CN104059233A - New method for preparing solid lignin quaternary ammonium salt and application of solid lignin quaternary ammonium salt - Google Patents
New method for preparing solid lignin quaternary ammonium salt and application of solid lignin quaternary ammonium salt Download PDFInfo
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Abstract
The invention discloses a new method for preparing solid lignin quaternary ammonium salt. Epichlorohydrin is added into tertiary amine, and a glycidyl quaternary ammonium salt intermediate is obtained after a reaction; on the condition that an initiating agent exists, the intermediate reacts with alkali lignin; then a reactant is added into a polarity organic solvent, and a precipitate is the solid lignin quaternary ammonium salt. According to the new method for preparing the solid lignin quaternary ammonium salt, the raw materials and reagents are easy to obtain, the reaction path is short, the reaction condition is moderate, and postprocessing is simple. The invention further discloses the application of the solid lignin quaternary ammonium salt obtained through the method.
Description
Technical field
The present invention relates to xylogen field.More specifically, relate to a kind of the prepare novel method of solid lignin quaternary ammonium salt and the application of this solid lignin quaternary ammonium salt.
Background technology
As one of renewable resources the abundantest on the earth, xylogen is extensively present in spermatophyte, with the basic framework of Mierocrystalline cellulose and hemicellulose formation plant.The quantity that xylogen exists at occurring in nature is very huge, estimates that the annual whole world can produce 1,500 hundred million tons of xylogen by plant-growth.Industrial lignin is the unique aromatics that can obtain from renewable resources, and wherein deriving from the industrial lignin producing in pulp and paper industry has 30,000,000 tons.
Xylogen is a kind of complicated phenol polymer being formed by 3 kinds of alcohol monomers (to tonquinol, lubanol, sinapyl alcohol).Because of structural unit difference, xylogen can be divided into 3 types: syringyl lignin (Syringyllignin, S-xylogen), guaiacyl xylogen (Guajacyl lignin, G-xylogen), p-hydroxybenzene xylogen (Hydroxy-phenyl lignin, H-xylogen), their structural formula is as follows respectively:
Xylogen itself has certain ion-exchange and absorption property and cheap, nontoxic, therefore has stronger competitive power, but because its performance is desirable not enough, its application is restricted.
In lignin molecule, contain phenolic hydroxyl group, alcoholic extract hydroxyl group, aldehyde radical, ketone group, carboxyl, methoxyl group isoreactivity group, many modified-reactions such as graft copolymerization, crosslinked, oxidation, reduction, sulfomethylation, alkoxide, alkali activation, methylolation, Mannich (Mannich) reaction can occur.These reactions can change spatial network, content of phenolic hydroxyl groups, the carboxyl-content of xylogen or in xylogen, introduce other function bases.In industry by lignin modification can be prepared to the Lignin-Based Adsorption Material that various functions differ.
Lignin quaternary is an important class lignin modification material, and it shows some unique character owing to having quaternary ammonium salt group, often as tensio-active agent, is widely used.At present, common synthetic lignin quaternary has two kinds of methods.
First method is first xylogen and aldehydes (formaldehyde, acetaldehyde, furfural etc.) and aminated compounds (primary amine, secondary amine, amino acid etc.) to be generated to lignin amine by Mannich reaction, and then reacts with alkylating reagent (methyl iodide, methyl-sulfate etc.) and generate lignin quaternary.As: the < < process for synthesis of lignin quaternary cation flocculant > > of Wan Peng etc. wishes in Tsing-Hua University.But this method has following shortcoming: reactions steps is more, use quantity of solvent larger, need strong acid catalysis, in raw material, alkylating reagent is partly highly toxic product.These shortcomings have restricted the promotion and application of the method to a certain extent.
