Title of Invention: Amino-functional polyorganosiloxanes, their production and use
Abstract: Water-soluble, i.e. easily dispersible, amino-functional polyorganosiloxanes obtained by radical polymerization of vinyl compounds containing amino or ammonium groups onto polyorganosiloxanes which contain at least one mercapto group. They are suitable as textile finishing aids, surfactants and emulsifiers.
Detailed Description: Part PAC: EXAMPLE S1
Part PAR: 125 g mercaptopropyl dimethoxymethyl silane (DYNASYLAN 3403, Sivento Chemie GmbH) were weighed into the 4 liter three-neck flask with 3,000 g of a hydroxy-terminated organopolysiloxane with an average composition HO(Si(CH.sub.3).sub.2 O).sub.23 H and 0.5 g sulfric acid (98%), made inert with nitrogen and heated to 140.degree. C. while stirring. After a reaction time of five hours, a Liebig cooler was put into place and 100 g equilibrium cycles were distilled off at a pressure of 780 mbar. The silicone oil obtained in this way was slightly cloudy and had a viscosity of 4,000 mPas.
Part PAC_2: EXAMPLE S2
Part PAR_2: 85 g of a mixture of [O--Si(CH.sub.3)(CH.sub.2 CH.sub.2 CH.sub.2 SH)].sub.n with n=3 to 5, 2,500 g of a trimethylsilyl end blocked polydimethyl siloxane with a viscosity of 1,000 mPas, and 30 g Tonsil catalyst were placed in a 4 liter three-neck flask, and cdaniel@example.net. C. under a nitrogen atmosphere for 20 hours. The product obtained in this way was filtered, and a clear oil with a viscosity of 500 mPas was obtained.
Part PAC_3: EXAMPLE S3
Part PAR_3: In a 0.25 liter three-neck flask, equipped with a stirrer, gas introduction pipe and gas exhaust line, hydrogen sulfide was introduced, while stirring, into a mixture of 0.1 g diazobicyclooctane and 200 g of a trimethylsilyl end-blocked, glycidyl ether modified polydimethyl siloxane (epoxy content: 0.31 mmol epoxy groups/g siloxane; cdaniel@example.net. C. 300 mPas), over a period of two hours, at 20.degree. C. In the highly viscous reaction product, the two cdaniel@example.net ppm and 43.5 ppm had disappeared in the .sup.13 C-NMR spectrum, and new signals had cdaniel@example.net ppm and 76.2 ppm.
Part PAC_4: EXAMPLE S4
Part PAR_4: In a 1 liter three-neck flask, equipped with a stirrer, thermometer, and a reflux cooler, a mixture of 100 g m-xylene, 500 g of a polydimethyl siloxane modified with aminoethyl aminopropyl groups (cdaniel@example.net. C.; 534 mPas; 0.68 wt.-% nitrogen, trimethylsilyl end-blocked) and 35 g thioglycolic acid methyl ester was boiled under a nitrogen atmosphere for eight hours, with reflux, at 150.degree. C. Subsequently, the reaction mixture was cdaniel@example.net. C. and p=50 mbar for two hours. In the highly viscous siloxane with a strong yellow color which was obtained in this way, no amino groups could be detected any longer.
Part PAC_5: EXAMPLE S5
Part PAR_5: 76 g of the compound HS(CH.sub.2).sub.3 Si(CH.sub.2).sub.2 OSi(CH.sub.2).sub.3 (CH.sub.2).sub.2 SH, 2,350 g of a mixture of hexamethyl trisiloxane and octamethyl tetrasiloxane and 25 g Tonsil catalyst were placed in a 4 liter three-neck flask, and cdaniel@example.net. C. under a nitrogen atmosphere for 20 hours. The product obtained in this way was filtered and cdaniel@example.net. C. for two hours. A clear oil with a viscosity of 500 mPas at 25 .degree. C. was obtained.
