DE102012007728A1 - Process for the preparation of crosslinkable polyolefin copolymers - Google Patents

Abstract

durch Übergangsmetall-katalysierte Copolymerisation von Olefinen der allgemeinen Formel [2] H₂C=CH-R¹ [2], mit Silanen der allgemeinen Formel [3]

in Gegenwart eines Übergangsmetallkatalysators (PK),
wobei
R¹, C_n, m, p, q, R², R³, R⁴ und R⁵ die in Anspruch 1 angegebenen Bedeutungen aufweisen,
die Copolymere der allgemeinen Formel [1], bei denen R¹ Kohlenwasserstoffrest mit 1 bis 20 Kohlenstoffatomen bedeutet, sowie ein Verfahren zur wasserfreien Vernetzung der Copolymere der allgemeinen Formel [1] mit Katalysatoren K, die ausgewählt werden aus Lewis-Säuren und Brönstedt-Säuren.The invention relates to a process for the preparation of crosslinkable copolymers of the general formula [1]

by transition-metal-catalyzed copolymerization of olefins of the general formula [2] H ₂ C = CH-R ¹ [2], with silanes of the general formula [3]

in the presence of a transition metal catalyst (PK),
in which
R ¹ , C _n , m, p, q, R ² , R ³ , R ⁴ and R ^{5 have} the meanings given in claim 1,
the copolymers of the general formula [1] in which R ^{1 is a} hydrocarbon radical having 1 to 20 carbon atoms, and a process for anhydrous crosslinking of the copolymers of the general formula [1] with catalysts K, which are selected from Lewis acids and Bronsted acids ,

Description

The invention relates to a process for the preparation of crosslinkable olefin copolymers by means of transition metal-catalyzed polymerization.

Silane-extended polyolefins can be prepared by either grafting or copolymerization. In the case of polyethylene, vinyltrimethoxysilane is mainly radically grafted onto the PE. The crosslinking of these polymers is relatively complicated, since it must take place at 90-120 ° C in a water bath or under superheated steam. The grafting is for example in US 3646155 A explained. However, the moisture crosslinking of such grafted moisture-crosslinking polymers takes place very slowly. Radical grafting on other poly-α-olefins such as polypropylene leads to chain degradation of the polyolefin and thus deterioration of the polymer properties.

The copolymerization of olefins and alkoxysilanes is largely limited to the high-pressure radical copolymerization of ethylene and vinyltrimethoxysilane. The radical copolymerization of propylene does not work due to the stability of the allylic radical. For the preparation of polypropylene copolymers is dependent on the transition metal-catalyzed copolymerization. However, vinyltrimethoxysilane is a catalyst poison and thus can not be copolymerized with olefins transition metal catalyzed.

The transition metal-catalyzed copolymerization of silanes with olefins is presented in various publications. M. Itoh et al. teach in Macromolecules 1998, 31, 5609 the polymerization of vinylsilanes with Ziegler-Natta catalysts.

at P. Longi et al. (Macromolecular Chemistry 1968, 116, 113 ) describes the copolymerization with a Ziegler-Natta catalyst of propene and allylsilane. The resulting polymer can then be crosslinked with potassium hydroxide.

A. Tsuchida et al. (Macromolecules 1997, 30, 2818-2824 ) and L. Zheng et al. (Macromolecules 2001, 34, 8034-8039) teach the copolymerization of olefins with silsesquioxanes using zirconocenes as catalysts.

In A. Nakamura et al. (Chem. Rev. 2009, 109, 5215-5244 ) gives an overview of the copolymerization of polar monomers with olefins. Only the copolymerization of trimethylvinyl- and triethylvinylsilane with ethene is described. In US 2010331483 A describes crosslinkable polymer blends containing at least one alkoxy silyl group of the type ≡Si-OC (R ¹ ) (R ² ) (R ³ ), and their use for the anhydrous silane crosslinking of siloxanes and organic polymers.

