CN104558440B - A kind of preparation method of lignin-graft copolymer - Google Patents
A kind of preparation method of lignin-graft copolymer Download PDFInfo
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Abstract
The present invention relates to a kind of preparation method of lignin-graft copolymer.The method prepares the graft copolymer of lignin and styrene monomer using catalyst and hydrogen peroxide redox initiator.The best graft copolymerization yield of the method is 96.6%, and the conversion ratio of styrene monomer is 96.3%, and percent grafting is 59.5%, and grafting degree is 53.7%.Lignin-graft copolymer can be widely used as thermoplasticity macromolecular surface active material.
Description
Technical field
The present invention relates to a kind of method for preparing lignin-graft copolymer.Specifically, the present invention relates to a kind of with urging
The method that agent and hydrogen peroxide redox initiator prepare lignin and the graft copolymer of styrene monomer.
Background technology
Lignin, as second largest most abundant, the most cheap renewable resource for being only second to cellulose and hemicellulose, accounts for
30% of all non-fossil sources or so on the earth.At present, the lignin that the whole world only paper industry is produced just reaches 50,000,000
Ton/year, this abundant renewable resource major part is used as the fuel of low value or throws away directly as discarded object, only 2%
It is used as the value-added product such as stabilizer, dispersant, binding agent and surfactant.This not only waste of resource, and severe contamination
Environment.The graft copolymer of research discovery, lignin and styrene monomer, as which has good compatibility and adhesion
Property, thermoplasticity macromolecular surface active material can be widely used as.Therefore, by the grafting of lignin and styrene monomer altogether
Poly- reaction is modified to lignin, not only can change its structure, develops new purposes, expands range of application, and for
The recycling of natural resources, reduce papermaking wastewater to the pollution of environment, improve environment, realize human society and the association of natural environment
The exhibition of readjusting the distribution all has important economic benefit and social benefit.
Koshijima groups (Journal of Polymer Science Part A-1:Polymer Chemistry,
1968,6(6), 1431-1440) and Phillips groups (Journal of Applied Polymer Science,1972,16A, 1-14) hydrochloric acid lignin and various sulphate softwood lignin and grafting of the styrene under radiation condition are reported respectively
Copolyreaction.Katu á k groups (Journal of Applied Polymer Science,1973,17(6), 1919-
1928) report the hydrochloric acid lignin and cinnamic graft copolymerization with ozone activation.Chen groups (Journal of Applied Polymer Science,1979,24(7), 1609-1618) report using ozone, hydrogen peroxide and protochloride
Iron catalysis causes calcium lignosulfonate and cinnamic graft copolymerization.Meister groups (Macromolecules,1991,24(26), 6843-6848；Macromolecules,1996,29(5), 1389-1398) lignin and styrene are reported in chlorine
The method that graft copolymer is prepared under the common catalytic action for changing calcium and hydrogen peroxide.
Chinese invention patent CN 1148051A are disclosed
The method of the graft copolymer of monomer, the anode material of the method electrode used therein material is gold, platinum and titanium pole or ceramic base plating dioxy
Change lead, but due to gold and platinum electrode be noble metal, it is relatively costly, and titanium pole or ceramic base plating lead dioxide electrode stability and
The not high range of application for limiting the method for electro catalytic activity.Patent of invention CN 1693342 discloses the wood being modified with esterifying agent
The method that mahogany sulfonate and acrylic monomer prepare graft copolymer, what the method was obtained be lignin-graft copolymer be with
The mixture of acrylic acid ester emulsion, and ammoniacal liquor, emulsifier op-10 and sodium hydrogensulfite, the phosphorus added in process of grafting
The inorganic salts such as sour disodium hydrogen and there is no homopolymers of graft reaction etc. and all mix wherein and cannot separate, which limits wood
Quality graft copolymer is used as adhesive or the applicability of resin.And patent of invention CN 1071436A is then disclosed and is used lignin
Prepare in the presence of the redox type initiator constituted by the salt and peroxide for passing through halide with vinyl monomer and connect
The method of graft copolymer, although the method prepares the yield of lignin-graft copolymer very well, but grafting efficiency is not but high.
