CN1733815A - Preparation method of high-intensity water absorbent material - Google Patents
Preparation method of high-intensity water absorbent material Download PDFInfo
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Abstract
The invention relates to a preparation method for high-strength water-absorption material, which comprises: (1) mixing all the material in deionized water, placing for 0~72h at -20~30Deg; (2) putting the mixed liquid into reaction kettle with condenser, mixing and reacting for 2~8h at constant temperature of 60~80Deg with or without nitrogen; (3) neutralizing the reacted product with or without NaOH solution, holding temperature at 90~95Deg for 1~2h; cutting into slice to put into deionized water for 3~12h; clearing to dewater with carbinol, and cleaning the carbinol with anhydrous alcohol; (4) drying or baking the obtained product to constant weight, mashing, sieving, and obtaining the water-absorption material with high gel strength, well dispersion and controllable size and shape.
Description
Technical field
The present invention relates to material synthesis technology, specifically is the preparation method who has than the high-intensity water absorbent material of high-gel strength.
Background technology
High-absorbent material is called super absorbent resin again.Because it had both had remarkable absorbent function and water retention capacity, the advantage that possesses macromolecular material again, thereby purposes is very extensive, and in farming, woods, gardening, petrochemical industry, commodity chemical industry, or building material industry, health care, communications and transportation etc. all are widely used.Particularly become indispensable material in fields such as agricultural, health cares.Just because of this, pay much attention to for its research and application both at home and abroad.But present research mainly concentrates on how to improve its suction salt absorbing rate, improves its suction and inhales on the salt speed.To improving research that its suction inhales gel-strength after salt then seldom.The gel-strength that method synthetic super absorbent resins suctions such as employing solution polymerization, suspension polymerization and radio polymerization are inhaled after the salt is not high usually, even the one-tenth flow-gel after the portioned product suction suction salt.And in building material industry, medical and health, Application Areass such as agricultural gardening are that higher requirement (for example Water in Water Shutoff in Oil Field agent, muddy water shielding construction agent, foundation stabilization agent, soft contact lens, artificial liver, flower culture fertilizer etc.) is arranged to the intensity after the resin suction suction salt.In theory, can improve gel-strength, but, do like this and will cause suction suction salt speed, multiplying power significantly to reduce according to the Flory formula by the way that improves the surface-crosslinked degree of water-absorbing resin.Up to now, have only a small amount of bibliographical information to improve its gel-strength by adding a certain amount of inorganic materials.Contain bentonitic partial hydrolysis cross-linked polyacrylamide super absorbent resin as adopting wilkinite and kaolin to synthesize respectively, it is the resin of 461-802 that the starch graft copolymer system that aforesaid method adopts has obtained the suction multiple; Prior art is also utilized Repone K hierarchy of control viscosity, is monomer at vinylformic acid-acrylamide, and carries out polymerization after silicon sol mixes, and synthesizes a kind of super absorbent resin that can improve the water-retaining agent gel-strength.Prior art adopts acrylamide polymerization in addition, improves gel-strength after the water-absorbing resin suction by the method for adding kaolin powder.
Though above-mentioned interpolation inorganic powder can improve its gel-strength, because used inorganic powder material structure and composition are indefinite, its physical strength is not high, thereby the increase rate of its gel-strength is limited, and the products obtained therefrom repeat usage is not high.Thereby the present invention is by adding crystal type molecular sieve preparation high-intensity water absorbent resin in reaction mixture, domestic and foreign literature did not have relevant report as yet so far.General inorganic powder material is different with adding, and behind the interpolation crystal type molecular sieve, because molecular sieve has regular porous property, hole wall surface has abundant silanol hydroxyl, can play link, crosslinked action respectively in water-absorbing resin; The more important thing is that molecular sieve provides a stable skeleton for water-absorbing resin, thereby make the network structure of water-absorbing resin more regular, more firm, thereby the gel-strength after its suction is strengthened greatly.
Summary of the invention
The objective of the invention is deficiency at existing method, a kind of preparation method of high-intensity water absorbent material is provided, in the raw material of existing preparation High hydrophilous resin, add the crystal type molecular sieve, prepare water-absorbing material by solution polymerization, suspension polymerization or radio polymerization with high-gel strength.
