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    • 专利摘要:
    A process for the production of modified polymers, preferable in organic solvents, by radical-initiated polymerization of (Ia) 70 to 99.9 parts by weight of esters of the formula CH2=C(R)-COOR'(Ia) IN WHICH R is -H or -CH3 and R' are 1 to 18 C-alkyl radicals, at least 50% by weight of the esters of (Ia) being those in which R' are 1 to 4 C-alkyl radicals, (Ib) 0, 1 to 20 parts by weight of omega -hydroxyalkyl esters of acrylic, methacrylic, maleic and/or fumaric esters, the said dicarboxylic acids are possibly etherified on the second carboxylic group with 1 to 12 C-atoms containing alcohols and (Ic) 0 to 10 parts by weight of other unsaturated monomers, the sum of (Ia), (Ib) and (Ic) amounting to 100 parts by weight, in the presence of (II) 5 to 40 parts by weight of terminal blocked alkyl-hydrogen polysiloxanes, the alkyl radicals containing 1 to 4 carbon atoms, with a viscosity of 20 to 1000 cP at 20 DEG C., the ratio of alkyl radicals to hydrogen atoms thereof being from 13 : 1 to 1 : 1, in which ratios the terminal groups are not included. Organic solvents containing the obtained modified polymers and usual curing agents for alkyl-hydrogen polysiloxanes are useful for treating fibrous material to give water-tight and water-repellent effects.
    公开号:SU793405A3
    申请号:SU772455513
    申请日:1977-03-01
    公开日:1980-12-30
    发明作者:Дайнер Ханс；Санднер Бернхард；Бернхайм Вилли
    申请人:Хемише Фабрик Пферзее Г М Б Х (Фирма)；
    IPC主号:
    专利说明:

    (54) METHOD OF OBTAINING PRIVATED COPOLYMERS
    The invention relates to the field of graft copolymers, suitable for treating textiles. A method is known for producing graft copolymers by radical polymerization of 100 parts by weight of a mixture of esters of (meth) acrylic acids with unsaturated compounds in the presence of 5-40 parts by weight. polyorpanosiloxanes in an organic solvent l. In the known method, dialkyl polysilanes are used as polyorganosiloxanes, unsaturated compounds (meth) acrylic acids are used as unsaturated compounds, and the process is carried out in an inert liquid, for example, which is distilled off at the end of the reaction, resulting in a polymer used to prepare elastomers serving as sealing agents, molding compounds, lubricants and coatings. However, this copolymer cannot be used for treating textiles, since there are no hydrogen atoms with silicon atoms in their structure. The purpose of the invention is to obtain copolymers suitable for the treatment of textiles. This goal is achieved by the fact that in the method of obtaining graft copolymers by radical polymerization, 100 weight parts. mixtures of esters of (meth) acrylic acids with unsaturated compounds in the presence of 5-40 parts by weight polyorganosiloxanes in an organic solvent environment, 0.1-20 parts by weight are used as unsaturated compounds. esters of (meth) acrylic acids and / or mono- and diesters of fumaric and maleic acids containing free hydroxyl groups, and as polyorganosiloxanes - methyl hydrogen polysiloxane, in which the ratio of alkyl residues associated with silicon to silicon atoms of hydrogen from 13: 1 to 1: 1 with a viscosity of 30-230 cP at 20 ° C, as well as the fact that the polymerization is carried out in a solvent that is not miscible with water. For the process according to the invention, the following components are taken into account as the esters of acrylic and methacrylic acids of the component Ta), which, under known conditions, in the branched, alkyl residue contain 1-18 C-atoms. As examples, methyl, ethyl, butyl and octylacrylate and methacrylate and esters of acrylic and methacrylic acids of 2-ethylhexanol, as well as n-dodecanol and n-octadecanol should be mentioned here. Of the monomers of formula 1a, at least 50% by weight, preferably 70% by weight, are used. acrylic or methacrylic acid esters and alcohols with 1-4 C-atoms. In general, acrylic esters are preferred. In the polymerization, it is advisable to use components 1a esters containing terminal free hydroxyl groups in addition to complex esters, since in this case, additional advantages are achieved. These esters, designated as component 16, are derived from acrylic, methacrylic, maleic and fumaric acids which are esterified with a hydroxyl