CN102675563B - Preparation method of water-absorbable material by crofton weed - Google Patents
Preparation method of water-absorbable material by crofton weed Download PDFInfo
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- CN102675563B CN102675563B CN201210152433.XA CN201210152433A CN102675563B CN 102675563 B CN102675563 B CN 102675563B CN 201210152433 A CN201210152433 A CN 201210152433A CN 102675563 B CN102675563 B CN 102675563B
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- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000000463 material Substances 0.000 title abstract description 12
- 244000217401 Ageratina adenophora Species 0.000 title abstract 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 51
- 229920005989 resin Polymers 0.000 claims abstract description 35
- 239000011347 resin Substances 0.000 claims abstract description 35
- 238000000034 method Methods 0.000 claims abstract description 32
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 31
- 239000002994 raw material Substances 0.000 claims abstract description 31
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 30
- 241000196324 Embryophyta Species 0.000 claims abstract description 16
- 239000007864 aqueous solution Substances 0.000 claims abstract description 15
- 238000005406 washing Methods 0.000 claims abstract description 13
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- 238000012216 screening Methods 0.000 claims abstract description 10
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- 238000007605 air drying Methods 0.000 claims abstract description 6
- 238000007789 sealing Methods 0.000 claims abstract description 6
- 238000010528 free radical solution polymerization reaction Methods 0.000 claims abstract description 3
- 244000025254 Cannabis sativa Species 0.000 claims description 82
- 241000735527 Eupatorium Species 0.000 claims description 81
- 239000011487 hemp Substances 0.000 claims description 80
- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 claims description 79
- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 claims description 79
- 235000009120 camo Nutrition 0.000 claims description 79
- 235000005607 chanvre indien Nutrition 0.000 claims description 79
- 239000011236 particulate material Substances 0.000 claims description 31
- 239000011358 absorbing material Substances 0.000 claims description 29
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- 238000006243 chemical reaction Methods 0.000 claims description 26
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 16
- 230000008569 process Effects 0.000 claims description 16
- 238000000605 extraction Methods 0.000 claims description 13
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 12
- 238000012545 processing Methods 0.000 claims description 12
- 238000000944 Soxhlet extraction Methods 0.000 claims description 10
- 239000004159 Potassium persulphate Substances 0.000 claims description 8
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- 230000035484 reaction time Effects 0.000 claims description 8
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- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 4
- 239000003082 abrasive agent Substances 0.000 claims description 2
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- 230000001105 regulatory effect Effects 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 29
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 abstract description 20
- 239000012153 distilled water Substances 0.000 abstract description 13
- 239000011780 sodium chloride Substances 0.000 abstract description 10
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- 238000003786 synthesis reaction Methods 0.000 abstract description 4
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- 238000004108 freeze drying Methods 0.000 abstract 2
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- 239000012024 dehydrating agents Substances 0.000 abstract 1
- 239000002274 desiccant Substances 0.000 abstract 1
- 238000003898 horticulture Methods 0.000 abstract 1
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- 239000002250 absorbent Substances 0.000 description 21
- 230000002745 absorbent Effects 0.000 description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000007788 liquid Substances 0.000 description 9
- 238000011160 research Methods 0.000 description 9
- 239000000178 monomer Substances 0.000 description 7
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- 239000000126 substance Substances 0.000 description 4
- 229920000742 Cotton Polymers 0.000 description 3
- 230000033228 biological regulation Effects 0.000 description 3
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- 229920003002 synthetic resin Polymers 0.000 description 3
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- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Natural products CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
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- -1 acetic acid bornyl ester Chemical class 0.000 description 2
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- DSSYKIVIOFKYAU-XCBNKYQSSA-N (R)-camphor Chemical compound C1C[C@@]2(C)C(=O)C[C@@H]1C2(C)C DSSYKIVIOFKYAU-XCBNKYQSSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 150000000703 Cerium Chemical class 0.000 description 1