The preparation method of high-intensity water absorbent material of the present invention comprises the steps:
(1) outfit of reaction mixture: raw material, initiator, linking agent, molecular sieve are mixed in deionized water by mass ratio 100: 0.05～3: 0.05～5: 0.1～10, placed 0～72 hour, and obtained reaction mixture for 30 ℃～-20 ℃;
(2) polymerization: the reaction mixture that step (1) is obtained places the reactor of being with condenser, logical or obstructed nitrogen, 60 ℃～80 ℃ stirring reactions of constant temperature 2～8 hours;
(3) separate to clean: the reaction product that step (2) is obtained with/or without the neutralization of NaOH solution, then 90～95 ℃ of constant temperature 1～2 hour; Thinly slice, put into deionized water and soaked 3～12 hours, washing; With methyl alcohol the product after washing is dewatered, use the methyl alcohol in the dehydrated alcohol flush away dehydrate then;
(4) dry, pulverize: the dehydrate that step (3) is obtained is dry or dry to constant weight, pulverizes, and sieves;
Described raw material is starch, Mierocrystalline cellulose or protein or/and one or more mixture in the vinyl cyanide, vinylformic acid, acrylamide, MALEIC ANHYDRIDE, acrylate, polyvinyl alcohol; Described initiator is peroxide initiator, azo-initiator or redox initiator; Described linking agent is meant and contains two or more organic compound in the two keys of activity functional groups, hydroxyl, amino, imino-, carboxyl, the epoxy; Described molecular sieve is meant MCM series molecular sieve, SBA-n series molecular sieve, MSU-X series molecular sieve, APMs molecular sieve or crystal type molecular sieve.
The water-intake rate of the high-intensity water absorbent material that obtains can reach 400g/g～2500g/, and gel-strength is 2000N/kg～2500N/kg.
The polymerization of step (2) also can be carried out in following condition: by monomer: the mass ratio of dispersion agent=100: 1～6 is dissolved in oil phase/water with dispersion agent, and (quality is than oil phase: water=1～5: 1) in the medium, stir and logical nitrogen, add the reaction mixture that step (1) obtains, the constant temperature stirring reaction is 2～8 hours under 60 ℃～80 ℃ temperature; Step (3) is separated when cleaning, and topples over oil-phase medium, takes out reaction product, thinly slices, and puts into anhydrous methanol and soaks 3～12 hours, cleans 2～3 times with dehydrated alcohol again.
Described dispersion agent is a tensio-active agent; Used oil-phase medium is the mixture of arene, alkanes, sherwood oil or sherwood oil and hexanaphthene.
Described tensio-active agent is Span80, Span85, Span60, Span40, Span20, Tween80, Tween60, hexadecyl phosphate monoester, octadecyl phosphate monoester, polyoxyethylene nonylphenol or Triethylene glycol.
Described arene oil-phase medium is benzene, toluene or dimethylbenzene; Described alkanes oil-phase medium is normal hexane, hexanaphthene, heptane, octane-iso or isomery paraffinic hydrocarbon.
The water-intake rate of the high-intensity water absorbent material that obtains can reach 1000g/g～3300g/g, and gel-strength is 2000N/kg～4000N/kg.
The polymerization of step (2) can also be carried out in following condition: do not add initiator the reaction mixture liquid that step (1) obtains is placed the irradiation bottle, letting nitrogen in and deoxidizing is placed on chamber, cobalt source, carries out radiation copolymerization 2～8 hours under the dose rate of 10Kgy/min～80Kgy/min; Step (3) is taken out reaction product after being directly cooling from the irradiation bottle.
The water-intake rate of the high-intensity water absorbent material that obtains can reach 800g/g～3200g/g, and gel-strength is 2100N/kg～3000N/kg.
In the aforesaid method, described starch is native starch wheat starch, W-Gum, Starch rice, yam starch, sweet potato starch or their resolvent, derivative or Alpha-starch or separating starch or physical treatment starch; Described Mierocrystalline cellulose is natural cellulose gossypin, wood-cellulose, straw fiber element or flaxen fiber element or cellulosic derivative cellulose acetate, methoxyl group Mierocrystalline cellulose, carboxymethyl cellulose, carboxyethyl cellulose, Natvosol, hydroxypropylcellulose, cellulose xanthate or hydroscopic cellulose derivative; Described protein is plant protein or animal protein.
Described peroxide initiator is benzoyl peroxide, hydrogen peroxide, ammonium persulphate or Potassium Persulphate; Described azo-initiator is Diisopropyl azodicarboxylate or 2,2'-Azobis(2,4-dimethylvaleronitrile) etc.; Described redox initiator is hydrogen peroxide-ferrous sulfate, ammonium persulphate-sodium bisulfite or Potassium Persulphate-Sulfothiorine.
