CN109289696B - Preparation method of imidazoline amphoteric surfactant - Google Patents
Preparation method of imidazoline amphoteric surfactant Download PDFInfo
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- CN109289696B CN109289696B CN201811271877.9A CN201811271877A CN109289696B CN 109289696 B CN109289696 B CN 109289696B CN 201811271877 A CN201811271877 A CN 201811271877A CN 109289696 B CN109289696 B CN 109289696B
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- MTNDZQHUAFNZQY-UHFFFAOYSA-N imidazoline Chemical compound C1CN=CN1 MTNDZQHUAFNZQY-UHFFFAOYSA-N 0.000 title claims abstract description 84
- 239000002280 amphoteric surfactant Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 63
- 239000003513 alkali Substances 0.000 claims abstract description 58
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 56
- FDRCDNZGSXJAFP-UHFFFAOYSA-M sodium chloroacetate Chemical compound [Na+].[O-]C(=O)CCl FDRCDNZGSXJAFP-UHFFFAOYSA-M 0.000 claims abstract description 33
- 239000002253 acid Substances 0.000 claims abstract description 25
- 238000003756 stirring Methods 0.000 claims abstract description 24
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000000243 solution Substances 0.000 claims abstract description 20
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 19
- 239000004094 surface-active agent Substances 0.000 claims abstract description 18
- 235000019864 coconut oil Nutrition 0.000 claims abstract description 17
- 239000003240 coconut oil Substances 0.000 claims abstract description 17
- 239000003054 catalyst Substances 0.000 claims abstract description 15
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 14
- 239000007864 aqueous solution Substances 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 56
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 29
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 239000002537 cosmetic Substances 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 239000013543 active substance Substances 0.000 claims 1
- 238000003860 storage Methods 0.000 abstract description 5
- 239000000047 product Substances 0.000 description 19
- 239000008367 deionised water Substances 0.000 description 16
- 229910021641 deionized water Inorganic materials 0.000 description 16
- 210000003298 dental enamel Anatomy 0.000 description 16
- 239000000463 material Substances 0.000 description 16
- 238000005057 refrigeration Methods 0.000 description 11
- 239000007788 liquid Substances 0.000 description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 9
- 229910052593 corundum Inorganic materials 0.000 description 9
- 229910001845 yogo sapphire Inorganic materials 0.000 description 9
- 230000018044 dehydration Effects 0.000 description 8
- 238000004090 dissolution Methods 0.000 description 8
- 150000003839 salts Chemical class 0.000 description 8
- 229910001220 stainless steel Inorganic materials 0.000 description 8
- 239000010935 stainless steel Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 5
- KWIUHFFTVRNATP-UHFFFAOYSA-N glycine betaine Chemical compound C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 4
- HLERILKGMXJNBU-UHFFFAOYSA-N norvaline betaine Chemical compound CCCC(C([O-])=O)[N+](C)(C)C HLERILKGMXJNBU-UHFFFAOYSA-N 0.000 description 4
- 239000002453 shampoo Substances 0.000 description 4
- 125000000129 anionic group Chemical group 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 229960003237 betaine Drugs 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000010779 crude oil Substances 0.000 description 2
- 239000003599 detergent Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- OPGYRRGJRBEUFK-UHFFFAOYSA-L disodium;diacetate Chemical compound [Na+].[Na+].CC([O-])=O.CC([O-])=O OPGYRRGJRBEUFK-UHFFFAOYSA-L 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- 239000008233 hard water Substances 0.000 description 2
- 150000002462 imidazolines Chemical class 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000007794 irritation Effects 0.000 description 2
- 239000000787 lecithin Substances 0.000 description 2
- 235000010445 lecithin Nutrition 0.000 description 2
- 239000006210 lotion Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000004753 textile Substances 0.000 description 2
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 1
