CN105498622A - Selenium-containing surfactant as well as preparation method and application thereof - Google Patents
Selenium-containing surfactant as well as preparation method and application thereof Download PDFInfo
- Publication number
- CN105498622A CN105498622A CN201510915772.2A CN201510915772A CN105498622A CN 105498622 A CN105498622 A CN 105498622A CN 201510915772 A CN201510915772 A CN 201510915772A CN 105498622 A CN105498622 A CN 105498622A
- Authority
- CN
- China
- Prior art keywords
- selenium
- surfactant
- acetate
- seleno
- chain alkyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
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
- A61K8/58—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing atoms other than carbon, hydrogen, halogen, oxygen, nitrogen, sulfur or phosphorus
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- 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
- A61Q17/02—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 containing insect repellants
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q19/00—Preparations for care of the skin
- A61Q19/06—Preparations for care of the skin for countering cellulitis
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q19/00—Preparations for care of the skin
- A61Q19/08—Anti-ageing preparations
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q19/00—Preparations for care of the skin
- A61Q19/10—Washing or bathing preparations
-
- 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
- A61Q5/02—Preparations for cleaning the hair
-
- 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
- C11D10/00—Compositions of detergents, not provided for by one single preceding group
- C11D10/04—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap
- C11D10/042—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap based on anionic surface-active compounds and soap
-
- 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
- C11D1/02—Anionic compounds
- C11D1/04—Carboxylic acids or salts thereof
Landscapes
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Dermatology (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Birds (AREA)
- Epidemiology (AREA)
- Plant Pathology (AREA)
- Pest Control & Pesticides (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Gerontology & Geriatric Medicine (AREA)
- Materials Engineering (AREA)
- Cosmetics (AREA)
- Detergent Compositions (AREA)
Abstract
The invention discloses a selenium-containing surfactant as well as a preparation method and application thereof and belongs to the technical field of a daily chemical industry. The surfactant is long-chain alkyl selenium base acetate, and a structural character of the surfactant is shown as a formula (1) as shown in the specification; in the formula (1), n is an integer from 11 to 15; M<+> is one of a sodium ion, a potassium ion or an ammonium ion. The preparation method of the selenium-containing surfactant is simple, and has moderate synthesis conditions, no special requirements on equipment and relatively low energy consumption; raw materials are easy to obtain and the product does not contain hydroxyl acetate and chloroacetate; the selenium-containing surfactant has relatively high surface activity, excellent foaming and foam stabilization performance, unique hard water resistance and oxidation resistance and free radical removing capability, and relatively low cytotoxicity, aquatic organism acute toxicity and skin irritation.
Description
Technical field
The present invention relates to a kind of manufacture method containing selenium surfactant and the application of this surfactant in the daily washing chemicals such as soap, shampoo, shower cream, belong to daily chemical industry technical field.
Background technology
Selenium (Se) is a kind of element with important physiologically active, exists in life entity with Selenonic protein form, is often the activated centre of Selenonic protein enzyme.Human body lacks selenium can cause serious disease, and oral organic Se-rich carbohydrate or protein substance are often the methods that human body mends selenium, but security risk is higher, because inorganic selenium and organic selenium compounds have strong oral toxic and side effect mostly.Human body skin inflammatory reaction often has the oxidative species such as free radical to be formed, containing selenium material, there is good anti-oxidation efficacy, for this reason, the present invention designs a kind of manufacture method containing selenium surfactant and for the manufacture of containing selenium soap, containing selenium shampoo with containing daily washing chemicals such as selenium shower creams, the basic physics and chemistry function both containing selenium surfactant with the surfactant required by general daily washing chemical of the present invention, there is again the anti-oxidant and excellent scavenging free radicals performance not available for general surfactant, skin irritation is little, aquatile acute toxicity is little, simultaneously, also there is the beneficial effects such as excellent formula compound synergic compatibility performance.
Summary of the invention
The object of the invention is to provide a kind of manufacture method containing selenium surfactant and the application of this surfactant in the daily washing chemicals such as soap, shampoo and shower cream.
For achieving the above object, the technical solution used in the present invention is as follows:
Of the present invention containing selenium surfactant, this surfactant is chain alkyl seleno acetate, and its architectural feature following general formula (1) represents
(1)
In formula, n is the integer of 11 to 15, M
+for the one in sodium ion, potassium ion or ammonium radical ion.
Preparation method containing selenium surfactant of the present invention is as follows:
Under nitrogen protection, get positive structure chain alkyl diselenide and be dissolved in oxolane, the ice water solution of sodium borohydride is dripped under ice-water bath condition, and react 2-3 hour under ice-water bath after, in above-mentioned reactant liquor, drip methyl chloroacetate, ice-water bath reaction, after 0.3-0.7 hour, obtains organic phase with dichloromethane extraction, to dewater and after volatilizing solvent, upper silicagel column obtains chain alkyl seleno methyl acetate with the mixed solvent wash-out of ethyl acetate and benzinum; Getting chain alkyl seleno methyl acetate is dissolved in the mixed solvent of first alcohol and water under nitrogen protection; NaOH or potassium hydroxide or ammoniacal liquor is added in above-mentioned solution; room temperature reaction 3 hours; obtain solid product after filtration, recycle silicon glue post obtains chain alkyl seleno acetate with the mixed solvent wash-out of ethyl acetate and benzinum volume ratio 1:5.
