• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    A composition capable of absorbing more than 45% of its weight of water without dissolution at room temperature to form a hydrogel is made by blending (1) 40 to 98% by weight of water-soluble polymer of a vinyl lactam having the structure <IMAGE> in which X represents an alkylene bridge having three to five carbon atoms or a copolymer thereof with 1 to 90 mole percent of a copolymerizable monomer containing a polymerizable ethylenic unsaturation; and (2) 2 to 60% by weight of a water-insoluble copolymer formed of 50% to 90% by weight based on the total copolymer of a hydrophobic water-insoluble ethylenically unsaturated monomer, 2 to 12% by weight of an ethylenically unsaturated monomer containing an acid group, and 0 to 50% by weight of a hydrophilic ethylenically unsaturated monomer free from acidic groups.
    公开号:SU1243627A3
    申请号:SU802925602
    申请日:1980-05-26
    公开日:1986-07-07
    发明作者:Рамандал Шах Кишор
    申请人:Дзе Кендалл Компани (Фирма)；
    IPC主号:
    专利说明:

    The invention relates to high-molecular compounds, specifically to a composition capable of absorbing water at an ambient temperature without dissolving more than 45% with the formation of a hydrogel that can be found; use in me (Dicine, for example, for covering wounds and burns, dp of making soft contact lenses, etc., as well as in other areas, in particular in the automotive and aviation industry for manufacturing, coatings of glass surfaces, for example glasses to protect them from fogging.
    The aim of the invention is to vary the hydration properties of the resulting gels. I
    Examples 1-13. In these examples, each of the copolymers is prepared by the usual method of solution polymerization, a solution in a suitable solvent, the required proportions of monomers and when using small amounts (0.2-0.4% by weight of monomers) of a free-radical initiator such as polymerization initiator as azobisisobutyronitrile or 2-tertboots1azo-2-cyanopropane. Polymerization is carried out at 80-95 ° C, to high degrees of conversion. Sosta copolymerization mixture is described in table. 1 The copolymers of Examples 1-3 were precipitated from methanol in the reaction mixture, collected by filtration and dried: at 100 ° C under vacuum, and the copolymer of Example 4 was removed by removing the volatile components by heating under vacuum at 100 ° C.
    Each of the mixed compositions according to the examples is obtained by dissolving in N, N-dimethylpharmacy in the right proportions of a water-insoluble copolymer and polyvinylpyrrolidone (mol. Mass. 360000) dC concentration of the polymer mixture in a solution equal to 10 - 15 wt.%. Thereafter, the mixture solution is heated under vacuum to remove the solvent to obtain a mass of optically transparent solid mixture. The thermoplastic mixture is pressed into a disc in a heated form at 150 C. The molded disc is placed in deionized water for 72 hours, during which it absorbs water and forms a hydrogel. In tab. Figure 2 shows the composition of the mixtures, their physical properties and the equilibrium water content in the hydrogels of these mixtures.
    Examples 12-13. In a 500 ml round-bottomed flask, 20.8 g (0.10 mol) of phosphorus pentachloride are placed, and 17.4 g (0.084 mol) of pulverized powder are slowly added to it three chilled in an ice bath.
    p-styrene sulfonate sodium. The mixture is thoroughly stirred on a magnetic stirrer. After 30 min, the mixture is heated under reflux at 50-60 ° C for 2 hours. The product is cooled, poured into 100 g of crushed ice and extracted with 100 ml of chloroform. The organic layer containing p-styrene sulfonyl chloride is separated and washed several times with distilled water.
    and dried over magnesium sulphate.
    A solution of p-styrene sulfone 1 chloride in chloroform (100 ml) was added to 340 ml of 30% - Hoii ammonium hydroxide (specific weight 0.90) with mechanical stirring and simultaneous cooling with ice for approximately 30 minutes. The mixture is heated at 50 ° C under reflux for 5 hours and then cooled to room temperature.
    The organic layer is separated, dried over anhydrous magnesium sulphate, evaporated to a dry residue and a white solid is obtained, a solid powder of p-styrenesulfonamide, which is purified by recrystallization from a water-ethanol mixture, and approximately 6.0 g of sulfonamide are obtained, m.p. 130-132 C.
    The infrared spectra of sulfonamide detect absorption bands.
    at 3350 and 3260 cm (NH bond fluctuations), 1600 (aromatic bond), 1305 and 1160 cm bond vibrations) and 840 cm (p-substituted benzene, vibrations of two adjacent CH).
    A copolymer of 62% n-butyl methacrylate, 30% p-styrene sulfonamide, prepared as described, and 8% of acrylo-LO1OI acid are prepared in the usual way, as described in examples 1-4,
    using 33% monomer concentration in a mixture of ethyl alcohol and dioxane. The copolymer is purified by precipitating .m of the reaction mixture in chloroform, after which it is isolated by filtration.
    and dried under vacuum at 100 C.
