WO2018120056A1 - 含有可聚合表面活性剂的丙烯酸吸水树脂及其制备方法及应用 - Google Patents

含有可聚合表面活性剂的丙烯酸吸水树脂及其制备方法及应用 Download PDF

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WO2018120056A1
WO2018120056A1 PCT/CN2016/113587 CN2016113587W WO2018120056A1 WO 2018120056 A1 WO2018120056 A1 WO 2018120056A1 CN 2016113587 W CN2016113587 W CN 2016113587W WO 2018120056 A1 WO2018120056 A1 WO 2018120056A1
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acrylic
water absorbing
polymerizable surfactant
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PCT/CN2016/113587
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French (fr)
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王刚
李春
张志宇
达省辉
黄岐善
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万华化学集团股份有限公司
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by heteroatoms or groups containing heteroatoms
    • C08F212/30—Sulfur
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by heteroatoms or groups containing heteroatoms
    • C08F212/22—Oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F216/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
    • C08F216/12—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F216/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
    • C08F216/12—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
    • C08F216/14—Monomers containing only one unsaturated aliphatic radical
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F218/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
    • C08F218/14—Esters of polycarboxylic acids
    • C08F218/16—Esters of polycarboxylic acids with alcohols containing three or more carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/36—Amides or imides
    • C08F222/38—Amides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
    • C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2333/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2351/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
    • C08J2351/08—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds

Definitions

  • the present invention relates to the field of chemical polymer materials, and more particularly to an acrylic water absorbing resin containing a polymerizable surfactant and a preparation method thereof.
  • Water-absorbent resin is widely used in the form of water-absorbing materials in the sanitary industry such as baby diapers, sanitary napkins, adult diapers, agricultural and forestry water retention agent industry, oil field water blocking, etc., because it has the characteristics of absorbing hundreds or even thousands of times of pure water. In industrial production.
  • Acrylic water absorbing resin has a strong water retention property and a pressure absorbing property because of its crosslinked network structure, which makes it the mainstream in the current water absorbing material market, and more than 80% of the water absorbing resin is polymerized by acrylic acid.
  • the acrylic acid polymerization method is divided into an aqueous solution polymerization method and a reverse phase suspension polymerization method, wherein the aqueous solution polymerization method is a mainstream process for producing an acrylic water absorbing resin.
  • the acrylic water absorbing resin must have a porous structure in order to meet the characteristics of water absorption. Therefore, in the polymerization process, the system often contains a large number of tiny bubbles; and in order to reduce the interfacial tension and prevent the bubbles from agglomerating and disappearing, the formulation of the system includes a surfactant.
  • Surfactants currently used in the production of acrylic water absorbing resins are mainly conventional surfactants such as sodium dodecylbenzene sulfonate, sodium lauryl sulfate, spar, Tween and the like.
  • the polymerizable surfactant is a polymerization-active surfactant having an unsaturated group, which includes not only hydrophilic and lipophilic groups, but also surface active as conventional surfactants; and also contains polymerizable non-polymerizable surfactants. Saturated group. Therefore, the polymerizable surfactant acts as a surfactant before the polymerization reaction, lowers the interfacial tension of the system, stabilizes the reaction liquid system, participates in the polymerization reaction after the start of the polymerization reaction, and finally distributes on the surface of the polymer particles in the form of chemical bonds.
  • the polymerizable surfactant can be classified into allyl type, allyloxy type, acrylic or methacrylic type, maleic acid type, acrylic acid type and styrene. type. From the first report of the synthesis and application of polymerizable surfactants by Freedman et al in 1958, polymerizable surfactants have been mainly used in emulsion polymerization or microemulsion polymerization to prevent surfactants from desorbing from latex particles or in latex films. Migration to increase the stability of the emulsion.
  • Acrylic water absorbing resin is mainly used in the sanitary industry, although a small amount of free surfactant does not cause harm to the human body; however, when the sanitary product is discarded into the environment, the free surfactant contained therein is released into the water body to produce a rich foam. Reduce the amount of dissolved oxygen in the water, harm aquatic organisms, and pollute the water environment. Therefore, the state has been in the water environment
  • the content of linear alkylbenzene sulfonate (LAS) is strictly regulated. ⁇ (LAS) ⁇ 5mg/L in industrial production wastewater and ⁇ (LAS) ⁇ 0.3mg/L in natural water.
  • the invention provides an acrylic water absorbing resin containing a polymerizable surfactant and a preparation method thereof.
  • An acrylic water absorbing resin containing a polymerizable surfactant wherein the raw material for preparing the same comprises at least one polymerizable surfactant, and the polymerizable surfactant molecule includes, in addition to a hydrophilic group and a lipophilic group, It includes at least one carbon-carbon double bond structure which can be polymerized in an amount of 0.01 to 3% by weight based on the mass of the acrylic acid.
  • the method for preparing the above acrylic water-absorbent resin containing a polymerizable surfactant comprises an aqueous solution polymerization method or a reverse phase suspension polymerization method, wherein the preparation raw material includes at least one polymerizable surfactant, the polymerizable surfactant molecule
  • the preparation raw material includes at least one polymerizable surfactant, the polymerizable surfactant molecule
  • at least one carbon-carbon double bond structure which can be polymerized is added in an amount of 0.01 to 3% by weight based on the mass of the acrylic acid.
  • the hydrophilic group comprises one or more of an amide group, a sulfonic acid group, a hydroxyl group, a carboxyl group, an ester group, an ethoxy group, a phosphate group, and a quaternary ammonium salt group.
  • the oleophilic group includes an aliphatic carbon chain and/or a carbon chain containing an aromatic ring.
  • the polymerizable carbon-carbon double bond is located at the hydrophilic group end or the lipophilic group end or the hydrophilic group end of the polymerizable surfactant and the lipophilic group end. Polymerized carbon-carbon double bonds.
  • the polymerizable surfactant may be nonionic, cationic, anionic or amphoteric.
  • the polymerizable surfactant is one of an allyl type, an allyloxy type, an acrylic or methacrylic type, a maleic acid type, an acrylamide type, and a styrene type or A variety of, preferably acrylic or methacrylic, maleic, acrylamide, more preferably acrylic or methacrylic.
  • the allyl type is The allylic oxygen type is The acrylic type is The methacrylic type is The maleic acid type is The acrylamide type is The styrene type is
  • the acrylic water absorbing resin in the preparation of a water absorbing material; the water absorbing material is preferably applied to a baby diaper, a feminine sanitary napkin or an adult diaper.
