CN115975184A - Cationic biopolymer and preparation method and application thereof - Google Patents
Cationic biopolymer and preparation method and application thereof Download PDFInfo
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- 125000002091 cationic group Chemical group 0.000 title claims abstract description 94
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- 239000000203 mixture Substances 0.000 claims abstract description 49
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 46
- 150000001413 amino acids Chemical class 0.000 claims abstract description 37
- 238000006467 substitution reaction Methods 0.000 claims abstract description 35
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- 230000002378 acidificating effect Effects 0.000 claims abstract description 9
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- 239000007864 aqueous solution Substances 0.000 claims description 51
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- Polyamides (AREA)
Abstract
The invention relates to a cationic biopolymer and a preparation method thereof, wherein the cationic biopolymer is a cationized poly acidic amino acid, and is formed by substituting hydrogen atoms of carboxyl groups in at least one part of side chains of the poly acidic amino acid by groups with quaternary ammonium cationic groups; the preparation method of the cationic biopolymer combines the cationization reagent with the side chain carboxyl of the polyacid amino acid stably through a covalent bond, has controllable degree of substitution, is easy to regulate and control the production and processing technology of hair washing and protecting products, and is beneficial to improving the quality of the hair washing and protecting products; in addition, the preparation method uses water as a solvent for homogeneous reaction, and is simple, efficient and environment-friendly. The invention also relates to a composition for hair care and washing. The composition takes the cationic biopolymer as a main active ingredient, has relatively excellent hair damage repairing and conditioning effects, and is beneficial to improving the quality of hair washing and protecting products.
Description
Technical Field
The invention belongs to the technical field of biomacromolecule modification preparation, and relates to a cationic biopolymer and a preparation method and application thereof.
Background
The side chain of the poly-acidic amino acid (including aspartic acid, glutamic acid and the like and polymers obtained by different configurations thereof) has a large number of carboxyl groups, and the water solubility is excellent. It not only has the physical and chemical properties of common carboxyl polymer, but also has good biodegradability and biocompatibility. Therefore, the method has wide research and application in various fields such as agriculture, water treatment, daily chemical products, medicine and the like. Particularly, in the cosmetic industry, the polyacid amino acid and the salt thereof used as functional components such as a humectant, a thickener or a stabilizer have excellent use characteristics when being applied to skin care products, shampoos, cleaning solutions and the like.
However, the acidic polyamino acid has too strong ionic property, so that the process conditions need to be controlled by great attention after the acidic polyamino acid is added into a water-oil mixed system such as emulsion, cream and the like, or the problems of viscosity reduction, emulsion breaking and the like can be caused. In addition, the side chain carboxyl of the polyacid amino acid forms a large amount of anions in the solution, so that the polyacid amino acid has the conditioning, repairing and other functions which are not as good as those of a cationic compound as a cosmetic component. Therefore, how to improve the polyacid-type amino acid into the cationic polymer by chemical or physical methods is one of the important research points of scientific research and performance improvement.
Disclosure of Invention
The technical problem to be solved by the present invention is to provide a cationic biopolymer and a preparation method thereof, aiming at the defects of the prior art. The cationic biopolymer prepared by the method is characterized in that a cationization reagent is stably combined with side chain carboxyl of the polyacid amino acid through a covalent bond, and the substitution degree is controllable; the preparation process adopts water as a solvent for homogeneous reaction, and the method is simple, efficient and environment-friendly.
The invention also provides a hair care composition. The composition takes the cationic biopolymer as a main active ingredient, has relatively excellent hair damage repairing and conditioning effects, and is beneficial to improving the quality of hair washing and protecting products.
To this end, the present invention provides, in a first aspect, a cationic biopolymer which is a cationized acidic amino acid formed by substituting at least a part of the hydrogen atoms of carboxyl groups in its side chain with a group having a quaternary ammonium cationic group, and having a molecular structure represented by formula (i):
in the formula (I), A is a hydrogen atom or a substituent shown in the following formula (II) or formula (III); the average degree of substitution of the above-mentioned substituents is 30 to 80%, m and n are positive integers representing the degree of polymerization and represent the number of the polymerized monomer residues of only two configurations, respectively, the sum of m and n is 10 to 2500,
in the formula (II) or (III), R1 represents an alkylene group having 1 to 2 carbon atoms, and R2, R3 and R4 each represent an alkyl group having 1 to 3 carbon atoms.
According to the invention, the cationized biopolymer is obtained by reacting polyacid amino acid with a cationizing agent, wherein the cationizing agent comprises one or more compounds with molecular structures shown in a formula (IV):
in the formula (IV), R 5 Represents an alkylene group having 1 to 3 carbon atoms, R 2 、R 3 And R 4 Each represents an alkyl group having 1 to 3 carbon atoms, and X represents a halogen atom.
In a second aspect, the present invention provides a method for preparing the cationic biopolymer according to the first aspect of the present invention, comprising the steps of:
s1, placing polysuccinimide in an alkaline aqueous solution, and stirring at room temperature to obtain a polyacid amino acid salt aqueous solution through a ring-opening hydrolysis reaction;
s2, adjusting the pH value of the polyacid amino acid salt aqueous solution to acidity by using a water-soluble acid aqueous solution, then adding a cationizing agent, and carrying out ring-opening esterification reaction to obtain a cationic biopolymer aqueous solution;
and S3, removing small molecular substances from the cationic biopolymer aqueous solution, and drying to obtain a white or light yellow or brown yellow powdery cationic biopolymer.
According to the invention, in step S1, the molecular weight of the poly-acidic amino acid salt is 1-250 kDa; and/or the concentration of the poly acidic amino acid salt aqueous solution is 8-55 wt%.
