DE102004027793A1 - Ethylene copolymer with comonomer units containing photochemically-activatable groups, used for the production of separating membranes, chromato-graphic stationary phases, lacquer, printing ink and toners - Google Patents

Abstract

Ethylene copolymers (ECP) with at least one comonomer unit containing a photochemically-activatable group (PAG). Independent claims are also included for (1) a method (M1) for the production of ECP by polymerisation of (a) ethylene with (b) comonomer(s) containing PAG and (c) unsaturated carboxylic acid(s) or ester(s) at 170-300[deg]C and 500-4000 bar (2) a method (M2) for the production of ECP by polymerising (a) with (c) as above and then reacting the polymer with a compound of formula H-(X)n-(A)m-P* (IV) (3) materials (MECP) made from ECP for separating substances (4) a method (M3) for the production of MECP by exposing ECP to actinic radiation (5) a method (M4) for separating substances using MECP (6) a method (M4) for the production of lacquers, printing ink and toners by using ECP (7) micronised ECP with a number-average particle diameter of not more than 30 microns (8) lacquers, printing ink and toners containing or made from ECP (9) a method (M5) for printing substrates using such lacquers, ink and toners (10) printed substrates obtained by M5 .

Description

The The present invention relates to ethylene copolymers useful as comonomers Ethylene and at least one comonomer that is a photochemically activatable Contains group, polymerized, process for their preparation and 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 applied, as well Chromatography, ultrafiltration, dialysis and electrodialysis. Big meaning In doing so, the selection of the material used for substance separation occurs to.

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 carry bis-trifluoromethyldiphenylidenmethane units, 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. Those described in the cited references Polyimides can although under certain conditions for the separation of olefin-alkane mixtures used, but occurs in 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 of al. report in Radiat. Phys. Chem. 1983, 22, 635, that certain polymers are then suitable as membrane materials, when they are radiation-initiated by graft copolymerization modified. The disclosed method, however, is cumbersome.

It is known that special polyethylene waxes can be added, for example printing inks, s. For example, WO 01/98416 and EP-A 0 890 619. In EP 0 890 619 It is proposed to use molecular products that are as uniform as possible, and recommends polyethylene waxes prepared by means of metallocene catalysis. However, the metallocene catalysts employed are quite expensive and the surface friction resistance of the disclosed prints can be improved.

In EP 1 120 395 it is proposed to esterify pentaerythritol with three equivalents of montanic acid and to esterify the fourth hydroxyl group with acrylic acid, and recommended a corresponding product as a radiation-curable material. However, the process is relatively cumbersome and is based on expensive starting materials. Also, the durability of such materials is not good.

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.

It It was also the object of printing inks, toners and paints in particular To provide pressure varnishes, and there was the task of a process to provide for printing of substrates.

Accordingly, were found the ethylene copolymers defined above.

photochemical Activatable groups are known as such. By treating with Actinic radiation they are excited in the photochemically State convicted and can subsequently Reactions such as, for example, oxidations or, in particular, polymerizations initiate.

ethylenically unsaturated Double bond or double bonds and photochemically activatable group are either direct or over a so-called spacer covalently connected to each other.

In an embodiment The present invention is at least one Comonomer with photochemically activatable groups around a derivative an α-decay, i.e. The copolymerized comonomer breaks down upon photochemical excitation and thus starts a polymerization reaction or a Crosslinking reaction. examples for Derivatives of α-decayers are derivatives of benzil dimethyl ketal. Further examples of derivatives of α decayers are derivatives of benzoin, isobutylbenzoin ether, phosphine oxides, especially mono- and bisacylphosphine oxides, e.g. 2,4,6-trimethylbenzoyl. Derivatives of α-decayers included to make it a comonomer in the context of the present invention are suitable, at least one ethylenically unsaturated double bond and, for example one of the aforementioned groups, such as a benzildimethalketal group.

In a preferred embodiment The present invention is in at least one comonomer photochemically activatable group selected from the group of hydrogen-abstracting photoinitiators, for example of the type of substituted acetophenones, anthraquinones, Thioxanthones, benzoic acid esters or optionally multiply substituted benzophenones. Especially preferred examples are substituted isopropylthioxanthones, benzophenones, 4-methylbenzophenones, halomethylated benzophenones, anthrones, Michler's ketone (4,4'-bis-dimethylaminobenzophenone), 4-chlorobenzophenone, 4,4'-dichlorobenzophenone. Contain derivatives of hydrogen-abstracting photoinitiators, thus suitable as a comonomer in the context of the present invention are at least one ethylenically unsaturated double bond and, for example one of the aforementioned groups, such as a benzildimethalketal group.

In an embodiment The present invention is in at least one comonomer photochemically activatable group via a spacer to an ethylenic unsaturated Tied double bond.

• (a) 50 bis 99,9 Gew.-%, bevorzugt 60 bis 90 Gew.-% Ethylen,
• (b) 0,1 bis 50 Gew.-%, bevorzugt 10 bis 40 Gew.-% eines oder mehrerer Comonomere, enthaltend mindestens eine photochemisch aktivierbare Gruppe, wobei Angaben in Gew.-% jeweils auf die Gesamtmasse an erfindungsgemäßem Ethylencopolymer bezogen sind.

In a preferred embodiment of the present invention, ethylene copolymers according to the invention comprise copolymerized comonomers

• (a) 50 to 99.9% by weight, preferably 60 to 90% by weight of ethylene,
• (B) 0.1 to 50 wt .-%, preferably 10 to 40 wt .-% of one or more comonomers containing at least one photochemically activatable group, wherein in wt .-% in each case based on the total weight of inventive ethylene copolymer.

in der die Variablen wie folgt definiert sind:
R¹ und R² sind gleich oder verschieden;
R¹ wird gewählt aus 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;
und besonders bevorzugt Wasserstoff.
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.
Y wird gewählt aus einer Carbonylgruppe und einer Einfachbindung, bevorzugt ist eine Carbonylgruppe.
X wird gewählt aus Sauerstoff, Schwefel und N-R³, bevorzugt sind Sauerstoff und N-R³.
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.
A ein Spacer, gewählt aus C₁-C₂₀-Alkylen, ein- oder mehrfach substituiert beispielsweise mit C₁-C₄-Alkyl oder unsubstituiert, in dem ein oder mehrere nichtbenachbarte C-Atome gleich oder verschieden ersetzt sein können durch Sauerstoffatome, Carbonsäureestergruppen, -O-C(O)-O-Gruppen (Carbonatgruppen), Ketogruppen, Carbonsäureamidgruppen oder Harnstoffgruppen, gleich oder verschiedenIn 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 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-butyl 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 particularly preferably hydrogen.
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.
Y is selected from a carbonyl group and a single bond, preferably a carbonyl group.
X is selected from oxygen, sulfur and NR ³ , preferred are oxygen and NR ³ .
R ³ are different or preferably the same 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, isobutyl 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.
A is a spacer selected from C ₁ -C ₂₀ -alkylene, mono- or polysubstituted, for example, by C ₁ -C ₄ -alkyl or unsubstituted, in which one or more nonadjacent carbon atoms may be replaced identically or differently by oxygen atoms, carboxylic acid ester groups , -OC (O) -O- (carbonate) groups, keto groups, carboxylic acid amide groups or urea groups, the same or different

