CN1587289A - Process for preparing high water absorption resin - Google Patents
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- CN1587289A CN1587289A CNA2004100527637A CN200410052763A CN1587289A CN 1587289 A CN1587289 A CN 1587289A CN A2004100527637 A CNA2004100527637 A CN A2004100527637A CN 200410052763 A CN200410052763 A CN 200410052763A CN 1587289 A CN1587289 A CN 1587289A
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Abstract
The preparation process of high water absorption resin includes following steps: neutralizing acrylic acid monomer with alkali solution to 60-90 % neutralizing degree, adding functional monomer in 0.5-50 % of total monomer weight, water soluble initiator or oxidation-reduction system in 0.05-0.5 % and water soluble cross-linking agent in 0.005-0.2 %; feeding the said mixed liquid into reactor, adding non-polar organic solvent in 2-10 times the volume of the mixed liquid and containing non-ionic surfactant, stirring to form inverse suspended polymerizing system; heating to 35-80 deg.c for free radical cross-linking copolymerization while adding oil soluble cross-linking agent in 0.005-0.3 % total monomer weight; dewatering after finishing polymerization, separation and drying to obtain the high water absorption resin. The obtained polyacrylate resin has the advantages of powerful water absorption, high salt tolerance, high gel strength and fast water absorption speed.
Description
Technical field
The present invention relates to a kind of preparation method of High hydrophilous resin, relate in particular to vinylformic acid, acrylate and at least a functional monomer, under water-soluble/oil soluble multiple crosslinking agent effect, prepare High hydrophilous resin by inverse suspension polymerization.The invention belongs to technical field of chemical engineering.
Background technology
Super absorbent resin is meant that water regain is tens times and even a family macromolecule material of several thousand times of deadweight.It the earliest by the Fanta of USDA north institute etc. by pasted starch and acrylonitrile graft copolymer development are obtained.1975, the Sanyo company of changing into of Japan succeeded in developing starch-polyacrylic acid graft copolymer High hydrophilous resin, and in beginning suitability for industrialized production in 1978, was world-famous for the commodity of trade mark Sannet IM-300.Afterwards, the Sumitomo of the Hercules company of the U.S., National Starch company, Japan, flower Wang Shi alkali, catalyst chemical company also succeed in developing various types of High hydrophilous resins in succession.At present, its world is about 900,000 tons/year to the aggregate demand of super absorbent resin entirely, and the trend that increases is year by year arranged.About 10,000 tons/year of the throughput of present domestic High hydrophilous resin, actual output is about 5000 tons/year, and consumption is about 20,000 tons/year, the therefore annual a large amount of foreign exchange import High hydrophilous resins, especially high-grade High hydrophilous resin of all need spending.
High hydrophilous resin obtains application widely in fields such as physiological hygiene articles for use, agricultural gardening, daily-use chemical industry, fresh keeping product, foodstuffs industry, building trade, medical material, textiless.The physiological hygiene articles for use are that super absorbent resin also is maximum Application Areas the earliest.High hydrophilous resin is at the modifying agent and the water-holding agent that can be used as soil aspect agricultural, the gardening, especially at arid area effect highly significant.Aspect building, High hydrophilous resin is a kind of efficient construction water-absorbing material, water stop sealing material.Aspect weaving, can be used for making anti-undershirt, Sweat-proof shoes pad etc.Aspect food-processing, super absorbent resin can be used as refrigerant and Perserving materials etc.In addition, super absorbent resin also is widely used in every field such as artificial intelligence, daily-use chemical industry, electronic material and coating, printing and recording materials, fibre technology, fire-fighting.Along with science and technology development, its application will be more and more wider.
But, the rate of water absorption of common High hydrophilous resin is slow, can improve its rate of water absorption though reduce the water-absorbing resin particle diameter, but when the resin particle diameter too hour, meticulous particle can not disperse in water well, forms " son " as dough/pasta easily, and outside surface is water-swelling, the inside or anhydrous powder make water-intake rate descend on the contrary.In addition, because the gel-strength of water-absorbing resin suction back formation is lower, easily broken or distortion during use, thus cause the liquid retention characteristic of these articles for use to reduce and the increase of fluid seepage amount, limited its application.Increase content of crosslinking agent, can improve the cross-linking density of gel network, increase gel-strength, rate of water absorption also increases, but the corresponding decline of water absorbent rate.Therefore, it is very necessary to develop the water-absorbing resin that a kind of water-intake rate height, rate of water absorption are fast, suction back gel-strength is high.Domestic patent (publication number 1165152A) once disclosed a kind of synthetic method of crosslinked salt polyacrylate class High hydrophilous resin, and improved its application performance by chemical conversion treatment.Concrete grammar is to adopt Acrylic Acid Monomer and at least a functional monomer to close reaction through aqueous solution copolymerization, reaction finishes the back and carries out chemical conversion treatment with water-soluble surface crosslinking agent and the formulated mixing solutions of small molecules organic solvent, thereby obtains the water-absorbing resin of improved performance.But this technology polymerization middle and later periods system viscosity height conduct heat to stir difficulty, and rate of polymerization is low, causes that the molecular resin amount is low, intensity is little, water-intake rate is low, and product pulverizes and the aftertreatment complexity, is unfavorable for large-scale commercial production.
