Preparation of polyorganosiloxanes by interfacial polymerization

• US 5,629,401 A
• Filed: 04/01/1996
• Issued: 05/13/1997
• Est. Priority Date: 04/01/1996
• Status: Expired due to Fees

• Current Assignee: Dow, Inc.
• Original Assignee: Dow, Inc.
• Inventors: Graiver, Daniel, Lomas, Arnold W.
• Primary Examiner(s): Marquis, Melvyn I.
• Application Number:
  US08/626,711
• Time in Patent Office: 407 Days
• Field of Search: 528/43, 528/37, 528/18, 528/14, 528/38, 528/32, 528/34
• US Class Current: 528/43
• CPC Class Codes: C08G 77/04 Polysiloxanes
• CPC Class Codes: C08G 77/06 Preparatory processes C08G77/045 takes precedence

Abstract

An interfacial polymerization process wherein organosilicon reactants are dissolved in mutually immiscible, nonaqueous solvents, and a condensation product is formed at the interface. This technique has many of the advantages of analogous organic interfacial polymerization, and may be used, for example, to prepare crosslinked films, fibers, particles, or encapsulants. Structures which cannot be prepared by other routes can be made. In particular, a well-defined alternating dimethyl/diphenyl siloxane block copolymer can be prepared by condensing a dihalo organosilicon compound such as diphenyldichlorosilane (C₆ H₅)₂ SiCl₂ in diphenyl ether with a dimethyl silanolate in cyclohexane. The advantages are ability to control polymer structure, and there is no rearrangement during polymerization.

Claims

1. A method of making a copolymer comprising (A) reacting (i) a nonaqueous, organic solvent solution of a dihalo organosilicon compound or a diacyloxy organosilicon compound at or near an interface formed by the nonaqueous organic solvent solution and (ii) an immiscible nonaqueous organic solvent solution of a silanolate or organosilanolate of formula R"_x Si(OM)_4-x or MO(R"₂ SiO)_n M where R" is an alkyl radical of 1-6 carbon atoms, an aryl radical, an alkenyl radical, an alkylamino radical, or an epoxy radical;

x is 0-2;

n is at least one; and

M is an alkali metal; and

(B) recovering the copolymer at or near the interface of the solvent solutions.

2. A method according to claim 1 in which the organic solvent for the dihalo or diacyloxy organosilicon compound is selected from the group consisting of diphenyl ether, mineral oil, hexane, and acetonitrile;

and the organic solvent for the silanolate or organosilanolate is selected from the group consisting of cyclohexane, a polyethylene glycol [400] of the formula H(OCH₂ CH₂)_n OH where n is about 400, and dimethylformamide.

3. A method according to claim 1 in which the silanolate or organosilanolate has the formula MO(R"₂ SiO)_n M where R" is an alkyl radical of 1-6 carbon atoms, an aryl radical, an alkenyl radical, an alkylamino radical, or an epoxy radical;

n is 1-20; and

M is an alkali metal.

4. A method according to claim 3 in which the silanolate or organosilanolate is potassium polydimethylsilanolate KO[(CH₃)₂ SiO]_n K where n is 3-20.

5. A method according to claim 1 in which the dihalo organosilicon compound is an organodichlorosilane selected from the group consisting of 2-acetoxyethylmethyldichlorosilane, 3-acetoxypropylmethyldichlorosilane, allylmethyldichlorosilane, amyldichlorosilane, amylmethyldichlorosilane, 5-(bicycloheptenyl)methyldichlorosilane, 2-(bicycloheptyl)methyldichlorosilane, bis-(3-chloropropyl)dichlorosilane, bis(3-cyanopropyl)dichlorosilane, 4-butenyldichloromethylsilane, 2-(carbomethoxy)ethylmethyldichlorosilane, 2-chloroethylmethyldichlorosilane, chloromethylmethyldichlorosilane, chlorophenylmethyldichlorosilane, 3-chloropropyldichlorosilane, 3-chloropropylhexyldichlorosilane, 3-chloropropylmethyldichlorosilane, 2-cyanoethylmethyldichlorosilane, 3-cyanopropylmethyldichlorosilane, [2-(3-cyclohexenyl)ethyl]methyldichlorosilane, cyclohexyldichlorosilane, cyclopentamethylenedichlorosilane, cyclopentyldichlorosilane, cyclotetramethylenedichlorosilane, cyclotrimethylenedichlorosilane, n-decylmethyldichlorosilane, diamyldichlorosilane, di-n-butyldichlorosilane, di-t-butyldichlorosilane, (dichloromethyl)methyldichlorosilane, dichlorosilane, dicyclohexyldichlorosilane, diethyldichlorosilane, di-n-hexyldichlorosilane, dimesityldichlorosilane, dimethyldichlorosilane, dioctyldichlorosilane, diphenyldichlorosilane, di-n-propyldichlorosilane, n-docosylmethyldichlorosilane, ethyldichlorosilane, ethylmethyldichlorosilane, n-heptylmethytdichlorosilane, hexadecyldichlorosilane, hexyldichlorosilane, n-hexylmethyldichlorosilane, isobutyldichlorosilane, 3-methacryloxypropylmethyldichlorosilane, 3-(4-methoxyphenyl)propylmethyldichlorosilane, methylcyclohexyldichlorosilane, methyldichlorosilane, methyldodecyldichlorosilane, methylisopropyldichlorosilane, methyl-n-octadecyldichlorosilane, methyl-n-octyldichlorosilane, (p-methylphenethyl)methyldichlorosilane, methyl(2-phenethyl)dichlorosilane, methylphenyldichlorosilane, methyl-n-propyldichlorosilane, phenylallyldichlorosilane, phenyl(3-chloropropyl)dichlorosilane, phenyldichlorosilane, phenylethyldichlorosilane, phenylvinyldichlorosilane, 1-propyl(3-chloropropyl)dichlorosilane, n-propyldichlorosilane, p-tolylmethyldichlorosilane, (3,3,3-trifluoropropyl)methyldichlorosilane, vinylethyldichlorosilane, and vinylmethyldichlorosilane.

6. A method according to claim 1 in which the diacyloxy organosilicon compound is an organodiacetoxysilane selected from the group consisting of diethyldiacetoxysilane, dimethyldiacetoxysilane, diphenyldiacetoxysilane, di-t-butoxydiacetoxysilane, methyldiacetoxysilane, and methylphenyldiacetoxysilane.

7. A method according to claim 5 in which the dihalo organosilicon compound is diphenyldichlorosilane.