durch Übergangsmetall-katalysierte Copolymerisation von Olefinen der allgemeinen Formel [2] H₂C=CH-R¹ [2], mit Silanen der allgemeinen Formel [3]

in Gegenwart eines Übergangsmetallkatalysators (PK),
wobei
R¹ Wasserstoff oder Kohlenwasserstoffrest mit 1 bis 20 Kohlenstoffatomen,
C_n zweiwertiger unsubstituierter oder substituierter Kohlenwasserstoffrest mit 1 bis 50 Kohlenstoffatomen,
m die Werte 1, 2 oder 3,
p ganzzahlige Werte von 1 bis 100000,
q ganzzahlige Werte von 1 bis 100000
R² Wasserstoff, Halogen, unsubstituierten oder substituierten Kohlenwasserstoffrest mit 1 bis 20 Kohlenstoffatomen, Alkyloxyrest mit 1 bis 6 Kohlenstoffatomen, Acyloxyrest mit 1 bis 6 Kohlenstoffatomen, Alkenyloxyrest mit 1 bis 6 Kohlenstoffatomen, OH, Metalloxyrest -O-M oder Rest -CH₂-W, wobei W ein Heteroatom, ausgewählt aus N, O, P, S, darstellt und die freien Valenzen am Heteroatom durch Kohlenwasserstoffreste mit 1 bis 20 Kohlenstoffatomen abgesättigt sind,
R³, R⁴, R⁵ Wasserstoff, Halogen, unsubstituierten oder substituierten Kohlenwasserstoffrest mit 1 bis 20 Kohlenstoffatomen, Acylrest mit 1 bis 6 Kohlenstoffatomen oder Carbonsäureestergruppe eines aliphatischen Alkohols mit 1 bis 6 Kohlenstoffatomen, wobei zwei oder drei der Reste R³, R⁴, R⁵ miteinander verbunden sein können, mit der Maßgabe, dass höchstens 2 der Reste R³, R⁴, R⁵ Wasserstoff sind, bedeuten,
wobei die Copolymere der allgemeinen Formel [1] als statistische Copolymere, Block- oder Multiblockcopolymere oder Mischungen davon vorliegen.The invention relates to a process for the preparation of crosslinkable copolymers of the general formula [1]

by transition-metal-catalyzed copolymerization of olefins of the general formula [2] H ₂ C = CH-R ¹ [2], with silanes of the general formula [3]

in the presence of a transition metal catalyst (PK),
in which
R ^{1 is} hydrogen or hydrocarbon radical having 1 to 20 carbon atoms,
C _{n is a} divalent unsubstituted or substituted hydrocarbon radical having 1 to 50 carbon atoms,
m the values 1, 2 or 3,
p integer values from 1 to 100,000,
q integer values from 1 to 100000
R ^{2 is} hydrogen, halogen, unsubstituted or substituted hydrocarbon radical having 1 to 20 carbon atoms, alkyloxy radical having 1 to 6 carbon atoms, acyloxy radical having 1 to 6 carbon atoms, alkenyloxy radical having 1 to 6 carbon atoms, OH, metalloxy radical -OM or radical -CH ₂ -W, wherein W is a heteroatom selected from N, O, P, S, and the free valencies on the heteroatom are saturated by hydrocarbon radicals having 1 to 20 carbon atoms,
R ³ , R ⁴ , R ^{5 are} hydrogen, halogen, unsubstituted or substituted hydrocarbon radical having 1 to 20 carbon atoms, acyl radical having 1 to 6 carbon atoms or carboxylic acid ester group of an aliphatic alcohol having 1 to 6 carbon atoms, wherein two or three of the radicals R ³ , R ⁴ , R ^{5 may} be linked to one another, with the proviso that at most 2 of the radicals R ³ , R ⁴ , R ^{5 are} hydrogen,
wherein the copolymers of the general formula [1] are present as random copolymers, block or multiblock copolymers or mixtures thereof.

Another object of the invention are the copolymers of general formula [1], in which R ^{1 is a} hydrocarbon radical having 1 to 20 carbon atoms.

The copolymers of the general formula [1] are easy to prepare and are easily crosslinkable without the addition of water or other crosslinkers.

