CN105085933A - Method for synthesizing surfactant by alkylating sodium lignin sulfonate - Google Patents
Method for synthesizing surfactant by alkylating sodium lignin sulfonate Download PDFInfo
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- sodium lignosulfonate
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- lignin sulfonate
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Abstract
The invention discloses a method for synthesizing a surfactant by alkylating sodium lignin sulfonate. The method includes the following steps that the sodium lignin sulfonate with the molecular weight over 1.5w is selected as a raw material; the sodium lignin sulfonate and purified water are mixed and added with saccharifying enzymes, after uniform dissolution, the solution is treated for 30-40 min at the temperature of 30 DEG C under ultrasonic waves, solvent is removed through ultrasonic liquid reduced pressure distillation, and residues are dried in vacuum at the constant temperature of 60 DEG C for 24 h to obtain a brown solid namely activated sodium lignin sulfonate; the activated sodium lignin sulfonate reacts through a conventional method under the protection of nitrogen with 1-bromododecane as an alkylating reagent and pyridine as a catalyst to prepare the alkylated sodium lignin sulfonate. The saccharifying enzymes and the ultrasonic waves have a coalitive synergism function, compared with modification only through the ultrasonic waves, the reaction time of the method is further shortened, and the obtained alkylated sodium lignin sulfonate is high in capacity for promoting decrease of surface tension and has high market potential.
Description
Technical field
The invention belongs to macromolecule chemical industry technical field, be specifically related to a kind of method of sodium lignosulfonate alkylation synthetic surfactant.
Background technology
Xylogen is the natural high polymer with aromatic structure that nature content second enriches, and be extremely important renewable biological source, nature about can produce 6 × 10 every year
14t.The tradition exhaustion of ore resource and the enhancing of mankind's environmental consciousness utilize to the fundamental research of xylogen and industrialization and bring strong impetus.Sulfonated lignin are derivatives of xylogen, and its modification preparation table surface-active agent is flourish in recent years and achieve serial impressive progress, and modified product is widely used for industrial and agricultural production.Xylogen is by guaiacyl, Syringa oblata Lindl. base and is interconnected by C-C key and C-O key hydroxyphenyl three phenylpropyl alcohol alkyl structure unit, random coupling and the baroque natural high moleculer eompound formed.But for the molecular structure of sulfonated lignin, there is scholar to think tridimensional network, also have and think three-dimensional spherical structure, there is no unified understanding at present.Sulfonated lignin also exist-CHCH-, the structure of-OH and phenyl ring conjugation, the phenolic hydroxyl group of industrial lignin sulfonate also may form complex compound with heavy metal ion.These special molecular structures make sulfonated lignin with special color, and its chromogenic mechanism is studied clear so far not yet completely, constrain the work of lignin sulfonate modified preparation table surface-active agent.Color prepares the difficult problem that Novel wooden quality sulfosalt surfactant must overcome, and mainly relies on: the method for (1) physics is separated removing foreign pigment; (2) study the chromogenic mechanism of lignosulfonate molecules itself, carry out molecular designing from the angle of electromagnetic energy absorption, structurally-modified process is removed or is closed chromophore, makes sulfonated lignin not produce between visible region or only produce weak absorption.
The active group phenolic hydroxyl group that the tridimensional network of sodium lignosulfonate complexity makes it important is wound closed, Existential Space steric hindrance. the content of the reactive group phenolic hydroxyl group that non-activated industrial lignin sodium sulfonate is important is little, reactive behavior is low, carries out the graft modification difficulties such as alkylation.Prior art is disclosed the method using Catalyzed by Ultrasonic Wave sodium lignosulfonate alkylation synthetic surfactant.
The present invention aims to provide a kind of method of being combined to tensio-active agent by ultrasonic wave and enzyme associating Catalytic lignin sodium sulfonate alkyl.Compared to single use Catalyzed by Ultrasonic Wave, its reaction times shortens further, and the ability that obtained alkylate impels surface tension to decline is also stronger.Similar technical scheme was not also in the news.
