CN105498622B - A kind of surfactant containing selenium and its preparation method and application - Google Patents
A kind of surfactant containing selenium and its preparation method and application Download PDFInfo
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- CN105498622B CN105498622B CN201510915772.2A CN201510915772A CN105498622B CN 105498622 B CN105498622 B CN 105498622B CN 201510915772 A CN201510915772 A CN 201510915772A CN 105498622 B CN105498622 B CN 105498622B
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- 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
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- 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
- A61K8/58—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing atoms other than carbon, hydrogen, halogen, oxygen, nitrogen, sulfur or phosphorus
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- A61Q17/00—Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
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- A61Q5/02—Preparations for cleaning the hair
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- 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
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- 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
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Abstract
The invention discloses a kind of surfactant containing selenium and its preparation method and application, belong to daily chemical industry technical field.The surfactant is chain alkyl seleno acetate, and its architectural feature is represented with below formula (1)(1) n is 11 to 15 integer, M in formula+For one kind in sodium ion, potassium ion or ammonium ion.The preparation method of the surfactant containing selenium is simple, and synthesis condition is gentle, and no especial equipment requirements, energy consumption is relatively low, and raw material is easy to get, and hydroxyl acetate and chloracetate are not contained in product；Surface-active of gained surfactant containing selenium itself is higher, and with outstanding foaming and foam stability energy, with the hard water resistance of uniqueness, antioxygenic property and Scavenging ability, and cytotoxicity, aquatile acute toxicity and skin irritation are relatively low.
Description
Technical field
The present invention relates to a kind of manufacture method of surfactant containing selenium and the surfactant in soap, shampoo, wash one's hair
Application in the daily washing chemical such as bath lotion, belongs to daily chemical industry technical field.
Background technology
Selenium (Se) is a kind of element with important physiologically active, is existed in life entity with Selenonic protein form, Chang Wei
The activated centre of Selenonic protein enzyme.Human body selenium deficiency can cause serious disease, oral organic Se-rich carbohydrate or protein substance
It is often the method for human body selenium-supply, but security risk is higher, because inorganic selenium and organic selenium compounds have by force mostly
Strong oral toxic side effect.Human body skin inflammatory reaction often has the oxidative species such as free radical to be formed, and material containing selenium has good
Anti-oxidation efficacy, therefore, the manufacture method of a kind of surfactant containing selenium of present invention design and for manufacturing soap containing selenium, containing selenium
The daily washing chemical such as shampoo and shower cream containing selenium, surfactant containing selenium of the present invention had both had typically daily wash
The basic physics and chemistry function of the surfactant required by chemicals is washed, is had again anti-oxidant not available for general surfactant
With excellent removing free radical performance, skin irritation is small, and aquatile acute toxicity is small, simultaneously, it may have excellent formula
The beneficial effects such as compound synergic compatibility performance.
The content of the invention
Present invention aims at provide the manufacture method and the surfactant of a kind of surfactant containing selenium in soap, hair washing
Application in the daily washing chemical such as shampoo and shower cream.
To achieve the above object, the technical solution adopted by the present invention is as follows：
The surfactant containing selenium of the present invention, the surfactant is chain alkyl seleno acetate, and its architectural feature is used
Below formula (1) is represented
(1)
N is 11 to 15 integer, M in formula+For one kind in sodium ion, potassium ion or ammonium ion.
The preparation method of the surfactant containing selenium of the present invention is as follows：
Under nitrogen protection, take positive structure chain alkyl diselenide to be dissolved in tetrahydrofuran, hydroboration is added dropwise under the conditions of ice-water bath
The ice water solution of sodium, and under ice-water bath react 2-3 hours after, methyl chloroacetate is added dropwise into above-mentioned reaction solution, ice-water bath is anti-
Answer after 0.3-0.7 hours, organic phase is obtained by extraction with dichloromethane, be dehydrated and volatilize after solvent, upper silicagel column is with ethyl acetate
Chain alkyl seleno methyl acetate is afforded with the mixed solvent of petroleum ether；Chain alkyl seleno methyl acetate is taken to be protected in nitrogen
The in the mixed solvent of first alcohol and water is dissolved under shield, sodium hydroxide or potassium hydroxide or ammoniacal liquor are added into above-mentioned solution, room temperature is anti-
Answer 3 hours, solid product is obtained after filtering, then with silicagel column with ethyl acetate and petroleum ether volume ratio 1:5 mixed solvent is washed
It is de- to obtain chain alkyl seleno acetate.
