CN101463050B - Modification method of humic acid, product obtained therefrom, and use thereof in skin-protection health products or medicaments preparation - Google Patents

Modification method of humic acid, product obtained therefrom, and use thereof in skin-protection health products or medicaments preparation Download PDF

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CN101463050B
CN101463050B CN 200810205101 CN200810205101A CN101463050B CN 101463050 B CN101463050 B CN 101463050B CN 200810205101 CN200810205101 CN 200810205101 CN 200810205101 A CN200810205101 A CN 200810205101A CN 101463050 B CN101463050 B CN 101463050B
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humic acid
humic acids
modifying
humic
degradation product
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CN101463050A (en
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周霞萍
仲恒昊
孙伟芬
喻波
程斌
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SHIPING SCIENCE AND TECHNOLOGY BUREAU
East China University of Science and Technology
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SHIPING SCIENCE AND TECHNOLOGY BUREAU
East China University of Science and Technology
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Abstract

The invention discloses a modification method of humic acid. The method comprises the following steps: (1) under ultrasonic wave, activating and oxidating and degrading a pulverized raw materials containing the humic acid or the humic acid in water in the presence of basic copper salt and alkali to prepare a humic acid degradation product; and (2) allowing the humic acid degradation product obtained in the step (1) to react with urea to prepare a modified humic acid substance. The invention further relates to the modified humic acid substance prepared by the method and application thereof to preparing skincare health products or skincare medicines. The modified humic acid substance has better efficacies on caring skin, resisting cracking, enhancing cutin softening and promoting skin lesions extinction and healing, has higher application value and simple preparation method, and is applicable to industrialized production.

Description

A kind of method of modifying of humic acids and products obtained therefrom and the application in preparation skin-protection health products or medicine thereof
Technical field
The present invention relates to a kind of method of modifying and products obtained therefrom and the application in preparation skin-protection health products or medicine thereof of humic acids.
Background technology
Humic acids (Humic Acid writes a Chinese character in simplified form HA) is the animals and plants remains, is mainly the remains of plant, through decomposition and the conversion of microorganism, and a series of chemical process and a type organic matter that accumulates.It has the functions such as good physiologically active and absorption, complexing, exchange by the polymeric organic acid that aromatic series and multiple functional group thereof consist of.Humic acids extensively is present in soil, lake, river, ocean, and in peat (claiming again the peat composed of rotten mosses), brown coal and weathered coal etc.According to the solvability in solvent and color classification, humic acids can be divided into xanthohumic acid, ulmic acid and Ulmic acids etc.
The research of the mankind to humic acids obtained existing 214 years history first from soil from 1786.If " coal is loose " that enroll in China's " medicine holy " famous medical scholar's LI Shi-Zhen Compendium of Material Medica works of the Ming Dynasty for an example, the application of that humic acids has more than 400 year.At present, humic acids is as organic matter raw material, has been widely used in agriculture, woods, herds, the every field such as oil, chemical industry, building materials, medicine, health, environmental protection.China's resource of humic acid is very abundant, and its reserves is large, distributes wide, and grade is good.According to the pertinent data statistics, 124.8 hundred million tons, peat is arranged, occupy the 4th, the world; 1,265 hundred million tons, brown coal also have a large amount of weathered coals.Therefore, the research and development of resource of humic acid had great development prospect.
At present, in the application of field of medicaments, find that humic acids has the effect of blood coagulation, hemostasis, and effect is similar to Yunnan white powder.In the application in skin care field, find that it has similar Unidasa and catalatic metabolism.(" coal is loose " power-assist skin care product go back to nature Huang Liangcai, humic acids, 2004,5:30-31) think, humic acids has the effects such as the blood circulation of enhancing, hemostasis and pain-relieving, antiulcer agent, exudation resistance and promotion wound healing, itself and the skin moisture-keeping factor etc. are mixed with protective skin cream (the happy U.S. frost of skin) for control chapped skin, skin pruritus and pernio etc., good relieving itching and eliminating swelling is arranged, promote the fast texts of little wound healing.Xu Chuanzhong, Zhu Yaqin (patent publication No.: CN1213665) with natural peat and sodium hydroxide effect salify, and through dissolved deliming patent medicine grade peat sodium fulvic acids such as ethanol or hydrochloric acid.This finished product molecular-weight average is little, and multiple biologically active gene is arranged, and oral administration or external application are mainly as the Chinese medicine additive of broad-spectrum antimicrobial.
