Polyethylene glycol mink oleate surfactant and preparation method thereof
阅读说明：本技术 一种聚乙二醇水貂油酸酯表面活性剂及其制备方法 (Polyethylene glycol mink oleate surfactant and preparation method thereof ) 是由 巩凯 张大权 李存浩 刘彦其 于 2020-05-21 设计创作，主要内容包括：本发明公开了一种聚乙二醇水貂油酸酯表面活性剂及其制备方法,属于表面活性剂、胶体与界面化学领域技术领域。本发明的聚乙二醇水貂油酸酯表面活性剂由水貂油和聚乙二醇反应而制得。本发明的表面活性剂结构由水貂油的长链烷基作为疏水性基团和聚乙二醇作为亲水基,具有良好的生物相容性,提高水貂油性能,具有更好的泡沫稳定性,性能温和；而且本发明得到的聚乙二醇水貂油酸酯表面活性剂的HLB值达到12.5以上,与液体石蜡通过乳化形成的乳液稳定时间在430s以上。(The invention discloses a polyethylene glycol mink oleate surfactant and a preparation method thereof, belonging to the technical field of surfactants, colloids and interfacial chemistry.A polyethylene glycol mink oleate surfactant is prepared by the reaction of mink oil and polyethylene glycol.A surfactant structure of the invention takes long-chain alkyl of mink oil as a hydrophobic group and polyethylene glycol as a hydrophilic group, has good biocompatibility, improves the performance of mink oil, has better foam stability and mild performance, and the H L B value of the polyethylene glycol mink oleate surfactant obtained by the invention reaches more than 12.5, and the emulsion stabilization time formed by emulsification with liquid paraffin is more than 430 s.)
1. The polyethylene glycol mink oleate surfactant is characterized in that the preparation method comprises the following steps:
adding mink oil, polyethylene glycol and a catalyst into a reactor for reaction; after the reaction is finished, adding dichloromethane into the reaction solution to obtain a mixed solution; washing the mixed solution with an alkaline solution to obtain an organic phase solution; and then drying, filtering and rotary evaporating to obtain the polyethylene glycol mink oleate surfactant.
2. The polyethylene glycol mink oleate surfactant of claim 1, wherein the mink oil comprises a compound having a structure represented by formula 1:
wherein R' is H; r is respectively CH3(CH2)10、CH3(CH2)12、CH3(CH2)13、CH3(CH2)14、CH3(CH2)15、CH3(CH2)16、CH3(CH2)7CH＝CH(CH2)7、CH3(CH2)4CH＝CHCH2CH＝CH(CH2)7、CH3(CH2)18、CH3(CH2)4(CH＝CH-CH2)4(CH2)2、CH3(CH2)4CH＝CHCH2CH＝CHCH2CH＝CH(CH2)4And CH3(CH2CH＝CH)3(CH2)7。
3. The polyethylene glycol mink oleate surfactant of claim 1, wherein the polyethylene glycol mink oleate surfactant comprises a compound having a structure represented by formula 2:
wherein R is CH respectively3(CH2)10、CH3(CH2)12、CH3(CH2)13、CH3(CH2)14、CH3(CH2)15、CH3(CH2)16、CH3(CH2)7CH＝CH(CH2)7、CH3(CH2)4CH＝CHCH2CH＝CH(CH2)7、CH3(CH2)18、CH3(CH2)4(CH＝CH-CH2)4(CH2)2、CH3(CH2)4CH＝CHCH2CH＝CHCH2CH＝CH(CH2)4And CH3(CH2CH＝CH)3(CH2)7。
4. The polyethylene glycol mink oleate surfactant according to claim 1, wherein the synthetic route of the polyethylene glycol mink oleate surfactant is as follows:
wherein R is CH respectively3(CH2)10、CH3(CH2)12、CH3(CH2)13、CH3(CH2)14、CH3(CH2)15、CH3(CH2)16、CH3(CH2)7CH＝CH(CH2)7、CH3(CH2)4CH＝CHCH2CH＝CH(CH2)7、CH3(CH2)18、CH3(CH2)4(CH＝CH-CH2)4(CH2)2、CH3(CH2)4CH＝CHCH2CH＝CHCH2CH＝CH(CH2)4And CH3(CH2CH＝CH)3(CH2)7。
5. The polyethylene glycol mink oleate surfactant according to claim 1, wherein the mass ratio of mink oil to polyethylene glycol is 1: (2-10).
