CN114539505B - Amino acid modified waterborne polyurethane acrylate and preparation method thereof - Google Patents

Amino acid modified waterborne polyurethane acrylate and preparation method thereof Download PDF

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CN114539505B
CN114539505B CN202210056149.6A CN202210056149A CN114539505B CN 114539505 B CN114539505 B CN 114539505B CN 202210056149 A CN202210056149 A CN 202210056149A CN 114539505 B CN114539505 B CN 114539505B
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amino acid
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waterborne polyurethane
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CN114539505A (en
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翁子骧
李坤嵘
吴立新
巫国宝
钟伟博
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Westan Xiamen Industrial Co ltd
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
    • C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00—Biological treatment of water, waste water, or sewage
    • C02F3/34—Biological treatment of water, waste water, or sewage characterised by the microorganisms used
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
    • C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
    • C08G18/4269—Lactones
    • C08G18/4277—Caprolactone and/or substituted caprolactone
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4825—Polyethers containing two hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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    • C08G18/48—Polyethers
    • C08G18/4833—Polyethers containing oxyethylene units
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/671—Unsaturated compounds having only one group containing active hydrogen
    • C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
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    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
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Abstract

The invention provides a preparation method of amino acid modified waterborne polyurethane acrylic ester, S1, taking 30-45 parts of polyol, 11-18 parts of diisocyanate and 0.5 part of catalyst, uniformly mixing, reacting for 2-4 hours in nitrogen atmosphere at 70-80 ℃, then adding 2-3 parts of alcohol micromolecule chain extender with carboxylic acid groups and 5-10 parts of organic solvent, and reacting for 1-3 hours at 70-85 ℃ to obtain waterborne polyurethane prepolymer; s2, adding 2-6 parts of acrylic ester, reacting for 3-8 hours at 70-80 ℃, and introducing a photo-curing group; s3, adding 2-4 parts of neutralizer, reacting for 0.5-1 h at 30-45 ℃ and neutralizing carboxylic acid groups; s4, adding 1-3 parts of amino acid micromolecular chain extender and 90-200 parts of deionized water, and reacting for 0.5-1 h under stirring at 30-45 ℃ and 1000-2000 rpm to obtain aqueous polyurethane dispersion with 25-45% of solid content; s5, adding 0.4-2 parts of photoinitiator, stirring uniformly, and removing the organic solvent and triethylamine by rotary evaporation to obtain the material. The material has excellent hydrolysis resistance, biocompatibility and mechanical property.

Description

Amino acid modified waterborne polyurethane acrylate and preparation method thereof
Technical Field
The invention relates to amino acid modified waterborne polyurethane acrylate and a preparation method thereof, belonging to the technical field of photo-curing resin.
Background
The bio-enhancement technology is a technology for improving the concentration of effective microorganisms, enhancing the degradation capability of refractory organics, improving the degradation rate thereof and improving the removal efficiency of the refractory organics of the original biological treatment system by introducing microorganisms with specific functions into the traditional biological treatment system. The biological strengthening technology provides a potential solution for water environment pollution restoration and standard improvement of sewage treatment plants. In the bio-enhancement technology, the effect of directly adding the strain in the traditional method cannot last, and the microorganism needs to be immobilized by adopting a bio-immobilization material. The most commonly adopted biological immobilization materials at present are polyvinyl alcohol, sodium alginate and the like, but the mechanical properties of the biological immobilization materials are not ideal enough, so that the application of the biological immobilization materials is limited. Therefore, development of a biological anchoring material excellent in mechanical properties is urgently required.
The aqueous polyurethane is a novel polyurethane system which uses water instead of an organic solvent as a dispersion medium, and is also called water-dispersible polyurethane, aqueous polyurethane or water-based polyurethane. The aqueous polyurethane takes water as a solvent, has the advantages of no pollution, safety, reliability, excellent mechanical property, good compatibility, easy modification and the like, and has been closely paid attention to by vast scientific researchers. However, when the aqueous polyurethane is applied to the technical field of sewage treatment, the hydrolysis resistance and the biocompatibility of the aqueous polyurethane are still not ideal.
