CN108484794A - A kind of hyaluronic acid quaternary ammonium radical derivative and its prepare and purify method - Google Patents
A kind of hyaluronic acid quaternary ammonium radical derivative and its prepare and purify method Download PDFInfo
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- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/006—Heteroglycans, i.e. polysaccharides having more than one sugar residue in the main chain in either alternating or less regular sequence; Gellans; Succinoglycans; Arabinogalactans; Tragacanth or gum tragacanth or traganth from Astragalus; Gum Karaya from Sterculia urens; Gum Ghatti from Anogeissus latifolia; Derivatives thereof
- C08B37/0063—Glycosaminoglycans or mucopolysaccharides, e.g. keratan sulfate; Derivatives thereof, e.g. fucoidan
- C08B37/0072—Hyaluronic acid, i.e. HA or hyaluronan; Derivatives thereof, e.g. crosslinked hyaluronic acid (hylan) or hyaluronates
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Abstract
The invention discloses a kind of hyaluronic acid quaternary ammonium radical derivatives, have following structure, R is CH in Formulas I2CH(OH)CH2N+Me3Cl or R is H.Also disclose a kind of preparation and purification method of hyaluronic acid quaternary ammonium radical derivative, beneficial effects of the present invention：Hyaluronic acid quaternary ammonium radical derivative after modification just can be adsorbed in the surface of hair and skin well, its good wetability and ductility can be assigned, simultaneously because quaternary ammonium salt group carries the cationic side chain unfolded, with strongly hydrophilic, the hyaluronic acid accessed after quaternary ammonium salt group can enhance itself outstanding humectant properties.The hyaluronic acid quaternary ammonium radical derivative that gained is prepared is then particularly suitable in hair care product and cleaning class cosmetics, this is because its good adsorptivity even across flowing water rinse also can the overwhelming majority be retained in hair and skin surface and persistently play its unique moisture-keeping function.
Description
Technical field：
The invention belongs to daily use chemicals and biotechnologies, and in particular to a kind of hyaluronic acid quaternary ammonium radical derivative and its prepare and pure
Change method.
Background technology：
Hyaluronic acid (Hyaluronic acid, HA) also known as Hyaluronic Acid are by the Portugals (1-3) -2-N- acetylaminohydroxyphenylarsonic acid 2- deoxidation-D-
The disaccharides repeated arrangement of grape sugar-(1-4)-O- β-D-Glucose aldehydic acid and a kind of acid straight chain poly mucopolysaccharide formed, have
Very strong hydrophily and extraordinary performance of keeping humidity are the best substances of the performance of keeping humidity that is found in current nature, international
Cosmetic industry is known as optimal natural moisturizing factor, is widely used in cosmetic industry.
Hyaluronic acid characteristic most outstanding is exactly its unique humectant, due to the anionic properties function such as carboxyl
Group, thus it is usually negatively charged, and the surface of the hair of human body, skin is generally also negatively charged.Hair is handled when using hyaluronic acid
When hair, since the two is all negatively charged and mutually exclusive, for this purpose, hyaluronic acid is generally difficult to be adsorbed on hair, skin well
Surface, just majority is rinsed hyaluronic acid when passing through the flushing of flowing water using hyaluronic acid treated hair, can not be continued
It plays it and moistens the effect of moisturizing, to influence the application effect of Related product.From such background, one is we provided
Kind hyaluronic acid quaternary ammonium radical derivative and its preparation and purification method, by chemical modification to hyalomitome in hyaluronan molecule
The quaternary ammonium group that positive electricity is carried in acid grafting, makes it have certain electropositive, due to attracting each other for positive and negative charge, after modification
Hyaluronic acid quaternary ammonium radical derivative just can be adsorbed in the surface of hair and skin well, can assign its good wetability and
Ductility has strongly hydrophilic, after having accessed quaternary ammonium salt group simultaneously because quaternary ammonium salt group carries the cationic side chain unfolded
Hyaluronic acid can enhance itself outstanding humectant properties.The hyaluronic acid quaternary ammonium radical derivative that gained is prepared is then special
It is not useful in hair care product and cleaning class cosmetics, this is because its good adsorptivity is rinsed even across flowing water
The energy overwhelming majority is retained in hair and skin surface and persistently plays its unique moisture-keeping function.
