CN101255202B - p-benzoyl amido benzoyl chitosan and preparation thereof - Google Patents
p-benzoyl amido benzoyl chitosan and preparation thereof Download PDFInfo
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- CN101255202B CN101255202B CN2007101154242A CN200710115424A CN101255202B CN 101255202 B CN101255202 B CN 101255202B CN 2007101154242 A CN2007101154242 A CN 2007101154242A CN 200710115424 A CN200710115424 A CN 200710115424A CN 101255202 B CN101255202 B CN 101255202B
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Abstract
The invention discloses a p-benzamido benzoyl chitosan derivative, wherein n is 500-600, the benzene ring and C=O is chromophore, the compound has large ultraviolet absorption peak at 280 nm in acetate solution of 1g/L. The derivative is white powder solid and dissolves in water and ethylene glycol and the molecular weight is 110-130 KD. The benzamido benzoyl chitosan derivative has red shift to the absorption peak of benzamido benzoyl chitosan, therefore the benzamido benzoyl chitosan derivative has ultraviolet absorption and hairedressing effect and can be used for sunproof cosmetic additive.
Description
Technical field
The present invention relates to a kind of functional deriv, its preparation method of chitosan and as the sun care preparations Application of Additives.
Background technology
As everyone knows, chitosan is the deacetylated product of chitin, and it is to have unique a kind of alkaline polysaccharide in the organic sphere in a large number.Because of the effect of intramolecularly and intermolecular hydrogen bonding, chitosan only is dissolved in acid and acidic aqueous solution.Contain modifiable groups such as a large amount of hydroxyls, amino on the chitosan molecule chain, can obtain various derivatives, therefore can enlarge its range of application by chemical modification with specific function.Biocompatibility that the chitosan tool is good and film-forming properties, bacteria resistance function and whitening effect, preserve moisture, function such as moisture absorption, irritation cell regeneration, but only can be dissolved in the tart solution, limit its range of application.Usually people introduce quaternary ammonium salt, alkyl, mineral acid etc. on chitosan molecule, but can only improve the solvability or the flocculence of chitosan.A kind of para-amino benzoic acid compound is arranged, its to keep skin health, lubricate, delay wrinkle Exposure to Sunlight appears, resists, alleviate skin because of burn, scald the shouting pain that causes etc. positive effect arranged.But because intermolecular hydrogen bond action makes it form crystal easily, to the pH sensitivity, free amine group is easily oxidation in air, thereby makes its use be restricted.
Summary of the invention
The objective of the invention is to overcome the shortcoming separately of above-claimed cpd, a kind of novel chitosan derivatives is provided, this chitosan derivatives has uv-absorbing and cosmetic result, can be used as the additive of sun care preparations.
The objective of the invention is to be realized by following technical scheme: develop a kind ofly to benzamido benzoyl chitosan derivatives, its structure is:
Wherein, n is between 500-600, and phenyl ring in the said structure and C=O are the functional group of adding lustre to, and this compound is that the ultra-violet absorption spectrum 283nm place of 1g/L acetum has big absorption peak in concentration; The physical and chemical indexes of this compound: the white powder solid, water-soluble and ethylene glycol, molecular weight are 110-130KD.
The present invention prepares the benzene carbon amide yl benzoic acid by para-amino benzoic acid and Benzoyl chloride reaction.The benzene carbon amide yl benzoic acid is put into three-necked bottle to what drying was crossed, add a certain amount of anhydrous diethyl ether, add sulfur oxychloride again, put in the ultrasonic washer of 30 ℃ of water temperatures, reacted 10 minutes.In three-necked bottle, add the certain amount of chitosan acetic acid solution, 5 ℃ of-45 ℃ of following ultra-sonic oscillation 1.5 hours, standing over night then.After reaction is finished, add a large amount of acetone product be precipitated out, filter, soak suction filtration after 24 hours with the mixed solvent of dehydrated alcohol and anhydrous diethyl ether again, again the filter cake behind the suction filtration is carried out Soxhlet with acetone and extracted 24 hours, after the vacuum-drying product.