    Mixtures of the copolymer with polyvinylpyrrolidone (PVP, mol. May.360000) are prepared as described in examples 5-
    31
    11, by dissolving the copolymer and PVP in dimethylformamide and subsequent evaporation of the solvent in vacuo at. Mixtures containing 10% by weight and 30% by weight of copolymer and the corresponding amount of polyvinylpyrrolidone as the remainder are optically transparent solid compounds. As found, the molded disks of the two mixtures, prepared in the same way as described in examples 5-11, absorb water and form transparent hydrogels containing, respectively, 84.6 and 62.5% by weight of water, when held to equilibrium. in deionized water at room temperature for 72 hours.
    Examples 14-17. Hydroxyethyl methacrylate (HEMA) is purified by extraction (4-6 times) of a 1: 1 polymer solution in water with petroleum ether, then the aqueous monomer solution is saturated with sodium chloride and the monomer is extracted with chloroform. The combined chloroform extracts are dried n: hell with anhydrous magnesium sulphate and the solution is distilled under vacuum (about 0.1 mm Hg) using monovalent copper as an inhibitor. The monomer fraction is driven at 70-82 ° C.
    A copolymer containing 52% butyl methacrylate, 40% HEMA and 8% acrylic acid is prepared in the usual way, as described in examples 1-4, using a 25% concentration. monomer in a mixture of ethyl alcohol and dioxane.
    Optically translucent copolymer mixtures in various ratios with polyvinylpyrrolidone (PVP, mol.may. 360,000) are prepared, as described in examples 5-11, by dissolving the copolymer and PVP in dimethylformamide and subsequent evaporation of the solvent at 100 ° C in a vacuum, Forming under pressure is obtained from a mixture of plates with a thickness of approximately 0.2032-0.3048 mm, which is held for 72 hours in deionized water at room temperature until equilibrium. As found, mixtures containing 70, 80, and 90% VES.% PVP form hydrogels containing, respectively, 75.8, 82.3. and 88.9% water.
    Examples 18 - 24. A copolymer of 62% butyl methacrylate, 8% ac; rilic acid and 30% meta
    five
    0 5 o
    five
    five
    five
    0
    2.1
    Krlamide is prepared according to the general procedure described in Examples 1-4, and also as described in Examples 14-17, optically transparent mixtures of a copolymer with different amounts of the same polyvinylpyrrolidone are obtained.
    It was found that there is a linear relationship between the proportion (from 10 to 40%) of the copolymer in the mixture and the equilibrium water content in the hydrogel, as shown in Table. 3. In order to take into account changes in the properties of PVP in the mixture due to the introduction of a copolymer, the hydration of one fraction of PVP is calculated, on the assumption that the swelling of the copolymer in water can be neglected. The results are presented in the last column of the table. 3. It is again found that the equilibrium water content in the PVP fraction is inversely proportional to the amount of copolymer in the mixture.
    Examples 25-32. A series of water-soluble N-vinylpyrrolidone copolymers containing various amounts of vinyl acetate, N, N-dimethyl methacrylamide and mixtures of these latter two were prepared by dissolving the desired proportions of monomers in paBHbix volumes of methanol and using c. the initiator quality is about 0, 15 wt.% (relative to the weight of the monomers) of a free-radical initiator, such as 2,2-azobis-isobutyronitrile. The polymerization is carried out by boiling the solvent under reflux to a conversion degree of approximately 90-95% and after evaporation of the solvent and the residual monomer under vacuum, the copolymer is obtained in the form of a brittle transparent and colorless solid residue.
    Water-insoluble copolymer is obtained from a mixture of 62 parts by weight p-butylmetacrylate, 30 weight.h. methacrylamide and 8 weight.h. acrylic acid according to the method described in examples 1-4.
    Mixtures of water-soluble and water-insoluble copolymers are prepared as described in examples 14-17.
    In tab. 4 shows the compositions of copolymers of vinylpyrrolidone, the amount of copolymers in a mixture with a water-insoluble copolymer, and the equilibrium water content in each hydrogel mixture when kept in water for 72 hours at room temperature. In each case, the mixtures are
    is an optically transparent solid compound that forms opt1Lesky transparent hydrogels at equilibrium soaking in water. . ,
    The mixtures according to the invention possess such properties as thermoplasticity, melting ability, solubility in organic solvents and ability to hydrate. Although they retain thermoplasticity, melting ability and solubility in organic solvents of the polymer or copolymer vinyl lactam part, mixtureI} it.and possess different hydration properties depending on the amount of copolymer present.
    EXAMPLE 33. Each of examples 6-13 was repeated, replacing PVP with an amount of poly-caprolactam equal in weight (maximum mol. May 33.3000). This polylact is prepared as follows: 200 mg of azobisisobutyronitrile (AIBN) are dissolved in 100 g of N-vinyl-β-caprolactam, which is preheated to 45 ° C in a crusher. The solution was held in an oven at 75 ° C for 4 hours and: During this time, the composition was polymerized to a solid mass. The solid mass is dissolved in one liter of chloroform and the solution is added dropwise to 10 liters of petroleum ether (boiling point 30-60 ° C) with: stirring, to obtain a granulated polymer precipitate. The polymer is separated by filtration and dried in a vacuum oven (for 3 hours at 10 mm Hg). The yield is 75 grams of polymer, the max.