Summary of the invention
The preparation method of the High hydrophilous resin that the purpose of this invention is to provide a kind of technological operation resin simple, preparation and have that water-retaining capacity is strong, absorption speed fast, gel-strength is high after the good salt tolerance, suction.
Its method steps is as follows:
1) Acrylic Acid Monomer is neutralized to 60～90% degree of neutralization with alkaline solution after, add the functional monomer account for monomer total mass 0.5～50%, the water soluble starter of monomer total mass 0.05～0.5% or the water-soluble cross-linker of oxidation-reduction system and relative monomer total mass 0.005～0.2% relatively;
2) above mixed solution is joined in the reactor, to add volume simultaneously be 2～10 times of above mixed solutions, contain the non-polar organic solvent of nonionic surface active agent, stirs and form the inverse suspension polymerization system; Be warming up to 35～80 ℃ and carry out the radical crosslinking copolyreaction, carry out in the process adding the oil soluble linking agent of relative monomer total mass 0.005～0.3% in reaction; Polymerization obtains High hydrophilous resin through dehydration, separation, drying after finishing.Advantage of the present invention is:
(1) because synthetic water-absorbing resin of the present invention, surface-crosslinked density is higher, but its internal crosslinking density do not enlarge markedly, and in water absorption course, inner colloidal sol is difficult for overflowing, and water-intake rate is improved;
(2) because synthetic water-absorbing resin of the present invention has formed certain cross-linking density gradient " outer hard interior soft " structure, avoided " dough " effect in the common water-absorbing resin water absorption course effectively, so rate of water absorption improves greatly;
(3) because the structure of " outer hard in soft " that the synthetic water-absorbing resin exists, the back gel-strength that causes absorbing water strengthens greatly;
(4) because the present invention has inserted second functional monomer, and the surface formed one deck by the crosslinked upper layer of hydrophobicity linking agent, so synthetic resin salt tolerance is improved;
(5) the present invention adopts inverse suspension method, and this technology has overcome aqueous solution polymerization middle and later periods system viscosity height, conducts heat to stir difficulty, rate of polymerization is low, and product is pulverized and the shortcoming of aftertreatment complexity, helps improving the molecular weight of resin, and the control easily of particle form size has promotion prospect very much.
Embodiment
For suction, salt tolerant and the gel-strength that improves polyacrylate type high water absorption resin, the present invention adopts water-soluble/oil soluble linking agent to carry out the composite crosslinking copolymerization with vinylformic acid, alkali metal salts of acrylic acids and other at least a functional monomer monomer as the preparation High hydrophilous resin.Acrylic acid concentration is 10～45% (weight) in the above-mentioned reaction system, and the vinylformic acid degree of neutralization is 60～90%.Neutralizing agent adopts sodium hydroxide, yellow soda ash, potassium hydroxide and sodium bicarbonate.Another functional monomer is selected from Methacrylamide, acrylamide, methyl acrylate, ethyl propenoate, Hydroxyethyl acrylate, Propylene glycol monoacrylate, fumaric acid, methacrylic acid, methylene-succinic acid, toxilic acid (acid anhydride), the above-mentioned functions monomer heavily contains 0.5～50% (weight) at per 100 parts of heavy water-absorbing resins.
