WO2009033908A2 - Polymères réticulables par voie humide, à base de silanes substitués par hétéroatomes en alpha - Google Patents

Polymères réticulables par voie humide, à base de silanes substitués par hétéroatomes en alpha Download PDF

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WO2009033908A2
WO2009033908A2 PCT/EP2008/060617 EP2008060617W WO2009033908A2 WO 2009033908 A2 WO2009033908 A2 WO 2009033908A2 EP 2008060617 W EP2008060617 W EP 2008060617W WO 2009033908 A2 WO2009033908 A2 WO 2009033908A2
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alkyl
radical
group
polymer
silanes
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PCT/EP2008/060617
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German (de)
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WO2009033908A3 (fr
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Jürgen Oliver DAISS
Oliver Fuhrmann
Michael Geck
Jürgen STOHRER
Richard Weidner
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Wacker Chemie Ag
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/42—Introducing metal atoms or metal-containing groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
    • C07F7/1804—Compounds having Si-O-C linkages

Definitions

  • the present invention relates to polymers (P) preparable by grafting polymers with ⁇ -heteroatom-substituted silanes, their preparation by grafting, their crosslinking with water, their use and silanes suitable for grafting.
  • 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.
  • fast crosslinking processes are desired.
  • 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 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),
  • 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
  • silanes containing Si-H groups 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.
  • 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
  • Substituents Q substituted Ci-Cis alkyl or C ⁇ -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 ⁇ -heteroatom.
  • 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.
  • 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),
  • HDPE high-density polyethylene
  • MDPE medium-density polyethylene
  • LDPE low-density polyethylene
  • LLDPE linear low-density polyethylene
  • ethylene-CC-olefin copolymer for example, ethylene-propylene copolymer, ethylene-butene copolymer,
  • 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-C ⁇ 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.
  • R 3 , R 3 ', R 3 are hydrogen or alkyl, aryl, alkoxy, aryloxy, acyloxy, alkoxycarbonyl, aryloxycarbonyl, amide, imide, acylamino or carbamate groups.
  • 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,
  • 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 ] -,
  • 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 ,
  • 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 ⁇ -heteroatom are referred to hereinafter as "CC silanes”.
  • the ⁇ -silanes are grafted onto polymers (PI), preferably polyolefins, in a free-radical grafting reaction to give the grafted polymers (P).
  • PI polymers
  • P grafted polymers
  • PI1 polymers
  • P1 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
  • 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.
  • useful chemical radical initiators are described, for example, in D. Sloanu, in Plastics Additives Handbook, 5th Edition, Hanser Verlag, Kunststoff 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.
  • 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.
  • one or more further additives are admixed, for example fillers, such as magnesium oxide, silica or clay, antioxidants or catalysts.
  • 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),
  • 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
  • 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 1 is an unsubstituted or by one or more
  • Substituents Q substituted Ci-Cis alkyl or C ⁇ -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,
  • 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 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,
  • 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
  • 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
  • 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.
  • 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.
  • 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.
  • crosslinking without added catalyst.
  • Catalyst blended polymer (P) at temperatures that ensure the moldability of the modified polymer (P), brought into the desired shape.
  • 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.
  • the crosslinked polymer (PV) according to DIN EN
  • 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,
  • G 1 is a radical of general formula Va
  • X 1 is a hydrolyzable group selected from alkoxy
  • 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
  • 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.
  • 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-C ⁇ -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-C ⁇ -alkyl or phenyl or Ci-C ⁇ -alkoxy, in particular methyl or ethyl radical, methoxy or ethoxy.
  • R 21 Preferred meanings for R 21 are given above for R 1 in the general formulas Ia, Ib, IIa and IIb.
  • silanes of the general formulas III and IV namely silanes of the general formula VI X-, R 4 V e SiG 2 (vi:
  • G 2 is a radical of the general formula VIa
  • 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
  • R 48 is a Ci-C ⁇ -alkyl or C 7 -C 2 o-alkyl group or a group
  • 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
  • a 44 is a heteroatom-containing divalent radical, e, f are 1, 2 or 3.
  • R 44 Preferred meanings for R 44 are given above for R 1 in the general formulas Ia, Ib, IIa and IIb.
  • R 48 are methyl or -C (O) -A 44 -R 49 .
  • 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
  • G 3 is a radical of the general formula VIIa
  • 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 ) -, -
  • 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 phen
  • R 51 Preferred meanings for R 1 are given above for R 1 in the general formulas Ia, Ib, IIa and IIb.
  • silanes of the general formulas III and IV namely silanes of the general formula VIII
  • X 6 is a hydrolyzable group selected from alkoxy
  • 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
  • g is 1, 2 or 3rd
  • R 61 Preferred meanings for R 61 are given above for R 1 in the general formulas Ia, Ib, IIa and IIb.
  • R is hydrogen or methyl.
  • Preferred meanings for g are the values 2 or 3.
  • silanes of the general formulas III and IV namely silanes of the general formula IX
  • 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
  • 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.
  • 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 ,
  • R 73, R 76 and R 77 is an optionally substituted Ci-C ⁇ -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-C ⁇ -alkyl or C 7 -C 20 alkyl or C 6 -C 0 aryl and a is the values 1, 2 or 3.
  • Z 7 are OC (O) R 74 , N (R 75 ) C (O) OR 73 ,
  • R 71 , R 72 are hydrogen or unsubstituted C 1 -C 6 -alkyl radicals.
  • the heteroatoms through which R may be interrupted are preferably 0, S, N or Si.
  • a is preferably the value 1.
  • OC silanes of the general formulas V to VIII are the (trimethoxysilyl) methyl, (Dimethoxymethylsilyl) methyl, (triethoxysilyl) methyl and
  • N-allylformamide N-allylacetamide, N-allylmethanesulfonamide, N-allylbenzenesulfonamide and N-allyl-4-methylbenzenesulfonamide,
  • silanes in which the silicon-bonded methoxy and ethoxy groups are mixed such as for example (ethoxy) (methoxy) (methyl) silyl,
  • Example 1 Preparation of fumaric acid (trimethoxysilylmethyl) ⁇ methylester / maleic acid (trimethoxysilylmethyl) methyl ester (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.
  • 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 7 Preparation of (W-allyl-4-methylbenzenesulfonamidomethyl) trimethoxysilane ( ⁇ -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 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):
  • the medium density polyethylene used is by a
  • 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.
  • the peroxide used was di-tert-butyl peroxide (DTBP, Merck).
  • 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
  • Silane C (CC-methacrylatomethyl) trimethoxysilane (GENIOSIL® XL
  • 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 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
  • 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):
  • 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 ],
  • the unit Polymer ⁇ C represents a residue of the medium density polyethylene used.
  • 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.
  • a metering balance Brabender
  • 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.
  • compositions of the catalyst masterbatches are summarized in Table 2 below.
  • Example 11a-f Preparation of test pieces for cross-linking
  • Example 9a-e 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)
  • Example 11a-f 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%.
  • 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.
  • Example 12a CC silane-grafted PE, catalyst DBN
  • Example 12b vinyltrimethoxysilane-grafted PE, catalyst DBN
  • 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- ⁇ -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).
  • Example 12c Vinyltrimethoxysilane-grafted PE, catalyst dibutyltin dilaurate
  • Example 12d (CC-methacrylatomethyl) trimethoxysilane grafted PE, catalyst dibutyltin dilaurate) shows that when the grafted polymer of Example 9d crosslinked using a non-inventive ( ⁇ -methacrylatomethyl ) silanes (silane C) (Sequence Example 9d -> Example Hd ->
  • Example 12d 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 ( ⁇ -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).
  • Example 12f CC silane-grafted PE, catalyst-free
  • Example 12e vinyltrimethoxysilane-grafted PE, catalyst-free
  • 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)
  • Example 9c prepared using a non-inventive non-OC silane
  • the addition of a catalyst for a sufficient crosslinking rate is required.
  • Example 12e 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).
  • 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.
  • Example 12e 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.

