CN101327416B - Lignose alcohol ether carboxylate surfactant and preparation method thereof - Google Patents
Lignose alcohol ether carboxylate surfactant and preparation method thereof Download PDFInfo
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Abstract
The present invention discloses a lignin alcohol ether carboxylate novel surfactant preparation method. 100 weight proportions of lignin alcohol ether and base catalyst with 1 to 1.2 times of the weight proportions of the lignin alcohol ether react for 30 to 60 minutes under 90 to 110 DEG C; low-boiling substance is removed by decompressing under subtractive 0.1MP; halogenated acid with the substance quantity of 1.2 to 1.5 times of the lignin alcohol ether is added to react for 4 to 8 hours to obtain the lignin alcohol ether carboxylate. In the reaction steps, the lignin alcohol ether is prepared by self; the halogenated acid can be any one of 2-chloropropionic acid, chloroacetic acid, 2-bromo propionate or bromoacetic acid; the base catalyst is KOH or NaOH. In the characterization of thelignin alcohol ether carboxylate, foam performance water hardness is 150 multiplied by 10<subtractive 6>ppm as being measured by a Rockwell latherometer; sample content is 0.25 percent under 40 DEG C, the foam height is measured as the start height of 150mm; the foam height is 130mm after 5 minutes; when surface tension (delta) sample contents are 0.01 percent and 0.05 percent respectively, the surface tensions are respectively 57.2mN/m and 51.2mN/m; critical micelle concentration (CMC) measured value is 5.0g/L.
Description
Technical field
The invention belongs to the preparation field of surfactant, relate in particular to a kind of preparation method of lignose alcohol ether carboxylate novel surfactant.
Background technology
At present, because petroleum resources shortage rise in price, all actively use natural reproducible resource to produce product in the manufacturing of surfactant, lignin is as the accessory substance of wood hydrolysis industry and paper industry, owing to be not fully utilized, become one of primary pollution source in the paper industry, not only caused serious environmental to pollute, also caused the significant waste of resource.Lignin mainly is made up of carbon, hydrogen, three kinds of elements of oxygen, It is generally accepted that lignin is the natural phenolic macromolecular compound of the crosslinking net that is formed by connecting by C one O key or C-C key by phenylpropyl (C9) unit.Owing to contain a large amount of phenolic hydroxyl groups and alcoholic extract hydroxyl group, general formula often is designated as R-OH.Pulp industry is by methods such as alkali or acid catalysis, make the ehter bond in the lignin molecule take place to rupture and separate with hemicellulose with cellulose, and be dissolved in the water with the form of salt, form so-called black liquor or red liquid, industrial lignin is actually the fragment by the natural lignin that extracts in the black liquor, its relative molecular mass at hundreds of between millions of.Molecular weight ranges accounts for 50% 20000～50000.Account for 45% between the 1000-20000.At present, lignin is all used by modification in industry.For example: at publication number is that CN1360969 was 2002.07.31 in open day, in " a kind of preparation of lignin surfactant that is applicable to complex oil displacing " patent of invention of invention Ren Wei Wei Handao, disclose and use electroxidation, alkylation, sulfonation prepare the method for lignin surfactant.This surfactant can form 6 * 10 with aviation kerosine in the composite oil-displacing system of high salinity and high divalent ion concentration
-3The ultralow interfacial tension of mN/m.The publication number of South China Science ﹠ Engineering University is that CN101157531 was in " alkali lignin modified sulfamate high-effective water reducer and preparation method thereof " patent of invention of 2007.9.13 in open day, disclose with alkali lignin, phenols, water, condensing agent, alkaline conditioner, amino phenyl sulfonyl hydrochlorate through a series of reaction, be prepared into the alkali lignin sulfamate, can improve concrete flowability significantly, improve compression strength.The publication number of Tsing-Hua University is that CN1146999 was in " process for synthesis of lignin quaternary cation flocculant " patent of invention of 1997.04.09 in open day, disclose by mannich condensation reaction and rabbet the ammonium salt group on the lignin skeleton, alkylation prepares quaternary cation flocculant then.This product has flocculation preferably.
But the preparation method who uses lignin to prepare alcohol ether carboxylate surfactant does not appear in the newspapers.
Summary of the invention
The invention provides a kind of lignose alcohol ether carboxylate surfactant and preparation method thereof, the lignose alcohol ether carboxylate surfactant that obtains has good surface-active, and the preparation method is simple.
