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    • 专利摘要:
    1. THE METHOD OF PREPARATION acids use compounds of the general formula CFj- | cPt) jf- Cjttn.-SO, -Tjr lW 0 c6-C "CH, CHsi -.AY ShESML I rfairmam, or the general formula SGZ- {SG2) d-C2HGO-CO -C CHg, where P 3, 5, 7, 9, 11, 13 or 15; RH, CH, as dialkylaminoalkylmethacrylate - -: N, N-dimethylaminoethylmethacrylate or tert-butypaminoethylmethacrylate, in the reaction mixture additionally Y-vinylpyrrolidone-2 is added to the reaction mixture, and copolymerization is carried out in the following comonomer ratio f May.%: The set. 57-87 of the above formulas N, S-Dimethylaminoethyl methacrylate or tert-butylaminoethyl methacryl-14 lat 1-40 S-Vinylpyrrolidone-2: n: l 2. The method according to claim 1, about t JI and by the same the mixture is additionally introduced up to 10 wt.% from the initial mixture of vinyl acetate comonomers ata, ethyl acrylate or hydroxyethyl methacrylate.
    公开号:SU1155161A3
    申请号:SU813372849
    申请日:1981-12-22
    公开日:1985-05-07
    发明作者:Дессэн Андре
    申请人:Продюи Шимик Южин Кюльман (Фирма)；
    IPC主号:
    专利说明:

    This invention relates to a process for the preparation of new fluoride-containing copolymers used in coatings and in the impregnation of substrates such as textiles, leather, wood, nonwovens, metal, concrete, paper, etc. to give them oil-repellent and water-repellent properties. Various fluorinated compounds capable of imparting these properties are known. However, if these derivatives show good results on textiles and leather, then for giving similar properties to papers and similar products it is necessary to use too large quantities of the active substance (in this case fluorine associated with carbon) to obtain economically acceptable results. the use of polyfluoroalkylphosphates, cycloalkylphosphates and polyfluoroalkylhydroxypropylphosphates for treating papers and paper products. However, these compounds do not impart water-repellent properties to papers, and fluorine-containing copolymers known as additives to various materials for imparting oil repellency properties are known. These copolymers are prepared by a method that is technically close to the one proposed, which is carried out by copolymerization of one or more fluorine-containing acrylic or methacrylic acid esters (outfluorine-em- mer patterning patterns, a patterned pattern, or patterned polymers or acrylic acid; acrylate in the form of their amino acids quaternary ammonium salts or N-oxide) in solution in the presence of a radical initiator lj A disadvantage of the known method is that the obtained fluorine-containing copolymers exhibit a very weak water-repellent ability. In order to make the materials (mainly paper) water-repellent, it is necessary to use copolymers with an increased content of the active substance. The purpose of the invention is to impart water-repellent properties to fluorine-containing copolymers. The goal is achieved in that according to the method of producing fluorine-containing copolymers by copolymerization of one or more fluorine-containing acrylic or methacrylic acid esters with dialkylaminoalkyl methacrylate in solution in the presence of a radical initiator, compounds of the general formula CFy- as a fluoride-containing acrylic or methacrylic acid esters are used: CFy- (i). SOJ- rC} H, -0-CO-C CH7 CHj K or the general formula CF3- (cF2) ir 2HrO-co-e eH :, where, .5, 7.9, 11, 13 or 15, R H, SI,, as dialkylaminoalkyl methacryogate - N, N-dimethylaminoethyl necryl. T or t ret-butylaminoethyl acacrylate, while Nvinylpyrrolidone-2 is additionally introduced into the reaction mixture, and the copolymerisation is carried out in the following comonomer ratio, wt.%: Fluorine-containing esters of the indicated formulas 57-87 N, N-Dimethyrminoethyl methacrylate or tert-butyl-aminoethylmethacrylate, ahydroxymethylaminoethylmethacrylate or tertbutylaminoethylmethacrylate; -40 At the same time, up to 10% by weight of the initial mixture of comonomers of vinyl acetate, ethyl acrylate or hydroxyethyl methacrylate can be additionally introduced into the reaction mixture. New fluorine-containing compounds when applied to paper and similar materials ate. they are informed at the same time by the low content of fluorine used, an excellent degree of sizing and very good water-and-oil-repellent properties, resulting in that paper and similar products treated with these compounds acquire the effect of an obstacle to the action of water and organic solvents, t , e, resists penetration of aqueous or oily liquids, fats and numerous organic solvents. In addition, these new compounds applied to other substrates also provide them with very good oil and water repellency properties. The starting fluorine-containing esters can be obtained by known methods, for example, by esterifying the corresponding alcohols with alkene monocarboxylic acids, such as acrylic, methacrylic, in the presence of an acid catalyst, for example sulfuric acid or toluene hydrochloric acid. Instead of alkene monocarboxylic acids, their esters, anhydrides, can