Preferably, the alkaline aqueous solution is an aqueous solution of NaOH or KOH; preferably, the concentration of the alkaline aqueous solution is 1 to 10mol/L.
In the invention, the water-soluble acid comprises one or more of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid and citric acid; preferably, the concentration of the aqueous solution of the water-soluble acid is 1 to 3mol/L.
In some embodiments of the present invention, in step S2, the reaction conditions of the ring-opening esterification reaction include: the pH value is 4.20-4.90, the reaction temperature is 40-70 ℃, and the reaction time is 1-8 h.
In other embodiments of the present invention, in step S3, the method for removing small molecule substances by using the cationic biopolymer aqueous solution is membrane filtration, and the drying method includes freeze drying and spray drying.
In a third aspect, the present invention provides a composition for hair care comprising a cationic biopolymer according to the first aspect of the present invention or a cationic biopolymer produced by the process according to the second aspect of the present invention, said composition being capable of repairing and/or conditioning damaged hair.
In the invention, the cationic biopolymer is white, light yellow or brown yellow powder, or colorless, light yellow or brown yellow aqueous solution.
In some embodiments of the invention, the cationic biopolymer is present in the composition in an amount of 20wt% to 50wt%.
According to the invention, the composition also comprises water and a polyol.
In some embodiments of the present invention, the ratio of the components is 10-25 wt% of the cationic biopolymer, 100wt% of water Qsp, and 50wt% or less of the polyol.
Preferably, the polyhydric alcohol comprises one or more of ethylene glycol, propylene glycol, butylene glycol, hexylene glycol and glycerol.
According to the invention, the composition also comprises cosmetically acceptable solvents, surfactants, foaming agents and other adjuvants.
In a fourth aspect, the invention provides the use of a composition according to the third aspect of the invention in the manufacture of a hair washing composition.
In a fifth aspect of the invention there is provided a hair washing or conditioning composition comprising a composition according to the third aspect of the invention.
The embodiment of the invention has the beneficial effects that:
(1) The cationic biopolymer provided by the invention has the advantages that the cationic quaternary ammonium salt derivative is combined with the polyacid amino acid side chain carboxyl by a covalent bond, the cationic biopolymer is effective and firm, the stability of a cosmetic formula process is facilitated, the cationic biopolymer serving as a cosmetic component is easily absorbed by hair, the combing property of the hair can be improved, and the hair flake can be better repaired.
(2) The preparation process of the cationic biopolymer, disclosed by the invention, has the advantages that only one step of working procedures is added on the basis of the traditional synthesis method of the poly-acidic amino acid, the separation and purification of intermediate products are not needed, and the operation is simple and easy. The reaction is carried out under homogeneous conditions, and the substitution density of the product is uniform and the substitution degree is controllable.
(3) The preparation process of the cationic biopolymer takes water as a solvent, has no organic solvent in the whole process, is green and environment-friendly, has low cost, and is suitable for large-scale industrial production.
Drawings
For the present invention to be readily understood, the following description is made with reference to the accompanying drawings.
FIG. 1 is a schematic flow diagram of a method for preparing a cationic biopolymer according to the present invention;
FIG. 2 is an IR spectrum of the cationic biopolymer obtained in example 1;
FIG. 3 is a 1H-NMR spectrum of the cationic biopolymer obtained in example 1;
FIG. 4 is a 13C-NMR spectrum of the cationic biopolymer obtained in example 1;
FIG. 5 shows hair combing performance test results;
fig. 6 is a scanning electron micrograph of hair damage repair, wherein a is a blank control, b is a negative control, and c is a sample solution.
Detailed Description
In order that the invention may be readily understood, a detailed description of the invention is provided below. However, before the present invention is described in detail, it is to be understood that this invention is not limited to particular embodiments described. It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments only, and is not intended to be limiting.
Where a range of values is provided, it is understood that each intervening value, to the extent that there is no stated or intervening value in that stated range, to the extent that there is no such intervening value, is encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included in the smaller ranges, and are also encompassed within the invention, subject to any specifically excluded limit in the stated range. Where a specified range includes one or both of the limits, ranges excluding either or both of those included limits are also included in the invention.
Unless otherwise defined, all terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although any methods and materials similar or equivalent to those described herein can also be used in the practice or testing of the present invention, the preferred methods and materials are now described.
Term (I)
The term "water" as used herein means deionized water, ultrapure water or distilled water unless otherwise specified.
The symbol "Δ" used in the present invention represents heating.
The terms "glycidyl trimethyl ammonium chloride", "glycidyl ether trimethyl ammonium chloride", "glycidyl trimethyl ammonium chloride", "glycidyltrimethyl ammonium chloride" and "glycidyltrimethyl ammonium chloride" as used herein are used interchangeably. Likewise, the terms "glycidyl triethylammonium chloride", "glycidyl ether triethylammonium chloride", "glycidyl triethylammonium chloride", "glycidyltriethylammonium chloride" and "glycidyltriethylammonium chloride" may be used interchangeably. In addition, the phrase "glycidyl trimethyl ammonium chloride substituted for polyaspartic acid" may also be expressed as "polyaspartic acid-3-hydroxy-3-trimethyl ammonium chloride propyl ester" according to IUPAC organic nomenclature, and the phrase "glycidyl triethyl ammonium chloride substituted for polyaspartic acid" may also be expressed as "polyaspartic acid-3-hydroxy-3-triethyl ammonium chloride propyl ester" according to IUPAC organic nomenclature.
