CN102127232A - Graft modification method for lignosulfonate - Google Patents
Graft modification method for lignosulfonate Download PDFInfo
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- CN102127232A CN102127232A CN 201010592788 CN201010592788A CN102127232A CN 102127232 A CN102127232 A CN 102127232A CN 201010592788 CN201010592788 CN 201010592788 CN 201010592788 A CN201010592788 A CN 201010592788A CN 102127232 A CN102127232 A CN 102127232A
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- xylogen
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- lignin
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Abstract
The invention discloses a production process for preparing lignosulfonate copolymer by adopting a radiation chemical method. Under the condition of radiation, the graft copolymerization reaction can be performed in a liquid phase or solid phase, a grafting monomer is high-activity-terminal oligomer, and the reaction conditions are that: the radiation dose is 5-30Mrad and the reaction is performed at room temperature for 12 to 48 hours. Compared with the chemical method, the method has the advantages of high efficiency, mild reaction conditions, no pollution and the like. The lignosulfonate copolymer prepared by the method can be used for preparing adhesives, flocculating agents, rubber additives, dispersing agents and the like.
Description
Technical field
The present invention relates to a kind of graft-modification method of sulfonated lignin.
Background technology
1838, French Agricultural Scientist P.Payen isolated the cellulosic while from timber, found the compound that a kind of carbon content is higher, called after lignin, just our said xylogen.
Xylogen is a class complexity, noncrystalline, three-dimensional netted phenols high molecular polymer, and it extensively is present in the higher plant cell, is one of basic chemical constitution of coniferals, deciduous tree class and straw or like vegetable.Because different plant origins, even the resulting xylogen of the different separation methods of kindred plant, the limitation at structure and qualitative diversity and processing means has limited the application of xylogen.The lignin product of being developed at present only is that xylogen is used as a kind of stopping composition or additive, yet there are no the product that relies on xylogen fully.
For the better utilised xylogen, China and foreign countries' researcher has been done a large amount of research work at xylogen.Adopt the whole bag of tricks to change the characteristic of xylogen, it is fully reasonably used to reach.Radiation graft process is one of them.The radiation grafting polymerization is the graft reaction that utilizes high-energy ionization radiation to cause, and is a kind of peculiar and effective high molecular polymer method of modifying.Its principle is under the high-energy ionization radiation condition, and the high molecular polymer surface produces free radical, and free radical combines with grafted monomer, reaches the purpose that changes the high molecular polymer performance.The radiation grafting polymerization is compared with traditional chemical method, and environmental pollution is little and operate easily and control.But the people who at present the radiation grafting polyreaction is used for lignin modification research is also few.
The end of the sixties, Testsco Koshijlma and Einosuke Muraki (Testsco Koshijlma andEinosuke Muraki, Radical Grafting on Lignin.Part I Radiation-Induced Grafting ofStyrene onto Hydrochloric Acid Lignin[J], Journal of Polymer Science:PartA-1,6:1131-1140,1968) cinnamic method of hydrochloric acid xylogen radiation grafting and reaction mechanism have been reported.
The beginning of the seventies, R.B.Phillips, W.Brown and V.Stannett (The graftcopolymerization of styrene and lignin.I.Hydrochloric acid lignin Journal of AppliedPolymer Science 15 (12), 2929-2940,1971; The Graft Copolymerization of Styreneand Lignin.II.Kraft Lignin, Journal ofApplied Polymer Science, 16:1-11,1972; Thegraft copolymerization of styrene and lignin.III.Chain transfer reactions of ligninand lignin model compounds, Journal of Applied Polymer Science, 17 (2), 443-451,1973) studied alkali lignin and cinnamic irradiation grafting copolyreaction, and reaction conditions and reaction mechanism have been gone through.
1984, John J.Meister, Damodar R.Patil, Larry R.Field, and John C.Nicholson (John J.Meister, Damodar R.Patil, Larry R.Field, and John C.Nicholson, Synthesisand Characterization of Graft Copolymers from Lignin and 2-Propenamide, Journalof Polymer Science:Polymer Chemistry Edition, 22,1963-1980,1984) the radiation grafting polymeric method and the principle of 2-acrylamide and xylogen have been studied.