For example, A can stand for the following spacers:
-CH ₂ -, -CH ₂ -CH ₂ -, - (CH ₂ ) ₃ -, - (CH ₂ ) 4-, - (CH ₂ ) ₅ -, - (CH ₂ ) ₆ -, - (CH ₂ ) ₇ -, - (CH ₂ ) 8 -, - (CH ₂ ) ₉ -, - (CH ₂ ) ₁₀ -, - (CH ₂ ) ₁₂ -, - (CH ₂ ) ₁₄ -, - (CH ₂ ) ₁₆ - , - (CH ₂ ) ₁₈ -, - (CH ₂ ) ₂₀ -, preferably - (CH ₂ ) _x -; -CH ₂ -CH (CH ₃ ) -, -CH ₂ -CH (C ₂ H ₅ ) -, -CH ₂ -CH (CH [CH ₃ ] ₂ ) -, -CH ₂ -CH (nC ₃ H ₇ ) -, - [CH (CH ₃ )] ₂ -, -CH (CH ₃ ) -CH ₂ -CH ₂ -CH (CH ₃ ) -, -CH (CH ₃ ) -CH ₂ -CH (CH ₃ ) -, -CH ₂ -C (CH ₃ ) ₂ -CH ₂ -, -CH ₂ -CH (nC ₄ H ₉ ) -, -CH ₂ -CH (tC ₄ H ₉ ) -,
-CH ₂ -O-, -CH ₂ -O-CH ₂ -, - (CH ₂ ) ₂ -O- (CH ₂ ) ₂ -, - [(CH ₂ ) ₂ -O] ₂ - (CH ₂ ) ₂ -, - [(CH ₂ ) ₂ -O] ₃ - (CH ₂ ) ₂ -,
-COO-, -O-CO-, -CH ₂ -COO-, -CH ₂ -O-CO-, - (CH ₂ ) _x -COO-, - (CH ₂ ) _x -O-CO-, -COO (CH ₂ ) _x , -O-CO (CH ₂ ) _y ,
- (CH ₂ ) _y -COO- (CH ₂ ) _y , -CH ₂ -O-CO-CH ₂ -, -CH (CH ₃ ) -COO-CH ₂ -, - (CH ₂ ) _x -O-CO -CH ₂ -, -CH ₂ -O-CO- (CH ₂ ) _x , -CH ₂ -COO- (CH ₂ ) _x , -COO-CH ₂ -COO-, -CH ₂ -COO-CH ₂ -COO -, -COO- (CH ₂ ) _x -O-CO-, O-CO- (CH ₂ ) _x -COO-, -COO-CH (CH ₃ ) -,
-OC (O) -O-, -CH ₂ -OC (O) -O-, - (CH ₂ ) _x -OC (O) -O-, -OC (O) -O- (CH ₂ ) _x , -CH ₂ -OC (O) -O-CH ₂ -, - (CH ₂ ) _x -OC (O) -O-CH ₂ -, -CH ₂ -OC (O) -O- (CH ₂ ) _x ,
-CO-, -CH ₂ -CO-, -CO-CH ₂ -, -CH ₂ -CO-CH ₂ -, -CH (CH ₃ ) -CO-CH ₂ -,
-CO-N (R ³ ) -, -N (R ³ ) -CO-, - (CH ₂ ) _y -CO-N (R ³ ) -, - (CH ₂ ) _y -N (R ³ ) -CO -, - (CH ₂ ) _y -N (R ³ ) -CO- (CH ₂ ) _y ,
-N (R ³ ) -CO-N (R ³ ) -, - (CH ₂ ) _y -N (R ³ ) -CO-N (R ³ ) -, - (CH ₂ ) _y -N (R ³ ) -CO-N (R ³ ) - (CH ₂ ) _y , - (CH ₂ ) _y -N (R ³ ) -CO-N (R ³ ) - (CH ₂ ) -N (R ³ ) -CO-N (R ³ ) -,
y is in each case an integer, identical or different, in the range from 1 to 10, preferably from 2 to 8 and particularly preferably up to 6;
x is an integer in the range of 2 to 10, preferably 2 to 6 and more preferably 4.

If a spacer A carries a plurality of radicals R ³ , the radicals R ^{3 may be} identical or different.

wobei R⁷ gewählt wird aus C₁-C₁₀-Alkyl und C₃-C₁₂-Cycloalkyl, die jeweils wie vorstehend definiert sind.
und insbesondere

wobei Z gewählt wird aus Wasserstoff und Hydroxyl.
m, n sind unabhängig voneinander gewählt aus 0 oder 1.Particularly preferred spacers A are
-CH ₂ -CH ₂ -O-, - (CH ₂ ) ₂ -O-CO-O-, - (CH ₂ ) ₃ -O-CO-O-, - (CH ₂ ) ₄ -O-CO-O -, - (CH ₂ ) ₆ -O-CO-O-, -NH-CH ₂ -NH-CO-, -NH-CH ₂ -NH-CO- (CH ₂ ) ₂ -, -NH-CH ₂ - NH-CO- (CH ₂ ) ₃ -, -NH-CH ₂ -NH-CO- (CH ₂ ) ₂ -O-, -NH-CH ₂ -NH-CO- (CH ₂ ) ₃ -O-, NH-CH ₂ -NH-CO = (CH ₂ ) ₄ -O-.
P * are photochemically activatable groups, for example

wherein R ^{7 is} selected from C ₁ -C ₁₀ alkyl and C ₃ -C ₁₂ cycloalkyl each defined as above.
and particularly

where Z is selected from hydrogen and hydroxyl.
m, n are independently selected from 0 or 1.

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.

wobei die Variablen wie oben stehend definiert sind.In a most preferred embodiment of the present invention, comonomer (b) is selected from the following comonomers b1 to b8,

the variables being as defined above.

In an embodiment The present invention includes ethylene copolymers of the invention no more comonomers over (a) and (b) polymerized in addition.

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, insbesondere 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, Cyclodecyl, Cycloundecyl und Cyclododecyl; bevorzugt sind Cyclopentyl, Cyclohexyl und Cycloheptyl,
und insbesondere Wasserstoff.In another embodiment of the present invention, ethylene copolymers according to the invention comprise at least one comonomer (c) of the general formula III in copolymerized form,

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, 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;
Vinyl -CH = CH ₂ and (Z) and preferably (E) -allyl-CH = CH-CH ₃ .
R ⁵ is selected from straight-chain and branched 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; 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 ⁶ is selected from straight-chain and branched 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; 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, cyclodecyl, 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.

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

Do you wish in inventive ethylene copolymers to at least copolymerize at least one comonomer (c) of general formula III, so you can total 0.1 to 60 wt .-% comonomer (c) or comonomers (c) copolymerize, based on the sum of (a) and (b), preferably 1 to 40% by weight.

