WO2019233375A1 - 一种氨基酸自组装超分子聚合物及其制备和应用 - Google Patents

一种氨基酸自组装超分子聚合物及其制备和应用 Download PDF

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WO2019233375A1
WO2019233375A1 PCT/CN2019/089816 CN2019089816W WO2019233375A1 WO 2019233375 A1 WO2019233375 A1 WO 2019233375A1 CN 2019089816 W CN2019089816 W CN 2019089816W WO 2019233375 A1 WO2019233375 A1 WO 2019233375A1
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Prior art keywords
amino acid
alanine
lauroyl
salt
self
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PCT/CN2019/089816
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English (en)
French (fr)
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张健
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苏州欧丽特生物医药有限公司
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Priority claimed from CN201810562220.1A external-priority patent/CN108752228B/zh
Priority claimed from CN201810562197.6A external-priority patent/CN108451783A/zh
Priority claimed from CN201810562174.5A external-priority patent/CN108653025A/zh
Application filed by 苏州欧丽特生物医药有限公司 filed Critical 苏州欧丽特生物医药有限公司
Priority to AU2019280295A priority Critical patent/AU2019280295B2/en
Priority to EP19814824.9A priority patent/EP3805200A4/en
Priority to BR112020024723-5A priority patent/BR112020024723A2/pt
Priority to MX2020013130A priority patent/MX2020013130A/es
Priority to KR1020207037733A priority patent/KR20210018331A/ko
Priority to JP2021517889A priority patent/JP2021527117A/ja
Priority to US16/972,461 priority patent/US11566110B2/en
Publication of WO2019233375A1 publication Critical patent/WO2019233375A1/zh

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Definitions

  • the invention belongs to the technical field of amino acid-type surfactant preparation, in particular to an amino acid self-assembling supramolecular polymer, and preparation and application thereof.
  • Surfactants are an indispensable component in many fields such as daily chemical industry, agriculture, and pharmaceutical industry. There are dozens of surfactants currently used in the market, but the main commonly used are sodium dodecylbenzenesulfonate (SLS), sodium lauryl alcohol polyoxyethylene ether sulfate (AES), and sodium lauryl sulfate ( K12). Since these three surfactants have been used for decades or even hundreds of years, their negative effects have gradually emerged during their use, and their impact on human safety and the environment is often reported.
  • SLS sodium dodecylbenzenesulfonate
  • AES sodium lauryl alcohol polyoxyethylene ether sulfate
  • K12 sodium lauryl sulfate
  • surfactants such as saccharide alkyl glycosides (APG), amino acid surfactants, such as lauroyl-L-glutamic acid, lauroyl glycine, lauroyl sarcosine and the like.
  • APG saccharide alkyl glycosides
  • amino acid surfactants such as lauroyl-L-glutamic acid, lauroyl glycine, lauroyl sarcosine and the like.
  • APG saccharide alkyl glycosides
  • amino acid surfactants such as lauroyl-L-glutamic acid, lauroyl glycine, lauroyl sarcosine and the like.
  • N-lauroyl-L-alanine as a surfactant, has good wetting, foaming, antibacterial and anti-corrosive and anti-static capabilities, and is basically non-toxic and harmless. It is mild to the skin and its degradation products are Amino acids and fatty acids have almost no effect on the environment, and they also have a good compatibility with other surfactants.
  • N-lauroyl-L-alanine As a surfactant for testing, it is found that its detergency is not without theory It is so high. After a series of exploratory experiments, the inventor found that the main reason for the low detergency of N-lauroyl-L-alanine is the N-lauroyl-L-alanine prepared by this method. Contains a higher content of lauric acid, and the presence of lauric acid causes it to fail to form a self-assembled polymer, and the effect data of the sodium salt compound prepared by it is not as good as the present invention.
  • the purpose of the present invention is to overcome the defects of N-lauroyl-L-alanine prepared in the prior art with low purity, high impurity content, and severely affecting product quality.
  • Preparation method and application of acid self-assembling polymer the prepared N-lauroyl-L-alanine self-assembling supermolecular polymer has good biodegradability, strong detergency, and can be well applied in the daily chemical industry , Agriculture and pharmaceutical industries.
  • the amino acid self-assembling supramolecular polymer according to the present invention has the structure:
  • the amino acid self-assembling supramolecular polymer according to the present invention uses N-lauroyl-L-alanine as a basic unit and self-assembles into a supramolecular polymer through hydrogen bonding.
  • the polymer is substantially free of lauric acid. Basically, it means that lauric acid cannot be detected by HPLC and GC.
  • the invention discloses an amino acid self-assembling supramolecular polymer, which uses N-lauroyl-L-alanine as a basic unit and self-assembles into a supramolecular polymer through hydrogen bonding.
  • the weight average molecular weight data of the supramolecular polymer is between 2000 and 2000. -5 million.
  • a method for preparing an amino acid self-assembling supramolecular polymer substantially free of lauric acid according to the present invention includes the following steps:
  • the preparation of the aforementioned crude N-lauroyl-L-alanine includes the following steps:
  • the metal inorganic base in the step (1) is selected from one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, and potassium carbonate.
  • the organic solvent in the step (1) is selected from one or more of acetone, methanol, ethanol, acetonitrile, and tetrahydrofuran.
  • the metal inorganic base in the step (2) is selected from one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, and potassium carbonate.
  • the solvent in step (4) is selected from acetone, methanol, ethanol, acetonitrile, tetrahydrofuran, or a mixed solvent made of the solvent and water.
  • step (4) is selected from one or more of sulfuric acid, p-toluenesulfonic acid, and an emulsifier.
  • step (4) wherein the stirring conditions in step (4) are: a temperature of 25 ° C. to 100 ° C., a pressure of 5 kg to 50 kg, and a time of 1-3 h.
  • the invention also relates to a sodium salt of an amino acid self-assembled supramolecular polymer which is substantially free of lauric acid, and has the following structure:
  • n is the number of molecules in which N-lauroyl-L-alanine forms a self-assembled supramolecular polymer.
  • the invention also discloses an amino acid self-assembling supramolecular polymer sodium salt, which uses sodium N-lauroyl-L-alanine as a basic unit and self-assembles into a supramolecular polymer through hydrogen bonding. Between 2800-770,000.
  • An amino acid self-assembling supramolecular polymer is obtained according to the above-mentioned preparation method according to the present invention, and is used as a surfactant in applications in the field of daily chemicals, agriculture, and medicine.
  • a supramolecular amino acid according to the present invention wherein the supramolecular amino acid is formed by hydrogen bonding between N-lauroyl-L-alanine monomers obtained by the preparation method described above.
  • the method for preparing an amino acid self-assembling supramolecular polymer according to the present invention has simple process steps, and is formed by condensing natural lauric acid and natural L-alanine. It is stable under normal conditions and is non-toxic and harmless to the human body. After entering the human body and nature, it will be quickly degraded into lauric acid and L-alanine. The degradation products are natural products, which can be recycled, and the reaction conditions are mild, suitable for industrial production.
  • the lauric acid content in the amino acid self-assembled supramolecular polymer prepared according to the method of the present invention cannot be detected by HPLC and GC, that is, the lauric acid content does not produce the structure and performance of N-lauroyl-L-alanine Effect, effectively avoid the effect of lauric acid on product quality.
  • the amino acid self-assembling supramolecular polymer obtained according to the method of the present invention has a three-dimensional network structure and has strong adsorption of organic matters such as oil stains.
  • the pH is 6-7, which is more suitable for human pH requirements. Above 90% is sodium It exists in the form of salt, and the remaining part exists in the form of acid, coexisting in two-dimensional and three-dimensional ways, which gives strong washing ability, adsorption of bacteria, pesticides, odor and other properties.
  • the amino acid self-assembling supramolecular polymer prepared according to the method of the present invention has stable structural properties and has supramolecular properties.
  • the molecule exists in solution due to various gel factors such as hydrogen bonding, electrostatic force, hydrophobic force, and The interaction of ⁇ - ⁇ drives the liquid components to stand still, forming an amino acid with a three-dimensional three-dimensional network space structure, which has the characteristics of physical sterilization, odor removal, and pesticide residue removal.
  • the inhibition rate of Bacillus, Staphylococcus aureus and Candida albicans can all reach 100%; effective removal of pesticide residues, the removal rate of methamidophos can reach 64.63%, and the removal rate of methamidophos can reach 74.66% ; At the same time, it has good deodorizing performance.
  • amino acid self-assembling supramolecular polymer prepared according to the method of the present invention exists in the form of numerous pillars, and there are huge gaps between the molecules, which can encapsulate organic substances such as drug molecules, pesticide residues and tiny inorganic particles.
  • amino acid self-assembling supramolecular polymers can encapsulate drug molecules, and slowly release active pharmaceutical ingredients under the action of enzymes, acting as a slow-release agent.
  • amino acid self-assembling supramolecular polymers It can wrap pesticides to prevent pesticides from penetrating into the plants.
  • amino acid self-assembled supramolecular polymer In the application of cosmetics, the combination of amino acid self-assembled supramolecular polymer and natural oils will change the physical properties of oils and oils, which are close to the body's own secreted oils, and have a good experience.
  • Amino acid self-assembling supramolecular polymers can wrap cosmetic active substances, which makes the active substances difficult to be oxidized and inactivated, and can evenly disperse particles and suspend them in the cosmetic system.
  • Example 1 is a chemical reaction formula for preparing N-lauroyl-L-alanine according to the synthesis method in Example 3 of the present invention
  • Example 2 is an infrared spectrum of an N-lauroyl-L-alanine self-assembled polymer obtained according to the synthesis method in Example 3 of the present invention
  • Example 3a is a 1 H-NMR spectrum of an N-lauroyl-L-alanine self-assembled polymer obtained according to the synthesis method in Example 3 of the present invention
  • 3b is a 13 C-NMR spectrum of an N-lauroyl-L-alanine self-assembled polymer obtained according to the synthesis method in Example 3 of the present invention
  • Figure 4 is a standard chromatogram of N-lauroyl-L-alanine
  • Example 5 is a high performance liquid chromatogram of the N-lauroyl-L-alanine self-assembled polymer obtained under the same conditions as in FIG. 4 obtained according to the synthesis method in Example 3 of the present invention;
  • FIG. 8 is a high performance liquid chromatogram of N-lauroyl-L-alanyl-L-alanine obtained by columnar preparation and measured under the same conditions as in FIG. 4; FIG.
  • FIG. 9 is a structure formation diagram of a N-lauroyl-L-alanine monomer forming a supramolecular amino acid obtained according to the synthesis method in Example 3 of the present invention.
  • 10a is a 300-times electron microscope image of the N-lauroyl-L-alanine self-assembled polymer obtained according to the synthesis method in Example 3 of the present invention
  • 10b is a 1000-fold electron microscope image of the N-lauroyl-L-alanine self-assembled polymer obtained according to the synthesis method in Example 3 of the present invention.
  • FIG. 10c is a 2000-fold electron microscope image of the N-lauroyl-L-alanine self-assembled polymer obtained according to the synthesis method in Example 3 of the present invention.
  • FIG. 11a is a 500-fold electron microscope image of a commercially available N-lauroyl-L-alanine (containing 2-5% lauric acid);
  • FIG. 11a is a 500-fold electron microscope image of a commercially available N-lauroyl-L-alanine (containing 2-5% lauric acid);
  • 11b is a 1000-fold electron microscope image of a commercially available N-lauroyl-L-alanine (containing 2-5% lauric acid);
  • FIG. 11c is a 2000-fold electron microscope image of a commercially available N-lauroyl-L-alanine (containing 2-5% lauric acid); FIG.
  • FIG. 12 is a diagram illustrating a process of further forming a supermolecular amino acid sodium salt of N-lauroyl-L-alanine obtained according to the synthesis method in Example 3 of the present invention.
  • FIG. 13 is a molecular weight data chart of N-lauroyl-L-alanine further formed into a supramolecular amino acid sodium salt according to the synthesis method in Example 3 of the present invention, wherein
  • Polydispersity refers to the average molecular weight of homologs
  • Figure 17 shows the effect of amino acid toothpaste on the teeth of patients before cleaning
  • Figure 18 shows the effect of amino acid toothpaste on patients' teeth after cleaning
  • FIG. 19 is a test result of the decontamination ability of the laundry liquid
  • Example 20 is a mass spectrum of an N-lauroyl-L-alanine self-assembled polymer obtained according to the synthesis method in Example 3 of the present invention.
  • the inventors found that the polymer formed by self-assembly of N-lauroyl-L-alanine monomers through hydrogen bonding can be substantially free or free of lauric acid through specific methods, and Forming an elastic void-containing structure, this structure can cure oily substances; after the polymer forms a salt with the base, the polymer salt can serve as a surfactant. Based on this, the present invention has been completed.
  • the polymer or a salt thereof provided by the present invention is substantially free of or free of lauric acid
  • the N-lauroyl-L-alanine salt involved in the present invention is sodium N-lauroyl-L-alanine and / or potassium N-lauroyl-L-alanine. It may also be a salt formed of N-lauroyl-L-alanine with a basic amino acid, such as a salt formed with arginine, histidine, lysine, and the like.
  • the invention provides an amino acid self-assembling supramolecular polymer or a salt thereof.
