EP1015681A1

EP1015681A1 - Aminosiloxane polyether polymers

Info

Publication number: EP1015681A1
Application number: EP98947464A
Authority: EP
Inventors: Hans-Jürgen Lautenschlager; Anton Heller
Original assignee: Wacker Chemie AG
Current assignee: Wacker Chemie AG
Priority date: 1997-09-11
Filing date: 1998-08-27
Publication date: 2000-07-05
Also published as: BR9812448A; HUP0003057A2; JP2001515969A; ID23979A; CN1269853A; DE19739991A1; KR20010023779A; PL339187A1; WO1999013151A1; US6326061B1

Abstract

The invention relates to a method for treating textiles, using a composition containing at least one A) silane or organosiloxane which has at least one monovalent SiC-bonded radical with primary, secondary and/or tertiary amino groups, and at least one B) Si-O-C-bonded (iso) oxyalkyl radical.

Description

Aminosiloxane polyether polymers

The invention relates to a process for textile treatment in which a composition based on organopolysiloxane having aminoalkyl and (iso) oxyalkyl groups is used, and new aminosiloxane-polyether polymers.

Several recent patents describe modifications of the polyoxyalkylene chain or the organopolysiloxane to optimize the property for a variety of applications. The functional groups and the polyoxyalkylene chains can be linked to the organopolysiloxane via Si-O-C or Si-C bonds.

DE 3928867 describes the use of polysiloxane-polyoxyalkylene block copolymers which contain at least one amino-functional group bonded to a silicon atom in the production of polyurethane foams. The polyoxyalkylene group and the amino-functional group can be Si-O- or Si-C-bonded. The polyoxyalkylene group and the amino functional group can be either terminal or pendant. The amino functional group contains at least two nitrogen atoms, of which the terminal must be completely substituted with alkyl groups. Polysiloxane-polyoxyalkylene block copolymers which contain an amino-functional group bonded to a silicon atom with only one nitrogen atom or those which contain two or more nitrogen atoms in the side chain and in which the terminal groups are substituted by at least one oxygen atom are not described. The use of the polymers described in DE 3928867 for fiber finishing is also not described.

US-A-5075403 and EP-A-0404698 describe a polydiorganosiloxane with pendant amino and polyoxyalkylene groups.

The functional groups are Si-C bonded. The production takes place via hydrosilylation. The application of he polymers according to the invention as wetting and dispersing agents, additive in Fabric softeners or anti-foam powders are described.

Si-O-C-bonded polyoxyalkylene groups are not described.

EP-A-0579999 describes an agent for defoaming aqueous, in particular alkaline, preparations based on organo-functional modified organopolysiloxanes and finely divided silica. The organopolysiloxane used in the preparation is an aminosiloxane, the amine groups of which are linked to the organopolysiloxane via a Si-C or Si-O-C bond. In addition to the amine groups, the organopolysiloxane can also contain polymer radicals which are bonded to the organopolysiloxane via a Si-C or Si-O-C bond.

The combination of amino-functional parts and polyalkylene oxide-containing groups on the organopolysiloxane is also known. Alkylamine-polyalkylene oxide-polydimethylsiloxane terpolymers and polydimethylsiloxanaminopolyalkylene oxide block copolymers are already used for finishing textiles (cf. A.M. Czech et al., "Modified Silicone Softeners for Fluorocarbon Soil Release Treatments"). The polyalkylene oxide groups are linked to the organopolysiloxane via a Si-C bond.

A disadvantage of the prior art is that Si-C-bonded polyalkylene oxide groups are only accessible via the hydrosilylation reaction of allylpolyalkylene oxide groups on H-containing silanes and organopolysiloxanes. This process requires more expensive raw materials and special safety measures, since hydrogen elimination can be expected in hydrosilylation reactions. Furthermore, Si-C-bonded polyalkylene oxide groups cannot easily be split off when required, as is desired to improve the pull-out capacity and durability in textile finishing.

The object of the invention is to overcome the disadvantages of the prior art. The invention relates to a method for textile treatment, in which a composition containing at least one

(A) silane or organosiloxane which has at least one monovalent SiC-bonded radical with primary, secondary and / or tertiary amino groups, and at least one

(B) (Iso) -Oxyalkylrest, which is Si-O-C- bound, is used.

