POLYISOCYANATE-POLYADDITION PRODUCTIONS
The invention relates to polyisocyanate polyaddition products and to the use of specific catalysts for their preparation, and to their use, in particular for the coating sector.
1 .- 15 . (canceled)
16 . A polyisocyanate polyaddition product obtained from
a) at least one aliphatic, cycloaliphatic, araliphatic and/or aromatic polyisocyanate,
b) at least one NCO-reactive compound,
c) at least one inorganic, tin-comprising catalyst,
d) optionally further catalysts and/or activators other than c),
e) optionally fillers, pigments, additives, thickeners, antifoams and/or other auxiliary substances and added ingredients, and
f) a protonic acid in an amount which is at least equimolar based on the catalyst mentioned under c) and not more than equimolar based on the NCO-reactive groups from the compound from b),
wherein the ratio of the weight of the tin from component c) and of the weight of component a) is less than 1000 ppm when component a) is an aliphatic polyisocyanate and less than 80 ppm when component a) is an aromatic polyisocyanate,
wherein the catalyst c) is a cyclic tin compound of formula I, II or III:
where n>1,
where n>1,
wherein
D represents —O—, —S— or —N(R 1 )—,
wherein R 1 represents a saturated or unsaturated, linear or branched, aliphatic or cycloaliphatic or an optionally substituted, aromatic or araliphatic radical having up to 20 carbon atoms, which can optionally comprise heteroatoms from the group oxygen, sulfur, nitrogen, or represents hydrogen or the radical
or R1 and L3 together represent —Z-L 5 -, and
D* represents —O— or —S—, and
X, Y and Z represent the same or different radicals selected from alkylene radicals of the formula —C(R 2 )(R 3 )—, —C(R 2 )(R 3 )—C(R 4 )(R 5 )— or —C(R 2 )(R 3 )—C(R 4 )(R 5 )—C(R 6 )(R 7 )— or ortho-arylene radicals of the formula
wherein R 2 to R 11 independently of one another represent saturated or unsaturated, linear or branched, aliphatic or cycloaliphatic or optionally substituted, aromatic or araliphatic radicals having up to 20 carbon atoms, which can optionally comprise heteroatoms from the group oxygen, sulfur, nitrogen, or represent hydrogen, and
L 1 , L 2 and L 5 independently of one another represent —O—, —S—, —OC(═O)—, —OC(═S)—, —SC(═)—, —SC(═S)—, —OS(═O) 2 O—, —OS(═O) 2 — or —N(R12)—,
wherein R 12 represents a saturated or unsaturated, linear or branched, aliphatic or cycloaliphatic or an optionally substituted, aromatic or araliphatic radical having up to 20 carbon atoms, which can optionally comprise heteroatoms from the group oxygen, sulfur, nitrogen, or represents hydrogen; and
L 3 and L 4 independently of one another represent —OH, —SH, —OR 13 , -Hal, —OC(═O)R 14 , —SR 15 , —OC(═S)R 16 , —OS(═O) 2 OR 17 , —OS(═O) 2 R 18 or —NR 19 R 20 , or L 3 and L 4 together represent -L 1 -X-D-Y-L 2 -,
wherein R 13 to R 20 independently of one another represent saturated or unsaturated, linear or branched, aliphatic or cycloaliphatic or optionally substituted, aromatic or araliphatic radicals having up to 20 carbon atoms, which can optionally comprise heteroatoms from the group oxygen, sulfur, nitrogen, or represent hydrogen.
17 . The polyisocyanate polyaddition product according to claim 16 , wherein L 3 and L 4 together represent -L 1 -X-D-Y-L 2 .
18 . The polyisocyanate polyaddition product according to claim 16 , wherein D is —N(R 1 )— and R 1 is hydrogen or an alkyl, aralkyl, alkaryl or aryl radical having up to 20 carbon atoms, or is the radical
19 . The polyisocyanate polyaddition product according to claim 17 , wherein R 1 is hydrogen or a methyl, ethyl, propyl, butyl, hexyl, octyl, Ph-, or CH 3 Ph- radical or is the radical
and wherein propyl, butyl, hexyl and octyl represent all isomeric propyl, butyl, hexyl and octyl radicals.
20 . The polyisocyanate polyaddition product according to claim 16 , wherein D* is —O—.
21 . The polyisocyanate polyaddition product according to claim 16 , wherein X, Y and Z independently of one another are alkylene radicals of the formula —C(R 2 )(R 3 )— or —C(R 2 )(R 3 )—C(R 4 )(R 5 )— or ortho-arylene radicals of the formula
and R 2 to R 5 independently of one another are hydrogen, alkyl, aralkyl, alkaryl or aryl radicals having up to 20 carbon atoms, and R 8 to R 11 independently of one another are hydrogen or alkyl radicals having up to 8 carbon atoms.
22 . The polyisocyanate polyaddition product according to claim 20 , wherein the radicals R 2 to R 5 independently of one another are hydrogen or alkyl radicals having up to 8 carbon atoms, and R 8 to R 11 independently of one another are hydrogen or methyl.
