CN102198053B - Synthesis and application of similar quaternized chitosan sunscreen - Google Patents
Synthesis and application of similar quaternized chitosan sunscreen Download PDFInfo
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- CN102198053B CN102198053B CN 201110136833 CN201110136833A CN102198053B CN 102198053 B CN102198053 B CN 102198053B CN 201110136833 CN201110136833 CN 201110136833 CN 201110136833 A CN201110136833 A CN 201110136833A CN 102198053 B CN102198053 B CN 102198053B
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- sunscreen
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Abstract
The invention relates to a synthesis method of similar quaternized chitosan sunscreen and an application of the quaternized chitosan sunscreen as hair sunscreen, belonging to the technical field of functional cosmetic. The product in the invention is obtained through the following two reaction steps: first step, 2-hydroxypropyltrimethyl ammonium chloride chitosan is synthesized from 3-chloro-2-hydroypropyltrimethyl amino and chitosan under alkali condition; second step, 2-hydroxypropyltrimethyl ammonium chloride chitosan is dissolved in dimethyl sulfoxide, and acyl chloride (sulfonyl chloride) and bind acid agent triethylamine are added in the solution to synthesize the final product quaternized chitosan sunscreen. Wherein, the acyl chloride (sulfonyl chloride) group grafted in the second step has quite strong ultraviolet absorption performance; besides, grafting quaternary ammonium group on the chitosan not only improves the water solubility of the chitosan and enlarges the application scope, but also enables the product to adhere to hairs with negative electricity. Measurement of tryptophan content in hairs proves that the product has sun-screening effect for hairs to some extent.
Description
Technical field
The present invention relates to the synthetic of a class n-trimethyl chitosan chloride sunscreen and use, specially refer to that preparation is a kind of to be adsorbed onto chitosan derivatives of having the absorbing ultraviolet effect on the hair and preparation method thereof, belong to function cosmetics technical field.
Background technology
The factor of damage hair totally is divided three classes: mechanical factor; Chemical factor; Environmental factors.It is nocuous that ultraviolet is considered in all environmental factorss tool.Hair is exposed in the ultraviolet radiation, melanin can fade because being subject to oxidation, solar radiation also can make the group generation light degradation such as cystine in the keratin, tyrosine, tryptophan in addition, make the link fracture between the aminoacid, the basic structure of hair is thereupon destroyed, hair so withered, fragile, dim, the cardability variation that becomes.
The hair sunscreen seldom mainly contains the amino benzoyl aminopropyl dimethyl methyl ammonium benzene sulfonate (DDABDT) of flavone compound, dodecyl dimethyl in the natural plants at present.
People have recognized the importance that hair is sun-proof, but development hair sunscreen need to solve following problem: (1) at present used sunscreen is the skin sunscreen mostly, affinity and film property to hair are all relatively poor, are difficult for forming uniform protecting film; (2) very large dissolubility to be arranged in water; (3) otherwise produce sticky sensation; Do not affect the gloss of hair when (4) being adsorbed on the hair surface; (5) scalp there is not zest.
Chitosan is a kind of natural polysaccharide of extensive existence, has good biocompatibility, and is nontoxic, nonirritant, and easily degraded, film property, antibiotic properties etc. are widely used in a lot of fields such as medicine, food, daily use chemicals.But the dissolubility of chitosan own is relatively poor, only can be dissolved in the diluted acid, so its application is limited by very large.
2-Hydroxyproyl Trimethyl ammonium chitosan has good water solublity, but the product that it is carried out further modification is seldom arranged.Change the reaction factors such as response time, temperature, material ratio, can change the quaternized degree of chitosan, remaining amino and 6-hydroxyl can carry out other chemical modification.
Summary of the invention
Purpose of the present invention: for the unreacted amino and the 6-hydroxyl that exist on the 2-Hydroxyproyl Trimethyl ammonium chitosan, react with acyl chlorides (sulfonic acid chloride), group with very strong UV absorbability and the 2-Hydroxyproyl Trimethyl ammonium chitosan with good aqueous solubility, film property, adsorptivity are effectively combined, obtain a kind ofly with positive charge, have good aqueous solubility, non-irritating macromolecule hair sunscreen.
Technical scheme of the present invention: n-trimethyl chitosan chloride sunscreen of the present invention, it is comprised of following structure:
R wherein
1For: H ,-COCH
3,
Wherein R is: H,
Wherein the molar substitution of 2-Hydroxyproyl Trimethyl ammonium group is 40%-80%; The molar substitution of acyl group (sulfonyl) group is 4%-20%, and acetyl group molar substitution 18%-20% is because the deacetylation of chitosan is about 80%.Molar substitution refers to the molal quantity of grafting 2-Hydroxyproyl Trimethyl ammonium group, acyl group or sulfonyl group, Acetyl Groups on 1 mole of sugar unit.