Described initiator is ceric ammonium nitrate, iron trichloride or pentavalent vanadic salts.
Described linking agent is ethylene glycol, glycerol, TriMethylolPropane(TMP), N, N-dimethyl bisacrylamide, glycerine allyl ether etc., N hydroxymethyl acrylamide, glycidyl methacrylate, glycidyl acrylate, quadrol, oxalic acid, phthalic acid, divinylbenzene or biethenyl-xylene.
Described MGM series molecular sieve is MCM-41, MCM-48, MCM-49, MCM-22, MCM-50 or MCM-56, described SBA-n series molecular sieve is SBA-1, SBA-2, SBA-3, SBA-6, SBA-11, SBA-12, SBA-15 or SBA-16, and the aperture of described crystal type molecular sieve is the pure silicon molecular sieve of micropore, mesopore or macropore or the silica-based molecular sieve that is doped with one or more elements among Al, Fe, Mn, Zn, Cu, V, Ti, Mo, the P.
In aforesaid method, the separation of dispersion system and filter method adopt method commonly used.The drying of product or furnace drying method adopt 40 ℃～150 ℃ common dryings or vacuum-dryings 3～48 hours down, and the pulverizing of product adopts pulverizer to carry out.
The present invention compares with the technology of preparing of existing super absorbent resin, has following advantage and effect:
(1) diversity of synthetic method.Both can adopt lower-cost solution polymerization process synthetic during synthesizing high-hydroscopicity resin of the present invention, it is synthetic also can to adopt the product aftertreatment to be easy to suspension polymerization, or radiation polymerization, can also adopt other polymerization process to synthesize, as methods such as letex polymerizations.
(2) popularity of material choice.The present invention is when synthesizing high-hydroscopicity resin, and selected synthesis material both can be a natural matter cheap and easy to get, as starch, Mierocrystalline cellulose, protein etc.; Also can be petroleum products, as vinyl cyanide, vinylformic acid, acrylate, acrylamide etc.Thereby selection is more convenient.
(3) superiority of product performance.The super absorbent resin that the present invention prepares has: higher gel-strength, along with its gel-strength of increase of molecular sieve add-on is significantly improved, its ultimate compression strength can reach 2000N/kg～3000N/kg (testing method that its strength test method reference [5] is taked), and the product gel-strength that does not add molecular sieve is at 100N/kg～1000N/kg; Higher suction salt absorbing rate, its water-intake rate and salt absorbing rate can reach 400g/g～4000g/g and 60g/g～150g/g respectively; Higher water retention and guarantor's salt rate, along with its water retention of increase of molecular sieve add-on with protect the salt rate and be significantly improved, place 12 hours its water retentions for 50 ℃ and reach 25%～50%, compare with the product that does not add molecular sieve, its water retention and guarantor's salt rate have improved 5～20 times; Salt speed is inhaled in suction preferably, and absorbing water can reach 60～80% of saturated water adsorptive value in 5 minutes, inhales salt and can reach 60～80% of saturated suction salt amount in 20 minutes; Higher repeat usage, its repeat usage reach 8～12 times.
(4) good product dispersibility of suspension polymerization.The present invention is owing to introduced the crystal type molecular sieve, and it is water-fast.The polymer that forms in reaction process is isolated mutually because of surface band same sex electric charge, makes polymerisate be not easy to bond together.So molecular sieve also plays the effect of auxiliary dispersants therein, can obtain favorable dispersity, the narrow product of particle size distribution by regulatory molecule sieve particle size, shape.
(5) product is easily realized industrialized mass production.The present invention is because selected synthesis material is extensive, the crystal type molecular sieve of being introduced does not have additional requirement to production unit, thereby the present invention not only can be used for the synthetic of laboratory scale level, can also realize the batch process under its technical scale under the existing manufacturing condition of producing high suction type resin.And the product cost of producing is low, and big in batches, performance is good.