Preferred technical scheme is: under nitrogen protection, get positive structure chain alkyl diselenide (carbon atom number is 12 to 16) and be dissolved in oxolane, according to sodium borohydride under ice-water bath condition: chain alkyl diselenide mol ratio 4:1 to 8:1 scope drips the ice water solution of sodium borohydride, and react under ice-water bath after 2.5 hours, again according to methyl chloroacetate: chain alkyl diselenide mol ratio 2:1 to 2.5:1 scope drips methyl chloroacetate, after ice-water bath reacts 0.5 hour, organic phase is obtained with dichloromethane extraction, to dewater and after volatilizing solvent, upper silicagel column obtains chain alkyl seleno methyl acetate with the mixed solvent wash-out that ethyl acetate and benzinum volume ratio are 1:10, yield is 84% to 93%.Get in the methyl alcohol and water mixed solvent that chain alkyl seleno methyl acetate uses volume ratio 4:1 under nitrogen protection; again according to NaOH: chain alkyl seleno methyl acetate mol ratio 1.5:1 to 2:1 scope adds NaOH room temperature reaction 3 hours; solid product is obtained after filtration; recycle silicon glue post obtains chain alkyl seleno sodium acetate with the mixed solvent wash-out of ethyl acetate and benzinum volume ratio 1:5, and yield is 90.1% to 98.4%.Use the NaOH in potassium hydroxide or ammoniacal liquor replacement above-mentioned steps instead, then can obtain chain alkyl seleno potassium acetate (yield is 87.7% to 93.8%) and chain alkyl seleno ammonium acetate (yield is 91.3% to 98.2%) respectively.
The technical scheme that the manufacture method containing selenium soap of the present invention adopts is as follows:
With parts by weight, get 100 parts of basic soap heating and melting, then drop into 0.1-5 part containing selenium surfactant and mix, add other auxiliary materials such as essence and colouring agent as required, rolling slivering stripping and slicing can obtain containing selenium soap.
Described basic soap is commercially available soap base or commercially available finished product soap.
Of the present invention containing selenium shampoo and the technical scheme that adopts containing the manufacture method of selenium shower cream as follows:
With parts by weight, get 100 parts of commercially available shampoos or commercially available shower cream, then drop into 0.1-5 part containing selenium surfactant and mix, can obtain respectively containing selenium shampoo with containing selenium shower cream.
The technology of the present invention has the following advantages: the preparation method containing selenium surfactant is simple, and synthesis condition is gentle, and without especial equipment requirements, energy consumption is lower, and raw material is easy to get, not containing hydroxyl acetate and chloracetate in product, gained is higher containing the surface-active of selenium surfactant own, has outstanding foaming and foam stability energy, have unique anti-hard water, antioxygenic property and Scavenging ability, and cytotoxicity, aquatile acute toxicity and skin irritation is all lower, gained is containing selenium soap, all have good antioxygenic property containing selenium shampoo with containing selenium shower cream, and pathogenic bacteria are antibacterial and mite performance of going out is outstanding, significantly promote the reparation of inflammatory cutaneous and eliminate the discomfort of inflammatory cutaneous, gained chain alkyl seleno acetate compatibility in basic soap is good, can improve the crystal property of basic soap, and gained chain alkyl seleno potassium salt or ammonium salt can significantly improve foaming and the foam stability energy of basic soap, and foam is fine and smooth, gained chain alkyl seleno acetate compatibility in shampoo and shower cream is good, wherein chain alkyl seleno acetic acid sodium salt can have extra pearly-lustre performance, gained can be given containing selenium shampoo and the pearly-lustre characteristic containing selenium shower cream uniqueness, and chain alkyl seleno potassium salt and ammonium salt significantly can promote foaming and the foam stability energy of shampoo and shower cream, and foam is fine and smooth, rear hair gloss and have more cardability is more washed containing selenium shampoo, rear skin skinfeel comfort level is washed higher containing selenium shower cream, can obviously eliminate pruitus symptom, there is good antibacterial miticidal effect.
Accompanying drawing explanation
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.
Detailed description of the invention
Embodiment 1: carbon number is the manufacture of the positive structure chain alkyl diselenide of 12 to 16
Get 6.36g selenium powder (0.04mol) to cool with 52g water mixing ice-water bath under nitrogen protection, separately getting after 6.67g sodium borohydride (0.16mol) is dissolved in frozen water completely joins in the mixed solution of selenium powder and water, room temperature reaction is after 20 minutes, 70 degrees Celsius of reactions 20 minutes are warmed up to after dropping into 0.04mol selenium powder again, again according to bromo long-chain normal paraffin: selenium mol ratio 2:1 drops into bromododecane (or the bromotetradecane dissolved with oxolane in advance, or bromohexadecane), 55 degrees Celsius of stirring reactions 18 hours, organic phase is obtained with dichloromethane extraction, to dehydrate and after volatilizing solvent, residue with ethyl acetate recrystallization obtains chain alkyl diselenide yellow crystals, the yield of dodecyl diselenide is 83%, the yield of myristyl diselenide is 87.2%, the yield of cetyl diselenide is 86.7%.