Disclosure of Invention
The invention provides amino acid modified waterborne polyurethane acrylic ester and a preparation method thereof, which can effectively solve the problems.
The invention is realized in the following way:
the preparation method of the amino acid modified waterborne polyurethane acrylate comprises the following steps:
s1, taking 30-45 parts of polyol, 11-18 parts of diisocyanate and 0.5 part of catalyst, uniformly mixing, reacting for 2-4 hours in a nitrogen atmosphere at 70-80 ℃, then adding 2-3 parts of alcohol micromolecular chain extender with carboxylic acid groups and 5-10 parts of organic solvent, and reacting for 1-3 hours at 70-85 ℃ to obtain waterborne polyurethane prepolymer;
s2, adding 2-6 parts of acrylic ester into the product obtained in the step S1, reacting for 3-8 hours at 70-80 ℃, and introducing a photo-curing group;
s3, adding 2-4 parts of neutralizing agent into the product of the step S2, and reacting for 0.5-1 h at 30-45 ℃ to neutralize carboxylic acid groups; removing the residual organic solvent under vacuum;
s4, adding 1-3 parts of amino acid micromolecular chain extender and 90-200 parts of deionized water into the product of the step S3, and reacting for 0.5-1 h under stirring at 30-45 ℃ and 1000-2000 rpm to obtain aqueous polyurethane dispersion liquid with 25-45% of solid content;
and S5, adding 0.4-2 parts of photoinitiator into the product obtained in the step S4, uniformly stirring, and removing the organic solvent and triethylamine by rotary evaporation to obtain the amino acid modified waterborne polyurethane acrylate.
As a further improvement, the polyol is one or more of polyols such as poly epsilon-caprolactone glycol (PCL), polyethylene glycol (PEG), polypropylene glycol (PPG), and polydiacid glycol ester glycol.
As a further improvement, the diisocyanate is one or more of isophorone diisocyanate (IPDI), lysine ethyl ester diisocyanate (LDI).
As a further improvement, the catalyst is one or two of dibutyl tin dilaurate or stannous octoate.
As a further improvement, the carboxylic acid group-containing alcohol small molecule chain extender is 2, 2-dimethylolpropionic acid (DMPA).
As a further improvement, the acrylate is hydroxyethyl methacrylate (HEMA) or hydroxyethyl acrylate (HEA).
As a further improvement, the amino acid small molecule chain extender is a diamine amino acid.
As a further improvement, the photoinitiator is selected from 2959, LAP, VA-086.
The amino acid modified waterborne polyurethane acrylic ester prepared by the method.
The application of the amino acid modified waterborne polyurethane acrylate in biological fixing materials.
The beneficial effects of the invention are as follows:
the invention introduces the photo-curing group end-capping agent acrylic ester and the amino acid micromolecular chain extender into the aqueous polyurethane, and the prepared amino acid modified aqueous polyurethane acrylic ester has excellent hydrolysis resistance, biocompatibility and mechanical property, can be used as an ideal biological fixing material, and has good application prospect.
The amino acid modified waterborne polyurethane acrylic ester prepared by the invention is nontoxic, pollution-free, safe and reliable.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the embodiments will be briefly described below, it being understood that the following drawings only illustrate some examples of the present invention and therefore should not be considered as limiting the scope, and other related drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a schematic diagram of a tensile test provided by an embodiment of the present invention.
FIG. 2 is a graph of the results of a tensile test provided by an embodiment of the present invention.
FIG. 3 is a graph showing the results of hydrolysis resistance tests provided by the examples of the present invention.