A kind of chemical molecular formula of lignose alcohol ether carboxylate surfactant is:
In the formula: it is Lignin-(O-CH that R represents lignose alcohol ether
2-CH
2-)
n-OH; N=2～15 wherein; Lignin is that the English name of lignin is represented lignin structure here, and M is Na or K.
In the time of with 2-chloropropionic acid and NaOH reaction, reaction equation is:
The preparation method of described lignose alcohol ether carboxylate surfactant is made by following steps:
With lignose alcohol ether and halogenated acid under base catalyst catalysis, reaction temperature is 30～150 ℃, mixing speed is 140 rev/mins, reaction 2～10h, obtain the end product lignose alcohol ether carboxylate, the mol ratio of lignose alcohol ether and base catalyst is 1: 1～1.2, and the mol ratio of lignose alcohol ether and halogenated acid is 1: 1.2～1.5.
In the above reactions steps, lignose alcohol ether, self-control; Halogenated acid is any one in 2-chloropropionic acid, chloroacetic acid, 2 bromopropionic acid, the bromoacetic acid; Base catalyst is KOH or NaOH.
Lignose alcohol ether prepares by the following method:
The first step, get the lignin mass fraction in purifying lignin 100 mass parts more than 95%, catalyst n aOH 0.1～5 mass parts, solvent toluene 20～100 mass parts, the oxygen-free environment reaction, reaction temperature is 80～150 ℃, reaction pressure is 0.3～1.0MPa, stir, the oxirane of 10～100 mass parts, the expoxy propane of 10～100 mass parts are divided into 2～10 groups;
Second the step, feed 1 group of oxirane afterreaction 30～60min at every turn after, feed 1 group of propylene oxide reaction 30～60min again;
The 3rd step repeated for second step, after all oxirane and propylene oxide reaction finish, stop reaction and stop heating, be cooled to and stop after the room temperature stirring, mend inert gas to 1 atmospheric pressure, the low boiling fraction is removed in decompression distillation then, obtains the product lignose alcohol ether.
The The performance test results of end product lignose alcohol ether carboxylate novel surfactant:
1. the Luo Shi foam meter is measured foaming properties (FP) with reference to GB13173-91: water hardness 150ppm, measure temperature constant at 40 ℃, sample size is 0.25%, and recording foam height is starting altitude 150mm, foam height is 130mm behind the 5min, and foam height is 120mm behind the 10min.
2. the mensuration of surface tension (δ) is with reference to GB5546-85: the surface tension that sample size was respectively 0.01%, 0.05%, 0.10%, 0.50%, 1.00%, 2.00% o'clock is respectively 57.2mN/m, 51.2mN/m, 42.4mN/m, 37.2mN/m, 36.9mN/m, 35.9mN/m.
3. critical concentration of micelle (CMC) is tried to achieve by δ-logc curve break, and measured value is 5.0g/L.
The present invention has following beneficial effect:
1. use method of the present invention and use the natural reproducible resource lignin, make major pollutants in the paper industry become the useful surfactant of living, not only changed the serious environmental pollution that present paper industry causes, also made full use of resource people.
2. lignose alcohol ether carboxylate has good foaming characteristic as surfactant product, has biodegradablely, and reaction condition gentleness, reaction temperature are 30～150 ℃, the technology characteristic of simple.
3. the Luo Shi foam meter is measured foaming properties (FP) with reference to GB13173-91: water hardness 150ppm, measure temperature constant at 40 ℃, sample size is 0.25%, and recording foam height is starting altitude 150mm, foam height is 130mm behind the 5min, and foam height is 120mm behind the 10min.
4. the mensuration of surface tension (δ) is with reference to GB5546-85: the surface tension that sample size was respectively 0.01%, 0.05%, 0.10%, 0.50%, 1.00%, 2.00% o'clock is respectively 57.2mN/m, 51.2mN/m, 42.4mN/m, 37.2mN/m, 36.9mN/m, 35.9mN/m.
5. critical concentration of micelle (CMC) is tried to achieve by δ-logc curve break, and measured value is 5.0g/L.
6. the Krafft mensuration of ordering: measure lignose alcohol ether carboxylate Krafft point＜0 ℃, illustrate that this surfactant has stronger hydrophily.
Description of drawings
Fig. 1 is the infrared spectrum spectrogram of lignose alcohol ether.
Fig. 2 is the infrared spectrum spectrogram of lignose alcohol ether carboxylate.
