CN111978552B - Amphiphilic polymer biosurfactant and preparation method and application thereof - Google Patents
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- 229920000642 polymer Polymers 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000003876 biosurfactant Substances 0.000 title claims abstract description 12
- 239000004094 surface-active agent Substances 0.000 claims abstract description 32
- 239000000839 emulsion Substances 0.000 claims abstract description 29
- 229920002678 cellulose Polymers 0.000 claims abstract description 28
- 239000001913 cellulose Substances 0.000 claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 229920002689 polyvinyl acetate Polymers 0.000 claims abstract description 11
- 239000011118 polyvinyl acetate Substances 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 9
- 230000008569 process Effects 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 claims description 10
- 239000004354 Hydroxyethyl cellulose Substances 0.000 claims description 10
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 claims description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 229920001577 copolymer Polymers 0.000 claims description 9
- 235000019441 ethanol Nutrition 0.000 claims description 9
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 9
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical group C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 8
- 238000001291 vacuum drying Methods 0.000 claims description 8
- -1 polyethylene Polymers 0.000 claims description 7
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical group CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 239000004698 Polyethylene Substances 0.000 claims description 6
- 229920000573 polyethylene Polymers 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 239000002202 Polyethylene glycol Substances 0.000 claims description 5
- 229920001223 polyethylene glycol Polymers 0.000 claims description 5
- 238000006277 sulfonation reaction Methods 0.000 claims description 5
- 239000012024 dehydrating agents Substances 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 239000013067 intermediate product Substances 0.000 claims description 4
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 4
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 239000013078 crystal Substances 0.000 claims description 3
- 239000005457 ice water Substances 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 230000001376 precipitating effect Effects 0.000 claims description 3
- 238000002390 rotary evaporation Methods 0.000 claims description 3
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 2
- 238000000967 suction filtration Methods 0.000 claims description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 abstract description 7
- 239000000853 adhesive Substances 0.000 abstract description 6
- 230000001070 adhesive effect Effects 0.000 abstract description 6
- 239000000693 micelle Substances 0.000 abstract description 5
- 230000004048 modification Effects 0.000 abstract description 3
- 238000012986 modification Methods 0.000 abstract description 3
- 239000002023 wood Substances 0.000 abstract description 3
- 235000003301 Ceiba pentandra Nutrition 0.000 abstract description 2
- 244000146553 Ceiba pentandra Species 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 230000000694 effects Effects 0.000 description 7
- 239000000523 sample Substances 0.000 description 5
- 238000007792 addition Methods 0.000 description 4
- 229920001427 mPEG Polymers 0.000 description 3
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 230000001804 emulsifying effect Effects 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000004816 latex Substances 0.000 description 2
- 229920000126 latex Polymers 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000007142 ring opening reaction Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 230000009471 action Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 229920013724 bio-based polymer Polymers 0.000 description 1
- 239000012496 blank sample Substances 0.000 description 1
- 229920003174 cellulose-based polymer Polymers 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 238000000703 high-speed centrifugation Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- PSGAAPLEWMOORI-PEINSRQWSA-N medroxyprogesterone acetate Chemical compound C([C@@]12C)CC(=O)C=C1[C@@H](C)C[C@@H]1[C@@H]2CC[C@]2(C)[C@@](OC(C)=O)(C(C)=O)CC[C@H]21 PSGAAPLEWMOORI-PEINSRQWSA-N 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 1
- 238000005063 solubilization Methods 0.000 description 1
- 230000007928 solubilization Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 239000000375 suspending agent Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B3/00—Preparation of cellulose esters of organic acids
- C08B3/12—Preparation of cellulose esters of organic acids of polybasic organic acids
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
Abstract
The scheme relates to an amphiphilic polymer biosurfactant, a preparation method and application thereof. The cellulose adopted by the scheme is derived from wood or kapok, the raw material is easy to obtain, the modification process is simple, and the cost performance is high; the cellulose-based amphiphilic polymer surfactant prepared by the invention has lower critical micelle concentration and surface tension; the modified cellulose surfactant participates in emulsion polymerization of polyvinyl acetate, so that good stability is provided for the emulsion, the emulsion conversion rate is improved, and the adhesive force and strength of the emulsion are improved; the modified cellulose can be used as a novel biosurfactant and meets the requirement of green chemistry.
Description
Technical Field
The invention relates to the field of emulsion surfactants, in particular to an amphiphilic polymer biosurfactant and a preparation method and application thereof.
