CN104147977A - Lignin-based anion-cation type high-molecular surface active agent and preparation method thereof - Google Patents
Lignin-based anion-cation type high-molecular surface active agent and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a lignin-based anion-cation type high-molecular surface active agent and a preparation method thereof. The lignin-based anion-cation type high-molecular surface active agent comprises the following components in parts by weight: 100 parts of lignin sulfonate, 10-30 parts of epoxy chloropropane, 50-200 parts of polyethylene glycol, 1-3 parts of catalyst and 5-30 parts of quaternary-ammonium-salt type cationic surface active agent. The preparation method comprises the following steps: adopting the lignin sulfonate, the polyethylene glycol and the quaternary-ammonium-salt type cationic surface active agent as main materials, firstly synthesizing lignin sulfonate polyoxyethylene ether, and then compositing with the quaternary-ammonium-salt type cationic surface active agent to prepare the lignin-based anion-cation type high-molecular surface active agent. The novel lignin-based anion-cation type high-molecular surface active agent prepared by the invention has a controllable water draining skeleton and a polyoxyethylene-ether flexible hydrophilic side chain, has lower critical aggregation concentration and surface tension compared with the traditional lignin sulfonate, and can be applied in the industrial fields of pesticide dispersing agents and the like as a novel functional additive.
Description
Technical field
The present invention relates to a kind of high molecular surfactant, particularly relate to a kind of lignin-base anion and cation high molecular surfactant and preparation method thereof.
Background technology
Lignin is the second largest natural reproducible resource of nature, is the valuable source of human future.The lignin of industrial use is mainly from the accessory substance of paper-making industry, cheap and output is large.Paper industry mainly be take chemical pulping as main, is divided into two kinds of alkaline process and acid systems.Lignosulfonates are accessory substances of acid polishing, have C
9hydrophobic framework also has sulfonate radical strong hydrophilicity group and carboxylic acid outward, and the weak ionizing group such as phenolic hydroxyl group has water-solublely preferably, is a kind of natural polymer anion surfactant.Can be widely used in industrial circle, as useful as concrete water reducer, slurries additive agent, oil field sacrifice agent, pesticide dispersing agent etc.The application of lignosulfonates mainly can be adsorbed in particle surface based on it and play stably dispersing effect.Although the application of lignosulfonates water soluble polymer in industry is very extensive and ripe, but the fine chemical product that is conventionally considered to a kind of " balm " formula, although of many uses, but usefulness is generally general, be difficult to develop into the Additives Products of efficient, the main flow of certain or some industrial circles.
In the past decades, the composite existing of cationic and anionic surfactant much studied.Because compound system interacts with the strong electrostatic interaction between the ion head base of opposite charges and the hydrophobic between alkyl, its aqueous solution shows complicated phase behavior and abundant microstructure.The strong interaction of the composite rear generation of anion surfactant and cationic surfactant, easily forms micella, and compound has lower critical micelle concentration (CMC), and surface-active obviously improves.(the YB Li such as Li, XD Chen, MQ Zhang, et al.Macromolecular Aggregation of Aqueous Polyacrylic Acid in the Presence of Surfactants Revealed by Resonance Rayleigh Scattering.Macromolecules, 2008,41:4873 ?4880) by Rayleigh light scattering method, studied the interaction of polyacrylic acid (PAA) and anion surfactant quaternary ammonium salt cationic surfactant (CTAB).Result shows that anion surfactant and cationic surfactant exist strong interaction force, the difference of CTAB addition, and PAA chain presents winding and dispersity, and CTAB forms globular micelle between two PAA chains.(the M.Sajid Ali such as Sajid Ali, M.Suhail, G Ghosh, et al.Interactions between cationic gemini/conventional surfactants with polyvinylpyrrolidone:Specific conductivity and dynamic lightscattering studies.Colloids and Surfaces A:Physicochem.Eng.Aspects, 2009, 350:51 ?56) studied the compound system of polyvinylpyrrolidone and CTAB, result shows that the CAC of compound decreases, when CTAB addition increases, the particle diameter of compound increases to some extent.(the J.Penfold such as Penfold, R.K.Thomas, D.J.F.Taylor.Polyelectrolyte/surfactant mixtures at the air ?solution interface.Current Opinion in Colloid & Interface Science, 2006, 11:337 ?344) studied the composite mechanism of polymer and surfactant, think that control surface is capable in order that surperficial energy, and the surface-active competition of the structure of polymer/surfactant and polymer/surfactant is key factor, but need to set up surface kinetics Study Polymer Melts and surfactant interaction mechanism better.Kogej etc. (K.Kogej.Association and structure formation in oppositely charged polyelectrolyte ?surfactant mixtures.Advances in Colloid and Interface Science, 2010,158:68 ?83) studied gathering behavior and the conformation change of polyelectrolyte and the surfactant of opposite charges, result shows that violent effect between opposite charges material is mainly from electrostatic interaction, but the configuration of hydrophobic chain and characteristic also have certain influence.