In the composition, the silane or organosiloxane (A) preferably has a unit of the general formula (I)

R aζbSiO (, 4.-a-, b), (_ I,)

and all other siloxane units have the general formula (II) in the case of an organopolysiloxane

R cSiO (, 4.-cv),, (_ I_I.)

and an (iso) oxyalkyl radical of the formula

(0C _n H _n (-R) _n ) _ (III)

in which

R can be the same or different and hydrogen or one

Methyl residue means

The (iso) -oxyalkyl radicals having the general formula (0C _n H _n (R) _n ) _o can also be linked at one or both ends to the organopolysiloxane via a Si-OC bond. The (iso) -oxyalkyl radicals are preferably adducts of polyethylene oxide, polypropylene oxide and their copolymers. By

Changing the polyethylene oxide / polypropylene oxide ratio can influence the hydrolysis stability of the Si-OC bond. R is the same or different, monovalent, optionally fluorine, chlorine or bromine-substituted C -, - to C ₁₈ -hydrocarbon radicals, hydrogen atoms, C- _j _- to C ₁₂ ^-A l ^{k; oχ} y or ^{hydroxyl radicals} or alkylglycol ^radicals , Q is a group of the general formula (III)

-R ² - [NR ³ (CH ₂ ) _m ] _d N (R ³ ) ₂ (III)

■ 10 means where

R denotes a divalent C- ^ - to C - ^ - hydrocarbon residue,

R represents a hydrogen atom or an optionally fluorine, 15 chlorine or bromine or C - ^ - to C ₅ -alkoxy-substituted C- _j _- to C ₁₈ -hydrocarbon radical, a the values 0 1 or 2, b the values 1 2 or 3, c the values 0 1, 2 or 3,

20 dd ddiiee WWeerrttee 00, 1, 2, 3 or 4, m the values 2 3, 4, 5 or 6, n the values 2, 3 or 4 and o the values 1 to 100 and the sum of a and b maximum 4 is. ^■ 25

Examples of C - ^ - to C- ^ g hydrocarbon radicals are alkyl radicals, such as the methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, tert. -Butyl-, n-pentyl-, iso-pentyl-, neo-pentyl-, tert. Pentyl residue; Hexyl radicals, such as the n-hexyl radical;

30 heptyl residues, such as the n-heptyl residue; Octyl residues, such as the n-

Octyl radical and iso-octyl radicals, such as the

2, 2, 4-trimethylpentyl; Nonyl radicals, such as the n-nonyl radical; Decyl radicals, such as the n-decyl radical; Dodecyl radicals, such as the n-dodecyl radical; Cycloalkyl radicals, such as cyclopentyl, cyclohexyl, cy-35 cloheptyl radicals and methylcyclohexyl radicals; Aryl radicals such as the phenyl and naphthyl radicals; Alkaryl groups such as o-, m-, p-tolyl groups, xylyl groups and ethylphenyl groups; Aralkyl radicals, such as the benzyl radical, the alpha- or ß-phenylethyl radical. The above hydrocarbon radicals R optionally contain an aliphatic double bond. Examples are alkenyl radicals, such as vinyl, allyl, 5-hexen-1-yl, 5 E-4-hexen-1-yl, Z-4-hexen-1-yl, 2- (3rd -Cyclohexenyl) ethyl and cyclododeca-4, 8-dienyl. Preferred radicals R with an aliphatic double bond are the vinyl, allyl and 5-hexen-1-yl radicals.

10 Preferably, however, at most 1% of the hydrocarbon radicals R contain a double bond.

Examples of C -, _- to C ₁₈ -hydrocarbon radicals substituted by fluorine, chlorine or bromine atoms are the ■ 15 3, 3, 3-trifluoro-n-propyl radical, the

2, 2, 2, 2 ', 2', 2 '-hexafluoroisopropyl radical, the heptafluoroisopropyl radical, and the o-, m- and p-chlorophenyl radical.

Examples of the divalent C- _j _- bis

20 C ₁₈ hydrocarbon radicals R are saturated straight or branched chain or cyclic alkylene radicals such as the methylene and ethylene radical as well as propylene, butylene, pentylene, hexylene, 2-methylpropylene, cyclohexylene and octadecylene radicals or unsaturated Alkylene or arylene residues such as the hexenylene

25 radical and phenylene radicals, the n-propylene radical and the 2-methylpropylene radical being particularly preferred.