Background
Conventional emulsions with a large oil/water interface are thermodynamically extremely unstable systems, and the addition of surfactants can effectively reduce surface tension and promote long-term stability of the emulsion. However, in conventional emulsion polymerization, the presence of small molecule surfactants can affect the properties of the polymer. Compared with the traditional surfactant, the macromolecular surfactant has excellent dispersibility, O/W emulsion stability, salt resistance and anti-deposition effect because the hydrophobic side chain of the macromolecular surfactant is associated in water to form a hydrophobic group, but the capacity of the macromolecular surfactant for reducing the surface tension is generally lower, and the surface activity is not obvious.
Polyvinyl acetate (PVAc) latex is widely used in various aspects of wood processing, construction, furniture, textile, paper making, and daily life. PVAc latex is typically prepared by conventional emulsion or suspension polymerization, and the nature of the emulsifying or suspending agent often affects its performance in use, e.g., modeling, adhesion, water resistance, etc. And with the enhancement of the environmental awareness of people, the use of green chemicals is more and more emphasized. Therefore, the preparation of bio-based polymer surfactants with high surface activity is a problem to be solved.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to modify natural macromolecular compound cellulose as a carrier to prepare a biological-based surfactant with high surface activity, and the biological-based surfactant acts in polyvinyl acetate emulsion to improve the adhesive force and strength of the emulsion.
In order to achieve the purpose, the invention provides the following technical scheme:
a preparation method of an amphiphilic polymer biosurfactant comprises the following steps:
s1: adding polyethylene glycol (mPEG) and fluorocaprolactone into a reaction bottle, adding stannous octoate, vacuumizing, and reacting for 24 hours in a constant-temperature oil bath at 140 ℃; cooling, adding dichloromethane for dissolving, dripping the solution into cold anhydrous ether, precipitating, filtering, and vacuum drying to obtain polyethylene glycol-caprolactone copolymer (PEG-PCL);
s2: adding hydroxyethyl cellulose (HEC) into a reaction bottle, adding 90% ethanol/water solution, adding sodium hydroxide, performing constant-temperature water bath at 45 ℃, then slowly dropwise adding ethanol solution of maleic anhydride, continuing to react for 2 hours after dropwise adding, adjusting the pH to be neutral by using hydrochloric acid solution, then centrifuging twice at high speed by using absolute ethanol, and performing vacuum drying to obtain hydroxyethyl cellulose maleate;
s3: adding the hydroxyethyl cellulose maleate into a reaction bottle, adding sodium sulfite sodium hydrogen solution, dropwise adding a catalyst cetyl trimethyl ammonium bromide to perform sulfonation reaction, removing the solvent through rotary evaporation, and drying to obtain an intermediate product;
s4: dissolving the polyethylene glycol-caprolactone copolymer into DMF, adding a dehydrating agent, carrying out nitrogen protection, adding the intermediate product, stirring at a low speed, then dropwise adding a DMF solution dissolved with a catalyst, stirring at a normal temperature for reacting for 48 hours, extracting with ethyl acetate, crystallizing an extract in ice water, washing the crystal with glacial ethanol, carrying out suction filtration, and carrying out vacuum drying to obtain the cellulose-based amphiphilic polymer surfactant.
Preferably, in the preparation method, the molar ratio of the polyethylene glycol to the fluorocaprolactone is 1: 50.
Preferably, in the preparation method, the catalyst is 4-Dimethylaminopyridine (DMAP).
Preferably, in the preparation method, the mass ratio of the maleic anhydride to the cellulose is 1: 5.
Preferably, in the preparation method, the temperature of the sulfonation reaction is 80 ℃, and the reaction time is 2 h.
Preferably, in the preparation method, the dehydrating agent is N, N' -Dicyclohexylcarbodiimide (DCC).
The amphiphilic polymer biosurfactant prepared by the preparation method is provided.
The application of the amphiphilic polymer biosurfactant prepared by the preparation method is preferably used as a surfactant in polyvinyl acetate emulsion.
The macromolecular surfactant consists of two parts of hydrophilic and lipophilic groups, the mPEG ring-opening fluorocaprolactone generates amphiphilic degradable copolymer PEG-PCL, and m in the formula is the number of the repeating units of the PCL, preferably 40-60. The invention selects water-soluble hydroxyethyl cellulose as a carrier, and utilizes the amphiphilic copolymer to graft and modify the carrier. The method comprises the following steps of carrying out ring-opening reaction on maleic anhydride and cellulose under the action of a catalyst, introducing double bonds and carboxyl, carrying out esterification reaction on the carboxyl and hydroxyl at the tail end of PEG-PCL, grafting an amphiphilic polymer chain onto the surface of the cellulose, and carrying out sulfonation reaction on the double bonds to generate sulfonate, thereby preparing the cellulose-based amphiphilic polymer surfactant.
The grafted and modified cellulose is used as a surfactant and added into a polymerization solution of vinyl acetate, acts on an interface layer between emulsion droplets and a water phase, and forms a nucleophilic protective layer around thick liquid droplets, which is favorable for the stability of the emulsion, and the viscosity of the polymer emulsion is increased by the high-molecular-weight long-chain copolymer.
