CN115926006B - PH sensitive emulsifier and preparation method thereof - Google Patents
PH sensitive emulsifier and preparation method thereof Download PDFInfo
- Publication number
- CN115926006B CN115926006B CN202211672482.6A CN202211672482A CN115926006B CN 115926006 B CN115926006 B CN 115926006B CN 202211672482 A CN202211672482 A CN 202211672482A CN 115926006 B CN115926006 B CN 115926006B
- Authority
- CN
- China
- Prior art keywords
- emulsion
- hours
- emulsifier
- carboxymethyl cellulose
- weighed
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000003995 emulsifying agent Substances 0.000 title claims abstract description 71
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims abstract description 105
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims abstract description 72
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- -1 carboxyl polysaccharide Chemical class 0.000 claims abstract description 26
- 229920001282 polysaccharide Polymers 0.000 claims abstract description 19
- 239000005017 polysaccharide Substances 0.000 claims abstract description 18
- 150000008282 halocarbons Chemical class 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 238000005886 esterification reaction Methods 0.000 claims abstract description 8
- 150000004676 glycans Chemical class 0.000 claims abstract 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 73
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 72
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 72
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 72
- 238000006467 substitution reaction Methods 0.000 claims description 54
- 238000001816 cooling Methods 0.000 claims description 31
- 235000010413 sodium alginate Nutrition 0.000 claims description 23
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 22
- 239000000661 sodium alginate Substances 0.000 claims description 22
- 229940005550 sodium alginate Drugs 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 15
- VMKOFRJSULQZRM-UHFFFAOYSA-N 1-bromooctane Chemical compound CCCCCCCCBr VMKOFRJSULQZRM-UHFFFAOYSA-N 0.000 claims description 12
- MPPPKRYCTPRNTB-UHFFFAOYSA-N 1-bromobutane Chemical compound CCCCBr MPPPKRYCTPRNTB-UHFFFAOYSA-N 0.000 claims description 11
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 claims description 10
- 229940073608 benzyl chloride Drugs 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 2
- 230000001376 precipitating effect Effects 0.000 claims 1
- 239000000839 emulsion Substances 0.000 abstract description 136
- 230000001804 emulsifying effect Effects 0.000 abstract description 42
- 238000004945 emulsification Methods 0.000 abstract description 8
- 230000004044 response Effects 0.000 abstract description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 3
- 230000035945 sensitivity Effects 0.000 abstract description 3
- 230000008859 change Effects 0.000 abstract description 2
- 230000002209 hydrophobic effect Effects 0.000 abstract description 2
- 239000002245 particle Substances 0.000 abstract description 2
- 239000004094 surface-active agent Substances 0.000 abstract description 2
- 230000008901 benefit Effects 0.000 abstract 2
- 239000003054 catalyst Substances 0.000 abstract 1
- 230000035484 reaction time Effects 0.000 abstract 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 60
- 239000002904 solvent Substances 0.000 description 52
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 33
- 238000010438 heat treatment Methods 0.000 description 32
- 229940057995 liquid paraffin Drugs 0.000 description 30
- 150000002148 esters Chemical class 0.000 description 22
- 125000001165 hydrophobic group Chemical group 0.000 description 18
- 238000001556 precipitation Methods 0.000 description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 4
- 229920002678 cellulose Polymers 0.000 description 4
- 239000001913 cellulose Substances 0.000 description 4
- 125000004185 ester group Chemical group 0.000 description 4
- 238000002329 infrared spectrum Methods 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 229920003144 amino alkyl methacrylate copolymer Polymers 0.000 description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000002159 nanocrystal Substances 0.000 description 3
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 3
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- VUQPJRPDRDVQMN-UHFFFAOYSA-N 1-chlorooctadecane Chemical compound CCCCCCCCCCCCCCCCCCCl VUQPJRPDRDVQMN-UHFFFAOYSA-N 0.000 description 2
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- VFEVXBKBGMAKME-UHFFFAOYSA-N butane;hydrobromide Chemical compound Br.CCCC VFEVXBKBGMAKME-UHFFFAOYSA-N 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 2
- 150000004804 polysaccharides Chemical class 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 230000008719 thickening Effects 0.000 description 2
- YAYNEUUHHLGGAH-UHFFFAOYSA-N 1-chlorododecane Chemical compound CCCCCCCCCCCCCl YAYNEUUHHLGGAH-UHFFFAOYSA-N 0.000 description 1
- 241000220479 Acacia Species 0.000 description 1
- 102000009027 Albumins Human genes 0.000 description 1
- 108010088751 Albumins Proteins 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- 235000010643 Leucaena leucocephala Nutrition 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 229920002873 Polyethylenimine Polymers 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- AWUXTOKKDIWYEK-UHFFFAOYSA-N dodecane;hydrochloride Chemical compound Cl.CCCCCCCCCCCC AWUXTOKKDIWYEK-UHFFFAOYSA-N 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 125000001302 tertiary amino group Chemical group 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change
Landscapes
- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
The invention discloses a novel emulsifier with pH sensitivity, and belongs to the technical field of emulsifier preparation. The invention utilizes esterification reaction of carboxyl polysaccharide and halogenated hydrocarbon to synthesize a novel emulsifier, and uses triethylamine as a catalyst to introduce a hydrophobic long carbon chain into dimethyl sulfoxide, and prepares the pH sensitive emulsifier under the conditions of a certain reaction temperature and a certain reaction time. Compared with the conventional emulsifier, the emulsifier provided by the invention has the advantages of wider raw materials, cost saving and economy, low particle concentration, low surfactant concentration and better benefit. Readjusting the pH after breaking the emulsion can be repeated for emulsification with an emulsifier. The pH response type polysaccharide emulsifier can be demulsified as required by adjusting the pH so as to change the emulsifying property, and has wide prospect in preparing the stimulus response type emulsifier.
Description
Technical Field
The invention belongs to the technical field of preparation of emulsifying agents, and particularly relates to a pH sensitive emulsifying agent and a preparation method thereof.
Background
The emulsifying agent is capable of forming uniform and stable emulsion of mutually insoluble liquid, and can reduce the surface tension of the solution, so that the mutually insoluble liquid can be emulsified. The molecules used as emulsifiers generally contain hydrophilic and lipophilic groups that allow the emulsifier to aggregate at the oil/water interface. Emulsifiers can be classified into two major classes, water-in-oil (W/O type) and oil-in-water (O/W type).
Common polysaccharide emulsifying agents include acacia, gelatin, albumin, sucrose monoesters, sorbitol derivatives and the like, are widely applied to the industries of medical treatment, daily chemicals, food and the like, are widely renewable in source, are environment-friendly, and are green and pollution-free. Carboxymethyl cellulose and sodium alginate can also be used as polysaccharide emulsifiers, wherein the carboxymethyl cellulose (CMC) is obtained by carboxymethyl cellulose, is the cellulose type with the widest application range and the largest dosage, and is mainly used for thickening, gluing and the like. Sodium alginate mainly comprises sodium salt of alginic acid, and is mainly used for thickening, stabilizing, gelling and the like. The carboxymethyl cellulose and the sodium alginate have emulsifying property, and the application range of the carboxymethyl cellulose and the sodium alginate can be enlarged by increasing the emulsifying capacity of the carboxymethyl cellulose and the sodium alginate.
