# US 5,707,434 A · Water soluble ammonium siloxane compositions and their use as fiber treatment agents

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- Number: US 5,707,434 A
- Document ID: US5707434A
- Status: Granted
- Kind: A
- Application number: 08/730,982
- Filed: 1996-10-16
- Granted: 1998-01-13
- Earliest claimed: 1996-10-16
- Assignees: Dow Corning Corporation
- Inventors: Daniel Joseph Halloran; Dawn Marie Hoffman
- Web page: https://patentgrep.com/patent/US5707434A

## CPC

- C04B 41/009: {characterised by the material treated}
- C04B 41/4961: {Polyorganosiloxanes, i.e. polymers with a Si-O-Si-O-chain; "silicones"}
- C04B 41/64: Compounds having one or more carbon-to-metal of carbon-to-silicon linkages
- C08L 83/08: containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
- D06M 15/643: containing silicon in the main chain
- D06M 15/6436: {containing amino groups}
- C04B: LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE {(roofing granules E04D7/005)}; CERAMICS (devitrified glass-ceramics C03C10/00); REFRACTORIES; TREATMENT OF NATURAL STONE
- C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06)
- D06M: TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS

## Abstract

The present invention relates to a water soluble ammonium siloxane composition comprising (A) an aminosiloxane solution comprising a mixture of (i) a triorganosilyl-endblocked aminofunctional siloxane, (ii) an aminofunctional siloxane which it triorganosiloxy-endblocked at one end and hydroxy-endblocked at the other end, and (iii) a hydroxy-endblocked aminofunctional siloxane, (B) a cyclic aminofunctional siloxane, and (C) a polydimethylcyclosiloxane where the aminofunctional group is selected from --R.sup.3 --.sup.+ NHR.sup.5 --R.sup.4 --.sup.+ NH.sub.2 R.sup.5.2A.sup.-, --R.sup.3 --.sup.+ NH.sub.2 --R.sup.4 --.sup.+ NHR.sup.6.A.sup.-, --R.sup.3 --NR.sup.6 --R.sup.4 --.sup.+ NH.sub.3.A.sup.-, --R.sup.3 --.sup.+ NH.sub.2 R.sup.5.A.sup.-, where R.sup.3 is a divalent hydrocarbon radical, R.sup.4 is a divalent hydrocarbon radical, R.sup.5 is hydrogen, alkyl, aryl, or arylalkyl, R.sup.6 is a --C(O)R.sup.7 group where R.sup.7 is a monovalent hydrocarbon group or aryl, and A.sup.- is a halide anion, carboxylate anion, or inorganic oxoanion. This invention further relates to a method of making the water soluble ammonium siloxane composition, and to a method of treating a substrate with the water soluble ammonium siloxane composition.