23 . The polyisocyanate polyaddition product according to claim 16 , wherein L 1 , L 2 and L 5 independently of one another are —N(R 12 )—, —S—, —SC(═S)—, —SC(═O)—, —OC(═S)—, —O— or —OC(═O)—, and R 12 is hydrogen or an alkyl, aralkyl, alkaryl or aryl radical having up to 20 carbon atoms.
24 . The polyisocyanate polyaddition product according to claim 22 , wherein L 1 , L 2 and L 5 independently of one another are —N(H)—, —N(CH 3 )—, —N(C 2 H 5 )—, —N(C 4 H 9 )—, —N(C 8 H 17 )—, —N(C 6 H 5 )—, —S—, —SC(═S)—, —SC(═O)—, —OC(═S)—, —O— or —OC(═O)—.
25 . The polyisocyanate polyaddition product according to claim 16 , wherein L 3 and L 4 independently of one another are —OH, —SH, —OR 13 , -Hal or —OC(═O)R 14 , and the radicals R 13 and R 14 have up to 20 carbon atoms.
26 . The polyisocyanate polyaddition product according to claim 24 , wherein L 3 and L 4 independently of one another are Cl—, MeO—, EtO—, PrO—, BuO—, HexO—, OctO—, PhO—, formate, acetate, propanoate, butanoate, pentanoate, hexanoate, octanoate, laurate, lactate or benzoate, wherein Pr, Bu, Hex and Oct represent all isomeric propyl, butyl, hexyl and octyl radicals.
27 . A process for the preparation of the polyisocyanate polyaddition product according to claim 16 , comprising reacting
a) at least one aliphatic, cycloaliphatic, araliphatic and/or aromatic polyisocyanate,
b) at least one NCO-reactive compound,
c) at least one inorganic, tin-comprising catalyst,
d) optionally further catalysts and/or activators other than c),
e) optionally fillers, pigments, additives, thickeners, antifoams and/or other auxiliary substances and added ingredients, and
f) a protonic acid in an amount which is at least equimolar based on the catalyst mentioned under c) and not more than equimolar based on the NCO-reactive groups from the compound from b),
with one another, wherein the ratio of the weight of the tin from component c) and of the weight of component a) is less than 1000 ppm when component a) is an aliphatic polyisocyanate and less than 80 ppm when component a) is an aromatic polyisocyanate, wherein the catalyst c) is a cyclic tin compound of formula I, II or III:
where n>1,
where n>1,
wherein
D represents —O—, —S— or —N(R 1 )—,
wherein R 1 represents a saturated or unsaturated, linear or branched, aliphatic or cycloaliphatic or an optionally substituted, aromatic or araliphatic radical having up to 20 carbon atoms, which can optionally comprise heteroatoms from the group oxygen, sulfur, nitrogen, or represents hydrogen or the radical
or R1 and L3 together represent —Z-L 5 - and,
D* represents —O— or —S—, and
X, Y and Z represent the same or different radicals selected from alkylene radicals of the formula —C(R 2 )(R 3 )—, —C(R 2 )(R 3 )—C(R 4 )(R 5 )— or —C(R 2 )(R 3 )—C(R 4 )(R 5 )—C(R 6 )(R 7 )— or ortho-arylene radicals of the formula
wherein R 2 to R 11 independently of one another represent saturated or unsaturated, linear or branched, aliphatic or cycloaliphatic or optionally substituted, aromatic or araliphatic radicals having up to 20 carbon atoms, which can optionally comprise heteroatoms from the group oxygen, sulfur, nitrogen, or represent hydrogen, and
L 1 , L 2 and L 5 independently of one another represent —O—, —S—, —OC(═O)—, —OC(═S)—, —SC(═)—, —SC(═S)—, —OS(═O) 2 O—, —OS(═O) 2 — or —N(R12)—,
wherein R 12 represents a saturated or unsaturated, linear or branched, aliphatic or cycloaliphatic or an optionally substituted, aromatic or araliphatic radical having up to 20 carbon atoms, which can optionally comprise heteroatoms from the group oxygen, sulfur, nitrogen, or represents hydrogen; and
L 3 and L 4 independently of one another represent —OH, —SH, —OR 13 , -Hal, —OC(═O)R 14 , —SR 15 , —OC(═S)R 16 , —OS(═O) 2 OR 17 , —OS(═O) 2 R 18 or —NR 19 R 20 , or L 3 and L 4 together represent -L 1 -X-D-Y-L 2 -,
wherein R 13 to R 20 independently of one another represent saturated or unsaturated, linear or branched, aliphatic or cycloaliphatic or optionally substituted, aromatic or araliphatic radicals having up to 20 carbon atoms, which can optionally comprise heteroatoms from the group oxygen, sulfur, nitrogen, or represent hydrogen.
28 . A coating composition comprising the polyisocyanate polyaddition product according to claim 16 .
29 . A coating obtained from the coating composition according to claim 28 .
30 . A substrate coated with the coating of claim 29 .