- IIZPXYDJLKNOIY-JXPKJXOSSA-N 1-palmitoyl-2-arachidonoyl-sn-glycero-3-phosphocholine Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@H](COP([O-])(=O)OCC[N+](C)(C)C)OC(=O)CCC\C=C/C\C=C/C\C=C/C\C=C/CCCCC IIZPXYDJLKNOIY-JXPKJXOSSA-N 0.000 description 1
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical compound [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 description 1
- 239000004614 Process Aid Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000011938 amidation process Methods 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000013040 bath agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005202 decontamination Methods 0.000 description 1
- 230000003588 decontaminative effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000000249 desinfective effect Effects 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000004872 foam stabilizing agent Substances 0.000 description 1
- -1 imidazoline quaternary ammonium salts Chemical class 0.000 description 1
- 239000002563 ionic surfactant Substances 0.000 description 1
- 229940067606 lecithin Drugs 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- DVEKCXOJTLDBFE-UHFFFAOYSA-N n-dodecyl-n,n-dimethylglycinate Chemical compound CCCCCCCCCCCC[N+](C)(C)CC([O-])=O DVEKCXOJTLDBFE-UHFFFAOYSA-N 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000005956 quaternization reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- 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
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
- A61K8/494—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with more than one nitrogen as the only hetero atom
- A61K8/4946—Imidazoles or their condensed derivatives, e.g. benzimidazoles
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q5/00—Preparations for care of the hair
- A61Q5/12—Preparations containing hair conditioners
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
- C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/88—Ampholytes; Electroneutral compounds
- C11D1/90—Betaines
Abstract
The invention provides a preparation method of imidazoline amphoteric surfactant, which is characterized by comprising the following steps: adding coconut oil acid, diethylenetriamine, a water carrying agent and a catalyst into a reactor provided with a water separator and a high vacuum protection device, performing dehydration reaction for 4-5h at the temperature of 120-; (2) dropwise adding sodium chloroacetate aqueous solution into the imidazoline intermediate for 3-6 times at room temperature, and stirring while dropwise adding; (3) after the addition, sodium hydroxide solution is added step by step; (4) after the alkali is added, keeping the temperature at 60-80 ℃ and reacting for 2-8 h; (5) heating to 80-100 ℃ and continuing to react for 2-8 hours to obtain the imidazoline surfactant. The product prepared by the invention has the advantages of good stability, good water solubility, long low-temperature storage time and good transparency, and is very suitable for being made into transparent products.
Description
Technical Field
The invention belongs to the technical field of mild imidazoline quaternary ammonium salts, and particularly relates to a preparation method of an imidazoline amphoteric surfactant.
Background
Disodium cocoyl amphodiacetate is an imidazoline-type amphoteric surfactant. Amphoteric surfactants contain both anionic and cationic groups and can carry ionic charges of different nature at different pH ranges. Therefore, the amphoteric surfactant has a plurality of excellent performances, not only has extremely low toxicity, irritation to skin and eyes and good biodegradability, but also has excellent decontamination, foaming, emulsification, wetting, hard water resistance, acid and alkali resistance, stability to various metal ions, good compatibility with other ionic surfactants, and good antistatic, sterilizing, disinfecting and corrosion resistance, thereby having wide application prospect in the daily chemical industry and having more and more extensive application in the industries of textile, paper making, chemical fiber, metal processing and the like.
Amphoteric surfactants are mainly classified into four categories according to their structure: surface active betaines, amphoteric imidazolines, amino acids, and lecithins.
