Functional degradable waterborne polyurethane and preparation method and application thereof

Abstract

The application discloses a kind of functional degradable waterborne polyurethane and its preparation method and application, belong to organic synthesis technical field.The technical problem to be solved is to improve the stability, film-forming property and degradability of waterborne polyurethane.The technical solution points are as follows: a kind of preparation method of functional degradable waterborne polyurethane, comprising the following steps: using dibasic acid as catalyst, epoxy soybean oil and ethylene glycol are reacted to obtain soybean oil-based polyol;Soybean oil-based polyol, polycaprolactone diol and beta-cyclodextrin are mixed, isophorone diisocyanate is added and stirred, 2,2-dimethylol butyric acid and dibutyltin dilaurate are added and stirred, 1,4-butanediol and dimethylacetamide are added and reacted, finally, triethylamine and gamma-aminopropyl triethoxysilane are added and reacted, emulsified with water, dialysis, and obtained.

Description

Technical Field

[0001] This invention belongs to the field of organic synthesis technology, specifically relating to a functionalized biodegradable waterborne polyurethane, its preparation method, and its application. Background Technology

[0002] Film-forming agents, as key functional ingredients in setting sprays, directly determine the adhesion, staying power, and skin feel of makeup. Traditional petroleum-based film-forming agents (such as PVP and acrylate copolymers) generally suffer from poor water resistance, insufficient adhesion, and a tight feeling on the skin, making it difficult to meet the growing market demand for "green beauty" and "skincare-inspired makeup." Therefore, synthesizing a sustainable cosmetic ingredient that combines superior performance with environmental friendliness has become a development trend.

[0003] Waterborne polyurethane (WPU), using water as the primary dispersion medium, boasts advantages such as tunable structure, excellent film-forming properties, and good biocompatibility, making it widely used in coatings, biomedicine, and cosmetics. Due to the designability of the WPU molecular structure, active ingredients with skin-care properties can be introduced into the molecular chain through chemical bonding or physical inclusion, giving it both skin-care and cosmetic functions. Traditionally, the raw materials for WPU are mainly derived from non-renewable petroleum resources. With the deepening of sustainable development strategies, the development of high-performance bio-based WPUs utilizing renewable biomass resources, especially abundant and inexpensive vegetable oils, has become a research hotspot in both academia and industry.

[0004] Soybean oil, as one of the world's largest-produced vegetable oils, is considered an ideal alternative to petroleum-based polyols due to its wide availability, low price, highly modifiable molecular structure, and inherent long-chain fatty acid structure. The main component of soybean oil is triglycerides, whose molecular structure contains unsaturated double bonds and ester groups. Hydroxyl groups can be introduced through chemical reactions such as epoxidation, ring-opening, hydroxylation, and amidation to prepare soybean oil-based polyols, which can then replace some or all of the petroleum-based polyols in the synthesis of polyurethanes.

[0005] Cyclodextrin (CD) is a cyclic oligosaccharide with a unique cavity structure of "hydrophilic on the outside and hydrophobic on the inside." It can not only participate in polyurethane synthesis as a polyhydroxy component, but also load poorly soluble active ingredients through host-guest inclusion interactions, providing a new dimension for the functional design of waterborne polyurethanes. Resveratrol (RES) is widely used in the cosmetics industry due to its outstanding antioxidant and anti-aging effects, but its poor water solubility and low photostability severely limit its application in water-based setting products. Addressing the bottleneck of the natural antioxidant resveratrol's poor water solubility and easy oxidation and inactivation, the use of cyclodextrin-modified waterborne polyurethane to construct a loading system holds promise for solving its stability problem in water-based formulations. Summary of the Invention

[0006] The purpose of this invention is to provide:

[0007] A method for preparing functionalized biodegradable waterborne polyurethane, and related technologies, to solve technical problems such as improving the stability, film-forming properties, and degradability of waterborne polyurethane, or combinations thereof.

[0008] Terminology Explanation:

[0009] Unless otherwise defined, all technical terms in this invention have the same meanings as commonly understood by one of ordinary skill in the art to which the subject matter pertains. Unless otherwise stated, all patents, patent inventions, and disclosures referenced in this invention are incorporated herein by reference in their entirety. If multiple definitions exist for terms in this invention, the definitions in this chapter shall prevail.

[0010] It should be understood that the above brief description and the following detailed description are exemplary and for illustrative purposes only, and do not limit the subject matter of the invention in any way. In this invention, the singular is used in conjunction with the plural unless otherwise specifically stated. It should also be noted that, unless otherwise stated, the use of “or” or “or” means “and / or”. Furthermore, the use of the term “comprising” and other forms such as “including,” “containing,” and “contains” are not limiting.

[0011] The definition of the standard chemical term can be found in the reference "Functional Polymer Materials", Luo Xianglin, Chemical Industry Press, 2010.

[0012] Unless otherwise stated, conventional methods within the scope of the art, such as contact angle and mechanical property testing, shall be used.

[0013] Unless specifically defined, the use of various commercially available products in this invention employs standard techniques. For example, it may be carried out using the manufacturer's instructions for use with the reagent kit, or in accordance with methods known in the art or the description of this invention. The techniques and methods described herein can generally be implemented according to conventional methods well known in the art, based on the descriptions in the various summary and more specific documents cited and discussed in this specification.

[0014] In a first aspect, the present invention provides:

[0015] A method for preparing functionalized biodegradable waterborne polyurethane includes the following steps:

[0016] (1) Using diacid as a catalyst, epoxidized soybean oil and ethylene glycol are reacted to obtain soybean oil-based polyol;

[0017] (2) Mix soybean oil-based polyol, polycaprolactone diol and β-cyclodextrin, add isophorone diisocyanate and stir, then add 2,2-dimethylolbutyric acid and dibutyltin dilaurate and continue stirring, then add 1,4-butanediol and react, then add dimethylacetamide, and finally add triethanolamine and γ-aminopropyltriethoxysilane and react, emulsify with water, and dialyze to obtain the product;

[0018] The dicarboxylic acid mentioned in step (1) is: malic acid, tartaric acid, glutaric acid or succinic acid.

[0019] Includes: the amount of dicarboxylic acid used; the molar ratio of epoxidized soybean oil and ethylene glycol; the reaction conditions described in step (1); the reactant ratio, etc.

[0020] The amount of dicarboxylic acid used in step (1) is 0.5-1% of the mass of epoxidized soybean oil.

[0021] The preferred amount of the dicarboxylic acid is 0.5%, 0.6%, 0.7%, 0.8% or 1% of the mass of the epoxidized soybean oil.

[0022] The preferred amount of the dicarboxylic acid is 0.5-0.7% of the mass of the epoxidized soybean oil.

[0023] The amount of the dicarboxylic acid used is more preferably 0.5%, 0.6% or 0.7% of the mass of the epoxidized soybean oil.

[0024] The molar ratio of epoxidized soybean oil and ethylene glycol in step (1) is 0.8-1.2:1.

[0025] The preferred molar ratio of epoxidized soybean oil to ethylene glycol is 0.8:1, 0.9:1, 1:1, or 1.2:1.

[0026] The molar ratio of the epoxidized soybean oil to ethylene glycol is further preferably 1:1 to 1.2:1.

[0027] The molar ratio of the epoxidized soybean oil to ethylene glycol is further preferably 1:1 or 1.2:1.

[0028] The reaction in step (1) is carried out in a nitrogen atmosphere at a speed of 200-400 rpm, at a temperature of 120-150℃, and for a time of 3-5 h.

[0029] The preferred temperature for the reaction is 120°C, 130°C, 140°C or 150°C, and the preferred reaction time is 3h, 3.5h, 4h, 4.5h or 5h.

[0030] The reaction temperature is further preferably 130-140℃, and the reaction time is further preferably 3-4 h.

[0031] The mass-to-volume ratio of polycaprolactone diol, β-cyclodextrin, soybean oil-based polyol, isophorone diisocyanate, 2,2-dimethylolbutyric acid, dibutyltin dilaurate, 1,4-butanediol, dimethylacetamide, triethylamine, and γ-aminopropyltriethoxysilane in step (2) is 2.5-2.7 g:0.05-0.09 g:0.14-0.18 g:2.1-2.15 g:0.2-0.3 g:0.02 g:0.25-0.3 g:5 mL:0.2-0.27 g:0.1-0.12 g.

[0032] The mixing temperature in step (2) is 70-90℃.

[0033] The mixing temperature is preferably 70°C, 75°C, 80°C, 85°C, or 90°C.

[0034] The mixing temperature is further preferably 75-85℃.

[0035] In step (2), the stirring speed after adding isophorone diisocyanate is 200-400 rpm, and the stirring time after adding isophorone diisocyanate is 1-2 h.

[0036] The preferred stirring speed after adding isophorone diisocyanate is 200 rpm, 300 rpm, or 400 rpm, and the preferred stirring time after adding isophorone diisocyanate is 1 h, 1.5 h, or 2 h.

[0037] The stirring speed after adding isophorone diisocyanate is preferably 200-300 rpm, and the stirring time after adding isophorone diisocyanate is preferably 1-1.5 h.

[0038] The stirring speed in step (2) is 200-400 rpm, and the stirring time is 2-3 h.

[0039] The preferred stirring speed is 200 rpm, 300 rpm, or 400 rpm, and the preferred stirring time is 2 h, 2.5 h, or 3 h.

[0040] The stirring speed is further preferably 200-300 rpm, and the stirring time is further preferably 2-2.5 h.

[0041] The reaction temperature for adding 1,4-butanediol in step (2) is 75-85℃, and the reaction time for adding 1,4-butanediol is 1.5-2.5 h.

[0042] The preferred temperature for the reaction of adding 1,4-butanediol is 75°C, 80°C, or 85°C, and the preferred reaction time for adding 1,4-butanediol is 1.5 h, 2 h, or 2.5 h.

[0043] In step (2), the reaction temperature for adding triethylamine and γ-aminopropyltriethoxysilane is 35-45℃, and the reaction time for adding triethylamine and γ-aminopropyltriethoxysilane is 1-2 h.

[0044] The preferred temperature for the reaction of adding triethylamine and γ-aminopropyltriethoxysilane is 35°C, 40°C, or 45°C, and the preferred reaction time is 1 h, 1.5 h, or 2 h.

[0045] Based on further solutions to the technical problems of the present invention, or simultaneous solutions to multiple technical problems, the preferred solution in the technical solution provided in the first aspect of the present invention includes:

[0046] The first preferred solution is that the amount of dicarboxylic acid used in step (1) is 0.5-1% of the mass of epoxidized soybean oil. This technical solution not only solves the technical problem of "poor stability, film-forming properties and degradation of waterborne polyurethane", but also further solves the technical problem of "improving the makeup holding effect and antioxidant properties of cosmetic film-forming agents".

[0047] The second preferred embodiment: In step (1), the molar ratio of epoxidized soybean oil to ethylene glycol is 0.8-1.2:1; the reaction is carried out under a nitrogen atmosphere at a speed of 200-400 rpm; the reaction temperature is 120-150℃, and the reaction time is 3-5 h. This technical solution, while addressing the technical problem of "poor stability, film-forming properties, and degradability of waterborne polyurethane," further solves the technical problem of "improving the makeup-holding effect and antioxidant properties of cosmetic film-forming agents," etc.

[0048] The third preferred embodiment: The mass-to-volume ratio of polycaprolactone diol, β-cyclodextrin, soybean oil-based polyol, isophorone diisocyanate, 2,2-dimethylolbutyric acid, dibutyltin dilaurate, 1,4-butanediol, dimethylacetamide, triethylamine, and γ-aminopropyltriethoxysilane in step (2) is 2.5-2.7 g:0.05-0.09 g:0.14-0.18 g:2.1-2.15 g:0.2-0.3 g:0.02 g:0.25-0.3 g:5 mL:0.2-0.27 g:0.1-0.12 g. This technical solution, based on solving the technical problem of "poor stability, film-forming properties, and degradability of waterborne polyurethane," further solves the technical problem of "improving the makeup-holding effect and antioxidant properties of cosmetic film-forming agents," etc.

[0049] The fourth preferred embodiment: In step (2), the mixing temperature is 70-90℃; the stirring speed after adding isophorone diisocyanate is 200-400 rpm, and the stirring time after adding isophorone diisocyanate is 1-2 h; the stirring speed for continued stirring is 200-400 rpm, and the stirring time for continued stirring is 2-3 h. This technical solution, based on solving the technical problem of "poor stability, film-forming properties and degradation of waterborne polyurethane", further solves the technical problem of "improving the makeup-holding effect and antioxidant properties of cosmetic film-forming agents", etc.

[0050] The fifth preferred embodiment: In step (2), the temperature for adding 1,4-butanediol for the reaction is 75-85℃, and the reaction time is 1.5-2.5 h. This technical solution, based on solving the technical problem of "poor stability, film-forming properties and degradation of waterborne polyurethane", further solves the technical problem of "improving the makeup-holding effect and antioxidant properties of cosmetic film-forming agents".

[0051] The sixth preferred embodiment: In step (2), the reaction temperature for adding triethylamine and γ-aminopropyltriethoxysilane is 35-45℃, and the reaction time for adding triethylamine and γ-aminopropyltriethoxysilane is 1-2 h. This technical solution, while addressing the technical problem of "poor stability, film-forming properties, and degradability of waterborne polyurethane," further solves the technical problem of "improving the makeup-holding effect and antioxidant properties of cosmetic film-forming agents," etc.

[0052] Examples 1-8 of the present invention at least support the protection scope of "the amount of dicarboxylic acid used in step (1) is 0.5-1% of the mass of epoxidized soybean oil".

[0053] The "amount of diacid" is derived from the aforementioned explanation and / or the corresponding technical features in Examples 1-8, such as the amount of malic acid being 0.5% of the mass of epoxidized soybean oil and the amount of malic acid being 1% of the mass of epoxidized soybean oil, through the common feature "amount of diacid". Therefore, those skilled in the art can reasonably infer that the technical feature "amount of diacid", the subordinate concept of "amount of diacid", the technical means that are basically equivalent to "amount of diacid", and the technical means that can replace "amount of diacid" based on the existing technical level within the scope of conventional technical means and common knowledge should all fall within the protection scope of the above-mentioned technical solution. For example, if other technical features remain unchanged, replacing "amount of diacid" with 0.7% or 0.8% of the mass of epoxidized soybean oil still falls within the protection scope of the above-mentioned technical solution.

[0054] Examples 1-8 of this invention at least support the protection range of "in step (1), the molar ratio of epoxidized soybean oil and ethylene glycol is 0.8-1.2:1; the reaction is carried out in a nitrogen atmosphere at a speed of 200-400 rpm; the reaction temperature is 120-150℃ and the reaction time is 3-5 h".

[0055] The "molar ratio of epoxidized soybean oil to ethylene glycol" is summarized from the common feature "molar ratio of epoxidized soybean oil to ethylene glycol" in the foregoing explanation and / or the corresponding technical features in Examples 1-8, such as the theoretical molar ratio of epoxidized soybean oil to ethylene glycol being 1:1; the theoretical molar ratio of epoxidized soybean oil to ethylene glycol being 1.2:1; and the theoretical molar ratio of epoxidized soybean oil to ethylene glycol being 0.8:1. Therefore, based on reasonable presumption, those skilled in the art can determine that the technical feature "molar ratio of epoxidized soybean oil to ethylene glycol," the subordinate concept of "molar ratio of epoxidized soybean oil to ethylene glycol," the technical means that are essentially equivalent to "molar ratio of epoxidized soybean oil to ethylene glycol," and the technical means that can replace "molar ratio of epoxidized soybean oil to ethylene glycol" within the scope of conventional technical means and common knowledge based on the existing technical level should all fall within the protection scope of the above-mentioned technical solution. For example, if other technical features remain unchanged, replacing "molar ratio of epoxidized soybean oil to ethylene glycol" with 0.9:1, 1.1:1, etc., still falls within the protection scope of the above-mentioned technical solution.

[0056] Examples 1-8 of this invention at least support the protection scope of "the mass-to-volume ratio of polycaprolactone diol, β-cyclodextrin, soybean oil-based polyol, isophorone diisocyanate, 2,2-dimethylolbutyric acid, dibutyltin dilaurate, 1,4-butanediol, dimethylacetamide, triethylamine and γ-aminopropyltriethoxysilane in step (2) is 2.5-2.7 g:0.05-0.09 g:0.14-0.18 g:2.1-2.15 g:0.2-0.3 g:0.02 g:0.25-0.3 g:5 mL:0.2-0.27 g:0.1-0.12 g".

[0057] The mass-to-volume ratio of polycaprolactone diol, β-cyclodextrin, soybean oil-based polyol, isophorone diisocyanate, 2,2-dimethylolbutyric acid, dibutyltin dilaurate, 1,4-butanediol, dimethylacetamide, triethylamine, and γ-aminopropyltriethoxysilane, as explained above and / or according to the corresponding technical features in Examples 1-8, is as follows: 2.64 g of vacuum-dehydrated polycaprolactone diol, 0.05 g of β-cyclodextrin, and 0.144 g of soybean oil-based polyol ESO-M (accounting for 20% of the total molar amount of hydroxyl groups in the PCL soft segment) are added to a three-necked flask equipped with a stir bar and a condenser. After heating to 80°C, 2.15 g of isophorone diisocyanate is added. After stirring at 300 rpm for 1 h, 0.25 g of the hydrophilic chain extender 2,2-dimethylolbutyric acid and 0.02 g of the catalyst dibutyltin dilaurate are added, and the mixture is stirred at a constant speed for 2 h. After adding 0.3 g of chain extender 1,4-butanediol and continuing the reaction for 2 h, 5 mL of dimethylacetamide was added. After cooling to 40 °C, 0.27 g of triethylamine and 0.12 g of γ-aminopropyltriethoxysilane were added at 100% neutralization and the reaction was allowed to proceed for 1.5 h. 2.5 g of vacuum-dehydrated polycaprolactone diol, 0.09 g of β-cyclodextrin, and 0.14 g of soybean oil-based polyol ESO-M (accounting for 20% of the total molar amount of hydroxyl groups in the PCL soft segment) were added to a three-necked flask equipped with a stir bar and a condenser. After heating to 85 °C, 2.1 g of isophorone diisocyanate was added, and the mixture was stirred at 400 rpm for 1 h. Then, 0.2 g of hydrophilic chain extender 2,2-dimethylolbutyric acid and 0.02 g of catalyst dibutyltin dilaurate were added, and the mixture was stirred at a constant speed for 2 h. After adding 0.25 g of chain extender 1,4-butanediol and continuing the reaction for 2 h, 5 mL of dimethylacetamide was added. After cooling to 45℃, 0.2 g of triethylamine and 0.12 g of γ-aminopropyltriethoxysilane were added at 100% neutralization and reacted for 2 h. The reaction was then summarized by the common characteristic of "mass-volume ratio of polycaprolactone diol, β-cyclodextrin, soybean oil-based polyol, isophorone diisocyanate, 2,2-dimethylolbutyric acid, dibutyltin dilaurate, 1,4-butanediol, dimethylacetamide, triethylamine, and γ-aminopropyltriethoxysilane".Therefore, by reasonable presumption, those skilled in the art can recognize the subordinate concepts of the technical features “mass-volume ratio of polycaprolactone diol, β-cyclodextrin, soybean oil-based polyol, isophorone diisocyanate, 2,2-dimethylolbutyric acid, dibutyltin dilaurate, 1,4-butanediol, dimethylacetamide, triethylamine and γ-aminopropyltriethoxysilane”, “mass-volume ratio of polycaprolactone diol, β-cyclodextrin, soybean oil-based polyol, isophorone diisocyanate, 2,2-dimethylolbutyric acid, dibutyltin dilaurate, 1,4-butanediol, dimethylacetamide, triethylamine and γ-aminopropyltriethoxysilane”, and “polycaprolactone diol, β-cyclodextrin”. The following technical means are essentially equivalent to the "mass-volume ratio of soybean oil-based polyol, isophorone diisocyanate, 2,2-dimethylolbutyric acid, dibutyltin dilaurate, 1,4-butanediol, dimethylacetamide, triethylamine and γ-aminopropyltriethoxysilane", and technical means that can replace the "mass-volume ratio of polycaprolactone diol, β-cyclodextrin, soybean oil-based polyol, isophorone diisocyanate, 2,2-dimethylolbutyric acid, dibutyltin dilaurate, 1,4-butanediol, dimethylacetamide, triethylamine and γ-aminopropyltriethoxysilane" based on existing technology, conventional technical means, and common knowledge, should all fall within the protection scope of the above-mentioned technical solutions.

[0058] Examples 1-8 of the present invention at least support the protection range of "in step (2), the mixing temperature is 70-90℃; the stirring speed after adding isophorone diisocyanate is 200-400 rpm, the stirring time after adding isophorone diisocyanate is 1-2 h; the stirring speed is 200-400 rpm, and the stirring time is 2-3 h".

[0059] The term "mixing temperature" is derived from the common feature "mixing temperature" as explained above and / or from the corresponding technical features in Examples 1-8, such as heating to 85°C, heating to 80°C, and heating to 75°C. Therefore, those skilled in the art can reasonably infer that the technical feature "mixing temperature," its subordinate concepts, the technical means essentially equivalent to "mixing temperature," and the technical means that can replace "mixing temperature" based on existing technology and conventional technical means and common knowledge should all fall within the protection scope of the above-mentioned technical solutions. For example, replacing "mixing temperature" with 72°C, 78°C, etc., while keeping other technical features unchanged, still falls within the protection scope of the above-mentioned technical solutions.

[0060] The "stirring speed and time after adding isophorone diisocyanate" is summarized from the common feature "stirring speed and time after adding isophorone diisocyanate" in the above explanation and / or the corresponding technical features in Examples 1-8, such as adding 2.15 g of isophorone diisocyanate and stirring at 300 rpm for 1 h; adding 2.1 g of isophorone diisocyanate and stirring at 400 rpm for 1 h; adding 2.15 g of isophorone diisocyanate and stirring at 300 rpm for 1 h. Therefore, based on reasonable presumption, those skilled in the art can determine that the technical feature "stirring speed and time after adding isophorone diisocyanate", the subordinate concept of "stirring speed and time after adding isophorone diisocyanate", the technical means that are basically equivalent to "stirring speed and time after adding isophorone diisocyanate", and the technical means that can replace "stirring speed and time after adding isophorone diisocyanate" based on the existing technical level and conventional technical means and common knowledge should all fall within the protection scope of the above-mentioned technical solution. For example, if other technical features remain unchanged, replacing "stirring speed and time after adding isophorone diisocyanate" with stirring at 250 rpm for 1.5 h still falls within the protection scope of the above-mentioned technical solution.

[0061] Examples 1-8 of the present invention at least support the protection range of "in step (2), the temperature of adding 1,4-butanediol for reaction is 75-85°C and the reaction time of adding 1,4-butanediol for reaction is 1.5-2.5 h".