The content of the invention
It is an object of the invention to provide a kind of preparation method of lignin-graft copolymer.
The present invention adopts catalyst and hydrogen peroxide redox initiator to prepare connecing for lignin and styrene monomer
Graft copolymer.
A kind of preparation method of lignin-graft copolymer, it is characterised in that the method step is：
A, lignin is dissolved in dimethyl sulfoxide, adds the methanol solution of catalyst to be simultaneously sufficiently stirred for dissolving, described catalysis
Agent is frerrous chloride or ferrous sulfate, adds initiator under nitrogen protection, and initiator is the hydrogen peroxide of 30wt%, then
Styrene monomer is added, 25 ~ 35oAfter 36 ~ 60 h of C stirring reactions, watery hydrochloric acid is added to dilute, filter, wash with water
Wash, be dried, obtain polymer；
B, polymer is carried out with organic solvent 12 ~ 24 h of surname extraction, concentration, is dried, obtain graft copolymer with
The blend of homopolymers；
C, blend is dissolved in polar solvent it is configured to solution, is added in the non-polar solven of 8 ~ 10 times of volumes through normal
The precipitation of rule, filtration, dry run obtain lignin-graft copolymer.
Lignin of the present invention is dealkalize lignin.
Styrene monomer of the present invention is represented with following formula：
In formula, R is methyl, bromine or OCH3。
The mol ratio of styrene monomer, initiator, catalyst described in step A is [styrene monomer]/[draw
Send out agent]/[catalyst]=175 ~ 225：40~60：1.
Organic solvent described in step B is any one in benzene, toluene or ethyl acetate.
Polar solvent described in step C is arbitrary in dichloromethane, chloroform, ethyl acetate or tetrahydrofuran
Kind.
Non-polar solven described in step C is appointing in pentane, n-hexane, normal heptane, hexamethylene or petroleum ether
It is a kind of.
The method that the present invention prepares lignin-graft copolymer, best graft copolymerization yield are 96.6%, styrene
The conversion ratio of class monomer is 96.3%, and percent grafting is 59.5%, and grafting degree is 53.7%.
The invention has the characteristics that：
1st, the lignin-graft copolymer that the present invention is provided can be widely used as thermoplasticity macromolecular surface active material.
2nd, the preparation of lignin-graft copolymer according to the present invention, catalyst amount used are few, and reaction condition is gentle,
It is easy to prepare product in a large number, realizes industrialization.
3rd, the preparation of lignin-graft copolymer according to the present invention, converts with higher graft reaction yield, monomer
Rate, percent grafting and grafting degree, can greatly improve the utilization rate of lignin, slow down lignin to the pollution caused by environment.
Specific embodiment
The present invention can be illustrated with the following example, but the present invention is not limited by listed implementation example.
Embodiment 1
A. 0.2 g lignin is dissolved in into 5 mL dimethyl sulfoxides, adds the first of 1.0 0.1 mmol of mL/mL frerrous chlorides
Alcoholic solution is simultaneously sufficiently stirred for dissolving, and Jing freezes repeatedly-vacuumizes-oxygen that removes in solution of the cyclic process of nitrogen charging, in nitrogen
The lower hydrogen peroxide for adding 0.5 mL 30% of protection, 10 min of stirring reaction is subsequently adding 2.08 g styrene, 30oC is stirred
Mix 48 h of reaction.Add 80 mL watery hydrochloric acid to dilute, filter, be washed with water to neutrality, 40oC is dried under vacuum to constant weight and obtains
Polymer.
B. the polymer of above-mentioned gained is carried out with benzene after 12 h of surname extraction, is concentrated, 40oC is dried under vacuum to constant weight
Obtain the blend of graft copolymer and homopolymers.
C. graft copolymer is dissolved in into dichloromethane with the blend of homopolymers and is configured to 1 g/mL solution, be then added to
Precipitate in the n-hexane of 9 times of volumes, with the mixed solvent of dichloromethane and n-hexane, (volume ratio is 1：9) wash, filter, 40oC is dried under vacuum to constant weight, obtains final product lignin-graft copolymer.The yield of graft copolymerization is 96.6%, cinnamic conversion
Rate is 96.3%, and percent grafting is 59.5%, and grafting degree is 53.7%.