6. The polyethylene glycol mink oleate surfactant as claimed in claim 1, wherein the reaction temperature is 60-100 ℃ and the reaction time is 6-12 h.
7. The polyethylene glycol mink oleate surfactant as claimed in claim 1, wherein the volume/mass ratio of dichloromethane to mink oil is 150-: 30.
8. the polyethylene glycol mink oleate surfactant according to claim 1, wherein the polyethylene glycol is one or more of polyethylene glycol 600, polyethylene glycol 1000, polyethylene glycol 2000, polyethylene glycol 3000, methoxypolyethylene glycol 1000, methoxypolyethylene glycol 2000, and multi-arm polyethylene glycol 4000.
9. The method of making a polyethylene glycol mink oleate surfactant as claimed in any one of claims 1 to 8.
10. Use of the polyethylene glycol mink oleate surfactant according to any one of claims 1 to 8 in a daily cosmetic.
Technical Field
The invention relates to a polyethylene glycol mink oleate surfactant and a preparation method thereof, belonging to the technical field of surfactants, colloids and interfacial chemistry.
Background
The surfactant mainly comprises an anionic surfactant and a nonionic surfactant, and the nonionic surfactant has excellent wetting and washing functions, strong detergency, good emulsification and permeability, and good foaming, foam stabilizing, antistatic and sterilizing effects; the stability is high, the water-soluble polymer is not ionized in aqueous solution, and is not influenced by strong electrolyte, strong acid and strong alkali, and is not influenced by calcium and magnesium ions in hard water; the compatibility with other types of surfactants is good, and the surfactant is compatible with both anionic surfactants and cationic surfactants; no toxicity, no irritation and good biodegradability, and is a new generation of green product.
With the attention of people on environmental protection, the novel green surfactant becomes a hotspot for research of numerous scholars. The grease-based high molecular surfactant is a nonionic surfactant, such as polyethylene glycol distearate, polyglycerol fatty acid ester, polyethylene glycol monoricinoleate and the like, and has the advantages that: the oil substances have wide sources, and a certain amount of oil exists in seeds of various plants and tissues and organs of animals; the use of grease-based substances conforms to a sustainable development strategy; the novel high molecular surfactant synthesized by taking natural oil substances as raw materials has wide application, belongs to renewable resources, is easy to biodegrade, is safe to human bodies and environment, and is developed towards multifunction and high efficiency at present.
Mink Oil (Mink Oil) is fatty Oil obtained from subcutaneous fat of Mink, contains abundant nutrients, has physical and chemical properties similar to those of human body fat, has good permeability, and can be easily absorbed by skin. However, mink oil has a special odor, and is mainly derived from secretion of anal line, mainly amines, thiols, indoles and some lower fatty acids, due to its own metabolism. Therefore, mink oil needs to be refined, and patent numbers CN1050740A, CN102191127B and the like disclose a method for refining mink oil, so that the smell of the mink oil is improved. Patent CN1031250A discloses a preparation method of ethyl ester of mink oil, which improves the performance of mink oil to a certain extent, expands the application range, but does not fully exert the performance of mink oil. Therefore, the development of a mink oil surfactant with better performance is needed, so that the product development requirement and the market requirement are met.