In an embodiment The present invention includes ethylene copolymers of the invention furthermore at least up to 5% by weight, based on the sum of (a), (b) and optionally (c), at least one further comonomer in copolymerized form. Preferred further copolymerized comonomers are for example, isobutene and vinyl acetate.

In an embodiment of the present invention Ethylene copolymers according to the invention Melt flow rate (MFI) 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 Ethylene copolymers according to the invention dynamic melt viscosity n in the range of 500 to 60,000 mPa · s, preferably in the range of 550 to 55,000 mPa · s have, measured at 120 ° C.

In an embodiment The present invention relates to the melting ranges of the ethylene copolymers 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 copolymer 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 The present invention relates to the melting points of ethylene copolymer 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 copolymers 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 10 to 300 mg KOH / g of ethylene copolymer are preferred 50 to 230 mg KOH / g ethylene copolymer, determined according to DIN 53402.

Ethylene copolymers according to the invention can alternating copolymers or block copolymers or preferably random copolymers.

One Another aspect of the present invention is a method for Preparation of ethylene copolymers according to the invention.

Ethylene copolymers according to the invention can for example, by free-radically initiated copolymerization of Ethylene having at least one comonomer (b) containing at least one contains photochemically activatable group, optionally at least a comonomer (c) and optionally one or more others Comonomers are prepared under high pressure conditions, hereinafter also inventive polymerization called. The implementation the polymerization process according to the invention 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 process according to the invention 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 V.

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 ⁸ and R ^{9 are} identical 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 ⁸ and R ⁹ are covalently linked together to form a 4- to 13-membered ring. For example, R ⁸ and R ⁹ 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 VIa bis VIc.
  

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 VIa to VIc.
  

• – 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 ¹⁰ to R ^{15 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, iso-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 VIa to VIc 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 copolymers used according to the invention, because comonomer (b) and - if used - comonomer (c) generally more readily incorporated into ethylene copolymers of the invention be as ethylene.

In a preferred embodiment the present invention is the sum of the proportions of comonomer (b) and (c) below 30 wt .-% of the total feed of comonomer, preferred below 20% by weight.

comonomer (b) and - if used - comonomer (c) and ethylene become common dosed together or separately.

The used 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 brought 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 copolymer, from the man - if required - still Existing residual monomer can remove, for example with the help an extruder.

In another embodiment The present invention provides ethylene copolymer wax according to the invention By making wax, available by copolymerization of ethylene and at least one comonomer with functional group, in the sense of a polymer-analogous reaction with at least one substance, the at least one photochemical activatable group and a reactive group that carries with the functional Group of at least one copolymerized comonomer for the reaction capable is.

• (c) mindestens einer mindestens einfach ethylenisch ungesättigten Carbonsäure oder mindestens einem mindestens einfach ungesättigten Carbonsäureester

bei Temperaturen im Bereich von 170 bis 300°C und Drücken im Bereich von 500 bis 4000 bar polymerisiert und danach mit mindestens einer Verbindung der allgemeinen Formel IV

umsetzt. Die Variablen in Formel IV sind definiert wie in Formel II.Preferably, this is done so that one with ethylene

• (C) at least one at least monoethylenically unsaturated carboxylic acid or at least one at least monounsaturated carboxylic acid ester

polymerized at temperatures ranging from 170 to 300 ° C and pressures in the range of 500 to 4000 bar and thereafter with at least one compound of general formula IV

implements. The variables in formula IV are defined as in formula II.

mit mindestens einer Verbindung der Formel IV gegebenenfalls in Gegenwart eines Katalysators um, vorzugsweise in Gegenwart eines sauren Katalysators, wobei
R¹⁶ Wasserstoff oder C₁-C₄-Alkyl wie Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl und tert.-Butyl.In a preferred embodiment of the present invention, wax obtainable by copolymerization of ethylene with at least one comonomer of general formula VII,

with at least one compound of formula IV optionally in the presence of a catalyst, preferably in the presence of an acidic catalyst, wherein
R ^{16 is} hydrogen or C ₁ -C ₄ -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl.

When Catalyst can also be used one or more enzymes.

The Copolymerization of ethylene with at least one comonomer with functional group can be by the skilled person common methods carry out.

The Copolymerization of ethylene with at least one compound of general formula VII can be carried out by methods familiar to those skilled in the art high pressure polymerization of ethylene as described 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

The polymer-analogous reaction can be, for example, in a solvent carry out. Suitable temperatures for the implementation can For example, be room temperature up to 150 ° C.

und gegebenenfalls mit einem oder mehreren Comonomeren (c) copolymerisieren und anschließend mit einem reaktiven Derivat von P* kuppeln. Diese Ausführungsform ist insbesondere dann sinnvoll, wenn Verbindung VIII eine terminate OH-Gruppe oder eine terminale -NHR³-Gruppe aufweist.In a further embodiment of the present invention, ethylene can be reacted with one or more comonomers of the general formula VIII

and optionally copolymerizing with one or more comonomers (c) and then coupling with a reactive derivative of P *. This embodiment is particularly useful when compound VIII has a terminal OH group or a terminal -NHR ³ group.

One Another object of the present invention is the use of inventive ethylene copolymer 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.

you may be materials according to the invention for the separation of substances to produce a copolymer according to the invention treated with actinic radiation.

In one embodiment of the preparation process according to the invention, first of all ethylene copolymer according to the invention is mixed with one or more solvents and a solution of erfin is obtained according to the ethylene copolymer.

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 copolymer according to the invention in the solution in the range of 1 to 10 wt .-%, in particular from 3 to 5 wt .-%.

Then brings one solution of inventive ethylene copolymer on a substrate.

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, forms a homogeneous-looking film, which in Also referred to below as inventive evaporation Residue is referred to and may still contain residues of solvent.

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

According to the invention, the evaporation residue is subsequently treated with actinic radiation, for example by exposing it to actinic radiation. As actinic radiation, for example, electromagnetic radiation having a wavelength range of 200 nm to 450 nm are suitable. It is possible to expose the evaporation residue according to the invention to actinic radiation having an energy in the range from 70 mW / cm ² to 1500 mW / cm ² . Actinic radiation can be introduced, for example, continuously or in the form of flashes.

Usually If one sets evaporation residue according to the invention over a Period from 1 second to 5 minutes of actinic radiation; but you can also longer or shortly periods choose.

If Benzophenone derivatives, for example of the formula b1 or b3 bis b8 has polymerized, is a proportion of UV-C radiation of 250 up to 260 nm wavelength important for networking over the benzophenone group can enter.

In an embodiment the present invention can be the evaporation residue after exposure to actinic radiation for 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 The present invention can be evaporation residue prior to exposure to actinic radiation for 5 to 48 hours, preferably 12 to 36 hours at a temperature in the range of 45 to 150 ° C, preferably Temper above the melting point.

In another embodiment The present invention dispenses with storage at elevated temperature and on the tempering.

In an embodiment The present invention processes a solution containing Ethylene copolymer according to the invention, in a form as used as a stationary phase for chromatography columns for analytical or preparative Applicable, evaporates the solvent or solvents and expose to actinic radiation.

