DE10343901A1 - Amide group-containing ethylene terpolymers and their use - Google Patents

Abstract

Ethylenes terpolymers copolymerized as comonomers include: (a) ethylene, (b) at least one cyclic amide having at least one ethylenically unsaturated group, (c) at least one at least monoethylenically unsaturated carboxylic acid or at least one ester of an at least monoethylenically unsaturated carboxylic acid, further Process for their preparation and their use.

Description

The The present invention relates to ethylene terpolymers useful as comonomers in copolymerized form contain: (a) ethylene, (b) at least one cyclic Amide having at least one ethylenically unsaturated group, (c) and at least an at least monoethylenically unsaturated carboxylic acid or at least one ester of at least one ethylenically unsaturated Carboxylic acid.

• (a) 45 bis 95 Gew.-% Ethylen,
• (b) 0,1 bis 50 Gew.-% mindestens ein cyclisches Amid mit mindestens einer ethylenisch ungesättigten Gruppe,
• (c) 0,1 bis 40 Gew.-% mindestens einer mindestens einfach ethylenisch ungesättigten Carbonsäure oder mindestens einem Ester einer mindestens einfach ethylenisch ungesättigten Carbonsäure,

wobei Angaben in Gew.-% jeweils auf die Gesamtmasse an Ethylenterpolymer bezogen sind.Specifically, the present invention relates to ethylene terpolymers incorporated in copolymerized form as comonomers

• (a) 45 to 95% by weight of ethylene,
• (b) 0.1 to 50% by weight of at least one cyclic amide having at least one ethylenically unsaturated group,
• (c) from 0.1 to 40% by weight of at least one at least monoethylenically unsaturated carboxylic acid or at least one ester of an at least monoethylenically unsaturated carboxylic acid,

where in wt .-% are each based on the total weight of ethylene terpolymer.

Farther The present invention relates to a process for the preparation inventive ethylene terpolymer as well as their use.

In Methods for the separation of substances are in addition to classical methods like crystallization and distillation also modern, fast, less energy-intensive processes such as membrane separation processes examined, as well Chromatography, ultrafiltration, dialysis and electrodialysis. Great meaning comes while selecting the material used for substance separation.

there These materials will be used below under Materials for separation understood, for example, by adsorption-desorption processes or due to different permeability properties, the separation or enrichment of individual components from mixtures of substances. Examples include membranes and stationary phases for chromatography columns.

Next play the price for Material separation materials in particular factors such as selectivity, permeability and mechanical Stability, especially at high feed pressure, a role. In addition, materials for Separation of substances in organic solvents only slightly sources.

It has been proposed many times, polymers as materials for material separation use. Thus, certain polyimides have already been proposed the bis-trifluoromethyldiphenylidenemethane units wear, s. for example W.J. Koros et al., J. Membr. Sci. 1988 37, 45; J. Koros et al., Prog. Polym. Sci. 1988, 13, 399; K. Tanaka et al., Polym. Sci. Part B, 1995, 33, 1907; T.H. Kim et al., J. Membr. Sci. 1993, 50, 45; Tanaka, K., et al., J. Membr. Sci. 1996 121, 197, C. Staudt-Bickel et al., J. Membr. Sci. 2000, 170, 205; C. Staudt-Bickel et al., J. Membr. Sci. 1999, 155, 145. The in the Although cited polyimides described under certain Conditions are used for the separation of olefin-alkane mixtures, however, occurs at separations under technically interesting conditions in many cases strong swelling on what the mechanical properties of for example Membranes adversely affected. Besides, the suggested ones are Materials awkward produce and therefore unfavorable price.

G. Ellinghaus et al. report in Radiat. Phys. Chem. 1983, 22, 635, that certain polymers are then suitable as membrane materials, when viewed by radiation-initiated graft copolymerization modified. The disclosed method, however, is cumbersome.

R.A. Terteryan et al. Report in Plasticheskie Massy 1989, 7, 18-21 on the Synthesis of ethylene-N-vinylpyrrolidone copolymers and ethylene-N-vinylpyrrolidone-vinyl acetate terpolymers with melt flow indices in the range of 0.08 to 170 and 1 to 700, respectively g / 10 min at 125 ° C.

Out US 3,626,025 For example, ethylene-N-vinylpyrrolidone copolymers and ethylene-N-vinylpyrrolidone-vinyl acetate terpolymers and their use in the dyeing of nylon are known.

It the task was to provide material for the separation of substances, which have an improved application profile. Continue to exist the task, a method for the production of materials for the separation of substances to provide. Furthermore, the task, a method to prepare for the separation of substance mixtures.

Accordingly, were found the above-defined ethylene terpolymers.

• (a) 45 bis 95 Gew.-% Ethylen, bevorzugt 65 bis 90 Gew.-%,
• (b) 0,1 bis 50 Gew.-% mindestens ein cyclisches Amid mit mindestens einer ethylenisch ungesättigten Gruppe, bevorzugt 5 bis 35 Gew.-%,
• (c) 0,1 bis 40 Gew.-% mindestens einer mindestens einfach ethylenisch ungesättigten Carbonsäure oder mindestens einem Ester einer mindestens einfach ethylenisch ungesättigten Carbonsäure, bevorzugt 0,2 bis 30 Gew.-%.

In one embodiment of the present invention, ethylene terpolymers according to the invention contain in copolymerized form as comonomers:

• (a) 45 to 95% by weight of ethylene, preferably 65 to 90% by weight,
• (b) 0.1 to 50% by weight of at least one cyclic amide having at least one ethylenically unsaturated group, preferably 5 to 35% by weight,
• (C) 0.1 to 40 wt .-% of at least one at least monoethylenically unsaturated carboxylic acid or at least one ester of an at least monoethylenically unsaturated carboxylic acid, preferably 0.2 to 30 wt .-%.

there are weight percentages in each case based on the total weight of ethylene terpolymer according to the invention based.

Preferably the proportions of (b) and (c) together amount to at least 5% by weight, particularly preferably at least 10% by weight.