The lecithin is natural amphoteric surfactant, the other three are chemically synthesized, the first three are most applied at present, the betaine is simple to produce, low in price and maximum in production, the amphoteric imidazoline is connected with high grade after being eaten by people, the imidazoline is really famous and not lost, and the amphoteric imidazoline has the characteristics of common amphoteric surfactant, has milder performance and good compatibility with polymerized cationic surfactant, and is particularly suitable for preparing infant shampoo and cleaning sanitary products. The application is wider. However, the development of amphoteric imidazoline in China is not smooth, and the amphoteric imidazoline occupies a dominant position in one time in the eighties, and then gradually decreases, because the technology has great problems in the production of amphoteric imidazoline, and the product is unstable. In the years, along with the improvement of living standard of people, the mild surfactant is widely applied, the demand of dodecyl betaine is reduced, the market demand of the mild propyl betaine and amphoteric imidazoline surfactant is increased rapidly, many production units take cocoyl propyl betaine as a main product, take cocoyl amphoteric diacetate disodium as a key development object, and the production technology is mature gradually. Propyl betaine is a mild surfactant, but it has been tested for its allergenicity, and amphoteric imidazolines are comparatively milder and higher-grade surfactants than cocoyl propyl betaine. At present, the national production units of coconut oil-based disodium diacetate are not few, but the problems of poor product stability, short storage time under low temperature condition, easy turbidity and inconvenience for customers to make transparent products commonly exist; the problem of unstable product and poor transparency at low temperature also becomes a difficult problem in the industry, and many professional technicians are actively exploring and researching. However, no effective solution to this problem has been reported, and how to solve these problems is a problem to be solved urgently in the art.
Disclosure of Invention
In view of the above, the invention aims to provide a preparation method of an imidazoline amphoteric surfactant, and the surfactant prepared by the method has the characteristics of environmental friendliness, stable product, good water solubility, long low-temperature storage time and good transparency.
In order to achieve the purpose, the technical scheme of the invention is realized as follows:
a preparation method of imidazoline amphoteric surfactant is characterized in that: comprises the following steps of (a) carrying out,
(1) adding coconut oil acid, diethylenetriamine, a water carrying agent and a catalyst into a reactor provided with a water separator and a high vacuum protection device, performing dehydration reaction for 4-5h at the temperature of 120-;
(2) dropwise adding sodium chloroacetate aqueous solution into the imidazoline intermediate for 3-6 times at room temperature, and stirring while dropwise adding;
(3) adding sodium hydroxide solution step by step after adding, starting adding alkali 10-30% of total alkali each time, reaction interval time is 0.5-2h, when adding alkali to total alkali 60-80%, adding alkali 5-15% of total alkali each time, reaction interval time is 1-2 h; (ii) a
(4) After the alkali is added, keeping the temperature at 60-80 ℃ and reacting for 2-8 h;
(5) heating to 80-100 ℃ and continuing to react for 2-8 hours to obtain the imidazoline surfactant.
Preferably, in the step (1), the molar ratio of the coconut oil acid to the diethylenetriamine is 1:1.1-1.3, the adding amount of the water carrying agent is 20-30% of the total amount of the feed, and the adding amount of the catalyst is 0.1-0.3% of the mass of the coconut oil acid.
Preferably, in step (1), the water-carrying base is toluene, and the catalyst is Al2O3。
Preferably, in the step (2), the molar ratio of the imidazoline intermediate to the sodium chloroacetate is 1: 2-3; the total water addition amount is 48-65% of the total mass of the sodium chloroacetate aqueous solution after the sodium chloroacetate aqueous solution is dropwise added in the step (2).
Preferably, in step (3), the amount of sodium hydroxide added is 15% -30% of the imidazoline intermediate.
The invention also provides the application of the surfactant obtained by the preparation method of the imidazoline amphoteric surfactant in washing cosmetics.
Compared with the prior art, the invention has the beneficial effects that:
the coco imidazoline betaine amphoteric surfactant prepared by the preparation method is suitable for being used as a conditioner of various shampoos, bath agents, baby lotions and dish detergents, is used in washing products, and can improve the product quality and improve the performance. The application field is as follows: in the manufacture of cosmetics, high-grade special hair care shampoo is widely prepared. In the textile industry, as detergents, fiber softeners, antistatic agents and other process aids. And also as foam stabilizers in foam extinguishants. The product has low irritation to eyes and skin, and can be used as a good base for baby liquid and body cleaning lotion, besides general shampoo. The invention has excellent foaming power and foam stability. Has good compatibility with anionic and nonionic surfactants. Is stable to hard water. The toxicity is low, and the LD50 is 5871 mg/Kg. The microorganism is easy to decompose.