The copolymerization of the olefin and silane monomers of the general formulas [2] and [3] is carried out with a transition metal catalyst (PK).

Suitable catalysts PK are all known in the art for insertion polymerization based on early transition metals such as Ti, Zr, Hf, V, based on late transition metals such as Cr, Ni, Pd and metallocene catalysts. Preference is given to catalysts based on later transition metals such as Cr, Ni, Pd and metallocene catalysts. Very particular preference is given to metallocene catalysts based on early transition metals such as Ti, Zr, Hf, V. An example of this is dichloro [rac-ethylenebis (indenyl)] zirconium (IV).

To activate the catalysts, all common cocatalysts and combinations of cocatalysts can be used. Examples of cocatalysts are methylaluminoxane, trimethylaluminum, triethylaluminum, triisobutylaluminum, tris (pentafluorophenyl) borane, trityltetrakis (pentafluorophenyl) borate, tris (pentafluorophenyl) borane / butylhydroxytoluene or trityltetrakis (pentafluorophenyl) borate / butylhydroxytoluene.

The catalysts PK can be used as homogeneous or as heterogeneous catalysts.

As olefins of the general formula [2] it is possible to use all olefins which can be polymerized with the catalysts PK. R ¹ may be an alkyl or aryl radical. The alkyl radicals may be open-chain or cyclic. Preferably, R ^{1 is} hydrogen or alkyl radical or aryl radical having 1 to 8 carbon atoms. Particularly preferred olefins of the general formula [2] are ethene, propene, 1-butene, 1-hexene, 1-octene and styrene.

It can also be used mixtures of olefins in any composition, such as. Example, ethene / propene or ethene / 1-hexene or ethene / 1-octene mixtures.

The molecular weight M _{w of} the copolymers is preferably in the range from 1000 to 20 000 g / mol, more preferably in the range from 10000-500000 g / mol, in each case measured by GPC.

The content of monomer 3 in the copolymer is preferably 0.1-30% by weight, more preferably 0.5-15% by weight, more preferably 1-10% by weight.

The copolymerization can be carried out in solution, as a precipitation polymerization, in gas phase, in suspension or in emulsion. Polymerization temperatures are preferably in the range of 0-150 ° C. The duration of the polymerization is preferably 1-600 min.

If the polymerization is carried out in solution, so are all common non-polar organic solvents that do not deactivate the catalyst system, in particular aliphatic and aromatic hydrocarbons such. For example, toluene, hexane, heptane, Cylclohexan, benzene, xylene.

C _n preferably has from 2 to 30, in particular from 3 to 15, carbon atoms. C _n is preferably an aliphatic hydrocarbon radical. When C _{n is} substituted, the preferred substituents are halo and cyano groups.

p is preferably integer values from 2 to 100,000, in particular from 250 to 100,000.

q is preferably integer values from 2 to 100,000, in particular from 10 to 50,000.

The hydrocarbon radicals R ² preferably have at most 10, in particular at most 3, carbon atoms. The radicals R ² are preferably hydrogen, chlorine, methyl, ethyl, propyl, butyl, phenyl, methoxy, ethoxy, propoxy, acetoxy, vinyl, OH. When R ^{2 is} a radical -CH ₂ -W, the free valences on the heteroatom are saturated by alkyl or aryl radicals having preferably 1 to 6 carbon atoms.

The radical R ² particularly preferably represents methyl, ethyl, propyl or butyl.

The radicals R ³ , R ⁴ , R ⁵ preferably have 1 to 12, in particular 1 to 6 carbon atoms. The radicals R ³ , R ⁴ , R ⁵ particularly preferably represent methyl, ethyl, propyl, butyl, vinyl, phenyl or carboxyl radicals -C (O) OCH ₃ .

When two or three of R ³ , R ⁴ , R ⁵ are joined together, the resulting residue may have been formed from a diol.

Halogen is preferably at the radicals R ³ , R ⁴ , R ⁵ and the substituents of R ² , R ³ , R ⁴ , R ⁵ and C _{n is} chlorine or fluorine.

