CN102093573A - Method for preparing modified lignosulfonate - Google Patents
Method for preparing modified lignosulfonate Download PDFInfo
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- CN102093573A CN102093573A CN2009102167198A CN200910216719A CN102093573A CN 102093573 A CN102093573 A CN 102093573A CN 2009102167198 A CN2009102167198 A CN 2009102167198A CN 200910216719 A CN200910216719 A CN 200910216719A CN 102093573 A CN102093573 A CN 102093573A
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Abstract
The invention discloses a method for preparing modified lignosulfonate, which is characterized by comprising the following steps of: adding 20 to 60 grams of sodium lignosulfonate into a round bottomed flask into which a thermometer is inserted, adding 80 to 120 milliliters of water, stirring uniformly by magnetic force, dripping 0.9 to 1.5 milliliters of diethylenetriamine into the round bottomed flask, dripping formaldehyde solution slowly, heating to the temperature of between 70 and 90 DEG C, and keeping the temperature for 6 to 7 hours; and dripping 8 to 12 percent of NaOH solution into the round bottomed flask, regulating the pH value of the integral solution to be between 7 and 8, dripping long-carbon chain fatty acyl chloride within the time range of 2 to 3 hours and the like. The surface tension of the prepared modified lignosulfonate can be lower than 40 mN/m when the concentration of the solution is 1g/L, a critical micelle concentration (cmc) value is 0.084 g/L, so the modified lignosulfonate has the typical property of a surfactant, and has the excellent dispersive performance and capacity of reducing oil-water interfacial tension.
Description
Technical field
The present invention relates to a kind of preparation method, specifically be meant a kind of preparation method of modified lignin mahogany sulfonate.
Background technology
Xylogen claims lignin again, is the complicated macromolecular compound of forming with phenylpropyl alcohol alkanes structural unit, contains various active functional groups such as methoxyl group, phenolic hydroxyl group, alcoholic extract hydroxyl group, carbonyl.Xylogen extensively exists in higher plant, is the main component that constitutes the plant skeleton, estimates that the annual whole world can produce 1,500 hundred million tons of xylogen by plant-growth.At present, industrial lignin is mainly derived from papermaking wastewater, and wherein China produces 5,000,000 tons every year approximately, and industrial lignin utilization ratio less than 10% is most of as discharging of waste liquid.Because country is to the requirement of environmental protection increasingly stringent, the increasing mass-producing of paper pulp enterprise for reclaiming xylogen as the Industrial products condition of providing convenience, also provides cheap widely source for xylogen as industrial chemicals.Though chemistry of lignin has the history in 150 years nearly, its major cause that is not widely used is the chemical structure complexity, and chemical property is general.In recent decades, lignin modification is obtained remarkable achievement.Xylogen has enlarged the range of application of xylogen by reaction modifyings such as sulfonation, oxidation, graft copolymerization, condensation reaction, Mannich reaction, alkylated reactions.
Sulfonated lignin contain sulfonic group, and polarity is bigger, and hydrophilicity is better, have only the lipophilicity that improves xylogen could obtain highly active lignin modification product.This just need be incorporated into fatty clan elder's carbochain in the molecular structure of xylogen.The normal at present method of modifying that adopts mainly contains following three kinds: first kind is and the alkylphenol condensation; Second kind is by phenolic hydroxyl group and alkylating reagent condensation; The third is for using the aliphatic amide modification.
But for first method, the adjustable range and the handiness of modification are little, still can not be used the modified lignin mahogany sulfonate that can reach ultralow oil-water interfacial tension separately.For second method, the alkyl chain of introducing in alkylated reaction then generates the water soluble surfactant active if contain 6～18 carbon atoms; If contain 18～24 carbon atoms, then generate oil soluble surfactant.With modified sulphur hydrochlorate xylogen 3% solution that this method is made, interfacial tension can be reduced to 0.1mN/m.With sulfonated organic solvent xylogen and the reaction of halo dodecane, be catalyzer with the pyridine, the mol ratio of add-on and bromoalkane 1: 1, at 60 ℃ of reaction 6h, product is through the dialysis postlyophilization.Product is identical with Reax-85A character as dye dispersant.Its surface tension can be lower than 40mN/m in strength of solution during for 1g/L, and critical micelle concentration cmc value has extraordinary dispersing property simultaneously for 0.084g/L is an exemplary surfactants character.Though after with preceding two kinds of methods xylogen being carried out modification, the activity of gained lignin product has had and significantly improves, the ability that reduces oil-water interfacial tension is still limited.For the third method, according to the constructional feature of xylogen, the hydrogen on its phenolic hydroxyl group ortho position is very active, fully can with fatty amine and aldehyde generation Mannich reaction, but rare both at home and abroad at present relevant report.
