Fibers made of cycloolefin copolymers

Details Fibers made of cycloolefin copolymers Fibers made of cycloolefin copolymers

1995-06-01

2002-10-01

Zitomer, Fred (Department: 1713)

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

Synthetic resins

Treating polymer containing material or treating a solid...

C526S281000, C526S170000, C528S486000, C528S491000, C528S495000, C528S497000, C528S50200C, C528S50200C

Reexamination Certificate

active

06458919

ABSTRACT:

The invention relates to fibers made of partly crystal-line copolymers of polycyclic olefins.
Polyolefin fibers based on polyethylene and polypropylene are already known. A very advantageous property of these polyolefin fibers is their high solvent resistance. They are essentially stable to all polar solvents (for example ketones, alcohols, organic acids, ester compounds, amide compounds) and aqueous media (for example aqueous acids, alkalis), and at room temperature are also resistant to nonpolar solvents such as saturated hydrocarbons (for example oils, petroleum fractions). This property, combined with a high chemical resistance, has given the polyolefin fibers wide areas of application in the textile sector and in industry. Highly oriented fibers made of high-molecular-weight PE are known for their very high tensile strength at room temperature. PE and PP fibers are also used for the manufacture of woven fabrics and nonwovens.
The thermal shape stability, for example in connection with the sterilizability or other processes in which higher temperatures occur (for example, nonwovens for filtering of hot water and gas), frequently plays an important role here. Unfavorably, the mechanical properties of PE fibers begin to fall off only just above room temperature. A significant deterioration is observed above about 70 to 80° C.
Cycloolefin copolymers incorporating a high proportion of cycloolefin and also cycloolefin homopolymers have, because of their high glass transition temperature, very high thermal shape stability and hence good mechanical properties. Furthermore, they have outstanding resistance to polar solvents such as water, alcohol, acetone and dimethylformamide, and also to aqueous acids and alkalis. However, on the unfavorable side, they dissolve readily in aliphatic and aromatic hydrocarbons or they are greatly swollen by these.
It is an object of the invention to provide polyolefin fibers which are comparable with polyethylene and polypropylene fibers in respect of their solvent resistance and at the same time have a higher thermal shape stability than these known polyolefin fibers and can be spun from the melt.
It has been found that this object can be achieved by fibers made of partly crystalline cycloolefin copolymers which contain less than 100 ppm (based on the total weight of the polymer) of catalyst residues.
The preparation of partly crystalline cycloolefin copolymers is described in EP-A-0 503 422. Tests have shown that the polymers thus prepared contain above 100 ppm of catalyst residues (i.e. metallocene and cocatalyst residues). During processing via the melt (at about 300° C.) these products prove to be thermally labile. This is shown by the polymer turning brown. Thin pressed plates (thickness 200 &mgr;m) showed distinct gel particles (fish eyes) which probably arose through localized crosslinking of the polymer, triggered by catalyst residues. Spinning tests on fibers produced in accordance with EP-A 503 422 gave unsatisfactory results, since the gel particles led to fiber breakage. It was established that such cycloolefin polymers are only suitable for fiber production if the residual catalyst content is less than 100 ppm.
Cycloolefins polymerize in bulk or in solvents in the presence of metallocene catalysts with retention of the rings (EP 407870, DE 84036264). The solvents used are mainly hydrocarbons.
The invention accordingly provides fibers which comprise at least one cycloolefin copolymer which can be prepared by polymerization of from 30 to 99.9% by weight, based on the total amount of monomers, of at least one symmetrical, polycyclic olefin of the formula I, II, III, IV, V or VI
in which R
1
, R
2
, R
3
, R
4
, R
5
, R
6
, R
7
and R
8
are identical or different and are a hydrogen atom, a C
6
-C
16