  • the polymerizable surfactant used in the present invention contains not only hydrophilic and lipophilic groups but also carbon-carbon double bonds which can be polymerized. Therefore, it not only has the function of a conventional surfactant, but also lowers the solution interface before polymerization of acrylic acid. Tension, stable bubbles, is conducive to the production of a porous structure of hydrogel; and can participate in the polymerization after the start of the reaction, embedded in the hydrogel network
  • the surface of the structure improves the hydrophilicity of the surface of the water absorbing resin product, and promotes the surface wetting process when the water absorbing resin absorbs water, thereby increasing the liquid absorption rate of the product.
  • the polymerizable surfactant does not remain in the free form in the resin product as compared with the conventional surfactant, so it is safer, healthier and more environmentally friendly.
  • the aqueous solution polymerization method mainly includes a neutralization process, a polymerization process, a drying process, and a surface treatment process; the neutralization process is an incomplete neutralization of an aqueous solution of acrylic acid and hydroxide.
  • the reaction is carried out to obtain a neutralizing liquid containing acrylic acid and an acrylate; the polymerization process is to uniformly mix the neutralizing liquid with a crosslinking agent, a polymerizable surfactant and other auxiliary agents, and initiate polymerization by an initiator at a certain temperature to obtain a polymerization.
  • the polymer hydrogel in the drying process, the polymer hydrogel is sheared into tiny colloidal particles, which are dried under high temperature conditions, and then crushed, ground and sieved to obtain primary acrylic acid having a particle size of 150-800 ⁇ m.
  • Resin powder the surface treatment process is to spray an aqueous solution containing a functional auxiliary agent onto the surface of the primary acrylic water absorbing resin powder, and after reacting at a certain temperature, an acrylic water absorbing resin powder product is obtained.
  • the order of the neutralization process and the polymerization process can be reversed, that is, the polymerization reaction can be carried out after the neutralization reaction, or the neutralization reaction can be carried out after the polymerization reaction.
  • the reverse phase suspension polymerization method mainly comprises a neutralization process, a polymerization and distillation dehydration process, and a surface treatment and a distillation desolvation process;
  • the neutralization process is an acrylic acid and a hydroxide.
  • the aqueous solution is subjected to incomplete neutralization reaction to obtain a neutralized liquid containing acrylic acid and acrylate;
  • the polymerization and distillation dehydration process is to add an organic solution, a crosslinking agent, a polymerizable surfactant and other auxiliary agents to the neutralizing liquid, and stir and mix. Uniform, the reaction liquid is obtained, and the polymerization is initiated by the initiator at a certain temperature.
  • the water in the system is removed by a distillation process; the surface treatment and the distillation solvent removal process are to add several kinds of functional assistants to the system at a suitable temperature.
  • the organic solvent and other small liquid components in the system are removed by a distillation process to obtain an acrylic water-absorbent resin powder product.
  • the raw materials used include a crosslinking agent and an initiator.
  • the crosslinking agent is N,N-methylenebisacrylamide, ethylene glycol, ethylene glycol diglycidyl ether, propylene glycol, propylene glycol diglycidyl ether, polyethylene glycol, polyethylene glycol diacrylate, Polyethylene glycol diglycidyl ether, glycerin, glycerol triacrylate, ethoxylated glycerol triacrylate, pentaerythritol, pentaerythritol triacrylate, pentaerythritol triallyl ether, trimethylolpropane triacrylate and ethoxylate
  • One or more of the trimethylolpropane triacrylates are preferably pentaerythritol triallyl ether; the crosslinking agent is added in an amount of 0.05 to 0.8% by weight based on the mass of the acrylic acid.
  • Crosslinker is prepared One of the key raw materials for acrylic water-absorbing resin, its structure and addition amount seriously affect the shape, size and strength of the gel network.
  • the addition amount is too small, the gel network is difficult to form, the gel strength is low, and the content of extractable components in the resin product is high; when the addition amount is too large, the gel network has high crosslink density and high strength, which limits water swelling. process.
  • the amount of the crosslinking agent added is 0.05 to 0.8% by weight based on the mass of the acrylic acid, the acrylic water absorbing resin has excellent application properties.
  • the initiator used is one or two or more of hydrogen peroxide, sodium persulfate, potassium persulfate, ammonium persulfate, t-butyl hydroperoxide and di-tert-butyl peroxide.
  • ammonium persulfate is preferred; the initiator is added in an amount of from 0.05 to 0.8% by weight based on the mass of the acrylic acid.
  • the drying process of the aqueous solution polymerization method of the present invention is carried out at a high temperature, and the aqueous gel obtained after granulation is placed at a temperature of 100 to 200 ° C and dried for 30 to 240 minutes to obtain Dry granules; the drying process of the inverse suspension polymerization process is carried out by a distillation process.
  • the auxiliary agent used in the foregoing surface treatment process comprises one or more of water, a polyol, an epoxy compound and a metal compound; and the amount of the auxiliary agent is 2 to 10% by weight based on the mass of the acrylic acid.
  • the polyols described in the surface treatment include, but are not limited to, ethylene glycol, 1,2-propylene glycol, 1,3-propanediol, glycerol, diethylene glycol, triethylene glycol or 1,4-butanediol.
  • the epoxy compound includes, but is not limited to, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, ethylene carbonate or propylene carbonate.
  • the metal compounds described include, but are not limited to, sodium sulfate, magnesium sulfate, aluminum sulfate, sodium chloride, magnesium chloride, calcium chloride, aluminum chloride or zinc chloride.
  • the acrylic water-absorbent resin product containing a polymerizable surfactant in the present invention has a physiological saline absorption rate of not less than 40 s, and a polymerizable surfactant residual amount of not more than 300 ppm.
  • a polymerizable surfactant is substituted for a conventional surfactant for use in the production of acrylic water absorbing resin.
  • the polymerizable surfactant not only contains hydrophilic and lipophilic groups, but also has surface activity like a conventional surfactant, can reduce the interfacial tension of the solution, stabilize microbubbles in the system, and is advantageous for producing a hydrogel having a porous structure; Moreover, it also includes a carbon-carbon double bond which can be polymerized, can participate in polymerization after the reaction starts, is embedded on the surface of the hydrogel network structure, improves the hydrophilicity of the surface of the water-absorbent resin product, and promotes the surface wetting process when the water-absorbent resin absorbs water, thereby Increase the rate of product absorption. When the amount added is compared The acrylic water-absorbent resin product containing a polymerizable surfactant absorbs physiological saline at a rate of not less than 40 s at 0.01 to 30% by weight based on the
  • polymerizable surfactants are more safe, hygienic and environmentally friendly because they have carbon-carbon double bonds to participate in the polymerization reaction and do not remain in the free-form form in the acrylic water-absorbent resin product.