The alkoxy radicals are alkyl radicals bonded via an oxygen atom and described above. The examples of alkyl radicals ■ 30 also apply in full to the alkoxy radicals R.

The alkylglycol radicals R preferably have the general formula (IV)

35 -R ² - [0 (CHR ³ ) _d ] _n OR ⁴ (IV)

in which R 2, R3 and d have the above meanings, n has the value 1 to 100 and R is a hydrogen atom, a Radical R3 or a group of the general formula - (C = 0) -R. means, where R 5 is the radical R3 or 0-R. means.

In the general formulas (I) to (IV) above, preferably mean

R represents a methyl, phenyl, C _j _- to C ₃ alkoxy or hydroxyl radical or a radical of general formula (IV), R is a divalent C ₂ - to Cg-hydrocarbon radical, a hydrogen atom, a methyl radical or cyclohexyl radical, a the values 0 or 1, b the value 1, c the values 2 or 3 and d the value 1.

Linear polydimethylsiloxanes, optionally substituted _C] _- are particularly preferred to C ₃ alkoxy or hydroxyl end groups have. In these polymethylsiloxanes Q is preferably a group H ₂ N (CH ₂ ) ₂ NH (CH ₂ ) 3 or H ₂ N (CH ₂ ) ₂ NHCH ₂ CH (CH3) CH ₂ -.

The invention further provides (A) silane or organosiloxane which has at least one monovalent SiC-bonded radical with primary, secondary and / or tertiary amino groups, with the proviso that the organopolysiloxane has only M and D units and the terminal amino-functional group has at least one hydrogen atom and and at least one

(B) (Iso) -oxyalkyl radical. The (iso) -oxyalkyl radicals with the general formula (0C _n H _n (R) _n ) _o can also at one or both ends

Si-OC bond can be linked to the organopolysiloxane. The (iso) -oxyalkyl radicals are preferably adducts of polyethylene oxide, polypropylene oxide and their copolymers. The hydrolysis stability of the Si-OC bond can be influenced by changing the polyethylene oxide / polypropylene oxide ratio. The ratio of the siloxane units of the general formula (I) to the siloxane units of the general formula (II) is preferably 1:10 to 30,000, in particular 1:20 to 300.

The weight ratio of polyorganosiloxane to polyoxyalkylene groups is 99: 1 to 10:90, in particular 95: 5 to 30:70. The ratio of amino-substituted Si to Si overall is preferably 1: 500 to 1: 5, in particular 1: 200 to 20.

The amine content of the composition according to the invention is preferably 0.01 to 2 mequiv / g, in particular 0.1 to 0.7 mequiv / g, measured as the consumption of In hydrochloric acid in ml / g organopolysiloxane A during the titration to the neutral point.

A type of silane or organosiloxane (A) can be used. However, a mixture of at least two different types of silane and / or organosiloxane (A) can also be used.

The silane or organosiloxane (A) or a mixture of at least two different types of silane and / or organosiloxanes (A) preferably has an average viscosity of 1 to 100,000 mPa's, in particular 1 to 10,000 mPa's at 25 ° C.

Another object of the invention is a method for producing the compositions according to the invention by at least one

(A) silane or organosiloxane which has at least one monovalent, SiC-bonded radical with primary, secondary and / or tertiary amino groups, and a glycol which has at least one

(B) (Iso) -oxyalkyl radical can be used.

The silanes or organosiloxanes (A) are made from (E) compounds that are selected from

(El) organosilanes which have at least one monovalent SiC-bonded radical with primary, secondary and / or tertiary Have amino groups and at least one C 1 -C ₄ alkoxy group and

(E2) organosiloxanes containing at least one monovalent SiC-bonded radical with primary, secondary and / or tertiary amino groups 5 and at least one C _j _- to C ₄ alkoxy and / or silanol group and having

(F) compounds selected from

(Fl) organosilanes which contain at least a _C-j _- to C ₄ alkoxy group include and 10 (F2) organosiloxanes having at least one C - ^ - have to C ₄ alkoxy and / or silanol group,

(G) glycols of the formula

15 H (0C _n H _n (-R) _n ) _o 0H,

in which

R = methyl, H means

20 and basic or acidic catalysts

manufactured .