The expression "water Qsp 100% by weight" as used in the present invention means that the balance of water to 100%, i.e. "balance water", in a liquid phase mixture, in addition to the contents of the components already exemplified or specified.
Any numerical value mentioned in this specification, if there is only a two unit interval between any lowest value and any highest value, includes all values from the lowest value to the highest value incremented by one unit at a time. For example, if it is stated that the amount of a component, or a value of a process variable such as temperature, time, etc., is 50 to 90, it is meant in this specification that values of 51 to 89, 52 to 88 … … and 69 to 71 and 70 to 71, etc., are specifically enumerated. For non-integer values, units of 0.1, 0.01, 0.001, or 0.0001 may be considered as appropriate. These are only some specifically indicated examples. In a similar manner, all possible combinations of numerical values between the lowest value and the highest value enumerated are to be considered to be disclosed in this application.
Embodiments II
As mentioned above, the ionic property of the polyacid amino acid is too strong, so that the polyacid amino acid needs to be added into a water-oil mixing system such as emulsion, cream and the like, and then great attention needs to be paid to control the process conditions, otherwise the problems of viscosity reduction, emulsion breaking and the like of the mixing system can be caused. In addition, the side chain carboxyl of the polyacid-type amino acid forms a large amount of anions in the solution, so that the polyacid-type amino acid has the conditioning, repairing and other functions which are not as good as those of a cationic compound as a hair care cosmetic component. Therefore, how to improve the polyacid-type amino acid into the cationic polymer by chemical or physical methods is one of the key points of scientific research and performance improvement. The present inventors have conducted extensive studies on this.
The present inventors have found that, in the existing research reports, one of the methods for imparting cationic properties to a polyacid-type amino acid is to utilize the electrostatic interaction between the carboxyl group of the side chain of the polyacid-type amino acid and the cationic group such as amino group, quaternary ammonium salt, etc., and the winding structure of the main polymer chain thereof, to bond the polyacid-type amino acid and the cationic compound by physical adsorption. The method is simple and easy to implement, but the combination effect between the two is not firm, and the effect of improving the formula process and the performance of the cosmetic is not obvious.
In the other method, a synthetic precursor polysuccinimide of polyaspartic acid is used as a raw material, and the polysuccinimide reacts with an amino-containing, amino-containing derivative or quaternary ammonium salt compound in an organic solvent in a homogeneous or solvent-free condition to obtain the polysuccinimide which is partially ring-opened and has a side chain containing the amino-containing, amino-containing derivative or quaternary ammonium salt, and then the polysuccinimide is hydrolyzed to obtain the cationic biopolymer. The method can obtain stable polyaspartic acid substituted by cationic groups, and the substitution degree is controllable; however, the process conditions are complex and harsh, and a large amount of organic solvent is required.
The invention further researches and discovers that the reaction of the polyacid amino acid and the cationizing agent can obtain the cationized biopolymer, wherein the cationized biopolymer is formed by substituting at least one part of hydrogen atoms of carboxyl groups in the side chain of the polyacid amino acid by a group with a quaternary ammonium cation group, and the molecular structure of the cationized biopolymer is shown as the formula (I):
in the formula (I), A is a hydrogen atom or a substituent represented by the following formula (II) or formula (III); the average degree of substitution of the above-mentioned substituents is 30 to 80%, preferably 40 to 55%, m and n are positive integers representing the degree of polymerization and represent the number of the polymerized monomer residues of only two configurations, respectively, irrespective of whether the main chain is block, alternating or random polymerized, and the sum of m and n is 10 to 2500, preferably 100 to 500;
in the formula (II) or (III), R1 represents an alkylene group having 1 to 2 carbon atoms, and R2, R3 and R4 each represent an alkyl group having 1 to 3 carbon atoms.
The cationizing agent comprises one or more compounds with molecular structures shown as a formula (IV):
in the formula (IV), R 5 Represents an alkylene group having 1 to 3 carbon atoms, R 2 、R 3 And R 4 Each represents an alkyl group having 1 to 3 carbon atoms, and X represents a halogen atom.
As will be understood by those skilled in the art, the phrase "the cationizing agent comprises one or more compounds having a molecular structure represented by formula (IV)" means that the cationized polyacid amino acid having a molecular structure represented by formula (I) can be obtained by reacting the polyacid amino acid with one compound having a molecular structure represented by formula (IV) or a mixture of two or more compounds having a molecular structure represented by formula (IV) in any ratio.
The schematic diagram of the process flow of the preparation method of the cationic biopolymer related to the present invention is shown in fig. 1, and it can be seen that the preparation method of the cationic biopolymer specifically comprises the following steps:
s1, placing polysuccinimide in an alkaline aqueous solution, and stirring at room temperature to obtain a polyacid amino acid salt aqueous solution through a ring-opening hydrolysis reaction;
s2, adjusting the pH value of the polyacid amino acid salt aqueous solution to acidity by using a water-soluble acid aqueous solution, then adding a cationizing agent with a molecular structure shown as a formula (IV), and carrying out ring-opening esterification reaction to obtain a cationic biopolymer aqueous solution;
and S3, removing small molecular substances from the cationic biopolymer aqueous solution, and drying to obtain a white or light yellow or brown yellow powdery cationic biopolymer.
In the preparation process of the cationic biopolymer:
in step S1, the molecular weight of the poly acidic amino acid salt is 1-250 kDa, preferably 10-50 kDa; and/or the concentration of the aqueous solution of the poly acidic amino acid salt is 8 to 55wt%, preferably 20 to 35wt%.
Preferably, the alkaline aqueous solution is an aqueous solution of NaOH or KOH; preferably, the concentration of the alkaline aqueous solution is 1 to 10mol/L, more preferably 1 to 3mol/L.