  • the amount added is 0.01 to 3% by weight based on the mass of the acrylic acid, the residual amount of the polymerizable surfactant in the acrylic water absorbing resin product is not more than 300 ppm.
  • the present invention is not limited to the above-listed substances, and any polymerizable surfactant including a hydrophilic group and an oleophilic group and at least one polymerizable carbon-carbon double bond can be used.
  • step b) drying process: the hydrogel obtained in step b) is cut into 2-20 mm rubber particles, and then dried in an oven at 160 ° C for 140 min, and then subjected to crushing, grinding and sieving steps to obtain 150-800 ⁇ m.
  • Primary acrylic water absorbing resin powder is
  • step d) surface treatment process preparing ethylene glycol diglycidyl ether, aluminum sulfate, ethylene glycol, water in a mass ratio of 2:10:15:50 to prepare a surface crosslinking auxiliary, and the primary acrylic acid obtained in step c) absorbs water
  • the surface of the resin powder was uniformly sprayed, the amount of the auxiliary agent was 7% by weight based on the mass of the acrylic acid, and finally dried in an oven at 150 ° C for 80 minutes to obtain an acrylic water absorbing resin powder containing a polymerizable surfactant.
  • step b) adding 0.336 g of a polymerizable surfactant SF2 and 1.68 g of N, methylenebisacrylamide to the neutralized liquid obtained in the step a), stirring uniformly, and flowing the neutralized liquid in the reaction tank into the polymerization tank.
  • 16.8 g of the prepared 10 wt% potassium persulfate aqueous solution was added to the neutralization solution at the outlet of the reaction vessel, and a hydrogel was obtained after 15 minutes of polymerization.
  • step b) The hydrogel obtained in step b) is cut into 2-20 mm colloidal particles, and then dried in an oven at 160 ° C for 140 min, and then subjected to crushing, grinding and sieving steps to obtain 150-800 ⁇ m of primary acrylic acid. Resin powder.
  • step c) preparing ethylene glycol diglycidyl ether, aluminum sulfate, 1,3-propanediol, water in a mass ratio of 2:10:15:40 to prepare a surface crosslinking assistant, and the primary acrylic water absorbing resin powder obtained in the step c)
  • the surface was uniformly sprayed, the amount of the auxiliary agent was 6% by weight based on the mass of the acrylic acid, and finally dried in an oven at 150 ° C for 80 minutes to obtain an acrylic water absorbing resin powder containing a polymerizable surfactant.
  • step b) granulating the polymer obtained in step a) in a granulator, and simultaneously adding 2240 g of a 50% strength aqueous sodium hydroxide solution, and obtaining 2-20 mm colloidal particles from the granulator outlet, and then at 160 ° C After drying in an oven for 140 min, the crushing, grinding and sieving steps were sequentially carried out to obtain 150-800 ⁇ m of primary acrylic water absorbing resin powder.
  • step c) preparing ethylene glycol diglycidyl ether, aluminum sulfate, glycerol, water in a mass ratio of 1:10:13:40 to prepare a surface crosslinking assistant, and uniformly to the surface of the primary acrylic water absorbing resin powder obtained in the step c) Spraying, the amount of the auxiliary agent was 6% by weight based on the mass of the acrylic acid, and finally dried in an oven at 150 ° C for 80 minutes to obtain an acrylic water absorbing resin powder containing a polymerizable surfactant.
  • step b) granulating the polymer obtained in step a) in a granulator, and simultaneously adding 2134 g of a 50% aqueous solution of sodium hydroxide, 2-20 mm of colloidal particles from the granulator outlet, and then at 160 ° C After drying in an oven for 140 min, the crushing, grinding and sieving steps were sequentially carried out to obtain 150-800 ⁇ m of primary acrylic water absorbing resin powder.
  • step c) preparing ethylene glycol diglycidyl ether, aluminum sulfate, 1,2-propanediol, water in a mass ratio of 2:10:15:45 to prepare a surface crosslinking assistant, and the primary acrylic water absorbing resin powder obtained in the step c)
  • the surface was uniformly sprayed, the amount of the auxiliary agent was 7% by weight based on the mass of the acrylic acid, and finally dried in an oven at 150 ° C for 80 minutes to obtain an acrylic water absorbing resin powder containing a polymerizable surfactant.
  • step b) The hydrogel obtained in step b) is cut into 2-20 mm colloidal particles, and then dried in an oven at 160 ° C for 140 min, and then subjected to crushing, grinding and sieving steps to obtain 150-800 ⁇ m of primary acrylic acid. Resin powder.
  • step c) preparing ethylene glycol diglycidyl ether, aluminum sulfate, ethylene glycol, water in a mass ratio of 1.5:9:12:40 to prepare a surface crosslinking assistant, and uniformly obtaining the surface of the primary acrylic water absorbing resin powder obtained in the step c) Spraying, the amount of the auxiliary agent was 6% by weight based on the mass of the acrylic acid, and finally dried in an oven at 150 ° C for 80 minutes to obtain an acrylic water absorbing resin powder containing a polymerizable surfactant.
  • step b) preparing ethylene glycol diglycidyl ether, 1,3-propanediol, water in a mass ratio of 4:15:50 to prepare a surface crosslinking auxiliary agent, and adding it to the reaction kettle of step b), the amount of the auxiliary agent is compared After 5 wt% of the acrylic acid mass, after 1 h of reaction, the solvent n-heptane and a small amount of other liquid components in the system were distilled off to obtain an acrylic water-absorbent resin powder containing a polymerizable surfactant.
  • step b) preparing ethylene glycol diglycidyl ether, ethylene glycol and water in a mass ratio of 3:18:55 to prepare a surface crosslinking assistant, and adding it to the reaction vessel of step b), the amount of the auxiliary agent is compared to acrylic acid After 8 wt% of the mass, after 1 h of reaction, the solvent n-heptane and a small amount of other liquid components in the system were distilled off to obtain an acrylic water-absorbent resin powder containing a polymerizable surfactant.
  • step b) adding 2.72 g of trimethylolpropane triacrylate to the neutralized liquid obtained in the step a), stirring uniformly, flowing the neutralized liquid in the reaction tank into the polymerization tank, and simultaneously neutralizing at the outlet of the reaction vessel 136 g of a prepared 10 wt% aqueous solution of ammonium persulfate was added to the solution, and a hydrogel was obtained after 15 minutes of polymerization.
  • step b) The hydrogel obtained in step b) is cut into 2-20 mm colloidal particles, and then dried in an oven at 160 ° C for 140 min, and then subjected to crushing, grinding and sieving steps to obtain 150-800 ⁇ m of primary acrylic acid. Resin powder.
  • auxiliary agent 6% by weight based on the mass of the acrylic acid, and finally dried in an oven at 150 ° C for 80 minutes to obtain an acrylic water absorbing resin powder containing a polymerizable surfactant.
