CN100365068C - Environment friendly lignin resin of high water absorbence and its preparation method - Google Patents
Environment friendly lignin resin of high water absorbence and its preparation method Download PDFInfo
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- CN100365068C CN100365068C CNB2004100408943A CN200410040894A CN100365068C CN 100365068 C CN100365068 C CN 100365068C CN B2004100408943 A CNB2004100408943 A CN B2004100408943A CN 200410040894 A CN200410040894 A CN 200410040894A CN 100365068 C CN100365068 C CN 100365068C
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Abstract
The present invention relates to environment-friendly lignin resin with high water absorption, which belongs to the technical field of lignin material compounds and is characterized in that the environment-friendly lignin resin with high water absorption comprises the components according to the proportion of weight of 30 to 80 portions of high-pure lignin, 10 to 40 portions of water-soluble macro-molecule, 2 to 10 portions of initiating agent, 2 to 10 portions of cross linker, 1 to 5 portions of foaming agent and 100 to 200 portions of water. The preparation method for the environment-friendly lignin resin comprises four steps that raw materials are processed, and the high-pure lignin is separated and purified; the high-pure lignin, the water-soluble macro-molecules, the initiating agents, the cross linkers, etc. are metered according to the proportion of weight; activation, stem grafting, crosslinking and copolymerization are carried out at the temperature of 60 to 180 DEG C; the foaming agents are added to a high-speed mixing machine after spraying and drying, and thus, the environment-friendly lignin resin with high water absorption is obtained. The products of the present invention have favorable performance of water absorption, water retention and film forming, and has important popularization and application value in the fields of farming, forestry, gardening, petroleum, chemical industry, environmental protection, building materials, etc.
Description
(1) technical field
The present invention relates to eco-friendly lignin High hydrophilous resin and preparation method thereof, belong to the composition that contains lignin material, is the modification and the new product development of natural lignin.
(2) background technology
On the earth natural plant material-lignin next in number only to Mierocrystalline cellulose, estimate that the annual whole world can produce 1,500 hundred million tons of lignins by plant-growth.The history in existing several thousand of human use's Mierocrystalline cellulose, and lignin really to begin one's study be thing after nineteen thirty, and well do not utilize so far, the Nature offers human large resource, wasted every year.In the art matter cellulosic material three big components, have only lignin not obtain effectively to utilize, and become obstacle and the environmental pollutant of related industries in using, so the utilization of lignin resource still is that the human social angle sees that meaning is all very great from the nature Carbon cycle.
High hydrophilous resin is a series of new functional macromolecule material, and it has absorb the very ability of large quantity of moisture and good water retention property from surrounding environment, and itself does not dissolve.High hydrophilous resin can be widely used in aspects such as farming, woods, gardening, medicine, physiological hygiene, oil, chemical, daily necessities, environment protection, beauty treatment, cosmetic, building materials, biochemical technology, food now, has given play to the power of its specific function day by day.But in these practical applications, the moisture overwhelming majority that need absorb from surrounding environment and keep is not a distilled water, and most of field all requires High hydrophilous resin can absorb and keep a large amount of natural water or solution.The High hydrophilous resin of use absorbs and keeps the ability root of nature water or solution low at present, generally has only about 10% of the saturated suction distillation water yield, therefore improves the High hydrophilous resin absorption and keeps the ability of nature water or solution to be very important.Make full use of the lignin resource of China's abundant preciousness, help realizing ecological benefits, social benefit and economic benefit three's unification, Sustainable development has important application prospects and meaning to economy and society.
(3) summary of the invention
1, to the purpose of this invention is to provide a kind of be raw material with the native lignin to goal of the invention, and the method for production environment close friend's lignin High hydrophilous resin is the service that large-scale develops and utilizes of renewable resources native lignin.
2, technical scheme technical scheme of the present invention is: by weight ratio with meterings such as high purity lignin, water-soluble polymer, initiator, linking agents; Under 60～180 ℃ of conditions, activate, grafting, crosslinked, copolyreaction; Spray-dried back adds whipping agent mixing in high-speed mixer, promptly eco-friendly lignin High hydrophilous resin.
Each component is by weight: high purity lignin 30～80, water-soluble polymer 10～40, initiator 2～10, linking agent 2～10, whipping agent 1～5, water 100～200.
High purity lignin is by organic solvent processing, purification or spissated lignin.Utilize lignin to be dissolved in organic solvent and in organic solvent, be easy to the cohesion, the polymeric characteristic, black, red liquid that organic solvent slurrying, alkaline process, sulfite pulping, the slurrying of imido method, mechanical feedback, biological process slurrying are obtained, after concentrating, the ratio in 1: 1～10 adds hot organic solvent; Raw material is the general industry lignin products, then add hot organic solvent stirring and dissolving in 1: 1～6 ratio after, centrifugal or remove by filter impurity, distillation obtains high purity lignin after reclaiming organic solvent, molecular weight＞more than 1000, purity＞more than 60%, second-order transition temperature＞100 ℃.
