CN109433099A - A kind of preparation method and applications of lignin-base sodium alcohol ether carboxylate - Google Patents
A kind of preparation method and applications of lignin-base sodium alcohol ether carboxylate Download PDFInfo
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- CN109433099A CN109433099A CN201811605205.7A CN201811605205A CN109433099A CN 109433099 A CN109433099 A CN 109433099A CN 201811605205 A CN201811605205 A CN 201811605205A CN 109433099 A CN109433099 A CN 109433099A
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Abstract
The present invention relates to a kind of preparation method and applications of lignin-base sodium alcohol ether carboxylate.Include the following steps: that the alkali lignin water slurry for being 10~30% by concentration is ultrasonically treated, alkali lignin pH of suspension after adjusting ultrasonic treatment with sodium hydroxide or potassium hydroxide aqueous solution, it is mixed by alkali lignin with mass ratio 5:1~3 of octyl glycidyl ether, react 4h, vacuum distillation removes water, it is washed with dehydrated alcohol, is dried to obtain lignin-base alcohol ether in 65 DEG C；8~14 parts of lignin-base alcohol ethers are dissolved in 100 parts of sodium hydrate aqueous solutions, is that 3- chloropropionic acid is added in 1:1~2 by the mass ratio of lignin-base alcohol ether and 3- chloropropionic acid, reacts 4h, vacuum distillation removes water, after being washed with dehydrated alcohol, re-dry obtains lignin-base sodium alcohol ether carboxylate.Lignin-base sodium alcohol ether carboxylate of the invention is as graphene dispersing solution auxiliary agent application.
Description
Technical field
The invention belongs to the preparation fields of surfactant, and in particular to a kind of preparation of lignin-base sodium alcohol ether carboxylate agent
Method and its application.
Background technique
Lignin is only second to the compound aromatic base of cellulose as content in nature, have it is from a wealth of sources, it is renewable,
Nontoxic advantage.Industrial lignin is mainly derived from paper-making pulping, and according to the difference of pulping process, industrial lignin is divided into alkali wood
Quality and lignosulfonates.Lignosulfonates are shown well with groups such as strong hydrophilicity group sulfonate radical and carboxyls
Water solubility belongs to natural polymeric anion type surfactant.But compared with low-molecular-weight surfactant, due to lignin
Lack long alkyl chain on sulfonate structures, lipophilic very poor, surface-active is lower.Lack hydrophily chain in the structure of alkali lignin
Section, poorly water-soluble, it is difficult to be used as surfactant.
Although industrial lignin is difficult to use directly as surfactant, various functions are contained on lignin structure
Group, it may be considered that lignin-base surfactant is synthesized by chemical modification, its surface-active and other performance is improved, widens
The application range of lignin and field.CN101327416A discloses a kind of lignose alcohol ether carboxylate surfactant, utilizes
Lignin reacts with ethylene oxide, propylene oxide catalysis and prepares lignose alcohol ether, is then acidified with halogenated acid, obtains lignin alcohol
Ether carboxylate.Reaction process needs high temperature and pressure, while using the toluene being more toxic as solvent, the inadequate ring of production technology
It protects.CN103755973A discloses a kind of in the alkali lignin modified method for preparing surfactant.The invention is with industrial production
In the alkali lignin discarded be raw material, first with lauryl diglycidyl ether, N, N- dimethyl benzylamine reacts in dimethyl sulfoxide,
Then it is reacted with chlorosulfonic acid, product obtains a kind of lignin-base alcohol ether sulfonate after neutralizing, dialysing.The reaction process is used
Dimethyl sulfoxide toxicity it is stronger, have permeability, inadequate safety and environmental protection to human skin.
Summary of the invention
The object of the present invention is to provide a kind of preparation methods of lignin-base sodium alcohol ether carboxylate, to overcome existing synthetic route
Need high temperature and pressure, a large amount of defects for using solvent.
Second object of the present invention is to provide a kind of application of lignin-base sodium alcohol ether carboxylate.