  • step b) granulating the polymer obtained in step a) in a granulator, and simultaneously adding 2134 g of a 50% aqueous solution of sodium hydroxide, 2-20 mm of colloidal particles from the granulator outlet, and then at 160 ° C After drying in an oven for 140 min, the crushing, grinding and sieving steps were sequentially carried out to obtain 150-800 ⁇ m of primary acrylic water absorbing resin powder.
  • step c) preparing ethylene glycol diglycidyl ether, aluminum sulfate, 1,2-propanediol, water in a mass ratio of 2:10:15:45 to prepare a surface crosslinking assistant, and the surface of the primary acrylic water absorbing resin obtained in the step c)
  • the spray was uniformly sprayed, and the amount of the auxiliary agent was 7% by weight based on the mass of the acrylic acid, and finally dried in an oven at 150 ° C for 80 minutes to obtain an acrylic water-absorbent resin powder containing a polymerizable surfactant.
  • Example 2 33 79
  • Example 3 27 148
  • Example 4 25 195
  • Example 5 31 127
  • Example 6 25 264
  • Example 7 twenty three 238 Comparative example 1 49
  • the absorption rate of the acrylic water absorbing resin was very slow, nearly 50 seconds; whereas in the comparative example 2 using the conventional surfactant, the residual amount of the acrylic water absorbing resin was very large. High, close to 8000ppm.
  • the acrylic water-absorbent resin containing a polymerizable surfactant in the examples not only has a fast liquid absorption rate of less than 40 s, but also has a low surfactant residual amount of less than 300 ppm. Therefore, the acrylic water-absorbent resin containing the polymerizable surfactant prepared by the present invention has more excellent application properties and is healthier and more environmentally friendly.

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Abstract

本发明提供一种含有可聚合表面活性剂的丙烯酸吸水树脂及其制备方法。这种可聚合表面活性剂不仅含有亲水和亲油基团，而且还包括可以聚合的碳碳双键，因此它不仅能在丙烯酸聚合前降低溶液界面张力，稳定气泡，有利于制得多孔结构的水凝胶；而且能在反应开始后参与聚合，镶嵌在水凝胶网络结构表面，改善吸水树脂表面的亲水性，从而提高产品的吸液速率。另外，与常规表面活性剂相比，可聚合表面活性剂不会以游离态形式残留在树脂产品中，更加安全、卫生、环保。添加量为相比于丙烯酸质量计的0.01-3wt％，所得丙烯酸吸水树脂产品吸生理盐水速率不低于40s，可聚合表面活性剂残留量不高于300ppm。

Description

含有可聚合表面活性剂的丙烯酸吸水树脂及其制备方法及应用 技术领域
本发明涉及化工高分子材料领域，更具体地说，本发明涉及一种含有可聚合表面活性剂的丙烯酸吸水树脂及其制备方法。
背景技术
吸水树脂由于具有能吸收自身重量上百倍甚至千倍纯水的特性，而被广泛以吸水材料的形式应用于婴儿尿片、卫生巾、成人纸尿裤等卫生行业、农林保水剂行业及油田堵水等工业生产中。丙烯酸吸水树脂由于具有交联网络结构，所以有很强的保水性能和加压吸液性能，这使其成为目前吸水材料市场上的主流，80％以上的吸水树脂是经丙烯酸聚合而成。丙烯酸聚合方法分为水溶液聚合法和反相悬浮聚合法，其中水溶液聚合法是生产丙烯酸吸水树脂的主流工艺。无论采取何种聚合工艺，为了满足吸水的特性要求，丙烯酸吸水树脂必须具有多孔结构。因此在聚合过程中，体系往往含有大量的微小气泡；而为了降低界面张力，防止气泡聚并破裂消失，体系的配方中都包括表面活性剂。现在用于生产丙烯酸吸水树脂的表面活性剂主要是常规表面活性剂，如十二烷基苯磺酸钠、十二烷基硫酸钠、司盘、吐温等。