In an embodiment the present invention provides a solution containing the ethylene copolymer according to the invention, as a layer with a thickness in the range of 1 micron and 1000 microns on the inner wall of the chromatography or on shaped bodies, as a filling for one chromatography column are suitable, on and evaporates the solvent or solvents and then treated with actinic radiation.

In a further embodiment of the present invention, a solution comprising ethylene copolymer according to the invention, a suitable shaping process for the production of moldings suitable, for example, as a filling for chromatography columns, evaporates the solvent (s) and then processes with actinic radiation to form moldings forth, which are suitable as a filling for chromatography columns. This one can proceed to the shaping so that preparing a solution of ethylene copolymer according to the invention and adding silica gel in the form of particles. The solvent (s) are then evaporated off under vacuum at room temperature so that a film coating forms on the silica gel particles but is not yet cross-linked. By action of actinic radiation then the crosslinking of the silica gel particles, which can be used as a column material after cooling.

In a further embodiment In the present invention, membranes are prepared by adding a Mixture containing ethylene copolymer, in the form of a film on a Apply the object with a smooth surface. Then you evaporate that or the solvents and treated with actinic radiation. Finally, you can get the membrane simply peel off the object with a smooth surface.

In a particular embodiment The present invention provides materials for material separation by using ethylene copolymer according to the invention in the presence of at least one compound having at least two polymerizable double bonds treated with actinic radiation. Another object of the present invention is therefore a Process for the preparation of materials for material separation by Treatment of inventive ethylene copolymer in the presence of at least one compound having at least two polymerizable double bonds with actinic radiation. One Another object of the present invention are those by treatment of inventive ethylene copolymer in Presence of at least one compound having at least two polymerizable Double bonds available Materials for substance separation.

Preferably is polymerizable double bonds to terminate ethylenic double bonds.

in denen die Variablen wie folgt definiert sind:
R¹⁸ gleich oder verschieden und gewählt aus Methyl und Wasserstoff;
a eine ganze Zahl von 0 bis 2, bevorzugt 1;
A² CH₂ oder -CH₂-CH₂- oder R¹⁷-CH oder para-C₆H₄ für den Fall, dass m = 0, CH, R¹⁷-C oder 1,3,5-C₆H₃ für den Fall, dass a = 1,
und Kohlenstoff für den Fall, dass a = 2;
R¹⁷ gewählt aus C₁-C₄-Alkyl, wie beispielsweise n-C₄H₉, n-C₃H₇, iso-C₃H₇ und vorzugsweise C₂H₅ und CH₃,
oder Phenyl,
A³, A⁴, A⁵ gleich oder verschieden und gewählt aus
C₁-C₂₀-Alkylen, wie beispielsweise -CH₂-, -CH(CH₃)-, -CH(C₂H₅)-, -CH(C₆H₅)-, -(CH₂)₂-, -(CH₂)₃-, -(CH₂)₄-, -(CH₂)₅-, -(CH₂)₆-, -(CH₂)₇-, -(CH₂)₈-, -(CH₂)₉-, -(CH₂)₁₀-, -CH(CH₃)-(CH₂)₂-CH(CH₃)-;
cis- oder trans-C₄-C₁₀-Cycloalkylen, wie beispielsweise cis-1,3-Cyclopentyliden, trans-1,3-Cyclopentyliden cis-1,4-Cyclohexyliden, trans-1,4-Cyclohexyliden;
C₁-C₂₀-Alkylen, in denen von einem bis zu sieben jeweils nicht benachbarte C-Atome durch Sauerstoff ersetzt sind, wie beispielsweise -CH₂-O-CH₂-, -(CH₂)₂-O-CH₂-, -(CH₂)₂-O-(CH₂)₂-, -[(CH₂)₂-O]₂-(CH₂)₂-, -[(CH₂)₂-O]₃-(CH₂)₂-;
C₁-C₂₀-Alkylen, substituiert mit bis zu 4 Hydroxylgruppen, wobei in C₁-C₂₀-Alkylen von einem bis zu sieben jeweils nicht benachbarte C-Atome durch Sauerstoff ersetzt sind, wie beispielsweise -CH₂-O-CH₂-CH(OH)-CH₂-, -CH₂-O-[CH₂-CH(OH)-CH₂]₂-, -CH₂-O-[CH₂-CH(OH)-CH₂]₃-;
C₆-C₁₄-Arylen, wie beispielsweise para-C₆H₄.As compounds having at least two polymerizable double bonds, compounds of the general formula IX may be mentioned, for example:

where the variables are defined as follows:
R ^{18 is the} same or different and selected from methyl and hydrogen;
a is an integer of 0 to 2, preferably 1;
A ² CH ₂ or -CH ₂ -CH ₂ - or R ¹⁷ -CH or para-C ₆ H ₄ in the event that m = 0, CH, R ¹⁷ -C or 1,3,5-C ₆ H ₃ in the case that a = 1,
and carbon in the case that a = 2;
R ^{17 is} chosen from C ₁ -C ₄ -alkyl, such as, for example, nC ₄ H ₉ , nC ₃ H ₇ , isoC ₃ H ₇ and preferably C ₂ H ₅ and CH ₃ ,
or phenyl,
A ³ , A ⁴ , A ^{5 are the} same or different and selected from
C ₁ -C ₂₀ -alkylene, such as -CH ₂ -, -CH (CH ₃ ) -, -CH (C ₂ H ₅ ) -, -CH (C ₆ H ₅ ) -, - (CH ₂ ) ₂ - , - (CH ₂ ) ₃ -, - (CH ₂ ) ₄ -, - (CH ₂ ) ₅ -, - (CH ₂ ) ₆ -, - (CH ₂ ) ₇ -, - (CH ₂ ) ₈ -, - (CH ₂ ) ₉ -, - (CH ₂ ) ₁₀ -, -CH (CH ₃ ) - (CH ₂ ) ₂ -CH (CH ₃ ) -;
cis- or trans-C ₄ -C ₁₀ -cycloalkylene, such as, for example, cis-1,3-cyclopentylidene, trans-1,3-cyclopentylidene, cis-1,4-cyclohexylidene, trans-1,4-cyclohexylidene;
C ₁ -C ₂₀ -alkylene in which from one to seven non-adjacent C atoms in each case are replaced by oxygen, for example -CH ₂ -O-CH ₂ -, - (CH ₂ ) ₂ -O-CH ₂ - , - (CH ₂ ) ₂ -O- (CH ₂ ) ₂ -, - [(CH ₂ ) ₂ -O] ₂ - (CH ₂ ) ₂ -, - [(CH ₂ ) ₂ -O] ₃ - (CH ₂ ) ₂ -;
C ₁ -C ₂₀ -alkylene, substituted by up to 4 hydroxyl groups, wherein in C ₁ -C ₂₀ -alkylene of one to seven non-adjacent C-atoms are replaced by oxygen, such as -CH ₂ -O-CH ₂ -CH (OH) -CH ₂ -, -CH ₂ -O- [CH ₂ -CH (OH) -CH ₂ ] ₂ -, -CH ₂ -O- [CH ₂ -CH (OH) -CH ₂ ] ₃ -;
C ₆ -C ₁₄ -arylene, such as para-C ₆ H ₄ .