in der die Variablen wie folgt definiert sind:
R¹ und R² sind gleich oder verschieden;
R¹ wird gewählt aus Wasserstoff und unverzweigtem und verzweigtem C₁-C₁₀-Alkyl, wie beispielsweise Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl, tert.-Butyl, n-Pentyl, iso-Pentyl, sec.-Pentyl, neo-Pentyl, 1,2-Dimethylpropyl, iso-Amyl, n-Hexyl, iso-Hexyl, sec.-Hexyl, n-Heptyl, n-Octyl, 2-Ethylhexyl, n-Nonyl, n-Decyl; besonders bevorzugt C₁-C₄-Alkyl wie Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl und tert.-Butyl, insbesondere Methyl;
R² wird gewählt aus unverzweigten und verzweigten C₁-C₁₀-Alkyl wie beispielsweise Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl, tert.-Butyl, n-Pentyl, iso-Pentyl, sec.-Pentyl, neo-Pentyl, 1,2-Dimethylpropyl, iso-Amyl, n-Hexyl, iso-Hexyl, sec.-Hexyl, n-Heptyl, n-Octyl, 2-Ethylhexyl, n-Nonyl, n-Decyl; besonders bevorzugt C₁-C₄-Alkyl wie Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl und tert.-Butyl, insbesondere Methyl;
und ganz besonders bevorzugt Wasserstoff.
R³ sind verschieden oder vorzugsweise gleich und gewählt aus Wasserstoff und verzweigten und bevorzugt unverzweigten C₁-C₁₀-Alkyl, beispielsweise Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl, tert.-Butyl, n-Pentyl, iso-Pentyl, sec.-Pentyl, neo-Pentyl, 1,2-Dimethylpropyl, iso-Amyl, n-Hexyl, iso-Hexyl, sec.- Hexyl, n-Heptyl, n-Octyl, 2-Ethylhexyl, n-Nonyl, n-Decyl; bevorzugt Methyl, Ethyl, n-Propyl, n-Butyl, n-Pentyl, iso-Pentyl, n-Hexyl, n-Heptyl, n-Octyl, n-Nonyl, n-Decyl; besonders bevorzugt C₁-C₄-Alkyl wie Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl und tert.-Butyl, ganz besonders bevorzugt Methyl;
C₃-C₁₂-Cycloalkyl wie beispielsweise Cyclopropyl, Cyclobutyl, Cyclopentyl, Cyclohexyl, Cycloheptyl, Cyclooctyl, Cyclononyl, Cyclodecyl, Cycloundecyl und Cyclododecyl; bevorzugt sind Cyclopentyl, Cyclohexyl und Cycloheptyl
wobei zwei benachbarte Reste R³ miteinander unter Bildung eines gegebenenfalls mit C₁-C₄-Alkylresten substituierten 3- bis 10-gliedrigen, bevorzugt 5- bis 7-gliedrigen Rings verbunden sein können,
in einer besonders bevorzugten Ausführungsform sind zwei benachbarte Reste R³ zusammen

In a preferred embodiment, at least one comonomer (b) corresponds to the general formula I.

where the variables are defined as follows:
R ¹ and R ² are the same or different;
R ¹ is selected from hydrogen and unbranched and branched C ₁ -C ₁₀ -alkyl, such as, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl, sec-pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec-hexyl, n-heptyl, n-octyl, 2- Ethylhexyl, n-nonyl, n-decyl; particularly preferably C ₁ -C ₄ -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl, in particular methyl;
R ² is selected from unbranched and branched C ₁ -C ₁₀ -alkyl, such as, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl iso-pentyl, sec-pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n Nonyl, n-decyl; particularly preferably C ₁ -C ₄ -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl, in particular methyl;
and most preferably hydrogen.
R ³ are different or preferably identical and selected from hydrogen and branched and preferably unbranched C ₁ -C ₁₀ -alkyl, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl, sec-pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec-hexyl, n-heptyl, n Octyl, 2-ethylhexyl, n-nonyl, n-decyl; preferably methyl, ethyl, n-propyl, n-butyl, n-pentyl, iso-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl; particularly preferably C ₁ -C ₄ -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl, very particularly preferably methyl;
C ₃ -C ₁₂ cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl and cyclododecyl; preferred are cyclopentyl, cyclohexyl and cycloheptyl
wherein two adjacent radicals R ^{3 may be joined} together to form a 3 to 10-membered, preferably 5 to 7-membered ring optionally substituted by C ₁ -C ₄ -alkyl radicals,
In a particularly preferred embodiment, two adjacent radicals R ^{3 are} together

Most preferably, all R ^{3 are the} same and each is hydrogen.
n is an integer in the range of 2 to 10, more preferably 3 or 4.

In one embodiment of the present invention, R ¹ and R ^{2 are} each hydrogen.

In one embodiment of the present invention, R ^{1 is} hydrogen or methyl and R ^{2 is} hydrogen, n is selected from 3 and 4 and all R ³ are the same and are each hydrogen.

in der die Variablen wie folgt definiert sind:
R⁴ und R⁵ sind gleich oder verschieden.
R⁴ wird gewählt aus Wasserstoff und
unverzweigtem und verzweigtem C₁-C₁₀-Alkyl, wie beispielsweise Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl, tert.-Butyl, n-Pentyl, iso-Pentyl, sec.-Pentyl, neo-Pentyl, 1,2-Dimethylpropyl, iso-Amyl, n-Hexyl, iso-Hexyl, sec.-Hexyl, n-Heptyl, n-Octyl, 2-Ethylhexyl, n-Nonyl, n-Decyl; besonders bevorzugt C₁-C₄-Alkyl wie Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl und tert.-Butyl, insbesondere Methyl;
Vinyl -CH=CH₂ und (Z) und vorzugsweise (E)-Allyl -CH=CH-CH₃.
R⁵ wird gewählt aus unverzweigten und verzweigten C₁-C₁₀-Alkyl wie beispielsweise Methyl, Ethyl; n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl, tert.-Butyl, n-Pentyl, iso-Pentyl, sec.-Pentyl, neo-Pentyl, 1,2-Dimethylpropyl, iso-Amyl, n-Hexyl, iso-Hexyl, sec.-Hexyl, n-Heptyl, n-Octyl, 2-Ethylhexyl, n-Nonyl, n-Decyl; besonders bevorzugt C₁-C₄-Alkyl wie Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl und tert.-Butyl, ganz besonders bevorzugt Methyl;
und ganz besonders bevorzugt Wasserstoff.
R⁶ wird gewählt aus
unverzweigten und verzweigten C₁-C₁₀-Alkyl wie beispielsweise Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl, tert.-Butyl, n-Pentyl, iso-Pentyl, sec.-Pentyl, neo-Pentyl, 1,2-Dimethylpropyl, iso-Amyl, n-Hexyl, iso-Hexyl, sec.-Hexyl, n-Heptyl, n-Octyl, 2-Ethylhexyl, n-Nonyl, n-Decyl; besonders bevorzugt C₁-C₄-Alkyl wie Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl und tert.-Butyl, insbesondere Methyl;
C₃-C₁₂-Cycloalkyl wie Cyclopropyl, Cyclobutyl, Cyclopentyl, Cyclohexyl, Cycloheptyl, Cyclooctyl, Cyclononyl, Cyclodexyl, Cycloundecyl und Cyclododecyl; bevorzugt sind Cyclopentyl, Cyclohexyl und Cycloheptyl,
und insbesondere Wasserstoff.In a preferred embodiment of the present invention, at least one comonomer (c) corresponds to the general formula II,

where the variables are defined as follows:
R ⁴ and R ⁵ are the same or different.
R ⁴ is selected from hydrogen and
unbranched and branched C ₁ -C ₁₀ -alkyl, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl , sec-pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n decyl; particularly preferably C ₁ -C ₄ -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl, in particular methyl;
Vinyl -CH = CH ₂ and (Z) and preferably (E) -allyl-CH = CH-CH ₃ .
R ⁵ is selected from straight and branched C ₁ -C ₁₀ alkyl such as methyl, ethyl; n-propyl, iso -propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl, sec-pentyl, neo-pentyl, 1,2-dimethylpropyl, iso -Amyl, n-hexyl, iso -hexyl, sec-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl; particularly preferably C ₁ -C ₄ -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl, very particularly preferably methyl;
and most preferably hydrogen.
R ⁶ is selected
unbranched and branched C ₁ -C ₁₀ -alkyl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl, sec-pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n- decyl; particularly preferably C ₁ -C ₄ -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl, in particular methyl;
C ₃ -C ₁₂ cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodexyl, cycloundecyl and cyclododecyl; preferred are cyclopentyl, cyclohexyl and cycloheptyl,
and especially hydrogen.

In one embodiment of the present invention, R ^{4 is} hydrogen or methyl. Most preferably, R ^{4 is} hydrogen.