Summary of the invention
Technical problem to be solved by this invention is for a kind of new application approach of humic acids is provided, and provide a kind of method of modifying of humic acids, and preparedly have better promotion cutin softening, skin care anticracking, promote skin to damage to disappear the modified humic acid substance of healing effect by the method, and the application in preparation skin-protection health products or medicine.
Method of the present invention comprises the steps:
(1) raw material that contains humic acids or the humic acids that will pulverize, in water, under ultrasonic wave, under the existence of alkali type nantokite and alkali, activated oxidative degradation makes humic acid degradation product.
Wherein, the described raw material that contains humic acids is the existing natural matter that contains humic acids, as contains peat, brown coal or the weathered coal etc. of humic acids.The abundant natural peat of preferred resources in the present invention, especially preferred natural low moor pat.Described natural low moor pat is to be grown by the place of low-lying place, seasonal ponding or long-term ponding, need the more plant of nutrient inorganic salt, as each kind of plant the broken branches and fallen leaves that Carex, reed belong to and alluviation is got off, peat through accumulation formation for many years, its general degree of decomposition is higher, acidity is lower, and ash oontent is higher.The preferred humic acids total content of the present invention is the natural low moor pat of 35~65wt%.Natural low moor pat has a large amount of distributions in Southwestern China, Central China, North China and northeast, the natural low moor pat of the present invention preferred Yunnan stone screen.Described humic acids is by the humic acids that extracts in above-mentioned various natural matters or artificial humic acids, the humic acids that preferably extracts from natural low moor pat.
Wherein, the raw material that contains humic acids of described pulverizing or the particle diameter of humic acids are advisable more fully can realize the active oxidation degraded, and that better is 20~100nm, and that better is 20~50nm.The method of pulverizing can adopt the conventional breaking method in this area, and better for to pulverize in the ultra-high speed pulverizer, that the linear speed of ultra-high speed pulverizer is better is 100~250m/s, and that better is 150~200m/s.Pulverize better carrying out under 30~80 ℃, better carries out under 50~60 ℃.
Better, will use after the described raw material that contains humic acids or the air-dry removal moisture of humic acids, effect is better.Air-dryly adopt natural air drying or artificial drying, better condition is: at the temperature of 15~35 ℃, through 5~10 days natural air dryings, perhaps in thermostatic drying chamber, at the temperature of 50~75 ℃, through oven dry in 1~3 hour, at the temperature of 60~70 ℃ that better is, through oven dry in 2 hours.
Wherein, described raw material or the humic acids that contains humic acids, with the mass volume ratio of water better be 1g/30~70ml, that better is 1g/50ml.That described alkali type nantokite is better is Cu 2(NO 3) (OH) 3And/or Cu 2CO 3(OH) 2What described alkali was better is mineral alkali, and as potassium hydroxide, sodium hydroxide and ammoniacal liquor etc., better is potassium hydroxide and/or sodium hydroxide.What the total concn of described alkali type nantokite and alkali was better is mass percent 5~20%, and better is mass percent 10~15%.What the mass ratio of described alkali type nantokite and alkali was better is 1: 5~1: 20, and better is 1: 8~1: 12, and best is 1: 9.
That wherein, described hyperacoustic frequency is better is 50~100KHZ.What the temperature of described active oxidation degraded was better is 20~100 ℃, and better is 30~80 ℃.The time of described active oxidation degraded is generally 10~40min, and that better is 20~30min.
Active oxidation degraded can directly be carried out the next step after finishing, and also the available alcoholic solvent aqueous solution or ketones solvent aqueous solution extraction, get organic phase, carry out the next step after dry solid again.
(2) under microwave condition, humic acid degradation product and urea reaction with step (1) makes namely make modified humic acid substance.