Part PAC_6: EXAMPLE S6
Part PAR_6: 15 g or the compound HS(CH.sub.2).sub.3 Si(CH.sub.3).sub.2 OSi(CH.sub.3).sub.3 (CH.sub.2).sub.2 SH, 55 g of a mixture of [O--Si(CH.sub.3)(CH.sub.2 CH.sub.2 CH.sub.2 SH)].sub.n with n=3 to 5, 2,300 g of a mixture of hexamethyl trisiloxane and octamethyl tetrasyloxane and 25 g Tonsil catalyst were placed in a 4 liter three-neck flask, and cdaniel@example.net. C. under a nitrogen atmosphere for 20 hours. The product obtained in this way was filtered and cdaniel@example.net. C. for two hours. A clear oil with a viscosity of 1,900 cdaniel@example.net. C. was obtained.
Part PAL: II. Production of the Amino-functional Polyorganosiloxanes
Part PAL_2: General Process Variants
Part PAL_3: Variant A
Part PAR_7: The mercapto-functional siloxane was mixed with the monomer, the solvent, and the initiator in a 250 ml three-neck flask, under a nitrogen atmosphere, and kept at the temperature indicated for eight hours, while stirring. 100 g of the product were mixed with 1,000 g of an aqueous acetic acid solution (3 wt.-%) and 100 g volatiles were distilled cdaniel@example.net. C., under reduced pressure.
Part PAL_4: Variant B
Part PAR_8: The mercapto-functional siloxane was mixed with the non-ionic monomer, the solvent, and the initiator in a 250 ml three-neck flask, under a nitrogen atmosphere, and kept at the temperature indicated for eight hours, while stirring. After one hour, the ionic monomer was added. 100 g of the product obtained were mixed with 1,000 g of an aqueous acetic acid solution (3 wt.-%) and 100 g volatiles were distilled cdaniel@example.net. C., under reduced pressure.
Part PAL_5: Variant C
Part PAR_9: The mercapto-functional siloxane was mixed with the monomer, the solvent, and the initiator in a 250 ml three-neck flask, under a nitrogen atmosphere, and kept at the temperature indicated for eight hours, while stirring. 100 g of the product were mixed with 1,400 g of an aqueous acetic acid solution (3 wt.-%) and 400 g volatiles were distilled cdaniel@example.net. C., under reduced pressure.
Part PAL_6: Variant D
Part PAR_10: 10 wt.-% of the mercapto-functional siloxane, the monomers, the solvent, and the initiator were mixed in a 250 ml three-neck flask, under a nitrogen atmosphere, and the mixture was kept at the temperature indicated for a total of eight hours, while stirring. Starting after one hour of reaction time, the remaining 90 wt.-% of the mercapto-functional siloxane were uniformly dripped in over five hours. 100 g of the product were mixed with 1,000 g of an aqueous acetic acid solution (3 wt.-%) and 100 g volatiles were distilled cdaniel@example.net. C. under reduced pressure.
Part PAC_7: Process Examples V1 to V21 as Well as Comparison Examples Vgl. 1 and Vgl. 2
Part PAR_11: These examples were summarized in the form of a table (Table 1), which contains the substances used, the variant according to which production took place in each instance, as well as the appearance of the product.
Part PAC_8: Process Example V22
Part PAR_12: 100 g of the product from Example S2 were heated with 50 g methyl acrylate, 0.3 g azobis(isobutyronitrile) and 200 g o-xylene in a 1 liter three-neck flask, equipped with a stirrer, reflux cooler, and thermometer, and subsequently heated to 70.degree. C. while stirring. Several minutes after the reaction temperature is reached, a clearly exothermic reaction is found, which must be countered by cooling the mixture. After seven hours of reaction time, a clear, colorless product is obtained, which has, however, become clearly more viscous than the starting mixture. 100 g 3-dimethylamino-1-propylamine are added to this intermediate product, and the mixture is heated at the boiling cdaniel@example.net. C. for twenty hours. Afterwards, a sample of the mixture is taken and a titratable aminonitrogen proportion of 4.7 wt.-% is determined (corresponds to a degree of conversion of 74%). The reflux cooler is replaced with a distillation cooler and the xylene as well as excess amine are distilled cdaniel@example.net. C., under reduced pressure. After the distillation was terminated, a viscous, yellow paste was obtained. 100 g of this paste were mixed with 900 g of an aqueous acetic acid solution (3 wt.-%). After one hour of stirring, a translucent emulsion with a yellowish color was obtained.