The specific embodiment
Feedstock production:
The lignin mass fraction is in the preparation of the purifying lignin more than 95%:
Get thick alkali lignin 100 mass parts, be made into the aqueous solution of 10% mass fraction, NaOH regulator solution pH value with 10% mass fraction is 12, all dissolve to lignin, after 6000r/rain centrifugation 5min removes not dissolved impurity, filtrate is heated to 60 ℃, sulphur acid for adjusting pH value with 20% mass fraction is 3, leaves standstill, and removes supernatant liquor, the sediment washing, through 6000r/rain centrifugation 10min, sediment is washed till neutrality, at 105 ℃ of dry back grind into powders, weighing obtains 70 mass parts purifying lignin, and sealing is preserved standby.The chemical composition of the purifying lignin that obtains is: the lignin mass fraction is 95%, and the total reducing sugar mass fraction is 2.70%, and the ash content mass fraction is 1.70%, and the phenolic hydroxyl group molality is 2.60mol/kg.
The preparation of lignose alcohol ether:
The first step, get the lignin mass fraction in purifying lignin 100 mass parts more than 95%, catalyst n aOH 0.1～5 mass parts, solvent toluene 20～100 mass parts, the oxygen-free environment reaction, reaction temperature is 80～150 ℃, reaction pressure is 0.3～1.0MPa, stir, the oxirane of 10～100 mass parts, the expoxy propane of 10～100 mass parts are divided into 2～10 groups;
Second the step, feed 1 group of oxirane afterreaction 30～60min at every turn after, feed 1 group of propylene oxide reaction 30～60min again;
The 3rd step repeated for second step, after all oxirane and propylene oxide reaction finish, stop reaction and stop heating, be cooled to and stop after the room temperature stirring, mend inert gas to 1 atmospheric pressure, the low boiling fraction is removed in decompression distillation then, obtains the product lignose alcohol ether.It is 556.6mg/g. that sampling is measured hydroxyl value by acetic anhydride among the GB7384-87-pyridine method
The preparation method of lignose alcohol ether carboxylate is made by following steps:
The base catalyst of 1～1.2 times of amount of substance that with lignose alcohol ether 100 mass parts and amount of substance is lignose alcohol ether is at 90～110 ℃ of reaction 30～60min,-0.1MP decompression down extracts low boilers, adding amount of substance is 1.2～1.5 times halogenated acid of lignose alcohol ether, reaction 4～8h obtains lignose alcohol ether carboxylate.
Wherein base catalyst can be 1,1.1,1.2 times of amount of substance of lignose alcohol ether, reaction temperature can be 90 ℃, 100 ℃, 110 ℃, reaction time can be 30min, 45min, 60min, the amount of halogenated acid can be 1.2 times, 1.35 times, 1.5 times, and the reaction time can be 4h, 5.5h, 8h.Halogenated acid can be any one in 2-chloropropionic acid, chloroacetic acid, 2 bromopropionic acid, the bromoacetic acid; Base catalyst is KOH or NaOH.
Embodiment 2
The preparation method of lignose alcohol ether carboxylate:
With lignose alcohol ether 100 mass parts, 1.2 times the amount that catalyst n aOH presses the amount of substance of lignose alcohol ether adds, at 90～100 ℃ of reaction 30min, decompression extracts water, by the mol ratio of lignose alcohol ether and chloroacetic acid is that 1: 1.2 minim adds chloroacetic acid, reaction 4h obtains the lignose alcohol ether carboxylic acid sodium salt.Sampling and measuring lignose alcohol ether carboxylic acid sodium salt hydroxyl value is 40mg/g.
The IR atlas analysis of the plain alcohol ether of lignose alcohol ether carboxylic acid sodium salt IR and raw material wood compares: at 3700cm
-1～3030cm
-1The place absorbs and reduces, and illustrates that the hydroxyl in the lignose alcohol ether is reacted, and causes 3418.18cm
-1Absorb and reduce.。At 1096.25cm
-1The absorption peak strength that the place occurs reduces, and shows that hydroxy radical content reduces; At 1726.65cm
-1Near absworption peak obviously strengthens, and illustrates that carbonyl content increases, and is the result of chloroacetic acid and lignose alcohol ether reaction.
The lignose alcohol ether carboxylate performance characterization:
1. the Luo Shi foam meter is measured foaming properties (FP) with reference to GB13173-91: the water hardness 150 * 10
-6Ppm, 40 ℃, sample size is 0.25%, and recording foam height is starting altitude 150mm, and foam height is 130mm behind the 5min, and foam height is 120mm behind the 10min.