Among the present invention 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride and acyl chlorides (sulfonic acid chloride) can with chitosan on amino and 6-hydroxyl reaction.
The synthetic route of n-trimethyl chitosan chloride sunscreen:
R wherein
2CO(R
2SO
2) be:
The synthetic method of n-trimethyl chitosan chloride sunscreen of the present invention, the method may further comprise the steps:
(1) synthetic 2-Hydroxyproyl Trimethyl ammonium chitosan: 4g 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride and 1g chitosan are dispersed in the 50mL water, in reaction system, slowly drip 20mL 0.5mol/L NaOH, 90 ℃ of magnetic agitation reaction 30h, acetone with 3 times of volumes is separated out flocky precipitate, obtains 2-Hydroxyproyl Trimethyl ammonium chitosan.
(2) synthesis of quaternary ammonium chitosan sunscreen: with the 50mL dimethyl sulfoxine with the synthetic abundant swelling of 1g 2-Hydroxyproyl Trimethyl ammonium chitosan that obtains of step (1) after, to the triethylamine that wherein adds 0.012mol acyl chlorides (sulfonic acid chloride) and 0.012mol, the room temperature lower magnetic force stirs, reaction 24h.Ethanol with 3 times of volumes is separated out product, behind the sand core funnel sucking filtration, uses ethanol Soxhlet extraction 4 days, obtains the n-trimethyl chitosan chloride sunscreen.
Solvent in above-mentioned (2) is dimethyl sulfoxine.
Acyl chlorides (sulfonic acid chloride) in above-mentioned (2) is: 4-methoxyl group cinnamoyl chloride, salicylic acid acyl chlorides, p-benzoyl chlorine, to dimethylamino Benzenecarbonyl chloride., 2-cyano group-3; 3-diphenyl-2-acryloyl chloride, lignocaine oxybenzene formoxyl Benzenecarbonyl chloride., 4; 4'; 4''-(1; 3; 5-triazine-2; 4,6-, three imino groups) tri-benzoyl chlorine, 2-Phenylbenzimidazole-5-sulfonic acid chloride, ESCALOL 567-5-sulfonic acid chloride, 2-hydroxyl-4-methoxyl group-5-sulfonic acid chloride benzophenone, to sulfonic acid chloride vinyl benzene, sulfonic acid chloride vinyl benzene.
The application of this class n-trimethyl chitosan chloride sunscreen, it can be used in the hair product such as hair conditioner, suppurative mastitis, treatment oil, hair jelly, shampoo.
The sun-proof performance test of n-trimethyl chitosan chloride sunscreen:
The hair sample pretreatment: 2mL mass concentration 0.5% n-trimethyl chitosan chloride sunscreen product solution is smeared 1g hair (simulation cleaning-free hair conditioner), 2mL mass concentration 0.5% n-trimethyl chitosan chloride sunscreen product solution washing 1g hair (simulation can be washed hair conditioner and shampoo), the matched group hair of not processing with product solution.
Above-mentioned hair sample is with 5.5mol/L sodium hydroxide hydrolysis 20h under 110 ℃, in sodium dihydrogen phosphate-sodium hydroxide buffer solution of pH 10.5, excitation wavelength is 280nm, emission wavelength is the fluorescence intensity that the 364nm place measures tryptophan, has measured respectively the fluorescence intensity with the hair of ultra violet lamp different time.Calculate tryptophane and the damage index of hair sample by fluorescence intensity and tryptophan standard curve.
The damage index computing formula:
Beneficial effect of the present invention: the present invention introduces cation group in chitosan molecule, the skin sunscreen that simultaneously grafting is commonly used, and the water solublity of chitosan is greatly improved; Chitosan derivatives has high positive charge simultaneously, can produce electrostatic interaction with the negative charge of hair fiber; Add non-stimulated, the film property of chitosan itself, so that this product can be used as the hair sunscreen.
Description of drawings
The infrared spectrum of Fig. 1 raw materials of chitosan and quaternized methoxyl group cinnamoyl chitosan (acyl chlorides is 4-methoxyl group cinnamoyl chloride).
Fig. 2 raw materials of chitosan and quaternized methoxyl group cinnamoyl chitosan (acyl chlorides is 4-methoxyl group cinnamoyl chloride)
1The H-NMR spectrogram.