## Claims

### Claim 1

A water soluble ammonium siloxane composition comprising:
(A) 0.01 to 90 weight percent of an aminosiloxane blend comprising a mixture of:
(i) an aminofunctional siloxane having its formula selected from the group consisting of:
(a) R.sub.3 SiO(Me.sub.2 SiO).sub.x (RR.sup.1 SiO).sub.y (RR.sup.2 SiO).sub.z SiR.sub.3 and
(b) R.sub.3 SiO(Me.sub.2 SiO).sub.x (RR.sup.1 SiO).sub.y SiR.sub.3 ; and
(ii) an aminofunctional siloxane having its formula selected from the group consisting of:
(a) R.sub.3 SiO(Me.sub.2 SiO).sub.x (RR.sup.1 SiO).sub.y (RR.sup.2 SiO).sub.z SiR.sub.2 OH and
(b) R.sub.3 SiO(Me.sub.2 SiO).sub.x (RR.sup.1 SiO).sub.y SiR.sub.2 OH; and
(iii) an aminofunctional siloxane having its formula selected from the group consisting of:
(a) HOR.sub.2 SiO(Me.sub.2 SiO).sub.x (RR.sup.1 SiO).sub.y (RR.sup.2 SiO).sub.z SiR.sub.2 OH and
(b) HOR.sub.2 SiO(Me.sub.2 SiO).sub.x (RR.sup.1 SiO).sub.y SiR.sub.2 OH;
(B) 0.1 to 90 weight percent of a cyclic aminofunctional siloxane having the average formula: ##STR19## and (C) 0.1 to 10 weight percent of a compound having the average formula: ##STR20## wherein Me denotes methyl, R is independently a monovalent hydrocarbon radical having from 1 to 6 carbon atoms or an aryl radical, R.sup.1 is a group having its formula selected from the group consisting of --R.sup.3 --.sup.+ NHR.sup.5 --R.sup.4 --.sup.+ NH.sub.2 R.sup.5.2A.sup.-, --R.sup.3 --.sup.+ NH.sub.2 --R.sup.4 --NHR.sup.6.A.sup.-, --R.sup.3 --NR.sup.6 --R.sup.4 --.sup.+ NH.sub.3.A.sup.-, --R.sup.3 --.sup.+ NH.sub.2 R.sup.5.A.sup.-, and wherein R.sup.3 is a divalent hydrocarbon radical having at least 3 carbon atoms, R.sup.4 is a divalent hydrocarbon radical having at least 2 carbon atoms, R.sup.5 is selected from the group consisting of hydrogen, an alkyl radical having from 1 to 6 carbon atoms, an aryl radical, and an arylalkyl radical, R.sup.6 is a --C(O)R.sup.7 group where R.sup.7 is selected from the group consisting of a monovalent hydrocarbon group having from 1 to 20 carbon atoms and an aryl radical, and A.sup.- is an anion selected from the group consisting of halide anions, carboxylate anions, and inorganic oxoanions, R.sup.2 is independently selected from the group consisting of a monovalent hydrocarbon radical having from 2 to 6 carbon atoms and an aryl radical, x has a value of 10 to 10,000, y has a value of 1 to 8,000, z has a value of 1 to 250, x' has an average value of 1 to 8 and y' has an average value of 1 to 8 with the proviso that the value of x'+y' is from 4 to 9, n has an average value of 4 to 9, and with the proviso that the value of y/x+y+z+2 is at least 0.1.

### Claim 2 (depends on 1)

A composition according to claim 1, wherein R is methyl or phenyl.

### Claim 3 (depends on 1)

A composition according to claim 1, wherein R.sup.2 is independently selected from the group consisting of ethyl, propyl, butyl, hexyl, phenyl, tolyl, and xylyl.

### Claim 4 (depends on 1)

A composition according to claim 1, wherein R.sup.3 is selected from the group consisting of propylene, butylene, pentylene, trimethylene, 2-methyltrimethylene, pentamethylene, hexamethylene, 3-ethyl-hexamethylene, and octamethylene.

### Claim 5 (depends on 1)

A composition according to claim 1, wherein R.sup.4 is selected from the group consisting of ethylene, propylene, butylene, pentylene, trimethylene, 2-methyltrimethylene, pentamethylene, hexamethylene, 3-ethyl-hexamethylene, and octamethylene.

### Claim 6 (depends on 1)

A composition according to claim 1, wherein R.sup.5 is selected from the group consisting of hydrogen, methyl, phenyl, --COCH.sub.3, and --CH.sub.2 C.sub.6 H.sub.5.

### Claim 7 (depends on 1)

A composition according to claim 1, wherein A.sup.- is selected from the group consisting of CH.sub.3 COO.sup.-, Cl.sup.-, HOCH.sub.2 COO.sup.-, C.sub.6 H.sub.5 COO.sup.-, and HOC.sub.6 H.sub.4 COO.sup.-.

