CN101735395B - Preparation method of water absorbing material of industrial hemp stalk core cellulose - Google Patents
Preparation method of water absorbing material of industrial hemp stalk core cellulose Download PDFInfo
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- CN101735395B CN101735395B CN200910163221XA CN200910163221A CN101735395B CN 101735395 B CN101735395 B CN 101735395B CN 200910163221X A CN200910163221X A CN 200910163221XA CN 200910163221 A CN200910163221 A CN 200910163221A CN 101735395 B CN101735395 B CN 101735395B
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- 244000025254 Cannabis sativa Species 0.000 title claims abstract description 43
- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 title claims abstract description 43
- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 title claims abstract description 43
- 235000009120 camo Nutrition 0.000 title claims abstract description 43
- 235000005607 chanvre indien Nutrition 0.000 title claims abstract description 43
- 239000011487 hemp Substances 0.000 title claims abstract description 43
- 229920002678 cellulose Polymers 0.000 title claims abstract description 30
- 239000001913 cellulose Substances 0.000 title claims abstract description 30
- 239000011358 absorbing material Substances 0.000 title claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims description 11
- 239000000835 fiber Substances 0.000 claims abstract description 55
- 238000000034 method Methods 0.000 claims abstract description 46
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 27
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 21
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000000178 monomer Substances 0.000 claims abstract description 9
- 230000001376 precipitating effect Effects 0.000 claims abstract description 9
- 238000005406 washing Methods 0.000 claims abstract description 9
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims abstract description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000003518 caustics Substances 0.000 claims abstract description 7
- 239000001301 oxygen Substances 0.000 claims abstract description 7
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 7
- 239000007864 aqueous solution Substances 0.000 claims abstract description 5
- 238000010528 free radical solution polymerization reaction Methods 0.000 claims abstract description 3
- 238000007789 sealing Methods 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 34
- 239000002994 raw material Substances 0.000 claims description 16
- 238000002203 pretreatment Methods 0.000 claims description 15
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 14
- 239000003795 chemical substances by application Substances 0.000 claims description 13
- 239000004160 Ammonium persulphate Substances 0.000 claims description 12
- 235000019395 ammonium persulphate Nutrition 0.000 claims description 12
- 230000035484 reaction time Effects 0.000 claims description 10
- 239000003999 initiator Substances 0.000 claims description 8
- 238000006386 neutralization reaction Methods 0.000 claims description 8
- 230000015572 biosynthetic process Effects 0.000 claims description 6
- 238000004061 bleaching Methods 0.000 claims description 6
- 238000009835 boiling Methods 0.000 claims description 6
- 239000012295 chemical reaction liquid Substances 0.000 claims description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N hydrogen peroxide Substances OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- 235000015110 jellies Nutrition 0.000 claims description 6
- 238000003786 synthesis reaction Methods 0.000 claims description 6
- 238000007710 freezing Methods 0.000 claims description 4
- 230000008014 freezing Effects 0.000 claims description 4
- 235000010265 sodium sulphite Nutrition 0.000 claims description 2
- 238000010009 beating Methods 0.000 abstract description 14
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 abstract description 11
- 239000000463 material Substances 0.000 abstract description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 238000000227 grinding Methods 0.000 abstract 3
- QMLOYPZQTXJZKV-UHFFFAOYSA-N OO.O=[Cl]=O Chemical compound OO.O=[Cl]=O QMLOYPZQTXJZKV-UHFFFAOYSA-N 0.000 abstract 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 abstract 1
- 238000010411 cooking Methods 0.000 abstract 1
- 239000003431 cross linking reagent Substances 0.000 abstract 1
- 238000004108 freeze drying Methods 0.000 abstract 1
- 238000009897 hydrogen peroxide bleaching Methods 0.000 abstract 1
- 230000000977 initiatory effect Effects 0.000 abstract 1
- 230000033116 oxidation-reduction process Effects 0.000 abstract 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 abstract 1
- 239000002002 slurry Substances 0.000 description 16
- 239000002657 fibrous material Substances 0.000 description 12
- 229920005989 resin Polymers 0.000 description 12
- 239000011347 resin Substances 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- 239000003153 chemical reaction reagent Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 239000000047 product Substances 0.000 description 6
- 239000011837 N,N-methylenebisacrylamide Substances 0.000 description 5