Examples of preferred silanes of the general formula [3] are the following structures:

Another object of the invention is the anhydrous crosslinking of the copolymers of general formula [1] with catalysts K.

Preferred catalysts (K) are Lewis acids and Bronsted acids. Examples of suitable Lewis acids are tin, tin oxide and tin compounds, such as. As dibutyltin dilaurate (DBTL), titanium, titanium oxide and titanium compounds, such as. As titanium (IV) isopropanolate, titanium (IV) acetylacetonate, copper, copper oxide and copper compounds, such as. As copper (I) trifluoromethanesulfonate, iron, iron oxide and iron compounds, such as. As iron (III) chloride, iron (III) acetylacetonate, manganese, manganese oxide and manganese compounds, such as. B. manganese (II) acetylacetonate, aluminum, aluminum oxide and aluminum compounds, such as. B.

Aluminum (III) chloride, aluminum (III) isopropanolate, trimethylaluminum, boron, boron oxide and boron compounds, such as. As boron trichloride, zirconium, zirconium and zirconium compounds, such as. As Zr (IV) acetylacetonate, gallium, gallium oxide and gallium, z. B. gallium (III) acetylacetonate, cerium, cerium oxide and cerium compounds, such as. As cerium (III) chloride and zinc, zinc oxide and zinc compounds, such as. B. zinc laurinate or zinc pivalate.

Examples of suitable Bronsted acids are carboxylic acids such as lauric acid, sulfonic acids such as trifluoromethanesulfonic acid, p-toluenesulfonic acid and dodecylbenzenesulfonic acid, mineral acids such as hydrochloric acid, nitric acid and phosphoric acid.

Preference is also given to compounds which, on irradiation with high-energy radiation, such as UV light or electron radiation, release protons with decomposition. Examples of such compounds are diaryliodonium compounds, such as, for example, {4 - [(2-hydroxytetradecyl) -oxy] -phenyl} phenyliodonium hexafluoroantimonate, diphenyliodonium nitrate, bis (4-tert-butylphenyl) iodonium p-toluenesulfonate, bis (4-tert. butylphenyl) iodonium trifluoromethanesulfonate, triarylsulfonium compounds such as 4- (thiophenoxyphenyl) -diphenylsulfonium hexafluoroantimonate, (4-bromophenyl) diphenylsulfonium trifluoromethanesulfonate and N-hydroxynaphthalimidetrifluoromethanesulfonate and 2- (4-methoxystyryl) -4,6-bis (trichloromethyl) -1, Called 3,5-triazine.

In particular, catalysts (K) are used which accelerate a condensation between two silanol groups, between a silanol group and an alkoxysilyl group, between a silanol group and an Si-Cl group or between an alkoxysilyl group or Si-Cl group and water.

In addition, mixtures of different catalysts (K) can be used. The catalyst (K) is preferably used in a concentration of at least 10 ppm, particularly preferably at least 0.1% by weight, based in each case on the copolymers of the general formula [1]. The catalyst (K) is preferably used in a concentration of at most 20 wt .-%, more preferably at most 10 wt .-%, in particular at most 2 wt .-%, each based on the copolymers of general formula [1].

The crosslinking of the copolymers of the general formula [1] with the catalysts K can preferably be carried out under the following conditions. Heating the polymer blend with catalyst K for 1 s to 48 h at 5 ° C to 300 ° C. Preferred is a temperature of 5 ° C to 190 ° C.

The copolymers of the general formula [1] are preferably brought to a temperature of at least 50 ° C., in particular at least 80 ° C., for crosslinking. Preferably, the crosslinking is carried out at a temperature of at most 180 ° C, in particular at most 150 ° C.

As energy sources for the crosslinking by heating are preferably ovens, for. As circulating air drying cabinets, heating channels, heated rollers, heated plates, infrared radiant heaters or microwaves used.

Preferably, the crosslinking can also be effected by irradiation with ultraviolet light or electron radiation.