Embodiment 2
A. 0.20 g lignin is dissolved in into 5 mL dimethyl sulfoxides, adds the first of 0.5 0.2 mmol of mL/mL frerrous chlorides
Alcoholic solution is simultaneously sufficiently stirred for dissolving, and Jing freezes repeatedly-vacuumizes-oxygen that removes in solution of the cyclic process of nitrogen charging, in nitrogen
The lower hydrogen peroxide for adding 0.5 mL 30% of protection, 10 min of stirring reaction is subsequently adding 2.08 g styrene, 30oC is stirred
Mix 60 h of reaction.Add 80 mL watery hydrochloric acid to dilute, filter, be washed with water to neutrality, 40oC is dried under vacuum to constant weight and obtains
Polymer.
B. the polymer of above-mentioned gained is carried out with toluene after 24 h of surname extraction, is concentrated, 40oC is dried under vacuum to perseverance
Restore the blend of graft copolymer and homopolymers.
C. graft copolymer is dissolved in into chloroform with the blend of homopolymers and is configured to 1 g/mL solution, be then added to
Precipitate in the pentane of 9 times of volumes, with the mixed solvent of chloroform and pentane, (volume ratio is 1：8) wash, filter, 40oC is dried under vacuum to constant weight, obtains final product lignin-graft copolymer.The yield of graft copolymerization is 96.8%, cinnamic conversion
Rate is 96.5%, and percent grafting is 58.1%, and grafting degree is 51.5%.
Embodiment 3
A. 0.20 g lignin is dissolved in into 5 mL dimethyl sulfoxides, adds the first of 0.5 0.2 mmol of mL/mL frerrous chlorides
Alcoholic solution is simultaneously sufficiently stirred for dissolving, and Jing freezes repeatedly-vacuumizes-oxygen that removes in solution of the cyclic process of nitrogen charging, in nitrogen
The lower hydrogen peroxide for adding 0.6 mL 30% of protection, 10 min of stirring reaction is subsequently adding 2.08 g styrene, 30oC is stirred
Mix 48 h of reaction.Add 60 mL watery hydrochloric acid to dilute, filter, be washed with water to neutrality, 40oC is dried under vacuum to constant weight and obtains
Polymer.
B. the polymer of above-mentioned gained is carried out with toluene after 24 h of surname extraction, is concentrated, 40oC is dried under vacuum to perseverance
Restore the blend of graft copolymer and homopolymers.
C. graft copolymer is dissolved in into ethyl acetate with the blend of homopolymers and is configured to 0.8 g/mL solution, Ran Houjia
Precipitate in the petroleum ether of 10 times of volumes, with the mixed solvent of ethyl acetate and petroleum ether, (volume ratio is 1：10) wash, filter,
40oC is dried under vacuum to constant weight, obtains final product lignin-graft copolymer.The yield of graft copolymerization is 96.2%, cinnamic
Conversion ratio is 95.9%, and percent grafting is 57.3%, and grafting degree is 50.6%.
Embodiment 4
A. 0.20 g lignin is dissolved in into 5 mL dimethyl sulfoxides, adds 0.33 0.3 mmol of mL/mL frerrous chlorides
Methanol solution is simultaneously sufficiently stirred for dissolving, and Jing vacuumized repeatedly-oxygen that removes in solution of the cyclic process of nitrogen charging, under nitrogen atmosphere
The hydrogen peroxide of 0.5 mL 30%, 10 min of stirring reaction is added to be subsequently adding 1.82 g styrene, 30oC stirring reactions
48 h.Add 70 mL watery hydrochloric acid to dilute, filter, be washed with water to neutrality, 40oC is dried under vacuum to constant weight and is polymerized
Thing.
B. the polymer of above-mentioned gained is carried out with ethyl acetate after 18 h of surname extraction, is concentrated, 40oC is vacuum dried
The blend of graft copolymer and homopolymers is obtained to constant weight.
