CN1648137A - Method for producing high water absorptive resin by wave polymerization - Google Patents
Method for producing high water absorptive resin by wave polymerization Download PDFInfo
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- CN1648137A CN1648137A CN 200410101888 CN200410101888A CN1648137A CN 1648137 A CN1648137 A CN 1648137A CN 200410101888 CN200410101888 CN 200410101888 CN 200410101888 A CN200410101888 A CN 200410101888A CN 1648137 A CN1648137 A CN 1648137A
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Abstract
The present invention provides a kind of wave polymerization process of preparing high hydroscopicity resin. The wave polymerization process in water phase system includes: neutralizing acrylic acid with 25-30 wt% concentration sodium hydroxide solution to pH 6-7 at 0-10 deg.c; adding acrylamide, initiator, cross-linking agent, 2-acrylamide-2-methylpropyl sulfonic acid via stirring; pouring the mixture liquid into cylindrical reactor and heating to decompose the initiator to initiate reaction; eliminating heat source after initiating reaction and maintaining reaction with heat wave the polymerization produces until all the monomer is converted into polymer gel. The prepared resin has homogeneous structure and low cost, and may be used in producing sanitary towel, napkin, farm soil regulator, etc.
Description
Technical field
The invention belongs to the resins technical field, a kind of method of producing high water absorptive resin by wave polymerization particularly is provided, prepared resin can be used for producing sanitary towel, paper nappy and agricultural soil conditioning agent etc.
Background technology
Water-absorbing resin is widely used in the release control agent of personal hygiene article, water-loss reducer of soil, dewatering agent, sludge coagulating agent, thickening material, coagulation-prevention agent and various pharmaceutical chemicalss etc.At present the preparation method of water-absorbing resin mainly contains inverse suspension polymerization method and water solution polymerization process, and these two kinds of methods are existing the announcement in Japan, the U.S. and Chinese patent, as clear 57 (1982)-198,714, and US-4,286,082 and CN 1381507A.The inverse suspension polymerization method needs a large amount of organic solvents, and therefore the shortcoming of following is that organic solvent not only damages Working environment, and can be owing to flash distillation sets off an explosion.Simultaneously, the price of organic solvent itself is higher; The use of a large amount of organic solvents has also reduced concentration of reactants, and production efficiency is low; From product, remove residual organic matter expense costliness.These all make production cost greatly improve.Another shortcoming of inverse suspension polymerization method is that polymerization product is the minor diameter pearl, when this bead-like resin is used to handle diaper, may makes the generation pulp of fiber absorbs core and loses efficacy.
Though water solution polymerization process does not have above-mentioned shortcoming, also no all roses, the deficiency that this method exists is: for the ease of temperature control, avoid sudden and violent poly-, monomer keeps lower concentration in the solution polymerization, so just causes rate of polymerization slow, and equipment capacity and utilization ratio are low; Simultaneously, the result that low monomer concentration and polymeric chain shift to solvent generates low-molecular-weight polymkeric substance, thereby reduces product performance.In addition, disclose as patent CN 1031234A and CN 1468866A, solution polymerization process need be led to nitrogen protection, and polymerization process needed 1.5-5 hour to continue heating, thereby energy expenditure is big, the production cost height.
The ripple polymerization is that a kind of keeping by polyreaction self liberated heat reacted a kind of polymerization process that carries out, do not need extraneous lasting heating.The reaction system that contains monomer and initiator just produces the polymerization heat wave once lighting, and heat wave spreads from trend unreacted zone, and until whole reactor, after the heat wave, conversion of monomer is a polymkeric substance.This technology biggest advantage is not need extraneous heat supply, the save energy of continuing; Because reaction is progressively to spread to carry out, the monomer conversion height, the material structure of preparation is even.
The ripple polymerization is found by the Chechilo of USSR (Union of Soviet Socialist Republics) at first, then the Pojman of the U.S. and colleague thereof have carried out big quantity research to the ripple polymerization, developed the ripple polymerization process under the normal pressure, and be applied to material preparation aspects such as thermochromic material, optical function gradient material, epoxy resin cure, but do not see the report that the ripple polymerization technique is applied to prepare super absorbent resin both at home and abroad as yet at present.
