CN1715304A - Process for preparing cellulose modified high water absorption resin - Google Patents
Process for preparing cellulose modified high water absorption resin Download PDFInfo
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- CN1715304A CN1715304A CN 200410050060 CN200410050060A CN1715304A CN 1715304 A CN1715304 A CN 1715304A CN 200410050060 CN200410050060 CN 200410050060 CN 200410050060 A CN200410050060 A CN 200410050060A CN 1715304 A CN1715304 A CN 1715304A
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- natural cellulose
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- acrylic acid
- water
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- 229920002678 cellulose Polymers 0.000 title claims abstract description 46
- 239000001913 cellulose Substances 0.000 title claims abstract description 46
- 229920005989 resin Polymers 0.000 title claims abstract description 42
- 239000011347 resin Substances 0.000 title claims abstract description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 238000010521 absorption reaction Methods 0.000 title abstract 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 55
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 23
- 239000003999 initiator Substances 0.000 claims abstract description 19
- 238000002360 preparation method Methods 0.000 claims abstract description 16
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 5
- 239000000047 product Substances 0.000 claims description 33
- 238000006243 chemical reaction Methods 0.000 claims description 30
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 17
- 239000003795 chemical substances by application Substances 0.000 claims description 17
- 238000006386 neutralization reaction Methods 0.000 claims description 17
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 16
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 16
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 16
- 239000012043 crude product Substances 0.000 claims description 15
- XMPZTFVPEKAKFH-UHFFFAOYSA-P ceric ammonium nitrate Chemical compound [NH4+].[NH4+].[Ce+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O XMPZTFVPEKAKFH-UHFFFAOYSA-P 0.000 claims description 14
- 239000002250 absorbent Substances 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 13
- 238000010298 pulverizing process Methods 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 8
- 230000002745 absorbent Effects 0.000 claims description 8
- VVWRJUBEIPHGQF-UHFFFAOYSA-N propan-2-yl n-propan-2-yloxycarbonyliminocarbamate Chemical compound CC(C)OC(=O)N=NC(=O)OC(C)C VVWRJUBEIPHGQF-UHFFFAOYSA-N 0.000 claims description 8
- 239000012567 medical material Substances 0.000 claims description 6
- 239000004159 Potassium persulphate Substances 0.000 claims description 5
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 5
- 235000019394 potassium persulphate Nutrition 0.000 claims description 5
- 239000004160 Ammonium persulphate Substances 0.000 claims description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 4
- 235000019395 ammonium persulphate Nutrition 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 4
- 238000010559 graft polymerization reaction Methods 0.000 claims description 3
- 239000000243 solution Substances 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 239000012286 potassium permanganate Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 16
- 238000006116 polymerization reaction Methods 0.000 abstract description 6
- 230000008569 process Effects 0.000 abstract description 5
- 238000005516 engineering process Methods 0.000 abstract description 2
- 239000003431 cross linking reagent Substances 0.000 abstract 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 30
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 28
- 229910052757 nitrogen Inorganic materials 0.000 description 16
- 230000004048 modification Effects 0.000 description 15
- 238000012986 modification Methods 0.000 description 15
- 239000000178 monomer Substances 0.000 description 15
- 239000002504 physiological saline solution Substances 0.000 description 15
- 239000008367 deionised water Substances 0.000 description 13
- 229910021641 deionized water Inorganic materials 0.000 description 13
- 238000012360 testing method Methods 0.000 description 11
- 238000005406 washing Methods 0.000 description 11
- 238000011160 research Methods 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- 229920002472 Starch Polymers 0.000 description 5
- 239000008107 starch Substances 0.000 description 5
- 235000019698 starch Nutrition 0.000 description 5
- 230000009471 action Effects 0.000 description 3
- 238000012662 bulk polymerization Methods 0.000 description 3
- 238000004587 chromatography analysis Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 238000004166 bioassay Methods 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000375 suspending agent Substances 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- PQUXFUBNSYCQAL-UHFFFAOYSA-N 1-(2,3-difluorophenyl)ethanone Chemical compound CC(=O)C1=CC=CC(F)=C1F PQUXFUBNSYCQAL-UHFFFAOYSA-N 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 239000011358 absorbing material Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- -1 detector: TCD Substances 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 239000006196 drop Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 238000010413 gardening Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 230000015784 hyperosmotic salinity response Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000002444 silanisation Methods 0.000 description 1
- 229940047670 sodium acrylate Drugs 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 description 1
- 238000010558 suspension polymerization method Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 239000006200 vaporizer Substances 0.000 description 1
- 230000003245 working effect Effects 0.000 description 1
Landscapes
- Graft Or Block Polymers (AREA)
- Polymerisation Methods In General (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The present invention relates to the preparation process of high water absorption resin with cellulose grafted acrylic acid and lower low molecular weight matter residue. Natural cellulose or its derivative and acrylic acid produce grafting copolymerization in water solution in the presence of cross-linking agent in the amount of 0.2-4.5 wt% of natural cellulose or its derivative and initiator in the amount of 1.2-8 wt% of natural cellulose or its derivative at 30-75 deg c for 2-8 hr; and the product is then washed, dried and crushed to become the required high water absorption resin. The present invention has improved polymerization process and post-treatment process, and compared with available technology, the product have acrylic acid content decades of times lower and obviously lower initiator and cross-linking agent residue, and is especially suitable for use in making medical sanitary material.