2. the mensuration of surface tension (δ) is with reference to GB5546-85: the surface tension that sample size was respectively 0.01%, 0.05%, 0.10%, 0.50%, 1.00%, 2.00% o'clock is respectively 57.2mN/m, 51.2mN/m, 42.4mN/m, 37.2mN/m, 36.9mN/m, 35.9mN/m.
3. critical concentration of micelle (CMC) is tried to achieve by δ-logc curve break, and measured value is 5.0g/L.
4. the Krafft mensuration of ordering: measure lignose alcohol ether carboxylate Krafft point＜0 ℃, illustrate that this surfactant has stronger hydrophily.
Embodiment 3
With lignose alcohol ether 100 mass parts, catalyst KOH extraordinarily goes into by 1.2 of the amount of substance of lignose alcohol ether, at 100～110 ℃ of reaction 60min, decompression extracts water, 1.3 times that press the lignose alcohol ether amount of substance drip chloroacetic acid, and reaction 8h obtains lignose alcohol ether carboxylic acid sylvite.
Embodiment 4
With lignose alcohol ether 100 mass parts, extraordinarily go into catalyst n aOH at 100～110 ℃ of reaction 50min by 1.2 of the amount of substance of lignose alcohol ether, decompression extracts water, press 1.3 times of dropping 2-chloropropionic acids of lignose alcohol ether amount of substance, reaction 9h obtains the lignose alcohol ether carboxylic acid sodium salt.
Embodiment 5
With lignose alcohol ether 100 mass parts, extraordinarily go into catalyst n aOH at 110 ℃ of reaction 60min by 1.2 of the amount of substance of lignose alcohol ether, decompression extracts water, press 1.5 times of dropping 2-chloropropionic acids of lignose alcohol ether amount of substance, reaction 9h obtains the lignose alcohol ether carboxylic acid sodium salt.
Embodiment 6
With lignose alcohol ether 100 mass parts, extraordinarily go into catalyst n aOH at 110 ℃ of reaction 60min by 1.1 of the amount of substance of lignose alcohol ether, decompression extracts water, presses 1.2 times of dripping bromine acetate of lignose alcohol ether amount of substance, reaction 8h obtains the lignose alcohol ether carboxylic acid sodium salt.
Embodiment 7
With lignose alcohol ether 100 mass parts, extraordinarily go into catalyst n aOH at 110 ℃ of reaction 60min by 1.2 of the amount of substance of lignose alcohol ether, decompression extracts water, press 1.2 times of dropping 2 bromopropionic acids of lignose alcohol ether amount of substance, reaction 9h obtains the lignose alcohol ether carboxylic acid sodium salt.
Embodiment 8
With lignose alcohol ether 100 mass parts, extraordinarily go into catalyst n aOH at 110 ℃ of reaction 60min by 1.0 of the amount of substance of lignose alcohol ether, decompression extracts water, press 1.0 times of dropping 2 bromopropionic acids of lignose alcohol ether amount of substance, reaction 6h obtains that salt of lignose alcohol ether carboxylic acid.
Embodiment 9
With lignose alcohol ether 100 mass parts, extraordinarily go into catalyst n aOH at 110 ℃ of reaction 60min by 1.0 of the amount of substance of lignose alcohol ether, decompression extracts water, presses 1.0 times of dripping bromine acetic acidreaction 7h of lignose alcohol ether amount of substance, obtains lignose alcohol ether carboxylate.
With lignose alcohol ether 100 mass parts, extraordinarily go into catalyst n aOH at 110 ℃ of reaction 60min by 1.2 of the amount of substance of lignose alcohol ether, decompression extracts water, and 1.2 times that press the lignose alcohol ether amount of substance drip 2 bromopropionic acid reaction 8h, obtain the lignose alcohol ether carboxylic acid sodium salt.
Embodiment 11
With 100 parts of lignose alcohol ethers, the KOH of 1.4 times of mol ratios of catalyst is 90～100 ℃ of reaction a period of times, and decompression extracts water, drips the chloroacetic acid of 1.4 times of mol ratios, and reaction 4～8h obtains lignose alcohol ether carboxylic acid sylvite.
Embodiment 12
With 100 parts of lignose alcohol ethers, the NaOH of 1.6 times of mol ratios of catalyst is 100～110 ℃ of reaction a period of times, and decompression extracts water, drips the chloroacetic acid of 1.2 times of mol ratios, and reaction 4～8h obtains the lignose alcohol ether carboxylic acid sodium salt.