Concrete embodiment
Synthesizing of embodiment 1 starch graft copolymer acrylamide high-intensity water absorbent resin
Accurately take by weighing acrylamide, benzoyl peroxide, N, (quality is than acrylamide: benzoyl peroxide: N for N-dimethyl bisacrylamide, Al/MCM-4l (aperture 2.5nm) molecular sieve, N-dimethyl bisacrylamide: Al/MCM-4l=80: 0.1: 0.5: 2) place reaction vessel, the distilled water that adds certain volume, stir, get reaction mixture.With reaction mixture and the starch-grafted thing of 20 mass parts (preparation method: a certain amount of W-Gum, vinylformic acid are joined in the reactor that agitator, prolong (device), thermometer are housed, add a certain amount of distilled water, under the condition of logical nitrogen, in 80 ℃ of constant temperature gelatinizations 0.5 hour.Then system is cooled to room temperature and promptly gets starch-grafted thing) mix, stirring is placed on-10 ℃ of refrigerator and cooled and froze 24 hours.Then reaction mixture is transferred in the reactor, under the condition of logical nitrogen, 60 ℃ of reactions of constant temperature 3 hours.After reaction is finished, stop logical nitrogen, add the neutralization of NaOH solution, 95 ℃ of constant temperature 2 hours.Hydrolysate was soaked 10 hours washing with deionized water.With methyl alcohol the product after washing is dewatered again, use the methyl alcohol in the dehydrated alcohol flush away dehydrate then.Dehydrate is placed baking oven, and 80 ℃ of vacuum-drying, was sieved through grinding to constant weight in 12 hours, and can obtain water-intake rate is 1600g/g, and gel-strength is the super absorbent resin of 2360N/kg.
The preparation of the three-component grafted composite high water absorption resin of embodiment 2 starch
Having agitator, prolong (device), in the 250ml flask of logical nitrogen conduit under certain temperature 30g gelatinization Alpha-starch 1 hour, reduce to room temperature, logical nitrogen stirred 30 minutes, added Diisopropyl azodicarboxylate and the glycerine allyl ether of 0.5g, 1g more respectively, add then in 40% and after vinylformic acid (containing vinylformic acid 42g), 28g acrylamide and 8gMCM-48 (phosphorous 5% hydridization) molecular sieve make mixed solution and stir after 1.5 hours, place 0 ℃ refrigerator and cooled to freeze 36 hours.Be transferred to then in the reactor, logical nitrogen was warming up to 70 ℃ and insulation reaction 4 hours then.After reaction finishes, the neutralization of NaOH solution, 90 ℃ of constant temperature 2 hours.Take out gel, put into deionized water after the section and soaked 8 hours, use methanol dehydration after the filtration again, with the unnecessary methyl alcohol of washing with alcohol, product gets the finished product 60 ℃ of following vacuum-dryings 24 hours after the pulverizing.Its water-intake rate reaches 2500g/g, and gel-strength reaches 2500N/kg.
The inverse suspension polymerization of embodiment 3 cellulose graft vinylformic acid super absorbent resins
With the methoxyl group Mierocrystalline cellulose of 100 mass parts and vinylformic acid (quality is than methoxyl group Mierocrystalline cellulose: vinylformic acid=30: 70) and sodium hydroxide in water, mix stirring and dissolving.Add 1 mass parts hydrogen peroxide-ferrous sulfate then, the molecular sieve SBA-15 of 3 mass parts N-n-methylolacrylamide and 0.1 mass parts (aperture 30nm) behind the stirring 2h, is placed them 72 hours in 20 ℃.Then it is joined (mass ratio, oil phase: water=1: 1), be warming up to 70 ℃, reacted 5 hours in the oil-phase medium dimethylbenzene of the Span-80/Tween80 (mass ratio 1: 1) that contains 1 mass parts.After reaction finishes, 90 ℃ of constant temperature 2 hours.Filter, put it into then in the deionized water and soaked 12 hours, clean 2～3 times with dehydrated alcohol again.80 ℃ of vacuum-drying 12 hours is pulverized, product.Its water-intake rate can reach 1000g/g, and gel-strength can reach 2350N/kg.
The preparation of embodiment 4 native cellulose fibres-acrylonitrile graft copolymer super absorbent resin
With the gossypin of 100 mass parts and vinyl cyanide, ceric ammonium nitrate by quality than gossypin: vinyl cyanide: ceric ammonium nitrate=in deionized water mix at 30: 70: 0.2, the SBA-2 molecular sieve that adds 0.1 mass parts phthalic acid and 4 mass parts then successively to it, stirred 1.5 hours, and placed-20 ℃ of following refrigerator and cooled to freeze then 3 hours.It is transferred in the reactor, and logical nitrogen is in 70 ℃ of isothermal reactions 6 hours, and after reaction finished, 90 ℃ of constant temperature was 2 hours again.Add methyl alcohol then, the solution of sodium hydroxide and water carries out saponification, after the filtration, puts it in the deionized water and soaks 3 hours, cleans 2～3 times with dehydrated alcohol again.80 vacuum-dryings 12 hours are pulverized, and get product.Its water-intake rate can reach 800g/g, and gel-strength can reach 2200N/kg.