group of dihydric alcohols, the alkylene residue of which may also contain oxygen. As such, first of all, esters of the formula -COOR C 15) C „, J and / or R2.00C-CH CH-COORi CIS) are taken into account, moreover R. -H, -CH: ;; R - (CH2.) P-OH or - (() g „-OH and RI H or an alkyl residue with 1-12 C-atoms, where or 3. As compounds of formula 1b, for example, 2- OXYETHYL-, 3-hydroxypropyl-, and 4-hydroxybutyl acrylate or methacrylate. In addition, one-sidedly esterified with diethylene glycol or dipropylene glycol is also suitable for acrylic or methacrylic acid. As compounds of the formula 16 for R; group of mono - or diethylene glycol, propylene - or butylene glycol, and also dipropylene glycol In the case of diesters of formula 1b (RI alkyl residue with 1-12 C-atoms) the dL residue containing free hydroxyl groups has the same meaning as in the case of monoesters, and then it means, for example, methyl or 2- ethylhexyl residue In the preferred embodiment of modified polymerization products according to the invention, which contain free hydroxyl groups, esters are used containing terminal free hydroxyl groups (component 16 in such quantities as their fraction in relation to the sum of components 1a, 16 and 1b, it is 0.1-20, preferably 0.1-10, in particular 28% by weight. in the latter region, the most preferred results are obtained. Further, in the case of the process proposed according to the invention, along with esters of acrylic acid and methacrylic acids of formula 1a, and in known cases, component 16 also uses insignificant amounts capable of copolymerization with compounds of formula 1a and unsaturated compounds designated 1c. As such, take into account, for example, styrene, vinyltoluene and acrylic acid. However, their number in relation to the sum of components 1a, 16 and 1c should not exceed 10% by weight and in particular 5% by weight. All of these polymerizable compounds can be used in standard form. Polymerization is carried out in the presence of alkyl alkyl hydrogen polysiloxanes blocked at the ends. Methylhydrogen polysiloxanes are used as such. By these, first of all, it is necessary to understand such alkyl hydrogen polysiloxanes, in which the ratio of alkyl residue: hydrogen atoms without taking into account the terminal groups, such as trimethylsilyl groups, is about 1: 1. Along with them, however, alkyl hydrogen sulfides, in which the ratio of alkyl residues: a hydrogen atom is greater than 1: 1, namely approximately up to 13: 1, are also suitable. However, the products that are obtained by using alkyl hydrogen polysiloxanes, in which the ratio of alkyl residues: hydrogen is greater than 5: 1, are less suitable, since the advantages of the products obtained according to the invention and used according to the invention are primarily based on those associated with silicon and present in the modified polymers. hydrogen atoms. Alkylhydrogen polysiloxanes do not contain any hydrolysis sensitive groups or hydroxyl groups, and they are blocked at the ends, for example, with trimethylsilyl groups. Hydrogen polysiloxanes used in the framework of the process of the invention have a viscosity of 20-230 cP at 20 ° C, particularly preferred methyl hydrogen polysiloxanes have a viscosity of 20-350 cP at 20 ° C. The ratio of the polymerizing compounds used for the reaction (the sum of components 1a, 1b, and 1c) to alkyl hydrogen polysiloxanes f of component II) is 100 parts by weight. 5-40 weight.h. Higher proportions of alkylorodopolysiloxanes do not lead to any additional advantages, since at a ratio of 1 to II in the polymerization from 100 to 5-20 gee.h. get very well suitable products, this ratio is primarily preferable for economic reasons.
    Polymerization is carried out by conventional free-radical-forming initiators. As such, primarily organic peroxides are taken into account. Examples should be given; dialkyl peroxide, such as diethyl peroxide, diisopropyl peroxide, di-t-butyl peroxide; dilauryl peroxide; alkyl hydroperoxides such as tert-butyl hydroperoxide; diacyl peroxide as diacetyl peroxide, dilauroyl peroxide, dibenzoyl peroxide, bis-2,4-dichlorobenzoyl peroxide; ketone peroxide, as methyl ethyl ketone peroxide and cyclohexanone peroxide. Azo compounds are also suitable, such as, for example, azodiisobutyronitrile.
