Hydrosilylation reaction catalysts and curable compositions and methods for their preparation and use

Patent metadata

Field	Value
Publication number	US-9073950-B2
Application number	US-201214343581-A
Country	US
Kind code	B2
Filing date	Nov 8, 2012
Priority date	Dec 1, 2011
Publication date	Jul 7, 2015
Grant date	Jul 7, 2015

Abstract

A composition contains (A) a hydrosilylation reaction catalyst and (B) an aliphatically unsaturated compound having an average, per molecule, of one or more aliphatically unsaturated organic groups capable of undergoing hydrosilylation reaction. The composition is capable of reacting via hydrosilylation reaction to form a reaction product, such as a silane, a gum, a gel, a rubber, or a resin. Ingredient (A) contains an iron-organosilicon ligand complex that can be prepared by reacting an iron carbonyl compound and an organosilicon ligand.

First claim

The invention claimed is:

1. A composition comprising: either ingredients comprising
(A) a catalytically active reaction product of
i) an iron carbonyl compound having general formula (i): Fe a (CO) b , where
subscript a is an integer with a value ranging from 1 to 3,
subscript b is an integer with a value ranging from 5 to 12; and

ii) a silicon containing ligand that coordinates with Fe, where the silicon containing ligand has, per molecule, at least one atom of Si and at least one aliphatically unsaturated group; and

(B) an aliphatically unsaturated compound having an average, per molecule, of one or more aliphatically unsaturated organic groups capable of undergoing hydrosilylation reaction; and
optionally (C) an SiH functional compound having an average, per molecule, of one or more silicon bonded hydrogen atoms; which is distinct from ingredients (A) and (B);
with the proviso that when ingredient (B) lacks a silicon bonded hydrogen atom, then the composition includes ingredient (C); or

ingredients comprising
(A) a catalytically active reaction product of
i) an iron carbonyl compound having general formula (i): Fe a (CO) b , where
subscript a is an integer with a value ranging from 1 to 3,
subscript b is an integer with a value ranging from 5 to 12; and

ii) a polyorganosiloxane ligand that coordinates with Fe, where the ligand has, per molecule, at least one aliphatically unsaturated group, and where the ligand is present in a molar excess based on the molar amount of ingredient i); and

optionally (C) an SiH functional compound having an average, per molecule, of one or more silicon bonded hydrogen atoms; which is distinct from ingredient (A) and ingredient ii);
with the proviso that when ingredient ii) lacks a silicon bonded hydrogen atom, then the composition includes ingredient (C).

2. The composition of claim 1 , where the composition further comprises one or more additional ingredients, which are distinct from ingredients (A), (B), and (C), and which are selected from the group consisting of (D) a spacer; (E) an extender, a plasticizer, or a combination thereof; (F) a filler; (G) a filler treating agent; (H) a biocide; (I) a stabilizer, (J) a flame retardant; (K) a surface modifier; (L) a chain lengthener; (M) an endblocker; (N) a flux agent; (O) an anti-aging additive; (P) a pigment; (Q) an acid acceptor (R) a rheological additive; (S) a vehicle; (T) a surfactant; (U) a corrosion inhibitor; and a combination thereof.

3. A method comprising: 1) reacting a composition comprising
(A) a catalytically active reaction product of
i) an iron carbonyl compound having general formula (i): Fe a (CO) b , where
subscript a is an integer with a value ranging from 1 to 2,
subscript b is an integer with a value ranging from 5 to 12; and

ii) a silicon containing ligand that coordinates with Fe, where the silicon containing ligand has, per molecule, at least one atom of Si and at least one aliphatically unsaturated group; and

(B) an aliphatically unsaturated compound having an average, per molecule, of one or more aliphatically unsaturated organic groups capable of undergoing hydrosilylation reaction; and
optionally (C) an SiH functional compound having an average, per molecule, of one or more silicon bonded hydrogen atoms; which is distinct from ingredients (A) and (B);
with the proviso that when ingredient (B) lacks a silicon bonded hydrogen atom, then the composition includes ingredient (C).

4. The method of claim 3 , further comprising irradiating the iron carbonyl compound and the ligand to form the catalytically active reaction product of ingredient (A) before step 1).

5. The method of claim 4 , further comprising removing a by-product from the catalytically active reaction product to yield an Fe-ligand complex free of the by-product before step 1).

6. A method for making the composition of claim 1 , comprising: mixing ingredients comprising ingredient (A), ingredient (B), and optionally ingredient (C) so as to make the composition.

7. A reaction product prepared by the method of claim 3 .

8. The reaction product of claim 7 , where the reaction product has a form selected from a silane, a gum, a gel, a rubber, and a resin.

