This patent describes a process for producing highly water-absorbent polymer beads. The process involves dispersing and suspending an aqueous solution of a water-soluble monomer and crosslinking agent in a hydrocarbon dispersion medium. Polymerization occurs in the presence of a water-soluble initiator and a cellulose ester or ether protecting colloid that is oil-soluble at the reaction temperature. The resulting polymer beads are then separated. The process aims to produce beads that have a high water absorption capacity and rate while being less prone to dusting or forming difficult-to-dissolve lumps when contacted with water.
This patent describes a process for producing highly water-absorbent polymer beads. The process involves dispersing and suspending an aqueous solution of a water-soluble monomer and crosslinking agent in a hydrocarbon dispersion medium. Polymerization occurs in the presence of a water-soluble initiator and a cellulose ester or ether protecting colloid that is oil-soluble at the reaction temperature. The resulting polymer beads are then separated. The process aims to produce beads that have a high water absorption capacity and rate while being less prone to dusting or forming difficult-to-dissolve lumps when contacted with water.
This patent describes a process for producing highly water-absorbent polymer beads. The process involves dispersing and suspending an aqueous solution of a water-soluble monomer and crosslinking agent in a hydrocarbon dispersion medium. Polymerization occurs in the presence of a water-soluble initiator and a cellulose ester or ether protecting colloid that is oil-soluble at the reaction temperature. The resulting polymer beads are then separated. The process aims to produce beads that have a high water absorption capacity and rate while being less prone to dusting or forming difficult-to-dissolve lumps when contacted with water.
(54) WATER-ABSORBENT PROCESS FOR PREPARATION OF HIGH POLYMER BEADS 4,135,943 1/1979 Morishita et al. ................... 524/733 FOREIGN PATENT DOCUMENTS (75) Inventors: Harumasa Yamasaki; Shoichiro 50–7826 1/1975 Japan ..................................... 524/40 Harada, both of Wakayama, Japan 7309099 1/1974 Netherlands .......................... 524/40 73 Assignee: Kao Soap Co., Ltd., Tokyo, Japan Primary Examiner-John Kight, III 21 Appl. No.: 360,496 Assistant Examiner-Nathan M. Nutter 22 Filed: Mar. 22, 1982 Attorney, Agent, or Firm-Flynn, Thiel, Boutell & Tanis 30 Foreign Application Priority Data 57 ABSTRACT Mar. 25, 1981 JP Japan .................................. 56-43488 Water-insoluble, high water-absorbent polymer beads 51) Int. Cl............................ C08L 5/00; B01J 31/06 are prepared by dispersing and suspending an aqueous 52 U.S.C. ........................................ 524/40; 524/37; solution of a water-soluble, ethylenically unsaturated 524/38; 524/39; 524/42; 524/457; 524/502; monomer containing a small amount of a crosslinking 524/513; 524/733; 523/202; 523/207 agent in a dispersion medium of a hydrocarbon or a 58). Field of Search ....................... 524/27, 35, 37, 38, halogenated aromatic hydrocarbon, carrying out the 524/39, 40, 42, 457, 501, 502, 513, 733; bead polymerization in the presence of a water-soluble 523/201, 202, 207, 210 radical polymerization initiator and a protecting colloid (56) References Cited comprising a cellulose ester or cellulose ether which is oil-soluble at the polymerization temperature, and sepa U.S. PATENT DOCUMENTS rating the resulting beads. 3,498,938 3/1970 Grommers et al. ................... 524/42 4,093,776 6/1978 Aoki et al. .......................... 428/402 2 Claims, No Drawings 4,446,261 1. 2 More specifically, in accordance with the present PROCESS FOR PREPARATION OF HIGH invention, there is provided a process for the prepara WATER-ABSORBENT POLYMER BEADS tion of highly water-absorbent polymer beads, which comprises dispersing and suspending an aqueous solu The present invention relates to a process for prepar tion of a water-soluble, ethylenically unsaturated mono ing a water-absorbing material which is not soluble in mer containing a small amount of a crosslinking agent in water, highly absorbs a large quantity of an aqueous a hydrocarbon or a halogenated aromatic hydrocarbon liquid and holds the absorbed aqueous liquid stably. and performing polymerization by using a water-soluble More particularly, the present invention relates to a radical polymerization initiator, said process being process for preparing a highly water-absorbent, bead 10 characterized in that a cellulose ester or cellulose ether like polymer having a high water-absorbing property which is oil-soluble at the polymerization