Other preferred examples of compounds having at least two polymerizable double bonds are polyester (meth) acrylates obtainable, for example, by reacting hydroxyl-terminated polyesters having a molecular weight M _n preferably in the range from 250 to 4000 g / mol or polyethers having a molecular weight M _n in the range from 400 to 4000 g / mol, with (meth) acrylic acid, as described, for example, in EP-B 0 126 341

Do you wish one or more compounds with polymerizable double bonds amounts in the range of 1 to 25 wt .-%, are preferred 5 to 20 wt .-%, particularly preferably up to 10 wt .-%, based on Ethylene copolymer according to the invention, prefers.

In another embodiment The present invention is directed to the production of materials according to the invention for the separation of substances such that ethylene copolymer according to the invention, if appropriate together with one or more compounds with polymerisable Double bonds, melts, for example by means of an extruder, on a substrate and subsequently exposed to actinic radiation.

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 which have a lower polarity than the respective alcohols, the substance separation material according to the invention having the higher permeance 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 to 200, preferably 0 to 120, particularly preferably 20 to 80 ° C.

advantageous permeate pressures are 0.01 to 100, preferably 0.1 to 50, particularly preferably 1 to 20 bar absolute, with the permeate pressure always lower than the feed pressure have to 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.

Inventive materials for the separation of substances prove to be very stable, especially against organic Solvent, so that the inventive method for substance separation with little interference carry out can.

One Another object of the present invention are toners, inks and lacquers, in particular printing lacquers, comprising at least one inventive ethylene copolymer. Another object of the present invention is the use of ethylene copolymers according to the invention for the production of toners, printing inks and varnishes, in particular Overprint varnishes. Another object of the present invention are processes for the preparation of toners, printing inks and Paints, in particular printing lacquers.

Around inventive toners, Printing inks and printing inks, is in one embodiment of the present invention in large-scale facilities usually as semolina Ethylene copolymer according to the invention micronized. For micronizing you can use for example mills, in particular air jet mills.

In A particular variant of the present invention is ground Ethylene copolymer according to the invention first in a mill and then dispersed in a ball mill, preferably in the presence of at least one solvent such as for example Water, methanol or ethanol.

In another variant of the present invention is omitted on milling steps and melts inventive ethylene copolymer and sprayed it. You get spherical Micropowder.

By the micronization falls Ethylene copolymer according to the invention as so-called micropowder or micronized ethylene copolymer with the average particle diameter (mass or volume average) 30 μm does not exceed preferably 25 μspecially preferably 15 μm, and that is also the subject of the present invention. Of the minimum average particle diameter may be, for example, 1 μm.

to Production of printing inks according to the invention, Toners and paints, especially printing varnishes, you can, for example proceed by mixing their ingredients together.

• (A) 0,05 bis 65 Gew.-%, bevorzugt 0,1 bis 10 Gew.-% und besonders bevorzugt 0,5 bis 3 Gew.-% vorzugsweise mikronisiertes erfindungsgemäßes Ethylencopolymer,
• (B) 5 bis 25 Gew.-%, bevorzugt 10 bis 20 Gew.-% Farbmittel,
• (C) 5 bis 35 Gew.-%, bevorzugt 6 bis 30 Gew.-% und besonders bevorzugt 10 bis 25 Gew.-% Bindemittels,
• (D) 40 bis 80 Gew.-%, bevorzugt 50 bi 60 Gew.-% Lösungsmittel,
• (E) 0 bis 20 Gew.-%, bevorzugt bis 10 Gew.-% Zuschlagstoffe.

wobei Angaben in Gew.-% jeweils auf die gesamte erfindungsgemäße Druckfarbe bezogen sind.Ingredients of printing inks and toners according to the invention are:

• (A) 0.05 to 65 wt .-%, preferably 0.1 to 10 wt .-% and particularly preferably 0.5 to 3 wt .-% preferably micronized inventive ethylene copolymer,
• (B) 5 to 25% by weight, preferably 10 to 20% by weight of colorant,
• (C) 5 to 35% by weight, preferably 6 to 30% by weight and particularly preferably 10 to 25% by weight of binder,
• (D) 40 to 80% by weight, preferably 50 to 60% by weight of solvent,
• (E) 0 to 20 wt .-%, preferably up to 10 wt .-% of aggregates.

wherein in wt .-% in each case based on the total printing ink of the invention.

• (A) vorzugsweise mikronisiertes erfindungsgemäßes Ethylencopolymer als Hauptkomponente, beispielsweise in Anteilen von 40 bis 65 Gew.-%, und
• (C) Lösungsmittel in Anteilen von 0 bis 25 Gew.-%

und weitere Ingredienzien (B), (D) und (E) wie oben beschrieben.One can define toner - for example for copiers - as a special variant of printing inks; they contain

• (A) preferably micronized ethylene copolymer according to the invention as a main component, for example in proportions of 40 to 65 wt .-%, and
• (C) Solvents in proportions of 0 to 25% by weight

and other ingredients (B), (D) and (E) as described above.

• – anorganische Pigmente wie beispielsweise Titandioxid-Pigmente, Eisenblaupigmente oder Eisenoxidpigmente,
• – Interferenzpigmente wie beispielsweise Perlmuttglanz oder Perlglanz, Ruß,
• – Metallpulver wie insbesondere Aluminiumpulver („Silberbronze"), Messingpulver („Goldbronze") oder Kupferpulver („Cu-Bronze"), sowie
• – organische Pigmente wie Azo-, Phthalocyanin- oder Isoindolin-Pigmente geeignet.

Suitable colorants (B) are, for example, dyes and in particular pigments, for example

• Inorganic pigments such as, for example, titanium dioxide pigments, iron blue pigments or iron oxide pigments,
• Interference pigments such as pearlescent or pearlescent, soot,
• - Metal powder such as in particular aluminum powder ("silver bronze"), brass powder ("gold bronze") or copper powder ("Cu bronze"), and
• - Organic pigments such as azo, phthalocyanine or isoindoline pigments suitable.

Pigments can be processed particularly well for the production of printing inks according to the invention if they are used in the form of so-called pigment preparations, for example dispersed with water and at least one surfactant such as a polyalkoxylated C ₁₀ -C ₂₀ alkanol, preferably polyalkoxylated C ₁₀ -C ₂₀ -n-alkanol.

suitable Binders (C) are, for example, polyvinyl butyral, nitrocellulose, Polyamides and polyacrylates. The combination has proven particularly advantageous at least one ethylene copolymer of the invention with nitrocellulose. Another particularly suitable combination comprises at least one copolymer of the invention and at least a polyacrylate, for example with a dynamic viscosity up to 150 mPa.s, preferably up to 100 mPa · s, determined according to ISO 2555.

suitable solvent (D) are alcohols such as, for example, ethanol, 1-propanol, 2-propanol, Ethylene glycol, propylene glycol, diethylene glycol, substituted alcohols such as ethoxypropanol, esters such as ethyl acetate, Isopropyl acetate, n-propyl or n-butyl acetate and water. Most notably preferred are mixtures of ethanol with at least one other solvent such as water, with ethanol accounting for the majority.