Disclosure of Invention
In order to solve at least one problem, the invention takes mink oil as a raw material to prepare the polyethylene glycol mink oleate surfactant. According to the invention, the polyethylene glycol hydrophilic group is introduced, so that the performance of the mink oil product is improved, the smell and color of the mink oil are improved, the advantages of the mink oil are fully exerted, the emulsifying property is good, and the application in the daily chemical field is expanded.
The first purpose of the invention is to provide a polyethylene glycol mink oleate surfactant, and the preparation method comprises the following steps:
adding mink oil, polyethylene glycol and a catalyst into a reactor for reaction; after the reaction is finished, adding dichloromethane into the reaction solution to obtain a mixed solution; washing the mixed solution with an alkaline solution to obtain an organic phase solution; and then drying, filtering and rotary evaporating to obtain the polyethylene glycol mink oleate surfactant.
In one embodiment, the preparation method comprises the following steps: adding mink oil, polyethylene glycol and a catalyst into a reactor for reaction; after the reaction is finished, adding dichloromethane into the reaction solution to obtain a mixed solution; the mixed solution is respectively treated with NaHCO3Washing the aqueous solution, saturated saline water and water to obtain an organic phase solution; then adopting anhydrous Na2SO4And drying the organic phase solution, and finally filtering and rotationally evaporating to obtain the polyethylene glycol mink oleate surfactant.
In one embodiment, the polyethylene glycol is one or more of polyethylene glycol 600(PEG-600), polyethylene glycol 1000(PEG-1000), polyethylene glycol 2000(PEG-2000), polyethylene glycol 3000(PEG-3000), methoxy polyethylene glycol 1000(mPEG-1000), methoxy polyethylene glycol 2000(mPEG-2000), and multi-arm polyethylene glycol 4000 (bPEG-4000).
In one embodiment, the mink oil comprises a compound having the structure shown in formula 1:
wherein R' is H; r is CH3(CH2)10、CH3(CH2)12、CH3(CH2)13、CH3(CH2)14、CH3(CH2)15、CH3(CH2)16、CH3(CH2)7CH＝CH(CH2)7、CH3(CH2)4CH＝CHCH2CH＝CH(CH2)7、CH3(CH2)18、CH3(CH2)4(CH＝CH-CH2)4(CH2)2、CH3(CH2)4CH＝CHCH2CH＝CHCH2CH＝CH(CH2)4And CH3(CH2CH＝CH)3(CH2)7。
In one embodiment, the mink oil of step (1) is obtained from the Daoqi Fine chemical Co., Ltd, Zhuhai.
In one embodiment, the polyethylene glycol mink oleate surfactant comprises a compound having the structure shown in formula 2:
wherein R is CH3(CH2)10、CH3(CH2)12、CH3(CH2)13、CH3(CH2)14、CH3(CH2)15、CH3(CH2)16、CH3(CH2)7CH＝CH(CH2)7、CH3(CH2)4CH＝CHCH2CH＝CH(CH2)7、CH3(CH2)18、CH3(CH2)4(CH＝CH-CH2)4(CH2)2、CH3(CH2)4CH＝CHCH2CH＝CHCH2CH＝CH(CH2)4And CH3(CH2CH＝CH)3(CH2)7。
In one embodiment, the synthetic route for the polyethylene glycol mink oleate surfactant is as follows:
wherein R is CH3(CH2)10、CH3(CH2)12、CH3(CH2)13、CH3(CH2)14、CH3(CH2)15、CH3(CH2)16、CH3(CH2)7CH＝CH(CH2)7、CH3(CH2)4CH＝CHCH2CH＝CH(CH2)7、CH3(CH2)18、CH3(CH2)4(CH＝CH-CH2)4(CH2)2、CH3(CH2)4CH＝CHCH2CH＝CHCH2CH＝CH(CH2)4And CH3(CH2CH＝CH)3(CH2)7。
In one embodiment, the mass ratio of mink oil to polyethylene glycol is 1: (2-10).
In one embodiment, the catalyst is H2SO4One or more than two of p-toluenesulfonic acid and acidic ionic liquid.
