CN104059233B - 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 lignin field.More particularly, to a kind of new method preparing solid lignin quaternary ammonium salt and
The application of this solid lignin quaternary ammonium salt.
Background technology
As one of the abundantest Renewable resource on the earth, lignin is widely present in seed plant, with cellulose
Constitute the basic framework of plant with hemicellulose.Lignin quantity present in nature is very huge, estimates full generation every year
Boundary can produce 150,000,000,000 tons of lignins by plant growing.Industrial lignin is the aromatic series that uniquely can obtain from Renewable resource
Compound, wherein derives from the industrial wood producing in pulp and paper industry and have 30,000,000 tons.
Lignin is a kind of complexity phenol polymer being formed by 3 kinds of alcohol monomers (to tonquinol, 4-hydroxy-3-methoxycinnamic alcohol, sinapinic alcohol).
Because construction unit is different, lignin can be divided into 3 types：(Syringyl lignin, S- are wooden for syringyl lignin
Element), guaiacyl lignin (Guajacyl lignin, G- lignin), p-hydroxybenzene lignin (Hydroxy phenyl
Lignin, H- lignin), their structural formula is as follows respectively：
It is with absorption property and cheap, nontoxic that lignin has certain ion exchange in itself, therefore has stronger
Competitiveness, but because its performance ideal not enough is so that its application is restricted.
Phenolic hydroxyl group, alcoholic extract hydroxyl group, aldehyde radical, ketone group, carboxyl, methoxyl group isoreactivity group, Ke Yifa is contained in lignin molecule
Raw graft copolymerization, crosslinking, oxidation, reduction, sulfomethylation, alkoxide, alkali activation, methylolation, Mannich (Mannich) reaction
Deng many modified-reactions.These reactions can change the spatial network of lignin, content of phenolic hydroxyl groups, carboxyl-content or in lignin
Middle introducing other functions base.By lignin modification can be prepared the lignin-base adsorption material that various functions differ in industry
Material.
Lignin quaternary is an important class lignin modification material, and it shows one due to having quaternary ammonium salt group
Unique property a bit, through being widely used frequently as surfactant.At present, common synthesis lignin quaternary has two kinds of sides
Method.
First method be first by lignin and aldehydes (formaldehyde, acetaldehyde, furfural etc.) and aminated compoundss (primary amine, secondary amine,
Aminoacid etc.) lignin amine is generated by Mannich reaction, then anti-with alkylating reagent (iodomethane, dimethyl sulfate etc.) again
Lignin quaternary should be generated.As：Tsing-Hua University wishes Wan Peng's etc.《Process for synthesis of lignin quaternary cation flocculant》.But
This method has the disadvantage that：Reactions steps are more, larger using quantity of solvent, need strong acid catalyst, alkylating reagent portion in raw material
Dividing is toxic articles.These shortcomings constrain the promotion and application of the method to a certain extent.
Second method is first with epoxychloropropane, tertiary amine or its hydrochlorate to be prepared into the intermediate monomer of quaternary ammonium salt,
Then this intermediate monomer reacts to generate lignin quaternary with alkali lignin in the basic conditions.As Liu Zuguang《Wooden
The preparation of plain cationic emulsifier and its surface activity》, Yang Yiqin《The synthesis of Lignin Cation Surfactants and property
Energy》And WANG Xiaohong《The synthesis of lignin quaternary surfactant》In all synthesized lignin quaternary ammonium by this method
Salt.But the shortcoming of this method is：It is to prepare lignin quaternary solution under basic conditions, obtains after concentration
Product is that lignin quaternary viscous solution (mainly contains：Glycidyl quaternary ammonium salt intermediate, sodium hydroxide, lignin quaternary).