C. graft copolymer is dissolved in into tetrahydrofuran with the blend of homopolymers and is configured to 0.8 g/mL solution, Ran Houjia
Precipitate in the n-hexane of 10 times of volumes, with the mixed solvent of tetrahydrofuran and n-hexane, (volume ratio is 1：10) wash, filter,
40oC is dried under vacuum to constant weight, obtains final product lignin-graft copolymer.The yield of graft copolymerization is 95.9%, cinnamic
Conversion ratio is 95.4%, and percent grafting is 57.1%, and grafting degree is 48.7%.
Embodiment 5
A. 0.20 g lignin is dissolved in into 5 mL dimethyl sulfoxides, adds the first of 0.5 0.2 mmol of mL/mL frerrous chlorides
Alcoholic solution is simultaneously sufficiently stirred for dissolving, and Jing freezes repeatedly-vacuumizes-oxygen that removes in solution of the cyclic process of nitrogen charging, in nitrogen
The hydrogen peroxide of 0.5 mL 30%, 10 min of stirring reaction is added to be subsequently adding 2.08 g styrene, 35 under atmosphereoC is stirred
React 48 h.Add 80 mL watery hydrochloric acid to dilute, filter, be washed with water to neutrality, 40oC is dried under vacuum to constant weight and is gathered
Compound.
B. the polymer of above-mentioned gained is carried out with ethyl acetate after 18 h of surname extraction, is concentrated, 40oC is vacuum dried
The blend of graft copolymer and homopolymers is obtained to constant weight.
C. graft copolymer is dissolved in into dichloromethane with the blend of homopolymers and is configured to 1.2 g/mL solution, Ran Houjia
Precipitate in the normal heptane of 8 times of volumes, with the mixed solvent of dichloromethane and normal heptane, (volume ratio is 1：8) wash, filter,
40 oC is dried under vacuum to constant weight, obtains final product lignin-graft copolymer.The yield of graft copolymerization be 93.8%, cinnamic turn
Rate is 93.2%, and percent grafting is 56.6%, and grafting degree is 56.3%.
Embodiment 6
A. 0.20 g lignin is dissolved in into 5 mL dimethyl sulfoxides, adds the first of 0.5 0.2 mmol of mL/mL ferrous sulfate
Alcoholic solution is simultaneously sufficiently stirred for dissolving, and Jing freezes repeatedly-vacuumizes-oxygen that removes in solution of the cyclic process of nitrogen charging, in nitrogen
The lower hydrogen peroxide for adding 0.5 mL 30% of protection, 10 min of stirring reaction is subsequently adding 2.08 g styrene, 30oC is stirred
Mix 48 h of reaction.Add 90 mL watery hydrochloric acid to dilute, filter, be washed with water to neutrality, 40oC is dried under vacuum to constant weight and obtains
Polymer.
B. the polymer of above-mentioned gained is carried out with toluene after 18 h of surname extraction, is concentrated, 40oC is dried under vacuum to perseverance
Restore the blend of graft copolymer and homopolymers.
C. graft copolymer is dissolved in into dichloromethane with the blend of homopolymers and is configured to 1 g/mL solution, be then added to
Precipitate in the n-hexane of 9 times of volumes, with the mixed solvent of dichloromethane and n-hexane, (volume ratio is 1：9) wash, filter, 40oC is dried under vacuum to constant weight, obtains final product lignin-graft copolymer.The yield of graft copolymerization is 95.3%, cinnamic conversion
Rate is 94.9%, and percent grafting is 59.4%, and grafting degree is 54.4%.
Embodiment 7
A. 0.20 g lignin is dissolved in into 5 mL dimethyl sulfoxides, the methyl alcohol of 0.5 0.2 mmol of mL/mL frerrous chlorides is molten
Liquid is simultaneously sufficiently stirred for dissolving, and Jing freezes repeatedly-vacuumizes-oxygen that removes in solution of the cyclic process of nitrogen charging, under nitrogen atmosphere
The hydrogen peroxide of 0.5 mL 30%, 10 min of stirring reaction is added to be subsequently adding 2.36 g p-methylstyrenes, 30oC is stirred
Mix 48 h of reaction.Add 80 mL watery hydrochloric acid to dilute, filter, be washed with water to neutrality, 40oC is dried under vacuum to constant weight and obtains
Polymer.