Summary of the invention
Based on the technical problem that background technology exists, the present invention is directed to background technology Problems existing, the invention provides a kind of method of being combined to tensio-active agent by ultrasonic wave and enzyme associating Catalytic lignin sodium sulfonate alkyl.Compared to single use Catalyzed by Ultrasonic Wave, its reaction times shortens further, and the ability that obtained alkylate impels surface tension to decline is also stronger.
Ultrasonic wave refers to that frequency is 2 × 10
4~ 1 × 10
7the sound wave of Hz, when it propagates in medium, pass through cavitation, machinery and heat effect can produce a series of mechanics, calorifics and chemical effect. the hole caused when particularly ultrasonic wave is propagated in a liquid, there is unique chemical effect, the microvesicle that hole effect produces provides a powerful shearing force field, for the fracture of chemical bond provides mechanical energy, even directly break chemical bond. simultaneously, ultrasonic hole effect causes the local environment of High Temperature High Pressure, the generation of free radical and other high reaction activity kind can be promoted. therefore, ultrasonic wave has a wide range of applications in the activation treatment of biorefinery and biomass.
Object of the present invention is achieved through the following technical solutions:
A method for sodium lignosulfonate alkylation synthetic surfactant, step is as follows:
(1) lignosulfonic acid sodium raw materials is chosen: choose the sodium lignosulfonate of molecular weight at more than 1.5w as raw material;
(2) sodium lignosulfonate and pure water mixing, add saccharifying enzyme, at 30 DEG C after being uniformly dissolved, under ultrasonic wave, process 30-40min, ultrasonic liquid underpressure distillation removes desolventizing, the dry 24h of residuum 60 DEG C of constant-temperature vacuums, obtain brown solid, obtain the sodium lignosulfonate after activating;
(3) sodium lignosulfonate after activation is alkylating reagent through 1-bromo-dodecane, and pyridine is catalyzer, under the protection of nitrogen, through ordinary method reaction preparation alkylation sodium lignosulfonate.
As preferably, concrete scheme of the present invention is:
Step (1): choose lignosulfonic acid sodium raw materials: choose the sodium lignosulfonate of molecular weight at more than 1.5w as raw material.
Step (2) is: xylonic acid sodium and pure water are the ratio mixing of 1:11-13 according to weight ratio, add the saccharifying enzyme of 3-5U/g sodium lignosulfonate, at 30 DEG C after being uniformly dissolved, be 22-25khz through frequency, power is process 30-40min under the ultrasonic wave of 120-145w, and ultrasonic liquid underpressure distillation removes desolventizing, the dry 24h of residuum 60 DEG C of constant-temperature vacuums, obtain brown solid, obtain the sodium lignosulfonate after activating;
Step (3) is: the sodium lignosulfonate after activation and alcohol water mixed solution are poured in the there-necked flask with reflux condensing tube and thermometer, reaching 10 ~ 11. with the pH that the sodium hydroxide solution of 1mol/L is adjusted to system to add a certain amount of 1-bromo-dodecane be alkylating reagent and pyridine (w (pyridine): w (1-bromo-dodecane hydrocarbon)=1: 2) is catalyzer. under the protection of nitrogen, about 80 DEG C condensing reflux reaction 8h. stopped reaction, reaction solution sherwood oil (boiling range 90 ~ 120 DEG C) washs, removing unreacted 1-bromo-dodecane hydrocarbon. underpressure distillation is except desolventizing, the dry 24h of residuum 60 DEG C of constant-temperature vacuums, obtain brown-black powder and be alkylating sodium lignosulfonate.
Usefulness of the present invention is:
The simply good operation of technique, saccharifying enzyme and ultrasonic wave serve joint synergy, compare only with ultrasonically-modified, and the method reaction times of the present invention shortens further, it is very capable that obtained alkylating sodium lignosulfonate impels surface tension to decline, and very has market potential.
Embodiment
embodiment 1:
Raw material wood element sodium sulfonate of the present invention is bought and is obtained, and the content of sodium lignosulfonate is all greater than 99%.