Invention content：
The present invention addresses the above problem, provides a kind of hyaluronic acid quaternary ammonium radical derivative and its prepares and purifies method,
Treated, and hyaluronic acid quaternary ammonium radical derivative can be adsorbed in the surface of hair and skin well, assign good wetability and
Ductility also makes hyaluronic acid enhance itself outstanding humectant properties, and being rinsed even across flowing water also can overwhelming majority guarantor
Hair and skin surface are stayed in, its unique moisture-keeping function is persistently played.
In order to realize that the above-mentioned purpose of the present invention, the present invention use following technical scheme：
A kind of hyaluronic acid quaternary ammonium salt derivative has structure shown in formula I：
I
R is CH in Formulas I2CH(OH)CH2N+Me3Cl or R is H.
A kind of preparation and purification method of hyaluronic acid quaternary ammonium salt derivative, includes the following steps：
（1）Clean blender, reflux condenser and three-necked flask are taken, it is spare；
（2）Blender and reflux condenser are fitted into three-necked flask, it is molten to prepare the organic solvent containing 10%-60% ratio water
Liquid is preheated to 30-80 DEG C.
（3）Suitable hyaluronic acid or its salt solid powder are taken, step 2 is slowly added into）Organic solvent solution obtained
In, feed liquid a is obtained, hyaluronic acid or the mass volume ratio of its salt solid powder and organic solvent solution are 1：10-40.
（4）Grafting agent and 0.05-0.8mmol/L reaction initiators are slowly added into step 3 respectively successively）It is obtained
In feed liquid a, feed liquid b is obtained, hyaluronic acid or the weight ratio of its salt solid powder and grafting agent are 1:0.5-10, hyaluronic acid
Or the weight ratio of its salt solid powder and reaction initiator is 1:0.5-10.
（5）It is passed through protection gas into three-necked flask, catches up with the oxygen in most flask.
（6）It is slowly stirred feed liquid b0.2-10h in 30-80 DEG C of water-bath, carries out graft reaction, obtains reaction solution.
（7）Reaction solution is stood into 2-40min, it is made fully to be layered, supernatant liquor is removed, filters and collect to obtain sediment
a。
（8）The organic solvent with reaction solution same liquid volume is added in sediment a, washing precipitate a twice, is washed successively
Supernatant liquor is removed after washing, and to remove remaining grafting agent and reaction initiator, is filtered and is collected to obtain sediment b.
（9）Sediment b is added in purified water, stirring makes it fully dissolve, and obtains feed liquid c, sediment b and purified water
Mass volume ratio be 1:10-30.
（10）The purified salt of 2%-15% is added into feed liquid c, stirring makes it fully dissolve, adjust the pH value of feed liquid b to
6.0-7.5 obtains feed liquid d.
（11）Ethyl alcohol is added into feed liquid d, stands 5-60min after being slowly stirred 10-35min, removes supernatant liquor ethyl alcohol,
Sediment c is filtered and collects to obtain, feed liquid c is 1 with ethanol liquid volume ratio：1-5.
（12）Sediment c is added in purified water, stirring makes it fully dissolve, and obtains feed liquid e, sediment c and purifying
The mass volume ratio of water is 1：10-30.
（13）Ethyl alcohol is added into feed liquid e, stands 5-60min after being slowly stirred 10-35min, removes supernatant liquor ethyl alcohol,
Filter and collect to obtain sediment d, the liquid volume ratio of feed liquid e and ethyl alcohol is 1：1-5.
（14）It carries out 3 washings successively to sediment d using 60%-80% ethyl alcohol, it is miscellaneous to remove trace remaining in sediment d
Matter, obtains sediment e, and the mass volume ratio of sediment d and 60%-80% ethyl alcohol is 1:1.
（15）Sediment e is dehydrated using absolute ethyl alcohol, obtains material, material is filtered out is put into vacuum drying
Vacuum drying 6-12h is carried out in case, both obtains hyaluronic acid quaternary ammonium salt derivative.
The step（2）And step（8）In, organic solvent used can be isopropanol, ethyl alcohol, methanol, acetone etc., have
A concentration of 40%-90% of solvent.
The step（4）In, grafting agent is using 2,3- epoxypropyltrimethylchloride chlorides or the chloro- 2- hydroxypropyls of 3- three
Ammonio methacrylate, reaction initiator is using Cericammoniumsulfate or ammonium ceric nitrate or ceric sulfate.
The step（5）In protection gas be nitrogen.
The step（9）And step（12）In purified water be drinking water through the way of distillation, ion-exchange, hyperfiltration
Or the water of hyoscine made from other suitable methods, be free of any additive.
Described mass volume ratio, i.e. 1g solids correspond to 1ml amount of liquid in the present invention.
Described liquid volume ratio, i.e. 1ml reaction solutions correspond to 1ml purified waters in the present invention.
Hyaluronic acid solid powder described in preparation method of the present invention is the cosmetics-stage hyaluronic acid of our company's production, matter
Amount meets QB/T-4416-2012《Raw material Sodium Hyaluronate used for cosmetic》Professional standard quality requirement and my company's internal control quality
Standard.
Beneficial effects of the present invention：It is transformed by chemical molecular in hyaluronan molecule, upper band is grafted to hyaluronic acid
The quaternary ammonium group for having positive electricity makes it have certain electropositive, due to attracting each other for positive and negative charge, the hyaluronic acid after modification
Quaternary ammonium radical derivative just can be adsorbed in the surface of hair and skin well, can assign its good wetability and ductility, together
When the cationic side chain unfolded carried due to quaternary ammonium salt group, there is strongly hydrophilic, accessed the hyalomitome after quaternary ammonium salt group
Acid can enhance itself outstanding humectant properties.Be prepared gained hyaluronic acid quaternary ammonium radical derivative then it is particularly suitable
In hair care product and cleaning class cosmetics, this is because its good adsorptivity also can portion big absolutely even across flowing water flushing
Code insurance stays in hair and skin surface and persistently plays its unique moisture-keeping function.
Specific implementation mode：
The present invention is further explained in the light of specific embodiments, and protection scope of the present invention be not only limited to it is following
Embodiment.
The grafting rate of hyaluronic acid quaternary ammonium salt derivative prepared by the method for the invention is the hydrogen atom quilt on 4 hydroxyls
Substituted ratio, theoretical value 0-4.0, grafting rate are calculated according to the nitrogen content of product, grafting rate=(N1-N0)/
N0, wherein N1 are the nitrogen contents of the product after grafting, and N0 is the nitrogen content of HA itself.
Embodiment 1
90% ethyl alcohol of 200ml volumes is taken to be put into the three-necked flask equipped with blender and reflux condenser, water-bath is preheated to 30
℃.The Sodium Hyaluronate salt solid powder that 10g molecular weight is 1.36 MDa is weighed, is under stiring added slowly to solid powder pre-
In the alcohol solvent of heat.Then the reaction for sequentially adding the 2,3- glycidyltrimetiiylammoniums ammonium chloride and 0.05mmol/l of 5g is drawn
Agent Cericammoniumsulfate is sent out, is passed through into three-necked flask and gas nitrogen is protected to catch up with the oxygen in most flask.In nitrogen in 30 DEG C of water-baths
It is stirred to react 0.2h under protection.After reaction, standing 2min makes reaction solution fully be layered, and topples over removal supernatant liquor, filters
Collect solid precipitation.The isopropanol that 200ml90% is added washes twice, and removes supernatant, precipitation is collected by filtration.200ml purifying is added
Water, stirring make acquisition head product precipitate fully dissolving, into dissolved feed liquid be added 2% purified salt, adjusting material liquid pH to
6.0-7.5, the ethyl alcohol that 1 times of volume is added are precipitated.0.5h is stood after precipitation and removes supernatant alcohol, by the secondary dissolving of sediment
In the purified water of 200ml, the ethyl alcohol that 1 times of volume is added again carries out secondary precipitation.Supernatant alcohol is removed after secondary precipitation, is adopted
It is washed 2 times with 60% ethyl alcohol of 200ml, with the remaining trace impurity of removal.It is dehydrated, taken off using absolute ethyl alcohol after washing
Material filtered out after water and is put into vacuum drying chamber drying 6h and obtains 9.3g.After testing, the loss on drying of white solid powder
It is 3,68%, grafting rate 0.85, pH 6.8, protein residues 0.03%, residue on ignition 6.4%.
Embodiment 2
90% isopropanol for measuring 200ml volumes is put into the three-necked flask equipped with blender and reflux condenser, water-bath preheating
To 60 DEG C.The Sodium Hyaluronate salt solid powder that 10g molecular weight is 1.36 MDa is weighed, under stiring slowly adds solid powder
Into the isopropanol solvent of preheating.Then the 2,3- glycidyltrimetiiylammoniums ammonium chloride and 0.3mmol/l of 15g are sequentially added
Reaction initiator Cericammoniumsulfate is passed through into three-necked flask and gas nitrogen is protected to catch up with the oxygen in most flask.In 60 DEG C of water-baths
It is stirred to react 5h under the protection of nitrogen.After reaction, standing 10min makes reaction solution fully be layered, and topples over removal supernatant liquor,
Solid precipitation is collected by filtration.The isopropanol that 200ml90% is added washes twice, and removes supernatant, precipitation is collected by filtration.200ml is added
Purified water, stirring make the head product of acquisition precipitate fully dissolving, and 5% purified salt is added into dissolved feed liquid, adjusts feed liquid
PH to 6.0-7.5, the ethyl alcohol that 2 times of volumes are added are precipitated.0.5h is stood after precipitation removes supernatant alcohol, sediment is secondary
It is dissolved in the purified water of 200ml, the ethyl alcohol that 2 times of volumes are added again carries out secondary precipitation.Upper pure mellow wine is removed after secondary precipitation
Essence is washed 2 times using 80% ethyl alcohol of 200ml, with the remaining trace impurity of removal.It is taken off using absolute ethyl alcohol after washing
Material filters out to be put into vacuum drying chamber drying 10h to obtain white solid powder 10.7g be refined saturating after water, dehydration
Bright matter acid quaternary ammonium salt derivative product.After testing, the loss on drying of white solid powder is 4.46%, grafting rate 1.24, and pH is
7.2, protein residues 0.03%, residue on ignition 6.8%.
Embodiment 3
90% acetone of 200ml volumes is taken to be put into the three-necked flask equipped with blender and reflux condenser, water-bath is preheated to 80
℃.The Sodium Hyaluronate salt solid powder that 10g molecular weight is 1.36 MDa is weighed, is under stiring added slowly to solid powder pre-
In the acetone solvent of heat.Then the reaction for sequentially adding the 2,3- glycidyltrimetiiylammoniums ammonium chloride and 0.8mmol/l of 20g is drawn
Agent Cericammoniumsulfate is sent out, is passed through into three-necked flask and gas nitrogen is protected to catch up with the oxygen in most flask.In nitrogen in 80 DEG C of water-baths
It is stirred to react 10h under protection.After reaction, standing 40min makes reaction solution fully be layered, and topples over removal supernatant liquor, filters
Collect solid precipitation.The acetone that 200ml90% is added washes twice, and removes supernatant, precipitation is collected by filtration.200ml purifying is added
Water, stirring make the head product of acquisition precipitate fully dissolving, and 15% purified salt is added into dissolved feed liquid, adjusts material liquid pH
To 6.0-7.5, the ethyl alcohol that 5 times of volumes are added is precipitated.0.5h is stood after precipitation removes supernatant alcohol, sediment is secondary molten
For solution in the purified water of 200ml, the ethyl alcohol that 2 times of volumes are added again carries out secondary precipitation.Supernatant alcohol is removed after secondary precipitation,
It is washed 2 times using 80% ethyl alcohol of 200ml, with the remaining trace impurity of removal.Be dehydrated using absolute ethyl alcohol after washing,
Material filtered out after dehydration and is put into vacuum drying chamber drying 10h and obtains the hyalomitome that white solid powder 10.g is refined
Sour quaternary ammonium salt derivative product.After testing, the loss on drying of white solid powder is 4.23%, grafting rate 0.92, pH 7.3,
Protein residues are 0.03%, residue on ignition 6.2%.
By contrast, the product that embodiment 2 obtains meets the requirements, and both application effect of products was good.
Claims (6)
1. a kind of hyaluronic acid quaternary ammonium salt derivative, which is characterized in that have structure shown in formula I：
I
R is CH in Formulas I2CH(OH)CH2N+Me3Cl or R is H.
2. a kind of preparation and purification method of hyaluronic acid quaternary ammonium salt derivative described in claim 1, which is characterized in that including
Following steps：
（1）Clean blender, reflux condenser and three-necked flask are taken, it is spare；
（2）Blender and reflux condenser are fitted into three-necked flask, it is molten to prepare the organic solvent containing 10%-60% ratio water
Liquid is preheated to 30-80 DEG C；
（3）Suitable hyaluronic acid or its salt solid powder are taken, step 2 is slowly added into）In organic solvent solution obtained, obtain
To feed liquid a, hyaluronic acid or the mass volume ratio of its salt solid powder and organic solvent solution are 1：10-40；
（4）Grafting agent and 0.05-0.8mmol/L reaction initiators are slowly added into step 3 respectively successively）Feed liquid obtained
In a, feed liquid b is obtained, hyaluronic acid or the weight ratio of its salt solid powder and grafting agent are 1:0.5-10, hyaluronic acid or its
The weight ratio of salt solid powder and reaction initiator is 1:0.5-10；
（5）It is passed through protection gas into three-necked flask, catches up with the oxygen in most flask；
（6）It is slowly stirred feed liquid b0.2-10h in 30-80 DEG C of water-bath, carries out graft reaction, obtains reaction solution；
（7）Reaction solution is stood into 2-40min, it is made fully to be layered, supernatant liquor is removed, filters and collect to obtain sediment a；
（8）The organic solvent with reaction solution same liquid volume is added in sediment a, successively washing precipitate a twice, after washing
Removal supernatant liquor filters to remove remaining grafting agent and reaction initiator and collects to obtain sediment b；
（9）Sediment b is added in purified water, stirring makes it fully dissolve, and obtains feed liquid c, the matter of sediment b and purified water
It is 1 to measure volume ratio:10-30；
（10）The purified salt of 2%-15% is added into feed liquid c, stirring makes it fully dissolve, and adjusts the pH value of feed liquid b to 6.0-
7.5, obtain feed liquid d；
（11）Ethyl alcohol is added into feed liquid d, 5-60min is stood after being slowly stirred 10-35min, removes supernatant liquor ethyl alcohol, filtering
And collect and obtain sediment c, feed liquid c is 1 with ethanol liquid volume ratio：1-5；
（12）Sediment c is added in purified water, stirring makes it fully dissolve, and obtains feed liquid e, sediment c and purified water
Mass volume ratio is 1：10-30；
（13）Ethyl alcohol is added into feed liquid e, 5-60min is stood after being slowly stirred 10-35min, removes supernatant liquor ethyl alcohol, filtering
And collect and obtain sediment d, the liquid volume ratio of feed liquid e and ethyl alcohol is 1：1-5；
（14）It carries out 3 washings successively to sediment d using 60%-80% ethyl alcohol, removes trace impurity remaining in sediment d,
Obtain sediment e, the mass volume ratio of sediment d and 60%-80% ethyl alcohol is 1:1；
（15）Sediment e is dehydrated using absolute ethyl alcohol, obtains material, material is filtered out is put into vacuum drying chamber
Vacuum drying 6-12h is carried out, hyaluronic acid quaternary ammonium salt derivative is both obtained.
3. the preparation and purification method of hyaluronic acid quaternary ammonium salt derivative according to claim 2, it is characterised in that：It is described
The step of（2）And step（8）In, organic solvent used can be isopropanol, ethyl alcohol, methanol, acetone etc., the concentration of organic solvent
For 40%-90%.