### Claim 8 (depends on 1)

A composition according to claim 1, wherein (A)(i) is an aminofunctional siloxane having the formula Me.sub.3 SiO(Me.sub.2 SiO).sub.x (MeR.sup.1 SiO).sub.y SiMe.sub.3, (A)(ii) is an aminofunctional siloxane having the formula Me.sub.3 SiO(Me.sub.2 SiO).sub.x (MeR.sup.1 SiO).sub.y SiMe.sub.2 OH, (A)(iii) is an aminofunctional siloxane having the formula HOMe.sub.2 SiO(Me.sub.2 SiO).sub.x (MeR.sup.1 SiO).sub.y SiMe.sub.2 OH, and (B) is a cyclic aminofunctional siloxane having the formula: ##STR21## wherein R.sup.1 is a group having its formula selected from the group consisting of: ##STR22## wherein A.sup.- is selected from the group consisting of CH.sub.3 COO.sup.-, Cl.sup.-, HOCH.sub.2 COO.sup.-, C.sub.6 H.sub.5 COO.sup.-, and HOC.sub.6 H.sub.4 COO.sup.- wherein x, y, x', and y' are as defined above.

### Claim 9 (depends on 1)

A composition according to claim 1, wherein x has a value of 10 to 100, y has a value of 5 to 50, x' has a value of 2 to 3.5, and y' has a value of 0.5 to 2 with the proviso that the value of x'+y' is from 4 to 9.

### Claim 10 (depends on 1)

A composition according to claim 1, wherein x has a value of 10 to 100, y has a value of 5 to 50, x' has a value of 2 to 3.5, and y' has a value of 0.5 to 2 with the proviso that the value of x'+y' is from 4 to 9.

### Claim 11

A method of making a water soluble ammonium siloxane composition comprising mixing:
(I) a solution comprising:
(A) 0.01 to 90 weight percent of an aminosiloxane solution comprising a mixture of:
(i) an aminofunctional siloxane having its formula selected from the group consisting of:
(a) R.sub.3 SiO(Me.sub.2 SiO).sub.x (RR.sup.1 SiO).sub.y (RR.sup.2 SiO).sub.z SiR.sub.3 and
(b) R.sub.3 SiO(Me.sub.2 SiO).sub.x (RR.sup.1 SiO).sub.y SiR.sub.3 ; and
(ii) an aminofunctional siloxane having its formula selected from the group consisting of:
(a) R.sub.3 SiO(Me.sub.2 SiO).sub.x (RR.sup.1 SiO).sub.y (RR.sup.2 SiO).sub.z SiR.sub.2 OH and
(b) R.sub.3 SiO(Me.sub.2 SiO).sub.x (RR.sup.1 SiO).sub.y SiR.sub.2 OH; and
(iii) an aminofunctional siloxane having its formula selected from the group consisting of:
(a) HOR.sub.2 SiO(Me.sub.2 SiO).sub.x (RR.sup.1 SiO).sub.y (RR.sup.2 SiO).sub.z SiR.sub.2 OH and
(b) HOR.sub.2 SiO(Me.sub.2 SiO).sub.x (RR.sup.1 SiO).sub.y SiR.sub.2 OH;
(B) 0.1 to 90 weight percent of a cyclic aminofunctional siloxane having the average formula: ##STR23## and (C) 0.1 to 10 weight percent of a compound having the average formula: ##STR24## wherein Me denotes methyl, R is independently a monovalent hydrocarbon radical having from 1 to 6 carbon atoms or an aryl radical, R.sup.1 is a group having its formula selected from the group consisting of --R.sup.3 NH--R.sup.4 --NH.sub.2 and --R.sup.3 --NH.sub.2 wherein R.sup.3 is a divalent hydrocarbon radical having at least 3 carbon atoms, R.sup.4 is a divalent hydrocarbon radical having at least 2 carbon atoms, R.sup.2 is independently selected from the group consisting of a monovalent hydrocarbon radical having from 2 to 6 carbon atoms and an aryl radical, x has a value of 10 to 10,000, y has a value of 1 to 8,000, z has a value of 1 to 250, x' has an average value of 1 to 8 and y' has an average value of 1 to 8 with the proviso that the value of x'+y' is from 4 to 9, n has an average value of 4 to 9, and with the proviso that the value of y/x+y+z+2 is at least 0.1;
(II) an acid compound; and
(III) water.