    As initiators, it is particularly preferable to use such which, primarily in the temperature range from about 50 to about in certain cases in the presence of a suitable solvent, can form enough radicals to initiate (initiate) the polymerization. Of these compounds, peroxide 6IS-C2,4-dichlorobenzoyl), dibenzoyl peroxide, tert-butyl peroctoate and dilauroyl peroxide can be mentioned. In the same way, azodiisobutyronitrile is also suitable for the method of the invention.
    As already known, the proposed method for producing modified polymerizates is preferably carried out in an organic solvent. The solvent performs three tasks: first, it contributes to the fact that the reaction proceeds under controlled conditions, i.e. in order to avoid overheating during the exothermic polymerization; secondly, it affects the decomposition of the initiator into radicals; and thirdly, due to the organic solvent, care is taken that the reaction mixture remains well stirred, as the reaction mixture viscosity is affected during the reaction.
    As organic solvents for the proposed method, along with water-soluble or limited water-soluble solvents, such as dioxane, ethyl acetate and methyl ethyl ketone, take into account primarily water-insoluble, substitute hydrocarbons, such as gasoline, octane, cyclohexane, benzene, toluene, xylene, under certain conditions and chlorobenzene. However, it is also suitable esters and ketones, such as, for example, butyl acetate, methyl butyrate, methyl eobutyl ketone and many others. Toluene is particularly suitable as a solvent. The amount of solvent is chosen such that the concentration of the modified polymerizate (solid) is about 300 to 60% by weight.
    The interaction is carried out in such a way that a part of the polymerizable compounds (component 1a) and, under known conditions of 16 and 1c, the alkyl hydrogen polysiloxane (component I) and, in certain cases, the solvent, are added to a suitable solution beforehand. initiator and then heated.
    0
    It is advisable to flush (purge) the nitrogen before adding these components. After the start of polymerization, which is recognized by the increasing viscosity and increase in the temperature of the reaction mixture, slowly
    5, it is possible to add the remaining amount of monomers and, in certain cases, still a solvent. Finally, it is advisable to add the initiator again and leave to react further at elevated temperature.
    D In the presence of a solvent, it is usually operated in such a way that the reaction mixture is boiled under reflux during the reaction and at the subsequent reaction. The entire reaction is complete after about 2-3 hours.
    After cooling, viscous, clear or turbid solutions or stable dispersions are obtained, depending on the type and amount of
    0 solvent and the type and amount of monomers used. Hydrogen removal from alkyl hydrogen polysiloxanes during polymerization is extremely insignificant. It has been shown that in the target product there are approximately
    5 85-95% of hydrogen used for hydrogen alkylpolysiloxane bound to silicon.
    The amount of solvent is chosen so that the resulting
    0 modified polymers had a dry matter content of about 30-6C) wt.%. For the application of the modified polymers obtained according to the invention, in particular
    5 for the coating, it is advisable to direct the polymerization so that after the termination of the polymerization in this concentration range a viscosity of 5000-35000 cP is obtained at 20 ° C. This control can be carried out, for example, due to the fact that the solvent is only partially added during the polymerization. It goes without saying that the genus also plays a role here.
    5; applied solvent and genus
    and the amount of the initiator used. Further, naturally, the viscosity can also be adjusted at the end of the polymerization by partial distillation or addition of further amounts of solvent. Whether alkyl polysiloxanes are used with a ratio of alkyl residue: hydrogen of 1: 1 or up to 13: 1 has only a relatively minor effect on the viscosity of the target products.
    If desired, minor amounts of unreacted monomers and the solvent can be removed by distillation under reduced pressure. Since the obtained modified polymers are used in the form of solutions in organic solvents, such treatment is generally not required.
    The reaction yields are very high, which, for example, follows from the fact that in an experiment in which they work without a solvent, after distillation of the volatile constituents in vacuum, a nonvolatile reaction product is obtained with a yield of 98% of theory.