In the technology of above-mentioned synthesizing super absorbent resin, used linking agent comprises two kinds of water-soluble and oil solubles.Water-soluble cross-linker is selected from poly-hydroxy alcohols, polynary aldehydes, polynary amine, bisacrylamide class; The oil soluble linking agent is selected from Vinylstyrene, glycol methacrylate, ethylene glycol diacrylate, contract glycol ether double methyl methacrylate, polyoxyethylene glycol double methyl methacrylate, polyoxyethylene glycol double methacrylate, glycerol diacrylate, glycidyl methacrylate, 1, ammediol double methacrylate.The consumption of linking agent has remarkable influence to the water-intake rate of water-absorbing resin.When dosage of crosslinking agent was very few, polymkeric substance failed to form three-dimensional net structure, show as on the macroscopic view water-soluble, so water-intake rate is not high; When dosage of crosslinking agent was too high, the cross-linking set in the polymer network structure increased, and the network chain between the cross-linking set shortens, micropore in the network structure diminishes, make the cyberspace of resin diminish, therefore the amount of liquid that can hold also reduces, so the water-intake rate of polymkeric substance descends.For this polymerization reaction system, the suitable consumption of water-soluble cross-linker is 0.005～0.2% (weight) of monomer consumption, and the suitable consumption of oil soluble linking agent is 0.005～0.3% (weight) of monomer consumption.
The present invention passes through inverse suspension polymerization, add water-soluble cross-linker at aqueous phase respectively, add the oil soluble linking agent in the oil phase, water-soluble cross-linker is at the polymkeric substance internal crosslinking, and the oil soluble linking agent is because its hydrophobic nature is difficult for entering gel inside, thereby carry out crosslinking reaction at polymer surfaces, form the gel of higher " the outer hard interior soft " structure of surface-crosslinked density, reduce the gel blockage effect effectively, improve its rate of water absorption.Owing to formed higher " the outer hard interior soft " structure of surface-crosslinked density, under the situation that has guaranteed the high water absorbent rate of water-absorbing resin, improved gel-strength greatly, thereby made water-absorbing resin after suction, have higher gel stability simultaneously.
In above-mentioned inverse suspension polymerization, used initiator comprises Potassium Persulphate, ammonium persulphate, Sodium Persulfate or oxidation-reduction trigger system, its oxygenant is selected from: hydrogen peroxide, persulphate, hydroperoxide, reductive agent is selected from: ferrous salt, cuprous salt, sodium bisulfite, S-WAT and Sulfothiorine.The consumption of initiator has tangible influence to the water-intake rate of water-absorbing resin, because its consumption directly has influence on polymerization rate, thereby is related to the molecular weight and the cross-linking density of polymkeric substance.The suitable consumption of initiator is 0.05～0.5% (weight) of monomer consumption.
In above-mentioned crosslinking copolymerization reaction process, polymerization temperature is controlled at 35～80 ℃, and polymerization reaction time is 0.5～4 hour.
Reaction is carried out azeotropic water removing after finishing.The azeotropic temperature scope is 70～90 ℃, and water removal should be above 75% of water-content in the reaction system.Product is through vacuum-drying, and drying temperature is 60～100 ℃.
By the water-absorbing resin that aforesaid method makes, adopt the tea bag weighting method to measure its water absorbent rate and rate of water absorption.Water absorbent rate calculates with following formula:
Rate of water absorption is the rate of water absorption index with leaving standstill 10 minutes water absorbent rate A (10) and 60 minutes likening to of water absorbent rate A (60), i.e. A (10)/A (60).
Gel-strength is then represented with the gel elastomer modulus after the suction.Adopt Zwick/RoellZ202 universal material experimental machine (Germany produces) to measure.
Describe the present invention in detail below in conjunction with embodiment:
Embodiment 1
Take by weighing the 5.785g sodium hydroxid, be dissolved in 40 ml deionized water, be cooled to room temperature.Measure 13.5 milliliters of vinylformic acid (through rectification under vacuum) in the beaker, under stirring aqueous sodium hydroxide solution is slowly introduced vinylformic acid and carry out neutralization reaction, the cooling back adds 2.415g second monomer Methacrylamide and 0.006g 1, and the ammediol linking agent is stirred to dissolving fully.
0.8g department class 80 and 0.4g polysorbas20 are had in 500 milliliters of 4 mouthfuls of jacket reactors of thermometer with the adding of 130 ml n-hexanes, stirring and dissolving under the room temperature, then add above-mentioned monomer solution and initiator dicumyl peroxide 0.09g, in reactor, add 0.006g polyoxyethylene glycol double methyl methacrylate simultaneously, logical nitrogen deoxygenation, be warming up to 50 ℃ after cold the stirring, reacted 2 hours.Reaction finishes back 80 ℃ of azeotropic water removings.
Dewatering finishes, and obtains the thin bead-like resin of white through methanol extraction and filtration.Promptly get product after the vacuum-drying.Measure its water absorbent rate respectively, absorb the ability of 0.9% physiological saline, uptake rate and gel-strength.The results are shown in subordinate list.
