Process for making an aminosiloxane polymer nanoemulsion

Patent metadata

Field	Value
Publication number	US-10150844-B2
Application number	US-201515500256-A
Country	US
Kind code	B2
Filing date	Jul 24, 2015
Priority date	Jul 28, 2014
Publication date	Dec 11, 2018
Grant date	Dec 11, 2018

Abstract

Nanoemulsions are prepared by:
a) solubilizing a silicone resin in an organic solvent system to yield a silicone resin solution concentration of 80% or less, wherein the organic solvent system comprises diethyleneglycol monobutyl ether and at least one additional solvent; b) mixing the silicone resin solution from a) with an aminosiloxane polymer to obtain an aminosiloxane polymer: silicone resin mixture; c) allowing the resin mixture to age for at least about 6 hours at ambient temperature; d) adding the resin mixture to a vessel; e) optionally adding with agitation an additional organic solvent to the resin mixture; f) mixing until homogenous; g) adding a protonating agent; h) adding an aqueous carrier in an amount to produce a desired concentration of emulsion.

First claim

The invention claimed is:

1. A method of making a nanoemulsion, comprising the steps of:
a) solubilizing a silicone resin in an organic solvent system to yield a silicone resin solution concentration of 80% or less, wherein the organic solvent system comprises diethyleneglycol monobutyl ether and at least one additional solvent selected from the group consisting of monoalcohols, polyalcohols, ethers of monoalcohols, ethers of polyalcohols, fatty esters, Guerbet alcohols, isoparaffins, naphthols, glycol ethers or mixtures thereof, provided that if the additional solvent is a glycol ether it is not diethyleneglycol monobutyl ether;
b) mixing the silicone resin solution from a) with an aminosiloxane polymer to obtain an aminosiloxane polymer:silicone resin mixture having an aminosiloxane polymer to silicone resin weight ratio of 20:1;
c) allowing the aminosiloxane polymer:silicone resin mixture to age for at least 6 hours at ambient temperature;
d) adding the aminosiloxane polymer:silicone resin mixture to a vessel;
e) optionally adding with agitation an additional organic solvent to the aminosiloxane polymer:silicone resin mixture;
f) mixing until homogenous;
g) adding a protonating agent; and
h) adding an aqueous carrier in an amount to produce an aqueous nanoemulsion.

2. The method of making a nanoemulsion of claim 1 , wherein the nanoemulsion is substantially free of surfactant.

3. A method of making a nanoemulsion of claim 1 , wherein at least one silicone resin is a silicone resin comprising at least 80 mol % of units of the formulas 3, 4, 5, and 6:
i) R 3 SiO 1/2   (3),

ii) R 2 SiO 2/2   (4),

iii) RSiO 3/2   (5),

iv) SiO 4/2   (6),

in which R is H, —OR 10 , —OH, or a monovalent hydrocarbon residue with 1 to 40 carbon atoms optionally substituted with halogens, where at least 20 mol % of the units are units of the formulas 5 and 6, where R 10 is a monovalent hydrocarbon residue with 1 to 10 carbon atoms, and a maximum of 10 wt % of the R residues are —OR and —OH residues.

4. A method of making a nanoemulsion of claim 2 , wherein at least one silicone resin is a silicone resin comprising at least 80 mol % of units of the formulas 3, 4, 5, and 6:
i) R 3 SiO 1/2   (3),

ii) R 2 SiO 2/2   (4),

iii) RSiO 3/2   (5),

iv) SiO 4/2   (6),

in which R is H, —OR 10 , —OH, or a monovalent hydrocarbon residue with 1 to 40 carbon atoms optionally substituted with halogens, where at least 20 mol % of the units are units of the formulas 5 and 6, where R 10 is a monovalent hydrocarbon residue with 1 to 10 carbon atoms, and a maximum of 10 wt % of the R residues are —OR and —OH residues.