In the invention, the water-soluble acid is one or more of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid and citric acid; preferably, the concentration of the aqueous solution of the water-soluble acid is 1 to 3mol/L, more preferably 1 to 1.5mol/L.
In S2, the cationizing agent comprises a compound with a structure represented by a general formula (IV) or a mixture of two or more compounds with structures represented by the general formula (IV) in any proportion.
Wherein R5 represents an alkylene group having 1 to 3 carbon atoms, R2, R3 and R4 each represents an alkyl group having 1 to 3 carbon atoms, and X represents a halogen atom;
examples of suitable cationizing agents corresponding to formula (IV) are glycidyl trialkyl ammonium halides, specific examples include: glycidyl trimethyl ammonium chloride, glycidyl triethyl ammonium chloride, and the like.
In step S2, the reaction conditions of the ring-opening esterification reaction include: the pH value is 4.20-4.90, preferably 4.40-4.60; the reaction temperature is 40-70 ℃, and preferably 45-60 ℃; the reaction time is 1 to 8 hours, preferably 4 to 6 hours.
In step S3, the method for removing small molecular substances from the cationic biopolymer aqueous solution is membrane filtration, specifically, nanofiltration and ultrafiltration; the drying method comprises freeze drying and spray drying.
Research results show that the cationic biopolymer prepared by the method disclosed by the invention has the advantages that a cationization reagent is stably combined with side chain carboxyl of the polyacid amino acid through a covalent bond, and the substitution degree is controllable; the preparation process adopts water as a solvent for homogeneous reaction, and the method is simple, efficient and environment-friendly.
The present inventors have further studied and found that a composition for hair care containing the cationized polyacid amino acid as a main active ingredient has a better conditioning, repairing, or the like effect than an anionic polymer represented by a polyacid amino acid.
Accordingly, in a third aspect the present invention provides a composition for use in hair care comprising a cationic biopolymer according to the first aspect of the invention or a cationic biopolymer prepared according to the process of preparation of the second aspect of the invention, said composition being capable of repairing and/or conditioning damaged hair.
In the invention, the cationic biopolymer is white, light yellow or brown yellow powder, or colorless, light yellow or brown yellow aqueous solution.
In some embodiments of the invention, the cationic biopolymer is present in the composition in an amount of 20wt% to 50wt%.
According to the invention, the composition also comprises water and a polyol.
In some embodiments of the present invention, the composition for hair rinse comprises the following components: cationic polyaspartic acid, a polyol, and water.
According to the invention, the composition for washing and protecting hair comprises the following components in parts by weight: 10 to 25wt%, preferably 15 to 20wt%, of the cationic biopolymer, and not more than 50wt%, preferably 0 to 50wt%, more preferably 35 to 40wt%, of the polyol, with the balance being water.
Preferably, the polyhydric alcohol comprises one or more of ethylene glycol, propylene glycol, butylene glycol, hexylene glycol and glycerol.
It will be understood by those skilled in the art that the phrase "said polyol comprises one or more of ethylene glycol, propylene glycol, butylene glycol, hexylene glycol and glycerin" refers to one of the listed polyols, or a mixture of two or more of the listed polyols in any ratio.
According to the invention, the composition also comprises cosmetically acceptable solvents, surfactants, foaming agents and other adjuvants.
Among other things, acceptable solvents, surfactants, foaming agents and other adjuvants in the cosmetic compositions of the present invention include, but are not limited to, ingredients that can affect the sensory characteristics, skin penetration and bioavailability of the cosmetic active agents of the present invention. More specifically, it comprises: solvents such as water or oils, wherein oils include petroleum, animal, vegetable, or synthetic oils such as, but not limited to, peanut oil, soybean oil, mineral oil, sesame oil, castor oil; surfactants such as, but not limited to, polysorbates, sorbitan esters; biologically active ingredients such as, but not limited to, betaines, glycosides, maltosides; thickeners such as, but not limited to, fatty alcohols, nonoxynol, polyoxyethylene, polyethylene glycol, and the like.
The results of the studies show that the formulation of a composition for hair care with a cationic biopolymer according to the first aspect of the invention or a cationic biopolymer prepared according to the preparation process according to the second aspect of the invention has the following advantages:
(1) Compared with anionic polymers represented by poly-acid amino acid, the cationic biopolymer serving as the main active ingredient contained in the composition for hair washing and care has better hair conditioning, repairing and other effects;
(2) The main active ingredient of the cationic biopolymer contained in the composition for hair washing and care of the invention is the quaternary ammonium salt derivative thereof stably combined with the side chain carboxyl of the polyacid amino acid through covalent bonds, and the substitution degree is controllable.
(3) The cationic biopolymer, which is the main active ingredient contained in the composition for hair care of the present invention, is grafted based on a polypeptide chain obtained by polymerization of aspartic acid, and has good biocompatibility compared to other types of cationic polymers.
In a fourth aspect, the invention provides the use of a composition according to the third aspect of the invention in the manufacture of a hair washing composition.
In a fifth aspect of the invention there is provided a hair washing or conditioning composition comprising a composition according to the third aspect of the invention.
It will be readily appreciated that the third to fifth aspects described above relate to the use of a cationic biopolymer as described in the first aspect above or a cationic biopolymer prepared by the process of preparation as described in the second aspect above in hair care products.
III, detecting instrument and method
In the invention, the molecular weight of the polyacid-type amino acid is detected by a liquid chromatography (Shimadzu LC-20A).
The invention adopts an in-vitro experiment method to verify the efficacy of the composition for washing and protecting products.