be used. It is especially advisable to use for the copolymerization a mixture of fluorine containing esters. Copolymerization (os5ttsestvl may be in a solvent or mixture of solvents such as, for example, acetone, metshtetilketon, J-butyrolactone, methylcyclohexanone, N-methyl-2-pyrrolidone, methanol, ztanol, isopropyl alcohol, butanol, ethylene glycol, diacetone alcohol, fenilme, tilkarbonil , isophorone, tetrahydrofuran, dioxane, ethyl acetate, glycol acetate, ethylene or polyethylene glycol monomethyl, or monoalkyl ether, formamide, dimethylforma mid, acetonitrile, toluene, trifluorotoluene, trichlorfluoroethane. are water miscible, such as acetone and isopropyl alcohol. The polymerization is carried out in the presence of an appropriate catalyst, for example, benzoyl peroxide, lauroyl peroxide, acetyl peroxide, succinyl peroxide, 2.2 azo-bis-isobutyronitrile, 2,2-azobis- ( 2,4-dimethyl-4-methoxyvaleronitrile), 4,4-azo-bis (4-cyanopentane) acid, azodicarbonamide, tert-butyl perpivalate. The amount of catalyst used can be 0.01-5%, and preferably 0.1 to 1.5% with respect to the total weight of the monomers used; In addition, the method in can be wasp schestvl using ultra violet radiation source in the presence of photoinitiators such as benzophenone, 2r-methylanthraquinone or 2-hlortrioksanton. The temperature at which the reaction takes place may vary widely, i.e. from the ambient temperature to the boiling point of the reaction mixture. It is advisable to use a temperature of 50 - 90 ° C. 614 When regulating the molecular weight of the copolymers, it is possible to use chain transfer agents, for example, alkyl mercaptans - terciodeodecylme. Rcaptan, n-dodecyl mercaptan, P-octyl mercaptan, carbon tetrachloride. triphenylmethane. The amount of the compound used is dependent on the desired molecular weight and can vary from 0.01 to 3% relative to the total weight of the monomers, and it is preferable to use chain transfer agents in an amount of 0.05-0.5%. copolymer in salt can occur With: using mineral or strong or moderately strong organic acids, i.e. acids, the dissociation constant of which or the first dissociation constant is above 10, for example hydrochloric acid, hydrogen bromide, sulfuric acid, nitric acid, phosphoric acid, acetic acid, formic acid, propionic acid. It is preferable to use acetic acid. Instead of converting the copolymer to a salt, it is possible to convert it to a quaternary base using an appropriate agent for the formation of a chetuvertically base, for example, methyl iodide, ethyl iodide, dimethyl sulfate, diethyl sulfate, benzyl chloride, trimethyl phosphate, L-toluene methyl sulfonate. The solution of the copolymer obtained can be diluted with a polymerization solvent or with another solvent, using a mixture of solvent and water. If desired, it is also possible to isolate with: the polymer by removing solvent or solvents. As substrates which, by means of the proposed compounds, become water-repellent and oil-repellent, paper, cardboard and similar materials are used in the base. In addition, there are other materials that are different from those mentioned, for example, woven and non-woven materials based on cellulose and regenerated cellulose, natural fibers, artificial or synthetic fibers, such as cotton, cellulose cetate, wool, silk, polyamide fibers, polyester fibers, polyolefin fibers, based on fibers from polyurethane or polyacrylonitrile, leather, plastic materials, glass, wood, metals, phosphorus, masonry, painted surfaces. In the case when paper is processed and the map solutions of the proposed copolymers are mainly applied to the treated surfaces from an aqueous medium, it is also possible to use a solvent medium or a mixture of water and a solvent using known methods of applying solutions, for example, watering, soaking, dipping, spraying, by applying the solution with a brush, as well as padding, laying down. On paper, an aqueous solution of a compound can be applied both as a surface (but already finally separated substrate) and introduced into the mass, i.e. into pulp or pulp. Thus, the treated substrates acquire good water-repellent and oil-draining properties after ordinary drying at ambient temperature or at a temperature whose value is somewhat elevated, and possibly. Subsequent heat treatment, which can be carried out depending on the type of substrate at a temperature reaching. In order to obtain a reliable fixation of the proposed copolymers on the rubstrata, which is treated with these copolymers, and in order to enhance a particular effect, it is sometimes advisable to combine these copolymers with some additives, polymers, thermal condensation agents and appropriate catalysts capable of helping to form a network structure between substrate and deposited copolymers. These compounds include condensates and preliminary condensates of urea or melaminformalin, meth. iloldioxy ethylene urea and its derivatives, methyl polyethylene urea, methylol propylene urea, methylol triazones, dicyandiamidformalin condensates, methylol carbamates, methylol