Synthesizing of the three-component grafted high-intensity water absorbent material of embodiment 5 silks
Get dried silk and immerse vinylformic acid, the methacrylic acid (three kinds of raw materials add up to 100 mass parts) and 1 that neutralized, (the dried silk of mass ratio: vinylformic acid: methacrylic acid: 1 in the 6-hexanediyl ester aqueous solution, 6-hexanediyl ester=15: 75: 10: 0.5), after stirring, Potassium Persulphate-the Sulfothiorine that once adds 3 mass parts then, 0.1 the APMs molecular sieve of the divinylbenzene of mass parts and 6 mass parts, stir after 1.5 hours, the refrigerator and cooled that is placed on-10 ℃ was frozen 12 hours.Be transferred to then in the reactor, logical nitrogen is warming up to 60 ℃, isothermal reaction 8 hours, and 95 ℃ of constant temperature is 1.5 hours again.Product is put into 50% methanol aqueous solution, with in the sodium hydroxide and after put it in the anhydrous methanol and to soak 12 hours, clean 2-3 time with dehydrated alcohol again.60 ℃ of vacuum-drying 12 hours is pulverized, product.Its water-intake rate can reach 400g/g, and gel-strength can reach 2000N/kg.
The preparation of embodiment 6 high-intensity water absorbent material PAANa
The vinylformic acid of 100 mass parts is joined in the solution that is made into by 30gNaOH and 20g water, under cooling conditions, stir, neutralization.Add the pentavalent vanadic salts of 0.05 mass parts, the N of 0.05 mass parts then successively, the molecular sieve MSU-1 of N-methylene-bisacrylamide and 10 mass parts and, Al/MCM-4l (mass ratio MSU-1: Al/MCM-4l=1: 1), stirred 2 hours, take out reaction solution, it is transferred in the reactor, logical nitrogen is in 65 ℃ of following isothermal reactions 5 hours, and 95 ℃ of constant temperature is 2 hours again.Take out product, thinly slice, put it in the deionized water and soaked 12 hours, clean 2～3 times with dehydrated alcohol again.40 ℃ of vacuum-drying 48 hours is pulverized, product.Its water-intake rate can reach 1000g/g, and gel-strength can reach 2350N/kg.
The preparation of embodiment 7 polyvinyl alcohol super absorbent resins
In reactor, add the pva powder of 40 mass parts and add toluene and make its abundant swelling.The maleic acid liver that other takes by weighing 60 mass parts is dissolved in the acetone, then it is added in the reactor and mix with above-mentioned polyvinyl alcohol, other adds the ammonium persulphate-sodium bisulfite of 5 mass parts N hydroxymethyl acrylamides, 1.5 mass parts, the MCM-22 molecular sieve of 5 mass parts, stirs it is mixed.Froze 24 hours in-20 ℃ of refrigerator and cooled then.It is transferred in the reactor, 80 ℃ of following isothermal reactions 2 hours, 95 ℃ of constant temperature is 1 hour again.After reaction was finished, system was cooled to room temperature, with methyl alcohol-aqueous hydrolysis of a certain amount of NaOH.Take out product, put it in the deionized water and soaked 8 hours, clean 2～3 times with dehydrated alcohol again.150 ℃ of vacuum-drying 3 hours is pulverized, product.Its water-intake rate can reach 850g/g, and gel-strength can reach 2300N/kg
The copolymerized high-intensity water absorbent material of embodiment 8 inverse suspension polymerization acrylic acid synthesizing-acrylamides
The vinylformic acid of getting 70 mass parts is made into 80% solution, drips 13% Na then to it
2CO
3Solution, making its degree of neutralization is 80%.Stir after 5 minutes, add acrylamide, Potassium Persulphate, N successively, (quality is than vinylformic acid: acrylamide: Potassium Persulphate: N for N-methylene-bisacrylamide and molecular sieve MCM-4l (aperture 10nm), N-methylene-bisacrylamide: MCM-4l=70: 30: 0.8: 2: 7), fully stir after 1.5 hours, get reaction mixture.Placed 72 hours for 30 ℃.The Span-80 of 4 mass parts is scattered in (mass ratio, oil phase: water=5: 1), load onto prolong (device), stirred 1 hour for 45 ℃ in water-bath, limit logical nitrogen limit stirring in the hexanaphthene.Reaction mixture is taken out, and logical nitrogen 30 minutes joins it in oil phase by preceding gained then, is warming up to 70 ℃, isothermal reaction 5 hours, and 95 ℃ of constant temperature is 1 hour again.Pour out hexanaphthene, take out product, put into anhydrous methanol then and soaked 12 hours, clean 2～3 times with dehydrated alcohol again.80 ℃ of vacuum-drying 12 hours is pulverized, the finished product.Its water-intake rate can reach 1000g/g, and gel-strength can reach 4000N/kg.