    As mentioned, the modified polymers obtained by the proposed method together with hardeners well known for curing alkyl hydrogen polysiloxanes are suitable for treating a fibrous material, in particular, a textile material.
    Compared with unmodified polymerizate modified polymerizate have improved water repellent action. This effect is further enhanced if, when prepared according to the proposed method, as unsaturated, esters are used in conjunction with those that contain free hydroxyl groups (components 1b and 1b. In addition, the typical silicone neck of the treated textile materials is further maintained; Compared to hydrogen hydrogen-polysiloxanes The resulting modified polymers have the advantage of improved water resistance, and, moreover, fiber finishing materials are also attached to the fibrous materials. with the filling effect. Finally, the modified polymers obtained by the invention when used in comparison with mixtures of unmodified polymers and hydrogen alkyl polysiloxanes, in addition to improved product stability, have the advantage of improved water repellency and water resistance and their permanence
    In general, it is important that the Modified polymers are obtained by the use of acrylic esters (component 1a and under known conditions 16),
    preferred for use because of their more favorable properties. Thus, modified polymers, obtained using methacrylic acid esters, often produce an undesirably hard neck on the fibrous material.
    For example, the following hardening agents are suitable for curing the modified polymers: organometallic compounds such as aluminum, zirconium, titanium and zinc salts with organic acids, aluminum alkoxides, zirconium and titanium, tin organic compounds, especially dioorganic carboxylates, such as dioctyl tin acetic acid, dibutyl tin, and dibutyl tin; However, amines and amino alcohols are also taken into account. Under amines need to be understood primarily alkylenediamine. It is advisable to use amines in the form of their salts with organic or inorganic acids.
    Further, the modified polymers obtained according to the invention, since they are obtained using esters containing free hydroxyl groups (component 16), are also crosslinked with compounds that contain at least two isocyanate groups.
    For processing fibrous material, especially textile materials, modified polymers, diluted with a further amount of solvent, under known conditions, are used together with hardeners in the form of their solutions in organic solvents :. Aliphatic and aromatic hydrocarbons, such as gasolines, toluene, benzene and xylene, chlorinated aliphatic and aromatic hydrocarbons, such as trichlorethylene and chlorobenzene, and esters, such as butyl acetate, are taken into account as solvents for this. Trichlorethylene is particularly suitable. Solutions can be applied to the fibrous material by dipping and pressing (plus, plus, spray, in particular. However, by conventional application methods. The concentration of modified polymers in solvents is determined according to the method of application. In the method of addition, the finish baths generally contain 1-10 wt. % modified polymerizate, in. calculated on solid matter. On the contrary, when coating textile materials, the modified polymerizate is used in a concentration of 15-60 wt.% (solid). The amount of hardener used is 0.5-10% by weight, preferably 1-5% by weight, relative to the modified polymer; (solid). The processing baths may contain other organic textiles used for processing substances such as, for example, apparating agents, etc. When coating is applied, white and / or dye pigments may also be used, such as titanium dioxide, white barite, carbon black or ordinary inorganic or organic pigment dyes or also fillers, how colloid on silicic acid, kaolin or talc. After treatment with solutions of treating substances, the solvent is evaporated at heating up to 120 ° C and then, in known cases, for solidification it is heated for a short time at 120-190 ° C. The modified polymers obtained according to the invention serve for the treatment of fibrous materials of all kinds, especially textile materials of all kinds, whether they are in the form of fabrics, knitted fabrics or silt. They can be made from natural fibers, such as cellulose fibers or keratin