acrylamides or methacrylamides, their polymers or copolymers, divinyl sulfone, polyamide; epoxy derivatives, for example, diglycideIlglycerol, epoxypropyltrialkyl (aryl) ammonium hapogenides, for example, (2,3-epoxypropyl) -trimetapammoxy chloride, N-MeTHji-N- (2,3-epoxypropyl) -morpholine chloride, some halogenated derivatives, n-ace, halogenated derivatives, for example, for example, chloro-chlorofuran, morphine-3-epoxypropyl) polar compounds such as the disodium salt of trisulfoxyethylsulfonium betaine and the pnridine containing ethylene glycol chloromethyl ether. In order to evaluate the advantages of substrates treated with compound 01 obtained by the proposed method, the following tests are used. The test for the inconsistency or the number of whales, which makes it possible to assess the inconsistency of the substrates with mixtures of resin oil, toluene, and heptane, is presented in Table 1, These mixtures contain varying amounts of each of the three components. I The test is that Drops of this mixture are carefully applied to the treated paper and left on the paper for 15 seconds, after which they carefully examine the appearance of the paper or paperboard and evaluate wetting or noticeable penetration by sweat, or the surface of the paper or paperboard. The number corresponding to the mixture containing the highest percentage of heptane, which has not penetrated or not on, was weeding the paper, is the number of paper whales and is regarded as an indicator of oil repellency of the treated paper. The higher the number of whales, the better. Oil-repellent paper. The test for turpentine oil wasp is as follows. On the 4th sheet of paper, which is placed on white Bristol cardboard, 5 g of sand, washed in acids, are placed, and then 1.1 ml of anhydrous turpentine oil and 0.5 g / l colored organol BS are painted onto this sand. the oil is drunk, turn on the chronometer, and begin to move the paper for all 30 seconds on the Bristol card. The time is noticed when a spot appears on the bri sock cardboard. At a time of 30 min, it can be considered that the test is no longer indicative, and that studying the “1st substrate has excellent characteristics. In the experiment using seven samples made from the same. Record the values found from the smallest to the largest and then note the value having an average value. The test for studying the effect of the barrier to the action of solvents is performed as follows. In anhydrous turpentine oil. stained with red organol BS, taken in an amount of 0.5 g / l, immerse a rectangular sample of the substrate under investigation to a depth of 1 cm (sample size 10x1 cm). The immersion is carried out in a 500 ml closed zipindric vessel for 24 hours. Then, the surface, mm, formed by the spot due to the raised colored liquid on that portion of the substrate under study, which is not immersed in oil, is measured. The test for the study of the effect of obstacles to the action of water followups. In a water colored with rhodamine B, taken in an amount of 0.5 g / l, the rectangular sample (10x1 cm) of the test substrate is immersed to a depth of 3 cm. The immersion is carried out in a cylindrical closed vessel with a capacity of 500 mp for 24 hours. Then, the mm spot, formed due to the raised colored liquid, is measured on the immersed portion of the substrate under study. Test arb. The POW test is codified by the Research Committee of the Central Laboratory of the Swedish Paper Industry, which consists in determining the weight of water, g absorbed for 1 minute, m of paper, containing a column of water, 1 cm in height. Test for oil repellency. With respect to some substrates 1, the asterotting is determined by a method that assesses the non-wettability of a substrate by a number of oils, the surface tension of which is increasingly lower and lower, the water repellency test, the water repellency being carried out on several substrates using the known method. In the examples, parts and percentages refer to weight (with the exception of special references). In the examples for the use of the degree of mordant or spin,%, shows the weight of the treatment solution (x h) in 100 parts of the substrate. . Example 1. In a 10QO reactor equipped with a stirring, reflux condenser, thermometer, nitrogen inlet and heating device, 20.4 hours of acetone, 45 hours of isopropyl alcohol, 8 hours of dimethylaminoethyl methacrylate, 16 hours of N-vinylpyrrolidone, 0.8 h. 2,2 - azo-bis-isobutyronitrile and 81.6 h of a mixture of polyfluoro with monomers containing them, having the formula CFHCrj) -CilVSO, - MC, HfO-CO-CH-CHj, de p is 3 , 5, 7, 9, 11, 13, 15, weight ratios 1; 50: 31: 10: 3: 1: 1. Heating was carried out at 5 ° C for 15 hours under an azo atmosphere, followed by the addition of 160 parts of water.
    9
    250 parts of isopropyl alcohol and 8 parts of acetic acid. The mixture obtained is kept at 75 ° C for 2 hours and cooled to ambient temperature.
    Thus, 563 parts of a solution of a copolymer are obtained, which contain 18.8% of non-volatile substances and 6.6% of fluorine.