B. the polymer of above-mentioned gained is carried out with ethyl acetate after 18 h of surname extraction, is concentrated, 40oC is vacuum dried
The blend of graft copolymer and homopolymers is obtained to constant weight.
C. graft copolymer is dissolved in into dichloromethane with the blend of homopolymers and is configured to 1.2 g/mL solution, Ran Houjia
Precipitate in the n-hexane of 8 times of volumes, with the mixed solvent of dichloromethane and n-hexane, (volume ratio is 1：8) wash, filter,
40 oC is dried under vacuum to constant weight, obtains final product lignin-graft copolymer.The yield of graft copolymerization be 94.1%, cinnamic turn
Rate is 93.5%, and percent grafting is 57.1%, and grafting degree is 53.9%.
Embodiment 8
A. 0.20 g lignin is dissolved in into 5 mL dimethyl sulfoxides, adds the first of 0.5 0.2 mmol of mL/mL frerrous chlorides
Alcoholic solution is simultaneously sufficiently stirred for dissolving, and Jing freezes repeatedly-vacuumizes-oxygen that removes in solution of the cyclic process of nitrogen charging, in nitrogen
The lower hydrogen peroxide for adding 0.5 mL 30% of protection, 10 min of stirring reaction are subsequently adding 2.36 g 3- methyl styrenes,
30 o48 h of C stirring reactions.Add 80 mL watery hydrochloric acid to dilute, filter, be washed with water to neutrality, 40oC is dried under vacuum to perseverance
Restore polymer.
B. the polymer of above-mentioned gained is carried out with ethyl acetate after 18 h of surname extraction, is concentrated, 40oC is vacuum dried
The blend of graft copolymer and homopolymers is obtained to constant weight.
C. graft copolymer is dissolved in into dichloromethane with the blend of homopolymers and is configured to 1 g/mL solution, be then added to
Precipitate in the n-hexane of 9 times of volumes, with the mixed solvent of dichloromethane and n-hexane, (volume ratio is 1：9) wash, filter, 40oC is dried under vacuum to constant weight, obtains final product lignin-graft copolymer.The yield of graft copolymerization is 94.9%, cinnamic conversion
Rate is 94.4%, and percent grafting is 58.5%, and grafting degree is 51.3%.
Embodiment 9
A. 0.20 g lignin is dissolved in into 5 mL dimethyl sulfoxides, adds the first of 0.5 0.2 mmol of mL/mL frerrous chlorides
Alcoholic solution is simultaneously sufficiently stirred for dissolving, and Jing freezes repeatedly-vacuumizes-oxygen that removes in solution of the cyclic process of nitrogen charging, in nitrogen
The lower hydrogen peroxide for adding 0.5 mL 30% of protection, 10 min of stirring reaction is subsequently adding 3.66 g 3- bromstyrols, 30o48 h of C stirring reactions.Add 60 mL watery hydrochloric acid to dilute, filter, be washed with water to neutrality, 40oC is dried under vacuum to constant weight
Obtain polymer.
B. the polymer of above-mentioned gained is carried out with ethyl acetate after 24 h of surname extraction, is concentrated, 40oC is vacuum dried
The blend of graft copolymer and homopolymers is obtained to constant weight.
C. graft copolymer is dissolved in into dichloromethane with the blend of homopolymers and is configured to 1 g/mL solution, be then added to
Precipitate in the n-hexane of 9 times of volumes, with the mixed solvent of dichloromethane and n-hexane, (volume ratio is 1：9) wash, filter, 40oC is dried under vacuum to constant weight, obtains final product lignin-graft copolymer.The yield of graft copolymerization is 93.3%, cinnamic conversion
Rate is 92.6%, and percent grafting is 55.3%, and grafting degree is 51.6%.
