WO2009033908A2

WO2009033908A2 - Moisture cross-linkable polymers based on alpha-heteroatom substituted silanes

Info

Publication number: WO2009033908A2
Application number: PCT/EP2008/060617
Authority: WO
Inventors: Jürgen Oliver DAISS; Oliver Fuhrmann; Michael Geck; Jürgen STOHRER; Richard Weidner
Original assignee: Wacker Chemie Ag
Priority date: 2007-09-10
Filing date: 2008-08-13
Publication date: 2009-03-19
Also published as: DE102007042948A1; WO2009033908A3

Abstract

The invention relates to a method for the production of polymers (P), containing at least one structural element selected from the general formulas (Ia), (Ib), (IIa), and (IIb), wherein R1, R2, R3, R3', R3'', R4, R5, X, Y, Z, polymer≡C-, j, m, n, p, and q have the meanings stated in claim 1, to the polymers (P) produced in such manner, to the cross-linking thereof using water, to the corresponding cross-linked polymers (PV), to the use thereof, and to silanes suitable for the production of the polymers (P) by means of grafting.

Description

Moisture-crosslinkable polymers based on α-heteroatom-substituted silanes

The present invention relates to polymers (P) preparable by grafting polymers with α-heteroatom-substituted silanes, their preparation by grafting, their crosslinking with water, their use and silanes suitable for grafting.

The crosslinking of polymers after shaping is decisive for their mechanical and thermal stability. This crosslinking may e.g. be effected by a thermally or photochemically switchable chemical reaction or by the action of water on a moisture-crosslinkable polymer. In order to ensure high production capacities, fast crosslinking processes are desired.

As for example in US 3,075,948, in US 3,646,155, in US 4,117,195, in Polymerics Materials Science and Engineering, 1983, 49, pp. 283-287 and in Plastics Additives Handbook, 5th Edition, Hanser-Verlag, Munich 2001, p. 725 No. 811 (D. Munteanu), is the radical grafting of a silane bearing (a) hydrolyzable groups (eg methoxy, ethoxy or acetoxy) and (b) an olefinic group (eg vinyl or 3-methacrylatopropyl) a method established for polyolefins for converting non-moisture-crosslinkable polymers into moisture-crosslinkable polymers. The radical grafting of the silane onto the polymer can be carried out as a batch reaction or continuously, for example in an extruder. The principle of grafting explains equation (i): (i) Polymer≡CH + H ₂ C = CH-R-SiFT ₃ + Radical initiator ->

Polymer≡CH ₂ C-CH ₂ -R-SiR ' ₃

In the case of silanes used in this process, the radicals R 'are hydrolyzable radicals (for example methoxy, ethoxy, acetoxy) and -R- is, for example, a bonding electron pair or 3-carbonyloxypropyl. Radical initiators used are, for example, dicumyl peroxide or di-tert-butyl peroxide. The polymer equipped with a hydrolyzable silyl group is named l.d.R. admixed with a catalyst which, in the presence of water, causes the hydrolysis and / or the condensation to siloxanes to accelerate. The grafting, if appropriate admixing of the catalyst and the shaping can optionally be carried out in one step or in separate steps. Following shaping, removal into water or steam, l.d.R. at elevated temperature to effect crosslinking according to equations (n) and (m),

(ii) Polymer≡CH ₂ C-CH ₂ -R-SiR ₃ + H ₂ O -> Polymer≡CH ₂ C-CH ₂ -R-SiR ₂ (OH) + R '-H

(in) 2 Polymer≡CH ₂ C-CH ₂ -R-SiR ^' ₂ (OH) ->

[Polymer≡CH ₂ C-CH ₂ -R-SiR ¹ _n] ₂ 0 + H ₂ O

For the formation of a network it is necessary that at least two hydrolyzable groups Si-R 'are attached per polymer molecule. For efficient crosslinking, the grafting of several hydrolyzable silane groups, which can react in the sense of the equations (n) and (in), per polymer molecule is desired.

In the process described above, vinyltnmethoxysilane, alternatively also vinyltrimethoxysilane, vinyl triacetoxysilane or (3-methacrylatopropyl) trimethoxysilane used. Polyolefins used are preferably polyethylene, polyethylene-polypropylene copolymers or copolymers of ethylene with higher 1-olefins. See, for example, EP 1 508 579 A1.

EP 252372 A1 describes a process (as well as the products resulting therefrom) in which polymers bearing aliphatically unsaturated groups are functionalized with hydrolyzable silanes by covalently attaching the silanes

Polymer scaffold are connected. The attachment of silanes can be accomplished by hydrosilylation of silanes containing Si-H groups by adding the Si-H function to the unsaturated group of the polymer, or by attaching silanes containing thiol groups (ie, SH groups). by adding the SH function radically to the unsaturated group of the polymer.

EP 1 303 569 B1 describes the preparation of graft polymers which contain at least two silane groups. These can be done, for example, by reaction of an organofunctional group on the silane or a Si-H function on the one hand with an organofunctional group on the graft polymer on the other hand, wherein a covalent bond between silane and polymer is formed. Alternatively, the as

Grafting polymer are grafted with a mixture of at least two unsaturated monomers, of which at least one is a silane.

However, the moisture crosslinking of such grafted moisture-crosslinking polymers takes place very slowly and is related to the production capacity of the decisive step. Faster networking systems would allow an increase in production capacity.

The object of the invention is therefore to provide grafted moisture-crosslinking polymers which enable faster moisture crosslinking with simultaneously high gel content of the crosslinked polymers.

The invention relates to a process for preparing polymers (P) in which polymers (PI) containing CH-graftable units are grafted under free-radical conditions with silanes which (i) contain at least one unsaturated hydrocarbon group capable of sufficiently grafting, (ii) carry at least one hydrolyzable group on the silicon and (iii) at least one C-C heteroatom, wherein the use of (methacrylatomethyl) silanes, (acrylatomethyl) silanes and (but-3-enoxymethyl) triethoxysilane is excluded, and wherein the produced polymers (P) contain at least one structural element which is selected from the general formulas Ia, Ib, IIa and IIb

Polymer≡CR ³ ₂ C-CH (R ^{3 '} ) - (R ² Jp-Y-CH ₂ -SiX _n R ¹ SI ₁ (Ia),

(R ³ ₂ CH-) (Polymer≡C-) C (R ^{3 '} ) - (R ² Jp-Y-CH ₂ -SiX _n R ¹ SH (Ib)

Polymer≡CR ³ "C-CH ₂ (R ⁵⁾ - (R ⁴⁾ q-SiXnRS-mn (CH ₃ - _D Z _D) _m (IIa), ⁽³ R" ₂ CH-) (Polymer≡C-) C (R ⁵⁾ - ⁽⁴ R) _q -SiX _n R ¹ ₃ - _m - _n (CH ₃ - _D Z _D) _m (Hb), wherein R ^{1 is} an unsubstituted or by one or more

Substituents Q substituted Ci-Cis alkyl or Cε-Cio-aryl or Sii-Si2o siloxy or condensed silane hydrolyzate of silanes with 1, 2, 3 or 4 hydrolyzable groups,

R ^{2 is} a di- or trivalent, unsubstituted or substituted by one or more substituents Q, optionally interrupted by one to three heteroatoms hydrocarbon radical having 1-20 C atoms, R ³ , R ³ ', R ³ "hydrogen, fluorine, chlorine or an unsubstituted or substituted by one or more substituents Q, optionally containing one to three hetero atoms hydrocarbon radical,

R ^{4 has} the meaning of R ² and may additionally contain a Sii-Si 2o siloxane unit, or an optionally interrupted by groups R ² Sii-Si 2o siloxane unit,

R ^{5 has} the meaning of R ³ and can additionally assume the same meaning as Z,

Q is a fluoro, chloro, bromo, iodo, silyl, silylalkyl, silylaryl, siloxy, siloxyalkyl, siloxyaryl, oxo, hydroxy, alkoxy, aryloxy, acyloxy, sulfonato, Sulfato, sulfinato, amino, alkylamino, dialkylamino, acylamino, imido, sulfonamido, imino, mercapto, alkylthio or arylthio substituents, X is a hydrolyzable group,

Y is a heteroatom-containing di- or trivalent radical which is bound by a heteroatom to the group -CH ₂ -SiX _n R ¹ SI ₁ ,

Z is a fluorine, chlorine, bromine or iodine substituent or a monovalent radical attached via oxygen, sulfur, nitrogen or phosphorus,

Polymer≡C- a polymer residue of an organic polymer containing CH units, j the values 1, 2 or 3, n the values 1, 2 or 3, n + m in the general formulas IIa and IIb the values 1, 2 or 3, p, q the values 0 or 1, m if R ⁵ is a hydrogen atom or a hydrocarbon radical optionally containing one to three heteroatoms, has the value 1 or 2, or, if R ^{5 takes on} one of the meanings of Z, has the value 0, 1 or 2, and q, if m is 0 is also 0, wherein R ¹ , R ² , R ³ , R ³ ', R ³ ", R ⁴ , R ⁵ , X, Y, Z and Q within the general formulas Ia, Ib, IIa and IIb are interconnected can, so that form one or more rings.