Research shows, after anionic-cationic surfactant mixed system, its performance generally can be significantly improved, but very easily occurs deposited phenomenon after charging neutrality.According to dlvo theory, between the molecule of polyelectrolyte, there is the interaction forces such as electrostatic force, Van der Waals'attractive force, sterically hindered and aquation, in composite system, exist molecule monomer and the aggregation of different structure form, these power interact and cause flocculating between wherein larger aggregation, if but sterically hindered increase has certain inhibitory action to cohesion or deposited phenomenon.Had not yet to see this anion surfactant of lignosulfonates and cationic surfactant composite.Because lignosulfonates are a kind of anionic polyelectrolytes, when itself and cationic surfactant compound tense, due in positive and negative charge and after very easily occur that flocculation precipitates, thereby be difficult to obtain water miscible anion and cation combination product.The present invention is in order to solve the flocculation sediment problem of compound tense, first in lignin sulfonic acid molecules of salt, introduce APEO chain hydrophilic chain, synthetic lignosulfonates APEO graft (SL ?PEO), the SL that contains hydrophobic framework and hydrophilic backbone with this again ?PEO molecule and quaternary ammonium salt cationic surfactant to carry out negative and positive compound, prepare lignin-base anion and cation high molecular surfactant.
Summary of the invention
The object of the present invention is to provide that a kind of surface tension is lower, the good Novel wooden quality of surface-active base anion and cation high molecular surfactant.
Another object of the present invention is also to provide the preparation method of described lignin-base anion and cation high molecular surfactant.
The present invention is directed to and when lignosulfonates and cationic surfactant are compound prepares macromolecule cationic and anionic surfactant, very easily occur flocculation sediment and cannot make this technical barrier, in lignin sulfonic acid molecules of salt, introduce polyoxyethylene chain hydrophilic chain and prepare lignosulfonates APEO graft, the SL that contains hydrophobic framework and hydrophilic backbone with this again ?PEO molecule and quaternary ammonium salt cationic surfactant to carry out negative and positive compound, prepare lignin-base anion and cation high molecular surfactant.The present invention be take lignosulfonates as raw material, with Huan oxygen Lv Bing Wan ?polyethylene glycol intermediate in alkaline aqueous solution, carry out electrophilic substitution reaction and make lignosulfonates APEO, and it is compound that the lignosulfonates APEO of preparation and quaternary ammonium salt cationic surfactant are carried out to zwitterion, makes lignin-base anion and cation high molecular surfactant.