Fig. 4 is a graph of the results of a biocompatibility test provided by an embodiment of the present invention.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, based on the embodiments of the invention, which are apparent to those of ordinary skill in the art without inventive faculty, are intended to be within the scope of the invention. Thus, the following detailed description of the embodiments of the invention, as presented in the figures, is not intended to limit the scope of the invention, as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, based on the embodiments of the invention, which are apparent to those of ordinary skill in the art without inventive faculty, are intended to be within the scope of the invention.
In the description of the present invention, the terms "first," "second," and the like are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include one or more such feature. In the description of the present invention, the meaning of "a plurality" is two or more, unless explicitly defined otherwise.
The invention provides a preparation method of amino acid modified waterborne polyurethane acrylic ester, which comprises the following steps:
s1, taking 30-45 parts of polyol, 11-18 parts of diisocyanate and 0.5 part of catalyst, uniformly mixing, wherein the diisocyanate is excessive, the catalyst is small, reacting for 2-4 hours in a nitrogen atmosphere at 70-80 ℃ to obtain a prepolymer of-NCO groups, and when the-NCO groups are not reduced, adding 2-3 parts of alcohol micromolecular chain extender with carboxylic acid groups and 5-10 parts of organic solvent, wherein the organic solvent is low-boiling-point organic solvent such as acetone, butanone and tetrahydrofuran, and the low-boiling-point organic solvent can adjust the viscosity of the system. Then reacting for 1-3 h at 70-85 ℃ until the-NCO group reaches a theoretical value, thus obtaining the waterborne polyurethane prepolymer. The polyalcohol is one or more of polyalcohols such as poly epsilon-caprolactone glycol (PCL), polyethylene glycol (PEG), polypropylene glycol (PPG), polydiacid glycol ester glycol and the like; the molecular weight of the polyalcohol is 1000-2000, and the polyalcohol has excellent biocompatibility and is suitable for being used as a raw material of synthetic biological resin. The diisocyanate is one or more of isophorone diisocyanate (IPDI) and lysine ethyl ester diisocyanate (LDI), preferably isophorone diisocyanate (IPDI). The catalyst is one or two of dibutyl tin dilaurate or stannous octoate; the carboxylic acid group-containing alcohol small molecule chain extender is 2, 2-dimethylolpropionic acid (DMPA). The alcohol small molecule chain extender with carboxylic acid groups is 2, 2-dimethylolpropionic acid (DMPA), and the carboxylic acid groups can enhance the water solubility of the prepolymer, so that the prepolymer has better dispersibility in water.
S2, adding 2-6 parts of acrylic ester into the product obtained in the step S1, reacting for 3-8 hours at 70-80 ℃, and introducing a photo-curing group. The acrylic ester is hydroxyethyl methacrylate (HEMA) or hydroxyethyl acrylate (HEA).
S3, adding 2-4 parts of triethylamine into the product of the step S2, reacting for 0.5-1 h at the temperature of 30-45 ℃ and neutralizing carboxylic acid groups; the remaining organic solvent was removed under vacuum. Triethylamine was used as a neutralizing agent and added at a neutralization degree of 100%.
S4, adding 1-3 parts of amino acid micromolecular chain extender and 90-200 parts of deionized water into the product of the step S3, and reacting for 0.5-1 h at 30-45 ℃ under stirring at a rotating speed of 1000-2000 rpm (high-speed stirring), thus obtaining the aqueous polyurethane dispersion liquid with the solid content of 25-45%. The amino acid small molecule chain extender is diamine amino, namely amino acid with two amino groups such as arginine and lysine, so that the stability of the waterborne polyurethane in water is enhanced, the biotoxicity is reduced, and the biodegradation is greener.
And S5, adding 0.4-2 parts of photoinitiator into the product obtained in the step S4, uniformly stirring, and removing the organic solvent and triethylamine by rotary evaporation to obtain the amino acid modified waterborne polyurethane acrylate. The photoinitiator is selected from 2959, LAP and VA-086, and has the characteristics of good water solubility and low biotoxicity.