可聚合表面活性剂是带有不饱和基团的具有聚合活性的一类表面活性剂，它不仅包括亲水和亲油基团，如常规表面活性剂一样具有表面活性；而且还含有可聚合的不饱和基团。因此，可聚合表面活性剂在聚合反应前起着表面活性剂的作用，降低体系界面张力，稳定反应液体系；在聚合反应开始后参与聚合反应，最终以化学键的形式分布于聚合物粒子表面。根据可参与聚合反应的不饱和基团类型划分，能将可聚合表面活性剂划分为烯丙基型、烯丙氧型、丙烯酸或甲基丙烯酸型、马来酸型、丙烯酸胺型和苯乙烯型。从1958年Freedman等首次报道可聚合表面活性剂的合成及应用至今，可聚合表面活性剂主要应用于乳液聚合或微乳液聚合中，用以防止表面活性剂从乳胶粒子上解吸或在乳胶膜中迁移，从而提高乳液的稳定性。
丙烯酸吸水树脂主要应用于卫生行业中，虽然其中微量游离态的表面活性剂不会对人体造成危害；但是当卫生制品废弃进入环境后，其中含有的游离态表面活性剂会释放到水体中，产生丰富泡沫，降低水中溶氧量，危害水生生物，污染水环境。因此，国家已对水环境中的 直链烷基苯磺酸盐(LAS)含量作了严格规定，工业生产污水中ρ(LAS)≦5mg/L，天然水体中ρ(LAS)≦0.3mg/L。
发明内容
本发明提供一种含有可聚合表面活性剂的丙烯酸吸水树脂及其制备方法。
本发明所提供的一种技术方案如下：
一种含有可聚合表面活性剂的丙烯酸吸水树脂，其中，制备它的原料包含至少一种可聚合表面活性剂，此种可聚合表面活性剂分子除了包括亲水基团和亲油基团外，还至少包括一个可以聚合的碳碳双键结构，其添加量为相比于丙烯酸质量计的0.01-3wt％。
制备上述含有可聚合表面活性剂的丙烯酸吸水树脂的方法包括水溶液聚合法或反相悬浮聚合法，其中，所述制备原料中至少包括一种可聚合表面活性剂，所述可聚合表面活性剂分子除了包括亲水基团和亲油基团外，还至少包括一个可以聚合的碳碳双键结构，其添加量为相比于丙烯酸质量计的0.01-3wt％。
本发明的具体实施方案中，所述亲水基团包括酰胺基、磺酸基、羟基、羧基、酯基、乙氧基、磷酸盐基团和季铵盐基团中的一种或多种，所述亲油基团包括脂肪族碳链和/或含有芳环的碳链。
本发明的具体实施方案中，所述可以聚合的碳碳双键位于可聚合表面活性剂的亲水基团端或亲油基团端或亲水基团端与亲油基团端同时含有可以聚合的碳碳双键。
本发明的具体实施方案中，所述可聚合表面活性剂可以是非离子型、阳离子型、阴离子型或两性型。
本发明的具体实施方案中，所述可聚合表面活性剂为烯丙基型、烯丙氧型、丙烯酸或甲基丙烯酸型、马来酸型、丙烯酰胺型和苯乙烯型中的一种或多种，优选丙烯酸或甲基丙烯酸型、马来酸型、丙烯酰胺型，更优选丙烯酸或甲基丙烯酸型。
优选地，所述烯丙基型为
Figure PCTCN2016113587-appb-000001
所述烯丙氧型为
Figure PCTCN2016113587-appb-000002
所述丙烯酸型为
Figure PCTCN2016113587-appb-000003
所述甲基丙烯酸型为
Figure PCTCN2016113587-appb-000004
Figure PCTCN2016113587-appb-000005
所述马来酸型为
Figure PCTCN2016113587-appb-000006
所述丙烯酰胺型为
Figure PCTCN2016113587-appb-000007
所述苯乙烯型为
Figure PCTCN2016113587-appb-000008
前述可聚合表面活性剂在制备丙烯酸吸水树脂中的应用。
所述丙烯酸吸水树脂在制备吸水材料中的应用；所述吸水材料优选应用于婴儿尿片、妇女卫生巾或成人纸尿裤等。
本发明中所使用的可聚合表面活性剂不仅含有亲水和亲油基团，而且还包括可以聚合的碳碳双键，因此，它不仅具有常规表面活性剂的功能，在丙烯酸聚合前降低溶液界面张力，稳定气泡，有利于制得多孔结构的水凝胶；而且能在反应开始后参与聚合，镶嵌在水凝胶网 络结构表面，改善吸水树脂产品表面的亲水性，促进吸水树脂吸水时的表面润湿过程，从而提高产品的吸液速率。另外，与常规表面活性剂相比，可聚合表面活性剂不会以游离态形式残留在树脂产品中，所以更加安全、卫生、环保。
在制备丙烯酸吸水树脂的一个实施方案中，所述的水溶液聚合法主要包括中和过程、聚合过程、干燥过程和表面处理过程；中和过程是将丙烯酸与氢氧化物的水溶液进行不完全中和反应，得到含丙烯酸和丙烯酸盐的中和液；聚合过程是将中和液与交联剂、可聚合表面活性剂及其它助剂等混合均匀，在一定温度下由引发剂引发聚合，得到聚合物水凝胶；干燥过程是将聚合物水凝胶剪切成微小胶粒，在高温条件下干燥后，依次经过破碎、研磨、筛分环节后，得到粒径为150-800μm的初级丙烯酸吸水树脂粉末；表面处理过程是向初级丙烯酸吸水树脂粉末表面喷洒含功能助剂的水溶液，在一定温度下反应后，得到丙烯酸吸水树脂粉末产品。在水溶液聚合法中，中和过程与聚合过程的顺序可以调换，即可以先进行中和反应后进行聚合反应，也可以先进行聚合反应后进行中和反应。
在制备丙烯酸吸水树脂的一个实施方案中，所述的反相悬浮聚合法主要包括中和过程、聚合及蒸馏脱水过程和表面处理及蒸馏脱溶剂过程；中和过程是将丙烯酸与氢氧化物的水溶液进行不完全中和反应，得到含丙烯酸和丙烯酸盐的中和液；聚合及蒸馏脱水过程是向中和液里添加有机溶液、交联剂、可聚合表面活性剂和其它助剂，搅拌混合均匀，得到反应液，在一定温度下由引发剂引发聚合，反应完成后通过蒸馏工艺脱去体系中的水；表面处理及蒸馏脱溶剂过程是向体系中添加若干种功能助剂，在适宜温度下反应一段时间后，通过蒸馏工艺脱去体系中的有机溶剂和其它少量液体组分，即得到丙烯酸吸水树脂粉末产品。
如前所述，在制备丙烯酸吸水树脂的前述两种实施方案中，所用的原料包括交联剂和引发剂。
所述交联剂为N,N-亚甲基双丙烯酰胺、乙二醇、乙二醇二缩水甘油醚、丙二醇、丙二醇二缩水甘油醚、聚乙二醇、聚乙二醇二丙烯酸酯、聚乙二醇二缩水甘油醚、甘油、甘油三丙烯酸酯、乙氧基化甘油三丙烯酸酯、季戊四醇、季戊四醇三丙烯酸酯、季戊四醇三烯丙基醚、三羟甲基丙烷三丙烯酸酯和乙氧基化三羟甲基丙烷三丙烯酸酯中的一种或多种，优选季戊四醇三烯丙基醚；交联剂的添加量为相比于丙烯酸质量计的0.05-0.8wt％。交联剂是制备 丙烯酸吸水树脂的关键原料之一，它的结构及添加量都严重影响凝胶网络的形状、大小和强度。当添加量太小时，凝胶网络难以形成，凝胶强度低，树脂产品中的可萃取组分含量高；当添加量太大时，凝胶网络交联密度大，强度高，限制了吸水膨胀过程。当交联剂的添加量为相比于丙烯酸质量计的0.05-0.8wt％时，丙烯酸吸水树脂具有优异的应用性能。