The polymers (P) comprise at least one structural element of the general formulas Ia, Ib, IIa and IIb which has silyl groups which contain (i) at least one hydrolyzable group and (ii) at least one heteroatom bonded to the silicon via a C-1 spacer (a so-called CC heteroatom) wear. These polymers (P) crosslink faster under water access than corresponding systems without such an α-heteroatom.

In the case of the polymer (P), the C-C heteroatom may optionally form part of the linker between the silicon atom and the polymer residue P1 (as defined below), or may be bonded to the silicon via another group than that which causes the bond to the polymer residue P1 , wearing.

Polymer≡C- is the residue of a polymer (PI) containing CH-graftable units. Preferably, the polymer (P1) is a

Polyolefin, such as polyethylene (eg high-density polyethylene (HDPE), medium-density polyethylene (MDPE), low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE)), a branched, hyperbranched or hyperbranched polyethylene, an ethylene-CC-olefin copolymer, for example, ethylene-propylene copolymer, ethylene-butene copolymer, ethylene-hexene copolymer and ethylene-octene copolymer, vinyl polymer, such as polyvinyl acetate, polyamide (nylon ® or Perlon® type),

Acrylate polymer and copolymers, for example copolymer of ethylene and acrylates, methacrylates or acetates, for example ethylene-butyl acrylate copolymer, ethylene-ethyl acrylate copolymer and ethylene-vinyl acetate copolymer.

R ¹ is preferably an unsubstituted Ci-Cε alkyl or phenyl radical, in particular methyl or ethyl radical.

R ² is preferably an unsubstituted organic radical having 1-10 C atoms, which may be interrupted by O or N.

Examples of R ³ , R ³ ', R ³ are hydrogen or alkyl, aryl, alkoxy, aryloxy, acyloxy, alkoxycarbonyl, aryloxycarbonyl, amide, imide, acylamino or carbamate groups. Preferably, R ³ , R ³ ', R ^{3 "} contain from 1 to 20, especially 1 to 6 carbon atoms, or are hydrogen atoms.

Preferred radicals of R ⁴ are the preferred radicals and Si-Si-siloxane units given for R ²

Preferred radicals X are alkoxy, alkenoxy, acyloxy, alkylcarbonato, amino, hydrocarbylamino, acylamino, preferably methoxy, ethoxy, propen-2-oxy, formoxy, acetoxy, methylcarbonato, ethylcarbonato, iso-propylcarbonato,

Butylcarbonato, tert-butylcarbonato, isobutylcarbonato, amino, C 1 -C 10 -alkylamino, C ₅ -C 2 -aryl-arylamino, C 1 -C 10 -dialkylamino, C ₅ -C 20- Diarylamino and Cs-C ^ arylCi-Cio-alkylamino, especially methoxy and ethoxy.

Y is preferably -O-, -N (R ⁶ ) -, -C (O) -O-, -O-C (O) -O-, -O-C (O) -N (R ⁶ ) -, -N (R ⁶ ) -C (O) -O-, -S (O) -, -S (O) ₂ -, -S (O) -O-, -S (O) ₂ - O-, - 0-S (O) ₂ -O-, -C (O) -N (R ⁶ ) -, -S (O) ₂ -N (R ⁶ ) -, -S (O) ₂ -N [C (O ) R ⁸ ] -,

-O-S (O) ₂ -N (R ⁶ ) -, -N (R ⁶ ) -S (O) ₂ -O-, -P (O) (OR ') -O-, -O-P ( O) (OR ') -, -

0-P (0) (OR ⁷ ) -0-, -P (0) (OR ⁷ ) -N (R ⁶ ) -, -N (R ⁶ ) -P (0) (OR ⁷ ) -, -0 -

P (O) (OR ⁷ ) -N (R ⁶ ) -, -N (R ⁶ ) -P (O) (OR ⁷ ) -O-, -N [C (O) R ⁸ ] -, - N = C (R ⁸ ) -O-, -C (R ⁸ ) = NO-, -C (O) -N [C (O) R ⁸ ] -, - N [S (O) ₂ R ⁹ ] -, - C (O) -N [S (O) ₂ R ⁹ ] - or -N [P (O) R ¹⁰ ₂ ] -, where R ⁶ , R ⁷ and R ^{8 represent} hydrogen or optionally substituted C ₁ -C ₂ 0- alkyl or C6-C are ₂ -aryl radicals, R ⁹ ₂ o alkyl or _C6-C2o-aryl stands for an optionally substituted Ci-C, and R ¹⁰ is an optionally substituted _Ci-C2o-alkyl , C _δ -C ₂ o-Aryl, Ci-C ₂ o-alkoxy or Cβ ~ C ₂ o-Aryloxyrest.

Z preferably represents groups OR ¹¹ , OC (O) R ¹² , OC (O) OR ¹¹ , OC (O) NR ¹³ ₂ , N (R ¹³ JC (O) OR ¹¹ , N (R ¹³ ) C (O) NR ¹³ ₂ , NR ¹³ ₂ , N (R ¹³ ) [C (O) R ¹² ], N [C (O) R ¹² ] ₂ , N (R ¹³ ) S (O) ₂ R ¹⁴ , N [C (0 ) R ¹² ] [S (O) ₂ R ¹⁴ ], N [S (O) ₂ R ¹⁴ ] ₂ ,

S (O) ₂ R ¹⁴ , OS (O) ₂ R ¹⁴ , S (O) R ¹⁴ , OS (O) R ¹⁴ , P (O) (OR ¹⁵ ) ₂ , 0-N = C (R ¹² ) ₂ , F, Cl, Br or I, wherein R ¹¹ , R ¹⁴ and R ^{15 are} optionally substituted Ci-C ₂₀ alkyl or C ₆ -C ₂₀ aryl radicals and R ¹² and R ^{13 is} hydrogen or optionally substituted Ci-C ₂ o-alkyl or C ₆ -C ₂₀ aryl radicals and R ¹¹ , R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ may be linked together within a group Z, so that rings are formed.

n is preferably 2 or 3.

m, j are preferably the value 1. Silanes which (i) contain at least one sufficiently unsaturated group capable of grafting, (ii) carry at least one hydrolyzable group on the silicon and (iii) have at least one α-heteroatom are referred to hereinafter as "CC silanes".

The α-silanes are grafted onto polymers (PI), preferably polyolefins, in a free-radical grafting reaction to give the grafted polymers (P). In this case, preferably a mixture containing 100 parts of polymer (P1), 0.1-10 parts, in particular 0.5-6 parts of CC silane and 0.01-1, in particular 0.05-0.4 parts of radical initiator, the the reaction conditions released free radicals implemented.

The grafting is generally carried out at temperatures of 80 - carried out 300 ⁰ C - 350 ⁰ C, preferably at 120th Examples of suitable free-radical initiators in the process according to the invention are di-tert-butyl peroxide, 2,5-dimethyl-2,5-di- (tert-butylperoxy) hexane, dicumyl peroxide,

Dibenzoyl peroxide, CC, CC 'azobisisobutyronitrile or dilauroyl peroxide. Further examples of useful chemical radical initiators are described, for example, in D. Munteanu, in Plastics Additives Handbook, 5th Edition, Hanser Verlag, Munich 2001, pp. 741-742. The grafting can be carried out in solution, suspension, emulsion or in bulk, for example in boiler reactors or in extruders. When carried out in the extruder, the CC silane and the free radical initiator at a suitable temperature point of the extruder to the polymer or to a mixture containing the polymer dosed. The metered addition of CC silane and free radical initiator can be carried out separately or in the form of a mixture of both, more in each case Additives may be added. The addition is controlled in such a way that the radical initiator has not reacted or has not completely reacted on contact of the OC silane with the polymer. The residence time of the reaction mixture, consisting of OC silane, radical initiator and polymer, in the extruder is preferably 0.1 to 30 minutes, more preferably 0.5 to 10 minutes.

In the method according to the invention, before, during or after the grafting reaction, optionally in the same step or in a preceding or downstream process step, one or more further additives are admixed, for example fillers, such as magnesium oxide, silica or clay, antioxidants or catalysts.

In Monatshefte für Chemie, 2003, 134, 1081 - 1092, there is a proposal to use (CC-methacrylatomethyl) silanes for grafting polymers in order to produce moisture-crosslinkable polymers. As demonstrated by present example 12d with respect to (α-methacrylatomethyl) trimethoxysilane in Table 4, these silanes are not suitable for the preparation of fast crosslinking polymers (P) with simultaneously high gel content of the crosslinked polymers (PV).