Embodiment 2: the manufacture of dodecyl seleno acetate
Under nitrogen protection; get dodecyl diselenide 4.96g and be dissolved in 40mL oxolane; the solution that 1.52g sodium borohydride is dissolved in 50mL frozen water is dripped under ice-water bath condition; after ice-water bath reacts 2.5 hours; drip 15mL oxolane and 2.18g methyl chloroacetate; after ice-water bath reacts 0.5 hour; organic phase is obtained with dichloromethane extraction; to dewater and after volatilizing solvent; upper silicagel column obtains dodecyl seleno methyl acetate with the mixed solvent wash-out that ethyl acetate and benzinum volume ratio are 1:10, and yield is 93%.Getting 2g dodecyl seleno methyl acetate is again dissolved in 80mL methyl alcohol and 20mL water under nitrogen protection; again according to NaOH: the ratio of dodecyl seleno methyl acetate mol ratio 2:1 adds NaOH; room temperature reaction 3 hours; after filtering, solid silicagel column obtains dodecyl seleno sodium acetate with the mixed solvent wash-out of ethyl acetate and benzinum volume ratio 1:5, and yield is 90.1%.If use the NaOH in potassium hydroxide or ammoniacal liquor replacement above-mentioned steps instead, then can obtain dodecyl seleno potassium acetate (yield is 87.7%) and dodecyl seleno ammonium acetate (yield is 91.3%) respectively.
It is 98.2% to 99.3% scope that all dodecyl seleno acetate products adopting said method manufacture to obtain analyze active matter content through diphasic titration.The Krafft point of dodecyl seleno sodium acetate, for being not less than 90 degrees Celsius, has good pearly-lustre performance, and the Krafft point of dodecyl seleno potassium acetate is about 8 degrees Celsius, and the Krafft point of dodecyl seleno ammonium acetate is about 10 degrees Celsius.Adopt the foaming power improving Ross-Miles method mensuration gained dodecyl seleno potassium acetate and dodecyl seleno ammonium acetate to improve 51% and 46% respectively than lauryl sodium sulfate, foam stability improves 35% and 38% respectively.Under the nitrogen airflow function of identical flow velocity, finer and smoother than lauryl sodium sulfate of the foam of dodecyl seleno potassium acetate and dodecyl seleno ammonium acetate.When 25 degrees Celsius, the critical micelle concentration that suspension ring method records dodecyl seleno potassium acetate and dodecyl seleno ammonium acetate is respectively 3.24mmol/L and 3.98mmol/L.Compared with the sodium long-chain fatty acid salts of similar carbon atom number, anti-performance of hard water improves 25 times.
Embodiment 3: the manufacture of myristyl seleno acetate
Under nitrogen protection; get myristyl diselenide 3.34g and be dissolved in 40mL oxolane; the solution that 1.45g sodium borohydride is dissolved in 30mL frozen water is dripped under ice-water bath condition; after ice-water bath reacts 2.5 hours; drip 10mL oxolane and 1.66g methyl chloroacetate; after ice-water bath reacts 0.5 hour; organic phase is obtained with dichloromethane extraction; to dewater and after volatilizing solvent; upper silicagel column obtains myristyl seleno methyl acetate with the mixed solvent wash-out that ethyl acetate and benzinum volume ratio are 1:10, and yield is 91.2%.Getting 2g myristyl seleno methyl acetate is dissolved in 80mL methyl alcohol and 20mL water under nitrogen protection; again according to NaOH: the ratio of myristyl seleno methyl acetate mol ratio 2.2:1 adds NaOH; room temperature reaction 3 hours; after filtering, solid silicagel column obtains myristyl seleno sodium acetate with the mixed solvent wash-out of ethyl acetate and benzinum volume ratio 1:5, and yield is 98.4%.If use the NaOH in potassium hydroxide or ammoniacal liquor replacement above-mentioned steps instead, then can obtain myristyl seleno potassium acetate (yield is 91.3%) and myristyl seleno ammonium acetate (yield is 91.3%) respectively.Fig. 1 is the infared spectrum of gained myristyl seleno sodium acetate, and Fig. 2 is the hydrogen nuclear magnetic resonance collection of illustrative plates of gained myristyl seleno sodium acetate.