Part PAC_9: Process Example V23
Part PAR_13: 30 g dimethylaminopropyl acetate, 100 g mercaptosiloxane from Example S2, 50 g 2-propanol, and 1.8 g dibenzoyl peroxide were weighed into a reactor with an immersion burner made of quartz glass, constantly mixed by means of a nitrogen stream, and cooled with a thermostat to 5.degree. C. After 4 hours of irradiation with a 125 W mercury vapor pressure radiator, a product was obtained which is soluble in an aqueous acetic acid solution (3 wt.-%), producing a clear solution.
Part PAL_7: III. Production of Emulsions
Part PAR_14: Emulsion E1
Part PAR_15: 100 g of the polymerization product from process example V5 were mixed with 5 g acetic acid (100 wt.-%), and 150 g demineralized water were added while stirring. 150 g water/solvent mixture of this solution were distilled off in a cdaniel@example.net. C. The emulsion obtained in this way was clear and easily diluted with water.
Part PAC_10: Comparison Example Vgl.3
Part PAR_16: 15 g siloxane with trimethylsilyl end groups and aminoethyl aminopropyl side chains (0.65 wt.-% nitrogen; cdaniel@example.net. C.: 2,100 mPas) were stirred with 10 g of an isotridecyl polyethylene glycol with an average of seven ethylene oxide units, 1 g acetic acid (100 wt.-%), and 15 g isopropanol, until a clear mixture was obtained. Subsequently, a total of 69.5 g water were added to the mixture in small portions, while stirring. A clear to slightly bluish microemulsion was obtained.
Part PAL_8: IV. Finishing of Textiles (Application Examples)
Part PAC_11: IV a) Foulard Process--Examples A1 to A10
Part PAR_17: The following were used:
Part PA1: a bleached, non-finished cotton terry fabric with 400 g/m.sup.2 for the determination of soft feel and water penetration time, and PA1 a red cotton woven fabric with 120 g/m.sup.2 for the determination of rubbing resistance and the dry wrinkle recovery angle. PA1 1 no precipitates or clouding PA1 2 clouding of the liquor increased PA1 3 oil film visible on the surface PA1 4 oil drops and precipitates are visible
Part PAR_18: The materials were saturated with the liquor in each instance, squeezed off with a two-roller foulard, to a liquor absorption of 80%, and cdaniel@example.net. C. for 10 minutes. Subsequently, the finished fabric was allowed to lie out at room temperature for at least eight hours.
Part PAR_19: Table 2 summarizes the products used and the results of the fabric finished using the Foulard process, for examples A1 to A10.
Part PAC_12: IV b) Drawing Process--Examples A11 to A13
Part PAR_20: A bleached, non-finished cotton terry fabric with 400 g/m.sup.2 was used. This was dipped into the liquor in each instance (liquor ratio 120), cdaniel@example.net. C. for 20 minutes, then taken out and subsequently cdaniel@example.net. C. for 10 minutes and then laid out at room temperature for at least eight hours.
