Silanol condensation catalysts for the cross-linking of filled and unfilled polymer compounds

Abstract

The invention relates to a composition of an organofunctional silane compound, particularly of a mono-unsaturated silane compound, and of an organic acid or a precursor compound which releases said organic acid, and to a method for the production of polymer compounds such as granulates and/or finished products from thermoplastic base polymers and/or monomers and/or prepolymers of the thermoplastic base polymer utilizing the composition, the organic acid, or the precursor compound which releases said organic acid. The invention also relates to the produced polymers, filled plastics such as, for example, granulates, finished products, molded bodies and/or articles such as pipes or cables. In addition, the invention relates to a kit containing the composition.

1 . A composition, comprising:
 a) at least one silicon-comprising precursor compound of an organic acid, and/or one organofunctional silane compound;   and, optionally,   b) one organic acid, and/or one silicon-free precursor compound comprising an organic acid.   
     
     
         2 . The composition of  claim 1 , wherein
 in a),   i) the at least one silicon-comprising precursor compound of an organic acid corresponds to formula I and/or II
   (A) z SiR 2   x (OR 1 ) 4-z-x    (I)
 
   (R 1 O) 3-y-u (R 2 ) u (A) y Si-A-Si(A) y (R 2 ) u (OR 1 ) 3-y-u    (II),
 
   wherein   mutually independently, z is 0, 1, 2, or 3, x is 0, 1, 2, or 3, y is 0, 1, 2, or 3, and u is 0, 1, 2, or 3, with the proviso that in formula L z+x is smaller than or equal to (≦)3, and, in formula II, y+u is independently smaller than or equal to (≦)2,   A is mutually independently in formula I and/or II a monovalent olefin group, and A in the form of a divalent moiety in formula II is a divalent olefin group,   R 1  is, mutually independently, a carbonyl-R 3  group, where R 3  corresponds to a hydrocarbon moiety, having from 1 to 45 carbon atoms, and   R 2  corresponds, mutually independently, to a hydrocarbon group, and/or   ii) the organofunctional silane compound corresponds to an unsaturated alkoxysilane of formula III
   (B) b SiR 4   a (OR 5 ) 3-b-a    (III),
 
   wherein   mutually independently, b is 0, 1, 2, or 3, and a is 0, 1, 2, or 3, with the proviso that in formula III, b+a is smaller than or equal to 3,   B, mutually independently, is
 a monovalent (R 7 ) 2 C═C(R 7 )-E q - group in formula III, in which R 7  are identical or different, and R 7  is a hydrogen atom or a methyl group or a phenyl group, E is —CH 2 —, —(CH 2 ) 2 —, —(CH 2 ) 3 —, —O(O)C(CH 2 ) 3 —, or —C(O)O—(CH 2 ) 3 —, q is 0 or 1, or 
 isoprenyl, hexenyl, cyclohexenyl, terpenyl, squalanyl, squalenyl, polyterpenyl, betulaprenoxy, cis/trans-polyisoprenyl, or 
 an R 6 -D p -[C(R 6 )═C(R 6 )—C(R 6 )═C(R 6 )] t -D p - group, in which R 6  are identical or different, and R 6  is a hydrogen atom or an alkyl group having from 1 to 3 carbon atoms, or an aryl group, or an aralkyl group, groups D are identical or different, and D is —CH 2 —, —(CH 2 ) 2 —, —(CH 2 ) 3 —, —O(O)C(CH 2 ) 3 —, or —C(O)O—(CH 2 ) 3 —, p is 0 or 1, and t is 1 or 2, 
   R 5  is, mutually independently, methyl, ethyl, n-propyl, or isopropyl,   R 4  is, mutually independently, a substituted or unsubstituted hydrocarbon group.   
     
     
         3 . The composition of  claim 1 , wherein b) is present and, in b), the at least one organic acid is present and comprises at least one selected from the group consisting of
 iii.a) a saturated fatty acid, and unsaturated fatty acid, a natural amino acid, a synthetic amino acid,   iii.b) an acid-comprising silicon-free precursor compound, an anhydride, and an ester.   
     
     
         4 . The composition of  claim 1 , further comprising c), at least one free-radical generator. 
     
     
         5 . The composition of  claim 4 , wherein the at least one free-radical generator is selected from the group consisting of an organic peroxide and an organic perester. 
     
     
         6 . The composition of  claim 1 , further comprising
 d), at least one selected from the group consisting of a stabilizer and a further added substance.   
     
     
         7 . The composition of  claim 1 , further comprising
 e), a thermoplastic parent polymer, a silane-grafted parent polymer, or a silane-copolymerized parent polymer, and/or a monomer and/or prepolymer of said parent polymers, and/or a mixture of these.   
     