The object of the invention is to be achieved through the following technical solutions:
A preparation method for lignin-base anion and cation high molecular surfactant, comprises the following steps and process conditions:
(1) polyethylene glycol is heated up melting, adds catalyst, after stirring, drips epoxychloropropane, after dropwising, at (40～60) ℃ reaction (1～2) h, obtains chloro polyethylene glycol intermediate;
(2) solution that is 30%～40% by lignosulfonates and water mixed preparing mass percent concentration, in (60～80) ℃, drip described chloro polyethylene glycol intermediate, ℃ reaction (2～4) h in 7 (0～90), pH to 12～13 of adjusting reactant liquor; PH to 6.0～8.0 that reaction finishes rear adjusting product, are cooled to room temperature; Obtain lignosulfonates polyoxyethylene ethereal solution, more spray-dried, make powdery lignosulfonates APEO;
(3) lignosulfonates APEO is mixed with to solution, then under agitation that lignosulfonates polyoxyethylene ethereal solution and quaternary ammonium salt cationic surfactant is compound according to mass ratio 10:1～10:5, make lignin-base anion and cation high molecular surfactant; The general formula of described quaternary ammonium salt cationic surfactant be [R ?N (R
1r
2r
3)] X, in formula, R is C
10～C
22chain alkyl, R
l, R
2or R
3for methyl or ethyl, or R
l, R
2and R
3one of them is benzyl or chain alkyl; X is chlorine, bromine or iodine;
In mass fraction, the consumption of lignosulfonates, epoxychloropropane, polyethylene glycol, catalyst, quaternary ammonium salt cationic surfactant is respectively 100 parts, 10～30 parts, 50～200 parts, 1～3 part, 20～100 parts;
Described lignosulfonates are one or more in sodium lignin sulfonate, lignin sulfonic acid potassium, ammonium lignosulphonate, calcium lignosulfonate, magnesium lignosulfonate, Iron lignosulfonate, and its solids content mass fraction is 95%;
Described polyethylene glycol is that molecular weight is one or more in 200,400,600,1000,2000,4000;
Described catalyst is one or more in antimony pentafluoride, boron trifluoride etherate, aluminium chloride, butter of tin, Antimony pentachloride, TBAB;
In described step (1) and (2), adopt NaOH, KOH or H
2sO
4, HCl regulates pH value;
For further real the object of the invention, preferably, the temperature of described melting is (40～60) ℃.Described dropping epoxychloropropane is to dropwise in (30～60) min.Dripping described chloro polyethylene glycol intermediate is to dropwise in (1～2) h.It is described that lignosulfonates APEO is mixed with to solution is that lignosulfonates APEO is mixed with to mass percent concentration is 30% solution.
A kind of lignin-base anion and cation high molecular surfactant and preparation method thereof, is made by above-mentioned preparation method.
Novel surfactant of the present invention belongs to high molecular type surfactant, in molecule, contain a plurality of hydrophobic long-chains, there is the capillary ability of the obvious reduction aqueous solution, and contain hydrophilic APEO long-chain, can form multi-point-anchoring absorption at the surface of solids, form fine and close space bit resistance layer.
The present invention except lignosulfonates all by pure content meter.
The present invention compares with lignosulfonates has following outstanding advantages and effect:
1, course of reaction of the present invention is carried out under atmospheric low-temperature, and easy operating is controlled, and owing to directly accessing APEO hydrophilic radical by graft reaction in lignin sulfonic acid molecules of salt, side reaction is few, very little to the destruction of lignin structure; Only need two-step reaction, the reaction time is shorter.Product good water solubility, environment-protecting asepsis.
2,, than lignosulfonates, lignosulfonates APEO graft of the present invention can to carry out negative and positive compound with quaternary ammonium salt cationic surfactant.The compound novel surfactant obtaining is compared log mahogany sulfonate and is had a plurality of typical hydrophobic long-chains, can form multi-point-anchoring absorption at the surface of solids, therefore can improve absorption property and the application performance of lignosulfonates; In molecule, also contain in addition a plurality of hydrophilic APEO long-chains, can provide larger sterically hindered active force for adsorption layer.
3, the surface-active of lignosulfonates is poor, and it is poor that it reduces the capillary ability of the aqueous solution, and this has limited its range of application and effectiveness.Lignin-base anion and cation high molecular surfactant prepared by the present invention has stronger surface-active, and it reduces the capillary ability of the aqueous solution and improves, and range of application broadens, and usefulness improves.
Accompanying drawing explanation
Fig. 1 sodium lignin sulfonate, APEO, SL ?PEO, SL ?PEO ?the infrared spectrum of CTAB.
Fig. 2 is the particle diameter distribution maps of embodiment 3 gained lignin-base anion and cation high molecular surfactants in the aqueous solution.
Fig. 3 is the AFM figure of embodiment 3 gained lignosulfonates APEO grafts.
Fig. 4 is the AFM figure of embodiment 3 gained lignin-base anion and cation high molecular surfactants.
Fig. 5 is the critical aggregate concentrations of embodiment 3 gained lignin-base anion and cation high molecular surfactants in the aqueous solution.