Description
Technical field
The present invention relates to the super absorbent resin preparation methods, relate to particularly by the preparation of cellulose graft vinylformic acid and can significantly reduce the wherein super absorbent resin of low-molecular material residual quantity, this resin material that utilizes the inventive method to obtain is particularly useful for medical material.
Background of invention
High hydrophilous resin is a kind of new functional macromolecule material that grows up nearly decades; be a kind of have self tens of times to thousands of times water-retaining capacities and also difficult functional high molecule material that dewaters of pressurization; because of having unique suction and water retention capacity, keep a full stand of seedings in agricultural, fields such as sanitary material, petrochemical complex, environment protection have all obtained exploitation widely and used.What suitability for industrialized production was more at present is the High hydrophilous resin of starch conversion class and synthetic resin.The research that relevant starch conversion is produced water-absorbing resin has had a large amount of reports to be disclosed, because it has excellent water absorbing properties, but the resin that this class utilizes starch conversion to obtain has the gel-strength reduction that the suction back forms, cause solution loss easily and influence water retention capacity and reduce work-ing life, and the starch segment is subject to the microorganism etch and loses water retention capacity, can feel to harden when contacting with physiological liquid and lose elasticity, the use field is restricted.
Mierocrystalline cellulose is a natural polymer, has good adaptability with human body, itself promptly is a kind of water-absorbing material, if its modification will be increased substantially water-retaining capacity.So, utilize natural cellulose, for example carboxymethyl cellulose is implemented the research concern extremely in the industry that modification by copolymerization prepares High hydrophilous resin.The modification by copolymerization carboxymethyl cellulose that passes through of at present existing research and report prepares the High hydrophilous resin technology and mainly contains two kinds of methods:
The inverse suspension polymerization method is a dispersion medium with solvent (oil phase) promptly, and monomer or polymer are water drop or particle, and initiator or catalyzer are dissolved in the polymerization that aqueous phase carries out more, and post-treating method is to adopt azeotropic dehydration, oven dry.The product water-intake rate that obtains is 800g/g, and inhaling 0.9% physiological saline is 120-140g/g.Its shortcoming is owing to add lower-molecular substances such as organic solvent, suspension agent, causes the various low molecular impurity in the product more.
Disc type method (mass polymerization) is about to reaction monomers, initiator, leaves standstill and carries out polymerization and oven dry, can obtain product after pulverizing through putting into the pallet heating after the prepolymerization.The product water-intake rate that obtains is 1000g/g, and inhaling 0.9% physiological saline is 140-160g/g.This bulk polymerization is easy to generate because condition control is improper phenomenons such as implode and reaction be inhomogeneous in actually operating.
On the other hand, in these research that is disclosed reports, what grafted monomer was many is to select vinyl cyanide or acrylamide, and initiator is then selected expensive ceric ammonium nitrate, but the toxicity of vinyl cyanide and acrylamide monomer is bigger, and the use of product is restricted equally.The research of adopting vinylformic acid or sodium acrylate monomers modified-cellulose and obtaining High hydrophilous resin is also arranged in the recent period, but the monomer residue in how can controlling polymers still there not be the report of being correlated with.