  • the polymer is formed by hydrogen bonding between N-lauroyl-L-alanine monomers; the polymer is substantially free of or does not contain Contains lauric acid.
  • N-lauroyl-L-alanine monomers are connected through hydrogen bonding to form a structure as shown in formula (I):
  • the weight average molecular weight of the amino acid self-assembling supramolecular polymer provided by the present invention is between 20-5 million, and its melting point is 82-84 ° C.
  • the present invention also provides a salt of the above-mentioned amino acid self-assembling supramolecular polymer, the salt formed by the polymer and a base; the base includes an inorganic base and an organic base.
  • the inorganic base is selected from sodium hydroxide, potassium hydroxide, or lithium hydroxide.
  • the organic base is a natural basic amino acid (arginine, lysine or histidine).
  • the maximum solubility of the sodium salt of the above-mentioned amino acid self-assembling supramolecular polymer provided by the present invention is 15w / v%, which is determined by the solubility method ("Chinese Pharmacopoeia” (2015 edition) examples), that is, at 25 ° C, 1 atmosphere, Up to 15 grams of self-assembled polymerized sodium N-lauroyl-L-alanine dissolved per 100 ml of water.
  • an amino acid self-assembling supramolecular polymer sodium salt is provided, which is formed by hydrogen bonding between sodium N-lauroyl-L-alanine monomers; the polymer sodium The salt is substantially free or free of lauric acid.
  • N-lauroyl-L-alanine monomers are connected through hydrogen bonding to form a structure as shown in formula (II):
  • n is the number of molecules in which N-lauroyl-L-alanine forms a self-assembled supramolecular polymer.
  • n N-lauroyl-L-alanine sodiums are sequentially connected in the same plane through hydrogen bonding, or n N-lauroyl-L-alanine sodiums are connected sequentially through hydrogen bonding and end-to-end hydrogen bonding is used to form a Columnar.
  • the weight average molecular weight of the sodium salt of the amino acid self-assembling supramolecular polymer provided is between 28 and 770,000; it can be inferred that n is in the range of 10 to 3000, and the solubility of the obtained sodium salt in water does not exceed 15 g / 100ml.
  • the present invention also provides a composition containing the amino acid self-assembling supramolecular polymer or a salt thereof provided by the present invention, and an N-lauroyl-L-alanyl-L-alanine monomer.
  • N-lauroyl-L-alanyl-L-alanine monomers are connected through hydrogen bonding to form a structure as shown in formula (I '):
  • N-lauroyl-L-alanyl-L-alanine monomers can also form a structure as shown in formula (II ') through hydrogen bonding:
  • n 8-20000; n N-lauroyl-L-alanyl-L-alanine sodiums are sequentially connected through hydrogen bonding in the same plane, or n N-lauroyl-L-alanine sodiums are passed through The hydrogen bonds are sequentially connected and the ends are connected by hydrogen bonds to form a columnar shape.
  • the weight average molecular weight of the polymer sodium salt as shown by formula II ' is between 50 and 5 million.
  • the invention provides a method for preparing an amino acid self-assembling supramolecular polymer.
  • the method includes the following steps:
  • L-alanine and a metal inorganic base are dissolved in a mixed solution of distilled water and an organic solvent and stirred to obtain an L-alanine salt solution;
  • lauryl chloride and a metal inorganic base are sequentially added to the obtained L-alanine salt solution so that the pH of the reaction system is 8-10, and then stirring is continued under certain conditions to obtain a paste N-lauroyl- L-alanine salt;
  • a solvent, L-alanine and a catalyst are added to the crude N-lauroyl-L-alanine obtained above, and stirred under certain conditions to obtain an amino acid self-assembling supramolecular polymer provided by the present invention.
  • the volume ratio of the distilled water and the organic solvent in the first step is 1: (1-1.5).
  • the molar ratio of the L-alanine to the metal inorganic base in the first step is 1: (1-1.5).
  • the metal inorganic base in the first step is selected from one or two or more of sodium hydroxide, potassium hydroxide, sodium carbonate, and potassium carbonate.
  • the organic solvent in the first step is selected from one or two or more of acetone, methanol, ethanol, acetonitrile, and tetrahydrofuran.
  • the molar ratio of lauroyl chloride to L-alanine in the second step is (0.8-1): 1.
  • the stirring conditions in the second step are: a temperature of 5-50 ° C, and a time of 0.5-3.5 hours.
  • the concentration of the metal inorganic base in the second step is 30-80%; the metal inorganic base is selected from one of sodium hydroxide, potassium hydroxide, sodium carbonate, and potassium carbonate. One or two or more.
  • the solvent in the fourth step is selected from the group consisting of acetone, methanol, ethanol, acetonitrile, tetrahydrofuran, or a mixed solvent made of the solvent and water.
  • the catalyst in the fourth step is selected from one or two or more of sulfuric acid, p-toluenesulfonic acid, and an emulsifier.
  • the mixed molar ratio of the crude N-lauroyl-L-alanine, the solvent, the L-alanine, and the catalyst described in the fourth step is 1: (5-10) : (0.2-1.1) :( 0.001-0.2); preferably 1: (5-10) :( 0.2-0.5) :( 0.01-0.2).
  • the stirring conditions described in the fourth step are: a temperature of 25 ° C. to 100 ° C., a pressure of 5 kg to 50 kg, and a time of 1-3 hours.
  • the fourth step is cooled and filtered after stirring, and the obtained solid is washed and dried to obtain N-lauroyl-L-alanine self-assembled polymer that is substantially free of lauric acid. .
  • the amino acid self-assembling supramolecular polymer provided by the present invention can be used for curing oil substances, and its salt can be used as a surfactant.
  • the amino acid self-assembling supramolecular polymer or a salt thereof provided by the present invention can be widely used in the daily chemical field, agriculture, or the pharmaceutical industry, such as, but not limited to, used in the preparation of toothpaste, skin care composition, laundry liquid, soap, laundry Powder, dishwashing liquid, facial mask, etc.
  • a mixed solvent of water and acetone, L-alanine and p-toluenesulfonic acid are added to the crude N-lauroyl-L-alanine, among which the crude N-lauroyl-L-alanine, water and acetone
  • the mixed solvent, L-alanine and p-toluenesulfonic acid were added in a molar ratio of 1: 7.5: 0.35: 0.002 and stirred at a temperature of 60 ° C and a pressure of 27 kg for 2 hours, so that a small amount of lauric acid was completely consumed. Then, it was cooled and filtered, and the obtained solid was washed twice with pure water and finally dried at 60 ° C. to obtain N-lauroyl-L-alanine self-assembled polymer.
  • the mass of the obtained N-lauroyl-L-alanine self-assembled polymer was 250.5 g, the yield was 92.3%, the purity was higher than 97%, the lauric acid content was undetectable, and the melting point was 82-84 ° C.
  • a mixed solvent of water and acetone, L-alanine and p-toluenesulfonic acid are added to the crude N-lauroyl-L-alanine, among which the crude N-lauroyl-L-alanine, water and acetone
  • the mixed solvent, L-alanine and p-toluenesulfonic acid were added in a molar ratio of 1: 10: 0.3: 0.003 and stirred at a temperature of 25 ° C and a pressure of 43 kg for 2 hours, so that a small amount of lauric acid was completely consumed. Then, it was cooled and filtered, and the obtained solid was washed twice with pure water and finally dried at 60 ° C. to obtain N-lauroyl-L-alanine self-assembled polymer.
  • the mass of the obtained N-lauroyl-L-alanine self-assembled polymer was 243.7 g, the yield was 89.8%, the purity was higher than 97%, the lauric acid content could not be detected, and the melting point was 82-84 ° C.
  • a mixed solvent of water and acetone, L-alanine and p-toluenesulfonic acid are added to the crude N-lauroyl-L-alanine, among which the crude N-lauroyl-L-alanine, water and acetone
  • the mixed solvent, L-alanine and p-toluenesulfonic acid were added in a molar ratio of 1: 5: 0.2: 0.002 and stirred at a temperature of 100 ° C and a pressure of 50 kg for 2 hours, so that a small amount of lauric acid was completely consumed. Then, it was cooled and filtered, and the obtained solid was washed twice with pure water and finally dried at 60 ° C. to obtain N-lauroyl-L-alanine self-assembled polymer.
  • the mass of the obtained N-lauroyl-L-alanine self-assembled polymer was 217.2 kg, the yield was 98.5%, the purity was higher than 97%, the lauric acid content could not be detected, and the melting point was 82-84 ° C.
  • N-lauroyl-L-alanine Methanol solution, L-alanine and sulfuric acid are added to the crude N-lauroyl-L-alanine, in which crude N-lauroyl-L-alanine, methanol solution, L-alanine and sulfuric acid are added in accordance with Add the amount of 1: 5: 0.2: 0.005 and stir at a temperature of 25 ° C and a pressure of 5 kg for 1 h, so that a small amount of lauric acid is completely consumed, and then cooled and filtered. The obtained solid is washed twice with pure water, and finally N-lauroyl-L-alanine self-assembled polymer was obtained by drying at 70 ° C.
  • the mass of the obtained N-lauroyl-L-alanine self-assembled polymer was 244.7 g, the yield was 90.2%, the purity was higher than 97%, the lauric acid content could not be detected, and the melting point was 82-84 ° C.
  • N-lauroyl-L-alanine Methanol solution, L-alanine and p-toluenesulfonic acid are added to the crude N-lauroyl-L-alanine, among which crude N-lauroyl-L-alanine, methanol solution, and L-alanine , P-toluenesulfonic acid is added in an amount of 1: 5: 0.2: 0.002 and stirred at a temperature of 100 ° C and a pressure of 50 kg for 3 hours, so that a small amount of lauric acid is completely consumed, and then cooled and filtered. It was washed twice with water and finally dried at 40 ° C to obtain N-lauroyl-L-alanine self-assembled polymer.
  • the mass of the obtained N-lauroyl-L-alanine self-assembled polymer was 235.4 g, the yield was 86.7%, the purity was higher than 97%, the lauric acid content could not be detected, and the melting point was 82-84 ° C.
  • Tetrahydrofuran solution, L-alanine and p-toluenesulfonic acid are added to the crude N-lauroyl-L-alanine, among which crude N-lauroyl-L-alanine, tetrahydrofuran solution, and L-alanine , P-toluenesulfonic acid is added in an amount of 1: 7.5: 0.2: 0.002 and stirred at a temperature of 63 ° C. and a pressure of 22.5 kg for 2 h, so that a small amount of lauric acid is completely consumed, and then cooled and filtered, and the obtained solid is reused Pure water was washed twice, and finally dried at 60 ° C. to obtain N-lauroyl-L-alanine self-assembled polymer.
  • the mass of the obtained N-lauroyl-L-alanine self-assembled polymer was 218.2 kg, the yield was 99.0%, the purity was higher than 97%, the lauric acid content could not be detected, and the melting point was 82-84 ° C.
  • FIG. 2 is an infrared spectrum of an N-lauroyl-L-alanine self-assembled polymer synthesized according to the method in Example 3 of the present invention.
  • the infrared spectrum data of the N-lauroyl-L-alanine self-assembled polymer synthesized according to the method in Example 3 is:
  • the N-lauroyl-L-alanine self-assembled polymer was analyzed by NMR using a UNITY-400 NMR spectrometer.
  • 3a is a 1 H-NMR spectrum of an N-lauroyl-L-alanine self-assembled polymer obtained according to the synthesis method in Example 3 of the present invention
  • FIG. 3b is obtained by a synthesis method according to Example 3 of the present invention 13 C-NMR spectrum of N-lauroyl-L-alanine self-assembling polymer.
  • the data obtained according to NMR are as follows:
  • HPLC uses a UV detector to identify and identify N-lauroyl-L-alanine self-assembled polymers.
  • the sample N-lauroyl-L-alanine self-assembled polymer was compared with its standard to identify the substance by its retention time, and the area normalization method was used for quantification.
  • reagents are chromatographically pure, and water is ultrapure water.
  • 20mmol buffered salt solution (pH 3.0) preparation method Weigh 1.36g of potassium dihydrogen phosphate (KH 2 PO 4 ), accurate to 0.001g, in a 100mL beaker, add water to dissolve and transfer to a 500mL volumetric flask. To the scale, a 20 mmol potassium dihydrogen phosphate solution is obtained, and the pH is adjusted to 3.0 with phosphoric acid to obtain a buffered salt solution
  • High performance liquid chromatograph equipped with UV detector; Column: ODS-2 HYPERSIL C18 250 * 4.6mm 5 ⁇ m; mobile phase vacuum filtration degassing device and 0.45 ⁇ m organic filter membrane.
  • Adjust the instrument parameters according to the chromatographic conditions After the baseline of the instrument is stable, inject 20 ⁇ L of standard solution and sample solution into the column, and record the chromatograms of N-lauroyl-L-alanine standard solution and sample solution.
  • the N-lauroyl-L-alanine chromatographic peak in the sample was qualitatively determined based on the retention time of the standard solution.
  • the area normalization method was used to determine the percentage content of the test substance from the peak area of the sample.
  • FIG. 4 is a standard chromatogram of N-lauroyl-L-alanine
  • FIG. 5 is a comparison of N-lauroyl-L-alanine self-assembled polymer obtained according to the synthesis method in Example 3 of the present invention.