A method for sodium lignosulfonate alkylation synthetic surfactant, step is as follows:
(1) lignosulfonic acid sodium raw materials is chosen: choose the sodium lignosulfonate of molecular weight at more than 1.5w as raw material;
(2) sodium lignosulfonate and pure water are the ratio mixing of 1:11 according to weight ratio, add the saccharifying enzyme of 3U/g sodium lignosulfonate, at 30 DEG C after being uniformly dissolved, be 22khz through frequency, power is process 30min under the ultrasonic wave of 120w, and ultrasonic liquid underpressure distillation removes desolventizing, the dry 24h of residuum 60 DEG C of constant-temperature vacuums, obtain brown solid, obtain the sodium lignosulfonate after activating;
Now, the molecular weight and molecular weight of the sodium lignosulfonate after activation is 102000, and content of phenolic hydroxyl groups brings up to 1.85% by 0.62%.
(3) sodium lignosulfonate after activation and alcohol water mixed solution are poured in the there-necked flask with reflux condensing tube and thermometer, reaching 10 ~ 11. with the pH that the sodium hydroxide solution of 1mol/L is adjusted to system to add a certain amount of 1-bromo-dodecane be alkylating reagent and pyridine (w (pyridine): w (1-bromo-dodecane hydrocarbon)=1: 2) is catalyzer. under the protection of nitrogen, about 80 DEG C condensing reflux reaction 8h. stopped reaction, reaction solution sherwood oil (boiling range 90 ~ 120 DEG C) washs, removing unreacted 1-bromo-dodecane hydrocarbon. underpressure distillation is except desolventizing, the dry 24h of residuum 60 DEG C of constant-temperature vacuums, obtain brown-black powder and be alkylating sodium lignosulfonate.
Obtained alkylating sodium lignosulfonate is under 1% mass concentration, and surface tension is 19.8mN/m, and micelle-forming concentration (cmc) is 1.1 × 10
-2g/L.
embodiment 2:
A method for sodium lignosulfonate alkylation synthetic surfactant, step is as follows:
(1) lignosulfonic acid sodium raw materials is chosen: choose the sodium lignosulfonate of molecular weight at more than 1.5w as raw material;
(2) sodium lignosulfonate and pure water are the ratio mixing of 1:11-13 according to weight ratio, add the saccharifying enzyme of 5U/g sodium lignosulfonate, at 30 DEG C after being uniformly dissolved, be 25khz through frequency, power is process 40min under the ultrasonic wave of 145w, and ultrasonic liquid underpressure distillation removes desolventizing, the dry 24h of residuum 60 DEG C of constant-temperature vacuums, obtain brown solid, obtain the sodium lignosulfonate after activating;
Now, the molecular weight and molecular weight of the sodium lignosulfonate after activation is 108000, and content of phenolic hydroxyl groups brings up to 1.69% by 0.62%.
(3) sodium lignosulfonate after activation and alcohol water mixed solution are poured in the there-necked flask with reflux condensing tube and thermometer, reaching 10 ~ 11. with the pH that the sodium hydroxide solution of 1mol/L is adjusted to system to add a certain amount of 1-bromo-dodecane be alkylating reagent and pyridine (w (pyridine): w (1-bromo-dodecane hydrocarbon)=1: 2) is catalyzer. under the protection of nitrogen, about 80 DEG C condensing reflux reaction 8h. stopped reaction, reaction solution sherwood oil (boiling range 90 ~ 120 DEG C) washs, removing unreacted 1-bromo-dodecane hydrocarbon. underpressure distillation is except desolventizing, the dry 24h of residuum 60 DEG C of constant-temperature vacuums, obtain brown-black powder and be alkylating sodium lignosulfonate.