Embodiment 2
Take by weighing 4.235g sodium hydroxide, be dissolved in 30 ml deionized water, be cooled to room temperature.Measure 12.1 milliliters of vinylformic acid (through rectification under vacuum) in the beaker, under stirring aqueous sodium hydroxide solution is slowly introduced vinylformic acid and carry out neutralization reaction, the cooling back adds the 1.625g second monomer methyl acrylate and 0.004g 1-ethyl-3-[3-(dimethylamino) propyl group] carbodiimide, be stirred to dissolving fully.
65 and 170 milliliters of hexanaphthenes addings of class of 0.8g dispersion agent department are had in 500 milliliters of 4 mouthfuls of jacket reactors of thermometer, stirring and dissolving under the room temperature, then add above-mentioned monomer solution and initiator potassium persulfate 0.05g, and adding 0.004g glycol methacrylate, logical nitrogen deoxygenation, be warming up to 65 ℃ after cold the stirring, reacted 0.5 hour.Reaction finishes back 90 ℃ of following azeotropic water removings.
Dewatering finishes, and obtains the thin bead-like resin of white through methanol extraction and filtration.Promptly get product after the vacuum-drying.Measure its water absorbent rate respectively, absorb the ability of 0.9% physiological saline, uptake rate and gel-strength.The results are shown in subordinate list.
Embodiment 3
Take by weighing 7.398g potassium hydroxide, be dissolved in 30 ml deionized water, be cooled to room temperature.Measure 12.5 milliliters of vinylformic acid (through rectification under vacuum), under stirring potassium hydroxide aqueous solution is slowly introduced vinylformic acid and carry out neutralization reaction, the cooling back adds 0.075g second monomer methacrylic acid and 0.004g glutaraldehyde, is stirred to dissolving fully.
60 and 170 milliliters of toluene addings of class of 0.8g dispersion agent department are had in 500 milliliters of 4 mouthfuls of jacket reactors of thermometer, stirring and dissolving under the room temperature, then add above-mentioned monomer solution and initiator ammonium persulfate 0.05g, logical nitrogen deoxygenation, be warming up to 65 ℃ after cold the stirring, reacted 1 hour, and in reactor, added the 0.054g ethylene glycol diacrylate, continue reaction 1 hour.Reaction finishes back 85 ℃ of following azeotropic water removings.
Dewatering finishes, and obtains the thin bead-like resin of white through methanol extraction and filtration.Promptly get product after the vacuum-drying.Measure its water absorbent rate respectively, absorb the ability of 0.9% physiological saline, uptake rate and gel-strength.The results are shown in subordinate list.
Embodiment 4
Take by weighing 7.001g yellow soda ash, be dissolved in 30 ml deionized water, be cooled to room temperature.Measure 12.1 milliliters of vinylformic acid (through rectification under vacuum) in the beaker, under stirring aqueous sodium carbonate is slowly introduced vinylformic acid and carry out neutralization reaction, the cooling back adds 10.575g second monomer ethyl propenoate and 0.036g methylene-bisacrylamide, is stirred to dissolving fully.
Class 60 of 0.8g dispersion agent department is had in 500 milliliters of 4 mouthfuls of jacket reactors of thermometer with polysorbate40 and 80 milliliters of hexanaphthenes addings, stirring and dissolving under the room temperature, then add above-mentioned monomer solution and initiator Sodium Persulfate 0.05g, logical nitrogen deoxygenation, be warming up to 60 ℃ after cold the stirring, reacted 3 hours, and in reactor, added the 0.01g one glycol ether double methyl methacrylate that contracts, continue reaction 1 hour.Reaction finishes the back azeotropic water removing.
Dewatering finishes, and obtains the thin bead-like resin of white through methanol extraction and filtration.Promptly get product after the vacuum-drying.Measure its water absorbent rate respectively, absorb the ability of 0.9% physiological saline, uptake rate and gel-strength.The results are shown in subordinate list.
Embodiment 5
Take by weighing 5.284g sodium hydroxide, be dissolved in 30 ml deionized water, be cooled to room temperature.Measure 12.1 milliliters of vinylformic acid (through rectification under vacuum) in the beaker, under stirring aqueous sodium hydroxide solution is slowly introduced vinylformic acid and carry out neutralization reaction, the cooling back adds 2.412g second monomer acrylamide (recrystallization purification) and 0.006g methylene-bisacrylamide, is stirred to dissolving fully.