    Example 2, PV apparatus, similar to that specified in Example 1, was charged with 19.2 parts of acetone, 45 parts of isopropyl alcohol, Including dimethylaminoethyl methacrylate, 21 hours of N-vinylpyrrolidone, 0.8 parts of .2.2-azo-bisisobutyronitrile and 76.8 parts of a mixture of polyfluorine-containing monomers, similar to that indicated in Example 1. Heating is carried out at 75 ° for 15 hours under a nitrogen atmosphere, after which 160 hours, water, 250 hours, isopropyl alcohol and 8 are added to this mixture. h, acetic acid. The mixture was kept for another 2 hours at 7 5 C, then cooled to ambient temperature. Thus, I get 585 hours of a copolymer solution that contains 18.2% non-volatile substances and 6% fluorine,
    b}. This copolymer and the copolymer prepared in Example 1 were tested at an equal fluorine content by comparison with the following compounds,
    516110
    A, Copolymer based on 85% of a mixture of polyfluorine-containing monomers, similar to that described in Example 1, and 15%
    dimethylaminoethyl methacrylate, converted into salt and N-oxide, obtained according to a known method,
    B, Copolymer based on 70% of a mixture of polyfluorine-containing monomers, similar to that described in Example 1, and 30% of dimethylaminoethyl methacrylate, converted into salt and N-oxide, prepared according to a known method.
    Known phosphate polyfluorine alcohol, having the formula
    L
    SGS (SG) y-SOi-ir-CjHi -O P- TASK
    These compounds are applied to non-glued paper having the following characteristics: a fibrous composition of 60% of the mass of Kraft, bleached on the basis of leafy, 40% of the mass of Kraft, bleached on the basis of coniferous; cleaning in the hydrofinor 00 to 35 ° SR; talc additives added 15%, preservative agent 3%; paper weight 70-71 paper moisture 4-5%,
    For this, five solutions are prepared, each of which contains 0.7 g of fluorine per liter and has the composition shown in Table 2.
    table 2
    In Example 1 In Example 2 of Copolymer A, containing 16.6% non-volatile cix substances and 6.5% fluorine of Copolymer B, containing 15.3% non-volatile cix, substances and 4.9% fluorine Compound C, containing 35.7% non-volatile substances and 18.8% of fluorine 989.4 988,
    Total:
    1000
    1000
    1000 1000 1000 89.2 985.6 996.2
    Five sheets of non-glued paper are processed in five respectively. solutions with a degree of mordant equal to 85%. After scanning for 90 seconds, sheets of paper are obtained that have grease-repellent properties and
    Solution treated paper
    Specifications
    n TilQIII Oil-repellent number whale Test for tolerance More More. 10 min. New oil 30 min. 30 min.
    36
    ABOUT
    According to the results given in table. 2, it can be seen that the papers processed by copolymers obtained by the proposed method (solutions 1 and 2) have not only excellent grease repellency, but also have remarkable effects.
    Components of the solution
    Following the example of t
    15.1 For example 2
    Copolymer A,
    containing
    16.6% non-volatile substances and 6.5% fluorine
    Copolymer B containing 15.3% non-volatile substances and 4.9% fluorine
    the effects of barriers to the action of water barriers to the action of solvents, expressed more or less strongly.
    The obtained characteristics of the processed paper are given in table. 3 in comparison with the characteristics of raw paper.
    Table 3
    Raw paper 9
    50 207 477 700
    700
    More
    30 G40 780 155 900
    obstacles to the action of water and obstacles to the action of solvents.
    f Prepare five solutions containing each f g of fluorine per liter and having the composition shown in table. four.
    Table 4
    Composition, g / l
    iiinz
    ten
    16.6
    15.4
    20.4 5 Less than Less than 30 from 30 minutes 30 minutes
    13 Compounds C containing 35.7% non-volatile substances and 18.8% fluorine 984.9 983.4 Water 1000 1000 Total:
    Five sheets of unglued paper weighing 77 g / m are treated respectively in these five solutions with a degree of dressing of 95%. After drying for 90 s at 110 ° C so
    SOVE
    20
    20 From tab. 5 it follows that the paper treated with the proposed copolymers (solutions 6 and 7) has an excellent degree of sizing. Example 3, In an apparatus similar to that indicated in Example 1, 25 parts of acetone, 45 parts of isopropyl alcohol, 12 hours of dimethylaminoethylmethacrylate, 3 hours of N-vinylpyrrolidone, 0.4 hours of 2,2-azo bis isobutyronitrile and 100 h of a mixture of polyfluorine-containing monomers, similar to that indicated in Example 1. The mixture of the indicated Hbix components is heated to 75 ° C and incubated for 17 h under a nitrogen atmosphere, after which 165 parts of water, 250 h of isopropyl alcohol and 8 h of acetic acid are introduced. This mixture is kept for another 2 hours at 75 ° C, then it is cooled to ambient temperature. Thus, 589 hours of the solution (S,) of the proposed copolymer are obtained, which contain 19.1% non-volatile substances and 7.8% fluorine. This copolymer, after treating it with paper similar to that specified in Example 26, under the processing conditions
    U
    1155161 Continuation of table 4
    processed and untreated on paper are tested according to the TIEW test.
    The results are shown in Table. five.