At present, the application of China's xylogen resource is scarcely out of swaddling-clothes, and its product is mainly used in concrete additive and petroleum chemicals, as the viscosity-depression agent of petroleum drilling, intensified oil reduction with chemical agent, water blockoff blender etc.The scientific research group of meanwhile domestic each institute and institution of higher learning has carried out big quantity research to xylogen performance and application, and the irradiation grafting copolymerization process also is used by chance.For example, Cai Yu in 2008 is graceful to have studied high-boiling alcohol lignin and cinnamic graft copolymerization under the radiation condition, and the optimum proportion and the irradiation dose of grafted monomer and xylogen have been discussed.But up to the present, patent disclosure and article report are not seen in the graft copolymerization of adopting irradiation to draw active end group oligomer and xylogen.
Summary of the invention
The present invention is the grafting main body with sulfonated lignin, and the active end group oligomer is a grafted monomer, adopts the radiation grafting polymerization technique that sulfonated lignin are carried out modification processing, has provided a kind of graft-modification method of new sulfonated lignin.Grafted monomer active end group oligomer adopts high-activity polyisobutene, and high-activity polyisobutene is the low-molecular-weight polyisobutylene of high α-terminal double link content, and terminal double link content has the high reaction activity characteristic generally greater than 80%.By this invention, improved the molecular characterization of sulfonated lignin, can widen the application approach of sulfonated lignin.
The present invention is a kind of xylogen graft copolymer preparation method.
The present invention is based on the irradiation grafting copolyreaction, grafting macromole long-chain on lignin molecule.On irradiation grafting polymerization theory basis, furtherd investigate the optimum new formulation of xylogen irradiation grafting polymeric and determined grafted monomer and preparation technology.
The preparation method of xylogen irradiation grafting multipolymer:
Xylogen and Mierocrystalline cellulose and hemicellulose form the plant materials skeleton jointly, are that occurring in nature quantitatively is only second to cellulosic second largest natural macromolecular material.All regenerate with 600,000,000,000,000 tons speed every year, thereby be the renewable resources that has potentiality.Pulp and paper industry will be isolated about 1.4 hundred million tons of Mierocrystalline celluloses every year from plant, obtain the xylogen byproduct about 5,000 ten thousand tons simultaneously, but up to now, surpass 95% xylogen still mainly as the waste of industrial slurrying, with waste water directly enter rivers or concentrate after burn, efficiently utilized less extremely.
Its major cause is the complicacy of lignin molecule structure, the polymolecularity of molecular weight, and the chemical reaction of following in the pulping process is as sulfonation, hydrolysis and condensation, oxidation, molecular transposition, dehydration, sulfo--sulfinic acidization and sulfuration etc.; And the lignin reaction's active passivation that causes thus, all applied obstruction seriously to the research of xylogen utilization and lignin products.
The characteristics of radiation processing technology are less demanding to raw-material performance state and reaction conditions.Therefore, the irradiation grafting copolymerization has avoided complex apparatus to require and harsh reaction conditions, for the study on the modification of xylogen provides convenience.
(1) raw material
Grafting main body: sulfonated lignin; These sulfonated lignin mainly comprise sodium salt, calcium salt, ammonium salt etc.
Grafted monomer: high-activity polyisobutene; Molecular weight (M
w) scope comprises: 1000,1300,2300.
(2) production unit
60Co source of radiation or rumbatron
(3) preparation technology
Adopt kneader, sulfonated lignin and high-activity polyisobutene are mixing even, and the quality ratio of components is 100: 10～100: 50, utilizes single screw extrusion machine that the material degassing that mixes is extruded into band then, extrusion moulding is simultaneously at band both sides overlay film, to reach the secluding air sealing function.
Send into radiation chamber irradiation, irradiation source is
60Co or rumbatron, irradiation measure at 5～30Mrad, irradiation time 12～48h.The graft modification sulfonated lignin needn't be purified and can directly be used.