It is preferred that technical scheme be：Under nitrogen protection, take positive structure chain alkyl diselenide (carbon atom number is 12 to 16)
Tetrahydrofuran is dissolved in, according to sodium borohydride under the conditions of ice-water bath:Chain alkyl diselenide mol ratio 4:1 to 8:1 scope is added dropwise
The ice water solution of sodium borohydride, and under ice-water bath react 2.5 hours after, according still further to methyl chloroacetate:Chain alkyl diselenide
Mol ratio 2:1 to 2.5:Methyl chloroacetate is added dropwise in 1 scope, after ice-water bath reacts 0.5 hour, is obtained by extraction with dichloromethane organic
Phase, is dehydrated and volatilizes after solvent, and upper silicagel column is using ethyl acetate and petroleum ether volume ratio as 1:10 mixed solvent is afforded
Chain alkyl seleno methyl acetate, yield is 84% to 93%.Chain alkyl seleno methyl acetate is taken to use volume under nitrogen protection
Than 4:In 1 methanol and water mixed solvent, according still further to sodium hydroxide:Chain alkyl seleno methyl acetate mol ratio 1.5:1 to 2:1
Scope adds sodium hydroxide and reacted at room temperature 3 hours, and solid product is obtained after filtering, then with silicagel column with ethyl acetate and petroleum ether
Volume ratio 1:5 mixed solvent affords chain alkyl seleno sodium acetate, and yield is 90.1% to 98.4%.Use potassium hydroxide instead
Or ammoniacal liquor substitution above-mentioned steps in sodium hydroxide, then can respectively obtain chain alkyl seleno potassium acetate (yield be 87.7% to
93.8%) with chain alkyl seleno ammonium acetate (yield is 91.3% to 98.2%).
The technical scheme that the manufacture method of the soap of the present invention containing selenium is used is as follows：
In parts by weight, 100 parts of basic soap heating and meltings are taken, then put into 0.1-5 parts of surfactants containing selenium and are well mixed,
Other auxiliary materials such as essence and colouring agent are added as needed, are rolled into bar stripping and slicing and be can be prepared by soap containing selenium.
The basic soap is commercially available soap base or commercially available finished product soap.
The technical scheme that the manufacture method of shampoo containing selenium and the shower cream containing selenium of the present invention is used is as follows：
In parts by weight, 100 parts of commercially available shampoos or commercially available shower cream are taken, then puts into the 0.1-5 parts of work of surface containing selenium
Property agent be well mixed, you can obtain shampoo containing selenium and shower cream containing selenium respectively.
The technology of the present invention has advantages below：The preparation method of the surfactant containing selenium is simple, and synthesis condition is gentle, no spy
Different equipment requirement, energy consumption is relatively low, and raw material is easy to get, and hydroxyl acetate and chloracetate are not contained in product；Live on gained surface containing selenium
Property agent surface-active itself it is higher, with outstanding foaming and foam stability energy, with unique hard water resistance, antioxygenic property and clear
Except free radical ability, and cytotoxicity, aquatile acute toxicity and skin irritation are relatively low；Gained soap containing selenium, wash containing selenium
Hair-care shampoo and shower cream containing selenium are respectively provided with good antioxygenic property, and pathogenic bacteria antibacterial and mite performance of going out are outstanding, remarkably promote inflammation
Property skin reparation and eliminate inflammatory cutaneous discomfort；Gained chain alkyl seleno acetate compatibility in basic soap
It is good, the crystal property of basic soap can be improved, gained chain alkyl seleno potassium salt or ammonium salt can significantly improve basis
The foaming of soap and foam stability energy, foam are fine and smooth；Gained chain alkyl seleno acetate compatibility in shampoo and shower cream
Good, wherein chain alkyl seleno acetic acid sodium salt can have extra pearly-lustre performance, can assign gained shampoo containing selenium and containing selenium
The unique pearly-lustre characteristic of shower cream, and chain alkyl seleno potassium salt and ammonium salt can be obviously improved shampoo and shower cream
Foaming and foam stability energy, and foam is fine and smooth, and shampoo containing selenium is washed rear hair more gloss and more cardability, washed one's hair containing selenium
It is higher that bath lotion washes rear skin skin sense comfort level, skin itching symptom can be substantially eliminated, with good antibacterial miticidal effect.
Brief description of the drawings
Fig. 1 is the infared spectrum of myristyl seleno potassium acetate.
Fig. 2 is the hydrogen nuclear magnetic resonance collection of illustrative plates of myristyl seleno potassium acetate.