Suitable additives (E) are fillers, plasticizers, fatty acid amides, dispersing agents and adhesion promoters. Examples of fillers are calcium carbonate, barium sulfate, silica, alumina hydrate or aluminum or magnesium silicate (kaolin or talcum), furthermore fatty acid amides, which can be used to increase the surface smoothness. Plasticizers serve to increase the elasticity of the dried film. Examples of plasticizers are phthalic acid esters such as dibutyl phthalate, diisobutyl phthalate, dioctyl phthalate, citric acid or esters of adipic acid. For dispersing the pigments dispersing agents may be used, for example surfactants. Exemplary of adhesion promoters is called Ti (acac) ₃ .

Inventive printing lacquers contain no colorants, but apart from that have the same ingredients on printing inks according to the invention as described above. The amounts the rest Increase ingredients accordingly.

to Production of paints according to the invention, in particular printing inks of the invention, and printing inks according to the invention and toners according to the invention For example, you proceed in such a way that the above-mentioned ingredients (B) to (E) in dissolvers said high-speed stirrers according to the invention preferably premixed micronized ethylene copolymer. Preproducts according to the invention are obtained. Admirable can one inventive precursors For example, in stirred ball mills with Reibspalt, with grinding beads of a diameter from 0.05 to 5 mm diameter, preferably 0.5 to 2.5 and particularly preferably 2 mm diameter, continue to mix and then optional through at least one three-roll mill, for example, under stirring oxygen to remove. Alternatively, one can paint according to the invention or printing ink according to the invention also degas by applying a vacuum.

One Another object of the present invention is a method for printing on substrates, also called printing method according to the invention, using lacquers according to the invention, in particular printing lacquers according to the invention, printing inks according to the invention and toners according to the invention. Another object of the present invention are printed Substrates, available according to the printing method according to the invention.

Printed according to the invention Substrates are characterized by special mechanical stability of the printing made, in particular abrasion resistance, further by special shine.

When Substrates are for example suitable: paper, cardboard, metal foils, Polymer films, leather, imitations of leather, non-wovens produced, for example of polypropylene fibers, and curved surfaces such as can sheets.

Inventive inks and paints according to the invention, in particular printing inks according to the invention can be used in principle by all printing methods known per se print, for example, high pressure such as letterpress printing and flexographic printing, flat printing such as offset printing and lithography and gravure printing such as gravure printing and steel engraving. You can print texts and / or patterns as well as substrates flat in one color print.

In a variant of the printing method according to the invention, substrates printed according to the invention after exposure to the actual printing are exposed to actinic radiation, for example by exposing them to actinic radiation. As actinic radiation, for example, electromagnetic radiation having a wavelength range of 200 nm to 450 nm and an energy in the range of 70 mW / cm ² to 1500 mW / cm ^{2 are} suitable. Actinic radiation can be introduced, for example, continuously or in the form of flashes. By exposure, prints of a particular quality according to the invention are obtained.

The Invention will be explained by working examples.

working examples

Production of Inventive Ethylene Copolymer

zunächst auf einen Zwischendruck von 260 bar verdichtet und anschließend zusammen mit Ethylen unter dem Reaktionsdruck von 1700 bar in den Hochdruckautoklaven kontinuierlich eingespeist. Gleichzeitig wurde eine Lösung von Propionaldehyd in Isododekan gemäß Tabelle 1 zunächst auf den Zwischendruck von 260 bar verdichtet und anschließend zusammen mit Ethylen und b8.1 unter dem Reaktionsdruck von 1700 bar in den Hochdruckautoklaven kontinuierlich eingespeist. Getrennt davon wurde die in Tabelle 1 angegebene Menge Initiatorlösung, bestehend aus tert.-Butylperoxypivalat (TBPP) in Isododekan (Konzentration siehe Tabelle 1) unter dem Reaktionsdruck von 1700 bar in den Hochdruckautoklaven kontinuierlich eingespeist. Die Reaktionstemperatur betrug etwa 215 bis 222°C. Man erhielt erfindungsgemäßes Ethylencopolymer mit den aus Tabelle 2 ersichtlichen analytischen Daten.In a high-pressure autoclave, as described in the literature (M. Buback et al., Chem. Ing. Tech., 1994, 66, 510), ethylene, b8.1 and optionally methacrylic acid were continuously copolymerized. Ethylene (12.0 kg / h) under the reaction pressure of 1700 bar in the high pressure autoclave conti fed in a nutshell. Separately, the amount of b8.1 indicated in Table 1 was determined to be 35% by weight solution in toluene (Examples 1.1 and 1.3) or in ortho-xylene (Examples 1.2 and 1.4),

initially compressed to an intermediate pressure of 260 bar and then continuously fed together with ethylene under the reaction pressure of 1700 bar in the high-pressure autoclave. At the same time, a solution of propionaldehyde in isododecane according to Table 1 was first compressed to the intermediate pressure of 260 bar and then continuously fed together with ethylene and b8.1 under the reaction pressure of 1700 bar in the high-pressure autoclave. Separately, the amount indicated in Table 1 initiator solution consisting of tert-butyl peroxypivalate (TBPP) in isododecane (concentration see Table 1) was fed continuously under the reaction pressure of 1700 bar in the high-pressure autoclave. The reaction temperature was about 215 to 222 ° C. Inventive ethylene copolymer was obtained with the analytical data shown in Table 2.

In In Examples 1.3 and 1.4, methacrylic acid was first pressurized to an intermediate pressure compressed by 260 bar and then together with ethylene and toluene solution of b8.1 under the reaction pressure of 1700 bar in the high-pressure autoclave continuously fed.

Table 1 Preparation of Ethylene Copolymers According to the Invention

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

Abbreviations:

• MAS:

  methacrylic acid,

  LM:

  Solvents, namely toluene in nos. 1.1 and 1.3 and ortho-xylene in Nos. 1.2 and 1.4

  PO:

  tert-butyl peroxypivalate, ECP: ethylene copolymer

  c (PO):

  Concentration of TBPP in ID in mol / l

  PA:

  Propionaldehyde. The Values refer to the metered amount of propionaldehyde / h. Propionaldehyde was each fed as a solution in isododecane, namely in Examples 1.1 and 1.2 in a solution propionaldehyde : Isododecane as 1: 1 15 (parts by weight), in Examples 1.3 and 1.4 as 1: 9 (parts by weight).

Of the Sales refers to ethylene and is expressed in weight percent

Table 2: Analytical data of ethylene copolymers according to the invention

ν:

kinematische Schmelzeviskosität, gemessen bei 120°C nach DIN 51562. Die kinematische Schmelzeviskosität von erfindungsgemäßem Ethylencopolymer 1.4 wurde abweichend von 1.1 und 1.2 bei 160°C bestimmt.

SZ:

Säurezahl, bestimmt nach DIN 53402

"Content" is to be understood as meaning the proportion of copolymerized ethylene or b8.1 or MAS in the respective ethylene copolymer.