### Claim 12 (depends on 11)

A method according to claim 11, wherein R is methyl or phenyl.

### Claim 13 (depends on 11)

A method according to claim 11, wherein R.sup.2 is independently selected from the group consisting of ethyl, propyl, butyl hexyl, phenyl, tolyl, and xylyl.

### Claim 14 (depends on 11)

A method according to claim 11, wherein R.sup.3 is selected from the group consisting of propylene, butylene, pentylene, trimethylene, 2-methyltrimethylene, pentamethylene, hexamethylene, 3-ethyl-hexamethylene, and octamethylene.

### Claim 15 (depends on 11)

A method according to claim 11, wherein R.sup.4 is selected from the group consisting of ethylene, propylene, butylene, pentylene, trimethylene, 2-methyltrimethylene, pentamethylene, hexamethylene, 3-ethyl-hexamethylene, and octamethylene.

### Claim 16 (depends on 11)

A method according to claim 11, wherein (A)(i) is an aminofunctional siloxane having the formula Me.sub.3 SiO(Me.sub.2 SiO).sub.x (MeR.sup.1 SiO).sub.y SiMe.sub.3, (A)(ii) is an aminofunctional siloxane having the formula Me.sub.3 SiO(Me.sub.2 SiO).sub.x (MeR.sup.1 SiO).sub.y SiMe.sub.2 OH, (A)(iii) is an aminofunctional siloxane having the formula HOMe.sub.2 SiO(Me.sub.2 SiO).sub.x (MeR.sup.1 SiO).sub.y SiMe.sub.2 OH, and (B) is a cyclic aminofunctional siloxane having the formula: ##STR25## wherein R.sup.1 is a group having its formula selected from the group consisting of --CH.sub.2 CH.sub.2 CH.sub.2 --NH--CH.sub.2 CH.sub.2 --NH.sub.2, --CH.sub.2 CH(CH.sub.3)CH.sub.2 --NH--CH.sub.2 CH.sub.2 --NH.sub.2, and --CH.sub.2 CH.sub.2 CH.sub.2 --NH.sub.2 wherein x, y, x', and y' are as defined above.

### Claim 17 (depends on 16)

A method according to claim 16, wherein x has a value of 10 to 100, y has a value of 5 to 50, x' has a value of 2 to 3.5, and y' has a value of 0.5 to 2 with the proviso that the value of x'+y' is from 4 to 9.

### Claim 18 (depends on 11)

A method according to claim 11, wherein x has a value of 10 to 100, y has a value of 5 to 50, x' has a value of 2 to 3.5, and y' has a value of 0.5 to 2 with the proviso that the value of x'+y' is from 4 to 9.

### Claim 19 (depends on 11)

A method according to claim 11, wherein (II) is selected from the group consisting of CH.sub.3 COOH, HOCH.sub.2 COOH, C.sub.6 H.sub.5 COOH, HOC.sub.6 H.sub.4 COOH, and (CH.sub.3 CO).sub.2 O.

### Claim 20 (depends on 11)

A method according to claim 11, wherein the method further comprises adding an acid anhydride during step (I).

### Claim 21 (depends on 20)

A method according to claim 20, wherein the acid anhydride is selected from the group consisting of acetic anhydride, benzoic anhydride, proprionic anhydride, butyric anhydride, hexanoic anhydride, decanoic anhydride, lauric anhydride, palmitic anhydride, and stearic anhydride.

### Claim 22 (depends on 11)

A method according to claim 11, wherein the method further comprises adding an aryl halide during step (I).

### Claim 23 (depends on 22)

A method according to claim 22, wherein the aryl halide is selected from the group consisting of benzyl chloride, benzyl bromide, benzyl iodide, benzyl fluoride, phenyl chloride, phenyl bromide, and phenyl fluoride.