Second method is first tertiary amine or its hydrochloride and epoxy chloropropane to be prepared into the intermediate monomer of quaternary ammonium salt, and then this intermediate monomer reacts to generate lignin quaternary under alkaline condition with alkali lignin.As all synthesized by this method lignin quaternary in the synthetic > > of the < < lignin quaternary tensio-active agent of synthetic and performance > > and the WANG Xiaohong of the < < Lignin Cation Surfactants of the preparation of the < < Tension of Lignin Quaternary Ammonium Salt of Liu Zuguang and surfactivity > >, Yang Yiqin.But the shortcoming of this method is: it is under highly basic condition, to prepare lignin quaternary solution, and the product obtaining after concentrating is lignin quaternary viscous fluid (mainly containing: epoxypropyl quaternary ammonium salt intermediate, sodium hydroxide, lignin quaternary).Due to epoxypropyl quaternary ammonium salt intermediate, under alkaline condition, stable existence and lignin quaternary solution constantly strengthen at aftertreatment concentration process neutral and alkali environment for a long time, easily make lignin quaternary decompose, be unfavorable for the preparation of lignin quaternary solid.When lignin quaternary is used as dispersion agent, emulsifying agent and flocculation agent as tensio-active agent, it is generally to use in water, can directly use lignin quaternary solution and without being isolated into solid.But when needs are packed mutually (as food desiccant) or use in non-water surrounding to be dried grain, for example remove some volatile organic matter in gas phase, just can not use this lignin quaternary solution, other components that this just need to remove in solution, obtain dry lignin quaternary solid.But owing to containing many kinds of substance in this lignin quaternary solution, rotary evaporation can obtain viscous liquid, can not obtain dry lignin quaternary solid.
In the synthetic and adsorption uranium performance study > > of the < of Chen Zhiqiang < xylogen sorbent material, the lignin quaternary viscous fluid obtaining and formaldehyde solution are continued to react 10 hours, finally throw out is filtered out to the solid lignin quaternary ammonium salt sorbent material after being cross-linked.The method, owing to by increasing reactions steps, quaternary ammonium salt being continued to Cross-linked, makes spended time many, and method is loaded down with trivial details, and after crosslinked, change has also occurred some physico-chemical properties of quaternary ammonium salt, causes the water-soluble of it significantly to reduce.
Therefore, need to provide a kind of novel method of preparing solid lignin quaternary ammonium salt.
Summary of the invention
First technical problem that the present invention will solve is to provide a kind of novel method of preparing solid lignin quaternary ammonium salt.Raw material used in the present invention, reagent are easy to get, and reaction scheme is short, reaction conditions gentle (without high temperature, highly basic strong acid condition, and easily controlling), and aftertreatment is simple, and the productive rate of intermediate and final product is all higher; The present invention is by using initiator to carry out free radical reaction, and the unfavorable factor of having avoided alkaline environment to bring, obtains the lignin quaternary solid that purity is higher smoothly.
Second technical problem that the present invention will solve is to provide the application of the solid lignin quaternary ammonium salt being prepared by aforesaid method.
For solving above-mentioned first technical problem, the present invention adopts following technical proposals:
A novel method of preparing solid lignin quaternary ammonium salt, comprises the following steps:
1) epoxy chloropropane is joined in tertiary amine ,-10-0 ℃ react to system be homogeneous phase solution state, afterwards 20-40 ℃ of reaction, obtain epoxypropyl quaternary ammonium salt intermediate;
Preferably, epoxy chloropropane is slowly joined in tertiary amine.Because this reaction is more violent, if epoxy chloropropane can be produced to a large amount of heat disposable adding in tertiary amine, be easy to allow lower boiling tertiary amine volatilize and make reaction not exclusively.More preferably, step 1) in, epoxy chloropropane is dropwise joined in tertiary amine.
First, at-10-0 ℃ low-temp reaction, can reduce the volatilization of tertiary amine; In this thermotonus for some time, to system from two phase liquid state, become homogeneous phase settled solution state, at this moment in system, only remain a small amount of tertiary amine, then 20-40 ℃ of comparatively high temps reaction, be conducive to add the carrying out of fast response.Can be by adding a small amount of silver nitrate solution to judge in reaction system the reaction times of 20-40 ℃; If adularescent precipitation shows to react completely, if there is brown precipitate, show that reaction is also incomplete.
2) under initiator exists, by step 1) the epoxypropyl quaternary ammonium salt intermediate that obtains and alkali lignin 40-70 ℃ react to system be homogeneous phase solution state, obtain lignin quaternary solution;
Alkali lignin is compared with the xylogen that other commercial runs make, and has the advantages that molecular size is moderate, reactive behavior is high.