Preferably in the process CC silanes are selected from the general formulas III and IV

R ² C = C (R ^J ⁾ - ⁽ R ²⁾ _p -Y-CH ₂ -SiX _n R ¹ ₃ -n (in:

R ³ _"2 C = C (R ⁵⁾ - ⁽⁴ R) _q -SiX _n R ¹ ₃ - _m - _n (CH ₃ - _j Z _j) _m (IV),

where R ¹ , R ² , R ³ , R ³ ', R ³ ", R ⁴ , R ⁵ , X, Y, Z, m, n, p and q have the meanings given above. Preferably, in the silanes, the sufficiently graftable unsaturated group is part of a vinyl ester group, a vinyl carbonate group, a vinylsilane group, an allyl ester, allyl carbonate, allylamide, allylsulfonamide, allyl carbamate or allyl urea group

Maleic acid ester group, a crotonic acid ester group, a fumaric acid ester group, a maleic, fumaric or crotonic acid amide group, a maleimide group or a bicyclo [2.2.1] heptane system.

Particularly preferred silanes of the general formulas III and IV which can be used in the process are:

The invention further provides polymers (P) which can be prepared by the process described above and contain at least one structural element which is selected from the general formulas Ia, Ib, IIa and IIb

(R ³ ₂ CH-) (Polymer≡C-) C (R ^{3 '} ) - (R ² Jp-Y-CH ₂ -SiX _n R ¹ SH (Ib) Polymer≡CR ^J _"2 C-CH (R") - (R ⁴⁾ _q -SiX _n R 3-m-n (CH ₃ - _D Z _D) _m (IIa;

(R ³ _"2 CH-) (Polymer≡C-) C (R ⁵⁾ - ⁽⁴ R) _q -SiX _n R ¹ ₃ - _m - _n (CH ₃ - _D Z _D) _m (Hb), wherein

R ^{1 is} an unsubstituted or by one or more

Substituents Q substituted Ci-Cis alkyl or Cε-Cio-aryl or Sii-Si ₂ O siloxy or condensed silane hydrolyzate of silanes with 1, 2, 3 or 4 hydrolyzable groups,

R ^{2 is} a di- or trivalent, unsubstituted or substituted by one or more substituents Q, optionally interrupted by one to three heteroatoms hydrocarbon radical having 1-20 C atoms, R ³ , R ³ ', R ³ "hydrogen, fluorine, chlorine or an unsubstituted or substituted by one or more substituents Q, optionally containing one to three heteroatoms hydrocarbon radical, R ^{4 has} the meaning of R ² and additionally contains a Sii-Si2o siloxane, or optionally interrupted by groups R ² Sii-Si2o siloxane unit R ^{5 can have} the meaning of R ³ and can additionally assume the same meaning as Z,

Y is a heteroatom-containing di- or trivalent radical which is bonded by a heteroatom to the group -CH ₂ -SiX _n R ¹ SI ₁ is, wherein the meanings -CH ₂ S-, carbamate or

Z is a fluorine, chlorine, bromine or iodine substituent or a monovalent bound via oxygen, sulfur, nitrogen or phosphorus remainder,

Polymer≡C- a polymer residue of an organic polymer, the

In the general formulas IIa and IIb, the values 1, 2 or 3, p, q denote the values 0 or 1 , m when R ^{5 is} a hydrogen atom or a hydrocarbon radical optionally containing one to three heteroatoms, has the value 1 or 2, or if R ^{5 is} one of

If Z is 0, 1 or 2, and q is 0, then m is also 0, where R ¹ , R ² , R ³ , R ³ ', R ³ ", R ⁴ , R ⁵ , X, Y, Z and Q can be interconnected within the general formulas Ia, Ib, IIa and IIb, so that one or more rings are formed, the structural elements of the general formulas Ia and Ib are excluded, in which R ³ a Hydrogen atom, R ³ 'is a hydrogen atom or a methyl radical, -Y- is a group -C (O) O- and p is 0, and wherein the structural elements of the general formulas

Polymer≡CR ² '- (Y') _y -CH ₂ -CH ₂ -O-CH ₂ -Si (OEt) ₃ and

Polymer 4CR ^{2 '} -C (R ^3'' ) ₂ -NR ^{1 6} -CH ₂ -SiX ₃

are excluded in which

R ² 'has the meanings of R ² , Y 'is a divalent radical -0-, -NH- or trivalent

Radical = N-, Et means an ethyl radical, y denotes 0 or 1, R ³ '^"has the meanings of R ³ and R ¹⁶ denotes a hydrogen atom or an alkyl radical.

The invention also provides a process for crosslinking the polymers (P) with water.

The water required for crosslinking can be used as steam and / or liquid water.

The above-mentioned catalysts can effect the acceleration of moisture crosslinking of the polymers (P) by catalyzing the hydrolysis of the hydrolyzable silyl groups contained in the polymer (P) under water action and / or their condensation to form siloxanes. The crosslinking is usually carried out in a grafting subsequent process step. The polymer (P) is mixed in the melt, for example, with a masterbatch of the catalyst, ie a mixture of the catalyst with a suitable same or different polymer, which preferably contains 100 parts of polymer and 0.1 to 20 parts of the catalyst in an extruder. Preferably, the polymer crosslinks (P) with 0.0001 - 5% by weight, in particular 0.001 - 1, particularly preferably at most 0.1% by weight of catalyst. Examples of suitable catalysts are organotin compounds, such as dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin oxide, dioctyltin oxide, aza compounds, such as 1,8-diazabicyclo [5.4.0] undec-7-ene, 1,5-diazabicyclo [4.3.0] non-5-ene , 1,4-diazabicyclo [2.2.2] octane, bases, for example organic amines, such as triethylamine, tributylamine, ethylenediamine, inorganic or organic Acids, such as toluenesulfonic acid, dodecylbenzenesulfonic acid, stearic acid, palmitic acid or myristic used. The crosslinking of the polymer (P) without added tin or compounds of the tin is particularly preferably carried out, in particular the content of Sn in the polymer (P) is <30 ppm, more preferably Sn <5 ppm.

Particularly preferred is the crosslinking without added catalyst.

Preferably, if appropriate with additives and / or

Catalyst blended polymer (P) at temperatures that ensure the moldability of the modified polymer (P), brought into the desired shape. Examples of forms are pipes or cable insulation. The polymer (P) is then preferably crosslinked to give the mold, optionally taking into account shrinkage or expansion, by Wasserauslagerung. The contact with water can be carried out, for example, by immersion in a water bath, in steam or by contact with atmospheric air, the water content of which has optionally been increased by suitable humidifying methods.

The removal of water preferably takes place at ambient temperature or at elevated temperature, preferably at 10-180 ^° C., more preferably at 20-150 ^° C.

Preferably, the crosslinked polymer (PV) according to DIN EN

579 gel contents of preferably> 50%, particularly preferably> 65% after a maximum of 24 hours of water removal.

The invention also relates to crosslinked polymers (PV) which have been prepared by moisture crosslinking of formulations which contain polymers (P). Such formulations may also be blends of non-crosslinking material. The invention also relates to the use of the polymers (P) and the crosslinked polymers (PV) alone or as blends for cable insulation, pipes, chemical containers and heat-resistant material.

The invention also provides silanes of the general formulas III and IV, namely silanes of the general formula V,

X ¹ ₀ R ²¹ _3-0 S iG ¹ (V),

where G ^{1 is} a radical of general formula Va

-CH ₂ -A ² -C (O) - (CR ²³ ₂ : _r - (OCR ²⁴ ₂ CR ²⁵ ₂ :

(C (O)) _t - (A ²² ) _u - (CR ²⁶ ₂ ) _V -CR ²⁷ = CR ²⁸ ₂ (Va)

which means a single aliphatic unsaturated

X ^{1 is} a hydrolyzable group selected from alkoxy,

Alkenoxy, acyloxy, alkylcarbonato, amino,

Hydrocarbon amino and acylamino, R ^{21 is} a C ₁ -C ₆ alkyl or C ₇ -C ₁₈ alkyl or C ₆ -C ₁₀ aryl or

Si ₁ -Si ₂₀ -Siloxy or condensed silane hydrolyzate of silanes with 1, 2, 3 or 4 hydrolyzable groups, R ²³ , R ²⁴ , R ^{25 is} a hydrogen atom or a methyl group, R, R, R is a hydrogen atom or a C ₁ -C _6- alkyl radical, A ^{2 is} a heteroatom-containing divalent radical which is replaced by a

Heteroatom is bonded to the group X ¹ ₀ R ²¹ _3-0 Si-CH ₂ -, A ^{22 is} a heteroatom-containing divalent radical, v, t, u are the values 0 or 1, r, s are integer values from 0 to 10, r + s + t + u + v is an integer value> 0 and o are the values 1, 2 or 3, wherein for -A ²² - the meaning -NH-C (R ²⁹ ) ₂ - [P-CeH ₄ ] - except and wherein R ^{29 is} a hydrogen atom or a Ci-Cio alkyl group and PC _O H _{4 is} an aromatic para-phenylene group.

Preferred meanings for X ¹ are given above for X in the general formulas Ia, Ib, IIa and IIb.

