Title of Invention

NEW BIODEGRADABLE ORGANO SILICONE POLYMER

Abstract

Wherein R = CH3 and R2 = fatty acid or a mixture of fatty acids/glycerides m = 7 -15, n = 50 -100, p = 10 - 30 which would be advantageously biodegradable and therefore environment friendly and also be suitable for use as softener for textiles and for varied other applications including as a polish and as a lubricant for use in yarn/thread manufacture. The organo silicone polymer can be obtained in desired form, liquid or solid (wax) depending upon the required end use.

Full Text

The invention relates to amido-containing organosilicon cambounds, their preparation and their use. Conventionally aminosilicone emulsions or cationic softeners or mixtures thereof are used in the softening treatment of textiles and garments, by- exhaust or padding method. But such softeners apart from not being easily biodegradable have some undesir- able effects on the fabric after treatment as discussed hereunder: (i) Cationic softener has softening effect but it doesn't have permanent anchorage to the textile. Moreover these cationic softeners are alkaline in nature, thus causing yellowing of the textile. (ii) Conventional aminosilicone emulsion has good softening effect as well as permanent bond to the fabric but causes yellowing of fabric. (iii) Mixtures of aminosilicone emulsion and cationic softener have a good to moderate softening effect but high alkalinity of such mixtures also causes yellowing of the textile. Also, because they are mixtures of cationic softener and conventional aminosilicone emulsion, they provide less anchorage to the textile because of their cationic component. US-A 4,104,296 (Union Carbide Corporation, issued 1 August 1978) and US-A 3.440,261 (Dow Corning Corporation, issued 22 April 1969) describe amido- containing organosilicon compounds. The invention has for its object to provide organosilicon compounds that are useful as softeners for textiles, confer a soft hand on textiles, have good adhesion to textiles, confer good protection against ozone fading on textiles and do not cause yellowing of textiles. It is a further object to provide organo- silicon compounds that can be present both in liquid and in solid form, that are readily emulsifiable and capable of forming (micro) emulsions and that , are biodegradable and environmentally friendly. These objects are achieved by the invention. The invention accordingly provides amido- containing organosilicon compounds of the general formula where R, which may differ, is a monovalent hydrocarbon radical, R1, which may differ, is a hydrogen atom, an alkyl radical or an alkoxyalkyl radical, Y, which may differ, is a radical of the formula : -(R4-NA-)ZR4-NR3A, where R3, which may differ, is a hydrogen atom or an alkyl radical, R4 is a divalent hydrocarbon radical, A is an R3 radical or a radical F of the formula -C{=0)R2 where R2, which may differ, is a monovalent saturated or unsaturated hydrocarbon radical of at least 15 carbon atoms, preferably of a fatty acid, z is 0 or an integer from 1 to 10, preferably 0 or 1, 2, 3, a is 0, 1, 2 or 3, c is 0, 1 or 2 and d is 0, 1, 2 or 3, subject to the proviso that the sum total of a, c and d in the units of the formula (I) is not more than 3 and each molecule contains at least one Y radical with at least one F radical. The invention further provides a process for preparing the amido-containing organosilicon compounds, wherein amino-containing organosilicon compounds (1) of the general formula where R, R1, a and d are each as defined above, X is a radical of the formula where R4 and z are each as defined above, R5, which may differ, is a hydrogen atom or an alkyl radical, subject to the proviso that a hydrogen atom is attached to at least one nitrogen atom in the X radical, b is 0, 1 or 2, subject to the proviso that the sum total of a, b and d in the units of the formula (II) is not more than 3 and each molecule contains at least one X radical, are reacted with fatty acids (2) having at least 16 carbon atoms or with glycerides thereof. R is preferably a monovalent hydrocarbon radical of 1 to 18 carbon atoms. Examples of R are alkyl radicals, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert- pentyl, hexyl, such as n-hexyl, heptyl, such as n-heptyl, octyl, such as n-octyl and isooctyl, such as 2,2,4-trimethylpentyl, nonyl, such as n-nonyl, decyl, such as n-decyl, dodecyl, such as n-dodecyl, octadecyl, such as n-octadecyl; alkenyl, such as vinyl and allyl, cycloalkyl, such as cyclopentyl, cyclohexyl, cyclo- heptyl