Process and composition for promoting hydrosilylation reactions using sterically hindered nitrogen-containing and phosphorus-containing compounds

• US 5,191,103 A
• Filed: 12/30/1991
• Issued: 03/02/1993
• Est. Priority Date: 12/30/1991
• Status: Expired due to Term

• Current Assignee: General Electric Company
• Original Assignee: Union Carbide Chemicals & Plastics Technology Corporation (Dow, Inc.)
• Inventors: Mehta, Kunj R., Reedy, James D.
• Primary Examiner(s): Shaver, Paul F.
• Application Number:
  US07/815,821
• Time in Patent Office: 428 Days
• Field of Search: 556/479, 502/162, 502/167
• US Class Current: 556/479
• CPC Class Codes: B01J 2231/323 Hydrometalation, e.g. bor-, alumin-, silyl-, zirconation or analoguous reactions like carbometalation, hydrocarbation
• CPC Class Codes: B01J 2531/828 Platinum
• CPC Class Codes: B01J 31/1805 the ligands containing nitrogen
• CPC Class Codes: B01J 31/181 Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
• CPC Class Codes: B01J 31/24 Phosphines , i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
• CPC Class Codes: C07F 7/0801 General processes
• CPC Class Codes: C07F 7/14 Preparation thereof from optionally substituted halogenated silanes and hydrocarbons hydrosilylation reactions
• CPC Class Codes: C08G 77/38 Polysiloxanes modified by chemical after-treatment C08G77/045 takes precedence
• CPC Class Codes: C08G 77/46 containing polyether sequences

Abstract

A process and a catalytic composition for carrying out a platinum catalyzed hydrosilylation reaction between an SiH-containing material and a terminal olefin. The process of the invention involves heating the reactants in the presence of a platinum catalyst and a promoter which is a hindered amine or phosphine, or acid salt thereof, the promoter containing at least 6 carbon atoms and having the formula ##STR1## Q is N or P; when Q is N, R is H, alkyl of 1-18 carbon atoms, nonterminal alkenyl of 4-18 carbon atoms, arylalkyl of 7-25 carbon atoms, or a derivative thereof; when Q is P, R is alkyl of 1-18 carbon atoms, nonterminal alkenyl of 4-18 carbon atoms, arylalkyl of 7-25 carbon atoms, or a derivative thereof; x is 0 or 1; R'"'"' is alkyl of 1-18 carbon atoms, nonterminal alkenyl of 4-18 carbon atoms, arylalkyl of 7-25 carbon atoms, or a derivative thereof; y is 0, 1, or 2; R" is a branched group having a 2° or 3° carbon atom bonded directly to Q, and is alkyl of 3-18 carbon atoms, nonterminal alkenyl of 4-18 carbon atoms, arylalkyl of 7-25 carbon atoms, or a derivative thereof; z is 1, 2, or 3 and z=3-x-y; and two R'"'"' groups, two R" groups, or one R'"'"' and one R" may be taken together to constitute a divalent moiety forming a 5-7 membered ring containing a Q atom. The catalytic composition comprises a catalytically active platinum-containing material and a promoter as defined above.

Claims

1. A process for carrying out a platinum catalyzed hydrosilylation reaction between an SiH-containing material and a terminal olefin, comprising:

heating said SiH-containing material and said olefin in the presence of a platinum catalyst and a promoter, said promoter comprising;

a hindered amine or phosphine, or acid salt thereof, containing at least 6 carbon atoms and having the formula ##STR6## Q is N or P;

when Q is N, R is H, alkyl of 1-18 carbon atoms, nonterminal alkenyl of 4-18 carbon atoms, arylalkyl of 7-25 carbon atoms, or a derivative thereof;

when Q is P, R is alkyl of 1-18 carbon atoms, non-terminal alkenyl of 4-18 carbon atoms, arylalkyl of 7-25 carbon atoms, or a derivative thereof;

x is 0 or 1;

R'"'"' is alkyl of 1-18 carbon atoms, nonterminal alkenyl of 4-18 carbon atoms, arylalkyl of 7-25 carbon atoms, or a derivative thereof;

y is 0, 1, or 2;

R" is a branched group having a 2°

or 3°

carbon atom bonded directly to Q, and is alkyl of 3-18 carbon atoms, nonterminal alkenyl of 4-18 carbon atoms, arylalkyl of 7-25 carbon atoms, or a derivative thereof;

z is 1, 2, or 3 and z=3-x-y; and

two R'"'"' groups, two R" groups, or one R'"'"' and one R" may be taken together to constitute a divalent moiety forming a 5-7 membered ring containing a Q atom.

2. The process of claim 1 wherein the hydrosilylation reaction is carried out in the absence of a solvent.

3. The process of claim 1 wherein the promoter comprises at least two R" groups.

4. The process of claim 1 wherein the promoter comprises a 5-7 membered ring containing a Q atom.

5. The process of claim 1 wherein the SiH-containing material is a polysiloxane or a silane, and the olefin is an alpha olefin.

6. The process of claim 1 wherein said olefin is an allyl started polyether containing at least 50% by weight oxyethylene units and at least one hydroxyl functionality.

7. The process of claim 1 wherein said promoter and the platinum catalyst are premixed before being employed in the hydrosilylation reaction.

8. The process of claim 1 wherein said promoter is 2,2,6,6-tetramethyl-4-piperidinol.

9. The process of claim 1 wherein said promoter is 2,2,6,6-tetramethyl-4-piperidinone.

10. A composition for use in hydrosilylation reactions, comprising:

(a) a catalytically active platinum-containing material; and

(b) a promoter as defined in claim 1.