Preferably, step 2) at 40-70 ℃ of reaction 2-4h.Not exclusively, the reaction times, the long productive rate increasing was limited for too short reaction of reaction times.
Step 2) the lignin quaternary solution obtaining mainly contains lignin quaternary, initiator and epoxypropyl quaternary ammonium salt intermediate.
3) by step 2) the lignin quaternary solution that obtains joins in polar organic solvent, and precipitate is solid lignin quaternary ammonium salt.
Preferably, by step 2) the lignin quaternary solution that obtains slowly joins in polar organic solvent.If quick or disposable, lignin quaternary solution is joined in organic solvent, in the solid obtaining, can comprise part intermediate and the solid block that obtains larger.More preferably, by step 2) the lignin quaternary solution that obtains dropwise joins in organic solvent.Most preferably, add fashionablely, stir polar organic solvent.The lignin quaternary solid obtaining is like this thinner pulverulent solids.Polar organic solvent is the epoxypropyl quaternary ammonium salt intermediate in dissolved lignin's quaternary ammonium salt solution effectively.
Step 1) in, described tertiary amine is excessive, complete to guarantee epichlorohydrin reaction.Preferably, step 1) in, the mol ratio of described tertiary amine and epoxy chloropropane is 1.1-1.5:1.
Preferably, step 1) in, described tertiary amine is Trimethylamine 99, triethylamine or tripropyl amine.
Preferably, step 2), in, described initiator is that ceric ammonium nitrate, ammonium persulphate, Potassium Persulphate, Fenton reagent (are H
2o
2-Fe
2+system) one or more mixtures in.
Step 2) in, described epoxypropyl quaternary ammonium salt intermediate is excessive, to guarantee that alkali lignin reacts completely.Preferably, step 2), in, the mol ratio of described epoxypropyl quaternary ammonium salt intermediate and alkali lignin (take average structure unit molecular weight 167) is 1.2-2.0:1.When this scope, can guarantee that epoxypropyl quaternary ammonium salt intermediate is excessive, transformation efficiency is high and can promote that alkali lignin reacts completely.Epoxypropyl quaternary ammonium salt intermediate consumption is crossed waste at most; Crossing alkali lignin at least can not react completely.
Preferably, step 2) in, the 1-5% of the quality that the consumption of described initiator is alkali lignin.
Preferably, step 3) in, described polar organic solvent is one or more mixtures in methyl alcohol, ethanol, ethyl acetate, acetone, acetonitrile, dioxane.
Preferably, step 3) in, the volume ratio of described lignin quaternary solution and polar organic solvent is 1:8-20.The present invention utilizes lignin quaternary at the different solubility of water and organic phase, obtains solid lignin quaternary ammonium salt.The too high waste of polar organic solvent consumption, consumption is too low owing to also existing a small amount of water to affect the amount of separating out of lignin quaternary solid in lignin quaternary solution.
Preferably, step 3) in, after first being concentrated, described lignin quaternary solution joins in polar organic solvent again.Due to the good water solubility of xylogen, in not concentrated lignin quaternary solution, contain aqueous solvent, can reduce lignin quaternary separating out in polar organic solvent.
Preferably, step 3) in, when described lignin quaternary solution is joined in polar organic solvent, stirring while adding, stirring velocity is 250-450r/min.
Precipitate after filtration, dry after, obtain final solid lignin quaternary ammonium salt.
For solving above-mentioned second technical problem, the present invention adopts following technical proposals:
The application of the solid lignin quaternary ammonium salt that aforesaid method prepares, it can be used on and in cigarette, reduces the organic burst size of part in cigarette.
Further, the order number of described solid lignin quaternary ammonium salt is 60 order-100 orders.
Further, the addition of described solid lignin quaternary ammonium salt is 10mg, 15mg, 20mg.