By the scheme, the invention at least has the following advantages: the cellulose adopted by the scheme is derived from wood or kapok, the raw material is easy to obtain, the modification process is simple, and the cost performance is high; the cellulose-based amphiphilic polymer surfactant prepared by the invention has lower critical micelle concentration and surface tension; the modified cellulose surfactant participates in emulsion polymerization of polyvinyl acetate, so that good stability is provided for the emulsion, the emulsion conversion rate is improved, and the adhesive force and strength of the emulsion are improved; the grafted modified cellulose can be used as a novel biosurfactant and meets the requirement of green chemistry.
Detailed Description
The technical solutions in the embodiments of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1:
adding 5g of HEC into a reaction bottle, adding 90% ethanol/water solution to prepare 20% wt solution, adding sodium hydroxide to adjust the pH value to be alkaline, carrying out constant-temperature water bath at 45 ℃, then slowly dropwise adding ethanol solution containing 1g of maleic anhydride, continuing to react for 2h after dropwise adding, adjusting the pH value to be neutral by using hydrochloric acid solution, then carrying out high-speed centrifugation twice by using absolute ethyl alcohol, and carrying out vacuum drying; and adding the dried product into a reaction bottle, adding sodium bisulfite solution, dropwise adding a catalyst of cetyl trimethyl ammonium bromide, reacting for 2 hours at 80 ℃, removing the solvent through rotary evaporation, and drying to obtain the maleic anhydride modified cellulose surfactant.
Example 2:
adding 0.8g of polyethylene glycol (mPEG) and 2.64g of fluorocaprolactone into a reaction bottle, adding stannous octoate, vacuumizing, and reacting in a constant-temperature oil bath at 140 ℃ for 24 hours; cooling, adding dichloromethane to dissolve, dripping the solution into cold anhydrous ether, precipitating, filtering, and vacuum drying to obtain polyethylene glycol-caprolactone copolymer (PEG-PCL).
Dissolving polyethylene glycol-caprolactone copolymer into DMF, adding DCC (dimethyl dichloroisocyanurate), protecting with nitrogen, adding maleic anhydride modified cellulose surfactant with equal mass, stirring at low speed, then dropwise adding DMF solution dissolved with DMPA, stirring at normal temperature for reaction for 48h, extracting with ethyl acetate, crystallizing the extract in ice water, washing the crystal with glacial ethanol, filtering, and drying in vacuum to obtain the cellulose-based amphiphilic polymer surfactant.
The modified cellulose surfactant participates in the emulsion polymerization of vinyl acetate, the surface performance can be improved, and the preparation method of the emulsion can refer to the following steps:
the PVAc emulsion with general purpose can be obtained by emulsion polymerization of the formula at 70 ℃.
Example 3: PVAc emulsion was prepared as a blank according to the preparation method described above.
Example 4: an emulsion was prepared as test sample 1 by the above preparation method, formulation and addition of 1 part of maleic anhydride-modified cellulose surfactant (example 1).
Example 5: an emulsion was prepared as test sample 2 by adding 1 part of PEG-PCL graft modified cellulose surfactant (example 2) to the formulation according to the above preparation method.
The lower the Critical Micelle Concentration (CMC), i.e. the lowest concentration of surfactant molecules that associate in a solvent to form micelles, indicates that the lower the concentration of such an active agent required to form micelles, the lower the concentration to reach surface saturation adsorption, and thus the lower the concentration required to modify the surface properties to effect wetting, emulsification, solubilization, foaming, etc. The data in table 1 show that the minimum surface tension value of HEC under CMC concentration condition is 54.21mN/m, the minimum surface tension of cellulose modified by small molecular maleic anhydride is 46.62mN/m, which indicates that modifying fiber can improve its ability to reduce water surface tension, and on this basis, long chain of amphiphilic polymer is introduced, the obtained cellulose-based amphiphilic surfactant can reduce water surface tension to 36.73mN/m, the corresponding CMC value is 0.71g/L, i.e. the required surfactant concentration is small, and the ability to reduce water surface tension is large, thus having good surface performance.
TABLE 1
The addition of the surfactant in the emulsion polymerization can play a role in improving the performance of the emulsion, and the hydrophilic, lipophilic and amphiphilic chain segment is grafted on the cellulose, so that the good surface activity is maintained, and the cellulose has better performances of thickening, emulsifying, dispersing and the like. As can be seen from the data in Table 2, the conversion rate and the solid content of the emulsion are both increased, and various physical properties of the emulsion of the test sample are obviously improved, which indicates that the addition of the graft modified cellulose has better surface activity; meanwhile, the viscosity and the bonding strength of the emulsion are increased, because the cellulose-based polymer surfactant has longer hydrophilic-lipophilic amphiphilic chain segments, the adhesive force is stronger, and the adhesive force and the strength of the polyvinyl acetate emulsion are improved to a certain extent.