The tryptophane of the hair sample of Fig. 3 Different treatments.4, the natural law in 9,18 expression processing times.
The specific embodiment
Following example will the invention will be further elaborated.
Synthesizing of 2-Hydroxyproyl Trimethyl ammonium chitosan
In the 250mL there-necked flask, add 1g chitosan, 4g 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride and 50ml deionized water, in reaction system, slowly drip 20ml 0.5mol/L NaOH, 90 ℃ of magnetic agitation reaction 30h, acetone with 3 times of volumes is separated out flocky precipitate, obtains 2-Hydroxyproyl Trimethyl ammonium chitosan.
Synthesizing of n-trimethyl chitosan chloride sunscreen
In flask at the bottom of the 100mL garden, add 1g 2-Hydroxyproyl Trimethyl ammonium chitosan and 50mL dimethyl sulfoxine, after the abundant swelling of magnetic agitation, to the triethylamine that wherein adds again 0.012mol acyl chlorides (sulfonic acid chloride) and 0.012mol, the room temperature lower magnetic force stirs, reaction 24h, and product precipitates with dehydrated alcohol, behind the sucking filtration, extracted 4 days with the dehydrated alcohol Soxhlet, obtain purer n-trimethyl chitosan chloride sunscreen, dry in the shade.
Described acyl chlorides or sulfonic acid chloride are: 4-methoxyl group cinnamoyl chloride, salicylic acid acyl chlorides, p-benzoyl chlorine, to dimethylamino Benzenecarbonyl chloride., 2-cyano group-3; 3-diphenyl-2-acryloyl chloride, lignocaine oxybenzene formoxyl Benzenecarbonyl chloride., 4; 4'; 4''-(1; 3; 5-triazine-2; 4,6-, three imino groups) tri-benzoyl chlorine, 2-Phenylbenzimidazole-5-sulfonic acid chloride, ESCALOL 567-5-sulfonic acid chloride, 2-hydroxyl-4-methoxyl group-5-sulfonic acid chloride benzophenone, to sulfonic acid chloride vinyl benzene, sulfonic acid chloride vinyl benzene.
Fig. 1 is the infrared spectrum of raw materials of chitosan and quaternized methoxyl group cinnamoyl chitosan
As seen from Figure 1 on the infrared spectrum of quaternized methoxyl group cinnamoyl chitosan: 1600 cm
-1, 1558cm
-1There are two peaks at the place, and this is the C=C stretching vibration peak of phenyl ring; At 831 cm
-1The place is phenyl ring para-orientation=C-H out-of-plane bending vibration; At 1249 cm
-1The peak at place is the C-O stretching vibration peak of phenylate, proves that 4-methoxyl group cinnamoyl is grafted on the chitosan.In addition at 1477 cm
-1The peak, place strengthens
3Upper C-H bending vibration peak proves that grafted by quaternary ammonium group is on chitosan.
Fig. 2 is raw materials of chitosan and quaternized methoxyl group cinnamoyl chitosan
1The H-NMR spectrogram.
Chitosan
1δ in the H-NMR spectrogram=5.28(B) and 3.34(D) be-NH
2The characteristic peak of upper two hydrogen, δ=5.05(C) be-NHCOCH
3Hydrogen characteristic peak on the nitrogen, the peak area integration of B and C is than being 1:0.25; δ=4.15-4.28 is the characteristic peak of the upper H2-6 of sugar ring.
Quaternized methoxyl group cinnamoyl chitosan
1δ in the H-NMR spectrogram=8.06,7.97,7.49, the 7.43rd, the characteristic peak of hydrogen on the para-orientation phenyl ring, δ=7.00, the 6.48th, the characteristic peak of hydrogen on the alkene; The peak area integration of B and C reduces than obviously, and while δ=3.34(D) locate the peak also to reduce has illustrated part-NH
2React away; δ=3.65(E) is the characteristic peak of methyl on the quaternary ammonium group, δ=3.13,2.63(F) be the characteristic peak of methylene on the quaternary ammonium group.The sun-proof group of these data declarations and quaternized ammonium groups are grafted on the chitosan.
The tryptophane of the hair sample of Fig. 3 Different treatments.4, the natural law in 9,18 expression processing times.