Beneficial effect of the present invention is as follows:
The present invention be take alkali lignin as raw material, goes through two-step reaction and an aftertreatment just obtains solid lignin quaternary ammonium salt;
Raw material used in the present invention, reagent are easy to get, reaction scheme is short, reaction conditions is gentle (without high temperature, highly basic strong acid condition, and easily control), aftertreatment is simple, intermediate can directly be used for carrying out next step reaction, and the productive rate > 85% of final product (actual value of lignin quaternary and the ratio between maximum theoretical), to preparation solid lignin quaternary ammonium salt, provide a kind of effective method, simultaneously also augmentation the range of application of lignin quaternary;
The present invention is by using initiator to carry out free radical reaction, and the unfavorable factor of having avoided alkaline environment to bring, obtains the lignin quaternary solid that purity is higher smoothly;
The present invention utilizes the difference of lignin quaternary and epoxypropyl quaternary ammonium salt intermediate solubleness in organic solvent, in the situation that reacting completely, excessive intermediate dissolves in polar organic solvent, and lignin quaternary solid can effectively be separated out from organic solution;
By solid lignin quaternary ammonium salt of the present invention, solve lignin quaternary to the studying a question of gas adsorption, widened the Application Areas of lignin quaternary.
Accompanying drawing explanation
Below in conjunction with accompanying drawing, the specific embodiment of the present invention is described in further detail.
Fig. 1 is the synthetic route schematic diagram of solid lignin quaternary ammonium salt of the present invention.
Fig. 2 is the infrared spectrogram of the solid lignin quaternary ammonium salt of embodiments of the invention 1.
Embodiment
In order to be illustrated more clearly in the present invention, below in conjunction with preferred embodiment, the present invention is described further.It will be appreciated by those skilled in the art that specifically described content is illustrative and nonrestrictive below, should not limit the scope of the invention with this.
Embodiment 1
1) take 33% trimethylamine aqueous solution 4.6g and put into single port flask, under the cryosels of-5 ℃ are bathed, stir 15min, then take 2.0g epoxy chloropropane, it is progressively added drop-wise in trimethylamine aqueous solution.Dropwise rear continuation and stir 30min, be then placed in the water-bath of 40 ℃, stirring reaction 2h, obtains faint yellow epoxypropyl quaternary ammonium salt intermediate.Wherein the mol ratio of Trimethylamine 99 and epoxy chloropropane is 1.24:1.
2) take 2.5g alkali lignin and put into there-necked flask, add 8mL distilled water, add 0.05g ammonium persulphate after being warming up to 50 ℃, stir and add in a moment the epoxypropyl quaternary ammonium salt intermediate making, after stirring reaction 3.5h, obtain black lignin quaternary solution.Wherein the mol ratio of quaternary ammonium salt intermediate and alkali lignin is 1.45:1, and catalyst levels is 2.0% of alkali lignin quality.
3) the lignin quaternary solution making is concentrated into 5mL by rotary evaporation, then concentrated solution is joined with in the 40mL dehydrated alcohol stirring, mixing speed remains on 350r/min, after lignin quaternary is all separated out by its filtering drying, obtain the beige solid lignin quaternary ammonium salt of 4.0g, productive rate is 85%.Wherein water and organic solvent are than being 1:8.
Fig. 1 is the synthetic route schematic diagram of solid lignin quaternary ammonium salt of the present invention.
Wherein,
R is CH
3, C
2h
5, C
3h
8; R
3refer to 3 R;
R
1for H, CH
3o;
R
2for H, CH
3o.
Fig. 2 is the infrared spectrogram of the solid lignin quaternary ammonium salt of embodiments of the invention 1.The solid lignin quaternary ammonium salt obtaining detects through infrared spectra and ultimate analysis, has detected respectively the feature 1488cm of its quaternary ammonium salt group
-1the obvious raising of place's absorption peak and nitrogen content.The solvability of solid lignin quaternary ammonium salt is also greatly improved compared with raw material alkali lignin, from indissoluble, becomes Yi Rong, and nothing is obviously separated out in acidic aqueous solution.Result shows, final product prepared by present method is lignin quaternary solid.