Embodiment 13
With 100 parts of lignose alcohol ethers, the KOH of 1.7 times of mol ratios of catalyst is 90～100 ℃ of reaction a period of times, and decompression extracts water, drips the chloroacetic acid of 1.1 times of mol ratios, and reaction 4～8h obtains lignose alcohol ether carboxylic acid sylvite.
Embodiment 14
With 100 parts of lignose alcohol ethers, the KOH of 1.8 times of mol ratios of catalyst is 100～110 ℃ of reaction a period of times, and decompression extracts water, drips the chloroacetic acid of 1.4 times of mol ratios, and reaction 4～8h obtains lignose alcohol ether carboxylic acid sylvite.
Embodiment 15
With 100 parts of lignose alcohol ethers, the NaOH of 2 times of mol ratios of catalyst is 100～110 ℃ of reaction a period of times, and decompression extracts water, drips the chloroacetic acid of 1.2 times of mol ratios, and reaction 4～8h obtains the lignose alcohol ether carboxylic acid sodium salt.
Embodiment 16
With 100 parts of lignose alcohol ethers, the KOH of 2 times of mol ratios of catalyst is 100～110 ℃ of reaction a period of times, and decompression extracts water, drips the chloroacetic acid of 1.5 times of mol ratios, and reaction 4～8h obtains lignose alcohol ether carboxylic acid sylvite.
Claims (3)
1. the preparation method of a lignose alcohol ether carboxylate surfactant is characterized in that being made by following steps:
The first step, get the lignin mass fraction in purifying lignin 100 mass parts more than 95%, catalyst n aOH 0.1～5 mass parts, solvent toluene 20～100 mass parts, the oxygen-free environment reaction, reaction temperature is 80～150 ℃, reaction pressure is 0.3～1.0MPa, stir, the oxirane of 10～100 mass parts, the expoxy propane of 10～100 mass parts are divided into 2～10 groups;
Second the step, feed 1 group of oxirane afterreaction 30～60min at every turn after, feed 1 group of propylene oxide reaction 30～60min again;
The 3rd step repeated for second step, after all oxirane and propylene oxide reaction finish, stop reaction and stop heating, be cooled to and stop after the room temperature stirring, mend inert gas to 1 atmospheric pressure, the low boiling fraction is removed in decompression distillation then, obtains the product lignose alcohol ether;
The 4th step, with lignose alcohol ether and halogenated acid under base catalyst catalysis, reaction temperature is 30～150 ℃, mixing speed is 140 rev/mins, reaction 2～10h, obtain the end product lignose alcohol ether carboxylate, the mol ratio of lignose alcohol ether and base catalyst is 1: 1～1.2, and the mol ratio of lignose alcohol ether and halogenated acid is 1: 1.2～1.5.
2. the preparation method of lignose alcohol ether carboxylate surfactant as claimed in claim 1 is characterized in that described halogenated acid is any one in 2-chloropropionic acid, chloroacetic acid, 2 bromopropionic acid, the bromoacetic acid.
3. the preparation method of lignose alcohol ether carboxylate surfactant as claimed in claim 1 is characterized in that described base catalyst is KOH or NaOH.
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| CN101824154B (en) * | 2010-04-23 | 2012-08-15 | 北京嘉禾木科技有限公司 | Preparation method of carboxylated lignin |
| CN109294547B (en) * | 2018-10-23 | 2020-11-20 | 天津大港油田滨港集团博弘石油化工有限公司 | Anionic and nonionic amphoteric surfactant for oil displacement and preparation method thereof |
| CN109433099A (en) * | 2018-12-26 | 2019-03-08 | 广东省稀有金属研究所 | A kind of preparation method and applications of lignin-base sodium alcohol ether carboxylate |
| CN113372570B (en) * | 2021-05-14 | 2022-07-26 | 佳化化学（茂名）有限公司 | Lignin glyceryl ether phosphate and preparation method and application thereof |
| CN115363027B (en) * | 2022-09-14 | 2024-06-07 | 四川国光农化股份有限公司 | Pesticide ultra-low volume liquid and preparation method and application thereof |
| CN117105807B (en) * | 2023-06-20 | 2024-02-20 | 南京先进生物材料与过程装备研究院有限公司 | Lignin-based polyether amide surfactant and preparation method thereof |
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