- 241000723346 Cinnamomum camphora Species 0.000 description 1
- WTEVQBCEXWBHNA-UHFFFAOYSA-N Citral Natural products CC(C)=CCCC(C)=CC=O WTEVQBCEXWBHNA-UHFFFAOYSA-N 0.000 description 1
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- USNWAMPROKAEIT-UHFFFAOYSA-N [Na].C(C=C)(=O)O Chemical compound [Na].C(C=C)(=O)O USNWAMPROKAEIT-UHFFFAOYSA-N 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
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- 229930008392 geranic acid Natural products 0.000 description 1
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- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
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- Cosmetics (AREA)
Abstract
The invention discloses a preparation method of water-absorbable material by harmful invasive species, i.e. crofton weed, which comprises the following steps of: carrying our air drying on the whole plant of crofton weed and grinding, extracting with diethyl ether after screening, removing hydrophobic poison components from particle raw materials, carrying out graft copolymerization synthesis on the extracted crofton weed particle-shaped raw material by an aqueous solution polymerization method, precipitating a graft copolymerization synthetic with absolute methanol, dispersing and washing, carrying out freeze drying, grinding, carrying out freeze drying again, and sealing, to obtain crofton weed water-absorbable resin; the water-absorbable material prepared by the method has the distilled water absorbing multiplying power of 930g/g highest, and the distilled water absorbing speed of 20min; the 0.9% sodium chloride water solution absorbing rate can reach to 320g/g highest, and the 0.9% sodium chloride water solution absorbing rate is 40min; and the preparation method is applicable to the soil conditioner water and the cultivation agent in the aspects of the agriculture, the forestry and the horticulture, and the desiccating agent and the dehydrating agent in the aspect of the industry.
Description
Technical field
The present invention relates to the harmful invasive species of a kind of utilization---the method for Hemp Eupatorium manufacture water-absorbing material, belongs to natural macromolecular material technical field.
Background technology
Hemp Eupatorium (Eupatorium adenophorum Spreng) belongs to composite family Eupatorium, because its stem, petiole are purple, and therefore named Hemp Eupatorium.Hemp Eupatorium plant strain growth is lignifying after 1.5 days, is perennial, the shape subshrub plant that grows thickly, and high 1.0-1.5 rice, is up to 3 meters of left and right.Hemp Eupatorium be about the 1950's from the injurious weed of South East Asia successor China, be distributed widely in Yunnan, Guizhou, spread all over the ground such as Sichuan, Guangxi, Tibet, just with the speed of annual approximately 60 hectares, constantly to Central China and East China, spread at present.In recent years, due to the invasion of Hemp Eupatorium big area, procreation, overflows everywhere, to the ecosystem, causes very large harm.Only Yunnan Province just has 10 Ge Di ,Zhou98Ge cities and counties generation areas to reach 24.8 ten thousand hectares of 67% of ，Zhan the whole province areas that are affected.The husbandry direct losses that cause to Yunnan Province are every year up to more than 700,000,000 yuan, not count enable of indirect loss.In the domestic 16 kinds of alien species Black Lists of first batch of invasion that in March, 2003, ， State Environmental Protection Administration announced, Hemp Eupatorium taking the first place.To the work of preventing and kill off of Hemp Eupatorium the whole nation by all kinds of means, omnibearing expansion, but, in the situation that cannot eradicating completely at present, to the utilization of Hemp Eupatorium, can not ignore, therefore, adopt the means of the comprehensive regulation to be controlled and become extremely urgent important business spreading of these species.
In the data of the chemical composition of relevant Hemp Eupatorium complete stool, show that this kind of raw material contains 67.16% holocellulose, illustrate that Hemp Eupatorium has the utility value as fibrous material.Meanwhile, this raw material is similar to other plant raw material, still contains the organic extraction material of a certain amount of lower molecular weight.In organic extractum, contain in this section that geranial, geranic acid, acetic acid bornyl ester, camphor etc. are multiple has volatile poisonous and harmful component.Therefore, how low molecular organic material harmful in Hemp Eupatorium is removed, refining is also made good use of fibre fractionation useful in raw material and will be become the key content in early stage of this patent.This patent early stage implementation step and pulping and paper-making expertise combine closely, utilizing the means of papermaking plant material chemical composition analysis---ether extract measuring method removes the harmonic component organic constituent of toxic in Hemp Eupatorium, to carry out raw material for the synthetic water-absorbing material of lower step, prepares.
