Method of stabilizing imino-functional silane

Patent metadata

Field	Value
Publication number	US-11230563-B2
Application number	US-201916574704-A
Country	US
Kind code	B2
Filing date	Sep 18, 2019
Priority date	Jul 15, 2016
Publication date	Jan 25, 2022
Grant date	Jan 25, 2022

Abstract

A method of stabilizing imino-functional silane involving adding thereto at least one Brønsted-Lowry base to inhibit, suppress or prevent the addition reactions of the imino-functional silane with itself to form a imino- and amino-functional silane and the subsequent deamination reactions to form conjugated carbon-carbon double bond-containing imino-functional silanes and stabilized imino-functional silanes containing the at least one Brønsted-Lowry base.

First claim

The invention claimed is:

1. A stabilized imino-functional silane which contains less than about 15 ppm proton source based on the weight of the stabilized imino-functional silane and contains less than about 2 weight percent conjugated carbon-carbon double bond-containing imino-functional silane based on the total weight of conjugated carbon-carbon double bond-containing imino-functional silane and imino-functional silane after storage at 25° C. for 4 weeks and wherein the imino-functional silane is an imino-functional alkoxysilane of general formula (I):

wherein:
R 0 is hydrogen, a monovalent hydrocarbon group of from 1 to about 20 carbon atoms or a monovalent heterocarbon group of from 1 to about 20 carbon atoms containing one or more heteroatoms;
R 1 is a divalent hydrocarbon group of from 1 to about 20 carbon atoms or a divalent heterocarbon group of from 1 to about 20 carbon atoms;
R 2 is an alkyl group of from 1 to about 5 carbon atoms;
R 3 is phenyl or an alkyl group of from 1 to about 8 carbon atoms;
G is a monovalent or polyvalent hydrocarbon group of from 1 to about 30 carbon atoms or a heterocarbon group of from 1 to about 30 carbon atoms containing one or more heteroatoms where the carbon of G which connects to the imino group is unsubstituted;
subscript a is 0, 1 or 2; and,
subscript x is 1 or 2.

2. The stabilized imino-functional silane of claim 1 , wherein the stabilized imino-functional silane contains less than about 1 ppm proton source based on the weight of the imino-functional silane.

3. The stabilized imino-functional silane of claim 1 , wherein the stabilized imino-functional silane contains less than about 0.1 weight percent conjugated carbon-carbon double bond-containing imino-functional silane based on the total weight of conjugated carbon-carbon double bond-containing imino-functional silane and contains less than about 1 ppm proton source based on the weight of the imino-functional silane.

4. The stabilized imino-functional silane of claim 1 , wherein the imino-functional silane is at least one member selected from the group consisting of:
aldimino-functional silane of general formula (IV):

wherein:
R 1 is a divalent hydrocarbon group of up to about 20 carbon atoms or a divalent heterocarbon group of up to about 20 carbon atoms containing one or more heteroatoms;
R 2 is an alkyl group of from 1 to about 5 carbon atoms;
R 3 is phenyl or an alkyl group of from 1 to about 8 carbon atoms;
Y 1 and Y 2 are hydrogen;
Y 3 is hydrogen, an unsubstituted or substituted alkyl group of up to about 10 carbon atoms containing one or more heteroatoms, an unbranched or branched alkyl or alkylenyl group of up to about 10 carbon atoms, a substituted or unsubstituted aryl or arylalkyl group of up to about 20 carbon atoms, or an —OR 4 , —OC(═O)—R 4 , —C(═O)OR 4 or C(═O)R 4 group in which R 4 is an unsubstituted or substituted alkyl group of from 3 to about 20 carbon atoms; and,
subscript a is 0, 1 or 2,

an aldimino-functional silane of general formula (VI):

wherein:
R 1 , R 2 , R 3 and subscript a have the aforestated meanings for aldimino-functional silane (IV);
R 5 and R 6 are hydrogen;
R 7 is hydrogen, a monovalent hydrocarbon group of up to about 20 carbon atoms, a heterocarbon group containing up to about 20 carbon atoms and one or more heteroatoms, or an alkoxycarboxyl group of from 2 to about 20 carbon atoms; and,
R 8 and R 9 each independently is a monovalent hydrocarbon group of up to about 20 carbon atoms, a heterocarbon group containing up to about 20 carbon atoms and one or more heteroatoms, or an alkoxycarboxyl group of from 2 to about 20 carbon atoms, or R 8 and R 9 and the carbon atom to which they are bonded form an unsubstituted or substituted ring of from about 5 to about 12 carbon atoms containing zero, one or more heteroatoms,

and a ketimino-functional silane of general formula (VIII):

wherein:
R 1 , R 2 , R 3 and subscript a each have one of the same meanings stated above for aldimino-functional silane (IV);
R 10 and R 11 each independently is a monovalent hydrocarbon group of up to about 20 carbon atoms or a monovalent heterocarbon group of up to about 20 carbon atoms containing one or more heteroatoms where the carbon of R 11 which connects to the imino group is unsubstituted; and,
subscript a is 0, 1 or 2.

5. The stabilized imino-functional silane of claim 1 , wherein the imino-functional silane is (1,3-dimethyl-butylidene)-(3-triethoxy-silanyl-propyl)-amine, (1,3-dimethyl-butylidene)-(3-trimethoxy-silanyl-propyl)-amine, (1,3-dimethyl-butylidene)-(2,2-dimethyl-4-triethoxysilanyl-butyl)-amine, isopropylidene-(3-methyl-diethoxy-silanyl-propyl)-amine, sec-butylidene-(3-triethoxy-silanyl-propyl)-amine, [3-(triethoxy-silanyl)-propyl]-(1-phenyl-ethylidene)-amine, ethylidene-(3-dimethyl-ethoxy-silanyl-propyl)-amine, (3-methyl-butylidene)-(3-triethoxy-silanyl-propyl)-amine, N sec-butylidene-N′-(3-trimethoxy-silanyl-propyl)-ethane-1,2-diamine or 3-(1-octylidene aminopropyltrimetheoxysilane.

6. The stabilized imino-functional silane of claim 1 , further comprising a Brønsted-Lowry base.

7. The stabilized imino-functional silane of claim 6 , wherein the amount of Brønsted-Lowry base added to the imino-functional silane is sufficient to inhibit self-addition and deamination reactions of the imino-functional silane.

8. The stabilized imino-functional silane of claim 6 , wherein the amount of Brønsted-Lowry base added to the imino-functional silane is at least 1 molar equivalent based on the moles of proton source present in the imino-functional silane.

9. The stabilized imino-functional silane of claim 6 , wherein the Brønsted-Lowry base is from about 0.0001 to about 0.1 weight percent, based on the weight of the imino-functional silane.

10. The stabilized imino-functional silane of claim 6 , wherein the Brønsted-Lowry base is at least one member selected from the group consisting of alkali metal and alkaline metal hydroxides, alkoxides and oxides.

11. The stabilized imino-functional silane of claim 10 , wherein the Brønsted-Lowry base is at least one member selected from the group consisting of LiOH, NaOH, KOH, CsOH, Mg(OH) 2 , Ca(OH) 2 , Ba(OH) 2 , NaOMe, KOMe, NaOEt, KOEt, CaO, MgO and BaO.

12. The stabilized imino-functional silane of claim 6 , wherein the imino-functional silane is (1,3-dimethyl-butylidene)-(3-triethoxy-silanyl-propyl)-amine, (1,3-dimethyl-butylidene)-(3-trimethoxy-silanyl-propyl)-amine, (1,3-dimethyl-butylidene)-(2,2-dimethyl-4-triethoxysilanyl-butyl)-amine, isopropylidene-(3-methyl-diethoxy-silanyl-propyl)-amine, sec-butylidene-(3-triethoxy-silanyl-propyl)-amine, [3-(triethoxy-silanyl)-propyl]-(1-phenyl-ethylidene)-amine, ethylidene-(3-dimethyl-ethoxy-silanyl-propyl)-amine, (3-methyl-butylidene)-(3-triethoxy-silanyl-propyl)-amine, N sec-butylidene-N′-(3-trimethoxy-silanyl-propyl)-ethane-1,2-diamine or 3-(1-octylidene aminopropyltrimetheoxysilane.

13. The stabilized imino-functional silane of claim 12 , wherein the Brønsted-Lowry base is at least one member selected from the group consisting of LiOH, NaOH, KOH, CsOH, Mg(OH) 2 , Ca(OH) 2 , Ba(OH) 2 , NaOMe, KOMe, NaOEt, KOEt, CaO, MgO and BaO.

Assignees

• Momentive Performance Mat Inc

Inventors

• Cruse Richard W
• Pinnow Matthew

Classifications

• C07F7/1804 Primary

  Compounds having Si-O-C linkages (Si-O-acyl linkages C07F7/1896) · CPC title

• C07F7/20

  Purification, separation · CPC title

• C07F7/1872 Primary

  Preparation; Treatments not provided for in C07F7/20 · CPC title

• C01D1/04

  Hydroxides · CPC title

• C07C31/04

  Methanol · CPC title