The organic solvent of described extraction high purity lignin is selected dioxane, acetyl bromide and derivative for use; Methyl alcohol, ethanol, hexafluoro propyl alcohol class and derivative; Acetone, butanone class and derivative; Formic acid, acetate, propionic acid class and derivative; Ethyl formate, ethyl acetate class and derivative; Lower paraffin hydrocarbons hydramine and derivative; The single solvent or the double solvents of ammonia, ammoniacal liquor etc. and ammonium salt class.
Water-soluble polymer is selected one or more arbitrary combination in polyvinyl alcohol (PVA), polyoxyethylene glycol (PEG), polyacrylamide (PAM), polyacrylic acid and multipolymer (PAA), polymaleic anhydride, polycondensation resinoid, modified-cellulose, treated starch, natural glue and the polymerization silicate for use.
Initiator is selected benzoyl peroxide, lauroyl peroxide, chloro benzoyl peroxide, acetyl peroxide, cumene peroxide, a for use, a '-two (t-butyl peroxy di-isopropyl) benzene, ditertiary butyl peroxide, 2,5-(t-butyl peroxy) hexane, 1,1-t-butyl peroxy-3,3,5-trimethyl-cyclohexane, t-butyl peroxy pivalate, t-butyl peroxy-2-ethyl acid ester, t-butyl peroxy benzoic ether, two (4-tert-butylcyclohexyl) peroxide two carbonic ethers, diisopropyl peroxydicarbonate, BPIC (t butyl peroxy isopropyl carbonate); With one or more the arbitrary combination in the azobis isobutyronitrile class.
Linking agent is selected one or more the arbitrary combination in aldehydes, alcohols, amine and the boron compound for use.
Whipping agent is selected yellow soda ash, sodium bicarbonate, CO for use
2, one or more the arbitrary combination in the kautschin, Cellmic C 121, Diisopropyl azodicarboxylate.
By weight ratio with meterings such as high purity lignin, water soluble resin, initiator, linking agents; Under 60～180 ℃ of conditions, activate, grafting, crosslinked, copolyreaction; Spray-dried back adds whipping agent mixing in high-speed mixer, promptly eco-friendly lignin High hydrophilous resin.
3, beneficial effect is main raw material development environment close friend's lignin High hydrophilous resin with reproducible native lignin, cause by chemistry, the lignin shape of molecule is converted into linear polymers by Einstein ball and closely curling body, with water-soluble polymer copolymerization, the crosslinked lignin High hydrophilous resin that obtains having highly suction, water retention characteristic, the functional performance that also has slowly-releasing, packing, carrier simultaneously, and can degrade fully under physical environment (light, heat, microorganism etc.) condition, its degraded can be controlled inductive phase.Progressively the lignin High hydrophilous resin after the degraded can be transformed into humic acid fertilizer in soil, and can improve soil aggregate.Have broad application prospects at aspects such as chemical fertilizer, agricultural chemicals, environmental improvements.The water-absorbing material that also can be used as heavy metal wastewater thereby, radioactive wastewater and cationic treatment of Organic Wastewater.
(4) embodiment
Below in conjunction with embodiment the present invention is described in further details.
High purity lignin produce 1: get black, red liquid that the imido method obtains, heating is concentrated into Baume more than 20 °, ratio in 1: 1～8 adds 50 ℃ ethyl acetate, heat after the airtight stirring to 80 ℃, leave standstill cooling 2 hours, after the liquid layering to be mixed, remove the impurity of bottom, ethyl acetate is reclaimed in upper strata liquid distillation, and the solid substance that obtains is high purity lignin after drying.Molecular weight＞more than 1000, purity＞more than 60%, second-order transition temperature＞100 ℃.
High purity lignin produce 2: getting industrial lignin is raw material, dioxane in 90 ℃ of 1: 6 ratio addings, add HCl and regulate pH＜6, heat after the airtight stirring to 100 ℃, leave standstill cooling 2 hours, after the liquid layering to be mixed, remove the impurity of bottom, ethyl acetate is reclaimed in upper strata liquid distillation, and the solid substance that obtains is high purity lignin after drying.Molecular weight＞more than 1000, purity＞more than 60%, second-order transition temperature＞100 ℃.