Due to glycidyl quaternary ammonium salt intermediate be unable in the basic conditions long-time stable exist and lignin quaternary solution rear
Process concentration process neutral and alkali environment constantly to strengthen, so that lignin quaternary is decomposed, be unfavorable for lignin quaternary solid
Preparation.When lignin quaternary is used as dispersant, emulsifying agent and flocculant as surfactant, it usually exists
Use in aqueous phase, lignin quaternary solution can be used directly and solid need not be separated into.But when needs are to be dried grain phase
When being packed (as food desiccant) or using in non-water environment, for example, remove some volatile organic matters in gas phase,
This lignin quaternary solution cannot be used, this is accomplished by removing the other components in solution, to obtain the wooden of drying
Plain quaternary ammonium salt solid.But contain many kinds of substance due in this lignin quaternary solution, rotary evaporation can obtain thick liquid
Body, can not obtain the lignin quaternary solid of drying.
In Chen Zhiqiang《The synthesis of lignin adsorbent and adsorption uranium performance study》In, by the lignin quaternary obtaining
Viscous solution continues reaction 10 hours with formalin, finally filters out precipitate, obtains the solid lignin season after crosslinking
Ammonium salt adsorbent., due to quaternary ammonium salt being continued Cross-linked so that the cost time is many by increasing reactions steps, method is numerous for the method
Trivial, and after crosslinking, some physicochemical properties of quaternary ammonium salt also there occurs change, leads to its water solublity to be greatly reduced.
Accordingly, it is desirable to provide a kind of new method preparing solid lignin quaternary ammonium salt.
Content of the invention
The invention solves the problems that first technical problem be provide a kind of new method preparing solid lignin quaternary ammonium salt.This
Invent used raw material, reagent is easy to get, reaction scheme is short, reaction condition is gentle (without high temperature, highly basic strong acid condition, and to be held
Easy to control), post processing is simple, and the yield of intermediate and final product is all higher；By the present invention in that being carried out with initiator certainly
Reacted by base, it is to avoid the unfavorable factor that alkaline environment brings, smoothly obtain the higher lignin quaternary solid of purity.
The invention solves the problems that second technical problem be that the solid lignin quaternary ammonium that prepared by said method is provided
The application of salt.
For solving above-mentioned first technical problem, the present invention adopts following technical proposals：
A kind of new method preparing solid lignin quaternary ammonium salt, comprises the following steps：
1) epoxychloropropane is added in tertiary amine, reacting to system at -10-0 DEG C is homogeneous phase solution state, exists afterwards
20-40 DEG C of reaction, obtains glycidyl quaternary ammonium salt intermediate；
Preferably, epoxychloropropane is slowly added in tertiary amine.Because this reaction is more violent, if by epoxy chlorine
Propane disposably adds and can produce substantial amounts of heat in tertiary amine it is easy to allow the volatilization of lower boiling tertiary amine make reaction not complete
Entirely.It is highly preferred that step 1) in, epoxychloropropane is added dropwise in tertiary amine.
First in -10-0 DEG C of low-temp reaction, the volatilization of tertiary amine can be reduced；In this thermotonus for a period of time to system by two
Phase solution state is changed into homogeneous settled solution state, at this moment remaining a small amount of tertiary amine in system, then in 20-40 DEG C of higher temperature
Reaction, is conducive to accelerating the carrying out of reaction.A small amount of silver nitrate can be added 20-40 DEG C of response time in passing through to reaction system
Solution is being judged；Show reaction completely if there are white precipitate, then show that reaction is not also complete if there are brown precipitate.
2) in the presence of initiator, by step 1) the glycidyl quaternary ammonium salt intermediate that obtains and alkali lignin be in 40-70
DEG C reacting to system is homogeneous phase solution state, obtains lignin quaternary solution；
Compared with the lignin that alkali lignin and other commercial runs are obtained, have that molecular size is moderate, reactivity is high
Feature.
Preferably, step 2) react 2-4h at 40-70 DEG C.Not exclusively, the response time is long for response time too short then reaction
The yield then increasing is limited.
Step 2) the lignin quaternary solution that obtains mainly contains lignin quaternary, initiator and glycidyl quaternary ammonium
Salt intermediate.
3) by step 2) the lignin quaternary solution that obtains is added in polar organic solvent, and precipitate is solid wood
Quality quaternary ammonium salt.