    Table 5
    30,160
    160 984.6 979.6 994.7 1000 1000 1000 also similar to those in Example 2b (ie, 9 g of solution S per 1 l of treatment solution), gives the paper the following properties: oil repellency (number of whales) 9; test for turpentine oil for more than 30 minutes; water barrier effect, spot area 40 mm; barrier effect to the action of solvents, area: spot 10 mm. Example 4 20.5 hours of acetone, 45 hours, isopropyl alcohol, 13 hours, D1stetilaminoethylmethacrylate, 5 hours, N-vin-pyrrolidone, 0.8 hours, 4., L-azo bis (4-cyanopentanoic) acid and 82 h of a mixture of polyfluorine-containing monomers of Example 1, This mixture is heated at and kept for 4 h in an atmosphere of nitrogen, after which 160 h, water, 250 h, isopropyl alcohol and 10 h are introduced, acetic acid. The resulting mixture is left for another 2 hours at, and then cooled) to ambient temperature. Thus, 580 hours of a solution () of a copolymer, which contains
    There are 17.2% non-volatile substances and 6.5% fluorine.
    Used for treating paper similar to that shown in Example 26 and also carried out under conditions and proportions similar to that indicated in Example 26 (i.e. 10.8 g of solution S per 1 l of treatment solution), this copolymer gives the paper the following properties: oil repellency (number of whales) 9; turpentine oil test over 30 min.
    Example 5. 21.4 hours of acetone, 46 h; Isopropyl alcohol, 10 parts of dimeshtaminoethyl methacrylate, tO parts of N-vinylpyrnol- dium, 0.8 hours of 2,2-azo-6s-iso-6-uthionitrile are loaded into the apparatus analogous to that indicated in example 1 and 85.6 hours, mixtures of polyfluorine-containing monomers, similar to those indicated in Example 1. Heating is heated at 70 ° C for 22 hours under nitrogen atmosphere, after which the barrier effect of solvents is added.
    spot area, mm Value of SOWB Example 6. A solution for padding is obtained consisting of 40 parts of solution S {according to example 1, 40 parts of an aqueous 65% solution of preliminary condensate of trimethyl ether hexamethylol melamine, 4 parts of lactic acid and 916 parts of water. Three types of fabrics of different composition: fabric from acrylic fibers (Dralon), fabric from polyester fibers (Tergal) and fabric from
    516116
    16Q h, water, 250 parts of isopropyl alcohol and 10 parts of acetic acid. The resulting mixture was stirred for 1 h at 70 ° C, then cooled 5 to ambient temperature.
    In this way, 530 parts of solution S are obtained from the copolymer which contains 19.1% non-volatile substances and 7.1% fluorine.
    By mixing 0.42 g of Sy solution, 4 g of dry mass of bleached bisulfite and 156 g of water, a water mass is obtained containing 0.03 g of fluorine. This mass is then diluted with 4 liters of water, stirred for 30 seconds and filtered under vacuum. The pulp thus obtained is dried under vacuum for 10 minutes at 90 ° C. In the end, get a paper sheet, treated (O) in its mass, the properties of which are given in table. 6 and are given in comparison with the properties of raw (BUT) paper sheet.
    About 29
    More than 900 168 blends of polyester with cotton 66/33, subjected to padding in the specified solution with a degree of pressing, respectively, equal to 112, 87 and 70%, then the fabric is treated for 3 minutes at 165 C in a thermocondenser. The properties of the thus treated tissues (o) are given in table. 7 and shown in comparison with the properties of tissues that are not processed (BUT).
    From tab. 7, it follows that the fabrics an interpreted by copolymers, are obtained according to the proposed method, possess a repellent property, i.e. fatty and other spots are not formed on these fabrics.
    Example 7; Two pieces of different leathers are applied with a brush.
    Oil repellency Example 8. In an apparatus analogous to that indicated in Example 1, 21.4 parts of acetone, 90 parts of isopropyl alcohol, 8 parts of dimethylamino ethyl methacrylate, 12 parts of N-vinylpyrrondone, 0.8 parts of 4.4 are loaded. -Azo-bis- (4-cyanopentanoic) acid and 85.6 parts of a polyfluorine-containing monomer of the general formula CjF, 5-Crgc-Bog-C7H | go-d-sng sng The mixture is heated for 10 hours under azo atmosphere. followed by the addition of 160 parts of water, 205 parts of isopropyl alcohol and 5 parts of acetic acid. The mixture is kept for another 2 h at, then it is cooled to ambient temperature. Thus, 580 parts of a solution S of a copolymer are obtained, which contain 17.6% non-volatile with substances and 6.5% fluorine.
    Table 7
    a solution of Sj, similar to that indicated in example 2a, at the rate of 100 g / m and dried them for 24 hours at room temperature. Skins with excellent water and oil repellent properties are obtained, which is confirmed by the characteristics given in Table. eight.