Embodiment 1: get high purity lignin 30, polyvinyl alcohol 20, benzoyl peroxide 3, formaldehyde 1, borax 1, water 150 by weight, in reactor, descend reaction after 10 hours in 80 ℃, after reactant evaporation concentration and the spraying drying, the kautschin that adds 2 weight part ratios, mixing in high-speed mixer, promptly eco-friendly lignin High hydrophilous resin.
Embodiment 2: get high purity lignin 60, polyoxyethylene glycol 10, gelatin 1, dicumyl peroxide 1, diisopropyl peroxydicarbonate 1, hexamethylenetetramine 1, water 180 by weight, in reactor, descend reaction after 9 hours in 100 ℃, after reactant evaporation concentration and the spraying drying, the Cellmic C 121 that adds 5 weight part ratios, mixing in high-speed mixer, promptly eco-friendly lignin High hydrophilous resin.
Embodiment 3: get high purity lignin 80, polyacrylamide 30, lauroyl peroxide 3, formaldehyde 1, hexamethylenetetramine 1, water 200 by weight, in reactor, descend reaction after 12 hours in 90 ℃, after reactant evaporation concentration and the spraying drying, add the Diisopropyl azodicarboxylate of 1 weight part ratio and the sodium bicarbonate of 1 weight part ratio, mixing in high-speed mixer, promptly eco-friendly lignin High hydrophilous resin.
Claims (8)
1. eco-friendly lignin High hydrophilous resin, comprise the mixture that high purity lignin, water-soluble polymer, initiator, linking agent, whipping agent form, it is characterized in that, described each component of lignin High hydrophilous resin is by weight: molecular weight＞1000, purity＞60%, high purity lignin 30～80, water-soluble polymer 10～40, initiator 2～10, linking agent 2～10, whipping agent 1～5, the water 100～200 of second-order transition temperature＞100 ℃; Above-mentioned batching was got product in 1～10 hour in 60～180 ℃ of following activation, grafting, copolymerization, crosslinking reaction in reactor.
2. eco-friendly lignin High hydrophilous resin according to claim 1 is characterized in that, described high purity lignin is handled, purified or concentrate by organic solvent, molecular weight＞1000, purity＞60%, the lignin of second-order transition temperature＞100 ℃.
3. eco-friendly lignin High hydrophilous resin according to claim 1, it is characterized in that water-soluble polymer is selected one or more arbitrary combination in polyvinyl alcohol (PVA), polyoxyethylene glycol (PEG), polyacrylamide (PAM), polyacrylic acid (PAA) and multipolymer, polymaleic anhydride, modified-cellulose, treated starch, natural glue and the polymerization silicate for use.
4. eco-friendly lignin High hydrophilous resin according to claim 1, it is characterized in that, initiator is selected benzoyl peroxide for use, lauroyl peroxide, chloro benzoyl peroxide, acetyl peroxide, cumene peroxide, a, a '-two (t-butyl peroxy di-isopropyl) benzene, ditertiary butyl peroxide, 2,5-(t-butyl peroxy) hexane, 1,1-t-butyl peroxy-3,3, the 5-trimethyl-cyclohexane, the t-butyl peroxy pivalate, t-butyl peroxy-2-ethylhexanoate, the t-butyl peroxy benzoic ether, two (4-tert-butylcyclohexyl) peroxide two carbonic ethers, diisopropyl peroxydicarbonate, BPIC (t butyl peroxy isopropyl carbonate); With one or more the arbitrary combination in the azobis isobutyronitrile.
5. eco-friendly lignin High hydrophilous resin according to claim 1 is characterized in that, linking agent is selected one or more the arbitrary combination in aldehydes, alcohols, amine and the boron compound for use.
6. eco-friendly lignin High hydrophilous resin according to claim 1 is characterized in that whipping agent selects yellow soda ash, sodium bicarbonate, CO for use
2, one or more the arbitrary combination in the kautschin, Cellmic C 121, Diisopropyl azodicarboxylate.
7. prepare the method for eco-friendly lignin High hydrophilous resin as claimed in claim 1, the steps include:
The first step, the preparation high purity lignin, utilize lignin to be dissolved in organic solvent and in organic solvent, be easy to the cohesion, the polymeric characteristic, black, red liquid that organic solvent slurrying, alkaline process, sulfite pulping, the slurrying of imido method, mechanical feedback or biological process slurrying are obtained, be concentrated into Baume more than 20 °, add hot organic solvent in the ratio of lignin and organic solvent 1: 1～10; Raw material is the general industry lignin products, after then adding hot organic solvent stirring and dissolving in the ratio of lignin and organic solvent 1: 1～6, centrifugal or remove by filter impurity, distillation obtains high purity lignin after reclaiming organic solvent, molecular weight＞more than 1000, purity＞more than 60%, second-order transition temperature＞100 ℃;
In second step, batching is got high purity lignin 30～80, water-soluble polymer 10～40, initiator 2～10, linking agent 2～10, water 100～200, whipping agent 1～5 by weight ratio;
Second step, except that whipping agent, with above-mentioned batching in reactor in 60～180 ℃ of following activation, grafting, copolymerization, crosslinking reaction 1～10 hour;
In the 4th step, after reactant evaporation concentration and the spraying drying, add whipping agent mixing in high-speed mixer, promptly eco-friendly lignin High hydrophilous resin.