     
         8 . The composition of  claim 1 , wherein the silicon-comprising precursor compound of an organic acid is present and is in a form that is liquid, waxy, solid, or bound on a carrier material, and/or the organofunctional silane compound is present and is in a form that is liquid, highly viscous, waxy, solid, or bound on a carrier material. 
     
     
         9 . A masterkit, comprising the composition of  claim 1 , comprising:
 as component A, 0.1 to 10% by weight, in component A, of the at least one silicon-comprising precursor compound of an organic acid, or the at least one organic acid, or the one silicon-free precursor compound comprising an organic acid, is present, and,   making up 100% by weight of component A, one carrier material, one stabilizer, one added substance, or a mixture of these, and   optionally, as component B, from 60 to 99.9% by weight, in component B, of the organofunctional silane compound of the formula III
   (B) b SiR 4   a (OR 5 ) 3-b-a    (III),
 
   wherein   mutually independently, b is 0, 1, 2, or 3, and a is 0, 1, 2, or 3, with the proviso that, in formula III, b+a is smaller than or equal to (≦)3,   B, mutually independently, is
 a monovalent (R 7 ) 2 C═C(R 7 )-E q - group in formula III, in which R 7  are identical or different, and R 7  is a hydrogen atom or a methyl group or a phenyl group, E is —CH 2 —, —(CH 2 ) 2 —, —(CH 2 ) 2 —, —O(O)C(CH) 3 —, or —C(O)O—(CH 2 ) 2 —, q is 0 or 1, or 
 isoprenyl, hexenyl, cyclohexenyl, terpenyl, squalanyl, squalenyl, polyterpenyl, betulaprenoxy, cis/trans-polyisoprenyl, or 
 an R 6 -D p -[C(R 6 )═C(R 6 )—C(R 6 )═C(R 6 )] t -D p - group, in which R 6  are identical or different, and R 6  is a hydrogen atom or an alkyl group having from 1 to 3 carbon atoms, or an aryl group, or an aralkyl group, groups D are identical or different, and D is —CH 2 —, —(CH 2 ) 2 —, —(CH 2 ) 3 —, —O(O)C(CH 2 ) 3 —, or —C(O)O—(CH 2 ) 3 —, p is 0 or 1, and t is 1 or 2, 
   R 5  is, mutually independently, methyl, ethyl, n-propyl, or isopropyl,   R 4  is, mutually independently, a substituted or unsubstituted hydrocarbon group, and   optionally, from 0.05 to 10% by weight of a free-radical generator and,   optionally, from 0.05 to 10% by weight of at least one stabilizer, and/or   from 0.05 to 99.99% by weight of at least one carrier material, stabilizer, added substance, or a mixture of these,   summing to a total of 100% by weight in component B.   
     
     
         10 . A process for producing a compounded polymer material, the process comprising:
 1) reacting a mixture comprising at least one thermoplastic parent polymer with a) at least one silicon-comprising precursor compound of an organic acid and/or one organofunctional silane compound and, optionally, b) an organic acid, a silicon-free precursor compound comprising an organic acid, and a free-radical generator, in a compounding apparatus, or   2) reacting the mixture, first, with a) the organofunctional silane compound, and the free-radical generator, to give a material, and shaping the material subsequently, with addition of the at least one silicon-comprising precursor compound of an organic acid, the one silicon-free precursor compound comprising an organic acid, and/or the one organic acid, to give a second material, and crosslinking the second material by exposure to moisture, or   3) reacting the mixture first with a) at least one olefinic silicon-comprising precursor compound of an organic acid, and the free-radical generator, to give a material and shaping the material in a subsequent step, with addition of the at least one silicon-comprising precursor of an organic acid, the one silicon-free precursor compound comprising an organic acid, and/or the one organic acid, to give a second material, and crosslinking the second material by exposure to moisture, or   4) reacting a different mixture comprising at least one monomer and/or prepolymer of the at least one thermoplastic parent polymer with   a) the organofunctional silane compound, and the free-radical generator, to give a material, and shaping the material, subsequently, with addition of the at least one silicon-comprising precursor compound of an organic acid, the one organic acid, and/or the one silicon-free precursor compound comprising an organic acid, to give a second material, and then crosslinking the second material with exposure to moisture.   
     