Wherein, that the frequency of described microwave is better is 915~2450MHz, and that the power of microwave is better is 350~500W.That the time of described reaction is better is 5~25min, and that better is 10~20min.Most preferred reaction conditions is: microwave frequency 2450MHz, microwave power 500W, time 10~20min.
Wherein, the consumption of described urea is better is 1.5~2.5 times of humic acid degradation product molar weight, and better is 2 times.In the present invention, the molar weight of described humic acid degradation product is calculated with following formula: humic acid degrading amount ÷ humic acid degradation product molecular-weight average; Described humic acid degradation product molecular-weight average can be measured (concrete grammar reference: Li Shanxiang with dark type viscometer or ebullioscopic method, humic acids product analysis and standard, Chemical Industry Press, in September, 2007, p110~112, p112~113), generally recording the humic acid degradation product molecular-weight average is 130~320.
If without aftertreatment, directly carry out the reaction of step (2) after the active oxidation DeR of step (1) finishes, do not need solubilizing agent again.If after the active oxidation DeR of step (1) finishes to get the humic acid degradation product solid by aftertreatment, then carry out the reaction of step (2), need add solvent.Solvent can be the mixed solvent of this area alcoholic solvent commonly used, the ketones solvent aqueous solution, water or above-mentioned solvent, preferred alcohol, acetone or water, and the consumption of solvent is advisable to obtain semi-solid, is generally 1g/3~5g humic acid degradation product solid.
After the end of step (2) reaction, gained modified humic acid substance convection drying can be used, usually can be used for preparing pulvis.Also the gained modified humic acid substance with the aqueous solution of alcoholic solvent or the aqueous solution extraction of ketones solvent, organic phase can be got, with further purification, the preparation liquid preparation can be directly used in, also can be dry rear for the preparation of pulvis.Described alcoholic solvent or ketones solvent are this area alcohols commonly used or organic solvent of ketone, preferred alcohol or acetone.
In method of modifying of the present invention, but the optimum condition arbitrary combination of above steps namely obtains each preferred embodiments of the present invention.
The invention still further relates to the modified humic acid substance that is made by aforesaid method.This modified humic acid substance has better skin care, anticracking, promotion cutin softening, promotes skin to damage the effect that disappears and heal.
Therefore, the invention further relates to the application of modified humic acid substance of the present invention in preparation skin-protection health products or skin care medicine.As required, modified humic acid substance of the present invention can be mixed with skin-protection and health-care field or the acceptable various conventional auxiliary materials of pharmaceutical field, make the product of various formulations, as paste, liquid agent or pulvis etc.
Agents useful for same of the present invention and raw material be commercially available getting all.
Positive progressive effect of the present invention is: modified humic acid substance of the present invention has better skin care, anticracking, promotion cutin softening, promotes skin to damage the effect that disappears and heal, and than the common drug humic acids, have stronger pharmacological, the more single-minded characteristics of action target spot, using value is higher.In addition, its preparation method is simple, is easy to suitability for industrialized production.The present invention provides new way for taking full advantage of humic acids.
Embodiment
The below further illustrates the present invention with embodiment, but the present invention is not limited.
In following examples, natural low moor pat is provided by Shiping County, Yunnan science and technology office, and its humic acids content is 57wt%.
In following examples, the humic acid degradation product molecular-weight average is measured (concrete reference: Li Shanxiang, humic acids product analysis and standard, Chemical Industry Press, in September, 2007, p112~113) by ebullioscopic method.
Embodiment 1
100g through 30 ℃ of natural air dryings natural low moor pat of 5 days, under 50 ℃, in the ultra-high speed pulverizer of linear velocity 200m/s, is ground into the particulate of 20~30nm.Afterwards, containing Cu 2(NO 3) (OH) 3With in the aqueous solution of potassium hydroxide, (5000ml, total concn is 10wt%, Cu 2(NO 3) (OH) 3With the potassium hydroxide mass ratio be 1: 20), under the ultrasonic wave of 100KHz, 65 ℃ of temperature, activated oxidative degradation, the reaction 20min, namely make natural low moor pat humic acid degradation product.