### Claim 24

A method of treating a substrate, the method comprising the step of:
(I) applying to a substrate a water soluble ammonium siloxane composition wherein the water soluble ammonium siloxane composition comprises:
(A) 0.01 to 90 weight percent of an aminosiloxane solution comprising a mixture of:
(i) an aminofunctional siloxane having its formula selected from the group consisting of:
(a) R.sub.3 SiO(Me.sub.2 SiO).sub.x (RR.sup.1 SiO).sub.y (RR.sup.2 SiO).sub.z SiR.sub.3 and
(b) R.sub.3 SiO(Me.sub.2 SiO).sub.x (RR.sup.1 SiO).sub.y SiR.sub.3 ; and
(ii) an aminofunctional siloxane having its formula selected from the group consisting of:
(a) R.sub.3 SiO(Me.sub.2 SiO).sub.x (RR.sup.1 SiO).sub.y (RR.sup.2 SiO).sub.z SiR.sub.2 OH and
(b) R.sub.3 SiO(Me.sub.2 SiO).sub.x (RR.sup.1 SiO).sub.y SiR.sub.2 OH; and
(iii) an aminofunctional siloxane having its formula selected from the group consisting of:
(a) HOR.sub.2 SiO(Me.sub.2 SiO).sub.x (RR.sup.1 SiO).sub.y (RR.sup.2 SiO).sub.z SiR.sub.2 OH and
(b) HOR.sub.2 SiO(Me.sub.2 SiO).sub.x (RR.sup.1 SiO).sub.y SiR.sub.2 OH;
(B) 0.1 to 90 weight percent of a cyclic aminofunctional siloxane having the average formula: ##STR26## and (C) 0.1 to 10 weight percent of a compound having the average formula: ##STR27## wherein Me denotes methyl, R is independently a monovalent hydrocarbon radical having from 1 to 6 carbon atoms or an aryl radical, R.sup.1 is a group having its formula selected from the group consisting of --R.sup.3 --.sup.+ NHR.sup.5 --R.sup.4 --.sup.+ NH R.sup.5.2A.sup.-, --R.sup.3 --.sup.+ NH.sub.2 --R.sup.4 --NHR.sup.6.A.sup.-, --R.sup.3 --NR.sup.6 --R.sup.4 --.sup.+ NH.sub.3.A.sup.-, --R.sup.3 --.sup.+ NH.sub.2 R.sup.5.A.sup.-, and wherein R.sup.3 is a divalent hydrocarbon radical having at least 3 carbon atoms, R.sup.4 is a divalent hydrocarbon radical having at least 2 carbon atoms, R.sup.5 is selected from the group consisting of hydrogen, an alkyl radical having from 1 to 6 carbon atoms, an aryl radical, and an arylalkyl radical, R.sup.6 is a --C(O)R.sup.7 group where R.sup.7 is selected from the group consisting of a monovalent hydrocarbon group having from 1 to 20 carbon atoms and an aryl radical, and A.sup.- is an anion selected from the group consisting of halide anions, carboxylate anions, and inorganic oxoanions, R.sup.2 is independently selected from the group consisting of a monovalent hydrocarbon radical having from 2 to 6 carbon atoms and an aryl radical, x has a value of 10 to 10,000, y has a value of 1 to 8,000, z has a value of 1 to 250, x' has an average value of 1 to 8 and y' has an average value of 1 to 8 with the proviso that the value of x'+y' is from 4 to 9, n has an average value of 4 to 9, and with the proviso that the value of y/x+y+z+2 is at least 0.1.

### Claim 25 (depends on 24)

A method according to claim 24, wherein the method further comprises heating the substrate after step (I).

### Claim 26 (depends on 24)

A method according to claim 24, wherein (A)(i) is an aminofunctional siloxane having the formula Me.sub.3 SiO(Me.sub.2 SiO).sub.x (MeR.sup.1 SiO).sub.y SiMe.sub.3, (A)(ii) is an aminofunctional siloxane having the formula Me.sub.3 SiO(Me.sub.2 SiO).sub.x (MeR.sup.1 SiO).sub.y SiMe.sub.2 OH, (A)(iii) is an aminofunctional siloxane having the formula HOMe.sub.2 SiO(Me.sub.2 SiO).sub.x (MeR.sup.1 SiO).sub.y SiMe.sub.2 OH, and (B) is a cyclic aminofunctional siloxane having the formula: ##STR28## wherein R.sup.1 is a group having its formula selected from the group consisting of: ##STR29## wherein A.sup.- is selected from the group consisting of CH.sub.3 COO.sup.-, Cl.sup.-, HOCH.sub.2 COO.sup.-, C.sub.6 H.sub.5 COO.sup.-, and HOC.sub.6 H.sub.4 COO.sup.- wherein x, y, x', and y' are as defined above.