Summary of the invention
The object of the present invention is to provide a kind of method of producing high water absorptive resin by wave polymerization, realize low-cost preparation water-absorbing resin, the water-absorbing resin of preparation has good water-absorbent and does not almost have residual monomer.
The present invention adopts ripple polymerization technique prepared in reaction super absorbent resin in aqueous phase system, concrete technology is: under 0～10 ℃ temperature, with the sodium hydroxide solution of 25～30% weight with vinylformic acid with being neutralized to pH value 6～7, add acrylamide, initiator, linking agent, 2-acrylamide-2-methyl propane sulfonic acid respectively, fully mix.Mixed liquid is injected in the cylindrical reactor, in any end heating of reactor, make the initiator decomposes, light reaction and begin with thermals source such as any type of heating such as resistance wire, spark, flat plate heats.After the reaction beginning, withdraw thermal source, the heat wave that produces by polymerization exotherm is kept reaction and is carried out, and is converted into polymer gel fully up to all monomers of whole reactor.Dry in warm air, pulverize, sieve the granularity that requires then.
The weight proportion of raw material of the present invention and each component is:
Vinylformic acid 59～69%
Acrylamide 24～30%
2-acrylamide-2-methyl propane sulfonic acid 0～9.8%
Initiator 1.1～2.9%
Linking agent 0.02%
Above-mentioned initiator is a water-soluble radical polymerization initiator, and as Potassium Persulphate, ammonium persulphate, hydrogen peroxide, above initiator can use separately, also can be used with S-WAT, L-xitix, obtains redox initiator.
Above-mentioned linking agent is water-soluble bi-vinyl monomer, as N, and N '-methylene-bisacrylamide, ethylene glycol bis glycidyl ether.
The invention has the advantages that: adopt ripple polymerization technique prepared in reaction super absorbent resin in aqueous phase system, not not with an organic solvent, under high monomer and initiator concentration, react, reaction is fast, the water-absorbing resin even structure of preparation, the monomer conversion height does not need to continue heating, is the low-cost preparation of a kind of very ideal water-absorbing resin technology.The water-absorbing resin of preparation has good water-absorbent and does not almost have residual monomer.
Embodiment
Embodiment 1
A kind of metal, plastics or glassiness cylindrical container of end sealing, 100 milliliters of its internal volumes, this container is used as reactor.In ice-water bath (temperature is 0～10 ℃) with in the sodium hydroxide solution of 30% (weight percentage) and 14 gram vinylformic acid to pH be 7, add 6 gram acrylamides, 0.004 gram N,N methylene bis acrylamide, 0.5 gram ammonium persulphate.After mixing, in the injecting reactor, in any end heating of reactor, make the initiator decomposes with resistance wire.After the reaction beginning, withdraw thermal source, keep to react by polymerization exotherm and carry out, be converted into polymer gel fully up to all monomers of whole reactor.After reactor is cooled to room temperature naturally, gel is taken out, rub with mincer, the granularity that requires is pulverized, sieved to 65 ℃ hot-air dry then.The water-intake rate that obtains product is 652g/g.
Embodiment 2
With embodiment 1.14 gram vinylformic acid are 7 with the sodium hydroxide neutralization solution to pH, adding 5 gram acrylamides, 1 gram 2-acrylamide-2-methyl propane sulfonic acid, 0.004 gram ethylene glycol bis glycidyl ether, 0.6 gram Potassium Persulphate.In any end heating of reactor, make the initiator decomposes with spark, light the reaction beginning.The water-intake rate of this product is 780g/g.
Embodiment 3
With embodiment 1.10 gram vinylformic acid, being neutralized to pH with sodium hydroxide is 7, adds 5 gram acrylamides, 1.5 gram 2-acrylamide-2-methyl propane sulfonic acids, 0.002 gram ethylene glycol bis glycidyl ether, 0.2 gram hydrogen peroxide-L-xitix.Heat in the reactor bottom with flat plate heat.The water-intake rate of this product is 880g/g.
Embodiment 4
With embodiment 1.12 gram vinylformic acid, being neutralized to pH with sodium hydroxide is 7, adds 6 gram acrylamides, 2 gram 2-acrylamide-2-methyl propane sulfonic acids, 0.004 gram N,N methylene bis acrylamide, 0.22 gram ammonium persulphate-S-WAT.Heat in the reactor bottom with flat plate heat.The water-intake rate of this product is 845g/g.