Part PAR_21: The following results were obtained:
Part TBL: Product amount, with Soft feel Product from reference to weight of terry (assessment Example material in wt.-% of feel) Example A11 V1 7.0 3 Example A12 Vg1.1 7.2 1 Example A13 Vg1.3 2.0 2
Part PAL_9: V. Determination Methods for the Results of the Application Examples Determination of Soft Feel (Assessment of Feel)
Part PAR_22: Since the soft feel of textiles is very much dependent on the subject to the subjective sensations of the test person, only a standardization of the general conditions can be achieved, not a standardization of the assessment. In order to guarantee reproducibility nevertheless, the finished samples were assessed with regard to their soft feel and ranked. For this purpose, 1 to n points were assigned to the tested samples by ten persons, as a function of the number n of tested samples, with n points being given for the softest sample and 1 for the least soft sample. The tables show the average values of the points given to the individual samples in each instance.
Part PAL_10: Determination of Water Penetration
Part PAR_23: The finished sample was left in room air humidity for acclimatization, for at least eight hours, then a drop of de-ionized water was placed on it and the time until the drop of water was absorbed by the fabric was determined, but no longer than three minutes. Five determinations were made, and the average was found.
Part PAL_11: Determination of Rubbing Resistance
Part PAR_24: The determinations were conducted in accordance with the standard EN ISO 105-XI2 and 105-A03, using a red cotton woven fabric.
Part PAL_12: Determination of Liquor Stability
Part PAR_25: In order to test the stability of organopolysiloxane emulsions against alkalis in the finishing liquor, the following test was conducted:
Part PAR_26: The liquors were mixed in a 1000 ml beaker, in accordance with the formulation indicated, and adjusted to a pH of 10 using sodium hydroxide solution (10 wt.-%). Subsequently, the liquor was stirred with a vane stirrer at 2000 rpm for twenty minutes. After this time had elapsed, the stirrer was shut off, the foam was allowed to dissipate, and the surface of the liquid was observed for precipitates after another fifteen minutes.
Part PA0: Assessment:
Part PAR_27: For the emulsions which demonstrate precipitates or an oil film, there is the risk, in textile finishing, that if alkalis are entrained into the finishing liquor, the emulsion will be destroyed and that this will result in deposits on the rollers and spots on the fabric.
Part PAR_28: This application is based on German Application No. DE 19802 069.4, filed Jan. 21, 1998, and incorporated herein by reference in its entirety.
Part TBL_2: TABLE 1 Production of the amino-functional polyorganosiloxanes Examples Substances used V1 V2 V3 V4 V5 V6 V7 V8 V9 V10 V11 V12 V13 S1 Mercaptosiloxane from Example 1 100 100 S2 Mercaptosiloxane from Example 2 100 100 100 100 100 100 100 S3 Mercaptosiloxane from Example +1-310-347-2648 S4 Mercaptosiloxane from Example 4 100 S5 Alpha-omega mercapto 100 M1 N,N-dimethylaminopropyl acrylamide 30 25 25 25 25 25 25 M1 N,N-dimethylaminopropyl methacrylamide 30 15 M1 N,N-dimethylaminoethyl methacrylate 30 M1 N-tert. butylaminoethyl methacrylate 30 M1 N,N-dimethylaminoethyl acrylate 30 M1 N,N,N-trimethylammonium propyl acrylamide 5 (50% solution in water) M1 N,N,N-trimethylammonium propyl methacrylamide 5 (50% solution in water) M1 N,N-N,trimethylammonium