In one embodiment of the present invention, R ⁴ and R ^{5 are} hydrogen. In one embodiment of the present invention R ^{4 is} hydrogen and R ^{5 is} methyl.

Most preferably, R ^{6 is} hydrogen or methyl.

Do you wish several at least monounsaturated ethylenically unsaturated Carboxylic acid esters for Production of in the process according to the invention For example, it is possible to use ethylene terpolymer used two different ethylenically unsaturated carboxylic acid esters use the general formula II such as methyl acrylate and methacrylic acid methyl ester.

In an embodiment The present invention is used for the preparation of the process according to the invention used Ethylenenterpolymer as ethylenically unsaturated carboxylic acid esters methyl acrylate or (meth) acrylic acid methyl ester one.

In an embodiment of the present invention contain ethylene terpolymers according to the invention no more comonomers over (a) and (b) polymerized in addition.

In one embodiment of the present invention, ethylene terpolymers according to the invention contain at least up to 5 parts by weight, based on the sum of (a), (b) and (c), of at least one other Comonomers copolymerized. Preferred further copolymerized comonomers are, for example, isobutene and vinyl acetate.

In an embodiment of the present invention Ethylenterpolymere according to the invention a Melt flow rate (MFR) in the range of 1 to 500 g / 10 min, preferably 5 to 250 g / 10 min, more preferably 7 to 50 g / 10 min, measured at 160 ° C and a load of 325 g according to DIN 53735.

In an embodiment of the present invention Ethylenterpolymere according to the invention a dynamic melt viscosity η in the range from 500 to 60,000 mPa · s, preferably in the range of 800 to 55,000 mPa · s.

In an embodiment The present invention provides the melting ranges of the ethylene terpolymers of the invention in the range of 60 to 115 ° C, preferably in the range of 65 to 110 ° C, determined by DSC according to DIN 51,007th

In an embodiment of the present invention the melting ranges of in ethylene terpolymer according to the invention broad and a temperature interval of at least 5 to at most 20 ° C, preferably at least 7 ° C until at most 15 ° C.

In an embodiment of the present invention are the melting points of ethylene-ethylene polymer of the invention sharp and are in a temperature range of less than 2 ° C, preferably less than 1 ° C, determined according to DIN 51007.

In one embodiment of the present invention, the density of the ethylene terpolymers according to the invention is 0.89 to 1.10 g / cm ³ , preferably 0.92 to 0.94 g / cm ³ , determined according to DIN 53479.

In an embodiment In the present invention, the acid value of the ethylene copolymer of the present invention can be in the range 30 to 300 mg KOH / g of ethylene copolymer are preferred 100 to 230 mg KOH / g ethylene copolymer, determined according to DIN 53402.

Inventive Ethylenenterpolymere can alternating copolymers or block copolymers or preferably random copolymers.

One Another aspect of the present invention is a method for Preparation of Ethylenterpolymers According to the Invention

Inventive Ethylenenterpolymere can advantageous by free-radically initiated copolymerization of ethylene with at least one cyclic amide having at least one ethylenic unsaturated Group (a) and at least one comonomer derived from an ester of a ethylenically unsaturated Group is derived, and optionally one or more others Comonomers are prepared under high pressure conditions, hereinafter also inventive polymerization called. The implementation of the inventive polymerization succeeds, for example, in stirred High pressure autoclaves or in high pressure tube reactors or in combinations from or in combinations of high pressure autoclave and high pressure tube reactor, which are connected in series. The implementation in stirred high pressure autoclave is preferred. stirred High pressure autoclave are known per se, a description will find one in Ullmann's Encyclopedia of Industrial Chemistry 5th edition, keywords: Waxes, Bd. A 28, p. 146 ff., Verlag Chemie Weinheim, Basel, Cambridge, New York, Tokyo, 1996. For them, the relationship between length and diameter is predominant at intervals of 5: 1 to 30: 1, preferably 10: 1 to 20: 1. The same applicable high-pressure tube reactors can also be found in Ullmann's Encyclopedia of Industrial Chemistry 5th edition, keywords: Waxes, Vol. A 28, p. 146 ff., Verlag Chemie Weinheim, Basel, Cambridge, New York, Tokyo; 1996th

suitable Printing conditions for the polymerization process according to the invention are 500 to 4000 bar, preferably 1500 to 2500 bar. conditions This type will be referred to below as high pressure. The Reaction temperatures are in the range of 170 to 300 ° C, preferably in the range of 195 to 280 ° C.

oder Mischungen derselben.The polymerization can be carried out in the presence of at least one regulator. The regulator used is, for example, hydrogen or at least one aliphatic aldehyde or at least one aliphatic ketone of the general formula III

or mixtures thereof.

• – Wasserstoff;
• – C₁-C₆-Alkyl wie Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl, tert.-Butyl, n-Pentyl, iso-Pentyl, sec.-Pentyl, neo-Pentyl, 1,2-Dimethylpropyl, iso-Amyl, n-Hexyl, iso-Hexyl, sec.-Hexyl, besonders bevorzugt C₁-C₄-Alkyl wie Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl und tert.-Butyl;
• – C₃-C₁₂-Cycloalkyl wie Cyclopropyl, Cyclobutyl, Cyclopentyl, Cyclohexyl, Cycloheptyl, Cyclooctyl, Cyclononyl, Cyclodecyl, Cycloundecyl und Cyclododecyl; bevorzugt sind Cyclopentyl, Cyclohexyl und Cycloheptyl.

The radicals R ⁷ and R ^{8 are the} same or different and selected from

• - hydrogen;
• C ₁ -C ₆ -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec. Pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec-hexyl, more preferably C ₁ -C ₄ alkyl such as methyl, ethyl, n-propyl, iso-propyl , n-butyl, iso-butyl, sec-butyl and tert-butyl;
• C ₃ -C ₁₂ cycloalkyl, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl and cyclododecyl; preferred are cyclopentyl, cyclohexyl and cycloheptyl.

In a particular embodiment, R ⁵ and R ⁶ are covalently bonded together to form a 4- to 13-membered ring. For example, R ⁶ and R ⁷ may be in common: - (CH ₂ ) ₄ -, - (CH ₂ ) ₅ -, - (CH ₂ ) ₆ , - (CH ₂ ) ₇ -, -CH (CH ₃ ) -CH ₂ -CH ₂ -CH (CH ₃ ) - or -CH (CH ₃ ) -CH ₂ -CH ₂ -CH ₂ -CH (CH ₃ ) -.

Examples for suitable Regulators are also alkylaromatic compounds, for example Toluene, ethylbenzene or one or more isomers of xylene. Examples for good suitable regulators are also paraffins such as isododecane (2,2,4,6,6-pentamethylheptane) or isooctane.

When Starter for The radical polymerization can be the usual radical starter for example, organic peroxides, oxygen or azo compounds be used. Also mixtures of several radical starters are suitable.