Preferred meanings for A ² , A ²² are -O-, -S-, -N (R ³⁴ ) -, -N [C (O) R ³⁵ ] -, -N [S (O) ₂ R ³⁶ ] "and -N [P (O) R ³⁷ _2] -. R ³⁴ and R ³⁵ denote hydrogen or optionally substituted Ci-C ₆ alkyl or C ₇ -C ₂₀ alkyl or C ₆ -C ₀ - aryl radicals, preferably unsubstituted C 1 -C 6 -alkyl or phenyl radicals, in particular methyl or ethyl radicals, R ³⁶ denotes an optionally substituted C ₁ -C 6 -alkyl or C ₇ -C 20 -alkyl or C ₁ -C 10 -aryl radical, preferably unsubstituted C ₁ -C 8 -cyclo Alkyl or phenyl or C ₇ -aryl, in particular methyl, phenyl or p-tolyl.

R ³⁷ represents an optionally substituted Ci-Cε-alkyl or C ₇ -C ₂₀ alkyl or C ₆ -C ₀ aryl, Ci-C ₆ -AIkOXy- or C ₇ -C ₂₀ - alkoxy or C6- Ci ₀ -Aryloxyrest, preferably unsubstituted Ci-Cδ-alkyl or phenyl or Ci-Cε-alkoxy, in particular methyl or ethyl radical, methoxy or ethoxy.

Preferred meanings for R ²¹ are given above for R ¹ in the general formulas Ia, Ib, IIa and IIb.

Preferred meanings for o are the values 2 or 3.

The invention also silanes of the general formulas III and IV, namely silanes of the general formula VI X-, R ⁴ V _e SiG ² (vi:

where G ^{2 is} a radical of the general formula VIa

-CH ₂ -A-C (O) -CH = CH-R ⁴⁰ (VIa),

which has a single aliphatically unsaturated bond,

X ^{4 is} a hydrolyzable group selected from alkoxy, alkenoxy, acyloxy, alkylcarbonato, amino, hydrocarbylamino and acylamino,

R ^{41 is} a C ₁ -C ₆ -alkyl or C ₇ -C ₈ -alkyl or C ₆ -C 10 -aryl or Si-Si _{2 0} -siloxy radical or condensed silane hydrolyzate of

Silanes having 1, 2, 3 or 4 hydrolyzable groups, R ^{48 is} a Ci-Cε-alkyl or C ₇ -C ₂ o-alkyl group or a group

-C (O) -A ⁴⁴ -R ⁴⁹ ,

R ⁴⁹ is a Ci-C ₆ alkyl or C ₇ -C ₂ o alkyl or C ₆ -C ₀ aryl group, a group -CH ₂ -SiX ⁴⁴ _f R ⁴⁴ ₃ -, or _f, with the proviso that: - A ⁴ - is not equal to -N (H) -, a hydrogen atom, X ^{44 is} a hydrolyzable group,

R ⁴⁴ a Ci-C ₆ alkyl or C ₇ -C ₈ alkyl or C ₆ -C ₀ aryl or SII Si ₂ O siloxy group or condensed silane hydrolysis of silanes having 1, 2, 3 or 4 hydrolyzable groups .

A ^{4 is} a heteroatom-containing divalent radical which is replaced by a

Heteroatom to the group X ⁴ _e R ⁴¹ ₃ - _e Si-CH ₂ - is bonded, A ^{44 is} a heteroatom-containing divalent radical, e, f are 1, 2 or 3.

Preferred meanings for X ⁴ , X ⁴⁴ are given above for X in the general formulas Ia, Ib, IIa and IIb. Preferred meanings for R ⁴¹ are given above for R ¹ in the general formulas Ia, Ib, IIa and IIb.

Preferred meanings for A ⁴ , A ⁴⁴ are given above for A ² in the general formula V.

Preferred meanings for R ⁴⁴ are given above for R ¹ in the general formulas Ia, Ib, IIa and IIb.

Preferred meanings for R ⁴⁸ are methyl or -C (O) -A ⁴⁴ -R ⁴⁹ .

Preferred meanings for R ⁴⁹ are methyl, ethyl or -CH ₂ -SiX ⁴⁴ fR ⁴⁴ ₃ -f.

Preferred meanings for e, f are the values 2 or 3.

The invention also provides silanes of the general formulas III and IV, namely silanes of the general formula VII

X ⁵ _c R ⁵¹ 3- _c S iG ³ (VI I), where i

G ^{3 is} a radical of the general formula VIIa

-CH ₂ -A ⁵ - (CR ⁵² ₂ ) d -CR ⁵³ = CR ⁵⁴ ₂ (VIIa), which has a single aliphatically unsaturated bond,

X ^{5 is} a hydrolyzable group selected from alkoxy, alkenoxy, acyloxy, alkylcarbonato, amino, hydrocarbylamino and acylamino, R ⁵¹ a Ci-C ₆ alkyl or C ₇ -C ₈ alkyl or C ₆ -C ₀ aryl or Sii-Si2O siloxy group or condensed silane hydrolysis of silanes having 1, 2, 3 or 4 hydrolyzable groups,

R ⁵² , R ⁵³ , R ^{54 is} hydrogen or C ₁ -C ₆ -alkyl or C ₇ -C ₈ -alkyl, A ^{5 is} a heteroatom-containing bivalent radical selected from -O-, -N (R ⁵⁶ ) -, -S (O ) -, -S (O) ₂ -, -O-S (O) -, -O-S (O) ₂ -, -O-S (O) ₂ -O-, -N (R ⁵⁹ ) -S (O) ₂ -, - N [C (O) R ⁵⁵ JS (O) ₂ -, - N (R ⁵⁹ ) -S (O) ₂ -O-, -O-S (O) ₂ -N (R ⁵⁹ ) -, -P (0) (OR ⁵⁰ ) -O-, -O-P (O) (OR ⁵⁰ ) -, -O-P (O) (OR ⁵⁰ ) -O-, -N (R ⁵⁹ ) -P (O) (OR ⁵⁰ ) -, -O-P (O) (OR ⁵⁰ ) -N (R ⁵⁹ ) -, -N (R ⁵⁹ ) -P (O) (OR ⁵⁰ ) -O-, -N [C (O) R ⁵⁵ ] -, -OC (R ⁵⁵ ) = N-, -N [S (O) ₂ R ⁵⁸ ] - or -N [P (O) R ⁵⁷ ₂ ] -,

R ^50, R ⁵⁵ and R ⁵⁹ is hydrogen or optionally substituted Ci-C ₆ alkyl or C ₇ -C ₂₀ alkyl or C ₆ -C ₀ aryl radicals, preferably unsubstituted Ci-C ₆ alkyl or phenyl groups, especially methyl or ethyl radicals,

R ⁵⁶ is an optionally substituted Ci-C ₆ alkyl or C ₇ - C ₂ o alkyl or C ₆ -Cio aryl group, preferably unsubstituted Ci-C ₆ - alkyl or phenyl radical, in particular methyl or ethyl, R ⁵⁷ an optionally substituted Ci-C ₆ alkyl or C ₇ - C ₂₀ alkyl or C ₆ -C ₀ aryl, Ci-C ₆ alkoxy or C ₇ -C ₂₀ - alkoxy or C ₆ -C ₀ -Aryloxyrest, preferably unsubstituted Ci-C ₆ alkyl or phenyl radical, in particular methyl or ethyl radical, methoxy or ethoxy radical, R ^{58 is} an unsubstituted Ci-C ₆ alkyl or C ₇ -C ₂₀ alkyl or optionally substituted C ₆ -C ₀ aryl, preferably unsubstituted Ci-C ₆ alkyl or phenyl or C ₇ - aryl radical, in particular methyl, phenyl or p-tolyl radical, the values of d is 0 or 1 and c has the values 2 or 3 wherein W-AlIyI-N- [(trimethoxysilyl) methyl] ethyl carbamate is excluded. Preferred meanings for X ⁵ are given above for X in the general formulas Ia, Ib, IIa and IIb.

Preferred meanings for R ⁵¹ are given above for R ¹ in the general formulas Ia, Ib, IIa and IIb.

The invention also silanes of the general formulas III and IV, namely silanes of the general formula VIII

in which

X ^{6 is} a hydrolyzable group selected from alkoxy,

Alkenoxy, acyloxy, alkylcarbonato, amino, hydrocarbylamino and acylamino,

R ⁶¹ a Ci-C ₆ alkyl or C ₇ -C ₈ alkyl or C ₆ -C ₀ aryl or Sii-Si2O ~ siloxy group or condensed silane hydrolysis of silanes having 1, 2, 3 or 4 hydrolyzable groups, R ^62, R ₆ alkyl or C ₇ -C ⁶³ hydrogen or _Ci-C2o-alkyl radical, and g is 1, 2 or 3rd

Preferred meanings for X ⁶ are given above for X in the general formulas Ia, Ib, IIa and IIb.

Preferred meanings for R ⁶¹ are given above for R ¹ in the general formulas Ia, Ib, IIa and IIb.

Preferred meanings for R, R are hydrogen or methyl. Preferred meanings for g are the values 2 or 3.