In the amidation process, high vacuum is adopted, the proportion of coconut oil acid and diethylenetriamine is reasonable, the main reaction is strengthened, and the generation of byproducts is reduced; in the quaternization process, a reasonable proportioning process is adopted, water is used as a reaction medium, an organic solvent is not required to be added, energy is saved, raw material consumption is reduced, and the method is very environment-friendly and accords with the current trend. Sodium chloroacetate is added step by step or dropwise, alkali is added step by step, and the time and the amount of the alkali are determined according to the reaction condition and the pH change; the violent reaction is controlled by the method of firstly feeding at low temperature and then aging at high temperature. The product has the advantages of good stability, good water solubility, long low-temperature storage time and good transparency by the measures, and is very suitable for being made into transparent products.
Detailed Description
Unless defined otherwise, technical terms used in the following examples have the same meanings as commonly understood by one of ordinary skill in the art to which the present invention belongs. The test reagents used in the following examples, unless otherwise specified, are all conventional biochemical reagents; the experimental methods are conventional methods unless otherwise specified.
The present invention will be described in detail with reference to examples.
Example 1
The preparation method of the imidazoline amphoteric surfactant comprises the following steps:
1. 400kg of coconut oil acid, 227kg of diethylenetriamine, 125kg of toluene and catalyst Al2O30.4kg of the imidazoline intermediate is added into a stainless steel reactor provided with a water separator and a high vacuum (less than-75 mmHg) device, the first dehydration is carried out at the temperature of 120 plus materials and 150 ℃, the reaction is carried out for 4 hours until no water is separated out, the temperature is heated to 200 plus materials and 230 ℃, the dehydration reaction is carried out for 4-6 hours, the water carrying agent and the unreacted diethylenetriamine are evaporated, the acid value is measured to be 0.64, the imidazoline intermediate is qualified, and 594kg of the imidazoline intermediate is obtained.
2. 200KG of imidazoline intermediate is taken and added into an enamel reaction kettle, 300KG of deionized water is added into the other enamel kettle, 171KG of sodium chloroacetate is added under stirring, after full dissolution, sodium chloroacetate solution is added to the imidazoline intermediate for 3 times, and the imidazoline intermediate is added under stirring.
3. Preparing alkali liquor: 40kg of 99% sodium hydroxide was added to 75kg of deionized water and stirred uniformly for further use.
4. After the sodium chloroacetate is added, the sodium hydroxide solution is added step by step, the alkali adding amount is 30kg at the beginning, the reaction interval time is 1h, after the alkali is added for 3 times, the alkali adding amount is changed to 10kg at each time, and the reaction interval time is 1.5 h.
5. After the alkali is added, the temperature is kept at 70 ℃ for reaction for 5 h.
6. Raising the temperature to 85 ℃ and continuing the reaction for 8 hours to obtain the imidazoline surfactant with the content of 50%.
7. The sample was examined for a dry content of 50.35%, a pH (10%) of 8.45, a salt content of 11.34%, a pale yellow transparent liquid in color, and a refrigeration time of 84 h.
Example 2
The preparation method of the imidazoline amphoteric surfactant comprises the following steps:
1. 400kg of coconut oil acid, 247.6kg of diethylenetriamine, 125kg of toluene and catalyst Al2O30.4kg of the imidazoline intermediate is added into a stainless steel reactor provided with a water separator and a high vacuum (less than-75 mmHg) device, the first dehydration is carried out at the temperature of 120 plus materials and 150 ℃, the reaction is carried out for 4 hours until no water is separated out, the temperature is heated to 200 plus materials and 230 ℃, the dehydration reaction is carried out for 4-6 hours, the water carrying agent and the unreacted diethylenetriamine are evaporated, the acid value is measured to be 0.32, and 600kg of the imidazoline intermediate is obtained.