temperature is and a high water-absorbing speed. used as a protecting colloid. Paper, pulp and sponge have heretofore been used as The W/O suspension polymerization process using water-absorbing or water-retaining materials for sani an oil-soluble cellulose ester or cellulose ether as a pro tary materials such as sanitary napkins and paper dia 15 tecting colloid is disclosed in, for example, Japanese pers and in the agricultural field. However, these mate Patent Application Laid-Open Specification No. rials are poor in the absorbent capacity and water once 7825/80, in which water-soluble sodium polyacrylate or absorbed in these materials is substantially squeezed out polyacrylamide is mainly prepared. This known tech under pressure. As water-absorbing materials that can nique can be applied to the present invention. be used instead of the foregoing materials, there have 20 As the water-soluble, ethylenically unsaturated mon recently been proposed hydrolyzed starch-acrylonitrile omer that is used in the present invention, there can be graft copolymers, modified cellulose ethers and modi mentioned, for example, acrylic acid, methacrylic acid, fied polyethylene oxides. However, these materials salts (such as sodium and ammonium salts) of acrylic cannot be regarded as satisfactory water-absorbing ma acid and methacrylic acid, acrylamide, methacrylam terials because the water-absorbing capacity is insuffi 25 ide, N-substituted acrylamides, N-substituted metha cient, there is a risk of putrefaction owing to use of a crylamides, 2-acryloylethane-sulfonic acid, 2-metha natural material as the starting material, or the prepara cryloylethane-sulfonic acid, salts of 2-acryloylethane tion process is complicated. sulfonic acid and 2-methacryloylethane-sulfonic acid, We previously proposed a process for the preparation styrene-sulfonic acid, salts of styrene-sulfonic acid, 2 of water-absorbing materials in which these defects are 30 hydroxyethyl acrylate and 2-hydroxyethyl methacry eliminated (see Japanese Patent Publication No. late. 30710/79). Sodium acrylate, acrylamide, 2-acrylamido-2-methyl As the properties ordinarily required for a water propane-sulfonic acid and sodium styrene-sulfonate are absorbing materials, there can be mentioned (1) a large preferred. These monomers may be used in the form of absorbent capacity, (2) a high absorbency rate, (3) a 35 a mixture of two or more of them. In the present inven high gel strength after absorption of water and (4) a tion, it is important that such monomer should be copo good shape-retaining property. Only a material having lymerized with a small amount of a water-soluble cross all of the above properties can be regarded as a satisfac linking agent. As the crosslinking agent that is used in tory water-absorbing material. the present invention, there can be mentioned, for ex Water-absorbing materials prepared according to the 40 ample, N,N'-methylene-bis-acrylamide, N,N'-methy process disclosed in Japanese Patent Publication No. lene-bis-methacrylamide, N-methylolacrylamide, N 30710/79 are still defective in various points. methylolmethacrylamide, glycidyl acrylate, glycidyl Since a sorbitan fatty acid ester is used as a protecting methacrylate, polyethylene glycol diacrylate, polyeth colloid in the W/O suspension polymerization process, ylene glycol dimethacrylate, polyvalent metal salts of the particle size of the obtained polymer is very fine and 45 acrylic acid and methacrylic acid, phosphoacrylates, smaller than 100 um. A special measure should be taken phosphomethacrylates, and polyol polyglycidyl ethers for preventing dusting when the resulting powder is such as ethylene glycol diglycidyl ether, glycerin tri handled. Furthermore, when the powder is contacted glycidyl ether, glycerin diglycidyl ether and polyethyl with an aqueous liquid, formation of a difficult-to-dis ene glycol diglycidyl ether. The amount of the cross solve lump of the powder is readily caused and hence, 50 linking agent used for obtaining a water-absorbent poly the water-absorbing speed is very low. mer may be changed in a broad range, but if the amount We made researches with a view to developing a of the crosslinking agent is large, the swelling property water-absorbing material having all of the above-men to water is reduced or lost. Accordingly, in the present tioned properties while eliminating the foregoing de invention, the crosslinking agent is used in such an fects, and we found that in the W/O suspension poly 55 amount that the absorbent capacity, defined hereinafter, merization process comprising dispersing and suspend is 30 to 150 g/g, preferably 50 to 100 g/g. The concrete ing an aqueous solution of a monomer