# US 12,215,117 B2 · Method of preparing acryloxy-functional organosilicon compounds

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- Number: US 12,215,117 B2
- Document ID: US12215117B2
- Status: Granted
- Kind: B2
- Application number: 17/418,949
- Filed: 2019-12-27
- Published: 2022-04-21
- Granted: 2025-02-04
- Earliest claimed: 2018-12-31
- Assignees: Dow Silicones Corporation; Dow Global Technologies LLC
- Applicants: Dow Silicones Corporation; Dow Global Technologies LLC
- Inventors: Jason Fisk; Nanguo Liu; Muhunthan Sathiosatham; Michael Telgenhoff; Thu Vi
- Web page: https://patentgrep.com/patent/US12215117B2

## CPC

- 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}
- B01J 31/1616: {Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts (catalysts comprising molecular sieves B01J29/00)}
- C08G 77/16: to hydroxy groups
- C08G 77/20: containing silicon bound to unsaturated aliphatic groups
- C08G 77/38: Polysiloxanes modified by chemical after-treatment
- C08K 5/101: of monocarboxylic acids
- C07F: ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM (metal-containing porphyrins C07D487/22)
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08K: Use of inorganic or non-macromolecular organic substances as compounding ingredients (paints, inks, varnishes, dyes, polishes, adhesives C09)

## Abstract

A method of preparing an acryloxy-functional organosilicon compound is provided. The method comprises reacting (A) an initial organosilicon compound and (B) an acrylate compound in the presence of (C) a catalyst. The initial organosilicon compound (A) has one alcohol functional group (i.e., is monohydroxyl functional). The catalyst (C) has the formula M[RC(O)CHC(O)R]4, where M is a group IV transition metal and each R is an independently selected substituted or unsubstituted hydrocarbyl group. An acryloxy-functional organosilicon compound prepared by the method is also provided. The acryloxy-functional organosilicon compound is prepared in increased purity, without relying on toxic catalysts.

## Claims

### Claim 1

A method of preparing an acryloxy-functional organosilicon compound, said method comprising:
reacting (A) an initial organosilicon compound having one alcohol group and (B) an acrylate compound in the presence of (C) a catalyst having the formula M[RC(O)CHC(O)R]4, where M is a group IV transition metal and each R is an independently selected substituted or unsubstituted hydrocarbyl group, thereby preparing the acryloxy-functional organosilicon compound;
wherein the initial organosilicon compound (A) is mono-hydroxy functional and comprises a branched siloxy group.

### Claim 2 (depends on 1)

The method of claim 1, wherein in the catalyst (C): (i) M is Zr or Hf; (ii) each R is independently CH3 or CH2CH3; or (iii) both (i) and (ii).

### Claim 3 (depends on 1)

The method of claim 1, wherein the initial organosilicon compound (A) has the following formula:
[R33SiO1/2]a[R32SiO2/2]b[R3SiO3/2]c[SiO4/2]d,
where each R3 is independently selected from substituted or unsubstituted hydrocarbyl groups and linear or branched siloxy groups, with the proviso that one R3 comprises an alcohol group; and subscripts a, b, c, and d are each mole fractions such that a+b+c+d=1, with the proviso that a+b+c>0.

### Claim 4 (depends on 1)

The method of claim 1, wherein: (i) the initial organosilicon compound (A) and the acrylate compound (B) are reacted in a molar ratio of from 0.1 to 20 (A):(B); (ii) the initial organosilicon compound (A) and the acrylate compound (B) are reacted at a temperature of from 25 to 180° C., optionally from 80 to 120° C.; (iii) the catalyst (C) is utilized in the reaction in an amount of from 0.05 to 10 mole % based on the combined amounts of components (A), (B), and (C); or (iv) any combination of (i) to (iii).

### Claim 5 (depends on 1)

The method of claim 1, wherein the acrylate compound (B) has the following formula:
where R1 is selected from substituted or unsubstituted hydrocarbyl groups and H; and R2 is a substituted or unsubstituted hydrocarbyl group having from 1 to 4 carbon atoms.