It is 99.2% to 99.6% scope that all myristyl seleno acetate products adopting said method manufacture to obtain analyze active matter content through diphasic titration.The Krafft point of myristyl seleno sodium acetate, for being not less than 90 degrees Celsius, has good pearly-lustre performance, and the Krafft point of myristyl seleno potassium acetate is about 10 degrees Celsius, and the Krafft point of myristyl seleno ammonium acetate is about 11 degrees Celsius.Adopt the foaming power improving Ross-Miles method mensuration gained myristyl seleno potassium acetate and myristyl seleno ammonium acetate to improve 54% and 49% respectively than lauryl sodium sulfate, foam stability improves 38% and 41% respectively.Under the nitrogen airflow function of identical flow velocity, finer and smoother than lauryl sodium sulfate of the foam of myristyl seleno potassium acetate and myristyl seleno ammonium acetate.When 25 degrees Celsius, the critical micelle concentration that suspension ring method records myristyl seleno potassium acetate and myristyl seleno ammonium acetate is respectively 0.48mmol/L and 0.51mmol/L.Compared with the sodium long-chain fatty acid salts of similar carbon atom number, anti-performance of hard water improves 55 times.
Embodiment 4: the manufacture of cetyl seleno acetate
Under nitrogen protection; get cetyl diselenide 5.52g and be dissolved in 40mL oxolane; the solution that 2.28g sodium borohydride is dissolved in 30mL frozen water is dripped under ice-water bath condition; after ice-water bath reacts 2.5 hours; drip 15mL oxolane and 2.71g methyl chloroacetate; after ice-water bath reacts 0.5 hour; organic phase is obtained with dichloromethane extraction; to dewater and after volatilizing solvent; upper silicagel column obtains myristyl seleno methyl acetate with the mixed solvent wash-out that ethyl acetate and benzinum volume ratio are 1:10, and yield is 84%.Getting 2g cetyl seleno methyl acetate is dissolved in 80mL methyl alcohol and 20mL water under nitrogen protection; again according to NaOH: the ratio of cetyl seleno methyl acetate mol ratio 2.5:1 adds NaOH; room temperature reaction 3 hours; after filtering, solid silicagel column obtains cetyl seleno sodium acetate with the mixed solvent wash-out of ethyl acetate and benzinum volume ratio 1:5, and yield is 97.1%.If use the NaOH in potassium hydroxide or ammoniacal liquor replacement above-mentioned steps instead, then can obtain cetyl seleno potassium acetate (yield is 93.8%) and cetyl seleno ammonium acetate (yield is 98.2%) respectively.
It is 98.7% to 99.7% scope that all cetyl seleno acetate products adopting said method manufacture to obtain analyze active matter content through diphasic titration.The Krafft point of cetyl seleno sodium acetate, for being not less than 90 degrees Celsius, has good pearly-lustre performance, and the Krafft point of cetyl seleno potassium acetate is about 14 degrees Celsius, and the Krafft point of cetyl seleno ammonium acetate is about 14 degrees Celsius.Adopt the foaming power improving Ross-Miles method mensuration gained cetyl seleno potassium acetate and cetyl seleno ammonium acetate to improve 47% and 41% respectively than lauryl sodium sulfate, foam stability improves 48% and 43% respectively.Under the nitrogen airflow function of identical flow velocity, finer and smoother than lauryl sodium sulfate of the foam of cetyl seleno potassium acetate and cetyl seleno ammonium acetate.When 25 degrees Celsius, the critical micelle concentration that suspension ring method records cetyl seleno potassium acetate and cetyl seleno ammonium acetate is respectively 3.66 × 10
-5mol/L and 3.81 × 10
-5mmol/L.Compared with the sodium long-chain fatty acid salts of similar carbon atom number, anti-performance of hard water improves 116 times.
Embodiment 5: carbon number is the biochemical property of the positive structure chain alkyl seleno acetate of 12 to 16
Gained chain alkyl seleno acetate in Example 2 to embodiment 4, carries out radicals scavenging, cytotoxicity and the evaluation of skin irritatin performance respectively.It is that the aqueous solution of 0.01% to 5% scope carries out external 1 that gained is configured to mass fraction containing the sylvite of selenium surfactant and ammonium salt, 1-diphenyl-2-picryl hydrazine (DPPH, CAS 1898-66-4) radicals scavenging experiment, DPPH free radical scavenging activity is not less than 91%; With HepG2 liver cell for model cell, mtt assay is adopted to test the IC50 numerical value of above-described embodiment 2 to embodiment 4 gained chain alkyl seleno acetate, the IC50 of institute's test agent is minimum is 11.2mg/L, and be 6.7mg/L with reference to the IC50 of sample neopelex, illustrate that embodiment 2 is less to the cytotoxicity of embodiment 4 gained chain alkyl seleno acetate sample; In the aquatile acute toxicity (LC50 with 24 hours) that the pseudo-Diaptomus of iS-One is model evaluation embodiment 2 to embodiment 4 gained chain alkyl seleno acetate, embodiment 2 is minimum to the LC50 of embodiment 4 gained chain alkyl seleno acetate is 112.8mg/L, and be 57.1mg/L with reference to the LC50 of sample lauryl sodium sulfate, illustrate that embodiment 2 is better to the aquatile security of embodiment 4 gained chain alkyl seleno acetate; Show that embodiment 2 is extremely low to the skin irritation of embodiment 4 gained chain alkyl seleno acetate with rabbit skin spreading experimental result.In Example 2 to embodiment 4, gained chain alkyl seleno acetate is made into 0.1% aqueous solution and carries out in-vitro antibacterial mite experimental result of going out and show, to Escherichia coli, gold-coloured staphylococci and acarid, there is obvious killing action, compared with similar carbon number soap sample, 113% is improved to the killing action of Escherichia coli and gold-coloured staphylococci, 351% is improved to the killing action of acarid.
