![]() Polymeric dispersion and method of producing same
专利摘要:
This invention discloses stable, aqueous polymeric dispersions comprised of at least 25% solids, dry basis, of a starch graft copolymer of a thinned and derivatized starch and at least one vinyl monomer. The starch has a degree of substitution of at least about 0.05 and an intrinsic viscosity of not less than about 0.12 deciliters per gram. The starch graft copolymers have a starch/monomer ratio of less than about 100/25. The dispersions are stable over extended periods of time at normal storage temperatures. Processes for the production of the dispersions are also disclosed. 公开号:SU1508965A3 申请号:SU813277450 申请日:1981-04-27 公开日:1989-09-15 发明作者:Пол Кайтлингер Адриан;Лоренс Спикмэн Эдвин;Томас Ван Дьюзи Грант 申请人:Стандарт Брэндз Инкорпорейтед (Фирма); IPC主号:
专利说明:
The invention relates to the field of chemical technology, specifically to a polymer dispersion for starch-based sizing agents and a process for its preparation, and can be used in the manufacture of paper. The aim of the invention is to increase the stability of the dispersion during storage. Example. A Q10% by weight of dry starch anhydrous sodium sulfate and 590 ml of caustic solution (solution of sodium hydroxide and chloride) are added to a suspension of corn starch (40.87% by weight of dry matter). sodium with 1.65 eq. titrated caustic per liter and a density of 27 Bome at 20 ° C). Alkalinity of suspension in ml 0.1 and. HCl solution (necessary to neutralize 30 ml of suspension) is 24.0. 8, each of the six 1.9 liter containers is added with 1597 ml of slurry (equivalent to 728 g of starch dry matter per volume). These containers, equipped with agitators and holes for the addition of reagents, are placed in a water bath at. The amount of acrylonitrile specified in SP x SP) SP cm 31508 tab. 1. After 16 h, the pH of the reaction mixtures was adjusted to 6.3, filtered, washed twice and dried at 82 ° C. Samples are analyzed for Kjeldahl nitrogen content and the degree of substitution of the cyanethyl groups is determined on the basis of the nitrogen number. EXAMPLE 2 The samples prepared in Example 1 are used from A-1 to A-5 to prepare graft copolymers as follows. In a plastic vessel with a capacity of 2 liters, equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen inlet tube, place b5O g of deionized water, then 350 g (dry matter) of the starch derivative, to make a paste. The pH is adjusted to 7, 8, and then 350 liquaphones of alpha-amylase, obtained from B. Subtils, are added. The paste is heated to 45 minutes and maintained at 78 ° C to a characteristic 0.14 dl / g, 0.185 DL / G, 0.273 dl / g. The enzyme is inactivated by heating to 9b C and the hydrolyzed starch is cooled to 60 ° C. At this temperature, the nitrogen supply is started and 12.5 g of Triton X surfactant: -200 is added, then 173.5 g of ethyl acrylate is added. 6.13 g of cerium ammonium nitrate is dissolved at 48-52 ° C and added to the reaction mixture. After completion of the exothermic reaction (temperature rise of about 20 ° C), the reaction temperature is maintained at 75 ° C for 3 hours. 0.5 g of ammonium persulfate and sodium metabisulfate are then added to the reaction mixture to reduce the amount of unreacted monomer. Maintain the mixture for another 1 hour, cool and adjust the pH to 8.5 with ammonium hydroxide, the content of grafted copolymer of starch in the dispersion is 45%. The ratio of starch derivative / / ethyl acrylate in the graft copolymer is 100/50 (wt.). The data on the stability of dispersions of grafted copolymers of cyanoethylated starch are presented in Table. 2 Primerz (by a known method). A. Starch paste is prepared by stirring b7.5 g of commercial corn starch, oxidized with sodium hypochlorite, containing about 1.0 carboxyl groups, to 143 g of water, and heating at 98-99 ° C for 30 minutes. After cooling, 613.5 g of water is added to the paste. 1.0 g of glacial acetic acid, 0.30 g of ferrous ammonium sulfate and 9.4 g of Igepal CO-887 (70% solution of nonylphenoxy polyoxyethylene ether, containing on average 30 oxyethylene groups per molecule) are added to this mixture. The resulting paste is cooled before and 67.5 g of ethyl acrylate is added, after which 1.55 g of hydrogen peroxide is added. After a few seconds, the temperature of the reaction mixture begins to rise. The temperature is set to 60 ° C and maintained at this value for 3 hours. During this time, the reaction mixture was continuously vigorously stirred. After 3 hours, the product is cooled to room temperature. The viscosity of the resulting product is 1380 cps at. Dispersion quickly peels off. B. Example A is repeated. However, the total solids content is increased to 25, reducing the amount of water to 410 g. The resulting product is a soft gel with a viscosity of more than 13,000 centipoise at 24 ° C. C. Example A is repeated, and the solids content is increased to 30%, reducing the water content to 320 g, the resulting product is a solid, gritty gel with a viscosity greater than 30,000 cP at 24 C. D. Example A is repeated with a higher loading of the solid part, which is increased to 48% by reducing the proportion of water. The resulting product is a solid rubbery mass. Viscosity cannot be measured.
