Process for the preparation of silylated polymers having low color and color stability
View Patent ↗A batch or continuous process for preparing silylated polymers having low color and color stability comprising silylating a prepolymer having reactive functional groups with a silylating agent and optionally quenching the silylated polymer, where a stabilizer package containing at least one phosphite stabilizing agent is used.
1. A quenched silylated polymer having the general Formula (11):
each occurrence of A 1 is a functional group selected from the group consisting of —O—, —S— and —NH—;
each occurrence of A 2 is a functional group selected from the group consisting of —S—, —NR 6 , where R 6 is selected from the group consisting of hydrogen, an alkyl group containing from 1 to about 10 carbon atoms, cycloalkyl group containing from about 5 to about 10 carbon atoms, an aralkyl group containing from about 7 to about 10 carbon atoms, phenyl and —CH[(C═O)OR 7 ]CHR 8 C(═O)OR 7 , where R 7 is an alkyl group of from 1 to about 10 carbon atoms, a cycloalkyl group of from about 5 to about 10 carbon atoms, an aryl group of from about 6 to about 10 carbon atoms, and aralkyl group of from about 7 to about 10 carbon atoms and R 8 is an alkyl group of from 1 to about 10 carbon atoms, a cycloalkyl group of from about 5 to about 10 carbon atoms, an aryl group of from about 6 to about 10 carbon atoms, and aralkyl group of from about 7 to about 10 carbon atoms;
R 1 is an organic group containing from about 50 to about 4,000 carbon atoms and at least one functional group selected from group consisting of —O—, —S—, —OC(═O)NH—, —R 2 NC(═O)NH—, —C(═O)O—, —OC(═O)O—, —OCHR 2 O—, —C(═O)NR 2 — and —NR 2 —, wherein each occurrence of R 2 is independently hydrogen, an alkyl group containing from 1 to about 6 carbon atoms or phenyl, preferably hydrogen;
R 4 is a divalent alkylene group containing from 1 to about 10 carbon atoms, a cycloalkylene group containing from about 5 to about 10 carbon atoms and an arylene group containing from about 6 to about 10 carbon atoms;
each occurrence of R 5 is an alkyl group of from 1 to about 18 carbon atoms or a —R 9 (OR 10 ) c OR 11 , where R 9 is an alkyl group of from 1 to about 18 carbon atoms, R 10 is a divalent alkylene group of from about 2 to about 4 carbon atoms, and R 11 is an alkyl group of from 1 to about 10 carbon atoms or —C(═O)R 12 , where R 12 is hydrogen, or an alkyl group of from 1 to about 6 carbon atoms, and
the subscripts a, b, c and h are integers where a is 2 to about 5, b is 0 to about 2, c is 0 to about 5, and h is 1 to 6, with the proviso that when A 1 is —O— or —S—, then A 2 is —NH—.
2. The quenched silylated polymer of claim 1 , wherein R 1 is derived from poly(oxyethylene) diols, the poly(oxypropylene) diols, poly(oxyethylene-oxypropylene)diols, polyoxyalkylene triols, polytetramethylene glycols, polyacetals, polyhydroxy polyacrylates, polyhydroxy polyester amides, polyhydroxy polythioethers, polycaprolactone diols or polycaprolactone triols.
3. The quenched silylated polymer of claim 1 , wherein R 1 is derived from a poly(alkylene oxide) diol.
4. The quenched silylated polymer of claim 2 , wherein poly(oxypropylene)diol has a number average molecular weight of from 4,000 to 20,000 grams/mole.
5. The quenched silylated polymer of claim 1 , wherein R 1 is derived from a diisocyanate extended poly(propylene oxide) diol.
6. The quenched silylated polymer of claim 1 , wherein R 4 is —CH 2 —, —CH 2 CH 2 —, —CH 2 CH 2 CH 2 — or —CH 2 CH(CH 3 )CH 2 —.
7. The quenched silylated polymer of claim 1 , wherein R 5 is —CH 3 or —CH 2 CH 3 .
8. The quenched silylated polymer of claim 1 , wherein A 1 is —O— or —NH—.
9. The quenched silylated polymer of claim 1 , wherein A 2 is —NH— or —NCH 3 —.
10. The quenched silylated polymer of claim 1 , where a is 2.
11. The quenched silylated polymer of claim 1 , where h is 1 or 2.
12. The quenched silylated polymer of claim 4 , wherein R 4 is —CH 2 —, —CH 2 CH 2 —, —CH 2 CH 2 CH 2 — or —CH 2 CH(CH 3 )CH 2 —; R 5 is —CH 3 or —CH 2 CH 3 ; A 1 is —O— or —NH—I—; A 2 is —NH— or —NCH 3 —; and a is 2.
13. The quenched silylated polymer of claim 5 , wherein R 4 is —CH 2 —, —CH 2 CH 2 —, —CH 2 CH 2 CH 2 — or —CH 2 CH(CH 3 )CH 2 —; R 5 is —CH 3 or —CH 2 CH 3 ; A 1 is —O— or —NH—; A 2 is —NH— or —NCH 3 —; and a is 2.
14. A silylated polymer composition comprising:
(i) a quenched silylated polymer having silylated polymer having the general Formula (11):
each occurrence of A 1 is a functional group selected from the group consisting of —O—, —S— and —NH—;
each occurrence of A 2 is a functional group selected from the group consisting of —S—, —NR 6 , where R 6 is selected from the group consisting of hydrogen, an alkyl group containing from 1 to about 10 carbon atoms, cycloalkyl group containing from about 5 to about 10 carbon atoms, an aralkyl group containing from about 7 to about 10 carbon atoms, phenyl and —CH[(C═O)OR 7 ]CHR 8 C(═O)OR 7 , where R 7 is an alkyl group of from 1 to about 10 carbon atoms, a cycloalkyl group of from about 5 to about 10 carbon atoms, an aryl group of from about 6 to about 10 carbon atoms, and aralkyl group of from about 7 to about 10 carbon atoms and R 8 is an alkyl group of from 1 to about 10 carbon atoms, a cycloalkyl group of from about 5 to about 10 carbon atoms, an aryl group of from about 6 to about 10 carbon atoms, and aralkyl group of from about 7 to about 10 carbon atoms;
R 1 is an organic group containing from about 50 to about 4,000 carbon atoms and at least one functional group selected from group consisting of —O—, —S—, —OC(═O)NH—, —R 2 NC(═O)NH—, —C(═O)O—, —OC(═O)O—, —OCHR 2 O—, —C(═O)NR 2 — and —NR 2 —, wherein each occurrence of R 2 is independently hydrogen, an alkyl group containing from 1 to about 6 carbon atoms or phenyl, preferably hydrogen;
R 4 is a divalent alkylene group containing from 1 to about 10 carbon atoms, a cycloalkylene group containing from about 5 to about 10 carbon atoms and an arylene group containing from about 6 to about 10 carbon atoms;
each occurrence of R 5 is an alkyl group of from 1 to about 18 carbon atoms or a —R 9 (OR 10 ) c OR 11 , where R 9 is an alkyl group of from 1 to about 18 carbon atoms, R 10 is a divalent alkylene group of from about 2 to about 4 carbon atoms, and R 11 is an alkyl group of from 1 to about 10 carbon atoms or —C(═O)R 12 , where R 12 is hydrogen, or an alkyl group of from 1 to about 6 carbon atoms, and
the subscripts a, b, c and h are integers where a is 2 to about 5, b is 0 to about 2, c is 0 to about 5, and h is 1 to 6, with the proviso that when A 1 is —O— or —S—, then A 2 is —NH—; and
(ii) a stabilizing package comprising a phosphite stabilizer.
15. The silylated polymer composition of claim 14 , wherein the phosphite stabilizer has the general Formula (7):
wherein
each occurrence of R 20 is independently selected from the group consisting of a monovalent hydrocarbon containing from 1 to about 25 carbon atoms, a monovalent hydrocarbon containing from 1 to about 25 carbon atoms and at least one heteroatom selected from the group consisting of oxygen atom, nitrogen atoms and sulfur atom, and a polyvalent hydrocarbon containing from 1 to about 25 carbon atoms in which at least one carbon atom is bonded to the oxygen of the oxygen-phosphorus group and at least one carbon atom is covalently bonded to a carbon atom of the R 21 group;
each occurrence of R 21 is independently selected from the group consisting of a monovalent hydrocarbon containing from 1 to about 25 carbon atoms, a monovalent hydrocarbon containing from 1 to about 25 carbon atoms and at least one heteroatom selected from the group consisting of oxygen atom, nitrogen atoms and sulfur atom, and a polyvalent hydrocarbon containing from 1 to about 25 carbon atoms in which at least one carbon atom is bonded to the oxygen of the oxygen-phosphorus group and at least one carbon atom is covalently bonded to a carbon atom of the R 20 group; and
each occurrence of R 22 is independently a monovalent hydrocarbon containing 1 to about 25 carbon atoms and optionally containing at least one heteroatom selected from the group consisting of oxygen atom, nitrogen atoms and sulfur atom.
16. The silylated polymer composition of claim 15 , wherein R 20 , R 21 and R 22 groups that are monovalent alkyl groups, aryl groups or alkyl-substituted aromatic hydrocarbon groups.
17. The silylated polymer composition of claim 16 , wherein the phosphite stabilizer is tris(2,4-di-tert-butylphenyl)phosphite; 2-(2,4,8,10-tetratert-butylbenzo[d][1,3,2]benzodioxaphosphepin-6-yl)oxy-N,N-bis[2-(2,4,8,10-tetratert-butylbenzo[d][1,3,2]benzodioxaphosphepin-6-yl)oxyethyl]ethanamine; bis(2,4-di-tert-butyl-6-methylphenyl)-ethyl-phosphite; 3,9-bis-(2,4-di-tert-butyl-phenoxy)-2,4,8,10-tetraoxa-3,9-diphospha-spiro[5.5]undecane; or mixtures thereof.
18. The silylated polymer composition of claim 16 , wherein the stabilization package comprises a sterically hindered phenol.
19. The silylated polymer composition of claim 18 , wherein the sterically hindered phenol has the general Formula (5):
wherein each occurrence of R 18 is a monovalent or polyvalent organic radical of from 1 to about 50 carbon atoms and optionally containing substituents selected from group consisting of a hydroxyl group —OH; an amide group —C(═O)N(−) 2 ; an ester group —C(═O)O—; an isocyanurate group
an ether group —O—; an amine group —NH—; a hydrazide group —C(═O)N(−)NH(−) 2 —; a sulfide group, —S—; and combinations thereof.
20. The silylated polymer composition of claim 18 , wherein the sterically hindered phenol has the general Formula (6):
wherein
R 19 is a divalent, trivalent or tetravalent organic group of from 1 to about 50 carbon atoms and optionally containing substituents selected from group consisting of a hydroxyl group —OH; an amide group —C(═O)N(−) 2 ; an ester group —C(═O)O—; an isocyanurate group
an ether group —O—; an amine group —NH—; a hydrazide group —C(═O)N(−)NH(−) 2 —; a sulfide group —S—; and combination thereof; and the subscript i is an integer of from about 2 to about 4.
21. The silylated polymer composition of claim 16 , wherein the sterically hindered phenol is 4-[[3,5[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]-2,4,6-trimethylphenyl]methyl]-2,6-ditert-butylphenol; octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate; 3-(3,5-ditert-butyl-4-hydroxyphenyl)-N′-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyl]propanehydrazide; ethylenebis(oxyethylene)bis-3,5-tert-butyl-4-hydroxy-m-tolyl)-propionate; pentaerythritol tetrakis(3-(3,5-di-tert-4-hydroxyphenyl)propionate; thiodiethylene bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate-N,N′-hexane-1,6-diylbis(3-(3,5-di-tert-butyl-4-hydroxylphenylpropionamide); 1,3,5-tris-(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3-5-triazine-2,4,6(1H,3H,5H—)-trione; 3,5-di-tert-buytl-4-hydroxy-toluene; 4,4-methylene-bis(3,5-di-tert-butylphenol); or mixtures thereof.
22. The silylated polymer composition of claim 14 , further comprising at least one other silylated polymer where the other silylated polymer has not been quenched.