Summary of the invention
The objective of the invention is to overcome the defective that does not prepare modified lignin mahogany sulfonate at present, a kind of preparation method of modified lignin mahogany sulfonate is provided by the aliphatic amide modification.
Purpose of the present invention is achieved through the following technical solutions: a kind of preparation method of modified lignin mahogany sulfonate, it is characterized in that, and mainly may further comprise the steps:
(a) sodium lignosulfonate that takes by weighing 20～60g joins in the round-bottomed flask that is inserted with thermometer, and the adding volume is the water of 80～120mL, magnetic agitation is even, and in round-bottomed flask, drip 0.9～1.5ml diethylenetriamine, be warming up to 70～90 ℃ after slowly dripping formaldehyde solution then, be incubated 6～7 hours;
(b) dripping concentration in round-bottomed flask is 8～12% NaOH solution, and the pH value of whole solution is transferred to is 7～8, dripped in 2～3 hours and grow the carbochain fat acyl chloride, and the dilute solution that drips sodium bicarbonate simultaneously is as acid binding agent;
(c) treat reinforced the end after, continue to stir 0.5～1.5 hour, dripping concentration simultaneously and be 3～7% NaOH solution keeps pH value of reactants between 7～8, and generation acyl chlorides, treat after the irritating smell completely dissolve of acyl chlorides, stop to stir, reactant is placed on drying, porphyrize can generate the lignin acid amides infrared lamp under;
(d) take by weighing the 40g lauric acid, add and be inserted with in the there-necked flask of thermometer, prolong and agitator, and be heated to 50 ℃～70 ℃, treat to start stirring after the lauric acid fusing, and in 1 hour, drip the 95g sulfur oxychloride with feed hopper, and after dripping end, be warming up to 70 ℃～80 ℃, back flow reaction 5h, after question response finished, first air distillation went out thionyl chloride, use vacuum distillation apparatus rectifying product again, collect 122 ℃/8mmHg cut and can generate lauroyl chloride;
(e) oleic acid that takes by weighing 20～30g adds in the round-bottomed flask of 100ml, is heated to 110 ℃～130 ℃ and keep 0.5～1h, till the no steam appearance in round-bottomed flask surface;
(f) whole round-bottomed flask is cooled to 45～50 ℃, and slowly drip 4～7g phosphorus trichloride, after dropwising, more whole round-bottomed flask is warming up to 55～60 ℃, continue stirring reaction 2h, leave standstill behind 4～5h the upper strata of this mixed solution separated and to generate oleoyl chloride;
(g) be 9 with made lignin acid amides, lauroyl chloride and the oleoyl chloride of getting ready in the ph value, thorough mixing reaction 3～5h gets final product under the condition when temperature is 60 ℃.
Further, the quality of the sodium lignosulfonate that is taken by weighing in the step (a) is 30～60g.
3, the preparation method of a kind of modified lignin mahogany sulfonate according to claim 1 is characterized in that: the concentration of the diethylenetriamine that is dripped in the step (a) is 1～1.3%.
4, the preparation method of a kind of modified lignin mahogany sulfonate according to claim 1 is characterized in that: the concentration of the NaOH solution that is dripped in step (b), the step (c) is 9～11%.
5, the preparation method of a kind of modified lignin mahogany sulfonate according to claim 1 is characterized in that: the lauric volumetric molar concentration that is taken by weighing in the step (d) is 0.2mol/L.
Preparation method of the present invention compares very simple than prior art, and preparation process is very fast, and the operation of not dangerous property in preparation process it is hereby ensured operator's safety.Simultaneously, prepared modified lignin mahogany sulfonate surface tension can be lower than 40mN/m in strength of solution during for 1g/L, critical micelle concentration cmc value has the ability of extraordinary dispersing property and reduction oil-water interfacial tension for 0.084g/L is an exemplary surfactants character.