  • FIG. 4 is a high performance liquid chromatogram measured under the same conditions
  • FIG. 6 is a high performance liquid chromatogram measured by lauric acid under the same conditions as in FIG. 4
  • FIG. 7 is L-alanine at the same conditions as in FIG. 4 HPLC chromatogram measured under the same conditions
  • Figure 8 shows the high efficiency of N-lauroyl-L-alanyl-L-alanine measured by the column preparation under the same conditions as in Figure 4. Liquid chromatogram.
  • the N-lauroyl-L-alanine self-assembled polymer prepared by this synthesis method does not contain lauric acid in impurities, and the purity can reach 97% or more.
  • the impurities are mainly N-lauroyl-L-alanyl-L-alanine.
  • N-lauroyl-L-alanine is further dehydrated with L-alanine and condensed.
  • the sample was injected through an Agilent 1200/6220 LC / MS and the mass spectrum of N-lauroyl-L-alanine was obtained.
  • the molecular formula of N-lauroyl-L-alanine is C 15 H 29 NO 3.
  • the theoretical value of the characteristic peak of the mass spectrum [M + H] + is 272.222, the measured value is 272.2223, and the deviation from the theoretical value is 1.03 ppm.
  • [M + Na] + was 294.204, the measured value was 294.2034, and the deviation from the theoretical value was 2.08 ppm.
  • the measured value of the sample coincided with the spectral characteristic peak of the substance of molecular formula C 15 H 29 NO 3 . No molecular ion peak of lauric acid was found from FIG. 20. Since the sensitivity of mass spectrometry is extremely high, it can be determined qualitatively by mass spectrometry that N-lauroyl-L-alanine does not contain lauric acid.
  • FIG. 9 is a structure formation diagram of the N-lauroyl-L-alanine monomer forming a supramolecular amino acid obtained according to the synthesis method in Example 3 of the present invention.
  • the N-lauroyl-L-alanine self-assembled polymer produced by the process of the present invention does not contain impurity lauric acid, and the N-lauroyl synthesized in the process -L-alanine can form two groups of hydrogen bonds, N-lauroyl-L-alanyl-L-alanine can form three groups of hydrogen bonds, two carboxyl groups of N-lauroyl-L-alanine Alkanes with eleven carbon chains at each end through hydrogen bonding.
  • the lipophilic end and the lipophilic end are connected in a chain, and the ends are connected to form a ring.
  • the ring and the ring In addition, hydrogen bonds and oil and oil are miscible with each other, and infinitely superimposed to form columnar molecular clusters, and columnar molecular clusters are infinitely superimposed to form a special spatial structure-called a self-assembled supramolecular amino acid polymer.
  • Figures 10a, 10b, and 10c show 300-fold, 1000-fold, and 2000-fold electron micrographs of the N-lauroyl-L-alanine self-assembled polymer obtained according to the synthesis method in Example 3 of the present invention, respectively.
  • the N-lauroyl-L-alanine self-assembled polymer of the present invention has a hemp-like structure and is entangled together to form a "supermolecular amino acid".
  • Figures 9, 10a, 10b, and 10c better demonstrate the formation principle and structure of N-lauroyl-L-alanine monomers to form supramolecular amino acids.
  • the supramolecular amino acid After the supramolecular amino acid is formed, the supramolecular amino acid further reacts with sodium hydroxide to form a sodium salt structure of the supramolecular amino acid as shown in FIG. 12.
  • N-lauroyl-L-alanine is a basic unit, which is self-assembled into a supramolecular polymer through hydrogen bonding.
  • the weight-average molecular weight is 125841, as shown in FIG. 13.
  • the sodium salt structure is hydrophilic on one side and lipophilic on the other.
  • the molecules are connected by hydrogen bonding to obtain a special two-dimensional network regular arrangement structure, which has a strong ability to combine with oil and can be used as Main surfactant is used.
  • the present application also performed an electron microscopy measurement on a commercially available N-lauroyl-L-alanine (purchased from Changsha Puji Biotechnology Co., Ltd.).
  • the N-lauroyl-L-propyl The amino acid contains 0.21% -5% lauric acid, and the scanning results are shown in Figs. 11a, 11b, 11c.
  • Figures 11a, 11b, and 11c show 500-, 1000-, and 2000-fold electron micrographs of commercially available N-lauroyl-L-alanine containing 0.21% -5% lauric acid, respectively, as shown in Figures 11a, 11b, As shown in Fig.
  • the commercially available N-lauroyl-L-alanine exhibits an irregularly arranged structural state, and corresponds to the corresponding N-lauroyl-L-alanine obtained by the process of the present invention.
  • the 300-, 1000-, and 2000-times electron microscope images are different, and no hemp-like or columnar structure appears in the electron microscope image of the N-lauroyl-L-alanine of the present invention.
  • the reason for this is that commercially available N-lauroyl-L-alanine contains lauric acid, and the presence of lauric acid will destroy the formation of infinite bonds of hydrogen bonds between N-lauroyl-L-alanine, Thereby changing the structure and properties of N-lauroyl-L-alanine.
  • the process of the present invention effectively solves the problem that the residue of impurity lauric acid destroys the structure of N-lauroyl-L-alanine, and further affects the performance of destroying N-lauroyl-L-alanine, so that N-lauroyl-L -Alanine is easy to form hydrogen bonds, infinitely connected, and has special properties.
  • the impurity N-lauroyl-L-alanyl-L-alanine produced by this process can also form hydrogen bonds like N-lauroyl-L-alanine, which strengthens the structural stability, and At the same time, it does not affect the performance of N-lauroyl-L-alanine.
  • this application used N-caproyl-L-alanine for structural research under the same conditions.
  • the above three-dimensional network structure was not found, which may be the carbon chain of N-caproyl-L-alanine The length is short, and the lipophilic ends of the two molecules cannot form a ring.
  • the carbon chain of the lipophilic group is between 12-18, and the fatty acyl-L-propyl group formed with L-alanine
  • Amino acids can also form the above-mentioned spatial structure by intermolecular hydrogen bonding and oil-oil compatibility under the condition of removing fatty acids. Once this structure is very stable, experiments have shown that adding a small amount of fatty acid below 10% will not destroy the stability and performance of the existing structure.
  • the N-lauroyl-L-alanine self-assembled polymer solution synthesized according to the method of the present invention has a significant inhibitory effect on E. coli, Staphylococcus aureus and Candida albicans. That is, after N-lauroyl-L-alanine self-assembling polymer solution was applied to E. coli for 2 minutes, the inhibition rate could reach 96.3%, and the inhibition rate could reach 100% after 5 minutes; and the original solution was applied to S. aureus for 2 minutes. After that, the inhibition rate of 100% can be reached; the inhibition rate of 5 minutes on Candida albicans can also reach 100%.
  • the size of bacteria is usually in the range of 0.5-5 ⁇ m, and the space between the pillars of the supramolecular structure formed by N-lauroyl-L-alanine without lauric acid used in the present invention is used. It is also micron-sized, so it can remove bacterial wrap, so it can be said to produce nano-scale foam micropores.
  • the surface-active substance N-lauroyl-L-alanine self-assembled polymer solution used in the present invention has a significant removal effect on methamidophos and acephate, after 2 minutes,
  • the removal rate of methamidophos can reach 64.63%; the removal rate of paramethionphos can reach 74.66%, and the effect is obvious.
  • the method for preparing the N-lauroyl-L-alanine self-assembling polymer of the present invention has simple process steps, mild reaction conditions, and is suitable for industrial production.
  • the N-lauroyl-L-alanine self-assembled polymer prepared according to the method of the present invention has high purity, which is basically above 97%, and the content of lauric acid is between 0.0001% and 0.02%, which effectively avoids laurel. Impact of acid on product quality.
  • the obtained N-lauroyl-L-alanine self-assembling polymer has stable structural performance; has a good bacteriostatic rate, and can inhibit 100% of E.
  • the removal rate of methamidophos can reach 64.63%, and the removal rate of acephate can reach 74.66%; meanwhile, it has good deodorizing performance, and can be used in daily chemical fields, agriculture, and pharmaceutical industries. There are good applications.
  • Natural oil blend contains 40% grape seed oil, 37.2% sunflower seed oil and 22.8% aloe oil.
  • the specific preparation steps according to Formula 1 shown in Table 3 include: adding 57% natural oil mixture and 40% corn starch to a mixer and homogenizing so that the particles are first dispersed.
  • the particles in the oil dispersion were then heated to 83-86 ° C while mixing.
  • 3% lauroyl-L-alanine was added to the mixer while heating.
  • the sample was heated and kept at 73-86 ° C for 5-10 min. It is then cooled to a temperature between 65-72 ° C while remaining miscible.
  • the sample was then poured into a 30 ml volume to obtain a skin care composition, which was saved and used for evaluation.
  • the methods for preparing the skin care composition in Formulas 2-6 adopt the same method as in Formula 1, and are not repeated here.
  • the skin care composition obtained according to the above embodiment wherein particles of different types and contents are added to the raw materials.
  • the results show that in addition to increasing the viscosity of the oil, the addition of N-lauroyl-L-alanine self-assembled polymers can also be used to stably suspend solid organic / inorganic particles or oil-mixed liquids such as glycerol in thickening Of natural oils for additional skin benefits.
  • oil-insoluble particles such as starch, TiO 2 , mica, boron nitride particles (Caress BN02 from Kobo), and an oil-miscible liquid such as glycerin.
  • the natural oil mixture components used in Formulas 1-6 are all the same, which include 40% grape seed oil, 37.2% sunflower seed oil, and 22.8% aloe oil.
  • the results showed that the compositions obtained from all the formulations shown in Table 3 were stable at room temperature and in an oven at 48 ° C without any particle separation problems.
  • lauroyl alanine (containing more than 2% of lauric acid) was used instead of the N-lauroyl-L-alanine self-assembled polymer in formula 1 for comparative experiments. As a result, the combination obtained was found. The material was unstable after 48 hours in an oven at 48 ° C, and there was an oil escaping phenomenon.
  • the total weight parts of the amino acid toothpaste paste in the examples are all 100.
  • the composition and specific content of each substance in the toothpaste are shown in Table 4:
  • the total weight parts of the amino acid toothpaste paste in the examples are all 100.
  • the composition and specific content of each substance in the toothpaste are shown in Table 5:
  • the specific steps include: putting 10 g of water, 37.5 g of sorbitol, 0.2 g of sodium saccharin, 2 g of polyethylene glycol-400, 5 g of glycerol, and 0.4 g of sodium benzoate into an aqueous solution. Paste machine.
  • Examples 5-13 were all prepared by the method described in Example 4, and will not be described in detail in the examples.
  • the amino acid toothpaste prepared according to the formula in Example 4-13 different weight parts of amino acid surfactants were used, and repeated formulation tests were repeated. 100 volunteers with frequent toothache and gum bleeding were entrusted to evaluate the effect. The use frequency is once a day in the morning and one in the evening, and the dosage is about 1g of paste / each time, each brushing time is about 5min. The obtained results show that toothpaste containing amino acid surface active ingredients has obvious analgesic, anti-inflammatory and anti-gingival bleeding effects. From the two aspects of taste and deodorization, the weight ratio of amino acid surface active ingredients to the toothpaste paste is 0.1. -25% is more suitable, the optimization is 0.5-10%, and the best optimization is 1-5%.
  • FIG. 17 and FIG. 18 respectively show the before and after comparison of the cleaning effect of the amino acid toothpaste on a patient's teeth obtained according to Example 4 of the present invention. It can be seen from the figure that after using the amino acid toothpaste of the present invention to brush teeth according to a normal brushing time of 3 minutes, the patient's teeth are significantly whiter and cleaner than before use.
  • the laundry detergent prepared according to Formula 1 was tested by Suzhou Product Quality Supervision and Inspection Institute. The detergency was greater than or equal to that of the standard laundry detergent. The obtained samples had a detergency of JB01, JB02, and JB03. JB01, JB02, JB03 stain cloth detergency.
  • the detergent liquid formulated according to Formula 2 was tested by Suzhou Product Quality Supervision and Inspection Institute, and the detergency was less than that of standard laundry detergent (Figure 19).
  • N-lauric acid-L-alanine self-assembling polymer with basic amino acids, such as arginine, organic salts formed in the aqueous phase system are more mild, non-irritating, and more suitable for sensitive skin. . While washing the skin, take care of the skin more.
  • Salts of N-lauric acid-L-alanine self-assembled polymers and N-lauroyl-L-alanyl-L-alanine self-assembled polymers under alkaline conditions as a cleansing surfactant , More gentle performance, without hurting hands, while stronger decontamination ability.

