Liquid purification or separation – Processes – Ion exchange or selective sorption
Reexamination Certificate
2000-06-15
2002-05-07
Cintins, Ivars (Department: 1724)
Liquid purification or separation
Processes
Ion exchange or selective sorption
Reexamination Certificate
active
06383396
ABSTRACT:
The present invention relates to absorbents which comprise cycloolefin copolymers (COC).
To eliminate contaminants of soil or waters with organic compounds which occasionally or constantly enter the environment, such as oils, complete absorption and disposal of these contaminants is necessary. Absorbents which absorb organic compounds selectively can be employed for this purpose. It is also necessary to use absorbents to eliminate contaminants, such as oils, which enter into liquids or gases during industrial process steps. Not only complete and ecologically acceptable removal of the contaminants but also rapid and easy separation with the minimum possible disturbance to the course of the process are important here.
It is known from the literature that polyolefins are suitable absorbents for absorbing oils on water surfaces (U.S. Pat. No. 3,770,627). DE 43 20 908 also describes the use of polyethylene for this application, this allowing the absorption of oil in a weight ratio of 1:3. This can be improved further by using fibrous polyethylene. Polypropylene powder and granules are likewise described as absorbents for hydrocarbons on water surfaces (JP 71 031 586, JP 56 005 176, EP 0 619 271). FR 2 288 709 describes the use of pulverulent polynorbornene for absorbing petrochemical products on solid and liquid surfaces. The invention includes the homopolymers of [2.2.1]bicycloheptene and also of 5-methyl-[2.2.1]bicyclo-2-heptene, prepared by ring-opening polymerization.
On the basis of this invention, mixtures of homopolymers of [2.2.1]bicycloheptene and also of 5-methyl-[2.2.1]bicyclo-2-heptene with various organic and inorganic additives or fillers which are said to facilitate the absorption of contaminants, in particular oils, above all in waters, or to improve the ease of handling, have been described (FR 0 383 640, FR 0 383 641, U.S. Pat. No. 5,045,579).
JP 03 122 188 describes the preparation of absorbent films which consist of incomplete ring-opened [2.2.1]bicycloheptene and derivatives therof. These films are suitable for absorption of oils on water surfaces.
FR 2 645 047 describes the corresponding absorbent mixed with plasticizing additives and mineral fillers and pressed to a mat.
The use of absorbents in filter units for filtering out contaminants from liquids or high-pressure air is described in JP 4 118 013. A pulverulent or bead-shaped polynorbornene resin glued in layers onto a filter cloth, for example polyester, is used. Filter cassettes are built up from this, but cannot be reused directly.
Taking into account the amount of absorbent which is required for complete absorption of contaminants such as oils and is handled and after use is usually dumped or burned it is desirable to achieve the maximum possible absorption capacity. It is furthermore important to optimize the ability of the absorbent to absorb contaminants permanently under stress, for example during absorption on surfaces, during transportation or under pressure. This property is dealt with rarely and in little detail in the literature, but has a decisive influence on the efficiency of the absorbent.
In addition to the actual absorption capacity for contaminants such as oils, it is important for use in practice that the absorbent can be handled for absorption of contaminants on solid and liquid surfaces, i.e. can be applied readily and after contact with the contaminants can be taken up without difficulties. While handling of pulverulent binders on solid surfaces is unproblematic in many cases, their use, for example, on a turbulent water surface is difficult. An improvement in the ease of handling of the absorbent was achieved by the proposals described for solving this problem, for example by using films, but here also the absorption capacity is still to be improved.
From the ecological standpoint, it is to be taken into account that combustion of systems of absorbents which comprise atoms other than carbon and hydrogen, for example elements of main groups III, IV, V, VI or VII, in particular nitrogen, phosphorus, oxygen, sulfur, fluorine, chlorine and bromine, is considerably more problematic than in the case of the pure polyolefins because of the by-products formed.
There was thus the object of providing an absorbent which avoids the disadvantages of the prior art. Surprisingly, it has been found that absorbents which comprise cycloolefin copolymers achieve this object.
The present invention relates to an absorbent comprising at least one cycloolefin copolymer which contains polymerized units which are derived from at least one cyclic, in particular polycyclic, olefin and at least one acyclic olefin.
The absorbent according to the invention comprises 10-100% by weight, preferably 50-100% by weight, particularly preferably 90-100% by weight, of one or more cycloolefin copolymers. The absorbent according to the invention can also essentially comprise only one or more cycloolefin copolymers. The polycyclic olefins preferably have 5 to 50, in particular 5 to 30, carbon atoms. The acyclic olefins are preferably &agr;-olefines having 2 to 40 carbon atoms.
The content of polymerized units which are derived from cyclic, in particular polycyclic, olefins is 0.1 bis 99% by weight, preferably 30-99% by weight, particularly preferably 60-99% by weight, based on the total weight of the cycloolefin copolymer. The content of polymerized units which are derived from acyclic olefins is 0.1 to 99% by weight, preferably 5-80% by weight, particularly preferably 10-60% by weight, based on the total weight of the cycloolefin copolymer.
The invention preferably relates to absorbents comprising at least one cycloolefin copolymer which contains 0.1-99% by weight, preferably 30-99% by weight, particularly preferably 60-99% by weight, based on the total weight of the cycloolefin copolymer, of polymerized units which are derived from one or more polycyclic olefins of the formulae 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 or a C
1
-C
20
-hydrocarbon radical, such as a linear or branched C
1
-C
8
-alkyl radical, a C
6
-C
18
-aryl radical, a C
7
-C
20
-alkylenearyl radical or a cyclic or acyclic C
2
-C
20
-alkenyl radical, or form a ring, where the same radicals R
1
to R
8
in the various formula I to VI can have a different meaning, and 0.1 to 99% by weight, based on the total weight of the cycloolefin copolymer, of polymerized units which are derived from one or more acyclic olefins of the formula VII
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
20
-hydrocarbon radical, such as a C
1
-C
8
-alkyl radical or a C
6
-C
18
-aryl radical.
The cycloolefin copolymer contained in the absorbent according to the invention can furthermore contain 0.1 to 95% by weight, based on the total weight of the cycloolefin copolymer, of polymerized units which are derived from one or more monocyclic olefins of the formula VIII
in which n is a number from 2 to 10.
The cycloolefin copolymers contained in the absorbent according to the invention preferably consist of polymerized units which are derived from one or more polycyclic olefins, in particular polycyclic olefins of the formulae I or III, and polymerized units which are derived from one or more acyclic olefins of the formula VII, in particular &agr;-olefins having 2-20 carbon atoms. Cycloolefin copolymers which consist of polymerized units which are derived from a polycyclic olefin of the formula I or III and an acyclic olefin of the formula VII are particularly preferred. Terpolymers which consist of polymerized units which are derived from a polycyclic monoolefin of the formula I or III, an acyclic monoolefin of the formula VII and a cyclic or acyclic olefin which contains at least two double bonds (polyene), in particular cyclic, preferably polycyclic, dienes, such as norbornadiene, or cyclic, particularly preferably polycyclic, alkenes which carry a C
2
-C
20
-alkenyl radical, such as vi
Helmer-Metzmann Freddy
Jacobs Alexandra
Connolly Bove & Lodge & Hutz LLP
Ticona GmbH
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