The history that the research and development of water-absorbing material only has decades.The 1950's, U.S. Goodrich company has developed cross linked polyacrylate, and this typical high-absorbent material was to use as thickening material at that time.Nineteen fifty-nine, the USDA north C. R. Rissell of institute starts to carry out the research of starch-grafted vinyl cyanide, has invented HSPAN starch acrylamide nitrile graft copolymerization hydrolyzate.Subsequently, the people such as G. F. Fanta continues research.In 1966, they caused third rare nitrile graft copolymerization on wheat starch by cerium salt, and product designation is P-PAN, and this product has very strong water-retaining capacity and good water retention property; This resin succeeds in Henkel Corporation industrialization at first, and its commodity are called SGP (Starch Graft Polymer).1975, SANYO GS changed into room, the increasing field justice of Co., Ltd. on the basis of the relevant research of USDA, with vinylformic acid, replaces third poisonous rare nitrile monomer to develop the super water-absorbing material of starch graft acrylic acid sodium.The launch products that the model of take for 1978 is IM-300.Afterwards, the Grain-Processing of the U.S., Hercules, National Starch, General Mills Chemical, SUMITOMO CHEMICAL chemistry, flower Wang Shi Jian Deng company has successfully developed the multiple high-hydroscopicity products such as GPC, Aqualon, Permasorb in succession.Proposed the eighties, with radioactive rays, various olefin oxides are carried out to crosslinking Treatment, synthesized non-ionic type high-absorbent material, its water-retaining capacity is 2000 times, thereby has opened the gate of nonionic high-absorbent material.Start from High hydrophilous resin and other inorganicss or the compound research that obtains high water absorption composite material of the organism eighties, after entering the nineties, had and developed faster and break through.
The research and development of China's water-absorbing resin is started in the eighties in 20th century.Nineteen eighty-two, first the people such as the yellow beautiful jade of Institute of Chemistry, Academia Sinica synthesize sodium polyacrylate high absorbency material at home.Over more than 20 year, research was in this respect engaged in the whole nation successively You40Duo Ge unit.At present, domestic priority You40Duo company and enterprise development are produced High hydrophilous resin, but throughput is lower, add the reason of the reverse side such as occupation rate in quality product and market, compare with external product, have sizable gap, therefore, domestic super absorbent resin fat prod mostly relies on import.
Now, 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 with respect to starch-series super-strong moisture absorbing resin, the research of the histiocytic water-absorbing material of natural phant is relatively less, and take the research that Hemp Eupatorium fiber is basic absorbent resin and remain blank out.
This application will be used Hemp Eupatorium complete stool (comprising stalk and leaf) to prepare water-absorbing material first, inquire into these species as the technical feasibility of super absorbent resin raw material, synthesize preferably resin of absorbent, be mainly used in the water conservation growth of agriculture and forestry plant, a new approach that utilizes with high added value is explored in the comprehensive regulation work that hews out brand-new road ，Ye Wei China Harmful species invasion for solving puzzlement " green desert " problem for a long time.Therefore the research of, carrying out the histocyte water-absorbing material of Hemp Eupatorium has important realistic meaning.
Summary of the invention
In the situation that cannot eradicating Hemp Eupatorium completely at present, to its effective utilization, can not ignore, therefore, the invention provides a kind of preparation method of Hemp Eupatorium water-absorbing material, the method is utilized this exotic invasive Harmful species, prepares every suction
Fluidity is water-absorbing material preferably, for effective exploitation utilizes Hemp Eupatorium, provides a brand-new comprehensive regulation road.
Realize the process technology scheme that the object of the invention takes as follows:
1. Hemp Eupatorium complete stool plant carries out milled processed after air-dry, makes Hemp Eupatorium particulate material after screening, and particulate material adopts ether extraction to process;
2. it is synthetic that the Hemp Eupatorium feed particulate material after adopting aqueous solution polymerization method to extracting is carried out graft copolymerization;
3. grafting copolymerization thing is carried out repeatedly to precipitating, dispersion and washing, lyophilize, milled processed, lyophilize again, sealing with anhydrous methanol, obtain Powdered finished product and be Hemp Eupatorium water-absorbing resin.