The organosilanes (El) preferably have the general formula (VI)

on in the

■ 30 R ^{6 is} a C _j _- C alkoxy or, e is the values 1, 2 or 3 and f is 1, 2 or 3, with the proviso that the sum of e and f is at most 4, and

35 Q and R have the above meanings. The organosiloxanes (E2) preferably have at least one siloxane unit of the above general formula (I) and at least one siloxane unit of the general formula (VII)

R ¹ gR ⁶ , hR ⁷ O1.SiO (, 4.-g-, h,) (, V _ττ I _τ I)

and all other siloxane units have the above general formula (II) where g is 0, 1 or 2, h is 1, 2 or 3 and i is 0 or 1, with the proviso that the sum of g, h and i is a maximum of 3 and

Q, 1 and R6 have the meanings given above and R7 is H or a C- _| _ to Cg alkyl group.

The organosilanes (F1) preferably have the general formula (VIII)

R ⁶ _j SiR ¹ ₍₄ _j ₎ (VIII)

where j is 1, 2, 3 or 4 and

R and have the above meanings.

The organosiloxanes (F2) preferably have at least one siloxane unit of the above general formula (VII) and all other siloxane units of an organopolysiloxane have the above general formula (II).

E is preferably 1.

The organopolysiloxanes (E2) and (F2) preferably have an average viscosity of 10 to 100000 mPa "s, preferably 20 to 10000 mPa" s, in particular 50 to 1000 mPa "s at 25 ° C. The acidic catalysts are preferably Lewis acids such as BF ₃ , MgCl ₂ and ZnCl and protonic acid compounds of the halogens such as HF, HC1, HBr and HI, and sulfuric acid compounds such as H ₂ S0 ₄ and H ₂ S0 ₃ .

The basic catalysts are catalysts, such as alkali metal hydroxides, in particular sodium, potassium and cesium hydroxide, alkali metal alcoholates, quaternary ammonium hydroxides, such as tetramethylammonium hydroxide, benzyltrimethylammonium hydroxide, benzyltriethylammonium hydroxide, benzyltrimethylethylethylammoniumethylammoniumethylammoniumethylammoniumethylammoniumethylammoniumethylammoniumethylammoniumethylammoniumethylammoniumethylammoniumethylammoniumethylammoniumethylammoniumethylammoniumethylammoniumethylammoniumethylammoniumethylammoniumethylammoniumethylammoniumethylammoniumethylammoniumethylammoniumethylammoniumethylammoniumethylammoniumethylammoniumethylammonium methylethylammoniumethylammoniumethylammoniumethylammoniumethylammoniumethylammoniumethylammoniumethylammoniumethylammoniumethylammoniumethylammoniumethylammoniumethylammoniumethylammoniumethylammoniumethylammoniumethylethylammonium Methylethylammonium Methylethylammonium Methylamine , quaternary phosphonium hydroxides, such as tetra-n-butylphosphonium hydroxide and tri-n-butyl-3- [tris (trimethylsiloxy) silyl] -n-propylphosphonium hydroxide, alkali metal siloxanolates and ammonium organosiloxanolates, such as benzyltrimethylammonium siloxate ammonate and tetramamethylamineate.

Preferably 10 pp to 1 wt%, in particular 50 to 1000 ppm, of catalyst, based in each case on the weight of the organosilicon compounds used, is used.

The amounts of (E) (F) (G) result from the required physical data.

Products containing acyl groups can be prepared by using acylated amino-functional silanes, or by reacting the aminopolyoxyalkylenesiloxane according to the invention with acylating reagents, such as carboxylic anhydrides, carboxylic esters, carboxylic acids, lactones, carbonates.

(A) is preferably prepared at temperatures from 50 to 300 ° C., in particular 80 to 200 ° C.

The reaction time in which 99 mol% of the starting compounds (E), (F) and (G) converted to silane or organosiloxane (A) is usually 1 hour to 20 days, especially 12 hours to 3 days.

It is important in the manufacture to remove all cleavage products, such as water, alcohol, ether, from the reaction mixture in order to avoid back reactions.