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Abstract

一种氨基酸自组装超分子聚合物及其制备方法，还提供了上述氨基酸自组装超分子聚合物在日化领域、农业、医药行业的应用。提供的氨基酸自组装超分子聚合物具有良好的性能，如在抑菌、除农药以及消除异味方面均具有明显的作用。提供的氨基酸自组装超分子聚合物可以应用于牙膏、皮肤护理组合物、洗衣液、香皂、洗衣粉、洗洁精、面膜等领域。

Description

一种氨基酸自组装超分子聚合物及其制备和应用 技术领域
本发明属于氨基酸型表面活性剂制备技术领域，具体地，涉及一种氨基酸自组装超分子聚合物及其制备和应用。
背景技术
表面活性剂是日化行业、农业、医药行业等许多领域必不可少的组成部分。目前市场使用的表面活性剂有几十种之多，但常用的主要以十二烷基苯磺酸钠(SLS)、月桂醇聚氧乙烯醚硫酸酯钠(AES)和月桂醇硫酸酯钠(K12)为主。由于这三大表面活性剂使用历史已有几十年甚至上百年，在使用的过程中它的负面影响已逐步显现出来，对人体的安全和环境的影响经常报道。
其它的表面活性剂，如糖类的烷基糖苷(APG)，氨基酸表面活性剂，如月桂酰-L-谷氨酸、月桂酰甘氨酸、月桂酰肌氨酸等。虽然它们属于生物物质为基础的表面活性剂，具有安全性高，生物降解性好和优良的肤感，也越来越受到人们的关注，但由于这类的表面活性剂去污能力较差，很少单独作为主表面活性剂来使用，常需与其它主表面活性剂来配合使用，没有从根本上解决日化主表面活性剂在安全性和生物降解性上的负面问题。
纯N-月桂酰-L-丙氨酸作为表面活性剂，具有良好的湿润性、起泡性、抗菌性以及抗蚀、抗静电能力，基本无毒无害，对皮肤温和，其降解产物为氨基酸和脂肪酸对环境基本没有影响，而且还具有与其他表面活性剂的相容性好的有点。
但是，通过将现有的方法如肖顿-鲍曼(Schotten-Banmann)缩合反应制备得到的N-月桂酰-L-丙氨酸作为表面活性剂进行试验，发现其去污能力并不没有理论上那么高，发明人在经过一系列探索试验后发现，导致N-月桂酰-L-丙氨酸去污能力低的主要原因是利用该方法制备得到的N-月桂酰-L-丙氨酸含有较高含量的月桂酸，而月桂酸的存在，导致其形成不了自组装的的聚合物，其制备的钠盐化合物效果数据，没有本发明好。有较高含量的月桂酸，导致产品纯度低，严重影响了N-月桂酰-L-丙氨酸的质量，去除杂质还需要 在原有的生产工艺上通过层析才能进一步提纯产品，操作麻烦，成本也高，难以实现工业化生产。
基于以上，期待一种氨基酸自组装超分子聚合物的制备和应用，通过该方法制备得到的N-月桂酰-L-丙氨酸自组装聚合物中月桂酸含量HPLC和GC检测不出来，去污效果好，同时该方法工艺简单，成本低，易于实现工业化生产。
发明内容
本发明的目的就是为了克服现有技术制备的N-月桂酰-L-丙氨酸纯度低，杂质含量高，严重影响产品质量的缺陷，而提出的一种N-月桂酰-L-丙氨酸自组装聚合物的制备方法及应用，所制备得到的N-月桂酰-L-丙氨酸自组装超分子聚合物生物降解性好，去污能力强，能够很好的应用于日化行业、农业及医药行业等领域。
本发明所述一种氨基酸自组装超分子聚合物，其结构为：
Figure PCTCN2019089816-appb-000001
本发明所述一种氨基酸自组装超分子聚合物，以N-月桂酰-L-丙氨酸为基本单元，通过氢键自组装成为超分子聚合物，所述聚合物中基本不含月桂酸，基本不含是指月桂酸用HPLC和GC检测不出。
本发明公开一种氨基酸自组装超分子聚合物，以N-月桂酰-L-丙氨酸为基本单元，通过氢键自组装成为超分子聚合物，超分子聚合物重均分子量数据介于2000-500万之间。
本发明的目的及解决其技术问题采用以下的技术方案来实现。依据本发明提出的基本不含月桂酸的一种氨基酸自组装超分子聚合物的制备方法，该方法包括以下步骤：
将N-月桂酰-L-丙氨酸粗品中加入溶剂、L-丙氨酸和催化剂并在一定条件下搅拌，之后冷却过滤，所得固体经洗涤后烘干，即得到基本不含月桂酸的N-月桂酰-L-丙氨酸自组装聚合物。
前述N-月桂酰-L-丙氨酸粗品的制备包含以下步骤：
(1)将L-丙氨酸与金属无机碱溶于蒸馏水和有机溶剂的混合溶液中搅拌均匀得到L-丙氨酸盐溶液；
(2)在向上述得到的L-丙氨酸盐溶液依次加入月桂酰氯和金属无机碱，然后在一定条件下继续搅拌，得到糊状的N-月桂酰-L-丙氨酸盐；
(3)将上述得到的糊状的N-月桂酰-L-丙氨酸盐酸化，逐渐析出白色固体，然后在冰浴下放置，过滤，得到N-月桂酰-L-丙氨酸粗品。
前述的方法，其中所述步骤(1)中所述L-丙氨酸与金属无机碱的摩尔比为1:(1-1.5)。
前述的方法，其中所述步骤(1)中所述金属无机碱选自氢氧化钠、氢氧化钾、碳酸钠、碳酸钾中的一种或多种。
前述的方法，其中所述步骤(1)中所述有机溶剂选自丙酮、甲醇、乙醇、乙腈、四氢呋喃中的一种或多种。
前述的方法，其中所述步骤(1)中所述蒸馏水和有机溶剂的体积比为1:(1-1.5)。
前述的方法，其中所述步骤(2)中所述月桂酰氯与L-丙氨酸的投料摩尔比为(0.8-1):1。
前述的方法，其中所述步骤(2)中所述搅拌条件为：温度5-50℃，时间0.5-3.5h。
前述的方法，其中所述步骤(2)中所述金属无机碱浓度为30-80％。
前述的方法，其中所述步骤(2)中所述金属无机碱选自氢氧化钠、氢氧化钾、碳酸钠、碳酸钾中的一种或多种。
前述的方法，其中所述步骤(4)中所述溶剂选自丙酮、甲醇、乙醇、乙腈、四氢呋喃或上述溶剂与水制成的混合溶剂。
前述的方法，其中所述步骤(4)中所述催化剂选自硫酸、对甲苯磺酸、乳化剂中的一种或多种。
前述的方法，其中所述步骤(4)中所述N-月桂酰-L-丙氨酸粗品、溶剂、L-丙氨酸、催化剂的摩尔比为1:(5-10):(0.2-0.6):(0.001-0.2)。
前述的方法，其中所述步骤(4)中所述烘干温度为40-70℃。
前述的方法，其中所述步骤(4)中所述搅拌条件为：温度25℃-100℃，压力5kg-50kg，时间1-3h。
本发明还涉及一种基本不含月桂酸的氨基酸自组装超分子聚合物钠盐，其结构如下：
Figure PCTCN2019089816-appb-000002
其中n表示N-月桂酰-L-丙氨酸钠形成自组装超分子聚合物的分子个数。
本发明还公开一种氨基酸自组装超分子聚合物钠盐，其以N-月桂酰-L-丙氨酸钠为基本单元，通过氢键自组装成为超分子聚合物，其重均分子量数据介于2800-77万之间。
本发明的目的及解决其技术问题还采用以下的技术方案来实现。依据本发明提出的一种如上所述的制备方法得到氨基酸自组装超分子聚合物，用作表面活性剂，在日化领域、农业、医药行业的应用。
本发明的目的及解决其技术问题还采用以下的技术方案来实现。依据本发 明提出的一种超分子氨基酸，其中所述超分子氨基酸是由如上所述的制备方法得到的N-月桂酰-L-丙氨酸单体之间通过氢键连接形成的。
与现有技术相比，本发明具有有益的技术效果：
1、本发明的氨基酸自组装超分子聚合物的制备方法工艺步骤简单，是用天然的月桂酸和天然的L-丙氨酸缩合而成的，在常态下稳定存在，对人体无毒无害，进入人体和自然也很快降解成月桂酸和L-丙氨酸，降解产物又是天然产品，可循环利用，并且反应条件温和，适于工业化生产。
2、根据本发明的方法制备得到的氨基酸自组装超分子聚合物中月桂酸含量HPLC和GC检测不出来，即月桂酸的含量对N-月桂酰-L-丙氨酸的结构和性能不产生影响，有效的避免了月桂酸对产品质量的影响。
3、根据本发明的方法得到的氨基酸自组装超分子聚合物是一个三维网状结构，具有强吸附油污等有机物，在使用中pH取6-7，更适合人体pH要求，90％以上以钠盐形式存在，其余部分以酸的形式存在，以二维和三维的方式共存，赋予了强的洗涤能力，吸附细菌、农药、气味等性能。
4、根据本发明的方法制备得到的氨基酸自组装超分子聚合物结构性能稳定，并具有超分子的性质，分子在溶液中由于各种凝胶因素存在，如氢键、静电力、疏水力以及π-π的相互作用，驱动液体成分静止，形成一种具有三维立体网络空间结构的氨基酸，这样就具有了物理除菌、除气味、除农药残留等特性：具有良好的抑菌率，对大肠杆菌、金黄色葡萄球菌和白假丝酵母菌的抑制率均可达到100％；有效去除农药残留，对甲胺磷的去除率可达64.63％，对乙酰甲胺磷的去除率可达74.66％；同时具有良好的除异味性能。
5、根据本发明的方法制备得到的氨基酸自组装超分子聚合物是一个以无数柱状体的形式存在，分子之间存在巨大的空隙，能包裹有机物如药物分子、农药残留及微小无机颗粒。在医药领域应用上，氨基酸自组装超分子聚合物能包裹药物分子，在酶的作用下缓慢释放药物有效成分，起到缓释剂的作用；在农药领域应用上，氨基酸自组装超分子聚合物能包裹农药，防止农药渗透，进入到植物内部；在化妆品领域应用上氨基酸自组装超分子聚合物与天然油脂结合后会改变油脂的物理性能，贴近人体自身分泌的油脂，具有良好的体验感。氨基酸自组装超分子聚合物能包裹化妆品活性物质，这样使活性物质 不易氧化、失活，还可使颗粒均匀分散，悬浮于化妆品体系内。
附图说明
图1为根据本发明的实例3中的合成方法制备N-月桂酰-L-丙氨酸的化学反应式；
图2为根据本发明的实例3中的合成方法得到的N-月桂酰-L-丙氨酸自组装聚合物的红外光谱图；
图3a为根据本发明的实例3中的合成方法得到的N-月桂酰-L-丙氨酸自组装聚合物的 1H-NMR谱；
图3b为根据本发明的实例3中的合成方法得到的N-月桂酰-L-丙氨酸自组装聚合物的 13C-NMR谱；
图4为N-月桂酰-L-丙氨酸的标准色谱图；
图5为根据本发明的实例3中的合成方法得到的N-月桂酰-L-丙氨酸自组装聚合物的在与图4相同的条件下测得的高效液相色谱图；
图6为月桂酸在与图4相同的条件下测得的高效液相色谱图；
图7为L-丙氨酸在与图4相同的条件下测得的高效液相色谱图；
图8为柱性制备分离得到的N-月桂酰-L-丙氨酰-L-丙氨酸的在与图4相同的条件下测得的高效液相色谱图；
图9为根据本发明的实例3中的合成方法得到的N-月桂酰-L-丙氨酸单体形成超分子氨基酸的结构形成图；
图10a为根据本发明实例3中合成方法得到的N-月桂酰-L-丙氨酸自组装聚合物的300倍电镜图；
图10b为根据本发明实例3中合成方法得到的N-月桂酰-L-丙氨酸自组装聚合物的1000倍电镜图；
图10c为根据本发明实例3中合成方法得到的N-月桂酰-L-丙氨酸自组装聚 合物的2000倍电镜图；
图11a为市售N-月桂酰-L-丙氨酸(含2-5％月桂酸)的500倍电镜图；
图11b为市售N-月桂酰-L-丙氨酸(含2-5％月桂酸)的1000倍电镜图；
图11c为市售N-月桂酰-L-丙氨酸(含2-5％月桂酸)的2000倍电镜图；
图12为根据本发明的实例3中的合成方法得到的N-月桂酰-L-丙氨酸进一步形成超分子氨基酸钠盐的形成过程图。
图13为根据本发明的实例3中的合成方法得到的N-月桂酰-L-丙氨酸进一步形成超分子氨基酸钠盐的分子量数据图，其中
GPC sample results：样品结果
Retention Time：保留时间
Mn：数均分子量
Mw：重均分子量
Mz：更高的平均分子量
Mp：峰尖分子量
Polydispersity:是指其是分子量是同系物的平均值；
图14-16为实施例3的氨基酸牙膏的检测报告；
图17为氨基酸牙膏对患者牙齿清洁前效果；
图18为氨基酸牙膏对患者牙齿清洁后效果；
图19为洗衣液去污能力检测结果；
图20为根据本发明的实例3中的合成方法得到的N-月桂酰-L-丙氨酸自组装聚合物的质谱。
具体实施方式