9. A method comprising: either
a step comprising
1) exposing to UV radiation, ingredients comprising:
i) an iron carbonyl compound having general formula (i): Fe a (CO) b , where
subscript a is an integer with a value ranging from 1 to 3,
subscript b is an integer with a value ranging from 5 to 12; and

ii) a silicon containing ligand that coordinates with Fe, where the silicon containing ligand has, per molecule, at least one atom of Si and at least one aliphatically unsaturated group; or

a step comprising
1) exposing to UV radiation, ingredients comprising
i) an iron carbonyl compound having general formula (i): Fe a (CO) b , where
subscript a is an integer with a value ranging from 1 to 3,
subscript b is an integer with a value ranging from 5 to 12; and

ii) a polyorganosiloxane ligand that coordinates with Fe, where the ligand has, per molecule, at least one aliphatically unsaturated group and where the ligand is present in a molar excess based on the molar amount of ingredient i); and
optionally (C) an SiH functional compound having an average, per molecule, of one or more silicon bonded hydrogen atoms; which is distinct from ingredient (A) and ingredient ii);
with the proviso that when ingredient ii) lacks a silicon bonded hydrogen atom, then the composition includes ingredient (C).

10. The method of claim 9 , where ingredient i) is selected from the group consisting of: iron(0)pentacarbonyl and diironnonacarbonyl.

11. The method of claim 9 , where the ligand comprises unit formula:
(R 1 R 2 2 Si—R 3 1/2 ) c (R 1 R 2 Si—R 3 2/2 ) d (R 2 Si—R 3 3/2 ) e (Si—R 3 4/2 ) f (R 2 3 Si—R 3 1/2 ) g (R 2 2 Si—R 3 2/2 ) h ;

where subscript c is 0 or more; subscript d is 0 or more; subscript e is 0 or more; subscript f is 0 or more; with the proviso that (c+d+e+f)>0; subscript g is 0 or more; subscript h is 0 or more; each R 1 is independently an alkynyl group or an alkenyl group; each R 2 is independently an alkyl group, a cycloalkyl group, or an aryl group; and each R 3 is an oxygen atom or an amino group of formula ═NH.

12. The method of claim 11 , where the ligand is a silane of formula (ii): R 1 i SiR 2 (4-i) , where each R 1 is Vi, each R 2 is Me, and subscript i is 2, 3, or 4.

13. The method of claim 11 , where the ligand is a cyclic organosilicon compound of formula (iii): (R 1 R 2 Si—R 3 ) j , where each R 1 is Vi, each R 2 is Me, each R 3 is O or ═NH, and subscript j is an integer with a value of 3 to 5.

14. The method of claim 13 , where the ligand is a linear organosilicon compound of formula (iv): (R 1 k R 2 2-k Si—R 3 )—(R 1 R 2 Si—R 3 ) m (R 2 2 Si—R 3 2/2 ) n —(SiR 1 k R 2 2-k ) where each R 1 is Vi, each R 2 is Me, each R 3 is O or ═NH, subscript m is 1 or more, subscript n is 0 or more, and subscript k is 0 or 1.

15. The method of claim 11 , where the the ligand is a linear polyorganosiloxane of formula: (R 1 k R 2 2-k Si—O)—(R 1 R 2 Si—O) m (R 2 2 Si—O 2/2 ) n —(SiR 1 k R 2 2-k ), where each R 1 is Vi, each R 2 is Me, subscript m is 1 or more, subscript n is 0 or more, and subscript k is 0 or 1.

16. The method of claim 11 , where the ligand is a branched organosilicon compound of formula (v): (R 1 R 2 2 Si—R 3 1/2 ) 3 (R 2 Si—R 3 3/2 ), where each R 1 is Vi, each R 2 is Me, and each R 3 is O.

17. The method of c

Assignees

• Dow Corning

Inventors

• Kownacka Agnieszka
• Kownacki Ireneusz
• Marciniec Bogdan
• Nguyen Binh
• Surgenor Avril
• Taylor Richard
• Tzou Ming-Shin

Classifications

• B01J2231/323

  Hydrometalation, e.g. bor-, alumin-, silyl-, zirconation or analoguous reactions like carbometalation, hydrocarbation · CPC title

• B01J31/0274

  containing silicon (ligands in coordination complexes B01J31/1608) · CPC title

• B01J37/345

  of ultraviolet wave energy · CPC title

• B01J31/124

  Silicones or siloxanes or comprising such units · CPC title

• B01J2531/842

  Iron · CPC title