The use of emulsifiers is very important both in living and in industry. For example: emulsifying agents are required to form stable emulsion for food preparation, drug synthesis and industrial reactions; on the other hand, some emulsions need to be stable and then quickly broken to meet the needs of the production application. Aiming at the production and living needs, stimulus response type emulsion exists at present, and the stimulus conditions such as pH, temperature, light and the like in the environment can be reacted to break the emulsion, so that the effect of stable emulsification and rapid breaking of the emulsion is achieved. Stimulus-responsive emulsions require that the emulsifier respond to stimulus factors by changing hydrophilic or hydrophobic groups so that the entire emulsion system changes and breaks.
At present, the pH sensitive emulsifier mainly has two modes: the first method uses different emulsifiers for compounding, such as Chen Xiaoqi (Chen Xiaoqi, zhou Mengmeng, xing Liangchen, etc. preparation and application of pH sensitive aminoalkyl methacrylate copolymer emulsion, engineering plastics application. 47,41-45 (2019)), etc. to prepare pH sensitive cationic aminoalkyl methacrylate copolymer emulsion, wherein Dimethylaminoethyl Methacrylate (DM), methyl Methacrylate (MMA) and Butyl Methacrylate (BMA) are used as main monomers, cationic and nonionic emulsifiers are used as a composite emulsifier system, and potassium persulfate is used as an initiator to prepare aminoalkyl methacrylate copolymer emulsion containing tertiary amino groups. The prepared emulsion has a pH response mechanism, but the preparation process is complex, excessive raw materials are involved, the cost is high, and the application range is limited. The second is to modify the molecular structure so as to achieve the pH sensitive emulsification effect, benzyl polyethyleneimine modified cellulose nanocrystals (Ben-PEI-CNCs) are prepared in the year 2020 Li Weixue (Weixue Li,BenzhiJu,Shufen Zhang.Novel amphiphilic cellulose nanocrystals for pH-responsive Pickering emulsions.[J].Carbohydrate Polymers,229,115401(2020).), which is an amphiphilic cellulose nanocrystal emulsifier of pH responsive Pickering emulsion, and the structure is provided with hydrophilic amino and hydrophobic benzyl, so that the Ben-PEI-CNCs have pH responsive amphipathy, but the process for preparing the Ben-PEI-CNCs is complex and the operation is more.
Disclosure of Invention
Since most of the raw materials of the pH sensitive emulsifier are not renewable at present, even if renewable raw materials are not industrialized, although carboxymethyl cellulose and sodium alginate have certain emulsifying property, the emulsifying property is not high, and higher concentration is needed to obtain better emulsifying property. The invention provides a preparation method of a pH sensitive emulsifier, which adopts carboxyl polysaccharide and halogenated hydrocarbon as raw materials, has mild reaction conditions in the preparation process, stable product quality and pH sensitivity, improves and enhances the existing emulsifying property of the raw materials, and can achieve good emulsifying property under the condition of low mass concentration.
The technical scheme of the invention is as follows:
a pH sensitive emulsifier having the chemical structural formula of formula (I) or formula (II):
wherein R is-CH 2 COONa, -CH 2COO(CH2)3CH3 or-CH 2COO(CH2)7CH3
Wherein R 1 is Na,- (CH 2)3CH3 or- (CH) 2)7CH3
The preparation method of the pH sensitive emulsifier is synthesized by using carboxyl polysaccharide and halogenated hydrocarbon as raw materials through esterification reaction, and comprises the following steps:
and (3) dispersing the carboxyl polysaccharide in dimethyl sulfoxide (DMSO) and continuously heating and stirring to obtain a solution A.
Step (2), mixing halogenated hydrocarbon and triethylamine according to a proportion to obtain a mixture B.
Step (3) and step (2) are gradually added into the solution A obtained in step (1), the reaction is carried out for 3 to 8 hours at the temperature of 70 to 140 ℃, and after the reaction is finished, the mixture is cooled, separated out, washed and dried, thus obtaining the pH sensitive emulsifier.
Further, in the step (1), the mass ratio of dimethyl sulfoxide to carboxyl polysaccharide is 5:1-15:1, wherein the carboxyl polysaccharide is one or more than two of carboxymethyl cellulose with 0.7 degree of substitution, carboxymethyl cellulose with 1.2 degree of substitution and sodium alginate.
Further, the molar ratio of the halogenated hydrocarbon in the step (2) to the carboxyl polysaccharide in the step (1) is 0.1:1-0.7:1, wherein the halogenated hydrocarbon is one or more of benzyl chloride, bromo-n-butane, bromo-n-octane, chloro-n-dodecane and chloro-n-octadecane.
Further, the mass ratio of triethylamine in step (2) to carboxypolysaccharide in step (1) is 0.01:1 to 0.07:1.
The beneficial results of the invention are:
1. The invention utilizes the sodium carboxylate (-COO -Na+) in carboxyl polysaccharide to gradually change carboxyl into-COOH to be separated out in water under the acidic condition, thereby reducing the surface activity and the emulsifying capacity and realizing demulsification. This feature is used to prepare emulsifiers with greater emulsifying capacity and pH sensitivity.
2. The pH sensitive emulsifier is prepared by carboxyl polysaccharide, wherein the carboxyl polysaccharide has wide and renewable raw material sources, the reaction process is simple to operate, and good surfactant can be obtained, and after a certain amount of hydrophobic groups are grafted, the emulsion volume fraction is more than 70% even after 24 hours under the condition of low-concentration mass concentration.
3. The pH sensitive emulsifier prepared by the invention has pH stimulus response capability, and can automatically break emulsion when the pH of the emulsion is regulated to be acidic.
Drawings
FIG. 1 is a hydrogen nuclear magnetic resonance spectrum of the modified carboxymethyl cellulose of example 1;
FIG. 2 is a carbon nuclear magnetic spectrum of the modified carboxymethyl cellulose of example 1;
FIG. 3 is an infrared spectrum of crude carboxymethyl cellulose and prepared examples 1, 5, 9 modified carboxymethyl cellulose;
FIG. 4 is a hydrogen nuclear magnetic resonance spectrum of the modified carboxymethyl cellulose of example 4;
FIG. 5 is a hydrogen nuclear magnetic resonance spectrum of the modified carboxymethyl cellulose of example 7;
FIG. 6 is an emulsion-break-re-emulsion diagram of modified carboxymethyl cellulose of example 15;
FIG. 7 is a graph of the emulsion and re-emulsion particle size of modified carboxymethyl cellulose of example 15.
Detailed Description
The following describes the embodiments of the present invention further with reference to the drawings and technical schemes.