Embodiment
Embodiment 1：Carbon number is the manufacture of 12 to 16 positive structure chain alkyl diselenide
6.36 g selenium powders (0.04 mol) are taken to be cooled down under nitrogen protection with 52 g water mixing ice-water baths；Separately take 6.67 g boron
Sodium hydride (0.16 mol), which is dissolved completely in, to be added to after frozen water in the mixed solution of selenium powder and water, after reacting at room temperature 20 minutes,
Put into again after 0.04 mol selenium powders be warming up to 70 degrees Celsius react 20 minutes, according still further to bromo long-chain normal paraffin:Selenium mol ratio
2:The bromododecane (either bromotetradecane or bromohexadecane) that 1 input is dissolved with tetrahydrofuran in advance, it is Celsius 55
Stirring reaction 18 hours are spent, organic phase is obtained by extraction with dichloromethane, dehydrates and volatilizes after solvent, residue with ethyl acetate
Chain alkyl diselenide yellow crystals are recrystallized to give, the yield of dodecyl diselenide is 83%, the receipts of myristyl diselenide
Rate is 87.2%, and the yield of cetyl diselenide is 86.7%.
Embodiment 2：The manufacture of dodecyl seleno acetate
Under nitrogen protection, take the g of dodecyl diselenide 4.96 to be dissolved in 40 mL tetrahydrofurans, be added dropwise under the conditions of ice-water bath
1.52 g sodium borohydrides are dissolved in the solution of 50 mL frozen water, after ice-water bath reacts 2.5 hours, and 15 mL tetrahydrofurans and 2.18 are added dropwise
G methyl chloroacetates, after ice-water bath reacts 0.5 hour, are obtained by extraction organic phase with dichloromethane, are dehydrated and volatilize after solvent, on
Silicagel column is using ethyl acetate and petroleum ether volume ratio as 1:10 mixed solvent affords dodecyl seleno methyl acetate, receives
Rate is 93 %.2 g dodecyl seleno methyl acetates are taken to be dissolved under nitrogen protection in 80 mL methanol and 20 mL water again, then
According to sodium hydroxide:Dodecyl seleno methyl acetate mol ratio 2:1 ratio adds sodium hydroxide, reacts at room temperature 3 hours, mistake
Solid silicagel column is with ethyl acetate and petroleum ether volume ratio 1 after filter:5 mixed solvent affords dodecyl seleno acetic acid
Sodium, yield is 90.1%.If using the sodium hydroxide in potassium hydroxide or ammoniacal liquor substitution above-mentioned steps instead, then ten can be respectively obtained
Selenium dialkyl guanidine-acetic acid potassium (yield is 87.7%) and dodecyl seleno ammonium acetate (yield is 91.3%).
All dodecyl seleno acetic acid product salts obtained are manufactured using the above method and analyze work by diphasic titration
Property thing content be 98.2% to 99.3% scope.The Krafft points of dodecyl seleno sodium acetate have to be not less than 90 degrees Celsius
Good pearly-lustre performance, the Krafft points of dodecyl seleno potassium acetate are about 8 degrees Celsius, dodecyl seleno ammonium acetate
Krafft points are about 10 degrees Celsius.Gained dodecyl seleno potassium acetate and dodecyl are determined using Ross-Miles methods are improved
51% and 46 % is respectively increased than lauryl sodium sulfate in the foaming power of seleno ammonium acetate, and 35% He is respectively increased in foam stability
38%.Under the nitrogen stream effect of identical flow velocity, the foam ratio ten of dodecyl seleno potassium acetate and dodecyl seleno ammonium acetate
Sodium dialkyl sulfate it is finer and smoother.At 25 degrees Celsius, suspension ring method measures dodecyl seleno potassium acetate and dodecyl seleno
The critical micelle concentration of ammonium acetate is respectively 3.24 mmol/L and 3.98 mmol/L.With the long-chain fat of similar carbon atom number
Acid sodium-salt is compared, and hard water resistance performance improves 25 times.
Embodiment 3：The manufacture of myristyl seleno acetate
Under nitrogen protection, take the g of myristyl diselenide 3.34 to be dissolved in 40 mL tetrahydrofurans, be added dropwise under the conditions of ice-water bath
1.45 g sodium borohydrides are dissolved in the solution of 30 mL frozen water, after ice-water bath reacts 2.5 hours, and 10 mL tetrahydrofurans and 1.66 are added dropwise
G methyl chloroacetates, after ice-water bath reacts 0.5 hour, are obtained by extraction organic phase with dichloromethane, are dehydrated and volatilize after solvent, on
Silicagel column is using ethyl acetate and petroleum ether volume ratio as 1:10 mixed solvent affords myristyl seleno methyl acetate, receives
Rate is 91.2%.2 g myristyl seleno methyl acetates are taken to be dissolved under nitrogen protection in 80 mL methanol and 20 mL water, then
According to sodium hydroxide:Myristyl seleno methyl acetate mol ratio 2.2:1 ratio adds sodium hydroxide, reacts at room temperature 3 hours,
Solid silicagel column is with ethyl acetate and petroleum ether volume ratio 1 after filtering:5 mixed solvent affords myristyl seleno second
Sour sodium, yield is 98.4%.If using the sodium hydroxide in potassium hydroxide or ammoniacal liquor substitution above-mentioned steps instead, then it can respectively obtain
Myristyl seleno potassium acetate (yield is 91.3%) and myristyl seleno ammonium acetate (yield is 91.3%).Fig. 1 is gained ten
The infared spectrum of tetraalkyl seleno sodium acetate, Fig. 2 is the hydrogen nuclear magnetic resonance collection of illustrative plates of gained myristyl seleno sodium acetate.