The solid lignin quaternary ammonium salt making is sieved by standard sieve, collect the solid particulate of order number between 60 orders and 80 orders, then taking 10mg lignin quaternary solid particulate joins in tri compound cigarette filter, be made into test cigarette, adopt tobacco industry standard method to detect tar and the phenol content discharging in its cigarette smoke.Test result shows, the tar content of test cigarette has reduced by 9.8%, and phenol content has reduced by 28.2%, and lignin quaternary solid adsorbent Pyrogentisinic Acid's adsorption selectivity is 18.4%.
Embodiment 2
Take 0.7g triethylamine liquid and put into single port flask, under the cryosel of 0 ℃ is bathed, stir 10min, then take 1.0g epoxy chloropropane, it is progressively added drop-wise in triethylamine.Dropwise rear continuation and stir 30min, be then placed under room temperature, stirring reaction 3h, obtains faint yellow epoxypropyl quaternary ammonium salt intermediate.Wherein the mol ratio of triethylamine and epoxy chloropropane is 1.11:1.
Take 1.2g alkali lignin and put into there-necked flask, add 5mL distilled water, add 0.02g Potassium Persulphate after being warming up to 60 ℃, stir and add in a moment the epoxypropyl quaternary ammonium salt intermediate making, after stirring reaction 3h, obtain black lignin quaternary solution.Wherein the mol ratio of quaternary ammonium salt intermediate and alkali lignin is 1.74:1, and catalyst levels is 1.6% of alkali lignin quality.
The lignin quaternary solution making is reduced to 3mL by rotary evaporation, then concentrated solution is joined with in the 48mL acetonitrile stirring, mixing speed remains on 250r/min, after lignin quaternary is all separated out by its filtering drying, obtain the beige solid lignin quaternary ammonium salt of 2.3g, productive rate is 89%.Wherein water and organic solvent are than being 1:16.
The solid lignin quaternary ammonium salt making is sieved by standard sieve, collect the solid particulate of order number between 80 orders and 100 orders, then taking 15mg lignin quaternary solid particulate joins in tri compound cigarette filter, be made into test cigarette, adopt tobacco industry standard method to detect tar and the nitrosamine NNK content discharging in its cigarette smoke.Test result shows, the tar content of test cigarette has reduced by 9.2%, and nitrosamine NNK content has reduced by 28.5%, and lignin quaternary solid adsorbent is 19.3% to the adsorption selectivity of nitrosamine NNK.
Embodiment 3
Take 33% trimethylamine aqueous solution 8.1g and put into single port flask, under the cryosels of-10 ℃ are bathed, stir 15min, then take 3.0g epoxy chloropropane, it is progressively added drop-wise in trimethylamine aqueous solution.Dropwise rear continuation and stir 30min, be then placed in the water-bath of 35 ℃, stirring reaction 3h, obtains faint yellow epoxypropyl quaternary ammonium salt intermediate.Wherein the mol ratio of triethylamine and epoxy chloropropane is 1.41:1.
Take 3.0g alkali lignin and put into there-necked flask, add 10mL distilled water, add 0.15g ceric ammonium nitrate after being warming up to 70 ℃, stir and add in a moment the epoxypropyl quaternary ammonium salt intermediate making, after stirring reaction 4h, obtain black lignin quaternary solution.Wherein the mol ratio of quaternary ammonium salt intermediate and alkali lignin is 1.81:1, and catalyst levels is 5% of alkali lignin quality.
The lignin quaternary solution making is concentrated into 5mL by rotary evaporation, then concentrated solution is joined with in the 60mL acetone stirring, mixing speed remains on 450r/min, after lignin quaternary is all separated out by its filtering drying, obtain the beige solid lignin quaternary ammonium salt of 4.98g, productive rate is 87%.Wherein water and organic solvent are than being 1:12.
The solid lignin quaternary ammonium salt making is sieved by standard sieve, collect the solid particulate of order number between 60 orders and 80 orders, then taking 15mg lignin quaternary solid particulate joins in tri compound cigarette filter, be made into test cigarette, adopt tobacco industry standard method to detect tar and the HCN content discharging in its cigarette smoke.Test result shows, the tar content of test cigarette has reduced by 12.8%, HCN content and reduced by 38.4%, and lignin quaternary solid adsorbent Pyrogentisinic Acid's adsorption selectivity is 25.6%.