In a particularly preferred embodiment of the process, the crosslinking of the copolymers of the general formula [1] takes place by thermal decomposition of the alkoxysilyl group of the general formula [4] Si (R ² ) _3-m (OC (R ³ ) (R ⁴ ) (R ⁵ )) _m to form silanol groups Si (R ²⁾ _3-m (OH) _m and a subsequent condensation of the silanol groups. In the thermal decomposition of the alkoxysilyl groups of the general formula [4], vinyl-functional compounds can be liberated as further cleavage products.

Particularly preferably, the crosslinking of the copolymers of the general formula [1] takes place without the ingress of (air) moisture.

The degree of crosslinking is 10-100%, preferably 50-100%, particularly preferably 90-100%.

The copolymers of general formula [1] are used alone or as part of formulations preferably as cable insulation, as pipes, as packaging material, as a chemical container, as a heat-resistant material, as a binder, as a hot-melt adhesive, as a reactive hot-melt adhesive, for the production of splices, bonded structures, Coatings, lacquers, adhesive tapes, adhesive films, pressure-sensitive adhesives or foams.

All the above symbols of the above formulas each have their meanings independently of each other. In all formulas, the silicon atom is tetravalent.

Examples

Unless otherwise indicated, all amounts and percentages are by weight, all pressures are 0.10 MPa (abs.) And all temperatures are 25 ° C.

In the use of hydrolysis and air-sensitive substances and in the polymerization was worked with Schlenk and glove box techniques. Only dry, water and oxygen-free solvents were used. Propen 2.5 was supplied by Westfalen AG, Germany and additionally purified by molecular sieve and a copper catalyst.

The ¹ H NMR (300 MHz) spectroscopic measurements of the polymers were taken at 100 ° C.

For the size exclusion chromatography (GPC) = for the determination of M _w, M _n and PDI M _w / M a Polymer Laboratories PL-GPC _n 220 high temperature chromatograph with 2 Olexis used ^® 300 7.5 mm columns. The detector was an RI detector. Eluent was BHT stabilized 1,2,4-trichlorobenzene. The measurements were carried out at 160 ° C. Calibration was based on polyethylene standards and the evaluation using evaluation software (CIRUS).

For differential scanning calorimetry (DSC), a TA Instruments DSC Q 2000 calibrated with indium was used. The measurements were carried out from -20 to 200 ° C at a heating rate of 10 K / min.

Example 1: Synthesis of 1-octenyl-8-dichloromethylsilane.

0.2 ml Karstedt catalyst (platinum (0) -1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex) solution in xylene (2 wt.% Pt) and 189.6 g (1.72 mol ) 1,7-octadiene was cooled to 0 ° C. Thereafter, 65.9 g (573 mmol) of dichloromethylsilane were slowly added dropwise to the solution and warmed to room temperature overnight. The solvent was removed under reduced pressure and the neat product was obtained by distillation (0.2 mbar, 55 ° C) with a yield of 91 g (71%).
¹ H-NMR (d8-toluene): δ 5.73 (m, 1H, = CH-), 4.99 (m, 2H, = CH ₂ ), 1.93 (m, 2H, -CH ₂ -), 1.28 (m, 4H , -CH ₂ -), 1.11 (m, 4H, -CH ₂ -), 0.40 (s, 3H, CH ₃ ).
²⁹ Si { ¹ H} -NMR (d8-toluene): δ - 32.7

Example 2: Synthesis of 1-octenyl-8-di-tert-butoxy-methylsilane.

62 g (553 mmol) of potassium tert-butoxide was dried in vacuo for one hour and then dissolved in 600 ml of dry THF. The solution was cooled to 0 ° C and 50 g (223 mmol) of 1-octenyl-8-dichloromethylsilane were added dropwise. After complete addition, the solution was warmed to room temperature overnight and then heated to 60 ° C for 1 h. The precipitate was separated and the solvent removed in vacuo. The product was obtained by distillation (0.05 mbar, 70 ° C) with a yield of 28 g (42%).
¹ H NMR (C ₂ D ₂ Cl ₄ ): δ 5.73 (m, 1H, = CH-), 4.99 (m, 2H, = CH ₂ ), 1.93 (m, 2H, -CH ₂ -), 1.50 ( m, 2H, -CH ₂ -), 1.33 (m, 4H, -CH ₂ -), 1.29 (s, 18 H, -C- (CH ₃ ) 3), 0.64 (m, 2H, -CH ₂ -) , 0.21 (s, 3H, -CH ₃ ).
²⁹ Si { ¹ H} -NMR (d8-toluene): δ - 19.50.
¹³ C { ¹ H} -NMR (CD ₂ Cl ₂ ): δ 139.72, 114.49, 72.16, 34.19, 33.59, 32.28, 29.26, 23.79, 19.26, 1.48