Obtained alkylating sodium lignosulfonate is under 1% mass concentration, and surface tension is 20.5mN/m, and micelle-forming concentration (cmc) is 1.2 × 10
-2g/L.
embodiment 3:
A method for sodium lignosulfonate alkylation synthetic surfactant, step is as follows:
(1) lignosulfonic acid sodium raw materials is chosen: choose the sodium lignosulfonate of molecular weight at more than 1.5w as raw material;
(2) sodium lignosulfonate and pure water are the ratio mixing of 1:12 according to weight ratio, add the saccharifying enzyme of 4U/g sodium lignosulfonate, at 30 DEG C after being uniformly dissolved, be 23khz through frequency, power is process 35min under the ultrasonic wave of 130w, and ultrasonic liquid underpressure distillation removes desolventizing, the dry 24h of residuum 60 DEG C of constant-temperature vacuums, obtain brown solid, obtain the sodium lignosulfonate after activating;
Now, the molecular weight and molecular weight of the sodium lignosulfonate after activation is 107000, and content of phenolic hydroxyl groups brings up to 1.75% by 0.62%.
(3) sodium lignosulfonate after activation and alcohol water mixed solution are poured in the there-necked flask with reflux condensing tube and thermometer, reaching 10 ~ 11. with the pH that the sodium hydroxide solution of 1mol/L is adjusted to system to add a certain amount of 1-bromo-dodecane be alkylating reagent and pyridine (w (pyridine): w (1-bromo-dodecane hydrocarbon)=1: 2) is catalyzer. under the protection of nitrogen, about 80 DEG C condensing reflux reaction 8h. stopped reaction, reaction solution sherwood oil (boiling range 90 ~ 120 DEG C) washs, removing unreacted 1-bromo-dodecane hydrocarbon. underpressure distillation is except desolventizing, the dry 24h of residuum 60 DEG C of constant-temperature vacuums, obtain brown-black powder and be alkylating sodium lignosulfonate.
Obtained alkylating sodium lignosulfonate is under 1% mass concentration, and surface tension is 20.8mN/m, and micelle-forming concentration (cmc) is 1.5 × 10
-2g/L.
embodiment 4:
A method for sodium lignosulfonate alkylation synthetic surfactant, step is as follows:
(1) lignosulfonic acid sodium raw materials is chosen: choose the sodium lignosulfonate of molecular weight at more than 1.5w as raw material;
(2) sodium lignosulfonate and pure water are the ratio mixing of 1:11 according to weight ratio, add the saccharifying enzyme of 5U/g sodium lignosulfonate, at 30 DEG C after being uniformly dissolved, be 25khz through frequency, power is process 38min under the ultrasonic wave of 120w, and ultrasonic liquid underpressure distillation removes desolventizing, the dry 24h of residuum 60 DEG C of constant-temperature vacuums, obtain brown solid, obtain the sodium lignosulfonate after activating;
Now, the molecular weight and molecular weight of the sodium lignosulfonate after activation is 103000, and content of phenolic hydroxyl groups brings up to 1.69% by 0.62%.
(3) sodium lignosulfonate after activation and alcohol water mixed solution are poured in the there-necked flask with reflux condensing tube and thermometer, reaching 10 ~ 11. with the pH that the sodium hydroxide solution of 1mol/L is adjusted to system to add a certain amount of 1-bromo-dodecane be alkylating reagent and pyridine (w (pyridine): w (1-bromo-dodecane hydrocarbon)=1: 2) is catalyzer. under the protection of nitrogen, about 80 DEG C condensing reflux reaction 8h. stopped reaction, reaction solution sherwood oil (boiling range 90 ~ 120 DEG C) washs, removing unreacted 1-bromo-dodecane hydrocarbon. underpressure distillation is except desolventizing, the dry 24h of residuum 60 DEG C of constant-temperature vacuums, obtain brown-black powder and be alkylating sodium lignosulfonate.
Obtained alkylating sodium lignosulfonate is under 1% mass concentration, and surface tension is 20.9mN/m, and micelle-forming concentration (cmc) is 1.6 × 10
-2g/L.
embodiment 5:
A method for sodium lignosulfonate alkylation synthetic surfactant, step is as follows:
(1) lignosulfonic acid sodium raw materials is chosen: choose the sodium lignosulfonate of molecular weight at more than 1.5w as raw material;
(2) sodium lignosulfonate and pure water are the ratio mixing of 1:12 according to weight ratio, add the saccharifying enzyme of 4U/g sodium lignosulfonate, at 30 DEG C after being uniformly dissolved, be 25khz through frequency, power is process 35min under the ultrasonic wave of 140w, and ultrasonic liquid underpressure distillation removes desolventizing, the dry 24h of residuum 60 DEG C of constant-temperature vacuums, obtain brown solid, obtain the sodium lignosulfonate after activating;
Now, the molecular weight and molecular weight of the sodium lignosulfonate after activation is 109000, and content of phenolic hydroxyl groups brings up to 1.75% by 0.62%.