Example 1:
5g of carboxymethyl cellulose with the substitution degree of 1.2 is weighed, dispersed in 25g of DMSO and stirred, 0.736g of benzyl chloride and 0.05g of triethylamine are weighed, mixed and added into a solvent, the solvent is heated to 70 ℃ for reaction for 3 hours, heating is stopped, and industrial ethanol is used for precipitation, drying, washing and crushing after cooling, so that the modified carboxymethyl cellulose ester is obtained, wherein the substitution degree of a hydrophobe is 0.077. The resulting product was dissolved as a 0.1wt% solution in mass concentration and liquid paraffin at 4:6 volume ratio the emulsion was emulsified for 1min at 10000rpm in a FA25 high speed emulsifier, after which the emulsion was kept at 25 ℃ for 24 hours with a volume fraction of 72%.
This example gives an emulsion which is rapidly broken by adjusting the ph=3 after standing for 24 hours. The layered emulsion was then separated by aspiration with a pipette. The bottom solution was adjusted to ph=7, emulsified again at an oil to water ratio of 6:4, and after 24 hours still had an emulsifying effect.
The hydrogen nuclear magnetic spectrum of the modified carboxymethyl cellulose ester prepared in the example is shown in figure 1, wherein 5.1-5.3ppm is the chemical shift of proton at the C1 position of glucose unit; 7.3-7.4ppm is chemical shift of benzene ring in benzyl. This demonstrates the success of the reaction to graft the hydrophobic group benzyl.
The carbon nuclear magnetic resonance chart of the modified carboxymethyl cellulose prepared in this example is shown in fig. 2, and the split peak appears at about 178ppm because the esterification reaction occurs, and the split peak is formed by the ester group and the original carboxyl group, thereby proving that the esterification reaction occurs.
FIG. 3 is an infrared spectrum of crude carboxymethyl cellulose and modified carboxymethyl cellulose produced. As can be seen from the graph, the absorption peak at about 1740cm -1 was a stretching vibration peak of the ester group, and it was also confirmed that the esterification reaction occurred. From this we can demonstrate successful grafting of hydrophobic groups to obtain modified carboxymethyl cellulose esters, i.e. pH sensitive emulsifiers.
Example 2:
5g of carboxymethyl cellulose with the substitution degree of 1.2 is weighed, dispersed in 25g of DMSO and stirred, 1.267g of benzyl chloride and 0.05g of triethylamine are weighed, mixed and added into a solvent, the solvent is heated to 70 ℃ for reaction for 3 hours, heating is stopped, and industrial ethanol is used for precipitation, drying, washing and crushing after cooling, so that the modified carboxymethyl cellulose ester with the substitution degree of hydrophobe of 0.098 is obtained. The resulting product was dissolved as a 0.1wt% solution in mass concentration and liquid paraffin at 4:6 volume ratio the emulsion was emulsified for 1min at 10000rpm in a FA25 high speed emulsifier, after which the emulsion was 76% by volume after 24 hours of standing at 25 ℃.
This example gives an emulsion which is rapidly broken by adjusting the ph=3 after standing for 24 hours. The layered emulsion was then separated by aspiration with a pipette. The bottom solution was adjusted to ph=7, emulsified again at an oil to water ratio of 6:4, and after 24 hours still had an emulsifying effect.
Example 3:
5g of carboxymethyl cellulose with the substitution degree of 1.2 is weighed, dispersed in 25g of DMSO and stirred, 1.717g of benzyl chloride and 0.05g of triethylamine are weighed, mixed and added into a solvent, the solvent is heated to 70 ℃ for reaction for 3 hours, heating is stopped, and industrial ethanol is used for precipitation, drying, washing and crushing after cooling, so that the modified carboxymethyl cellulose ester with the substitution degree of the hydrophobe of 0.110 is obtained. The resulting product was dissolved as a 0.1wt% solution in mass concentration and liquid paraffin at 4:6 volume ratio the emulsion was emulsified for 1min at 10000rpm in a FA25 high speed emulsifier, after which the emulsion was kept at 25 ℃ for 24 hours with a volume fraction of 81%.
This example gives an emulsion which is rapidly broken by adjusting the ph=3 after standing for 24 hours. The layered emulsion was then separated by aspiration with a pipette. The bottom solution was adjusted to ph=7, emulsified again at an oil to water ratio of 6:4, and after 24 hours still had an emulsifying effect.
Example 4:
5g of carboxymethyl cellulose with the substitution degree of 1.2 is weighed, dispersed in 50g of DMSO and stirred, 0.797g of bromo-n-butane and 0.25g of triethylamine are weighed, mixed and added into a solvent, the mixture is heated to 90 ℃ to react for 5 hours, then the heating is stopped, and after cooling, the mixture is separated out by using industrial ethanol, dried, washed and crushed, so as to obtain the modified carboxymethyl cellulose with the substitution degree of hydrophobe of 0.073. The resulting product was dissolved as a 0.1wt% solution in mass concentration and liquid paraffin at 4:6 volume ratio the emulsion was emulsified for 1min at 10000rpm in a FA25 high speed emulsifier, after which the emulsion was 73% by volume after standing at 25 ℃ for 24 hours.
This example gives an emulsion which is rapidly broken by adjusting the ph=3 after standing for 24 hours. The layered emulsion was then separated by aspiration with a pipette. The bottom solution was adjusted to ph=7, emulsified again at an oil to water ratio of 6:4, and after 24 hours still had an emulsifying effect.
The hydrogen nuclear magnetic spectrum of the modified carboxymethyl cellulose ester prepared in the example is shown in figure 4, wherein 5.2-5.8ppm is the chemical shift of proton at the C1 position of glucose unit; about 1.60ppm, 1.31ppm and 0.86ppm are chemical shifts of protons on methylene and methyl adjacent to the terminal in butyl, thereby proving that the reaction introduces a butyl group.
FIG. 3 is an infrared spectrum of crude carboxymethyl cellulose and modified carboxymethyl cellulose produced. As can be seen from the graph, the absorption peak at about 1740cm -1 was a stretching vibration peak of the ester group, and it was also confirmed that the esterification reaction occurred. From this we can demonstrate successful grafting of hydrophobic groups to obtain modified carboxymethyl cellulose esters, i.e. pH sensitive emulsifiers.
Example 5:
5g of carboxymethyl cellulose with the substitution degree of 1.2 is weighed, dispersed in 50g of DMSO and stirred, 1.327g of bromo-n-butane is weighed, 0.25g of triethylamine is mixed and added into a solvent, the solvent is heated to 90 ℃ for reaction for 5 hours, heating is stopped, and industrial ethanol is used for precipitation, drying, washing and crushing after cooling, so that the modified carboxymethyl cellulose ester is obtained, wherein the substitution degree of a hydrophobe is 0.095. The resulting product was dissolved as a 0.1wt% solution in mass concentration and liquid paraffin at 4:6 volume ratio the emulsion was 80% after emulsification for 1min at 10000rpm in a FA25 high speed emulsifier and then standing at 25℃for 24 hours.
This example gives an emulsion which is rapidly broken by adjusting the ph=3 after standing for 24 hours. The layered emulsion was then separated by aspiration with a pipette. The bottom solution was adjusted to ph=7, emulsified again at an oil to water ratio of 6:4, and after 24 hours still had an emulsifying effect.