Be that the starch conversion or the research of cellulose modified grafted High hydrophilous resin are all fast-developing, fields such as health care, agricultural gardening, desertification control, civil construction and daily-use chemical industry have been widely used in according to record, but the contriver finds under study for action, relevant research and open all be water absorbing properties at product, the screening of all processing condition is a target to obtain higher water-intake rate all.According to present research record, it is residual to contain a great deal of low-molecular material in the prepared graftomer, Acrylic Acid Monomer (AA) for example, generally can be higher than 1000ppm, initiator that building-up process is used and linking agent also can have more residual than higher in product, not only influence the performance of product, and when being used for medical field, security and biology performance can be had a greatly reduced quality also.So how to make product satisfy the biological assessment of medical material, have higher security, should be the problem of being paid close attention in studying in the industry at present.
Summary of the invention
Research and application present situation based on High hydrophilous resin, the invention provides a kind of method for preparing High hydrophilous resin, not only method is simple, by selective reaction monomer scientifically, the condition of control building-up process, low molecule residual quantity is significantly reduced, be particularly useful for the manufacturing and the application of medical material.
The method according to this invention, adopt natural cellulose or derivatives thereof and vinylformic acid that graft copolymerization takes place in the aqueous solution, wherein, the mass ratio of vinylformic acid and natural cellulose or derivatives thereof is 0.5-10, and N is adopted in described copolyreaction, N '-methylene-bisacrylamide is a linking agent, consumption is the 0.2-4.5% of natural cellulose or derivatives thereof quality, the consumption of initiator is the 1.2-8% of natural cellulose or derivatives thereof quality, reaction raw materials was 30-75 ℃ of reaction 2-8 hour, and product washs after drying, pulverizing.
According to preparation method provided by the invention, after polyreaction was finished, crude product also needed to carry out aftertreatment, generally product need be stirred, smashed, and washed then, precipitated, and finally carried out drying and pulverizing, with the impurity in the further elimination polymerisate.Preferably, the crude product of polyreaction can make one or more mixing solutionss in water, methyl alcohol, ethanol, the acetone wash.
The product that obtains is according to the method described above compared with the product of prior art for preparing, owing to do not add materials such as organic solvent and suspension agent, the residual remarkable minimizing of low molecular impurity, and owing to adopt water solution polymerization process, also overcome implode and reaction problem of non-uniform that mass polymerization is prone to, product quality will be raised naturally.Through the low residual mensuration of molecule, can confirm, like product is suitable aspect water-absorbent with at present for the cellulose modified water-absorbing resin that the inventive method obtains, water-intake rate can reach more than the 1200g/g, absorb the physiological saline rate and can reach more than the 128g/g, the low-molecular material residual quantity significantly reduces simultaneously.
Cellulosic material used in the present invention is the natural cellulose or derivatives thereof, can comprise materials such as Mierocrystalline cellulose, carboxymethyl cellulose (CMC) or Natvosol, preferably uses CMC.Adding proportion between Acrylic Acid Monomer in the reactant (AA) and the cellulosic material does not have substantial effect to the product result, but the mass ratio of preferred vinylformic acid and natural cellulose or derivatives thereof is about 4-7 times.
The contriver finds under study for action, further comprise N-vinyl pyrrolidone (NVP) as the monomer in the reactant, more help improving the water-absorbent and the salt tolerance of product, even can reach 1600g/g, when adding the N-vinyl pyrrolidone, the mass ratio of itself and natural cellulose or derivatives thereof is 0.1-6, equally, this ratio is not strict with yet, preferred this mass ratio is about 2-5, when selecting to use two kinds of monomer reactions, N-vinyl pyrrolidone and acrylic acid mass ratio can be about 0.1-5, preferably at 0.3-3.
Be the control speed of reaction, guarantee quality product, vinylformic acid preferably has certain degree of neutralization, can can in reactant, add the degree of neutralization that a certain amount of alkali (for example, sodium hydroxide, sodium bicarbonate, yellow soda ash etc.) is adjusted Acrylic Acid Monomer simultaneously at 10-100%, when with the common graft polymerization of N-vinyl pyrrolidone, acrylic acid degree of neutralization can suitably improve, and for example can determine at 60-100%, especially 70-100%.