Beneficial effect: 1. the prepared xylogen graft copolymer of present method is made of xylogen macromole kernel and long-chain polyolefine side chain two portions of being distributed in the surface thereof, does not add toxic substance and organic solvent in the course of processing.2. the sulfonated lignin graftomer that obtains behind the irradiation grafting has well water-soluble, and snappiness has strengthened, and the thermofixation performance keeping sulfonated lignin has characteristics such as tack height, makes its application more extensive.3. reacting nuisanceless, is a kind of cleaning activity.4. this reaction does not need high temperature, high pressure, can carry out at ambient temperature.Use the sulfonated lignin graft copolymer of method preparation provided by the invention, can be used to prepare tackiness agent, flocculation agent, rubber accelerator and dispersion agent etc.
Embodiment
Embodiment 1:
Sodium lignosulfonate 100g purifies with acetic acid earlier and cleans with acetone, adds high-activity polyisobutene (molecular weight is 1300) 50g, makes film after mixing and seals with plastics film;
60Co is a source of radiation, radiation dose 30Mrad, radiated time 24h, the xylogen graft copolymer of acquisition.The percentage of grafting of xylogen graft copolymer is 12.8%.
Embodiment 2:
Sulfomethylated lignin acid amide 100g purifies with acetic acid earlier and cleans with acetone, adds high-activity polyisobutene (molecular weight is 1300) 50g, makes film after mixing and seals with plastics film;
60Co is a source of radiation, radiation dose 30Mrad, radiated time 24h, the xylogen graft copolymer of acquisition.With three layers of glued board of the polymer bonding that is obtained, its shearing resistance reaches 1.75MPa.
Embodiment 3:
Calcium lignin sulphonate 100g purifies with acetic acid earlier and cleans with acetone, adds high-activity polyisobutene (molecular weight is 2300) 30g, makes film after mixing and seals with plastics film;
60Co is a source of radiation, radiation dose 15Mrad, radiated time 48h, the xylogen graft copolymer of acquisition.This xylogen graft copolymer can be used as rubber accelerator.
Embodiment 4:
Sodium lignosulfonate 100g purifies with acetic acid earlier and cleans with acetone, adds high-activity polyisobutene (molecular weight is 1000) 10g, makes film after mixing and seals with plastics film;
60Co is a source of radiation, radiation dose 5Mrad, radiated time 12h, the xylogen graft copolymer of acquisition.The percentage of grafting of xylogen graft copolymer is 5.3%.
Embodiment 5:
Calcium lignin sulphonate 100g purifies with acetic acid earlier and cleans with acetone, adds high-activity polyisobutene (molecular weight is 2300) 40g, makes film after mixing and seals with plastics film;
60Co is a source of radiation, radiation dose 30Mrad, radiated time 48h, the xylogen graft copolymer of acquisition.The percentage of grafting of xylogen graft copolymer is 8.7%.
Claims (6)
1. the preparation method of xylogen irradiation grafting multipolymer, its step is as follows:
(1) raw material
Grafting main body: sulfonated lignin; These sulfonated lignin mainly comprise sodium salt, calcium salt, ammonium salt etc.
Grafted monomer: high-activity polyisobutene; Molecular weight (M
w) scope comprises: 1000,1300,2300.
(2) production unit
60Co source of radiation or rumbatron.
(3) preparation technology
Sodium lignosulfonate is purified with acetic acid earlier and is cleaned with acetone; Adopting kneader, is that 100: 10～100: 50 sulfonated lignin and high-activity polyisobutene is mixing evenly with the quality ratio of components; Utilize single screw extrusion machine that the material degassing that mixes is extruded into band then, simultaneously at band both sides overlay film, to reach the secluding air sealing function; Send into radiation chamber irradiation, irradiation source is
60Co or rumbatron, irradiation measure at 5～30Mrad, and irradiation time 12～48h, graft modification sulfonated lignin needn't purify and can directly use.