Embodiment 9 inverse suspension polymerization acrylic acid synthesizing-methyl acrylates-acrylamide composite high-strength water-absorbing material
Get 90 mass parts vinylformic acid and methyl acrylate (mass ratio 80: 10) and be made into 80% the aqueous solution, drip 30% Na then to it
2CO
3Solution, making its degree of neutralization is 80%.After the stirring, add acrylamide, ammonium persulphate, TriMethylolPropane(TMP) successively and account for vinylformic acid gross weight 6% hydridization molecular sieve P/MCM-48 (quality is than vinylformic acid: methyl acrylate: acrylamide: ammonium persulphate: TriMethylolPropane(TMP): P/MCM-48=80: 10: 10: 2: 1: 6), fully stir reaction mixture.The refrigerator and cooled that is placed on-10 ℃ was frozen 48 hours.The Tween60 of 6 mass parts is scattered in (mass ratio, oil phase: water=5: 1), load onto prolong (device), stirred 1 hour for 45 ℃ in water-bath, limit logical nitrogen limit stirring in the dimethylbenzene.Reaction mixture is taken out, and logical nitrogen 30 minutes joins it in oil phase by preceding gained then, is warming up to 80 ℃, isothermal reaction 5 hours, and 95 ℃ of constant temperature is 1 hour again.Pour out dimethylbenzene, take out product, put into anhydrous methanol then and soaked 8 hours, clean 2～3 times with dehydrated alcohol again.100 ℃ of vacuum-drying 8 hours is pulverized, the finished product.Its water-intake rate can reach 3300g/g, and gel-strength can reach 2900N/kg.
The copolymerized high-intensity water absorbent material of embodiment 10 inverse suspension polymerization synthesis of acrylonitrile-acrylic acid-acrylamides
The compound monomer (vinyl cyanide, vinylformic acid, acrylamide, mass ratio 10: 80: 10) of getting 100 mass parts is made into 80% the aqueous solution, and to its NaOH solution that drips 20%, making its degree of neutralization is 70% then.After the stirring, add successively ceric ammonium nitrate, glycidyl methacrylate and molecular sieve ZnO/SBA-6 (aperture 4nm) (quality is than vinyl cyanide: vinylformic acid: acrylamide: ceric ammonium nitrate, glycidyl methacrylate: ZnO/SBA-6=10: 80: 10: 0.02: 0.5: 8), fully stir reaction mixture.The refrigerator and cooled that is placed on 0 ℃ was frozen 24 hours.The octadecyl phosphate monoester of 4 mass parts is scattered in (mass ratio, oil phase: water=3: 1), load onto prolong (device), stirred 1 hour in 45 ℃ of logical nitrogen in the sherwood oil.Reaction mixture is taken out, and logical nitrogen 30 minutes joins it in oil phase by preceding gained then, is warming up to 80 ℃, isothermal reaction 4 hours, and 95 ℃ of constant temperature is 2 hours again.Pour out sherwood oil, take out product, put into anhydrous methanol then and soaked 3 hours, clean 2～3 times with dehydrated alcohol again.120 ℃ of vacuum-drying 6 hours is pulverized, the finished product.Its water-intake rate can reach 2250g/g, and gel-strength can reach 2000N/kg.
Embodiment 11 radio polymerizations synthesize the sodium polyacrylate super absorbent resin
100g vinylformic acid is joined in the solution that is made into by 47gNaOH and 250g water, under cooling conditions, stir, neutralization, making its degree of neutralization is 80%.Add 4gN then successively, mixed molecular sieve MSU-1, the MCM-22 of N-methylene-bisacrylamide and 3g and SBA-1 (mass ratio MSU-1: MCM-22: SBA-1=1: 1: 2) stirred 2 hours, and the refrigerator and cooled that is placed on-10 ℃ was then frozen 12 hours.Take out reaction solution, it is transferred in the radiant bottles, chamber, the rearmounted cobalt source of logical N2 deoxygenation 20min.Under the room temperature, under the 10Kgy/min dose rate, carried out radiation copolymerization 8 hours.Take out the irradiation bottle after polymerization is finished, with the jelly chopping, 50 ℃ of vacuum-drying 36 hours is pulverized, the finished product.Its water-intake rate can reach 800g/g, and gel-strength can reach 2100N/kg.