- 229920002472 Starch Polymers 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 229920005615 natural polymer Polymers 0.000 description 5
- 230000009257 reactivity Effects 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- 239000008107 starch Substances 0.000 description 5
- 235000019698 starch Nutrition 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 239000002250 absorbent Substances 0.000 description 4
- 230000002745 absorbent Effects 0.000 description 4
- 238000009833 condensation Methods 0.000 description 4
- 230000005494 condensation Effects 0.000 description 4
- 230000009193 crawling Effects 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000008274 jelly Substances 0.000 description 4
- 238000007781 pre-processing Methods 0.000 description 4
- 239000003755 preservative agent Substances 0.000 description 4
- 230000002335 preservative effect Effects 0.000 description 4
- 238000004537 pulping Methods 0.000 description 4
- 229920003002 synthetic resin Polymers 0.000 description 4
- 239000000057 synthetic resin Substances 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 241000212978 Amorpha <angiosperm> Species 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000003209 petroleum derivative Substances 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 229920003043 Cellulose fiber Polymers 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- 238000012356 Product development Methods 0.000 description 1
- 108010009736 Protein Hydrolysates Proteins 0.000 description 1
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- 230000015556 catabolic process Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
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- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
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- 229930014626 natural product Natural products 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
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- 150000003384 small molecules Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- YMBCJWGVCUEGHA-UHFFFAOYSA-M tetraethylammonium chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC YMBCJWGVCUEGHA-UHFFFAOYSA-M 0.000 description 1
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- 239000002351 wastewater Substances 0.000 description 1
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Landscapes
- Graft Or Block Polymers (AREA)
- Paper (AREA)
Abstract
The invention relates to a technical process for manufacturing a water absorbing material by utilizing industrial hemp stalk core cellulose, belonging to the technical field of high molecular materials. The process of the invention comprises the following steps: (1) cooking an industrial hemp stalk core by caustic soda-anthraquinone (AQ), and then, carrying out oxygen delignification and chlorinedioxide-hydrogen peroxide bleaching in three sections to prepare the bleached pulp fiber of the industrial hemp stalk core; (2) grinding and pretreating the bleached pulp fiber by a mechanical beating machine, wherein the beating degree is 35-85 SR; (3) carrying out graft copolymerization on the bleached pulp fiber after grinding by using the aqueous solution polymerization method, wherein the graft copolymerization is completed by using ammonium persulfate and sodium bisulfite as an oxidation reduction initiating system, using N,N'-methylene-bisacrylamide as a cross-linking agent and using acrylic acid and acrylic amide as monomers; and (4) precipitating the copolymerization product with absolute ethyl alcohol, washing, freeze-drying, grinding, refreezing and sealing to obtain a finished product. The water absorbing material of the invention has high accessibility and water absorbing efficiency and can effectively develop and utilize the industrial hemp stalk core cellulose.
Description
Technical field
The present invention relates to a kind of Technology of utilizing the industrial hemp stalk core cellulose to make water-absorbing material, belong to technical field of polymer materials.
Background technology
Now, the water-absorbing material kind is a lot of.Mainly contain two big series by raw material sources, i.e. natural polymer subclass (comprising starch system, cellulose-based and other natural product systems) and petroleum product class water-absorbing material (comprising) according to acrylate system, polyethenol series, T 46155 system etc.
[1]As the raw material of water-absorbing material, Mierocrystalline cellulose and starch all are a kind of polyhydric natural compoundss, can react with multiple low molecule, synthesize the absorbency material with different qualities.Compare with the raw material of petroleum product class water-absorbing material, natural polymer raw material, especially Mierocrystalline cellulose and starch, wide material sources, of a great variety, cheap, and the synthetic water-absorbing material has the environment-friendly advantage of natural degradation.Therefore, natural polymer subclass water-absorbing material is an important directions of the nearly development of water-absorbing material during the last ten years.