and methylcyclohexyl, aryl, such as phenyl, naphthyl, anthryl and phenanthryl; alkylaryl, such as o-, m-, p-tolyl, xylyl and ethylphenyl; aralkyl, such as benzyl, a- and ß-phenylethyl, of which methyl, ethyl, n-propyl, isopropyl and n-butyl are preferred and methyl is particularly preferred. R1 is preferably alkyl of 1 to 4 carbon atoms. Examples of alkyl R1 are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl and tert-butyl, of which methyl and ethyl are preferred. Examples of alkoxyalkyl are methoxyethyl and ethoxyethyl. R2 is preferably a monovalent saturated or unsaturated hydrocarbon radical of 15 to 27 carbon atoms, preferably 15 to 23 carbon atoms, particularly preferably 15 to 19 carbon atoms. Examples of alkyl R are also fully applicable to alkyl R3 and alkyl R5. R4 is preferably a divalent hydrocarbon radical of 1 to 12 carbon atoms per radical. Examples of R4 are methylene, ethylene, propylene, butylene, cyclohexyl- ene, octadecylene, phenylene and butenylene, of which ethylene and n-propylene are preferred, in particular on account of their convenient obtainability. Examples of X are H2N(CH2)3- H2N(CH2)2NH(CH2)3- H2N (CH2) 2NHC (CH3) 2CH2- (H3C)2N(CH2)2NH(CH2)3- H2N(CH2)2- H3CNH(CH2)3- H2N(CH2)4- H2N(CH2)5- H(NHCH2CH2)3- C cyclo-C6H11NH(CH2)3-, of which H2N(CH2)3- H2N(CH2)2NH(CH2)3- are preferred. Examples of Y are therefore ANH(CH2)3- ANH(CH2)2NH(CH2)3- ANH(CH2)2NA(CH2)3- ANH (CH2) 2NHC (CH3) 2CH2 - ANH (CH2) 2NAC (CH3) 2CH2 - (H3C)2N(CH2)2NA(CH2)3- ANH(CH2)2- H3CNA(CH2)3- ANH(CH2)4- ANH(CH2)5- ANHCH2CH2NHCH2CH2NHCH2CH2 - ANHCH2CH2NACH2CH2NHCH2CH2 - ANHCH2CH2NACH2CH2NACH2CH2 - C4H9NA(CH2)2NA(CH2)2- and cyclo-C6HnNA(CH2)3-, of which preference is given to ANH(CH2)3- ANH(CH2)2NH(CH2)3- ANH(CH2)2NA(CH2)3-, wherein A is a radical of the formula -C(=0)R2 (where R2 is as defined above). The organosilicon compounds of the invention are preferably organopolysiloxanes. The organosilicon compounds of the invention preferably have a viscosity of 50 mPa. s at 25°C to 1 000 00 mPa.s at 60°C, more preferably 50 mPa. s at 25°C to 10 000 mPa.s at 60°C. The organosilicon compounds of the invention preferably have a molecular weight (Mn) of 500 to 1000000 g/mol, more preferably 500 to 100 000 g/mol. The organosilicon compounds of the invention preferably have an amine number of 0.01 to 4.0 mequiv/g, more preferably 0.1 to 2.0 mequiv/g. The organosilicon compounds of the invention can be present in liquid form or in solid form, for example in waxy form. The process of the invention is preferably carried out using amino-containing organosilicon compounds (1) that are organopolysiloxanes of the general formula where R and X are each as defined above, g is 0, 1 or 2, n is 0- or an integer from 1 to 1000, m is 0s or an integer from 1 to 100, subject, to the proviso that each molecule contains at least one X radical and the n-units (SiR2O) and the m-units (SiRXO) may have any distribution in the molecule. The organosilicon compound of the invention is therefore preferably an organopolysiloxane of the general formula where R and Y are each as defined above, g is 0, 1 or 2, n is 0 or an integer from 1 to 1000, p is 0 or an integer from 1 to 100, subject to the proviso that each molecule contains at least one Y radical with at least one F radical and the n-units (SiR20) and the p-units (SiRYO) may have any distribution in the molecule. The organosilicon compounds of the formula (I) according to the invention, as well as amido groups, may additionally contain amino groups, i.e. units of the formula (II), and the organopolysiloxanes" of the formula (IV) may additionally contain SiRXO units, if the X amino groups in the organopolysiloxanes of the formula (III) were not all converted into Y amido groups, for example because the reaction with fatty acids (2) was carried out substoichiometrically or did not go to completion. The organosilicon compounds (1) used in the process of the invention have a viscosity of preferably 10 to 100 000 mPa.s at 25°C, preferably 50 to 10 000 mPa.s at 25°C. The preparation of the organosilicon compounds (1) used is known to one skilled in the art. The organosilicon compounds (1) are preferably prepared by equilibration of organopolysiloxanes selected from the group consisting of linear organopolysiloxanes having terminal triorganosiloxy groups, linear-^organopoly- siloxanes having terminal hydroxyl groups, cyclic organopolysiloxanes and interpolymers of diorgano- siloxane and monoorganosiloxane units with amino- silanes, such as ?