Preferably, by step 2) the lignin quaternary solution that obtains is slowly added in polar organic solvent.If hurry up
Speed or disposably lignin quaternary solution is added in organic solvent, then can comprise in the solid obtaining moiety intermediate and
The solid block obtaining is larger.It is highly preferred that by step 2) the lignin quaternary solution that obtains is added dropwise to organic solvent
In.Most preferably, during addition, stir polar organic solvent.The lignin quaternary solid so obtaining is thinner powder
Solid.Polar organic solvent can effectively in dissolved lignin's quaternary ammonium salt solution glycidyl quaternary ammonium salt intermediate.
Step 1) in, described tertiary amine is excessive, complete to ensure epichlorohydrin reaction.Preferably, step 1) in, described
The mol ratio of tertiary amine and epoxychloropropane is 1.1-1.5：1.
Preferably, step 1) in, described tertiary amine is trimethylamine, triethylamine or tripropyl amine (TPA).
Preferably, step 2) in, described initiator is for ammonium ceric nitrate, Ammonium persulfate., potassium peroxydisulfate, Fenton reagent (i.e.
H2O2-Fe2+System) one of or two or more mixture.
Step 2) in, described glycidyl quaternary ammonium salt intermediate is excessive, to ensure alkali lignin reaction completely.Preferably,
Step 2) in, described glycidyl quaternary ammonium salt intermediate and alkali lignin (in terms of average structure unit molecular weight 167) mole
Than for 1.2-2.0：1.In this scope, can guarantee that glycidyl quaternary ammonium salt intermediate is excessive, high conversion rate simultaneously can promote alkali wood
Quality reaction is completely.Glycidyl quaternary ammonium salt intermediate consumption is crossed and is at most wasted；Cross alkali lignin at least and can not react complete.
Preferably, step 2) in, the consumption of described initiator is the 1-5% of the quality of alkali lignin.
Preferably, step 3) in, described polar organic solvent is methanol, ethanol, ethyl acetate, acetone, acetonitrile, dioxy six
One of ring or two or more mixture.
Preferably, step 3) in, described lignin quaternary solution is 1 with the volume ratio of polar organic solvent：8-20.This
Invention to obtain solid lignin quaternary ammonium salt using lignin quaternary in the different solubility of aqueous phase and organic faciess.Polarity has
Machine solvent load is too high, wastes, and consumption is too low, affects lignin due to also there is a small amount of water in lignin quaternary solution
The amount of precipitation of quaternary ammonium salt solid.
Preferably, step 3) in, it is then added to polar organic solvent after described lignin quaternary solution is first concentrated
In.Due to the good water solubility of lignin, contain aqueous solvent in the lignin quaternary solution not concentrated, lignin quaternary ammonium can be reduced
Precipitation in polar organic solvent for the salt.
Preferably, step 3) in, when described lignin quaternary solution is added in polar organic solvent, in addition
Stirring, mixing speed is 250-450r/min.
Precipitate, after filtering, being dried, obtains 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 said method prepares, it can be used on to reduce in the middle part of Medicated cigarette in Medicated cigarette
Divide the burst size of Organic substance.
Further, the mesh number of described solid lignin quaternary ammonium salt is 60 mesh -100 mesh.
Further, the addition of described solid lignin quaternary ammonium salt is 10mg, 15mg, 20mg.
Beneficial effects of the present invention are as follows：
The present invention, with alkali lignin as raw material, just obtains solid lignin quaternary ammonium after two-step reaction and a post processing
Salt；
Raw material used in the present invention, reagent are easy to get, and reaction scheme is short, and reaction condition is gently (without high temperature, highly basic strong acid
Condition, and be easily controlled), post processing is simple, and intermediate can be used directly to carry out next step reaction, and the yield of final product
＞ 85% (ratio between the actual value of lignin quaternary and maximum theoretical), provides to preparation solid lignin quaternary ammonium salt
A kind of effective method, the also augmentation range of application of lignin quaternary simultaneously；
By the present invention in that carry out radical reaction with initiator, it is to avoid the unfavorable factor that alkaline environment brings, smoothly
Obtain the higher lignin quaternary solid of purity；
The present invention utilizes the difference of lignin quaternary and glycidyl quaternary ammonium salt intermediate dissolubility in organic solvent,
In the case of reaction completely, excessive intermediate dissolves in polar organic solvent, and lignin quaternary solid can be effectively
Separate out from organic solution；
Solve lignin quaternary by the solid lignin quaternary ammonium salt of the present invention gas absorption is studied a question, open up
The wide application of lignin quaternary.
