• 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:
    This invention relates to novel partially saponified polyvinyl acetates with a degree of hydrolysis of 30 to 65 mole % which might be considered as vinyl alcohol-vinyl acetate block copolymers. The invention relates further to the application of said novel block copolymers as a pore-forming additive used together with at least one known protective colloid in the homo- and copolymerization of vinyl compounds, primarily of vinyl chloride in a pure aqueous medium.
    公开号:SU795489A3
    申请号:SU772444852
    申请日:1977-01-28
    公开日:1981-01-07
    发明作者:Мариаши Бела；Молнар Ласло；Тот Янош；Гулья Имре；Надь Миклош；Вольфрам Эрвин；Цриньи Миклош；Ковач Габор；Якцить Ласло
    申请人:Боршоди Ведьи Комбинат (Фирма)；
    IPC主号:
    专利说明:

    The calculated amount of the alkaline catalyst is either in solid form or in the form of a solution prepared with a polar solvent. After a short time, the homogenized mixture is left to stand. The system thickens in a short time in a gel, requires for this from 5 to 20 minutes, which depends on the temperature, the concentration of alkali used as a catalyst, the ratio of the two types of solvent and the concentration of polymers. The hydrolysis thus proceeds in the gel phase formed in this way. . Polyvinylacetate of any molecular weight can be used as the starting material for carrying out the process according to the invention. Partially hydrolyzed polyvinyl acetates; obtained according to the invention, which, to a lesser extent up to 65 mol.%, are hydrolyzed and are therefore water-soluble products, have, up to now, unknown new properties; a hazeresis of cloudiness that distinguishes them from other similar products. Therefore, they should be considered as new compounds. If the hydrolyzed less than 65 mol.% Non-water soluble products in a mixture of propanol and water, together with bifunctional aldehydes, such as glutaraldehyde, are exposed to acid, they form a gel for a short time (approximately 1 hour). In the case of such partially hydrolyzed polyvinyl acetate, such as Polyvik-202 Italian Sigma, known for its state of the art, this type of gelation is not observed, or it occurs only after 24 hours and only as a result of hydrolysis, caused by acid. By this experiment, it was proved that polyvinyl acetates hydrolyzed to less than 65 mol% according to the invention because of this new, previously unknown property can be considered as new compounds. The main advantages of the method according to the invention are as follows: a) shortly after the formation of a gel macrosineresis. As a result, most of the solvent mixture used is released from the gel phase, which greatly facilitates the separation of the product and the new use of the solvent mixture in hydrolysis; b) by selecting an appropriate alkali concentration and / or by neutralizing the alkali (for example, by adding hydrochloric or acetic acid) products of any degree of hydrolysis can be obtained ° c) the stabilizing-emulsifying properties of the partially hydrolyzed polyvinyl acetates obtained by the method according to the invention are much better than the properties of the best currently used commercial products (see table). The high stabilizing effect of the products obtained by the method according to the invention can only be explained from the point of view of a particular structure of the molecules. Evidence of this particular molecular structure, which is likely to form in a gel form. phase, in the case of water-soluble products, the occurrence of hysteresis clouding, and in the case of non-water soluble products, gel formation occurs in the presence of bifunctional aldehydes. An emulsification study was performed for a mixture consisting of 20 vol. .. chloroform and 8.0 vol% water.