Example 3: Copolymerization of propene and 1-octenyl-8-di-tert-butoxy-methylsilane.

The polymerization was carried out in a 250 ml Schlenk flask at constant pressure and temperature. The flask was charged with 50 mL of toluene and 0.55 mmol of triisobutylaluminum (TIBA) (1.1 mol / L in toluene), after stirring for 1 h, 1.2 mmol of butylhydroxytoluene (BHT) was added and stirred for an additional hour.

To preactivate the catalyst, 5 μmol of dichloro [rac-ethylenebis (indenyl)] zirconium (IV) was dissolved in 5 ml of toluene. Subsequently, 200 equivalents of TIBA (1.1 mol / l in toluene) were added, based on the amount of catalyst, and the solution was stirred at 60 ° C. for one hour. Thereafter, 2.2 mmol of BHT were added and the solution was stirred for one hour at RT. The solution with the preactivated complex and 1-octenyl-8-di-tert-butoxy-methylsilane (silane concentration: see Table 1 below) was added to the polymerization flask. Argon was removed by evacuation and the reaction mixture was saturated with propene. The polymerization was started by adding a toluene solution of tris (pentafluorophenyl) borane or trityl-tetrakis (pentafluorophenyl) borate (amounts see table below) via a septum into the polymerization solution.

The olefin consumption was measured with a gas flow meter (Bronkhorst F-111C-HA-33P); the pressure (Bronkhorst pressure controller P-602C-FAC-33P) and the olefin consumption were kept constant during the polymerization. After the polymerization, the reaction mixture was precipitated in dry isopropanol. The precipitate was filtered off, washed with dry isopropanol and dried under high vacuum for a few hours. Table 1 Versuchsnummmer C (silane) [mol / L] Catalyst activity [kg / mol / h] Silane content in the polymer T _m [° C] M _w [g / mol] PDI [Mol%] [Wt .-%] 1 ^a 0 3200 0 0 136 40000 4 2 ^b 0.0066 2800 0.4 2.8 134 40000 4 3 ^b 0.0132 920 0.5 4.1 132 40000 4 4 ^b 0.0198 800 0.7 5.4 130 40000 4 5 ^b 0.0264 680 1.1 7.9 129 40000 4 6 ^b 0.033 560 1.0 7.1 118 20000 2 7 ^c 0.33 200 1.4 10.2 125 40000 4 8 ^d 0.33 280 1.4 10.2 123 40000 4 ^E 0.33 240 1.4 10.2 125 40000 4 p (propene) = 1.2 bar; Polymerization time = 30 min; T = 60 ° C.
^a not according to the invention
^b Activation with 7.5 mmol trityl tetrakis (pentafluorophenyl) borate
^c Activation with 4.5 mmol trityl tetrakis (pentafluorophenyl) borate
^d Activation with 10 mmol tris (pentafluorophenyl) borane
^e Activation with 25 mmol tris (pentafluorophenyl) borane

Example 4: Crosslinking of Copolymers and Determination of Gel Content.

Networking:

500 mg of the polymer was dissolved in 5 ml of toluene at 100 ° C and 0.1 ml of trifluoromethanesulfonic acid was added. The solution was stirred at RT overnight and then the polymer was precipitated in methanol and dried in vacuo.