• – Didekanoylperoxid, 2,5-Dimethyl-2,5-di(2-ethylhexanoylperoxy)hexan, tert.-Amylperoxy-2-ethylhexanoat, Dibenzoylperoxid, tert.-Butylperoxy-2-ethylhexanoat, tert.-Butylperoxydiethylacetat, tert.-Butylperoxydiethylisobutyrat, 1,4-Di(tert.-butylperoxycarbonyl)-cyclohexan als Isomerengemisch, tert.-Butylperisononanoat 1,1-Di-(tert.-butylperoxy)-3,3,5-trimethylcyclohexan, 1,1-Di-(tert.-butylperoxy)-cyclohexan, Methyl-isobutylketonperoxid, tert.-Butylperoxyisopropylcarbonat, 2,2-Di-tert.-butylperox)butan oder tert.-Butylperoxacetat;
• – tert.-Butylperoxybenzoat, Di-tert.-amylperoxid, Dicumylperoxid, die isomeren Di-(tert.-butylperoxyisopropyl)benzole, 2,5-Dimethyl-2,5-di-tert.-butylperoxyhexan, tert.-Butylcumylperoxid, 2,5-Dimethyl-2,5-di(tert.-butylperoxy)-hex-3-in, Di-tert.- butylperoxid, 1,3-Diisopropylbenzolmonohydroperoxid, Cumolhydroperoxid oder tert.-Butylhydroperoxid; oder
• – dimere oder trimere Ketonperoxide oder cyclische Peroxide der allgemeinen Formel IV a bis IV c.

Suitable peroxides selected from commercially available substances are, for example

• Didecanoyl peroxide, 2,5-dimethyl-2,5-di (2-ethylhexanoylperoxy) hexane, tert-amylperoxy-2-ethylhexanoate, dibenzoyl peroxide, tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxydiethylacetate, tert-butyl peroxydiethyl isobutyrate , 1,4-di (tert-butylperoxycarbonyl) cyclohexane as a mixture of isomers, tert-butyl perisononanoate 1,1-di- (tert-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-di- (tert .-butylperoxy) -cyclohexane, methyl isobutyl ketone peroxide, tert-butyl peroxyisopropyl carbonate, 2,2-di-tert-butylperoxy) butane or tert-butyl peroxyacetate;
• Tert-butyl peroxybenzoate, di-tert-amyl peroxide, dicumyl peroxide, the isomeric di- (tert-butylperoxyisopropyl) benzenes, 2,5-dimethyl-2,5-di-tert-butylperoxyhexane, tert-butylcumyl peroxide, 2 , 5-dimethyl-2,5-di (tert-butylperoxy) -hex-3-yne, di-tert-butyl peroxide, 1,3-diisopropylbenzene monohydroperoxide, cumene hydroperoxide or tert-butyl hydroperoxide; or
• - dimeric or trimeric ketone peroxides or cyclic peroxides of the general formula IV a to IV c.

• – C₁-C₈-Alkyl wie Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, sec.-Butyl, iso-Butyl, tert.-Butyl, n-Pentyl, sec.-Pentyl, iso-Pentyl, n-Hexyl, n-Heptyl, n-Octyl; bevorzugt lineares C₁-C₆-Alkyl wie Methyl, Ethyl, n-Propyl, n-Butyl, n-Pentyl, n-Hexyl, besonders bevorzugt lineares C₁-C₄-Alkyl wie Methyl, Ethyl, n-Propyl oder n-Butyl, ganz besonders bevorzugt ist Methyl und Ethyl;
• – C₆-C₁₄-Aryl wie Phenyl, 1-Naphthyl, 2-Naphthyl, 1-Anthryl, 2-Anthryl, 9-Anthryl, 1-Phenanthryl, 2-Phenanthryl, 3-Phenanthryl, 4-Phenanthryl und 9-Phenanthryl, bevorzugt Phenyl, 1-Naphthyl und 2-Naphthyl, besonders bevorzugt Phenyl.

The radicals R ⁹ to R ^{14 are} identical or different and selected from

• C ₁ -C ₈ -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, sec-pentyl, isobutyl, Pentyl, n-hexyl, n-heptyl, n-octyl; preferably linear C ₁ -C ₆ -alkyl, such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, particularly preferably linear C ₁ -C ₄ -alkyl, such as methyl, ethyl, n-propyl or n Butyl, most preferably methyl and ethyl;
• C ₆ -C ₁₄ aryl, such as phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl and 9-phenanthryl , preferably phenyl, 1-naphthyl and 2-naphthyl, more preferably phenyl.

peroxides of the general formulas IVa to IVc and processes for their preparation are known from EP-A 0 813 550.

When Peroxides are di-tert-butyl peroxide, tert-butyl peroxypivalate, tert-butyl peroxyisononanoate or dibenzoyl peroxide or mixtures thereof are particularly suitable. Azobisisobutyronitrile ("AIBN") may be mentioned by way of example as azo compound will be in for Polymerizations usual Doses are metered.

numerous commercially available organic peroxides are added to so-called phlegmatizers, before they are sold, to make them easier to handle. When Phlegmatizers are, for example, white oil or hydrocarbons such as especially isododecane suitable. Under the conditions of high pressure polymerization can Such phlegmatizers have a molecular weight regulating effect to have. For the purposes of the present invention is intended to use of molecular weight regulators the additional use of further molecular weight regulators over the Use of such Phlegmatisierer addition to be understood.

The ratio Of comonomers in the dosage usually does not exactly match relationship the units in the ethylene terpolymers used according to the invention, because cyclic amides with ethylenically unsaturated groups and esters of at least simply ethylenically unsaturated carboxylic acids in the Generally more readily incorporated in the invention ethylene terpolymers be as ethylene.

In a preferred embodiment The present invention is the sum of the proportions of cyclic Amide with ethylenically unsaturated Groups and esters of at least monoethylenically unsaturated carboxylic acids, under 30 wt .-% of the total feed of comonomer, preferably less than 20 Wt .-%.

comonomers and ethylene become common dosed together or separately.

comonomers can be compressed in a compressor to the polymerization pressure. In another embodiment the method according to the invention the comonomers are first by means of a pump to an increased pressure of for example 150 to 400 bar, preferably 200 to 300 bar and in particular 260 bar and then with a compressor to the actual Polymerization.

The inventive polymerization optionally in the absence and in the presence of solvents carried out where mineral oils, White oil and others Solvent, during the Polymerization in the reactor are present and to phlegmatize the or the radical starter have been used, within the meaning of the present Invention not as a solvent be valid. Suitable solvents are, for example, toluene, isododecane, isomers of xylene.

By the polymerization process according to the invention receives according to the invention ethylene terpolymer, from the man - if required - still Existing residual monomer can remove, for example with the help an extruder.

One Another object of the present invention is the use of inventive ethylene terpolymer for the production of materials for substance separation.

One Another object of the present invention are materials for the separation of substances, prepared using copolymer according to the invention. examples for Inventive materials for substance separation are membranes and stationary phases for chromatography columns.

One Another object of the present invention is a method for the production of materials for material separation according to the invention, in the following also inventive production method called.

Mixed according to the invention Ethylenterpolymer with at least one metal alkoxide or at least one polyvalent epoxide and at least one solvent.

In an embodiment the method according to the invention If one sets according to the invention ethylene terpolymer in the form of a solution in one or more solvents and mixed with metal alcoholate or polyvalent epoxide.

In another embodiment is mixed according to the invention ethylene terpolymer with metal alcoholate or polyvalent epoxide and then mixed with one or more solvents.

When solvent In particular, aprotic organic solvents are suitable. Especially Well suited are cyclic and non-cyclic ethers, for example Tetrahydrofuran, 1,4-dioxane, tetrahydropyran, diisopropyl ether, Di-n-butyl ether and mixtures of the abovementioned solvents, especially tetrahydrofuran.

In an embodiment The present invention is the concentration of ethylene terpolymer according to the invention in the solution in the range of 1 to 10 wt .-%, in particular from 3 to 5 wt .-%.