    The table shows that partially hydrolyzed polyvinyl acetates obtained according to the invention, as highly efficient emulsifiers, have advantageous properties
    权利要求:
    Claims (4)
    [1]
    stabilize emulsions with respect to the uniform distribution of droplets to almost infinite constancy of droplets, and this stabilizing efficiency does not depend on the type of liquid that is not miscible with water or of organic matter insoluble in water. Partially hydrolyzed polyvinyl acetates obtained according to the invention can be used due to their stabilizing-emulsifying efficacy among other products that are used in the plastics processing and processing industry, in the production of food products, in the pharmaceutical industry as well as in the preparation of cosmetic products and when making plant protection products. Example 40 g polyvinyl acetate {degree of polymerization 1250) is dissolved in 100 ml of benzene. The resulting solution is added to 200 ml with a mixture prepared from 42.5 ml of methanol and 27.5 MP of benzene. The ratio of benzene and methanol is 3: 1, the concentration of the polymer is 20% of the estimates. Immediately after this, 10 ml of 2N are added to the mixture. methanol solution of sodium hydroxide. The concentration of alkali, calculated on the polymer, thus amounts to 2%. The mixture is stirred for 2 minutes and then left to stand for 180 minutes. Already after the first 5 NBIH, gel formation occurs. After this time, the product is isolated. Yield 98%, gel elastic modulus 5.10 dyne / cmg Cloud point: in 1% native solution 65 ° C, hydrolysis degree 78 mol%, polymerization degree 1250. The product is a highly effective colloid stabilizer and as such applied, for example, for the polymerization of vinyl compounds in suspension. Example
    [2]
    2. Work exactly as described in Example 1, with the difference that the reaction mixture was stopped for 240 bns (i.e., the duration of hydrolysis was 240 minutes. The yield and parameters of the resulting product were as follows: 97% yield , modulus of elasticity of gel 8 "Yudin / cm, cloud point: in a 1% aqueous solution, the degree of hydrolysis is 89 mol%. The product is similar to a highly efficient colloidal stabilizer prepared according to Example 1. Example
    [3]
    3. Work as described in Example 1, with the difference that the reaction mixture is left to stand for 400 minutes (the duration of hydrolysis is 400 minutes). Parameters of the product obtained with a yield of 95%, the following: gel elasticity of 1.5-10 dyne / cm, cloud point: in a 1% aqueous solution over 100 ° С, degree of hydrolysis is 96 mol /%. The product obtained according to the example can be used as a highly effective stabilizer for colloids. PRI me R
    [4]
    4. They work in the same way as described in example 1, with the difference that 127.5 MP of benzene is replaced with a mixture of xylene and benzene, prepared in a volume ratio of 1: 6, with the same amount. The duration of hydrolysis is 210 min. The parameters of the product obtained with a yield of 96% are as follows: the modulus of elasticity of the gel is 6, 5-10 dyne / cm-g cloud point: in a 1% aqueous solution over, the degree of hydrolysis is 92 mol.%. With this product, a mixture of chloroform and water prepared in a volume ratio of 1: 5 can be stabilized to such an extent that 60% of the droplets are in the range of 300500 mm, the remaining 20% are less than 200 mm, i.e. the distribution of the droplet size is uniform. PRI me R 5; They work in the same way as described in example 1, with the difference that the ratio of benzene and methanol is established not 3: 1, but 5: 1, instead of 10 ml 2 n. sodium hydroxide solution as a catalyst used 4 ml of 2N. the sodium hydroxide solution and the hydrolysis time was 70 minutes. The resulting product with a yield of 95% has the following parameters: the modulus of elasticity of the gel is 5-10 dyn / cm. Cloud point: not detectable, the degree of hydrolysis is 62 mol.%. The product obtained according to The measure is an effective stabilizer and blowing agent in the suspension polymerization of vinyl soeneny. P and measures 6. They work in the same way as described in example 1, with the difference that not 10 MP 2 n is used as a catalyst. sodium hydroxide solution, and only 1 ml of this solution and the duration of hydrolysis is 500 minutes. The product obtained with a 94% yield has the following parameters: gel elastic modal 6-U dyn / cm, cloud point is not limited, degree of hydrolysis is 35 mol. The product obtained according to the method can be used as a highly effective stabilizer for emulsions of the type water fat. EXAMPLE 7 The procedure described in Example 1 is the same, with the difference that not 40 g of olivine acetate is dissolved, but only 20 g in benol and the duration of hydrolysis is 180 minutes. The product obtained with a yield of 96% has the following parameters: the modulus of gel elasticity is g 10 d / cm, the point of crush: in a 1% aqueous solution is 65 C, the degree of hydrolysis is 82 mol.