    Table 8 The resulting copolymer is used for paper processing, the paper, the processing conditions and the proportions of the polymer being boosted are similar to those shown in example 26 (i.e. 10.8 g Sg solution per 1 l processing solution). The copolymer used gives the paper the following properties: Oil repellency 9, test for turpentine oil more than 30 min. Example 9. Using a brush, coat the board with a solution S, as indicated in Example 5, taken at the rate of 100 g / m, and dry for 24 hours at ambient temperature. The effect of water repellency on the thus treated substrate is determined by applying a few drops of each of the following seven solutions to the tree surface: 19 Quotation The composition of test solutions,% of water-repellent effect 100. propanol-2 50/50 propanol-2 / water 30 / 70 propanol-2 / water 20/80 propanol-2 / water 10/90 propanol-2 / water 5/95 propanol-2 / water 2/98 propanol-2 / water The quotation corresponds to the solution number most enriched with isopropyl alcohol 4, which does not wet the substrate. This wetting is due to the complete leakage of the bone or the darkening of the surface contact with the liquid. Oil repellency is measured using standard solutions. A few drops of each solution are applied to the surface of the tree. The quote corresponds to the number of the plant with the lowest value of the tension, which does not penetrate into the substrate or for which no darkening of the contact surface with the liquid is observed. I Compared with untreated wood, get the results presented in table. 9 .. Table Water repellency Oil repellency Example 10. 14.2 parts of acetone, 45 parts of isopropyl alcohol, 3 parts of dimethyl aminoethylmethacrylate, 40 parts of N-vinyl pyrrolidone, 0.8 parts are charged to an apparatus analogous to that indicated in Example 1. 4,4-azo-bis (4-cyanopvntanoic) acid and 56.8 of the same mixture of polyfluorine-containing monomers indicated in Example 1. The mixture is heated for 4 hours under nitrogen atmosphere, then 160 hours, water, 160 hours is added. isopropyl alcohol and 2 parts of acetic acid. Stand for 1 hour at 80 then cooled to room temperature 120 tours. Thus, 460 parts of a solution S of a copolymer are obtained, containing 21.2% non-volatile substances 5.5% fluorine. Using the same paper and working under conditions similar to those indicated in example 2c, but with a fluorine content in 1 liter of the solution equal to 0.8 g (or 14.5 g of the Sf solution per 1 liter of the processing solution), this copolymer gives the paper the following properties: oil repellency (number of whales) 9; turpentine oil more than 30 min. Example 11. In an apparatus analogous to that indicated in Example 1, 45 parts of isopropyl alcohol, 4 hours of dimethylaminostilmethacrylate, 6 hours of N-vinylpyrrolnone, 0.4 parts of 4.4 azo-bis- (4-cyanopentanoic) acid, and 40 hours of polyfluorine-containing monomer of the formula C8F, 7-CjH4-0-CO-CH CH2. The mixture was heated under nitrogen for 24 hours, after which 80 hours of water, 100 parts of isopropyl alcohol and 2 parts of acetic acid were added. Withstand semi-. The mixture at 80 ° C is still i h, then it is cooled to ambient temperature. environment. Thus, 275 parts of a Sg solution of a copolymer are obtained, which contain 17.8% of non-volatile substances and 8.8% of fluorine. In the plus solution, consisting of 10 parts of solution S and 990 parts of water, the branch is plus. polyester, i.e., 200 g / m with a spin degree of 230t, and then dried for 3 minutes with a thermocondenser. The characteristics of the nonwoven material treated in this way are listed in Table. 10. Compared with the untreated nonwoven fabric1 salon. Table 10 Polyester nonwoven material. Characteristics Water repellency, measured according to the method indicated in Example 9. Repulsion. Continuation Table Effect of a barrier to the action of water (area of a spot mm) Effect of a barrier to the action of solvents (area of a spot, mm) Example 12: 21.3 parts of acetone, 45 parts of isopropyl alcohol, 14 N, dime amino acid, 1 part of N-vinyl pyrrolidone, 0.8 parts , 4,4 -azo-bis (4-cyanopentanoic) acid and 85 polyfluorine-containing its monomer form ly. CiFtf-C2H -SOr -C2H, rO-CO-CftСНз
    Oil repellency (number of whales)
    Turpentine oil test
    The effect of barriers to the action of water (the surface of the spot, mm)
    The effect of the barrier to the action of solvents (spot surface, mm) for example -J tJ G-PparET from the analogous indicated in example 1, load 20.4 h, acetone, 45 h, isopropyl alcohol, 6 h, dimethylaminosyl methyl methacrylate, 16 h. N- vinylMore
    Less than 30 minutes 30 seconds
    More than 700