在具体的实施方案中，所用的引发剂为双氧水、过硫酸钠、过硫酸钾、过硫酸铵、叔丁基过氧化氢和二叔丁基过氧化物中的一种或两种或多种，优选过硫酸铵；引发剂的添加量为相比于丙烯酸质量计的0.05-0.8wt％。
在优选的实施方案中，本发明的水溶液聚合法的干燥过程在高温下进行，将造粒后所得到的含水凝胶放在温度为100-200℃的条件下，干燥30-240min，即得到干燥颗粒；反相悬浮聚合法的干燥过程则是通过蒸馏工艺完成。
在优选的实施方案中，前述表面处理过程所用助剂包含水、多元醇、环氧化合物和金属化合物中的一种或多种；助剂用量为相比于丙烯酸质量计的2-10wt％。
表面处理过程中所述的多元醇包括但不限于乙二醇、1,2-丙二醇、1,3-丙二醇、丙三醇、二乙二醇、三乙二醇或1,4-丁二醇，所述的环氧化合物包括但不限于乙二醇二缩水甘油醚、聚乙二醇二缩水甘油醚、丙二醇二缩水甘油醚、聚丙二醇二缩水甘油醚、碳酸乙烯酯或碳酸丙烯酯，所述的金属化合物包括但不限于硫酸钠、硫酸镁、硫酸铝、氯化钠、氯化镁、氯化钙、氯化铝或氯化锌。
本发明中含有可聚合表面活性剂的丙烯酸吸水树脂产品吸生理盐水速率不低于40s，可聚合表面活性剂残留量不高于300ppm。
本发明的具体实施方案与现有技术相比具有下列优点：
将可聚合表面活性剂代替常规表面活性剂，用于丙烯酸吸水树脂的生产中。这种可聚合表面活性剂不仅含有亲水和亲油基团，如常规表面活性剂一样具有表面活性，能降低溶液界面张力，稳定体系中的微小气泡，有利于制得多孔结构的水凝胶；而且还包括可以聚合的碳碳双键，能在反应开始后参与聚合，镶嵌在水凝胶网络结构表面，改善吸水树脂产品表面的亲水性，促进吸水树脂吸水时的表面润湿过程，从而提高产品的吸液速率。当添加量为相比 于丙烯酸质量计的0.01-3wt％时，含有可聚合表面活性剂的丙烯酸吸水树脂产品吸生理盐水速率不低于40s。
与常规表面活性剂相比，可聚合表面活性剂由于具有碳碳双键能参与聚合反应，不会以游离态形式残留在丙烯酸吸水树脂产品中，所以更加安全、卫生、环保。当添加量为相比于丙烯酸质量计的0.01-3wt％时，丙烯酸吸水树脂产品中可聚合表面活性剂的残留量不高于300ppm。
以下为具体实施方式中使用的可聚合表面活性剂的结构式：
Figure PCTCN2016113587-appb-000009
Figure PCTCN2016113587-appb-000010
但是，本发明实际可用的不只是上述列出的几种物质，凡是包括亲水基团和亲油基团以及至少包括一个可以聚合的碳碳双键的可聚合表面活性剂均可使用。
具体实施方式
为了更好的理解本发明，下面结合实施例进一步阐明本发明的内容，但本发明的内容不仅仅局限于下面的实施例。实施例中用到的可聚合表面活性剂结构简式如前所示，但本发明的可聚合表面活性剂不仅仅局限于列出的几种物质。
以下为实施例中所用的主要原料的来源。
原料 公司
SF1 日本艾迪科(ADEKA)
SF2 日本艾迪科(ADEKA)
SF3 法国阿科玛(ARKEMA)
SF4 法国阿科玛(ARKEMA)
SF5 法国阿科玛(ARKEMA)
SF6 法国罗地亚(RHODIA)
SF7 英国禾大(CRODA)
实施例1
a)中和过程：在配料罐中将640g氢氧化钠固体溶解于4960g水，然后将氢氧化钠水溶液倒入带有搅拌器的夹套反应釜内，加入2400g丙烯酸，控制反应釜内温度80℃。
b)聚合过程：向步骤a)所得的中和液中加入72g可聚合表面活性剂SF1和19.2g季戊四醇三丙烯酸酯，搅拌均匀后将反应釜内的中和液流进聚合槽，并同时在反应釜出口处向中和液中加入192g已配制好的10wt％过硫酸铵水溶液，聚合反应15min后得到水凝胶。
c)干燥过程：将步骤b)所得的水凝胶切成2-20mm的胶粒，然后在160℃的烘箱中干燥140min，再依次经过破碎、研磨、筛分工序后，得到150-800μm的初级丙烯酸吸水树脂粉末。
d)表面处理过程：将乙二醇二缩水甘油醚、硫酸铝、乙二醇、水按照2：10：15：50的质量比配制表面交联助剂，向步骤c)所得的初级丙烯酸吸水树脂粉末表面均匀喷洒，助剂用量为相比于丙烯酸质量计的7wt％，最后放入150℃的烘箱内干燥80min，即得到含有可聚合表面活性剂的丙烯酸吸水树脂粉末。
实施例2
a)在配料罐中将1200g氢氧化钠固体溶解于3440g水，然后将氢氧化钠水溶液倒入带有搅拌器的夹套反应釜内，加入3360g丙烯酸，控制反应釜内温度80℃。
b)向步骤a)所得的中和液中加入0.336g可聚合表面活性剂SF2和1.68gN,N-亚甲基双丙烯酰胺，搅拌均匀后将反应釜内的中和液流进聚合槽，并同时在反应釜出口处向中和液中加入16.8g已配制好的10wt％过硫酸钾水溶液，聚合反应15min后得到水凝胶。
c)将步骤b)所得的水凝胶切成2-20mm的胶粒，然后在160℃的烘箱中干燥140min，再依次经过破碎、研磨、筛分工序后，得到150-800μm的初级丙烯酸吸水树脂粉末。
d)将乙二醇二缩水甘油醚、硫酸铝、1,3-丙二醇、水按照2：10：15：40的质量比配制表面交联助剂，向步骤c)所得的初级丙烯酸吸水树脂粉末表面均匀喷洒，助剂用量为相比于丙烯酸质量计的6wt％，最后放入150℃的烘箱内干燥80min，即得到含有可聚合表面活性剂的丙烯酸吸水树脂粉末。
实施例3
a)将2880g丙烯酸和2880g水加入到捏合机内，然后加入14.4g可聚合表面活性剂SF3和11.52g季戊四醇三烯丙基醚，搅拌均匀后加入86.4g已配制好的10wt％过硫酸钠水溶液，在起始温度为80℃的条件下聚合2h。
b)将步骤a)所得的聚合物在造粒机中造粒，并同时加入2240g质量浓度为50％的氢氧化钠水溶液，从造粒机出口得到2-20mm的胶粒，然后在160℃的烘箱中干燥140min，再依次经过破碎、研磨、筛分工序后，得到150-800μm的初级丙烯酸吸水树脂粉末。
c)将乙二醇二缩水甘油醚、硫酸铝、丙三醇、水按照1：10：13：40的质量比配制表面交联助剂，向步骤c)所得的初级丙烯酸吸水树脂粉末表面均匀喷洒，助剂用量为相比于丙烯酸质量计的6wt％，最后放入150℃的烘箱内干燥80min，即得到含有可聚合表面活性剂的丙烯酸吸水树脂粉末。