fibers, as well as from synthetic fibers, such as polyacrylonitrile, polyamide, polyvinyl alcohol or polyester. It goes without saying that textile materials, which consist of mixtures of natural and synthetic fibers, are also taken into account. Especially it is necessary to emphasize that as easily (eingestellte) adjustable fabrics, like taffeta, or lightly adjustable poplin materials, can be trimmed or coated with a waterproof coating according to this method. It matters, for example, for protective clothing, like Apo raks, etc. Examples of. Example 1. A 2 L four-necked flask, equipped with a strong anchor stirrer, reflux condenser, thermometer and two drip funnels (for pouring vessels), after vigorous pre-flushing with nitrogen, was pre-placed with 100 ml of a mixture of 218.3 g of methyl acrylate, 109.1 g ethyl acrylate, 29.1 g of 2-ethylhexyl acrylate, 7.3 g of 2-hydroxyethyl acrylate, 36., 4 g of methylhydrous polysiloxane blocked at the ends with three methylsilyl groups (the ratio of methyl groups and hydrogen split 1: 1, viscosity at 20 ° С 30 SP) and 45 ml of toluene, in Hur ereKisi dissolved 0.19 g of benzoyl peroxide and heated to 8o-82 0. The remaining monomers are placed in the dropping funnel 1. The funnel 11 drops of hydrochloric gyumeigayut 455 g toluyl la. After the start of gasification, which begins with the reflux and increasing viscosity of the contents of the flask, the temperature rises to 90-92 ° C. At this temperature and the continuous refluxing of the phlegm, the rest of the monomeric mixture is added over a period of 20-30 minutes. By adding toluene, the viscosity is prevented from rising above the area where mixing is possible. At the end of the inflow of monomers, 0.56 g of benzoyl peroxide, dissolved in 100 g of toluene, is slowly added dropwise and at the boiling point under reflux. The remaining amount of toluene. The mixture is further stirred for approximately 1-1.5 hours with slight reflux until the temperature reaches approximately 1.5 ° C. After cooling, about 1 kg of a turbid solution is obtained with about 40% solids content, viscosity 25,000 cps (measured using a Brookfield viscometer, spindle type (, 10 rpm). The ability to crosslink the obtained modified polymerizate is approximately completely preserved, Since the obtained product contains about 90% more of the hydrogen electrolytic polysiloxane used, which is bound to silicon, is detached. Example 2. In Example 1, 36.4 g of methyl- hydrogen hydrogen polysiloxane (see Example 1), 72.8 g of methyl carbon were introduced into the reaction ilata, 218.3 g of butyl acrylate, 67.3 g of 2-ethylhexyl acrylate and 7.3 g of 2-hydroxyethyl acrylate when used in total 600 g of toluene. 1.0 g of bis- (2,4-dichlorobenzoyl peroxide, from which is first injected with 0.25 g and for the subsequent reaction of 0.75 g. After cooling, about 1 kg of a turbid solution is obtained with a content of about 40% by weight solids, a viscosity of about 14800 cP (measured as in Example 1). The product contains about 91% of the hydrogen that is cleaved, associated with silicon, used methyl hydrogen polysiloxane. Example 3. Example 1 is repeated, with 36.4 g of methyl hydrogen polysiloxane used as methyl hydrogen polysiloxane, in which the ratio of methyl groups and silicon atoms bound to silicon is 5: 1 (viscosity 200 cP at 20 ° C). 0.8 g of azodiisobutyronitrile are used as initiator. Approximately 1 kg of a turbid solution C is obtained, the solids content is approximately 40% by weight) with a viscosity of 19,600 cnw. Example 4. Example 3 is repeated, where instead of methyl hydrogen polysiloxane used is used such that the ratio of methyl residues to split hydrogen is 13: 1 (viscosity 230 cP.pri). This siloxane is also used 36.4 g. The resulting product (solid matter content 40% by weight) has a viscosity of 18,300 cP. Example 5. In a three-necked 1 L container with a stirrer, reflux condenser and thermometer 48 g of methylhydrogen polysiloxane (as in the example 1) along with 72 g of methyl acrylate, 36 g of ethyl acrylate, 9.6 g of 2-ethylhexyl acrylate and 2.4 g of 2-hydroxyethyl acrylate and after adding 2 g of benzoyl peroxide, gently heat up 90-100 0. After the start of the reaction, the temperature quickly rises to about 180 ° C , and a cloudy white viscous product is