The water-absorbing resin of the inventive method preparation, monomer conversion is higher, and suction is fast.The water absorbing properties of product sees the following form:
| Embodiment | Transformation efficiency % | Water-intake rate g/g | Fast g/gmin absorbs water |
| ?1 | ?94 | ?652 | ?65 |
| ?2 | ?94 | ?780 | ?85 |
| ?3 | ?95 | ?865 | ?123 |
| ?4 | ?93 | ?845 | ?130 |
Claims (4)
1, a kind of method of producing high water absorptive resin by wave polymerization, it is characterized in that: adopt ripple polymerization technique prepared in reaction super absorbent resin in aqueous phase system, concrete technology is: under 0～10 ℃ temperature, sodium hydroxide solution with 25～30% weight is neutralized to pH value 6～7 with vinylformic acid, add acrylamide, initiator, linking agent, 2-acrylamide-2-methyl propane sulfonic acid respectively, fully mix; Mixed liquid is injected in the cylindrical reactor,, make the initiator decomposes, light the reaction beginning in any end heating of reactor; After the reaction beginning, withdraw thermal source, the heat wave that produces by polymerization exotherm is kept reaction and is carried out, and is converted into polymer gel fully up to all monomers of whole reactor.
2, method according to claim 1 is characterized in that: reactive component and weight percent are: vinylformic acid is 59～69, acrylamide is 24～30, and 2-acrylamide-2-methyl propane sulfonic acid is 0～9.8, and initiator is 1.1～2.9, and linking agent is 0.02.
3, method according to claim 1 and 2 is characterized in that: described initiator is a water-soluble radical polymerization initiator, comprises Potassium Persulphate, ammonium persulphate, hydrogen peroxide, and initiator uses separately or is used with S-WAT, L-xitix.
4, method according to claim 1 and 2 is characterized in that: described linking agent is water-soluble bi-vinyl monomer, comprises N, N '-methylene-bisacrylamide, ethylene glycol bis glycidyl ether.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410101888 CN1286859C (en) | 2004-12-30 | 2004-12-30 | Method for producing high water absorptive resin by wave polymerization |
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| Application Number | Priority Date | Filing Date | Title |
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| CN 200410101888 CN1286859C (en) | 2004-12-30 | 2004-12-30 | Method for producing high water absorptive resin by wave polymerization |
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| CN1648137A true CN1648137A (en) | 2005-08-03 |
| CN1286859C CN1286859C (en) | 2006-11-29 |
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| CN 200410101888 Expired - Fee Related CN1286859C (en) | 2004-12-30 | 2004-12-30 | Method for producing high water absorptive resin by wave polymerization |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1322032C (en) * | 2005-10-20 | 2007-06-20 | 北京科技大学 | Method for preparing porous aquagel using wave polymerisation technology |
| CN100347209C (en) * | 2005-10-31 | 2007-11-07 | 山东大学 | Inverse emulsion process of preparing amphoteric polymer |
| CN101429425A (en) * | 2007-11-07 | 2009-05-13 | 中国石化集团中原石油勘探局钻井工程技术研究院 | Process for preparing vinyl sulphonate polymer drilling fluid finishing agent |
| CN107057002A (en) * | 2017-03-23 | 2017-08-18 | 国网山东省电力公司莒县供电公司 | A kind of water repellent electric cable structure with interior hydrophobic resin and preparation method thereof |
-
2004
- 2004-12-30 CN CN 200410101888 patent/CN1286859C/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1322032C (en) * | 2005-10-20 | 2007-06-20 | 北京科技大学 | Method for preparing porous aquagel using wave polymerisation technology |
| CN100347209C (en) * | 2005-10-31 | 2007-11-07 | 山东大学 | Inverse emulsion process of preparing amphoteric polymer |
| CN101429425A (en) * | 2007-11-07 | 2009-05-13 | 中国石化集团中原石油勘探局钻井工程技术研究院 | Process for preparing vinyl sulphonate polymer drilling fluid finishing agent |
| CN107057002A (en) * | 2017-03-23 | 2017-08-18 | 国网山东省电力公司莒县供电公司 | A kind of water repellent electric cable structure with interior hydrophobic resin and preparation method thereof |
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| Publication number | Publication date |
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| CN1286859C (en) | 2006-11-29 |
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