Examples
In order that the invention may be more readily understood, the invention will now be described in further detail with reference to the following examples, which are given by way of illustration only and are not intended to limit the scope of the invention. The starting materials or components used in the present invention may be commercially or conventionally prepared unless otherwise specified.
Example 1: preparation of cationic biopolymers with glycidyltrimethylammonium chloride substitution
272.0g of NaOH was accurately weighed, placed in 1800mL of deionized water and completely dissolved to give an aqueous NaOH solution. 600.0g of polysuccinimide (degree of polymerization: 310) was accurately weighed, and placed in the above aqueous NaOH solution and completely dissolved with stirring to obtain an aqueous sodium polyaspartate solution. The pH of the solution was adjusted to 4.50 with 1mol/L phosphoric acid aqueous solution. Adding 1034.0g of glycidyltrimethyl ammonium chloride, and reacting for 5h at the water bath temperature of 50 ℃ to obtain the polyaspartic acid/glycidyltrimethyl ammonium chloride aqueous solution. The aqueous solution is ultrafiltered to remove small molecular substances with molecular weight below 3kDa, and then is freeze-dried to obtain 959.6g light yellow powder, namely cationic biopolymer (cationized polyacid amino acid).
It was confirmed by GPC that low molecular compounds (free salts, unreacted reagents, etc.) were removed from the powder obtained.
The structural confirmation (see fig. 2) was performed by using IR (fourier infrared transform analyzer, varian3100, warian, usa), and it was confirmed that a characteristic peak of increasing ester bond carbonyl group near 1710 was detected in the sample relative to polyaspartic acid, and that propyl-trimethylammonium group was grafted with ester bond to side chain carboxyl group of polyaspartic acid. By using 1 When the structure was confirmed by H-NMR (nuclear magnetic resonance spectrometer, AV600, bruker, USA) (see FIG. 3), a signal derived from a methyl hydrogen atom of trimethylammonium was detected, and it was confirmed that a side chain carboxyl group of polyaspartic acid was grafted with a propyl-trimethylammonium group in an ester bond. By using 13 Structural confirmation by C-NMR (Nuclear magnetic resonance spectrometer, AV600, bruker, USA) (see FIG. 4), and the average degree of substitution can be determined by 13 The integral value of the methyl carbon atom peak and the amide bond carbon atom peak of C-NMR was calculated to obtain a degree of substitution of the cationic biopolymer of 54%.
Example 2: preparation of cationic biopolymers with glycidyltrimethylammonium chloride substitution
The process conditions were the same as in example 1 except that polysuccinimide having a degree of polymerization of 103 was used as a raw material. The degree of substitution of the product is determined by 13 The integrated value of the methyl carbon atom peak and the amide bond carbon atom peak in C-NMR was calculated to be 61%.
Example 3: preparation of cationic biopolymers with glycidyltrimethylammonium chloride substitution
The process conditions were the same as in example 1 except that polysuccinimide having a degree of polymerization of 488 was used as a raw material. The degree of substitution of the product is determined by 13 The integrated value of the methyl carbon atom peak and the amide bond carbon atom peak in C-NMR was calculated to be 49%.
Example 4: preparation of cationic biopolymers with glycidyltrimethylammonium chloride substitution
The addition of NaOH was 158.9g and of polysuccinimide was 350.0g, the process conditions being otherwise the same as in example 1. The degree of substitution of the product is determined by 13 The integrated value of the methyl carbon atom peak and the amide bond carbon atom peak in C-NMR was calculated to be 55%.
Example 5: preparation of cationic biopolymers with glycidyltrimethylammonium chloride substitution
The pH of the reaction system was adjusted to 4.85, and the remaining process conditions were the same as in example 1. The degree of substitution of the product is determined by 13 The integrated value of the methyl carbon atom peak and the amide bond carbon atom peak in C-NMR was calculated to be 39%.
Example 6: preparation of cationic biopolymers with glycidyltrimethylammonium chloride substitution
The temperature of the reaction system was adjusted to 40 ℃ and the remaining process conditions were the same as in example 1. The degree of substitution of the product is determined by 13 The integrated value of the methyl carbon atom peak and the amide bond carbon atom peak in C-NMR was calculated to be 44%.
Example 7: preparation of cationic biopolymers with glycidyltrimethylammonium chloride substitution
The reaction time was 24h and the remaining process conditions were the same as in example 1. The degree of substitution of the product is determined by 13 The integrated value of the methyl carbon peak and the amide bond carbon peak in C-NMR was calculated to be 57%.
Example 8: preparation of cationic biopolymers with glycidyltrimethylammonium chloride substitution
The same procedure as in example one was repeated except that the pH of the reaction system was adjusted to 4.61. The reaction yielded 889.4g as a pale yellow powder with a degree of substitution of 43%.
Example 9: preparation of cationic biopolymers with glycidyltrimethylammonium chloride substitution
The procedure is as in example one except that the reaction temperature is 60 ℃. The reaction yielded 939.9g as a pale yellow powder with a degree of substitution of 54%.
Example 10: preparation of cationic biopolymers with glycidyltrimethylammonium chloride substitution
The process was the same as in example one, except that the reaction time was 8h. The reaction yielded 921.8g of a pale yellow powder with a degree of substitution of 54%.