%. The product can be used as a highly effective stabilizer of colloids and a blowing agent in the suspension polymerization of vinyl polymers and vinyl copolymers Example. 60 g of polyvinyl acetate (degree of polymerization 300) are dissolved in the solvent mixture according to example 1. 2 ml of 2 N is used as a catalyst. sodium hydroxide solution. The duration of the hydrolysis is 300 minutes. The product obtained with a yield of 92% has the following parameters: the gel elasticity modulus is 3.5-10 dyn / cm, the turbidity is not detectable, the degree of hydrolysis is 48 mol%. Example 9. The procedure described in Example 8 was performed with the difference that instead of 60 g of polyvinyl acetate 100 g of polyvinyl acetate was used, instead of benzene, toluene was used instead of 2 ml of 3 ml of 2N. methanol solution of sodium hydroxide and the reaction is carried out at 15 ° C. The parameters of the obtained product are as follows: the elasticity modulus of the gel is 5–10 dd / cm, the cloud point cannot be measured, the reaction with glutaraldehyde is positive, the degree of hydrolysis is 38 mol%. Example 10 60 g of polyvinyl acetate (degree of polymerization 300) are dissolved in 153 MJI of benzene. To the resulting solution, a solution of 2.4 g of sodium hydroxide in 17 ml of methanol is added (i.e. the solvent mixture according to the invention consists of 90% benzene and 10% methanol). The mixture was incubated for 120 minutes. The parameters of the obtained product are as follows: the elastic modulus of the gel is 8-Yudin / cm, the reaction with glutaraldehyde is positive, the degree of hydrolysis is 52 mol%. The 5.6 and 8 products obtained in examples show a positive reaction with glutaraldehyde and do not have a cloud point. The products obtained in the examples have a block structure, i.e., in partially hydrolyzed polyvinyl acetates, hydroxy groups and acetate groups are located in separate blocks. In contrast, the partially hydrolyzed polyvinyl acetates known so far have a statistical structure, i.e., in their polymer chain, hydroxy groups and acetate groups are in a statistical distribution. Example (comparative). 30 polyvinyl acetate (M-130,000) is dissolved in 100 ml of methyl alcohol. To the resulting solution was added sodium hydroxide. The alkali concentration with respect to the polymer is 0.4%. The resulting mixture was allowed to stand for 120 minutes (i.e., the duration of the methanolysis was 120 minutes), then a methanolic hydrochloric acid solution was added in an amount equivalent to the amount of alkali. During the methanolysis, no gel phase occurs, and after the addition of the specified hydrochloric acid solution a white precipitate appears. The properties of this product are as follows: the degree of hydrolysis is 84.3 mol.%, The surface deposition in a 1% aqueous solution at 25 ° C, 53.0 dyn / cm, cloud point: in a 1% aqueous solution up to the boiling point of this solution not measurable. Example 12: & in example 11, with the difference that 100 ml of methyl alcohol is not used, and the mixture consisting of 50 ml of methyl alcohol and 50 ml of benzene, i.e. non-polar solvent in the smallest possible amount according to the invention) and the duration of hydrolysis is 240 minutes (in order to obtain a product with the same degree of hydrolysis as possible), on the 35th minute of hydrolysis a stable and elastic gel phase is formed, which no longer disappears. The properties of the obtained product are as follows: degree of hydrolysis: 83.0 mol.% Surface tension in 1% aqueous solution at 25 ° C 48.2 dyn / cm, cloud point in 1% aqueous solution 85 ° C. The difference in The property of products with practically the same composition clearly indicates that the partially hydrolyzed polyvinyl acetate obtained according to the invention in the gel phase has a cloud point, i.e., a property that is not. partially known, partially hydrolyzed polyvinyl acetates. The invention The method of obtaining partially hydrolyzed polyvinyl acetate by hydrolysis of polyvinyl acetate in an organic solvent at 10-80. in the presence of 0.1-5.0% (by weight of polyvinyl acetate) alkali, characterized in that, in order to obtain the final product of the block structure with a degree of hydrolysis of 3092 mol.% and a higher dispersibility, the hydrolysis is carried out in the polymer phase in the mixture solvents, consisting of 50-90% by volume of an aromatic hydrocarbon and 1050% by volume of methanol, and a salt of 5-
    79548910
    60 weight.h. on 100 ob.ch. mixtures of solution-1. Nikolaev A.F. Synthetic
    polyvinyl acetate. polymers and plastics on their
    Sources of information based. M.-L., Himi, 1964, p. 166 taken into account during the examination.