Embodiment 6: containing the manufacture of selenium perfumed soap
Get commercially available perfumed soap 100g to be heated to 45 degrees Celsius and to make it melt to 55 degrees Celsius, another Example 2 to embodiment 4 gained chain alkyl seleno acetate, add in the commercially available perfumed soap melted in advance according to raw material perfumed soap mass percent 0.1% to 5% scope, after being uniformly mixed, cooling forming can obtain containing selenium perfumed soap.Get gained containing selenium perfumed soap be made into 1% aqueous solution carry out external 1,1-diphenyl-2-picryl hydrazine (DPPH, CAS 1898-66-4) radicals scavenging experiment, DPPH free radical scavenging activity is all more than 95%; Be made into 1% aqueous solution containing selenium soap sample to carry out in-vitro antibacterial mite experimental result of going out and show, to Escherichia coli, gold-coloured staphylococci and acarid, there is obvious killing action, compared with raw material soap, 93% is improved to the killing action of Escherichia coli and gold-coloured staphylococci, 91% is improved to the killing action of acarid; Adopt and improve Ross-Miles method and measure ratio that gained improves than raw material perfumed soap containing the foaming power of selenium perfumed soap and foam stability all more than 11%, and foam is finer and smoother; Compared with the commercially available perfumed soap of raw material, soft durometer containing selenium soap is softer, the selenium soap sample cutter sectility mask that contains wherein containing chain alkyl seleno acetic acid sodium salt has asterism pearly-lustre, and visible embodiment 2 to embodiment 4 gained chain alkyl seleno acetate obviously can improve the crystal property of raw material soap; Rabbit skin experiment result shows that all skin irritations containing selenium soap sample are all low than the commercially available perfumed soap of raw material, all has significant repairing accelerant effect to ultraviolet ray burn skin; Show that all selenium perfumed soap samples that contains have obvious inhibition to pruitus through volunteer's test.
Embodiment 7: containing the manufacture of selenium transparent soap
Get commercial clear soap 500g to be heated to 45 degrees Celsius and to make it melt to 55 degrees Celsius, another Example 2 to embodiment 4 gained chain alkyl seleno potassium salt or ammonium salt, add according to raw material transparent soap mass percent 0.1% to 5% scope, after being uniformly mixed, cooling forming can obtain containing selenium transparent soap.Compared with raw material commercial clear soap, the soft durometer containing selenium transparent soap is softer, and transparent feel is stronger; Get gained containing selenium transparent soap be made into 1% aqueous solution carry out external DPPH radicals scavenging experiment, DPPH free radical scavenging activity is all more than 95%; Adopt and improve Ross-Miles method and measure ratio that gained improves than raw material transparent soap containing the foaming power of selenium transparent soap and foam stability all more than 17%, and foam is finer and smoother; Be made into 1% aqueous solution containing selenium transparent soap sample to carry out in-vitro antibacterial mite experimental result of going out and show, to Escherichia coli, gold-coloured staphylococci and acarid, there is obvious killing action, compared with raw material transparent soap, 94% is improved to the killing action of Escherichia coli and gold-coloured staphylococci, 97% is improved to the killing action of acarid.
Embodiment 8: containing the preparation of selenium soap
Get commercially available soap base 50Kg to be heated to 45 degrees Celsius and to make it melt to 55 degrees Celsius, another Example 2 to embodiment 4 gained chain alkyl seleno acetate, add in the commercially available soap base melted in advance according to raw material soap base mass percent 0.1% to 4.5% scope, add 1% colouring agent simultaneously, 0.1% fragrance for detergents, after being uniformly mixed, cooling forming can obtain containing selenium soap.Compared with the reference sample of not adding in above-mentioned formula containing selenium surfactant, soft durometer containing selenium soap is softer, the selenium soap sample cutter sectility mask that contains wherein containing chain alkyl seleno acetic acid sodium salt has asterism pearly-lustre, and visible embodiment 2 to embodiment 4 gained chain alkyl seleno acetate obviously can improve the crystal property of soap; Get gained containing selenium soap be made into 1% aqueous solution carry out external DPPH radicals scavenging experiment, DPPH free radical scavenging activity is all more than 95%.Be made into 1% aqueous solution containing selenium soap sample to carry out in-vitro antibacterial mite experimental result of going out and show, to Escherichia coli, gold-coloured staphylococci and acarid, there is obvious killing action, compared with raw material soap, 97% is improved to the killing action of Escherichia coli and gold-coloured staphylococci, 107% is improved to the killing action of acarid; Adopt and improve Ross-Miles method and measure ratio that gained improves than raw material soap base containing the foaming power of selenium soap and foam stability all more than 117%, and foam is finer and smoother.