All myristyl seleno acetic acid product salts obtained are manufactured using the above method and analyze work by diphasic titration
Property thing content be 99.2% to 99.6% scope.The Krafft points of myristyl seleno sodium acetate have to be not less than 90 degrees Celsius
Good pearly-lustre performance, the Krafft points of myristyl seleno potassium acetate are about 10 degrees Celsius, myristyl seleno ammonium acetate
Krafft points are about 11 degrees Celsius.Gained myristyl seleno potassium acetate and myristyl are determined using Ross-Miles methods are improved
54% and 49 % is respectively increased than lauryl sodium sulfate in the foaming power of seleno ammonium acetate, and 38% He is respectively increased in foam stability
41%.Under the nitrogen stream effect of identical flow velocity, the foam ratio ten of myristyl seleno potassium acetate and myristyl seleno ammonium acetate
Sodium dialkyl sulfate it is finer and smoother.At 25 degrees Celsius, suspension ring method measures myristyl seleno potassium acetate and myristyl seleno
The critical micelle concentration of ammonium acetate is respectively 0.48 mmol/L and 0.51 mmol/L.With the long-chain fat of similar carbon atom number
Acid sodium-salt is compared, and hard water resistance performance improves 55 times.
Embodiment 4：The manufacture of cetyl seleno acetate
Under nitrogen protection, take the g of cetyl diselenide 5.52 to be dissolved in 40 mL tetrahydrofurans, be added dropwise under the conditions of ice-water bath
2.28 g sodium borohydrides are dissolved in the solution of 30 mL frozen water, after ice-water bath reacts 2.5 hours, and 15 mL tetrahydrofurans and 2.71 are added dropwise
G methyl chloroacetates, after ice-water bath reacts 0.5 hour, are obtained by extraction organic phase with dichloromethane, are dehydrated and volatilize after solvent, on
Silicagel column is using ethyl acetate and petroleum ether volume ratio as 1:10 mixed solvent affords myristyl seleno methyl acetate, receives
Rate is 84 %.Take 2 g cetyl seleno methyl acetates to be dissolved under nitrogen protection in 80 mL methanol and 20 mL water, then press
According to sodium hydroxide:Cetyl seleno methyl acetate mol ratio 2.5:1 ratio adds sodium hydroxide, reacts at room temperature 3 hours, mistake
Solid silicagel column is with ethyl acetate and petroleum ether volume ratio 1 after filter:5 mixed solvent affords cetyl seleno acetic acid
Sodium, yield is 97.1%.If using the sodium hydroxide in potassium hydroxide or ammoniacal liquor substitution above-mentioned steps instead, then ten can be respectively obtained
Six alkyl selenide guanidine-acetic acid potassium (yield is 93.8%) and cetyl seleno ammonium acetate (yield is 98.2%).
All cetyl seleno acetic acid product salts obtained are manufactured using the above method and analyze work by diphasic titration
Property thing content be 98.7% to 99.7% scope.The Krafft points of cetyl seleno sodium acetate have to be not less than 90 degrees Celsius
Good pearly-lustre performance, the Krafft points of cetyl seleno potassium acetate are about 14 degrees Celsius, cetyl seleno ammonium acetate
Krafft points are about 14 degrees Celsius.Gained cetyl seleno potassium acetate and cetyl are determined using Ross-Miles methods are improved
47% and 41 % is respectively increased than lauryl sodium sulfate in the foaming power of seleno ammonium acetate, and 48% He is respectively increased in foam stability
43%.Under the nitrogen stream effect of identical flow velocity, the foam ratio ten of cetyl seleno potassium acetate and cetyl seleno ammonium acetate
Sodium dialkyl sulfate it is finer and smoother.At 25 degrees Celsius, suspension ring method measures cetyl seleno potassium acetate and cetyl seleno
The critical micelle concentration of ammonium acetate is respectively 3.66 × 10-5Mol/L and 3.81 × 10-5mmol/L.With similar carbon atom
Several sodium long-chain fatty acid salts are compared, and hard water resistance performance improves 116 times.