The damage index of the hair sample of table 1 Different treatments
| Sample | Damage index (%) |
| Be untreated-4 | 3.80 |
| Be untreated-9 | 13.05 |
| Be untreated-18 | 21.06 |
| Smear-4 | 0.87 |
| Smear-9 | 3.24 |
| Smear-18 | 8.19 |
| Washing-4 | 0.80 |
| Washing-9 | 6.36 |
| Washing-18 | 12.65 |
Claims (2)
1. the synthetic method of a class n-trimethyl chitosan chloride sunscreen is characterized in that synthesis step is:
(1) synthetic 2-Hydroxyproyl Trimethyl ammonium chitosan: 4g 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride and 1g chitosan are dispersed in the 50ml water, in reaction system, slowly drip 20ml 0.5mol/L NaOH, 90 ℃ of magnetic agitation reaction 30h, acetone with 3 times of volumes is separated out flocky precipitate, obtains 2-Hydroxyproyl Trimethyl ammonium chitosan;
(2) synthesis of quaternary ammonium chitosan sunscreen: with the 50mL dimethyl sulfoxine with the synthetic 1g 2-Hydroxyproyl Trimethyl ammonium chitosan complete swelling that obtains of step (1) after, to the triethylamine that wherein adds 0.012mol acyl chlorides and 0.012mol, the room temperature lower magnetic force stirs, reaction 24h, ethanol with 3 times of volumes is separated out product, behind the sand core funnel sucking filtration, use ethanol Soxhlet extraction 4 days, obtain the n-trimethyl chitosan chloride sunscreen;
Described acyl chlorides is: 4-methoxyl group cinnamoyl chloride.
2. use the application of the n-trimethyl chitosan chloride sunscreen of the described synthetic method preparation of claim 1, it is characterized in that this n-trimethyl chitosan chloride sunscreen can be used in hair conditioner, suppurative mastitis, treatment oil, hair jelly, the shampoo product.
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| CN103936886B (en) * | 2014-04-28 | 2016-03-02 | 华南理工大学 | O-thiazolidine methyl esters-N-trimethyl chitin quaternary ammonium salt and method for making and application |
| CN105997598A (en) * | 2016-04-14 | 2016-10-12 | 青岛科技大学 | Stripping type O-chitosan quaternary ammonium salt mask and preparation method thereof |
| CN106589166A (en) * | 2016-12-30 | 2017-04-26 | 齐鲁工业大学 | Preparation method of nitrogen-replaced chitosan quaternary ammonium salt |
| CN107163164B (en) * | 2017-06-02 | 2019-06-04 | 广西师范学院 | The preparation method of cross-linking type macromolecular light stabilizer |
| DE102017215873A1 (en) * | 2017-09-08 | 2019-03-14 | Henkel Ag & Co. Kgaa | Method and device for determining a thermal damage degree of hair |
| CN108049175A (en) * | 2017-11-09 | 2018-05-18 | 安徽美德发艺有限责任公司 | A kind of sun-screening agent for patch-type seamless sending and receiving |
| CN109276474B (en) * | 2018-09-30 | 2020-11-03 | 江南大学 | Preparation method of nano zinc oxide/cationic polysaccharide hybrid nano particles |
| CN111254728A (en) * | 2020-04-12 | 2020-06-09 | 刘俊文 | Sun-proof and ultraviolet-proof color fixing agent and preparation method thereof |
| CN111808206A (en) * | 2020-08-18 | 2020-10-23 | 江南大学 | Modified biomass with ultraviolet absorption function, preparation method and application |
| CN111888282B (en) * | 2020-08-18 | 2021-08-13 | 江南大学 | Sunscreen composition containing ultraviolet-absorbable modified biomass, preparation method and application |
| CN115746169A (en) * | 2022-12-13 | 2023-03-07 | 贵阳绿洲苑新材料有限公司 | Three-dimensional modified chitosan polymer and preparation method thereof |
| CN116554367A (en) * | 2023-05-12 | 2023-08-08 | 麦加芯彩新材料科技(上海)股份有限公司 | Cyclodextrin demulsifier and preparation method and application thereof |
| CN116987211B (en) * | 2023-09-25 | 2023-12-01 | 中国科学院烟台海岸带研究所 | Benzimidazole acid-containing hydroxypropyl trimethyl chitosan quaternary ammonium salt derivative and preparation and application thereof |
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| CN102695493B (en) * | 2009-11-06 | 2014-07-23 | 花王株式会社 | Oil-in-water-type emulsion cosmetic |
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| CN1352931A (en) * | 2000-11-10 | 2002-06-12 | 李晓红 | Sun-shielding spot-removing chitin cream |
| CN1944470A (en) * | 2006-06-29 | 2007-04-11 | 中国海洋大学 | P-acetyl amino benzoyl chitosan compound and its preparing method |
| CN101255202A (en) * | 2007-12-12 | 2008-09-03 | 中国海洋大学 | p-benzoyl amido benzoyl chitosan and preparation thereof |
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