formed. After stirring for 2 hours, the residual monomers are removed under reduced pressure. After cooling, 165 g of a cloudy-white product with a viscosity of about 18,000 centipoise are obtained. The viscosity of the product dissolved in toluene (solid content 40% by weight) is 8500 SP. The cleavable hydrogen in the target product is about 95% of the methyl hydrogen polysiloxane used. Example b. In a four-necked flask with a capacity of 2 liters, equipped as in Example 1, after pre-flushing with nitrogen, about 100 g of a mixture of 123.5 g of methyl acrylate, 33.3 g of ethyl methyl acrylate, 136.3 g of 2-ethylhexyl acrylate and 26.9 g of 3 are placed. oxypropylacrylate. After the addition of 77.4 g of methyl hydrogen polysiloxane {as in measure 1) and 0.22 g of benzoyl peroxide dissolved in 60 tvin n-butyl acetate with stirring, heated to about 75-80 ° C. After the start of the reaction, the procedure is then carried out in accordance with Example 1, with 0.64 g of benzoyl peroxide being added for the subsequent reaction. In the case, 600 g of n-butyl acetate is used; the result is approximately 40% solution. Muddy product is also not released after a longer standing. Example 7. In the manner described in Example 6, the following components were introduced into polymerization: 112.0 g of methyl acrylate, 78.7 g of ethyl acrylate, 110.4 g of 2-ethylhexyl acrylate, 9.0 g of styrene and 10.2 g of stearyl methacrylate. Limerization is carried out in the presence of 80.0 g of methyl hydrogen polysiloxane (ka in example 1). In particular, 600 g of tolu-el serve as the solvent. As a catalyst as a whole, 11.2 g of tert-butyl peroctoate, from which 0.3-g is first added, the rest is added for subsequent reaction, under the circumstances, dissolved in toluene. Example 8. In a four-necked flask with a capacity of 2 l (as in example 1), 80.0 g of methyl hydrogen polysiloxane (see example 1), 100 ml of a monomer mixture from 112.0 g of methyl acrylate, 78.4 g of ethyl acrylate, 110.4 g 2 were previously placed. - ethylhexyl acrylate, 10.2 g of lauryl acrylate and 9.0 g of maleic acid butyloxyethyl ester together with 50 g of trimethylbenzene. After the addition of 0.8 g of benzoyl peroxide, gently heat to 90100 ° C. After the start of the reaction, the temperature rises to 140-150 ° C. For about 30 minutes, the remaining monomer mixture is poured along with 420 g of trimethylbenzene. For the subsequent reaction, 1.2 g of benzoyl peroxide, dissolved in 30 g of trimethylbenzene, is added again, and the reaction mixture is kept for about 2 hours at a slight boil under reflux. After cooling, about 800 g of a turbid solution is obtained, in which also after 3 months no one precipitates. Example 9. Analogously to Example 1, 72.0 g of methyl acrylate, 36.0 g of ethyl acrylate, 9.6 g of 2-ethylhexyl acrylate, 1.0 g of maleoic acid monoxyethyl ester and 2.4 g of 2-hydroxyethyl acrylate in the presence of 48 are introduced into the reaction. , 0 g of methyl hydrogenpolysiloxane; see example 1} when using a total of 0.3 g of dibenzoyl peroxide. A total of 120 g of toluene serve as the solvent. After cooling, a viscous, slightly turbid solution is obtained with a solids content of 58.5 wt.%. Examples of application. A) The following coating weights are used to coat polyamide taffeta (approximately 70 g / m2-) and polyester taffeta (approximately 80 g / m): I.1000 g of modified polymerizate (40% by weight solids), according to Preparation Example 1 , 20 g of dibutyl tin dilaurate. II.1000 g of copolymerizate according to Production Example 1, however, without alkyl hydrogen polysiloxane, which has a solids content of 40% by weight (C, viscosity about 25,000 cP). IT1. 963.6 g of copolymerization, as in paragraph II. 36.4 Methylhydrogen polysiloxane (data, see Preparation Example 1). 20 g dibutyltin dialaurate. The coating is carried out using an air scraper at a speed of 10 m / min and the coated fabric is then continuously passed into the heated channel (the residence time of 2 mi is dried at 145 ° C and condensed. In the case of polyamide taffeta, the substrate is approximately 22 g / mi in
    In the case of polyester taffeta, approximately 24 g / m. Some of the trimmed textile fabrics are erased in the car in 5x40 ° C, the other part is chemically cleaned 3 times at 100 times.