The preparation method of lignin-base sodium alcohol ether carboxylate of the invention, comprising the following steps:
(1) the alkali lignin water slurry that concentration is 10~30% is ultrasonically treated 30 under the conditions of 25~35 DEG C~
120min adjusts the alkali lignin pH of suspension after being ultrasonically treated to 10 with the sodium hydroxide or potassium hydroxide aqueous solution of 1mol/L
~12, it is mixed by alkali lignin with mass ratio 5:1~3 of octyl glycidyl ether, is warming up to 60~80 DEG C, react 4h, decompression
Water is distilled off, is washed with dehydrated alcohol, is dried to obtain lignin-base alcohol ether in 65 DEG C；
(2) 8~14 parts of lignin-base alcohol ethers are dissolved in the sodium hydrate aqueous solution of 100 parts of 2mol/l, it is heated to 80~
100 DEG C, it is that 3- chloropropionic acid is added in 1:1~2 by the mass ratio of lignin-base alcohol ether and 3- chloropropionic acid, reacts 4h, vacuum distillation removes
Water is removed, after being washed with dehydrated alcohol, in 65 DEG C of dryings, obtains lignin-base sodium alcohol ether carboxylate.
The characteristics of present invention contains phenylpropyl alcohol alkyl hydrophobic grouping according to the structure of alkali lignin, lacks hydrophilic radical, if
Meter introduces the octyl glycidyl ether of short chain in the structure of alkali lignin, then introduces carboxyl through carboxy methylation, and balance alkali is wooden
The hydrophilic, hydrophobic segmented structure of element, improves the water solubility of alkali lignin, while assigning alkali lignin excellent surface-active and dispersion
Property.The water solubility and surface tension, dispersion force that final product is controlled by carboxymethylated degree make the lignin-base of synthesis
Sodium alcohol ether carboxylate has excellent surface-active and dispersion force, can be used as the dispersing aid of functionalization material graphene.By whole
The design and optimization of body formula makes lignin-base alcohol ether carboxylate natrium surfactant play good physicochemical property.
Preparation method of the invention has the following advantages that and effect:
1. the reaction medium that the present invention prepares lignin-base sodium alcohol ether carboxylate is water, realizes Diamond Search discharge, meet environmental protection and want
It asks；Preparation process is not necessarily to high temperature and pressure, and reaction condition is mild, and equipment requirement is low, is advantageously implemented industrialization.
2. lignin-base sodium alcohol ether carboxylate provided by the invention is a kind of surfactant, good surface activity, 1% it is water-soluble
Liquid surface tension can reach 28.0mN/m, and dispersion force is strong, can be used as the dispersing aid of graphene functionalized material, dispersion effect
Good, storage stability is good.
3. raw material alkali lignin used in the present invention is from a wealth of sources, renewable, non-toxic or low-toxic, and cheap, because
This is with a wide range of applications.
Specific embodiment
Below by embodiment come the present invention is described in detail, these embodiments be only capable of for explain invention and cannot
For explaining limitation of the present invention.
Embodiment 1
(1) the alkali lignin suspension that concentration is 20% is ultrasonically treated 60min under the conditions of 25 DEG C, with the hydrogen of 1mol/L
Aqueous solution of sodium oxide adjusts the alkali lignin pH of suspension after ultrasonic treatment to 10, by alkali lignin and octyl glycidyl ether
Mass ratio 5:2 mixing, is warming up to 80 DEG C, reacts 4h, and vacuum distillation removes water, washed with dehydrated alcohol, in 65 DEG C of dryings, obtained
Lignin-base alcohol ether；
(2) 8 parts of lignin-base alcohol ethers are dissolved in the sodium hydrate aqueous solution of 100 parts of 2mol/l, are heated to 80 DEG C, by wood
The mass ratio of quality base alcohol ether and 3- chloropropionic acid is that 3- chloropropionic acid is added in 1:1, reacts 4h, vacuum distillation removes water, with anhydrous second
After alcohol washing, in 65 DEG C of dryings, lignin-base sodium alcohol ether carboxylate is obtained.