### Claim 27 (depends on 24)

A method according to claim 24, wherein x has a value of 10 to 100, y has a value of 5 to 50, x' has a value of 2 to 3.5, and y' has a value of 0.5 to 2 with the proviso that the value of x'+y' is from 4 to 9.

### Claim 28 (depends on 24)

A method according to claim 24, wherein x has a value of 10 to 100, y has a value of 5 to 50, x' has a value of 2 to 3.5, and y' has a value of 0.5 to 2 with the proviso that the value of x'+y' is from 4 to 9.

### Claim 29 (depends on 24)

A method according to claim 24, wherein the substrate is selected from the group consisting of wool, cotton, nylon, polyester, acrylic fibers, polyester-cotton blends, leather, paper, gypsum board, and fiberfil.

### Claim 30

A composition of matter obtained by mixing the incipient ingredients:
(I) a solution comprising:
(A) 0.01 to 90 weight percent of an aminosiloxane solution comprising a mixture of:
(i) an aminofunctional siloxane having its formula selected from the group consisting of:
(a) R.sub.3 SiO(Me.sub.2 SiO).sub.x (RR.sup.1 SiO).sub.y (RR.sup.2 SiO).sub.z SiR.sub.3 and
(b) R.sub.3 SiO(Me.sub.2 SiO).sub.x (RR.sup.1 SiO).sub.y SiR.sub.3 ; and
(ii) an aminofunctional siloxane having its formula selected from the group consisting of:
(a) R.sub.3 SiO(Me.sub.2 SiO).sub.x (RR.sup.1 SiO).sub.y (RR.sup.2 SiO).sub.z SiR.sub.2 OH and
(b) R.sub.3 SiO(Me.sub.2 SiO).sub.x (RR.sup.1 SiO).sub.y SiR.sub.2 OH; and
(iii) an aminofunctional siloxane having its formula selected from the group consisting of:
(a) HOR.sub.2 SiO(Me.sub.2 SiO).sub.x (RR.sup.1 SiO).sub.y (RR.sup.2 SiO).sub.z SiR.sub.2 OH and
(b) HOR.sub.2 SiO(Me.sub.2 SiO).sub.x (RR.sup.1 SiO).sub.y SiR.sub.2 OH;
(B) 0.1 to 90 weight percent of a cyclic aminofunctional siloxane having the average formula: ##STR30## and (C) 0.1 to 10 weight percent of a compound having the average formula: ##STR31## wherein Me denotes methyl, R is independently a monovalent hydrocarbon radical having from 1 to 6 carbon atoms or an aryl radical, R.sup.1 is a group having its formula selected from the group consisting of --R.sup.3 NH--R.sup.4 --NH.sub.2 and --R.sup.3 --NH.sub.2 wherein R.sup.3 is a divalent hydrocarbon radical having at least 3 carbon atoms, R.sup.4 is a divalent hydrocarbon radical having at least 2 carbon atoms, R.sup.2 is independently selected from the group consisting of a monovalent hydrocarbon radical having from 2 to 6 carbon atoms and an aryl radical, x has a value of 10 to 10,000, y has a value of 1 to 8,000, z has a value of 1 to 250, x' has an average value of 1 to 8 and y' has an average value of 1 to 8 with the proviso that the value of x'+y' is from 4 to 9, n has an average value of 4 to 9, and with the proviso that the value of y/x+y+z+2 is at least 0.1;
(II) an acid compound; and
(III) water.