Example 11: preparation of cationic biopolymers with glycidyl triethylammonium chloride substitution
272.0g of NaOH was accurately weighed, placed in 1800mL of deionized water and completely dissolved to give an aqueous NaOH solution. 600.0g of polysuccinimide (degree of polymerization: 310) was accurately weighed, and placed in the above aqueous NaOH solution and completely dissolved with stirring to obtain an aqueous sodium polyaspartate solution. The pH of the solution was adjusted to 4.50 with 1mol/L phosphoric acid aqueous solution. Adding 1320.0g of glycidyl triethyl ammonium chloride, and reacting for 5h at the water bath temperature of 50 ℃ to obtain the polyaspartic acid/glycidyl triethyl ammonium chloride aqueous solution. Removing small molecular substances with the molecular weight of less than 3kDa from the aqueous solution by ultrafiltration, and freeze-drying to obtain 1049.8g of light yellow powder, namely the cationic biopolymer.
Sampling is carried out 13 C-NMR analysis and calculation using the integral value of the methyl carbon atom peak and the amide bond carbon atom peak gave a degree of substitution of the cationic biopolymer of 51%.
Example 12: pilot scale-up of cationic biopolymer production process
A250L reaction tank was charged with 90L of deionized water and 13.6kg NaOH was added slowly with stirring and introduction of cooling water. After NaOH was completely dissolved and the solution temperature was brought to room temperature, 30.0kg of polysuccinimide (degree of polymerization: 310) was slowly added to the reaction tank under stirring and with cooling water to completely dissolve it, to obtain an aqueous solution of sodium polyaspartate, and the pH of the above solution was adjusted to 4.50 with an aqueous solution of 1mol/L phosphoric acid. Then, the temperature of the reaction system in the reaction tank was stabilized to 50 ℃ by circulating hot water, 51.7kg of glycidyl trimethyl ammonium chloride was added to the reaction tank, and after reaction for 6 hours with stirring, an aqueous solution of polyaspartic acid/glycidyl trimethyl ammonium chloride was obtained. Removing small molecular substances with molecular weight below 3kDa from the above water solution by ultrafiltration, and spray drying to obtain 47.22kg of light yellow powder, i.e. cationic biopolymer. Sample it for 13 C-NMR analysis and use of methyl carbon peaks and acyl groupsThe degree of substitution of the cationic biopolymer was calculated to be 53% from the integrated value of the amine bond carbon atom peak.
Example 13: preparation of cationic biopolymer according to the procedure of example 1
272.0g of NaOH was accurately weighed, placed in 1800mL of deionized water and completely dissolved to give an aqueous NaOH solution. 600.0g of polysuccinimide (degree of polymerization: 310) was accurately weighed, and placed in the above aqueous NaOH solution and completely dissolved with stirring to obtain an aqueous solution of sodium polyamino acid. The pH of the solution was adjusted to 4.50 with 1mol/L phosphoric acid aqueous solution. Glycidyl trimethyl ammonium chloride 1034.0g is added to react for 5 hours at the water bath temperature of 50 ℃ to obtain the polyacid amino acid/glycidyl trimethyl ammonium chloride aqueous solution. Removing small molecular substances with molecular weight below 3kDa by ultrafiltration, and storing at low temperature.
The concentration of cationic biopolymer was determined to be 31.1wt% by drying. It was confirmed by GPC that low molecular compounds (free salts, unreacted reagents, etc.) were removed from the powder obtained. IR, 1H-NMR and 13C-NMR confirmed that the side chain carboxyl group of the poly-acidic amino acid was grafted with a propyl-trimethylammonium group by an ester bond, and the average degree of substitution was 54% as calculated from the integral values of the methyl carbon peak and the amide bond carbon peak of the 13C-NMR.
Example 14: preparation of hair washing and caring product composition
The cationic biopolymer powder obtained in the method of example 1 was mixed with deionized water to prepare a 20wt% solution, which was then sterilized at 90 ℃ for 30min. And adding hexanediol as an antibacterial component into the obtained sterilization solution according to the mass ratio of 30.
Example 15: in vitro efficacy evaluation
(1) Hair combing Performance test
The cationic biopolymer composition obtained in example 14 was subjected to a hair combing performance test. Materials and equipment required for the test include: undamaged real human hair bundles, an INSTRON 5942 tension tester and a clamp. The test samples were diluted with pure water to obtain test samples having concentrations of 0.40, 1.00, and 3.00 (%, W/V), respectively, and pure water was used as a blank control, and a 20wt% aqueous solution of sodium polyaspartate having a concentration of 1.00 (%, W/V) was used as a negative control.
The test method comprises the following steps:
(a) The experimental hair bundle is cleaned by deionized water and neutral shampoo before use, and is air-dried at room temperature overnight, and then the hair tip and the hair root are cut off. And then, spraying pure water and the solution of the sample to be detected with different concentration gradients on different hair strands respectively, and airing at room temperature at the humidity of 40% for later use.
(b) Tress combing test: debugging the tensile testing machine, connecting with a host computer, opening the testing software, preheating for half an hour, and setting related parameters (the hair thickness is 0.4cm, the hair width is 3cm, and the speed is 300 mm/min). Respectively taking the treated hair bundles, combing the hair bundles by a comb, fixing one end of the hair bundle to be tested by a proper clamp, naturally placing the hair bundle to be tested in the middle of the comb, and selecting a tension value between 20 and 90mm to perform a tension experiment. The same tress was tested 3 times in duplicate and averaged to reduce measurement errors due to different tresses.
The results of the above tests are shown in FIG. 5. It can be seen that the cationic biopolymer composition has a significant improvement in hair combing performance over a suitable concentration range.
(2) Hair damage repair test
The cationic biopolymer composition obtained in example 14 was subjected to a hair damage repair test. Materials and equipment required for the test include: heat damage to real human hair, SU1510 electron scanning electron microscope, SDC-500 contact angle tester. The test sample is diluted by pure water to obtain a sample to be tested with the concentration of 0.35 percent (W/V), pure water is used as a blank control, and 20wt percent of sodium polyaspartate aqueous solution with the concentration of 0.35 percent (W/V) is used as a negative control.
The test method comprises the following steps:
(a) Hair bundle pretreatment: the experimental hair bundle is cleaned by deionized water and neutral shampoo before use, and is air-dried at room temperature overnight, and then the hair tip and the hair root are cut off. Then, different hair strands are respectively immersed in the pure water and the sample solution, taken out after 30min, and dried overnight at room temperature under 40% humidity for later use.
(b) Observing the hair damage repairing performance by an electron microscope method: respectively randomly selecting 1 hair from the heat injury hair bundle treated by pure water and sample solution, cutting a complete part of the hair with the middle part of about 1cm to prepare an electron microscope sample, and observing the surface layer of the hair and the shape and distribution condition of scales of the hair under a scanning electron microscope.
(c) The hair damage repairing performance is observed by a hanging drop method: and respectively taking the pure water and the heat damage hair bundle treated by the sample solution, fixing the heat damage hair bundle on a clamp of a contact angle tester, and observing and recording the contact angle of the ultrapure water on the surface of the hair by taking the ultrapure water as a medium.
The results of the above tests are shown in FIG. 6 (a is blank control, b is negative control, and c is sample solution) and Table 1. Therefore, the cationic biopolymer can almost completely fill the peeling and damaged parts of hair scales, and the scales on the surface are overlapped in a tile shape to ensure that the hair becomes flat and smooth; and the contact angle between the hair bundle and the ultrapure water is larger than 90 degrees, the hair bundle is hydrophobic, and the hair bundle has obvious hair damage repairing performance.
TABLE 1 contact angle of ultrapure water with hair tress sample
(3) Hair adsorption Performance test
The cationic biopolymer composition obtained in example 14 was subjected to a hair adsorption performance test. Materials and equipment required for the test include: the real hair bundle is not damaged, and the electronic balance is adopted. The test samples are diluted by pure water to obtain samples to be tested with the concentrations of 0.20 and 0.65 percent (W/V), and pure water is used as a blank control, and a 20wt% sodium polyaspartate solution with the concentration of 0.65 percent (W/V) is used as a negative control.
The test method comprises the following steps:
(a) Hair bundle pretreatment: the experimental hair bundle is cleaned by deionized water and neutral shampoo before use, and is cut off to remove the tip and the root for standby after being dried overnight at room temperature.
(b) Adsorption Performance test
Soaking the hair bundle in pure water, control solution and sample solution with different concentration gradients, respectively, taking out after 10min, kneading and washing with distilled water for 3 times, and air drying at room temperature under 40% humidity for 8h. Each trial was run in parallel over 3 groups and averaged to reduce measurement error due to strand differences. The rate of absorption of the sample by the tress was calculated from the following formula.
Adsorption (%) = weight gain to hair/initial hair weight × 100%
The results of the above tests are shown in Table 2. It can be seen that the weight of the hair tresses treated with the sample solution is increased significantly, indicating that the cationic biopolymer has good affinity for hair.
TABLE 2 Hair tresses adsorption Performance test results
It should be noted that the above-mentioned embodiments are only preferred embodiments of the present invention, and are used for explaining the present invention, and do not constitute any limitation to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the claims and without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.
Claims (10)
1. A cationic biopolymer which is a cationized polyacid type amino acid formed by substituting at least a part of hydrogen atoms of carboxyl groups in the side chain of polyacid type amino acid by a group with a quaternary ammonium cation group, and the molecular structure of the cationized polyacid type amino acid is shown as the formula (I):
in the formula (I), A is a hydrogen atom or a substituent shown in the following formula (II) or formula (III); the average degree of substitution of the above-mentioned substituents is 30 to 80%, m and n are positive integers representing the degree of polymerization and represent the number of the polymerized monomer residues of only two configurations, respectively, the sum of m and n is 10 to 2500,
in the formula (II) or (III), R1 represents an alkylene group having 1 to 2 carbon atoms, and R2, R3 and R4 each represent an alkyl group having 1 to 3 carbon atoms.
2. The cationized biopolymer according to claim 1, wherein the cationized biopolymer is obtained by reacting a polyacid-type amino acid with a cationizing agent, wherein the cationizing agent comprises one or more compounds having a molecular structure represented by formula (IV):
in the formula (IV), R 5 Represents an alkylene group having 1 to 3 carbon atoms, R 2 、R 3 And R 4 Each represents an alkyl group having 1 to 3 carbon atoms, and X represents a halogen atom.
3. A method of preparing the cationic biopolymer of claim 1 or 2, comprising the steps of:
s1, placing the polysuccinimide in an alkaline aqueous solution, and stirring at room temperature to obtain a polyacid amino acid salt aqueous solution through a ring-opening hydrolysis reaction;
s2, adjusting the pH value of the polyacid amino acid salt aqueous solution to acidity by using a water-soluble acid aqueous solution, then adding a cationizing agent, and carrying out ring-opening esterification reaction to obtain a cationic biopolymer aqueous solution;
and S3, removing small molecular substances from the cationic biopolymer aqueous solution, and drying to obtain a white or light yellow or brown yellow powdery cationic biopolymer.
4. The production method according to claim 3,
in step S1, the molecular weight of the poly-acidic amino acid salt is 1-250 kDa; preferably, the concentration of the aqueous solution of the poly acidic amino acid salt is 8 to 55wt%;
and/or the alkaline aqueous solution is NaOH or KOH aqueous solution; preferably, the concentration of the alkaline aqueous solution is 1 to 10mol/L;
and/or the water-soluble acid comprises one or more of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid and citric acid; preferably, the concentration of the water-soluble acid in the water solution is 1 to 3mol/L.
