Process for the preparation of silylated polyurethane polymers using titanium-containing and zirconium-containing catalysts
The present invention relates to a process for preparing silylated polyurethane polymers which have increased stability under ambient condition or storage toward atmospheric moisture, in the presence of at least one of titanium-containing catalyst or zirconium-containing catalyst and to silylated polyurethane polymer compositions comprising these catalysts.
1. A process for the preparation of silylated polyurethane polymer (i) from the reaction of polyol (ii) and/or hydroxyl-terminated polyurethane (iii) with isocyanatosilane silylating agent (iv), or the reaction of isocyanate-terminated polyurethane (v) with amino-functional silane silylating agent (vi) and/or mercapto-functional silane silylating agent (vii), the process comprising
(a) employing at least one non-tin urethane-forming reaction catalyst (viii) for the preparation of hydroxyl-terminated polyurethane (iii), isocyanate-terminated polyurethane (v) and/or silylated polyurethane polymer (i), urethane-forming reaction catalyst (viii) being selected from the group consisting of titanium-containing catalyst and zirconium-containing catalyst having the general formula (II):
M (IV) L 4 (II)
wherein each M is titanium (IV) or zirconium (IV) , and L is a ligand selected from the group consisting of R 4 O—, where R 4 is a hydrocarbon group of from 1 to 10 carbon atoms, F—, Cl—, CH 3 C(═O)CH═CHC(CH 3 )O—, CH 2 ═CHC(═O)O—, CH 2 ═C(CH 3 )C(═O)O—, CH 2 CHC(═O)OCH 2 CH 2 C(═O)O—, CH 2 ═C(CH 3 )C(═O)OCH 2 CH 2 C(═O)O—, and cyclopentadienyl; and
(b) adding at least one color stabilizer selected from the group consisting of triphenyl phosphite, diphenyl-alkyl phosphites, phenyl-dialkyl phosphites, tris(nonylphenyl)phosphite, trilauryl phosphite, trioctadecyl phosphite, distearyl-pentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl) phosphite, diisodecyl pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl)-pentaerythritol diphosphite, bis(2,4-di-cumylphenyl)-pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl)-pentaerythritol diphosphite, diisodecyloxypentaerythritol diphosphite, bis(2,4-di-tert-butyl-6-methylphenyl)pentaerythritol diphosphite, bis(2,4,6-tris(tert-butylphenyl)pentaerythritol diphosphite, tristearyl sorbitol diphosphite, bis(2,4-di-tert-butyl-6-methylphenyl)-methyl phosphite, bis(2,4-di-tert-butyl-6-methylphenyl)-ethyl phosphite, 2,2′,2″-nitrilo-[triethyltris(3,3′,5,5′-tetra-tert-butyl-1,1′-biph-enyl-2,2′-diyl)phosphite], 2-ethylhexyl(3,3′,5,5′-tetra-tert-butyl-1,1′-biphenyl-2,2′-diyl)phosphite, trinonylphenol phosphite, phenyl diisodecyl phosphite, diphenyl isodecyl phosphite, diphenyl isooctyl phosphate, tetraphenyl dipropyleneglycol diphosphite, poly(dipropyleneglycol) phenyl phosphite, alkyl (C 12 -C 15 ) bisphenol A phosphite, alkyl (C 10 ) bisphenol A phosphite, triisodecyl phosphite, tris (tridecyl) phosphite and tris (dipropylene glycol) phosphite to the silylated polymer composition prepared in step (a).
2. The process of claim 1 wherein hydroxyl-terminated polyurethane (iii) is obtained by reacting a molar excess of the hydroxyl equivalents of polyol (ii) with respect to the isocyanate equivalents of polyisocyanate (ix) in the presence of urethane-forming reaction catalyst (viii).
3. The process of claim 1 wherein isocyanate-terminated polyurethane (v) is obtained by reacting a molar excess of the isocyanate equivalents of polyisocyanate (ix) with respect to the hydroxyl equivalents of polyol (ii) in the presence of urethane-forming reaction catalyst (viii).
4. The process of claim 1 wherein polyol (ii) is at least one member selected from the group consisting of polyether polyols, polyester polyols and polybutadienediols.