The initiator that uses in the polyreaction of the present invention can be conventional, preferably includes Potassium Persulphate, ammonium persulphate, ceric ammonium nitrate, potassium permanganate, hydrogen peroxide/S-WAT, Diisopropyl azodicarboxylate etc. or its mixing.When adopting two kinds of monomers, suitable initiator is preferably hydrogen peroxide/S-WAT, ceric ammonium nitrate, Diisopropyl azodicarboxylate etc. or its mixing, more preferably uses Diisopropyl azodicarboxylate.The consumption of initiator is the 1.2-8% of natural cellulose or derivatives thereof quality, is preferably 2-6%.
Polyreaction of the present invention is used N, and N '-methylene-bisacrylamide is a linking agent, and consumption is the 0.2-4.5% of natural cellulose or derivatives thereof quality, preferably can be 1-2%.
Preparation in accordance with the present invention, Mierocrystalline cellulose can first water gelatinization after, add raw materials such as vinylformic acid and linking agent and initiator again, temperature of reaction can be at 30-75 ℃, reaction times 2-8 hour, generally can be about 4-5 hour, can in this scope, take all factors into consideration and determine temperature of reaction and reaction times according to practical situation.Also can stop to stir when reacting approaching finishing, the insulation certain hour be controlled reaction process.Reaction generally is to carry out in non-oxygen atmosphere, for example feeds nitrogen or other protection of inert gas.
Prepare cellulose modified graft acrylic acid High hydrophilous resin compared with prior art according to method provided by the invention, except having higher water-absorbent, maximum difference is the residual remarkable reduction of low-molecular material in the product, the contriver once measured the low-molecular material content in certain commercially available acrylic acid or the like High hydrophilous resin, acrylic acid content wherein is more than 1000ppm, can be controlled at below the 65ppm and the vinylformic acid in the acrylic acid-grafted water-absorbing resin of the present invention's preparation is residual, when comprising AA and NVP in the polymerization single polymerization monomer, the NVP in the product is residual also will to be lower than 84ppm.The residual material of low molecule that influences in the product mainly is above-mentioned two kinds of monomers, and contriver's measurement result also shows, linking agent N in the High hydrophilous resin of the present invention's preparation, and the residual quantity of N '-methylene-bisacrylamide also can be lower than 3ppm.
The method of measuring vinylformic acid residual quantity in the solution can adopt bromometry method or liquid phase chromatography, can adopt the bromometry method when measuring roughly, but its result's accuracy is lower, because monomer residue is lower in the product of the present invention, preferably uses liquid phase chromatography to detect.
In a word, though cellulose modified High hydrophilous resin has a lot of researchs and report, water-absorbent is the important indicator that influences the usability of material really, find but this case contriver is unexpected under study for action, by improving polymerization technique and post-treating method, acrylic acid content in the product has reduced more than ten times and even tens of times than the product of prior art, and the residual of initiator and linking agent also obviously reduces.Manufacturing field at medical material, for the quality evalution of water-absorbing resin except its water-absorbent, security and biological assessment index also are strictly to investigate, use the residual water-absorbing resin that has been lowered of this low molecule, just mean the raising of the security of the finished product, perhaps, owing to omitted the process of aftertreatment, the cost of product also thereby significantly reduced.Consider that from this aspect enforcement of the present invention will be very significant for the contribution of prior art.
Embodiment
Below further specify of the present inventionly by specific embodiment, but can not constitute any restriction to protection scope of the present invention.(related consumption is mass parts among the embodiment.)
Vinylformic acid residual quantity in the polymerisate of following examples is detected, adopt liquid phase chromatography, chromatographic condition: chromatographic column KYATECHC18250 * 4.6mm, column temperature: room temperature, moving phase 0.02mol/LMOPS ion pair, flow velocity 0.8ml/min, detect wavelength: 210nm, sample size 2.0 μ l;
The residual quantity of N-vinyl pyrrolidone adopts gas chromatographic detection, chromatographic condition: chromatographic column in the polymerisate
The stainless steel column of 3mm, stationary liquid: Dienthyeneglycol succinate (20%), carrier: 60～80 order silanizations, 102 white carriers, detector: TCD, carrier gas: pure hydrogen, carrier gas flux: 28ml/min, column temperature: 145 ℃, the vaporizer temperature: 240 ℃, bridge stream: 200mA.