Embodiment 2
(1) suspension for the alkali lignin for being 10% by concentration is ultrasonically treated 30min under the conditions of 30 DEG C, with 1mol/L's
Sodium hydrate aqueous solution adjusts the alkali lignin pH of suspension after being ultrasonically treated to 11, by alkali lignin and octyl glycidyl ether
Mass ratio 5:1 mixing, be warming up to 60 DEG C, react 4h, vacuum distillation removes water, washed with dehydrated alcohol, in 65 DEG C of dryings, obtained
To lignin-base alcohol ether；
(2) 12 parts of lignin-base alcohol ethers are dissolved in the sodium hydrate aqueous solution of 100 parts of 2mol/L, are heated to 90 DEG C, press
The mass ratio of lignin-base alcohol ether and 3- chloropropionic acid is that 3- chloropropionic acid is added in 1:1, reacts 4h, vacuum distillation removes water, and use is anhydrous
After ethanol washing, in 65 DEG C of dryings, lignin-base sodium alcohol ether carboxylate is obtained.
Embodiment 3
(1) suspension for the alkali lignin for being 30% by concentration is ultrasonically treated 120min under the conditions of 35 DEG C, uses 1mol/L
Potassium hydroxide aqueous solution adjust ultrasonic treatment after alkali lignin pH of suspension to 12, by alkali lignin and octyl glycidyl
The mass ratio 5:3 of ether is mixed, and is warming up to 75 DEG C, reacts 4h, and vacuum distillation removes water, washed with dehydrated alcohol, in 65 DEG C of dryings,
Obtain lignin-base alcohol ether；
(2) 14 parts of lignin-base alcohol ethers are dissolved in the sodium hydrate aqueous solution of 100 parts of 2mol/l, are heated to 100 DEG C, press
The mass ratio of lignin-base alcohol ether and 3- chloropropionic acid is that 3- chloropropionic acid is added in 1:2, reacts 4h, vacuum distillation removes water, and use is anhydrous
After ethanol washing, in 65 DEG C of dryings, lignin-base sodium alcohol ether carboxylate is obtained.
The lignin-base alcohol ether carboxylic sodium that Examples 1 to 3 obtains is made into 1% aqueous solution, using surface tension instrument
K100MK2 carries out surface tension analysis to sample, and the corresponding surface tension of Examples 1 to 3 is respectively as follows: 29.8mN/ as the result is shown
M, 30.3mN/m and 28.0mN/m.
Lignin-base sodium alcohol ether carboxylate of the invention can be used as graphene dispersing solution auxiliary agent, in use, need with it is common
Surfactant compound advanced optimizes the dispersion effect and stability of graphene dispersing solution, lignin-base sodium alcohol ether carboxylate
Additive amount is 0.1~5mg/mL, and graphene dispersing solution concentration is 0.1~10mg/mL, preferably 0.5~3mg/mL.
Using the lignin-base sodium alcohol ether carboxylate of embodiment 3 as the ingredient of graphene dispersing solution, stone is configured as follows
Black alkene dispersion liquid: by lignin-base sodium alcohol ether carboxylate, hexadecyltrimethylammonium chloride, triton x-100 and graphene are 25
It is ultrasonically treated 8h in~35 DEG C of water-bath, stands for 24 hours, 30min is centrifuged with 2000r/min, removes bulky grain, collects upper liquid
Body, as graphene dispersing solution.As a comparison, table 1 is tetra- kinds of each component contents of graphene dispersing solution of A, B, C, D and E.
1 five kinds of each component contents of graphene dispersing solution (mg/mL) of table
Utilize absorbance, the concentration of UV-vis spectrophotometric analysis graphene dispersing solution A, B, C, D and E.Test wavelength
For 660nm.The graphene solution absorbance for first testing known concentration, the standard for establishing graphene solution absorbance and concentration are bent
Line.Absorbance is tested after the graphene dispersing solution of unknown concentration is diluted 250 times, the concentration of dispersion liquid is calculated by absorbance.
Graphene dispersion degree refers to the concentration of graphene in the supernatant liquid being collected after centrifugation.The yield Y=C of grapheneDispersion concentration/CInitial concentration,
Test result is shown in Table 2.