发明人经过广泛而深入的研究，发现可通过特定的方法可以使N-月桂酰-L- 丙氨酸单体通过氢键自组装形成的聚合物中基本不含或不含月桂酸，并且可形成有弹性含空隙的结构，这种结构可固化油类物质；当聚合物与碱成盐后，聚合物盐又可作为表面活性剂。在此基础上，完成了本发明。
如本文所用，“本发明提供的聚合物或其盐基本不含或不含月桂酸”是指是指例如采用高效液相色谱仪(配有紫外检测器；色谱柱：ODS-2HYPERSIL C18 250*4.6mm 5μm；流动相真空抽滤脱气装置及0.45μm有机滤膜)检测不出月桂酸。即月桂酸的含量不影响N-月桂酰-L-丙氨酸通过形成氢键来自组装成超分子聚合物的性质和结构。或是指通过质谱测定，获得的质谱图中检测不出月桂酸的分子离子峰特征。例如但不限于，通过Agilent 1200/6220液质联用仪获得如图20所示的质谱图。
本发明中涉及的N-月桂酰-L-丙氨酸盐为N-月桂酰-L-丙氨酸钠和/或N-月桂酰-L-丙氨酸钾。也可以是N-月桂酰-L-丙氨酸同碱性氨基酸形成的盐，例如同精氨酸、组氨酸、赖氨酸等形成的盐。
聚合物或其盐
本发明提供一种氨基酸自组装超分子聚合物或其盐，所述聚合物是N-月桂酰-L-丙氨酸单体之间通过氢键连接形成；所述聚合物基本不含或不含月桂酸。
所述N-月桂酰-L-丙氨酸单体之间通过氢键连接可形成如式(Ⅰ)所示的结构：
Figure PCTCN2019089816-appb-000003
。
本发明提供的氨基酸自组装超分子聚合物的重均分子量介于2000-500万之间，其熔点为82-84℃。
本发明还提供上述氨基酸自组装超分子聚合物的盐，所述盐为聚合物与碱形成；所述碱包括无机碱和有机碱。
在一优选例中，所述无机碱选自氢氧化钠、氢氧化钾、或氢氧化锂。
在一优选例中，所述有机碱为天然碱性氨基酸(精氨酸、赖氨酸或组氨酸)。
本发明提供的上述氨基酸自组装超分子聚合物的钠盐的最大溶解度为15w/v％，通过溶解度方法测定(《中国药典》(2015年版)凡例)，即在25℃，1个大气压下，每100ml水中溶解的自组装的聚合的N-月桂酰-L-丙氨酸钠最多为15克。
在本发明的一种实施方式中，提供一种氨基酸自组装超分子聚合物钠盐，是N-月桂酰-L-丙氨酸钠单体之间通过氢键连接形成；所述聚合物钠盐基本不含或不含月桂酸。
所述N-月桂酰-L-丙氨酸钠单体之间通过氢键连接可形成如式(Ⅱ)所示的结构：
Figure PCTCN2019089816-appb-000004
Figure PCTCN2019089816-appb-000005
其中n表示N-月桂酰-L-丙氨酸钠形成自组装超分子聚合物的分子个数。
n个N-月桂酰-L-丙氨酸钠在同一平面通过氢键依次连接，或n个N-月桂酰-L-丙氨酸钠通过氢键依次连接且首尾通过氢键连接以形成一柱状。
提供的氨基酸自组装超分子聚合物钠盐的重均分子量介于2800-77万之间；由此可以推断n在10至3000在范围内，所得的钠盐在水中的溶解度不超过15克/100ml。
本发明还提供一种组合物，所述组合物中含有本发明提供的氨基酸自组装超分子聚合物或其盐，和N-月桂酰-L-丙氨酰-L-丙氨酸单体之间通过氢键连接形成的聚合物或其盐，以组合物的总重量计，其中N-月桂酰-L-丙氨酰-L-丙氨酸单体之间通过氢键连接形成的聚合物或其盐的重量百分含量介于0-40％之间。
所述N-月桂酰-L-丙氨酰-L-丙氨酸单体之间通过氢键连接可形成如式(Ⅰ＇)所示的结构：
Figure PCTCN2019089816-appb-000006
其重均分子量介于5000-500万之间，其熔点为148-150℃。
所述N-月桂酰-L-丙氨酰-L-丙氨酸钠单体之间通过氢键连接也可形成如式(Ⅱ＇)所示的结构：
Figure PCTCN2019089816-appb-000007
Figure PCTCN2019089816-appb-000008
其中n为8-20000；n个N-月桂酰-L-丙氨酰-L-丙氨酸钠在同一平面通过氢键依次连接，或n个N-月桂酰-L-丙氨酸钠通过氢键依次连接且首尾通过氢键连接以形成一柱状。
如式Ⅱ＇所示的聚合物钠盐的重均分子量介于5000-500万之间。
聚合物或其盐的制备方法
本发明提供一种氨基酸自组装超分子聚合物的制备方法，所述方法包括步骤：
第一步，将L-丙氨酸与金属无机碱溶于蒸馏水和有机溶剂的混合溶液中搅拌均匀得到L-丙氨酸盐溶液；
第二步，向上述得到的L-丙氨酸盐溶液依次加入月桂酰氯和金属无机碱使得反应体系的pH＝8-10，然后在一定条件下继续搅拌，得到糊状的N-月桂酰-L-丙氨酸盐；
第三步，将上述得到的糊状的N-月桂酰-L-丙氨酸盐酸化至pH＝3-4，逐渐析出白色固体，然后在冰浴下放置1-3小时后过滤，得到N-月桂酰-L-丙氨酸粗品；
第四步，在上述得到的N-月桂酰-L-丙氨酸粗品中加入溶剂、L-丙氨酸和催化剂，并在一定条件下搅拌，得到本发明提供的氨基酸自组装超分子聚合物。
在本发明的一种实施方式中，上述第一步中所述蒸馏水和有机溶剂的体积比为1：(1-1.5)。
在本发明的一种实施方式中，上述第一步中所述L-丙氨酸与金属无机碱的摩尔比为1:(1-1.5)。
在本发明的一种实施方式中，上述第一步中所述金属无机碱选自氢氧化钠、氢氧化钾、碳酸钠、碳酸钾中的一种或两种以上。
在本发明的一种实施方式中，上述第一步中所述有机溶剂选自丙酮、甲醇、乙醇、乙腈、四氢呋喃中的一种或两种以上。
在本发明的一种实施方式中，上述第二步中所述月桂酰氯与L-丙氨酸的投料摩尔比为(0.8-1):1。
在本发明的一种实施方式中，上述第二步中所述搅拌条件为：温度5-50℃，时间0.5-3.5小时。
在本发明的一种实施方式中，上述第二步中所述金属无机碱浓度为30-80％；所述金属无机碱选自氢氧化钠、氢氧化钾、碳酸钠、碳酸钾中的一种或两种以上。
在本发明的一种实施方式中，上述第四步中所述溶剂选自丙酮、甲醇、乙醇、乙腈、四氢呋喃或上述溶剂与水制成的混合溶剂。
在本发明的一种实施方式中，上述第四步中所述催化剂选自硫酸、对甲苯磺酸、乳化剂中的一种或两种以上。
在本发明的一种实施方式中，上述第四步中所述N-月桂酰-L-丙氨酸粗品、溶剂、L-丙氨酸、催化剂的混合摩尔比为1:(5-10):(0.2-1.1):(0.001-0.2)；优选为1:(5-10):(0.2-0.5):(0.01-0.2)。
在本发明的一种实施方式中，上述第四步中所述搅拌条件为：温度25℃-100℃，压力5kg-50kg，时间1-3小时。
在本发明的一种实施方式中，上述第四步在搅拌后冷却过滤，所得固体经洗涤后烘干，即得到基本不含月桂酸的N-月桂酰-L-丙氨酸自组装聚合物。
聚合物或其盐的用途
本发明提供的氨基酸自组装超分子聚合物可用于固化油类物质，其盐可用作表面活性剂。
本发明提供的氨基酸自组装超分子聚合物或其盐可在日化领域、农业、或医药行业中广泛使用，例如但不限于，用于制备牙膏、皮肤护理组合物、洗衣液、香皂、洗衣粉、洗洁精、面膜等。
下面结合附图和实施例对本发明作进一步的阐述，应理解，这些实施例仅用于说明本发明而不用于限制本发明的范围。此外应理解，在阅读了本发明讲授的内容之后本领域技术人员可以对本发明做各种改动或修改，这些等价同样落于本申请所附权利要求书所限定的范围。
实施例1 N-月桂酰-L-丙氨酸自组装聚合物的合成
实例1
常温下，在1L的三口烧瓶中，将89g(1mol)L-丙氨酸和40g(1mol)氢氧化钠溶于150mL蒸馏水和150mL丙酮的混合溶液中搅拌均匀得到L-丙氨酸钠溶液。
在25℃的条件下，向L-丙氨酸盐溶液中缓慢滴加218.7g(1mol)月桂酰氯，再滴加50％的氢氧化钠溶液使得反应体系的pH＝9，滴加完毕后，在25℃下继续搅拌2h，得到糊状的N-月桂酰-L-丙氨酸盐。
在糊状的N-月桂酰-L-丙氨酸盐中加入盐酸酸化至pH＝3-4，逐渐析出白色固体，然后在冰浴下放置2h后过滤，得到N-月桂酰-L-丙氨酸粗品。
在N-月桂酰-L-丙氨酸粗品中加入水和丙酮的混合溶剂、L-丙氨酸和对甲苯磺酸，其中，N-月桂酰-L-丙氨酸粗品、水和丙酮的混合溶剂、L-丙氨酸、对甲苯磺酸按照摩尔比1:7.5:0.35:0.002的量加入并在温度为60℃、压力为27kg的条件下搅拌2h，使得少量的月桂酸完全消耗完，之后冷却过滤，所得固体再用纯水洗涤两次，最后在60℃下烘干，即得N-月桂酰-L-丙氨酸自组装聚合物。
所得到的N-月桂酰-L-丙氨酸自组装聚合物质量为250.5g，产率为92.3％，纯度高于97％，月桂酸含量检测不出，熔点82-84℃。
经试验发现，如果上述反应在常压下条件搅拌，我们经检测反应体系中还 存在少量的月桂酸，最后的产品不能获得N-月桂酰-L-丙氨酸自组装聚合物。
实例2
常温下，在1L的三口烧瓶中，将89g(1mol)L-丙氨酸和56g(1mol)氢氧化钾溶于150mL蒸馏水和150mL丙酮的混合溶液中搅拌均匀得到L-丙氨酸钠溶液。
在25℃的条件下，向L-丙氨酸盐溶液中缓慢滴加218.7g(1mol)月桂酰氯，再滴加50％的氢氧化钠溶液使得反应体系的pH＝9，滴加完毕后，在25℃下继续搅拌2h，得到糊状的N-月桂酰-L-丙氨酸盐。
在糊状的N-月桂酰-L-丙氨酸盐中加入盐酸酸化至pH＝3-4，逐渐析出白色固体，然后在冰浴下放置2h后过滤，得到N-月桂酰-L-丙氨酸粗品。
在N-月桂酰-L-丙氨酸粗品中加入水和丙酮的混合溶剂、L-丙氨酸和对甲苯磺酸，其中，N-月桂酰-L-丙氨酸粗品、水和丙酮的混合溶剂、L-丙氨酸、对甲苯磺酸按照摩尔比1:10:0.3:0.003的量加入并在温度为25℃、压力为43kg的条件下搅拌2h，使得少量的月桂酸完全消耗完，之后冷却过滤，所得固体再用纯水洗涤两次，最后在60℃下烘干，即得N-月桂酰-L-丙氨酸自组装聚合物。
所得到的N-月桂酰-L-丙氨酸自组装聚合物质量为243.7g，产率为89.8％，纯度高于97％，月桂酸含量检测不出，熔点82-84℃。
实例3
常温下，在1000L的反应釜中，将89kg(1Kmol)L-丙氨酸和40kg(1Kmol)氢氧化钠溶于150L蒸馏水和150L丙酮的混合溶液中搅拌均匀得到L-丙氨酸钠溶液。
在25℃的条件下，向L-丙氨酸盐溶液中缓慢滴加175kg(0.8Kmol)月桂酰氯，再滴加50％的氢氧化钠溶液使得反应体系的pH＝9，滴加完毕后，在25℃下继续搅拌2h，得到糊状的N-月桂酰-L-丙氨酸盐。
在糊状的N-月桂酰-L-丙氨酸盐中加入盐酸酸化至pH＝3-4，逐渐析出白色固 体，然后在冰浴下放置2h后过滤，得到N-月桂酰-L-丙氨酸粗品。
在N-月桂酰-L-丙氨酸粗品中加入水和丙酮的混合溶剂、L-丙氨酸和对甲苯磺酸，其中，N-月桂酰-L-丙氨酸粗品、水和丙酮的混合溶剂、L-丙氨酸、对甲苯磺酸按照摩尔比1:5:0.2:0.002的量加入并在温度为100℃、压力为50kg的条件下搅拌2h，使得少量的月桂酸完全消耗完，之后冷却过滤，所得固体再用纯水洗涤两次，最后在60℃下烘干，即得N-月桂酰-L-丙氨酸自组装聚合物。
所得到的N-月桂酰-L-丙氨酸自组装聚合物质量为217.2kg，产率为98.5％，纯度高于97％，月桂酸含量检测不出，熔点82-84℃。
实例4
常温下，在1L的三口烧瓶中，将89g(1mol)L-丙氨酸和106g(1mol)碳酸钠溶于150mL蒸馏水和150mL丙酮的混合溶液中搅拌均匀得到L-丙氨酸钠溶液。
在50℃的条件下，向L-丙氨酸盐溶液中缓慢滴加218.7g(1mol)月桂酰氯，再滴加30％的氢氧化钠溶液使得反应体系的pH＝8，滴加完毕后，在25℃下继续搅拌3.5h，得到糊状的N-月桂酰-L-丙氨酸盐。