The specific embodiment
For understanding better the present invention, below in conjunction with specific embodiments and the drawings, the invention will be further described, but embodiment does not form the restriction to the claimed scope of the present invention.
Embodiment 1
(1) 200 grams of Macrogol 600s are warming up to 40 ℃, add 1 gram of antimony pentafluoride catalyst, after being uniformly mixed, slowly drip 10 grams of epoxychloropropane, in 30min, dropwise, after dropwising, 50 ℃ reaction 1h, obtain Huan oxygen Lv Bing Wan ?Macrogol 600 intermediate;
(2) by 100 grams of sodium lignin sulfonates (by weight percentage, solid content is 95%) with the water mixed preparing mass percent concentration solution that is 30%, 70 ℃ of Huan oxygen Lv Bing Wan that prepare in slowly dripping steps (1) ?Macrogol 600 intermediate, in 1.5h, dropwise, after dropwising, at 80 ℃ of reaction 2h, dripping mass percent concentration simultaneously and be 15% sodium hydroxide solution regulates the pH of reactant liquor to maintain between 12～13, reaction finishes the pH to 7.0 of rear adjusting reactant liquor, is cooled to room temperature and obtains sodium lignin sulfonate polyoxyethylene ethereal solution.
(3) the sodium lignin sulfonate APEO in step (2) being made into mass percent concentration is 30% solution, then the ten alkyl trimethyl ammonium bromide cationic surfactants that the lignosulfonates polyoxyethylene ethereal solution that is under agitation 30% by 100 gram mass percent concentrations and 10 gram mass percent concentrations are 30% are solution combined, make lignin-base anion and cation high molecular surfactant.
Embodiment 2
(1) 100 grams of Macrogol 2000s are warming up to 60 ℃ of meltings, add 3 grams of Antimony pentachloride catalyst, after being uniformly mixed, slowly drip 15 grams of epoxychloropropane, in 60min, dropwise, after dropwising, 40 ℃ reaction 2h, obtain modified epoxy Lv Bing Wan ?Macrogol 2000 intermediate;
(2) Jiang100Ke ammonium lignosulphonate (by weight percentage, solid content is 95%) with the water mixed preparing mass percent concentration solution that is 40%, 60 ℃ of Huan oxygen Lv Bing Wan that prepare in slowly dripping steps (1) ?Macrogol 2000 intermediate, in 1h, dropwise, after dropwising, at 70 ℃ of reaction 3h, dripping mass percent concentration simultaneously and be 15% sodium hydroxide solution regulates the pH of reactant liquor to maintain between 12～13, reaction finishes the pH to 6.0 of rear adjusting reactant liquor, is cooled to room temperature and obtains ammonium lignosulphonate's polyoxyethylene ethereal solution.
(3) the sodium lignin sulfonate APEO in step (2) being made into mass percent concentration is 30% solution, then the INCROQUAT TMC-80 cationic surfactant that the lignosulfonates polyoxyethylene ethereal solution that is under agitation 30% by 100 gram mass percent concentrations and 50 gram mass percent concentrations are 30% is solution combined, makes lignin-base anion and cation high molecular surfactant.
Embodiment 3
(1) 100 grams of Macrogol 600s are warming up to 50 ℃, add 3 grams of TBAB catalyst, after being uniformly mixed, slowly drip 25 grams of epoxychloropropane, in 60min, dropwise, after dropwising, 50 ℃ reaction 2h, obtain Huan oxygen Lv Bing Wan ?Macrogol 600 intermediate;
(2) by 100 grams of sodium lignin sulfonates (by weight percentage, solid content is 95%) with the water mixed preparing mass percent concentration solution that is 40%, 70 ℃ of Huan oxygen Lv Bing Wan that prepare in slowly dripping steps (1) ?Macrogol 600 intermediate, in 1h, dropwise, after dropwising, at 80 ℃ of reaction 2h, dripping mass percent concentration simultaneously and be 15% sodium hydroxide solution regulates the pH of reactant liquor to maintain between 12～13, reaction finishes the pH to 7.0 of rear adjusting reactant liquor, is cooled to room temperature and obtains sodium lignin sulfonate polyoxyethylene ethereal solution.