containing a amount used of the crosslinking agent depends on the small quantity of a crosslinking agent in a hydrophobic kind of the crosslinking agent, but ordinarily, the liquid and conducting polymerization, when a cellulose amount used of the crosslinking agent is about 0.01 to ester or cellulose ether which is oil-soluble at the poly 60 about 5% by weight based on the water-soluble mono merization temperature is used as the protecting colloid e. and a hydrocarbon or a halogenated aromatic hydrocar The monomer concentration in the aqueous solution bon is used as the solvent, the particle size of the ob of the monomer can be changed within a broad range, tained polymer is large and exceeds 100 um and a wa but from the economical veiwpoint, it is preferred that ter-absorbing material having a high absorbent capacity 65 the monomer concentration be in the range of from and a high absorbency rate can be obtained. We have 30% by weight to the saturation concentration, espe now completed the present invention based on this cially from 35% by weight to the saturation concentra finding. tion. 4,446,261 3 4. The cellulose ester or cellulose ether oil-soluble at the more of these initiators may be used, and these initiators polymerization temperature, which is used as the pro may be used in the form of a redox type initiator. tecting colloid for the W/O suspension polymerization The most prominent difference between the present in the present invention, is a cellulose ester or cellulose invention and the invention disclosed in Japanese Patent ether which is insoluble or hardly soluble at room tem Application Laid-Open Specification No. 7825/80 re perature in the hydrocarbon or halogenated aromatic sides in whether the formed polymer is water-soluble or hydrocarbon used as the dispersion medium but be water-insoluble. comes soluble in the dispersion medium at the polymeri By the term “water-insoluble polymer' used herein is zation temperature (higher than 40 C.). meant a polymer having such characteristics that when As such cellulose ester or cellulose ether, there can be 10 the polymer is put in water and the mixture is stirred at mentioned, for example, cellulose acetate, cellulose room temperature, the polymer absorbs water and is propionate, cellulose butyrate, cellulose acetate propio swollen and gelled, and when stirring is stopped and the nate, cellulose acetate butyrate, cellulose acetate phthal mixture is allowed to stand still, the flowability is lost or ate, ethyl cellulose, benzyl cellulose and ethylhydrox phase separation takes place. By the term "water-solu yethyl cellulose. Cellulose acetate butyrate, ethyl cellu 5 ble polymer' is meant a polymer having such character lose and ethylhydroxyethyl cellulose are especially istics that when the polymer is added to water and the preferred. mixture is stirred, a homogeneous aqueous solution is In the present invention, a hydrocarbon having 6 to formed and when stirring is stopped and the solution is 10 carbon atoms or a halogenated aromatic hydrocar allowed to stand still at the same temperature, the ho bon is preferably used as the dispersion medium. For 20 mogeneous solution state is maintained. example, there can be mentioned aromatic hydrocar The polymer prepared according to the present in bons such as benzene, ethylbenzene, toluene and xylene, vention is substantially insoluble in water and has such alicyclic hydrocarbons such as cyclohexane, methylcy a peculiar property that it absorbs water and retains it clohexane, cyclooctane and decalin, aliphatic hydrocar therein. In order to impart this property to the formed bons such as hexane, heptane, octane and pentane, and 25 polymer, it is indispensable that the polymer obtained halogenated hydrocarbons such as chlorobenzene, bro by using the crosslinking agent should be insolubilized. mobenzene and dichlorobenzene. Toluene, xylene, cy When a water-soluble polymer is incorporated into the clohexane, methylcyclohexane, hexane, heptane, chlo water-insoluble polymer according to the present in robenzene and dichlorobenzene are especially pre vention, the absorbency rate is reduced, and the water ferred. A mixture of two or more of the foregoing sol 30 absorbed polymer becomes slimy and a dry feel is not vents may be used as the dispersion medium according given thereto, with the result that handling of the wa to the kind of the cellulose ester or cellulose ether used. ter-absorbed polymer becomes difficult. Accordingly, a Furthermore, a single solvent may be used as the disper water-soluble polymer is excluded from the polymer sion medium when a certain cellulose ester or cellulose according to the present invention. ether is selected