-aminopropylniethyldimethoxysilane or aminoethylaminopropylmethyldimethoxysilane, in the presence of catalysts that promote equilibration, more preferably basic catalysts, such as alkali metal hydroxides, e.g. sodium hydroxide or potassium hydroxide, or trimethylammonium hydroxide. Fatty acids useful as fatty acids (2) in the process of the invention preferably have 16 to 28 carbon atoms, more preferably 16 to 24 carbon atoms, particularly preferably 16 to 20 carbon atoms, i.e. are preferably fatty acids of the formula R2COOH, where R2 is as defined above. Saturated or unsaturated fatty acids or glycerides thereof can be used. One kind of fatty acid or two or more kinds of fatty acids may be used. The glycerides can be glycerol esters of mixtures of various fatty acids. Examples of fatty acids are palmitic acid (C16) , stearic acid (C18) , oleic acid (C18) , linoleic acid (C18) , linolenic acid (C18) , hexacosanoic acid (C26) and glycerides thereof, for example glycerol monostearate. It is further possible to use vegetable oils, such as safflower oil, sesame oil, soybean oil, maize oil, sunflower seed oil, olive oil, palm oil, coconut oil and castor oil. Depending on the molecular weight and the number of X amino groups in the organosilicon compounds (1) used, saturated fatty acids, such as stearic acid, or glycerides, such as glycerol monostearate, are preferably used to obtain the organosilicon compounds of the invention in solid form, for example as waxes, and unsaturated fatty acids, preferably polyunsaturated fatty acids, such as linoleic acid or linolenic acid, or the abovementioned vegetable oils are preferably used to obtain the organosilicon compounds of the invention in liquid form. The process of the invention utilizes the fatty acids (2) or the glycerol esters of these fatty acids in such amounts that the acid group in the fatty acid (2) is present in a molar ratio of preferably 0.1:1 to 1.2:1, more preferably 0.5:1 to 1.0:1, to N-attached hydrogen in the X radical of the c ganosilicon compound (1). The process of the invention is carried out at a temperature of preferably 120°C to 180°C, more preferably -130°C to 150°C, and preferably at the pressure of the ambient atmosphere, i.e. at 1020 hPa (absolute). However, the process of the invention can also be carried out at lower pressures, such as 3 to 500 hPa, or higher pressures. The process of the invention can be carried out in the presence or absence of an organic solvent. Examples of organic solvents are toluene, xylene, n-hexane and cyclohexane. The water formed in the process of the invention can be removed, preferably by azeotropic dis- tillation, in which case the azeotropic distillation can be carried out in the presence of a water-removing agent, such as dicyclohexylcarbodiimide. The organosilicon compounds of the invention can be emulsified and are then present in the form of (micro)emulsions. The emulsions are prepared by the organosilicon compounds of the invention being mixed with emulsifiers, such as neutral or ionic emulsifiers, and water and subsequently emulsified. The preparation of emulsions is known to one skilled in the art. The mixing and emulsifying can be carried out in customary mixing apparatus suitable for preparing emulsions, such as high-speed stator-rotor stirrers after Professor P. Willems of the kind known under the registered trademark "Ultra-Turrax". The organosilicon compounds of the invention have the advantage of being biodegradable and environmentally friendly The invention further provides a process for impregnating organic fibres with the organosilicon compounds of the invention. The organosilicon compounds of the invention can be used, preferably in liquid form, as softeners for textiles, in which case the textiles are impregnated with the organosilicon compounds of the invention. The organosilicon compounds of the invention have the advantage of imparting a soft hand effect to the treated textiles, of possessing good anchorage on the textiles and of conferring ozone fastness and stability to yellowing on the textile fabrics. The inventive process for impregnating organic fibres can be used to impregnate all organic fibres in the form of filaments, yarns, webs, mats, strands, woven, loop-formingly knitted or loop-drawingly knitted textiles as have hitherto been impregnable with organo- silicon compounds. Examples of impregnable fibres are fibres composed of keratin, especially wool, inter- polymers of vinyl acetate, cotton, rayon, hemp, natural silk, polypropylene, polyethylene, polyester, poly- urethane, polyamide, cellulose, viscose