As the metal alcoholate, one or more alkoxides of polyvalent metals are preferred, preferably of di- or tri-valent metals, more preferably of trivalent metals. As its divalent metals its for example called: Zn ²⁺ , Ca ²⁺ , Mg ²⁺ , Cu ²⁺ . Suitable trivalent metals are, for example, Fe ³⁺ , Cr ³⁺ , Ti ³⁺ , V ³⁺ and very particularly preferably Al ³⁺ .

When Metal alkoxide can be used mixed alcoholates such as Mixed ethanolates / methanolates or mixtures of different Alcoholates such as mixtures of ethanolates and methanolates or ethanolates and isopropylates. Preferably, however, one sets pure alcoholates.

wobei die Variablen wie folgt definiert sind:
M^+m ist ein Kation eines n-wertigen Metalls, beispielsweise Na⁺, K⁺, bevorzugt Ca²⁺, Mg²⁺, Fe³⁺, Cr³⁺, Ti³⁺, V³⁺ und ganz besonders bevorzugt Al³⁺,
m ist eine ganze Zahl im Bereich von 1 bis 4, bevorzugt 2 bis 3 und ganz besonders bevorzugt 3,
R¹⁷ Wasserstoff oder Methyl,
R¹⁵, R¹⁶ verschieden oder vorzugsweise gleich und gewählt aus C₁-C₄-Alkyl wie Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl und tert.-Butyl, insbesondere Methyl;
Phenyl,
C₁-C₆-Alkoxy wie Methoxy, Ethoxy, n-Propoxy, iso-Propoxy, n-Butoxy, iso-Butoxy, sec.-Butoxy, tert.-Butoxy, n-Pentoxy, iso-Pentoxy, n-Hexoxy und iso-Hexoxy, bevorzugt Methoxy, Ethoxy, n-Propoxy und n-Butoxy und besonders bevarzugt Ethoxy.Metal alkoxides, such as, for example, metal methoxides, metal ethanolates, isopropylates, metal tert-butylates, as well as metal phenolates and, in particular, metal enolates, can be used as the metal alcoholate. Preferably, metal alcoholates are derived from those alcohols having a boiling point at room temperature of up to 150 ° C. Very particular preference is given to enolates of the general formula III

where the variables are defined as follows:
M ^{+ m} is a cation of an n-valent metal, for example Na ⁺ , K ⁺ , preferably Ca ²⁺ , Mg ²⁺ , Fe ³⁺ , Cr ³⁺ , Ti ³⁺ , V ³⁺ and most preferably Al ³⁺ .
m is an integer in the range of 1 to 4, preferably 2 to 3 and most preferably 3,
R ^{17 is} hydrogen or methyl,
R ¹⁵ , R ^{16 are} different or preferably identical and selected from C ₁ -C ₄ -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl, especially methyl;
phenyl,
C ₁ -C ₆ alkoxy such as methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, iso-butoxy, sec-butoxy, tert-butoxy, n-pentoxy, iso-pentoxy, n-hexoxy and iso-hexoxy, preferably methoxy, ethoxy, n-propoxy and n-butoxy, and especially ethoxy.

Most preferably, R ¹⁵ and R ^{16 are the} same and methyl.

In an embodiment The present invention is used in the range from 1 to 10% by weight. Metal alcoholate, based on ethylene copolymer, one, preferably 2 to 5% by weight.

In an embodiment The present invention can be carried out by reacting metal alcoholate and ethylene copolymer in amounts such that the molar ratio of COOH groups from ethylene copolymer to metal cation in the range of 1: 1 to 1: 6.

In another embodiment In the present invention, ethylene copolymer with metal alcoholate is first mixed and then move with one or more of the abovementioned solvents, the proportions being as mentioned above.

Then evaporated one or the solvent slowly, for example at room temperature or at slightly elevated temperature such as 30 or 35 ° C. While the solvent (s) evaporate, forming a homogeneous-looking film.

Around To facilitate the evaporation, one can under reduced pressure work, for example when pressing in the range of 100 to 990 mbar.

Treated according to the invention the evaporation residue subsequently thermally.

In an embodiment the present invention can be the evaporation residue 5 to 48 hours, preferably 12 to 36 hours at a temperature in the range of 45 to 130 ° C, preferably 60 to 120 ° C to store.

In another embodiment In the present invention, the residue of evaporation can be gradually heat. So you can, for example, first at 70 to 90 ° C heat, subsequently you store for 1 to 5 hours at 70 to 90 ° C, and then heated one at 110 to 130 ° C and store for another 1 to 5 hours.

It is assumed without preference to a particular theory should be that thereby acid residues, to different molecules of inventive ethylene terpolymer belong, in deprotonated form attach to a polyvalent metal cation.

In another embodiment mixed ethylene copolymer with one or more polyvalent Epoxides and at least one solvent.

When Polyvalent epoxides are, for example, dendrimeric epoxides with at least two epoxide groups conceivable, furthermore hyperbranched polymers with at least two epoxide groups, wherein so-called hyperbranched Polymers of dendrimers due to their molecular heterogeneity see, for example, news from chemistry, technology and Laboratory, 2002, 50, 1218.

in denen A wie folgt gewählt werden kann:
C₁-C₂₀-Alkylen, unsubstituiert oder substituiert mit einer oder mehreren C₁-C₄-Alkylgruppen, einer oder mehrerer C₆-C₁₄-Arylgruppen, einer oder mehreren OH-Gruppen, die mit C₁-C₆-Alkanol oder Glycidylalkohol verethert sein können, wobei ein oder mehrere nicht-benachbarte C-Atome auch durch Sauerstoff ersetzt sein können; bevorzugt sind -CH₂-, -CH₂-CH₂-, -(CH₂)₃-, -(CH₂)₄-, -(CH₂)₅-, -(CH₂)₆-, -(CH₂)₁₀-, -(CH₂)₂₀-,
-CH(CH₃)-, -CH(C₂H₅)-, -CH(C₆H₅)-, -CH(OH)-, -[CH(OH)]₂-, -CH(OCH₃)-,
-CH(OC₂H₅)-, -CH(O-Gylcidyl)-;
-O-(CH₂)₂-O-, -O-(CH₂)₄-O-, -[O-(CH₂)₂)₂-O-, -[O-(CH₂)₂]₃-O-, -[O-(CH₂)₂]₄-O-,
C₄-C₁₀-Cycloalkylen, beispielsweise cis- oder trans-l,3-Cyclobutylen, cis- oder trans-1,3-Cyclopentylen, cis- oder trans-l,4-Cyclohexylen,
C₆-C₁₄-Arylen, beispielsweise meta-Phenylen, para-Phenylen, 4,4'-Bipenylen