In one embodiment, the amount (mass) of the catalyst is 10-20% of that of the mink oil, namely when the amount of the mink oil is 1g, the amount of the catalyst is 0.1-0.2 g.
In one embodiment, the reaction temperature is 60-100 ℃ and the reaction time is 6-12 h.
In one embodiment, a molecular sieve can be added in the preparation method, wherein the molecular sieve is a 4A molecular sieve, and the mass ratio of the molecular sieve to the mink oil is 1: 6.
In one embodiment, when the molecular sieve is added in the preparation method, filtration is required at the end of the reaction, the molecular sieve is removed to obtain a filtrate, and then dichloromethane is added into the filtrate.
In one embodiment, the preparation method can further comprise adding an organic solvent (added into the preparation system together with mink oil), wherein the organic solvent is one or two of cyclohexane and toluene, the volume/mass ratio of the organic solvent to the mink oil is 50-100: 30, namely when the amount of the mink oil is 30g, the amount of the organic solvent is 50-100m L.
In one embodiment, after the organic solvent is added in the preparation method, the organic solvent is removed by rotary evaporation after the reaction is finished, and then dichloromethane is added into the concentrated solution.
In one embodiment, the volume/mass ratio of the dichloromethane to the mink oil is 150-.
In one embodiment, said NaHCO3The volume/mass ratio of the aqueous solution, the saturated saline, the water and the mink oil is 100: 30, i.e. NaHCO when mink oil is used in an amount of 30g3The amount of the aqueous solution, saturated saline and water was 100m L.
In one embodiment, said NaHCO3The mass fraction of the aqueous solution was 10%.
The second purpose of the invention is to provide a preparation method of the polyethylene glycol mink oleate surfactant.
The third purpose of the invention is to use the polyethylene glycol mink oleate surfactant in daily cosmetics.
In one embodiment, the polyethylene glycol mink oleate surfactant provided by the invention is applied to the skin lotion, and the skin lotion comprises the following specific components: 15 parts of polyethylene glycol mink oleate surfactant, 1 part of imidazolidinyl urea, 4 parts of beeswax, 4 parts of cetyl alcohol, 7 parts of glyceryl monostearate, 1 part of di-tert-butyl-p-cresol, 8 parts of white oil, 5 parts of polyethylene glycol, 10 parts of urea, 3 parts of sorbitan monooleate and 60 parts of water; the preparation method comprises the following steps: mixing all the materials, and stirring at 80-90 deg.C for 60-90 min.
The invention has the beneficial effects that:
(1) according to the invention, mink oil reacts with polyethylene glycol to obtain the polyethylene glycol mink oil acid ester surfactant, so that the smell of the mink oil is better improved, the performance of the mink oil is improved, the types of the mink oil surfactant are expanded, and the mink oil acid ester surfactant has better foam stability and mild performance; the preparation process is simple, the production cost is low, the selected raw materials are natural grease, the source is wide, the environment is protected, and the biodegradability is realized.
(2) The H L B value of the polyethylene glycol mink oil acid ester surfactant obtained by the invention reaches more than 12.5, and the stabilization time of forming emulsion with liquid paraffin is more than 430 s.
Drawings
FIG. 1 is an infrared spectrum of the polyethylene glycol mink oleate surfactant prepared in example 1.
FIG. 2 shows the polyethylene glycol mink oleate surfactant prepared in example 11H NMR spectrum.
FIG. 3 shows the results of H L B measurements of the polyethylene glycol mink oleate surfactants prepared in examples 1-6.
Detailed Description
The following description of the preferred embodiments of the present invention is provided for the purpose of better illustrating the invention and is not intended to limit the invention thereto.
And (3) infrared testing: measured using a BRUKER VECTOR 22 infrared spectrometer.
1H NMR spectrum test: using Bruker Advance DRX 500 typeNuclear magnetic resonance apparatus (400MHz) in CDCl3As solvent, TMS as internal standard.