Embodiment 1
The CMC and a certain amount of deionized water that in there-necked flask, add 10 parts; under nitrogen protection; stir and be heated to predetermined temperature of reaction with water-bath; after carrying out gelatinization half an hour; add 80 parts in vinylformic acid (adjusting degree of neutralization to about 20% with sodium hydroxide in advance) and N; 0.03 part of N '-methylene-bisacrylamide; after mixing; add 0.6 part of Potassium Persulphate initiator; reacted about 4 hours in water-bath about 65 ℃ and nitrogen protection and under stirring, be incubated half an hour, obtain crude product; after taking-up is smashed; use washing with acetone, to constant weight, desciccate is pulverized with pulverizer in 60 ℃ of following vacuum-dryings; finally obtain white powder shape product, be natural cellulose modification High hydrophilous resin 1 of the present invention.
Inhale deionized water 1216g/g, absorb physiological saline and reach 135g/g;
Liquid chromatographic detection, acrylic acid residual quantity wherein is 62ppm.
Embodiment 2
After 10 parts of CMC are carried out gelatinization with a certain amount of deionized water, add 20 parts in vinylformic acid (degree of neutralization is adjusted to 30%), 0.5 part of ammonium persulphate, linking agent N, 0.1 part of N '-methylene-bisacrylamide, stirring reaction obtained crude product after 5 hours under 45 ℃ of water-baths and nitrogen protection, taking-up is smashed, with ethanol sedimentation, washing, filter the back oven dry, pulverize, obtain natural cellulose modification High hydrophilous resin 2 of the present invention, water-intake rate 1265g/g, suction physiological saline is 137g/g;
According to the method for embodiment 1 record after testing, acrylic acid residual quantity is 33ppm.
Embodiment 3
After 10 parts of CMC are carried out gelatinization with a certain amount of deionized water, add 60 parts in vinylformic acid (degree of neutralization is adjusted to 50%), 0.8 part of ceric ammonium nitrate, linking agent N, 0.15 part of N '-methylene-bisacrylamide, stirring reaction obtained crude product after 3 hours under 35 ℃ of water-baths and nitrogen protection, taking-up is smashed, with ethanol sedimentation, washing, filter the back oven dry, pulverize, obtain natural cellulose modification High hydrophilous resin 3 of the present invention, water-intake rate 1230g/g inhales physiological saline rate 128g/g;
After testing, acrylic acid residual quantity is 65ppm.
Embodiment 4
After 10 parts of CMC are carried out gelatinization with a certain amount of deionized water, add 10 parts in vinylformic acid (degree of neutralization is adjusted to 70% with sodium hydroxide), 0.3 part of Diisopropyl azodicarboxylate, linking agent N, 0.2 part of N '-methylene-bisacrylamide, stirring reaction is after 3.5 hours under 42 ℃ of water-baths and nitrogen protection, obtain crude product, taking-up is smashed, behind methyl alcohol, water mixing, washing, drying, pulverizing obtain natural cellulose modification High hydrophilous resin 4 of the present invention, water-intake rate 1382g/g inhales physiological saline rate 130g/g;
After testing, acrylic acid residual quantity is 49ppm.
Embodiment 5
After 10 parts of CMC are carried out gelatinization with a certain amount of deionized water, add 70 parts in vinylformic acid (degree of neutralization is adjusted to 60% with sodium hydroxide), 0.55 part of Potassium Persulphate, linking agent N, 0.18 part of N '-methylene-bisacrylamide obtains crude product in reaction under 70 ℃ of water-baths and the nitrogen protection after 7 hours, taking-up is smashed, behind methyl alcohol, ethanol mixing, washing, drying, pulverizing obtain natural cellulose modification High hydrophilous resin 5 of the present invention, water-intake rate 1297g/g inhales physiological saline rate 148g/g;
After testing, acrylic acid residual quantity is 38ppm.