Stickstoff, substituiert mit C₁-C₁₀-Alkyl wie beispielsweise Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl, tert.-Butyl, n-Pentyl, iso-Pentyl, sec.-Pentyl, neo-Pentyl, 1,2-Dimethylpropyl, iso-Amyl, n-Hexyl, iso-Hexyl, sec.-Hexyl, n-Heptyl, n-Octyl, 2-Ethylhexyl, n-Nonyl, n-Decyl; besonders bevorzugt C₁-C₄-Alkyl wie Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl und tert.-Butyl, insbesondere Methyl;
Stickstoff, substituiert mit C₆-C₁₄-Aryl, das seinerseits substituiert sein kann mit einer oder mehreren C₁-C₄-Alkylgruppen, einer oder mehrerer C₆-C₁₄-Arylgruppen, einer oder mehreren OH-Gruppen, die die mit C₁-C₆-Alkanol oder Glycidylalkohol verethert sein können.Particularly suitable polyfunctional epoxides are polyfunctional epoxides of the general formula IV:

where A can be chosen as follows:
C ₁ -C ₂₀ -alkylene, unsubstituted or substituted by one or more C ₁ -C ₄ -alkyl groups, one or more C ₆ -C ₁₄ -aryl groups, one or more OH groups, which are C ₁ -C ₆ -alkanol or glycidyl alcohol may be etherified, wherein one or more non-adjacent C atoms may also be replaced by oxygen; preferred are -CH ₂ -, -CH ₂ -CH ₂ -, - (CH ₂ ) ₃ -, - (CH ₂ ) ₄ -, - (CH ₂ ) ₅ -, - (CH ₂ ) ₆ -, - (CH ₂ ) ₁₀ -, - (CH ₂ ) ₂₀ -,
-CH (CH ₃ ) -, -CH (C ₂ H ₅ ) -, -CH (C ₆ H ₅ ) -, -CH (OH) -, - [CH (OH)] ₂ -, -CH (OCH ₃ ) -,
-CH (OC ₂ H ₅ ) -, -CH (O-glycidyl) -;
-O- (CH ₂ ) ₂ -O-, -O- (CH ₂ ) ₄ -O-, - [O- (CH ₂ ) ₂ ) ₂ -O-, - [O- (CH ₂ ) ₂ ] ₃ -O-, - [O- (CH ₂ ) ₂ ] ₄ -O-,
C ₄ -C ₁₀ -cycloalkylene, for example cis- or trans-1, 3-cyclobutylene, cis- or trans-1,3-cyclopentylene, cis- or trans-1,4-cyclohexylene,
C ₆ -C ₁₄ arylene, for example meta-phenylene, para-phenylene, 4,4'-bipenylene

Nitrogen substituted with C ₁ -C ₁₀ -alkyl, such as, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl , sec-pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n decyl; particularly preferably C ₁ -C ₄ -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl, in particular methyl;
Nitrogen substituted with C ₆ -C ₁₄ -aryl, which in turn may be substituted with one or more C ₁ -C ₄ alkyl groups, one or more C ₆ -C ₁₄ -aryl groups, one or more OH groups, with the C ₁ -C ₆ alkanol or glycidyl alcohol may be etherified.

Particularly preferably used polyfunctional epoxides correspond to the formulas VII a to VII h

to Production of materials for substance separation is given, for example polyfunctional epoxide and ethylene terpolymer according to the invention in such Together, set that the molar ratio of COOH groups inventive ethylene terpolymer to epoxide groups in the range of 100: 1 to 1: 1, preferably 30: 1 to 10: 1.

In an embodiment of the present invention one inventive ethylene terpolymer and polyvalent epoxide in at least one solvent, preferably THF. You leave the solvent (s) evaporates and observes the formation of a film. Man treated subsequently thermally at temperatures in the range of 70 to 150 ° C, preferably from 90 to 120 ° C, and receives Material suitable for substance separation.

In an embodiment In the present invention, a mixture containing Metal alcoholate or polyhydric epoxide and ethylene terpolymer according to the invention, to membranes. Membranes can be made in the form of films where you make films as self-supporting films or - to increase the mechanical stability - as composites, e.g. by nonwovens, for example polyester nonwovens or polyacrylonitrile coated polyester fleece, support can.

In one embodiment of the present invention, a mixture containing Me tallalkoholat and ethylene terpolymer, in a form useful as a stationary phase for chromatography columns for analytical or preparative applications.

In an embodiment In the present invention, a mixture containing Metal alcoholate and ethylene terpolymer, as a layer having a thickness in the range of 1 μm and 1000 μm on the inner wall of the chromatographic column or on shaped bodies, the as a filling for one chromatography column are suitable, on and evaporates the solvent or solvents and then treated thermally.

In a further embodiment In the present invention, a mixture containing Metal alcoholate or polyhydric epoxide and ethylene terpolymer according to the invention and at least one solvent, a suitable molding process for the production of moldings, the for example, as a filling suitable for chromatography columns are, evaporates the solvent or solvents and then treat thermally and thus produces moldings which are suitable as a filling for chromatography columns are. This one can proceed to the shaping so that one mix from inventive ethylene terpolymer and metal alcoholate or polyhydric epoxide and at least one Solvent prepares and silica gel. Then the solvent is evaporated under vacuum Room temperature, so that forms a film coating on the silica gel particles, but not yet networked. By heating, the crosslinking then takes place the silica gel particles, which can then be used as a column material after cooling.

In a further embodiment In the present invention, membranes are prepared by adding a Mixture containing metal alkoxide and ethylene terpolymer, in the form of a film on an object with a smooth surface. After that you evaporate the solvent or solvents and treated thermally. After all It is possible to remove a membrane after thermal treatment from the object with a smooth surface just pull off.

In another embodiment The present invention produces materials for the separation of substances, by using ethylene terpolymer according to the invention with at least one solvent mixed, the solvent or solvents evaporated and the evaporation residue thermally treated. You can in principle as described above but works without the use of metal alcoholate and polyvalent epoxide.

Inventive membranes can be designed as integral asymmetric or as composite membranes in which the actual separating layer, which has a thickness of 0.01 to 100, preferably 0.1 to 20 microns has, applied to one or more meso and / or macroporous support (s) is, the / from one or more organic, especially polymeric and / or inorganic material, for example ceramic, carbon, Metal is or exist.

Inventive membranes can be in the form of flat, cushion, capillary, mono-channel or use multi-channel pipe elements. The geometries are the expert in itself from other membrane separation processes such as ultrafiltration or reverse osmosis, see, e.g. R. Rautenbach "Membrane Process, Basics of module and system design ", 1997, Springer Verlag. For membrane elements with tube geometry can the release layer is on the inside or outside of the tube.

In a further embodiment The present invention surrounds membranes according to the invention with one or more housings of polymeric, metallic or ceramic material, wherein the Connection between housing and membrane by a sealing polymer (e.g., elastomer) or is formed by an inorganic material.

One Another object of the present invention is a method for the separation of mixtures using material according to the invention for substance separation, for example in the form of membranes or of stationary Phases for Chromatography columns. Inventive method for the separation of mixtures using material according to the invention for the separation of substances, the following will also be used for the separation process according to the invention called.

• – Abtrennung von Alkoholen aus Mischungen mit organischen Verbindungen, die eine geringere Polarität als die jeweiligen Alkohole aufweisen, wobei das erfindungsgemäße Material zur Stofftrennung die höhere Permeanz bzw. Affinität für Alkohole aufweist;
• – Abtrennung von Ammoniak oder Aminen aus Mischungen mit organischen Verbindungen, die eine geringere Polarität als Ammoniak oder die jeweiligen Amine aufweisen, wobei das erfindungsgemäße Material zur Stofftrennung die höhere Permeanz bzw. Affinität für den Ammoniak oder die Amine aufweist;
• – Trennung Sauerstoff/Stickstoff, wobei das erfindungsgemäße Material zur Stofftrennung die höhere Permeanz bzw. Affinität für Sauerstoff aufweist;
• – Abtrennung von Wasser, Ammoniak, H₂S oder organischen Verbindungen aus Gemischen mit Stickstoff oder Luft, wobei das erfindungsgemäße Material zur Stofftrennung die höhere Permeanz bzw. Affinität für Wasser, Ammoniak, H₂S oder die organischen Verbindungen aufweist;
• – Abtrennung von Olefinen oder Dienen aus Gemischen mit Kohlenwasserstoffen, die einen höheren Sättigungsgrad aufweisen als die jeweiligen Olefine oder Diene, wie z.B. die Trennung Olefin/Alkan. Kohlenwasserstoffe weisen dann einen höheren Sättigungsgrad auf, wenn die Zahl der C-Doppel- oder Dreifachbindungen im Verhältnis zu den C-C-Einfachbindungen niedriger ist, wobei das erfindungsgemäße Material zur Stofftrennung die höhere Permeanz bzw. Affinität für Kohlenwasserstoffe mit niedrigeren Sättigungsgrad aufweist.