The principal reaction that relates to of the present invention had four steps:
1), preparation Benzoyl chloride:
2), prepare the benzene carbon amide yl benzoic acid:
3), prepare the benzamido Benzoyl chloride:
4), prepare benzamido benzoyl chitosan:
The preparation method of described acetaminol base chitosan, its step is as follows:
(1) para-amino benzoic acid with weighing is dissolved in the 50-65 ℃ of distilled water hot suction filtration;
(2) filtrate cool to room temperature, at room temperature suction filtration;
(3) get filter cake, vacuum-drying again obtains purified para-amino benzoic acid;
(4) getting the 3g phenylformic acid puts in the round-bottomed flask, add the 30ml anhydrous diethyl ether, phenylformic acid dissolves fully, add the 5ml sulfur oxychloride again, put into water temperature and be in 20-40 ℃ the ultrasonic washer, ultra-sonic oscillation 10-60 minute, add a certain amount of dry para-amino benzoic acid of crossing again, ultra-sonic oscillation 10-30 minute, left standstill 60 minutes, the liquid that reacted in the round-bottomed flask is slowly poured in the beaker that is added with 100ml distilled water, use 10ml distilled water flushing flask again, the liquid that washed is also poured in the beaker, leaves standstill 5-10 minute, the suction filtration aqueous solution obtains the benzoic wet product of benzamido, and vacuum-drying gets dryed product;
(5) get a certain amount of dry cross the benzene carbon amide yl benzoic acid is put into three-necked bottle, the anhydrous diethyl ether that adds 30ml, add excessive a little sulfur oxychloride again, put into water temperature and be in 20-40 ℃ the ultrasonic washer, ultra-sonic oscillation 10-60 minute, reaction product was to the benzamido Benzoyl chloride;
(6) reaction product in cooling (5) step is got the 0.5g chitosan and is dissolved in the 10ml anhydrous acetic acid to 0-30 ℃, again it is added in the three-necked bottle, and at 5-45 ℃ of following ultra-sonic oscillation 1-3.5 hour, standing over night;
(7) reaction product with (6) step adds a large amount of acetone, makes product acetaminol base chitosan be precipitated out suction filtration;
(8) use the mixed solvent of dehydrated alcohol and anhydrous diethyl ether to soak after 12-24 hour again, suction filtration is got filter cake;
(9) filter cake that again (8) is gone on foot carries out Soxhlet extraction 24-30 hour with acetone, gets acetaminol chitosan product after the vacuum-drying.
The processing condition of the suction filtration in described (1) step all are: dried by the fire 1-3 hour in 50-65 ℃ of baking oven with filter flask and B, get reaction solution with the water pump suction filtration down at 50-65 ℃ again, suction filtration is poured into filtrate in the clean beaker rapidly after finishing.
The processing condition of described (2), (7) and (8) suction filtration in the step all are: dried by the fire 1-3 hour in 50-65 ℃ of baking oven with filter flask and B, at room temperature get reaction solution with the water pump suction filtration again, suction filtration is poured into filtrate in the clean beaker rapidly after finishing.
Described para-amino benzoic acid: sulfur oxychloride: the weight ratio that feeds intake of chitosan is 1-5: 3-9: 1.
The dehydrated alcohol in described (8) step and the mixed volume ratio of anhydrous diethyl ether are 1: 1-10.
The Soxhlet in described (9) step is extracted, and its processing condition are: 55-65 ℃ of heating in water bath, extracted 24-30 hour.
The vacuum-drying in described (9) step, its processing condition are: under 30-50 ℃, vacuum tightness is 8 * 10
4Pa, dry 12-24 hour.
A kind of described to benzamido benzoyl chitosan as preparation sun care preparations Application of Additives.