2. the preparation method of xylogen irradiation grafting multipolymer as claimed in claim 1, its step is as follows:
Sodium lignosulfonate is purified with acetic acid earlier and is cleaned with acetone, with the quality ratio of components is that 100: 50 sulfonated lignin and high-activity polyisobutene are mixing evenly, the molecular weight of high-activity polyisobutene is 1300, makes film after mixing and seals with plastics film;
60Co is a source of radiation, radiation dose 5Mrad, radiated time 24h, the xylogen graft copolymer of acquisition.
3. the preparation method of xylogen irradiation grafting multipolymer as claimed in claim 1, its step is as follows:
Sulfomethylated lignin acid amide 100g purifies with acetic acid earlier and cleans with acetone, adds high-activity polyisobutene (molecular weight is 1300) 50g, makes film after mixing and seals with plastics film;
60Co is a source of radiation, radiation dose 30Mrad, radiated time 24h, the xylogen graft copolymer of acquisition.
4. the preparation method of xylogen irradiation grafting multipolymer as claimed in claim 1, its step is as follows:
Calcium lignin sulphonate 100g purifies with acetic acid earlier and cleans with acetone, adds high-activity polyisobutene (molecular weight is 2300) 30g, makes film after mixing and seals with plastics film;
60Co is a source of radiation, radiation dose 15Mrad, radiated time 48h, the xylogen graft copolymer of acquisition.
5. the preparation method of xylogen irradiation grafting multipolymer as claimed in claim 1, its step is as follows:
Sodium lignosulfonate 100g purifies with acetic acid earlier and cleans with acetone, adds high-activity polyisobutene (molecular weight is 1000) 10g, makes film after mixing and seals with plastics film;
60Co is a source of radiation, radiation dose 5Mrad, radiated time 12h, the xylogen graft copolymer of acquisition.
6. the preparation method of xylogen irradiation grafting multipolymer as claimed in claim 1, its step is as follows:
Calcium lignin sulphonate 100g purifies with acetic acid earlier and cleans with acetone, adds high-activity polyisobutene (molecular weight is 2300) 40g, makes film after mixing and seals with plastics film;
60Co is a source of radiation, radiation dose 30Mrad, radiated time 48h, the xylogen graft copolymer of acquisition.
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| CN 201010592788 CN102127232A (en) | 2010-12-17 | 2010-12-17 | Graft modification method for lignosulfonate |
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| CN 201010592788 CN102127232A (en) | 2010-12-17 | 2010-12-17 | Graft modification method for lignosulfonate |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104419007A (en) * | 2013-08-30 | 2015-03-18 | 北京化工大学 | Biomass polysaccharide/polyisobutene grafted copolymer and preparation method thereof |
| CN106589257A (en) * | 2016-12-09 | 2017-04-26 | 孙安顺 | Preparation method of lignin grafted and copolymerized polymer flocculation type profile modifying/water plugging agent |
| CN110170313A (en) * | 2019-06-04 | 2019-08-27 | 湖南省核农学与航天育种研究所 | A kind of method that irradiation grafting prepares lignin adsorbent |
-
2010
- 2010-12-17 CN CN 201010592788 patent/CN102127232A/en active Pending
Non-Patent Citations (1)
| Title |
|---|
| 《中国优秀硕士学位论文全文数据库》 20090215 刘晓秋 木质素的改性及应用研究 第1-68页 1-6 , 2 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104419007A (en) * | 2013-08-30 | 2015-03-18 | 北京化工大学 | Biomass polysaccharide/polyisobutene grafted copolymer and preparation method thereof |
| CN104419007B (en) * | 2013-08-30 | 2017-10-31 | 北京化工大学 | Biomass polysaccharides/polyisobutene graft copolymer and preparation method thereof |
| CN106589257A (en) * | 2016-12-09 | 2017-04-26 | 孙安顺 | Preparation method of lignin grafted and copolymerized polymer flocculation type profile modifying/water plugging agent |
| CN110170313A (en) * | 2019-06-04 | 2019-08-27 | 湖南省核农学与航天育种研究所 | A kind of method that irradiation grafting prepares lignin adsorbent |
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Application publication date: 20110720 |