(3) the sodium lignin sulfonate APEO in step (2) being made into mass percent concentration is 30% solution, then the softex kw cationic surfactant that the lignosulfonates polyoxyethylene ethereal solution that is under agitation 30% by 100 gram mass percent concentrations and 20 gram mass percent concentrations are 30% is solution combined, makes lignin-base anion and cation high molecular surfactant.
Embodiment 4
(1) 100 grams of cetomacrogol 1000s are warming up to 60 ℃ of meltings, add 3 grams of boron trifluoride etherate catalyst, after being uniformly mixed, slowly drip 30 grams of epoxychloropropane, in 60min, dropwise, after dropwising, 50 ℃ reaction 2h, obtain Huan oxygen Lv Bing Wan ?cetomacrogol 1000 intermediate;
(2) by 100 grams of calcium lignosulfonates (by weight percentage, solid content is 95%) with the water mixed preparing mass percent concentration solution that is 35%, 60 ℃ of Huan oxygen Lv Bing Wan that prepare in slowly dripping steps (1) ?cetomacrogol 1000 intermediate, in 1h, dropwise, after dropwising, at 70 ℃ of reaction 2h, dripping mass percent concentration simultaneously and be 15% sodium hydroxide solution regulates the pH of reactant liquor to maintain between 12～13, reaction finishes the pH to 7.0 of rear adjusting reactant liquor, is cooled to room temperature and obtains calcium lignosulfonate polyoxyethylene ethereal solution.
(3) the sodium lignin sulfonate APEO in step (2) being made into mass percent concentration is 30% solution, then the DTAB cationic surfactant that the lignosulfonates polyoxyethylene ethereal solution that is under agitation 30% by 100 gram mass percent concentrations and 30 gram mass percent concentrations are 30% is solution combined, makes lignin-base anion and cation high molecular surfactant.
Embodiment 5
(1) 100 grams of Macrogol 2000s are warming up to 60 ℃ of meltings, add 3 grams of aluminum chloride catalysts, after being uniformly mixed, slowly drip 35 grams of epoxychloropropane, in 60min, dropwise, after dropwising, 60 ℃ reaction 2h, obtain modified epoxy Lv Bing Wan ?Macrogol 2000 intermediate;
(2) by 100 grams of sodium lignin sulfonates (by weight percentage, solid content is 95%) with the water mixed preparing mass percent concentration solution that is 40%, 70 ℃ of Huan oxygen Lv Bing Wan that prepare in slowly dripping steps (1) ?Macrogol 2000 intermediate, in 1h, dropwise, after dropwising, at 80 ℃ of reaction 4h, dripping mass percent concentration simultaneously and be 15% sodium hydroxide solution regulates the pH of reactant liquor to maintain between 12～13, reaction finishes the pH to 7.0 of rear adjusting reactant liquor, is cooled to room temperature and obtains sodium lignin sulfonate polyoxyethylene ethereal solution.
(3) the sodium lignin sulfonate APEO in step (2) being made into mass percent concentration is 30% solution, then the Cetyltrimethylammonium bromide cationic surfactant that the lignosulfonates polyoxyethylene ethereal solution that is under agitation 30% by 100 gram mass percent concentrations and 40 gram mass percent concentrations are 30% is solution combined, makes lignin-base anion and cation high molecular surfactant.
The explanation of embodiment effect
By embodiment 3 product sample preparations, adopt AFM to carry out pattern observation to it, and measure its surface tension, particle diameter distributes and critical aggregate concentration.Fig. 2 is the topographic profile of lignosulfonates APEO graft; Fig. 3 is the topographic profile of embodiment 3 products; Fig. 1 is embodiment 3 products and the particle diameter distribution map contrast of lignosulfonates APEO graft in the aqueous solution; Fig. 3 be SL ?the critical aggregate concentration contrast in the aqueous solution of PEO, embodiment 3 products and softex kw.Table 1 be embodiment 3 products, SL ?PEO and sodium lignin sulfonate as dispersant, prepare the performance comparison of dimethomorph aqueous suspension agent.