Positively effect of the present invention is: owing to earlier the amino in the para-amino benzoic acid is protected with benzoyl; can prevent that it is oxidized; again the acetaminol base is incorporated into and prepares novel chitosan derivatives on the chitosan molecule; the 283nm place is arrived in its ultraviolet absorption peak red shift, thereby has uv-absorbing and cosmetic result.Simultaneously, benzamido benzoyl chitosan and cationic, anionic property and amphoterics there are excellent compatibility, have good moisture absorption and moisture retention, can be used as the additive of sun care preparations.
Description of drawings
Fig. 1 is the chitosan infrared spectrogram.
Fig. 2 is the prepared infrared spectrogram to benzamido benzoyl chitosan.
Fig. 3 is the uv absorption spectra of the acetic acid solution of chitosan.
Fig. 4 is the uv absorption spectra to the acetic acid solution of benzamido benzoyl chitosan.
Fig. 5 does not add benzamido benzoyl chitosan derivatives uv-absorbing spectrogram in the sunscreen.
Fig. 6 adds benzamido benzoyl chitosan derivatives uv-absorbing spectrogram in the sunscreen.
Fig. 1 is the infrared spectrogram of chitosan, and Fig. 2 is the infrared spectrogram of the derivative of prepared chitosan.Analyze two infrared spectrums as seen, 1588cm in the chitosan infrared spectrum
-1The place is amino N-H formation vibration peak, 3431cm
-1, 3365cm
-1Belong to the absorption peak of N-H stretching vibration and O-H stretching vibration in the chitosan molecule respectively, 1086cm
-1The place is the stretching vibration absorption peak of C-OH; Chitosan derivatives is at 1707cm
-1The stretching vibration absorption peak of C=O appears in the place, and 1589cm
-1Place's amino N-H formation vibration peak disappears, at 1605cm
-1And 1503cm
-1The absorption peak of phenyl ring C=C stretching vibration has appearred in the place, and C-OH stretching vibration absorption peak is displaced to 1111cm
-1, can know by inference mainly and on the amino of chitosan, reaction take place.
Fig. 3 and 4 is for being solvent with the acetum of 1g/L, with chitosan with benzamido benzoyl chitosan is made concentration is 1 * 10
-4The solution of g/ml records its uv absorption spectra.At the 283nm place a maximum absorption peak is arranged among Fig. 4, strong ultraviolet radiation absorption peak value is promptly arranged at the 283nm place.Absorbance is 1.7 herein, and uv-absorbing can reach the 300nm place, has reached the UVB district.And the uv-absorbing spectrogram of the acetic acid solution of chitosan shows among Fig. 3, and the 240-350nm place does not have absorption peak substantially, and ultraviolet absorptivity is also very little.To the difference of the addition of benzamido benzoyl chitosan, uv-absorbing intensity is also different.
Embodiment
Embodiment 1:
Getting the 3g phenylformic acid puts in the round-bottomed flask of 150ml, add the 30ml anhydrous diethyl ether, phenylformic acid dissolves fully, it is 30 ℃ ultrasonic washer that round-bottomed flask is put into water temperature, in flask, add the 5ml sulfur oxychloride again, ultra-sonic oscillation 10 minutes, add the dry para-amino benzoic acid of crossing of 3g again, ultra-sonic oscillation 20 minutes left standstill 60 minutes, the liquid that reacted in the round-bottomed flask is slowly poured in the beaker that is added with 100ml distilled water, use 10ml distilled water flushing flask again, the liquid that washed is also poured in the beaker, leaves standstill 5 minutes, the suction filtration aqueous solution obtains the benzoic wet product of benzamido, and vacuum-drying gets dryed product.
