Aluminosiloxanes, titanosiloxanes, (poly)stannosiloxanes, and their preparation

• US 5,614,654 A
• Filed: 05/28/1996
• Issued: 03/25/1997
• Est. Priority Date: 05/30/1995
• Status: Expired due to Fees

• Current Assignee: Shin-Etsu Chemical Company Limited
• Original Assignee: Shin-Etsu Chemical Company Limited
• Inventors: Aoki, Shunji, Miyake, Masatoshi
• Primary Examiner(s): Shaver, Paul F.
• Application Number:
  US08/654,147
• Time in Patent Office: 301 Days
• Field of Search: 556/10, 556/173
• US Class Current: 556/10
• CPC Class Codes: C07F 7/0838 Compounds with one or more Si-O-Si sequences compounds with a ring containing only alternating Si and O atoms, i.e. cyclosilanes C07F7/21
• CPC Class Codes: C07F 7/2224 Compounds having one or more tin-oxygen linkages

Abstract

Novel aluminosiloxanes having an Al--O--Si linkage, titanosiloxanes having a Ti--O--Si linkage, and stannosiloxanes having a Sn--O--Si linkage in a molecule are provided. Aluminosiloxanes are formed by reacting aluminum alkoxides with cyclotrisiloxanes. Titanosiloxanes are formed by reacting titanium alkoxides with cyclotrisiloxanes. Stannosiloxanes are formed by reacting diorganotin dialkoxides with cyclotrisiloxanes. Reaction processes are simple.

Claims

1. An aluminosiloxane having at least one Al--O--Si linkage in its molecule and represented by the following general formula (1):

##STR27## wherein R is a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, R'"'"' is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, letters k, m, and n are positive integers inclusive of 0, and k+m+n≧

1.

2. A method for preparing an aluminosiloxane represented by the following general formula (1) of claim 1:

##STR28## wherein R is a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, R'"'"' is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, letters k, m, and n are positive integers inclusive of 0, and k+m+n≧

1,

said method comprising the step of reacting an aluminum alkoxide of the following general formula (2);

space="preserve" listing-type="equation">Al(OR'"'"').sub.3 (

     2)

wherein R'"'"' is as defined above with a cyclotrisiloxane of the following general formula (3);

##STR29## wherein R is as defined above.

9. The aluminosiloxane of claim 1, wherein the R groups are, independently, an alkyl, cycloalkyl, phenyl, tolyl or alkenyl group of 1-20 carbon atoms optionally substituted by cyano groups, alkoxy groups or halogen atoms;

the R'"'"' groups are, independently, an alkyl, cycloalkyl, phenyl or tolyl group of 1-10 carbon atoms optionally substituted by cyano groups, alkoxy groups or halogen atoms;

k, m and n are from 0 to 5 and k+m+n=1-15.

10. The method of claim 2, wherein the R groups are, independently, an alkyl, cycloalkyl, phenyl, tolyl or alkenyl group of 1-20 carbon atoms optionally substituted by cyano groups, alkoxy groups or halogen atoms;

the R'"'"' groups are, independently, an alkyl, cycloalkyl, phenyl or tolyl group of 1-10 carbon atoms optionally substituted by cyano groups, alkoxy groups or halogen atoms;

k, m and n are from 0 to 5 and k+m+n=1-15.

11. The method of claim 2, wherein the molar ratio of aluminum alkoxide to cyclotrisiloxane is from 3/1 to 45/1.

3. A titanosiloxane having at least one Ti--O--Si linkage in its molecule and represented by the following general formula (4 ):

##STR30## wherein R is a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, R'"'"' is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, letters a, b, c, and d are positive integers inclusive of 0, and a+b+c+d≧

1.

4. A method for preparing a titanosiloxane represented by the following general formula (4) of claim 3:

##STR31## wherein R is a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, R'"'"' is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, letters a, b, c, and d are positive integers inclusive of 0, and a+b+c+d≧

1,

said method comprising the step of reacting a titanium alkoxide of the following general formula (5);

space="preserve" listing-type="equation">Ti(OR'"'"').sub.4 (

     5)

wherein R'"'"' is as defined above with a cyclotrisiloxane of the following general formula (3);

##STR32## wherein R is as defined above.

12. The titanosiloxane of claim 3, w3herein the R groups are, independently, an alkyl, cycloalkyl, phenyl, tolyl or alkenyl group of 1-20 carbon atoms optionally substituted cyano groups, alkoxy groups or halogen atoms;

the R'"'"' groups are, independently, an alkyl, cycloalkyl, phenyl or tolyl group of 1-10 carbon atoms optionally substituted by cyano groups, alkoxy groups or halogen atoms;

a, b, c and d are from 0 to 5 and a+b+c+d=1-20.

13. The method of claim 4, wherein the R groups are, independently, an alkyl cycloalkyl, phenyl, tolyl or alkenyl group of 1-20 carbon atoms optionally substituted by cyano groups, alkoxy groups or halogen atoms;

the R'"'"' groups are, independently, an alkyl, cycloalkyl, phenyl or tolyl group of 1-10 carbon atoms optionally substituted by cyano groups, alkoxy groups or halogen atoms;

a, b, c and d are from 0 to 5 and a+b+c+d=1-20.