Example 6:
5g of carboxymethyl cellulose with the substitution degree of 1.2 is weighed, dispersed in 50g of DMSO and stirred, 1.859g of bromo-n-butane is weighed, 0.25g of triethylamine is mixed and added into a solvent, the solvent is heated to 90 ℃ for reaction for 5 hours, heating is stopped, and industrial ethanol is used for precipitation, drying, washing and crushing after cooling, so that the modified carboxymethyl cellulose ester with the substitution degree of the hydrophobe of 0.106 is obtained. The resulting product was dissolved as a 0.1wt% solution in mass concentration and liquid paraffin at 4:6 volume ratio the emulsion was emulsified for 1min at 10000rpm in a FA25 high speed emulsifier, after which the emulsion was 88% by volume after 24 hours of standing at 25 ℃.
This example gives an emulsion which is rapidly broken by adjusting the ph=3 after standing for 24 hours. The layered emulsion was then separated by aspiration with a pipette. The bottom solution was adjusted to ph=7, emulsified again at an oil to water ratio of 6:4, and after 24 hours still had an emulsifying effect.
Example 7:
5g of carboxymethyl cellulose with the substitution degree of 1.2 is weighed, dispersed in 75g of DMSO and stirred, 1.228g of bromo-n-octane and 0.35g of triethylamine are weighed, mixed and added into a solvent, the solvent is heated to 110 ℃ for 7 hours, then the heating is stopped, and after cooling, the product is separated out by using industrial ethanol, dried, washed and crushed, so as to obtain the modified carboxymethyl cellulose ester, wherein the substitution degree of hydrophobe is 0.068. The resulting product was dissolved as a 0.1wt% solution in mass concentration and liquid paraffin at 4:6 volume ratio the emulsion was emulsified for 1min at 10000rpm in a FA25 high speed emulsifier, after which the emulsion was 75% by volume after standing at 25 ℃ for 24 hours. .
This example gives an emulsion which is rapidly broken by adjusting the ph=3 after standing for 24 hours. The layered emulsion was then separated by aspiration with a pipette. The bottom solution was adjusted to ph=7, emulsified again at an oil to water ratio of 6:4, and after 24 hours still had an emulsifying effect.
The hydrogen nuclear magnetic spectrum of the modified carboxymethyl cellulose prepared in the embodiment is shown in fig. 5, wherein 5.2-5.8ppm is the chemical shift of protons at the C1 position of the glucose unit; about 1.61ppm, 1.22ppm, 1.11ppm, and 0.81ppm are chemical shifts of protons on terminal adjacent methylene groups and methyl groups in octyl groups, whereby it can be confirmed that the reaction introduces octyl groups.
FIG. 3 is an infrared spectrum of crude carboxymethyl cellulose and modified carboxymethyl cellulose produced. As can be seen from the graph, the absorption peak at about 1740cm -1 was a stretching vibration peak of the ester group, and it was also confirmed that the esterification reaction occurred. From this we can demonstrate successful grafting of hydrophobic groups to obtain modified carboxymethyl cellulose esters, i.e. pH sensitive emulsifiers.
Example 8:
5g of carboxymethyl cellulose with the substitution degree of 1.2 is weighed, dispersed in 75g of DMSO and stirred, 1.871g of bromo-n-octane and 0.35g of triethylamine are weighed, mixed and added into a solvent, the solvent is heated to 110 ℃ for 7 hours, then the heating is stopped, and after cooling, the product is separated out by using industrial ethanol, dried, washed and crushed, so as to obtain the modified carboxymethyl cellulose ester, wherein the substitution degree of hydrophobe is 0.098. The resulting product was dissolved as a 0.1wt% solution in mass concentration and liquid paraffin at 4:6 volume ratio the emulsion was 80% after emulsification for 1min at 10000rpm in a FA25 high speed emulsifier and then standing at 25℃for 24 hours.
This example gives an emulsion which is rapidly broken by adjusting the ph=3 after standing for 24 hours. The layered emulsion was then separated by aspiration with a pipette. The bottom solution was adjusted to ph=7, emulsified again at an oil to water ratio of 6:4, and after 24 hours still had an emulsifying effect.
Example 9:
5g of carboxymethyl cellulose with the substitution degree of 1.2 is weighed, dispersed in 75g of DMSO and stirred, 2.620g of n-octyl bromide and 0.35g of triethylamine are weighed, mixed and added into a solvent, the solvent is heated to 110 ℃ for 7 hours, the heating is stopped, and after cooling, the product is separated out by using industrial ethanol, dried, washed and crushed, so that the modified carboxymethyl cellulose ester with the substitution degree of the hydrophobe of 0.109 is obtained. The resulting product was dissolved as a 0.1wt% solution in mass concentration and liquid paraffin at 4:6 volume ratio the emulsion was emulsified for 1min at 10000rpm in a FA25 high speed emulsifier, after which the emulsion was 87% by volume after standing at 25 ℃ for 24 hours.
This example gives an emulsion which is rapidly broken by adjusting the ph=3 after standing for 24 hours. The layered emulsion was then separated by aspiration with a pipette. The bottom solution was adjusted to ph=7, emulsified again at an oil to water ratio of 6:4, and after 24 hours still had an emulsifying effect.
Example 10:
5g of carboxymethyl cellulose with 0.7 substitution degree is weighed, dispersed in 25g of DMSO and stirred, 0.871g of benzyl chloride and 0.05g of triethylamine are weighed, mixed and added into a solvent, the solvent is heated to 70 ℃ for reaction for 3 hours, heating is stopped, and industrial ethanol is used for precipitation, drying, washing and crushing after cooling, so that the modified carboxymethyl cellulose ester is obtained, wherein the substitution degree of hydrophobic groups is 0.053. The resulting product was dissolved as a 0.1wt% solution in mass concentration and liquid paraffin at 4:6 volume ratio the emulsion was emulsified for 1min at 10000rpm in a FA25 high speed emulsifier, after which the emulsion was kept at 25 ℃ for 24 hours with a volume fraction of 70%.
This example gives an emulsion which is rapidly broken by adjusting the ph=3 after standing for 24 hours. The layered emulsion was then separated by aspiration with a pipette. The bottom solution was adjusted to ph=7, emulsified again at an oil to water ratio of 6:4, and after 24 hours still had an emulsifying effect.
Example 11:
5g of carboxymethyl cellulose with 0.7 substitution degree is weighed, dispersed in 25g of DMSO and stirred, 1.451g of benzyl chloride and 0.05g of triethylamine are weighed, mixed and added into a solvent, the solvent is heated to 70 ℃ for reaction for 3 hours, heating is stopped, and industrial ethanol is used for precipitation, drying, washing and crushing after cooling, so that the modified carboxymethyl cellulose ester with the substitution degree of the hydrophobe of 0.164 is obtained. The resulting product was dissolved as a 0.1wt% solution in mass concentration and liquid paraffin at 4:6 volume ratio of the emulsion at 10000rpm for 1min in an FA25 type high-speed emulsifying machine, and then standing at 25 ℃ for 24 hours, wherein the volume fraction of the emulsion is 75%
This example gives an emulsion which is rapidly broken by adjusting the ph=3 after standing for 24 hours. The layered emulsion was then separated by aspiration with a pipette. The bottom solution was adjusted to ph=7, emulsified again at an oil to water ratio of 6:4, and after 24 hours still had an emulsifying effect.