ν:

kinematic melt viscosity, measured at 120 ° C. according to DIN 51562. The kinematic melt viscosity of inventive ethylene copolymer 1.4 was determined differently from 1.1 and 1.2 at 160 ° C.

SZ:

Acid number, determined according to DIN 53402

The Melt flow rate (MFI) of inventive ethylene copolymer 1.3 was 5 g / 10 min, measured at 160 ° C and a load of 325 g according to DIN 53735.

The content of ethylene, methacrylic acid and b8.1 in ethylene copolymers 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 Membrane made of uncrosslinked ethylene copolymer 1.4

500 mg of ethylene copolymer 1.4 were dissolved in 15 ml of tetrahydrofuran (THF). The solution was placed in a metal ring (diameter 9.8 cm) on membrane substructure Made of polyester fleece, coated with polyacrylonitrile, as suitable Poured underground, 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 dried. The resulting film was about 50 μm thick and soluble in THF. He was as membrane of the invention 2.1 tested (s.u.).

2.2. Production of networked Membranes of ethylene copolymer 1.4 by means of actinic radiation

2.2.1 Example A

Experiment 2.1 was repeated and the resulting film was then exposed to actinic radiation. The source was a UVC lamp. The irradiance was 514 mW / cm ² (sum of UV-A, UV-B, UV-C and UV-VIS radiation) and the irradiation time 60 sec. The crosslinked film thus obtained was about 50 microns thick and not soluble in THF. It was tested as membrane 2.2.1 according to the invention (see below).

2.2.2. Example B

Experiment 2.1 was repeated and the resulting film was then exposed to actinic radiation. The source was a UVC lamp. The irradiance was 514 mW / cm ² (sum of UV-A, UV-B, UV-C and UV-VIS radiation) and the irradiation time 120 sec. The crosslinked film thus obtained was about 50 microns thick and insoluble in THF , It was tested as membrane 2.2.2 according to the invention (see below).

2.2.3 Example C

Experiment 2.1 was repeated and the resulting film was then exposed to actinic radiation. The source was a UVC lamp. The irradiance was 514 mW / cm ² (sum of UV-A, UV-B, UV-C and UV-VIS radiation) and the irradiation time 180 sec. The crosslinked film thus obtained was about 50 microns thick and not soluble in THF. It was tested as membrane 2.2.3 according to the invention (see below).

2.3. Make a crosslinked membrane of a compound having at least 2 polymerizable Double bonds and ethylene copolymer 1.4 by means of actinic radiation.

wurden in 15 ml Tetrahydrofuran (THF) gelöst. Die Lösung wurde in einen Metallring (Durchmesser 9,8 cm) auf Membranunterstruktur aus Polyestervlies, beschichtet mit Polyacrylnitril, 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 getrocknet.500 mg ethylene copolymer 1.4 and 24.9 mg IX.1

were dissolved in 15 ml of tetrahydrofuran (THF). The solution was poured into a metal ring (diameter 9.8 cm) on a membrane mat of polyester nonwoven coated with polyacrylonitrile as a suitable substrate, covered with a funnel (to prevent dust entry) and the solvent slowly evaporated at room temperature. It formed a movie. The film was then removed from the substrate and dried first between two layers of filter paper, which were each covered with aluminum foil for stabilization, at room temperature overnight.

The resulting film was then exposed to actinic radiation. The source was a UVC lamp. The irradiance was 514 mW / cm ² (sum of UV-A, UV-B, UV-C and UV-VIS radiation) and the irradiation time 60 sec. The crosslinked film thus obtained was about 50 microns thick and insoluble in THF and was tested as membrane 2.3 according to the invention.

you repeated Example 2.3, but instead of polyester fleece, visited with polyacrylonitrile as a substrate, in further experiments Glass, polyethylene and silanized polyethylene film. Glass, polyethylene and silanized polyethylene film were also suitable.

3. Implementation of separation tests

The permeation and separation measurements were carried out in a thermostatted flat cell with an effective membrane area of 33 cm ² . A membrane according to the invention was in each case attached in such a way that it lay on the permeate side 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 wt .-% isooctane and 8.8 wt .-% toluene, with a temperature of 60 ° C and a pressure of 1.013 bar flowed in. The permeate was collected by condensation in a cold trap and contained enriched toluene.The flow was determined by weighing the amount of condensate determined.

By Gas chromatographic analysis determined the composition in the permeate and determined the separation factor α.

Further Details are listed in Table 3.

Table 3 Separation experiments with membranes according to the invention.

The separation coefficient α is defined as

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

4. Preparation of printing inks according to the invention

4.1. Producing a micronized according to the invention Ethylene copolymer, general specification

Ethylene polymers of the invention were first ground to a powder in a coffee grinder until the average particle diameter was 2 mm. After that were
30 g of ethylene copolymer (powder) according to the invention
150 g of ethanol and
300 g steel balls (diameter: 3 mm)
in a ball mill of the type Skandex BA-S16 color mixer dispersed by repeatedly repeated dispersing operations. Each dispersion took 20 minutes. After each dispersion, an aliquot was taken and determined by means of a Galai CIS-1 particle analyzer particle diameter distribution and mean particle diameter (volume average).

you received micronized ethylene copolymers of the invention according to Table 4th

Table 4: micronized ethylene copolymers according to the invention

4.2 Production of printing inks according to the invention (general working instructions)

In a 150 ml wide-mouth bottle was made with the aid of a stirrer (Dispermat) dispersed with each other:

An automatic dispersing machine from Skandex was charged with:
300 g steel balls with a diameter of 3 mm,
10 g of Cu phthalocyanine
32 g of a 35 wt .-% aqueous dispersion of polyacrylate, partially neutralized with NaOH, pH 6, viscosity 100 mPa · s, measured according to DIN 255 at 20 ° C with a Brookfield viscometer, acid number 73 mg KOH / g, determined according to DIN EN ISO 3682,
1.5 g of 25% by weight aqueous ammonia,
16 g of isopropanol,
40.5 g of distilled water.

you dispersed for 30 min and received a dispersion.

Then parted one fills the steel balls the steel ball-free dispersion in a 150 ml wide-mouth bottle, added 1 g of micropolymerized ethylene copolymer according to Table 4 and dispersed with a stirrer of type Dispermat 2 minutes at 2000 revolutions / minute.

you received the respective printing ink of the invention according to the table 4th

As comparative ink V5-1, a printing ink was prepared according to the above-mentioned formulation, which was composed as follows:
32 g of a 35 wt .-% aqueous dispersion of polyacrylate, partially neutralized with NaOH, pH 6, viscosity 100 mPa · s, measured according to DIN 255 at 20 ° C with a Brookfield viscometer, acid number 73 mg KOH / g, determined according to DIN EN ISO 3682,
1.5 g of 25% by weight aqueous ammonia,
16 g of isopropanol,
40.5 g of distilled water
10 g of Cu phthalocyanine
1 g of polyethylene wax (homopolymer, viscosity 200 mPa · s, melting point 115 ° C).