and used. In this case, recycling of the 35 The present invention is advantageous in that since dispersion medium is facilitated, and the process is car the particle size of the formed polymer is increased, ried out very advantageously from the industrial view special measures need not be adopted for coping with point. dusting and since a material having a high absorbent When toluene, xylene, ethylbenzene, chlorobenzene capacity and a high absorbency rate can be obtained, or dichlorobenzene is used singly as the dispersion me 40 the fields of application of the polymer can be broad dium, ethyl cellulose having an ethoxy group content of ened. For example, if the polymer of the present inven 43 to 47% by weight or cellulose acetate butyrate hav tion is used in combination with a conventional water ing a butyryl group content of 20 to 50% by weight is retaining agent, water can be removed in a moment preferably used as the cellulose derivative. When cyclo from an oil-water mixture. hexane, cyclopentane, methylcyclohexane or decalin is 45 Namely, the polymer of the present invention can be used singly as the dispersion medium, ethyl cellulose used not only as a water-removing agent but also as a having an ethoxy group content of 47 to 50% by weight material of a sanitary product. More specifically, when is preferably used as the cellulose derivative. When the polymer of the present invention is used in the field n-hexane, n-heptane or n-octane is used singly as the where a large quantity of a liquid such as urine should dispersion medium, ethylhydroxyethyl cellulose is pref. 50 be absorbed at one time, a material prepared from the erably used as the cellulose derivative. polymer of the present invention can absorb the liquid The protecting colloid is used in an amount of 0.05 to in a moment without leakage or wet feel and no un 10% by weight, preferably 0.5 to 5% by weight, based pleasant feel is left after absorption of the liquid. on the dispersion medium. The absorbent capacity referred to in the present The volume ratio between the dispersion medium and 55 invention is determined according to the following the aqueous solution of the monomer can be changed in method. More specifically, about 1 g of the polymer is a broad range, but from the viewpoints of removal of dispersed in an excess amount of physiological saline the polymerization heat and control of the polymeriza solution to swell the polymer sufficiently. Then, the tion temperature, the above volume ratio is preferably polymer is passed through an 80-mesh sieve. The absor controlled within the range of from 1:1 to 5:1. 60 bent capacity is obtained by measuring the weight W of For effecting polymerization of the monomer, there the swollen polymer and dividing the obtained value W is used a known amount of a water-soluble radical poly by the original weight Wo of the polymer. In short, the merization initiator. As the polymerization initiator, absorbent capacity is calculated according to the foll there can be mentioned, for example, persulfates such as lowing formula: potassium persulfate and ammonium persulfate, hydro 65 Absorbent capacity (g/g)=W/Wo peroxides such as t-butyl hydroperoxide and cumene The absorbency rate is expressed by the time required hydroperoxide, and azo compounds such as 2,2'-azobis for 0.5g of the polymer to absorb 5 ml of physiological 2-amizinopropane hydrochloride. A mixture of two or saline solution. 4,446,261 6 5 The present invention will now be described in detail of 2-acrylamido-2-methylpropane-sulfonic acid were with reference to the following Examples and Compar neutralized with 61.0 g of 98% caustic sodium hydrox ative Examples. ide dissolved in 220g of deionized water. Furthermore, The contents of acetyl, butyryl and ethoxy groups in 0.5 g of ammonium persulfate and 0.75 g (0.5% by the cellulose ester and cellulose ether used in these weight based on the monomer) of N-methylolacryla Examples are as follows: - mide were incorporated and dissolved in the solution to Cellulose acetate butyrate (CAB 381-20 manufac form an aqueous monomer solution. The monomer tured by Eastman Kodak Co.): concentration in the aqueous phase was about 42% by acetyl group content=13% by weight, butyryl group weight. content=37% by weight O Then, the procedures of Example 1 were repeated in Ethyl cellulose (N-200 manufactured by Hercules the same manner to obtain spherical particles in which Co.): the central particle size was 100 to 350 pum. ethoxy group content=47.5-49.0% by weight EXAMPLE 5 EXAMPLE 1. The procedures of Example 4 were repeated in the A 2-liter capacity, 4-neck, round-bottom flask same manner except that 120g of acrylic acid was neu equipped with a