Example 12:
5g of carboxymethyl cellulose with 0.7 substitution degree is weighed, dispersed in 25g of DMSO and stirred, 2.032g of benzyl chloride and 0.05g of triethylamine are weighed, mixed and added into a solvent, the solvent is heated to 70 ℃ for reaction for 3 hours, heating is stopped, and industrial ethanol is used for precipitation, drying, washing and crushing after cooling, so that the modified carboxymethyl cellulose ester with the substitution degree of the hydrophobe of 0.176 is obtained. The resulting product was dissolved as a 0.1wt% solution in mass concentration and liquid paraffin at 4:6 volume ratio the emulsion was 80% after emulsification for 1min at 10000rpm in a FA25 high speed emulsifier and then standing at 25℃for 24 hours.
This example gives an emulsion which is rapidly broken by adjusting the ph=3 after standing for 24 hours. The layered emulsion was then separated by aspiration with a pipette. The bottom solution was adjusted to ph=7, emulsified again at an oil to water ratio of 6:4, and after 24 hours still had an emulsifying effect.
Example 13:
5g of carboxymethyl cellulose with 0.7 substitution degree is weighed, dispersed in 50g of DMSO and stirred, 0.943g of bromo-n-butane is weighed, 0.25g of triethylamine is mixed and added into a solvent, the solvent is heated to 90 ℃ for reaction for 5 hours, heating is stopped, and industrial ethanol is used for precipitation, drying, washing and crushing after cooling, so that the modified carboxymethyl cellulose ester with the substitution degree of the hydrophobe of 0.132 is obtained. The resulting product was dissolved as a 0.1wt% solution in mass concentration and liquid paraffin at 4:6 volume ratio the emulsion was emulsified for 1min at 10000rpm in a FA25 high speed emulsifier, after which the emulsion was 73% by volume after standing at 25 ℃ for 24 hours.
This example gives an emulsion which is rapidly broken by adjusting the ph=3 after standing for 24 hours. The layered emulsion was then separated by aspiration with a pipette. The bottom solution was adjusted to ph=7, emulsified again at an oil to water ratio of 6:4, and after 24 hours still had an emulsifying effect.
Example 14:
5g of carboxymethyl cellulose with 0.7 substitution degree is weighed, dispersed in 50g of DMSO and stirred, 1.571g of bromo-n-butane is weighed, 0.25g of triethylamine is mixed and added into a solvent, heating is carried out for 5 hours after reaction is carried out at 90 ℃, heating is stopped, industrial ethanol is used for precipitation, drying, washing and crushing after cooling, and the modified carboxymethyl cellulose ester is obtained, wherein the substitution degree of a hydrophobic group is 0.253. The resulting product was dissolved as a 0.1wt% solution in mass concentration and liquid paraffin at 4:6 volume ratio the emulsion was 80% after emulsification for 1min at 10000rpm in a FA25 high speed emulsifier and then standing at 25℃for 24 hours.
This example gives an emulsion which is rapidly broken by adjusting the ph=3 after standing for 24 hours. The layered emulsion was then separated by aspiration with a pipette. The bottom solution was adjusted to ph=7, emulsified again at an oil to water ratio of 6:4, and after 24 hours still had an emulsifying effect.
Example 15:
5g of carboxymethyl cellulose with 0.7 substitution degree is weighed, dispersed in 50g of DMSO and stirred, 2.200g of bromo-n-butane is weighed, 0.25g of triethylamine is mixed and added into a solvent, the solvent is heated to 90 ℃ for reaction for 5 hours, heating is stopped, and industrial ethanol is used for precipitation, drying, washing and crushing after cooling, so that the modified carboxymethyl cellulose ester with the substitution degree of hydrophobe of 0.270 is obtained. The resulting product was dissolved as a 0.1wt% solution in mass concentration and liquid paraffin at 4:6 volume ratio the emulsion was emulsified for 1min at 10000rpm in a FA25 high speed emulsifier, after which the emulsion was 88% by volume after 24 hours of standing at 25 ℃.
This example gives an emulsion which is rapidly broken by adjusting the ph=3 after standing for 24 hours. The layered emulsion was then separated by aspiration with a pipette. The bottom solution was adjusted to ph=7, emulsified again at an oil to water ratio of 6:4, and after 24 hours still had an emulsifying effect. The procedure shown in FIG. 6 and the electron micrograph of the emulsion shown in FIG. 7.
Example 16:
5g of carboxymethyl cellulose with 0.7 substitution degree is weighed, dispersed in 75g of DMSO and stirred, 1.329g of bromo-n-octane and 0.35g of triethylamine are weighed, mixed and added into a solvent, the solvent is heated to 110 ℃ for 7 hours, then the heating is stopped, and after cooling, the solvent is separated out by using industrial ethanol, dried, washed and crushed, so as to obtain the modified carboxymethyl cellulose with the substitution degree of hydrophobe of 0.079. The resulting product was dissolved as a 0.1wt% solution in mass concentration and liquid paraffin at 4:6 volume ratio the emulsion was emulsified for 1min at 10000rpm in a FA25 high speed emulsifier, after which the emulsion was 76% by volume after 24 hours of standing at 25 ℃.
This example gives an emulsion which is rapidly broken by adjusting the ph=3 after standing for 24 hours. The layered emulsion was then separated by aspiration with a pipette. The bottom solution was adjusted to ph=7, emulsified again at an oil to water ratio of 6:4, and after 24 hours still had an emulsifying effect.
Example 17:
5g of carboxymethyl cellulose with 0.7 substitution degree is weighed, dispersed in 75g of DMSO and stirred, 2.215g of bromo-n-octane and 0.35g of triethylamine are weighed, mixed and added into a solvent, the solvent is heated to 110 ℃ for 7 hours, the heating is stopped, and after cooling, the solvent is separated out by using industrial ethanol, dried, washed and crushed, so that the modified carboxymethyl cellulose ester with the substitution degree of the hydrophobe of 0.140 is obtained. The resulting product was dissolved as a 0.1wt% solution in mass concentration and liquid paraffin at 4:6 volume ratio the emulsion was emulsified for 1min at 10000rpm in a FA25 high speed emulsifier, after which the emulsion was 79% by volume after standing at 25 ℃ for 24 hours.
This example gives an emulsion which is rapidly broken by adjusting the ph=3 after standing for 24 hours. The layered emulsion was then separated by aspiration with a pipette. The bottom solution was adjusted to ph=7, emulsified again at an oil to water ratio of 6:4, and after 24 hours still had an emulsifying effect.
