in the homogeneous phase. Likewise cationic transition metal complexes, in particular nickel complexes, are described by Goodall et al., Proceedings of the Sixth International Business Forum on Speciality Polyolefins (SPO '96) as highly active catalysts for the addition polymerization of norbornene. Subject to the condition that the cationic metal center forms exclusively coordinate bonds to olefinic ligands and a &dgr; bond to a carbon atom, polynorbornene derivatives having high molecular weights M
n
(>1,000,000 g/mol) are obtained at short reaction times. These polymer products are readily soluble in simple hydrocarbon solvents such as heptane or cyclohexane. However, the complexes used, eg. [Pd(NCCH
3
)
4
](BF
4
)
2
or [(&eegr;
3
-allyl)M(COD)]
+
PF
6
−
and [(&eegr;
3
-allyl)M(COD)]
+
PF
6
−
(where M is nickel or palladium and COD=cycloocta-1,4-diene), are extremely sensitive to oxygen and moisture and can be synthesized only with difficulty. In addition, the complexes described by Goodall et al. do not have a rigid coordination sphere which straight away greatly reduces the possibility of stereocontrol or regiocontrol in linking reactions.
Abu-Surrah et al., J. Organomet. Chem. 1996, 512, 243-251, describe chiral Pd(II) complexes which are stabilized by means of bridged, bidentate, tertiary amine ligands, but without giving information about their specific catalytic usefulness.
It is an object of the present invention to provide a process for the preparation of polymers comprising cycloolefinic monomer units which makes possible high yields and short reaction times with retention of the ring structure together with good reaction control and unproblematical catalyst handling.
We have found that this object is achieved by a novel process for preparing homopolymers, copolymers or block copolymers comprising cycloolefinic monomer units, wherein the polymerization of the monomer units is carried out in the presence of a catalyst of the formula (I)
where the substituents and indices have the following meanings:
M is a metal from group VIII B of the Periodic Table of the Elements,
E
1
, E
2
are each, independently of one another, an element from group VA of the Periodic Table of the Elements,
Z is a bridging structural unit comprising one, two, three or four substructural units of elements of groups IVA, VA and VIA of the Periodic Table of the Elements,
Ar are, independently of one another, fused-on aryl units,
L
1
, L
2
are formally uncharged Lewis base ligands,
X are monovalent or divalent anions,
k is 1 or 2,
l, m, n are 1 or 2,
where m×n=l, and, if desired, an additive.
Furthermore, we have found a novel process for preparing homopolymers, copolymers or block copolymers comprising cycloolefinic monomer units in which the polymerization of the monomer units is carried out in the presence of the above-described catalyst of the formula (I) and in the presence of an additive containing a polarized double bond.
We have also found homopolymers, copolymers and block copolymers comprising cycloolefinic monomer units whose end groups have hydroxyl units.
Also found has been the use of the metal complexes of the formula (I) as catalyst in the polymerization of cycloolefinic monomer units.
The catalysts used for the process of the present invention are preferably metal complexes which have the formula (I) below:
where the substituents and indices have the following meanings:
Z is methylene, 1,2-ethylene, 1,3-propylene or 1,4-butylene,
L
1
, L
2
are formally uncharged Lewis base ligands,
X are monovalent or divalent anions,
k is 1 or 2,
m, n are 1 or 2,
where m×n=2.
Suitable polymerization catalysts are in general metal compounds of the eighth transition group of the Periodic Table of the Elements (VIII B) which are in the form of a defined metal is complex (I). For the purposes of the present invention, a defined metal complex is preferably a compound which is prepared separately before use in the polymerization process. The active catalyst species can, however, likewise be generated in situ. If desired, additives having an activating action can be added to the metal compounds.
Suitable metals M are, apart from iron, cobalt, ruthenium, rhodium, osmium, iridium or platinum, preferably the metals nickel and palladium, with particular preference being given to palladium. The metals nickel, palladium and platinum essentially have a formal double positive charge in the complexes; iron, ruthenium and osmium generally have a single positive charge and cobalt and rhodium generally have a single or triple, preferably single, positive charge.
Suitable elements E
1
, E
2
, which can interact coordinatively with the metal center in (I) are the elements of main group V of the Periodic Table of the Elements (group VA), ie. nitrogen, phosphorus, arsenic, antimony or bismuth. Particularly suitable elements are nitrogen or phosphorus, in particular nitrogen. In a metal complex, E
1
and E
2
do not necessarily have to be identical. However, E
1
and E
2
are preferably identical, with preference being given to nitrogen.
The bridging structural unit Z connects the two elements E
1
and E
2
to one another. Z can be formed by linked substructural units each consisting of an atom of group IVA, VA or VIA of the Periodic Table of the Elements, where the possible free valences of these bridging atoms can be variously occupied, for example by substitution by hydrogen or by functional groups based on elements of groups IVA, VA, VIA and VIIA of the Periodic Table of the Elements, eg. silyl, alkyl, amino or alkoxy groups or halogen. The substituents can form ring structures with one another or with the bridging atom. Accordingly, the bridging structural unit Z can be, for example, a saturated or unsaturated carbon chain having up to four carbon atoms, where individual carbon atoms of the chain may be replaced by elements of groups IVA, VA and VIA of the Periodic Table of the Elements. For example, ether-, thioether-, amino-, phosphino-, imino- or sila-bridged systems Z are possibilities. Likewise, for example when E
1
=E
2
=phosphorus, heteroatom-terminated bridging structural units Z such as —O—(CH
2
)
2
—O— are possible. The bridging structure Z can also be terminated by non-identical substructural units, eg. by an N atom and a C atom, as in —N(R*)—CH
2
— or —N(R*)—(CH
2
)
2
— (R* is, for example, hydrogen, alkyl or aryl).
Readily bridging structural units Z are those comprising one, two, three or four elements from group IVA of the Periodic Table of the Elements, for example methylene (—CH
2
—), 1,2-ethylene (—CH
2
CH
2
—), 1,3-propylene (—CH
2
CH
2
CH
2
—), 1,4-butylene, 1,3-disilapropylene (—R
b
R
a
Si—CH
2
—SiR
a
R
b
, where R
a
, R
b
are C
1
-C
10
-alkyl or C
6
-C
10
-aryl), ethylidene (CH
3
(H)C═), 2-propylidene ((CH
3
)
2
C═), diphenylmethylene ((C
6
H
5
)
2
C═) or ortho-phenylene.
Particularly suitable bridging structural u

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