在糊状的N-月桂酰-L-丙氨酸盐中加入盐酸酸化至pH＝3-4，逐渐析出白色固体，然后在冰浴下放置3h后过滤，得到N-月桂酰-L-丙氨酸粗品。
在N-月桂酰-L-丙氨酸粗品中加入甲醇溶液、L-丙氨酸和硫酸，其中，N-月桂酰-L-丙氨酸粗品、甲醇溶液、L-丙氨酸、硫酸按照1:5:0.2:0.005的量加入并在温度为25℃、压力为5kg的条件下搅拌1h，使得少量的月桂酸完全消耗完，之后冷却过滤，所得固体再用纯水洗涤两次，最后在70℃下烘干，即得N-月桂酰-L-丙氨酸自组装聚合物。
所得到的N-月桂酰-L-丙氨酸自组装聚合物质量为244.7g，产率为90.2％，纯度高于97％，月桂酸含量检测不出，熔点82-84℃。
实例5
常温下，在1L的三口烧瓶中，将89g(1mol)L-丙氨酸和106g(1mol)碳酸钠溶于150mL蒸馏水和150mL丙酮的混合溶液中搅拌均匀得到L-丙氨酸钠溶 液。
在5℃的条件下，向L-丙氨酸盐溶液中缓慢滴加218.7g(1mol)月桂酰氯，再滴加80％的氢氧化钠溶液使得反应体系的pH＝10，滴加完毕后，在50℃下继续搅拌0.5h，得到糊状的N-月桂酰-L-丙氨酸盐。
在糊状的N-月桂酰-L-丙氨酸盐中加入盐酸酸化至pH＝3-4，逐渐析出白色固体，然后在冰浴下放置1h后过滤，得到N-月桂酰-L-丙氨酸粗品。
在N-月桂酰-L-丙氨酸粗品中加入甲醇溶液、L-丙氨酸和对甲苯磺酸，其中，N-月桂酰-L-丙氨酸粗品、甲醇溶液、L-丙氨酸、对甲苯磺酸按照1:5:0.2:0.002的量加入并在温度为100℃、压力为50kg的条件下搅拌3h，使得少量的月桂酸完全消耗完，之后冷却过滤，所得固体再用纯水洗涤两次，最后在40℃下烘干，即得N-月桂酰-L-丙氨酸自组装聚合物。
所得到的N-月桂酰-L-丙氨酸自组装聚合物质量为235.4g，产率为86.7％，纯度高于97％，月桂酸含量检测不出，熔点82-84℃。
实例6
常温下，在1000L的反应釜中，将89kg(1Kmol)L-丙氨酸和40kg(1Kmol)氢氧化钠溶于150L蒸馏水和150L丙酮的混合溶液中搅拌均匀得到L-丙氨酸钠溶液。
在25℃的条件下，向L-丙氨酸盐溶液中缓慢滴加175kg(0.8Kmol)月桂酰氯，再滴加50％的氢氧化钠溶液使得反应体系的pH＝9，滴加完毕后，在25℃下继续搅拌2h，得到糊状的N-月桂酰-L-丙氨酸盐。
在糊状的N-月桂酰-L-丙氨酸盐中加入盐酸酸化至pH＝3-4，逐渐析出白色固体，然后在冰浴下放置2h后过滤，得到N-月桂酰-L-丙氨酸粗品。
在N-月桂酰-L-丙氨酸粗品中加入四氢呋喃溶液、L-丙氨酸和对甲苯磺酸，其中，N-月桂酰-L-丙氨酸粗品、四氢呋喃溶液、L-丙氨酸、对甲苯磺酸按照1:7.5:0.2:0.002的量加入并在温度为63℃、压力为22.5kg的条件下搅拌2h，使得少量的月桂酸完全消耗完，之后冷却过滤，所得固体再用纯水洗涤两次，最后在60℃下烘干，即得N-月桂酰-L-丙氨酸自组装聚合物。
所得到的N-月桂酰-L-丙氨酸自组装聚合物质量为218.2kg，产率为99.0％，纯度高于97％，月桂酸含量检测不出，熔点82-84℃。
实施例2 N-月桂酰-L-丙氨酸自组装聚合物的结构表征
1、红外光谱分析(GBT 6040-2002)
仪器：傅里叶变换红外光谱仪(FTS-1000)
光谱条件：将待测样品N-月桂酰-L-丙氨酸自组装聚合物与溴化钾(光谱纯，CP，购自国药化学试剂集团)按1:100的比例充分混合，研磨，压片；波数扫描范围为4000cm -1—400cm -1，分辨率为4cm -1；扫描次数为16次。
图2为根据本发明的实例3中的方法合成的N-月桂酰-L-丙氨酸自组装聚合物的红外光谱图。如图2所示，根据实例3中的方法合成的N-月桂酰-L-丙氨酸自组装聚合物的红外光谱数据为：
IR Vmax(KBr)：3322cm-1(N-H)；2955cm-1,2871cm-1,1377cm-1(CH3)；2919cm-1,2850cm-1,1469cm-1,720cm-1(＝CH2)；1646cm-1(C＝O)；1541cm-1(C-N,N-H)；1271cm-1,2120cm-1(COOH)；1707cm-1(C＝O)；1414cm-1(-OH)；1241cm-1(C-O)。
2、NMR分析(JY/T 007-1996)
采用UNITY-400NMR谱仪对得到的N-月桂酰-L-丙氨酸自组装聚合物进行NMR分析。图3a为根据本发明的实例3中的合成方法得到的N-月桂酰-L-丙氨酸自组装聚合物的 1H-NMR谱；图3b为根据本发明的实例3中的合成方法得到的N-月桂酰-L-丙氨酸自组装聚合物的 13C-NMR谱。根据NMR得到的数据如下：
1H NMR(DMSO):δ7.95(d,1H)；4.15(m,1H)；2.08(t,2H)；1.48(m,2H)；1.2(m,19H)；0.86(t,3H)；
13C NMR(CDCl3):δ174.63；171.77；47.74；35.11；31.33；29.08；29.06；29.01；28.87；28.76；28.67；25.24；22.13；18.03；13.92。
3、HPLC分析(GBT 16631-2008)
高效液相色谱法采用紫外检测器来识别和确定N-月桂酰-L-丙氨酸自组装聚合物。样品N-月桂酰-L-丙氨酸自组装聚合物与其标准品比较其保留时间来识别物质，并采用面积归一法进行定量。除另有规定外，试剂均为色谱纯，水为超纯水。
20mmol的缓冲盐溶液(pH 3.0)配制方法：称取磷酸二氢钾(KH 2PO 4)1.36g，精确到0.001g，于100mL的烧杯中，加水溶解转移至500mL容量瓶中，加水定容至刻度，即得20mmol的磷酸二氢钾溶液，用磷酸调节pH至3.0，得到缓冲盐溶液
仪器：高效液相色谱仪：配有紫外检测器；色谱柱：ODS-2 HYPERSIL C18 250*4.6mm 5μm；流动相真空抽滤脱气装置及0.45μm有机滤膜。
测定：
(1)标准样品溶液的准备
精确称取30mg N-月桂酰-L-丙氨酸的标准样品，取适量流动相溶解，并定容至10mL容量瓶中，摇匀。用0.45μm有机滤膜过滤，滤液待用。
(2)供试品溶液制备
精确称取150mg N-月桂酰-L-丙氨酸自组装聚合物的待测样品，取适量流动相溶解，并定容至50mL容量瓶中，摇匀。用0.45μm有机滤膜过滤，滤液待用。
(3)色谱条件
流动相：甲醇：20mmol的缓冲盐溶液(pH 3.0)＝70:30(v/v)；流速:1.0mL/min；柱温：30℃；检测波长：210nm；进样量：20μL
(4)试样测定
按色谱条件调整仪器参数，待仪器基线稳定后，于色谱柱中分别注入20μL标准液和试样液，记录N-月桂酰-L-丙氨酸标准液及试样液的色谱图。根据标准液的保留时间定性样品中N-月桂酰-L-丙氨酸色谱峰，由样品的峰面积，采用面积归一化法测定供试物的百分含量。
图4为N-月桂酰-L-丙氨酸的标准色谱图；图5为根据本发明的实例3中的合成方法得到的N-月桂酰-L-丙氨酸自组装聚合物的在与图4相同的条件下测得的高效液相色谱图；图6为月桂酸在与图4相同的条件下测得的高效液相色谱图；图7为L-丙氨酸在与图4相同的条件下测得的高效液相色谱图；图8为柱性制备分离得到的N-月桂酰-L-丙氨酰-L-丙氨酸的在与图4相同的条件下测得的高效液相色谱图。根据图4-8可以看出，采用本合成方法所制得的N-月桂酰-L-丙氨酸自组装聚合物，其杂质中不含有月桂酸，纯度可以达到97％以上，其所含杂质主要为N-月桂酰-L-丙氨酰-L-丙氨酸，分析其在反应过程中，N-月桂酰-L-丙氨酸进一步和L-丙氨酸脱水，缩合而成。
4、质谱分析
通过Agilent 1200/6220液质联用仪进样，分析获得N-月桂酰-L-丙氨酸的质谱图20。N-月桂酰-L-丙氨酸的分子式是C 15H 29NO 3，其质谱特征峰理论值[M+H]+为272.222，实测值为272.2223，与理论值偏差为1.03ppm。[M+Na]+为294.204，实测值为294.2034，与理论值偏差为2.08ppm，样品实测值与分子式C 15H 29NO 3物质的质谱特征峰值相吻合。从图20上没有发现月桂酸的分子离子峰，由于质谱的灵敏度极高，因此可以通过质谱来定性的判断N-月桂酰-L-丙氨酸中不含有月桂酸。
5、旋光度分析
根据旋光仪测得N-月桂酰-L-丙氨酸的(比)旋光度：
Figure PCTCN2019089816-appb-000009
至-16.7°(C＝2，CH 3OH)
6、结构特征描述
图9为根据本发明的实例3中的合成方法得到的N-月桂酰-L-丙氨酸单体形成超分子氨基酸的结构形成图。根据上述红外、NMR、HPLC分析以及旋光度测定可知，采用本发明的工艺生产的N-月桂酰-L-丙氨酸自组装聚合物不含有杂质月桂酸，工艺中合成得到的N-月桂酰-L-丙氨酸可以形成两组氢键，N-月桂酰-L-丙氨酰-L-丙氨酸可以形成三组氢键，两个N-月桂酰-L-丙氨酸的羧基通过氢键连接，两端各有十一个碳链的烷烃结构，根据油油相溶原则，亲油端与亲油端链条式契合，首尾相连接，形成一个圆环，圆环与圆环之间又通过氢键及油 油相溶，无限叠加形成柱状分子簇，柱状分子簇又无限叠加形成特殊的空间结构—称为自组装超分子氨基酸聚合物。
图10a、10b和10c分别示出了根据本发明的实例3中的合成方法得到的N-月桂酰-L-丙氨酸自组装聚合物的300倍、1000倍以及2000倍电镜图。如图10a、10b和10c所示，本发明的N-月桂酰-L-丙氨酸自组装聚合物，其微观结构呈麻绳状并且缠绕在一起构成了“超分子氨基酸”。图9、10a、10b和10c更好的证明了N-月桂酰-L-丙氨酸单体形成超分子氨基酸的形成原理及结构。
在超分子氨基酸形成之后，超分子氨基酸进一步与氢氧化钠反应生成如图12所示的超分子氨基酸的钠盐结构。N-月桂酰-L-丙氨酸钠为基本单元，通过氢键自组装成为超分子聚合物，经检测，重均分子量为125841，如图13所示。根据图12所示，其钠盐结构一面亲水，一面亲油，分子间通过氢键相连接，得到一个特殊的二维网状规则排列结构，具有强的跟油污相结合的能力，可作为主表面活性剂使用。
此外，本申请还对市售的N-月桂酰-L-丙氨酸(购自长沙普济生物科技股份有限公司)进行了电镜扫描测定，其中，经测定该N-月桂酰-L-丙氨酸中含有0.21％-5％月桂酸，扫描结果示于图11a，11b，11c。图11a，11b，11c分别示出了市售的含有0.21％-5％月桂酸的N-月桂酰-L-丙氨酸的500倍、1000倍、2000倍电镜图，如图11a，11b，11c所示，市售的N-月桂酰-L-丙氨酸其电镜图呈现无规则的排列的结构状态，并且与根据本发明的工艺得到的N-月桂酰-L-丙氨酸的相应的300倍、1000倍、2000倍电镜图均不同，并没有出现本发明的N-月桂酰-L-丙氨酸的电镜图中的麻绳状或柱状结构。出现这种情况的原因是市售的N-月桂酰-L-丙氨酸含有月桂酸，而月桂酸的存在会破坏N-月桂酰-L-丙氨酸之间氢键的无限连接形成，从而改变了N-月桂酰-L-丙氨酸的结构和性能。
本本发明的工艺有效解决了杂质月桂酸的残留破坏N-月桂酰-L-丙氨酸结构，并进一步影响破坏N-月桂酰-L-丙氨酸性能的问题，使得N-月桂酰-L-丙氨酸之间易于形成氢键，无限连接，具有特殊性能。本工艺所产生的杂质N-月桂酰-L-丙氨酰-L-丙氨酸同N-月桂酰-L-丙氨酸一样也能形成氢键，这样就加强了结构的稳定性，并且同时不影响N-月桂酰-L-丙氨酸的性能。