Materials according to the invention for separating substances, for example membranes according to the invention or chromatography columns, are suitable, for example, for the following separation tasks, ie for the separation of the following mixtures of substances:

• - Separation of alcohols from mixtures with organic compounds having a lower polarity than the respective alcohols, wherein the material for separation of the invention, the higher Permeanz or affinity for alcohols;
• - Separation of ammonia or amines from mixtures with organic compounds having a lower polarity than ammonia or the respective amines, wherein the material for separating material according to the invention has the higher permeance or affinity for the ammonia or amines;
• - Separation oxygen / nitrogen, wherein the material for material separation according to the invention has the higher permeance or affinity for oxygen;
• Separation of water, ammonia, H ₂ S or organic compounds from mixtures with nitrogen or air, the material for material separation according to the invention having the higher permeance or affinity for water, ammonia, H ₂ S or the organic compounds;
• - Separation of olefins or dienes from mixtures with hydrocarbons, which have a higher degree of saturation than the respective olefins or dienes, such as the separation olefin / alkane. Hydrocarbons have a higher degree of saturation when the number of C double or triple bonds is lower relative to the CC single bonds, with the material separation material of the present invention having the higher permeance for lower saturation hydrocarbons.

there can in the context of the present invention under separation of mixtures also the enrichment or depletion of components from mixtures be understood.

When by the method according to the invention mixtures to be separated are in particular olefin-alkane mixtures with 2 to 10, especially 2 to 6 carbon atoms.

If it is desired to carry out the process according to the invention for the separation of substance mixtures with the aid of a membrane according to the invention, the following parameters have proven to be preferred:
The device in which one or more membranes according to the invention are incorporated is also referred to below as membrane apparatus.

Of the Pressure on the feed side of the membrane according to the invention is generally greater than 6 bar, preferably 8 to 50, particularly preferably 10 to 35 bar.

The Temperature on the feed side of the membrane is generally so selected that of this temperature corresponding boiling pressure of the feed mixture less than 130%, preferably less than 120%, more preferably is less than 110% of the feed pressure.

• – entweder durch Verdichten eines gasförmig vorliegenden Feedstroms mittels dem Fachmann an sich bekannter Verdichter
• – oder durch Fördern eines flüssig vorliegenden Feedstroms mittels dem Fachmann an sich bekannter Pumpen.

The structure of the feed pressure can take place

• - either by compressing a gaseous feed stream by means of those skilled in the known compressor
• - Or by conveying a liquid present feed stream by means of the skilled person known per se pumps.

The Setting the desired Temperature can by means of the skilled person known per se heat exchanger take place, the leaving the or the heat exchanger and stream entering the membrane apparatus may be liquid, gaseous or two-phase gaseous / liquid can. If the stream entering the membrane apparatus is liquid, then is the special case of pervaporation.

advantageous Feed temperatures are -50 up to 200 ° C, preferably 0 to 120 ° C, more preferably 20 to 80 ° C.

advantageous permeate pressures are 0.01 to 100 bar absolute, preferably 0.1 to 50 bar absolute, more preferably 1 to 20 bar absolute, wherein the permeate pressure always lower than the feed pressure must be.

The separation process according to the invention can be single-stage are, i. Permeate from a membrane apparatus or combined permeates from several consecutively from the feed and / or parallel flowed through membrane devices form the component (s) mentioned without further treatment higher permeance enriched stream and non-permeated portion (retentate) forms without further treatment, the said at component (s) with lower Permeanz enriched stream.

The separation process according to the invention can be carried out in two or more stages, with one step the permeate is fed as a feed in the respective following stage and the retentate from this stage feeds to the former stage is mixed.

The Invention will be explained by working examples.

working examples

1. Production of inventive ethylene terpolymer

In a high pressure autoclave as described in the literature (Buback, M., et al., Chem. Ing. Tech., 1994, 66, 510), were ethylene, methacrylic acid and N-vinylpyrrolidone continuously copolymerized. For this purpose, ethylene (10.0 kg / h) under the reaction pressure of 1700 bar in the high pressure autoclave continuously fed. Separately, those shown in Table 1 were given Amounts of methacrylic acid, optionally diluted with the amount of isododecane shown in Table 1, column 6, and N-vinylpyrrolidone first compressed to an intermediate pressure of 260 bar and then with Help another compressor under the reaction pressure of 1700 bar continuously fed into the high-pressure autoclave. Separated from it was the specified in Table 1 amount initiator solution consisting from tert-butyl peroxypivalate (TBPP) and tert-butyl peroxyethylhexanoate (TBPEH) in isododecane (concentration see Table 1), under the reaction pressure of 1700 bar in the high-pressure autoclave continuously fed. Separately, if necessary the amount of propionaldehyde given in Table 1, dissolved in isododecane, first compressed to an intermediate pressure of 260 bar and then with Help another compressor under the reaction pressure of 1700 bar continuously fed into the high-pressure autoclave. The reaction temperature was about 230 to 241 ° C. Inventive ethylene terpolymer was obtained with the analytical data shown in Table 2.

Table 1 Preparation of inventive ethylene terpolymers

T _reactor is the maximum internal temperature of the high pressure autoclave to understand.

Abbreviations: NVP: N-vinylpyrrolidone, MAS: methacrylic acid, PA: propionaldehyde, ID:
Isododecane (2,2,4,6,6-pentamethylheptane),
PA in ID: solution of propionaldehyde in isododecane, total volume of solution,
Volume ratio PA to ID: 1 to 9.
PO: tert-butyl peroxypivalate, ETP: ethylene terpolymer
c (PO): concentration of TBPP or TBPEH in ID in mol / l
The conversion refers to ethylene and is given in% by weight

By "content" is meant the proportion of polymerized ethylene or NVP or MAS in the respective ethylene terpolymer.
η: dynamic melt viscosity, measured at 120 ° C according to DIN 51562,
SZ: acid number, determined in accordance with DIN 53402

The content of ethylene, methacrylic acid and N-vinylpyrrolidone in ethylene terpolymers according to the invention was determined by ¹ H-NMR spectroscopy.

The density was determined according to DIN 53479. The melting point T _melt or melting range was determined by DSC (differential scanning calorimetry, differential thermal analysis) to DIN 51007 determined.