Embodiment 5：Carbon number is the biochemical property of 12 to 16 positive structure chain alkyl seleno acetate
The gained chain alkyl seleno acetate into embodiment 4 of Example 2, carries out radicals scavenging, cell toxicant respectively
Property and skin irritatin performance evaluate.By the sylvite and ammonium salt of gained surfactant containing selenium be configured to mass fraction for 0.01% to
It is real that the aqueous solution of 5% scope carries out external 1,1- diphenyl -2- picryls hydrazine (DPPH, CAS 1898-66-4) radicals scavenging
Test, DPPH free radical scavenging activities are not less than 91%；Using HepG2 liver cells as model cell, above-described embodiment 2 is tested using mtt assay
To the IC50 numerical value of the gained chain alkyl seleno acetate of embodiment 4, minimum 11.2 mg/L of IC50 of institute's test agent, and join
The IC50 of product neopelex is 6.7 mg/L in the same old way, illustrates that embodiment 2 arrives the gained chain alkyl seleno second of embodiment 4
The cytotoxicity of hydrochlorate sample is smaller；By model evaluation embodiment 2 of the pseudo- Diaptomus of iS-One to the gained chain alkyl selenium of embodiment 4
The aquatile acute toxicity (in terms of the LC50 of 24 hours) of guanidine-acetic acid salt, embodiment 2 arrives the gained chain alkyl seleno of embodiment 4
Minimum 112.8 mg/L of LC50 of acetate, and the LC50 of reference sample lauryl sodium sulfate is 57.1 mg/L, illustrates real
The aquatile security for applying example 2 to the gained chain alkyl seleno acetate of embodiment 4 is preferable；With family's rabbit skin spreading experiment knot
Fruit shows that the skin irritation of embodiment 2 to the gained chain alkyl seleno acetate of embodiment 4 is extremely low.Example 2 is to implementation
In example 4 gained chain alkyl seleno acetate be made into the 0.1 % aqueous solution carry out in-vitro antibacterial go out mite test result indicates that, to large intestine
Bacillus, gold-coloured staphylococci and acarid have obvious killing action, compared with similar carbon number soap sample, to big
The killing action of enterobacteria and gold-coloured staphylococci improves 113%, and 351% is improved to the killing action of acarid.
Embodiment 6：The manufacture of the perfumed soap containing selenium
Taking the commercially available g of perfumed soap 100 to be heated to 45 degrees Celsius to 55 degrees Celsius melts it, another Example 2 to embodiment 4
Gained chain alkyl seleno acetate, is added to the city melted in advance according to the % of raw material perfumed soap mass percent 0.1 to 5 % scopes
Sell in perfumed soap, after being uniformly mixed, being cooled and shaped can obtain perfumed soap containing selenium.Take gained perfumed soap containing selenium to be made into 1% aqueous solution to enter
External 1,1- diphenyl -2- picryls hydrazine (DPPH, CAS 1898-66-4) the radicals scavenging experiment of row, DPPH radicals scavengings
Rate is more than 95 %；The sample of soap containing selenium be made into 1% aqueous solution carry out in-vitro antibacterial go out mite test result indicates that, to Escherichia coli, gold
Color staphylococcus and acarid have obvious killing action, compared with raw material soap, and Escherichia coli and gold-coloured staphylococci are killed
The effect of going out improves 93%, and 91% is improved to the killing action of acarid；Gained perfumed soap containing selenium is determined using Ross-Miles methods are improved
The ratio that foaming power and foam stability are improved than raw material perfumed soap is more than 11 %, and foam is finer and smoother；With the commercially available perfume (or spice) of raw material
Soap is compared, and the soft durometer of the soap containing selenium is softer, wherein the sample knife sectility of soap containing selenium containing chain alkyl seleno acetic acid sodium salt
Face has asterism pearly-lustre, it is seen that embodiment 2 to the gained chain alkyl seleno acetate of embodiment 4 can be obviously improved raw material soap
Crystal property；Rabbit skin experiment result shows that the skin irritation of all samples of soap containing selenium perfumed soap all more commercially available than raw material is low,
All there is significant repairing accelerant effect to ultraviolet ray burn skin；Show all samples of perfumed soap containing selenium to skin through volunteer's experiment
Skin itch has obvious inhibition.