That gets dry mistake puts into three-necked bottle to benzene carbon amide yl benzoic acid 1g, adds the 30ml anhydrous diethyl ether, adds sulfur oxychloride again, puts in the ultrasonic washer of 30 ℃ of water temperatures, reacts 10 minutes.Be cooled to 25 ℃, the 0.5g chitosan is dissolved in the 10ml acetate, it is being added in three-necked bottle, and 25 ℃ of following ultra-sonic oscillation 1 hour, standing over night.After reaction is finished; adding a large amount of acetone is precipitated out product; suction filtration; use the mixed solvent (volume ratio is 1: 1) of dehydrated alcohol and anhydrous diethyl ether to soak suction filtration after 24 hours again; again the filter cake behind the suction filtration is carried out Soxhlet with acetone and extracted 24 hours, get product after the vacuum-drying---to benzamido benzoyl chitosan.
Embodiment 2:
That gets dry mistake puts into three-necked bottle to benzene carbon amide yl benzoic acid 1g, adds the 30ml anhydrous diethyl ether, adds sulfur oxychloride again, puts in the ultrasonic washer of 30 ℃ of water temperatures, reacts 10 minutes.Be heated to 45 ℃, the 0.5g chitosan is dissolved in the 10ml acetate, it is being added in three-necked bottle, and 45 ℃ of following ultra-sonic oscillation 1 hour, standing over night.After reaction is finished; adding a large amount of acetone is precipitated out product; suction filtration; use the mixed solvent of dehydrated alcohol and anhydrous diethyl ether to soak suction filtration after 24 hours again; again the filter cake behind the suction filtration is carried out Soxhlet with acetone and extracted 24 hours, get product after the vacuum-drying---to benzamido benzoyl chitosan.
Embodiment 3:
That gets dry mistake puts into three-necked bottle to benzene carbon amide yl benzoic acid 1g, adds the 30ml anhydrous diethyl ether, adds sulfur oxychloride again, puts in the ultrasonic washer of 30 ℃ of water temperatures, reacts 10 minutes.Be cooled to 5 ℃, the 0.5g chitosan is dissolved in the 10ml acetate, it is being added in three-necked bottle, and 5 ℃ of following ultra-sonic oscillation 1 hour, standing over night.After reaction is finished; adding a large amount of acetone is precipitated out product; suction filtration; use the mixed solvent of dehydrated alcohol and anhydrous diethyl ether to soak suction filtration after 24 hours again; again the filter cake behind the suction filtration is carried out Soxhlet with acetone and extracted 24 hours, get product after the vacuum-drying---to benzamido benzoyl chitosan.
Embodiment 4:
Products therefrom of the present invention has the embodiment of good compatibility stability (after 7 days) to benzamido benzoyl chitosan and cationic, anionic property and amphoterics
| Tensio-active agent (0.1g/ml) | 0.01g/ml products therefrom of the present invention | 0.05g/ml products therefrom of the present invention |
| Sodium dodecyl sulfate solution | Not stratified nothing precipitation | Not stratified nothing precipitation |
| Palmityl trimethyl ammonium chloride solution | Not stratified nothing precipitation | Not stratified nothing precipitation |
| Varion CDG-K solution | Not stratified nothing precipitation | Not stratified nothing precipitation |
Embodiment 5: products therefrom of the present invention adds shampoo to benzamido benzoyl chitosan
| Component | Weight ratio (part) |
| Dimethyl hydroxy methylene stearylamine trimethyl- |
40 |
| To benzamido benzoyl chitosan | 2 |
| Lactic acid (10%) | 2 |
| Palmityl trimethyl ammonium chloride (50%) | 5 |
| Deionized water | 51 |
Embodiment 6: products therefrom of the present invention adds shampoo to benzamido benzoyl chitosan
| Component | Weight ratio (part) |
| |
30 |
| |
5 |
| To |
5 |
| |
1 |
| |
1 |
| Deionized water | 58 |
Implement 7: products therefrom of the present invention adds shampoo to benzamido benzoyl chitosan
| Component | Weight ratio (part) |
| Palmityl trimethyl ammonium chloride | 6 |
| The Soxylat A 25-7 stearate | 3 |
| Hexadecanol | 9 |
| Vaseline | 3 |
| To benzamido benzoyl chitosan | 3 |
| |
15 |
| Essence | 2.5 |
| Sanitas | 0.5 |
| Deionized water | 58 |
Implement 8: products therefrom of the present invention is to the application example of benzamido benzoyl chitosan in sun care preparations
Emulsion-type frost cream: prescription one
| Component | Weight ratio (part) |