Embodiment 6
After 10 parts of CMC are carried out gelatinization with a certain amount of deionized water, add 40 parts in vinylformic acid (degree of neutralization is adjusted to 90% with sodium hydroxide), Potassium Persulphate/ammonium persulphate mixes 0.2 part of (mass ratio is 2: 1) initiator, N, 0.2 part of N '-methylene-bisacrylamide, after reacting 8 hours under 50 ℃ of water-baths and the nitrogen protection, obtain crude product, taking-up is smashed, behind ethanol, acetone mixing, washing, drying, pulverizing obtain natural cellulose modification High hydrophilous resin 6 of the present invention, water-intake rate is 1249g/g, and inhaling the physiological saline rate is 146g/g;
After testing, acrylic acid residual quantity is 31ppm.
Embodiment 7
In there-necked flask, add after 10 parts CMC and a certain amount of deionized water carry out gelatinization, add 60 parts in vinylformic acid (degree of neutralization is adjusted to 90% with sodium hydroxide), 30 parts of N-vinyl pyrrolidones, 0.2 part of initiator Diisopropyl azodicarboxylate, linking agent N, 0.1 part of N '-methylene-bisacrylamide, reaction is 5 hours under 70 ℃ of water-baths and nitrogen protection, obtains crude product, taking-up is smashed, use methyl alcohol, behind the ethanol mixing, washing, to constant weight, pulverize with pulverizer 60 ℃ of following vacuum-dryings, finally obtain white powder shape product, be natural cellulose modification High hydrophilous resin 7 of the present invention, water-intake rate 1593g/g inhales physiological saline rate 137g/g;
After testing, acrylic acid residual quantity is 22ppm, and the residual quantity of N-vinyl pyrrolidone is 55ppm.
Embodiment 8
10 parts of CMC and 20 parts of N-vinyl pyrrolidones and a certain amount of deionized water, 30 parts in vinylformic acid (degree of neutralization is adjusted to 100% with sodium hydroxide), 0.15 part of ceric ammonium nitrate initiator, linking agent N, 0.15 part of N '-methylene-bisacrylamide, reaction is 5 hours under 35 ℃ of water-baths and nitrogen protection, obtain crude product, taking-up is smashed, behind methyl alcohol, water mixing, washing, drying, pulverizing obtain natural cellulose modification High hydrophilous resin 8 of the present invention, water-intake rate 1686g/g inhales physiological saline rate 170g/g;
After testing, the residual quantity of N-vinyl pyrrolidone is 66ppm.
Embodiment 9
After 10 parts CMC and a certain amount of deionized water carried out gelatinization, add 40 parts in vinylformic acid (degree of neutralization is adjusted to 95% with sodium hydroxide), 40 parts of N-vinyl pyrrolidones, 0.6 part of Diisopropyl azodicarboxylate, linking agent N, 0.1 part of N '-methylene-bisacrylamide, stirring reaction is 6 hours under 40 ℃ of water-baths and nitrogen protection, obtain crude product, taking-up is smashed, behind ethanol, water mixing, washing, drying, pulverizing, obtain natural cellulose modification High hydrophilous resin 9 of the present invention, water-intake rate 1663g/g inhales physiological saline rate 179g/g;
After testing, acrylic acid residual quantity wherein is 25ppm, and the residual quantity of N-vinyl pyrrolidone is 73ppm.
Embodiment 10
After 10 parts CMC and a certain amount of deionized water carried out gelatinization, add 20 parts in vinylformic acid (degree of neutralization is adjusted to 90% with sodium hydroxide), 40 parts of N-vinyl pyrrolidones, 0.2 part of hydrogen peroxide/S-WAT (mass ratio is 1: 1) initiator, linking agent N, 0.2 part of N '-methylene-bisacrylamide, stirring reaction is 5 hours under 50 ℃ of water-baths and nitrogen protection, obtain crude product, taking-up is smashed, after methanol wash, drying, pulverizing, obtain natural cellulose modification High hydrophilous resin 10 of the present invention, water-intake rate 1754g/g inhales physiological saline rate 182g/g;
After testing, acrylic acid residual quantity wherein is 37ppm, and the residual quantity of N-vinyl pyrrolidone is 64ppm.