Brief description
Below in conjunction with the accompanying drawings the specific embodiment of the present invention is described in further detail.
Fig. 1 is the synthetic route schematic diagram of the 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.
Specific embodiment
In order to be illustrated more clearly that the present invention, with reference to preferred embodiment, the present invention is described further.Ability
Field technique personnel should be appreciated that following specifically described content is illustrative and be not restrictive, and should not limit this with this
The protection domain of invention.
Embodiment 1
1) weigh 33% trimethylamine aqueous solution 4.6g to put in single-necked flask, under -5 DEG C of ice salt bath, stir 15min,
Then weigh 2.0g epoxychloropropane, it is progressively added drop-wise in trimethylamine aqueous solution.Continue stirring 30min after completion of dropping,
It is subsequently placed in 40 DEG C of water-bath, stirring reaction 2h, obtain faint yellow glycidyl quaternary ammonium salt intermediate.Wherein trimethylamine and ring
The mol ratio of oxygen chloropropane is 1.24：1.
2) weigh 2.5g alkali lignin to put in there-necked flask, add 8mL distilled water, after being warming up to 50 DEG C, add 0.05g
Ammonium persulfate., stirring adds prepared glycidyl quaternary ammonium salt intermediate in a moment, after stirring reaction 3.5h, obtains black wooden
Plain quaternary ammonium salt solution.The mol ratio of wherein quaternary ammonium salt intermediate and alkali lignin is 1.45:1, catalyst amount is alkali lignin
The 2.0% of quality.
3) the lignin quaternary solution being obtained is concentrated into 5mL by rotary evaporation, then concentrated solution is added
To in the 40mL dehydrated alcohol with stirring, speed of agitator is maintained at 350r/min, will after lignin quaternary all separates out
Its filtering drying, obtains 4.0g beige solid lignin quaternary ammonium salt, and yield is 85%.Wherein water and organic solvent are than for 1：
8.
Fig. 1 is the synthetic route schematic diagram of the solid lignin quaternary ammonium salt of the present invention.
Wherein,
R is CH3,C2H5,C3H8；R3Refer to 3 R；
R1For H, CH3O；
R2For H, CH3O.
Fig. 2 is the infrared spectrogram of the solid lignin quaternary ammonium salt of embodiments of the invention 1.The solid lignin season obtaining
Ammonium salt detects through infrared spectrum and elementary analysiss, detected feature 1488cm of its quaternary ammonium salt group respectively-1Place absworption peak and
The significantly improving of nitrogen content.The dissolubility of solid lignin quaternary ammonium salt is also greatly improved, by difficulty compared with raw material alkali lignin
Molten be changed into readily soluble, and no substantially separate out in acidic aqueous solution.Result shows, the final product of this method preparation is lignin season
Ammonium salt solid.
The solid lignin quaternary ammonium salt being obtained is sieved by standard screen, collects solid between 60 mesh and 80 mesh for the mesh number
Granule, then weighs 10mg lignin quaternary solid particle and is added in tri compound cigarette filter, be made into test
Medicated cigarette, detects the tar of release and phenol content in its cigarette smoke using tobacco business standard method.Test result shows, surveys
The tar content of paper cigarette reduces 9.8%, and phenol content reduces 28.2%, lignin quaternary solid absorbent Pyrogentisinic Acid
Adsorptive selectivity be 18.4%.