Because it is super absorbent resin is just being brought into play more and more important effect in national economy and daily life, more active in the research in this field both at home and abroad.But, be water-absorbing resin with respect to starch, cellulose-based water-absorbing resin research is less relatively.Tracing it to its cause mainly is because compare with the starch polymer, and there is the problem of reaction accessibility in Mierocrystalline cellulose.Cellulosic accessibility, promptly reaction reagent arrives at the complexity of Mierocrystalline cellulose hydroxyl, is an important factor of cellulose chemistry reaction.Cellulosic accessibility mainly receives the influence of the ratio of Mierocrystalline cellulose crystallizing field and pars amorpha.Research shows
[2], for the cellulosic hydroxyl of high-crystallinity, small molecules reagent can only arrive at wherein 10%～15%.And most of reaction reagents can only be penetrated into cellulosic pars amorpha, and can not get into crystallizing field closely.Therefore, greatly reduce its various chemosynthesis reaction performances, thereby had a strong impact on each item performance of cellulose-based water-absorbing material.For example, in the preparation of paper cellulose graft copolymerization acrylonitrile compolymer Water Absorbent Material from Hydrolysate, the water-intake rate of the finished product is merely 88.1 times
[3]Therefore, can find out that the existence of cellulosic crystallizing field has influenced reactivity worth greatly, the water-retaining capacity that finally causes synthetic product to reduce.Yet, adopt one or more particular chemical reagent (for example, DMSO 99.8MIN./etamon chloride mixing solutions now mostly in order to improve cellulosic accessibility in the plant material
[4], lithium chloride/N,N-DIMETHYLACETAMIDE mixing solutions
[5], copper ammon solution
[6], sodium hydroxide solution
[6]Or the like) Mierocrystalline cellulose is carried out the swollen pre-treatment, destroy its crystallizing field thereby play, improve the subsequent reactions performance.But prove through previous experiments, the pretreated method of chemical swollen often have complicated operation, operation tediously long, test that length consuming time, investment are huge, cost that solvent recuperation and recycling are used is high and chemical swollen after waste water environment is caused the various shortcoming of certain burden etc.Therefore, in order to promote the accessibility of natural polymer cellulose chemistry reaction, improve the water-taking efficiency of its product, the Mierocrystalline cellulose pretreatment process of the economic and practical type that exploitation makes new advances is necessary.
Industrial hemp is the hemp kind that THC (THC) content meets the European Union's standard (THC＜0.3%) that extensively adopts in the world
[7]Industrial hemp does not have the drugs utility value, its objective is the output that improves fiber, seed or oil to greatest extent, improves its quality, so this kind hemp mainly is already to carry out directive breeding to paper-making industry, textile industry and oil plant
[8]Industrial hemp comprises two kinds of different fibers: phloem fiber and stalk core fibre.Phloem fiber since the advantage of its staple length (in the 10-20mm scope
[9]), in extensive fiber production such as weaving, papermaking, natural-fiber composite material, bringing into play important effect; And the stalk core fibre because of the limitation of its length (greatly about about 0.5mm
[9]) received considerable restraint in the fiber Application in Manufacturing Industry.But for water-absorbing material, the requirement of raw fibre length is just so not harsh.Therefore; Research at the water-absorbing material that is the basis with industrial hemp stalk core fibre remains under the prerequisite of blank out; Industrial hemp stalk core is used to prepare super absorbent resin, natural resource are utilized effectively, can also expand the road of stalk core fibre high value added utilization.