The preparations for textile treatment according to the invention preferably contain (A) silane or organosiloxane in amounts of 1 to 60% by weight, preferably 1 to 30% by weight, and water in amounts of 40 to 99% by weight.

The compounds according to the invention can be used as agents for treating leather, nonwovens, cellulose, fibers, textiles, nonwovens and tissues, as a constituent of defoamer formulations, as wetting agents, as a paint additive and as a PU foam stabilizer.

The advantages are the very good gliding action and excellent softness with very good hydrophilicity, depending on the composition, easily emulsifiable - self-dispersing - soluble in water, depending on the composition, high compatibility with liquor, surprising hydrolysis stability for forced application from an aqueous liquor, good extensibility through targeted partial hydrolysis of the Si-OC bonds. Furthermore, the compositions according to the invention have good stability, which can be years. Furthermore, the stability can also be adjusted by the specific choice of the glycol and the pH, the pH preferably being 7 to 9.

Production Example 1

693.75 g of an OH-terminated polydimethylsiloxane with a viscosity of 50 mPa's are mixed with 21.38 g of aminoethylaminopropylmethyldimethoxysilane, 358.07 g of polyethylene glycol 400 and a basic catalyst. A whitish-cloudy mixture is created. With stirring, the mixture is gradually heated up to 200 ° C, volatile components removed by applying a vacuum. The clear to slightly cloudy oil with a viscosity of 430 mPas and an amine number of 0.23 is obtained.

Production Example 2

693.75 g of an OH-terminated polydimethylsiloxane with a viscosity of 50 mPas are mixed with 21.38 g of aminoethylaminopropylmethyldimethoxysilane, 358.07 g of polyethylene glycol 400 and a basic catalyst. A whitish-cloudy mixture is created. The mixture is gradually heated to 200 ° C. with stirring, volatile constituents being removed by applying a vacuum. After cooling to 60 ° C. and aerating, 10.10 g of succinic acid anhydride are added to the oil. After 90 min. the yellow Ö12 is obtained with a viscosity of 702 mPas and an amine number of 0.12.

Production Example 3

555.00 g of an OH-terminated polydimethylsiloxane with a viscosity of 50 mPas are mixed with 17.10 g of aminoethylaminopropylmethyldimethoxysilane, 573.60 g of 400 polyethylene glycol and a basic catalyst. A whitish-cloudy mixture is created. With stirring, the mixture is gradually heated up to 200 ° C, volatile components are removed by applying a vacuum. Clear to slightly cloudy Ö13 with a viscosity of 209 mPas and an amine number of 0.17 is obtained.

Production Example 4

555.00 g of an OH-terminated polydimethylsiloxane with a viscosity of 50 mPas are mixed with 17.10 g of aminoethylaminopropylmethyldimethoxysilane, 573.60 g of 400 polyethylene glycol and a basic catalyst. A whitish-cloudy mixture is created. With stirring, the mixture is gradually heated up to 200 ° C, volatile components removed by applying a vacuum. After cooling to 60 ° C and aeration, the oil is mixed with 8.00 g of succinic anhydride. After 90 min. the yellow Ö14 is obtained with a viscosity of 249 mPas and an amine number of 0.09.

Comparative example

Example 5

A mixture of 967 g of OH-terminated polydimethylsiloxane with a viscosity of approx. 70 mPas at 25 ° C., 33 g of aminoethylaminopropyldimethoxymethylsilane and a 40% solution of a quaternary ammonium hydroxide in methanol is heated to 80 ° C. for 4 hours under nitrogen and with stirring warmed up. Then the quaternary ammonium hydroxide is rendered ineffective by heating for 60 minutes at 150 ° C. and applying a vacuum, and at the same time the organopolysiloxane is freed from components boiling under these conditions. The organopolysiloxane thus obtained has a viscosity of 1000 mPas at 25 ° C and a titratable amine content of 0.3 ml IN HCl / g substance (Ö15).

Application example (AWB)

20 parts of oil are stirred into 80 parts of water which has been acidified to pH 3 with acetic acid. A slightly cloudy dispersion (AWB1) is obtained.

20 parts of Ö12 are stirred into 80 parts of water. A slightly cloudy dispersion (AWB2) is obtained.

20 parts of Ö13 are stirred into 80 parts of water which has been acidified to pH 3 with acetic acid. A clear solution (AWB3) is obtained.