Embodiment 9: containing the preparation of selenium shampoo
Get commercially available shampoo 100g, another Example 2 to embodiment 4 gained chain alkyl seleno potassium salt or ammonium salt, after under agitation adding be uniformly mixed according to raw material shampoo mass percent 0.1% to 5% scope, can obtain containing selenium shampoo.Gained proves containing the formulation stability of selenium shampoo with raw material commercially available shampoo compared with all do not have notable difference through 45 degrees Celsius with subzero 4 degrees Celsius of accelerated tests containing selenium shampoo, shows that embodiment 2 to embodiment 4 gained chain alkyl seleno potassium salt and ammonium salt have the composite compatibility of good formula; Get containing selenium shampoo sample be made into 1% aqueous solution carry out external DPPH radicals scavenging experiment, DPPH free radical scavenging activity is all more than 96.8%, be made into 1% aqueous solution containing selenium shampoo sample to carry out in-vitro antibacterial mite experimental result of going out and show, to Escherichia coli, gold-coloured staphylococci and acarid, there is obvious killing action, compared with raw material shampoo, 89% is improved to the killing action of Escherichia coli and gold-coloured staphylococci, 93.8% is improved to the killing action of acarid; Adopt the ratio improving foaming power and foam stability shampoo raising more commercially available than raw material that Ross-Miles method mensuration gained contains selenium shampoo all more than 83%, and foam is finer and smoother; Compared with the commercially available shampoo of raw material, after washing containing selenium shampoo, the cardability of hair is better, and the reflecting feel washing rear hair is stronger; Show that all selenium shampoos that contains all have significant inhibition to scalp pruritis through volunteer's result of the test.
Embodiment 10: pearly-lustre is containing the preparation of selenium shampoo
Get not containing commercially available certain shampoo 100g of pearling agent, lower interpolation embodiment 2 to embodiment 4 gained chain alkyl seleno acetic acid sodium salt is stirred according to raw material shampoo mass percent 0.1% to 5% scope, after fully mixing, outward appearance be obvious pearly-lustre containing selenium shampoo, visible chain alkyl seleno sodium acetate can the thick formula of imparting body with pearly-lustre, the basis without the need to additionally adding pearling agent greatly improves the outward appearance class of product.With subzero 4 degrees Celsius of accelerated tests, gained proves that pearly-lustre does not all have notable difference containing the formulation stability of selenium shampoo compared with the commercially available shampoo of raw material through 45 degrees Celsius containing selenium shampoo, show to have good composite compatibility containing selenium surfactant; Get containing selenium shampoo sample be made into 1% aqueous solution carry out external DPPH radicals scavenging experiment, DPPH free radical scavenging activity is all more than 98.2%; Be made into 1% aqueous solution containing selenium shampoo sample to carry out in-vitro antibacterial mite experimental result of going out and show, to Escherichia coli, gold-coloured staphylococci and acarid, there is obvious killing action, compared with raw material shampoo, 95.7% is improved to the killing action of Escherichia coli and gold-coloured staphylococci, 98.7% is improved to the killing action of acarid; Adopt the ratio improving foaming power and foam stability shampoo raising more commercially available than raw material that Ross-Miles method mensuration gained contains selenium bead light shampoo all more than 35%, and foam is finer and smoother; Compared with the commercially available shampoo of raw material, the cardability of hair after pearly-lustre is washed containing selenium shampoo is better, the reflecting feel washing rear hair is stronger, moreover, wash the cardability of rear hair after hair dryer dries up and reflecting feel still keeps, and there is no the fluffy sense of obvious electrostatic, visible embodiment 2 to embodiment 4 gained chain alkyl seleno acetic acid sodium salt not only has the compatible and advantage of Synergistic of significant formula, but also has obvious antistatic effect; Show that all pearly-lustres all have significant inhibition containing selenium shampoo to scalp pruritis through volunteer's result of the test.
Embodiment 11: containing the preparation of selenium shower cream
Get commercially available shower cream 100g, another Example 2 to embodiment 4 gained chain alkyl seleno potassium salt or ammonium salt, after under agitation adding be uniformly mixed according to raw material shower cream mass percent 0.1% to 5% scope, can obtain containing selenium shower cream.Gained proves containing the formulation stability of selenium shower cream with raw material commercially available shower cream compared with all do not have notable difference through 45 degrees Celsius with subzero 4 degrees Celsius of accelerated tests containing selenium shower cream, shows that embodiment 2 to embodiment 4 gained chain alkyl seleno potassium salt and ammonium salt have the composite compatibility of good formula; Get containing selenium shower cream sample be made into 1% aqueous solution carry out external DPPH radicals scavenging experiment, DPPH free radical scavenging activity is all more than 97.8%, be made into 1% aqueous solution containing selenium shower cream sample to carry out in-vitro antibacterial mite experimental result of going out and show, gained has obvious killing action containing selenium shower cream to Escherichia coli, gold-coloured staphylococci and acarid, compared with raw material shower cream, 63% is improved to the killing action of Escherichia coli and gold-coloured staphylococci, 51% is improved to the killing action of acarid; Adopt the ratio improving foaming power and foam stability shower cream raising more commercially available than raw material that Ross-Miles method mensuration gained contains selenium shower cream all more than 73%, and foam is finer and smoother; Compared with the commercially available shower cream of raw material, through containing selenium shower cream wash after skin bright and clean sense and lubrication sense stronger; Show that all selenium shower creams that contains all have significant inhibition to pruitus symptom through volunteer's result of the test.