Example 18:
5g of carboxymethyl cellulose with 0.7 substitution degree is weighed, dispersed in 75g of DMSO and stirred, 3.100g of bromo-n-octane is weighed, 0.35g of triethylamine is mixed and added into a solvent, the solvent is heated to 110 ℃ for 7 hours, the heating is stopped, and after cooling, the solvent is separated out by using industrial ethanol, dried, washed and crushed, so that the modified carboxymethyl cellulose ester with the substitution degree of the hydrophobe of 0.164 is obtained. The resulting product was dissolved as a 0.1wt% solution in mass concentration and liquid paraffin at 4:6 volume ratio the emulsion was emulsified for 1min at 10000rpm in a FA25 high speed emulsifier, after which the emulsion was kept at 25 ℃ for 24 hours with a volume fraction of 82%.
This example gives an emulsion which is rapidly broken by adjusting the ph=3 after standing for 24 hours. The layered emulsion was then separated by aspiration with a pipette. The bottom solution was adjusted to ph=7, emulsified again at an oil to water ratio of 6:4, and after 24 hours still had an emulsifying effect.
Example 19:
2.5g of carboxymethyl cellulose with the substitution degree of 0.7 and 2.5g of carboxymethyl cellulose with the substitution degree of 1.2 are weighed, dispersed in 50g of DMSO and stirred, 2.200g of bromo-n-butane and 0.25g of triethylamine are weighed, mixed and added into a solvent, the solvent is heated to 90 ℃ to react for 5 hours, heating is stopped, industrial ethanol is used for precipitation, drying, washing and crushing after cooling, and the modified carboxymethyl cellulose ester with the substitution degree of hydrophobe of 0.270 is obtained. The resulting product was dissolved as a 0.1wt% solution in mass concentration and liquid paraffin at 4:6 volume ratio the emulsion was emulsified for 1min at 10000rpm in a FA25 high speed emulsifier, after which the emulsion was kept at 25 ℃ for 24 hours with a volume fraction of 82%.
This example gives an emulsion which is rapidly broken by adjusting the ph=3 after standing for 24 hours. The layered emulsion was then separated by aspiration with a pipette. The bottom solution was adjusted to ph=7, emulsified again at an oil to water ratio of 6:4, and after 24 hours still had an emulsifying effect.
Example 20:
5g of sodium alginate is weighed and dispersed in 25g of DMSO and stirred, 1.598g of benzyl chloride and 0.05g of triethylamine are weighed and mixed and added into a solvent, the mixture is heated to 70 ℃ to react for 3 hours, then the heating is stopped, and after cooling, the mixture is separated out by using industrial ethanol, dried, washed and crushed to obtain the modified sodium alginate ester, wherein the substitution degree of hydrophobic groups is 0.140. The resulting product was dissolved as a 0.1wt% solution in mass concentration and liquid paraffin at 4:6 volume ratio the emulsion was emulsified for 1min at 10000rpm in a FA25 high speed emulsifier, after which the emulsion was 75% by volume after standing at 25 ℃ for 24 hours.
This example gives an emulsion which is rapidly broken by adjusting the ph=3 after standing for 24 hours. The layered emulsion was then separated by aspiration with a pipette. The bottom solution was adjusted to ph=7, emulsified again at an oil to water ratio of 6:4, and after 24 hours still had an emulsifying effect.
Example 21:
5g of sodium alginate is weighed and dispersed in 25g of DMSO and stirred, 2.237g of benzyl chloride and 0.05g of triethylamine are weighed and mixed and added into a solvent, the mixture is heated to 70 ℃ to react for 3 hours, then the heating is stopped, and after cooling, the mixture is separated out by using industrial ethanol, dried, washed and crushed to obtain the modified sodium alginate ester, wherein the substitution degree of hydrophobic groups is 0.164. The resulting product was dissolved as a 0.1wt% solution in mass concentration and liquid paraffin at 4:6 volume ratio is emulsified for 1min at 10000rpm in a FA25 type high-speed emulsifying machine, and then the volume fraction of the emulsion is 85% after standing for 24 hours at 25 ℃.
This example gives an emulsion which is rapidly broken by adjusting the ph=3 after standing for 24 hours. The layered emulsion was then separated by aspiration with a pipette. The bottom solution was adjusted to ph=7, emulsified again at an oil to water ratio of 6:4, and after 24 hours still had an emulsifying effect.
Example 22:
5g of sodium alginate is weighed and dispersed in 50g of DMSO and stirred, 1.038g of n-butane bromide and 0.25g of triethylamine are weighed and mixed and added into a solvent, the mixture is heated to 90 ℃ to react for 5 hours, then the heating is stopped, and after cooling, the mixture is separated out by using industrial ethanol, dried, washed and crushed to obtain the modified sodium alginate ester, wherein the substitution degree of hydrophobic groups is 0.047. The resulting product was dissolved as a 0.1wt% solution in mass concentration and liquid paraffin at 4:6 volume ratio the emulsion was emulsified for 1min at 10000rpm in a FA25 high speed emulsifier, after which the emulsion was 78% by volume after 24 hours of standing at 25 ℃.
This example gives an emulsion which is rapidly broken by adjusting the ph=3 after standing for 24 hours. The layered emulsion was then separated by aspiration with a pipette. The bottom solution was adjusted to ph=7, emulsified again at an oil to water ratio of 6:4, and after 24 hours still had an emulsifying effect.
Example 23:
5g of sodium alginate is weighed and dispersed in 50g of DMSO and stirred, 1.730g of bromon-butane and 0.25g of triethylamine are weighed and mixed and added into a solvent, the heating is stopped after the reaction is carried out for 5 hours at 90 ℃, and the sodium alginate is separated out by using industrial ethanol, dried, washed and crushed after the cooling, so as to obtain the modified sodium alginate ester, wherein the substitution degree of hydrophobic groups is 0.070. The resulting product was dissolved as a 0.1wt% solution in mass concentration and liquid paraffin at 4:6 volume ratio the emulsion was 80% after emulsification for 1min at 10000rpm in a FA25 high speed emulsifier and then standing at 25℃for 24 hours.
This example gives an emulsion which is rapidly broken by adjusting the ph=3 after standing for 24 hours. The layered emulsion was then separated by aspiration with a pipette. The bottom solution was adjusted to ph=7, emulsified again at an oil to water ratio of 6:4, and after 24 hours still had an emulsifying effect.
Example 24:
5g of sodium alginate is weighed and dispersed in 50g of DMSO and stirred, 2.422g of bromon-butane and 0.25g of triethylamine are weighed and mixed and added into a solvent, the heating is stopped after the reaction is carried out for 5 hours at 90 ℃, and the sodium alginate is separated out by using industrial ethanol, dried, washed and crushed after the cooling, so as to obtain the modified sodium alginate ester, wherein the substitution degree of hydrophobic groups is 0.086. The resulting product was dissolved as a 0.1wt% solution in mass concentration and liquid paraffin at 4:6 volume ratio the emulsion was emulsified for 1min at 10000rpm in a FA25 high speed emulsifier, after which the emulsion was 87% by volume after standing at 25 ℃ for 24 hours.