-aryl or a C
1
-C
8
-alkyl radical,
from 0 to 50% by weight, based on the total amount of monomers, of a monocyclic olefin of the formula VII
in which n is a number from 2 to 10, and from 70 to 0.1% by weight, based on the total amount of monomers, of at least one acyclic olefin of the formula VIII
in which R
9
, R
10
, R
11
and R
12
are identical or different and are a hydrogen atom or a C
1
-C
8
-alkyl radical or a C
6
-C
16
-aryl radical, at temperatures from −78 to 150° C. and a pressure from 0.01 to 64 bar, in the presence of a catalyst which comprises an aluminoxane of the formula IX
for the linear type and/or of the formula X
for the cyclic type, where in the formulae IX and X the radicals R
13
are identical or different and are a C
1
-C
6
-alkyl group or phenyl or benzyl and n is an integer from 0 to 50, and a metallocene of the formula XI
in which
M
1
is titanium, zirconium, hafnium, vanadium, niobium or tantalum,
R
14
and R
15
are identical or different and are a hydrogen atom, a halogen atom, a C
1
-C
10
-alkyl group, a C
1
-C
10
-alkoxy group, a C
6
-C
10
-aryl group, a C
6
-C
10
-aryloxy group, a C
2
-C
10
-alkenyl group, a C
7
-C
40
-arylalkyl group, a C
7
-C
40
-alkylaryl group or a C
8
-C
40
-arylalkenyl group,
m=1 or 2
R
16
and R
17
are different and are a monocyclic or polycyclic hydrocarbon radical which can form a sandwich structure with the central atom M
1
, where the part of the molecule formed by R
16
, R
17
and M
1
has C
1
symmetry,
R
18
is
 ═BR
19
═AlR
19
, —Ge—, —Sn—, —O—, —S—, ═SO, ═SO
2
, ═NR
19
, ═CO, ═PR
19
or ═P(O)R
19
, where R
19
, R
20
and R
21
are identical or different and are a hydrogen atom, a halogen atom, a C
1
-C
10
-alkyl group, a C
1
-C
10
-fluoroalkyl group, a C
6
-C
10
-fluoroaryl group, a C
6
-C
10
-aryl group, a C
1
-C
10
-alkoxy group, a C
2
-C
10
-alkenyl group, a C
7
-C
40
-arylalkyl group, a C
8
-C
40
-arylalkenyl group or a C
7
-C
40
-alkylaryl group or R
19
and R
20
or R
19
and R
21
form a ring with the atoms linking them in each case, and
M
2
is silicon, germanium or tin, wherein the residual catalyst content is less than 100 ppm.
Alkyl is here a straight-chain or branched alkyl.
The monocyclic olefin of the formula VII may, for the purposes of the invention, also be substituted (for example by aryl or alkyl radicals).
The polymerization is preferably carried out in the liquid cycloolefin monomer, cycloolefin monomer mixture or in concentrated solutions.
In the polymerization reaction, at least one symmetrical polycyclic olefin of the formula I, II, III, IV, V or VI, preferably a symmetrical polycyclic olefin of the formula I or III in which R
1
, R
2
, R
3
, R
4
, R
5
, R
6
, R
7
and R
8
are identical or different and are a hydrogen atom or a C
1
-C
8
-alkyl radical, is polymerized.
If desired, a monocyclic olefin of the formula VII in which n is a number from 2 to 10 is also used. Another comonomer is an acyclic olefin of the formula VIII in which R
9
, R
10
, R
11
and R
12
are identical or different and are a hydrogen atom or a C
1
-C
8
-alkyl radical. Ethylene or propylene is preferred.
In particular, copolymers of polycyclic olefins, preferably of the formulae I and III, with the acyclic olefins of the formula VIII are prepared.
Particularly preferred cycloolefins are norbornene and tetracyclododecene, with these able to be substituted by (C
1
-C
6
)-alkyl. They are preferably copolymerized with ethylene; ethylene
orbornene copolymers are of particular importance.
The cycloolefin copolymers of the invention are preferably obtained when the ratio of cycloolefin to acyclic olefin is optimized.
If the selected concentration of the acyclic olefin at a given cycloolefin concentration is too high, the cycloolefin content of the copolymer falls below 50 mol %. The melting point is shifted to lower temperatures or disappears entirely.
If the concentration of the acyclic olefin at a given cycloolefin concentration is too low, there is a fall, in particular, in the activity of catalysis and in the molecular weight of the copolymer.
The cycloolefin copolymers prepared according to the process described here contain the symmetrical polycyclic 30 olefin of the formula I, II, III, IV, V or VI in an amount fro

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