Embodiment 12: pearly-lustre is containing the preparation of selenium shower cream
Get commercially available not containing the shower cream 100g of pearling agent, another Example 2 to embodiment 4 gained chain alkyl seleno acetic acid sodium salt, after under agitation adding be uniformly mixed according to raw material shower cream mass percent 0.1% to 5% scope, pearly-lustre can be obtained containing selenium shower cream.With subzero 4 degrees Celsius of accelerated tests, gained pearly-lustre proves that pearly-lustre does not all have notable difference containing the formulation stability of selenium shower cream compared with the commercially available shower cream of raw material through 45 degrees Celsius containing selenium shower cream, show that embodiment 2 to embodiment 4 gained chain alkyl seleno acetic acid sodium salt has the composite compatibility of good formula; Get pearly-lustre containing selenium shower cream sample be made into 1% aqueous solution carry out external DPPH radicals scavenging experiment, DPPH free radical scavenging activity is all more than 97.2%, pearly-lustre is made into 1% aqueous solution containing selenium shower cream sample to carry out in-vitro antibacterial mite experimental result of going out and shows, gained has obvious killing action containing selenium shower cream to Escherichia coli, gold-coloured staphylococci and acarid, compared with raw material shower cream, 67% is improved to the killing action of Escherichia coli and gold-coloured staphylococci, 53% is improved to the killing action of acarid; Adopt the ratio improving foaming power and foam stability shower cream raising more commercially available than raw material that Ross-Miles method mensuration gained pearly-lustre contains selenium shower cream all more than 61%, and foam is finer and smoother; Compared with the commercially available shower cream of raw material, through pearly-lustre containing selenium shower cream wash after skin bright and clean sense and lubrication sense stronger; Show that all pearly-lustres all have significant inhibition containing selenium shower cream to pruitus symptom through volunteer's result of the test.
Claims (9)
1., containing a selenium surfactant, it is characterized in that this surfactant is chain alkyl seleno acetate, its architectural feature following general formula (1) represents
(1)
In formula, n is the integer of 11 to 15, M
+for the one in sodium ion, potassium ion or ammonium radical ion.
2. the preparation method containing selenium surfactant according to claim 1, it is characterized in that: under nitrogen protection, get positive structure chain alkyl diselenide and be dissolved in oxolane, the ice water solution of sodium borohydride is dripped under ice-water bath condition, and react 2-3 hour under ice-water bath after, methyl chloroacetate is dripped in above-mentioned reactant liquor, ice-water bath reaction is after 0.3-0.7 hour, organic phase is obtained with dichloromethane extraction, to dewater and after volatilizing solvent, upper silicagel column obtains chain alkyl seleno methyl acetate with the mixed solvent wash-out of ethyl acetate and benzinum; Getting chain alkyl seleno methyl acetate is dissolved in the mixed solvent of first alcohol and water under nitrogen protection; NaOH or potassium hydroxide or ammoniacal liquor is added in above-mentioned solution; room temperature reaction 3 hours; obtain solid product after filtration, recycle silicon glue post obtains chain alkyl seleno acetate with the mixed solvent wash-out of ethyl acetate and benzinum volume ratio 1:5.
3. the preparation method containing selenium surfactant according to claim 2, is characterized in that: described sodium borohydride and chain alkyl diselenide mole be 4 ~ 8:1.
4. the preparation method containing selenium surfactant according to claim 2, is characterized in that: described methyl chloroacetate and chain alkyl diselenide mol ratio are 2 ~ 2.5:1.
5. the preparation method containing selenium surfactant according to claim 2, is characterized in that: in the mixed solvent of described ethyl acetate and benzinum, ethyl acetate and benzinum volume ratio are 1:10.
6. the preparation method containing selenium surfactant according to claim 2, is characterized in that: in the mixed solvent of described first alcohol and water, the volume ratio of first alcohol and water is 4:1.
7. containing according to claim 1 containing selenium surfactant containing a selenium soap, it is characterized in that: containing 0.1-5 weight portion in the soap of every 100 weight portions containing selenium surfactant.
8. containing according to claim 1 containing selenium surfactant containing a selenium shampoo, it is characterized in that: containing 0.1-5 weight portion in the shampoo of every 100 weight portions containing selenium surfactant.