The preparation method of Hemp Eupatorium water-absorbing material of the present invention, concrete operations are as follows:
1. the set-up procedure of Hemp Eupatorium raw material: Hemp Eupatorium plant is after air-dry processing, wherein the moisture of air-dry raw material is different and different according to different areas Various Seasonal atmospheric moisture, general moisture control is in 7～20% scope, grind, abrasive material is Hemp Eupatorium particulate material after 100～400 object sieve screenings;
2. in order to remove harmful toxic matter potential in Hemp Eupatorium plant, particulate material after crushing and screening carries out ether extraction processing, extracting treating processes is as follows: the ratio of adding 250～1100ml ether in 5～20g Hemp Eupatorium particulate material, take Hemp Eupatorium particulate material and wrap with qualitative filter paper, put into Soxhlet extraction device, add ether, carry out extracting processing, regulating temperature to make ether boiling speed is that the circulation in Soxhlet extraction device per hour is no less than 3～5 times, repeatedly after extracting 24h～72h, take out particulate material, natural air drying, standby;
The acrylic acid solution of becoming reconciled in 3. adding in raw material after extracting, vinylformic acid consumption is 8:1～19:1 with the ratio of over dry extracting raw materials quality, and vinylformic acid degree of neutralization is 25～80%, then stirring reaction at 45～90 ℃ passes into N simultaneously
2, logical N
2after 30～60 min, add persulfate aqueous solution and N, N, N
,, N
,the mixed solution of-Tetramethyl Ethylene Diamine, starts graft copolymerization, carries out after 30～60min, then add linking agent N, N in reaction
,-methylene-bisacrylamide carries out crosslinking reaction simultaneously, and graft copolymerization/cross-linking reaction time is 4.5～15.0 hours; Wherein initiator potassium persulfate consumption is 0.008～0.035:1 with over dry extracting raw materials quality ratio, Potassium Persulphate and N, N, N
,, N
,-Tetramethyl Ethylene Diamine mass ratio is 1:1～3:1, linking agent N, N
,-methylene-bisacrylamide consumption and vinylformic acid mass ratio are 0.01～0.04:1; In the synthetic process of graft copolymerization, over dry raw materials quality is 1g:80～200ml with the ratio of reaction liquid cumulative volume; Persulfate aqueous solution concentration is 0.8～3.5g/L;
4. after graft copolymerization is synthesized, with anhydrous methanol to synthetic product precipitating, washing repeatedly, until transparency becomes yellow-green colour jelly completely, after cleaning, the pH of washings is 6.0～8.0, synthetic product is ground to 80～200 orders after lyophilize, lyophilize is processed 12～36 hours again, obtains Powdered Hemp Eupatorium water-absorbing resin.
Acrylic Acid Monomer often reactivity worth is too active, so will neutralize with sodium hydroxide before reaction, makes its reactivity within controlled range; In the present invention, acrylic acid neutralization operates according to a conventional method.
Detection and the method for calculation of the absorbent of Hemp Eupatorium water-absorbing resin are as described below: adopt natural filtration method to measure, the foundation that is determined as with the liquid absorbency rate of distilled water (or 0.9% salt solution), take 1.000～1.100 g resins and put into 400 order mesh bags, and mesh bag is placed in beaker, the distilled water (or 0.9% salt solution) that adds 1000 ml, at room temperature standing imbibition, every 10min, take out a mesh bag and hang to weigh after 30.0 min filter unnecessary liquid and calculate liquid absorbency rate by following formula, until liquid absorbency rate no longer increases.
The invention has the beneficial effects as follows: utilize Invasive Alien Species----Hemp Eupatorium is as the raw material of water-absorbing resin, the whole strain plant of Hemp Eupatorium (comprising stalk and leaf) is obtained after mechanical mill, screening to the particulate material of specified dimension, the milled processed of its Raw can be destroyed the crystalline texture of Hemp Eupatorium Mierocrystalline cellulose and xylogen well, thereby expose more activity hydroxy, can fully improve graft copolymerization ability.By ether extraction, process the hydrophobic nature that is soluble in neutral organic solvent removing in Hemp Eupatorium particulate material and poison composition, for follow-up synthesizing " green " Hemp Eupatorium absorbent resin carry out raw material and prepare, the related experiment condition providing according to the application, detected result shows that the absorbent of Hemp Eupatorium water-absorbing material is as follows: inhale distilled water multiplying power and can reach 930 g/g, inhaling distilled water speed is 20 min; Inhale 0.9% sodium chloride aqueous solution multiplying power and reach as high as 320 g/g, inhaling 0.9% sodium chloride aqueous solution speed is 40 min; It is Powdered that this water-absorbing material is pistac, is applicable to agricultural, gardening aspect and makes anti-drought water-retaining agent and cultivating agent, industrial aspect as siccative and dewatering agent.