    Over 900 122 The mixture obtained is heated at 70 ° C for 6 hours under a nitrogen atmosphere, after which 160 hours of water, 160 parts of isopropyl alcohol and 8 hours of acetic acid are added. This mixture is kept for another 1 h at, after which it is cooled to ambient temperature. In this way, 490 parts of a solution (S,) of a copolymer are obtained which contain 20% non-volatile substances and 7.8% fluorine. In a plus solution consisting of 10 hours, a solution of S and 990 parts of water, a non-woven cellulose-based material (wet method) having a weight of 46 g / m with a wringing degree of 150% is added, after which it is dried for 3 min at 16 5 C in the thermocondenser. The characteristics of the material thus treated are given in Table 11, in comparison with the untreated non-woven material, Pyrrolidone, T a b and c 11, 2 h, f aT-t monomethacrylate. - - - ъ. l. ethylene glycol, 0.8 h, 4,4-azo-bic (4-cyanopentanoic) acid and 81.6 h, mixtures of polyfluorine-containing monomers, analogous to that specified in example 1, the resulting mixture is heated at 80 ° C for 4 h under nitrogen atmosphere, then 160 hours of water, 230 parts of isopropyl alcohol and 6 parts of acetic acid are added. This mixture is kept for another 2 hours at 80 ° C, after which it is cooled to ambient temperature. Thus, 583 parts of a solution of 5.0 copolymer are obtained, which contain 18.1% non-volatile substances and 6.4% fluorine. The resulting copolymer is used to process paper, with paper, processing conditions and proportions similar to those shown in example 26 (or 11 g of solution 5, per 1 l of treatment solution). The copolymer used gives the paper the following properties: oil repellency (number of whales) 9; turpentine oil test over 30 min. Example 14. 18.4 parts of acetone, 50 parts of isopropyl jioBoro alcohol, 8 hours of methacrylate of tertbutylaminoethyl, 16 hours of N-vinclpyrrolidone, 0.8 parts of 4,4-azo- are loaded into the apparatus, which is similar to that indicated in example 1. bis- (4-cyanopentanoic) acid and 73.6 parts of a mixture of polyfluorine-containing monomers, similar to that described in example 1. The mixture is heated at 80 ° C for 6 hours under nitrogen atmosphere, then 160 hours of water is added to it, 200 hours Isopropyl alcohol and 4 parts of acetic acid. This mixture is kept for another 1 h at 80 ° C, then cooled to ambient temperature. In this way, 560 parts of solution S are obtained (a copolymer that contains 17.3% non-volatile substances and 6% fluorine. The resulting copolymer is used to process paper, with paper and processing conditions similar to those indicated in Example 26 (or 11.6 g of diluent S ((per liter of treatment solution). The copolymer used gives the paper the following properties: oil repellency (number of whales) 9; test for turpentine oil for more than 30 minutes. Example 15. In the apparatus, similar to that specified in Example 1, load 18.7 including acetone, 50 parts of isopropyl alcohol, T2 parts of dimethylamine oz methyl methacrylate, 10 parts H-vinylpyrrolidone, 6 parts vinyl acetate, 0.8 parts 4,4-azo bis (4-cyanopentanoic acid, and 74.7 parts a mixture of polyfluoro-containing monomers, analogous to that specified in Example 1, The mixture is heated for 6 hours under an atmosphere of yozot, then 160 parts of water, 250 parts of isopropyl alcohol and 12 parts of acetic acid are added to it.The mixture is cured for an additional hour, at 80 ° C, then cooled to environment. Thus, 572 parts of a Sfj solution of a copolymer are obtained which contain 17.6% non-volatile substances and 5.9% fluorine. The resulting copolushcher is used to process paper, with paper and processing conditions similar to those indicated in Example 2b (or 11.8 g of solution per 1 l of treatment solution). This copolymer gives the following properties: oil removal nodding (number of whales) 9; turpentine oil test over 30 min. Example 16 Into an apparatus analogous to that indicated in Example 1, 5 parts of acetone, 40 parts of isopropyl alcohol, 4 parts of dimethylaminoethylmethacrylate, 8 parts of N-vinppirrolidone, 5 parts of ethyl acrylate, 0.4 parts, 4,4-azo are charged. -bis- (4-cyanopentanoic) acid and 33 parts of a mixture of polyfluorine-containing monomers of the formula CF3- (CF2) jj-C2H -0-CO-C CH2 where n is 3, 5, 7, 9, 11, 13, 15, These are in weight ratios 1: 50: 31: 10: 3: 1: 1. The composition is maintained at 70 ° C for 5 h under nitrogen atmosphere. Further, 62.5 parts of water, 62.5 hours, isopropyl alcohol and 6 parts of acetic acid are added. The composition BE is kept for another 2 hours at 70 ° C and then cooled to room temperature. Thus, 220 parts of solution S, j of copolymer are obtained, which contain 21.8% of nonvolatile substances and% fluorine. Being used on the same bug and under the same conditions as in prier 26, but with 1.3 g / l of fluorine (15.5 g of solution S per 1 l of bath), this olimer