Embodiment 7：The manufacture of the transparent soap containing selenium
Taking the g of commercial clear soap 500 to be heated to 45 degrees Celsius to 55 degrees Celsius melts it, another Example 2 to embodiment
4 gained chain alkyl seleno potassium salts or ammonium salt, add according to the % of raw material transparent soap mass percent 0.1 to 5 % scopes, stir
Mix after being well mixed, being cooled and shaped can obtain transparent soap containing selenium.Compared with raw material commercial clear soap, the transparent soap containing selenium it is soft or hard
Degree is softer, and transparent feel is stronger；Take gained transparent soap containing selenium to be made into 1% aqueous solution and carry out external DPPH radicals scavengings experiment,
DPPH free radical scavenging activities are more than 95 %；Using the foaming power and bubble for improving Ross-Miles methods measure gained transparent soap containing selenium
The ratio that foam stability is improved than raw material transparent soap is more than 17 %, and foam is finer and smoother；The sample of transparent soap containing selenium is made into 1%
The aqueous solution carry out in-vitro antibacterial go out mite test result indicates that, to Escherichia coli, gold-coloured staphylococci and acarid have significantly kill
The effect of going out, compared with raw material transparent soap, improves 94% to the killing action of Escherichia coli and gold-coloured staphylococci, acarid is killed
The effect of going out improves 97%.
Embodiment 8：The preparation of the soap containing selenium
Taking the commercially available Kg of soap base 50 to be heated to 45 degrees Celsius to 55 degrees Celsius melts it, another Example 2 to embodiment 4
Gained chain alkyl seleno acetate, is added to what is melted in advance according to the % of raw material soap base mass percent 0.1 to 4.5 % scopes
In commercially available soap base, while 1% colouring agent is added, 0.1% fragrance for detergents, after being uniformly mixed, being cooled and shaped can obtain containing selenium
Soap.Compared with above-mentioned formula without the reference sample of the surfactant containing selenium, the soft durometer of the soap containing selenium is softer, wherein containing
The sample knife cut section of soap containing selenium for having chain alkyl seleno acetic acid sodium salt has asterism pearly-lustre, it is seen that embodiment 2 to the institute of embodiment 4
The crystal property of soap can be obviously improved by obtaining chain alkyl seleno acetate；Take gained soap containing selenium to be made into 1% aqueous solution and carry out body
Outer DPPH radicals scavengings experiment, DPPH free radical scavenging activities are more than 95 %.The sample of soap containing selenium is made into 1% aqueous solution and carries out body
Outer antibacterial go out mite test result indicates that, there is obvious killing action to Escherichia coli, gold-coloured staphylococci and acarid, with raw material
Soap is compared, and 97% is improved to the killing action of Escherichia coli and gold-coloured staphylococci, and 107% is improved to the killing action of acarid；Adopt
Surpassed than the ratio that raw material soap base is improved with the foaming power and foam stability that improve Ross-Miles methods measure gained soap containing selenium
117 % are crossed, and foam is finer and smoother.
Embodiment 9：The preparation of the shampoo containing selenium
Take the commercially available g of shampoo 100, another Example 2 to the gained chain alkyl seleno potassium salt of embodiment 4 or ammonium
Salt, is added after being uniformly mixed under agitation according to the % of raw material shampoo mass percent 0.1 to 5 % scopes, you can
To shampoo containing selenium.Gained shampoo containing selenium is proved containing selenium hair washing by 45 degrees Celsius and subzero 4 degrees Celsius of accelerated tests
The formulation stability of shampoo, all without notable difference, shows embodiment 2 to the gained of embodiment 4 compared with the commercially available shampoo of raw material
Chain alkyl seleno potassium salt and ammonium salt have good formula compounding compatibility；The sample of shampoo containing selenium is taken to be made into 1% water
Solution carries out external DPPH radicals scavengings experiment, and DPPH free radical scavenging activities are more than 96.8 %, the sample of shampoo containing selenium
Be made into 1% aqueous solution carry out in-vitro antibacterial go out mite test result indicates that, have to Escherichia coli, gold-coloured staphylococci and acarid bright
Aobvious killing action, compared with raw material shampoo, 89 % are improved to the killing action of Escherichia coli and gold-coloured staphylococci, right
The killing action of acarid improves 93.8 %；Using the foaming power and bubble for improving Ross-Miles methods measure gained shampoo containing selenium
The ratio that the shampoo more commercially available than raw material of foam stability is improved is more than 83 %, and foam is finer and smoother；With the commercially available shampoo of raw material
Compare, more preferably, the reflecting feel for washing rear hair is stronger for the cardability of hair after being washed through shampoo containing selenium；Through volunteer's result of the test
Show that all shampoos containing selenium all have significant inhibition to scalp pruritis.