Get the urea of the above-mentioned natural low moor pat humic acid degradation product (molecular-weight average 280) that makes of 3080g (11mol) and 1320g (22mol), be microwave frequency 2450MHz, under microwave power 500W, react, after reaction 12min, namely get natural low moor pat modified humic acid substance.Again through the aqueous ethanolic solution of 50wt% under the normal temperature of 10~35 ℃, after extraction 25min, get organic phase, dry 60min under 25~45 ℃ gets final product to get the natural low moor pat modified humic acid substance solid of purifying.
Embodiment 2
100g through 15 ℃ of natural air dryings natural low moor pat of 10 days, under 30 ℃, in the ultra-high speed pulverizer of linear velocity 250m/s, is ground into the particulate of 70~80nm.Afterwards, containing Cu 2(CO 3) (OH) 2With in the aqueous solution of potassium hydroxide, (6000ml, total concn is 20wt%, Cu 2(CO 3) (OH) 2With the potassium hydroxide mass ratio be 1: 10), under the ultrasonic wave of 50KHz, 100 ℃ of temperature, activated oxidative degradation, the reaction 23min, make natural low moor pat humic acid degradation product.
Get the urea of the above-mentioned natural low moor pat humic acid degradation product (molecular-weight average 220) that makes of 3200g (14.5mol) and 1740g (29mol), at microwave frequency 2450MHz, under microwave power 500W, react, after reaction 20min, get final product to get natural low moor pat modified humic acid substance solid.
Embodiment 3
100g through 35 ℃ of natural air dryings natural low moor pat of 8 days, under 80 ℃, in the ultra-high speed pulverizer of linear velocity 150m/s, is ground into the particulate of 80~100nm.Afterwards, containing Cu 2(NO 3) (OH) 3With in the aqueous solution of sodium hydroxide, (7000ml, total concn is 15wt%, Cu 2(NO 3) (OH) 3With the sodium hydroxide mass ratio be 1: 5), under the ultrasonic wave of 80KHz, 30 ℃ of temperature, activated oxidative degradation, the reaction 10min, make natural low moor pat humic acid degradation product.
Get the urea of the above-mentioned natural low moor pat humic acid degradation product (molecular-weight average 320) that makes of 3200g (10mol) and 900g (15mol), at microwave frequency 2450MHz, under microwave power 500W, react, after reaction 10min, namely get natural low moor pat modified humic acid substance.Again through the aqueous propanol solution of 50wt% under the normal temperature of 10~35 ℃, after extraction 15min, get organic phase, dry 30min under 25~45 ℃ gets final product to get the natural low moor pat modified humic acid substance solid of purifying.
Embodiment 4
100g through 50 ℃ of oven dry of thermostatic drying chamber natural low moor pat of 3 hours, under 60 ℃, in the ultra-high speed pulverizer of linear velocity 100m/s, is ground into the particulate of 50~60nm.Afterwards, containing Cu 2(CO 3) (OH) 2With in the aqueous solution of sodium hydroxide, (4000ml, total concn is 5wt%, Cu 2(CO 3) (OH) 2With the sodium hydroxide mass ratio be 1: 8), under the ultrasonic wave of 60KHz, 80 ℃ of temperature, activated oxidative degradation, the reaction 32min, make natural low moor pat humic acid degradation product.
Get the urea of the above-mentioned natural low moor pat humic acid degradation product (molecular-weight average 160) that makes of 3200g (20mol) and 3000g (50mol), at microwave frequency 915MHz, under microwave power 500W, react, after reaction 25min, namely get natural low moor pat modified humic acid substance.Again through 50% aqueous ethanolic solution under the normal temperature of 10~35 ℃, after extraction 20min, get organic phase, dry 50min under 25~45 ℃,, get final product to get the natural low moor pat modified humic acid substance solid of purifying.