4. the preparation and purification method of hyaluronic acid quaternary ammonium salt derivative according to claim 2, it is characterised in that：It is described
The step of（4）In, grafting agent uses 2,3- epoxypropyltrimethylchloride chlorides or 3- chloro-2-hydroxypropyl-trimethyl ammonium chlorides,
Reaction initiator is using Cericammoniumsulfate or ammonium ceric nitrate or ceric sulfate.
5. the preparation and purification method of hyaluronic acid quaternary ammonium salt derivative according to claim 2, it is characterised in that：It is described
The step of（5）In protection gas be nitrogen.
6. the preparation and purification method of hyaluronic acid quaternary ammonium salt derivative according to claim 2, it is characterised in that：It is described
The step of（9）And step（12）In purified water be drinking water through the way of distillation, ion-exchange, hyperfiltration or other are suitable
The water of hyoscine made from method is free of any additive.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111560086A (en) * | 2020-05-25 | 2020-08-21 | 山东众山生物科技有限公司 | Method for preparing cationic hyaluronate by semidry method |
| CN114397399A (en) * | 2021-12-31 | 2022-04-26 | 华熙生物科技股份有限公司 | Method for determining content of quaternary ammonium salt in hyaluronic acid-quaternary ammonium salt polymer |
| CN116041565A (en) * | 2022-11-18 | 2023-05-02 | 山东焦点福瑞达生物股份有限公司 | Preparation and purification method of sodium hyaluronate cationic quaternary ammonium salt in homogeneous medium |
| WO2023125790A1 (en) * | 2021-12-31 | 2023-07-06 | 华熙生物科技股份有限公司 | Cationized hyaluronic acid or salt thereof, and preparation method therefor |
| CN117137829A (en) * | 2023-10-30 | 2023-12-01 | 广州悦瑞化妆品有限公司 | Oil-pearl secondary polishing essence and preparation method thereof |
| CN117257715A (en) * | 2023-11-10 | 2023-12-22 | 广东碧茜生物科技有限公司 | Make-up spray with oil control effect and preparation method thereof |
| WO2024141003A1 (en) * | 2022-12-30 | 2024-07-04 | 华熙生物科技股份有限公司 | Hyaluronic acid derivative, preparation method therefor and use thereof |
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| CN101715457A (en) * | 2007-04-24 | 2010-05-26 | 丘比株式会社 | Cationized hyaluronic acid and/or salt thereof, method for producing the same, and hair modifying agent, cuticle repairing agent, skin modifying agent and cosmetic preparation each using the same |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111560086A (en) * | 2020-05-25 | 2020-08-21 | 山东众山生物科技有限公司 | Method for preparing cationic hyaluronate by semidry method |
| CN114397399A (en) * | 2021-12-31 | 2022-04-26 | 华熙生物科技股份有限公司 | Method for determining content of quaternary ammonium salt in hyaluronic acid-quaternary ammonium salt polymer |
| WO2023125790A1 (en) * | 2021-12-31 | 2023-07-06 | 华熙生物科技股份有限公司 | Cationized hyaluronic acid or salt thereof, and preparation method therefor |
| CN116041565A (en) * | 2022-11-18 | 2023-05-02 | 山东焦点福瑞达生物股份有限公司 | Preparation and purification method of sodium hyaluronate cationic quaternary ammonium salt in homogeneous medium |
| CN116041565B (en) * | 2022-11-18 | 2024-02-09 | 山东焦点福瑞达生物股份有限公司 | Preparation and purification method of sodium hyaluronate cationic quaternary ammonium salt in homogeneous medium |
| WO2024141003A1 (en) * | 2022-12-30 | 2024-07-04 | 华熙生物科技股份有限公司 | Hyaluronic acid derivative, preparation method therefor and use thereof |
| CN117137829A (en) * | 2023-10-30 | 2023-12-01 | 广州悦瑞化妆品有限公司 | Oil-pearl secondary polishing essence and preparation method thereof |
| CN117257715A (en) * | 2023-11-10 | 2023-12-22 | 广东碧茜生物科技有限公司 | Make-up spray with oil control effect and preparation method thereof |
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