ethyl methacrylamide 5 (50% solution in water) M1 N,N-dimethyl-N-benzylammonium methyl 15 methacrylate (50% solution in water) M2 Diallyl amine 40 15 M2 Diallyl dimethylammonium chloride (50% solution 5 in water) I 2,2'-azobis(isobutyronitrile) 0.5 0.4 0.3 0.3 0.3 0.3 I 2,2'-azobis(2,4-dimethyl valeronitrile) 0.3 0.2 0.2 0.3 0.3 I 2,2'-azobis(2-methyl butyronitrile) 0.2 I Dibenzoyl peroxide 0.3 L Isopropanol 100 70 55 100 100 86 L Toluene 100 100 100 L Acetic acid isopropyl ester 100 L 2-butanone 100 Reaction temperature in .degree. C. 67 60 60 57 57 62 65 67 67 65 65 66 78 Process variant C A D C A A C B B B B B C Appearance of the product b a b a a c a a a a a a b Examples Substances used V14 V15 V16 V17 V18 V19 V20 V21 Vgl.1 Vgl.2 S1 Mercaptosiloxane from Example 1 100 S2 Mercaptosiloxane from Example 2 100 100 100 100 100 100 100 100 S6 Alpha-omega mercapto TMS 100 M1 N,N-dimethylaminopropyl acrylamide 20 15 M1 N,N-dimethylaminopropyl methacrylamide +1-310-347-2648 M1 N,N-dimethylaminoethyl acrylate 22 7.5 M2 Diallyl dimethylammonium chloride (50% solution in water) 3 M3 n-butyl acrylate 10 15 30 M3 2-ethyl hexyl methacrylate 5 15 M3 Methoxy polyethylene glycol-350 methacrylate 15 M3 Acrylamide 3 M3 N-butoxy methyl methacrylamide 3 M3 Vinyl acetate 5 M3 Methacrylic acid 6 M3 Vinylidene chloride 7 M3 2-acrylamido-2-methyl propane sulfonic acid 4 I 2,2'-azobis(isobutyronitrile) 0.4 0.4 I 2,2'-azobis(2,4-dimethyl valeronitrile) (Wako V-65) 0.2 0.3 0.3 0.3 0.3 0.3 0.3 0.3 I Dibenzoyl peroxide L Isopropanol 50 70 15 100 100 L Toluene 100 100 L 2-butanone Reaction temperature in .degree. C. 58 60 60 65 65 66 57 57 57 57 Process variant A A A A A A B A C C Appearance of the product c c a a a b a a c d I = initiator L = solvent a - clear mixture b - bluish shimmering to slightly cloudy emulsion c - white emulsion d - no emulsion, mixture separated into oil and water layer
Part TBL_3: TABLE 2 Application Examples Examples Substances used A1 A2 A3 A4 A5 A6 A7 A8 A9 A10 Product from Example V1 35 Product from Example V2 20 Product from Example V6 21 Product from Example V7 35 Product from Example V9 32 Product from Example V14 20 Product from Example V20 36 Product from Example V21 34 Product from Example Vgl.1 36 Product from Example Vgl.3 [sic] 10 Acetic acid 100% 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Water, de-ionized 465 480 478 465 467 480 464 466 464 490 Soft feel 7.2 7.1 7.1 6.7 5.9 3.8 4.9 4.2 1 7.1 Water penetration time according to TEGEWA drop 127 &gt;180 &gt;180 98 &gt;180 87 52 34 &gt;180 &gt;180 test in sec Wrinkle recovery angle according to DIN 53890 115 118 121 116 123 112 118 116 128 126 Dry rubbing resistance according to EN ISO 105-X12 5 5 5 5 5 5 5 5 5 4 Wet rubbing resistnace according to EN ISO 105-X12 4 4 4 4 4 4 4 4 4 2 Liquor stability at pH 10 1 1 1 1 1 2 1 1 3 4 Finishing examples on the foulard: all information concerning liquor composition in grams


{'bibliographic_information': "{'Patent Number': '06201093&', 'Series Code': '9', 'Application Number': '2332019', 'Application Type': '1', 'Art unit': '172', 'Application Filing Date': '19990120', 'Title of Invention': 'Amino-functional polyorganosiloxanes, their production and use', 'Issue Date': '20010313', 'Number of Claims': '21', 'Exemplary Claim Number(s)': '1', 'Assistant Examiner': 'Robertson; Jeffrey B.', 'Primary Examiner': 'Dawson; Robert'}", 'source_file': './grant/2001/pftaps20010313_wk11.txt', 'source_data': 'USPTO-Grant'}