Process for preparing fluoroalkyl-containing organosilicon compounds, and their use

• US 5,869,728 A
• Filed: 10/21/1997
• Issued: 02/09/1999
• Est. Priority Date: 10/26/1996
• Status: Expired due to Term

• Current Assignee: Evonik Degussa GmbH
• Original Assignee: Huels Aktiengesellschaft
• Inventors: Monkiewicz, Jaroslaw, Standke, Burkhard, Horn, Michael, Frings, Albert-Johannes, Jenker, Peter
• Primary Examiner(s): Shaver, Paul F.
• Application Number:
  US08/955,290
• Time in Patent Office: 476 Days
• Field of Search: 556/465, 556/485, 556/479, 556/454, 556/450, 556/457, 556/458, 528/15
• US Class Current: 556/479
• CPC Class Codes: C03C 17/30 with silicon-containing compounds
• CPC Class Codes: C04B 41/4933 containing halogens, i.e. organohalogen silanes
• CPC Class Codes: C07F 7/14 Preparation thereof from optionally substituted halogenated silanes and hydrocarbons hydrosilylation reactions
• CPC Class Codes: C07F 7/1876 by reactions involving the formation of Si-C linkages
• CPC Class Codes: C08G 77/385 containing halogens
• CPC Class Codes: C23C 30/00 Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process C23C26/00, C23C28/00 take precedence
• CPC Class Codes: D06M 13/517 containing silicon-halogen bonds
• CPC Class Codes: D06M 15/657 containing fluorine

Abstract

Fluoroalkyl organosilicon compounds are prepared by reacting fluoroolefins with organosilicon compounds that contain at least one H--Si group, in the presence of a Pt(0) complex catalyst. Further, fluoroalkylalkoxy organosilicon compounds are prepared by esterifying fluoroalkyl organosilicon compounds. The process proceeds uniformly under mild conditions with high yields and selectivities.

Claims

1. A process for preparing fluoroalkyl organosilicon compounds comprising:

reacting, in the presence of a Pt(0) complex catalyst,

at least one fluoroolefin with

at least one organosilicon compound that contains at least one H--Si group.

2. The process as claimed in claim 1, wherein said Pt(0) complex catalyst comprises a KARSTEDT catalyst.

3. The process as claimed in claim 1, wherein said Pt(0) complex catalyst contains 0.01 to 20% by weight of platinum.

4. The process as claimed in claim 2, wherein said KARSTEDT catalyst is selected from the group consisting of bis 1,3-bis(eta-2-ethenyl)- 1,1,3,3-tetramethyidisiloxane!platinum(0), triphenylphosphine- 1,3bis(eta-2-ethenyl)-1,1,3,3-tetramethyldisiloxane!platinum(0) and 2,4,6,8-tetraethenyl-2,4,6,8-tetramethylcyclotetrasiloxaneplatinum(0).

5. The process as claimed in claim 1, wherein said fluoroolefin comprises a fluorolefin having the general formula (I):

space="preserve" listing-type="equation">R.sup.1 YCH═

CH.sub.2 (I)

wherein R¹ is a mono-, oligo-, or perfluorinated alkyl group having 1 to 20 carbon atoms or a mono-, oligo-, or perfluorinated aryl group having 6 to 10 carbon atoms, and Y is a --CH₂ --, --O-- or --S-- group.

6. The process as claimed in claim 1, wherein said organosilicon compound that contains at least one H--Si group comprises a hydrosilane having the general formula (II):

space="preserve" listing-type="equation">H.sub.(4-a-b) SiR.sup.2.sub.a X.sub.b (II)

wherein

R² is identical or different alkyl groups having 1 to 20 carbon atoms or aryl groups having 6 to 10 carbon atoms,

X is independently Cl or Br, and

a=0, 1, 2, or 3 and b=0, 1, 2, or 3 wherein 1≦

(a+b)≦

3.

7. The process as claimed in claim 1, wherein said organosilicon compound that contains at least one H--Si group comprises a disiloxane having the general formula (III):

space="preserve" listing-type="equation">R.sup.2.sub.a X.sub.b H.sub.(3-a-b) SiOSiH.sub.(3-a-b) R.sup.2.sub.a X.sub.b(III)

wherein

R² is identical or different alkyl groups of 1 to 20 carbon atoms or aryl groups having 6 to 10 carbon atoms,

X is independently Cl or Br, and

a=0, 1, or 2 and b=0, 1, or 2 wherein 1≦

(a+b)≦

2.

8. The process as claimed in claim 1, wherein organosilicon compound that contains at least one H--Si group comprises a cyclic siloxane having the general formula (IV):

space="preserve" listing-type="equation">(R.sup.2.sub.a X.sub.b SiO).sub.x (R.sup.2.sub.s X.sub.t H.sub.(2-s-t) SiO).sub.y (IV)

wherein

R² is identical or different alkyl groups of 1 to 20 carbon atoms or aryl groups having 6 to 10 carbon atoms,

X is independently Cl or Br,

a=0, 1, or 2 and b=0, 1, or 2 where (a+b)=2, and x is 0 to 5, s=0 or 1 and t=0 or 1 where 0≦

(s+t)≦

1, and y is 1 to 5 wherein 3 ≦

(x+y)≦

5.