     
         11 . A process for producing a compounded polymer material, the process comprising
 1) reacting a mixture comprising at least one thermoplastic parent polymer with component B of the masterkit and component A of the masterkit of  claim 9 , in a compounding apparatus, or   2) reacting the mixture first component B of the masterkit of  claim 9 , to give a material, and shaping the material subsequently, with addition of component A of the masterkit of  claim 9 , and crosslinking the second material by exposure to moisture, or   3) reacting a different mixture comprising at least one monomer and/or prepolymer of the at least one thermoplastic parent polymer with component B of the masterkit of  claim 9 , to give a material, and shaping the material subsequently, with addition of component A of the masterkit of  claim 9 , to give a second material, and then crosslinking the second material by exposure to moisture, or   4) reacting the mixture with a composition comprising: a) at least one silicon-comprising precursor compound of an organic acid, and/or one organofunctional silane compound; and, optionally, b) one organic acid, and/or one silicon-free precursor compound comprising an organic acid, or the masterkit of  claim 9 , in a monosil process, or   5) reacting the mixture with a composition comprising: a) at least one silicon-comprising precursor compound of an organic acid, and/or one organofunctional silane compound; and, optionally, b) one organic acid, and/or one silicon-free precursor compound comprising an organic acid, or the masterkit of  claim 9 , in a sioplas process, or   6) reacting the different mixture with a composition comprising: a) at least one silicon-comprising precursor compound of an organic acid, and/or one organofunctional silane compound; and, optionally, b) one organic acid, and/or one silicon-free precursor compound comprising an organic acid, or the masterkit of  claim 9 , in a copolymerization process.   
     
     
         12 . The process of  claim 1 , wherein at least one silane-grafted or silane-copolymerized, and/or filled or unfilled compounded polymer material, and/or crosslinked, filled, or crosslinked, unfilled polymer is produced. 
     
     
         13 . A polymer, a compounded polymer material, or an unfilled or filled plastic, obtained by the process of  claim 10 . 
     
     
         14 . A molding, obtained by the process of  claim 10 . 
     
     
         15 . A polymer kit, comprising:
 a composition comprising: a) at least one silicon-comprising precursor compound of an organic acid, and/or one organofunctional silane compound;   and, optionally,   b) one organic acid, and/or one silicon-free precursor compound comprising an organic acid, and/or the masterkit of  claim 9 , and   separately therefrom, at least one selected from the group consisting of a thermoplastic parent polymer, a silane-grafted parent polymer, a silane-copolymerized parent polymer, a monomer of the parent polymer, and prepolymer of the parent polymer.   
     
     
         16 . (canceled) 
     
     
         17 . The composition of  claim 3 , wherein the ester is present and is selected from the group consisting of a natural triglyceride, a synthetic triglyceride, and a phosphoglyceride. 
     
     
         18 . The composition of  claim 4 , wherein the free-radical generator is at least one selected from the group consisting of tert-butyl peroxypivalate, tert-butyl 2-ethylperoxyhexanoate, dicumyl peroxide, di-tert-butyl peroxide, tert-butyl cumyl peroxide, 1,3-di(2-tert-butylperoxyisopropyl)benzene, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hex-3-yne, di-tert-amyl peroxide, 1,3,5-tris(2-tert-butylperoxyisopropyl)benzene, 1-phenyl-1-tert-butylperoxyphthalide, alpha,alpha′-bis(tert-butylperoxy)diisopropylbenzene, 2,5-dimethyl-2,5-di-tert-butylperoxyhexane, 1,1-di(tert-butylperoxy)-3,3,5-trimethylcyclohexane, n-butyl 4,4-di(tert-butylperoxy)valerate, ethyl (3,3-di(tert-butylperoxy)butyrate, and 3,3,6,9,9-hexamethyl-1,2,4,5-tetraoxacyclononane. 
     
     
         19 . The masterkit of  claim 10 , wherein as component A, the at least one silicon-comprising precursor compound has formula I and/or II
   (A) z SiR 2   x (OR 1 ) 4-z-x    (I)
     (R 1 O) 3-y-u (R 2 ) u (A) y Si-A-Si(A) y (R 2 ) u (OR 1 ) 3-y-u    (II),
   wherein   mutually independently, z is 0, 1, 2, or 3, x is 0, 1, 2, or 3, y is 0, 1, 2, or 3, and u is 0, 1, 2, or 3, with the proviso that, in formula I, z+x is smaller than or equal to (≦)3, and, in formula II, y+u is independently smaller than or equal to (≦)2,   A is mutually independently in formula I and/or II a monovalent olefin group, and A in the form of a divalent moiety in formula II is a divalent olefin group,   R 1  is, mutually independently, a carbonyl-R 3  group, where R 3  corresponds to a hydrocarbon moiety, having from 1 to 45 carbon atoms, and   R 2  corresponds, mutually independently, to a hydrocarbon group.   
     
     
         20 . The composition of  claim 3 , further comprising:
 c), at least one free-radical generator.   
     
     
         21 . The composition of  claim 3 , further comprising:
 d), at least one selected from the group consisting of a stabilizer and a further added substance.