Table 1
Table 1 explanation:
(1) form formula is: former medicine content 40%, dispersant volume 4%, excess water are filled to 100%; Adopt planetary ball mill (QM ?3SP2, Nanjing Univ. Instrument Factory) ball milling 3h to prepare dimethomorph aqueous suspension agent;
(2) sodium lignin sulfonate is commercially available prod, derives from wood pulp sulphite acid polishing effluent;
(3) heat storage stability of suspending agent press GB/T19136 ?2003 method measure;
(4) before and after the heat of suspending agent storage suspensibility press GB/T14825 ?2006 method mensuration;
(5) the apparent viscosity assay method of suspending agent: adopting HAKKE MARS III modularization flow graph work station (Thermo Scientific company) and supporting CC26Ti type rotor is 100s at 25 ℃, shear rate
?1time apparent viscosity;
(6) particle diameter of dimethomorph suspending agent adopts laser particle size particle shape analyzer (EyeTech ?Laser, Ankersmid company) test to average for three times.
As shown in table 1, embodiment 3 products, sodium lignin sulfonate, SL ?the surface tension of PEO be respectively 39.05mN/m, 62.975mN/m, 57.57mN/m, the surface tension of embodiment 3 products than lignosulfonates and SL ?PEO little, this explanation embodiment 3 products than SL ?PEO there is stronger surface-active.Better surface-active can be improved embodiment 3 products at the application performance in the fields such as emulsifying agent, dispersant, can improve its emulsifying capacity and dispersive property.The good fluidity of dimethomorph suspending agent prepared by embodiment 3 products, before and after heat storage, change of size is very little, and average grain diameter is all less than 5 μ m, and suspensibility is all greater than 95%, it is stronger that its stability to suspending agent is compared sodium lignin sulfonate, and every the key technical indexes is all better than sodium lignin sulfonate.
The functional group content of table 2 sample
From table 2, SL ?the molecular weight of PEG600 be far longer than the molecular weight of SL, SL ?the content of phenolic hydroxyl groups of PEG600 be significantly less than SL, this explanation PEG600 has been grafted on SL molecule, and is grafted on the phenolic hydroxyl group of SL.
The Zeta potential value of the different embodiment products of table 3
From table 3, the SL under different proportion ?PEG ?the Zeta potential of CTAB molecular surface be different, this be due to CTAB with positive charge neutralized SL ?negative electrical charge in PEG molecule.
As shown in Figure 1, SL ?in PEG infrared spectrum, 3387cm
?1for hydroxyl stretching vibration absworption peak, 2875cm
?1for C in methyl, methylene ?the stretching vibration absworption peak of H, with respect to SL, absorb remarkable grow, 1612cm
?1, be lignin phenyl ring skeleton rocking vibration absworption peak, 1450cm
?1, 1350cm
?1for C in methyl, methylene ?the in-plane bending vibration absworption peak of H, 1110cm
?1for ehter bond C ?the stretching vibration absworption peak of O, with respect to SL, absorb remarkable grow, the 1216 phenolic hydroxyl group C of SL ?the stretching vibration peak of O disappear, there is the 950cm of PEG
?1, 835cm
?1absworption peak be respectively ehter bond C ?O stretching vibration peak, C ?the out-of-plane bending vibration peak of H.Infrared spectrum explanation PEG is successfully grafted on SL.SL ?PEG ?in CTAB infrared spectrum, 2850cm
?1for C in alkane ?H stretching vibration peak, with respect to SL ?PEO obviously strengthen, illustrate CTAB and SL ?PEG1000 be combined formed SL ?PEG1000 ?CTAB.
As shown in Figure 2, utilize Dynamic Light Scattering Determination embodiment 3 products and SL ?the particle diameter of PEO solution distribute, as can be seen from the figure the particle diameter of embodiment 3 products becomes bimodal distribution, little molecule peak is distributed in 10nm left and right, aggregation peak is distributed in 40nm left and right; SL ?the little molecule peak of PEO be distributed in 2nm left and right, but intensity is very little, little aggregation is distributed in 20nm left and right, large aggregation is distributed in 250nm left and right.The particle diameter of embodiment 3 products much smaller than SL ?PEO, and particle in solution, distribute more even, little molecule peak is stronger, narrow distribution.It is more even that this shows that embodiment 3 products distribute in solution, can be at the adsorption layer of gas/liquid interface formation densification, thus be conducive to reduce solution surface tension.
