Method for making an amino-functional polydiorganosiloxane using a removable acid catalyst
A method for preparing an amino-functional polydiorganosiloxane employs a removable catalyst. The method differs from previous methods in the selection of catalyst, order of addition of catalyst with respect to other starting materials, and catalyst removal.
1. A method for preparing an amino-functional polydiorganosiloxane comprising:
1) mixing and heating, at a temperature of 50° C. to 150° C., starting materials comprising
A) a silanol functional polydiorganosiloxane,
B) an aminoalkyl-functional alkoxysilane,
where amounts of starting materials A) and B) are such that a molar excess of silanol groups with respect to alkoxy groups is present, and
C) 0.1% to 0.5%, based on combined weights of all starting materials, of an endblocker having triorganosilyl groups; and thereafter
2) adding starting material D) 0.01% to 5%, based on weight of starting material B), of a carboxylic acid having a boiling temperature of 90° C. to 150° C. and pKa value of 1 to 5; thereby forming a reaction mixture;
3) mixing and heating the reaction mixture to form the reaction product and reduce amount of residual acid in the form of the carboxylic acid and/or carboxylate salt to 0 to <500 ppm, based on the weight of the amino-functional polydiorganosiloxane.
2. The method of claim 1 , where in step 2) the amount of the residual acid is reduced to 0 to <300 ppm, based on the weight of the amino-functional polydiorganosiloxane.
3. The method of claim 1 , where starting material A) is selected from the group consisting of
A1) a silanol end-blocked polydimethylsiloxane with a viscosity of 30 cP to 70 cP at room temperature, and
A2) a silanol end-blocked polydimethylsiloxane with a degree of polymerization of 4 to 8000.
4. The method of claim 1 , where starting material B) is selected from the group consisting of:
B1) 3-aminopropylmethyl dimethoxysilane,
B2) 3-aminopropylmethyl diethoxysilane,
B3) aminoethyl-aminoisobutyl methyl dimethoxy silane,
B4) aminoethyl-aminoisobutyl methyl diethoxysilane
B5) 3-aminopropyldimethyl ethoxysilane,
B6) 3-aminopropyldimethyl methoxysilane,
B7) 3-(2-aminoethylamino)propyl-dimethoxymethylsilane,
B8) 3-(2-aminoethylamino)propyl-diethoxymethylsilane,
B9) aminopropyl methyl dimethoxy silane,
B10) aminopropyl methyl diethoxysilane, and
B11) a combination of two or more of B1) to B10).
5. The method of claim 1 , where starting material C) is selected from the group consisting of:
C1) hexamethyldisilazane,
C2) trimethylmethoxysilane,
C3) trimethylethoxysilane, and
C4) a combination of two or more of C1), C2) and C3).
6. The method of claim 1 , where starting material D) is selected from the group consisting of:
D1) acetic acid,
D2) propionic acid, and
D3) both D1) and D2).
7. The method of claim 1 , where: i) all or a portion of starting material C) is added in step 1), ii) all or a portion of starting material D) is added in step 2), or both i) and ii).
8. The method of claim 7 , where: i) a portion of starting material C) is added in step 1), ii) a portion of starting material D) is added in step 2), or both i) and ii); and the method further comprises iii) adding a second portion of starting material C), iv) adding a second portion of starting material D), or both iii) and iv), in an additional step added to the method after step 2) and before step 3).
9. The method of claim 7 , where all of starting material C) is added in step 1), and all of starting material D) is added in step 2).
10. The method of claim 1 , where starting materials A) and B) are present in amounts such that a molar ratio of silanol groups to respect alkoxy groups is at least 1.1:1.
11. The method of claim 10 , where the molar ratio ranges from 1.2:1 to 2.0:1.
12. The method of claim 1 , where the catalyst is acetic acid or propionic acid, and step 3) is performed by heating the reaction product at a temperature of at least 90° C. at a pressure <100 mmHg for at least 2 hours.
13. The method of claim 12 , where step 3) is performed by heating the reaction product at a temperature of 100° C. to 150° C. at a pressure of 0 to <100 mmHg for 2 to 8 hours.
14. The method of claim 1 , where starting material B) comprises an amino-functional monoalkoxysilane.
15. The method of claim 1 , where the amino-functional polydiorganosiloxane is endcapped with an amino-functional group.
16. The method of claim 1 , the endblocker comprises C1) a monoalkoxysilane, C2) a silazane, or C3) both C1) and C2).
17. The method of claim 16 , the monoalkoxysilane has formula (V): R 4 3 SiOR 5 , where each R 4 is independently a monovalent organic group unreactive with silanol functionality and each R 5 is independently a monovalent hydrocarbon group of 1 to 6 carbon atoms.
18. The method of claim 16 , the silazane has formula (VI): (R 6 R 7 2 Si) 2 NH, where each R 6 is independently selected from the group consisting of a monovalent hydrocarbon group and a monovalent halogenated hydrocarbon group, each R 7 is an independently selected monovalent hydrocarbon group of 1 to 6 carbon atoms.