Embodiment 12 radiation synthesis terpolymer high-intensity water absorbent resins
Get vinylformic acid and be made into 40% (mass percent) aqueous solution.With 30%NaOH (quality) under frozen water cooling slowly in and vinylformic acid to degree of neutralization 80%, adjust acrylic acid concentration with distilled water, be made into 36% part neutral acrylic acid aqueous solution.With in 36% part and acrylic acid aqueous solution and 45% acrylamide solution, 2-methylacryoyloxyethyl trimethyl ammonium chloride, the SBA-16 molecular sieve (aperture 60nm) and the deionized water that account for (vinylformic acid+acrylamide) gross weight 9% mix (quality is than vinylformic acid: acrylamide: 2-methylacryoyloxyethyl trimethyl ammonium chloride: mixing SBA-16=50: 50: 2: 9), fully stir reaction mixture.Its refrigerator and cooled in-5 ℃ was frozen 12 hours.Take out reaction solution, chamber, the rearmounted cobalt source of logical N2 deoxygenation.Under the room temperature, under the 80Kgy/min dose rate, carried out radiation copolymerization 2 hours.Take out the irradiation bottle after polymerization is finished, with the product chopping, 60 ℃ of vacuum-drying 24 hours is pulverized, the finished product.Its water-intake rate can reach 3200g/g, and gel-strength can reach 3000N/kg.
Embodiment 13 polyvinyl alcohol graft copolymerized vinylformic acid radio polymerization synthesizing high-strength water-absorbing resins
Polyvinyl alcohol is dissolved in 90 ℃ hot water, be cooled to room temperature, add sodium acrylate and vinylformic acid, N hydroxymethyl acrylamide and account for the Ti/MCM-48 molecular sieve of polyvinyl alcohol gross weight 8% (quality is than polyvinyl alcohol: sodium acrylate: vinylformic acid: N hydroxymethyl acrylamide: Ti/MCM-48=40: 20: 40: 0.8: 8), fully stir reaction mixture, it was placed 24 hours in 20 ℃.Take out reaction solution, chamber, the rearmounted cobalt source of logical N2 deoxygenation.Under the room temperature, under the 60Kgy/min dose rate, carry out radio polymerization graft copolymerization 4 hours.After finishing, polymerization takes out the irradiation bottle, with the methyl alcohol-aqueous hydrolysis of product with NaOH.Take out product, 120 ℃ of vacuum-drying 10 hours is pulverized, the finished product.Its water-intake rate can reach 2400g/g, and gel-strength can reach 2800N/kg.
By embodiment as seen, because the adding of crystal type molecular sieve, thereby make the performance of prepared super absorbent resin obtain very big improvement, especially its gel-strength is improved greatly.
Claims (10)
1, a kind of preparation method of high-intensity water absorbent material is characterized in that comprising the steps:
(1) outfit of reaction mixture: raw material, initiator, linking agent, molecular sieve are mixed in deionized water by mass ratio 100: 0.05～3: 0.05～5: 0.1～10, placed 0～72 hour, and obtained reaction mixture for 30 ℃～-20 ℃;
(2) polymerization: the reaction mixture that step (1) is obtained places the reactor of being with condenser, logical or obstructed nitrogen, 60 ℃～80 ℃ stirring reactions of constant temperature 2～8 hours;
(3) separate to clean: the reaction product that step (2) is obtained with/or without the neutralization of NaOH solution, then 90～95 ℃ of constant temperature 1～2 hour; Thinly slice, put into deionized water and soaked 3～12 hours, washing; With methyl alcohol the product after washing is dewatered, use the methyl alcohol in the dehydrated alcohol flush away dehydrate then;
(4) dry, pulverize: the dehydrate that step (3) is obtained is dry or dry to constant weight, pulverizes, and sieves;
Described raw material is starch, Mierocrystalline cellulose or protein or/and one or more mixture in the vinyl cyanide, vinylformic acid, acrylamide, MALEIC ANHYDRIDE, acrylate, polyvinyl alcohol; Described initiator is peroxide initiator, azo-initiator or redox initiator; Described linking agent is meant and contains two or more organic compound in the two keys of activity functional groups, hydroxyl, amino, imino-, carboxyl, the epoxy; Described molecular sieve is meant MCM series molecular sieve, SBA-n series molecular sieve, MSU-X series molecular sieve, APMs molecular sieve or crystal type molecular sieve.
