DE102007061224A1 - Reducing adhesiveness of molded body from polymer, comprises contacting polar solvents on the surface of polymer, where the polar solvent is hydroxylgroup containing compound, and/or carbonylgroup containing compound; and gluing - Google Patents

Abstract

Reducing adhesiveness of a molded body from polymer, comprises contacting polar solvents on the surface of polymer in the absence of non-polar solvent, where the polar solvent is hydroxylgroup containing compound, and/or carbonylgroup containing compound, and the polar solvent do not contain non volatile salt-like or polymer character ingredients; and gluing an essential portion of the polar solvent and/or their mixture on the surface of the molded body. Reducing adhesiveness of a molded body from polymer, comprises contacting polar solvents on the surface of polymer in the absence of non-polar solvent, where the polar solvent is hydroxylgroup containing compound of formula (R1>-(O-A)n-OH), and/or carbonylgroup containing compound of formula (R2>-CO-X-R3>), and the polar solvent do not contain non volatile salt-like or polymer character ingredients; and gluing an essential portion of the polar solvent and/or their mixture on the surface of the molded body. R1>, R2>2-20C alkyl, 2-20C alkenyl, 5-20C cycloalkyl, 6-20C aryl, 20C alkylaryl or 20C arylalkyl; A : 2-4C alkylene; n : 0-10, preferably 0; X : O, S or chemical bond (if R2> is not hydrogen); and R3>1-20C alkyl, 1-20C alkenyl, 5-20C cycloalkyl, 6-20C aryl, 6-20C alkylaryl or 6-20C arylalkyl.

Description

The present invention relates to a process for reducing the stickiness of polymer moldings such as films, pellets or irregularly structured particles, in particular of moldings of polymers whose polymer main chains have branches, especially branched polyolefins such as Isobutenhomo- or copolymers having a weight average molecular weight M. _w from 10,000 to 10,000,000, by contacting these shaped bodies in the absence of non-polar solvents with certain polar solvents.

Lots Shaped bodies of polymers, especially those of highly branched Polyolefins, especially if they are freshly prepared are - a high stickiness, which is often too Problems in the processing or bottling process.

The prior art suggests some solutions to this problem, but these are unsatisfactory. So (honors the SU 430 144 (1) that the tackiness of polyisobutenes is reduced by adding a 5 to 15% by weight alcohol solution of low molecular weight polyvinyl acetate followed by drying. From the British Patent 928,120 (2) it is known that coating polyisobutene with polyethylene or polypropylene reduces its tackiness. in the U.S. Patent 2,491,526 (3) describes the reduction in stickiness of isobutene-styrene copolymers by adding zinc salts.

It was an object of the present invention to provide an efficient process for reducing the stickiness of polymer moldings, in particular those of polymers whose polymer main chains have branches, especially of branched polyolefins such as isobutene homo- or copoly mers having a weight-average molecular weight M _w of 10,000 to 10,000,000, which also at the same time allows the reinstatement of the original sticking behavior after passing through the disordered by the sticky behavior process or processing steps.

The object was achieved by a process for reducing the stickiness of shaped articles of polymers, which is characterized in that the surface of these moldings in the absence of non-polar solvent with at least one polar solvent selected from hydroxyl-containing compound of general formula I. R ¹ - (OA) _n -OH (I) in the
R ¹ denotes hydrogen, a C ₂ - to C ₂₀ -alkyl or -alkenyl radical, a C ₅ - to C ₂₀ -cycloalkyl radical or a C ₆ - to C ₂₀ -aryl, -alkylaryl or -arylalkyl radical,
A is a C ₂ - to C ₄ -alkylene group and
n is an integer from 0 to 10,
and carbonyl-containing compounds of general formula II R ² -CO-XR ³ (II) in the
R ² denotes hydrogen, a C ₂ - to C ₂₀ -alkyl or -alkenyl radical, a C ₅ - to C ₂₀ -cycloalkyl radical or a C ₆ - to C ₂₀ -aryl, -alkylaryl or -arylalkyl radical,
X is oxygen, sulfur, or in the event that R ^{2 is} other than hydrogen, a chemical bond is and
R ^{3 is} a C ₁ to C ₂₀ alkyl or alkenyl radical, a C ₅ to C ₂₀ cycloalkyl radical or a C ₆ to C ₂₀ aryl, alkylaryl or arylalkyl radical,
or a mixture of said polar solvents, wherein the polar solvents or mixtures thereof contain no non-volatile ingredients salt-like or polymeric character, brings in contact and leaves a substantial part of the polar solvent or mixtures thereof adhere to the surface of the moldings.

Under the hydroxyl-containing compounds I subsume in particular Low and medium molecular weight alcohols and water, among the carbonyl group-containing Compounds II, in particular carboxylic acid esters and ketones. The use of low molecular weight alcohols and water at Manufacturing processes of isobutene or isobutene-containing monomer mixtures by polymerization is known.

On the one hand, such alcohols are used as complexing agents for the boron trifluoride polymerization catalysts in order to control the reactivity of the catalysts. The molar amount of alcohol used is of the order of magnitude of the molar amount of boron trifluoride, for example according to WO 2002/40533 (4) with a maximum of 2.5 times the molar amount of C ₁ -C ₄ alkanol, for example isopropanol or sec-butanol, with respect to the boron trifluoride. In the WO 2004/065432 (5) describes a complexed boron trifluoride catalyst containing as complexing agent a primary C ₁ -C ₅ -alkanol and / or a secondary C ₃ -C ₅ -alkanol and secondary alkanol having at least 6 carbon atoms, a primary alkanol having at least 6 carbon atoms and / or a tertiary alkanol.

On the other hand, in addition to acetonitrile, methanol and water or aqueous bases are also used as reagents to stop the polymerization reaction. So revealed the DE-A 27 02 604 (6) in Example 1, the use of 3 g of methanol per kg of reaction discharge as a termination reagent in the isobutene polymerization.