权利要求:
Claims (2) [1] 1. Polymer dispersion containing 45% by weight of hydrolyzed starch derivative and water, characterized in that, in order to increase storage stability, the dispersion contains a grafted copolymer of ethyl acrylate and cyanethylated starch hydrolyzed to characteristic viscosity as a hydrolyzed starch derivative 35% dispersion of 0.14-1.273 DL / g, with a degree of substitution according to 51 cyanoethyl groups of 0.0b9-0.1b1 and a weight ratio of cyanoethylated hydrolyzed starch: ethyl acrylate, equal to 100: 50. [2] 2. A method for producing a polymer dispersion, comprising mixing a hydrolyzed starch derivative with water and ethyl acrylate. And carrying out a modification, characterized in that, in order to obtain a dispersion stable during storage, a starch derivative is used 089656 cyanethylated starch with a degree of substitution of 0.0b9-0.1b1, prior to modification, the cyanethylated starch is hydrolyzed under the action of alpha-amylose to a characteristic viscosity of its 35% aqueous dispersion of 0, 273 dl / g, and modification Cyanoethylated hydrolyzed starch: ethyl acrylate, equal to 100: 50, with a dispersion concentration of 45 wt. Table Used acrylonitrile (calculated on the dry weight of starch),% 2.5 Nitrogen (analysis),% 0,585 Calculated. substitution degree 0,0b9 4.0 0.844 6.0 1,324 0.084 0.101 0.161 Table 2
类似技术:
公开号 | 公开日 | 专利标题 SU1508965A3|1989-09-15|Polymeric dispersion and method of producing same US4155888A|1979-05-22|Water-absorbent starches FI68634B|1985-06-28|STABIL DISPERSION INNEHAOLLANDE AMYLOPEKTINSTAERKELSEYMPKOPOLYMER US4330443A|1982-05-18|Dry chemical process for grafting acrylic and methyl acrylic ester and amide monomers onto starch-containing materials US4645812A|1987-02-24|Method of suspension polymerization of vinyl chloride GB1559766A|1980-01-23|Low ph preparation of cationic starches and flours JP3093351B2|2000-10-03|Dispersion stabilizer for suspension polymerization of vinyl chloride, its production method and suspension polymerization method of vinyl chloride Carr et al.1992|Graft polymerization of cationic methacrylate, acrylamide, and acrylonitrile monomers onto starch by reactive extrusion US5116927A|1992-05-26|Starch polymer graft composition and method of preparation US3969329A|1976-07-13|Process for producing high molecular weight acrylamide water-soluble polymers by controlling the viscosity of the polymerization reaction medium with a water-miscible organic solvent US3152102A|1964-10-06|Water-soluble polyvinyl alcohol-urea reaction products US4100339A|1978-07-11|Process for preparing acrylonitrile/vinyl chloride copolymers having an increased viscosity which comprises using anionic/non-ionic emulsifier blends US3935187A|1976-01-27|Process for depolymerizing amylaceous polymers EP0421150B1|1994-08-17|Dispersant system for making low-colour chlorinated polyvinyl chloride EP0741150A1|1996-11-06|A process for making a polymer of acrylonitrile, methacrylonitrile and olefinically unsaturated monomers US4072640A|1978-02-07|Copolymerization of vinyl monomers with cellulose and starch in copper ammonium solutions US5286828A|1994-02-15|Preparation of melt-processable acrylonitrile/methacrylonitrile copolymers CA1100668A|1981-05-05|Process for grafting vinyl chloride onto ethylene/vinyl-acetate or alkylacrylate copolymers JP2001151815A|2001-06-05|Method of manufacturing for chlorinated vinyl chloride resin US4345948A|1982-08-24|Method for dewatering starch slurries containing swollen starch granules US3962067A|1976-06-08|Process for the production of an aqueous solution of silicoformic acid US3761465A|1973-09-25|Preparation of water soluble derivatives of cellulose and compositions thereof US4326051A|1982-04-20|Acrylonitrile polymerization with organic solvent EP0802201B1|2003-03-05|Process for producing vinyl resin JP2004533472A|2004-11-04|Method for producing azo compound
同族专利:
公开号 | 公开日 HU190674B|1986-10-28| NZ196942A|1983-11-18| JPS5718714A|1982-01-30| GB2075525A|1981-11-18| BR8102550A|1982-01-05| DE3116797A1|1982-03-18| SE8102663L|1981-10-29| PT72928A|1981-05-01| AR227423A1|1982-10-29| AU543579B2|1985-04-26| FR2481297B1|1985-01-25| AU6988781A|1981-11-05| MX158448A|1989-02-02| FR2481297A1|1981-10-30| IT8121422D0|1981-04-28| BG36788A3|1985-01-15| US4301017A|1981-11-17| YU42566B|1988-10-31| FI811300L|1981-10-29| BE888604A|1981-10-28| NL191464C|1995-07-18| GB2075525B|1984-06-20| NL191464B|1995-03-16| JPH0212247B2|1990-03-19| FI68633B|1985-06-28| YU110781A|1983-10-31| FI68633C|1985-10-10| ES502297A0|1982-04-01| IT1136585B|1986-09-03| ES8203397A1|1982-04-01| SE452012B|1987-11-09| PT72928B|1982-04-12| NL8102092A|1981-11-16| CA1184688A|1985-03-26| DE3116797C2|1990-11-22|
引用文献:
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申请号 | 申请日 | 专利标题 US06/144,009|US4301017A|1980-04-28|1980-04-28|Stable, liquid starch graft copolymer composition| 相关专利
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