9. The process as claimed in claim 1, wherein said organosilicon compound that has at least one H--Si group comprises a linear polysiloxane having the general formula (V):

space="preserve" listing-type="equation">R.sup.2.sub.a X.sub.b SiO(R.sup.2.sub.f X.sub.i SiO).sub.q (R.sup.2.sub.s X.sub.t H.sub.(2-s-t) SiO).sub.r SiR.sup.2.sub.a X.sub.b (V)

wherein

R² is identical or different alkyl groups of 1 to 20 carbon atoms or aryl groups having 6 to 10 carbon atoms,

X is Cl or Br,

a=0, 1, 2, or 3 and b=0, 1, 2, or 3 wherein (a+b)=3, f=0, 1, or 2 and i=0, 1, or 2 wherein (f+i)=2, and q≧

0, s=0 or 1 and t=0 or 1 wherein 0 ≦

(s+t)≦

1 and r≧

1 wherein 50≦

(q+r)≦

50,000.

10. The process as claimed in claim 1, wherein the weight ratio of the total amount of platinum to the total amount of said fluoroolefin is 1:

100 to 1;

100,000.

11. The process as claimed in claim 1, wherein the reaction is carried out at a temperature of 10°

to 200°

C.

12. The process as claimed in claim 1, wherein the reaction is carried out at a pressure of 1 to 50 bar abs.

13. The process as claimed in claim 1, further comprising esterifying the obtained fluoroalkyl organosilicon compounds with an alcohol selected from the group consisting of methanol, ethanol, n-propinol, i-propanol, n-butanol, i-butanol, t-butanol, 2-methoxyethanol, and mixtures thereof.

14. The process as claimed in claim 1, further comprising purifying the obtained fluoroalkyl organosilicon compounds by distillation.

15. A process for preparing a fluoroalkylalkoxy organosilicon compound having the general formula (VI):

space="preserve" listing-type="equation">R.sup.1 -Y-(CH.sub.2).sub.2 SiH.sub.a R.sup.2.sub.b (OR.sup.3).sub.(3-a-b)(VI)

wherein

R¹ is a mono-, oligo-, or perfluorinated alkyl group having 1 to 20 carbon atoms or a mono-, oligo-, or perfluorinated aryl group having 6 to 10 carbon atoms, and Y is a --CH₂ --, --O--, or --S-- group,

R² is identical or different alkyl groups having 1 to 20 carbon atoms or aryl groups having 6 to 10 carbon atoms,

R³ is an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 10 carbon atoms, and a=0, 1, or 2 and b=0, 1, or 2 wherein (a+b)≦

2,

comprising the steps of;

reacting, in the presence of a Pt(0) complex catalyst,

at least one fluoroolefin with

at least one organosilicon compound that contains at least one H--Si group;

esterifying with an alcohol; and

purifying by distillation a fluoroalkylalkoxy organosilicon compound having the general formula (VI);

space="preserve" listing-type="equation">R.sup.1 -Y-(CH.sub.2).sub.2 SiH.sub.a R.sup.2.sub.b (OR.sup.3).sub.(3-a-b)(VI)

wherein

R¹ is a mono-, oligo-, or perfluorinated alkyl group having 1 to 20 carbon atoms or a mono-, oligo-, or perfluoriniated aryl group having 6 to 10 carbon atoms, and Y is a --CH₂ --, --O--, or --S-- group,

R² is identical or different alkyl groups having 1 to 20 carbon atoms or aryl groups having 6 to 10 carbon atoms,

R³ is an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 10 carbon atoms, and a=0, 1, or 2 and b=0, 1, or 2 wherein (a+b)≦

2.

16. The process as claimed in claim 15, wherein said Pt(0) complex catalyst comprises a KARSTEDT catalyst.

17. The process is claimed in claim 15, wherein said fluoroolefin comprises a fluoroolefin having the general formula (1):

space="preserve" listing-type="equation">R.sup.1 YCH═

CH.sub.2 (I)

wherein R¹ is a mono-, oligo-, or perfluorinated alkyl group having 1 to 20 carbon atoms or a mono-, oligo-, or perfluorinated aryl group having 6 to 10 carbon atoms, and Y is a --CH₂ --, --O-- or --S-- group.

18. The process as claimed in claim 15, wherein said organosilicon compound that contains at least one H--Si group comprises a hydrosilane having the general formula (II):

space="preserve" listing-type="equation">H.sub.(4-a-b) SiR.sup.2.sub.a X.sub.b (II)

wherein

R² is identical or different alkyl groups having 1 to 20 carbon atoms or aryl groups having 6 to 10 carbon atoms,

X is independently Cl or Br, and

a=0, 1, 2, or 3 and b=0, 1, 2, or 3 wherein 1≦

(a+b)≦

3.

20. A surface-treating agent, comprising the fluoroalkyl organosilicon compound prepared by the process of claim 18.

19. A fluoroalkyl organosilicon compound produced by a process comprising:

reacting, in the presence of a Pt(0) complex catalyst, at least one fluoroolefin with at least one organosilicon compound that contains at least one H--Si group.