Embodiment
Below in conjunction with embodiment the present invention is described in further detail, but embodiments of the present invention are not limited thereto.
Embodiment 1
Lignin acid amides preparation process is as follows: add the 20g sodium lignosulfonate in being inserted with the 150ml round-bottomed flask of thermometer, adding volume is the water of 80mL, magnetic agitation is even, drip the 0.9ml diethylenetriamine, be warming up to 70 ℃ after slowly dripping the formaldehyde solution of predetermined amount then, be incubated 6 hours, with synthetic lignin amine.
After treating that lignin amine is synthetic, be that 8% NaOH solution is adjusted this pH value of reactants to 7 with concentration.Dripped the long carbochain fat acyl chloride of predetermined amount in 2 hours, the dilute solution that drips sodium bicarbonate simultaneously is as acid binding agent.Behind reinforced the end, continue to stir 0.5 hour, drip concentration simultaneously and be 3% NaOH solution and keep pH value of reactants between 7～8.Treat after the irritating smell completely dissolve of acyl chlorides, stop to stir.Reactant is placed on dry, porphyrize under the infrared lamp, can obtains the lignin acid amides of brown ceramic powder.
The preparation method of lauroyl chloride is specific as follows: take by weighing 40g, the lauric acid of 0.2mol/L adds and to be inserted with in the 100ml there-necked flask of thermometer, prolong and agitator, is heated to 60 ℃, treat the lauric acid fusing after, start stirring.In 1h, drip 95g with feed hopper again, the sulfur oxychloride of 0.8mol/L, dropping is warming up to 78 ℃, back flow reaction 5h after finishing.After reaction finished, first air distillation went out thionyl chloride, uses vacuum distillation apparatus rectifying product again, collected 122 ℃/8mmHg cut, can obtain lauroyl chloride faint yellow, transparent, that irritating smell is arranged.Wherein, temperature can not be too high in vacuum distillation process, generally can not be above 200 ℃.
The preparation process of oleoyl chloride is as follows: earlier 20g oleic acid is added in the 100ml round-bottomed flask, be heated to 110 ℃, and keep constant temperature 0.5h, till occurring to the no steam in surface.When more whole round-bottomed flask being cooled to 45 ℃, slowly drip the 4g phosphorus trichloride, after dropwising, be warming up to 55 ℃, continue stirring reaction 2h.Leave standstill 4h then, its upper strata is oleoyl chloride, and lower floor is a phosphorous acid, divides sub-cloud phosphorous acid can obtain oleoyl chloride at last.
Is 9 with made lignin acid amides, lauroyl chloride and the oleoyl chloride of getting ready in the ph value, and thorough mixing reaction 3h gets final product under the condition when temperature is 60 ℃.
Embodiment 2
Lignin acid amides preparation process is as follows: add the 30g sodium lignosulfonate in being inserted with the 150ml round-bottomed flask of thermometer, adding volume is the water of 100mL, magnetic agitation is even, drip the 1.0ml diethylenetriamine, be warming up to 75 ℃ after slowly dripping the formaldehyde solution of predetermined amount then, be incubated 7 hours, with synthetic lignin amine.
After treating that lignin amine is synthetic, be that 9.5% NaOH solution is adjusted this pH value of reactants to 7.5 with concentration.Dripped the long carbochain fat acyl chloride of predetermined amount in 2.5 hours, the dilute solution that drips sodium bicarbonate simultaneously is as acid binding agent.Behind reinforced the end, continue to stir 1 hour, drip concentration simultaneously and be 5% NaOH solution and keep pH value of reactants between 7～8.Treat after the irritating smell completely dissolve of acyl chlorides, stop to stir.Reactant is placed on dry, porphyrize under the infrared lamp, can obtains the lignin acid amides of brown ceramic powder.