The invention also silanes of the general formulas III and IV, namely silanes of the general formula IX

G ⁴ Si (CZ ⁷ _a H ₃ _-a ) X ⁷ 2 (IX),

in which

G ^{4 is} a radical of general formula IXa

R ⁷¹ ₂ C = CR ⁷² -R ⁷⁸ - (IXa), which has a single aliphatically unsaturated bond,

R ⁷¹ , R ^{72 is} hydrogen or an optionally substituted

Ci-Ce-alkyl or C ₇ -C ₂ o alkyl or C ₆ -C ₀ aryl group, X ⁷ is a hydrolyzable group selected from alkoxy, alkenoxy, acyloxy, Alkylcarbonato, amino, Kohlenwasserstoffamino and acylamino, R ⁷⁸ is a divalent unsubstituted or substituted by one or more substituents Q ⁷ , optionally interrupted by one to three heteroatoms, bonded via a carbon atom to the silicon atom organic radical having 1-20 C-atoms, with the proviso that the bond between R and the silicon atom via or R ⁷⁹ , R ^{79 is} an optionally interrupted by groups R ⁷⁸ SIi-Si ₂ O.

Siloxane unit, or a bond, Q ^{7 is} a fluoro, chloro, bromo, iodo, silyl, silylalkyl, silylaryl, siloxy, siloxyalkyl, siloxyaryl, oxo, hydroxy, alkoxy, aryloxy, , Acyloxy, sulfonato, sulfato, sulfinato, amino, alkylamino, dialkylamino, Acylamino, imido, sulfonamido, imino, mercapto, alkylthio or arylthio substituents, Z ^{7 is} a monovalent group selected from OR ⁷³ , OC (O) R ⁷⁴ ,

OC (O) OR ^73, OC (O) NR ⁷⁵ _2, N (R ⁷⁵⁾ C (O) OR ^73, N (R ⁷⁵⁾ C (0) NR ⁷⁵ _2, NR ⁷⁵ _2, N (R ⁷⁵⁾ [ C (O) R ⁷⁴ ], N [C (O) R ⁷⁴ J ₂ , N (R ⁷⁵ ) S (O) ₂ R ⁷⁶ ,

N [C (O) R ⁷⁴ J [S (O) ₂ R ⁷⁶ ], N [S (O) ₂ R ⁷⁶ J ₂ , S (O) ₂ R ⁷⁶ , OS (O) ₂ R ⁷⁶ , S (O ) R ⁷⁶ , OS (O) R ⁷⁶ , P (O) (OR ⁷⁷ ) ₂ or 0-N = C (R ⁷⁴ ) ₂ F, Cl, Br or

I,

R ^73, R ⁷⁶ and R ⁷⁷ is an optionally substituted Ci-Cε-alkyl or C ₇ -C ₂₀ alkyl or C ₆ -C ₀ aryl,

R ⁷⁴ and R ^{75 are} hydrogen or an optionally substituted

Ci-Cε-alkyl or C ₇ -C ₂₀ alkyl or C ₆ -C ₀ aryl and a is the values 1, 2 or 3.

Preferred meanings for X ⁷ are given above for X in the general formulas Ia, Ib, IIa and IIb.

Preferred meanings for Z ⁷ are OC (O) R ⁷⁴ , N (R ⁷⁵ ) C (O) OR ⁷³ ,

N (R ⁷⁵ ) S (O) ₂ R ⁷⁶ or Cl

Preferred meanings for R ⁷¹ , R ⁷² are hydrogen or unsubstituted C 1 -C 6 -alkyl radicals.

Preferred meanings for Q ⁷ are given above for Q in the general formulas Ia, Ib, IIa and IIb.

The heteroatoms through which R may be interrupted are preferably 0, S, N or Si.

a is preferably the value 1.

Particularly preferred OC silanes of the general formulas V to VIII are the (trimethoxysilyl) methyl, (Dimethoxymethylsilyl) methyl, (triethoxysilyl) methyl and

(Diethoxymethylsilyl) methyl esters of cis- and trans-crotonate, monomethyl maleate, monomethyl fumarate, monoethyl maleate, monoethyl fumarate, monovinyl succinate, monoallyl succinate, monovinyl glutarate, monoallyl glutarate, monovinyl adipate, monoallyl adipate, and monoallyl carbonate,

such as

Maleic and fumaric di [(trimethoxysilyl) methyl], maleic and fumaric di [(dimethoxymethylsilyl) methyl], maleic and fumaric di [(triethoxysilyl) methyl] and maleic and fumaric di [(diethoxymethylsilyl) methyl] ester, maleic and and fumaric acid O- [(trimethoxysilyl) methyl] -O '-

[(triethoxysilyl) methyl] ester, maleic and fumaric O- [(dimethoxymethylsilyl) methyl] -O '-

[(diethoxymethylsilyl) methyl] ester, (maleimidomethyl) trimethoxysilane,

(Maleimidomethyl) dimethoxymethylsilane,

(Maleimidomethyl) triethoxysilane and

(Maleimidomethyl) diethoxymethylsilane,

as well as the

N- (trimethoxysilyl) methyl, N- (dimethoxymethylsilyl) methyl,

N- (triethoxysilyl) methyl and N- (diethoxymethylsilyl) methyl amides of

N-allylformamide, N-allylacetamide, N-allylmethanesulfonamide, N-allylbenzenesulfonamide and N-allyl-4-methylbenzenesulfonamide,

and analogous silanes in which the silicon-bonded methoxy and ethoxy groups are mixed, such as for example (ethoxy) (methoxy) (methyl) silyl,

Di (ethoxy) (methoxy) silyl or (ethoxy) di (methoxy) silyl

Groups .

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

In the following Examples and Comparative Examples, unless stated otherwise, all amounts and percentages are by weight and all reactions are carried out at a pressure of 0.10 MPa (abs.) And a temperature of 20 ⁰ C.

Examples

Synthesis of inventive α-silanes

Example 1: Preparation of fumaric acid (trimethoxysilylmethyl) ^■ methylester / maleic acid (trimethoxysilylmethyl) methyl ester (mixture of cis / trans isomers)

Maleic anhydride (250 g, 2.55 mol) was dissolved in methanol (250 ml) and allowed to stand at room temperature for 16 hours. Subsequently, a 5.54 M methanolic

Sodium methoxide added dropwise (438 ml, 2.43 mol NaOMe) (temperature rise to 55 ° C) and the mixture stirred for 30 minutes. The reaction was diluted with dimethylformamide (DMF, 1000 ml). Methanol was at 56 - 100 ⁰ C bottom temperature and gradual reduction of the pressure from 300 mbar to 30 mbar distilled off. The boiling point of pure DMF at the top of the column (72 ° C / 75 mbar) indicated that methanol was exhaustively removed from the bottom. It was allowed to cool; in the swamp, a solid precipitated on cooling. At 110 ⁰ C (dissolving of the solid) (chloromethyl) was trimethoxysilane (414 g, 370 ml, 2.43 mol) was added dropwise (a precipitate to form during the dropwise addition). The mixture was stirred at 110 ^° C. for 7 hours, then cooled and filtered. The filter cake was washed with 3 x 100 ml of methyl tert-butyl ether (MTBE), filtrate and washings were combined and the solvent mixture was separated by distillation under reduced pressure. The product (fumaric acid (trimethoxysilylmethyl) methyl ester / maleic acid (trimethoxysilylmethyl) methyl ester, mixture of cis / trans isomers, trans: ice about 8: 1) was after distillation (bp 118 - 122 ° C / 1.0 mbar ) in 62% yield as a colorless liquid (399 g, 1.51 mol, sum of the isomers).

Example 2: Preparation of (crotonatomethyl) trimethoxysilane (mixture of cis / trans isomers)

Crotonic acid (568 g, 6.60 mmol) was dissolved in DMF (700 mL). Subsequently, a 5.42 M methanolic sodium methoxide solution was added dropwise (1.13 1, 6.12 mol NaOMe) (temperature rise to 45 ° C, precipitation of a solid). Then the mixture was heated up to 100 ⁰ C, at the top of the apparatus (Vigreux column) methanol at 40 ° C / 300 mbar passed. Then about 50 ml of DMF were distilled off, the bottom cooled, (chloromethyl) trimethoxysilane (1.024 kg, 914 ml, 6.00 mol) was added and the mixture heated to 130 ⁰ C for a further 5 hours, cooled again and filtered. The filter cake was washed with 2 x 200 ml MTBE, filtrate and wash were combined and the solvent mixture was reduced pressure separated by distillation. The product ((crotonatomethyl) trimethoxysilane, mixture of cis / trans isomers, trans: ice about 19: 1) was obtained as a colorless liquid after distillation on a thin-film evaporator (transition 115 ° C heat source temperature / 0.8 mbar) in 65% yield (860 g, 3.90 mol, sum of the isomers).

Example 3 Preparation of (allylsuccinatomethyl) trimethoxysilane (allylsuccinatomethyl) trimethoxysilane was prepared analogously to the process of Example 1, by:

Maleic anhydride was replaced by succinic anhydride and methanol by allyl alcohol.