Out Document (4) is yet another purpose for using low molecular weight Alcohols in the isobutene polymerization, namely the addition of methanol, ethanol or a mixture of methanol and ethanol for discharge from the polymerization reactor for separation a boron trifluoride-rich alcohol phase which is separated and properly recycled back into the process can be. According to Table 2 of (4) the amount of alcohol so added a maximum of 20 g per liter of reaction.

The EP-A 322 241 (7) discloses that in principle the same compounds which are used as complexing agents for a boron trifluoride catalyst, namely C ₁ -C ₁₈ alcohols such as methanol, ethanol, propanols and butanols, acetic acid, trichloroacetic acid, hydrofluoric acid, trifluoroacetic acid, diethyl ether, water and mixtures thereof, also as Abbruchreagentien for isobutene polymerization can be used, in molar amounts with respect to the boron trifluoride catalyst of up to 1000: 1. Explicitly, however, only aqueous-methanolic caustic soda is called as a termination reagent.

In However, none of the cited prior art documents will mentioned or even hinted that by means of alcohols or other hydroxyl-containing compounds or by means of carbonyl group-containing Compounds the stickiness of moldings made from so Polymers can be reduced.

The term "C ₂ to C ₂₀ alkyl" for R ¹ , R ² and R ³ includes straight-chain and branched alkyl groups. Examples of such alkyl groups are ethyl, n-propyl, iso-propyl, n-butyl, 2-butyl, sec-butyl, tert-butyl, n-pentyl, 2-pentyl, 2-methylbutyl, 3-methylbutyl, 1 , 2-dimethylpropyl, 1,1-dimethylpropyl, 2,2-dimethylpropyl, 1-ethylpropyl, n-hexyl, 2-hexyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,2-dimethylbutyl, 1.3 Dimethylbutyl, 2,3-dimethylbutyl, 1,1-dimethylbutyl, 2,2-dimethylbutyl, 3,3-dimethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethylbutyl, 2 Ethyl butyl, 1-ethyl-2-methylpropyl, n-heptyl, 2-heptyl, 3-heptyl, 2-ethylpentyl, 1-propylbutyl, n-octyl, 2-ethylhexyl, 2-propylheptyl, n-nonyl, n-decyl , n-dodecyl, n-tridecyl, iso-tridecyl, n-tetradecyl (myristyl), n-hexadecyl (palmityl), n-octadecyl (stearyl) and n-eicosyl. Of these, preferred are C ₂ - to C ₁₃ -alkyl, in particular C ₂ - to C ₁₀ -alkyl, especially C ₂ - to C ₆ -alkyl.

Examples of "C ₂ - to C ₂₀ -alkenyl" are vinyl, 1-propenyl, 2-propenyl, oleyl, linolyl and linolenyl.

Examples of "C ₅ - to C ₂₀ -cycloalkyl" are C ₅ - to C ₇ -cycloalkyl groups, such as cyclopentyl, cyclohexyl and cycloheptyl, which may be substituted by alkyl groups, for example methyl radicals.

The term "C ₆ to C ₂₀ aryl, alkylaryl or arylalkyl" includes mononuclear, dinuclear, trinuclear and higher nuclear aromatic hydrocarbon radicals. The pure aryl radicals may, in the case of a substitution by the abovementioned alkyl and / or alkenyl radicals to alkylaryl or alkenylaryl radicals, carry 1, 2, 3, 4 or 5, preferably 1, 2 or 3 substituents. Typical examples are phenyl, tolyl, xylyl, mesityl, naphthyl, fluorenyl, anthracenyl, phenanthrenyl, naphthacenyl and styryl. A typical example of an arylalkyl radical is benzyl. Of these, C ₆ - to C ₁₅ -aryl, -alkylaryl or arylalkyl, especially C ₆ - to C ₈ -aryl, -alkylaryl or arylalkyl, are preferred.

Examples of C ₂ -C ₄ -alkylene groups are 1,1-ethylene, 1,2-propylene, 1,3-propylene, 1,2-butylene, 1,3-butylene, 1,4-butylene and in particular 1, 2-ethylene.

If the variable R ^{1 is} hydrogen and n is the number 0, the hydroxyl-containing Ver binding I water.

If the variable R ¹ denotes an alkyl, alkenyl, cycloalkyl or arylalkyl radical and n is the number 0, the hydroxyl-containing compound I is an alcohol. Typical of these are ethanol, n-propanol, isopropanol, n-butanol, 2-butanol, sec-butanol, tert-butanol, n-pentanol, 2-pentanol, 2-methylbutanol, 3-methylbutanol, n-hexanol, 2-hexanol, 2-methylpentanol, 3-methylpentanol, 4-methylpentanol, 2,3-dimethylbutanol, 2,2-dimethylbutanol, 3,3-dimethylbutanol, 2-ethylbutanol, 1-ethyl-2-methylpropanol, n-heptanol, n-octanol, 2-ethylhexanol, allyl alcohol, cyclopentanol, cyclohexanol and benzyl alcohol.

If the variable R ¹ denotes an aryl or alkylaryl radical and n is the number 0, the hydroxyl-containing compound I is a phenol. Typical representatives of these are unsubstituted phenol and o-, m- or p-cresol.

If the variable R ¹ denotes hydrogen and n is a number from 1 to 10, the hydroxyl-containing compound I is a polyalkylene glycol. Representatives thereof are 1,2-ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, diethylene glycol, dipropylene glycol, dibutylene glycol, triethylene glycol, tripropylene glycol and tributylene glycol , The number n is preferably 1, 2 or 3 in the presence of polyalkylene glycols.

If the variable R ¹ denotes an alkyl, alkenyl, cycloalkyl or arylalkyl radical and n is a number from 1 to 10, the hydroxyl-containing compound I is an aliphatic ether or an alkoxylated alcohol. Typical of these are diethyl ether, n-propyl ethyl ether, iso-propyl ethyl ether, di-n-propyl ether, di-iso-propyl ether, ethoxyethyl ethanol, ethoxyethyl propanol and ethoxyethyl butanol. By definition, the number n is 1 in the presence of aliphatic ethers and preferably 2 or 3 in the case of alkoxylated alcohols.