Reference
[1] Wu Jihuai, Lin Jianming, Wei Yuelin, Lin Songbai. the high water absorbing and retaining material. Beijing: Chemical Industry Press, 2005
[2] Ma Fengguo. synthetic, the performance of Super Absorbent Resin from Cellulose and applied research. Beijing Institute of Technology's doctorate paper, 2001
[3] Li Jingqing, Liu Jing, a woods. the technology of super absorbent resin and prescription. Beijing: Chemical Industry Press, 2004
[4] Xiao Changfa .DMS0/TEAC mixed solvent is to the research [J] of cellulose dissolution effect, spectroscopy and spectroscopic analysis, 1994, (4): 51-54
[5] Wang Tiejun, Ruan Jinyue etc., the solution characteristic [J] of Mierocrystalline cellulose Li/DMAc system, Mierocrystalline cellulose Science and Technology, 1996,4 (3)
[6] side of separating, Shao Ziqiang, the dissolution mechanism of native cellulose fibre and spining technology development, Huabei Polytechnical College journal, 2002,23 (2)
[7] Yang Ming, Guo Hongyan, Hu Xueli, Chen Yu etc. the feature and the cultivation technique [J] of industrial hemp new variety " cloud fiber crops No. 1 ". Yunnan agricultural science and technology, 2003 (6)
[8] Zhang Yunxiong. the new trend [J] of external industrial hemp research and product development. world agriculture, 2003, (9)
[9] Gao Xin, Chen Keli. world industry is used and the reviews and prospects of studying with the hemp pulp and paper industry. southwestern papermaking, 2006, (6)
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of water absorbing material of industrial hemp stalk core cellulose; Instead has the pretreated method of cellulose chemistry swollen now; Promote the accessibility of natural polymer cellulose chemistry reaction; Improve the water-taking efficiency of its product, and can effectively develop agricultural wastes---industrial hemp stalk core cellulose, product each item performance index of preparing are more excellent.
The process technology scheme that realization the object of the invention is taked is following:
1. industrial hemp stalk core process caustic soda-anthraquinone method boiling, follow-up oxygen delignification, dioxide peroxide-hydrogen peroxide tri-stage bleaching makes industrial hemp stalk core bleached pulp fiber; 2. adopt mechanical hollander to the pre-treatment of bleached pulp fiber defibrination, freeness is 35～85SR; 3. it is synthetic that the bleached pulp fiber after adopting aqueous solution polymerization method to defibrination carries out graft copolymerization; Promptly select for use ammonium persulphate and sodium sulfite anhy 96 as redox body initiator system; With N, N '-methylene-bisacrylamide is a linking agent, selects for use vinylformic acid and acrylic amide to accomplish as monomer simultaneously; 4. the copolymerization synthetics is carried out precipitating, washing, lyophilize, milled processed, freezing, sealing again with absolute ethyl alcohol, obtain finished product.
The concrete technical scheme of the object of the invention also comprises:
1. the hemp stalk core Mierocrystalline cellulose should be bleached bleached pulp and reaches Kappa number 9.5～0.5, k value 1100～950dm
3/ kg, whiteness value 55.0～92.5%; 2. the graft copolymerization synthesis condition is: vinylformic acid and acrylamide monomer consumption sum are 2: 1～20: 1 with the ratio of over dry raw materials quality, and the vinylformic acid degree of neutralization is 15～85%; The initiator ammonium persulfate consumption is 0.0001～0.02: 1 with the ratio of over dry raw material, and ammonium persulphate and S-WAT mass ratio are 1: 1～4: 1; Linking agent N,N methylene bis acrylamide consumption is 0.0001～0.02: 1 with the ratio of monomer total mass; Temperature of reaction is 30～80 ℃, and the reaction times is 3.5～15 hours; The over dry stock quality should be controlled in the scope of 1g: 100～200ml with the ratio of reaction liquid TV.
In the synthetic step of above-mentioned graft copolymerization, the vinylformic acid degree of neutralization is 70%.
After graft copolymerization is synthetic, with absolute ethyl alcohol to synthetics repeatedly precipitating, washing be ground to 70～200 mesh sieves after the lyophilize to becoming pH 7～8 white jellies fully, freezing time is 24～72 hours again.
The invention has the beneficial effects as follows: the industrial hemp stalk core bleached pulp fiber of preparation is a water-absorbing material; Can destroy the fiber crystallizing field well; Improve the graft copolymerization ability; Increase the effect of the absorbent of synthetic materials, inhale the zero(ppm) water multiplying power and reach 920.5g/g, inhaling zero(ppm) water speed is 20min; Inhale 0.9% sodium chloride aqueous solution multiplying power 300.6g/g, inhaling 0.9% sodium chloride aqueous solution speed is 20min; It is Powdered to be white in color.Can be used for agricultural, gardening aspect and make anti-drought water-retaining agent and cultivating agent, industrial aspect as siccative, dewatering agent, vegetable and fruit preservation agent, sanitary material imbibition agent etc.