Embodiment 11
N-vinyl pyrrolidone and a certain amount of deionized water of 10 parts CMC and 60 parts, 20 parts in vinylformic acid (degree of neutralization is adjusted to 85% with sodium hydroxide and sodium bicarbonate), 0.3 part of ceric ammonium nitrate, linking agent N, 0.18 part of N '-methylene-bisacrylamide, stirring reaction is 4 hours under 60 ℃ of water-baths and nitrogen protection, obtain crude product, taking-up is smashed, behind ethanol, methyl alcohol, water mixing, washing, drying, pulverizing obtain natural cellulose modification High hydrophilous resin 11 of the present invention, water-intake rate 1616g/g inhales physiological saline rate 157g/g;
After testing, acrylic acid residual quantity wherein is 38ppm, and the residual quantity of N-vinyl pyrrolidone is 61ppm.
Embodiment 12
After 10 parts CMC and a certain amount of deionized water carried out gelatinization, add 80 parts in vinylformic acid (degree of neutralization 70%), 30 parts of N-vinyl pyrrolidones, 0.75 part of Diisopropyl azodicarboxylate, linking agent N, 0.2 part of N '-methylene-bisacrylamide, stirring reaction is 5 hours under 45 ℃ of water-baths and nitrogen protection, obtain crude product, taking-up is smashed, behind washing with acetone, drying, pulverizing, obtain natural cellulose modification High hydrophilous resin 12 of the present invention, water-intake rate 1606g/g inhales physiological saline rate 162g/g;
After testing, acrylic acid residual quantity wherein is 41ppm, and the residual quantity of N-vinyl pyrrolidone is 75ppm.
Claims (12)
1, the preparation method of super absorbent resin, adopt natural cellulose or derivatives thereof and vinylformic acid that graft copolymerization takes place in the aqueous solution, wherein, the mass ratio of vinylformic acid and natural cellulose or derivatives thereof is 0.5-10, and N is adopted in described copolyreaction, N '-methylene-bisacrylamide is a linking agent, consumption is the 0.2-4.5% of natural cellulose or derivatives thereof quality, the consumption of initiator is the 1.2-8% of natural cellulose or derivatives thereof quality, reaction raw materials was 30-75 ℃ of reaction 2-8 hour, and product washs after drying, pulverizing.
2, the described preparation method of claim 1 wherein, also comprises the N-vinyl pyrrolidone in the reaction raw materials, the mass ratio of itself and natural cellulose or derivatives thereof is 0.1-6.
3, the described preparation method of claim 2, wherein, N-vinyl pyrrolidone and vinylformic acid mass ratio are 0.1-5.
4, claim 1 or 2 described preparation methods, wherein, described acrylic acid degree of neutralization is 10-100%.
5, the described preparation method of claim 4, wherein, described acrylic acid degree of neutralization is 60-100%.
6, the described preparation method of claim 1, wherein, described initiator comprises: Potassium Persulphate, ammonium persulphate, ceric ammonium nitrate, potassium permanganate, hydrogen peroxide/S-WAT, Diisopropyl azodicarboxylate or its mixing.
7, the described preparation method of claim 1, wherein, described natural cellulose or derivatives thereof comprises Mierocrystalline cellulose, carboxymethyl cellulose or Natvosol.
8, the described preparation method of claim 1, wherein, the crude product of polyreaction washs one or more the mixing solutions in water, methyl alcohol, ethanol, the acetone.
9, a kind of super absorbent resin, it is natural cellulose or derivatives thereof and acrylic acid graft polymerization product that the method according to claim 1 is prepared from, the vinylformic acid residual quantity in this product is lower than 65ppm.
10, a kind of super absorbent resin, it is natural cellulose or derivatives thereof and acrylic acid graft polymerization product that the method according to claim 2 is prepared from, vinylformic acid residual quantity in this product is lower than 65ppm, and the residual quantity of N-vinyl pyrrolidone is lower than 84ppm.
11, the described super absorbent resin of claim 9 is used for the manufacturing of medical material.
12, the described super absorbent resin of claim 10 is used for the manufacturing of medical material.
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