The dispersion degree and yield of 2 five kinds of graphene dispersing solutions of table
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (3)
1. a kind of preparation method of lignin-base sodium alcohol ether carboxylate, it is characterised in that include the following steps:
(1) the alkali lignin water slurry that concentration is 10~30% is ultrasonically treated 30~120min under the conditions of 25~35 DEG C,
Alkali lignin pH of suspension after adjusting ultrasonic treatment with the sodium hydroxide or potassium hydroxide aqueous solution of 1mol/L is pressed to 10~12
Alkali lignin is mixed with mass ratio 5:1~3 of octyl glycidyl ether, is warming up to 60~80 DEG C, reacts 4h, and vacuum distillation removes
Water is washed with dehydrated alcohol, is dried to obtain lignin-base alcohol ether in 65 DEG C；
(2) 8~14 parts of lignin-base alcohol ethers are dissolved in the sodium hydrate aqueous solution of 100 parts of 2mol/L, are heated to 80~100
DEG C, it is that 3- chloropropionic acid is added in 1:1~2 by the mass ratio of lignin-base alcohol ether and 3- chloropropionic acid, reacts 4h, vacuum distillation removes
Water after being washed with dehydrated alcohol, in 65 DEG C of dryings, obtains lignin-base sodium alcohol ether carboxylate.
2. application of the lignin-base sodium alcohol ether carboxylate as described in claim 1 as graphene dispersing solution auxiliary agent.
3. application of the lignin-base sodium alcohol ether carboxylate according to claim 2 as graphene dispersing solution auxiliary agent, feature
Be by lignin-base sodium alcohol ether carboxylate: 0.1~5mg/mL, hexadecyltrimethylammonium chloride: 0.1mg/mL, Qula lead to X-
100:0.1mg/mL and graphene: 0.1~10mg/mL is ultrasonically treated 8h in 25~35 DEG C of water-bath, stand for 24 hours, with
2000r/min is centrifuged 30min, removes bulky grain, collects supernatant liquid, as graphene dispersing solution.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113372570A (en) * | 2021-05-14 | 2021-09-10 | 佳化化学（茂名）有限公司 | Lignin glyceryl ether phosphate and preparation method and application thereof |
| CN114075106A (en) * | 2020-08-12 | 2022-02-22 | 广东省稀有金属研究所 | Preparation method of fatty alcohol ether carboxylic acid |
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| CN101327416A (en) * | 2008-08-01 | 2008-12-24 | 中国林业科学研究院林产化学工业研究所 | Lignose alcohol ether carboxylate surfactant and preparation method thereof |
| CN104876210A (en) * | 2015-04-13 | 2015-09-02 | 华南理工大学 | Method for preparing water-phase graphene dispersion liquid by employing ultrasonic stripping |
| EP2918627A1 (en) * | 2014-03-13 | 2015-09-16 | Nederlandse Organisatie voor toegepast- natuurwetenschappelijk onderzoek TNO | Lignin compound |
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2018
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Patent Citations (3)
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| CN101327416A (en) * | 2008-08-01 | 2008-12-24 | 中国林业科学研究院林产化学工业研究所 | Lignose alcohol ether carboxylate surfactant and preparation method thereof |
| EP2918627A1 (en) * | 2014-03-13 | 2015-09-16 | Nederlandse Organisatie voor toegepast- natuurwetenschappelijk onderzoek TNO | Lignin compound |
| CN104876210A (en) * | 2015-04-13 | 2015-09-02 | 华南理工大学 | Method for preparing water-phase graphene dispersion liquid by employing ultrasonic stripping |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114075106A (en) * | 2020-08-12 | 2022-02-22 | 广东省稀有金属研究所 | Preparation method of fatty alcohol ether carboxylic acid |
| CN114075106B (en) * | 2020-08-12 | 2023-09-12 | 广东省稀有金属研究所 | Preparation method of fatty alcohol ether carboxylic acid |
| CN113372570A (en) * | 2021-05-14 | 2021-09-10 | 佳化化学（茂名）有限公司 | Lignin glyceryl ether phosphate and preparation method and application thereof |
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Application publication date: 20190308 |