Example 4: Preparation of

(Vinylsuccinatomethyl) trimethoxysilane

(Vinylsuccinatomethyl) trimethoxysilane was prepared analogously to the procedure of Example 2 by replacing crotonic acid with succinic acid monovinyl ester (vinyl succinate) and the methanolic sodium methoxide solution with sodium hydride.

Example 5: Preparation of (W-allylacetamidomethyl) trimethoxysilane Method A.

(N-Allylacetamidomethyl) trimethoxysilane was prepared analogously to the procedure of Example 2, by crotonic acid was replaced by N-allylacetamide. Method B.

Acetic anhydride (2.80 g, 2.59 mL, 27.4 mmol) was added to (N-allylaminomethyl) trimethoxysilane (5.09 g, 26.6 mmol; prepared according to Example 8) (temperature rise to 83 ° C). The mixture was stirred for 2 hours and then distilled. The product (N-allylacetamidomethyl) trimethoxysilane was obtained in 21% yield (1.30 g, 5.57 mmol) as a clear, colorless liquid; Boiling point 97 ° C / 0.4 mbar.

Example 6: Preparation of (W-allylformamidomethyl) trimethoxysilane

Methyl formate (4.87 g, 5.00 mL, 81.1 mmol) was added dropwise to (N-allylaminomethyl) trimethoxysilane (5.04 g, 26.4 mmol, prepared according to Example 8). The mixture was stirred for 2 hours and then distilled. The product (N-allylformamidomethyl) trimethoxysilane was obtained in 64% yield (3.70 g, 16.9 mmol) as a clear, colorless liquid; Boiling point 88 ° C / 0.4 mbar.

Example 7: Preparation of (W-allyl-4-methylbenzenesulfonamidomethyl) trimethoxysilane (Ν-allyl-4-methylbenzenesulfonamidomethyl) trimethoxysilane was prepared analogously to the procedure of Example 2 by replacing crotonic acid with N-allyl-4-methylbenzenesulfonamide. Synthesis of a precursor

Example 8: Preparation of (W-allylaminomethyl) trimethoxysilane

Allylamine (122 g, 160 mL, 2.13 mol) became

(Chloromethyl) trimethoxysilane (45.2 g, 40 ml, 265 mmol) added dropwise (temperature rise to 50 ⁰ C). The mixture was stirred for 4 hours (cooled to 28 ⁰ C) and extracted with 1 x 100 ml and 2 x 50 ml of n-heptane. The n-heptane phases were combined, the solvent was distilled off at 350-500 mbar, the residue was filtered (low precipitation) and distilled. The product (W-allylaminomethyl) trimethoxysilane was obtained in 74% yield (37.5 g, 196 mmol) as a clear, colorless liquid; Bp 73 ⁰ C / 4 mbar.

Silane grafts on polymer

All parts given below mean parts by mass.

Example 9a-e: Silane grafts on polymer in the laboratory extruder

The grafting reaction was carried out in a co-rotating twin-screw extruder (ZE 25, Berstorff) at an L / D ratio of 47 and a screw diameter of 25 mm. The extruder was operated with the following parameters: Temperature profile (in ⁰ C):

130/130/150/190/210/215/215/210/210 (head temperature); Output approx. 10 kg / h; Speed 200 rpm

The medium density polyethylene used is by a

Melt index of 3.5 g / 10 min (2.16 kg / 190 ° C), a density of 944 kg / m ³ and a VICAT softening point of about 123 ° C characterized.

Silane and peroxide were mixed and were fed into the third heating zone at 150 ⁰ C with the aid of a metering pump of the Fa. Viscotec in the polymer melt.

For the experiments, the peroxide used was di-tert-butyl peroxide (DTBP, Merck).

The following silanes were used for the experiments: Silane A: Fumaric acid (trimethoxysilylmethyl) methyl ester / maleic acid (trimethoxysilylmethyl) methyl ester (mixture of cis / trans isomers) according to Example 1 according to the invention

Silane B: Vinyltrimethoxysilane (GENIOSIL® XL 10, Wacker

Chemie AG) - not according to the invention Silane C: (CC-methacrylatomethyl) trimethoxysilane (GENIOSIL® XL

33, Wacker Chemie AG) - not according to the invention Silane D: (Crotonatomethyl) trimethoxysilane (mixture of cis / trans isomers) according to Example 2 - according to the invention

The resulting graft polymers were pelleted and stored under nitrogen and moisture exclusion.

The silane grafts carried out are summarized in Table 1 below.

* corresponds to 135 mmol per kg MDPE ** corresponds to 67.5 mmol per kg MDPE *** not according to the invention

The graft polymer from Example 9a contains the following structural units (according to the invention): Polymer≡C-CH [C (O) OMe] -CH ₂ -C (O) O-CH ₂ -Si (OMe) ₃ and

Polymer≡C-CH [C (O) O-CH ₂ -Si (OMe) ₃ ] -CH ₂ -C (O) OMe;

the graft polymers of Examples 9b and 9c contain the following structural units (not according to the invention): polymer≡C-CH ₂ -CH ₂ -Si (OMe) ₃ and polymer≡C-CH (Me) -Si (OMe) ₃ ;

the graft polymer from Example 9d contains the following structural units (not according to the invention):

Polymer≡C-CH ₂ -CH (Me) -C (O) O-CH ₂ -Si (OMe) ₃ and

Polymer≡CC (Me ₂ ) -C (O) O-CH ₂ -Si (OMe) ₃ , because of the poor grafting efficiency of silane C, as will be shown below, is the number of these Structural units based on the amount of material used in silane C very low;

the graft polymer from Example 9e contains the following structural units (according to the invention): polymer≡C-CH (Me) -CH ₂ -C (O) O-CH ₂ -Si (OMe) ₃ and polymer≡C-CH (Et) [C ( 0) 0-CH ₂ -Si (OMe) ₃ ],

wherein in these structural units the unit Polymer≡C represents a residue of the medium density polyethylene used.

Example 10a-b: Preparation of the catalyst masterbatches

The preparation of the catalyst masterbatches was carried out in a co-rotating twin-screw extruder (ZE 25, Berstorff) at an L / D ratio of 47 and a screw diameter of 25 mm. The extruder was operated with the following parameters: Temperature profile (in ⁰ C): 130/130/150/190/210/215/215/210/210 (head temperature); Output approx. 10 kg / h; Speed 200 rpm

The carrier material used was medium density polyethylene having a melt index of 3.5 g / 10 min (2.16 kg / 190 ° C), a density of 944 kg / m ³ and a VICAT softening point of about 123 ° C is characterized.

The polyethylene was premixed with the catalyst. The mixture was metered by means of a metering balance (Brabender) into the catchment area of the twin-screw extruder. For the preparation of the catalyst masterbatches, the following catalysts were used:

Catalyst A: Dibutyltin dilaurate (DBTL), from Wacker Chemie AG Catalyst B: 1, 5-diazabicyclo [4.3.0] non-5-ene (DBN), from Fluka

The resulting catalyst masterbatches were pelleted and stored under nitrogen and moisture exclusion.

The compositions of the catalyst masterbatches are summarized in Table 2 below.

Table 2: Composition of the catalyst masterbatches (parts by weight)

Example 11a-f: Preparation of test pieces for cross-linking

The graft polymers prepared in Example 9a-e were blended with the catalyst masterbatches prepared in Example 10a-b as indicated in Table 3 below.

Table 3: Composition of test pieces for cross-linking (parts by weight)

*** not according to the invention

Example 12a-f: crosslinking characteristic

The mixtures according to Example 11a-f were extruded on a single-screw measuring extruder (Göttfert) with an L / D ratio of 20 and a screw diameter of 30 mm through a hole die (diameter 5 mm) to test bars.

The extruder was operated with the following parameters: temperature profile (in ⁰ C): 180/190/195/200 (head temperature); Speed 25 rpm; Filling level 100%.

The test specimens prepared according to Example 11a-f were cut into samples of about 5 cm in length and stored for each 1 h, 4 h and 24 h in a water bath at 90 ⁰ C.

After immersion in water and mechanical drying, chips were cut from the specimens with a thickness of Planed down 0.1 mm. The chips were extracted according to DIN EN 579 in boiling xylene for 8 h. The gel content was determined by differential weighing the sample before and after extraction and drying. The results are summarized in Table 4 below.

Table 4: Gel content (in%) after storage in water (1 h, 4 h, 24 h) and extraction according to DIN EN 579

*** not according to the invention

The comparison of Example 12a (CC silane-grafted PE, catalyst DBN) with Example 12b (vinyltrimethoxysilane-grafted PE, catalyst DBN) shows that the grafted polymer according to the invention according to Example 9a prepared according to the invention using a graftable CC silane according to Example 1 was crosslinked much faster by water exposure to the inventive crosslinked polymer according to Example 12a, as for the crosslinking of the grafted non-inventive polymer according to Example 9b (prepared using a non-inventive non-α-silane) to the crosslinked non-inventive Polymer according to Example 12b is the case. The compared polymers have the same molar loading respective silane (135 mmol silane / kg MDPE in the grafted polymer according to Example 9a, b).