5. The process of claim 2 wherein polyisocyanate (ix) is at least one member selected from the group consisting of 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 4,4′-diphenyl-methanediisocyanate, 2,4′-diphenyl-methanediisocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4′-diisocyanate, hexamethylene diisocyanate, bis-(4-isocyanatocyclohexyl)methane and mixture of 2,4- and 4,4′-diphenylmethane-diisocyanates.
6. The process of claim 3 wherein polyisocyanate (ix) is at least one member selected from the group consisting of 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 4,4′-diphenyl-methanediisocyanate, 2,4′-diphenyl-methanediisocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4′-diisocyanate, hexamethylene diisocyanate, bis-(4-isocyanatocyclohexyl)methane and mixture of 2,4- and 4,4′-diphenylmethane-diisocyanates.
7. The process of claim 1 wherein isocyanatosilane silylating agent (iv) is represented by general formula (I):
OCN—R 1 —Si(R 2 ) a (OR 3 ) 3-a (I)
wherein
R 1 is an alkylene group containing from 1 to 12 carbon atoms;
R 2 is alkyl group containing from 1 to 8 carbon atoms;
R 3 is independently alkyl group containing from 1 to 6 carbon atoms; and
a is 0, 1 or 2.
8. The process claim 7 wherein isocyanatosilane silylating agent (iv) is at least one member selected from the group consisting of isocyanatomethyltrimethoxysilane, 3-isocyanatopropyltrimethoxysilane, isocyanatoisopropyltrimethoxysilane, 4-isocyanato-n-butyltrimethoxysilane, isocyanato-t-butyltrimethoxysilane, isocyanatomethylmethyldimethoxysilane, 3-isocyanatopropylmethyldimethoxysilane, isocyanatomethyltriethoxysilane, 3-isocyanatopropyltriethoxysilane, isocyanatomethylmethyldiethoxysilane, 3-isocyanatopropylmethyldiethoxysilane isocyanatoisopropyltriethoxysilane, 4-isocyanato-n-butyltriethoxysilane, isocyanato-t-butyltriethoxysilane.
9. The process of claim 1 wherein urethane-forming reaction catalyst (viii) is represented by general formula (II):
M (IV) L 4 (II)
wherein each M is titanium (IV) and L is a ligand selected from the group consisting of R 4 O—, where R 4 is a hydrocarbon group of from 1 to 10 carbon atoms.
10. The process of claim 9 wherein urethane-forming reaction catalyst (viii) is at least one titanium-containing catalyst selected from the group consisting of tetraisopropyl titanate, tetrabutyl titanate, ethyl alcohol and isopropyl alcohol, and mixtures thereof.
11. The process of claim 1 wherein urethane-forming reaction catalyst (viii) is at least one zirconium-containing catalyst selected from the group consisting of zirconium(IV) tetra-ethoxide, and zirconium(IV) tetra-propoxide.
12. The process of claim 1 wherein amino-functional silane silylating agent (vi) and mercapto-functional silane silylating agent (vii) are represented by general formula (III):
X—R 6 —Si(R 7 ) b (OR 8 ) 3-b (III)
wherein
X is an active hydrogen-containing group that is reactive for isocyanate, for example, —SH—, —NHR 9 in which R 9 is H, a linear, branched or cyclic hydrocarbon group of up to 8 carbon atoms, —R 10 —Si(R 11 ) c (OR 12 ) 3-c , —CH[C(═O)OR 11 ]CH 2 C(═O)OR 11 , CH[C(═O)OR 11 ]CHR 7 C(═O)OR 11 or —CH 2 CH 2 C(═O)OR 11 ,
each R 6 and R 10 is independently divalent hydrocarbon group of up to 12 carbon atoms, optionally containing one or more heteroatoms,
each R 7 and R 11 is independently a monovalent hydrocarbon group containing up to 8 carbon atoms,
each R 8 and R 12 is independently an alkyl group containing from 1 to 6 carbon atoms, and
b and c each independently is 0, 1 or 2.