在进一步实验中，本申请用N-葵酰-L-丙氨酸在相同条件下进行了结构研究， 未发现上述三维网状结构，可能是N-葵酰-L-丙氨酸的碳链长度短，两个分子的亲油端之间不能成环，同样，由此可以推测亲油基团的碳链在12-18之间，与L-丙氨酸形成的脂肪酰-L-丙氨酸，在除去脂肪酸的条件下，通过分子间的氢键及油油相溶，也可以形成上述空间结构。这个结构一旦形成很稳定，实验证明，再少量添加脂肪酸10％以下，不会破坏已有结构的稳定性和性能应用。
实施例3 N-月桂酰-L-丙氨酸自组装聚合物的应用
应用例1 N-月桂酰-L-丙氨酸自组装聚合物对细菌的抑制作用评价
取根据实例3的方法合成的N-月桂酰-L-丙氨酸自组装聚合物10g加入水中，加10％的氢氧化钠水溶液中和至pH＝6-7，配制成100mL的水溶液。取5mL原液，将此溶液分别浸泡预先接种了金黄色葡萄糖球菌、大肠杆菌、铜绿假单胞菌、白假丝酵母菌等常见的细菌于果盘上，作用一定时间，用清水冲洗一次，然后测定果盘上的细菌残留。检测结果如表1：
表1：N-月桂酰-L-丙氨酸自组装聚合物的抑菌作用分析
Figure PCTCN2019089816-appb-000010
Figure PCTCN2019089816-appb-000011
由以上数据可以看出，根据本发明方法合成的N-月桂酰-L-丙氨酸自组装聚合物溶液对大肠杆菌、金黄色葡萄球菌和白假丝酵母菌具有明显的抑制作用，在原液即N-月桂酰-L-丙氨酸自组装聚合物溶液作用于大肠杆菌2min后，其抑制率可达到96.3％，5min后抑制率已经可以达到100％；而原液作用于金黄色葡萄球菌2min后，就可达到100％的抑制率；作用于白假丝酵母菌5min抑制率也同样可以达到100％。
根据本领域公知常识可知，细菌大小通常在0.5-5μm，而本发明所用的不含月桂酸的N-月桂酰-L-丙氨酸形成的超分子结构的柱团与柱团之间的空隙也是微米级的，所以能够将细菌包裹去除，所以可以称为能够产生纳米级的泡沫微孔。
应用例2 N-月桂酰-L-丙氨酸自组装聚合物对农药的去除效果评价
取100g事先喷洒过农药甲胺磷和乙酰甲胺磷的绿叶蔬菜(大青菜)两份，一份直接用清水1L浸泡，然后取出检测其蔬菜叶子上的农药残留，称为清洗前。另一份使用根据实例3的方法合成的N-月桂酰-L-丙氨酸自组装聚合物配制的溶液来清洗，称为清洗后。操作如下描述：
取根据实例3的方法合成的N-月桂酰-L-丙氨酸自组装聚合物10g加入水中，加10％的氢氧化钠水溶液中和至pH＝6-7，配制成100mL的水溶液。取5mL原液，将另一份事先喷洒过农药甲胺磷和乙酰甲胺磷的绿叶蔬菜(大青菜)100g，剪碎，浸泡在上述溶液中2分钟，取出后用500mL清水冲洗，然后取出检测其 蔬菜叶子上的农药残留。表2示出了清洗前后的农药数据残留对比：
表2：N-月桂酰-L-丙氨酸自组装聚合物对农药的去除效果分析
序号 检验项目 清洗前mg/kg 清洗后mg/kg 去除率％
1 甲胺磷 16.06 5.68 64.63
2 乙酰甲胺磷 38.48 9.75 74.66
根据以上数据可以看出，本发明所使用的表面活性物质N-月桂酰-L-丙氨酸自组装聚合物溶液对甲胺磷和乙酰甲胺磷具有明显的去除作用，作用2min后，对甲胺磷的去除率可达到64.63％；对乙酰甲胺磷的去除率可达到74.66％，效果明显。
应用例3 N-月桂酰-L-丙氨酸自组装聚合物对异味的消除效果评价
取根据实例3的方法合成的N-月桂酰-L-丙氨酸自组装聚合物10g加入水中，加10％的氢氧化钠水溶液中和至pH＝6-7，配制成100mL的水溶液。取5mL原液，将含有异味的(气味、机油味、臭味等)棉布10平方厘米浸泡在上述溶液中2分钟后，取出，用水清洗，晾干，实验结果发现棉布上异味全部消失，由此可知，根据本发明的方法合成的N-月桂酰-L-丙氨酸自组装聚合物具有良好的异味消除效果。
基于以上可知，本发明的N-月桂酰-L-丙氨酸自组装聚合物的制备方法工艺步骤简单，反应条件温和，适于工业化生产。根据本发明的方法制备得到的N-月桂酰-L-丙氨酸自组装聚合物纯度高，基本在97％以上，且月桂酸含量介于0.0001％-0.02％之间，有效的避免了月桂酸对产品质量的影响。所得到的N-月桂酰-L-丙氨酸自组装聚合物结构性能稳定；具有良好的抑菌率，对大肠杆菌、金黄色葡萄球菌和白假丝酵母菌的抑制率均可达到100％；有效去除农药残留，对甲胺磷的去除率可达64.63％，对乙酰甲胺磷的去除率可达74.66％；同时具有良好的除异味性能，在日化领域、农业、医药行业均可以有很好的应用。
应用例4 N-月桂酰-L-丙氨酸自组装聚合物在皮肤护理上的应用
表3：皮肤护理组合物组成原料及重量百分比含量
Figure PCTCN2019089816-appb-000012
*天然油混合物包含有40％的葡萄籽油、37.2％的向日葵籽油和22.8％的芦荟油。
根据表3所示的配方1的具体制备步骤包括：将57％天然油混合物和40％玉米淀粉加入到混合器中并匀化以使颗粒首先分散。然后将油分散体中的颗粒加热至83-86℃同时混合。在加热的同时将3％月桂酰-L-丙氨酸加入到混合器中。样品加热并保持在73-86℃下保持5-10min。然后将其冷却至65-72℃之间的温度，同时保持可混合。然后将样品倒入体积为30ml的罐中即得皮肤护理组合物，保 存并用于评估。其中，配方2-6中的皮肤护理组合物制备方法均采用与配方1中一样的方法，在此不再赘述。
根据以上实施例得到的皮肤护理组合物，其中原料中添加了不同种类及含量的颗粒物。结果表明，颗粒物的加入除了增加了油的粘度之外，N-月桂酰-L-丙氨酸自组装聚合物也可用于将固体有机/无机颗粒或油混合液体如甘油稳定地悬浮在增稠的天然油中以获得额外的皮肤益处。
使用四种油不溶性颗粒，例如淀粉、TiO 2、云母、氮化硼颗粒(来自Kobo的Caress BN02)以及一种油可混合液体如甘油。配方1-6中所用天然油混合物组分均一样，即包含40％的葡萄籽油、37.2％的向日葵籽油和22.8％的芦荟油。结果显示，表3中所示的所有配方得到的组合物在室温下和48℃烘箱中都是稳定的，没有任何颗粒分离问题。而配方7中使用了月桂酰丙氨酸(含月桂酸2％以上)代替了配方1中的N-月桂酰-L-丙氨酸自组装聚合物，用以对比试验，结果发现所得到组合物在48℃烘箱中48小时后不稳定的，有冒油现象。
实施例4-8
实施例中氨基酸牙膏膏体的总重量份数均为100。牙膏中各物质组成以及具体含量如表4所示：
表4：牙膏中各物质组成及含量
Figure PCTCN2019089816-appb-000013
Figure PCTCN2019089816-appb-000014
实施例9-13
实施例中氨基酸牙膏膏体的总重量份数均为100。牙膏中各物质组成以及具体含量如表5所示：
表5：牙膏中各物质组成及含量
Figure PCTCN2019089816-appb-000015
Figure PCTCN2019089816-appb-000016
根据实施例4的配方制备牙膏，具体步骤包括：将10g水、37.5g山梨(糖)醇、0.2g糖精钠、2g聚乙二醇-400、5g甘油、0.4g苯甲酸钠制成水溶液置于制膏机中。然后将4g羧甲基纤维素、35g水合硅石、0.2g邹波角叉菜提取物、0.1g甘草提取物以及0.1g马齿苋提取物混合后加入制膏机，搅拌研磨20-30min直至膏体均匀为止，然后真空脱泡；将4.4gN-月桂酰-L-丙氨酸钠聚合物、1g食用香精(薄荷香型)、0.1g CI42090依次加入制膏机中，搅拌研磨10-15min至膏体均匀，然后脱泡，即得氨基酸牙膏。图14-16为根据实施例4的配方及其制备方法得到的氨基酸牙膏的成分检验报告，根据该报告可以看出，本发明提供的氨基酸牙膏安全，各项检测均符合标准。
实施例5-13均采用实施例4中所述方法制备，在实施例中就不再具体赘述。
根据实施例4-13中的配方量制得的氨基酸牙膏，取不同重量份数的氨基酸表面活性剂，重复进行多次配方试验，分别委托100名经常牙痛和牙龈出血的志愿者进行效果评价，使用频率为每日早、晚各一次，用量约1g膏体/每次，每次刷牙时间约5min。得到的结果表明含有氨基酸表面活性成分的牙膏具有明显的镇痛、消炎和防止牙龈出血的功效，并且从使用口感和去味两方面评价，氨基酸表面活性成分占该牙膏膏体的重量比为0.1-25％比较适宜，优化为0.5-10％，最佳优化为1-5％。当氨基酸表面活性成分占该药物牙膏膏体的重量比为1-5％时，牙膏的药效与口感处于最佳平衡，而且去除口腔异味达到最佳水平，同时刷牙后立马吃水果不影响食用水果时的味道，不会觉得苦和干涩。图17和图18分别示出了根据本发明实施例4得到的氨基酸牙膏对患者牙齿的清洁效果前后对比。从图中可以看出，在使用本发明的氨基酸牙膏按照正常刷牙时间3min刷牙后，患者的牙齿明显比使用前要洁白干净。
应用例5超分子氨基酸在洗衣液中应用实例
表6超分子氨基酸洗衣液
Figure PCTCN2019089816-appb-000017
按照配方1所配成的洗衣液，经苏州市产品质量监督检验所检测，去污力大于等于标准洗衣液去污力，所得样品对JB01、JB02、JB03污布去污力大于标准洗衣液对JB01、JB02、JB03污布去污力。而按照配方2所配成的洗衣液，经苏州市产品质量监督检验所检测，去污力小于标准洗衣液去污力(图19)。
应用例6超分子氨基酸与碱性氨基酸成盐在洗面奶中应用实例
表6超分子氨基酸洗面奶
Figure PCTCN2019089816-appb-000018
Figure PCTCN2019089816-appb-000019
N-月桂酸-L-丙氨酸自组装聚合物同碱性氨基酸，例如精氨酸，在水相体系形成的有机盐作为清洁的表面活性剂更加温和，无刺激性，对于敏感肌肤更加适用。在洗净肌肤的同时，更加呵护肌肤。
应用例7自组装超分子聚合物和N-月桂酰-L-丙氨酰-L-丙氨酸形成的自 组装聚合物在洗衣液中应用实例
表7超分子氨基酸洗衣液
Figure PCTCN2019089816-appb-000020
N-月桂酸-L-丙氨酸自组装聚合物和N-月桂酰-L-丙氨酰-L-丙氨酸自组装聚合物在碱性条件下形成的盐，作为清洁的表面活性剂，表现更加温和，不伤手，同时去污能力更强。
此外，本领域的技术人员能够理解，尽管在此所述的一些实施例包括其它实施例中所包括的某些特征而不是其它特征，但是不同实施例的特征的组合意味着处于本发明的范围之内并且形成不同的实施例。例如，在下面的权利要求书中，所要求保护的实施例的任意之一都可以以任意的组合方式来使用。

Claims (50)

  1. 一种氨基酸自组装超分子聚合物或其盐，所述聚合物是N-月桂酰-L-丙氨酸单体之间通过氢键连接形成；所述聚合物基本不含或不含月桂酸。
  2. 如权利要求1所述的氨基酸自组装超分子聚合物或其盐，其特征在于，所述N-月桂酰-L-丙氨酸单体之间通过氢键连接形成如式(Ⅰ)所示的结构：
    Figure PCTCN2019089816-appb-100001
  3. 如权利要求1所述的氨基酸自组装超分子聚合物或其盐，其特征在于，所述聚合物的重均分子量介于2000-500万之间。
  4. 如权利要求1所述的氨基酸自组装超分子聚合物或其盐，其特征在于，所述聚合物的盐在水中的溶解度不超过15克/100ml；所述聚合物的熔点为82-84℃。
  5. 如权利要求1-4任一项所述的氨基酸自组装超分子聚合物或其盐，其特征在于，所述盐为聚合物与碱形成；所述碱包括无机碱和有机碱。
  6. 一种如权利要求1-5任一项所述的氨基酸自组装超分子聚合物的制备方法，其特征在于，所述方法包括步骤：