Embodiment 2
Weigh 0.7g triethylamine liquid to put in single-necked flask, stir 10min under 0 DEG C of ice salt bath, then weigh
1.0g epoxychloropropane, it is progressively added drop-wise in triethylamine.Continue stirring 30min after completion of dropping, be subsequently placed under room temperature,
Stirring reaction 3h, obtains faint yellow glycidyl quaternary ammonium salt intermediate.The mol ratio of wherein triethylamine and epoxychloropropane is
1.11：1.
Weigh 1.2g alkali lignin to put in there-necked flask, add 5mL distilled water, after being warming up to 60 DEG C, add 0.02g mistake
Potassium sulfate, stirring adds prepared glycidyl quaternary ammonium salt intermediate in a moment, after stirring reaction 3h, obtains black lignin season
Ammonium salt solution.The mol ratio of wherein quaternary ammonium salt intermediate and alkali lignin is 1.74:1, catalyst amount is alkali lignin quality
1.6%.
The lignin quaternary solution being obtained is reduced to 3mL by rotary evaporation, then concentrated solution is added to band
Have in the 48mL acetonitrile of stirring, speed of agitator is maintained at 250r/min, after lignin quaternary all separates out, filtered baking
Dry, obtain 2.3g beige solid lignin quaternary ammonium salt, yield is 89%.Wherein water and organic solvent are than for 1:16.
The solid lignin quaternary ammonium salt being obtained is sieved by standard screen, collects mesh number consolidating between 80 mesh and 100 mesh
Body granule, then weighs 15mg lignin quaternary solid particle and is added in tri compound cigarette filter, be made into survey
Paper cigarette, detects the tar of release and nitrosamine NNK content in its cigarette smoke using tobacco business standard method.Test result
Show, the tar content of test Medicated cigarette reduces 9.2%, and nitrosamine NNK content reduces 28.5%, lignin quaternary solid
Adsorbent is 19.3% to the adsorptive selectivity of nitrosamine NNK.
Embodiment 3
Weigh 33% trimethylamine aqueous solution 8.1g to put in single-necked flask, under -10 DEG C of ice salt bath, stir 15min,
Then weigh 3.0g epoxychloropropane, it is progressively added drop-wise in trimethylamine aqueous solution.Continue stirring 30min after completion of dropping,
It is subsequently placed in 35 DEG C of water-bath, stirring reaction 3h, obtain faint yellow glycidyl quaternary ammonium salt intermediate.Wherein triethylamine and ring
The mol ratio of oxygen chloropropane is 1.41：1.
Weigh 3.0g alkali lignin to put in there-necked flask, add 10mL distilled water, after being warming up to 70 DEG C, add 0.15g nitre
Sour cerium ammonium, stirring adds prepared glycidyl quaternary ammonium salt intermediate in a moment, after stirring reaction 4h, obtains black lignin season
Ammonium salt solution.The mol ratio of wherein quaternary ammonium salt intermediate and alkali lignin is 1.81:1, catalyst amount is alkali lignin quality
5%.
The lignin quaternary solution being obtained is concentrated into 5mL by rotary evaporation, then concentrated solution is added to
In 60mL acetone with stirring, speed of agitator is maintained at 450r/min, is filtered after lignin quaternary all separates out
Dry, obtain 4.98g beige solid lignin quaternary ammonium salt, yield is 87%.Wherein water and organic solvent are than for 1:12.
The solid lignin quaternary ammonium salt being obtained is sieved by standard screen, collects solid between 60 mesh and 80 mesh for the mesh number
Granule, then weighs 15mg lignin quaternary solid particle and is added in tri compound cigarette filter, be made into test
Medicated cigarette, detects the tar of release and HCN content in its cigarette smoke using tobacco business standard method.Test result shows, surveys
The tar content of paper cigarette reduces 12.8%, HCN content and reduces 38.4%, lignin quaternary solid absorbent Pyrogentisinic Acid
Adsorptive selectivity be 25.6%.