and mixtures of at least two such fibres. As is clear from the preced- ing recitation, the fibres can be of natural or synthetic origin. The textiles can be present in the form of fabric webs or garments or parts of garments. Application to the fibres to be impregnated can be effected in any manner known to be suitable for impregnating fibres, for example by dipping, brushing, casting, spraying, including spraying from an aerosol pack, rolling, padding or printing. The organosilicon compounds of the invention can further be used as lubricants for yarn or thread finishing. The organosilicon compounds of the invention can further be used, preferably in solid form, for example in the form of a wax, as a polish or polishing agent for ceramic surfaces and coatings. The organpsilicon compounds of the invention can further be used in cosmetics. The organosilicon compounds of the invention can further be used in hair care agents. The organosilicon compounds of the invention can further be used in liquids for reprography. The objects/advantages of the present invention and the means for executing it will now be more par- ticularly described with reference to non-limiting illustrative- embodiments. Examples Example 1 The reactor was charged with 4000 g of a silanol-terminated polydimethylsiloxane having a visco- sity of 80 cps (25°C) , 272 g of y-aminoethylaminopropyl- methyldimethoxysilane, 100 g of a trimethylsiloxy- terminated siloxane having a viscosity of 10 cps (25°C) and 50 g of tetramethylammonium siliconate catalyst. Nitrogen purging was started in the reaction. The reactor was heated to about 110°C and maintained at that temperature for about 4 h. After about 4 h of reaction the temperature inside the reactor was set to 150°C. The temperature inside the reactor was main- tained for 30 min. Vacuum was applied at 150°C after nitrogen purging was stopped, to obtain 510 g of volatiles. The reactor contents were cooled down to 135°C. Next 800 g of maize oil was introduced into the reactor and purged with nitrogen. Reaction was continued for 12 hours under vacuum. This gave 4650 g of a light brown clear polymer having a viscosity of 10 000 cps (25°C) and a volatiles content of 1.4%. Si29 NMR spectroscopy confirmed the desired structure of the polymer. The amine number of the polymer was found to be 0.3 mmol/g. Examples 2 to 4: Further examples (2, 3 and 4) were carried out using the same procedure as in Example.1. but with differente fatty acid/glycoside ratios. The resets are presented in Table 1. From Table I above it is apparent that the final polymer obtained is a liquid when unsaturated fatty acids are used and a wax when saturated fatty acid is used. Examples 5 to 12: Emulsions were made using the polymers of Examples 1 to 4 above and a conventional aminosilicone polymer having an amine number of 0.57 and a viscosity of 1300 cps at 25°C (designated as Example 5) as detailed under Table II. The emulsions (i.e. Examples 6 to 9) as reported in Table II were all made using the same emulsifiers and differ only in the biodegradable organosilicone polymer. Example 10 is the emulsion of Example 5, again using the same emulsifiers. Example 11 is a mixture of Example 5 and cationic softener. Example 12 is exclusively a catiohic softener. The soft hand characteristics of the various emulsions obtained under Examples 6 to 12 were tested as detailed hereunder. Example 13: Three different types of white textile, namely 100% polyester; blend of 60% viscose/40% polyester; and 100% cotton, were treated with these seven examples by padding. The padding bath was kept at 4% solid and applied at 1% pick-up. After padding, the textiles were conditioned at 160°C for 10 min. The thusly treated textiles were submitted to a panel of four panellists, to judge the softness, who had no idea which was treated with what. The panellists awarded the ratings reported in Table III below as per their individual feel of softness. From Table III it is clear that the new organo- silicon polymer softener (Examples 6 to 9) imparts i excellent softness compared with conventional amino- silicone or cationic softener or mixture thereof. Example 14: The new biodegradable silicone polymer of this invention was tested to determine the biodegradability of the polymer in comparison with conventional amino- silicone polymers. For the purpose of illustrating better biodegradability in wastewater streams three Examples 1, 4 and 5 were investigated. Three aqueous solutions of these examples were prepared at