This patent is used Hemp Eupatorium complete stool as the starting raw material of water-absorbing material first, by the Hemp Eupatorium particulate material to after ether extraction, directly carries out graft copolymerization/crosslinking reaction, can synthesize fast cheap absorbent resin.Water-absorbing material with existing xylogen/cellulose complex system is compared, and this material has higher water absorbent rate and very fast rate of water absorption.In the means that realize at water-absorbing resin, this patent utilizes the size of feed particles particle diameter to control the degree of graft copolymerization, thereby controls every absorbent of water-absorbing resin.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail, but protection domain of the present invention is not limited to described content.
Embodiment 1: the preparation method of Hemp Eupatorium water-absorbing material, and concrete operations are as follows:
(1) melting process of Hemp Eupatorium
Hemp Eupatorium complete stool plant carries out air-dry processing, and the air-dry plant that water ratio is 15% carries out mechanical mill processing, after 100 mesh sieve screenings, is then qualified Hemp Eupatorium particulate material;
(2) Hemp Eupatorium particulate material ether extraction is processed
Taking 5g Hemp Eupatorium particulate material wraps with qualitative filter paper, with cotton thread, tie, put in the Soxhlet extraction device of 250ml, add the analytical pure ether of 250ml, load onto condenser, connect extracting instrument, in water-bath, open water coolant, it is that the circulation in Soxhlet extraction device per hour is 5 times that the well heater of adjusting water-bath makes its ether boiling speed, repeatedly after extracting 24h, with tweezers, will expect that bag takes out, be placed in clean pallet natural air drying, standby;
(3) process of the synthetic preparation of water-absorbing material
The concrete graft copolymerization synthesis condition of Hemp Eupatorium particulate material after ether extraction is: vinylformic acid consumption is 8:1 with over dry raw materials quality ratio, and vinylformic acid degree of neutralization is 25%; Initiator potassium persulfate consumption is 0.008:1 with over dry raw materials quality ratio, and Potassium Persulphate and N, N, N
,, N
,-Tetramethyl Ethylene Diamine mass ratio is 2:1; Linking agent N, N
,-methylene-bisacrylamide consumption and Acrylic Acid Monomer mass ratio are 0.01:1; Temperature of reaction is 45 ℃; Total reaction time is 15.0 hours; Over dry stock quality is controlled at 1g:80ml with the ratio of reaction liquid cumulative volume.
The synthetic step of concrete graft copolymerization is: the over dry raw material taking after 1.00g extracting is put in three mouthfuls of reaction flasks, the acrylic acid solution of becoming reconciled in simultaneously pouring into (vinylformic acid 8.00g wherein, sodium hydroxide 1.11g), there-necked flask is put into the water-bath of 45 ℃ of constant temperature, start whipping appts, and in one end of there-necked flask, load onto the prolong water flowing condensation of crawling, the other end passes into N
2, logical N
2after 30min, to adding respectively 10.0ml concentration in reaction vessel, be to join potassium persulfate solution (react took 0.02g Potassium Persulphate medicine the same day dissolve in the volumetric flask of 25ml after constant volume gained) and 0.005ml N, N, N showing of 0.8g/L
,, N
,-Tetramethyl Ethylene Diamine liquid drug (density 0.78g/cm
3), starting timing, graft copolymerization starts, and when graft copolymerization starts 60 min, adds the N of 0.08g, N
,-methylene-bisacrylamide, carries out crosslinking reaction, then continues 14 hours reaction times.
(4) last handling process of water-absorbing material and method
After reaction finishes, synthetic resins is transferred in beaker by three mouthfuls of reaction flasks completely, with 200ml anhydrous methanol, carry out precipitating, washing, until transparency becomes yellow-green colour jelly completely, washings pH is 7.0, then gained resin dispersion is laid in the culture dish that is covered with preservative film, more than carrying out lyophilize 24h, after resin complete drying, carry out milled processed, the toner of crossing after 80 eye mesh screens is positioned in air-tight bottle, lyophilize is after 12 hours again, and sealing, is Powdered Hemp Eupatorium water-absorbing resin.