As shown in Figure 3 and Figure 4, embodiment 3 products and SL ?the AFM collection of illustrative plates of PEO.The Z axis height of embodiment 3 products is 2nm, granular size and distribute comparatively even, without obvious bulky grain, SL ?the Z axis height of PEO be 16nm, have bulky grain to exist, and skewness.Embodiment 3 products than SL ?PEO particle little and be evenly distributed, this with the particle diameter of Dynamic Light Scattering Determination distribute corresponding, further illustrate embodiment 3 products compared with SL ?PEO there is better performance.
As shown in Figure 5, embodiment 3 products, SL ?the critical aggregate concentration of PEO, CTAB be respectively 0.0058g/L, 0.015g/L, 0.3g/L.Can find out the more original two kinds of yin, yang ionic surface active agents of critical aggregate concentration all low of embodiment 3 products.During critical aggregate concentration, characterize material micro-variations, lower critical aggregate concentration illustrates that from microcosmic the transformation of structure can appear in embodiment 3 products under low concentration, and this has explained that from microcosmic embodiment 3 products have more low surface tension.The surface-active that simultaneously the shows compound cationic and anionic surfactant original two kinds of surfactants of comparing all have higher surface-active.
The raw material and the synthesis technique that due to other embodiment, adopt all have similar feature with embodiment 3, and after tested, the performance of other embodiment products obtained therefrom and embodiment 3 are also basically identical, therefore do not repeat one by one.
Claims (6)
1. a preparation method for lignin-base anion and cation high molecular surfactant, is characterized in that comprising the following steps and process conditions:
(1) polyethylene glycol is heated up melting, adds catalyst, after stirring, drips epoxychloropropane, after dropwising, at (40～60) ℃ reaction (1～2) h, obtains chloro polyethylene glycol intermediate;
(2) solution that is 30%～40% by lignosulfonates and water mixed preparing mass percent concentration, in (60～80) ℃, drip described chloro polyethylene glycol intermediate, ℃ reaction (2～4) h in 7 (0～90), pH to 12～13 of adjusting reactant liquor; PH to 6.0～8.0 that reaction finishes rear adjusting product, are cooled to room temperature; Obtain lignosulfonates polyoxyethylene ethereal solution, more spray-dried, make powdery lignosulfonates APEO;
(3) lignosulfonates APEO is mixed with to solution, then under agitation that lignosulfonates polyoxyethylene ethereal solution and quaternary ammonium salt cationic surfactant is compound according to mass ratio 10:1～10:5, make lignin-base anion and cation high molecular surfactant; The general formula of described quaternary ammonium salt cationic surfactant be [R ?N (R
1r
2r
3)] X-, in formula, R is C
10～C
22chain alkyl, R
l, R
2or R
3for methyl or ethyl, or R
l, R
2and R
3one of them is benzyl or chain alkyl; X is chlorine, bromine or iodine;
In mass fraction, the consumption of lignosulfonates, epoxychloropropane, polyethylene glycol, catalyst, quaternary ammonium salt cationic surfactant is respectively 100 parts, 10～30 parts, 50～200 parts, 1～3 part, 20～100 parts;
Described lignosulfonates are one or more in sodium lignin sulfonate, lignin sulfonic acid potassium, ammonium lignosulphonate, calcium lignosulfonate, magnesium lignosulfonate, Iron lignosulfonate, and its solids content mass fraction is 95%;
Described polyethylene glycol is that molecular weight is one or more in 200,400,600,1000,2000,4000;
Described catalyst is one or more in antimony pentafluoride, boron trifluoride etherate, aluminium chloride, butter of tin, Antimony pentachloride, TBAB;
In described step (1) and (2), adopt NaOH, KOH or H
2sO
4, HCl regulates pH value.
2. the preparation method of lignin-base anion and cation high molecular surfactant according to claim 1, is characterized in that: the temperature of described melting is (40～60) ℃.
3. the preparation method of lignin-base anion and cation high molecular surfactant according to claim 1, is characterized in that: described dropping epoxychloropropane is to dropwise in (30～60) min.