Embodiment 10：The preparation of pearly-lustre shampoo containing selenium
Commercially available certain shampoo 100 g without pearling agent is taken, according to the % to 5 of raw material shampoo mass percent 0.1
The lower addition embodiment 2 of % scopes stirring is to the gained chain alkyl seleno acetic acid sodium salt of embodiment 4, after being sufficiently mixed uniformly, you can
Outward appearance is in the shampoo containing selenium of obvious pearly-lustre, it is seen that chain alkyl seleno sodium acetate can assign it is thick be formulated with pearly-lustre,
Outward appearance class without greatly improving product on the basis of additionally addition pearling agent.Gained shampoo containing selenium is taken the photograph by 45
Family name's degree and subzero 4 degrees Celsius of accelerated tests prove the formulation stability and the commercially available shampoo phase of raw material of pearly-lustre shampoo containing selenium
Than all without notable difference, showing that surfactant containing selenium has good compounding compatibility；The sample of shampoo containing selenium is taken to match somebody with somebody
External DPPH radicals scavengings experiment is carried out into 1% aqueous solution, DPPH free radical scavenging activities are more than 98.2 %；Had one's hair wash containing selenium fragrant
Ripple sample be made into 1% aqueous solution carry out in-vitro antibacterial go out mite test result indicates that, to Escherichia coli, gold-coloured staphylococci and acarid
With obvious killing action, compared with raw material shampoo, the killing action of Escherichia coli and gold-coloured staphylococci is improved
95.7 %, 98.7 % are improved to the killing action of acarid；The gained perfume of pearl shining shampoo containing selenium is determined using Ross-Miles methods are improved
The ratio that foaming power and the foam stability shampoo more commercially available than raw material of ripple are improved is more than 35 %, and foam is finer and smoother；With original
Expect that commercially available shampoo is compared, the cardability after hair is washed through pearly-lustre shampoo containing selenium is more preferable, washes the reflecting feel of rear hair more
By force, moreover, wash the cardability after rear hair is dried up through hair dryer and reflecting feel is still kept, and it is fluffy without obvious electrostatic
Pine sense, it is seen that embodiment 2 to the gained chain alkyl seleno acetic acid sodium salt of embodiment 4, which not only has, is significantly formulated compatible and collaboration
The advantage of synergy, but also with obvious antistatic effect；Show that all pearly-lustres are had one's hair wash containing selenium through volunteer's result of the test fragrant
Ripple all has significant inhibition to scalp pruritis.
Embodiment 11：The preparation of the shower cream containing selenium
Take the commercially available g of shower cream 100, another Example 2 to the gained chain alkyl seleno potassium salt of embodiment 4 or ammonium salt,
Added under agitation according to the % of raw material shower cream mass percent 0.1 to 5 % scopes after being uniformly mixed, you can obtain containing selenium
Shower cream.Gained shower cream containing selenium proves that the formula of the shower cream containing selenium is steady by 45 degrees Celsius and subzero 4 degrees Celsius of accelerated tests
Qualitative notable difference all no compared with the commercially available shower cream of raw material, shows embodiment 2 to the gained chain alkyl seleno second of embodiment 4
Acid potassium salt and ammonium salt have good formula compounding compatibility；Take the sample of shower cream containing selenium to be made into 1% aqueous solution and carry out external DPPH
Radicals scavenging is tested, and DPPH free radical scavenging activities are more than 97.8 %, and the sample of shower cream containing selenium is made into 1% aqueous solution and carries out body
Outer antibacterial go out mite test result indicates that, gained shower cream containing selenium has obvious to Escherichia coli, gold-coloured staphylococci and acarid
Killing action, compared with raw material shower cream, improves 63%, to acarid to the killing action of Escherichia coli and gold-coloured staphylococci
Killing action improves 51%；Using the foaming power and foam stability ratio for improving Ross-Miles methods measure gained shower cream containing selenium
The ratio that the commercially available shower cream of raw material is improved is more than 73 %, and foam is finer and smoother；Compared with the commercially available shower cream of raw material, through containing selenium
The bright and clean sense and lubrication sense that shower cream washes rear skin are stronger；Show all shower creams containing selenium to skin scabies through volunteer's result of the test
Symptom of itching all has significant inhibition.