Embodiment
Embodiment 1
(1) produces the fibrous material bleached pulp
The industrial hemp that adopts is " cloud fiber crops No. 1 " industrial hemp kind.This hemp core is through the caustic soda-anthraquinone method boiling, and follow-up oxygen delignification, dioxide peroxide-hydrogen peroxide tri-stage bleaching make " cloud fiber crops No. 1 " stalk core bleached pulp fibrous material, and the characteristic of this bleached pulp is following: Kappa number 3.8, k value 1031dm
3/ kg, whiteness value 85.3% (ISO).
(2) mill (beating) of industrial hemp stalk core bleached pulp fiber is starched preprocessing process and method
In order to improve cellulosic reactivity worth in the fibrous material; Adopt machinery mill (beating) slurry process to replace adopting one or more particular chemical reagent that Mierocrystalline cellulose is carried out run-inflation effect now mostly; Promptly utilize the Valley hollander that " cloud fiber crops No. 1 " stalk core bleached pulp fiber is ground the pre-treatment of (beating) slurry, and carry out the The real time measure of this kind slurry pulping degree through Xiao Baier freeness determinator.The pre-treatment degree is 65SR for the freeness of " cloud fiber crops No. 1 " stalk core bleached pulp.
(3) process and the method for the synthetic preparation of water-absorbing material
The concrete graft copolymerization synthesis condition of " cloud fiber crops No. 1 " stalk core bleached pulp fiber of 65 ° of SR freenesss is: vinylformic acid and acrylamide monomer consumption sum are 15: 1 with the ratio of over dry raw materials quality, and the vinylformic acid degree of neutralization is 70%; The initiator ammonium persulfate consumption is 0.015: 1 with the ratio of over dry raw material, and ammonium persulphate and S-WAT mass ratio are 3: 1; Linking agent N,N methylene bis acrylamide consumption is 0.004: 1 with the ratio of monomer total mass; Temperature of reaction is 45 ℃; Reaction times is 5 hours; The over dry stock quality should be controlled at 1 (g) with the ratio of reaction liquid TV: in the scope of 100～200 (ml).
The synthetic step of concrete graft copolymerization is: take by weighing a certain amount of acrylic amide and put into three mouthfuls of reaction flasks that the pre-treatment disposed slurry is housed, the acrylic acid solution of becoming reconciled in pouring into simultaneously.There-necked flask is put into the water-bath of constant temperature (45 ℃), start whipping appts, and in the prolong water flowing condensation of crawling of an end device of there-necked flask.The other end feeds N
2, logical N
2Behind 20～30min, a certain amount of ammonium persulphate of adding and showing of S-WAT are joined solution in reaction vessel, and the opening entry reaction times.After graft copolymerization begins 60min, add a certain amount of N, N '-methylene-bisacrylamide carries out crosslinking reaction.
(4) last handling process of water-absorbing material and method
After reaction finishes, synthetic resins is transferred in certain volumetrical beaker by three mouthfuls of reaction flasks fully, add a certain amount of absolute ethyl alcohol and carry out precipitating, washing, so repeatedly, become white jelly fully until transparency, pH is 7～8.Then, the gained resin is tiled in the petridish that is covered with preservative film after disperseing, and carries out lyophilize.Treat to carry out milled processed behind the resin complete drying, the toner behind mistake 80 eye mesh screens is positioned in the air-tight bottle, lyophilize sealed for use after 24 hours once more.
Embodiment 2
(1) produces the fibrous material bleached pulp
The industrial hemp that adopts is " cloud fiber crops No. 1 " industrial hemp kind.This hemp core is through the caustic soda-anthraquinone method boiling, and follow-up oxygen delignification, dioxide peroxide-hydrogen peroxide tri-stage bleaching make " cloud fiber crops No. 1 " stalk core bleached pulp fibrous material, and the characteristic of this bleached pulp is following: Kappa number 6.5, k value 1081dm
3/ kg, whiteness value 66.9% (ISO).
(2) mill (beating) of industrial hemp stalk core bleached pulp fiber is starched preprocessing process and method
In order to improve cellulosic reactivity worth in the fibrous material; Adopt machinery mill (beating) slurry process to replace adopting one or more particular chemical reagent that Mierocrystalline cellulose is carried out run-inflation effect now mostly; Promptly utilize the Valley hollander that " cloud fiber crops No. 1 " stalk core bleached pulp fiber is ground the pre-treatment of (beating) slurry, and carry out the The real time measure of this kind slurry pulping degree through Xiao Baier freeness determinator.The pre-treatment degree is 70SR for the freeness of " cloud fiber crops No. 1 " stalk core bleached pulp.