stirrer, a reflux cooler, a dropping tralized with 51.0 g of 98% caustic sodium hydroxide funnel and a nitrogen gas-introducing tube was charged dissolved in 250 g of deionized water and then, 30 g of with 1150 ml of cyclohexane and 9.0 g of ethyl cellulose acrylamide, 4.5 g (3% by weight based on the mono (Ethyl Cellulose N-200 manufactured and supplied by 20 mer) of polyethylene glycol dimethacrylate (n=23) and Hercules Co.), and nitrogen gas was blown into the 0.3 g of potassium persulfate were further dissolved to flask to expel oxygen therefrom and the temperature form a monomer solution. The monomer concentration was elevated to 75° C. Separately, in a flask, 150 g of in the aqueous phase was 40% by weight. Thus, there acrylic acid was neutralized with 65.8g of 98% caustic were obtained spherical particles where the central sodium hydroxide dissolved in 200g of deionized water 25 particle size was 100 to 300 p.m. while cooling the charge from the outside. The mono EXAMPLE 6 mer concentration in the aqueous phase was 45% by weight. Then, 0.5g of potassium persulfate and 0.15g The same polymerization vessel as used in Example 1 (0.1% by weight based on acrylic acid) of N,N'-methy was charged with 1150 ml of monochlorobenzene and lene-bis-acrylamide were dissolved in the aqueous solu 30 11.5 g of cellulose acetate butyrate (CAB 381-20 sup tion, and nitrogen gas was blown to expel oxygen pres plied by Eastman Kodak Co.), and the temperature was ent in the aqueous solution. The solution in the flask was elevated to 80 C. Separately, in a flask, a monomer dropped into the charge of the above-mentioned 4-neck solution was prepared from 100g of acrylamide, 50g of flask over a period of 1 hour. After completion of the sodium styrene-sulfonate, 1% by weight based on the dropwise addition, reaction was carried out at 75 C. for 35 monomer of polyethylene glycol diacrylate (n=9), 280 1 hour. Cyclohexane was removed by distillation under g of deionized water and 0.3 g of ammonium persulfate. reduced pressure, and the residual swollen polymer was The monomer concentration in the aqueous phase was dried under reduced pressure at 80 to 100° C. to obtain 35% by weight. The subsequent treatments were con spherical particles in which the central particle size was ducted in the same manner as described in Example 1. 100 to 350 p.m. 40 COMPARATIVE EXAMPLE 1. EXAMPLE 2 A water-insoluble spherical polymer was obtained The procedures of Example 1 were repeated in the according to the process disclosed in Example 1 of same manner except that 0.75 g (0.5% by weight based Japanese Patent Publication No. 30710/79, which cor on acrylic acid) of polyethylene glycol diglycidyl ether 45 responds to U.S. Pat. No. 4,093,776. More specifically, (n=9) was incorporated and dissolved as the crosslink in the polymerization recipe described in Example 1 of ing agent in the aqueous solution of the monomer, the present invention, sorbitan monostearate was used whereby spherical particles having a central particle as the protecting colloid and polymerization was car size of 100 to 350 am were obtained. ried out in the absence of the crosslinking agent. The EXAMPLE 3 50 central particle size of the obtained polymer was 10 to 70 um. The procedures of Example 1 were repeated in the COMPARATIVE EXAMPLE 2 same manner except that 3 g (2% by weight based on acrylic acid) of polyethylene glycol dimethacrylate In the polymerization recipe of Example 1, sorbitan (n=14) was dissolved as the crosslinking agent in the 55 distearate was used as the protecting colloid. Polymeri solution of the monomer and 110 g of deionized water zation was carried out in the same manner as described was further added to the monomer solution. The mono in Example 1. The central particle size of the obtained mer concentration in the aqueous phase was 35% by polymer was 10 to 70 pum. weight. COMPARATIVE EXAMPLE 3 Thus, there were obtained spherical particles in 60 which the central particle size was 100 to 420 um. Polymerization was carried out in the same manner as EXAMPLE 4 described in Example 3 except that in the polymeriza tion recipe of Example 3, sorbitan monopalmitate was The same polymerization vessel as used in Example 1 used as the protecting colloid and 9 g (6% by weight was charged with 1150 ml of hexane and 13.02 g of 65 based on acrylic acid) of polyethylene glycol dimethac ethylhydroxyethyl cellulose (EHEC Low supplied by rylate (n=14) was used as the crosslinking agent. The Hercules Co.), and the temperature was elevated to 65 central particle size of the formed polymer was 10 to 70 C. Separately, in a flask, 130 g of acrylic acid and 20 g um. 7 4,446,261 8 COMPARATIVE EXAMPLE 4 ous solution containing from 30 wt.