This example gives an emulsion which is rapidly broken by adjusting the ph=3 after standing for 24 hours. The layered emulsion was then separated by aspiration with a pipette. The bottom solution was adjusted to ph=7, emulsified again at an oil to water ratio of 6:4, and after 24 hours still had an emulsifying effect.
Example 25:
5g of sodium alginate is weighed and dispersed in 75g of DMSO and stirred, 1.463g of n-octyl bromide and 0.35g of triethylamine are weighed and mixed and added into a solvent, the solvent is heated to 110 ℃ for reaction for 7 hours, then the heating is stopped, and after cooling, the sodium alginate is separated out by using industrial ethanol, dried, washed and crushed to obtain the modified sodium alginate ester, wherein the substitution degree of hydrophobic groups is 0.056. The resulting product was dissolved as a 0.1wt% solution in mass concentration and liquid paraffin at 4:6 volume ratio the emulsion was emulsified for 1min at 10000rpm in a FA25 high speed emulsifier, after which the emulsion was kept at 25 ℃ for 24 hours with a volume fraction of 72%.
This example gives an emulsion which is rapidly broken by adjusting the ph=3 after standing for 24 hours. The layered emulsion was then separated by aspiration with a pipette. The bottom solution was adjusted to ph=7, emulsified again at an oil to water ratio of 6:4, and after 24 hours still had an emulsifying effect.
Example 26:
5g of sodium alginate is weighed and dispersed in 75g of DMSO and stirred, 2.438g of n-octyl bromide and 0.35g of triethylamine are weighed and mixed and added into a solvent, the heating is stopped after the reaction is carried out for 7 hours at 110 ℃, and the sodium alginate is separated out by using industrial ethanol, dried, washed and crushed after the cooling, so as to obtain the modified sodium alginate ester, wherein the substitution degree of hydrophobic groups is 0.089. The resulting product was dissolved as a 0.1wt% solution in mass concentration and liquid paraffin at 4:6 volume ratio the emulsion was emulsified for 1min at 10000rpm in a FA25 high speed emulsifier, after which the emulsion was 83% by volume after standing at 25 ℃ for 24 hours.
This example gives an emulsion which is rapidly broken by adjusting the ph=3 after standing for 24 hours. The layered emulsion was then separated by aspiration with a pipette. The bottom solution was adjusted to ph=7, emulsified again at an oil to water ratio of 6:4, and after 24 hours still had an emulsifying effect.
Example 27:
5g of sodium alginate is weighed and dispersed in 75g of DMSO and stirred, 3.414g of bromo-n-octane and 0.35g of triethylamine are weighed and mixed and added into a solvent, the heating is stopped after the reaction is carried out for 7 hours at 110 ℃, and the sodium alginate is separated out by using industrial ethanol, dried, washed and crushed after the cooling, so as to obtain the modified sodium alginate ester, wherein the substitution degree of hydrophobic groups is 0.101. The resulting product was dissolved as a 0.1wt% solution in mass concentration and liquid paraffin at 4:6 volume ratio the emulsion was emulsified for 1min at 10000rpm in a FA25 high speed emulsifier, after which the emulsion was 88% by volume after 24 hours of standing at 25 ℃.
This example gives an emulsion which is rapidly broken by adjusting the ph=3 after standing for 24 hours. The layered emulsion was then separated by aspiration with a pipette. The bottom solution was adjusted to ph=7, emulsified again at an oil to water ratio of 6:4, and after 24 hours still had an emulsifying effect.
Example 28:
5g of sodium alginate is weighed and dispersed in 75g of DMSO and stirred, 0.691g of n-octyl bromide and 0.974 g of n-butane bromide are weighed, 0.35g of triethylamine is mixed and added into a solvent, the mixture is heated to 110 ℃ to react for 7 hours, then the heating is stopped, and after cooling, the mixture is separated out by using industrial ethanol, dried, washed and crushed, so as to obtain the modified sodium alginate ester, wherein the substitution degree of hydrophobic groups is 0.101. The resulting product was dissolved as a 0.1wt% solution in mass concentration and liquid paraffin at 4:6 volume ratio the emulsion was emulsified for 1min at 10000rpm in a FA25 high speed emulsifier, after which the emulsion was 76% by volume after 24 hours of standing at 25 ℃.
This example gives an emulsion which is rapidly broken by adjusting the ph=3 after standing for 24 hours. The layered emulsion was then separated by aspiration with a pipette. The bottom solution was adjusted to ph=7, emulsified again at an oil to water ratio of 6:4, and after 24 hours still had an emulsifying effect.
Example 29:
5g of 0.7 carboxymethyl cellulose is weighed, dispersed in 75g of DMSO and stirred, 0.470g of n-dodecane chloride and 0.35g of triethylamine are weighed, mixed and added into a solvent, the mixture is heated to 130 ℃ for reaction for 8 hours, heating is stopped, and after cooling, industrial ethanol is used for precipitation, drying, washing and crushing, so that modified sodium alginate ester is obtained, wherein the substitution degree of a hydrophobic group is 0.024. The resulting product was dissolved as a 0.1wt% solution in mass concentration and liquid paraffin at 4:6 volume ratio the emulsion was emulsified for 1min at 10000rpm in a FA25 high speed emulsifier, after which the emulsion was kept at 25 ℃ for 24 hours with a volume fraction of 72%.
This example gives an emulsion which is rapidly broken by adjusting the ph=3 after standing for 24 hours. The layered emulsion was then separated by aspiration with a pipette. The bottom solution was adjusted to ph=7, emulsified again at an oil to water ratio of 6:4, and after 24 hours still had an emulsifying effect.
Example 30:
5g of 0.7 carboxymethyl cellulose is weighed, dispersed in 75g of DMSO and stirred, 0.663g of chloro-n-octadecane and 0.35g of triethylamine are weighed, mixed and added into a solvent, the solvent is heated to 140 ℃ for reaction for 8 hours, heating is stopped, and industrial ethanol is used for precipitation, drying, washing and crushing after cooling, so that modified sodium alginate ester is obtained, wherein the substitution degree of hydrophobic groups is 0.024. The resulting product was dissolved as a 0.1wt% solution in mass concentration and liquid paraffin at 4:6 volume ratio the emulsion was emulsified for 1min at 10000rpm in a FA25 high speed emulsifier, after which the emulsion was 74% by volume after standing at 25 ℃ for 24 hours.
This example gives an emulsion which is rapidly broken by adjusting the ph=3 after standing for 24 hours. The layered emulsion was then separated by aspiration with a pipette. The bottom solution was adjusted to ph=7, emulsified again at an oil to water ratio of 6:4, and after 24 hours still had an emulsifying effect.
Claims (2)
1. A pH sensitive emulsifier, wherein the pH sensitive emulsifier has a chemical structural formula of formula (I) or formula (II):
The preparation method of the pH sensitive emulsifier is synthesized by using polysaccharide and halogenated hydrocarbon as raw materials through esterification reaction, and comprises the following steps:
step (1), carboxyl polysaccharide is firstly dispersed in dimethyl sulfoxide, and is continuously heated and stirred to obtain a solution A;
Step (2), mixing halogenated hydrocarbon and triethylamine according to a proportion to obtain a mixture B;
Step (3), step (2) obtaining a mixture B, gradually adding the mixture B into the solution A obtained in step (1), reacting for 3-8 hours at 70-140 ℃, cooling after the reaction is finished, precipitating, washing and drying to obtain the pH sensitive emulsifier;
In the step (1), the mass ratio of dimethyl sulfoxide to carboxyl polysaccharide is 5:1-15:1, wherein the carboxyl polysaccharide is one or more than two of carboxymethyl cellulose with 0.7 substitution degree, carboxymethyl cellulose with 1.2 substitution degree and sodium alginate;
the molar ratio of the halogenated hydrocarbon in the step (2) to the carboxyl polysaccharide in the step (1) is 0.1:1-0.7:1, wherein the halogenated hydrocarbon is one or more of benzyl chloride, bromo-n-butane and bromo-n-octane.
2. A pH sensitive emulsifier according to claim 1, wherein the mass ratio of triethylamine in step (2) to carboxypolysaccharide in step (1) is 0.01:1-0.07:1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211672482.6A CN115926006B (en) | 2022-12-26 | 2022-12-26 | PH sensitive emulsifier and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211672482.6A CN115926006B (en) | 2022-12-26 | 2022-12-26 | PH sensitive emulsifier and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115926006A CN115926006A (en) | 2023-04-07 |
| CN115926006B true CN115926006B (en) | 2024-05-03 |
Family
ID=86652357
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211672482.6A Active CN115926006B (en) | 2022-12-26 | 2022-12-26 | PH sensitive emulsifier and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115926006B (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4504656A (en) * | 1982-09-01 | 1985-03-12 | Daicel Chemical Industries, Ltd. | Esterified carboxymethyl celluloses |
| KR20100052434A (en) * | 2010-03-25 | 2010-05-19 | 성균관대학교산학협력단 | Ph and temperature sensitive polymers and the hydrogels with biodegradability and method for preparing the same |
| CN102180996A (en) * | 2009-12-30 | 2011-09-14 | 罗门哈斯公司 | Process for making uniform oligomeric droplets |
| JP2020182904A (en) * | 2019-05-08 | 2020-11-12 | 日本製紙株式会社 | Emulsifier including carboxymethylated cellulose |
| CN113913198A (en) * | 2021-09-09 | 2022-01-11 | 西南石油大学 | Preparation method and application of multiple-responsiveness Janus particle emulsifier |
| CN114349874A (en) * | 2021-12-23 | 2022-04-15 | 大连理工大学 | Preparation method of hydrophobically modified sodium carboxymethyl starch |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9126868B2 (en) * | 2011-06-10 | 2015-09-08 | Akzo Nobel Chemicals International B.V. | Process and additive to improve adhesion of compositions to substrates |
-
2022
- 2022-12-26 CN CN202211672482.6A patent/CN115926006B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4504656A (en) * | 1982-09-01 | 1985-03-12 | Daicel Chemical Industries, Ltd. | Esterified carboxymethyl celluloses |
| CN102180996A (en) * | 2009-12-30 | 2011-09-14 | 罗门哈斯公司 | Process for making uniform oligomeric droplets |
| KR20100052434A (en) * | 2010-03-25 | 2010-05-19 | 성균관대학교산학협력단 | Ph and temperature sensitive polymers and the hydrogels with biodegradability and method for preparing the same |
| JP2020182904A (en) * | 2019-05-08 | 2020-11-12 | 日本製紙株式会社 | Emulsifier including carboxymethylated cellulose |
| CN113913198A (en) * | 2021-09-09 | 2022-01-11 | 西南石油大学 | Preparation method and application of multiple-responsiveness Janus particle emulsifier |
| CN114349874A (en) * | 2021-12-23 | 2022-04-15 | 大连理工大学 | Preparation method of hydrophobically modified sodium carboxymethyl starch |
Non-Patent Citations (1)
| Title |
|---|
| "疏水化水溶性羧甲基纤维素的制备";潘向军 等;《天津化工》;第18卷(第01期);第12-14页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115926006A (en) | 2023-04-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Tang et al. | Pickering emulsions stabilized by hydrophobically modified nanocellulose containing various structural characteristics | |
| Wang et al. | Formulation of pH and temperature dual-responsive Pickering emulsion stabilized by chitosan-based microgel for recyclable biocatalysis | |
| CN112759772B (en) | Method for preparing Pickering emulsion from millet starch | |
| JP4946051B2 (en) | Method for producing water-soluble polymer | |
| KR100477162B1 (en) | Process for producing enlarged latex | |
| Mohamadnia et al. | Tragacanth gum-graft-polyacrylonitrile: synthesis, characterization and hydrolysis | |
| Bao et al. | Extraction of cellulose nanocrystals from microcrystalline cellulose for the stabilization of cetyltrimethylammonium bromide-enhanced Pickering emulsions | |
| Sadeghi et al. | Synthesis of pH-sensitive hydrogel based on starch-polyacrylate superabsorbent | |
| CN113544158B (en) | Method for producing resin modifier, and composite material | |
| CN109053960B (en) | Preparation method of temperature-sensitive beta-cyclodextrin nanoparticles | |
| CN109369814B (en) | Method for oxidizing-esterifying composite modified starch | |
| CN1194987A (en) | Cellulose ethers containing 2-propenyl groups and use thereof as protective colloids in polymerizations | |
| Pruettiphap et al. | Morphology and drug release behavior of N-isopropylacrylamide/acrylic acid copolymer as stimuli-responsive nanogels | |
| CN115926006B (en) | PH sensitive emulsifier and preparation method thereof | |
| Guo et al. | One-pot preparation of zwitterion-type lignin polymers | |
| Zhou et al. | Design and synthesis of waterborne light-responsive cellulose nanocrystal/fluorinated polyacrylate films toward oil/water repellent and self-healing properties | |
| Wang et al. | Preparation of starch-graft-poly (methyl methacrylate) via SET-LRP at molecular level and its self-assembly | |
| Liu et al. | Facile design of renewable lignin copolymers by photoinitiated RAFT polymerization as Pickering emulsion stabilizers | |
| US11485797B2 (en) | Production of chemically derivatized nanocellulose | |
| JP2000327705A (en) | Preparation of polymer | |
| Zhao et al. | Cationic tall oil lignin-starch copolymer as a flocculant for clay suspensions | |
| Tomanová et al. | Microwave-assisted synthesis of carboxymethylcellulose–based polymeric surfactants | |
| Aldajani et al. | Two-step modification pathway for inducing lignin-derived dispersants and flocculants | |
| WO2022118792A1 (en) | Vinyl chloride resin composition and method for manufacturing same, and molded body | |
| İlyasoğlu et al. | Lipophilization of chitin as novel polymeric stabilizer for improved oil-in-water emulsions |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant |