CN109679092A - A kind of preparation method of cosmetics-stage poly (sodium aspartate) - Google Patents
A kind of preparation method of cosmetics-stage poly (sodium aspartate) Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
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- 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
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
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- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q1/00—Make-up preparations; Body powders; Preparations for removing make-up
- A61Q1/02—Preparations containing skin colorants, e.g. pigments
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- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
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- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
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Abstract
The present invention relates to a kind of preparation methods of cosmetics-stage poly (sodium aspartate).This method is using L-Aspartic acid as raw material, using the mixed liquor of phosphate aqueous solution and citric acid as catalyst, by polymerization, crushing, washing separation, dry, hydrolysis, filtering, purifying, sterilizing, compounding or the techniques such as dry, cosmetics-stage poly (sodium aspartate) is made.The cosmetics-stage poly (sodium aspartate) molecular weight is between 2000-100000D, and purity is high, conductivity is low, of light color, no special odor, highly-safe, meets cosmetics quality and sanitary standard, is suitably applied daily chemicals field, especially cosmetic field.
Description
Technical field
The invention belongs to biochemical industry synthesis technical fields, and in particular to a kind of preparation of cosmetics-stage poly (sodium aspartate)
Method.
Background technique
Poly-aspartate is the homogeneous polyamino acid using aspartic acid as monomer, contains a free carboxylic in each monomer
Base and peptide bond are a kind of bioabsorbable polymer materials of Mobyneb, have the effects that extremely strong moisturizing, chelating, dispersion, absorption,
Be widely used in water treatment agent, fertilizer synergistic agent, metalworking fluid, household chemicals, detergent, dispersing agent, chelating agent and
The fields such as water-retaining agent.
The preparation method of the poly-aspartate of different field has very much, and Chinese patent CN106220846A discloses a kind of use
In the poly-aspartate and its preparation method and application of fertilizer synergist.Patent CN102674569A discloses a kind of poly- asparagus fern ammonia
The preparation method of sour antisludging agent.Patent CN103113584A discloses a kind of for the environmentally friendly of oil field ternary composite driving
The preparation method of poly-aspartate.But existing technology do not relate to poly-aspartate in the preparation method of cosmetic field and
Using also lacking the research of its application technology in cosmetics.
Poly-aspartate is used as effect type cosmetic additive agent, mainly in the form of poly-aspartate sodium salt.Currently,
In the field applied by poly (sodium aspartate), obtained product is without purification process, and product impurity content is high, ion concentration
Height, color is deep, and smell is larger, and very big influence is caused to cosmetics sense organ and formula system, is not appropriate in cosmetic field
Using.
Therefore, need to develop a kind of production technology of poly (sodium aspartate) suitable for cosmetic applications at present, it is desirable that institute
The poly (sodium aspartate) Product Safety of preparation is high, with high purity, of light color, smell is small, and stablizes in cosmetic formulations system
Property it is high.
Summary of the invention
The technical problem to be solved by the present invention is in view of the deficiencies of the prior art, provide a kind of poly- asparagus fern ammonia of cosmetics-stage
The preparation method of sour sodium.Purifying is easily isolated using product made from this method, thus obtained poly (sodium aspartate) product is pure
Degree is high, conductivity is low, it is of light color, without special odor, molecular weight is controllable, stability is high, meet cosmetics quality and sanitary standard.
For this purpose, first aspect present invention provides a kind of preparation method of cosmetics-stage poly (sodium aspartate) comprising:
Step A carries out polymerization reaction by raw material of aspartic acid under acidic catalyst effect, obtains polymerizate；
Step B, polymerizate is crushed, and product after being crushed respectively with the aqueous solution of basic salt and pure water, filtering is done
Polymerizate after being washed after dry；
Step C is added lye into the polymerizate after washing and reaction is hydrolyzed, obtains hydrolysate；
Step D, isolates and purifies hydrolysate, obtains purified product；
Step E carries out decolorization to purified product, obtains Decolorization product；
Step F carries out sterilization treatment to Decolorization product, obtains cosmetics-stage poly (sodium aspartate) after dry.
Some preferred real-time modes according to the present invention carry out sterilization treatment to Decolorization product, are added in step F
Anti-corrosion composition obtains cosmetics-stage poly (sodium aspartate) after dry.
In certain embodiments of the present invention, in step, the molar ratio of the aspartic acid and acidic catalyst is
1: (0.01-2.0), preferably 1: (0.01-1.0), more preferably 1: (0.025-0.1).
In the present invention, the aspartic acid is L-Aspartic acid.
In the present invention, the acidic catalyst is the mixed liquor of phosphate aqueous solution and citric acid.
In some embodiments of the invention, the phosphate aqueous solution concentration is 70wt%-85wt%.
In some embodiments of the invention, purity >=99% of the citric acid.
In some embodiments of the invention, in the mixed liquor of phosphate aqueous solution and citric acid, phosphoric acid and citric acid
Mass ratio is (0.1-1): 1, preferably (0.2-0.8): 1.
According to certain embodiments of the present invention, in step, the temperature of polymerization reaction is 120-200 DEG C, preferably
150-170℃。
According to certain embodiments of the present invention, in step, the time of polymerization reaction is 1-6h, preferably 2-4h.
According to certain embodiments of the present invention, in step, the pressure of polymerization reaction is -0.02-0.095MPa, excellent
It is selected as -0.05-0.08MPa.
In some preferred embodiments of the invention, the temperature of the polymerization reaction carries out in polymerization process
At least 1 subgradient decaying, it is preferable that the temperature of the polymerization reaction carries out 1-2 subgradient decaying in polymerization process.
In some preferred embodiments of the invention, the amplitude of the temperature damping of the polymerization reaction is 5-20 DEG C.
In some preferred embodiments of the invention, 1-2h is divided between the die-away time.
According to certain embodiments of the present invention, in stepb, the polymerizate is crushed as 40-200 mesh, preferably
For 60-200 mesh.
In the present invention, the basic salt includes sodium carbonate and/or sodium bicarbonate.
In some embodiments of the invention, in stepb, the mass concentration of the aqueous solution of the basic salt is 1%-
20%, further preferably 2%-15%.
In the present invention, the lye is the aqueous solution of sodium hydroxide.
In some embodiments of the invention, the mass concentration of the aqueous solution of the sodium hydroxide is 10%-50%, preferably
20%-40%.
According to certain embodiments of the present invention, in step C, the temperature of the hydrolysis is 30-60 DEG C.
According to certain embodiments of the present invention, in step C, the time of the hydrolysis is 0.5-6h, preferably 1-
2h。
According to certain embodiments of the present invention, the speed of agitator 70-120rpm in step C, in hydrolysis reaction.
In the present invention, the method isolated and purified described in step D includes physical partition method and/or fractionation, preferably
For physical partition method.
In some embodiments of the invention, the physical partition method includes filtering, ultrafiltration, nanofiltration, ion exchange and electricity
One or more of dialysis.
According to certain embodiments of the present invention, in step E, decolorization is carried out using decolorising agent.
In some embodiments of the invention, the decolorising agent includes active carbon, silica, aluminum sulfate and PA decolorising agent
One or more of (aluminium polychloride).
In some embodiments of the invention, the temperature of the decolorization is 40-70 DEG C, preferably 50-60 DEG C.
In some embodiments of the invention, the time of the decolorization is 0.5-2 hours.
In the present invention, sterilization treatment is carried out using high temperature or irradiation.
In some embodiments of the invention, the temperature of the sterilization treatment is 80-100 DEG C.
In some embodiments of the invention, the time of the sterilization treatment is 20-120min.
In the present invention, the anti-corrosion composition includes imidazolidinyl urea, Methyl p-hydroxybenzoate, propylben, Phenoxyethanol, second
One of base hexyl glycerol, butanediol, pentanediol, hexylene glycol, ethohexadiol, parahydroxyacet-ophenone and decoyl hydroximic acid are several
Kind.
In some embodiments of the invention, with the total weight of Decolorization product, the dosage of the anti-corrosion composition is
0.1wt%-10wt%, preferably 0.1wt%-5wt%.
Second aspect of the present invention provides a kind of cosmetics-stage poly (sodium aspartate), molecular weight 2000-100000Da,
Preferably 3000-50000Da；The aqueous solution conductivity of the poly (sodium aspartate) of 1wt% is 500-3000 μ s/cm, preferably
700-2000μs/cm；The poly-aspartate sodium water solution coloration of 20wt% is 50-700 °, preferably 100-500 °.
Third aspect present invention provides the poly- asparagus fern of cosmetics-stage made from another method as described in the first aspect of the invention
Propylhomoserin sodium or the cosmetics-stage poly (sodium aspartate) as provided by second aspect of the present invention are preparing skin care item, washing product and coloured silk
Application in cosmetics.
The preparation method of cosmetics-stage poly (sodium aspartate) provided by the present invention is using L-Aspartic acid as raw material, using phosphorus
The mixed liquor of aqueous acid and citric acid by polymerization, crushing, washing separation, dry, hydrolysis, filters, pure as catalyst
The techniques such as change, sterilizing, compounding or drying, are made cosmetics-stage poly (sodium aspartate).Using multiple in the method for the present invention polymerization process
Traditional single catalyst is replaced with catalyst, obtained product molecule active force is small, and viscosity is low, makees in basic salt and pure water
It is easy to for catalyst being kept completely separate under, is easier to carry out subsequent technique, finally obtained poly (sodium aspartate) molecular weight exists
Between 2000-100000Da, purity is high, conductivity is low, of light color, no special odor, highly-safe, meet cosmetics quality and
Sanitary standard is suitably applied daily chemicals field.
Detailed description of the invention
To be readily appreciated that the present invention, the present invention will now be explained with reference to the accompanying drawings.
Fig. 1 shows the use of the invention that Essence is improved using cosmetics-stage poly (sodium aspartate) as the skin of functional component
Measure of merit result, wherein a is the fresh porcine skin that Essence processing is improved without skin (as check sample)；B is through skin
Improve the pigskin that Essence impregnates.
Fig. 2 is to handle without of the invention by the hair conditioning nutrient solution of functional component of cosmetics-stage poly (sodium aspartate)
Damage hair scanning electron microscope (SEM) photograph.
It is the hair conditioning nutrient solution of functional component to damage that Fig. 3, which is using of the invention using cosmetics-stage poly (sodium aspartate),
Scanning electron microscope (SEM) photograph after hair treatment 15 days.
Specific embodiment
To be readily appreciated that the present invention, the present invention is described more detail below.But before describing the present invention in detail, it should be understood that
The present invention is not limited to the specific embodiments of description.It is also understood that term used herein is only for description specific implementation
Mode, and be not offered as restrictive.
In the case where providing numberical range, it should be understood that in the upper and lower bound of the range and the prescribed limit
Any other regulation or between two parties each of between numerical value numerical value is encompassed by the present invention between two parties.These small range of upper limits
It can independently be included in lesser range with lower limit, and be also covered by the present invention, obey any clear in prescribed limit
The limit of exclusion.Defined range include one or two limit in the case where, exclude any of the limit that those include or
The range of the two is also included in the present invention.
Unless otherwise defined, all terms used herein and those skilled in the art's is usual
Understand meaning having the same.Although similar or equivalent any method and material can also with method described herein and material
To use in implementation or test of the invention, but preferred method and material will now be described.
I. term
Heretofore described term " basic salt " refers to the aqueous solution of the salt in the salt of alkalinity.
" water " word used in the present invention refers to deionized water, ultrapure water or distillation in the case where not specifying
Water.
II. embodiment
Poly-aspartate is a kind of water-soluble polypeptide, the design feature containing peptide bond and carboxyl isoreactivity group, tool
There is the effects of extremely strong chelating, dispersion, absorption, is widely used in fertilizer synergistic, Treatment of Industrial Water, metalworking fluid, dailyization
Product, oil field and fields such as water filling auxiliary agent that this recovers the oil.In addition, poly-aspartate adds in detergent, high hydroscopic resin, water-coal-slurry
Agent, Photochemicals etc. is added also to have broad application prospects.But existing technology does not relate to poly-aspartate and is changing
The preparation method and application in cosmetic field also lacks the research of its application technology in cosmetics.
Poly-aspartate is as effect type cosmetic additive agent in use, mainly existing in the form of poly (sodium aspartate).
As previously mentioned, the poly (sodium aspartate) that the production technology of existing poly (sodium aspartate) obtains is without purification process, product impurity
Content is high, and color is deep, and smell is larger, is not appropriate in cosmetic field application.
Based on this, present inventor has conducted extensive research the preparation method of cosmetics-stage poly (sodium aspartate),
Creative discovery, using the mixed liquor of phosphate aqueous solution and citric acid as catalyst, is carried out using L-Aspartic acid as raw material
Polymerization reaction, polymerizate molecular force obtained is small, and viscosity is low, is easy to be catalyzed under basic salt and pure water effect
Agent is kept completely separate, and is easier to carry out subsequent technique, thus passes through polymerization reaction, crushing, washing, hydrolysis, filtering, separation
Purity is high, molecular weight can be made in 2000-100000Da controlled range in the techniques such as purifying, decoloration, sterilizing, compounding and drying
It is interior, of light color, without the good cosmetics-stage poly (sodium aspartate) of special odor, stability.
Therefore, the preparation method of cosmetics-stage poly (sodium aspartate) involved in first aspect present invention includes:
Step A carries out polymerization reaction by raw material of aspartic acid under acidic catalyst effect, obtains polymerizate；
Step B, polymerizate is crushed, and product after being crushed respectively with the aqueous solution of basic salt and pure water, filtering is done
Polymerizate after being washed after dry；
Step C is added lye into the polymerizate after washing and reaction is hydrolyzed, obtains hydrolysate；
Step D, isolates and purifies hydrolysate, obtains purified product；
Step E carries out decolorization to purified product, obtains Decolorization product；
Step F carries out sterilization treatment to Decolorization product, obtains cosmetics-stage poly (sodium aspartate) after dry.
Some preferred real-time modes according to the present invention carry out sterilization treatment to Decolorization product, are added in step F
Anti-corrosion composition obtains cosmetics-stage poly (sodium aspartate) after dry.
It is poly- succinyl that aspartic acid and acidic catalyst, which carry out the polymerizate obtained after polymerization reaction, in above-mentioned steps A
The mixture of imines (PSI) and catalyst.
In certain embodiments of the present invention, in step, the molar ratio of the aspartic acid and acidic catalyst is
1: (0.01-2.0), preferably 1: (0.01-1.0), more preferably 1: (0.025-0.1).
In the present invention, the aspartic acid is L-Aspartic acid.
In the present invention, the acidic catalyst is the mixed liquor of phosphate aqueous solution and citric acid.In some realities of the invention
It applies in example, the phosphate aqueous solution concentration is 70wt%-85wt%, preferably 85wt%；Purity >=99% of the citric acid.
In some embodiments of the invention, in the mixed liquor of phosphate aqueous solution and citric acid, phosphoric acid and citric acid
Mass ratio is (0.1-1): 1, preferably (0.2-0.8): 1.
Those skilled in the art will be appreciated that when the mixed liquor that acidic catalyst is phosphate aqueous solution and citric acid
When, the molar ratio of the aspartic acid and acidic catalyst is the total moles ratio of aspartic acid and acidic catalyst, i.e. asparagus fern ammonia
The molal quantity and the ratio between phosphoric acid and the total mole number of citric acid of acid.
According to certain embodiments of the present invention, in step, the temperature of polymerization reaction is 120-200 DEG C, preferably
150-170℃。
According to certain embodiments of the present invention, in step, the time of polymerization reaction is 1-6h, preferably 2-4h.
According to certain embodiments of the present invention, in step, the pressure of polymerization reaction is -0.02-0.095MPa, excellent
It is selected as -0.05-0.08MPa.
In some specific embodiments of the invention, polymeric reaction condition in step A: 120-200 DEG C of temperature, when reaction
Between 1-6h, reaction pressure be -0.02-0.095MPa.
In some specific preferred embodiments of the invention, polymeric reaction condition in step A: 150-170 DEG C of temperature, instead
2-4h between seasonable, reaction pressure are -0.05-0.08MPa.
In some preferred embodiments of the invention, the temperature of the polymerization reaction carries out in polymerization process
At least 1 subgradient decaying, it is preferable that the temperature of the polymerization reaction carries out 1-2 subgradient decaying in polymerization process.
In some preferred embodiments of the invention, the amplitude of the temperature damping of the polymerization reaction is 5-20 DEG C.
In some preferred embodiments of the invention, 1-2h is divided between the die-away time.
According to certain embodiments of the present invention, in stepb, the polymerizate is crushed as 40-200 mesh, preferably
For 60-200 mesh.
In the present invention, the basic salt includes sodium carbonate and/or sodium bicarbonate.
In some embodiments of the invention, in stepb, the mass concentration of the aqueous solution of the basic salt is 1%-
20%, further preferably 2%-15% are still more preferably 2%.
In some specific preferred embodiments of the invention, after alkaline wash crushed products, deionized water is used
Further progress is washed, and rear filtering, drying, drying temperature are 80-100 DEG C, and the dry matter moisture content after drying is less than
10wt%.
In certain embodiments of the present invention, washing facility is that machine, centrifuge, pressure is filtered by vacuum in stirring-type in step B
The washing facility commonly used in the art such as filter.
In the present invention, the lye is the aqueous solution of sodium hydroxide.
In some embodiments of the invention, the mass concentration of the aqueous solution of the sodium hydroxide is 10%-50%, preferably
20%-40%.
In some preferred embodiments of the invention, in stepb, washing to aqueous solution pH is stablized in 7-8, in this way may be used
Thoroughly to remove remaining catalyst.
According to certain embodiments of the present invention, in step C, the temperature of the hydrolysis is 30-60 DEG C.
According to certain embodiments of the present invention, in step C, the time of the hydrolysis is 0.5-6h, preferably 1-
2h。
According to certain embodiments of the present invention, the speed of agitator 70-120rpm in step C, in hydrolysis reaction.
In some specific embodiments of the invention, when reaction is hydrolyzed in step C, PSI and sodium hydroxide water
The mass ratio of solution is 1: (2-8), the solid content for obtaining poly-aspartate sodium water solution is 20wt%-50wt%.
In the present invention, the hydrolysate poly (sodium aspartate) obtained after step C hydrolysis has some solid impurities
With the impurity such as the salt of small molecule and excessive alkali, need to be isolated and purified.
In the present invention, the method isolated and purified described in step D includes physical partition method and/or fractionation, preferably
For physical partition method.
In some embodiments of the invention, the physical partition method includes filtering, ultrafiltration, nanofiltration, ion exchange and electricity
One or more of dialysis.
In some specific embodiments of the invention, the poly- asparagus fern ammonia of the hydrolysate obtained after step C hydrolysis
Sour sodium has some solid impurities, need to be filtered.
In some embodiments, step D is filtered hydrolysate, since product has certain viscosity, using diatom
As filter aid, the preferably diatomite of 50-200 mesh, filter cloth is 100-500 mesh for soil and/or active carbon, can reach good filtering
Effect.
In further embodiments, step D is filtered hydrolysate, using vertical type blotter press, horizontal pressure filter or
Centrifuge.
In some preferred embodiments, step D can add diatomite or work during being filtered to hydrolysate
Property the filter aids such as charcoal to improve filtrate filter efficiency filter out fine suspended matter, guarantee filtrate clarity.
In some further specific embodiments of the invention, in filtered poly-aspartate sodium water solution, contain
The impurity such as the salt of some small molecules and excessive alkali, need to be isolated and purified.
It in some preferred embodiments, is isolated and purified in step D using the method further progress of UF membrane, to remove
The impurity such as the salt of small molecule and excessive alkali.
In some particularly preferred embodiments, further progress separation is carried out using hollow fiber ultrafiltration membrane in step D
Purifying can be adjusted as needed with removing salt and impurity, the specification of hollow fiber ultrafiltration membrane such as excessive alkali of small molecule
It is whole.
According to certain embodiments of the present invention, in step E, decolorization is carried out using decolorising agent.
In some embodiments of the invention, the decolorising agent includes active carbon, silica, aluminum sulfate and PA decolorising agent
One or more of (aluminium polychloride).
In some embodiments of the invention, the temperature of the decolorization is 40-70 DEG C, preferably 50-60 DEG C.
In some embodiments of the invention, the time of the decolorization is 0.5-2 hours.
Poly (sodium aspartate) is rich in carbon source abundant and nitrogen source, provides good ring for the growth and breeding of microorganism
Border.If the poly (sodium aspartate) of non-sterilized processing is used for cosmetic industry, product quality can be largely effected on.Therefore, originally
Invention carries out sterilization treatment to Decolorization product in step F.
Biocidal treatment method is not particularly limited in the present invention, the sterilizing methods of this field routine can be used,
For example, can be using high-temperature sterilization processing and/or irradiation sterilization processing, it is preferred to use high-temperature sterilization processing.
In some embodiments of the invention, the temperature of high-temperature sterilization processing is 80-100 DEG C.
In some embodiments of the invention, the time of high-temperature sterilization processing is 20-120min.
In some specific embodiments of the invention, the temperature for carrying out sterilization treatment to filtered Decolorization product is
80-100 DEG C, time 20-120min.
In the present invention, the anti-corrosion composition includes imidazolidinyl urea, Methyl p-hydroxybenzoate, propylben, Phenoxyethanol, second
One of base hexyl glycerol, butanediol, pentanediol, hexylene glycol, ethohexadiol, parahydroxyacet-ophenone and decoyl hydroximic acid are several
Kind.
In some embodiments of the invention, with the total weight of Decolorization product, the dosage of the anti-corrosion composition is
0.1wt%-10wt%, preferably 0.1wt%-5wt%.The result of ISO 11930-2012 cosmetic product preservative efficacy evaluation
Show after adding anti-corrosion composition, liquid poly (sodium aspartate) product can reach to be suppressed growth of microorganism well.
Some preferred embodiments according to the present invention are dried in step F using centrifugal spray drying.
In some preferred embodiments of the invention, the inlet temperature of the centrifugal spray drying is 140-200 DEG C, out
Mouth temperature is 75-95 DEG C.
Other preferred embodiments according to the present invention are dried in step F using freeze-drying.
In some preferred embodiments of the invention, the temperature of the freeze-drying is -50 to -10 DEG C.
The preparation method of the above-mentioned cosmetics-stage poly (sodium aspartate) of the present invention is using L-Aspartic acid as raw material, using phosphoric acid water
The mixed liquor of solution and citric acid as catalyst, by polymerization reaction, crushing, washing, hydrolysis, filter, isolate and purify,
Decoloration, sterilizing, compounding and the techniques such as dry, resulting poly (sodium aspartate) purity is high, molecular weight are excellent in 2000-100000Da
Select in 3000-50000Da controlled range, color be it is colourless to faint yellow, no special odor, stability is good, 1wt% content gather
The aqueous solution conductivity of NaAsp is 500-3000 μ s/cm, preferably 700-2000 μ s/cm, the poly-aspartate of 20wt%
Sodium water solution coloration is 50-700 °, and preferably 100-500 °, safety indexes meet " cosmetics safety technical specification 2015 ", right
Human safety is high, can be used for skin care item, washing product and cosmetic.
The discovery of present inventor's creativeness, using L-Aspartic acid as raw material, using phosphate aqueous solution and citric acid
Mixed liquor as catalyst, by polymerization reaction, crushing, washing, drying, hydrolysis, filter, isolate and purify, decolourize, go out
The techniques such as bacterium, compounding and drying, acquisition poly (sodium aspartate) purity is high, molecular weight in 2000-100000Da controlled range,
Color be it is colourless to faint yellow, no special odor, stability is good, meets cosmetics quality and sanitary standard, property safe to the human body
Height can be used for skin care item, washing product and cosmetic.
Liquid chromatography is used in the present invention, by liquid chromatograph (Shimadzu LC-20A) to the molecular weight of poly-aspartate
It is detected.
Use colour comparatour (Hana/HI96727) to poly- according to GB/T 5750.4-2006 (platinum-cobalt method) in the present invention
The coloration of aspartic acid sodium water solution is detected.
In the present invention according to GB/T 11007-2008 (conductivity meter test method) using conductivity meter (Mei Tele/
FE30) conductivity of poly-aspartate sodium water solution is detected.
Liquid chromatography is used in the present invention, by liquid chromatograph (Shimadzu LC-20A) to the purity of poly-aspartate into
Row detection.
Skin moisture content uses skin moisture content tester (Comeometer) (CM825, Courage in the present invention
And Khazaka, Germany) it measures.
In the present invention skin water loss amount using skin water loss tester (Vapometer) (TM300-MDD,
Courage and Khazaka, Germany) it measures.
Hair surface is tested using electron scanning Electronic Speculum (SU1510, high and new technology company, Hitachi) in the present invention.
Embodiment
To keep the present invention easier to understand, below in conjunction with embodiment, present invention be described in more detail, these realities
Apply example only serve it is illustrative, it is not limited to application range of the invention.If raw material used in the present invention or component nothing
Specified otherwise can be made by commercial sources or conventional method.
Embodiment 1: cosmetics-stage poly (sodium aspartate) is prepared
By 2000 grams of L-Aspartic acids and 20 grams of phosphoric acid (phosphate aqueous solution, 85wt%) and 40 grams of citric acids (purity >=
99%) 170 DEG C are heated to react 2 hours, white polysuccinimide powder or particle is obtained, it is standby to smash it through 60 mesh screens
With being washed using the sodium bicarbonate aqueous solution of 2wt%, after washing neutrality, then washed with water, done in 80 DEG C of baking ovens
It is water-soluble that the sodium hydroxide that 4000g mass fraction is 40% is added in dry spare, after taking 1000 grams of dryings polysuccinimide powder
In liquid, 200 mesh filter-cloth filterings carry out ultrafiltration using the hollow-fibre membrane of molecular cut off 3000Da, add the amount of pure water for filtering
3 times of preceding solution, concentration add water 2 times.0.5wt% active carbon is added in obtained concentrate, carries out decoloration 0.5 at 50 °C
Hour, 80 DEG C of sterilizings after twenty minutes, are added 0.5% imidazolidinyl urea of mass ratio, obtain certain density poly- asparagus fern ammonia after filtering
Acid sodium aqueous solution, molecular weight 3000-10000Da.Color is colourless to faint yellow, no characteristic odor.
Embodiment 2: cosmetics-stage poly (sodium aspartate) is prepared
By 2000 grams of L-Aspartic acids and 80 grams of phosphoric acid (phosphate aqueous solution, 85wt%) and 160 grams of citric acids (purity >=
99%) 200 DEG C are heated to react 4 hours, faint yellow polysuccinimide powder or particle is obtained, it is standby to smash it through 60 mesh screens
With being washed using the sodium bicarbonate aqueous solution of 2wt%, after washing neutrality, then washed with water, done in 80 DEG C of baking ovens
It is water-soluble that the sodium hydroxide that 5000g mass fraction is 40% is added in dry spare, after taking 1000 grams of dryings polysuccinimide powder
In liquid, 200 mesh filter-cloth filterings carry out ultrafiltration using the hollow-fibre membrane of molecular cut off 10000Da, add the amount of pure water for filtering
0.5wt% active carbon is added in 5 times of preceding solution, obtained concentrate, decoloration 0.5 hour is carried out at a temperature of 60 DEG C, after filtering
80 DEG C of sterilizings after twenty minutes, are added 0.5% imidazolidinyl urea of mass ratio, obtain certain density poly-aspartate sodium water solution,
Molecular weight is 30000-50000Da.Color is faint yellow to yellow, no characteristic odor.
Embodiment 3: cosmetics-stage poly (sodium aspartate) is prepared
By 2000 grams of L-Aspartic acids and 20 grams of phosphoric acid (phosphate aqueous solution, 85wt%) and 40 grams of citric acids (purity >=
99%) 200 DEG C are heated to react 2 hours, white polysuccinimide powder or particle is obtained, it is standby to smash it through 60 mesh screens
With being washed using the sodium bicarbonate aqueous solution of 2wt%, after washing neutrality, then washed with water, done in 80 DEG C of baking ovens
It is water-soluble that the sodium hydroxide that 4000g mass fraction is 40% is added in dry spare, after taking 1000 grams of dryings polysuccinimide powder
In liquid, 200 mesh filter-cloth filterings carry out ultrafiltration using the hollow-fibre membrane of molecular cut off 3000Da, add the amount of pure water for filtering
3 times of preceding solution, obtained concentrate are added 0.5wt% active carbon, decolourize at 50 °C, 80 DEG C of sterilizings after filtering
After twenty minutes, centrifugal spray drying, white poly (sodium aspartate) powder, molecular weight 3000-10000Da, no characteristic odor.
Embodiment 4: cosmetics-stage poly (sodium aspartate) is prepared
By 2000 grams of L-Aspartic acids and 80 grams of phosphoric acid (phosphate aqueous solution, 85wt%) and 160 grams of citric acids (purity >=
99%) 200 DEG C are heated to react 4 hours, white polysuccinimide powder or particle is obtained, it is standby to smash it through 60 mesh screens
With being washed using the sodium bicarbonate aqueous solution of 2wt%, after washing neutrality, then washed with water, done in 80 DEG C of baking ovens
The dry spare polysuccinimide powder taken after 1000 grams of dryings, is added in 40% sodium hydrate aqueous solution, 200 mesh filter cloth mistakes
Filter carries out ultrafiltration using the hollow-fibre membrane of molecular cut off 10000Da, and adding the amount of pure water is 5 times for filtering preceding solution, obtains
Concentrate be added 0.5wt% active carbon, decolourize at a temperature of 60 DEG C, after filtering 80 DEG C sterilizing after twenty minutes, centrifugation spray
Mist is dry, obtains white poly (sodium aspartate) powder, molecular weight 30000-50000Da, no characteristic odor.
Embodiment 5: skin conditioning Essence is prepared using cosmetics-stage poly (sodium aspartate) and carries out measure of merit
1, skin improves essence formula of liquid
Using poly (sodium aspartate) as effect agent skin improve essence formula of liquid: with the Essence total weight include with
Lower ingredient:
2, measure of merit
(1) skin moisture content is tested
26 people of volunteer is selected, under conditions of 22 ± 1 DEG C of temperature, humidity (50 ± 5%), by guarantor prepared by above-mentioned formula
Wet liquid is coated on volunteer's skin surface, using skin moisture content tester (Comeometer) (CM825, Courage and
Khazaka, Germany) the moisture of skin parameter of volunteer is measured in 0h, 2h, 4h and 8h respectively, obtain aspiration in 8h
Person's skin moisture changes of contents, the results are shown in Table 1.
Table 1
As it can be seen from table 1 volunteer's skin increases in 2h, 4h and 8h skin moisture content conspicuousness, illustrate with poly- day
Aspartic acid sodium is that the moisture retention liquid of host agent has apparent moisture-keeping efficacy.Poly (sodium aspartate) formula moisture of skin parameter, which is not added, to be reduced
7-9%.
(2) skin water loss is tested
12 people of volunteer is selected, under conditions of 22 ± 1 DEG C of temperature, humidity (50 ± 5%), by guarantor prepared by above-mentioned formula
Wet liquid be coated on volunteer's skin surface, using skin water loss amount measurement examination instrument (Vapometer) (TM300-MDD,
Courage and Khazaka, Germany) the skin water loss amount of volunteer is surveyed in 0h, 2h, 4h and 8h respectively
It is fixed, volunteer's skin moisture number of dropouts variation in 8h is obtained, the results are shown in Table 2.
Table 2
From table 2 it can be seen that volunteer's skin reduces in 2h, 4h and 8h skin water loss amount conspicuousness, illustrate with poly-
NaAsp is that the Essence of host agent has apparent water lock effect, can improve the barrier function of skin.Not addition polymerization asparagus fern
Propylhomoserin sodium is formulated skin water loss amount and increases 1-2 (g/m2·h)
(3) animal experiment method is as follows: taking fresh porcine skin, in 15 DEG C of 35%RH (humidity), impregnates and take out after placing 2h, do
Dry placement 2h, it is as shown in Figure 1 that front and back compares picture.
In Fig. 1, a is the fresh porcine skin handled without nutrient essence, and b is the pigskin impregnated through nutrient essence, as a result
Show there is good affinity by the nutrient essence of effect agent and skin of poly (sodium aspartate), can softening skin, fill
Skin Cell inhibits skin contraction, increases skin elasticity, improves skin appearance.
Embodiment 6: shampoo is prepared using cosmetics-stage poly (sodium aspartate) and carries out measure of merit
1, shampoo formula
The shampoo includes following component with the shampoo total weight:
2, measure of merit
It is utilized respectively above-mentioned shampoo formula and carries out half a head reality with the above-mentioned shampoo formula that poly (sodium aspartate) is not added
It tests, subjective assessment is carried out to following test item by specialty evaluation teacher, obtains that the results are shown in Table 3, digital number of delegates in table.
Table 3
3 statistical result of table shows to add the shampoo that poly (sodium aspartate) is effect agent, and when hair washing, foam is fine and smooth, drying hair
Cardability, glossiness and antistatic effect have clear improvement.
Embodiment 7: hair conditioning nutrient solution is prepared using cosmetics-stage poly (sodium aspartate) and carries out measure of merit
1, hair conditioning nutrient solution prescription
Hair conditioning nutrient solution includes following component with the hair conditioning nutrient solution total weight:
2, measure of merit
Volunteer with boiling hot dye damage hair uses using poly (sodium aspartate) as the hair lotion of host agent, uses 15 days front and backs
It is tested with electronics scanning electron microscope (SU1510, high and new technology company, Hitachi), contrast effect is as shown in Fig. 2 and 3.
Attached drawing 2 is the scanning electron microscope (SEM) photograph of the damage hair handled without hair lotion, and Fig. 3 is after hair lotion is handled 15 days
Scanning electron microscope (SEM) photograph.The result shows that the damage of hair caused by a variety of causes can be repaired using poly (sodium aspartate) as the hair lotion of host agent
Wound.
It should be noted that embodiment described above for explaining only the invention, is not constituted to of the invention any
Limitation.By referring to exemplary embodiments, invention has been described, it should be appreciated that word used in it is descriptive
With explanatory vocabulary, rather than limited vocabulary.The present invention can be made within the scope of the claims by regulation
Modification, and the present invention is revised in without departing substantially from scope and spirit of the present invention.Although the present invention described in it relates to
And specific method, material and embodiment, it is not intended that the present invention is limited to particular case disclosed in it, on the contrary, this hair
It is bright to can be extended to other all methods and applications with the same function.
Claims (12)
1. a kind of preparation method of cosmetics-stage poly (sodium aspartate) comprising:
Step A carries out polymerization reaction by raw material of aspartic acid under acidic catalyst effect, obtains polymerizate；
Step B, polymerizate is crushed, product after being crushed respectively with the aqueous solution of basic salt and pure water, after filtering, drying
Polymerizate after being washed；
Step C is added lye into the polymerizate after washing and reaction is hydrolyzed, obtains hydrolysate；
Step D, isolates and purifies hydrolysate, obtains purified product；
Step E carries out decolorization to purified product, obtains Decolorization product；
Step F carries out sterilization treatment to Decolorization product, obtains cosmetics-stage poly (sodium aspartate) after dry.