60 and 150 milliliters of hexanaphthenes addings of class of 1.0g dispersion agent department are had in 500 milliliters of 4 mouthfuls of jacket reactors of thermometer, stirring and dissolving under the room temperature, then add above-mentioned monomer solution and initiator potassium persulfate 0.05g, logical nitrogen deoxygenation, be warming up to 60 ℃ after cold the stirring, reacted 3 hours, and in reactor, added the 0.0054g Vinylstyrene, continue reaction 1 hour.After reaction finishes, 75 ℃ of following azeotropic water removings.
Dewatering finishes, and filters through methanol extraction and obtains the thin bead-like resin of white.Promptly get product after the vacuum-drying.Measure its water absorbent rate respectively, absorb the ability of 0.9% physiological saline, uptake rate and gel-strength.The results are shown in subordinate list.
Embodiment 6
Take by weighing 1.974g potassium hydroxide, be dissolved in 40 ml deionized water, be cooled to room temperature.Measure 3.075 milliliters of vinylformic acid (through rectification under vacuum) in the beaker, under stirring potassium hydroxide aqueous solution is slowly introduced vinylformic acid and carry out neutralization reaction, the cooling back adds 0.875g second monomer Hydroxyethyl acrylate and 0.004g suceinic aldehyde, is stirred to dissolving fully.
Class 20 of 0.4g dispersion agent department is had in 500 milliliters of 4 mouthfuls of jacket reactors of thermometer with 0.2g polysorbate60 and 130 milliliters of o-Xylols addings, stirring and dissolving under the room temperature, then add above-mentioned monomer solution and initiator ammonium persulfate 0.01g, logical nitrogen deoxygenation, be warming up to 65 ℃ after cold the stirring, reacted 0.5 hour, and in reactor, added the 0.009g glycol methacrylate, continue reaction 1 hour.Reaction finishes back 80 ℃ of following azeotropic water removings.
Dewatering finishes, and obtains white resin through methanol extraction and filtration.Promptly get product after the vacuum-drying.Measure its water absorbent rate respectively, absorb the ability of 0.9% physiological saline, uptake rate and gel-strength.The results are shown in subordinate list.
Embodiment 7
Take by weighing 5.647g sodium hydroxide, be dissolved in 40 ml deionized water, be cooled to room temperature.Measure 12.1 milliliters of vinylformic acid (through rectification under vacuum), under stirring aqueous sodium hydroxide solution is slowly introduced vinylformic acid and carry out neutralization reaction, the cooling back adds 2.412g second monomer Propylene glycol monoacrylate and linking agent 0.008g ethylene glycol, is stirred to dissolving fully.
0.6g dispersion agent department class 40 and 0.25g polysorbas20 are had in 500 milliliters of 4 mouthfuls of jacket reactors of thermometer with 150 milliliters of addings of raffinating oil, stirring and dissolving under the room temperature, then add above-mentioned monomer solution and initiator Sodium Persulfate 0.06g, logical nitrogen deoxygenation, be warming up to 60 ℃ after cold the stirring, reacted 1 hour, and in reactor, added 0.024g polyoxyethylene glycol double methacrylate, continue reaction 2 hours.After reaction finishes, 85 ℃ of following azeotropic water removings.
Dewatering finishes, and filters through methanol extraction and obtains the thin bead-like resin of white.Promptly get product after the vacuum-drying.Measure its water absorbent rate respectively, absorb the ability of 0.9% physiological saline, uptake rate and gel-strength.The results are shown in subordinate list.
Embodiment 8
Take by weighing the 5.55g sodium bicarbonate, be dissolved in 16 ml deionized water, be cooled to room temperature.Measure 6.75 milliliters of vinylformic acid (through rectification under vacuum) in the beaker, under stirring sodium bicarbonate aqueous solution is slowly introduced vinylformic acid and carry out neutralization reaction, the cooling back adds 1.662g second monomer methyl acrylate and 0.003g methylene-bisacrylamide, is stirred to dissolving fully.
Class 80 of 0.5g dispersion agent department is had in 500 milliliters of 4 mouthfuls of jacket reactors of thermometer with 0.2g polysorbate65 and the adding of 225 ml n-hexanes, stirring and dissolving under the room temperature, then add above-mentioned monomer solution and initiator ammonium persulfate 0.009g, logical nitrogen deoxygenation, be warming up to 80 ℃ after cold the stirring, reacted 2 hours, and in reactor, added 0.008g polyoxyethylene glycol double methacrylate, continue reaction 1 hour.Reaction finishes the back azeotropic water removing.