If the variable R ¹ denotes an aryl or alkylaryl radical and n is a number from 1 to 10, the hydroxyl-containing compound I is an aromatic ether or an alkoxylated phenol. Typical representatives are phenylethyl ether and phenoxyethylethanol. By definition, the number n is 1 in the presence of aromatic ethers and preferably 2 or 3 in the case of alkoxylated phenols.

If the variable R ^{2 is} hydrogen and X is oxygen or sulfur, the carbonyl-containing compound II is a formic ester or an ester thioester. Typical examples of these are methyl formate, ethyl formate, n-propyl formate, isopropyl formate, n-butyl formate, allyl formate, cyclohexyl formate and phenyl formate.

If the variable R ² denotes an alkyl, alkenyl, cycloalkyl, aryl, alkylaryl or arylalkyl radical and X is oxygen or sulfur, the carbonyl-containing compound II is a carboxylic acid ester or carboxylic acid thioester. Typical of these are methyl acetate, methyl propionate, methyl butyrate, ethyl acetate, ethyl propionate, ethyl butyrate, n-propyl acetate, iso-propyl acetate, n-butyl acetate, allyl acetate, cyclohexyl acetate, phenyl acetate, methyl benzoate, ethyl benzoate, n-propyl benzoate, iso-propyl benzoate and n-butyl benzoate.

When the variable R ^{2 is} an alkyl, alkenyl, cycloalkyl, aryl, alkylaryl or arylalkyl radical and X is a chemical bond, the carbonyl group-containing compound II is a ketone. Typical of these are acetone, butanone (methyl ethyl ketone), diethyl ketone and acetophenone.

In a preferred embodiment, the process according to the invention is carried out in such a way that hydroxyl-containing compounds I are used as the polar solvent, in which the variable R ¹ denotes a C ₂ - to C ₆ -alkyl radical and n is the number 0. Very particular preference is given to the hydroxyl-containing compound isopropanol.

you can be used as a polar solvent individual representatives from the use connection groups I and II. But you can also Mixtures of two or more such polar solvents use, with representatives of the connection groups I among themselves or representatives of Liaison Groups II with each other or with representatives of compound groups I with representatives of compound groups II can be mixed.

It is essential that said polar solvents or mixtures thereof do not contain non-volatile ingredients because they could interfere with the desired, optionally reversible, control of tackiness. Such non-volatile ingredients are either salts, ie compounds having predominantly ionic character, for example alkali metal, alkaline earth metal or heavy metal salts, or polymeric compounds. Such salt-like and polymeric compounds have virtually no vapor pressure and thus remain indefinitely adhere to the surface of the polymer moldings.

When Shaped bodies in the sense of the present invention are intended in particular Materials suitable as materials with geometrically exactly definable Measures like strands, pipes, bands or In particular, films are understood which, for example, as Design elements or packaging materials can serve. Furthermore, as a shaped body in the sense of the present Invention for transport and further processing appropriately formulated polymer moldings in a suitable Denomination, for example, tablets, compacts and in particular Pellets and irregularly structured particles (Granules) to be understood. The ways of producing said Moldings of the underlying polymers are the Skilled in the art, for example films made of polyolefins, z. B. from polyisobutenes, by heating the precipitated Polymer powder or polymer granules to temperatures in the range the softening point of the polymers are produced.

The The method according to the invention comprises contacting the surface of the polymer molding with the mentioned polar solvents and adhering a essential part of these solvents on this surface. Under the contacting is essentially a wetting with the polar solvent used in excess can be understood. This step is done preferably by brushing, for example by means of a brush or a squeegee, by watering, for example, in one suitable bathing vessel, or by spraying, for example by means of one or more spray nozzles. excess Polar solvent is allowed to drain, drain and / or in mild conditions, for example at room temperature and normal pressure, evaporate, so that is guaranteed that a film of the polar solvent on the surface the polymer molding for the time of running the process of stickiness due to stickiness or processing steps sticks and the desired reduced stickiness causes.

The inventive method can be designed reversible be, d. H. It allows the reinstatement of the original Stickiness behavior after passing through the sticky behavior disturbed process or processing steps. For this purpose, the must on the surface of the polymer molding adhesive film of the polar solvent removed again which is usually due to heat input or washing processes with nonpolar solvents such as aliphatic, cycloaliphatic or aromatic hydrocarbons, e.g. Butane, pentane, hexane, Heptane, octane, isooctane, cyclopentane, cyclohexane, benzene, toluene or Xylenes, can be done.

The inventive method is used in principle for any polymer moldings that are sticky. Especially is an application in moldings of polymers whose Polymer main branches have branching, mainly branched Polyolefins such as isobutene homo- or copolymers, polypropylene or Polystyrene, into consideration. But you can also do it on moldings For example, apply polyethylene or polyoxymethylene, if these have adhesive properties due to their production. The mentioned polymers can be crosslinked, they are preferably but not networked.

In In a preferred embodiment, the invention is used Process on shaped bodies of polymers whose main polymer chains Have branching in the form of hydrocarbyl side chains, in particular branched polyolefins, with a degree of branching on average 0.1 to 1.5, especially 0.3 to 1.2, especially 0.5 to 1.0 hydrocarbyl side chains per carbon atom in the polymer main chain. As hydrocarbyl side chains are mainly short-chain alkyl radicals such as methyl, Ethyl, n-propyl or n-butyl and aryl radicals such as phenyl, tolyl or Xylyl into consideration. Such hydrocarbyl side chains have in the Rule 1 to 12, preferably 1 to 6 carbon atoms. For example a polyisobutene homopolymer has a degree of branching of 1.0, since every other carbon atom in the polymer backbone has two methyl groups carries, for which calculation the carbon atoms neglected at the ends of the polymer backbone should.