2. 200kg of imidazoline intermediate is taken and added into an enamel reaction kettle, 300kg of deionized water is added into the other enamel kettle, 179.5kg of sodium chloroacetate is added under stirring, after full dissolution, sodium chloroacetate solution is added to the imidazoline intermediate for 4 times, and the imidazoline intermediate is added under stirring.
3. Preparing alkali liquor: adding 43kg of 99% sodium hydroxide into 75kg of deionized water, and uniformly stirring for later use
4. After the sodium chloroacetate is added, the sodium hydroxide solution is added step by step, the alkali adding amount is 25kg each time, the reaction interval time is 1h, after the alkali is added for 4 times, the alkali adding amount is changed to 10kg each time, and the reaction interval time is 1.5 h.
5. After the alkali is added, the temperature is kept at 70 ℃ for reaction for 6 h.
6. Raising the temperature to 95 ℃ and continuing the reaction for 5 hours to obtain the imidazoline surfactant with the content of 50%.
7. The samples were examined for a dry content of 50.67%, a pH (10%) of 8.40, a salt content of 11.68%, a pale yellow transparent liquid in color, and a refrigeration time of 104 h.
Example 3
The preparation method of the imidazoline amphoteric surfactant comprises the following steps:
1. 400kg of coconut oil acid, 247.6kg of diethylenetriamine, 125kg of toluene and catalyst Al2O30.4kg of the imidazoline intermediate is added into a stainless steel reactor provided with a water separator and a high vacuum (less than-75 mmHg) device, the first dehydration is carried out at the temperature of 120 plus materials and 150 ℃, the reaction is carried out for 4 hours until no water is separated out, the temperature is heated to 200 plus materials and 230 ℃, the dehydration reaction is carried out for 4-6 hours, the water carrying agent and the unreacted diethylenetriamine are evaporated, the acid value is measured to be 0.66, and 598kg of the imidazoline intermediate is obtained.
2. 200kg of imidazoline intermediate is taken and added into an enamel reaction kettle, 300kg of deionized water is added into the other enamel kettle, 188kg of sodium chloroacetate is added under stirring, after full dissolution, sodium chloroacetate solution is added to the imidazoline intermediate for 4 times, and the imidazoline intermediate is added under stirring.
3. Preparing alkali liquor: adding 47kg of 99% sodium hydroxide into 75kg of deionized water, and uniformly stirring for later use
4. After the sodium chloroacetate is added, the sodium hydroxide solution is added step by step, the alkali adding amount is 20kg at the beginning of each time, the reaction interval time is 1h, after the alkali is added for 5 times, the alkali adding amount is changed to 10kg at each time, and the reaction interval time is 1.5 h.
5. After the alkali is added, the temperature is kept at 70 ℃ for reaction for 6 h.
6. Raising the temperature to 90 ℃ and continuing the reaction for 6 hours to obtain the imidazoline surfactant with the content of 50%.
7. The samples were examined for a dry content of 50.53%, a pH (10%) of 8.35, a salt content of 12.68%, a pale yellow transparent liquid in color, and a refrigeration time of 144 h.
Example 4
The preparation method of the imidazoline amphoteric surfactant comprises the following steps:
1. 400kg of coconut oil acid, 258kg of diethylenetriamine, 130kg of toluene and catalyst Al2O30.5kg of the imidazoline intermediate is added into a stainless steel reactor provided with a water separator and a high vacuum (less than-75 mmHg) device, the first dehydration is carried out at the temperature of 120 plus materials and 150 ℃, the reaction is carried out for 4 hours until no water is separated out, the temperature is heated to 200 plus materials and 230 ℃, the dehydration reaction is carried out for 4-6 hours, the water carrying agent and the unreacted diethylenetriamine are evaporated, the acid value is measured to be 0.53, and 603kg of the imidazoline intermediate is obtained.