Dewatering finishes, and obtains thin bead-like resin through methanol extraction and filtration.Promptly get product after the vacuum-drying.Measure its water absorbent rate respectively, absorb the ability of 0.9% physiological saline, uptake rate and gel-strength.The results are shown in subordinate list.
Embodiment 9
Take by weighing 5.284g sodium hydroxide, be dissolved in 30 ml deionized water, be cooled to room temperature.Measure 12.1 milliliters of vinylformic acid (through rectification under vacuum) in the beaker, under stirring aqueous sodium hydroxide solution is slowly introduced vinylformic acid and carry out neutralization reaction, the cooling back adds 15.1g second monomer fumaric acid and 0.004g methylene-bisacrylamide, is stirred to dissolving fully.
60 and the 170 ml n-hexanes adding of class of 0.8g dispersion agent department is had in 500 milliliters of 4 mouthfuls of jacket reactors of thermometer, stirring and dissolving under the room temperature, then add above-mentioned monomer solution and initiator ammonium persulfate 0.08g, logical nitrogen deoxygenation, be warming up to 60 ℃ after cold the stirring, reacted 3 hours, and in reactor, added the 0.018g glycidyl methacrylate, continue reaction 1 hour.Reaction finishes the back azeotropic water removing.
Dewatering finishes, and obtains the thin bead-like resin of white through methanol extraction and filtration.Promptly get product after the vacuum-drying.Measure its water absorbent rate respectively, absorb the ability of 0.9% physiological saline, uptake rate and gel-strength.The results are shown in subordinate list.
Embodiment 10
Take by weighing 7.398g potassium hydroxide, be dissolved in 30 ml deionized water, be cooled to room temperature.Measure 12.5 milliliters of vinylformic acid (through rectification under vacuum) in the beaker, under stirring potassium hydroxide aqueous solution is slowly introduced vinylformic acid and carry out neutralization reaction, the cooling back adds 0.825g second monomer methylene-succinic acid and 0.008g methylene-bisacrylamide, is stirred to dissolving fully.
60 and 250 milliliters of normal heptanes addings of class of 0.8g dispersion agent department are had in 500 milliliters of 4 mouthfuls of jacket reactors of thermometer, stirring and dissolving under the room temperature, then add above-mentioned monomer solution and initiator ammonium persulfate 0.05g, logical nitrogen deoxygenation, be warming up to 65 ℃ after cold the stirring, reacted 1.5 hours, and in reactor, added 0.03g glycerol diacrylate, continue reaction 1 hour.Reaction finishes the back azeotropic water removing.
Dewatering finishes, and obtains the thin bead-like resin of white through methanol extraction and filtration.Promptly get product after the vacuum-drying.Measure its water absorbent rate respectively, absorb the ability of 0.9% physiological saline, uptake rate and gel-strength.The results are shown in subordinate list.
Embodiment 11
Take by weighing 5.2841g sodium hydroxide, be dissolved in 30 ml deionized water, be cooled to room temperature.Measure 12.1 milliliters of vinylformic acid (through rectification under vacuum), under stirring aqueous sodium hydroxide solution is slowly introduced vinylformic acid and carry out neutralization reaction, the cooling back adds 10.625g second monomer toxilic acid and 0.0009g methylene-bisacrylamide, is stirred to dissolving fully.
80 and 130 milliliters of hexanaphthenes addings of class of 0.8g dispersion agent department are had in 500 milliliters of 4 mouthfuls of jacket reactors of thermometer, stirring and dissolving under the room temperature, then add above-mentioned monomer solution and oxidation-reduction initiator ammonium persulphate 0.05g and sodium bisulfite 0.002g, logical nitrogen deoxygenation, be warming up to 40 ℃ after cold the stirring, reacted 2 hours, in reactor, add 0.012g 1, the ammediol double methacrylate continues reaction 1 hour.Reaction finishes the back azeotropic water removing.
Dewatering finishes, and obtains the thin bead-like resin of white through methanol extraction and filtration.Promptly get product after the vacuum-drying.Measure its water absorbent rate respectively, absorb the ability of 0.9% physiological saline, uptake rate and gel-strength.The results are shown in subordinate list.
Embodiment 12
Take by weighing 7.398g potassium hydroxide, be dissolved in 30 ml deionized water, be cooled to room temperature.Measure 12.5 milliliters of vinylformic acid (through rectification under vacuum) in the beaker, under stirring potassium hydroxide aqueous solution is slowly introduced vinylformic acid and carry out neutralization reaction, the cooling back adds 1.625g second monomer maleic anhydride and 0.01g methylene-bisacrylamide, is stirred to dissolving fully.