2. Preparation of materials according to the invention for substance separation

2.1. Production of a Ionically crosslinked ethylene terpolymer membrane 1.2

500 mg of ethylene copolymer 1.2 were dissolved in 15 ml of tetrahydrofuran (THF) and 15 mg of aluminum acetylacetonate added. The solution was in a metal ring (Diameter 10.5 cm) on membrane substructure made of polyester fleece, coated with polyacrylonitrile, cast as suitable substrate, covered with a funnel (avoiding dust entry) and the solvent slowly evaporated at room temperature. It formed a movie. The movie was subsequently detached from the ground and first between two layers of filter paper, which stabilize each covered with aluminum foil, overnight at room temperature, then dried or crosslinked for 12 h in a vacuum oven at 120 ° C. The crosslinked film thus obtained containing the material of the invention for substance separation 2.1, was about 30 microns thick and insoluble in THF.

2.2. Production of a Ionically crosslinked ethylene terpolymer membrane 1.3

attempt 2.1 was repeated but with 500 mg of ethylene terpolymer 1.3 instead 1.2. The crosslinked film thus obtained containing the material of the invention for substance separation 2.2, was about 30 microns thick and insoluble in THF.

2.3. Production of a Diaphragm of polyfunctional epoxy crosslinked ethylene terpolymer 1.2

zugegeben. Die Lösung wurde in einen Metallring (Durchmesser 10,5 cm) auf einem Glasspiegel als geeignetem Untergrund gegossen, mit einem Trichter abgedeckt (Vermeidung von Staubeintrag) und das Lösungsmittel langsam bei Raumtemperatur verdampft. Es bildete sich ein Film. Der Film wurde anschließend vom Untergrund abgelöst und zunächst zwischen zwei Lagen aus Filterpapier, die zur Stabilisierung jeweils mit Aluminiumfolie bedeckt waren, über Nacht bei Raumtemperatur, dann 12 h im Vakuumtrockenschrank bei 120°C getrocknet bzw. vernetzt. Der so erhaltene vernetzte Film aus erfindungsgemäßem Material zur Stofftrennung 2.3, war etwa 30 um dick und in THF nicht löslich.500 mg of ethylene copolymer 1.2 were dissolved in 15 ml of tetrahydrofuran (THF) and 25 mg of glycerol l, 3-diglycidyl ether VII f

added. The solution was poured into a metal ring (10.5 cm diameter) on a glass mirror as a suitable substrate, covered with a funnel (to prevent dust entry), and the solvent was evaporated slowly at room temperature. It formed a movie. The film was then removed from the substrate and first dried or crosslinked between two layers of filter paper, which were each covered with aluminum foil for stabilization, overnight at room temperature, then 12 h in a vacuum oven at 120 ° C. The cross-linked film of material separation material 2.3 according to the invention thus obtained was about 30 μm thick and insoluble in THF.

Instead of Glass as a substrate were also polyethylene and silanized polyethylene film suitable.

2.4. Production of a Diaphragm of polyfunctional epoxy crosslinked ethylene terpolymer 1.3

attempt 2.3 was repeated but with 500 mg of ethylene terpolymer 1.3 instead 1.2. The resulting crosslinked film of material according to the invention for substance separation 2.4, was about 30 microns thick and not soluble in THF.

3. Implementation of separation tests

The permeation and separation measurements were carried out in a thermostated flat cell with an effective membrane area of 28 cm ² . A membrane according to the invention was applied so that it was permeate-faced on a stainless steel frit (pore diameter 0.07 mm and sealed on the side by a Kalretz ring (perfluorinated rubber).) The cell was fed through an isooctane-toluene mixture containing 91.2 % By weight of isooctane and 8.8% by weight of toluene, at a temperature of 60 ° C. and a pressure of 1.013 bar, The permeate was collected by condensation in a cold trap and contained enriched toluene Amount of condensate determined.

By gas chromatographic analysis, the composition was determined in the permeate and be agreed the separation factor α.

Further Details are listed in Table 3.

Table 3 Separation experiments with membranes according to the invention.

Of the Separation coefficient α is defined as

ever bigger the Separation coefficient α, the better the separation performance.

Claims (14)

Ethylenterpolymere that polymerized as comonomers contain: (a) ethylene, (b) at least one cyclic amide having at least an ethylenically unsaturated Group, (c) at least one at least monoethylenically unsaturated carboxylic acid or at least one ester of at least one ethylenically unsaturated Carboxylic acid. Ethylenterpolymere according to claim 1, which are used as comonomers incorporated in copolymerized form (a) 45 to 95% by weight of ethylene, (B) 0.1 to 50 wt .-% of at least one cyclic amide with at least an ethylenically unsaturated Group, (c) 0.1 to 40% by weight of at least one at least once ethylenically unsaturated carboxylic acid or at least one ester of at least one ethylenic unsaturated Carboxylic acid, in which In wt .-% in each case on the total weight of ethylene terpolymer are related. Ethylenterpolymere according to one of claims 1 or 2, characterized in that at least one comonomer (b) of the general formula I.

wherein the variables are defined as follows: R ¹ selected from hydrogen, unbranched and branched C ₁ -C ₁₀ alkyl, R ² selected from hydrogen, unbranched and branched C ₁ -C ₁₀ alkyl, R ^{3 are} identical or different and selected from hydrogen and linear and branched C ₁ -C ₁₀ -alkyl and C ₃ -C ₁₂ -cycloalkyl, where two R ^{3 's may be joined} together to form a 3 to 10 membered ring, n is an integer in the range of 2 until 10. Ethylenterpolymere according to one of claims 1 to 3, that at least one comonomer (c) corresponds to the general formula II

wherein the variables are defined as follows: R ⁴ selected from hydrogen, unbranched and branched C ₁ -C ₁₀ -alkyl, vinyl and allyl, R ⁵ selected from hydrogen, unbranched and branched C ₁ -C ₁₀ -alkyl, R ⁶ selected from hydrogen and unbranched and branched C ₁ -C ₁₀ -alkyl and C ₃ -C ₁₂ -cycloalkyl. Ethylenterpolymere according to one of claims 1 to 5, characterized in that the variables in formula I are defined as follows: R ^{1 is} hydrogen or methyl, R ^{2 is} hydrogen, R ³ is the same and hydrogen, n is selected from 3 and 4. Ethylenterpolymere according to one of claims 1 to 5, characterized in that the variables in formula II are defined as follows: R ^{4 is} hydrogen or methyl, R ^{5 is} hydrogen or methyl R ^{6 is} hydrogen. Process for the preparation of ethylene terpolymers according to one of the claims 1 to 6, characterized in that one (a) ethylene, (B) at least one cyclic amide having at least one ethylenic unsaturated Group, (c) at least one at least one ethylenic unsaturated carboxylic acid or at least one at least monounsaturated carboxylic acid ester, at Temperatures in the range of 170 to 300 ° C and pressures in the range of 500 to 4000 bar polymerized. Use of ethylene terpolymers according to one of claims 1 to 6 for the production of materials for material separation. Material separation materials, manufactured under Use of ethylene terpolymer according to any one of claims 1 to 6th Materials according to claim 8, characterized that they are membranes. Materials according to claim 8, characterized that it is stationary Phases of chromatography columns is. Process for the production of materials for separating substances, characterized in that ethylene terpolymer according to one of claims 1 to 6 with metal alcoholate or a polyhydric epoxy and at least a solvent mixed, the solvent or solvents evaporated and the evaporation residue thermally treated. Process for the production of materials for separating substances, characterized in that ethylene terpolymer according to one of claims 1 to 6 with at least one solvent mixed, the solvent or solvents evaporated and the evaporation residue thermally treated. Method of separating mixtures of substances using at least one material according to any one of claims 9 to 11th