(3) process and the method for the synthetic preparation of water-absorbing material
The concrete graft copolymerization synthesis condition of " cloud fiber crops No. 1 " stalk core bleached pulp fiber of 70 ° of SR freenesss is: vinylformic acid and acrylamide monomer consumption sum are 16: 1 with the ratio of over dry raw materials quality, and the vinylformic acid degree of neutralization is 55%; The initiator ammonium persulfate consumption is 0.010: 1 with the ratio of over dry raw material, and ammonium persulphate and S-WAT mass ratio are 3: 1; Linking agent N,N methylene bis acrylamide consumption is 0.003: 1 with the ratio of monomer total mass; Temperature of reaction is 50 ℃; Reaction times is 6.5 hours; The over dry stock quality should be controlled at 1 (g) with the ratio of reaction liquid TV: in the scope of 100～200 (ml).
The synthetic step of concrete graft copolymerization is: take by weighing a certain amount of acrylic amide and put into three mouthfuls of reaction flasks that the pre-treatment disposed slurry is housed, the acrylic acid solution of becoming reconciled in pouring into simultaneously.There-necked flask is put into the water-bath of constant temperature (50 ℃), start whipping appts, and in the prolong water flowing condensation of crawling of an end device of there-necked flask.The other end feeds N
2, logical N
2Behind 20～30min, a certain amount of ammonium persulphate of adding and showing of S-WAT are joined solution in reaction vessel, and the opening entry reaction times.After graft copolymerization begins 60min, add a certain amount of N, N '-methylene-bisacrylamide carries out crosslinking reaction.
(4) last handling process of water-absorbing material and method
After reaction finishes, synthetic resins is transferred in certain volumetrical beaker by three mouthfuls of reaction flasks fully, add a certain amount of absolute ethyl alcohol and carry out precipitating, washing, so repeatedly, become white jelly fully until transparency, pH is 7～8.Then, the gained resin is tiled in the petridish that is covered with preservative film after disperseing, and carries out lyophilize.Treat to carry out milled processed behind the resin complete drying, the toner behind mistake 100 eye mesh screens is positioned in the air-tight bottle, lyophilize sealed for use after 36 hours once more.
Embodiment 3
(1) produces the fibrous material bleached pulp
The industrial hemp that adopts is " cloud fiber crops No. 1 " industrial hemp kind.This hemp core is through the caustic soda-anthraquinone method boiling, and follow-up oxygen delignification, dioxide peroxide-hydrogen peroxide tri-stage bleaching make " cloud fiber crops No. 1 " stalk core bleached pulp fibrous material, and the characteristic of this bleached pulp is following: Kappa number 0.9, k value 967.3dm
3/ kg, whiteness value 90.7% (ISO).
(2) mill (beating) of industrial hemp stalk core bleached pulp fiber is starched preprocessing process and method
In order to improve cellulosic reactivity worth in the fibrous material; Adopt machinery mill (beating) slurry process to replace adopting one or more particular chemical reagent that Mierocrystalline cellulose is carried out run-inflation effect now mostly; Promptly utilize the Valley hollander that " cloud fiber crops No. 1 " stalk core bleached pulp fiber is ground the pre-treatment of (beating) slurry, and carry out the The real time measure of this kind slurry pulping degree through Xiao Baier freeness determinator.The pre-treatment degree is 50 ° of SR for the freeness of " cloud fiber crops No. 1 " stalk core bleached pulp.
(3) process and the method for the synthetic preparation of water-absorbing material
The concrete graft copolymerization synthesis condition of " cloud fiber crops No. 1 " stalk core bleached pulp fiber of 50 ° of SR freenesss is: vinylformic acid and acrylamide monomer consumption sum are 12: 1 with the ratio of over dry raw materials quality, and the vinylformic acid degree of neutralization is 60%; The initiator ammonium persulfate consumption is 0.015: 1 with the ratio of over dry raw material, and ammonium persulphate and S-WAT mass ratio are 3: 1; Linking agent N,N methylene bis acrylamide consumption is 0.005: 1 with the ratio of monomer total mass; Temperature of reaction is 45 ℃; Reaction times is 5.5 hours; The over dry stock quality should be controlled at 1 (g) with the ratio of reaction liquid TV: in the scope of 100～200 (ml).