实施例4
a)将2560g丙烯酸和3306g水加入到捏合机内，然后加入38.4g可聚合表面活性剂SF4和12.8g聚乙二醇二丙烯酸酯，搅拌均匀后加入179.2g已配制好的10wt％过硫酸钾水溶液，在起始温度为80℃的条件下聚合2h。
b)将步骤a)所得的聚合物在造粒机中造粒，并同时加入2134g质量浓度为50％的氢氧化钠水溶液，从造粒机出口得到2-20mm的胶粒，然后在160℃的烘箱中干燥140min，再依次经过破碎、研磨、筛分工序后，得到150-800μm的初级丙烯酸吸水树脂粉末。
c)将乙二醇二缩水甘油醚、硫酸铝、1,2-丙二醇、水按照2：10：15：45的质量比配制表面交联助剂，向步骤c)所得的初级丙烯酸吸水树脂粉末表面均匀喷洒，助剂用量为相比于丙烯酸质量计的7wt％，最后放入150℃的烘箱内干燥80min，即得到含有可聚合表面活性剂的丙烯酸吸水树脂粉末。
实施例5
a)在配料罐中将1200g氢氧化钠固体溶解于4080g水，然后将氢氧化钠水溶液倒入带有搅拌器的夹套反应釜内，加入2720g丙烯酸，控制反应釜内温度80℃。
b)向步骤a)所得的中和液中加入1.63g可聚合表面活性剂SF1、10.88g可聚合表面活性剂SF5和2.72g三羟甲基丙烷三丙烯酸酯，搅拌均匀后将反应釜内的中和液流进聚合槽，并同时在反应釜出口处向中和液中加入136g已配制好的10wt％过硫酸铵水溶液，聚合反应15min后得到水凝胶。
c)将步骤b)所得的水凝胶切成2-20mm的胶粒，然后在160℃的烘箱中干燥140min，再依次经过破碎、研磨、筛分工序后，得到150-800μm的初级丙烯酸吸水树脂粉末。
d)将乙二醇二缩水甘油醚、硫酸铝、乙二醇、水按照1.5：9：12：40的质量比配制表面交联助剂，向步骤c)所得的初级丙烯酸吸水树脂粉末表面均匀喷洒，助剂用量为相比于丙烯酸质量计的6wt％，最后放入150℃的烘箱内干燥80min，即得到含有可聚合表面活性剂的丙烯酸吸水树脂粉末。
以上实施例为水溶液聚合法的实施例，以下两个实施例为反相悬浮聚合法的实施例：
实施例6
a)在配料罐中将1067g氢氧化钠固体溶解于3733g水，然后将氢氧化钠水溶液倒入带有搅拌器的夹套反应釜内，加入3200g丙烯酸，控制反应釜内温度80℃，然后向反应釜内加入10800g正庚烷、19.2g可聚合表面活性剂SF1和57.6g可聚合表面活性剂SF6，搅拌均匀，得到反应液。
b)向步骤a)所得的反应液中加入6.4g甘油三丙烯酸酯，搅拌均匀后向反应釜中加入64g已配制好的10wt％过硫酸钠水溶液，聚合反应4h后，蒸馏除去体系中的水。
c)将乙二醇二缩水甘油醚、1,3-丙二醇、水按照4：15：50的质量比配制表面交联助剂，加入到步骤b)的反应釜中，助剂用量为相比于丙烯酸质量计的5wt％，反应1h后，蒸馏除去体系中的溶剂正庚烷和少量其它液体组分，即得到含有可聚合表面活性剂的丙烯酸吸水树脂粉末。
实施例7
a)在配料罐中将1148g氢氧化钠固体溶解于3812g水，然后将氢氧化钠水溶液倒入带有搅拌器的夹套反应釜内，加入3040g丙烯酸，控制反应釜内温度80℃，然后向反应釜内 加入8000g正庚烷和60.8g可聚合表面活性剂SF7，搅拌均匀，得到反应液。
b)向步骤a)所得的反应液中加入2.43g乙氧基化三羟甲基丙烷三丙烯酸酯，搅拌均匀后向反应釜中加入76g已配制好的10wt％过硫酸铵水溶液，聚合反应4h后，蒸馏除去体系中的水。
c)将乙二醇二缩水甘油醚、乙二醇、水按照3：18：55的质量比配制表面交联助剂，加入到步骤b)的反应釜中，助剂用量为相比于丙烯酸质量计的8wt％，反应1h后，蒸馏除去体系中的溶剂正庚烷和少量其它液体组分，即得到含有可聚合表面活性剂的丙烯酸吸水树脂粉末。
对比例1
a)在配料罐中将1200g氢氧化钠固体溶解于4080g水，然后将氢氧化钠水溶液倒入带有搅拌器的夹套反应釜内，加入2720g丙烯酸，控制反应釜内温度80℃。
b)向步骤a)所得的中和液中加入2.72g三羟甲基丙烷三丙烯酸酯，搅拌均匀后将反应釜内的中和液流进聚合槽，并同时在反应釜出口处向中和液中加入136g已配制好的10wt％过硫酸铵水溶液，聚合反应15min后得到水凝胶。
c)将步骤b)所得的水凝胶切成2-20mm的胶粒，然后在160℃的烘箱中干燥140min，再依次经过破碎、研磨、筛分工序后，得到150-800μm的初级丙烯酸吸水树脂粉末。
d)将乙二醇二缩水甘油醚、硫酸铝、乙二醇、水按照1.5：9：12：40的质量比配制表面交联助剂，向步骤c)所得的初级丙烯酸吸水树脂表面均匀喷洒，助剂用量为相比于丙烯酸质量计的6wt％，最后放入150℃的烘箱内干燥80min，即得到含有可聚合表面活性剂的丙烯酸吸水树脂粉末。
对比例2
a)将2560g丙烯酸和3306g水加入到捏合机内，然后加入38.4g十二烷基苯磺酸钠和12.8g聚乙二醇二丙烯酸酯，搅拌均匀后加入179.2g已配制好的10wt％过硫酸钾水溶液，在起始温度为80℃的条件下聚合2h。
b)将步骤a)所得的聚合物在造粒机中造粒，并同时加入2134g质量浓度为50％的氢氧化钠水溶液，从造粒机出口得到2-20mm的胶粒，然后在160℃的烘箱中干燥140min，再依次经过破碎、研磨、筛分工序后，得到150-800μm的初级丙烯酸吸水树脂粉末。
c)将乙二醇二缩水甘油醚、硫酸铝、1,2-丙二醇、水按照2：10：15：45的质量比配制表面交联助剂，向步骤c)所得的初级丙烯酸吸水树脂表面均匀喷洒，助剂用量为相比于丙烯酸质量计的7wt％，最后放入150℃的烘箱内干燥80min，即得到含有可聚合表面活性剂的丙烯酸吸水树脂粉末。
将各实施例和比较例中得到的丙烯酸吸水树脂按照如下方法进行性能测试，结果列入表1中。
1.吸液速率
(1)称取50g生理盐水(0.9％NaCl水溶液)，倒入容量为100ml的烧杯中；
(2)将烧杯置于恒温磁力搅拌器上，控制生理盐水温度为25℃，放入直径25mm的铁芯四氟搅拌子，开始搅拌；
(3)观察到烧杯中溶液漩涡出现并稳定后，加入2g丙烯酸吸水树脂，并开始计时，等到漩涡消失时的时间即为产品的吸液速率。
2.表面活性剂残留量