Embodiment 10
A. 0.20 g lignin is dissolved in into 5 mL dimethyl sulfoxides, adds the first of 0.5 0.2 mmol of mL/mL frerrous chlorides
Alcoholic solution is simultaneously sufficiently stirred for dissolving, and Jing freezes repeatedly-vacuumizes-oxygen that removes in solution of the cyclic process of nitrogen charging, in nitrogen
The lower hydrogen peroxide for adding 0.5 mL 30% of protection, 10 min of stirring reaction are subsequently adding 2.68 g 4- methoxy styrenes,
30o48 h of C stirring reactions.Add 80 mL watery hydrochloric acid to dilute, filter, be washed with water to neutrality, 40oC is dried under vacuum to
Constant weight obtains polymer.
B. the polymer of above-mentioned gained is carried out with ethyl acetate after 24 h of surname extraction, is concentrated, 40oC is vacuum dried
The blend of graft copolymer and homopolymers is obtained to constant weight.
C. graft copolymer is dissolved in into dichloromethane with the blend of homopolymers and is configured to 1 g/mL solution, be then added to
Precipitate in the n-hexane of 9 times of volumes, with the mixed solvent of dichloromethane and n-hexane, (volume ratio is 1：9) wash, filter, 40oC is dried under vacuum to constant weight, obtains final product lignin-graft copolymer.The yield of graft copolymerization is 94.5%, cinnamic conversion
Rate is 94.0%, and percent grafting is 54.8%, and grafting degree is 48.2%.
Claims (7)
1. a kind of preparation method of lignin-graft copolymer, it is characterised in that the method step is：
A, lignin is dissolved in dimethyl sulfoxide, adds the methanol solution of catalyst to be simultaneously sufficiently stirred for dissolving, described catalyst is
Frerrous chloride or ferrous sulfate, add initiator, initiator to be the hydrogen peroxide of 30wt%, be subsequently adding under nitrogen protection
Styrene monomer, 25 ~ 35oAfter 36 ~ 60 h of C stirring reactions, watery hydrochloric acid is added to dilute, filter, wash with water, do
It is dry, obtain polymer；
B, polymer is carried out with organic solvent 12 ~ 24 h of surname extraction, concentration, be dried, obtain graft copolymer and homopolymerization
The blend of thing；
C, blend is dissolved in polar solvent it is configured to solution, is added in the non-polar solven of 8 ~ 10 times of volumes through conventional
Precipitation, filtration, dry run obtain lignin-graft copolymer.
2. the method for claim 1, it is characterised in that described lignin is dealkalize lignin.
3. the method for claim 1, it is characterised in that described styrene monomer is represented with following formula：
In formula, R is methyl, bromine or OCH3。
4. the method for claim 1, it is characterised in that styrene monomer, initiator described in step A, catalysis
The mol ratio of agent is [styrene monomer]/[initiator]/[catalyst]=175 ~ 225：40~60：1.
5. the method for claim 1, it is characterised in that the organic solvent described in step B is benzene, toluene or acetic acid
Any one in ethyl ester.
6. the method for claim 1, it is characterised in that the polar solvent described in step C is dichloromethane, three chloromethanes
Any one in alkane, ethyl acetate or tetrahydrofuran.
7. the method for claim 1, it is characterised in that the non-polar solven described in step C be pentane, just oneself
Any one in alkane, normal heptane, hexamethylene or petroleum ether.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1071436A (en) * | 1988-12-19 | 1993-04-28 | 约翰·J·曼斯特 | Xylogen-acrylamide-phenylethene grafted copolymer, method for making and application |
| CN1824683A (en) * | 2006-02-05 | 2006-08-30 | 福州大学 | Method of preparing high boiling point alcohol lignin graft copolymer using rection extrusion method |
| CN102351997A (en) * | 2011-07-13 | 2012-02-15 | 东北林业大学 | Preparation of lignin polyacrylonitrile water absorbent |
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2013
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1071436A (en) * | 1988-12-19 | 1993-04-28 | 约翰·J·曼斯特 | Xylogen-acrylamide-phenylethene grafted copolymer, method for making and application |
| CN1824683A (en) * | 2006-02-05 | 2006-08-30 | 福州大学 | Method of preparing high boiling point alcohol lignin graft copolymer using rection extrusion method |
| CN102351997A (en) * | 2011-07-13 | 2012-02-15 | 东北林业大学 | Preparation of lignin polyacrylonitrile water absorbent |
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