In particular, the tack reducing method of the present invention is applicable to molded articles of isobutene homo- or copolymers having a weight-average molecular weight M _w of 10,000 to 10,000,000, preferably 25,000 to 5,000,000, more preferably 75,000 to 4,000,000, and above all from 150,000 to 3,000,000, suitable. Typical isobutene homopolymers have a weight average molecular weight M _w of 200,000 or 2,600,000.

Isobutene homopolymers are understood in the context of the present invention to be such polymers which are based on the polymer at least 98 mol%, preferably at least 99 mol% of isobutene. Accordingly, isobutene copolymers are understood to mean those polymers which contain more than 2 mol% of monomers in copolymerized form, which are different from isobutene.

in the Case of isobutene copolymers are preferred comonomers styrene, Styrene derivatives, in particular α-methylstyrene and 4-methylstyrene, Styrene and styrene derivatives-containing monomer mixtures, alkadienes such as butadiene and isoprene, as well as mixtures thereof.

For the use of isobutene or an isobutene-containing monomer mixture as the monomer to be polymerized isobutene source is both isobutene itself and also isobutene-containing C ₄ hydrocarbon streams, for example C ₄ raffinates, C ₄ cuts from the isobutane dehydrogenation, C ₄ cuts from steam crackers and FCC crackers (fluid catalytic cracking), provided that they are largely exempt from 1,3-butadiene contained therein. Suitable C ₄ hydrocarbon streams generally contain less than 500 ppm, preferably less than 200 ppm, butadiene. The presence of 1-butene and of cis- and trans-2-butene is largely uncritical in the preparation of isobutene homopolymers - with controlled reaction. Typically, the isobutene concentration in the C ₄ hydrocarbon streams is in the range of 40 to 60 weight percent. The isobutene-containing monomer mixture may contain small amounts of contaminants such as water, carboxylic acids or mineral acids, without resulting in critical yield or selectivity losses. It is expedient to avoid an accumulation of these impurities by removing such pollutants from the isobutene-containing monomer mixture, for example by adsorption on solid adsorbents such as activated carbon, molecular sieves or ion exchangers.

It can monomer mixtures of isobutene or the Isobutene-containing hydrocarbon mixture with olefinically unsaturated Monomers which are copolymerizable with isobutene reacted become. If monomer mixtures of isobutene with suitable comonomers is to be copolymerized, contains the monomer mixture preferably at least 5% by weight, more preferably at least 10 Wt .-% and in particular at least 20 wt .-% isobutene, and preferably at most 95% by weight, more preferably at most 90 wt .-% and in particular at most 80 wt .-% comonomers.

Suitable copolymerizable monomers for isobutene are, in particular, vinylaromatics such as styrene and α-methylstyrene, C ₁ -C ₄ -alkylstyrenes such as 2-, 3- and 4-methylstyrene and 4-tert-butylstyrene, alkadienes such as butadiene and isoprene and also isoolefins with 5 to 10 carbon atoms, such as 2-methylbutene-1, 2-methylpentene-1, 2-methylhexene-1, 2-ethylpentene-1, 2-ethylhexene-1 and 2-propylheptene-1. Suitable comonomers are furthermore olefins which have a silyl group, such as 1-trimethoxysilyl ethene, 1- (trimethoxysilyl) propene, 1- (trimethoxysilyl) -2-methylpropene-2, 1- [tri (methoxyethoxy) silyl] ethene , 1- [tri (methoxyethoxy) silyl] propene, and 1- [tri (methoxyethoxy) silyl] -2-methylpropene-2, as well as vinyl ethers such as tert-butyl vinyl ether.

Should Isobutene copolymers are prepared, the process can be so be configured that preferably random polymers or preferred Block copolymers are formed. For the preparation of block copolymers can For example, the different monomers in succession to the polymerization reaction feeding, with the addition of the second comonomer in particular takes place only when the first comonomer at least partially already polymerized. In this way, both diblock, triblock as well as higher block copolymers accessible depending on the order of monomer addition a block of one or the other Comonomers have as a terminal block. Block copolymers arise in some cases, even if all comonomers Although simultaneously fed to the polymerization reaction but one polymerizes significantly faster than that or the others. This is especially the case when isobutene and a vinyl aromatic compound, especially styrene, in the invention Process be copolymerized. In this case, preferably block copolymers are formed with a terminal polyisobutene block. This is due to, that the vinyl aromatic compound, especially styrene, significantly polymerized faster than isobutene.

The Polymerization can be both continuous and batch respectively. Continuous processes can be analogously to known methods of the prior art for continuous Polymerization of isobutene in the presence of Lewis acid catalysts be carried out in the liquid phase.

As polymerization catalysts for isobutene or isobutene-containing monomer mixtures, heterogeneous or, in particular, homogeneous catalysts from the class of Lewis acids are used. Lewis acids are electron-deficient compounds at their central atom and derive their catalytic activity from them. In particular, these Lewis acids are compounds of elements of the 3rd main group of the Periodic Table, that is, boron, aluminum, indium, gallium and thallium. However, you can It is also possible to use halides, in particular chlorides, of tin, of titanium, of antimony or of iron. Such Lewis acids are often referred to as Friedel-Crafts catalysts.

Boron and aluminum compounds, in particular boron and aluminum halides, for example anhydrous aluminum chloride, boron trichloride, boron trifluoride, boron tribromide, boron triiodide and in particular boron trihalide complexes with activators such as boron trifluoride etherates, eg. As boron trifluoride diethyl etherate, or boron trifluoride-alcohol complexes. If boron halides, in particular boron trifluoride, are used, it is advisable to use the additional activators in the complexes mentioned. A particularly preferred Akti vator for boron trifluoride is in this case an alcohol, in particular a C ₁ - to C ₄ -alkanol, z. As methanol, ethanol, isopropanol, isobutanol or sec-butanol.