(3) sodium lignosulfonate after activation and alcohol water mixed solution are poured in the there-necked flask with reflux condensing tube and thermometer, reaching 10 ~ 11. with the pH that the sodium hydroxide solution of 1mol/L is adjusted to system to add a certain amount of 1-bromo-dodecane be alkylating reagent and pyridine (w (pyridine): w (1-bromo-dodecane hydrocarbon)=1: 2) is catalyzer. under the protection of nitrogen, about 80 DEG C condensing reflux reaction 8h. stopped reaction, reaction solution sherwood oil (boiling range 90 ~ 120 DEG C) washs, removing unreacted 1-bromo-dodecane hydrocarbon. underpressure distillation is except desolventizing, the dry 24h of residuum 60 DEG C of constant-temperature vacuums, obtain brown-black powder and be alkylating sodium lignosulfonate.
Obtained alkylating sodium lignosulfonate is under 1% mass concentration, and surface tension is 20.1mN/m, and micelle-forming concentration (cmc) is 1.8 × 10
-2g/L.
embodiment 6 simultaneous test:
A method for sodium lignosulfonate alkylation synthetic surfactant, step is as follows:
(1) lignosulfonic acid sodium raw materials is chosen: choose the sodium lignosulfonate of molecular weight at more than 1.5w as raw material;
(2) sodium lignosulfonate and pure water are the ratio mixing of 1:11-13 according to weight ratio, at 30 DEG C after being uniformly dissolved, be 40khz through frequency, power is process 60min under the ultrasonic wave of 150w, ultrasonic liquid underpressure distillation is except desolventizing, the dry 24h of residuum 60 DEG C of constant-temperature vacuums, obtains brown solid, obtains the sodium lignosulfonate after activating;
Now, the molecular weight and molecular weight of the sodium lignosulfonate after activation is 102000, and content of phenolic hydroxyl groups brings up to 1.49% by 0.62%.
(3) sodium lignosulfonate after activation and alcohol water mixed solution are poured in the there-necked flask with reflux condensing tube and thermometer, reaching 10 ~ 11. with the pH that the sodium hydroxide solution of 1mol/L is adjusted to system to add a certain amount of 1-bromo-dodecane be alkylating reagent and pyridine (w (pyridine): w (1-bromo-dodecane hydrocarbon)=1: 2) is catalyzer. under the protection of nitrogen, about 80 DEG C condensing reflux reaction 8h. stopped reaction, reaction solution sherwood oil (boiling range 90 ~ 120 DEG C) washs, removing unreacted 1-bromo-dodecane hydrocarbon. underpressure distillation is except desolventizing, the dry 24h of residuum 60 DEG C of constant-temperature vacuums, obtain brown-black powder and be alkylating sodium lignosulfonate.
Obtained alkylating sodium lignosulfonate is under 1% mass concentration, and surface tension is 27.9mN/m, and micelle-forming concentration (cmc) is 5 × 10
-2g/L.
As can be seen here, saccharifying enzyme and ultrasonic wave serve joint synergy, compare only with ultrasonically-modified, and the method reaction times of the present invention shortens further, it is very capable that obtained alkylating sodium lignosulfonate impels surface tension to decline, and very has market potential.
The above; be only the present invention's preferably embodiment; but protection scope of the present invention is not limited thereto; anyly be familiar with those skilled in the art in the technical scope that the present invention discloses; be equal to according to technical scheme of the present invention and inventive concept thereof and replace or change, all should be encompassed within protection scope of the present invention.