such a concentration that the chemical oxygen demand (COD) was initially 5000. Then, for typical wastewater treatment, 2% hydrogen peroxide was added to each. At 32°C samples were taken at regular intervals to determine the residual COD. The values obtained are illustrated in the accompanying graph. It can be seen from Fig. 1 that the COD of Examples 1 and 4 has significantly decreased by the second day, whereas Example 5 remained at 2000 under the same conditions. This clearly reveals the low COD contents of the polymers of this invention, which demonstrates the fast biodegradability and thus the environmental friendliness of the polymer. claims 1. Amido-containing organosilicon compounds of the general formula where R, which may differ, is a monovalent hydrocarbon radical, R1, which may differ, is a hydrogen atom, an alkyl radical or an alkoxyalkyl radical, Y, which may. differ, is a radical of the formula where R3, which may differ, is a hydrogen atom or an alkyl radical, r4 is a divalent hydrocarbon radical, A is an R3 radical or a radical F of the formula where R , which may differ, is a monovalent saturated or unsaturated hydrocarbon radical of at least 15 carbon atoms, z is 0 or an integer from 1 to 10, a is 0, 1, 2 or 3, c is 0, 1 or 2 and d is 0, 1, 2 or 3, subject to the proviso that the sum total of a, c and d in the units of the formula (I) is not more than 3 and each molecule contains at least one Y radical with at least one F radical. 2. Organosilicon compounds according to Claim 1, characterized in that they are organopolysiloxanes of the general formula where R and Y are each as defined in Claim 1, g ,is 0, 1 or 2, n is 0 or an integer from 1 to 1000, p is 0 or an integer from 1 to 100, subject to the proviso that each molecule contains at least one Y radical with at least one F radical and the n-units (SiR2O) and the p-units (SiRYO) may have any distribution in the molecule. 3.- Organosilicon compounds according to Claim 1 or 2, characterized in that Y is a radical of the formula R2C(=O)NH-(CH2)3- or R2C(=O)NH-(CH2)2-NH-(CH2)3- or R2C(=O)NH-(CH2)2-NC(=O)R2-(CH2)3-, where R2 is as defined in Claim 1. 4. Process for preparing the amido-containing organosilicon compounds according to Claim 1, 2 or 3, characterized in that amino-containing organosilicon compounds (1) of the general formula where R, R1, a and d are each as defined above, X is a radical of the formula where R4 and z are each as defined in Claim 1, R5, which may differ, is a hydrogen atom or an alkyl radical, subject to the proviso that a hydrogen atom is attached to at least one nitrogen atom in the X radical, b is 0, 1 or 2, subject to the proviso that the sum total of a, b and d in the units of the formula (II) is not more than 3 and each molecule contains at least one X radical, are reacted with fatty acids (2) having at least 16 carbon atoms or with glycerides thereof. 5. Process according to Claim 4, characterized in that the amino-containing organosilicon compounds (1) are organopolysiloxanes of the general formula where R and X are each as defined in Claim 4, g is 0, 1 or 2, n is 0 or an integer from 1 to 1000, m is 0 or an integer from 1 to 100, subject to the proviso that each molecule contains at least one X radical and the n- units (SiR2O) and the m-units (SiRXO) may have any distribution in the molecule. 6. Process according to claim 4 or 5, characterized in that X is a radical of the formula 7. Process for impregnative organic fibres with the organosilicon comopounds according to claim 1, 2 or 3. Wherein R = CH3 and R2 = fatty acid or a mixture of fatty acids/glycerides m = 7 -15, n = 50 -100, p = 10 - 30 which would be advantageously biodegradable and therefore environment friendly and also be suitable for use as softener for textiles and for varied other applications including as a polish and as a lubricant for use in yarn/thread manufacture. The organo silicone polymer can be obtained in desired form, liquid or solid (wax) depending upon the required end use.

Documents:

814-CAL-1999-(09-03-2012)-FORM-27.pdf

814-cal-1999-granted-abstract.pdf

814-cal-1999-granted-claims.pdf

814-cal-1999-granted-correspondence.pdf

814-cal-1999-granted-description (complete).pdf

814-cal-1999-granted-examination report.pdf

814-cal-1999-granted-form 1.pdf

814-cal-1999-granted-form 18.pdf

814-cal-1999-granted-form 2.pdf

814-cal-1999-granted-form 3.pdf

814-cal-1999-granted-form 5.pdf

814-cal-1999-granted-pa.pdf

814-cal-1999-granted-reply to examination report.pdf

814-cal-1999-granted-specification.pdf