Embodiment 12：The preparation of pearly-lustre shower cream containing selenium
Take the commercially available g of shower cream 100 without pearling agent, another Example 2 to the gained chain alkyl seleno second of embodiment 4
Acid sodium-salt, is added after being uniformly mixed under agitation according to the % of raw material shower cream mass percent 0.1 to 5 % scopes, you can
Obtain pearly-lustre shower cream containing selenium.Gained pearly-lustre shower cream containing selenium proves pearl by 45 degrees Celsius and subzero 4 degrees Celsius of accelerated tests
The formulation stability of light shower cream containing selenium, all without notable difference, shows embodiment 2 to implementation compared with the commercially available shower cream of raw material
The gained chain alkyl seleno acetic acid sodium salt of example 4 has good formula compounding compatibility；Pearly-lustre shower cream containing selenium sample is taken to be made into
1% aqueous solution carries out external DPPH radicals scavengings experiment, and DPPH free radical scavenging activities are more than 97.2 %, and pearly-lustre is taken a shower containing selenium
Dew sample be made into 1% aqueous solution carry out in-vitro antibacterial go out mite test result indicates that, gained shower cream containing selenium is to Escherichia coli, gold
Staphylococcus and acarid have obvious killing action, compared with raw material shower cream, to Escherichia coli and gold-coloured staphylococci
Killing action improves 67%, and 53% is improved to the killing action of acarid；Gained pearly-lustre is determined containing selenium using Ross-Miles methods are improved
The ratio that the foaming power and foam stability of shower cream shower cream more commercially available than raw material are improved is more than 61 %, and foam more refinement
It is greasy；Compared with the commercially available shower cream of raw material, the bright and clean sense and lubrication sense of skin are stronger after being washed through pearly-lustre shower cream containing selenium；Through volunteer
Result of the test shows that all pearly-lustre shower creams containing selenium all have significant inhibition to skin itching symptom.
Claims (5)
1. the preparation method of a kind of surfactant containing selenium, it is characterised in that the surfactant is chain alkyl seleno acetic acid
Salt, its architectural feature is represented with below formula (1)
(1)
N is 11 to 15 integer, M in formula+For one kind in sodium ion, potassium ion or ammonium ion；
Its preparation method is：Under nitrogen protection, take positive structure chain alkyl diselenide to be dissolved in tetrahydrofuran, dripped under the conditions of ice-water bath
Plus the ice water solution of sodium borohydride, and under ice-water bath react 2-3 hours after, methyl chloroacetate is added dropwise into above-mentioned reaction solution,
Ice-water bath react 0.3-0.7 hours after, organic phase is obtained by extraction with dichloromethane, is dehydrated and volatilizes after solvent, upper silicagel column with
The mixed solvent of ethyl acetate and petroleum ether affords chain alkyl seleno methyl acetate；Take chain alkyl seleno methyl acetate
The in the mixed solvent of first alcohol and water is dissolved under nitrogen protection, and sodium hydroxide or potassium hydroxide or ammonia are added into above-mentioned solution
Water, reacts at room temperature 3 hours, solid product is obtained after filtering, then with silicagel column with ethyl acetate and petroleum ether volume ratio 1:5 it is mixed
Bonding solvent affords chain alkyl seleno acetate.
2. the preparation method of the surfactant according to claim 1 containing selenium, it is characterised in that：The sodium borohydride and length
Alkyl group diselenide mole be 4 ~ 8:1.
3. the preparation method of the surfactant according to claim 1 containing selenium, it is characterised in that：The methyl chloroacetate and
Chain alkyl diselenide mol ratio is 2 ~ 2.5:1.
4. the preparation method of the surfactant according to claim 1 containing selenium, it is characterised in that：The ethyl acetate and stone
The in the mixed solvent ethyl acetate and petroleum ether volume ratio of oily ether are 1:10.
5. the preparation method of the surfactant according to claim 1 containing selenium, it is characterised in that：The first alcohol and water it is mixed
The volume ratio of first alcohol and water is 4 in bonding solvent:1.
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| CN106753823A (en) * | 2016-11-30 | 2017-05-31 | 江南大学 | A kind of surfactant containing selenium responded with pH and redox dual-switch |
| CN107235880B (en) * | 2017-06-30 | 2018-10-30 | 江南大学 | One kind cationic surfactant containing selenium and its application |
| CN107998979B (en) * | 2017-12-15 | 2019-11-22 | 江南大学 | One kind interface emulsification agent of nonionic containing selenium and its preparation method and application |
| CN109762159B (en) * | 2018-12-19 | 2021-06-25 | 万华化学集团股份有限公司 | Selenium-containing surfactant and preparation method thereof |
| CN110082478B (en) * | 2019-05-20 | 2020-07-03 | 江南大学 | Switch circuit controlled by selenium-containing surfactant and application thereof |
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| US6046237A (en) * | 1995-07-14 | 2000-04-04 | Berge; Rolf | Non-β-oxidizable fatty acid analogues, their uses as therapeutic active medicaments |
| CN1281693A (en) * | 1999-02-03 | 2001-01-31 | 莱雅公司 | Washing cosmetics composition and application thereof |
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