2. preparation method according to claim 1, which is characterized in that in step F, carried out at sterilizing to Decolorization product
Reason is added anti-corrosion composition, obtains cosmetics-stage poly (sodium aspartate) after dry.
3. preparation method according to claim 1 or 2, which is characterized in that in step, the aspartic acid and acidity
The molar ratio of catalyst is 1: (0.01-2.0), preferably 1: (0.01-1.0), more preferable 1: (0.025-0.1)；The asparagus fern ammonia
Acid is ASPARTIC ACID；The acidic catalyst is the mixed liquor of phosphate aqueous solution and citric acid；Preferably, the phosphoric acid water
Solution concentration is 70wt%-85wt%, purity >=99% of the citric acid；Preferably, in phosphate aqueous solution and citric acid
In mixed liquor, the mass ratio of phosphoric acid and citric acid is (0.1-1): 1, preferably (0.2-0.8): 1.
4. preparation method described in any one of -3 according to claim 1, which is characterized in that in step, polymerization reaction
Temperature is 120-200 DEG C, preferably 150-170 DEG C；And/or the time of polymerization reaction is 1-6h, preferably 2-4h；And/or
The pressure of polymerization reaction is -0.02-0.095MPa, preferably -0.05-0.08MPa.
5. the preparation method according to claim 4, which is characterized in that the temperature of the polymerization reaction is in polymerization process
Middle progress at least 1 subgradient decaying, it is preferable that the temperature of the polymerization reaction carries out 1-2 subgradient in polymerization process
Decaying, it is further preferred that the amplitude of the temperature damping of the polymerization reaction is 5-20 DEG C；The time interval of the temperature damping
It is 1-2 hours.
6. preparation method described in any one of -5 according to claim 1, which is characterized in that in stepb, by the polymerization
It is 40-200 mesh, preferably 60-200 mesh that product, which crushes,；And/or the basic salt includes sodium carbonate and/or sodium bicarbonate；It is excellent
Selection of land, the mass concentration of the aqueous solution of the basic salt are 1%-20%, further preferably 2%-15%.
7. preparation method described in any one of -6 according to claim 1, which is characterized in that in step C, the lye is
The aqueous solution of sodium hydroxide；The mass concentration of the aqueous solution of the sodium hydroxide is 10%-50%, preferably 20%-40%；It is described
The temperature of hydrolysis is 30-60 DEG C；And/or the time of the hydrolysis is 0.5-6h, preferably 1-2h；And/or hydrolysis
Speed of agitator 70-120rpm in reaction process.
8. preparation method according to any one of claims 1-7, which is characterized in that isolated and purified described in step D
Method includes physical partition method and/or fractionation, preferably physical partition method；The physical partition method includes filtering, surpasses
One or more of filter, nanofiltration, ion exchange and electrodialysis.
9. preparation method described in any one of -8 according to claim 1, which is characterized in that in step E, using decolorising agent
Carry out decolorization；The decolorising agent includes one or more of active carbon, silica, aluminum sulfate and PA decolorising agent；Institute
The temperature for stating decolorization is 40-70 DEG C, preferably 50-60 DEG C；The time of the decolorization is 0.5-2 hours.
10. preparation method described in any one of -9 according to claim 1, which is characterized in that sterilization treatment described in step F
Temperature be 80-100 DEG C, time of the sterilization treatment is 20-120min；And/or the anti-corrosion composition includes imidazolidinyl
It is urea, Methyl p-hydroxybenzoate, propylben, Phenoxyethanol, Sensiva SC50, butanediol, pentanediol, hexylene glycol, ethohexadiol, right
One or more of hydroxy acetophenone and decoyl hydroximic acid；Preferably, with the total weight of Decolorization product, the anti-corrosion composition
Dosage be 0.1wt%-10wt%, preferably 0.1wt%-5wt%.
11. a kind of poly- asparagus fern ammonia of the cosmetics-stage of the preparation of preparation method described in any one of -10 according to claim 1
Sour sodium, molecular weight 2000-100000Da, preferably 3000-50000Da；The cosmetics-stage poly (sodium aspartate) of 1wt%
Aqueous solution conductivity is 500-3000 μ s/cm, preferably 700-2000 μ s/cm；The cosmetics-stage poly (sodium aspartate) of 20wt%
Aqueous solution coloration is 50-700 °, preferably 100-500 °.
12. cosmetics-stage poly (sodium aspartate) made from the method as described in any one of claim 1-10 or as described in 11
Cosmetics-stage poly (sodium aspartate) is preparing the application in skin care item, washing product and cosmetic.
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| CN116472262A (en) * | 2020-10-27 | 2023-07-21 | 威娜德国有限责任公司 | Cosmetic grade quality 2-methoxymethyl-p-phenylenediamine |
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| WO2012008009A1 (en) * | 2010-07-12 | 2012-01-19 | 三菱鉛筆株式会社 | Liquid cosmetic |
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| WO2012008009A1 (en) * | 2010-07-12 | 2012-01-19 | 三菱鉛筆株式会社 | Liquid cosmetic |
| CN103554495A (en) * | 2013-10-28 | 2014-02-05 | 烟台恒源生物股份有限公司 | Method for preparing 40% sodium polyaspartate aqueous solution |
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