14. The method of claim 4, wherein the molar ratio of titanium alkoxide to cyclotrisiloxane is from 3/1 to 60/1.

5. A stannosiloxane of the following general formula (6):

##STR33## wherein R¹ and R² are independently selected from substituted or unsubstituted monovalent hydrocarbon groups having 1 to 20 carbon atoms,

R³ is independently a hydrogen atom or substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms,

letters x and y are positive integers inclusive of 0 with the proviso that both x and y are not equal to 0 at the same time.

7. A method for preparing a stannosiloxane of the following general formula (6) of claim 5:

##STR35## wherein R¹ and R² are independently selected from substituted or unsubstituted monovalent hydrocarbon groups having 1 to 20 carbon atoms,

R³ is independently a hydrogen atom or substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms,

letters x and y are positive integers inclusive of 0 with the proviso that both x and y are not equal to 0 at the same time,

said method comprising the step of reacting a tin compound of the following general formula (8);

space="preserve" listing-type="equation">R.sup.2.sub.2 Sn(OR.sup.1).sub.2 (

     8)

wherein R¹ and R² are as defined above with a cyclotrisiloxane of the following general formula (9);

space="preserve" listing-type="equation">(R.sup.3.sub.2 SiO).sub.3 (

     9)

wherein R³ is as defined above.

15. The stannosiloxane of claim 5, wherein the R¹ and R² groups are, independently, an alkyl, cycloalkyl, phenyl, tolyl or alkenyl group of 1-20 carbon atoms optionally substituted by cyano groups, alkoxy groups or halogen atoms;

the R³ groups are, independently, an alkyl, cycloalkyl, phenyl, tolyl or alkenyl group of 1-10 carbon atoms optionally substituted by cyano groups, alkoxy groups or halogen atoms; and

, 1≦

x+y≦

33.

16. The method of claim 7, wherein the R¹ and R² groups are, independently, an alkyl, cycloalkyl, phenyl, tolyl or alkenyl group of 1-20 carbon atoms optionally substituted by cyano groups, alkoxy groups or halogen atoms;

the R³ groups are, independently, an alkyl, cycloalkyl, phenyl, tolyl or alkenyl group of 1-10 carbon atoms optionally substituted by cyano groups, alkoxy groups or halogen atoms; and

, 1≦

x+y≦

33.

6. A polystannosiloxane of the following general formula (7):

##STR34## wherein R² is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms,

R³ is a hydrogen atom or substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms,

R⁴ is a hydrogen atom or substituted or unsubstituted monovalent hydrocarbon groups having 1 to 20 carbon atoms,

letters x and y are positive integers inclusive of 0 with the proviso that both x and y are not equal to 0 at the same time, and z is an integer of at least 2.

8. A method for preparing a polystannosiloxane of the following general formula (7) of claim 6:

##STR36## wherein R² is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms,

R³ is a hydrogen atom or substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms,

R⁴ is a hydrogen atom or substituted or unsubstituted monovalent hydrocarbon groups having 1 to 20 carbon atoms,

letters x and y are positive integers inclusive of 0 with the proviso that both x and y are not equal to 0 at the same time, and z is an integer of at least 2,

said method comprising the step of subjecting to hydrolysis and polycondensation a stannosiloxane of the following general formula (6);

##STR37## wherein R¹ is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, and R², R³, x and y are as defined above.

17. The polystannosiloxane of claim 6, wherein the R² groups are, independently, an alkyl, cycloalkyl, phenyl, tolyl or alkenyl group of 1-20 carbon atoms optionally substituted by cyano groups, alkoxy groups or halogen atoms;

the R³ groups are, independently, an alkyl, cycloalkyl, phenyl, tolyl or alkenyl group of 1-10 carbon atoms optionally substituted by cyano groups, alkoxy group or halogen atoms;

the R⁴ groups are, independently, hydrogen or an alkyl, cycloalkyl, phenyl, tolyl or alkenyl group of 1-20 carbon atoms optionally substituted by cyano groups, alkoxy groups or halogen atoms;

1≦

x+y≦

33; and

, z=2-1000.

18. The method of claim 8, wherein the R² groups are, independently, an alkyl, cycloalkyl, phenyl, tolyl or alkenyl group of 1-20 carbon atoms optionally substituted by cyano groups, alkoxy groups or halogen atoms;

the R³ groups are, independently, an alkyl, cycloalkyl, phenyl, tolyl or alkenyl group of 1-10 carbon atoms optionally substituted by cyano groups, alkoxy groups or halogen atoms;

the R⁴ groups are, independently, hydrogen or an alkyl, cycloalkyl, phenyl, tolyl or alkenyl group of 1-20 carbon atoms optionally substituted by cyano groups, alkoxy groups or halogen atoms;

1≦

x+y≦

33; and

, z=2-1000.