    The molecular weight determined by gel permeation chromatography is 36,000. The IR spectrum showed an absorption at 1640 cm, which is a characteristic of lactam carbonyl.
    The results of Example 33 are comparable to those obtained in Examples 5-11.
    Example 34. Repeat Example 33, using higher molecular weight polyvinyl caprolactam (max. Mol. May. 800,000). it
    Polylactam is obtained by polymerization in solution in methyl alcohol. Thus, in a solution of 100 g of N-vinyl-caprolactam in 550 ml of methyl alcohol, 100 mg of isob is dissolved; sisobutyronitrile as an initiator. The polymer resin is dried in a vacuum oven at 50 ° C and 10 mm Hg. Maximum supposedly, May. 500,000. The results are similar to those obtained in examples 5-11.
    Example 35. Example 33 is repeated again using poly-N-vinyl-α-κ-caprolactam prepared in anap water: it is great how the polymer was obtained in example 34, but using water instead of methyl alcohol and 1.2 g potassium persulfate and 0.6 g of metabisulfite solution instead of AIBN. Temperature-time mode: 3 hours and then 60 ° C - 17 hours (instead of within 20 hours). Maximum mol. May equal to 600SUO.
     PRI me R 36. Examples 5–11 were repeated again, using the following polymers instead of PVP: polyvinyl oxazolidinone (M.M. 40000); polyvinyloxazolidinone (M.M. 350000); polyvinyl -2-piperidone (M.M. 250,000); polyvinyl-5-methyl-pyrrolidone (M.M. 360000) polyvinyl-5-ethyl-ok eazolidinone (M.M. 340000). The results are similar to those obtained in examples 5-11.
    Example 37. Examples 14-24 are repeated, except that the polymers of examples 33-36 are used instead of PVP. The results are comparable with the earlier examples.
    Example 38. Examples 25-32 are repeated, except that instead of N-vinyl-pyrrblidone, which is used as a component of the copolymer (examples 25-30), the following are used for the terpolymer a (examples 31 and 32): N- vinilokeazolidinone; K-vinyl-2-piperidone; L-vinyl-5-methyl-pyrrolidone; N-α-vinyl 4-methyl-5-butylokeazolidinone.
    Results are similar to other examples.
    65-303015 30
    -65
    5555
    --80 - y 65
    s
    100100100 100
     100100100 --- 100
    1 2 2 3
    70
    90 70 90 90
    70 90
    Transparent, hard
     PVP is polyvinylpyrrolidone.
    Table 1
    table 2

    but ,

    68
    91
    58 80 90
    77 90
    Note
    VNIINI Order 3722/60 Circulation 470 Subscription Production-polngr. pr-tie, Uzhgorod, st. Design, And
    Mix weight - - Weight HjO
    Table A
    gave - N-, N-dimethylacrylamide; VP - N-vinylpyrrolidone; VA - N-vinyl acetate ...
    权利要求:
    Claims (1)
    [1]
    A GEL-FORMING COMPOSITION containing a water-soluble polymer having N-vinyl lactam units and a molecular weight of at least 10,000, and a water-soluble polymer compound with carboxyl groups, which consists in that, in order to preserve the hydration properties of the resulting gels, as a water solubility a polymer having N-vinyl lactam units, and mol. no less than 10000, it uses a polymer selected from the group comprising poly-K-vinylpyrrolidone, a copolymer of N-vinylpyrrolidone with N, N-dimethylmethacrylamide and / or vinyl acetate, polyvinyl oxazolidinone, polyvinyl-2-piperidone, polyvinyl-5-methylpyrrolidone -5-ethyloxazolidinone, poly-Ν-vinyl-, t-caprolactam, poly-N-bhnyl-4-methyl-5-butyloxazolidinone, and a copolymer based on 50-80 wt.% Was used as a water-soluble polymer compound with carboxyl groups. % C 4 -C £ (-alkyl methacrylate, 2-ethylhexyl acrylate or styrene, 5-8 wt.% Acre sulphic acid and May 15-40.% methacrylamide, hydroxyethyl methacrylate or p-styrene-sulfonamide, with the following components, wt.%:
    A polymer having N-vinyl lactam units as defined above
    The polymer compound with carboxyl groups as described above
    12/05/79 - as a water-soluble polymer having N-vinyl lactam and mol. Mae units. not less than 10000, applied poly-Y-vinylpyrrolidone;
    10.27.80 - as a water-soluble polymer having N-vinyl lactam and mol. Mae units. not less than 10000, all other water-soluble polymers are applied according to the signs> SM
    1243627 High properties and equilibrium water content in hydrogels from these mixtures.
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    同族专利:
    公开号 | 公开日
    AU540694B2|1984-11-29|
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    FR2471213B1|1984-12-28|
    IT1218423B|1990-04-19|
    DK521480A|1981-06-06|
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    FR2471213A1|1981-06-19|
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    NO158811B|1988-07-25|
    PT72171B|1981-10-28|
    SE8008548L|1981-06-06|
    MX155719A|1988-04-20|
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    US10037579A| true| 1979-12-05|1979-12-05|
    US06/201,349|US4300820A|1978-11-06|1980-10-27|Water absorptive composition|
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