Embodiment 4
Take 5g tripropyl amine liquid and put into single port flask, under the ice-water bath of 0 ℃, stir 5min, then take 2.5g epoxy chloropropane, it is progressively added drop-wise in tripropyl amine.Dropwise rear continuation and stir 30min, be then placed under room temperature, stirring reaction 3h, obtains faint yellow epoxypropyl quaternary ammonium salt intermediate.Wherein the mol ratio of tripropyl amine and epoxy chloropropane is 1.3:1.
Take 2.25g alkali lignin and put into there-necked flask, add 12mL distilled water, add 0.08g Potassium Persulphate after being warming up to 50 ℃, stir and add in a moment the epoxypropyl quaternary ammonium salt intermediate making, after stirring reaction 3h, obtain black lignin quaternary solution.Wherein the mol ratio of quaternary ammonium salt intermediate and alkali lignin is 2:1, and catalyst levels is 3.6% of alkali lignin quality.
The lignin quaternary solution making is reduced to 6mL by rotary evaporation, then concentrated solution is joined with in the 60mL ethanol stirring and ethyl acetate mixed solvent (volume ratio is 1:1), mixing speed remains on 300r/min, after lignin quaternary is all separated out by its filtering drying, obtain the beige solid lignin quaternary ammonium salt of 4.17g, productive rate is 86%.Wherein water and organic solvent are than being 1:10.
The solid lignin quaternary ammonium salt making is sieved by standard sieve, collect the solid particulate of order number between 80 orders and 100 orders, then taking 20mg lignin quaternary solid particulate joins in tri compound cigarette filter, be made into test cigarette, adopt tobacco industry standard method to detect tar and the nitrosamine NNK content discharging in its cigarette smoke.Test result shows, the tar content of test cigarette has reduced by 12.2%, and nitrosamine NNK content has reduced by 36.7%, and lignin quaternary solid adsorbent is 24.5% to the adsorption selectivity of nitrosamine NNK.
Embodiment 5
Synthetic method is with embodiment 1, and unique variation is that initiator used is Fenton reagent.
The solid lignin quaternary ammonium salt making is sieved by standard sieve, collect the solid particulate of order number between 60 orders and 80 orders, then taking 15mg lignin quaternary solid particulate joins in tri compound cigarette filter, be made into test cigarette, adopt tobacco industry standard method to detect tar and the phenol content discharging in its cigarette smoke.Test result shows, the tar content of test cigarette has reduced by 10.2%, and phenol content has reduced by 35.3%, and lignin quaternary solid adsorbent Pyrogentisinic Acid's adsorption selectivity is 25.1%.
Embodiment 6
Synthetic method is with embodiment 1, and unique variation is the mixture (mass ratio is 1:1) that initiator used is comprised of Potassium Persulphate and ammonium persulphate.
The solid lignin quaternary ammonium salt making is sieved by standard sieve, collect the solid particulate of order number between 80 orders and 100 orders, then taking 20mg lignin quaternary solid particulate joins in tri compound cigarette filter, be made into test cigarette, adopt tobacco industry standard method to detect tar and the nitrosamine NNK content discharging in its cigarette smoke.Test result shows, the tar content of test cigarette has reduced by 10.4%, and nitrosamine NNK content has reduced by 30.5%, and lignin quaternary solid adsorbent is 20.1% to the adsorption selectivity of nitrosamine NNK.
Embodiment 7
Synthetic method is with embodiment 1, and unique variation is the mixture (mass ratio is 1:1) that initiator used is comprised of ceric ammonium nitrate and ammonium persulphate.
The solid lignin quaternary ammonium salt making is sieved by standard sieve, collect the solid particulate of order number between 60 orders and 80 orders, then taking 20mg lignin quaternary solid particulate joins in tri compound cigarette filter, be made into test cigarette, adopt tobacco industry standard method to detect tar and the HCN content discharging in its cigarette smoke.Test result shows, the tar content of test cigarette has reduced by 15.2%, HCN content and reduced by 44.3%, and lignin quaternary solid adsorbent Pyrogentisinic Acid's adsorption selectivity is 29.1%.