9. containing according to claim 1 containing selenium surfactant containing a selenium shower cream, it is characterized in that: containing 0.1-5 weight portion in the shower cream of every 100 weight portions containing selenium surfactant.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510915772.2A CN105498622B (en) | 2015-12-10 | 2015-12-10 | A kind of surfactant containing selenium and its preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510915772.2A CN105498622B (en) | 2015-12-10 | 2015-12-10 | A kind of surfactant containing selenium and its preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105498622A true CN105498622A (en) | 2016-04-20 |
| CN105498622B CN105498622B (en) | 2017-10-17 |
Family
ID=55707155
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510915772.2A Active CN105498622B (en) | 2015-12-10 | 2015-12-10 | A kind of surfactant containing selenium and its preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105498622B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN107235880A (en) * | 2017-06-30 | 2017-10-10 | 江南大学 | A kind of cationic surfactant containing selenium and its application |
| CN107998979A (en) * | 2017-12-15 | 2018-05-08 | 江南大学 | A kind of interface emulsification agent of nonionic containing selenium and its preparation method and application |
| CN109762159A (en) * | 2018-12-19 | 2019-05-17 | 万华化学集团股份有限公司 | One kind surfactant containing selenium and preparation method thereof |
| CN110082478A (en) * | 2019-05-20 | 2019-08-02 | 江南大学 | A kind of switching circuit and its application by the surfactant control containing selenium |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN1441671A (en) * | 2000-07-13 | 2003-09-10 | 蒂亚梅迪卡有限公司 | Fatty acid analogues for treatment of cancer |
| CN1466453A (en) * | 2000-09-27 | 2004-01-07 | ÷ | Fatty acid analogues for the treatment of proliferative skin disorders |
-
2015
- 2015-12-10 CN CN201510915772.2A patent/CN105498622B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN1441671A (en) * | 2000-07-13 | 2003-09-10 | 蒂亚梅迪卡有限公司 | Fatty acid analogues for treatment of cancer |
| CN1466453A (en) * | 2000-09-27 | 2004-01-07 | ÷ | Fatty acid analogues for the treatment of proliferative skin disorders |
Non-Patent Citations (1)
| Title |
|---|
| WILLIAM A. REINERTH ET AL.: ""Protecting groups for organoselenium compounds"", 《J. ORG. CHEM.》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN107235880A (en) * | 2017-06-30 | 2017-10-10 | 江南大学 | A kind of cationic surfactant containing selenium and its application |
| CN107998979A (en) * | 2017-12-15 | 2018-05-08 | 江南大学 | A kind of interface emulsification agent of nonionic containing selenium and its preparation method and 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 |
| CN109762159A (en) * | 2018-12-19 | 2019-05-17 | 万华化学集团股份有限公司 | One kind surfactant containing selenium and preparation method thereof |
| 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 |
| CN110082478A (en) * | 2019-05-20 | 2019-08-02 | 江南大学 | A kind of switching circuit and its application by the surfactant control containing selenium |
| CN110082478B (en) * | 2019-05-20 | 2020-07-03 | 江南大学 | Switch circuit controlled by selenium-containing surfactant and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105498622B (en) | 2017-10-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105498622A (en) | Selenium-containing surfactant as well as preparation method and application thereof | |
| US4233192A (en) | Detergent compositions | |
| US5560873A (en) | Mild cold pearlizing concentrates | |
| WO2007087977A1 (en) | 1-aza-3,7-dioxabicyclo[3.3.0]octane compounds and their use as pro-fragrances | |
| EP0255157A2 (en) | Novel sunscreen agents, sunscreen compositions and methods for preventing sunburn | |
| EP2144987B1 (en) | Inhibition of discoloration by washing and cleaning agents and/or cosmetic agents | |
| DE2422903A1 (en) | Antiperspirant SOAP | |
| CN106753823A (en) | A kind of surfactant containing selenium responded with pH and redox dual-switch | |
| EP0091237A1 (en) | Detergent composition | |
| WO2020127368A1 (en) | Process for producing metal organic frameworks | |
| US3223704A (en) | Quaternary ammonium sulfamates | |
| WO1991009923A1 (en) | Ultra mild surfactant with foam enhancer . | |
| CN106422960A (en) | Selenium-bearing betaine amphoteric ionic surfactant | |
| BR112019017520A2 (en) | COMPOSITION FOR HAIR CARE AND NON-THERAPEUTIC METHOD | |
| JPS6041979B2 (en) | Method for producing aqueous suspension | |
| EP0075906A2 (en) | Hair and body cleaning agent containing alkylsulfatobetaines | |
| KR101380902B1 (en) | Easy cleansing tissue | |
| US5981453A (en) | Process for the preparation of tenside mixtures | |
| US3193451A (en) | Fungicidal composition of undecylenic acid derivatives | |
| EP1102536B1 (en) | Use of oxathiazolones as microbicides | |
| JP4030746B2 (en) | Pearl luster imparting agent | |
| JPH02231412A (en) | Detergent composition with low irritancy | |
| US2353081A (en) | Sulphated monoethanolamides and process for the preparation thereof | |
| CN102093241A (en) | Method for preparing high-purity crystallization type N-acylglutamate | |
| EP0363215A2 (en) | Combination detergent and soap bar to enhance mildness |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |