# US 5,684,111 A · Silylated dioxolane polymers and monomeric compounds

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- Number: US 5,684,111 A
- Document ID: US5684111A
- Status: Granted
- Kind: A
- Application number: 08/683,514
- Filed: 1996-06-14
- Granted: 1997-11-04
- Earliest claimed: 1996-06-14
- Assignees: E. I. Du Pont de Nemours and Company
- Inventors: Michael Joseph Michalczyk; Ming-Hong Hung; Lech Wilczek
- Web page: https://patentgrep.com/patent/US5684111A

## CPC

- C07F 7/12: Organo silicon halides
- C07F 7/1804: {Compounds having Si-O-C linkages (Si-O-acyl linkages C07F7/1896)}
- C08G 77/48: in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms (C08G77/42 takes precedence)
- C08G 77/50: by carbon linkages
- 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

## Abstract

This invention relates to novel polymeric and monomeric silane substituted fluorinated 1,3-dioxolane compounds and their preparation from 4,5-difluoro-1,3-dioxolane and difunctional or monofunctional silicon hydrides.

## Claims

### Claim 1

A polymer, comprising repeat units of formula I ##STR11## wherein: x is an integer from 2 to 100;
m is an integer from 1 to 50;
R.sup.1, R.sup.2, R.sup.3 and R.sup.4 are each independently C.sub.1 to C.sub.20 alkyl, aryl, cycloalkyl, halogen, C.sub.1 to C.sub.20 alkoxy, C.sub.2 to C.sub.20 fluoroalkoxy, trifluoropropyl, aryloxy, C.sub.1 to C.sub.20 acyloxy, oxysilyl or hydrogen;
Z is a divalent group selected from the group consisting of: O, S, and R.sup.6 N;
R.sup.6 is C.sub.1 to about C.sub.8 alkyl;
R.sup.7 and R.sup.8 are each independently C.sub.1 to C.sub.8 fluoroalkyl or fluorine;
Y is (CR.sup.9 R.sup.10).sub.k CR.sup.11 HCR.sup.13 R.sup.14 ;
R.sup.9, R.sup.10, R.sup.11, R.sup.13 and R.sup.14 are each independently hydrogen, C.sub.1 to about C.sub.8 alkyl or aryl; and
k is an integer from 0 to 10.

### Claim 2 (depends on 1)

The polymer of claim 1 wherein Z is selected from the group consisting of O or S.

### Claim 3 (depends on 1)

The polymer of claim 1 wherein m is 1 to 3.

### Claim 4 (depends on 1)

The polymer of claim 1 wherein R.sup.1, R.sup.2, R.sup.3 and R.sup.4 are C.sub.1 to C.sub.4 alkyl, C.sub.1 to C.sub.4 alkoxy, C.sub.2 to C.sub.4 fluoroalkoxy or chlorine.

### Claim 5

A process for the preparation of a polymer comprising repeat units of formula I ##STR12## wherein: x is an integer from 2 to 100;
m is an integer from 1 to 50;
R.sup.1, R.sup.2, R.sup.3 and R.sup.4 are each independently C.sub.1 to C.sub.20 alkyl, aryl, cycloalkyl, halogen, C.sub.1 to C.sub.20 alkoxy, C.sub.2 to C.sub.20 fluoroalkoxy, aryloxy, C.sub.1 to C.sub.20 acyloxy, oxysilyl or hydrogen;
Z is a divalent group selected from the group consisting of: O, S, and R.sup.6 N;
R.sup.6 is C.sub.1 to about C.sub.8 alkyl;
R.sup.7 and R.sup.8 are each independently C.sub.1 to C.sub.8 fluoroalkyl or fluorine;
Y is (CR.sup.9 R.sup.10).sub.k CR.sup.11 HCR.sup.13 R.sup.14 ;
R.sup.9, R.sup.10, R.sup.11, R.sup.13 and R.sup.14 are each independently hydrogen, C.sub.1 to about C.sub.8 alkyl or aryl; and
k is an integer from 0 to 10,
comprising, contacting a silicon hydride of formula II ##STR13## wherein R.sup.5 is C.sub.1 to C.sub.20 alkyl, aryl, vinyl or hydrogen and m, Z, R.sup.1, R.sup.2, R.sup.3 and R.sup.4 are as defined for formula I, with a divinyl dioxolane of formula III ##STR14## wherein R.sup.7, R.sup.8, R.sup.9, R.sup.10, R.sup.11, R.sup.13, R.sup.14 and k are as defined for formula I, in the presence of a transition metal catalyst to form a polymer comprising repeat units of formula I.

### Claim 6 (depends on 5)

The process of claim 5 wherein for the silicon hydride R.sup.1, R.sup.2, R.sup.3, R.sup.4 and R.sup.5 are C.sub.1 to C.sub.4 alkyl, C.sub.1 to C.sub.4 alkoxy, or oxysilyl.

### Claim 7 (depends on 5)

The process of claim 5 wherein the silicon hydride is selected from the group consisting of: 1,1,3,3-tetramethyldisiloxane; 1,3-diphenyl-1,3-dimethyldisiloxane, HSi(CH.sub.3).sub.2 OSi(CH.sub.3).sub.2 OSi(CH.sub.3).sub.2 H; and HSi(CH.sub.3)(OSi(CH.sub.3).sub.3)OSi(CH.sub.3)(OSi(CH.sub.3).sub.3)H.

### Claim 8 (depends on 5)

The process of claim 5 wherein the catalyst is Co.sub.2 (CO).sub.8 and Co.sub.2 (CO).sub.8-z L.sub.z, wherein z is 0 or an integer of 1 to 7, each L is independently Co, PR.sup.20.sub.3 or P(OR.sup.21).sub.3 ; R.sup.20 is hydrocarbyl; R.sup.21 is hydrocarbyl; and provided that when L is PR.sup.20.sub.3 only one or two of R.sup.20 is aryl.

### Claim 9

A compound of formula IA ##STR15## wherein: m is an integer from 0 to 50;
R.sup.15, R.sup.16, R.sup.17 and R.sup.18 are each independently C.sub.1 to C.sub.20 alkyl, aryl, cycloalkyl, halogen, C.sub.1 to C.sub.20 alkoxy, C.sub.2 to C.sub.20 fluoroalkoxy, aryloxy, C.sub.1 to C.sub.20 acyloxy, C.sub.1 to C.sub.14 fluorocarboxy; oxysilyl or hydrogen;
R.sup.19 is C.sub.1 to C.sub.20 alkyl, aryl, C.sub.1 to C.sub.20 alkoxy, C.sub.2 to C.sub.20 fluoroalkoxy, C.sub.1 to C.sub.20 carboxy, C.sub.1 to C.sub.14 fluorocarboxy, halogen, vinyl or hydrogen;
Z is a divalent group selected from the group consisting of: O, S, and R.sup.6 N;
R.sup.6 is C.sub.1 to about C.sub.8 alkyl;
R.sup.7 and R.sup.8 are each independently C.sub.1 to C.sub.8 fluoroalkyl or fluorine;
Y is (CR.sup.9 R.sup.10).sub.k CR.sup.11 HCR.sup.13 R.sup.14 ;
R.sup.9, R.sup.10, R.sup.11, R.sup.13 and R.sup.14 are each independently hydrogen, C.sub.1 to about C.sub.8 alkyl or aryl; and
k is an integer from 0 to 10.

### Claim 10 (depends on 9)

The compound of claim 9 wherein m is 0.

### Claim 11 (depends on 9)

The compound of claim 9 wherein R.sup.15, R.sup.16, R.sup.17, R.sup.18 and R.sup.19 are independently selected from the group consisting of: C.sub.1 to C.sub.4 alkyl, aryl, C.sub.1 to C.sub.4 alkoxy, C.sub.1 to C.sub.6 acyloxy, C.sub.1 to C.sub.4 fluorocarboxy, chlorine or bromine.