The preparation method of lauroyl chloride is specific as follows: take by weighing 40g, the lauric acid of 0.2mol/L adds and to be inserted with in the 100ml there-necked flask of thermometer, prolong and agitator, is heated to 50 ℃, treat the lauric acid fusing after, start stirring.In 1h, drip 95g with feed hopper again, the sulfur oxychloride of 0.8mol/L, dropping is warming up to 80 ℃, back flow reaction 5h after finishing.After reaction finished, first air distillation went out thionyl chloride, uses vacuum distillation apparatus rectifying product again, collected 122 ℃/8mmHg cut, can obtain lauroyl chloride faint yellow, transparent, that irritating smell is arranged.
The preparation process of oleoyl chloride is as follows: earlier 23g oleic acid is added in the 100ml round-bottomed flask, be heated to 120 ℃, and keep constant temperature 1h, till occurring to the no steam in surface.When more whole round-bottomed flask being cooled to 45.5 ℃, slowly drip the 4g phosphorus trichloride, after dropwising, be warming up to 55 ℃, continue stirring reaction 2h.Leave standstill 4h then, its upper strata is oleoyl chloride, and lower floor is a phosphorous acid, divides sub-cloud phosphorous acid can obtain oleoyl chloride at last.
Is 9 with made lignin acid amides, lauroyl chloride and the oleoyl chloride of getting ready in the ph value, and thorough mixing reaction 4h gets final product under the condition when temperature is 60 ℃.
Embodiment 3
Lignin acid amides preparation process is as follows: add the 50g sodium lignosulfonate in being inserted with the 150ml round-bottomed flask of thermometer, adding volume is the water of 110mL, magnetic agitation is even, drip the 1.1ml diethylenetriamine, be warming up to 80 ℃ after slowly dripping the formaldehyde solution of predetermined amount then, be incubated 6.5 hours, with synthetic lignin amine.
After treating that lignin amine is synthetic, be that 10% NaOH solution is adjusted this pH value of reactants to 8 with concentration.Dripped the long carbochain fat acyl chloride of predetermined amount in 3 hours, the dilute solution that drips sodium bicarbonate simultaneously is as acid binding agent.Behind reinforced the end, continue to stir 1.5 hours, drip concentration simultaneously and be 6% NaOH solution and keep pH value of reactants between 7～8.Treat after the irritating smell completely dissolve of acyl chlorides, stop to stir.Reactant is placed on dry, porphyrize under the infrared lamp, can obtains the lignin acid amides of brown ceramic powder.
The preparation method of lauroyl chloride is specific as follows: take by weighing 40g, the lauric acid of 0.2mol/L adds and to be inserted with in the 100ml there-necked flask of thermometer, prolong and agitator, is heated to 70 ℃, treat the lauric acid fusing after, start stirring.In 1h, drip 95g with feed hopper again, the sulfur oxychloride of 0.8mol/L, dropping is warming up to 78 ℃, back flow reaction 5h after finishing.After reaction finished, first air distillation went out thionyl chloride, uses vacuum distillation apparatus rectifying product again, collected 122 ℃/8mmHg cut, can obtain lauroyl chloride faint yellow, transparent, that irritating smell is arranged.
The preparation process of oleoyl chloride is as follows: earlier 25g oleic acid is added in the 100ml round-bottomed flask, be heated to 110 ℃, and keep constant temperature 1h, till occurring to the no steam in surface.When more whole round-bottomed flask being cooled to 50 ℃, slowly drip the 4g phosphorus trichloride, after dropwising, be warming up to 55 ℃, continue stirring reaction 2h.Leave standstill 4.5h then, its upper strata is oleoyl chloride, and lower floor is a phosphorous acid, divides sub-cloud phosphorous acid can obtain oleoyl chloride at last.
Is 9 with made lignin acid amides, lauroyl chloride and the oleoyl chloride of getting ready in the ph value, and thorough mixing reaction 5h gets final product under the condition when temperature is 60 ℃.
Embodiment 4
Lignin acid amides preparation process is as follows: add the 55g sodium lignosulfonate in being inserted with the 150ml round-bottomed flask of thermometer, adding volume is the water of 120mL, magnetic agitation is even, drip the 1.3ml diethylenetriamine, be warming up to 90 ℃ after slowly dripping the formaldehyde solution of predetermined amount then, be incubated 6.5 hours, with synthetic lignin amine.