The synthetic step of concrete graft copolymerization is: take by weighing a certain amount of acrylic amide and put into three mouthfuls of reaction flasks that the pre-treatment disposed slurry is housed, the acrylic acid solution of becoming reconciled in pouring into simultaneously.There-necked flask is put into the water-bath of constant temperature (50 ℃), start whipping appts, and in the prolong water flowing condensation of crawling of an end device of there-necked flask.The other end feeds N
2, logical N
2Behind 20～30min, a certain amount of ammonium persulphate of adding and showing of S-WAT are joined solution in reaction vessel, and the opening entry reaction times.After graft copolymerization begins 60min, add a certain amount of N, N '-methylene-bisacrylamide carries out crosslinking reaction.
(4) last handling process of water-absorbing material and method
After reaction finishes, synthetic resins is transferred in certain volumetrical beaker by three mouthfuls of reaction flasks fully, add a certain amount of absolute ethyl alcohol and carry out precipitating, washing, so repeatedly, become white jelly fully until transparency, pH is 7～8.Then, the gained resin is tiled in the petridish that is covered with preservative film after disperseing, and carries out lyophilize.Treat to carry out milled processed behind the resin complete drying, the toner behind mistake 120 eye mesh screens is positioned in the air-tight bottle, lyophilize sealed for use after 24 hours once more.
Embodiment 4
(1) produces the fibrous material bleached pulp
The industrial hemp that adopts is " cloud fiber crops No. 1 " industrial hemp kind.This hemp core is through the caustic soda-anthraquinone method boiling, and follow-up oxygen delignification, dioxide peroxide-hydrogen peroxide tri-stage bleaching make " cloud fiber crops No. 1 " stalk core bleached pulp fibrous material, and the characteristic of this bleached pulp is following: Kappa number 2.5, k value 1004dm
3/ kg, whiteness value 88.6% (ISO).
(2) mill (beating) of industrial hemp stalk core bleached pulp fiber is starched preprocessing process and method
In order to improve cellulosic reactivity worth in the fibrous material; Adopt machinery mill (beating) slurry process to replace adopting one or more particular chemical reagent that Mierocrystalline cellulose is carried out run-inflation effect now mostly; Promptly utilize the Valley hollander that " cloud fiber crops No. 1 " stalk core bleached pulp fiber is ground the pre-treatment of (beating) slurry, and carry out the The real time measure of this kind slurry pulping degree through Xiao Baier freeness determinator.The pre-treatment degree is 80 ° of SR for the freeness of " cloud fiber crops No. 1 " stalk core bleached pulp.
(3) process and the method for the synthetic preparation of water-absorbing material
The concrete graft copolymerization synthesis condition of " cloud fiber crops No. 1 " stalk core bleached pulp fiber of 80 ° of SR freenesss is: vinylformic acid and acrylamide monomer consumption sum are 14: 1 with the ratio of over dry raw materials quality, and the vinylformic acid degree of neutralization is 50%; The initiator ammonium persulfate consumption is 0.012: 1 with the ratio of over dry raw material, and ammonium persulphate and S-WAT mass ratio are 3: 1; Linking agent N,N methylene bis acrylamide consumption is 0.003: 1 with the ratio of monomer total mass; Temperature of reaction is 45 ℃; Reaction times is 5.0 hours; The over dry stock quality should be controlled at 1 (g) with the ratio of reaction liquid TV: in the scope of 100～200 (ml).
The synthetic step of concrete graft copolymerization is: take by weighing a certain amount of acrylic amide and put into three mouthfuls of reaction flasks that the pre-treatment disposed slurry is housed, the acrylic acid solution of becoming reconciled in pouring into simultaneously.There-necked flask is put into the water-bath of constant temperature (50 ℃), start whipping appts, and in the prolong water flowing condensation of crawling of an end device of there-necked flask.The other end feeds N
2, logical N
2Behind 20～30min, a certain amount of ammonium persulphate of adding and showing of S-WAT are joined solution in reaction vessel, and the opening entry reaction times.After graft copolymerization begins 60min, add a certain amount of N, N '-methylene-bisacrylamide carries out crosslinking reaction.