Embodiment 5
100g through 75 ℃ of oven dry of thermostatic drying chamber natural low moor pat of 1 hour, under 70 ℃, in the ultra-high speed pulverizer of linear velocity 200m/s, is ground into the particulate of 60~70nm.Afterwards, containing Cu 2(NO 3) (OH) 3With in the aqueous solution of potassium hydroxide, (3000ml, total concn is 12wt%, Cu 2(NO 3) (OH) 3With the potassium hydroxide mass ratio be 1: 12), under the ultrasonic wave of 100KHz, 20 ℃ of temperature, activated oxidative degradation, the reaction 28min, make natural low moor pat humic acid degradation product.
Get the urea of the above-mentioned natural low moor pat humic acid degradation product (molecular-weight average 210) that makes of 3150g (15mol) and 1800g (30mol), at microwave frequency 2450MHz, under microwave power 500W, react, after reaction 5min, namely get natural low moor pat modified humic acid substance.Again through 50% aqueous ethanolic solution under the normal temperature of 10~35 ℃, after extraction 25min, get organic phase, dry 60min under 25~45 ℃ gets final product to get the natural low moor pat modified humic acid substance solid of purifying.
Embodiment 6
100g through 65 ℃ of oven dry of thermostatic drying chamber natural low moor pat of 2 hours, under 40 ℃, in the ultra-high speed pulverizer of linear velocity 250m/s, is ground into the particulate of 20~30nm.Afterwards, containing Cu 2(NO 3) (OH) 3With in the aqueous solution of potassium hydroxide, (5000ml, total concn is 10wt%, Cu 2(NO 3) (OH) 3With the potassium hydroxide mass ratio be 1: 9), under the ultrasonic wave of 100KHz, 65 ℃ of temperature, activated oxidative degradation, the reaction 30min, make natural low moor pat humic acid degradation product.
Get the urea of the above-mentioned natural low moor pat humic acid degradation product (molecular-weight average 189) that makes of 3213g (17mol) and 1980g (33mol), at microwave frequency 2450MHz, under microwave power 350W, react, after reaction 12min, namely get natural low moor pat modified humic acid substance.Again through the aqueous ethanolic solution of 50wt% under the normal temperature of 10~35 ℃, after extraction 20min, get organic phase, dry 60min under 25~45 ℃ gets final product to get the natural low moor pat modified humic acid substance solid of purifying.
Embodiment 7
100g without air-dry natural low moor pat, under 45 ℃, in the ultra-high speed pulverizer of linear velocity 200m/s, is ground into the particulate of 20~30nm.Afterwards, containing Cu 2(NO 3) (OH) 3With in the aqueous solution of potassium hydroxide, (5000ml, total concn is 10wt%, Cu 2(NO 3) (OH) 3With the potassium hydroxide mass ratio be 1: 8), under the ultrasonic wave of 100KHz, temperature 70 C, activated oxidative degradation, the reaction 40min, make natural low moor pat humic acid degradation product.Again through the aqueous ethanolic solution of 50wt% under the normal temperature of 10~35 ℃, after extraction 20min, get organic phase, dry 60min under 25~45 ℃ gets final product to get the natural low moor pat humic acid degradation product solid of purifying.
Get the urea of the above-mentioned natural low moor pat humic acid degradation product (molecular-weight average 139) that makes of 3200g (23mol) and 2760g (46mol), at microwave frequency 2450MHz, under microwave power 500W, react, after reaction 12min, namely get natural low moor pat modified humic acid substance.Again through 50% aqueous ethanolic solution under the normal temperature of 10~35 ℃, after extraction 20min, get organic phase, dry 60min under 25~45 ℃ gets final product to get the natural low moor pat modified humic acid substance solid of purifying.
Embodiment 8
Get the natural low moor pat modified humic acid substance 150g that embodiment 1 makes, whiteruss 100g, stearic acid 50g, glycerine 50g, add the 150ml deionized water dissolving, mixing is heated to 75 ℃, keep 15min, then condensing cooling, 500g humic acid in peat modifier cold cream got.
Effect embodiment
Following effect experiment is carried out in Quanzhou institute of traditional Chinese medicine.The humic acid in peat modifier cold cream that respectively embodiment 8 is made, wallantoin cold cream (sending auspicious specialization work company limited available from Changzhou) and common drug are with humic acids (refining humic acids, Hami Handilong humic acids company limited) be coated with use for each patient that 10 routine keratinization skin damages, evenly be applied to keratinization skin damage place, be coated with outside the part 2 every day, 2 weeks of the course for the treatment of.Result is as shown in table 1.