% up to the satura tion concentration of said monomer, into (2) a liquid Polymerization was carried out in the same manner as dispersion medium having a temperature of higher than in Example 3, except that polyethyleneglycol dimethac 40 C., said liquid dispersion medium consisting of an oil rylate (n=14) was not used. The obtained polymer material selected from the group consisting of hydro particles had a central size of 100 to 450 um, but were carbons having from 6 to 10 carbon atoms and haloge very sticky because they contained a large amount of nated aromatic hydrocarbons, and said oil material hav the water-soluble polymer. ing dissolved therein from 0.05 to 10% by weight, based COMPARATIVE EXAMPLE 5 on the weight of said oil material, of a protective colloid 10 selected from the group consisting of cellulose esters Polymerization was conducted in the same manner as and cellulose ethers which are not soluble in said oil in Example 6, except that polyethyleneglycol diacrylate material at room temperature but are soluble in said oil (n=9) was not used. The obtained polymer particles material at a temperature of higher than 40 C., had a central size of 100 to 250 pum, but were very sticky whereby to form a W/O suspension of said droplets in because of they contained a large amount of the water 15 said liquid dispersion medium, the volumetric ratio of soluble polymer. said dispersion medium/said aqueous solution being in Absorbent capacity and absorbency rate of the poly the range of 1:1 to 5:1; suspension polymerizing said mers obtained in Examples 1 through 6 and Compara monomer, at a temperature higher than 40 C. in the tive Examples 1 through 5 are shown in Table 1. presence of said crosslinking agent and said radical TABLE 1 20 polymerization initiator, whereby to form said beads; Absorbent Capacity and then recovering said beads from said liquid disper Run No. (g/g) Absorbency rate sion medium. Example 1 58 4 minutes and 10 seconds 2. Water-insoluble, highly water-absorbent polymer Example 2 52 4 minutes and 5 seconds beads which consist of a water-insoluble, crosslinked Example 3 63 5 minutes 25 polymer, which beads have a particle size of at least 100 Example 4 Example 5 60 68 4 minutes and 30 seconds 4 minutes and 50 seconds microns and have an absorbent capacity for physiolog Example 6 57 4 minutes and 25 seconds ical saline in the range of from 30 to 150 grams per one Comparative 54 16 minutes and 40 seconds gram of the dried polymer, which beads are prepared Example 1 by a process consisting essentially of the steps of dis- . Comparative Example 2 38 5 minutes 30 persing droplets of (1) an aqueous solution consisting Comparative 20 7 minutes and 30 seconds essentially of water-soluble, ethylenically unsaturated Example 3 monomer, water-soluble crosslinking agent, a water Comparative Example 4 could not be measured longer than 30 minutes soluble radical polymerization initiator and the balance Comparative could not be longer than 30 minutes is essentially water, into (2) a liquid dispersion medium Example 5 measured 35 having a temperature of higher than 40 C., said liquid dispersion medium consisting essentially of an oil mate rial selected from the group consisting of hydrocarbons The embodiments of the invention in which an exclu and halogenated aromatic hydrocarbons, said oil mate sive property or privilege is claimed are defined as rial having dissolved therein a protective colloid se follows: lected from the group consisting of cellulose esters and 1. A process for preparing beads consisting of water cellulose ethers which are not soluble in said oil mate insoluble, crosslinked polymer, which beads have a rial at room temperature but are soluble in said oil mate particle size of from 100 to 1000 microns and have an rial at a temperature of higher than 40 C., whereby to absorbent capacity for physiological saline in the range form a W/O suspension of said droplets in said liquid of from 30 to 150 grams per one gram of the dried poly 45 dispersion medium; suspension polymerizing said mon mer, which consists of the steps of: dispersing droplets omer, at a temperature higher than 40 C. in the pres of (1) an aqueous solution consisting of water-soluble, ence of said crosslinking agent and said radical poly ethylenically unsaturated monomer, from 0.01 to 5% by merization initiator, whereby to form said beads; and weight, based on the weight of said monomer, of water then recovering said beads from said liquid dispersion soluble crosslinking agent, a water-soluble radical poly 50 medium. merization initiator, and the balance is water, said aque s s s st
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