2. 200KG of imidazoline intermediate is taken and added into an enamel reaction kettle, 300KG of deionized water is added into the other enamel kettle, 213.7KG of sodium chloroacetate is added under stirring, after full dissolution, sodium chloroacetate solution is added into the imidazoline intermediate for 5 times, and the imidazoline intermediate is added under stirring.
3. Preparing alkali liquor: 65kg of 99% sodium hydroxide was added to 75kg of deionized water, and the mixture was stirred uniformly for further use.
4. After the sodium chloroacetate is added, the sodium hydroxide solution is added step by step, the alkali adding amount is 30kg at the beginning of each time, the reaction interval time is 1h, after the alkali is added for 4 times, the alkali adding amount is changed to 10kg at each time, and the reaction interval time is 1.5 h.
5. After the addition of the alkali is finished, the temperature is kept at 70 ℃ for reaction for 7 h.
6. Raising the temperature to 93 ℃ and continuing the reaction for 5 hours to obtain the imidazoline surfactant with the content of 50%.
7. The samples were examined for a dry content of 51.08%, a pH (10%) of 8.33, a salt content of 13.06%, a pale yellow transparent liquid in color, and a refrigeration time of 130 h.
Example 5
The preparation method of the imidazoline amphoteric surfactant comprises the following steps:
1. 400kg of coconut oil acid, 268kg of diethylenetriamine, 150kg of toluene and catalyst Al2O30.4kg of the imidazoline intermediate is added into a stainless steel reactor provided with a water separator and a high vacuum (less than-75 mmHg) device, the first dehydration is carried out at the temperature of 120 plus materials and 150 ℃, the reaction is carried out for 4 hours, when no water is separated out, the temperature is heated to 200 plus materials and 230 ℃, the dehydration reaction is carried out for 4-6 hours, the water carrying agent and the unreacted diethylenetriamine are evaporated, the acid value is measured to be 0.48, and 603kg of the imidazoline intermediate is obtained.
2. 200kg of imidazoline intermediate is taken and added into an enamel reaction kettle, 300kg of deionized water is added into the other enamel kettle, 205kg of sodium chloroacetate is added under stirring, after full dissolution, sodium chloroacetate solution is added to the imidazoline intermediate for 4 times, and the imidazoline intermediate is added under stirring.
3. Preparing alkali liquor: adding 60kg of sodium hydroxide with the content of 99% into 75kg of deionized water, and uniformly stirring for later use
4. After the sodium chloroacetate is added, the sodium hydroxide solution is added step by step, the alkali addition amount is 35kg at the beginning of each time, the reaction interval time is 1h, after the alkali is added for 3 times, the alkali addition amount is changed to 15kg at each time, and the reaction interval time is 1.5 h.
5. After the alkali is added, the temperature is kept at 70 ℃ for reaction for 8 h.
6. Raising the temperature to 90 ℃ and continuing the reaction for 7 hours to obtain the imidazoline surfactant with the content of 50%.
7. The sample was examined for a dry content of 50.88%, a pH (10%) of 8.26, a salt content of 12.78%, a pale yellow transparent liquid in color, and a refrigeration time of 192 h.
Example 6
The preparation method of the imidazoline amphoteric surfactant comprises the following steps:
1. 400kg of coconut oil acid, 248kg of diethylenetriamine, 150kg of toluene and catalyst Al2O30.4kg of the crude oil is added into a stainless steel reactor provided with a water separator and a high vacuum (less than-75 mmHg) device, the first dehydration is carried out at the temperature of 120 plus materials and 150 ℃, the reaction is carried out for 4 hours, when no water is separated out, the crude oil is heated to the temperature of 200 plus materials and 230 ℃ for dehydration reaction for 4-6 hours, and water carrying agent and unreacted diethyl glycol are evaporatedAlkene triamine, and the acid value is measured to be 0.42, so that 598kg of imidazoline intermediate is obtained.