Abstract

La présente invention concerne un procédé de fabrication de polymères (P) comportant un élément de structure choisi dans les formules générales (Ia), (Ib), (IIa) et (IIb) dans lesquelles R1, R2, R3, R3', R3'', R4, R5, X, Y, Z, polymère≡C-, j, m, n, p et q ont les significations mentionnées dans la revendication 1. L'invention concerne également les polymères (P) ainsi obtenus, leur réticulation avec de l'eau, les polymères réticulés correspondants (PV), leur utilisation, et les silanes convenant à la fabrication de ces polymères (P) par greffage.
PCT/EP2008/060617 2007-09-10 2008-08-13 Polymères réticulables par voie humide, à base de silanes substitués par hétéroatomes en alpha WO2009033908A2 (fr)

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WO2009147024A1 (fr) * 2008-06-02 2009-12-10 Wacker Chemie Ag Liant à base de polymères contenant des groupes alpha-silanes
WO2011120851A1 (fr) 2010-04-01 2011-10-06 Wacker Chemie Ag Polymère d'éthylène à réticulation humide à base de diacyloxysilane
US20120136082A1 (en) * 2009-08-07 2012-05-31 Wacker Chemie Ag Binding agents based on highly branched polyolefins comprising silane groups
DE102011002440A1 (de) 2011-01-04 2012-07-05 Wacker Chemie Ag Verfahren zur Vernetzung feuchtevernetzbarer Polymere mit einem Wasserspendersystem

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DE102010010598A1 (de) 2010-03-08 2011-09-08 Delo Industrie Klebstoffe Gmbh & Co. Kgaa Dual härtende Masse und deren Verwendung
WO2013090799A1 (fr) 2011-12-16 2013-06-20 Biogen Idec Ma Inc. Esters de l'acide fumarique contenant du silicium

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009147024A1 (fr) * 2008-06-02 2009-12-10 Wacker Chemie Ag Liant à base de polymères contenant des groupes alpha-silanes
US20120136082A1 (en) * 2009-08-07 2012-05-31 Wacker Chemie Ag Binding agents based on highly branched polyolefins comprising silane groups
JP2013501113A (ja) * 2009-08-07 2013-01-10 ワッカー ケミー アクチエンゲゼルシャフト シラン基を有する高分岐型のポリオレフィンを基礎とするバインダー
WO2011120851A1 (fr) 2010-04-01 2011-10-06 Wacker Chemie Ag Polymère d'éthylène à réticulation humide à base de diacyloxysilane
DE102010003588A1 (de) 2010-04-01 2011-10-06 Wacker Chemie Ag Diacyloxysilanbasierte feuchtevernetzbare Ethen-Polymere
DE102011002440A1 (de) 2011-01-04 2012-07-05 Wacker Chemie Ag Verfahren zur Vernetzung feuchtevernetzbarer Polymere mit einem Wasserspendersystem
WO2012093031A1 (fr) * 2011-01-04 2012-07-12 Wacker Chemie Ag Procédé de réticulation de polymères réticulables à l'humidité avec un système distributeur d'eau

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