13. The process of claim 12 wherein amino-functional silane silylating agent (vi) is at least one member selected from the group consisting of N-methyl-3-amino-2-methylpropyltrimethoxysilane, N-ethyl-3-amino-2-methylpropyltrimethoxysilane, N-ethyl-3-amino-2-methylpropyldiethoxymethylsilane, N-ethyl-3-amino-2-methylpropyltriethoxysilane, N-ethyl-3-amino-2-methylpropyl-methyldimethoxysilane, N-ethyl-3-amino-2,2-dimethylpropylmethyldimethoxysilane, N-ethyl-aminomethyltrimethoxysilane, N-ethyl-2-aminoethyltrimethoxysilane, N-ethyl-aminomethylmethyldimethoxysilane, N-butyl-3-aminopropyl trimethoxysilane, N-butyl-3-aminopropylmethydimethoxysilane, N-butyl-3-aminopropyl triethoxysilane, N-butyl-aminomethyltrimethoxysilane, N-butyl-2-aminoethylmethyldiethoxysilane, N-butyl-aminomethylmethydimethoxysilane, N-butyl-aminomethylmethydiethoxysilane, N-butyl-3-amino-2-methylpropyltrimethoxysilane, 3-(N-methyl-2-amino-1-methyl-1-ethoxy)-propyltrimethoxysilane, N-ethyl-4-amino-3,3-dimethyl-butyldimethoxymethylsilane, N-ethyl-4-amino-3,3-dimethylbutyltrimethoxy-silane, N-(cyclohexyl)-3-aminopropyltrimethoxysilane, N-(cyclohexyl)aminomethyltrimethoxysilane, N-(cyclohexyl) aminomethyltriethoxysilane, N-(cyclohexyl)aminomethyl methyldimethoxysilane, N-(cyclohexyl)aminomethyl methyldiethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltriethoxy-silane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N,N-bis-(3-trimethoxysilyl-2-methylpropyl)amine, N,H-bis-(3-trimethoxysilylmethyl)amine, N,N-bis-(triethoxysilylmethyl)amine, N,N-bis-(methyldimethoxysilylmethyl)amine, N,N-bis-(3-methyldiethoxysilylmethyl)amine, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane and N-(3-trimethoxysilylpropyl)-3-amino-2-methylpropyltrimethoxysilane, N-(3-methyldiethoxysilypropyl)-2-hydroxy-1-propyl carbamate and N-(3-methyldiethoxysilypropyl)-hydroxy-2-propyl carbamate.
14. The process of claim 12 wherein mercapto-functional silane silylating agent (vii) is at least one member selected from the group consisting of 2-mercaptoethyl trimethoxysilane, 3-mercaptopropyl trimethoxysilane, 2-mercaptopropyl triethoxysilane, 3-mercaptopropyl triethoxysilane, 3-mercaptopropyl tri-t-butoxysilane, 3-mercaptopropyl triisopropoxysilane, 2-mercaptoethyl dimethoxy ethoxysilane, 3-mercaptopropyl dimethoxy methylsilane, 3-mercaptopropyl methoxy dimethylsilane, 3-mercaptopropyl diethoxy methylsilane, 4-mercaptobutyl trimethoxysilane, 3-mercaptocyclohexyl-trimethoxysilane, 12-mercaptododecyl trimethoxy silane, 12-mercaptododecyl triethoxy silane, 2-mercapto-2-methylethyl-tripropoxysilane, 2-mercaptophenyl trimethoxysilane, 2-mercaptophenyl triethoxysilane, 2-mercaptotolyl trimethoxysilane, 2-mercaptotolyl triethoxysilane, 1-mercaptomethyltolyl trimethoxysilane, 1-mercaptomethyltolyl triethoxysilane, 2-mercaptoethylphenyl trimethoxysilane, 2-mercaptoethylphenyl triethoxysilane, 2-mercaptoethyltolyl trimethoxysilane, 2-mercaptoethyltolyl triethoxysilane, 3-mercaptopropylphenyl trimethoxysilane and 3-mercaptopropylphenyl triethoxysilane.
15. The process of claim 1 wherein urethane-forming reaction catalyst (viii) is employed in an amount of from 0.0003 to 0.01 part titanium or zirconium metal by weight based on 100 parts by weight of polyol (ii).
16. The silylated polyurethane polymer (i) of claim 15 containing urethane-forming reaction catalyst (viii) and being essentially tin-free.
17. An adhesive, sealant, composite, coating, or cosmetic product comprising the essentially tin-free silylated polyurethane polymer (i) of claim 16 .
18. The cured silylated polyurethane polymer obtained from silylated polyurethane polymer (i) of claim 15 and being essentially tin-free.