2. 200kg of imidazoline intermediate is taken and added into an enamel reaction kettle, 600kg of deionized water is added into the other enamel kettle, 188kg of sodium chloroacetate is added under stirring, after full dissolution, sodium chloroacetate solution is added to the imidazoline intermediate for 4 times, and the imidazoline intermediate is added under stirring.
3. Preparing alkali liquor: adding 53kg of 99% sodium hydroxide into 100kg of deionized water, and uniformly stirring for later use
4. After the sodium chloroacetate is added, the sodium hydroxide solution is added step by step, the alkali adding amount is 30kg at the beginning of each time, the reaction interval time is 1h, after the alkali is added for 4 times, the alkali adding amount is changed to 15kg at each time, and the reaction interval time is 1.5 h.
5. After the alkali is added, the temperature is kept at 70 ℃ for reaction for 6 h.
6. Raising the temperature to 90 ℃ and continuing the reaction for 7 hours to obtain the imidazoline surfactant with the content of 35%.
7. The sample was examined for a dry content of 36.08%, a pH (10%) of 8.26, a salt content of 8.78%, a pale yellow transparent liquid in color, and a refrigeration time of 144 h.
Example 7
The preparation method of the imidazoline amphoteric surfactant comprises the following steps:
1. 400kg of coconut oil acid, 258kg of diethylenetriamine, 150kg of toluene and catalyst Al2O30.4kg of the imidazoline intermediate is added into a stainless steel reactor provided with a water separator and a high vacuum (less than-75 mmHg) device, the first dehydration is carried out at the temperature of 120 plus materials and 150 ℃, the reaction is carried out for 4 hours, when no water is separated out, the temperature is heated to 200 plus materials and 230 ℃, the dehydration reaction is carried out for 4-6 hours, the water carrying agent and the unreacted diethylenetriamine are evaporated, the acid value is measured to be 0.73, and 606kg of the imidazoline intermediate is obtained.
2. 200kg of imidazoline intermediate is taken and added into an enamel reaction kettle, 600kg of deionized water is added into the other enamel kettle, 180kg of sodium chloroacetate is added under stirring, after full dissolution, sodium chloroacetate solution is added to the imidazoline intermediate for 4 times, and the imidazoline intermediate is added under stirring.
3. Preparing alkali liquor: 46.6kg of 99% sodium hydroxide was added to 100kg of deionized water, and the mixture was stirred uniformly for further use.
4. After the sodium chloroacetate is added, the sodium hydroxide solution is added step by step, the alkali adding amount is 25kg each time, the reaction interval time is 1h, after the alkali is added for 5 times, the alkali adding amount is changed to 15kg each time, and the reaction interval time is 1.5 h.
5. After the alkali is added, the temperature is kept at 70 ℃ for reaction for 5 h.
6. Raising the temperature to 95 ℃ and continuing the reaction for 6 hours to obtain the imidazoline surfactant with the content of 35%.
7. The sample was examined for a dry content of 36.18%, a pH (10%) of 8.28, a salt content of 8.64%, a pale yellow transparent liquid in color, and a refrigeration time of 152 h.
Comparative example 1
The preparation method of the imidazoline amphoteric surfactant comprises the following steps:
1. 400kg of coconut oil acid, 216.7.0kg of diethylenetriamine, 125kg of toluene and catalyst Al2O30.4kg of the aqueous solution is added into a stainless steel reactor provided with a water separator and a high vacuum (less than-75 mmHg) device, the first dehydration is carried out at the temperature of 120 plus materials and 150 ℃, the reaction is carried out for 4 hours until no water is separated out, the reaction is heated to the temperature of 200 plus materials and 230 ℃ for dehydration reaction for 4-6 hours, the water carrying agent and the unreacted diethylenetriamine are evaporated, the acid value is measured to be 2.32, and 588kg of imidazoline intermediate is obtained.