[0062] The "temperature and time for further reaction with 1,4-butanediol" is summarized from the foregoing explanation and / or the corresponding technical features in Examples 1-8: After heating to 80°C, 2.15 g of isophorone diisocyanate is added, and the mixture is stirred at 300 rpm for 1 h. Then, 0.25 g of the hydrophilic chain extender 2,2-dimethylolbutyric acid and 0.02 g of the catalyst dibutyltin dilaurate are added, and the mixture is stirred at a constant speed for 2 h. Then, 0.3 g of the chain extender 1,4-butanediol is added, and the reaction continues for 2 h. After heating to 85°C, 2.1 g of isophorone diisocyanate is added, and the mixture is stirred at 400 rpm for 1 h. Then, 0.2 g of the hydrophilic chain extender 2,2-dimethylolbutyric acid and 0.02 g of the catalyst dibutyltin dilaurate are added, and the mixture is stirred at a constant speed for 2 h. Finally, 0.25 g of the chain extender 1,4-butanediol is added, and the reaction continues for 2 h. This is obtained from the common feature "temperature and time for further reaction with 1,4-butanediol". Therefore, based on reasonable presumption, those skilled in the art can determine that the technical feature "temperature and time for further addition of 1,4-butanediol for reaction", the subordinate concept of "temperature and time for further addition of 1,4-butanediol for reaction", the technical means that are essentially equivalent to "temperature and time for further addition of 1,4-butanediol for reaction", and the technical means that can replace "temperature and time for further addition of 1,4-butanediol for reaction" based on the existing level of technology and within the scope of conventional technical means and common knowledge, should all fall within the protection scope of the above-mentioned technical solution.

[0063] Examples 1-8 of the present invention at least support the protection scope of "in step (2), the reaction temperature of adding triethylamine and γ-aminopropyltriethoxysilane is 35-45°C, and the reaction time of adding triethylamine and γ-aminopropyltriethoxysilane is 1-2 h".

[0064] The "temperature and time for reacting with triethylamine and γ-aminopropyltriethoxysilane" is summarized from the aforementioned explanation and / or the corresponding technical features in Examples 1-8, such as cooling to 40°C, adding 0.27 g of triethylamine and 0.12 g of γ-aminopropyltriethoxysilane at 100% neutralization, and reacting for 1.5 h; or cooling to 45°C, adding 0.2 g of triethylamine and 0.12 g of γ-aminopropyltriethoxysilane at 100% neutralization, and reacting for 2 h, etc., through the common feature "temperature and time for reacting with triethylamine and γ-aminopropyltriethoxysilane". Therefore, based on reasonable presumption, those skilled in the art can determine that the technical feature "the temperature and time for reacting with triethylamine and γ-aminopropyltriethoxysilane", the subordinate concept of "the temperature and time for reacting with triethylamine and γ-aminopropyltriethoxysilane", the essentially equivalent technical means of "the temperature and time for reacting with triethylamine and γ-aminopropyltriethoxysilane", and the technical means that can replace "the temperature and time for reacting with triethylamine and γ-aminopropyltriethoxysilane" based on the existing level of technology and within the scope of conventional technical means and common knowledge should all fall within the protection scope of the above-mentioned technical solution.

[0065] Secondly, the present invention provides:

[0066] The functionalized biodegradable waterborne polyurethane prepared by the above method.

[0067] Thirdly, the present invention provides:

[0068] The above-mentioned functionalized biodegradable waterborne polyurethane is used in the preparation of cosmetics.

[0069] The cosmetics include film-forming agents, antioxidants, moisturizers, and preservatives.

[0070] The beneficial effects of this invention are as follows:

[0071] (1) The functionalized biodegradable waterborne polyurethane (CPS-M) synthesized in this invention uses epoxidized soybean oil ring-opening derivatives as biodegradable soft segments to replace part of the petroleum-based polyols and reacts with isophorone diisocyanate. At the same time, β-cyclodextrin is used as a functional polyol component, and its hydroxyl groups participate in the polymerization reaction, so that it is stably embedded in the polyurethane network in the form of chemical bonds, thus synthesizing a waterborne polyurethane with biodegradability and active substance loading function.

[0072] (2) The functionalized biodegradable waterborne polyurethane synthesized in this invention has skin care potential due to the introduction of β-cyclodextrin with a cavity structure to construct a resveratrol inclusion system. Through antioxidant performance testing, the DPPH free radical scavenging rate can reach 86.25%, indicating that the material has antioxidant capacity and increases the added value of waterborne polyurethane film-forming agents.

[0073] (3) The functionalized biodegradable waterborne polyurethane prepared by the present invention can be degraded by 10.2% in 6 weeks under standard enzymatic hydrolysis conditions, and can be completely degraded in an alkaline environment, which is environmentally friendly.

[0074] (4) The functionalized biodegradable waterborne polyurethane prepared in this invention, when formulated into a setting spray, has good water resistance, makeup holding effect and anti-friction performance compared with setting sprays formulated with commercially available film-forming agents.

[0075] Furthermore, based on the present invention:

[0076] Based on the comparison of Examples 1-8 and Comparative Examples 1-4, the present invention employs the technical means of “a method for preparing a functionalized biodegradable waterborne polyurethane, comprising the following steps: (1) using a diacid as a catalyst, reacting epoxidized soybean oil and ethylene glycol to obtain soybean oil-based polyol; (2) mixing soybean oil-based polyol, polycaprolactone diol and β-cyclodextrin, adding isophorone diisocyanate and stirring, then adding 2,2-dimethylolbutyric acid and dibutyltin dilaurate, continuing stirring, then adding 1,4-butanediol and dimethylacetamide for reaction, and finally adding triethanolamine and γ-aminopropyltriethoxysilane for reaction, emulsifying with water, and dialysis to obtain the product,” achieving new technical effects: improving the stability, film-forming properties and degradability of waterborne polyurethane. The combined technical effect is superior to the sum of the effects of each technical means. Attached Figure Description

[0077] Figure 1 The FTIR spectra of the functionalized biodegradable waterborne polyurethanes prepared in Examples 1, 3, 5, and 7 are shown.

[0078] Figure 2 The images show the surface morphology of the functionalized biodegradable waterborne polyurethane prepared in Example 1 before and after biodegradation.

[0079] Figure 3 The images show the surface morphology of the functionalized biodegradable waterborne polyurethane prepared in Example 3 before and after biodegradation.

[0080] Figure 4 The images show the surface morphology of the functionalized biodegradable waterborne polyurethane prepared in Example 5 before and after biodegradation.

[0081] Figure 5 The surface morphology of the functionalized biodegradable waterborne polyurethane prepared in Example 7 before and after biodegradation is shown.

[0082] Figure 6 The images show the surface morphology of the functionalized biodegradable waterborne polyurethane prepared in Example 1 before and after hydrolysis and degradation.

[0083] Figure 7The images show the surface morphology of the functionalized biodegradable waterborne polyurethane prepared in Example 3 before and after hydrolysis and degradation.

[0084] Figure 8 The images show the surface morphology of the functionalized biodegradable waterborne polyurethane prepared in Example 5 before and after hydrolysis and degradation.

[0085] Figure 9 The images show the surface morphology of the functionalized biodegradable waterborne polyurethane prepared in Example 7 before and after hydrolysis and degradation.

[0086] Figure 10 The change in ΔE value of different test samples after immersion in water and sweat.

[0087] Note: Figures 2-9 In the image above, all images are before degradation, and all images below are after degradation. Detailed Implementation

[0088] The following non-limiting embodiments are intended to enable those skilled in the art to gain a more comprehensive understanding of the present invention, but do not limit the invention in any way. The following content is merely an exemplary description of the scope of protection claimed by the present invention, and those skilled in the art can make various changes and modifications to the present invention based on the disclosed content, and such changes should also fall within the scope of protection claimed by the present invention.