(5) absorbent of Hemp Eupatorium absorbent resin is measured
Take 1.000g resin and put into 400 order mesh bags, and mesh bag is placed in beaker, add the distilled water (or 0.9% salt solution) of 1000 ml, at room temperature after standing imbibition, take out mesh bag and hang 30 min and filter the calculating liquid absorbency rate of weighing after unnecessary liquid, calculation formula is as follows:
The absorbent of final Hemp Eupatorium water-absorbing material is as follows: inhale distilled water multiplying power and reach 516 g/g, inhaling distilled water speed is 40 min; Inhale 0.9% sodium chloride aqueous solution multiplying power 191 g/g, inhaling 0.9% sodium chloride aqueous solution speed is 80 min; Be pistac Powdered.
embodiment 2:the preparation method of Hemp Eupatorium water-absorbing material, concrete operations are as follows:
(1) melting process of Hemp Eupatorium
Hemp Eupatorium complete stool plant carries out air-dry processing, and the air-dry plant that water ratio is 7% carries out mechanical mill processing, after 300 mesh sieve screenings, is then qualified Hemp Eupatorium particulate material;
(2) Hemp Eupatorium particulate material ether extraction treating processes and method
Qualified Hemp Eupatorium particulate material is wrapped with qualitative filter paper to take 10g, with cotton thread, ties, and puts in the Soxhlet extraction device of 500ml specification, the analytical pure ether that adds 500ml, load onto condenser, connect extracting instrument, in water-bath, open water coolant, it is that the circulation in Soxhlet extraction device per hour is 4 times that the well heater of adjusting water-bath makes its ether boiling speed, so, after extracting 48h, with tweezers, will expect that bag takes out, be placed in clean pallet natural air drying, standby.
(3) process of the synthetic preparation of water-absorbing material
The concrete graft copolymerization synthesis condition of Hemp Eupatorium particulate material after ether extraction is: Acrylic Acid Monomer consumption is 15:1 with the ratio of over dry raw materials quality, and vinylformic acid degree of neutralization is 65%; Initiator potassium persulfate consumption is 0.020:1 with the ratio of over dry raw material, and Potassium Persulphate and N, N, N
,, N
,-Tetramethyl Ethylene Diamine mass ratio is 1:1; Linking agent N, N
,-methylene-bisacrylamide consumption and Acrylic Acid Monomer mass ratio are 0.025:1; Temperature of reaction is 70 ℃; Total reaction time is 6.5 hours; Over dry stock quality should be controlled at 1g:150ml with the ratio of reaction liquid cumulative volume.
The synthetic step of concrete graft copolymerization is: the raw material taking after 1.00g extracting is put in three mouthfuls of reaction flasks, the acrylic acid solution of becoming reconciled in simultaneously pouring into (vinylformic acid 15.00g wherein, sodium hydroxide 5.42g), there-necked flask is put into the water-bath of 70 ℃ of constant temperature, start whipping appts, and in one end of there-necked flask, load onto the prolong water flowing condensation of crawling, the other end passes into N
2, the other end passes into N
2, logical N
2after 45min, to adding respectively 10.0ml concentration in reaction vessel, be to join potassium persulfate solution (react took 0.05g Potassium Persulphate medicine the same day dissolve in the volumetric flask of 25ml after constant volume gained) and 0.026mlN, N, N showing of 2.0g/L
,, N
,-Tetramethyl Ethylene Diamine liquid drug (density 0.78g/cm
3), starting timing, graft copolymerization starts.When graft copolymerization starts 45 min, add the N of 0.375g, N
,-methylene-bisacrylamide, carries out crosslinking reaction, then continues 5.75 hours reaction times.
(4) last handling process of water-absorbing material and method
After reaction finishes, synthetic resins is transferred in beaker by three mouthfuls of reaction flasks completely, with 300ml anhydrous methanol, carry out precipitating, washing, until transparency becomes yellow-green colour jelly completely, washings pH is 6.0, then gained resin dispersion is laid in the culture dish that is covered with preservative film, more than carrying out lyophilize 24h, after resin complete drying, carry out milled processed, the toner of crossing after 200 eye mesh screens is positioned in air-tight bottle, lyophilize is after 24 hours again, and sealing, is Powdered Hemp Eupatorium water-absorbing resin.