TABLE 2
| Performance of | Blank sample | Test sample 1 | Test sample 2 |
| Solids content/% | 40 | 41 | 45 |
| Conversion of emulsion/% | 87 | 89 | 95 |
| pH | 6-7 | 6-7 | 6-7 |
| viscosity/mPas | 450 | 520 | 630 |
| Adhesive strength/MPa | 1.53 | 2.35 | 3.21 |
While the invention has been described above with reference to an embodiment, various modifications may be made and equivalents may be substituted for elements thereof without departing from the scope of the invention. In particular, the various features of the embodiments disclosed herein may be used in any combination, provided that there is no structural conflict, and the combinations are not exhaustively described in this specification merely for the sake of brevity and conservation of resources. Therefore, it is intended that the invention not be limited to the particular embodiments disclosed, but that the invention will include all embodiments falling within the scope of the appended claims.
Claims (8)
1. A preparation method of an amphiphilic polymer biosurfactant is characterized by comprising the following steps:
s1: adding polyethylene glycol and fluorocaprolactone into a reaction bottle, adding stannous octoate, vacuumizing, and reacting for 24 hours in a constant-temperature oil bath at 140 ℃; cooling, adding dichloromethane for dissolving, dripping the solution into cold anhydrous ether, precipitating, filtering, and vacuum drying to obtain polyethylene glycol-caprolactone copolymer;
s2: adding 90% ethanol/water solution into hydroxyethyl cellulose in a reaction bottle, adding sodium hydroxide, performing constant-temperature water bath at 45 ℃, then slowly dropwise adding ethanol solution of maleic anhydride, continuing to react for 2 hours after dropwise adding, adjusting the pH to be neutral by using hydrochloric acid solution, then centrifuging twice at high speed by using absolute ethyl alcohol, and performing vacuum drying to obtain hydroxyethyl cellulose maleate;
s3: adding the hydroxyethyl cellulose maleate into a reaction bottle, adding a sodium bisulfite solution, dropwise adding a catalyst of cetyl trimethyl ammonium bromide to carry out sulfonation reaction, removing the solvent through rotary evaporation, and drying to obtain an intermediate product;
s4: dissolving the polyethylene glycol-caprolactone copolymer into DMF, adding a dehydrating agent, carrying out nitrogen protection, adding the intermediate product, stirring at a low speed, then dropwise adding a DMF solution dissolved with a catalyst, stirring at a normal temperature for reacting for 48 hours, extracting with ethyl acetate, crystallizing an extract in ice water, washing the crystal with glacial ethanol, carrying out suction filtration, and carrying out vacuum drying to obtain the cellulose-based amphiphilic polymer surfactant.
2. The method according to claim 1, wherein the molar ratio of the polyethylene glycol to the fluorocaprolactone is 1: 50.
3. The method according to claim 1, wherein the mass ratio of the maleic anhydride to the cellulose is 1: 5.
4. The method according to claim 1, wherein the sulfonation reaction is carried out at a temperature of 80 ℃ for a reaction time of 2 hours.
5. The method of claim 1, wherein the catalyst is 4-dimethylaminopyridine.
6. The method according to claim 1, wherein the dehydrating agent is N, N' -dicyclohexylcarbodiimide.
7. An amphiphilic polymer biosurfactant prepared by the preparation method of any one of claims 1-6.
8. Use of an amphiphilic polymeric biosurfactant prepared by the process of any one of claims 1 to 6 as a surfactant in a polyvinyl acetate emulsion.
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| CN105061688A (en) * | 2015-08-20 | 2015-11-18 | 四川理工学院 | Synthetic method for amphiphilic polyethylene glycol (PEG)-polycyclic lactone copolymer including multiple bromine functional groups and thermo-sensitive polymer preparing method |
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| CN105061688A (en) * | 2015-08-20 | 2015-11-18 | 四川理工学院 | Synthetic method for amphiphilic polyethylene glycol (PEG)-polycyclic lactone copolymer including multiple bromine functional groups and thermo-sensitive polymer preparing method |
Non-Patent Citations (2)
| Title |
|---|
| Compatibilization of co-plasticized cellulose acetate/water soluble polymers blends by reactive extrusion;Robert Quintana等;《Polymer Degradation and Stability》;20161231;第126卷;31-38 * |
| Enhancement of catechin skin permeation via a newly fabricated mPEG-PCL-graft-2-hydroxycellulose membrane;Chao-Hsuan Chen等;《Journal of Membrane Science》;20111231;第371卷;134-140 * |
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