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    同族专利:
    公开号 | 公开日
    JPS52110797A|1977-09-17|
    RO70825A|1981-06-26|
    PL103972B1|1979-07-31|
    CS199660B2|1980-07-31|
    AT356891B|1980-05-27|
    RO71672A|1981-06-26|
    DE2702771C2|1983-05-11|
    SE7700857L|1977-07-29|
    NO770269L|1977-07-29|
    FR2339628A1|1977-08-26|
    US4258163A|1981-03-24|
    ATA41077A|1979-10-15|
    DE2702771A1|1977-08-04|
    GB1543282A|1979-04-04|
    FI770267A|1977-07-29|
    NL7700836A|1977-08-01|
    DD128135A5|1977-11-02|
    FR2339628B1|1981-05-29|
    YU21877A|1982-05-31|
    HU172617B|1978-11-28|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US2812318A|1955-10-06|1957-11-05|Goodrich Co B F|Method for granular polymerization of vinyl chloride|
    US3444125A|1967-05-11|1969-05-13|Du Pont|Moistenable,hot melt adhesives comprising random vinyl alcohol/vinyl ester copolymers|
    US3592800A|1967-11-29|1971-07-13|Werner Oschmann|Polymerization of vinyl chloride in aqueous suspension in the presence of low viscosity polyvinyl alcohol and a protective colloid|
    JPS5121671B2|1972-11-21|1976-07-03|IT1055887B|1976-02-17|1982-01-11|Sigma Italiana Prod Chimici|PROCESS PERFECTED FOR THE PRODUCTION OF POLIVINLI CHLORIDE|
    DE2629880B2|1976-07-02|1980-10-16|Wacker-Chemie Gmbh, 8000 Muenchen|Process for the production of polyvinyl chloride by the suspension process|
    IT1160355B|1978-12-15|1987-03-11|Sigma Italiana Prod Chimici|PROCESS PERFECTED FOR THE PRODUCTION OF POLYVINYL CHLORIDE|
    IT1140328B|1981-12-11|1986-09-24|Anic Spa|PROCEDURE FOR THE POLYMERIZATION AND COPOLYMERIZATION IN SUSPENSION OF VINYL CHLORIDE|
    US4464519A|1982-06-07|1984-08-07|Air Products And Chemicals, Inc.|Vinyl chloride-propylene copolymers having increased porosity|
    US4436867A|1982-06-17|1984-03-13|Kimberly-Clark Corporation|Creping adhesives containing poly 2-ethyl-2-oxazoline|
    US4440898A|1982-06-17|1984-04-03|Kimberly-Clark Corporation|Creping adhesives containing ethylene oxide/propylene oxide copolymers|
    US4525511A|1984-04-06|1985-06-25|Essex Specialty Products, Inc.|Method and compositions for improving bonding to painted surfaces|
    JPH0621125B2|1984-11-02|1994-03-23|日本合成化学工業株式会社|Dispersion stabilizer|
    PT86940B|1987-03-12|1992-05-29|Shinetsu Chemical Co|PROCESS FOR THE PREPARATION OF AN IMPROVED COMPOSITION OF POLYVINYL CHLORIDE RESIN|
    IT1241660B|1990-03-07|1994-01-26|3V Ltd|VINYL ACETATE / VINYL ALCOHOL COPOLYMER, PRODUCTION PROCESS OF ITSELF AND ITS USE|
    DE69121496T2|1990-04-05|1997-03-20|Kuraray Co|SUSPENSION POLYMERIZATION OF VINYL COMPOUNDS|
    TW222282B|1992-03-10|1994-04-11|Kuraray Co|
    JP3529857B2|1994-10-07|2004-05-24|株式会社クラレ|Dispersion stabilizer for suspension polymerization of vinyl compounds|
    WO2001040372A1|1999-12-03|2001-06-07|Kuraray Co., Ltd.|Aqueous emulsion and dispersant for suspension polymerization of vinyl compound|
    AT540082T|2007-04-16|2012-01-15|Kuraray Co|DISPERSION STABILIZER FOR SUSPENSION POLYMERIZATION|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    HU76BO00001595A|HU172617B|1976-01-28|1976-01-28|Process for producing partially hydrolyzed polyvinylacetate in phase gel|
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