• • Imidazoliumsalze, die eine positive Ladung im Imidazolring tragen, welche durch ein geeignetes Anion kompensiert wird, und an den Imidazolring-Stickstoffatomen und/oder den Imidazolring-Kohlenstoffatomen durch Alkyl-, substituierte Alkyl-, Cycloalkyl-, substituierte Cycloalkyl-, Heteroalkyl-, Heterocycloalkyl-, substituierte Heterocycloalkyl-, Aryl-, substituierte Aryl-, Heteroaryl-, substituierte Heteroaryl-, Alkoxy-, Aryloxy-, Acyl-, Silyl-, Boryl-, Phosphino-, Amino-, Thio- und/oder Seleno-Gruppen substituiert sein können, wobei als derartige Substituenten C₁- bis C₄-Alkylgruppen wie Methyl, Ethyl, Propyl oder Butyl bevorzugt werden und wobei vorzugsweise zumindest die beiden Imidazolring-Stickstoffatome solche C₁- bis C₄-Alkylgruppen tragen; typische Vertreter hierfür sind 1-Ethyl-3-methylimidazolium-salze;
• • Verbrückte Imidazoliumsalze aus zwei Imidazoliumringen und einer gegebenenfalls substituierten Kohlenwasserstoffbrücke zwischen entsprechenden Imidazolring-Stickstoffatomen, die eine positive Ladung im jedem Imidazolring tragen, welche durch geeignete Anionen kompensiert wird, und an den Imidazolring-Stickstoffatomen und/oder den Imidazolring-Kohlenstoffatomen jeweils durch Alkyl-, substituierte Alkyl-, Cycloalkyl-, substituierte Cycloalkyl-, Heteroalkyl-, Heterocycloalkyl-, substituierte Heterocycloalkyl-, Aryl-, substituierte Aryl-, Heteroaryl-, substituierte Heteroaryl-, Alkoxy-, Aryloxy-, Acyl-, Silyl-, Boryl-, Phosphino-, Amino-, Thio- und/oder Seleno-Gruppen substituiert sein können, wobei als derartige Substituenten C₁- bis C₄-Alkylgruppen wie Methyl, Ethyl, Propyl oder Butyl bevorzugt werden und wobei vorzugsweise zumindest jeweils die unverbrückten Imidazolring-Stickstoffatome solche C₁- bis C₄-Alkylgruppen tragen; typische Vertreter hierfür sind 1,4-Bis-(3-Methylimidazolium)butan-Salze;
• • Pyridinumsalze, die eine positive Ladung im Pyridinring tragen, welche durch ein geeignetes Anion kompensiert wird, und am Pyridinring-Stickstoffatom und/oder den Pyridinring-Kohlenstoffatomen durch Alkyl-, substituierte Alkyl-, Cycloalkyl-, substituierte Cycloalkyl-, Heteroalkyl-, Heterocycloalkyl-, substituierte Heterocycloalkyl-, Aryl-, substituierte Aryl-, Heteroaryl-, substituierte Heteroaryl-, Alkoxy-, Aryloxy-, Acyl-, Silyl-, Boryl-, Phosphino-, Amino-, Thio- und/oder Seleno-Gruppen substituiert sein können, wobei als derartige Substituenten C₁- bis C₄-Alkylgruppen wie Methyl, Ethyl, Propyl oder Butyl bevorzugt werden und wobei vorzugsweise zumindest das Pyridinring-Stickstoffatom eine solche C₁- bis C₄-Alkylgruppe trägt; typische Vertreter hierfür sind 1-Ethyl-3-methylpyridiniumsalze;
• • Pyrazoliumsalze, die eine positive Ladung im Pyrazolring tragen, welche durch ein geeignetes Anion kompensiert wird, und an den Pyrazolring-Stickstoffatomen und/oder den Pyrazolring-Kohlenstoffatomen durch Alkyl-, substituierte Alkyl-, Cycloalkyl-, substituierte Cycloalkyl-, Heteroalkyl-, Heterocycloalkyl-, substituierte Heterocycloalkyl-, Aryl-, substituierte Aryl-, Heteroaryl-, substituierte Heteroaryl-, Alkoxy-, Aryloxy-, Acyl-, Silyl-, Boryl-, Phosphino-, Amino-, Thio- und/oder Seleno-Gruppen substituiert sein können, wobei als derartige Substituenten C₁- bis C₄-Alkylgruppen wie Methyl, Ethyl, Propyl oder Butyl bevorzugt werden und wobei vorzugsweise zumindest die beiden Pyrazolring-Stickstoffatome solche C₁- bis C₄-Alkylgruppen tragen; typische Vertreter hierfür sind 1,2,4-Trimethylpyrazoliumsalze und 1,2,4-Triethylpyrazoliumsalze;
• • Ammoniumsalze, die eine positive Ladung tragen, welche durch ein geeignetes Anion kompensiert wird, und am Ammonium-Stickstoffatom durch Alkyl-, substituierte Alkyl-, Cycloalkyl-, substituierte Cycloalkyl-, Heteroalkyl-, Heterocycloalkyl-, substituierte Heterocycloalkyl-, Aryl-, substituierte Aryl-, Heteroaryl-, substituierte Heteroaryl-, Alkoxy-, Aryloxy-, Acyl-, Silyl-, Boryl-, Phosphino-, Amino-, Thio- und/oder Seleno-Gruppen substituiert sein können, wobei als derartige Substituenten C₁- bis C₂₀-Alkylgruppen, insbesondere C₁- bis C₄-Alkylgruppen wie Methyl, Ethyl, Propyl oder Butyl, bevorzugt werden und wobei vorzugsweise das Ammonium-Stickstoffatom drei oder vier derartiger C₁- bis C₂₀-Alkylgruppen trägt; typische Vertreter hierfür sind Tetrabutylammoniumsalze.