4. the preparation method of lignin-base anion and cation high molecular surfactant according to claim 1, is characterized in that: dripping described chloro polyethylene glycol intermediate is to dropwise in (1～2) h.
5. the preparation method of lignin-base anion and cation high molecular surfactant according to claim 1, is characterized in that: described lignosulfonates APEO is mixed with to solution is that lignosulfonates APEO is mixed with to mass percent concentration is 30% solution.
6. lignin-base anion and cation high molecular surfactant and preparation method thereof, is characterized in that, it is made by preparation method described in claim 1 ?5 any one.
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| EP3108940A1 (en) * | 2015-06-24 | 2016-12-28 | Procter & Gamble International Operations SA | Consumer goods product comprising functionalised lignin oligomer |
| CN106336296A (en) * | 2016-08-23 | 2017-01-18 | 安徽恒汇生态农业有限公司 | Water-retention and air-permeable slow release fertilizer special for bletilla striata |
| CN107129697A (en) * | 2017-05-11 | 2017-09-05 | 华南理工大学 | A kind of lignin with dual pH responses/inorganic oxide pickering emulsions and preparation method thereof |
| US9895445B2 (en) | 2015-06-24 | 2018-02-20 | The Procter & Gamble Company | Consumer goods product comprising functionalised lignin oligomer |
| US9901526B2 (en) | 2015-06-24 | 2018-02-27 | The Procter & Gamble Company | Consumer goods product comprising functionalised lignin oligomer |
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| US9907744B2 (en) | 2015-06-24 | 2018-03-06 | The Procter & Gamble Company | Consumer goods product comprising lignin oligomer |
| EP3108940A1 (en) * | 2015-06-24 | 2016-12-28 | Procter & Gamble International Operations SA | Consumer goods product comprising functionalised lignin oligomer |
| WO2016207811A1 (en) * | 2015-06-24 | 2016-12-29 | Procter & Gamble Inernational Operations Sa | Consumer goods product comprising functionalised lignin oligomer |
| US9895445B2 (en) | 2015-06-24 | 2018-02-20 | The Procter & Gamble Company | Consumer goods product comprising functionalised lignin oligomer |
| US9901526B2 (en) | 2015-06-24 | 2018-02-27 | The Procter & Gamble Company | Consumer goods product comprising functionalised lignin oligomer |
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| CN107129697A (en) * | 2017-05-11 | 2017-09-05 | 华南理工大学 | A kind of lignin with dual pH responses/inorganic oxide pickering emulsions and preparation method thereof |
| CN107827383A (en) * | 2017-09-22 | 2018-03-23 | 安徽省阜南绿原化工有限公司 | A kind of preparation method of the compound lignin sulfonate water reducer of zwitterion |
| CN108311058A (en) * | 2018-03-19 | 2018-07-24 | 青岛大学 | One kind anionic type Gemini surface active agent containing diphenyl propane and preparation method thereof |
| CN108892786A (en) * | 2018-06-04 | 2018-11-27 | 华南理工大学 | A kind of lignin/surfactant composite nanoparticle and preparation method thereof |
| CN108892786B (en) * | 2018-06-04 | 2020-09-22 | 华南理工大学 | Lignin/surfactant composite nano particle and preparation method thereof |
| CN109182308A (en) * | 2018-07-27 | 2019-01-11 | 华南理工大学 | A method of utilizing pH response type lignin-base polyethers recycled fiber element enzyme |
| CN109182308B (en) * | 2018-07-27 | 2020-12-22 | 华南理工大学 | Method for recovering cellulase by using pH response type lignin-based polyether |
| CN114524939A (en) * | 2022-02-21 | 2022-05-24 | 浙江理工大学绍兴柯桥研究院有限公司 | Preparation method and application of polyethylene glycol modified lignin azo dye dispersant |
| CN114806507B (en) * | 2022-06-06 | 2023-07-14 | 中国矿业大学(北京) | Environment-friendly dust suppressant and preparation method and application thereof |
| CN114806507A (en) * | 2022-06-06 | 2022-07-29 | 中国矿业大学(北京) | Environment-friendly dust suppressant and preparation method and application thereof |
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