Embodiment 8
Synthetic method is with embodiment 1, and variation is 2) in be warming up to 40 ℃; 3) Semi-polarity organic solvent is the mixture (volume ratio 1:1) of ethyl acetate and methyl alcohol.Result is similar to Example 1.
Embodiment 9
Synthetic method is with embodiment 1, and variation is 3) Semi-polarity organic solvent is the mixture (volume ratio 1:2) of dioxane and methyl alcohol.Result is similar to Example 1.
Obviously; the above embodiment of the present invention is only for example of the present invention is clearly described; and be not the restriction to embodiments of the present invention; for those of ordinary skill in the field; can also make other changes in different forms on the basis of the above description; here cannot give all embodiments exhaustive, every still row in protection scope of the present invention of apparent variation that technical scheme of the present invention extends out or change that belong to.
Claims (10)
1. a novel method of preparing solid lignin quaternary ammonium salt, is characterized in that, comprises the following steps:
1) epoxy chloropropane is joined in tertiary amine ,-10-0 ℃ react to system be homogeneous phase solution state, afterwards 20-40 ℃ of reaction, obtain epoxypropyl quaternary ammonium salt intermediate;
2) under initiator exists, by step 1) the epoxypropyl quaternary ammonium salt intermediate that obtains and alkali lignin 40-70 ℃ react to system be homogeneous phase solution state, obtain lignin quaternary solution;
3) by step 2) the lignin quaternary solution that obtains joins in polar organic solvent, and precipitate is solid lignin quaternary ammonium salt.
2. the novel method of preparation solid lignin quaternary ammonium salt according to claim 1, is characterized in that step 1) in, the mol ratio of described tertiary amine and epoxy chloropropane is 1.1-1.5:1.
3. the novel method of preparation solid lignin quaternary ammonium salt according to claim 1, is characterized in that step 2) in, the mol ratio of described epoxypropyl quaternary ammonium salt intermediate and alkali lignin is 1.2-2.0:1.
4. the novel method of preparation solid lignin quaternary ammonium salt according to claim 1, is characterized in that step 2) in, described initiator is one or more mixtures in ceric ammonium nitrate, ammonium persulphate, Potassium Persulphate, Fenton reagent.
5. according to the novel method of the preparation solid lignin quaternary ammonium salt described in claim 1 or 4, it is characterized in that step 2) in, the 1-5% of the quality that the consumption of described initiator is alkali lignin.
6. the novel method of preparation solid lignin quaternary ammonium salt according to claim 1, is characterized in that step 3) in, described polar organic solvent is one or more mixtures in methyl alcohol, ethanol, ethyl acetate, acetone, acetonitrile, dioxane.
7. the novel method of preparation solid lignin quaternary ammonium salt according to claim 1, is characterized in that step 3) in, the volume ratio of described lignin quaternary solution and polar organic solvent is 1:8-20.
8. the novel method of preparation solid lignin quaternary ammonium salt according to claim 1, is characterized in that step 3) in, described lignin quaternary solution is first concentrated, join in polar organic solvent more afterwards.
9. the novel method of preparation solid lignin quaternary ammonium salt according to claim 1, is characterized in that,
Preferably, step 1) in, described tertiary amine is Trimethylamine 99, triethylamine or tripropyl amine;
Preferably, step 1) in, epoxy chloropropane is slowly joined in tertiary amine; More preferably, step 1) in, epoxy chloropropane is dropwise joined in tertiary amine;
Preferably, step 2) at 40-70 ℃ of reaction 2-4h;
Preferably, step 3) in, by step 2) the lignin quaternary solution that obtains slowly joins in polar organic solvent; More preferably, step 3) in, by step 2) the lignin quaternary solution that obtains dropwise joins in polar organic solvent; Most preferably, step 3) in, by step 2) the lignin quaternary solution that obtains is while joining in polar organic solvent, stirs polar organic solvent.
10. the application of the solid lignin quaternary ammonium salt that the method as described in as arbitrary in claim 1-9 prepares, it can be used on and in cigarette, reduces the organic burst size of part in cigarette.
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