After treating that lignin amine is synthetic, be that 12% NaOH solution is adjusted this pH value of reactants to 8 with concentration.Dripped the long carbochain fat acyl chloride of predetermined amount in 3 hours, the dilute solution that drips sodium bicarbonate simultaneously is as acid binding agent.Behind reinforced the end, continue to stir 1.5 hours, drip concentration simultaneously and be 6.5% NaOH solution and keep pH value of reactants between 7～8.Treat after the irritating smell completely dissolve of acyl chlorides, stop to stir.Reactant is placed on dry, porphyrize under the infrared lamp, can obtains the lignin acid amides of brown ceramic powder.
The preparation method of lauroyl chloride is specific as follows: take by weighing 40g, the lauric acid of 0.2mol/L adds and to be inserted with in the 100ml there-necked flask of thermometer, prolong and agitator, is heated to 65 ℃, treat the lauric acid fusing after, start stirring.In 1h, drip 95g with feed hopper again, the sulfur oxychloride of 0.8mol/L, dropping is warming up to 75 ℃, back flow reaction 5h after finishing.After reaction finished, first air distillation went out thionyl chloride, uses vacuum distillation apparatus rectifying product again, collected 122 ℃/8mmHg cut, can obtain lauroyl chloride faint yellow, transparent, that irritating smell is arranged.
The preparation process of oleoyl chloride is as follows: earlier 25.5g oleic acid is added in the 100ml round-bottomed flask, be heated to 120 ℃, and keep constant temperature 0.5h, till occurring to the no steam in surface.When more whole round-bottomed flask being cooled to 45 ℃, slowly Dropwise 5 g phosphorus trichloride after dropwising, is warming up to 58 ℃, continues stirring reaction 2h.Leave standstill 4.5h then, its upper strata is oleoyl chloride, and lower floor is a phosphorous acid, divides sub-cloud phosphorous acid can obtain oleoyl chloride at last.
Is 9 with made lignin acid amides, lauroyl chloride and the oleoyl chloride of getting ready in the ph value, and thorough mixing reaction 5h gets final product under the condition when temperature is 60 ℃.
As mentioned above, just can well realize the present invention.
Claims (5)
1. the preparation method of a modified lignin mahogany sulfonate is characterized in that, mainly may further comprise the steps:
(a) sodium lignosulfonate that takes by weighing 20～60g joins in the round-bottomed flask that is inserted with thermometer, and the adding volume is the water of 80～120mL, magnetic agitation is even, and in round-bottomed flask, drip 0.9～1.5ml diethylenetriamine, be warming up to 70～90 ℃ after slowly dripping formaldehyde solution then, be incubated 6～7 hours;
(b) dripping concentration in round-bottomed flask is 8～12% NaOH solution, and the pH value of whole solution is transferred to is 7～8, dripped in 2～3 hours and grow the carbochain fat acyl chloride, and the dilute solution that drips sodium bicarbonate simultaneously is as acid binding agent;
(c) treat reinforced the end after, continue to stir 0.5～1.5 hour, dripping concentration simultaneously and be 3～7% NaOH solution keeps pH value of reactants between 7～8, and generation acyl chlorides, treat after the irritating smell completely dissolve of acyl chlorides, stop to stir, reactant is placed on drying, porphyrize can generate the lignin acid amides infrared lamp under;
(d) take by weighing the 40g lauric acid, add and be inserted with in the there-necked flask of thermometer, prolong and agitator, and be heated to 50 ℃～70 ℃, treat to start stirring after the lauric acid fusing, and in 1 hour, drip the 95g sulfur oxychloride with feed hopper, and after dripping end, be warming up to 70 ℃～80 ℃, back flow reaction 5h, after question response finished, first air distillation went out thionyl chloride, use vacuum distillation apparatus rectifying product again, collect 122 ℃/8mmHg cut and can generate lauroyl chloride;
(e) oleic acid that takes by weighing 20～30g adds in the round-bottomed flask of 100ml, is heated to 110 ℃～130 ℃ and keep 0.5～1h, till the no steam appearance in round-bottomed flask surface;
(f) whole round-bottomed flask is cooled to 45～50 ℃, and slowly drip 4～7g phosphorus trichloride, after dropwising, more whole round-bottomed flask is warming up to 55～60 ℃, continue stirring reaction 2h, leave standstill behind 4～5h the upper strata of this mixed solution separated and to generate oleoyl chloride;
(g) be 9 with made lignin acid amides, lauroyl chloride and the oleoyl chloride of getting ready in the ph value, thorough mixing reaction 3～5h gets final product under the condition when temperature is 60 ℃.