### Claim 6 (depends on 5)

The method of claim 5, wherein in the acrylate compound (B): (i) R1 is H or CH3; (ii) R2 is CH3, CH2CH3, or CH2(CH2)2CH3; or (iii) both (i) and (ii).

### Claim 7 (depends on 1)

The method of claim 1, wherein the initial organosilicon compound (A) has the following formula:
where X is a divalent linking group; and each R3 is independently selected from substituted or unsubstituted hydrocarbyl groups and linear or branched siloxy groups.

### Claim 8 (depends on 7)

The method of claim 7, wherein the divalent linking group X comprises: (i) a substituted or unsubstituted hydrocarbon group having from 1 to 16 carbon atoms; (ii) a hydrocarbon moiety having the formula —(CH2)n—, where subscript n is from 1 to 16; (iii) an ether moiety; (iv) an alkylamino moiety; or (v) any combination of (i) to (iv).

### Claim 9 (depends on 1)

The method of claim 1, wherein the initial organosilicon compound (A) and the acrylate compound (B) are reacted in the presence of (D) a polymerization inhibitor.

### Claim 10 (depends on 9)

The method of claim 9, wherein the polymerization inhibitor (D) comprises: (i) a radical scavenger; (ii) an antioxidant; (iii) a light stabilizer; (iv) a UV-absorber; or (v) any combination of (i) to (iv).

### Claim 11 (depends on 1)

The method of claim 1, wherein reacting the initial organosilicon compound (A) and the acrylate compound (B) forms a reaction product comprising the acryloxy-functional organosilicon compound; and wherein the method further comprises isolating the acryloxy-functional organosilicon compound from the reaction product.

### Claim 12 (depends on 11)

The method of claim 11, wherein the reaction product further comprises an organic alcohol formed by reacting the initial organosilicon compound (A) and the acrylate compound (B); and wherein the method further comprises removing the organic alcohol from the reaction product.

### Claim 13 (depends on 1)

An acryloxy-functional organosilicon compound prepared in accordance with the method of claim 1.

### Claim 14 (depends on 13)

The acryloxy-functional organosilicon compound of claim 13, having the following formula:
wherein Y comprises an organosilicon moiety; X is a divalent linking group; and R1 is independently selected from substituted or unsubstituted hydrocarbyl groups and H.

### Claim 15 (depends on 14)

The acryloxy-functional organosilicon compound of claim 14, wherein the organosilicon moiety Y is a silane moiety having the formula (R3)3Si—, where each R3 is independently selected from substituted or unsubstituted hydrocarbyl groups and linear or branched siloxy groups.

### Claim 16 (depends on 14)

The acryloxy-functional organosilicon compound of claim 14, wherein the organosilicon moiety Y is an organopolysiloxane having the formula:
[R33SiO1/2]a[R32SiO2/2]b[R3SiO3/2]c[SiO4/2]d,
where each R3 is independently selected from substituted or unsubstituted hydrocarbyl groups and linear or branched siloxy groups, with the proviso that one R3 is a silicon-bonded divalent linking group; and subscripts a, b, c, and d are each mole fractions such that a+b+c+d=1, with the proviso that a+b+c>0.

### Claim 17 (depends on 14)

The acryloxy-functional organosilicon compound of claim 14, wherein: (i) divalent linking group X is a substituted or unsubstituted hydrocarbon group having from 1 to 16 carbon atoms; (ii) R1 is H or CH3; or (iii) both (i) and (ii).

### Claim 18 (depends on 14)

The acryloxy-functional organosilicon compound of claim 14, wherein the divalent linking group X comprises: (i) a substituted or unsubstituted hydrocarbon group having from 1 to 16 carbon atoms; (ii) a hydrocarbon moiety having the formula —(CH2)n—, where subscript n is from 1 to 16; (iii) an ether moiety; (iv) an alkylamino moiety; or (v) any combination of (i) to (iv).