2, the preparation method of high-intensity water absorbent material according to claim 1, the following condition that is aggregated in that it is characterized in that step (2) is carried out: by monomer: the mass ratio of dispersion agent=100: 1～6 is dissolved in oil phase with dispersion agent: water=1～5: in oil phase/aqueous media of 1, stir and logical nitrogen, add the reaction mixture that step (1) obtains, the constant temperature stirring reaction is 2～8 hours under 60 ℃～80 ℃ temperature; Step (3) is separated when cleaning, and topples over oil-phase medium, takes out reaction product, thinly slices, and puts into anhydrous methanol and soaks 3～12 hours, cleans 2～3 times with dehydrated alcohol again;
Described dispersion agent is a tensio-active agent; Used oil-phase medium is the mixture of arene, alkanes, sherwood oil or sherwood oil and hexanaphthene.
3, the preparation method of high-intensity water absorbent material according to claim 2 is characterized in that described tensio-active agent is Span80, Span85, Span60, Span40, Span20, Tween80, Tween60, hexadecyl phosphate monoester, octadecyl phosphate monoester, polyoxyethylene nonylphenol or Triethylene glycol.
4, the preparation method of high-intensity water absorbent material according to claim 2 is characterized in that described arene oil-phase medium is benzene, toluene or dimethylbenzene; Described alkanes oil-phase medium is normal hexane, hexanaphthene, heptane, octane-iso or isomery paraffinic hydrocarbon.
5, the preparation method of high-intensity water absorbent material according to claim 1, the following condition that is aggregated in that it is characterized in that step (2) is carried out: the reaction mixture that step (1) is obtained when not adding initiator places the irradiation bottle, letting nitrogen in and deoxidizing is placed on chamber, cobalt source, carries out radiation copolymerization 2～8 hours under the dose rate of 10Kgy/min～80Kgy/min; Step (3) is direct cooling, takes out reaction product from the irradiation bottle.
6,, it is characterized in that described starch is native starch wheat starch, W-Gum, Starch rice, yam starch, sweet potato starch or their resolvent, derivative or Alpha-starch or separating starch or physical treatment starch according to the preparation method of claim 1 or 2 or 5 described high-intensity water absorbent materials; Described Mierocrystalline cellulose is natural cellulose gossypin, wood-cellulose, straw fiber element or flaxen fiber element or cellulosic derivative cellulose acetate, methoxyl group Mierocrystalline cellulose, carboxymethyl cellulose, carboxyethyl cellulose, Natvosol, hydroxypropylcellulose, cellulose xanthate or hydroscopic cellulose derivative; Described protein is plant protein or animal protein.
7,, it is characterized in that described peroxide initiator is benzoyl peroxide, hydrogen peroxide, ammonium persulphate or Potassium Persulphate according to the preparation method of claim 1 or 2 or 5 described high-intensity water absorbent materials; Described azo-initiator is Diisopropyl azodicarboxylate or 2,2'-Azobis(2,4-dimethylvaleronitrile) etc.; Described redox initiator is hydrogen peroxide-ferrous sulfate, ammonium persulphate-sodium bisulfite or Potassium Persulphate-Sulfothiorine.
8,, it is characterized in that described initiator is ceric ammonium nitrate, iron trichloride or pentavalent vanadic salts according to the preparation method of claim 1 or 2 or 5 described high-intensity water absorbent materials.
9, according to the preparation method of claim 1 or 2 or 5 described high-intensity water absorbent materials, it is characterized in that described linking agent is ethylene glycol, glycerol, TriMethylolPropane(TMP), N, N-dimethyl bisacrylamide, glycerine allyl ether etc., N hydroxymethyl acrylamide, glycidyl methacrylate, glycidyl acrylate, quadrol, oxalic acid, phthalic acid, divinylbenzene or biethenyl-xylene.
10, according to the preparation method of claim 1 or 2 or 5 described high-intensity water absorbent materials, it is characterized in that described MCM series molecular sieve is MCM-41, MCM-48, MCM-49, MCM-22, MCM-50 or MCM-56, described SBA-n series molecular sieve is SBA-1, SBA-2, SBA-3, SBA-6, SBA-11, SBA-12, SBA-15 or SBA-16, and the aperture of described crystal type molecular sieve is the pure silicon molecular sieve of micropore, mesopore or macropore or the silica-based molecular sieve that is doped with one or more elements among Al, Fe, Mn, Zn, Cu, V, Ti, Mo, the P.
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