(5) absorbent of Hemp Eupatorium absorbent resin
Detection method is with embodiment 1(5), the following institute of absorbent of final Hemp Eupatorium water-absorbing material: inhale distilled water multiplying power and reach 930 g/g, inhaling distilled water speed is 20 min; Inhale 0.9% sodium chloride aqueous solution multiplying power 320 g/g, inhaling 0.9% sodium chloride aqueous solution speed is 40 min; Be pistac Powdered.
embodiment 3:the preparation method of Hemp Eupatorium water-absorbing material, concrete operations are as follows:
(1) melting process of Hemp Eupatorium
Hemp Eupatorium complete stool plant carries out air-dry processing, and the air-dry plant that water ratio is 12% carries out mechanical mill processing, after 400 mesh sieve screenings, is then qualified Hemp Eupatorium particulate material;
(2) Hemp Eupatorium particulate material ether extraction treating processes and method
Qualified Hemp Eupatorium particulate material is wrapped with qualitative filter paper to take 20g, with cotton thread, ties, and puts in the Soxhlet extraction device of 1000ml specification, the analytical pure ether that adds 1000ml left and right, load onto condenser, connect extracting instrument, in water-bath, open water coolant, it is that the circulation in Soxhlet extraction device per hour is 3 times that the well heater of adjusting water-bath makes its ether boiling speed, so, after extracting 72h, with tweezers, will expect that bag takes out, be placed in clean pallet natural air drying, standby.
(3) process and the method for the synthetic preparation of water-absorbing material
The concrete graft copolymerization synthesis condition of Hemp Eupatorium particulate material after ether extraction is: Acrylic Acid Monomer consumption is 19:1 with the ratio of over dry raw materials quality, and vinylformic acid degree of neutralization is 80%; Initiator potassium persulfate consumption is 0.035:1 with the ratio of over dry raw material, and Potassium Persulphate and N, N, N
,, N
,-Tetramethyl Ethylene Diamine mass ratio is 3:1; Linking agent N, N
,-methylene-bisacrylamide consumption and Acrylic Acid Monomer mass ratio are 0.040:1; Temperature of reaction is 90 ℃; Total reaction time is 4.5 hours; Over dry stock quality should be controlled at 1g:200ml with the ratio of reaction liquid cumulative volume.
The synthetic step of concrete graft copolymerization is: the raw material taking after 1.00g extracting is put in three mouthfuls of reaction flasks, the acrylic acid solution of becoming reconciled in simultaneously pouring into (vinylformic acid 19.00g wherein, sodium hydroxide 8.44g), there-necked flask is put into the water-bath of 90 ℃ of constant temperature, start whipping appts, and in one end of there-necked flask, load onto the prolong water flowing condensation of crawling, the other end passes into N
2, the other end passes into N
2, logical N
2after 60min, to adding respectively 10.0ml concentration in reaction vessel, be to join potassium persulfate solution (react took 0.0875g Potassium Persulphate medicine the same day dissolve in the volumetric flask of 25ml after constant volume gained) and 0.015mlN, N, N showing of 3.5g/L
,, N
,-Tetramethyl Ethylene Diamine liquid drug (density 0.78g/cm
3), starting timing, graft copolymerization starts.When graft copolymerization starts 30 min, add the N of 0.76g, N
,-methylene-bisacrylamide, carries out crosslinking reaction, then continues 4.0 hours reaction times.
(4) last handling process of water-absorbing material and method
After reaction finishes, synthetic resins is transferred in beaker by three mouthfuls of reaction flasks completely, with 250ml anhydrous methanol, carry out precipitating, washing, until transparency becomes yellow-green colour jelly completely, washings pH is 8.0, then gained resin dispersion is laid in the culture dish that is covered with preservative film, more than carrying out lyophilize 24h, after resin complete drying, carry out milled processed, the toner of crossing after 150 eye mesh screens is positioned in air-tight bottle, lyophilize is after 36 hours again, and sealing, is Powdered Hemp Eupatorium water-absorbing resin.