In addition to the above-mentioned heterogeneous and homogeneous catalysts from the class of Lewis acids are suitable as polymerization catalysts for isobutene or isobutene-containing monomer mixtures continue to ionic liquids, as described for example in the WO 00/32658 are described. Ionic liquids consist of salts or salt mixtures which usually melt below + 100 ° C., preferably below -50 ° C. Suitable polymerization catalysts are in particular the following ionic liquids:

• Imidazolium salts carrying a positive charge in the imidazole ring which is compensated by a suitable anion and at the imidazole ring nitrogen atoms and / or the imidazole ring carbon atoms by alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, Heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy, acyl, silyl, boryl, phosphino, amino, thio and / or seleno groups C ₁ to C ₄ alkyl groups such as methyl, ethyl, propyl or butyl are preferred as such substituents and wherein preferably at least the two imidazole ring nitrogen atoms carry such C ₁ to C ₄ alkyl groups; typical representatives are 1-ethyl-3-methylimidazolium salts;
• Bridged imidazolium salts of two imidazolium rings and an optionally substituted hydrocarbon bridge between corresponding imidazole ring nitrogen atoms which carry a positive charge in each imidazole ring which is compensated by suitable anions and at the imidazole ring nitrogen atoms and / or the imidazole ring carbon atoms by alkyl , substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy, acyl, silyl, boryl , Phosphino, amino, thio and / or seleno groups, preference being given to such substituents C ₁ - to C ₄ -alkyl groups such as methyl, ethyl, propyl or butyl and wherein preferably at least in each case the unbridged imidazole ring Nitrogen atoms carry such C ₁ to C ₄ alkyl groups; typical representatives thereof are 1,4-bis (3-methylimidazolium) butane salts;
• Pyridinium salts carrying a positive charge in the pyridine ring which is compensated by a suitable anion and at the pyridine ring nitrogen atom and / or the pyridine ring carbon atoms by alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, heterocycloalkyl , substituted heterocycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy, acyl, silyl, boryl, phosphino, amino, thio and / or seleno groups substituted C ₁ to C ₄ alkyl groups such as methyl, ethyl, propyl or butyl are preferred as such substituents, and preferably at least the pyridine ring nitrogen carries such a C ₁ to C ₄ alkyl group; typical representatives thereof are 1-ethyl-3-methylpyridinium salts;
• Pyrazolium salts carrying a positive charge in the pyrazole ring which is compensated by a suitable anion, and at the pyrazole ring nitrogen atoms and / or the pyrazole ring carbon atoms by alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, Heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy, acyl, silyl, boryl, phosphino, amino, thio and / or seleno groups C ₁ to C ₄ alkyl groups such as methyl, ethyl, propyl or butyl are preferred as such substituents and wherein preferably at least the two pyrazole ring nitrogen atoms carry such C ₁ to C ₄ alkyl groups; typical representatives thereof are 1,2,4-trimethylpyrazolium salts and 1,2,4-triethylpyrazolium salts;
• Ammonium salts carrying a positive charge which is compensated by a suitable anion and at the ammonium nitrogen atom by alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy, acyl, silyl, boryl, phosphino, amino, thio and / or seleno groups may be substituted, wherein as such substituents C ₁ - are preferred to C ₂₀ -alkyl groups, in particular C ₁ - to C ₄ -alkyl groups such as methyl, ethyl, propyl or butyl, and wherein preferably the ammonium-nitrogen atom carries three or four such C ₁ - to C ₂₀ -alkyl groups; typical representatives for this are tetrabutylammonium salts.

In addition, ionic liquids based on phosphines, arsines, stibines, Ethern, thioethers or selenoethers find use.

Examples of suitable anions for compensating the positive charges in said ionic liquids are F ^- , Cl ^- , Br ^- , I ^- , BF ₄ ^- , BCl ₄ ^- , BBr ₄ ^- , Bl ₄ ^- , PF ₆ ^- , AsF ₆ ^-, SbF ₆ ^-, FeF ₄ ^-, FeCl ₄ ^-, FeBr ₄ ^-, NO ₂ ^-, NO ₃ ^-, SO ₄ ^2-, an unsubstituted or substituted carborane, an unsubstituted or substituted Metallocarboran, a phosphate, a phosphite, a Polyoxymetalate, an unsubstituted or substituted carboxylate, a triflate, a borate having one or more organic radicals or an aluminate of the formula [AlY _4-z Z _z ] ^- or the formula [AlZ ₄ · m AlZ ₃ ] ^- , in which Y is hydrogen , an organic group, a silyl group, a boryl group, a phosphino group, an amino group, a thioro group or a seleno group, Z represents a halogen atom, z represents the integer 0, 1, 2, 3 or 4 and m represents a number of 0 to 5, in particular 0 to 3, stands.

In a preferred embodiment, said anion denotes an aluminate of the formula [AlZ ₄ .m AlZ ₃ ] ^- in which Z is a halogen atom and m is a number from 0 to 1.5, in particular 0 to 1.2. Typical such anions are, for example, the tetrachloroaluminate anion [AlCl ₄ ] ^- = [AlCl ₄ .m AlCl ₃ ] ^- where m = 0 and the heptachlorodialuminate anion [Al ₂ Cl ₇ ] ^- = [AlCl ₄ .m AlCl ₃ ] ^- with m = 1.0.

typical ionic liquids for use as polymerization catalysts for isobutene or isobutene-containing monomer mixtures for example, 1,2,4-trimethylpyrazolium or 1,2,4-triethylpyrazolium tetrachloroaluminate, 1,2,4-trimethylpyrazolium or 1,2,4-triethylpyrazolium heptachlorodialuminate and 1-ethyl-3-methylimidazolium tetrachloroaluminate or 1-ethyl-3-methylimidazolium heptachlorodialuminate.

The The amount of polymerization catalyst to be used depends essentially according to the type of catalyst and the reaction conditions, in particular the reaction temperature and the desired molecular weight of the polymer. It can be based on fewer attempts at stabbing the respective reaction system can be determined. In general, will the polymerization catalyst in amounts of 0.0001 to 1 wt .-%, in particular from 0.0005 to 0.1% by weight, in particular from 0.001 to 0.01% by weight, in each case based on isobutene used.