Class 60 of 0.8g dispersion agent department is had in 500 milliliters of 4 mouthfuls of jacket reactors of thermometer with 0.1g polysorbate40 and the adding of 150 ml n-hexanes, stirring and dissolving under the room temperature, then add above-mentioned monomer solution and initiator benzoyl peroxide 0.009g, logical nitrogen deoxygenation, be warming up to 75 ℃ after cold the stirring, reacted 3 hours, and in reactor, added the 0.0009g Vinylstyrene, continue reaction 0.5 hour.Reaction finishes the back azeotropic water removing.
Dewatering finishes, and obtains the thin bead-like resin of white through methanol extraction and filtration.Promptly get product after the vacuum-drying.Measure its water absorbent rate respectively, absorb the ability of 0.9% physiological saline, uptake rate and gel-strength.The results are shown in subordinate list.
Embodiment 13
Take by weighing 5.284g sodium hydroxide, be dissolved in 30 ml deionized water, be cooled to room temperature.Measure 12.1 milliliters of vinylformic acid (through rectification under vacuum), under stirring aqueous sodium hydroxide solution is slowly introduced vinylformic acid and carry out neutralization reaction, the cooling back adds 0.175g second monomer ethyl propenoate and the 0.008g1, and ammediol is stirred to dissolving fully.
60 and 170 milliliters of kerosene addings of class of 0.8g dispersion agent department are had in 500 milliliters of 4 mouthfuls of jacket reactors of thermometer, stirring and dissolving under the room temperature, then add above-mentioned monomer solution and oxidation-reduction initiator ammonium persulphate 0.01g and iron protochloride 0.002g, logical nitrogen deoxygenation, be warming up to 45 ℃ after cold the stirring, reacted 1 hour, and in reactor, added the 0.036g ethylene glycol diacrylate, continue reaction 1 hour.Reaction finishes back 85 ℃ of following azeotropic water removings.
Dewatering finishes, and obtains the thin bead-like resin of white through methanol extraction and filtration.Promptly get product after the vacuum-drying.Measure its water absorbent rate respectively, absorb the ability of 0.9% physiological saline, uptake rate and gel-strength.The results are shown in subordinate list.
Embodiment 14
Take by weighing 3.258g potassium hydroxide, be dissolved in 30 ml deionized water, be cooled to room temperature.Measure 12.5 milliliters of vinylformic acid (through rectification under vacuum), under stirring potassium hydroxide aqueous solution is slowly introduced vinylformic acid and carry out neutralization reaction, the cooling back adds 0.175g second monomer methacrylic acid and 0.004g butyleneglycol, is stirred to dissolving fully.
60 and 130 milliliters of octane-iso addings of class of 1.1g dispersion agent department are had in 500 milliliters of 4 mouthfuls of jacket reactors of thermometer, stirring and dissolving under the room temperature, then add above-mentioned monomer solution and and oxidation-reduction initiator hydrogen peroxidase 10 .02g and cuprous chloride 0.004g, logical nitrogen deoxygenation, be warming up to 35 ℃ after cold the stirring, reacted 1 hour, and in reactor, added the 0.054g ethylene glycol diacrylate, continue reaction 1 hour.Reaction finishes back 85 ℃ of following azeotropic water removings.
Dewatering finishes, and obtains the thin bead-like resin of white through methanol extraction and filtration.Promptly get product after the vacuum-drying.Measure its water absorbent rate respectively, absorb the ability of 0.9% physiological saline, uptake rate and gel-strength.The results are shown in subordinate list.
Embodiment 15
Take by weighing 5.332g yellow soda ash, be dissolved in 30 ml deionized water, be cooled to room temperature.Measure 12.1 milliliters of vinylformic acid (through rectification under vacuum), under stirring the above-mentioned aqueous solution slowly introduced vinylformic acid and carry out neutralization reaction,
| Embodiment 5 | ????421 | ????67 | ????87 | ??4.5×10 4 |
| Embodiment 6 | ????405 | ????75 | ????79 | ??4.9×10 4 |
| Embodiment 7 | ????427 | ????80 | ????75 | ??5.4×10 4 |
| Embodiment 8 | ????375 | ????74 | ????85 | ??4.6×10 4 |
| Embodiment 9 | ????433 | ????78 | ????69 | ??4.3×10 4 |
| Embodiment 10 | ????416 | ????61 | ????65 | ??5.9×10 4 |
| Embodiment 11 | ????405 | ????71 | ????61 | ??4.1×10 4 |
| Embodiment 12 | ????384 | ????65 | ????71 | ??1.7×10 4 |
| Embodiment 13 | ????403 | ????69 | ????77 | ??3.7×10 4 |
| Embodiment 14 | ????421 | ????74 | ????72 | ??4.4×10 4 |
| Embodiment 15 | ????398 | ????62 | ????69 | ??2.9×10 4 |
| Embodiment 16 | ????401 | ????75 | ????81 | ??5.3×10 4 |
| Sample [annotating 5] | ????388 | ????47 | ????58 | ??0.95×10 4 |
[notes]:
1 water absorbent rate adopts the test of tea bag method.Absorbing medium is a deionized-distilled water.