5. The production method according to claim 3 or 4, wherein in step S2, the reaction conditions of the ring-opening esterification reaction include: the pH value is 4.20-4.90, the reaction temperature is 40-70 ℃, and the reaction time is 1-8 h; and/or in step S3, the method for removing the small molecular substances by the cationic biopolymer aqueous solution is membrane filtration, and the drying method comprises freeze drying and spray drying.
6. A composition for hair rinse comprising the cationic biopolymer according to claim 1 or 2 or the cationic biopolymer produced by the manufacturing process according to any one of claims 3-5, said composition being capable of repairing and/or conditioning damaged hair; preferably, the cationic biopolymer is present in the composition in an amount of 20wt% to 50wt%.
7. The composition of claim 6, further comprising water and a polyol; preferably, the composition comprises 10-25 wt% of cationic biopolymer, 100wt% of water Qsp and less than or equal to 50wt% of polyol; further preferably, the polyhydric alcohol comprises one or more of ethylene glycol, propylene glycol, butylene glycol, hexylene glycol and glycerol.
8. Composition according to claim 6 or 7, characterized in that it further comprises cosmetically acceptable solvents, surfactants, foaming agents and other adjuvants.
9. Use of a composition according to any one of claims 6 to 8 for the preparation of a hair care product.
10. A hair wash comprising a composition according to any one of claims 6 to 8.
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Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1162604A (en) * | 1995-10-05 | 1997-10-22 | 三井东压化学株式会社 | Polymer, preparation processes thereof, hair-treating compositions and cosmetic compositions |
| US5925728A (en) * | 1996-08-02 | 1999-07-20 | Basf Aktiengesellschaft | Water-soluble or water-dispersible polyaspartic acid derivatives, their preparation and their use |
| US5961965A (en) * | 1996-08-02 | 1999-10-05 | Basf Aktiengesellschaft | Water-soluble or water-dispersible polyaspartic acid derivatives their preparation and their use |
| US20050154180A1 (en) * | 2003-09-04 | 2005-07-14 | Yin Hessefort | Water-soluble polyaminoamides as sunscreen agents |
| WO2008143135A1 (en) * | 2007-05-15 | 2008-11-27 | Nippon Starch Chemical Co., Ltd. | Hair cosmetic comprising composition containing cationized trehalose derivative |
| CN102058534A (en) * | 2010-11-26 | 2011-05-18 | 天津大学 | Novel macromolecule liposome and preparation method thereof |
| CN102304225A (en) * | 2011-05-27 | 2012-01-04 | 天津大学 | Polymer liposomes based on polyamino acid and quaternary ammonium salt and preparation method for polymer liposomes |
| CN102834088A (en) * | 2011-04-12 | 2012-12-19 | 株式会社成和化成 | Cosmetic base material, and cosmetic containing said cosmetic base material |
| JP2017039920A (en) * | 2015-08-17 | 2017-02-23 | 三洋化成工業株式会社 | Polyaspartic acid derivative and detergent composition containing the same |
-
2022
- 2022-12-02 CN CN202211542079.1A patent/CN115975184A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1162604A (en) * | 1995-10-05 | 1997-10-22 | 三井东压化学株式会社 | Polymer, preparation processes thereof, hair-treating compositions and cosmetic compositions |
| US5925728A (en) * | 1996-08-02 | 1999-07-20 | Basf Aktiengesellschaft | Water-soluble or water-dispersible polyaspartic acid derivatives, their preparation and their use |
| US5961965A (en) * | 1996-08-02 | 1999-10-05 | Basf Aktiengesellschaft | Water-soluble or water-dispersible polyaspartic acid derivatives their preparation and their use |
| US20050154180A1 (en) * | 2003-09-04 | 2005-07-14 | Yin Hessefort | Water-soluble polyaminoamides as sunscreen agents |
| WO2008143135A1 (en) * | 2007-05-15 | 2008-11-27 | Nippon Starch Chemical Co., Ltd. | Hair cosmetic comprising composition containing cationized trehalose derivative |
| CN102058534A (en) * | 2010-11-26 | 2011-05-18 | 天津大学 | Novel macromolecule liposome and preparation method thereof |
| CN102834088A (en) * | 2011-04-12 | 2012-12-19 | 株式会社成和化成 | Cosmetic base material, and cosmetic containing said cosmetic base material |
| CN102304225A (en) * | 2011-05-27 | 2012-01-04 | 天津大学 | Polymer liposomes based on polyamino acid and quaternary ammonium salt and preparation method for polymer liposomes |
| JP2017039920A (en) * | 2015-08-17 | 2017-02-23 | 三洋化成工業株式会社 | Polyaspartic acid derivative and detergent composition containing the same |
Non-Patent Citations (2)
| Title |
|---|
| BEIBEI HOU ET AL.: ""Construction of near infrared light triggered nanodumbbell for cancer photodynamic therapy"", 《JOURNAL OF COLLOID AND INTERFACE SCIENCE》, 19 January 2017 (2017-01-19), pages 363 - 372 * |
| WENYA SU ET AL.: ""PEG/RGD-modified magnetic polymeric liposomes for controlled drug release and tumor cell targeting"", 《INTERNATIONAL JOURNAL OF PHARMACEUTICS》, 14 January 2012 (2012-01-14), pages 170 - 181, XP028463457, DOI: 10.1016/j.ijpharm.2012.01.013 * |
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