2. the preparation method of a kind of modified lignin mahogany sulfonate according to claim 1, it is characterized in that: the quality of the sodium lignosulfonate that is taken by weighing in the step (a) is 30～60g.
3. the preparation method of a kind of modified lignin mahogany sulfonate according to claim 1, it is characterized in that: the concentration of the diethylenetriamine that is dripped in the step (a) is 1～1.3%.
4. the preparation method of a kind of modified lignin mahogany sulfonate according to claim 1, it is characterized in that: the concentration of the NaOH solution that is dripped in step (b), the step (c) is 9～11%.
5. the preparation method of a kind of modified lignin mahogany sulfonate according to claim 1, it is characterized in that: the lauric volumetric molar concentration that is taken by weighing in the step (d) is 0.2mol/L.
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Cited By (8)
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| EP2711396A1 (en) * | 2012-09-19 | 2014-03-26 | Annikki GmbH | Copolymerizable lignin derivatives |
| CN105462444A (en) * | 2016-01-07 | 2016-04-06 | 长春顺风新城建筑材料有限公司 | Water-based anti-corrosion paint and preparing method thereof |
| CN113355914A (en) * | 2021-06-29 | 2021-09-07 | 武汉纺织大学 | Wool fabric shrink-proof finishing liquid containing lignin, and preparation method and application thereof |
| CN114395139A (en) * | 2022-01-13 | 2022-04-26 | 上海昶法新材料有限公司 | Modified lignin suitable for fully-degradable membrane bags and preparation method thereof |
| CN114672291A (en) * | 2020-12-24 | 2022-06-28 | 中国石油化工股份有限公司 | Lignin-based water shutoff profile control system and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| EP2711396A1 (en) * | 2012-09-19 | 2014-03-26 | Annikki GmbH | Copolymerizable lignin derivatives |
| CN105462444A (en) * | 2016-01-07 | 2016-04-06 | 长春顺风新城建筑材料有限公司 | Water-based anti-corrosion paint and preparing method thereof |
| CN114672291A (en) * | 2020-12-24 | 2022-06-28 | 中国石油化工股份有限公司 | Lignin-based water shutoff profile control system and preparation method and application thereof |
| CN114672292A (en) * | 2020-12-24 | 2022-06-28 | 中国石油化工股份有限公司 | High-temperature-resistant composite plugging and blending agent as well as preparation method and application thereof |
| CN114672294A (en) * | 2020-12-24 | 2022-06-28 | 中国石油化工股份有限公司 | Time-delay type composite blocking and adjusting system and preparation method and application thereof |
| CN114672292B (en) * | 2020-12-24 | 2023-05-30 | 中国石油化工股份有限公司 | High-temperature-resistant composite plugging agent and preparation method and application thereof |
| CN114672294B (en) * | 2020-12-24 | 2023-05-30 | 中国石油化工股份有限公司 | Time-delay type composite plugging system and preparation method and application thereof |
| CN114672291B (en) * | 2020-12-24 | 2023-05-30 | 中国石油化工股份有限公司 | Lignin-based water shutoff and profile control system and preparation method and application thereof |
| EP4261265A4 (en) * | 2020-12-24 | 2024-06-12 | China Petroleum & Chemical Corporation | Plugging agent for oil extraction in oilfield and a preparation method therefor and application thereof |
| CN113355914A (en) * | 2021-06-29 | 2021-09-07 | 武汉纺织大学 | Wool fabric shrink-proof finishing liquid containing lignin, and preparation method and application thereof |
| CN113355914B (en) * | 2021-06-29 | 2022-07-22 | 武汉纺织大学 | Lignin-containing wool fabric shrink-proof finishing liquid and preparation method and application thereof |
| CN114395139A (en) * | 2022-01-13 | 2022-04-26 | 上海昶法新材料有限公司 | Modified lignin suitable for fully-degradable membrane bags and preparation method thereof |
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| C06 | Publication | ||
| PB01 | Publication | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20110615 |