The anti-keratinization skin of table 1 modified humic acid substance cold cream damages effect
Title Skin damages area reducing rate % Keratinization epidermal thickness/mm
The blank group / 0.232~0.235
The common drug humic acids 15 0.235~0.242
The wallantoin cold cream 80 0.233~0.236
The modified humic acid substance cold cream 80 0.232~0.236
By table 1 result as seen, modified humic acid substance of the present invention has the effect of significant promotion cutin softening, skin care anticracking, and than the common drug humic acids, have stronger pharmacological, the more single-minded characteristics of action target spot, can travel in conjunction with top grade, health facility exploitation series product.

Claims (11)

1. the method for modifying of a humic acids, it comprises the steps:
(1) raw material that contains humic acids or the humic acids that will pulverize, in water, under ultrasonic wave, under the existence of alkali type nantokite and alkali, activated oxidative degradation makes humic acid degradation product;
(2) under microwave condition, humic acid degradation product and urea reaction with step (1) makes namely make modified humic acid substance;
In step (1), described alkali type nantokite is Cu 2(NO 3) (OH) 3And/or Cu 2CO 3(OH) 2Described alkali is potassium hydroxide and/or sodium hydroxide; The total concn of described alkali type nantokite and alkali is mass percent 5~20%; The mass ratio of described alkali type nantokite and alkali is 1: 5~1: 20; Described hyperacoustic frequency is 50~100KHz; The temperature of described active oxidation degraded is 30~80 ℃; The time of described active oxidation degraded is 10~40min.
2. method of modifying as claimed in claim 1, it is characterized in that: in step (1), the described raw material that contains humic acids is peat, brown coal or the weathered coal that contains humic acids.
3. method of modifying as claimed in claim 2, it is characterized in that: in step (1), described peat is that the humic acids total content is the natural low moor pat of mass percent 35~65%.
4. method of modifying as claimed in claim 2, it is characterized in that: in step (1), described peat is the natural low moor pat that originates from the Yunnan stone screen.
5. method of modifying as claimed in claim 1, it is characterized in that: in step (1), the raw material that contains humic acids of described pulverizing or the particle diameter of humic acids are 20~100nm.
6. method of modifying as claimed in claim 1 is characterized in that: in step (1), will use after the described raw material that contains humic acids or the air-dry removal moisture of humic acids.
7. method of modifying as claimed in claim 1 is characterized in that: in step (1), described raw material or the humic acids that contains humic acids, with the mass volume ratio of water be 1g/30~70ml.
8. method of modifying as claimed in claim 1, it is characterized in that: in step (2), the frequency of described microwave is 915~2450MHz, and the power of microwave is 350~500W, and the time of described reaction is 5~25min.
9. method of modifying as claimed in claim 1, it is characterized in that: in step (2), the consumption of described urea is 1.5~2.5 times of humic acid degradation product molar weight; The molar weight of described humic acid degradation product is calculated with following formula: humic acid degrading amount ÷ humic acids molecular-weight average.
10. the modified humic acid substance that makes of method of modifying as described in claim 1~9 any one.
11. the application of modified humic acid substance as claimed in claim 10 in preparation skin-protection health products or skin care medicine.
CN 200810205101 2008-12-30 2008-12-30 Modification method of humic acid, product obtained therefrom, and use thereof in skin-protection health products or medicaments preparation Expired - Fee Related CN101463050B (en)

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CN107541367A (en) * 2017-09-08 2018-01-05 东北师范大学 A kind of soap base acid-base neutralization auxiliary agent and its preparation method
CN108576058A (en) * 2018-05-31 2018-09-28 中国矿业大学 The extracting method of regenerated xanthohumic acid in a kind of low metamorphic lignite
CN112641708A (en) * 2021-02-05 2021-04-13 东晟源研究院(广州)有限公司 Formula and preparation method of humic acid essence for promoting wound healing

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