[0089] The present invention will be further described below by way of specific embodiments. Unless otherwise specified, all instruments, devices, equipment, reagents, products, etc., used in the embodiments of the present invention are obtained through conventional commercial means.

[0090] Among them, epoxidized soybean oil, with an average molecular weight of 975.4, was purchased from Shanghai Maclean Biochemical Technology Co., Ltd.; ethylene glycol, polycaprolactone diol, β-cyclodextrin, isophorone diisocyanate, malic acid, tartaric acid, glutaric acid, succinic acid, 2,2-dimethylolbutyric acid, dibutyltin dilaurate, 1,4-butanediol, dimethylacetamide, triethylamine, γ-aminopropyltriethoxysilane, and resveratrol were all of analytical grade.

[0091] Example 1

[0092] A functionalized biodegradable waterborne polyurethane, prepared by the following method:

[0093] 10 g of epoxidized soybean oil was weighed into a four-necked flask. Based on the theoretical molar ratio of epoxidized soybean oil to ethylene glycol of 1:1, the corresponding amount of ethylene glycol was calculated and measured, and added to the reaction system. Malic acid was then added, at a rate of 0.5% of the mass of the epoxidized soybean oil. The reaction was carried out under nitrogen protection, with a mechanical stirring speed of 300 rpm, a reaction temperature of 140℃, and a reaction time of 4 h to obtain soybean oil-based polyol ESO-M.

[0094] 2.64 g of vacuum-dehydrated polycaprolactone diol, 0.05 g of β-cyclodextrin, and 0.144 g of soybean oil-based polyol ESO-M (accounting for 20% of the total molar amount of hydroxyl groups in the PCL soft segment) were added to a three-necked flask equipped with a stir bar and a condenser. The mixture was heated to 80°C, and then 2.15 g of isophorone diisocyanate was added. After stirring at 300 rpm for 1 h, 0.25 g of the hydrophilic chain extender 2,2-dimethylolbutyric acid and 0.02 g of the catalyst dibutyltin dilaurate were added, and the mixture was stirred at a constant speed for 2 h. Then, 0.3 g of the chain extender 1,4-butanediol was added, and the reaction was continued for 2 h. Finally, 5 mL of dimethylacetamide was added. After cooling to 40℃, 0.27 g of triethylamine and 0.12 g of γ-aminopropyltriethoxysilane were added at a neutralization degree of 100% and reacted for 1.5 h. Finally, 15 g of deionized water was slowly added dropwise under high-speed stirring to emulsify the mixture. After dialysis to remove the solvent, functionalized biodegradable waterborne polyurethane (CPS-M) was obtained.

[0095] Infrared spectroscopy of CPS-M was performed using the tablet coating method, and the resulting spectrum is shown below. Figure 1 As shown.

[0096] Example 2

[0097] A functionalized biodegradable waterborne polyurethane, prepared by the following method:

[0098] 10 g of epoxidized soybean oil was weighed into a four-necked flask. Based on the theoretical molar ratio of epoxidized soybean oil to ethylene glycol of 1.2:1, the corresponding amount of ethylene glycol was calculated and measured, and added to the reaction system. Malic acid was then added at 1% of the mass of the epoxidized soybean oil. The reaction was carried out under nitrogen protection, with a mechanical stirring speed of 400 rpm, a reaction temperature of 130℃, and a reaction time of 3 h to obtain soybean oil-based polyol ESO-M.

[0099] 2.5 g of vacuum-dehydrated polycaprolactone diol, 0.09 g of β-cyclodextrin, and 0.14 g of soybean oil-based polyol ESO-M (accounting for 20% of the total molar amount of hydroxyl groups in the PCL soft segment) were added to a three-necked flask equipped with a stir bar and a condenser. After heating to 85°C, 2.1 g of isophorone diisocyanate was added, and the mixture was stirred at 400 rpm for 1 h. Then, 0.2 g of the hydrophilic chain extender 2,2-dimethylolbutyric acid and 0.02 g of the catalyst dibutyltin dilaurate were added, and the mixture was stirred at a constant speed for 2 h. After that, 0.25 g of the chain extender 1,4-butanediol was added, and the reaction was continued for 2 h. Finally, 5 mL of dimethylacetamide was added. After cooling to 45℃, 0.2 g of triethylamine and 0.12 g of γ-aminopropyltriethoxysilane were added at a neutralization degree of 100% and reacted for 2 h. Finally, 15 g of deionized water was slowly added dropwise under high-speed stirring to emulsify. After dialysis to remove the solvent, functionalized biodegradable waterborne polyurethane (CPS-M) was obtained.

[0100] Example 3

[0101] A functionalized biodegradable waterborne polyurethane, prepared by the following method:

[0102] 10 g of epoxidized soybean oil was weighed into a four-necked flask. Based on the theoretical molar ratio of epoxidized soybean oil to ethylene glycol of 1:1, the corresponding amount of ethylene glycol was calculated and measured, and added to the reaction system. Tartaric acid was then added at 0.5% of the mass of the epoxidized soybean oil. The reaction was carried out under nitrogen protection, with a mechanical stirring speed of 300 rpm, a reaction temperature of 140℃, and a reaction time of 4 h to obtain soybean oil-based polyol ESO-T.

[0103] 2.64 g of vacuum-dehydrated polycaprolactone diol, 0.05 g of β-cyclodextrin, and 0.148 g of soybean oil-based polyol ESO-T (accounting for 20% of the total molar amount of hydroxyl groups in the PCL soft segment) were added to a three-necked flask equipped with a stir bar and a condenser. After heating to 80°C, 2.15 g of isophorone diisocyanate was added, and the mixture was stirred at 300 rpm for 1 h. Then, 0.25 g of the hydrophilic chain extender 2,2-dimethylolbutyric acid and 0.02 g of the catalyst dibutyltin dilaurate were added, and the mixture was stirred at a constant speed for 2 h. After adding 0.3 g of the chain extender 1,4-butanediol, the reaction was continued for 2 h, and then 5 mL of dimethylacetamide was added. After cooling to 40℃, 0.27 g of triethylamine and 0.12 g of γ-aminopropyltriethoxysilane were added at a neutralization degree of 100% and reacted for 1.5 h. Finally, 15 g of deionized water was slowly added dropwise under high-speed stirring to emulsify the mixture. After dialysis to remove the solvent, functionalized biodegradable waterborne polyurethane (CPS-T) was obtained.

[0104] Infrared spectroscopy of CPS-T was performed using the tablet coating method, and the resulting spectrum is shown below. Figure 1 As shown.

[0105] Example 4

[0106] A functionalized biodegradable waterborne polyurethane, prepared by the following method:

[0107] 15 g of epoxidized soybean oil was weighed into a four-necked flask. Based on the theoretical molar ratio of epoxidized soybean oil to ethylene glycol of 1.2:1, the corresponding amount of ethylene glycol was calculated and measured, and added to the reaction system. Tartaric acid was then added at 1% of the mass of the epoxidized soybean oil. The reaction was carried out under nitrogen protection, with a mechanical stirring speed of 300 rpm, a reaction temperature of 130℃, and a reaction time of 4 h to obtain soybean oil-based polyol ESO-T.

[0108] 2.6 g of vacuum-dehydrated polycaprolactone diol, 0.06 g of β-cyclodextrin, and 0.145 g of soybean oil-based polyol ESO-T (accounting for 20% of the total molar amount of hydroxyl groups in the PCL soft segment) were added to a three-necked flask equipped with a stir bar and a condenser. After heating to 85°C, 2.1 g of isophorone diisocyanate was added, and the mixture was stirred at 400 rpm for 1 h. Then, 0.2 g of the hydrophilic chain extender 2,2-dimethylolbutyric acid and 0.02 g of the catalyst dibutyltin dilaurate were added, and the mixture was stirred at a constant speed for 2 h. After that, 0.25 g of the chain extender 1,4-butanediol was added, and the reaction was continued for 2 h. Finally, 5 mL of dimethylacetamide was added. After cooling to 45℃, 0.2 g of triethylamine and 0.1 g of γ-aminopropyltriethoxysilane were added at a neutralization degree of 100% and reacted for 2 h. Finally, 15 g of deionized water was slowly added dropwise under high-speed stirring to emulsify the mixture. After dialysis to remove the solvent, functionalized biodegradable waterborne polyurethane (CPS-T) was obtained.