The Polymerization of the isobutene or of the isobutene-containing monomer mixture is usually at a polymerization temperature of -80 carried out to + 100 ° C. It is in principle both for a low temperature implementation, z. B. at -70 to 0 ° C, as well as at higher Temperatures, d. H. at least 0 ° C, z. At 0 to 100 ° C, suitable. The polymerization is economical Reasons at least 0 ° C, z. At 0 to 100 ° C, especially at 10 to 60 ° C, aimed at achieving the energy and material consumption required for cooling is to keep as low as possible. It can be the same, however good technical result even at lower temperatures, eg. At -50 to <0 ° C, preferably at -40 to -10 ° C, performed become.

He follows the polymerization at or above the boiling point of polymerizing monomer or mixture of monomers, it is preferred in pressure vessels, for example in autoclaves or in pressure reactors.

Conveniently, the polymerization is carried out in the presence of an inert nonpolar solvent or Solvent mixture performed. The used Solvent should be suitable during the Polymerization reaction usually occurring increase to reduce the viscosity of the reaction solution to such an extent that the removal of the resulting heat of reaction can be guaranteed. They are such solvents or solvent mixtures which are opposite the starting materials and reagents used are inert. suitable non-polar solvents are preferably hydrocarbons, For example, aliphatic hydrocarbons such as butane, pentane, Hexane, heptane, octane and isooctane, cycloaliphatic hydrocarbons, such as cyclopentane and cyclohexane, or aromatic hydrocarbons, such as benzene, toluene and the xylenes. Preferably, solvents before using impurities like water, carboxylic acids or mineral acids, for example by adsorption to solid adsorbents such as activated carbon, molecular sieves or ion exchangers.

The polymerization is preferably carried out under largely aprotic conditions, in particular under anhydrous reaction conditions. Aprotic or anhydrous reaction conditions are understood to mean that the water content (or the content of protic impurities) in the reaction mixture is less than 50 ppm and in particular less than 5 ppm. As a rule, therefore, the feedstocks will be dried before use by physical and / or chemical means. in particular In particular, it has proven useful to use the inert hydrocarbons used as a solvent after conventional pre-cleaning and predrying with an organometallic compound, such as an organolithium, organomagnesium or organoaluminum compound, in an amount sufficient to remove the traces of water from the solvent remove. The solvent thus treated is then preferably condensed directly into the reaction vessel. Similarly, one can also with the monomers to be polymerized, in particular with isobutene or with the isobutene-containing mixtures, proceed. The drying with other conventional drying agents such as molecular sieves or predried oxides such as alumina, silica, calcium oxide or barium oxide is suitable. Vinylaromatic compounds and other starting materials which are not suitable for drying with metals such as sodium or potassium or a treatment with metal alkyls are freed from water (traces) with suitable drying agents, for example with calcium chloride, phosphorus pentoxide or molecular sieve.

The Polymerization of the isobutene or the isobutene-containing feedstock usually occurs spontaneously when contacting the polymerization catalyst with the monomer or the monomer mixture in the desired Reaction temperature. Here one can proceed in such a way that one that the Presents monomer or the monomer mixture in the solvent, brings to reaction temperature and then the polymerization catalyst admits. It is also possible to proceed in such a way that the polymerization catalyst presented in the solvent and then the Add monomer or the monomer mixture. As the beginning of polymerization then the time is at which all reactants in the reaction vessel are. The polymerization catalyst may be partially or completely dissolve in the reaction medium, as a suspension or as another liquid phase present.

suitable Reactor types for the described polymerization process of the isobutene or of the isobutene-containing starting material are customary in addition to stirred tank reactors, kneaders, extruders, thin-film evaporators, Falling film evaporators and helical tube evaporators loop reactors, Tubular reactors, fluidized bed reactors, fluidized bed reactors, stirred tank reactors with and without solvents and liquid bed reactors.

to The preparation of copolymers can be carried out in such a way that the monomers, optionally in solvent, and then submitted adding the polymerization catalyst. The setting of the reaction temperature can be done before or after the addition of the polymerization catalyst. It is also possible to proceed in such a way that one initially only one the monomers, optionally in solvent, presents, at closing the polymerization catalyst and admits only after a certain time, for example if at least 60%, at least 80% or at least 90% of the monomer are reacted, the one or more monomers added. Alternatively, the polymerization catalyst, optionally in solvent, submit, then add the monomers simultaneously or sequentially and then the set the desired reaction temperature. As the beginning of polymerization then the time at which the polymerization catalyst and at least one of the monomers in the reaction vessel are.

Next The discontinuous procedure described here can be make the polymerization as a continuous process. This leads to the starting materials, d. H. that or the to be polymerized monomers, optionally the solvent and optionally the polymerization catalyst of the polymerization reaction continuously and continuously withdraws reaction product, so that in the reactor more or less stationary polymerization conditions to adjust. The one or more monomers to be polymerized as such, diluted with a solvent or as a monomer-containing hydrocarbon stream, are supplied.

To the Reaction termination, the reaction mixture is preferably deactivated, for example, by adding a protic compound, in particular by adding small amounts of water, methanol or aqueous Base, e.g. As an aqueous solution of an alkali or alkaline earth metal hydroxides such as sodium hydroxide, potassium hydroxide, magnesium hydroxide or calcium hydroxide, an alkali or alkaline earth carbonate such as Sodium, potassium, magnesium or calcium carbonate, or an alkali metal or alkaline earth hydrogen carbonate such as sodium, potassium, magnesium or calcium hydrogencarbonate.

at the copolymerization of isobutene or isobutene-containing hydrocarbon cuts with at least one vinyl aromatic compound also arise with the simultaneous addition of the comonomers, preferably block copolymers, wherein the isobutene block is usually the terminal, d. H. the last one represents formed block.

For the preparation of such copolymers is isobutene or an isobutene-containing hydrocarbon cut copolymerized with at least one vinyl aromatic compound, especially styrene. Such a monomer mixture particularly preferably contains from 5 to 95% by weight, particularly preferably from 30 to 70% by weight, of styrene.