2 salt resistant characters adopt the test of tea bag method.Absorbing medium is 0.9% salt solution for NaCl concentration.
3 rate of water absorption adopt the test of tea bag method.The employing sample leaves standstill 10 minutes water absorbent rate A (10) and 60 minutes likening to of water absorbent rate A (60) is the rate of water absorption index, i.e. A (10)/A (60).
4 gel-strengths are meant the Young's modulus of the gel after resin fully absorbs water.Adopt Zwick/RoellZ202 universal material experimental machine (Germany produces) to measure.
The similar sample that 5 Japanese catalyst chemical companies provide.
Claims (9)
1. the preparation method of a High hydrophilous resin is characterized in that, the step of method is:
1) Acrylic Acid Monomer is neutralized to 60～90% degree of neutralization with alkaline solution after, add the functional monomer account for monomer total mass 0.5～50%, the water soluble starter of monomer total mass 0.05～0.5% or the water-soluble cross-linker of oxidation-reduction system and relative monomer total mass 0.005～0.2% relatively;
2) above mixed solution is joined in the reactor, to add volume simultaneously be 2～10 times of above mixed solutions, contain the non-polar organic solvent of nonionic surface active agent, stirs and form the inverse suspension polymerization system; Be warming up to 35～80 ℃ and carry out the radical crosslinking copolyreaction, carry out in the process adding the oil soluble linking agent of relative monomer total mass 0.005～0.3% in reaction; Polymerization obtains High hydrophilous resin through dehydration, separation, drying after finishing.
2. the preparation method of a kind of High hydrophilous resin according to claim 1, it is characterized in that said functional monomer is Methacrylamide, acrylamide, methyl acrylate, ethyl propenoate, Hydroxyethyl acrylate, Propylene glycol monoacrylate, fumaric acid, methacrylic acid, methylene-succinic acid, toxilic acid, maleic anhydride or above two kinds of monomeric mixtures.
3. the preparation method of a kind of High hydrophilous resin according to claim 1 is characterized in that said water-soluble cross-linker is poly-hydroxy alcohols, polynary aldehydes, polynary amine or bisacrylamide class.
4. the preparation method of a kind of High hydrophilous resin according to claim 1, it is characterized in that said oil soluble linking agent is Vinylstyrene, glycol methacrylate, ethylene glycol diacrylate, contract glycol ether double methyl methacrylate, polyoxyethylene glycol double methyl methacrylate, polyoxyethylene glycol double methacrylate, glycerol diacrylate, glycidyl methacrylate or 1, the ammediol double methacrylate.
5. the preparation method of a kind of High hydrophilous resin according to claim 1 is characterized in that said water soluble starter is single Potassium Persulphate, ammonium persulphate, Sodium Persulfate or both mixtures.
6. the preparation method of a kind of High hydrophilous resin according to claim 1, it is characterized in that in said water soluble oxidized-reduction initiating system, oxygenant is: hydrogen peroxide, persulphate or hydroperoxide, reductive agent is: ferrous salt, cuprous salt, sodium bisulfite, S-WAT or Sulfothiorine.
7. the preparation method of a kind of High hydrophilous resin according to claim 1 is characterized in that said nonionogenic tenside is one or both the mixture in class of department 20, class of department 40, class of department 60, class of department 65, class of department 80, polysorbas20, polysorbate40, polysorbate60, the polysorbate65.
8. the preparation method of a kind of High hydrophilous resin according to claim 1 is characterized in that said non-polar organic solvent is hexanaphthene, normal hexane, normal heptane, toluene, o-Xylol, octane-iso, kerosene, diesel oil or raffinates oil.
9. the preparation method of a kind of High hydrophilous resin according to claim 1 is characterized in that said oil soluble linking agent added in polymerization conversion any moment in 0～90% scope.
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