[0109] Example 5

[0110] A functionalized biodegradable waterborne polyurethane, prepared by the following method:

[0111] 10 g of epoxidized soybean oil was weighed into a four-necked flask. Based on the theoretical molar ratio of epoxidized soybean oil to ethylene glycol of 1:1, the corresponding amount of ethylene glycol was calculated and measured, and added to the reaction system. Glutaric acid was then added, at a rate of 0.5% of the mass of the epoxidized soybean oil. The reaction was carried out under nitrogen protection, with a mechanical stirring speed of 300 rpm, a reaction temperature of 140℃, and a reaction time of 4 h to obtain soybean oil-based polyol ESO-G.

[0112] 2.64 g of vacuum-dehydrated polycaprolactone diol, 0.05 g of β-cyclodextrin, and 0.166 g of soybean oil-based polyol ESO-G (accounting for 20% of the total molar amount of hydroxyl groups in the PCL soft segment) were added to a three-necked flask equipped with a stir bar and a condenser. The mixture was heated to 80°C, and then 2.15 g of isophorone diisocyanate was added. The mixture was stirred at 300 rpm for 1 h. 0.25 g of the hydrophilic chain extender 2,2-dimethylolbutyric acid and 0.02 g of the catalyst dibutyltin dilaurate were added, and the mixture was stirred for 2 h. Then, 0.3 g of the chain extender 1,4-butanediol was added, and the reaction was continued for 2 h. Finally, 5 mL of dimethylacetamide was added. After cooling to 40℃, 0.27 g of triethylamine and 0.12 g of γ-aminopropyltriethoxysilane were added at a neutralization degree of 100% and reacted for 1.5 h. Finally, 15 g of deionized water was slowly added dropwise under high-speed stirring to emulsify the mixture. After dialysis to remove the solvent, functionalized biodegradable waterborne polyurethane (CPS-G) was obtained.

[0113] Infrared spectroscopy of CPS-G was performed using the tablet coating method, and the resulting spectrum is shown below. Figure 1 As shown.

[0114] Example 6

[0115] A functionalized biodegradable waterborne polyurethane, prepared by the following method:

[0116] 10 g of epoxidized soybean oil was weighed into a four-necked flask. Based on the theoretical molar ratio of epoxidized soybean oil to ethylene glycol of 0.8:1, the corresponding amount of ethylene glycol was calculated and measured, and added to the reaction system. Glutaric acid was then added, at a rate of 0.5% of the mass of the epoxidized soybean oil. The reaction was carried out under nitrogen protection, with a mechanical stirring speed of 300 rpm, a reaction temperature of 140℃, and a reaction time of 3 h to obtain soybean oil-based polyol ESO-G.

[0117] 2.6 g of vacuum-dehydrated polycaprolactone diol, 0.05 g of β-cyclodextrin, and 0.17 g of soybean oil-based polyol ESO-G (accounting for 20% of the total molar amount of hydroxyl groups in the PCL soft segment) were added to a three-necked flask equipped with a stir bar and a condenser. After heating to 75°C, 2.1 g of isophorone diisocyanate was added, and the mixture was stirred at 400 rpm for 1.5 h. Then, 0.2 g of the hydrophilic chain extender 2,2-dimethylolbutyric acid and 0.02 g of the catalyst dibutyltin dilaurate were added, and the mixture was stirred at a constant speed for 2 h. Next, 0.25 g of the chain extender 1,4-butanediol was added, and the reaction was continued for 2 h. Finally, 5 mL of dimethylacetamide was added. After cooling to 45℃, 0.2 g of triethylamine and 0.12 g of γ-aminopropyltriethoxysilane were added at a neutralization degree of 100% and reacted for 2 h. Finally, 15 g of deionized water was slowly added dropwise under high-speed stirring to emulsify. After dialysis to remove the solvent, functionalized biodegradable waterborne polyurethane (CPS-G) was obtained.

[0118] Example 7

[0119] A functionalized biodegradable waterborne polyurethane, prepared by the following method:

[0120] 10 g of epoxidized soybean oil was weighed into a four-necked flask. Based on the theoretical molar ratio of epoxidized soybean oil to ethylene glycol of 1:1, the corresponding amount of ethylene glycol was calculated and measured, and added to the reaction system. Succinic acid was then added, at a rate of 0.5% of the mass of the epoxidized soybean oil. The reaction was carried out under nitrogen protection, with a mechanical stirring speed of 300 rpm, a reaction temperature of 140℃, and a reaction time of 4 h to obtain soybean oil-based polyol ESO-S.

[0121] 2.64 g of vacuum-dehydrated polycaprolactone diol, 0.05 g of β-cyclodextrin, and 0.171 g of soybean oil-based polyol ESO-S (accounting for 20% of the total molar amount of hydroxyl groups in the PCL soft segment) were added to a three-necked flask equipped with a stir bar and a condenser. The mixture was heated to 80°C, and then 2.15 g of isophorone diisocyanate was added. The mixture was stirred at 300 rpm for 1 h. Then, 0.3 g of the hydrophilic chain extender 2,2-dimethylolbutyric acid and 0.02 g of the catalyst dibutyltin dilaurate were added, and the mixture was stirred for 2 h. Finally, 0.3 g of the chain extender 1,4-butanediol was added, and the reaction was continued for another 2 h. Then, 5 mL of dimethylacetamide was added. After cooling to 40℃, 0.27 g of triethylamine and 0.12 g of γ-aminopropyltriethoxysilane were added at a neutralization degree of 100% and reacted for 1.5 h. Finally, 15 g of deionized water was slowly added dropwise under high-speed stirring to emulsify the mixture. After dialysis to remove the solvent, functionalized biodegradable waterborne polyurethane (CPS-S) was obtained.

[0122] Infrared spectroscopy of CPS-S was performed using the tablet coating method, and the resulting spectrum is shown below. Figure 1 As shown.

[0123] Example 8

[0124] A functionalized biodegradable waterborne polyurethane, prepared by the following method:

[0125] 10 g of epoxidized soybean oil was weighed into a four-necked flask. Based on the theoretical molar ratio of epoxidized soybean oil to ethylene glycol of 1.2:1, the corresponding amount of ethylene glycol was calculated and measured, and added to the reaction system. Succinic acid was then added at 1% of the mass of the epoxidized soybean oil. The reaction was carried out under nitrogen protection, with a mechanical stirring speed of 200 rpm, a reaction temperature of 130℃, and a reaction time of 4 h to obtain soybean oil-based polyol ESO-S.

[0126] 2.6 g of vacuum-dehydrated polycaprolactone diol, 0.08 g of β-cyclodextrin, and 0.18 g of soybean oil-based polyol ESO-S (accounting for 20% of the total molar amount of hydroxyl groups in the PCL soft segment) were added to a three-necked flask equipped with a stir bar and a condenser. The mixture was heated to 80°C, and then 2.15 g of isophorone diisocyanate was added. The mixture was stirred at 200 rpm for 1.5 h. Then, 0.3 g of the hydrophilic chain extender 2,2-dimethylolbutyric acid and 0.02 g of the catalyst dibutyltin dilaurate were added, and the mixture was stirred for 2 h. Next, 0.3 g of the chain extender 1,4-butanediol was added, and the reaction continued for 2 h. Finally, 5 mL of dimethylacetamide was added. After cooling to 35°C, 0.27 g of triethylamine and 0.12 g of γ-aminopropyltriethoxysilane were added at a neutralization degree of 100% and reacted for 1 h. Finally, 10 g of deionized water was slowly added dropwise under high-speed stirring to emulsify the mixture. After dialysis to remove the solvent, functionalized biodegradable waterborne polyurethane (CPS-S) was obtained.