Comparison of Example 12c (vinyltrimethoxysilane-grafted PE, catalyst dibutyltin dilaurate) with Example 12d ((CC-methacrylatomethyl) trimethoxysilane grafted PE, catalyst dibutyltin dilaurate) shows that when the grafted polymer of Example 9d crosslinked using a non-inventive (α-methacrylatomethyl ) silanes (silane C) (Sequence Example 9d -> Example Hd ->

Example 12d; not according to the invention), a significantly poorer gel content is achieved than in the crosslinking of the vinyltrimethoxysilane-grafted PE according to Example 9c (Sequence Example 9c -> Example Hc -> Example 12c, not according to the invention). This shows that (α-methacrylatomethyl) silanes do not graft sufficiently efficiently. The compared polymers have the same molar loading of respective silane (67.5 mmol silane / kg MDPE in the grafted polymer according to Example 9c, d).

The comparison of Example 12f (CC silane-grafted PE, catalyst-free) with Example 12e (vinyltrimethoxysilane-grafted PE, catalyst-free) shows that the grafted polymer of the invention according to Example 9e, which was prepared using a graftable CC silane according to the invention according to Example 2, Even without an added catalyst by water action can be crosslinked rapidly to the novel crosslinked polymer of Example 12f (Sequence Example 9e -> Example Hf -> Example 12f), while for the crosslinking of the grafted non-inventive polymer according to Example 9c (prepared using a non-inventive non-OC silane) for the crosslinked non-inventive polymer according to Example 12e (sequence Example 9c -> Example He -> Example 12e) the addition of a catalyst for a sufficient crosslinking rate is required. Without catalyst occurs in the case of Example 12e (not according to the invention) no significant cross-linking. The compared polymers have the same molar loading of respective silane (67.5 mmol silane / kg MDPE in the grafted polymer according to Example 9c, e).

By using the grafted polymers according to the invention which contain α-substituted hydrolyzable silyl groups, crosslinking to give the novel crosslinked polymers can thus achieve significantly higher production rates and thus significantly higher production capacities under comparable conditions than when using grafted polymers whose crosslinking is based on hydrolysis and Condensation is based on non-OC-substituted silyl groups. Furthermore, the comparison of Example 12e with Example 12f shows that, in the case of crosslinking of the polymers according to the invention which contain OC-substituted hydrolyzable silyl groups, addition of catalysts which accelerate the

Moisture crosslinking of the polymers, by catalyzing the hydrolysis of the hydrolyzable silyl groups contained in the polymer under the action of water and / or their condensation to form siloxanes, can be dispensed with, since sufficient crosslinking rates are achieved even without added catalyst. The grafted polymers of the present invention can be prepared by grafting the graftable CC silanes onto polymers.

Claims

claims

1. A process for the preparation of polymers (P), in which

Polymers (PI) containing CH-graftable units are grafted under free radical conditions with silanes containing (i) at least one unsaturated hydrocarbon group capable of sufficient grafting, (ii) bearing at least one hydrolyzable group on silicon, and (iii) at least one CC heteroatom, wherein the use of (methacrylatomethyl) silanes, (acrylatomethyl) silanes and (but-3-enoxymethyl) triethoxysilane is excluded, and wherein the thus preparable polymers (P) contain at least one structural element which is selected from the general Formulas Ia, Ib, IIa and IIb

Polymer≡CR ³ ₂ C-CH (R ^{3 '} ) - (R ² ) _P -Y-CH ₂ -SiX _n RVn (Ia),

Polymer≡CR ³ "C-CH ₂ (R ⁵⁾ - (R ⁴⁾ q-SiXnRS-mn (CH ₃ - _D Z _D) _m (IIa),

R ^{1 is} an unsubstituted or by one or more

R ^{2 is} a di- or trivalent, unsubstituted or substituted by one or more substituents Q, optionally interrupted by one to three heteroatoms hydrocarbon radical having 1-20 C atoms, R ³ , R ³ ', R ³ "is hydrogen, fluorine, chlorine or an unsubstituted or substituted by one or more substituents Q, optionally one to three

Heteroatom-containing hydrocarbon radical, R ^{4 has} the meaning of R ² and additionally a Sii-Si 2o

Siloxane unit, or one, optionally interrupted by groups R ² interrupted Sii-Si2o siloxane unit, R ^{5 has} the meaning of R ³ and additionally may have the same meaning as Z, Q is a fluoro, chloro, bromo, iodo, silyl , Silylalkyl,

Silylaryl, siloxy, siloxyalkyl, siloxyaryl, oxo,

Hydroxy, alkoxy, aryloxy, acyloxy, sulfonato, sulfato, sulfinato, amino, alkylamino, dialkylamino,

Acylamino, imido, sulfonamido, imino, mercapto,

Alkylthio or arylthio substituents, X is a hydrolyzable group,

Y is a heteroatom-containing di- or trivalent radical which is bound by a heteroatom to the group -CH ₂ -SiX _n R ¹ SI ₁ , Z is a fluorine, chlorine, bromine, iodine substituent or a monovalent via oxygen, sulfur, nitrogen or

Phosphorus-bonded radical, Polymer≡C- a polymer radical of an organic polymer, the

In the general formulas IIa and IIb, the values 1, 2 or 3, p, q denote the values 0 or 1 , m when R ^{5 is} a hydrogen atom or an optionally one to three hetero atoms containing hydrocarbon radical means, has the value 1 or 2, or, if R ^{5 takes} one of the meanings of Z, has the value 0, 1 or 2, and q, if m is 0, is also equal to 0 where R ¹ , R ² , R ³ , R ³ ', R ³ ", R ⁴ , R ⁵ , X, Y, Z and Q may be interconnected within the general formulas Ia, Ib, IIa and IIb, so that one or more rings are formed.

2. Polymers (P) preparable by the process according to claim 1, which contain at least one structural element selected from the general formulas Ia, Ib, IIa and IIb

Polymer≡CR ³ ₂ C-CH (R ^{3 '} ) - (R ² ) _P -Y-CH ₂ -SiX _n RVn (Ia),

Polymer≡CR ³ "C-CH ₂ (R ⁵⁾ - (R ⁴⁾ q-SiXnRS-mn (CH ₃ - _D Z _D) _m (IIa), ⁽³ R" ₂ CH-) (Polymer≡C-) C (R ⁵ ) - (R ⁴ ) _q -SiX _n R ¹ ₃ - _m - _n (CH ₃ - _D Z _D ) _m (Hb),

wherein the structural elements of the general formulas Ia and

Ib are excluded, in which Y takes on the meanings -CH ₂ S-, carbamate or urea group, or the meaning -N (R ⁶ ) - and R is simultaneously hydrogen or a

Alkyl group, or in which R ^{3 is} a hydrogen atom, R ³ 'a

Is a hydrogen atom or a methyl radical, -Y- is a group - C (O) O- and p is 0, and wherein the structural elements of the general formulas

Polymer≡CR ² '- (Y') _y -CH ₂ -CH ₂ -O-CH ₂ -Si (OEt) ₃ and Polymer≡CR ² '-C (R ³ ^"') ₂ -NR ¹⁶ -CH ₂ -SiX ₃

are excluded, in which R ² 'has the meanings of R ² ,

Y 'is a divalent radical -0-, -NH- or trivalent

Rest = N-, Et means an ethyl radical, y means 0 or 1, R ³ '^"has the meanings of R ³ and

R ^{16 represents} a hydrogen atom or an alkyl radical.

3. Method of crosslinking according to the method according to

Claim 1 or claim 2 produced polymers (P) with water.

4. Crosslinked polymers (PV) producible by moisture crosslinking of formulations containing the polymers (P) preparable according to the process of claim 1 or claim 2.

5. Use of the polymer (P) and the crosslinked polymer (PV) according to claim 4, which can be prepared according to the process according to claim 1 or claim 2, alone or as blends for cable insulation, pipes, chemical containers and heat-resistant material.

6. silanes of the general formula V,

X ¹ _O R ² S- _O SiG ¹ (V),

in which G ^{1 is} a radical of the general formula Va

-CH ₂ -A ² -C (O) - (CR ²³ ₂ ) _r - (OCR ²⁴ ₂ CR ²⁵ ₂ ) _s -

(C (O)) _t - (A ²² ) _u - (CR ²⁶ ₂ : ₇ -CR ²⁷ = CR ²⁸ ₂ (Va;

which has a single aliphatically unsaturated bond, X ^{1 is} a hydrolyzable group selected from alkoxy,

Alkenoxy, acyloxy, alkylcarbonato, amino, hydrocarbylamino and acylamino,

R ²¹ alkyl or C ₆ -C ₇ aryl or ₀ -C ₆ Sii-Si hydrolyzable a Ci-C ₈ alkyl or C ₂ o-siloxy group or condensed silane hydrolysis of silanes having 1, 2, 3 or 4 Groups, R ²³ , R ²⁴ , R ^{25 is} a hydrogen atom or a methyl group, R, R, R is a hydrogen atom or a C 1 -C ₆ -alkyl radical,

A ^{2 is} a heteroatom-containing divalent radical which is replaced by a

Heteroatom is bound to the group X ¹ QR ²¹ _S - _O Si-CH ₂ -, A ^{22 is} a heteroatom-containing divalent radical, v, t, u are the values 0 or 1, r, s integer values from 0 to 10, r + s + t + u + v is an integer value> 0 and o is 1, 2 or 3, where -A ²² - meaning -NH-C (R ²⁹ ) ₂ - [pC ₆ H ₄ ] - is excluded, and wherein R ^{29 is} a hydrogen atom or a Ci-Cio alkyl group and PC _O H _{4 is} an aromatic para-phenylene group.