8. eco-friendly lignin High hydrophilous resin according to claim 1 is characterized in that, the organic solvent of preparation high purity lignin is selected dioxane, acetyl bromide and derivative for use; Methyl alcohol, ethanol, hexafluoro propyl alcohol and derivative; Acetone, butanone and derivative; Formic acid, acetate, propionic acid and derivative; Ethyl formate, ethyl acetate and derivative; Lower paraffin hydrocarbons hydramine and derivative; The single solvent of ammonia, ammoniacal liquor and ammonium salt or double solvents.
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| CNB2004100408943A CN100365068C (en) | 2004-10-25 | 2004-10-25 | Environment friendly lignin resin of high water absorbence and its preparation method |
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| CNB2004100408943A CN100365068C (en) | 2004-10-25 | 2004-10-25 | Environment friendly lignin resin of high water absorbence and its preparation method |
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| CN100365068C true CN100365068C (en) | 2008-01-30 |
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Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2408847A1 (en) * | 2009-03-20 | 2012-01-25 | Sika Technology AG | Method for producing chemically modified lignin decomposition products |
| CN102459293A (en) * | 2009-05-28 | 2012-05-16 | 丽格诺创新有限公司 | Resin compositions comprising lignin derivatives |
| BRPI1014400B1 (en) | 2009-05-28 | 2019-04-24 | Fibria Innovations Inc. | LIGNIN AND COMPOSITION DERIVATIVE |
| WO2011097721A1 (en) | 2010-02-15 | 2011-08-18 | Lignol Innovations Ltd. | Carbon fibre compositions comprising lignin derivatives |
| CA2824446C (en) | 2010-02-15 | 2018-09-18 | Lignol Innovations Ltd. | Binder compositions comprising lignin derivatives |
| CN102153703B (en) * | 2011-03-23 | 2013-06-05 | 浙江理工大学 | Preparation method of cellulose-based high-water-absorption high-water-retention resin |
| EP2688959A4 (en) | 2011-03-24 | 2014-09-10 | Lignol Innovations Ltd | Compositions comprising lignocellulosic biomass and organic solvent |
| CN102850110B (en) * | 2012-03-20 | 2013-12-18 | 北京林业大学 | Carrier of hydrophilic slow-release fertilizer and slow-release fertilizer prepared by same |
| CN104140499A (en) * | 2014-02-26 | 2014-11-12 | 重庆文理学院 | Method for preparing super absorbent polymer (SAP) from carboxymethylcellulose (CMC) and maleic acid (MA) |
| CN104962096A (en) * | 2015-07-13 | 2015-10-07 | 深圳职业技术学院 | Preparation method of polyvinyl alcohol foamed plastics |
| CN106700368A (en) * | 2016-12-16 | 2017-05-24 | 吴中区穹窿山福顺生物技术研究所 | Modified water-absorbent resin and preparation method thereof |
| CN108752640A (en) * | 2018-04-04 | 2018-11-06 | 史国民 | A kind of hydrolyzable environment protection type water sucking material and preparation method |
| CN110219691B (en) * | 2019-06-27 | 2020-07-24 | 中国矿业大学 | Environment-friendly composite stopping agent for preventing coal spontaneous combustion and preparation method thereof |
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| CN1262644A (en) * | 1997-05-13 | 2000-08-09 | 杜邦-Mrc株式会社 | Wood-like molding, process for preparing same, and composition for molding |
| CN1356867A (en) * | 1999-06-22 | 2002-07-03 | 希乐克公司 | Texturized cellulosic and lignocellulosic materials and compositions and composites made therefrom |
| CN1465623A (en) * | 2002-06-21 | 2004-01-07 | 张惠民 | Environment protection type lignin fog-film |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1262644A (en) * | 1997-05-13 | 2000-08-09 | 杜邦-Mrc株式会社 | Wood-like molding, process for preparing same, and composition for molding |
| CN1356867A (en) * | 1999-06-22 | 2002-07-03 | 希乐克公司 | Texturized cellulosic and lignocellulosic materials and compositions and composites made therefrom |
| CN1465623A (en) * | 2002-06-21 | 2004-01-07 | 张惠民 | Environment protection type lignin fog-film |
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