| Hexadecanol | 7 |
| |
10 |
| Glycerol monosterate | 3 |
| To |
10 |
| Sanitas | 0.5 |
| Spices | 0.5 |
| Deionized water | 69 |
Emulsion-type frost cream: prescription two
| Component | Weight ratio (part) |
| Vaseline | 20 |
| Silicone oil | 3 |
| Cross linked polyacrylate | 0.5 |
| Squalane | 10 |
| To |
10 |
| Sanitas | 0.3 |
| Sodium hydroxide | 0.5 |
| Spices | 0.7 |
| Deionized |
55 |
Emulsion-type frost cream: prescription three
| Component | Weight ratio (part) |
| Stearyl alcohol | 0.5 |
| |
5 |
| Water-soluble polypropylene acid | 0.3 |
| |
5 |
| To benzamido |
10 |
| Trolamine | 1.7 |
| Deionized water | 76.7 |
| Spices | 0.5 |
| Sanitas | 0.3 |
The production technique of above-mentioned sun care preparations: heat water to 70-85 ℃, add water-soluble formula material, get water after the dissolving fully.Other is mixed in 50-65 ℃ of heat of solution with oil, fat material and antioxidant, ultraviolet absorbers, in stirring down oil phase material is added to the aqueous phase mixing and emulsifying then, behind the homogeneous, stirs cooling, and in 40 ℃ of adding spices and sanitas, packing obtains sunscreen.Use products therefrom of the present invention that benzamido benzoyl chitosan is added in the makeup, resulting this sunscreen has the ultraviolet ability of absorption.See the contrast experiment's of Fig. 5 and 6 uv-absorbing spectrogram.
Those of ordinary skill in the art can understand, and in protection scope of the present invention, makes amendment for the foregoing description, and it all is possible adding and replacing, and it does not all exceed protection scope of the present invention.
Claims (6)
1. one kind to benzamido benzoyl chitosan derivatives, and it is characterized in that: this derivative has structure shown in the following formula,
Wherein n is between 500-600; This compound is that the UV spectrum 283nm place of the acetum of 1g/L has big absorption peak in concentration; The physical and chemical indexes of this compound: the white powder solid, water-soluble and ethylene glycol, molecular weight are 110-130KD.
2. one kind according to claim 1 to the preparation method of benzamido benzoyl chitosan, and it is characterized in that: described preparation process is as follows:
(1) para-amino benzoic acid with weighing is dissolved in the 50-65 ℃ of distilled water hot suction filtration;
(2) filtrate cool to room temperature, at room temperature suction filtration;
(3) get filter cake, vacuum-drying again obtains purified para-amino benzoic acid;
(4) getting the 3g phenylformic acid puts in the round-bottomed flask of 150ml, add the 30ml anhydrous diethyl ether, phenylformic acid dissolves fully, it is 30 ℃ ultrasonic washer that round-bottomed flask is put into water temperature, in flask, add the 5ml sulfur oxychloride again, ultra-sonic oscillation 10 minutes, add the dry para-amino benzoic acid of crossing of 3g again, ultra-sonic oscillation 20 minutes left standstill 60 minutes, the liquid that reacted in the round-bottomed flask is slowly poured in the beaker that is added with 100ml distilled water, use 10ml distilled water flushing flask again, the liquid that washed is also poured in the beaker, leaves standstill 5 minutes, the suction filtration aqueous solution obtains the benzoic wet product of benzamido, and vacuum-drying gets dryed product;
(5) get dry cross benzene carbon amide yl benzoic acid 1g is put into three-necked bottle, add the 30ml anhydrous diethyl ether, add sulfur oxychloride again, put in the ultrasonic washer of 30 ℃ of water temperatures, reacted 10 minutes, reaction product is to the benzamido Benzoyl chloride;
(6) reaction product to 25 ℃ in cooling (5) step is got the 0.5g chitosan and is dissolved in the 10ml anhydrous acetic acid, again it is added in three-necked bottle, and 25 ℃ of following ultra-sonic oscillation 1 hour, standing over night;
(7) reaction product with (6) step adds a large amount of acetone, makes product be precipitated out suction filtration to benzamido benzoyl chitosan;
(8) be that suction filtration was got filter cake after the mixed solvent of 1: 1 dehydrated alcohol and anhydrous diethyl ether soaked 24 hours with volume ratio again;
(9) this filter cake that again (8) is gone on foot carries out Soxhlet extraction 24 hours with acetone, must be to benzamido benzoyl chitosan product after the vacuum-drying.
