# US 2014/0194627 A1 · Zinc Containing Hydrosilylation Catalysts and Compositions Containing the Catalysts

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- Number: US 2014/0194627 A1
- Document ID: US20140194627A1
- Status: Published application
- Kind: A1
- Application number: 14/235,819
- Filed: 2012-09-20
- Published: 2014-07-10
- Earliest claimed: 2011-09-20
- Applicants: Dow corning Corporation
- Inventors: Kurt Brandstadt; Simon Cook; Aswini Dash; Matthew Olsen; Avril Surgenor; Richard Taylor; Binh Nguyen; Ming-Shin Tzou
- Web page: https://patentgrep.com/patent/US20140194627A1

## CPC

- B01J 31/2295: {Cyclic compounds, e.g. cyclopentadienyls}
- B01J 31/0272: {containing elements other than those covered by B01J31/0201 - B01J31/0255}
- B01J 31/22: Organic complexes
- 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}
- B01J 31/2414: {comprising aliphatic or saturated rings}
- B01J 31/2433: {comprising aliphatic or saturated rings}
- B01J 37/00: Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- C07C 209/66: from or via metallo-organic compounds
- C07C 213/08: by reactions not involving the formation of amino groups, hydroxy groups or etherified or esterified hydroxy groups
- C07C 217/92: the nitrogen atom of at least one of the amino groups being further bound to a carbon atom of a six-membered aromatic ring
- C07D 213/32: Sulfur atoms
- C07D 213/38: having only hydrogen or hydrocarbon radicals attached to the substituent nitrogen atom
- C07D 213/53: Nitrogen atoms
- C07D 215/12: with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D 271/06: 1,2,4-Oxadiazoles; Hydrogenated 1,2,4-oxadiazoles
- C07D 295/135: with the ring nitrogen atoms and the substituent nitrogen atoms separated by carbocyclic rings or by carbon chains interrupted by carbocyclic rings
- C07D 307/52: Radicals substituted by nitrogen atoms not forming part of a nitro radical
- C07D 333/22: Radicals substituted by doubly bound hetero atoms, or by two hetero atoms other than halogen singly bound to the same carbon atom
- C07D 413/10: linked by a carbon chain containing aromatic rings
- C07D 413/14: containing three or more hetero rings
- C07F 1/00: Compounds containing elements of Groups 1 or 11 of the Periodic Table
- C07F 1/005: {without C-Metal linkages}
- C07F 1/08: Copper compounds
- C07F 3/06: Zinc compounds
- C07F 7/00: Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F 7/0805: {comprising only Si, C or H atoms}
- 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)}
- C07F 7/0872: {Preparation and treatment thereof}
- C07F 7/0879: {Hydrosilylation reactions}
- C07F 7/0889: {Reactions not involving the Si atom of the Si-O-Si sequence}
- C07F 7/0896: {Compounds with a Si-H linkage}
- C07F 7/1804: {Compounds having Si-O-C linkages (Si-O-acyl linkages C07F7/1896)}
- C07F 7/1876: {by reactions involving the formation of Si-C linkages}
- C07F 9/5045: {Complexes or chelates of phosphines with metallic compounds or metals}
- C07F 9/60: Quinoline or hydrogenated quinoline ring systems
- C07F 11/005: {compounds without a metal-carbon linkage}
- C07F 13/00: Compounds containing elements of Groups 7 or 17 of the Periodic Table
- C07F 13/005: {Compounds without a metal-carbon linkage}
- C07F 15/0033: {Iridium compounds}
- C07F 15/0046: {Ruthenium compounds}
- C07F 15/02: Iron compounds
- C07F 15/065: {without a metal-carbon linkage}
- C08G 77/08: characterised by the catalysts used
- G07F 13/00: Coin-freed apparatus for controlling dispensing or fluids, semiliquids or granular material from reservoirs
- B01J 2231/323: Hydrometalation, e.g. bor-, alumin-, silyl-, zirconation or analoguous reactions like carbometalation, hydrocarbation
- B01J 2531/16: Copper
- B01J 2531/17: Silver
- B01J 2531/46: Titanium
- B01J 2531/49: Hafnium
- B01J 2531/56: Vanadium
- B01J 2531/64: Molybdenum
- B01J 2531/74: Rhenium
- B01J 2531/821: Ruthenium
- B01J 2531/827: Iridium
- B01J 2531/842: Iron
- B01J 2531/845: Cobalt
- B01J 2531/847: Nickel
- C09K 3/00: Materials not provided for elsewhere
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07D: HETEROCYCLIC COMPOUNDS (macromolecular compounds C08)
- C07F: ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM (metal-containing porphyrins C07D487/22)
- C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- G07F: COIN-FREED OR LIKE APPARATUS (coin sorting G07D3/00; coin testing G07D5/00; {handling coins or paper currencies apart from payment activated apparatus G07D; payment architectures, schemes or protocols G06Q20/00})
- C09K: MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE

## 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 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 a metal-ligand complex that can be prepared by a method including reacting a metal precursor and a ligand.

## Claims

### Claim 1

A method comprising:
(1) combining ingredients comprising a Zn precursor and a ligand, thereby preparing a reaction product, where
the Zn precursor has formula (i) Zn-A2, where each A is independently a monovalent organic group, and
the ligand is one of
or
a compound of general formula (iii)
where Q1 is selected from N, S, and O, A51, is selected from nothing, H, and a monovalent organic group, A52, A53, A54, A55, A56, A57, A58, A59, A60, A61, and A62 are each independently selected from H and a monovalent organic group, with the provisos that
A58 is not MeO,
when Q1 is N, and A51 is H, then A52 is not C6H4OMe or mesityl,
when Q1 is S, A51 is nothing, A2 is alkyl or aryl, and A53 and A54 are monovalent organic groups,
when Q1 is O, A51 is nothing and A52 is selected from H and a monovalent organic group,
A62 and A61 may combine to form a ring structure,
A58 and A59 may combine to form a ring structure,
A59 and A60 may combine to form a ring structure, and
A60 and A61 may combine to form a ring structure.

### Claim 2 (depends on 1)

The method of claim 1, further comprising (2) combining a reducing agent with the reaction product.

### Claim 3

A method comprising:
(1) combining ingredients comprising a Zn precursor and a ligand, thereby preparing a reaction product, where
the Zn precursor has formula (i) Zn-A2, where each A is independently a halogen atom, and
the ligand is one of ligands
or
a compound of general formula (ii)
where, Q is selected from N and P, subscript b is an integer from 0 to 3, each A1 is independently selected from a monovalent organic group, a halogen atom, and H, A2 is selected from H, alkyl, aryl, aralkyl, and a heteroaromatic group, each A3 is independently selected from a halogen atom and a monovalent organic group, A4 is selected from H, alkyl, aryl, and aralkyl with the proviso that A4 is not phenyl, each A5 is independently selected from H, alkyl, aryl, and aralkyl; or
or
a group of general formula (vi)
where subscript g is an integer from 0 to 3, Q6 is selected from OH and a group of formula NHA27, where A27 is selected from H, alkyl, aryl, and aralkyl, Q7 is selected from groups of formula 0A28, SA29, and NHA30, where A28 and A29 are each independently selected from H, alkyl, and aryl, and A30 is selected from H, alkyl, and aryl, and aralkyl, and A21, A22, A23, A24, A25, and A26 are each independently selected from H, alkyl, and aryl; or
or
or
a compound of general formula (iii)
where Q1 is selected from N, S, and O, A51, is selected from nothing, H, and a monovalent organic group, A52, A53, A54, A55, A56, A57, A58, A59, A60, A61, and A62 are each independently selected from H and a monovalent organic group, with the provisos that
A58 is not MeO,
when Q1 is N, and A51 is H, then A52 is not C6H4OMe or mesityl,
when Q1 is S, A51 is nothing, A2 is alkyl or aryl, and A53 and A54 are monovalent organic groups,
when Q1 is O, A51 is nothing and A52 is selected from H and a monovalent organic group,
A62 and A61 may combine to form a ring structure,
A58 and A59 may combine to form a ring structure,
A59 and A60 may combine to form a ring structure, and
A60 and A61 may combine to form a ring structure; or
or
a compound of general formula (xiii)
where Q9 is selected from N and C, Q10 is selected from COOH and CSSH, A94, A95, and A97 are each independently selected from alkyl and aryl, A96 is selected from nothing, H, alkyl, and aryl, with the provisos that A95 and A96 may bond together to form a ring structure selected from a carbocycle, a heterocycle, aryl, aralkyl, and a heteroaromatic group; or
or
a compound of general formula (ix)
where each A86, A87, and A88 are each independently selected from H, alkyl, aryl, and a group of formula as
where * denotes a point of attachment, A39, A40, A41, A42, and A43 are each independently selected from H and a monovalent organic group, with the proviso A39, A41, and A43 are not methyl; or
or
a compound of general formula (v)
where subscript f is an integer from 0 to 4, each A17 is independently selected from alkyl and aryl, Q4 is selected from a group of formula COOH and a group of formula SA18, where A18 is selected from H, alkyl, and aryl, and Q5 is selected from a group of formula COOH and a group of formula NA19A20, where A19 and A20 are each independently selected from H, alkyl, and aryl; or
or
a compound of general formula (vii)
where Q8 is selected from O and S, A30 is selected from H, alkyl, and aryl, A31 is selected from H, alkyl, and aryl, A32, A33, and A34 are each independently selected from H and a monovalent organic group, each A35 is independently a monovalent organic group, and A36 is alkyl or aryl; or
or
a compound of general formula (x)
where Q10 is selected from O and S, subscript j is an integer from 0 to 5, each A44 is independently selected from H, alkyl, aryl, and a heteroatom containing group, and A45, A46, and A47 are each independently selected from H, alkyl, aryl, and a heteroatom containing group; or
or
a compound of general formula (xiv)
where A103, A101, A102, and A104 are each independently a monovalent organic group; or
or
a compound of general formula (iv),
where Q2 is selected from OH and a group of formula PA13A14, where A13 and A14 are each independently selected from alkyl, aryl, and cyclopentyl, Q3 is selected from OH and a group of formula NA15A16, where A15 and A16 are each independently selected from H and alkyl, and A11 and A12 are each independently selected from alkyl and aryl, subscript d is an integer from 0 to 4 and subscript e is an integer from 0 to 4; or
or
a compound of general formula (xv)
where subscript s is an integer from 0 to 3, each A110 is independently a monovalent organic group; A112 and A111 are each independently a monovalent organic group, A114 and A113 are each independently H or a monovalent organic group; or

### Claim 4 (depends on 3)

The method of claim 3, further comprising (2) combining an ionic activator with the reaction product.

### Claim 5

A method comprising:
(1) combining ingredients comprising a Zn precursor and a ligand, thereby preparing a reaction product, where
the Zn precursor has formula (i) Zn-A2, where each A is independently a halogen atom, and
the ligand is one of ligands
or
a compound of general formula (ii):
where, Q is selected from N and P, subscript b is an integer from 0 to 3, each A1 is independently selected from a monovalent organic group, a halogen atom, and H, A2 is selected from H, alkyl, aryl, aralkyl, and a heteroaromatic group, each A3 is independently selected from a halogen atom and a monovalent organic group, A4 is selected from H, alkyl, aryl, and aralkyl with the proviso that A4 is not phenyl, each A5 is independently selected from H, alkyl, aryl, and aralkyl; or
or
a compound of general formula (v)
where subscript f is an integer from 0 to 4, each A17 is independently selected from alkyl and aryl, Q4 is selected from a group of formula COOH and a group of formula SA18, where A18 is selected from H, alkyl, and aryl, and Q5 is selected from a group of formula COOH and a group of formula NA19A20, A19 and A20 are each independently selected from H, alkyl, and aryl; or
or
a compound of general formula (iii)
where Q1 is selected from N, S, and O, A51, is selected from nothing, H, and a monovalent organic group, A52, A53, A54, A55, A56, A57, A58, A59, A60, A61, and A62 are each independently selected from H and a monovalent organic group, with the provisos that
A58 is not MeO,
when Q1 is N, and A51 is H, then A52 is not C6H4OMe or mesityl,
when Q1 is S, A51 is nothing, A2 is alkyl or aryl, and A53 and A54 are monovalent organic groups,
when Q1 is O, A51 is nothing and A52 is selected from H and a monovalent organic group,
A62 and A61 may combine to form a ring structure,
A58 and A59 may combine to form a ring structure,
A59 and A60 may combine to form a ring structure, and
A60 and A61 may combine to form a ring structure; or
or
a compound of general formula (xiii)
where Q9 is selected from N and C, Q10 is selected from COOH and CSSH, A94, A95, and A97 are each independently selected from alkyl and aryl, A96 is selected from nothing, H, alkyl, and aryl, with the provisos that A95 and A96 may bond together to form a ring structure selected from a carbocycle, a heterocycle, aryl, aralkyl, and a heteroaromatic group; or
or
a compound of general formula (viii)
where Q8 and Q9 are each independently selected from O and S, A73 and A75 are each independently selected from H and a monovalent organic group, subscript i is an integer from 0 to 4, and each A74 is independently a monovalent organic group; or
or
a compound of general formula (iv),
where Q2 is selected from OH and a group of formula PA13A14, where A13 and A14 are each independently selected from alkyl, aryl, and cyclopentyl, Q3 is selected from OH and a group of formula NA15A18, where A15 and A16 are each independently selected from H and alkyl, and A11 and A12 are each independently selected from alkyl and aryl, subscript d is an integer from 0 to 4 and subscript e is an integer from 0 to 4; or
a compound of general formula (xi)
where subscript k is an integer from 0 to 4, each A48 is independently a monovalent organic group, A49, A50, and A51 are each independently a monovalent organic group; or
or
a compound of general formula (xii)
where subscript m is an integer from 0 to 4, Q12 is selected from OH, and a group of formula NA56A57, where A53, A54, A55, A56, and A57 are each independently selected from H and a monovalent organic group with the proviso that A54 or A55 are not tertiaryButyl.

### Claim 6 (depends on 5)

The method of claim 5, further comprising (2) combining the reaction product with an a reducing agent.

### Claim 7 (depends on 1)

The method of claim 1, where the reaction product comprises a Zn-ligand complex and a by-product of reaction of the Zn precursor and the ligand or of a side reaction therein.

### Claim 8 (depends on 7)

The method of claim 7, further comprising removing all or a portion of the by-product.

### Claim 9 (depends on 1)

The method of claim 1, further comprising using the product prepared by the method as a hydrosilylation catalyst.

### Claim 10 (depends on 2)

A composition comprising:
(A) a product prepared by the method of claim 2; 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
(c) a polyorganohydrogensiloxane.

### Claim 11 (depends on 4)

A composition comprising:
(A) a product prepared by the method of claim 4; 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
(C) a silane of formula R4eSiHf, where subscript e is 0, 1, 2, or 3; subscript f is 1, 2, 3, or 4, with the proviso that a sum of (e+f) is 4, and each R4 is independently a halogen atom or a monovalent organic group.

### Claim 12 (depends on 10)

The composition of claim 10, 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.

### Claim 13 (depends on 12)

A method for making the composition of claim 12, comprising:
mixing ingredients comprising ingredients (A), (B), and (C); or
mixing ingredients comprising ingredients (A) and (B), and optionally one or more of (D), (E), (F), (G), (H), (I), (J), (K), (L), (M), (N), (O), (P), (Q), (R), (S), (T), and (U) to form a curing agent and mixing ingredients comprising ingredients (B), and (C) and optionally one or more of (D), (E), (F), (G), (H), (I), (J), (K), (L), (M), (N), (O), (P), (O), (R), (S), (T), and (U) to form a base, and mixing the curing agent and the base;
so as to make the composition.

### Claim 14 (depends on 10)

A reaction product of the composition of claim 10.

### Claim 15 (depends on 6)

A composition comprising:
(A) a product prepared by the method of claim 6; 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
(C) a silane of formula R4eSiHf, where subscript e is 0, 1, 2, or 3; subscript f is 1, 2, 3, or 4, with the proviso that a sum of (e+f) is 4, and each R4 is independently a halogen atom or a monovalent organic group.

### Claim 16 (depends on 15)

The composition of claim 15, 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.

### Claim 17 (depends on 16)

A method for making the composition of claim 16, comprising:
mixing ingredients comprising ingredients (A), (B), and (C); or
mixing ingredients comprising ingredients (A) and (B), and optionally one or more of (D), (E), (F), (G), (H), (I), (J), (K), (L), (M), (N), (O), (P), (Q), (R), (S), (T), and (U) to form a curing agent and mixing ingredients comprising ingredients (B), and (C) and optionally one or more of (D), (E), (F), (G), (H), (I), (J), (K), (L), (M), (N), (O), (P), (Q), (R), (S), (T), and (U) to form a base, and mixing the curing agent and the base;
so as to make the composition.

### Claim 18 (depends on 15)

A reaction product of the composition of claim 15.

### Claim 19 (depends on 11)

The composition of claim 11, 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.

### Claim 20 (depends on 19)

A method for making the composition of claim 19, comprising:
mixing ingredients comprising ingredients (A), (B), and (C); or
mixing ingredients comprising ingredients (A) and (B), and optionally one or more of (D), (E), (F), (G), (H), (I), (J), (K), (L), (M), (N), (O), (P), (Q), (R), (S), (T), and (U) to form a curing agent and mixing ingredients comprising ingredients (B), and (C) and optionally one or more of (D), (E), (F), (G), (H), (I), (J), (K), (L), (M), (N), (O), (P), (Q), (R), (S), (T), and (U) to form a base, and mixing the curing agent and the base;
so as to make the composition.