Gelgehaltstest:

Based on DIN EN 579 100 mg of the samples in VA steel nets (mesh size 100 microns) were introduced. These were extracted with xylene (600 ml on 10 samples) with the addition of 1% by weight of 2,2'-methylenebis (6-tert-butyl-4-methylphenol) as antioxidant for 8 hours. The solvent was poured off hot, the samples rinsed well with acetone and dried to constant weight. The weight of the empty net (m ₁ ), the net with the sample (m ₂ ) and the net with sample after extraction (m ₃ ) were determined. The gel content G (crosslinked portion of the sample in%) is calculated as: G (%) = (m ₃ -m ₁ ) / (m ₂ -m ₁ ) × 100 Table 2 Versuchsnummmer c (silane) [mol / L] Gel content G after crosslinking [% by weight] 1* 0 0 2 0.0066 10 3 0.0132 98 ± 2 4 0.0198 98 ± 2 5 0.0264 98 ± 2 6 0.033 98 ± 2 7 0.33 98 ± 2 8th 0.33 98 ± 2 9 0.33 98 ± 2 * not according to the invention

Example 5 (not according to the invention): Copolymerization of propene and vinyltrimethoxysilane.

The polymerization was carried out in a 250 ml Schlenk flask at constant pressure and temperature. The flask was charged with 50 ml of toluene and 0.55 mmol of triisobutylaluminum (TIBA) (1.1 mol / l in toluene) based on the amount of catalyst and stirred for one hour. Thereafter, 1.2 mmol of butylhydroxytoluene (BHT) was added and stirred for an additional hour.

For the preactivation of the catalyst, 5 μmol of dichloro [rac-ethylenebis (indenyl)] zirconium (IV) was dissolved in 5 ml of toluene. Subsequently, 200 equivalents of TIBA (1.1 mol / l in toluene) were added and the solution was stirred at 60 ° C for one hour. Thereafter, 2.2 mmol of BHT were added and the solution was stirred for one hour at RT. The preactivated complex solution and vinyltrimethoxysilane (0.7 mmol, 0.1 g) were added to the polymerization flask. Argon was removed by evacuation and the reaction mixture was saturated with propene. The polymerization was started by adding 7.5 μmol of trityltetrakis (pentafluorophenyl) borate (solution in toluene) via a septum into the polymerization solution.

The olefin consumption was measured with a gas flow meter (Bronkhorst F-111C-HA-33P); the 1.2 bar proof pressure (Bronkhorst pressure controller P-602C-FAC-33P) and the propene consumption were kept constant during the polymerization. Pressure and propene consumption were recorded during the polymerization. After a polymerization time of 30 minutes, the reaction mixture was precipitated in dry isopropanol. No polymer could be isolated.

QUOTES INCLUDE IN THE DESCRIPTION

This list of the documents listed by the applicant has been generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

Cited patent literature

• US 3646155 A [0002]
• US 2010331483 A [0007]

Cited non-patent literature

• M. Itoh et al. teach in Macromolecules 1998, 31, 5609 [0004]
• P. Longi et al. (Macromolecular Chemistry 1968, 116, 113 [0005]
• A. Tsuchida et al. (Macromolecules 1997, 30, 2818-2824 [0006]
• L. Zheng et al. (Macromolecules 2001, 34, 8034-8039) [0006]
• A. Nakamura et al. (Chem. Rev. 2009, 109, 5215-5244 [0007]
• DIN EN 579 [0057]

Claims (11)

Process for the preparation of crosslinkable copolymers of the general formula [1]

by transition-metal-catalyzed copolymerization of olefins of the general formula [2] H ₂ C = CH-R ¹ [2], with silanes of the general formula [3]