    使N-月桂酰-L-丙氨酸粗品、溶剂、L-丙氨酸和催化剂混合、搅拌后得到如权利要求1-5任一项所述的氨基酸自组装超分子聚合物。
  7. 如权利要求6所述的方法，其特征在于，所述N-月桂酰-L-丙氨酸粗品通过如下步骤制备得到：
    (1)将L-丙氨酸与金属无机碱溶于蒸馏水和有机溶剂的混合溶液中搅拌均匀得到L-丙氨酸盐溶液；
    (2)向上述得到的L-丙氨酸盐溶液依次加入月桂酰氯和金属无机碱，继续 搅拌得到糊状的N-月桂酰-L-丙氨酸盐；
    (3)将上述得到的糊状的N-月桂酰-L-丙氨酸盐酸化，逐渐析出白色固体，然后在冰浴下放置，过滤，得到N-月桂酰-L-丙氨酸粗品。
  8. 如权利要求7所述的方法，其特征在于，步骤(1)中所述L-丙氨酸与金属无机碱的摩尔比为1:(1-1.5)；所述金属无机碱选自氢氧化钠、氢氧化钾、碳酸钠、碳酸钾中的一种或两种以上；所述有机溶剂选自丙酮、甲醇、乙醇、乙腈、四氢呋喃中的一种或两种以上。
  9. 如权利要求7所述的方法，其特征在于，步骤(2)中所述月桂酰氯与L-丙氨酸的投料摩尔比为(0.8-1):1；所述搅拌条件为：温度5-50℃，时间0.5-3.5小时；所述金属无机碱浓度为30-80％；所述金属无机碱选自氢氧化钠、氢氧化钾、碳酸钠、碳酸钾中的一种或两种以上。
  10. 如权利要求6所述的方法，其特征在于，所述溶剂选自丙酮、甲醇、乙醇、乙腈、四氢呋喃或上述溶剂与水制成的混合溶剂；所述催化剂选自硫酸、对甲苯磺酸、乳化剂中的一种或两种以上；所述N-月桂酰-L-丙氨酸粗品、溶剂、L-丙氨酸、催化剂的混合摩尔比为1:(5-10):(0.2-1.1):(0.001-0.2)；所述搅拌条件为：温度25℃-100℃，压力5kg-50kg，时间1-3小时。
  11. 一种氨基酸自组装超分子聚合物或其盐，所述聚合物通过如权利要求6-10任一项所述的方法制备得到。
  12. 一种氨基酸自组装超分子聚合物钠盐，其特征在于，是N-月桂酰-L-丙氨酸钠单体之间通过氢键连接形成；所述聚合物钠盐基本不含或不含月桂酸。
  13. 如权利要求12所述的氨基酸自组装超分子聚合物钠盐，其特征在于，所述N-月桂酰-L-丙氨酸钠单体之间通过氢键连接形成如式(Ⅱ)所示的结构：
    Figure PCTCN2019089816-appb-100002
    Figure PCTCN2019089816-appb-100003
    其中，n为10-3000；n个N-月桂酰-L-丙氨酸钠在同一平面通过氢键依次连接，或n个N-月桂酰-L-丙氨酸钠通过氢键依次连接且首尾通过氢键连接以形成一柱状。
  14. 如权利要求12所述的氨基酸自组装超分子聚合物钠盐，其特征在于，氨基酸自组装超分子聚合物钠盐的重均分子量介于2800-77万之间。
  15. 如权利要求12所述的氨基酸自组装超分子聚合物钠盐，其特征在于，所述聚合物钠盐在水中的溶解度不超过15克/100ml。
  16. 一种如权利要求1-5、11中任一项所述的氨基酸自组装超分子聚合物或其盐的用途，其特征在于，用作表面活性剂。
  17. 一种如权利要求12-15任一项所述的氨基酸自组装超分子聚合物钠盐的用途，其特征在于，用作表面活性剂。
  18. 如权利要求16或17所述的用途，其特征在于，所述表面活性剂用于日化领域、农业、医药行业。
  19. 一种组合物，其特征在于，所述组合物中含有如权利要求1-5、11中任一项所述的氨基酸自组装超分子聚合物或其盐，和N-月桂酰-L-丙氨酰-L-丙氨酸单体之间通过氢键连接形成的聚合物或其盐，以组合物的总重量计，其中N-月桂酰-L-丙氨酰-L-丙氨酸单体之间通过氢键连接形成的聚合物或其盐的重量百分含量介于0-40％之间。
  20. 一种氨基酸牙膏，包含摩擦剂、保湿剂、增稠剂和表面活性剂，所述表面活性剂选自N-月桂酰-L-丙氨酸或其盐、如权利要求1-5、11中任一项所述的氨基酸自组装超分子聚合物或其盐、或如权利要求12-15任一项所述的氨基酸自组装超分子聚合物钠盐；以牙膏的总重量计，其中含有表面活性剂0.1-25w/w％，摩擦剂10-50w/w％，保湿剂5-40w/w％，增稠剂0.1-6w/w％。
  21. 如权利要求20所述的氨基酸牙膏，其中所述的摩擦剂选自水合硅石、碳酸钙以及磷酸氢钙中的一种或几种的混合。
  22. 如权利要求20所述的氨基酸牙膏，其中所述的保湿剂选自山梨(糖)醇、聚乙二醇-400、甘油以及丙二醇中的一种或几种的混合。
  23. 如权利要求20所述的氨基酸牙膏，其中所述的增稠剂选自羧甲基纤维素、黄原胶、卡拉胶、卡姆胶、泊洛沙姆407以及硅酸铝镁中的一种或几种的混合。
  24. 如权利要求20-23任一项所述的氨基酸牙膏，所述氨基酸牙膏还包含如下重量百分比的物质：甜味剂0.1-0.3％，香精0.5-1.5％，水5-10％，中草药提取物0.3-0.5％，防腐剂0.3-0.5％，着色剂0.05-0.15％。
  25. 如权利要求24所述的氨基酸牙膏，其中所述的甜味剂选自糖精钠、木糖醇以及赤藓糖醇中的一种或几种的混合。
  26. 如权利要求24所述的氨基酸牙膏，其中所述的中草药提取物选自邹波角叉菜提取物、甘草提取物以及马齿苋提取物中的一种或几种的混合。
  27. 如权利要求24所述的氨基酸牙膏，其中所述的防腐剂选自苯甲酸钠、羟苯甲酯、三氯羟苯醚/共聚体以及生物溶菌酶中的一种或几种的混合。
  28. 如权利要求19所述的氨基酸牙膏，其中所述的着色剂选自CI77019、CI77891、CI42090、云母、二氧化钛、亮蓝中的一种或几种的混合。
  29. 如权利要求20所述的氨基酸牙膏，其中所述的氨基酸牙膏中不含十二烷基硫酸钠。
  30. 一种制备权利要求20-29任一项所述的氨基酸牙膏的方法，所述方法包括以下步骤：
    (1)将水、甜味剂、防腐剂、保湿剂制成水溶液置于制膏机中；
    (2)将增稠剂、摩擦剂、中草药提取物混合后加入制膏机，搅拌研磨直至膏体均匀为止，然后真空脱泡；
    (3)将表面活性剂、香精、着色剂依次加入制膏机中，搅拌研磨至膏体均 匀，然后脱泡，即得氨基酸牙膏；所述表面活性剂选自N-月桂酰-L-丙氨酸或其盐、如权利要求1-5、11中任一项所述的氨基酸自组装超分子聚合物或其盐、或如权利要求12-15任一项所述的氨基酸自组装超分子聚合物钠盐。
  31. 一种皮肤护理组合物，以相对于其总重量计，所述的组合物包含：
    油类                   50-95重量％；
    表面活性剂             0.5-30重量％
    悬浮颗粒               0-45重量％
    所述表面活性剂选自N-月桂酰-L-丙氨酸或其盐、如权利要求1-5、11中任一项所述的氨基酸自组装超分子聚合物或其盐、或如权利要求12-15任一项所述的氨基酸自组装超分子聚合物钠盐。
  32. 如权利要求31所述的皮肤护理组合物，其中所述油类选自凝固点在-50℃-6℃之间的天然油、合成油或其混合物。
  33. 如权利要求31所述的皮肤护理组合物，其中所述天然油包括植物油和动物油。
  34. 如权利要求31所述的皮肤护理组合物，其中所述植物油包括葡萄籽油、向日葵籽油、霍霍巴油、芦荟油、橄榄油、亚麻籽油、红花籽油、大豆油、杏仁油、茶油或其任意混合物。
  35. 如权利要求31所述的皮肤护理组合物，其中所述动物油包括马油和绵羊油。
  36. 如权利要求31所述的皮肤护理组合物，其中所述合成油包括新癸酸异癸酯和新戊二醇二庚酸酯。
  37. 如权利要求31所述的皮肤护理组合物，其中所述油类的含量为65重量％。
  38. 如权利要求31所述的皮肤护理组合物，其中所述油类的含量为85重量％。
  39. 如权利要求31所述的皮肤护理组合物，其中所述悬浮颗粒的粒度小于30μm。
  40. 如权利要求31所述的皮肤护理组合物，其中所述悬浮颗粒的粒度小于15μm。
  41. 如权利要求31所述的皮肤护理组合物，其中所述悬浮颗粒的粒度小于5μm。
  42. 如权利要求31所述的皮肤护理组合物，其中所述悬浮颗粒选自油不溶性的固体颗粒或油不混溶液体。
  43. 如权利要求31所述的皮肤护理组合物，其中所述油不溶性的固体颗粒包括云母、淀粉、氧化锌、二氧化钛、滑石粉和有机硅弹性体。
  44. 如权利要求31所述的皮肤护理组合物，其中所述油不混溶液体包括甘油、水和多元醇。
  45. 制备权利要求31-44中任一项权利要求所述的皮肤护理组合物的方法，该方法包括以下步骤：
    (1)将油类、表面活性剂和悬浮颗粒按照重量百分比为(50-95％)：(0.5-30％)：(0-45％)的量混合后在82-87℃下搅拌反应，待表面活性剂全部溶于所述油类后将混合物搅拌冷却至65-72℃；所述表面活性剂选自N-月桂酰-L-丙氨酸或其盐、如权利要求1-5、11中任一项所述的氨基酸自组装超分子聚合物或其盐、或如权利要求12-15任一项所述的氨基酸自组装超分子聚合物钠盐；
    (2)将上述得到的混合物冷却至室温，即得皮肤护理组合物。
  46. 一种氨基酸洗衣液，包含表面活性剂、柔软剂、螯合剂、去离子水、防腐剂和香精，所述氨基酸洗衣液中各物质重量百分比为：
    Figure PCTCN2019089816-appb-100004
    所述表面活性剂选自N-月桂酰-L-丙氨酸或其盐、如权利要求1-5、11中任一项所述的氨基酸自组装超分子聚合物或其盐、或如权利要求12-15任一项所述的氨基酸自组装超分子聚合物钠盐。
  47. 一种氨基酸香皂，包含表面活性剂、脂肪酸、甘油、柔软剂、螯合剂、填充剂和去离子水，所述氨基酸香皂中各物质重量百分比为：
    Figure PCTCN2019089816-appb-100005
    Figure PCTCN2019089816-appb-100006
    所述表面活性剂选自N-月桂酰-L-丙氨酸或其盐、如权利要求1-5、11中任一项所述的氨基酸自组装超分子聚合物或其盐、或如权利要求12-15任一项所述的氨基酸自组装超分子聚合物钠盐。
  48. 一种氨基酸洗衣粉，包含表面活性剂、摩擦剂，所述氨基酸洗衣粉中各物质重量百分比为：
    表面活性剂                10-50％，
    摩擦剂                    50-90％，
    所述表面活性剂选自N-月桂酰-L-丙氨酸或其盐、如权利要求1-5、11中任一项所述的氨基酸自组装超分子聚合物或其盐、或如权利要求12-15任一项所述的氨基酸自组装超分子聚合物钠盐。
  49. 一种氨基酸洗洁精，包含表面活性剂、去离子水、增稠剂、甘油、防腐剂和香精，所述氨基酸洗洁精中各物质重量百分比为：
    Figure PCTCN2019089816-appb-100007
    所述表面活性剂选自N-月桂酰-L-丙氨酸或其盐、如权利要求1-5、11中任一项所述的氨基酸自组装超分子聚合物或其盐、或如权利要求12-15任一项所述的氨基酸自组装超分子聚合物钠盐。
  50. 一种氨基酸面膜，包含表面活性剂、去离子水、甘油、防腐剂和香精，所述氨基酸面膜中各物质重量百分比为：
    Figure PCTCN2019089816-appb-100008
    所述表面活性剂选自N-月桂酰-L-丙氨酸或其盐、如权利要求1-5、11中任一项所述的氨基酸自组装超分子聚合物或其盐、或如权利要求12-15任一项所述的氨基酸自组装超分子聚合物钠盐。
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