将1g丙烯酸吸水树脂粉末倒入100g的二氯甲烷中，在60℃的条件下回流8小时，取上层清液，用液相色谱(HPLC)检测其中的表面活性剂含量C(ppm)，按下式计算丙烯酸吸水树脂产品中表面活性剂的残留量：W＝100*C——单位是ppm
表1各实施例及对比例中丙烯酸吸水树脂的性能
  吸液速率(s) 表面活性剂残留量(ppm)
实施例1 36 278
实施例2 33 79
实施例3 27 148
实施例4 25 195
实施例5 31 127
实施例6 25 264
实施例7 23 238
对比例1 49 0
对比例2 40 7982
由表1可知，不使用表面活性剂的对比例1，丙烯酸吸水树脂的吸液速率非常慢，接近50秒；而使用常规表面活性剂的对比例2，丙烯酸吸水树脂的表面活性剂残留量非常高，接近8000ppm。但是实施例中含有可聚合表面活性剂的丙烯酸吸水树脂不仅吸液速率快，都低于40s；而且表面活性剂残留量也低，都小于300ppm。因此，采用本发明制备的含有可聚合表面活性剂的丙烯酸吸水树脂具有更优异的应用性能，并且更加健康、环保。

Claims (15)

  1. 一种丙烯酸吸水树脂，其特征在于，制备它的原料包含至少一种可聚合表面活性剂，所述可聚合表面活性剂分子除了包括亲水基团和亲油基团外，还至少包括一个可以聚合的碳碳双键；在制备过程中所述可聚合表面活性剂的添加量为丙烯酸质量的0.01-3wt％。
  2. 根据权利要求1所述的丙烯酸吸水树脂，其特征在于，所述亲水基团包括酰胺基、磺酸基、羟基、羧基、酯基、乙氧基、磷酸盐基团和季铵盐基团中的一种或多种；所述亲油基团包括脂肪族链和/或含有芳环的碳链。
  3. 根据权利要求1所述的丙烯酸吸水树脂，其特征在于，所述可以聚合的碳碳双键位于所述可聚合表面活性剂的亲水基团端或亲油基团端或亲水基团端与亲油基团端同时含有碳碳双键。
  4. 根据权利要求1-3中任意一项所述的丙烯酸吸水树脂，其特征在于，所述可聚合表面活性剂可以是非离子型、阳离子型、阴离子型或两性型。
  5. 根据权利要求1-3中任意一项所述的丙烯酸吸水树脂，其特征在于，所述可聚合表面活性剂为烯丙基型、烯丙氧型、丙烯酸或甲基丙烯酸型、马来酸型、丙烯酰胺型和苯乙烯型中的一种或多种，优选丙烯酸或甲基丙烯酸型、马来酸型、丙烯酰胺型，更优选丙烯酸或甲基丙烯酸型。
  6. 根据权利要求5所述的丙烯酸吸水树脂，其特征在于，所述烯丙基型为
    Figure PCTCN2016113587-appb-100001
    所述烯丙氧型为
    Figure PCTCN2016113587-appb-100002
    所述丙烯酸型为
    Figure PCTCN2016113587-appb-100003
    所述甲基丙烯酸型为
    Figure PCTCN2016113587-appb-100004
    Figure PCTCN2016113587-appb-100005
    所述马来酸型为
    Figure PCTCN2016113587-appb-100006
    所述丙烯酰胺型为
    Figure PCTCN2016113587-appb-100007
    所述苯乙烯型为
    Figure PCTCN2016113587-appb-100008
  7. 一种制备丙烯酸吸水树脂的方法，包括水溶液聚合法或反相悬浮聚合法，其特征在于，所述的制备原料中至少包括一种可聚合表面活性剂，所述可聚合表面活性剂分子除了包括亲水基团和亲油基团外，还至少包括一个可以聚合的碳碳双键，在制备过程中其添加量为丙烯酸质量的0.01-3wt％。
  8. 根据权利要求7所述的制备方法，其特征在于，所述亲水基团包括酰胺基、磺酸基、羟基、羧基、酯基、乙氧基、磷酸盐基团和季铵盐基团中的一种或多种；所述亲油基团包括脂肪族碳链和/或含有芳环的碳链。
  9. 根据权利要求7所述的制备方法，其特征在于，所述可以聚合的碳碳双键位于所述可聚合表面活性剂的亲水基团端或亲油基团端或亲水基团端与亲油基团端同时含有碳碳双键。
  10. 根据权利要求7-9中任意一项所述的制备方法，其特征在于，所述可聚合表面活性剂可以是非离子型、阳离子型、阴离子型或两性型。
  11. 根据权利要求7-9中任意一项所述的丙烯酸吸水树脂，其特征在于，所述可聚合表面活性剂为烯丙基型、烯丙氧型、丙烯酸或甲基丙烯酸型、马来酸型、丙烯酰胺型和苯乙烯型中的一种或多种，优选丙烯酸或甲基丙烯酸型、马来酸型、丙烯酰胺型，更优选丙烯酸或甲基丙烯酸型。
  12. 根据权利要求11所述的丙烯酸吸水树脂，其特征在于，所述烯丙基型为
    Figure PCTCN2016113587-appb-100009
    所述烯丙氧型为
    Figure PCTCN2016113587-appb-100010
    所述丙烯酸型为
    Figure PCTCN2016113587-appb-100011
    所述甲基丙烯酸型为
    Figure PCTCN2016113587-appb-100012
    Figure PCTCN2016113587-appb-100013
    所述马来酸型为
    Figure PCTCN2016113587-appb-100014
    所述丙烯酰胺型为
    Figure PCTCN2016113587-appb-100015
    所述苯乙烯型为
    Figure PCTCN2016113587-appb-100016
  13. 根据权利要求1-6中任一项所述的丙烯酸吸水树脂或由权利要求7-12中任意一项制备方法制备得到的丙烯酸吸水树脂，其特征在于，所述丙烯酸吸水树脂产品吸生理盐水速率不低于40s，可聚合表面活性剂残留量不高于300ppm。
  14. 可聚合表面活性剂在制备丙烯酸吸水树脂中的应用。
  15. 根据权利要求1-6中任一项所述的丙烯酸吸水树脂或由权利要求7-12中任意一项制备方法制备得到的丙烯酸吸水树脂在制备吸水材料中的应用；所述吸水材料优选应用于婴儿尿片、妇女卫生巾或成人纸尿裤。
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