in the presence of a transition metal catalyst (PK), wherein R ^{1 is} hydrogen or a hydrocarbon radical having 1 to 20 carbon atoms, C _{n is a} divalent unsubstituted or substituted hydrocarbon radical having 1 to 50 carbon atoms, m is 1, 2 or 3, p is an integer value of 1 to 100 000, q are integer values from 1 to 100,000, R ^{2 is} hydrogen, halogen, unsubstituted or substituted hydrocarbon radical having 1 to 20 carbon atoms, alkyloxy radical having 1 to 6 carbon atoms, acyloxy radical having 1 to 6 carbon atoms, alkenyloxy radical having 1 to 6 carbon atoms, OH, metalloxy radical -OM or radical -CH ₂ -W, where W is a heteroatom selected from N, O, P, S, and the free valencies on the heteroatom are saturated by hydrocarbon radicals having 1 to 20 carbon atoms, R ³ , R ⁴ , R ^{5 is} hydrogen, Halogen, unsubstituted or substituted hydrocarbon radical having 1 to 20 carbon atoms, acyl radical having 1 to 6 carbon atoms or carboxylic acid ester group of an aliphatic alcohol having 1 to 6 carbon atoms, wherein two or three of the radicals R ³ , R ⁴ , R ^{5 may} be joined together, with the proviso that at most 2 of the radicals R ³ , R ⁴ , R ^{5 are} hydrogen where the copolymers of the general formula [1] are present as random copolymers, block or multiblock copolymers or mixtures thereof. Process according to claim 1, in which catalysts based on Ti, Zr, Hf, V, Cr, Ni and Pd are used as catalysts. A process according to any one of the preceding claims wherein the olefins of general formula [2] are selected from ethene, propene, 1-butene, 1-hexene, 1-octene and styrene. A process according to any one of the preceding claims, wherein Cn is an aliphatic hydrocarbon radical having from 2 to 30 carbon atoms. A process according to any one of the preceding claims wherein R ^{2 is} selected from chloro, methyl, ethyl, propyl, butyl, phenyl, methoxy, ethoxy, propoxy, acetoxy, vinyl and OH. A process according to any one of the preceding claims wherein the radicals R ³ , R ⁴ , R ^{5 are} selected from methyl, ethyl, propyl, butyl, vinyl, phenyl radicals and radicals -C (O) OCH ₃ . Crosslinkable Copolymers of the General Formula [1]

where R ^{1 is a} hydrocarbon radical having 1 to 20 carbon atoms, C _{n is a} divalent unsubstituted or substituted hydrocarbon radical having 1 to 50 carbon atoms, m is 1, 2 or 3, p is integer values of 1 to 100,000, q is integer values of 1 to 100,000, R ² Hydrogen, halogen, unsubstituted or substituted hydrocarbon radical having 1 to 20 carbon atoms, alkyloxy radical having 1 to 6 carbon atoms, acyloxy radical having 1 to 6 carbon atoms, alkenyloxy radical having 1 to 6 carbon atoms, OH, metalloxy radical -OM or radical -CH ₂ -W, where W is a heteroatom selected from N, O, P, S, and the free valencies on the heteroatom are saturated by hydrocarbon radicals having 1 to 20 carbon atoms, R ³ , R ⁴ , R ^{5 is} hydrogen, halogen, unsubstituted or substituted hydrocarbon radical having 1 to 20 Carbon atoms, acyl radical having 1 to 6 carbon atoms or carboxylic acid ester group of an aliphatic alcohol having 1 to 6 carbon atoms, where two or three of the radicals R ³ , R ⁴ , R ^{5 may} be linked to one another, with the proviso that at most 2 of the radicals R ³ , R ⁴ , R ^{5 are} hydrogen, where the copolymers of the general formula [1] as random copolymers, block or multiblock copolymers or mixtures thereof. Process for anhydrous crosslinking of the copolymers of the general formula [1] according to one of the preceding claims, with catalysts K selected from Lewis acids and Bronsted acids. A process according to claim 8, wherein the copolymers of the general formula [1] are brought to a temperature of 50 ° C to 180 ° C. The method of claim 8, wherein the copolymers of the general formula [1] are irradiated with UV light. Use of the copolymers of the general formula [1] according to claims 1 to 7 alone or as a constituent of formulations as cable insulation, as pipes, as packaging material, as chemical container, as heat-resistant material, as binder, as hot melt adhesive, as reactive hot-melt adhesive, for the production of splices, bonded structures, coatings, paints, adhesive tapes, adhesive films, pressure-sensitive adhesives or foams.