Embodiment 4
Weigh 5g tripropyl amine (TPA) liquid to put in single-necked flask, stir 5min under 0 DEG C of ice-water bath, then weigh 2.5g ring
Oxygen chloropropane, it is progressively added drop-wise in tripropyl amine (TPA).Continue stirring 30min after completion of dropping, be subsequently placed under room temperature, stirring is anti-
Answer 3h, obtain faint yellow glycidyl quaternary ammonium salt intermediate.The mol ratio of wherein tripropyl amine (TPA) and epoxychloropropane is 1.3：1.
Weigh 2.25g alkali lignin to put in there-necked flask, add 12mL distilled water, after being warming up to 50 DEG C, add 0.08g
Potassium peroxydisulfate, stirring adds prepared glycidyl quaternary ammonium salt intermediate in a moment, after stirring reaction 3h, obtains black lignin
Quaternary ammonium salt solution.The mol ratio of wherein quaternary ammonium salt intermediate and alkali lignin is 2:1, catalyst amount is alkali lignin quality
3.6%.
The lignin quaternary solution being obtained is reduced to 6mL by rotary evaporation, then concentrated solution is added to band
Have in the 60mL ethanol and ethyl acetate mixed solvent of stirring that (volume ratio is 1:1), speed of agitator is maintained at 300r/min, treats wood
By its filtering drying after the whole precipitation of quality quaternary ammonium salt, obtain 4.17g beige solid lignin quaternary ammonium salt, yield is
86%.Wherein water and organic solvent are than for 1:10.
The solid lignin quaternary ammonium salt being obtained is sieved by standard screen, collects mesh number consolidating between 80 mesh and 100 mesh
Body granule, then weighs 20mg lignin quaternary solid particle and is added in tri compound cigarette filter, be made into survey
Paper cigarette, detects the tar of release and nitrosamine NNK content in its cigarette smoke using tobacco business standard method.Test result
Show, the tar content of test Medicated cigarette reduces 12.2%, and nitrosamine NNK content reduces 36.7%, and lignin quaternary is solid
Body adsorbent is 24.5% to the adsorptive selectivity of nitrosamine NNK.
Embodiment 5
With embodiment 1, unique change is initiator used is Fenton reagent to synthetic method.
The solid lignin quaternary ammonium salt being obtained is sieved by standard screen, collects solid between 60 mesh and 80 mesh for the mesh number
Granule, then weighs 15mg lignin quaternary solid particle and is added in tri compound cigarette filter, be made into test
Medicated cigarette, detects the tar of release and phenol content in its cigarette smoke using tobacco business standard method.Test result shows, surveys
The tar content of paper cigarette reduces 10.2%, and phenol content reduces 35.3%, and lignin quaternary solid absorbent is to benzene
The adsorptive selectivity of phenol is 25.1%.
Embodiment 6
Synthetic method, with embodiment 1, uniquely changes initiator used and is made up of potassium peroxydisulfate and Ammonium persulfate.
(mass ratio is 1 to mixture:1).
The solid lignin quaternary ammonium salt being obtained is sieved by standard screen, collects mesh number consolidating between 80 mesh and 100 mesh
Body granule, then weighs 20mg lignin quaternary solid particle and is added in tri compound cigarette filter, be made into survey
Paper cigarette, detects the tar of release and nitrosamine NNK content in its cigarette smoke using tobacco business standard method.Test result
Show, the tar content of test Medicated cigarette reduces 10.4%, and nitrosamine NNK content reduces 30.5%, and lignin quaternary is solid
Body adsorbent is 20.1% to the adsorptive selectivity of nitrosamine NNK.
Embodiment 7
Synthetic method, with embodiment 1, uniquely changes initiator used and is made up of ammonium ceric nitrate and Ammonium persulfate.
(mass ratio is 1 to mixture:1).
The solid lignin quaternary ammonium salt being obtained is sieved by standard screen, collects solid between 60 mesh and 80 mesh for the mesh number
Granule, then weighs 20mg lignin quaternary solid particle and is added in tri compound cigarette filter, be made into test
Medicated cigarette, detects the tar of release and HCN content in its cigarette smoke using tobacco business standard method.Test result shows, surveys
The tar content of paper cigarette reduces 15.2%, HCN content and reduces 44.3%, lignin quaternary solid absorbent Pyrogentisinic Acid
Adsorptive selectivity be 29.1%.