    80
    100
    I I I
    Not processed
    100 90 90 Over
    Polyether
    90
    I I 100
    I I I
    Unclosed botano
    The covering weight Hi indicates, with respect to KopOTKyKj, the duration of use, which is usually insufficient for practical requirements.
    B) Application Example A is repeated using the following coating weight:
    1000 g of copolymerization, according to example 3,
    20 g of a 20% solution of diethylenetriamine in propanol,
    5 g of glacial acetic acid.
    The results further correspond to those of Example A) 1.
    c). A polyacrylonitrile blended fabric with cotton 60/40, 280 g / m, pre-cleaned in trichlorethylene to remove oiling) is added using the following finishing bath:
    30 g of copolymerizate according to Production Example 7,
    0.8 g of zinc octoate,
    969 g of trichlorethylene.
    The absorption of the bath is about 170%. The fabric is dried at 12 ° C until evaporation without a solvent is removed and then evolves (flattens out) with slight steaming (Dampfen). Thus, a fabric is obtained with hydrophobic properties and with a soft neck like wool, with improved shape stability and good elongation properties. Also, the presence of 2 g / l of conventional booster and 2 g / l of water.
    Results after conditioning in standard climatic conditions are presented in the table.
    150
    80
    150
    820 120
    About 390
    About 120
    30 500
    50
    ABOUT
    150
    200
    1000
    170
    420
    About 30
    O 50 190 520
    ABOUT
    cmyst versus untreated fabric.
    d) Example B is repeated with the help of the following finishing bath:
    five
    30 g of copolymerizate according to Production Example 6,
    0.8 g of zinc octoate,
    969 g of trichlorethylene.
    The results correspond to those
    0 of example B. However, the hydrophobic properties are more pronounced.
    Thus, the invention makes it possible to obtain copolymers suitable for treating textiles,
    45
    权利要求:
    Claims (2)
    [1]
    1. A process for the preparation of graft copolymers by radical polymerization of 100 parts by weight mixtures of esters of (; meth) acrylic acids with unsaturated compounds in the presence of 5-40 parts by weight. organic organosiloxanes in an organic solvent, characterized in that, in order to obtain copolymers suitable for treating textiles, 0.1 to 20 parts by weight are used as unsaturated compounds. Ester esters of acrylic acids and / or monoids of fumaric and maleic acid diesters containing free hydroxyl groups, and as polyorganosiloxanes - methyl hydrogen polysiloxane, in which the ratio of silicon-related alkyl residues to hydrogen-bonded silicon to hydrogen atoms is from 13: 1 to 1: 1 with a viscosity of 30–230 cP at.
    [2]
    2. The method according to p. 1, on tl and h a „ch AlV il L. f J L. Jt. P SD, tU-WI-CI by the fact that the polymerization is carried out in a water-immiscible solvent. Sources of information taken into account in the examination 1. French application No. 2260591, cl. G 08 F 283/12, published 1975 VJ UU) (prototype).
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    同族专利:
    公开号 | 公开日
    US4153640A|1979-05-08|
    BR7701324A|1978-01-03|
    IT1083703B|1985-05-25|
    JPS52107086A|1977-09-08|
    NL7702360A|1977-09-06|
    FR2343010B1|1981-02-27|
    CA1097835A|1981-03-17|
    DD128328A5|1977-11-09|
    GB1543862A|1979-04-11|
    FR2343010A1|1977-09-30|
    BE852032A|1977-09-05|
    DE2608894A1|1977-09-08|
    AT358280B|1980-08-25|
    ATA103177A|1980-01-15|
    引用文献:
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    DE19934116A1|1999-04-07|2000-10-19|S & C Polymer Silicon & Compos|Copolymers of hydrogen-siloxanes and unsaturated compounds, with silicon-hydrogen groups converted into silanol, used as adhesives for bonding condensation-cured silicone to plastic, e.g. dental impression trays|
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    DE19762608894|DE2608894A1|1976-03-04|1976-03-04|PROCESS FOR MANUFACTURING MODIFIED POLYMERIZES AND THEIR USE|
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