As comparative ink V5-2, a printing ink was prepared which was composed as follows:
32 g of a 35 wt .-% aqueous dispersion of polyacrylate, partially neutralized with NaOH, pH 6, viscosity 100 mPa · s, measured according to DIN 255 at 20 ° C with a Brookfield viscometer, acid number 73 mg KOH / g, determined according to DIN EN ISO 3682,
1.5 g of 25% by weight aqueous ammonia,
16 g of isopropanol,
40.5 g of distilled water
10 g of Cu phthalocyanine

Comparative ink So V5-2 did not contain any ethylene copolymer.

4.3 Printing substrates with the aid of printing inks according to the invention

With the help of a test printing device of the company Saueressig paper strips (dimension 650 x 50 mm) were printed flat with a doctor blade, each with a printing ink according to the invention. The contact pressure of the printing cylinder (120 raster) was 100 g / m ² . the wet pressure film had a thickness of 6 μm. Subsequently, printed substrates according to the invention were obtained as shown in Table 5. Thereafter, exposure was carried out for one minute with a UV lamp at wavelengths from 200 nm to 450 nm and a power of 514 mW / cm ² .

Analogous was printed with the reference ink V5-1. One received one printed comparison substrate V6-1.

Analogous was printed with the reference printing ink V5-2. One received one printed comparison substrate V6-2.

The abrasion resistance was then tested using a Scheuer tester Prüfbau Quartant at a contact pressure of 50 N / cm ² for 100 rubbing cycles and a rubbing speed of 15 cm / s. The intensity of the color transferred to a test sheet according to DIN 6174 was assessed, whereby a lower value is advantageous. The gloss was tested with micro TRI glass at a measuring angle of 85 °. The surface friction resistance was tested as follows:
It was stuck on a test table according to the invention printed substrate or non-inventive printed substrate that the printed side facing up. A second paper strip printed by the same method was applied opaque to the printed strip and loaded with a weight (75 g). Subsequently, the second printed paper strip was moved by means of a spring balance until the second printed paper strip mitglitt in the pulling direction. The value read on the spring balance corresponded to the surface friction resistance.

you received the results according to table 5th

Table 5: Results on substrates according to the invention and not printed according to the invention

Claims (27)

Ethylene copolymers containing ethylene as comonomers and at least one comonomer that is a photochemically activatable Contains group, incorporated in copolymerized form. Ethylene copolymers according to claim 1, characterized in that that in at least one comonomer a photochemically activatable Group selected is made from hydrogen-abstracting photoinitiator groups. Ethylene copolymers according to Claim 1 or 2, characterized in that in at least one comonomer a photochemical activatable group over a spacer is attached to an ethylenically unsaturated group. Ethylene copolymers according to at least one of claims 1 to 3, characterized in that they are copolymerized as comonomers contain (a) from 50% to 99.9% by weight of ethylene, (b) 0.1 to 50% by weight of one or more comonomers containing at least one photochemically activatable group, with data in% by weight each based on the total weight of ethylene copolymer. Ethylene copolymers according to one of claims 1 or 2, characterized in that at least one comonomer (b) of the general formula I

in which 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, Y selected from carbonyl groups and one Single bond, X selected from oxygen, sulfur and NR ³ , R ³ selected from hydrogen, unbranched and branched C ₁ -C ₁₀ -alkyl and C ₃ -C ₁₂ -cycloalkyl, A is a spacer selected from C ₁ -C ₂₀ -alkylene monosubstituted or polysubstituted by C ₁ -C ₄ -alkyl or unsubstituted in which one or more nonadjacent C atoms may be replaced identically or differently by oxygen atoms, carboxylic acid ester groups, OC (O) -O- groups, keto groups, Carboxylic acid amide groups or urea groups, P * is a photochemically activatable group, m, n independently selected from 0 or 1. Ethylene copolymers according to one of Claims 1 to 5, characterized in that P * corresponds to a group of the general formula II,

where Z is hydrogen or hydroxyl. Ethylene copolymers according to one of claims 1 to 6, characterized in that they contain at least one comonomer (c) of the general formula III in copolymerized form

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, unbranched and branched C ₁ -C ₁₀ -alkyl and C ₃ -C ₁₂ -cycloalkyl. Ethylene copolymers according to one of claims 1 to 7, characterized in that the variables in formula 1 are defined as follows: R ^{1 is} hydrogen or methyl, R ^{2 is} hydrogen, Y is a carbonyl group, X is an oxygen atom, A is a spacer of the formula - (CH ₂ ) _x -O-CO-O-, where x is an integer in the range of 2 to 10, P * is a photochemically activatable group of formula IIa

Ethylene copolymers according to any one of claims 1 to 8, characterized in that the variables in formula III are defined as follows: R ^{4 is} hydrogen or methyl, R ^{5 is} hydrogen R ^{6 is} hydrogen. Process for the preparation of ethylene copolymers according to one of the claims 1 to 9, characterized in that one (a) ethylene with (B) at least one comonomer containing at least one photochemical activatable group, and optionally with (c) at least an at least monoethylenically unsaturated carboxylic acid or at least one at least one ethylenically unsaturated Carbonsäureester at Temperatures in the range of 170 to 300 ° C and pressures in the range of 500 to 4000 bar polymerized. Process for the preparation of ethylene copolymers according to one of Claims 1 to 9, characterized in that (a) ethylene with (c) at least one at least monoethylenically unsaturated carboxylic acid or at least one at least monounsaturated carboxylic acid ester at temperatures in the range from 170 to 300 ° C and pressures in the range of 500 to 4000 bar and then polymerized with at least one compound of general formula IV

implements. Use of ethylene copolymers according to one of claims 1 to 9 for the production of materials for material separation. Material separation materials, manufactured under Use of ethylene copolymer according to one of claims 1 to 9th Materials according to claim 13, characterized that they are membranes. Materials according to claim 13, characterized that it is stationary Phases of chromatography columns is. Materials according to any one of claims 13 to 15 using ethylene copolymer according to any one of claims 1 to 9 and at least one compound having at least two polymerizable double bonds. Process for the production of materials for separating substances, characterized in that one ethylene copolymer according to one of claims 1 to 9 treated with actinic radiation. Method according to claim 17, characterized in that that ethylene copolymer in the presence of at least one compound with at least two polymerizable double bonds with actinic Radiation treated. Method of separating mixtures of substances using at least one material according to any one of claims 13 to 15th Use of ethylene copolymers according to one of claims 1 to 9 for the production of paints, printing inks and toners. Process for the production of paints, inks and toners using ethylene copolymers according to any one of claims 1 to 9. Micronised ethylene copolymer according to one of claims 1 to 9 with a mean particle diameter (number average) not more than 30 microns. Paints, printing inks and toners, containing at least An ethylene copolymer according to any one of claims 1 to 9. Paints, printing inks and toners, prepared using of at least one ethylene copolymer according to any one of claims 1 to 9th Method of printing substrates using of paints, inks and toners according to claim 23 or 24. Method according to claim 25, characterized in that that you have substrates first with a lacquer, a printing ink or a toner according to one of claims 23 or 24 contacted and then with actinic radiation exposed. Printed substrates, obtainable by a process according to claim 25 or 26.