[0127] Example 9

[0128] An aqueous polyurethane film-forming agent is prepared by the following method:

[0129] Take 10 mL of CPS-M prepared in Example 1, and slowly add a resveratrol ethanol solution (1 mg / mL) dropwise according to a molar ratio of β-cyclodextrin to resveratrol of 1:1. Stir for 4 h to promote host-guest inclusion. After standing overnight, centrifuge to remove unincluded resveratrol to obtain an aqueous polyurethane film-forming agent.

[0130] Example 10

[0131] An aqueous polyurethane film-forming agent is prepared by the following method:

[0132] Take 15 mL of CPS-M prepared in Example 1, and slowly add a resveratrol ethanol solution (0.8 mg / mL) dropwise according to the molar ratio of β-cyclodextrin to resveratrol in CPS-M of 0.8:1.2. Stir for 6 h to promote host-guest inclusion. After standing overnight, centrifuge to remove unincluded resveratrol to obtain an aqueous polyurethane film-forming agent.

[0133] Example 11

[0134] A setting spray, by weight percentage, comprises the following basic formulation: 3% film-forming agent (waterborne polyurethane prepared in Example 5), 1% niacinamide, 1.5% 1,3-butanediol, 0.05% EDTA-2Na, 1% preservative (phenoxyethanol ethylhexylglycerin), with the remainder made up to 100% with water, and mixed evenly to obtain setting spray F1.

[0135] A setting spray has the following basic formula: 3% film-forming agent (commercially available film-forming agent A: polyester-5), 1% niacinamide, 1.5% 1,3-butanediol, 0.05% EDTA-2Na, 1% preservative (phenoxyethanol ethylhexylglycerin), with the remainder made up to 100% with water. The mixture is stirred evenly to obtain setting spray F2.

[0136] Comparative Example 1

[0137] Compared with Example 1, the only difference is that the amount of soybean oil-based polyol added is 0.22 g.

[0138] Comparative Example 2

[0139] Compared with Example 1, the only difference is that the dosage of isophorone diisocyanate is 3.22 g.

[0140] Comparative Example 3

[0141] Compared with Example 1, the only difference is that the dosage of isophorone diisocyanate is 3.44 g.

[0142] Comparative Example 4

[0143] Compared with Example 1, the only difference is that malic acid is replaced with an equal mass of citric acid.

[0144] Detection Example 1

[0145] The performance of the functionalized biodegradable waterborne polyurethanes prepared in Examples 1, 2, 3, 5, 7 and Comparative Example 1 was tested respectively. Among them, PDI is the aggregation degree index, which reflects the relative content of different particle sizes in the sample. The smaller the value, the more uniform the distribution, and the larger the value, the more uneven the distribution. The stability was tested after the samples were placed at 25°C for 24 h.

[0146] Verification of technical effectiveness and / or analysis of solutions to technical problems:

[0147] The test results are shown in Table 1. It can be seen that the PDI values ​​of comparative examples 1 and 4 are relatively large, the particle size distribution is uneven, and the stability is poor.

[0148] Table 1 Test Results

[0149]

[0150] Detection Example 2

[0151] According to GB / T1040-2006, the functionalized biodegradable waterborne polyurethanes prepared in Examples 1, 3, 5, 7 and Comparative Examples 2, 3 were cut into standard dumbbell shapes using a cutting tool. The tensile strength and elongation at break were determined using a universal testing machine at a tensile rate of 50 mm / min. Three parallel experiments were conducted, and the results were taken as the arithmetic mean.

[0152] According to GB / T9286-2021 / ISO2409:2020, the adhesion of the functionalized biodegradable waterborne polyurethanes prepared in Examples 1, 3, 5, 7 and Comparative Examples 2, 3 was tested.

[0153] Verification of technical effectiveness and / or analysis of solutions to technical problems:

[0154] The mechanical property test results of functionalized biodegradable waterborne polyurethane are shown in Table 2.

[0155] Table 2 Mechanical properties of functionalized biodegradable waterborne polyurethane

[0156]

[0157] Detection Example 3

[0158] Appropriate amounts of the functionalized biodegradable waterborne polyurethanes prepared in Examples 1, 3, 5, and 7, and Comparative Examples 1, 2, and 3, and a commercially available film-forming agent (model: polyester-5) were taken and uniformly coated onto glass slides. After drying and forming films, the hydrophobicity of the films was tested using a contact angle meter. The volume of the water droplets selected for the test was 5 µL. Five test points were selected for each sample, and the contact angles were recorded and the average value was calculated. The commercially available film-forming agent was used as a control. Moderate hydrophobicity not only helps to improve the water resistance and makeup-holding performance of setting sprays, but also maintains the breathability of the material to a certain extent.

[0159] Verification of technical effectiveness and / or analysis of solutions to technical problems:

[0160] The contact angle data are shown in Table 3. As can be seen from Table 3, the contact angles of the functionalized biodegradable waterborne polyurethane film-forming agents prepared in Examples 1, 3, 5, and 7 are all greater than those of commercially available film-forming agents and Comparative Examples 2 and 3, indicating good waterproof and sweatproof properties. While Comparative Example 1 has a higher contact angle, its emulsion stability is poor (see Table 1), and it cannot form a continuous film, resulting in overall performance inferior to the examples.

[0161] Table 3 Contact Angle of Functionalized Biodegradable Waterborne Polyurethane

[0162]

[0163] Detection Example 4

[0164] Using ultrafiltration centrifugation, 5 mL of the aqueous polyurethane film-forming agent prepared in Example 9 was placed in an ultrafiltration centrifuge tube with a molecular weight cutoff of 3000. After centrifugation at 10000 r / min for 30 min, the bottom filtrate was collected, diluted 5 times, and its absorbance was measured at a wavelength of 306 nm. The inclusion rate (%) and loading rate (%) of resveratrol were calculated according to the standard curve and the following formula.

[0165]

[0166]

[0167] In the formula: m 1 represents the calculated mass of resveratrol in the filtrate, in g; m 0 represents the actual mass of resveratrol added, in g; m 2 represents the mass of resveratrol loaded, in g; m 总 The total mass of the inclusion complex is expressed in g.

[0168] Verification of technical effectiveness and / or analysis of solutions to technical problems:

[0169] Calculations showed that the inclusion rate of the waterborne polyurethane film-forming agent prepared in Example 9 for resveratrol was 96.65 ± 0.54%, and the loading rate was 0.16 ± 0.03%. This indicates that the functionalized biodegradable waterborne polyurethane exhibits excellent inclusion performance for resveratrol.

[0170] Case 5

[0171] Biodegradation: Appropriate amounts of the functionalized biodegradable waterborne polyurethane prepared in Examples 1, 3, 5, and 7 were uniformly coated onto a glass slide. After drying to form a film, the film was cut into 2 cm × 2 cm pieces and placed in a PBS buffer solution containing 1.5 mg / mL porcine pancreatic lipase. The slide was then placed in a constant-temperature shaker with the following parameters set: temperature 50℃, rotation speed 120 r / min. Samples were removed every week, rinsed multiple times with distilled water until a constant mass was achieved, and then stored in a desiccator. After 6 weeks of degradation, the surface morphology of the functionalized biodegradable waterborne polyurethane before and after degradation was systematically characterized using a JSM-7610F Plus field emission scanning electron microscope.

