Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Polymers from only ethylenic monomers or processes of...
Reexamination Certificate
2000-12-05
2003-06-24
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...
C526S348200, C526S348300, C526S348600, C526S943000, C526S160000, C526S904000
Reexamination Certificate
active
06583253
ABSTRACT:
The present invention relates to propene terpolymers consisting of from 80 to 99.5 mol % of structural units derived from propene, from 0.1 to 15 mol % of structural units derived from ethene or a C
4
-C
6
-1-olefin (I) and from 0.1 to 15 mol % of structural units derived from a further C
4
-C
12
-1-olefin (II) which is different from the C
4
-C
6
-1-olefin (I), which propene terpolymers have a proportion of regioregular ′1-2′-inserted propene units corresponding to the formula (1)
[
′
1
-
2
′
]
[
′
1
-
2
′
]
+
[
′
2
-
1
′
]
+
[
′
1
-
3
′
]
(
1
)
of more than 0.99, have a melting point (T
M
), determined from the DSC peak maximum, of less than 135° C. and a weight average molecular weight (M
W
) of more than 80,000 g/mol and have a xylene-soluble proportion (X
S
) in % by weight of the propene terpolymer which obeys the following inequality (2)
X
S
≦1411.21 exp(−0.0591 T
M
[° C.])−0.05 (2).
The present invention further relates to a process for preparing propene terpolymers, their use for preparing films, fibers and moldings, the films, fibers and moldings obtainable in this way and also heat-sealable coating materials obtainable therefrom.
Binary copolymers of propene with ethene or a higher 1-olefin as comonomer prepared by means of metallocene catalysts are, inter alia, very suitable as materials for heat-sealable coatings (EP-A 668 157, DE-A 19 533 337). Compared to heat-sealable coating materials prepared using conventional Ziegler-Natta catalysts, the binary copolymers of propene prepared using metallocene catalysts have a very regular comonomer incorporation independent of the degree of polymerization, which results in them having comparatively low extractables contents. At the same time, such binary copolymers of propene are, even at low melting points, less sticky than heat-sealable coating materials which are obtained using conventional Ziegler Natta catalysts, which is why the preparation of binary copolymers of propene having a relatively low melting point is possible even under industrial conditions. This is advantageous because a low melting point usually allows lower heat-sealing temperatures which enables the cycle times in the heat-sealing process to be reduced. However, even in the case of the binary copolymers of propene prepared using metallocene catalysts, the extractables content is found to increase with decreasing melting point. As a consequence, binary copolymers of propene having a relatively low melting point can be used only to a limited extent in certain applications, for example as heat-sealable coating materials in the food sector, because the extractables content is too high.
EP-A 685 498 discloses propene terpolymers which are prepared by means of metallocene catalysts in which simple metallocenes without substituents in the &agr; position to the bridge of the metallocene complex are used. Such propene terpolymers have a proportion of regioirregular propene units of more than 1% [T. Tsutsui et al., J. Mol. Catalysis 56, 237 (1989)]. In addition, the proportion of extractables, for example material which can be extracted in boiling pentane, in these propene terpolymers is still rather too high for some applications.
Furthermore, DE-A 4 317 654 describes terpolymers of propene with copolymerized ethene and 1-butene, where the polymerization is carried out using a supported metallocene catalyst comprising a metallocene complex having &agr; substituents which is activated by means of a mixture of two different aluminoxanes. Such terpolymers of propene likewise have extractables contents which are still capable of improvement for some applications.
It is an object of the present invention to remedy the abovementioned drawbacks and to provide terpolymers of propene whose extractables content is further reduced, which have a low melting point and a sufficiently high molecular weight for the production of films and can be used without any great changes in existing industrial processes for producing heat-sealable coating materials.
We have found that this object is achieved by the propene terpolymers defined at the outset.
We have also found a process for preparing the propene terpolymers of the invention and also their use for producing films, fibers and moldings. The present invention also extends to films, fibers and moldings and to heat-sealable coating materials comprising the propene terpolymers of the present invention.
The propene terpolymers of the present invention consist of from 80 to 99.5 mol % of structural units derived from propene, preferably from 85 to 99 mol %, in particular from 87 to 98 mol %, also from 0.1 to 15 mol % of structural units derived from ethene or a C
4
-C
6
-1-olefin (I), preferably from 0.5 to 13 mol %, in particular from 0.5 to 10 mol %, plus from 0.1 to 15 mol % of structural units derived from a further C
4
-C
12
-1-olefin (II) which is different from the C
4
-C
6
-1-olefin (I), preferably from 0.3 to 12 mol %, in particular from 0.3 to 10 mol %. The sum of the mol % is always 100.
Suitable C
4
-C
6
-1-olefins (I) are, for example, 1-butene, 1-pentene, 4-methyl-1-pentene or 1-hexene, with preference being given to using 1-butene, 1-pentene or 1-hexene.
Suitable C
4
-C
12
-1-olefins (II) are, in particular, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene or 1-octene with particular preference being given to using 1-butene, 1-pentene and 1-hexene.
Particularly preferred propene terpolymers contain from 0.1 to 15 mol %, preferably from 0.1 to 10 mol %, of structural units derived from ethene, 1-pentene or 1-hexene and from 0.1 to 15 mol %, preferably from 0.1 to 8 mol %, of structural units derived from 1-butene.
The melting point (T
M
) of the propene terpolymers of the present invention, determined from the DSC peak maximum, is less than 135° C., in particular less than 130° C.
The propene terpolymers of the present invention also have a weight average molecular weight (M
W
) of more than 80,000 g/mol, in particular more than 150,000 g/mol. The weight average molecular weight (M
W
) is determined by gel permeation chromatography (GPC).
Furthermore, the propene terpolymers of the present invention have a proportion of regioregular ′1-2′-inserted propene units corresponding to the formula (1)
[
′
1
-
2
′
]
[
′
1
-
2
′
]
+
[
′
2
-
1
′
]
+
[
′
1
-
3
′
]
(
1
)
of more than 0.99. The regioregular ′1-2′-insertion of propene, the regioirregular ′2-1′-insertion and the likewise regioirregular ′1-3′-insertion are known, for example, from P. Pino et al., Angew. Chemie 92, 869 (1980) or from A. Zambelli et al., Macromolecules 21, 617 (1988).
The determination of the respective proportions of the regioregular ′1-2′-insertion, the regioirregular ′2-1′-insertion and the regioirregular ′1-3′-insertion is carried out, for example, by
13
C-NMR spectroscopy as described in A. Zambelli et al., Macromolecules 21, 617 (1988).
The amount of xylene-soluble material (X
S
) in the propene terpolymer of the present invention, in percent by weight, obeys the following inequality (2)
X
S
≦1411.21 exp(−0.591 T
M
[° C.])−0.05 (2)
where T
M
is the melting point of the propene terpolymer in ° C.
In addition, preferred propene terpolymers of the present invention have a polydispersity (M
w
/M
n
) of less than 2.25, especially less than 2.1 and in particular less than 2.0. The determination of the polydispersity (M
w
/M
n
) is preferably carried out by means of gel permeation chromatography using 1,2,4-trichlorobenzene as solvent.
The propene terpolymers of the present invention are preferably prepared by a likewise novel process which comprises polymerizing the comonomers in the presence of a metallocene catalyst system comprising
A) an inorganic or organic support,
B) at least one metallocene complex and
C) at least one c
Bidell Wolfgang
Fischer David
Hingmann Roland
Jones Peter John Vaughan
Kersting Meinolf
Basell Polypropylen GmbH
Keil & Weinkauf
Lee Rip A
Wu David W.
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