Embodiment 8
With embodiment 1, change is 2 to synthetic method) in be warming up to 40 DEG C；3) in, polar organic solvent is ethyl acetate and first
Mixture (the volume ratio 1 of alcohol:1).Result is similar to Example 1.
Embodiment 9
With embodiment 1, change is 3 to synthetic method) in polar organic solvent be the mixture (volume of dioxane and methanol
Ratio 1:2).Result is similar to Example 1.
Obviously, the above embodiment of the present invention is only intended to clearly illustrate example of the present invention, and is not right
The restriction of embodiments of the present invention, for those of ordinary skill in the field, also may be used on the basis of the above description
To make other changes in different forms, all of embodiment cannot be exhaustive here, every belong to this
Obvious change that bright technical scheme is extended out or change the row still in protection scope of the present invention.
Claims (12)
1. a kind of application of solid lignin quaternary ammonium salt is it is characterised in that described solid lignin quaternary ammonium salt is used in Medicated cigarette
Reduce the burst size of partial organic substances in Medicated cigarette；
The preparation of described solid lignin quaternary ammonium salt comprises the following steps：
1) epoxychloropropane is added in tertiary amine, reacting to system at -10-0 DEG C is homogeneous phase solution state, afterwards in 20-
40 DEG C of reactions, obtain glycidyl quaternary ammonium salt intermediate；
2) in the presence of initiator, by step 1) the glycidyl quaternary ammonium salt intermediate that obtains and alkali lignin anti-at 40-70 DEG C
Should be homogeneous phase solution state to system, obtain lignin quaternary solution；
3) by step 2) the lignin quaternary solution that obtains is added in polar organic solvent, and precipitate is solid lignin
Quaternary ammonium salt.
2. the application of solid lignin quaternary ammonium salt according to claim 1 is it is characterised in that step 1) in, described three-level
The mol ratio of amine and epoxychloropropane is 1.1-1.5：1.
3. the application of solid lignin quaternary ammonium salt according to claim 1 is it is characterised in that step 2) in, described epoxy
Quaternary ammonium salts intermediate is 1.2-2.0 with the mol ratio of alkali lignin：1.
4. the application of solid lignin quaternary ammonium salt according to claim 1 is it is characterised in that step 2) in, described initiation
Agent is one of ammonium ceric nitrate, Ammonium persulfate., potassium peroxydisulfate, Fenton reagent or two or more mixture.
5. the application of the solid lignin quaternary ammonium salt according to claim 1 or 4 is it is characterised in that step 2) in, described draw
Send out the 1-5% for the quality of alkali lignin for the consumption of agent.
6. the application of solid lignin quaternary ammonium salt according to claim 1 is it is characterised in that step 3) in, described polarity
Organic solvent is one of methanol, ethanol, ethyl acetate, acetone, acetonitrile, dioxane or two or more mixture.
7. the application of solid lignin quaternary ammonium salt according to claim 1 is it is characterised in that step 3) in, described wooden
Plain quaternary ammonium salt solution is 1 with the volume ratio of polar organic solvent：8-20.
8. the application of solid lignin quaternary ammonium salt according to claim 1 is it is characterised in that step 3) in, by described wood
Quality quaternary ammonium salt solution first concentrates, and is then added to afterwards in polar organic solvent.
9. solid lignin quaternary ammonium salt according to claim 1 application it is characterised in that
Step 1) in, described tertiary amine is trimethylamine, triethylamine or tripropyl amine (TPA)；
Step 1) in, epoxychloropropane is slowly added in tertiary amine；
Step 2) react 2-4h at 40-70 DEG C；
Step 3) in, by step 2) the lignin quaternary solution that obtains is slowly added in polar organic solvent.
10. the application of solid lignin quaternary ammonium salt according to claim 1 is it is characterised in that step 1) in, by epoxy chlorine
Propane is added dropwise in tertiary amine.