[0172] Hydrolytic degradation: Appropriate amounts of the functionalized biodegradable waterborne polyurethane prepared in Examples 1, 3, 5, and 7 were uniformly coated onto a glass slide and dried to form a film. The film was then cut into 2 cm × 2 cm squares and placed in a prepared sample vial. 5 mL of a prepared 1 wt% sodium hydroxide solution was added, and the vial was placed in a 45°C incubator and allowed to stand for 4 hours. After 6 weeks of degradation, the surface morphology of the functionalized biodegradable waterborne polyurethane before and after degradation was systematically characterized using a JSM-7610F Plus field emission scanning electron microscope.

[0173] Verification of technical effectiveness and / or analysis of solutions to technical problems:

[0174] The surface morphology images of the functionalized biodegradable waterborne polyurethanes prepared in Examples 1, 3, 5, and 7 before and after biodegradation are shown below. Figures 2-5 As shown; the surface morphology images of the functionalized biodegradable waterborne polyurethanes prepared in Examples 1, 3, 5, and 7 before and after hydrolysis degradation are respectively shown in the figures. Figures 6-9 As shown, before degradation, all sample surfaces exhibited a smooth and flat morphology. After enzymatic and hydrolytic degradation, the surface roughness of the samples increased significantly, and varying degrees of erosion characteristics appeared. This indicates that both the enzyme solution and the 1 wt% NaOH solution can degrade the synthesized film-forming agent.

[0175] Case 6

[0176] To evaluate the makeup setting spray's staying power, a simulated water (sweat) scenario was used, employing an artificial sweat immersion method combined with color quantification analysis.

[0177] That is, using off-white smooth leather (3 cm × 3 cm) as the standard makeup surface simulation substrate, 0.001 ± 0.0002 g of eyeshadow was weighed using a precision balance and evenly applied to the substrate surface to form a uniform makeup layer. Then, the setting sprays F1 and F2 prepared in Example 11 were evenly sprayed onto the makeup surface, with commercially available setting spray F3 as the control and a sample sprayed with an equal amount of deionized water as the blank control.

[0178] After immersing the dried samples in water and artificial sweat for 1 hour, respectively, the L value at the center of the test area before and after immersion was measured using a colorimeter. a b The color difference ΔE is calculated using the following formula. The color difference ΔE value comprehensively reflects the overall degree of color shift in the makeup. The lower the ΔE value, the less makeup is removed due to soaking, and the better the water or sweat resistance of the sample. Measure 5-8 points on each sample, and perform 3 parallel tests.

[0179]

[0180] In the formula, L t0 , a t0 , b t0 The value was measured before soaking; L t1 , a t1 , b t1 These are the values ​​measured after soaking.

[0181] Verification of technical effectiveness and / or analysis of solutions to technical problems:

[0182] The changes in ΔE value after soaking in water and sweat are as follows: Figure 10 As shown. By Figure 10 It can be seen that the setting spray sample F1 can significantly improve the water and sweat resistance of the makeup, and its color difference ΔE value after soaking is the lowest.

[0183] Case 7

[0184] Weigh 3.94 mg of DPPH standard and dilute to 100 mL with anhydrous ethanol to prepare a 0.1 mM stock solution. Store protected from light. Before use, dilute with anhydrous ethanol by half to obtain a 0.05 mM DPPH working solution.

[0185] The setting spray F1 prepared in Example 11 was selected as the sample, and sample groups (1 mL sample + 1 mL DPPH working solution), sample background group (1 mL sample + 1 mL anhydrous ethanol), blank group (1 mL DPPH working solution + 1 mL anhydrous ethanol), positive control group (1 mL L-ascorbic acid + 1 mL DPPH working solution), and negative control group (1 mL sample CPS-M without resveratrol encapsulation + 1 mL DPPH working solution) were set up respectively. The negative control group was used to correct the interference of resveratrol's own color.

[0186] After adding the sample, immediately vortex for 5-10 seconds to mix thoroughly. Wrap the sample in aluminum foil or place it in the dark and incubate at room temperature (25±1℃) for 30 minutes in the dark. After the reaction, measure the absorbance at 517 nm using a microplate reader and calculate the DPPH clearance rate. The formula for calculating the DPPH clearance rate (%) is as follows:

[0187]

[0188] In the formula: A1 The absorbance of the sample group or control group. A2 The absorbance of the sample background group. A3 The absorbance is for the blank group.

[0189] Verification of technical effectiveness and / or analysis of solutions to technical problems:

[0190] The DPPH free radical scavenging rate of the setting spray F1 prepared in Example 11 is shown in Table 4.

[0191] Table 4 Results of DPPH free radical scavenging rate

[0192]

[0193] In summary, the functionalized biodegradable waterborne polyurethane prepared by this invention has good stability and film-forming properties, as well as excellent comprehensive performance and good biodegradation potential. The makeup setting spray made from it has good makeup-holding effect and antioxidant properties.

[0194] Finally, it should be noted that the above content is only used to illustrate the technical solution of the present invention, and is not intended to limit the scope of protection of the present invention. Simple modifications or equivalent substitutions made by those skilled in the art to the technical solution of the present invention do not depart from the essence and scope of the technical solution of the present invention.

Claims

1. A method for preparing functionalized biodegradable waterborne polyurethane, characterized in that, Includes the following steps: (1) Using diacid as a catalyst, epoxidized soybean oil and ethylene glycol are reacted to obtain soybean oil-based polyol; (2) Mix soybean oil-based polyol, polycaprolactone diol and β-cyclodextrin, add isophorone diisocyanate and stir, then add 2,2-dimethylolbutyric acid and dibutyltin dilaurate and continue stirring, then add 1,4-butanediol and react, then add dimethylacetamide, and finally add triethylamine and γ-aminopropyltriethoxysilane and react, emulsify with water, and dialyze to obtain the product; In step (1), the dicarboxylic acid is malic acid or tartaric acid; In step (2), the mass-to-volume ratio of polycaprolactone diol, β-cyclodextrin, soybean oil-based polyol, isophorone diisocyanate, 2,2-dimethylolbutyric acid, dibutyltin dilaurate, 1,4-butanediol, dimethylacetamide, triethylamine, and γ-aminopropyltriethoxysilane is 2.5-2.7 g:0.05-0.09 g:0.14-0.18 g:2.1-2.15 g:0.2-0.3 g:0.02 g:0.25-0.3 g:5 mL:0.2-0.27 g:0.1-0.12 g; In step (1), the amount of the dicarboxylic acid used is 0.5-1% of the mass of the epoxidized soybean oil; In step (1), the molar ratio of epoxidized soybean oil to ethylene glycol is 0.8-1.2:1; the reaction is carried out under a nitrogen atmosphere and a rotation speed of 200-400 rpm; the reaction temperature is 120-150℃ and the reaction time is 3-5 h. In step (2), the mixing temperature is 70-90℃; the stirring speed after adding isophorone diisocyanate is 200-400 rpm, and the stirring time after adding isophorone diisocyanate is 1-2 h; the stirring speed for continued stirring is 200-400 rpm, and the stirring time for continued stirring is 2-3 h.

2. The preparation method according to claim 1, characterized in that, In step (2), the temperature for adding 1,4-butanediol to react is 75-85℃, and the reaction time for adding 1,4-butanediol is 1.5-2.5 h.

3. The preparation method according to claim 1, characterized in that, In step (2), the reaction temperature of adding triethylamine and γ-aminopropyltriethoxysilane is 35-45℃, and the reaction time of adding triethylamine and γ-aminopropyltriethoxysilane is 1-2 h.

4. A functionalized biodegradable waterborne polyurethane prepared by the preparation method according to any one of claims 1-3.

5. The application of the functionalized biodegradable waterborne polyurethane as described in claim 4 in the preparation of cosmetics.

6. The application according to claim 5, characterized in that, The cosmetic product includes a film-forming agent, an antioxidant, a moisturizer, and a preservative; the film-forming agent is the functionalized biodegradable waterborne polyurethane as described in claim 4.

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