5. The method of making a nanoemulsion of claim 1 , wherein the aminosiloxane polymer is an aminoalkyl group containing polyorganosiloxane (P) comprising at least 80 mol % of units of the formulae 7, 8, 9 and 10
R 1 2 SiO (4-a-b)/2   (7),

R 1 a R 2 b SiO (4-a-b)/2   (8),

R 3 3 SiO (1/2)   (9),

R 3 2 R 4 SiO (1/2)   (10),

where
a is 0 or 1,
b is 1 or 2,
a+b is 2,
R 1 are monovalent hydrocarbyl radicals having 1-40 carbon atoms optionally substituted with halogens
R 2 are either
a) aminoalkyl radicals of the formula 11
—R 5 —NR 6 R 7   (11)

where
R 5 are divalent hydrocarbyl radicals having 1-40 carbon atoms,
R 6 are monovalent hydrocarbyl radicals having 1-40 carbon atoms, H, hydroxymethyl or alkanoyl radicals, and
R 7 are radicals of the formula 12
—(R 8 —NR 6 ) x R 6   (12)

where
x is 0 or an integer from 1 to 40, and
R 8 are divalent radicals of the formula 13
—(CR 9 2 —) y (13)

where
y is an integer from 1 to 6, and
R 9 are H or hydrocarbyl radicals having 1-40 carbon atoms, or
b) in the formula 11 R 6 and R 7 combine with the nitrogen atom to form a cyclic organic radical having 3 to 8 —CH 2 — units, wherein nonadjacent —CH 2 — units are optionally replaced by units selected from —C(═O)—, —NH—,—O—and —S—,
R 3 are hydrocarbyl radicals having 1-40 carbon atoms optionally substituted with halogens,
R 4 are —OR or —OH radicals, and
wherein, in the polyorganosiloxanes (P),
the average ratio of the sum of units of the formulae 7 and 8 to the sum of units of the formulae 9 and 10 is in the range from 0.5 to 500, the average ratio of units 9 to 10 being in the range from 1.86 to 100, and the polyorganosiloxanes (P) have an average amine number of at least 0.01 mequiv/g.

6. The method of making a nanoemulsion of claim 1 , wherein the protonating agent is a monoprotic or multiprotic, water-soluble or water-insoluble, organic or inorganic acid.

7. The method of making a nanoemulsion of claim 1 , wherein the Guerbet alcohol comprises 2-ethylhexanol, 2-butyl octanol, 2-hexyl decanol, or mixtures thereof.

8. The method of making a nanoemulsion of claim 1 , wherein at least one fatty ester is selected from the group consisting of isopropyl laurate, isopropyl palmitate, isopropyl myristate, isopropyl stearate, isopropyl oleate, isopropyl linoleate and mixtures thereof.

9. The method of making a nanoemulsion of claim 1 , wherein at least one glycol ether is selected from the group consisting of mono-, di-, or tri-ethyleneglycol alkyl ethers having ether moieties containing up to 8 carbon atoms, or mono-, di-, or tri-propyleneglycol alkyl ethers having ether moieties containing up to 8 carbon atoms.

10. The method of making a nanoemulsion of claim 1 , wherein the silicone resin is an MQ resin, having a ratio of M units to Q units of 0.5:1 to 1.5:1.

11. The method of making a nanoemulsion of claim 1 , wherein the silicone resin is an MQ resin, having a ratio of M units to Q units of about 0.67:1.

12. The method of making a nanoemulsion of claim 1 , wherein at least one protonating agent is selected from the group consisting of formic acid, acetic acid, sulphuric acid, phosphoric acid, hydrochloric acid, citric acid, and mixtures thereof.

13. A nanoemulsion prepared by the method of claim 1 .

Assignees

• Wacker Chemie Ag

Inventors

• Becker Richard
• Broening Harry William
• Fliter Kristi Lynn
• Merget Markus
• Schuster Stefanie
• Selbertinger Ernst
• Sivik Mark Robert
• Vetter Nicholas David
• Whiting Patrick Brian
• Wimmer Franz Xaver

Classifications

• C08J2483/04

  Polysiloxanes · CPC title

• C08L83/08 Primary

  containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen · CPC title

• C08G77/26

  nitrogen-containing groups · CPC title

• C08J3/07 Primary

  from polymer solutions · CPC title

• C08J3/03 Primary

  in aqueous media · CPC title