Preferably, the isobutene homo- or copolymers prepared as described above, especially the isobutene homopolymers, have a polydispersity (PDI = M _w / M _n ) of 1.0 to 3.0, especially of at most 2.0, preferably of 1.0 to 2.0, more preferably from 1.0 to 1.8 and especially from 1.0 to 1.5. In some variants of said preparation methods higher polydispersities may occur, then the Isobutenhomo- or copolymers produced, especially the Isobutenhomopolymere, preferably a polydispersity PDI of 1.0 to 30, especially of at most 20, preferably from 1.0 to 10, more preferably from 1.0 to 5 and especially from 1.0 to 3.

The inventive method is also distinguished characterized in that the invention with said polar solvents treated polymer molding in the form of films usually a stickiness value (Tack value), the 30% or less, especially 20% or less, especially 10% or less, of the corresponding stickiness value (Tack value) of the same polymer film that is not polar Solvents is treated.

at the determination of the tack value (tack value) becomes the separation energy which is necessary to produce a standardized stainless steel stamp, which with a defined contact pressure and a defined Contact pressure on a shaped body, in particular a film, the sample to be determined is driven according to a defined Contact time at a defined withdrawal speed back from to solve the molding or the film. A film The sample to be determined is usually previously by heating the sample of the molding and drawing the so flowable made substance in a defined thickness on a glass plate produced.

The obtained by the process according to the invention Polymer moldings are characterized by a significantly reduced Stickiness and are therefore suitable for process or processing steps, for example for filling processes manufactured polymer granules or polymer pellets, better manageable. The inventive method is also reversible, d. H. It allows the reinstatement of the original Stickiness behavior after passing through the sticky behavior disturbed process or processing steps.

The The following examples are intended to explain the present invention, without restricting it.

Examples

From polyisobutene having a weight-average molecular weight M _w of 2,600,000, films having a thickness of 150 μm were produced on glass plates by heating to 120 ° C. by means of a suitable doctor blade. For these, in the TA XT plus hand-held measuring device (stable micro systems), the separation energies (tack values) were determined under the following parameters: Stainless steel temple diameter 2.0 mm Anpressgeschwindigkeit 0.1 mm / s contact force 5,0 N contact time 1.0 s off speed 0.1 mm / s

Various polar solvents were soaked by means of a hereby Brushes thinly applied to the films. After this treatment The Tack values were determined directly without a separate drying step.

The following table shows the results of the determinations: Polar solvent Tack value [y / m] Without treatment 58.23 isopropanol 5.27 Water (distilled) 4.82 ethanol 8.81

QUOTES INCLUDE IN THE DESCRIPTION

This list The documents listed by the applicant have been automated generated and is solely for better information recorded by the reader. The list is not part of the German Patent or utility model application. The DPMA takes over no liability for any errors or omissions.

Cited patent literature

• - SU 430144 [0003]
• GB 928120 [0003]
• - US 2491526 [0003]
• WO 2002/40533 [0007]
• - WO 2004/065432 [0007]
• - DE 2702604 A [0008]
• - EP 322241A [0010]
• WO 00/32658 [0044]

Claims (8)

A method for reducing the tackiness of shaped articles of polymers, characterized in that the surface of these shaped articles in the absence of non-polar solvent with at least one polar solvent selected from hydroxyl-containing compound of the general formula I. R ¹ - (OA) _n -OH (I) in which R ¹ denotes hydrogen, a C ₂ - to C ₂₀ -alkyl or -alkenyl radical, a C ₅ - to C ₂₀ -cycloalkyl radical or a C ₆ - to C ₂₀ -aryl, -alkylaryl or -arylalkyl radical, A a C ₂ - to C ₄ -alkylene group and n is an integer from 0 to 10, and carbonyl-containing compounds of general formula II R ² -CO-XR ³ (II) in which R ^{2 is} hydrogen, a C ₂ to C ₂₀ alkyl or alkenyl radical, a C ₅ to C ₂₀ cycloalkyl radical or a C ₆ to C ₂₀ aryl, alkylaryl or arylalkyl radical, X for oxygen, sulfur or in the event that R ^{2 is} other than hydrogen, a chemical bond and R ^{3 is} a C ₁ - to C ₂₀ alkyl or alkenyl radical, a C ₅ - to C ₂₀ cycloalkyl radical or a C ₆ - to C ₂₀ -aryl, -Alkylaryl- or -Arylalkylrest means, or a mixture of said polar solvents, wherein the polar solvents or their mixtures do not contain non-volatile ingredients of salt-like or polymeric character, brings in contact and a substantial part of the polar Solvent or mixtures thereof can adhere to the surface of the moldings. Method according to claim 1, characterized in that that it is molded on polymers, their main polymer chains Branched in the form of hydrocarbyl side chains, with a degree of branching of on average from 0.1 to 1.5 hydrocarbyl side chains applies per carbon atom in the polymer main chain. Method according to claim 1 or 2, characterized that it is applied to polymer moldings in the form of films. Method according to claim 1 or 2, characterized that you put it on polymer shaped bodies in the form of pellets or unevenly structured particles applies. Process according to claims 1 to 4, characterized in that it is applied to moldings of isobutene homo- or copolymers having a weight-average molecular weight M _w of 10,000 to 10,000,000. Process according to claims 1 to 5, characterized characterized in that the contacting of the surfaces the polymer molding with the polar solvents by painting, watering or spraying. Process according to claims 1 to 6, characterized in that hydroxyl-containing compounds I are used as the polar solvent, in which the variable R ¹ denotes a C ₂ - to C ₆ -alkyl radical and n is the number 0. Process according to claims 1 to 7, characterized characterized in that with the polar solvents treated polymer moldings in the form of films one Tack value, which is 30% or less of the corresponding tack value (tack value) of the same polymer film, that was not treated with the polar solvents, is.