The application of 11. solid lignin quaternary ammonium salts according to claim 1 is it is characterised in that step 3) in, by step 2)
The lignin quaternary solution obtaining is added dropwise in polar organic solvent.
The application of 12. solid lignin quaternary ammonium salts according to claim 1 is it is characterised in that step 3) in, by step 2)
When the lignin quaternary solution obtaining is added in polar organic solvent, stir polar organic solvent.
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| IT201700007087A1 (en) * | 2017-01-24 | 2018-07-24 | Bridgestone Corp | RUBBER COMPOUNDS FOR TIRE PARTS INCLUDING LIGNINA AS A DISPERSANT AGENT |
| CN110485201A (en) * | 2018-05-15 | 2019-11-22 | 上海昶法新材料有限公司 | A kind of lignin Cypres and preparation method thereof |
| CN109174465B (en) * | 2018-09-14 | 2021-12-31 | 武汉工程大学 | Quaternary ammonium salt suitable for flotation |
| CN110939013B (en) * | 2019-12-17 | 2020-06-30 | 浙江金龙纸业有限公司 | Method for manufacturing high-bulk gray board paper |
| CN111333859A (en) * | 2020-02-17 | 2020-06-26 | 南京工业大学 | Aminated lignin and preparation method and application thereof |
| CN111558328B (en) * | 2020-05-25 | 2023-09-01 | 雅思汀娜（北京）科技有限公司 | Lignin cationic surfactant and preparation method thereof, and long-acting antibacterial agent and preparation method thereof |
| CN113046047B (en) * | 2021-03-12 | 2022-09-27 | 重庆化工职业学院 | Preparation method of temperature-resistant surfactant for oil displacement |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3407188A (en) * | 1965-09-01 | 1968-10-22 | West Virginia Pulp & Paper Co | Quaternary ammonium salts of lignin |
| CN1146999A (en) * | 1996-07-12 | 1997-04-09 | 清华大学 | Process for synthesis of lignin quaternary cation flocculant |
| CN1818211A (en) * | 2006-03-08 | 2006-08-16 | 红塔烟草(集团)有限责任公司 | Cigarette paper with low-quantitation and high-transparent for decreasing smoke carbon monoxide and production thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004057522A (en) * | 2002-07-30 | 2004-02-26 | Nippon Paper Industries Co Ltd | Deodorant and method for deodorization |
-
2014
- 2014-07-02 CN CN201410313362.6A patent/CN104059233B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3407188A (en) * | 1965-09-01 | 1968-10-22 | West Virginia Pulp & Paper Co | Quaternary ammonium salts of lignin |
| CN1146999A (en) * | 1996-07-12 | 1997-04-09 | 清华大学 | Process for synthesis of lignin quaternary cation flocculant |
| CN1818211A (en) * | 2006-03-08 | 2006-08-16 | 红塔烟草(集团)有限责任公司 | Cigarette paper with low-quantitation and high-transparent for decreasing smoke carbon monoxide and production thereof |
Non-Patent Citations (5)
| Title |
|---|
| "利用秸秆木质素制备阳离子絮凝剂的研究";罗渊;《中国优秀硕士学位论文全文数据库 工程科技I辑》;20100215(第2期);第B027-193页 * |
| "新型脱色絮凝剂木素季胺盐的研制及其絮凝性能与机理的研究";吴冰艳等;《化工环保》;19971030;第17卷(第5期);第268-272页 * |
| "木质素三甲基季铵盐为模板剂制备多孔氧化硅材料";王春海等;《北京林业大学学报》;20110731;第33卷(第4期);第118-123页 * |
| "阳离子絮凝剂木质素季胺盐的合成与脱色性能研究";方桂珍等;《林产化学与工业》;20030615;第23卷(第2期);第37-41页 * |
| "麦草碱木质素三甲基季铵盐对酸性染料溶液的絮凝性能影响";姜贵全等;《森林工程》;20120731;第28卷(第4期);第55-60页 * |
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