Claims (6)
1. a method for sodium lignosulfonate alkylation synthetic surfactant, step is as follows:
(1) lignosulfonic acid sodium raw materials is chosen: choose the sodium lignosulfonate of molecular weight at more than 1.5w as raw material;
(2) sodium lignosulfonate and pure water mixing, add saccharifying enzyme, at 30 DEG C after being uniformly dissolved, under ultrasonic wave, process 30-40min, ultrasonic liquid underpressure distillation removes desolventizing, the dry 24h of residuum 60 DEG C of constant-temperature vacuums, obtain brown solid, obtain the sodium lignosulfonate after activating;
(3) sodium lignosulfonate after activation is alkylating reagent through 1-bromo-dodecane, and pyridine is catalyzer, under the protection of nitrogen, through ordinary method reaction preparation alkylation sodium lignosulfonate.
2. the preparation method of sodium lignosulfonate alkylation synthetic surfactant according to claim 1, is characterized in that:
Step (1): choose lignosulfonic acid sodium raw materials: choose the sodium lignosulfonate of molecular weight at more than 1.5w as raw material.
3. the preparation method of the sodium lignosulfonate alkylation synthetic surfactant described in claim 1-2, is characterized in that:
Step (2) is: xylonic acid sodium and pure water are the ratio mixing of 1:11-13 according to weight ratio, add the saccharifying enzyme of 3-5U/g sodium lignosulfonate, at 30 DEG C after being uniformly dissolved, be 22-25khz through frequency, power is process 30-40min under the ultrasonic wave of 120-145w, and ultrasonic liquid underpressure distillation removes desolventizing, the dry 24h of residuum 60 DEG C of constant-temperature vacuums, obtain brown solid, obtain the sodium lignosulfonate after activating.
4. the preparation method of the sodium lignosulfonate alkylation synthetic surfactant described in claim 1-3, is characterized in that:
Step (3) is: the sodium lignosulfonate after activation and alcohol water mixed solution are poured in the there-necked flask with reflux condensing tube and thermometer, reaching 10 ~ 11. with the pH that the sodium hydroxide solution of 1mol/L is adjusted to system to add a certain amount of 1-bromo-dodecane be alkylating reagent and pyridine (w (pyridine): w (1-bromo-dodecane hydrocarbon)=1: 2) is catalyzer. under the protection of nitrogen, about 80 DEG C condensing reflux reaction 8h. stopped reaction, reaction solution sherwood oil (boiling range 90 ~ 120 DEG C) washs, removing unreacted 1-bromo-dodecane hydrocarbon. underpressure distillation is except desolventizing, the dry 24h of residuum 60 DEG C of constant-temperature vacuums, obtain brown-black powder and be alkylating sodium lignosulfonate.
5. the alkylation sodium lignosulfonate that the preparation method of the sodium lignosulfonate alkylation synthetic surfactant described in claim 1-4 prepares.
6. modified sodium lignosulfonate according to claim 5, is characterized in that: surface tension is at below 20.5mN/m.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107251897A (en) * | 2017-07-26 | 2017-10-17 | 安徽省益农化工有限公司 | Novel low-toxicity cell member herbicide of efficient high disintegration rate and preparation method thereof |
| CN107473635A (en) * | 2017-09-04 | 2017-12-15 | 东阳市新越建设有限公司 | Bituminous concrete and its preparation technology |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107251897A (en) * | 2017-07-26 | 2017-10-17 | 安徽省益农化工有限公司 | Novel low-toxicity cell member herbicide of efficient high disintegration rate and preparation method thereof |
| CN107251897B (en) * | 2017-07-26 | 2020-06-30 | 安徽省益农化工有限公司 | Low-toxicity cytometaherbicide with high efficiency and high disintegration rate and preparation method thereof |
| CN107473635A (en) * | 2017-09-04 | 2017-12-15 | 东阳市新越建设有限公司 | Bituminous concrete and its preparation technology |
| CN107473635B (en) * | 2017-09-04 | 2020-09-01 | 东阳市新越建设有限公司 | Asphalt concrete and preparation process thereof |
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