7. silanes of the general formula VI

X ⁴ _e R ⁴¹ ₃ - _e SiG ² (VI),

where G ^{2 is} a radical of the general formula VIa -CH ₂ -A ⁴ -C (O) -CH = CH-R ⁴⁸ (VI a),

which has a single aliphatically unsaturated bond,

R ⁴¹ a Ci-C ₆ alkyl or C ₇ -C ₈ alkyl or C ₆ -C ₀ aryl or Sii-Si2O ~ siloxy group or condensed silane hydrolysis of silanes having 1, 2, 3 or 4 hydrolyzable groups, R ^{48 is} a C 1 -C 6 -alkyl or C ₇ -C 20 -alkyl group or a group

-C (O) -A ⁴⁴ -R ^49, R ⁴⁹ is a Ci-C ₆ alkyl or C ₇ -C ₂ o alkyl or C ₆ -C ₀ aryl group, a group -CH ₂ -SiX ⁴⁴ _f R ⁴⁴ 3- _f or, provided that -A ⁴ - is not -N (H) -, a hydrogen atom, X ^{44 is} a hydrolyzable group,

R ⁴⁴ a Ci-C ₆ alkyl or C ₇ -C ₈ alkyl or C ₆ -C ₀ aryl or SII Si ₂ O siloxy group or condensed silane hydrolyzate of

Silanes with 1, 2, 3 or 4 hydrolyzable groups, A ⁴ a heteroatom-containing divalent radical which is replaced by a

Heteroatom to the group X ⁴ _e R ⁴¹ 3- _e Si-CH ₂ - is bonded, A ^{44 is} a heteroatom-containing divalent radical, e, f are 1, 2 or 3.

8. Silanes of the general formula VII

X ⁵ _c R ⁵¹ ₃ _-c S iG ³ (VI I),

where G ^{3 is} a radical of the general formula VIIa -CH ₂ -A ⁵ - (CR ⁵² ₂ ) d -CR ⁵³ = CR ⁵⁴ ₂ (VIIa), which has a single aliphatically unsaturated bond,

X ^{5 is} a hydrolyzable group selected from alkoxy, alkenoxy, acyloxy, alkylcarbonato, amino, hydrocarbylamino and acylamino,

R ⁵¹ a Ci-C ₆ alkyl or C ₇ -C ₈ alkyl or C ₆ -C ₀ aryl or SII Si ₂ O siloxy group or condensed silane hydrolysis of silanes having 1, 2, 3 or 4 hydrolyzable groups , R ⁵² , R ⁵³ , R ^{54 are} hydrogen or C ₁ -C ₆ -alkyl or C ₇ -C ₈ -alkyl,

A ^{5 is} a heteroatom-containing divalent radical selected from -O-, -N (R ⁵⁶ ) -, -S (O) -, -S (O) ₂ -, -O-S (O) -, -O-S (O ) ₂ -, -O-S (O) ₂ -O-, -N (R ⁵⁹ ) -S (O) ₂ -, -N [C (O) R ⁵⁵ ] JS (O) ₂ -, -N (R ⁵⁹ ) -S (O) ₂ -O-, -O-S (O) ₂ -N (R ⁵⁹ ) -, -P (O) (OR ⁵⁰ ) -O-, -O-P (O) (OR ⁵⁰ ) -, -O-P (O) (OR ⁵⁰ ) -O-, -N (R ⁵⁹ ) -P (O) (OR ⁵⁰ ) -,

-O-P (O) (OR ⁵⁰ ) -N (R ⁵⁹ ) -, -N (R ⁵⁹ ) -P (O) (OR ⁵⁰ ) -O-, -N [C (O) R ⁵⁵ ] -, -OC (R ⁵⁵ ) = N-, -N [S (O) ₂ R ⁵⁸ ] - or -N [P (O) R ⁵⁷ ₂ ] -,

R ⁵⁰ , R ⁵⁵ and R ^{59 are} hydrogen or optionally substituted

C ₆ alkyl or C ₇ -C ₂₀ alkyl or C ₆ -C ₀ aryl radicals, preferably unsubstituted Ci-C ₆ alkyl or phenyl radicals, in particular methyl or ethyl radicals,

R ⁵⁶ is an optionally substituted Ci-C ₆ alkyl or C ₇ - C ₂ o alkyl or C ₆ -Cio aryl group, preferably unsubstituted Ci-C ₆ - alkyl or phenyl radical, in particular methyl or ethyl radical,

R ⁵⁷ is an optionally substituted Ci-C ₆ alkyl or C ₇ - C ₂₀ alkyl or C ₆ -C ₀ aryl, Ci-C ₆ alkoxy or C ₇ -C ₂₀ - alkoxy or C ₆ -Ci ₀ -Aryloxyrest, preferably unsubstituted Ci-C ₆ alkyl or phenyl radical, in particular methyl or ethyl radical, methoxy or ethoxy radical,

R ⁵⁸ is an unsubstituted Ci-C ₆ alkyl or C ₇ -C ₂₀ alkyl or optionally substituted C ₆ -C ₀ aryl group, preferably unsubstituted C 1 -C 6 -alkyl or phenyl or C ₇ -aryl radical, in particular methyl, phenyl or p-tolyl radical, d denotes 0 or 1 and c denotes 2 or 3, where N-allyl-N- (trimethoxysilyl) methyl] ethyl carbamate is excluded.

9. Silanes of the general formula VIII

in which

X ^{6 is} a hydrolyzable group selected from alkoxy,

Alkenoxy, acyloxy, alkylcarbonato, amino, hydrocarbylamino and acylamino,

R ⁶¹ a Ci-C ₆ alkyl or C ₇ -C ₈ alkyl or C ₆ -C ₀ aryl or Sii-Si2O ~ siloxy group or condensed silane hydrolysis of silanes having 1, 2, 3 or 4 hydrolyzable groups, R ⁶² , R ^{63 is} hydrogen or C ₁ -C ₆ -alkyl or C ₇ -C ₂ 0-alkyl radical and, g are the values 1, 2 or 3.

10. Silanes of the general formula IX

G ⁴ S i (CZ ⁷ _a H ₃ _-a ) X ⁷ 2 (IX),

wherein G ^{4 is} a radical of the general formula IXa

R ⁷¹ ₂ C = CR ⁷² -R ⁷⁸ - (IXa), which means a single aliphatic unsaturated

Bond R ⁷¹ , R ^{72 is} hydrogen or an optionally substituted

C ₆ alkyl or C ₇ -C ₂ o alkyl or C ₆ -C ₀ aryl group, X ⁷ is a hydrolyzable group selected from alkoxy,

Alkenoxy, acyloxy, alkylcarbonato, amino,

Hydrocarbon amino and acylamino, R ⁷⁸ a divalent, unsubstituted or substituted by one or more substituents Q ⁷ , optionally interrupted by one to three heteroatoms, via a

Carbon atom bonded to the silicon atom organic

Radical having 1-20 C atoms, with the proviso that the bond between R and the silicon atom is prepared via a carbon atom, or is R ⁷⁹ , R ^{79 is} an optionally interrupted by R ⁷⁸ groups Sii-Si 2o

Siloxane unit, or a bond, Q ^{7 is} a fluoro, chloro, bromo, iodo, silyl, silylalkyl,

Silylaryl, siloxy, siloxyalkyl, siloxyaryl, oxo,

Acylamino, imido, sulfonamido, imino, mercapto,

Alkylthio or Arylthiosubstituenten, Z ^{7 is} a monovalent group selected from OR ⁷³ , OC (O) R ⁷⁴ ,

N [C (O) R ⁷⁴ J [S (O) ₂ R ⁷⁶ ], N [S (O) ₂ R ⁷⁶ J ₂ , S (O) ₂ R ⁷⁶ , OS (O) ₂ R ⁷⁶ ,

S (O) R ⁷⁶ , OS (O) R ⁷⁶ , P (O) (OR ⁷⁷ ) ₂ or 0-N = C (R ⁷⁴ ) ₂ F, Cl, Br or

I,

R ⁷⁴ and R ^{75 are} hydrogen or an optionally substituted

Ci-C ₆ alkyl or C ₇ -C ₂₀ alkyl or C ₆ -C ₀ aryl and a is the values 1, 2 or 3.