reports the following properties to the paper: oil repellency (number it ) ten; experience with turpentine oil for more than 30 min. Example 17. In the apparatus, the tax specified in example Ij load 5 hours of acetone, JSC hours of isopropyl ether, 4 hours of dimethylaminoethyl methacrylate,. N-vinyl pyrrolidone, 5 parts of eipacetate, 0.4 d4,4-azo-bis- (4-cyanopentanoic) acid and 32 parts of a fluorine-containing monomer of the formula sOj-K-c, H | f-o-ssun cHs cHj Composition of the stand (grilled for 5 hours at 70 ° C in a nitrogen atmosphere. Then 62.5 parts of water, 62.5 parts of isolate alcohol and 4 parts of acetic acid are added. The composition is kept for another 2 hours at then cooled to room temperature. As a result, 219 parts of a solution of copolymer 5 (4, which contains 22 parts of nonvolatile substances and 6.3% fluorine are obtained. Used on the same paper and under the same conditions as in Example 2 but with content 1.4 / l of fluorine (or 22 g of solution 8 (4 per 1 l of bath) this copolymer provides the following paper properties: oil repellency (number of whales) 10; testing with turpentine oil for more than 30 minutes. Example 18. In the apparatus, and logical as indicated in example 1 load 10 hours of acetone, 40 hours of isopropane
    71.3
    7,6
    72.6 7.6
    87
    10, A
    82
    13 9.5
    81
    81 7.6
    57 3 8
    80
    Table 12
    About About About About About
    about
    about sawing alcohol, 7 hours, dimethylaminoethyl methacrylate, 8 parts of N-vinylpyrrolidone, 0.4 parts of 4, A-azo-bis (4-cyanopentanoic) acid and 35 parts of fluorine-containing monomer of the formula SVTP-2H4-SOj-H-C2H -0-CO-CH CH7. CHj The composition is kept for 6 hours under nitrogen at 70 ° C and then 62.5 parts of water, 62.5 parts of isopropyl alcohol and 5 parts of acetic acid are added. The composition hold for another 2 h at 70 ° C and then cooled to room temperature. Get 225 hours of solution 5, a copolymer, which contains 21, And% non-volatile material and 7.5% fluorine. Used in the same non-woven cellulosic material, as in example 12, in the amount of 0.8 g of fluorine per 1 liter of water (ie 10.7 g S | 5 per 1 liter), this copolymer provides the following properties of the nonwoven material: oil repellency (number of whales) 8} test with turpentine oil for more than 30 minutes. In tab. 12, for each production example, the percentage of each monomer is indicated relative to the total weight of monomers used.
    权利要求:
    Claims (2)
    [1]
    1. METHOD FOR PRODUCING FLUORINE-CONTAINING POLYMERS by copolymerizing one or more fluorine-containing esters of acrylic or methacrylic acid with a dialkylaminoalkylmethacrylate in solution in the presence of a radical initiator, characterized in that, in order to give the fluorine-containing copolymers of water-repellent acrylic acid-containing compounds, they are used in their quality as methanol-containing acrylic acid-repellent acids or formulas
    CFj- {CP |) jT CjHb-SOj-X-CiH ^ -O-CO- ^ CH,
    CKj £ or general formula
    CFj-iCFj ^ CiHirO-CO-C-sCHi,
    R.
    where P = 3,5, 7, 9, 11, 13 or 15; R H, CH,.
    as dialkylaminoalkylmethacrylate -NjN-dimethylaminoethylmethacrylate or tert-butylaminoethylmethacrylate, wherein Y-vinylpyrrolidone-2 is additionally introduced into the reaction mixture, in the following ratio, wt.%:
    Fluorine esters of the indicated formulas N, N-Dimethylaminoethyl methacrylate or tert-butyl aminoethyl methacrylate
    N-vinylpyrrolidone-2 and copolymerization are carried out by comonome 57-87
    3-14
    1-40 and h at-l reaction
    [2]
    2. The method according to p. 1, which is based on the fact that the mixture is additionally introduced until
    10 wt.% Of the initial mixture of comonome 1 moat of vinyl acetate, ethyl acrylate or; hydroxyethyl methacrylate.
    SU ". 1155161
    类似技术:
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    同族专利:
    公开号 | 公开日
    JPH06122870A|1994-05-06|
    FI69086C|1985-12-10|
    FI69086B|1985-08-30|
    JPS56131612A|1981-10-15|
    ATA63481A|1982-03-15|
    JPH0377206B2|1991-12-09|
    CA1159195A|1983-12-20|
    ES8206570A1|1982-08-16|
    DE3163033D1|1984-05-17|
    NO810554L|1981-08-20|
    AT368762B|1982-11-10|
    US4366299A|1982-12-28|
    FR2476097A1|1981-08-21|
    NO160925B|1989-03-06|
    DD211353A5|1984-07-11|
    ES499565A0|1982-08-16|
    EP0034527A1|1981-08-26|
    NO160925C|1989-06-14|
    BR8100965A|1981-08-25|
    FI810497L|1981-08-20|
    AU6741781A|1981-08-27|
    DD156431A5|1982-08-25|
    AU536952B2|1984-05-31|
    DK70281A|1981-08-20|
    EP0034527B1|1984-04-11|
    ZA811075B|1982-03-31|
    JPH0774331B2|1995-08-09|
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    FR8003566A|FR2476097A1|1980-02-19|1980-02-19|
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