3. according to the described preparation method of claim 2 to benzamido benzoyl chitosan, it is characterized in that: the processing condition of suction filtration are in described (1) step: dried by the fire 1-3 hour in 50-65 ℃ of baking oven with filter flask and B, use water pump suction filtration reaction solution down at 50-65 ℃ again, suction filtration is poured into filtrate in the clean beaker rapidly after finishing;
(2), the processing condition of suction filtration all are in (7) and (8) step: dried by the fire 1-3 hour in 50-65 ℃ of baking oven with filter flask and B, at room temperature use water pump suction filtration reaction solution again, suction filtration is poured into filtrate in the clean beaker rapidly after finishing.
4. according to the described preparation method to benzamido benzoyl chitosan of claim 2, it is characterized in that: the processing condition that the Soxhlet in described (9) step is extracted are: 55-65 ℃ of heating in water bath, extracted 24 hours.
5. according to the described preparation method to benzamido benzoyl chitosan of claim 2, it is characterized in that: the vacuum drying processing condition in described (9) step are: under 30-50 ℃, vacuum tightness is 8 * 10
4Pa, dry 12-24 hour.
According to claim 1 described to benzamido benzoyl chitosan as preparation sun care preparations Application of Additives.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101649005B (en) * | 2009-09-09 | 2011-06-08 | 中国海洋大学 | Para aminobenzoyl chitosan and preparing method thereof |
| CN102153674B (en) * | 2011-03-15 | 2012-11-07 | 中国海洋大学 | P-aminobenzoate chitosan ester and preparation method thereof |
| CN102198053B (en) * | 2011-05-25 | 2013-01-23 | 江南大学 | Synthesis and application of similar quaternized chitosan sunscreen |
| CN104784741B (en) * | 2015-04-23 | 2018-01-26 | 武汉市思泰利医疗器械发展有限公司 | chitosan functional hydrocolloid medical dressing |
| CN105131152B (en) * | 2015-10-08 | 2017-04-05 | 中国科学院海洋研究所 | A kind of marine polysaccharide copper composition and prepare and as the application of disinfectant use in agriculture |
| CN105237655B (en) * | 2015-10-08 | 2017-04-12 | 中国科学院海洋研究所 | Marine organism polysaccharide Schiff base derivative, preparation method thereof, and application thereof as agricultural bactericide |
| CN108096627A (en) * | 2017-12-26 | 2018-06-01 | 庞庆华 | A kind of suture of continuous and effective bactericidal |
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| CN1944470A (en) * | 2006-06-29 | 2007-04-11 | 中国海洋大学 | P-acetyl amino benzoyl chitosan compound and its preparing method |
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| CN1944470A (en) * | 2006-06-29 | 2007-04-11 | 中国海洋大学 | P-acetyl amino benzoyl chitosan compound and its preparing method |
Non-Patent Citations (2)
| Title |
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| 常德富 等.对已酰氨基苯甲酰壳聚糖的制备和应用性能研究.日用化学工业37 3.2007,37(3),全文. |
| 常德富 等.对已酰氨基苯甲酰壳聚糖的制备和应用性能研究.日用化学工业37 3.2007,37(3),全文. * |
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