2. 200kg of imidazoline intermediate is taken and added into an enamel reaction kettle, 300kg of deionized water is added into the other enamel kettle, 179.5kg of sodium chloroacetate is added under stirring, after full dissolution, sodium chloroacetate solution is added to the imidazoline intermediate for 4 times, and the imidazoline intermediate is added under stirring.
3. Preparing alkali liquor: adding 43kg of 99% sodium hydroxide into 75kg of deionized water, and uniformly stirring for later use
4. After the sodium chloroacetate is added, the sodium hydroxide solution is added step by step, the alkali adding amount is 25kg each time, the reaction interval time is 1h, after the alkali is added for 4 times, the alkali adding amount is changed to 10kg each time, and the reaction interval time is 1.5 h.
5. After the alkali is added, the temperature is kept at 70 ℃ for reaction for 6 h.
6. Raising the temperature to 95 ℃ and continuing the reaction for 5 hours to obtain the imidazoline surfactant with the content of 50%.
7. The samples were tested for a dry content of 50.67%, a pH (10%) of 8.48, a salt content of 11.68%, a brown liquid in color, and a refrigeration time of 24 h.
The refrigeration time is the time from transparency to onset of haziness of the product when refrigeration is carried out at-5 ℃ to 0 ℃. The refrigeration time is an important index for inspecting the low-temperature transparency and the stability of the product, the product is a transparent viscous liquid dissolved in water at normal temperature, and the product is easy to be turbid and opaque at low temperature. The product is opaque at low temperature, namely the product has low solubility at low temperature and becomes turbid when becoming solid insoluble. The cold storage time is a good indicator of the low temperature transparency characteristic of the product stability.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (3)
1. A preparation method of imidazoline amphoteric surfactant is characterized in that: comprises the following steps of (a) carrying out,
(1) adding coconut oil acid, diethylenetriamine, a water carrying agent and a catalyst into a reactor provided with a water separator and a high vacuum protection device, performing dehydration reaction for 4-5h at the temperature of 120-;
(2) dropwise adding sodium chloroacetate aqueous solution into the imidazoline intermediate for 3-6 times at room temperature, and stirring while dropwise adding;
(3) adding sodium hydroxide solution step by step after adding, starting adding alkali 10-30% of total alkali each time, reaction interval time is 0.5-2h, when adding alkali to total alkali 60-80%, adding alkali 5-15% of total alkali each time, reaction interval time is 1-2 h;
(4) after the alkali is added, keeping the temperature at 60-80 ℃ and reacting for 2-8 h;
(5) heating to 80-100 ℃ and continuing to react for 2-8 hours to obtain imidazoline surfactant;
the imidazoline amphoteric surfactant is an active agent applied to washing or cosmetics;
in the step (1), the molar ratio of the coconut oil acid to the diethylenetriamine is 1:1.1-1.3, the adding amount of the water carrying agent is 20-30% of the total amount of the feed, and the adding amount of the catalyst is 0.1-0.3% of the mass of the coconut oil acid;
in the step (2), the molar ratio of the imidazoline intermediate to the sodium chloroacetate is 1: 2-3; the total water addition amount is 48-65% of the total amount of the sodium chloroacetate aqueous solution dropwise added in the step (2);
in the step (3), the addition amount of the sodium hydroxide is 15-30% of that of the imidazoline intermediate.
2. The method for producing an imidazoline amphoteric surfactant according to claim 1, wherein: in the step (1), toluene is taken as water carrying agent, and Al is taken as catalyst2O3。
3. Use of the surfactant obtained by the method for producing an imidazoline amphoteric surfactant according to claim 1 or 2 in washing or cosmetics.
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