### Claim 12 (depends on 9)

The compound of claim 9 wherein R.sup.9, R.sup.10, R.sup.11, R.sup.13 and R.sup.14 are hydrogen.

### Claim 13 (depends on 9)

The compound of claim 9 selected from the group consisting of: 2,2-bis(trifluoromethyl)-4,5-difluoro-4,5 bis(trichlorosilylethyl)-1,3-dioxolane; 2,2-bis(trifluoromethyl)-4,5-difluoro-4,5 bis(triethoxysilylethyl)-1,3-dioxolane; 2,2-bis(trifluoromethyl)-4,5-difluoro-4,5 bis(tris(2,2,-trifluoroethoxy)silylethyl)-1,3-dioxolane; and 2,2-bis(trifluoromethyl)-4,5-difluoro-4,5 bis(tris(1H,1H-heptafluorobutoxy)silylethyl)-1,3-dioxolane.

### Claim 14

A process for preparing a compound of formula IA ##STR16## wherein: m is an integer from 0 to 50;
R.sup.15, R.sup.16, R.sup.17 and R.sup.18 are each independently C.sub.1 to C.sub.20 alkyl, aryl, cycloalkyl, halogen, C.sub.1 to C.sub.20 alkoxy, C.sub.2 to C.sub.20 fluoroalkoxy, aryloxy, C.sub.1 to C.sub.20 acyloxy, C.sub.1 to C.sub.14 fluorocarboxy, oxysilyl or hydrogen;
R.sup.19 is C.sub.1 to C.sub.20 alkyl, aryl, C.sub.1 to C.sub.20 alkoxy, C.sub.2 to C.sub.20 fluoroalkoxy, C.sub.1 to C.sub.20 carboxy, C.sub.1 to C.sub.14 fluorocarboxy, halogen, vinyl or hydrogen;
Z is a divalent group selected from the group consisting of: O, S, and R.sup.6 N;
R.sup.6 is C.sub.1 to about C.sub.8 alkyl;
R.sup.7 and R.sup.8 are each independently C.sub.1 to C.sub.8 fluoroalkyl or fluorine;
Y is (CR.sup.9 R.sup.10).sub.k CR.sup.11 HCR.sup.13 R.sup.14 ;
R.sup.9, R.sup.10, R.sup.11, R.sup.13 and R.sup.14 are each independently hydrogen, C.sub.1 to about C.sub.8 alkyl or aryl; and
k is an integer from 0 to 10,
comprising: contacting a silicon hydride of formula IIA ##STR17## wherein m, Z, R.sup.15, R.sup.16, R.sup.17, R.sup.18 and R.sup.19 are as defined for formula IA, with a divinyl dioxolane of formula III ##STR18## wherein R.sup.7, R.sup.8, R.sup.9, R.sup.10, R.sup.11, R.sup.13, R.sup.14 and k are as defined for formula IA, in the presence of a transition metal catalyst to form a compound of formula IA.

### Claim 15 (depends on 14)

The process of claim 14 wherein contact is made in the presence of a solvent.

### Claim 16 (depends on 14)

The process of claim 14 wherein the silicon hydride has the formula R.sub.a SiH.sub.4-a wherein each R is independently C.sub.1 to C.sub.4 alkyl; aryl; chlorine; bromine; C.sub.1 to C.sub.4 alkoxy, C.sub.1 to C.sub.4 fluoroalkoxy; C.sub.1 to C.sub.4 fluorocarboxy; or acyloxy containing 1 to 6 carbon atoms, and a is 3.

### Claim 17 (depends on 14)

The process of claim 14 wherein R.sup.9, R.sup.10, R.sup.11, R.sup.13 and R.sup.14 are hydrogen.

### Claim 18 (depends on 14)

The process of claim 14 wherein for the silicon hydride m is 0 and R.sup.15, R.sup.16 and R.sup.19 are halogen, further comprising subsequently contacting the compound of formula IA with an alcohol or a fluoroalcohol to form a second compound of formula IA.