(4) last handling process of water-absorbing material and method
After reaction finishes, synthetic resins is transferred in certain volumetrical beaker by three mouthfuls of reaction flasks fully, add a certain amount of absolute ethyl alcohol and carry out precipitating, washing, so repeatedly, become white jelly fully until transparency, pH is 7～8.Then, the gained resin is tiled in the petridish that is covered with preservative film after disperseing, and carries out lyophilize.Treat to carry out milled processed behind the resin complete drying, the toner behind mistake 80 eye mesh screens is positioned in the air-tight bottle, lyophilize sealed for use after 24 hours once more.
Claims (2)
1. the preparation method of a water absorbing material of industrial hemp stalk core cellulose; It is characterized in that process step is: 1. industrial hemp stalk core is through the caustic soda-anthraquinone method boiling; Follow-up oxygen delignification, dioxide peroxide-hydrogen peroxide tri-stage bleaching makes industrial hemp stalk core bleached pulp fiber; The hemp stalk core Mierocrystalline cellulose should be bleached bleached pulp and reach Kappa number 9.5～0.5, k value 1100～950 dm
3/ kg, whiteness value 55.0～92.5 %; 2. adopt mechanical hollander to the pre-treatment of bleached pulp fiber defibrination, freeness is 35～85
°SR; 3. it is synthetic that the bleached pulp fiber after adopting aqueous solution polymerization method to defibrination carries out graft copolymerization, promptly selects for use ammonium persulphate and sodium sulfite anhy 96 as redox body initiator system, with N, and N
,-methylene-bisacrylamide is a linking agent; Select for use vinylformic acid and acrylic amide to accomplish simultaneously as monomer; The graft copolymerization synthesis condition is: vinylformic acid and acrylamide monomer consumption sum are 2:1～20:1 with the ratio of over dry raw materials quality, and the vinylformic acid degree of neutralization is 15～85%; The initiator ammonium persulfate consumption is 0.0001～0.02:1 with the ratio of over dry raw material, and ammonium persulphate and S-WAT mass ratio are 1:1～4:1; Linking agent N, N
,-methylene-bisacrylamide consumption is 0.0001～0.02:1 with the ratio of monomer total mass; Temperature of reaction is 30～80 ℃, and the reaction times is 3.5～15 hours; The over dry stock quality should be controlled in the scope of 1g:100～200ml with the ratio of reaction liquid TV; 4. the copolymerization synthetics is carried out precipitating, washing, lyophilize, milled processed, freezing, sealing again with absolute ethyl alcohol, obtain finished product.
2. by the preparation method of the described water absorbing material of industrial hemp stalk core cellulose of claim 1, it is characterized in that: 1. in graft copolymerization was synthetic, the vinylformic acid degree of neutralization was 70%; 2. graft copolymerization synthetic after, with absolute ethyl alcohol to synthetics repeatedly precipitating, washing be ground to 70～200 mesh sieves after the lyophilize to becoming pH 7～8 white jellies fully, freezing time is 24～72 hours again.
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| CN102040709B (en) * | 2010-10-27 | 2013-06-12 | 昆明理工大学 | Method for preparing bleaching bamboo pulp cellulose water absorbing material |
| CN102504460B (en) * | 2011-11-11 | 2014-03-19 | 苏州大学 | Sweetcane bark fiber composite and preparation method thereof |
| CN103554372B (en) * | 2013-10-21 | 2015-09-16 | 昆明理工大学 | The preparation method of industrial hemp stalk core cellulose base temperature-sensitivcomposite composite hydrogel |
| CN107176881A (en) * | 2017-06-28 | 2017-09-19 | 常州麒通国际贸易有限公司 | A kind of Water-retaining slow-release fertilizer and preparation method thereof |
| CN108559035B (en) * | 2018-04-27 | 2020-07-24 | 南京林业大学 | Method for modifying super absorbent resin by using main components of papermaking black liquor and material thereof |
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