20 parts of Ö14 are stirred into 80 parts of water. A clear solution (AWB4) is obtained. 4 parts of the emulsifier Genapol X060 (Hoechst AG) and 4 parts of water are mixed homogeneously. 20 parts of Ö15 are now worked in slowly and in portions. The homogeneous mixture is diluted slowly with 74.5 parts of water, then quickly. The emulsion is filtered through fine perlon fabric. 1.5 parts of acetic acid (conc.) Are then added to the emulsion (AWB5).

50 g AWB1 to AWB5 are mixed with 950 g demineralized water. Polyester / cotton fabric (PES / Bw fabric) (65/35) is well immersed in it and squeezed off using a foulard (load 30 kg). The PES / Bw fabrics Gl to G5 are dried at 150 ° C for 5 minutes.

The grip evaluation was carried out in a hand test on a relative scale of 0-10, with the value 10 representing the best soft grip in each case.

The hydrophilicity of the tissue is defined by the time, measured in seconds, that a drop of water takes to a) wet the tissue and b) to be completely absorbed by the tissue.

Fabric soft grip hydrophilicity

Wetting time [s] suction time [s]

Eq 8 1 7

G2 8 1 6 G3 6 1 3

G4 6 1 3

G5 10 50 156

Blank value 0 1 5

The result shows that the silicone oils to Ö14 according to the invention maintain the absorbency of the fabrics treated with them outstandingly and at the same time give them very good soft feel.

Claims

claims

1. Process for textile treatment, in which a composition containing at least one

(A) silane or organosiloxane, the at least one monovalent SiC-bonded radical with primary, secondary and / or tertiary amino groups and at least one

(B) (Iso) -Oxyalkylrest, which is Si-O-C-bonded, is used.

2. A method for textile treatment, in which a composition according to claim 1 is used, characterized in that (B) is the (iso) -oxyalkyl radical (0C _n H _n (-R)) _o , wherein

R can be the same or different and hydrogen or one

Methyl radical means, n have the values 2, 3 or 4 o have the values 1 to 100.

3. Process for textile treatment, in which a composition according to claim 1 or 2 is used, in which the silane or organosiloxane (A) at least one siloxane unit of the general formula (I)

Ra Q b, SiO (, 4.-a-, b _λ ), ( _τ Is)

and all other siloxane units of an organopolysiloxane have the general formula (II)

R ¹ SiO c (4-c), (II) 2

have, where i

R is the same or different monovalent, optionally fluorine, chlorine or bromine-substituted C - ^ - to C ₁₈ -hydrocarbon radicals, hydrogen atoms, C- _j _- to C ₁₂ alkoxy or hydroxyl radicals or alkyl glycol radicals, Q is a group of general formula (III)

-R ² - [NR ³ (CH ₂ ) _m ] _d N (R ³ ) ₂ (III)

means where

₂ R denotes a divalent C- _j _ to C ₁₈ hydrocarbon radical,

₃ R is a hydrogen atom or an optionally fluorine,

Chlorine or bromine or C - ^ - to C ₅ ~ alkoxy-substituted ^ _ - bis

C ₁₈ hydrocarbon residue means a the values 0, 1 or 2, b the values 1, 2 or 3, c the values 0, 1, 2 or 3, d the values 0, 1, 2, 3 or 4 and m the Have values 2, 3, 4, 5 or 6 and the sum of a and b is a maximum of 4.

4. Process for textile treatment, in which compositions according to one or more of claims 1 to 3 are used, in which the amine contents of the compositions are 0.01 to 2 mequiv / g, measured as consumption of In hydrochloric acid in ml / g of the composition ( A), and (B) titrate to neutral.

5. A process for the preparation of the compositions according to any one of claims 1 to 4 by at least one

(A) silane or organosiloxane which has at least one monovalent SiC-bonded radical having primary, secondary and / or tertiary amino groups, and a glycol which has at least one (B) (iso) -oxyalkyl radical can be used.

6. (A) silane or organosiloxane which has at least one monovalent SiC-bonded radical with primary, secondary and / or tertiary amino groups, with the proviso that the organopolysiloxane has only M and D units and the terminal amino-functional group at least one Has hydrogen atom and at least one

(B) (Iso) -oxyalkyl radical.