(5) absorbent of Hemp Eupatorium absorbent resin
Detection method is with embodiment 1(5), the following institute of absorbent of final Hemp Eupatorium water-absorbing material: inhale distilled water multiplying power and reach 708 g/g, inhaling distilled water speed is 10 min; Inhale 0.9% sodium chloride aqueous solution multiplying power 266 g/g, inhaling 0.9% sodium chloride aqueous solution speed is 15 min; Be pistac Powdered.
Claims (2)
1. a preparation method for Hemp Eupatorium water-absorbing material, is characterized in that carrying out as follows:
1. Hemp Eupatorium complete stool plant carries out milled processed after air-dry, makes Hemp Eupatorium particulate material after screening, and particulate material adopts ether extraction to process;
2. it is synthetic that the Hemp Eupatorium feed particulate material after adopting aqueous solution polymerization method to extracting is carried out graft copolymerization;
3. grafting copolymerization thing is carried out to precipitating, dispersion and washing, lyophilize, milled processed, lyophilize again, sealing with anhydrous methanol, obtain Powdered finished product and be Hemp Eupatorium water-absorbing resin;
Wherein the concrete operations of aforesaid method are as follows:
1. by Hemp Eupatorium complete stool plant after air-dry processing, grind, abrasive material is Hemp Eupatorium particulate material after crossing 100～400 mesh sieves screenings;
2. Hemp Eupatorium particulate material adopts ether extraction to process, in 5～20g Hemp Eupatorium particulate material, add the ratio of 250～1100ml ether, take Hemp Eupatorium particulate material and wrap with qualitative filter paper, put into Soxhlet extraction device, add ether, carry out extracting processing, regulating temperature to make ether boiling speed is that the circulation in Soxhlet extraction device per hour is no less than 3～5 times, repeatedly after extracting 24～72h, take out particulate material, natural air drying, standby;
The acrylic acid solution of becoming reconciled in 3. adding in raw material after extracting, vinylformic acid consumption is 8:1～19:1 with the ratio of over dry extracting raw materials quality, and vinylformic acid degree of neutralization is 25～80%, then stirring reaction at 45～90 ℃ passes into N simultaneously
2, logical N
2after 30～60 min, add persulfate aqueous solution and N, N, N
,, N
,the mixed solution of-Tetramethyl Ethylene Diamine, starts graft copolymerization, carries out after 30～60min, then add linking agent N, N in reaction
,-methylene-bisacrylamide carries out crosslinking reaction simultaneously, and graft copolymerization/crosslinked total reaction time is 4.5-15.0 hour; Wherein initiator potassium persulfate consumption is 0.008～0.035:1 with over dry extracting raw materials quality ratio, Potassium Persulphate and N, N, N
,, N
,-Tetramethyl Ethylene Diamine mass ratio is 1:1～3:1, linking agent N, N
,-methylene-bisacrylamide consumption and vinylformic acid mass ratio are 0.01～0.04:1; In the synthetic process of graft copolymerization, over dry raw materials quality is 1g:80～200ml with the ratio of reaction liquid cumulative volume; Persulfate aqueous solution concentration is 0.8～3.5g/L;
4. after graft copolymerization is synthesized, with anhydrous methanol, synthetic product is carried out to precipitating, washing, until transparency becomes yellow-green colour jelly completely, after cleaning, the pH of washings is 6.0～8.0, synthetic product is ground to 80～200 orders after lyophilize, lyophilize is processed 12～36 hours again, obtains Powdered Hemp Eupatorium water-absorbing resin.
2. by the preparation method of Hemp Eupatorium water-absorbing material claimed in claim 1, it is characterized in that: in 1g over dry raw material, add the ratio of 200～300ml anhydrous methanol, with anhydrous methanol, synthetic product is carried out to precipitating.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101519476A (en) * | 2009-03-30 | 2009-09-02 | 中国科学技术大学 | Method for preparing high-hydroscopicity resin in homogeneous aqueous medium by using straw as raw material |
| CN102344532A (en) * | 2011-07-21 | 2012-02-08 | 东华大学 | Method for synthesizing super absorbent resin by using invasive plant |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101519476A (en) * | 2009-03-30 | 2009-09-02 | 中国科学技术大学 | Method for preparing high-hydroscopicity resin in homogeneous aqueous medium by using straw as raw material |
| CN102344532A (en) * | 2011-07-21 | 2012-02-08 | 东华大学 | Method for synthesizing super absorbent resin by using invasive plant |
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