The embodiment of the invention also provides the amino acid modified waterborne polyurethane acrylate prepared by the method. The raw materials of the amino acid modified waterborne polyurethane acrylic ester comprise 30-45 parts of polyhydric alcohol, 11-18 parts of diisocyanate, 0.5 part of catalyst, 2-3 parts of alcohol micromolecule chain extender with carboxylic acid groups, 5-10 parts of organic solvent, 2-6 parts of acrylic ester, 2-4 parts of triethylamine, 1-3 parts of amino acid micromolecule chain extender, 90-200 parts of deionized water and 0.4-2 parts of photoinitiator.
The embodiment of the invention also provides the application of the amino acid modified waterborne polyurethane acrylate in the biological fixing material, and the material has good hydrolysis resistance, biocompatibility and mechanical property and can be used as an ideal biological fixing material.
Example 1
The production raw materials are as follows: the amino acid modified waterborne polyurethane acrylic ester is synthesized by the following raw materials in percentage by mass: 28 parts of molecular weight 2000 polybutylene adipate glycol (PBA), 2 parts of molecular weight 2000 polyethylene glycol (PEG), 11.7 parts of isophorone diisocyanate (IPDI), 0.5 part of stannous octoate, 2 parts of 2, 2-dimethylolpropionic acid (DMPA), 8 parts of acetone, 2.5 parts of hydroxyethyl acrylate (HEA), 2.7 parts of triethylamine, 1.7 parts of lysine, 118 parts of deionized water and 0.4 part of photoinitiator LAP.
The preparation method comprises the following steps:
(1) Preparation of novel aqueous polyurethane prepolymer: 250ml of a three-neck flask equipped with a stirrer and a reflux condenser is placed in an oil bath pot with adjustable temperature, 28 parts of 2000 molecular weight polybutylene adipate glycol (PBA) and 2 parts of polyethylene glycol (PEG) which are dehydrated in advance are added, the temperature is raised to 70 ℃, and the mixture is stirred uniformly at 120 r/min. 11.7 parts of isophorone diisocyanate (IPDI) was added and reacted for 3 hours under the condition of 0.5 part of stannous octoate catalyst. The temperature was raised to 85℃and 2 parts of 2, 2-dimethylolpropionic acid (DMPA) and 8 parts of a small amount of acetone were added to react for 2 hours.
(2) Introduction of photo-curing groups: the temperature was lowered to 70℃and 2.5 parts of hydroxyethyl acrylate (HEA), a small molecular monomer having a photo-curing group, was added thereto and reacted for 5 hours with stirring at 120 r/min.
(3) Neutralization of carboxylic acid groups: the reaction temperature is reduced to 40 ℃, and triethylamine with the mass fraction of 2.7 parts is added for neutralization for 30min.
(4) Amino acid modification and preparation of aqueous polyurethane dispersion: 1.7 parts of lysine is dissolved in 118 parts of deionized water, slowly added dropwise into a three-neck flask, the solid content is regulated to 30%, and the mixture is dispersed for 40 minutes under the stirring of 1200r/min to obtain the aqueous polyurethane with good biocompatibility.
(5) Adding a photoinitiator: 0.4 part of photoinitiator LAP is added into the waterborne polyurethane and stirred uniformly.
(6) Acetone and triethylamine are removed through a rotary evaporator, and finally the finished amino acid modified waterborne polyurethane acrylic ester is obtained.
Example 2
The production raw materials are as follows: the amino acid modified waterborne polyurethane acrylic ester is synthesized by the following raw materials in percentage by mass: 42 parts of poly epsilon-caprolactone diol (PCL) with molecular weight of 2000, 3 Parts of Polypropylene Glycol (PPG) with molecular weight of 2000, 18 parts of lysine ethyl ester diisocyanate (LDI), 0.8 part of dibutyltin dilaurate, 3 parts of 2, 2-dimethylolpropionic acid (DMPA), 10 parts of butanone, 4 parts of hydroxyethyl acrylate (HEA), 4 parts of triethylamine, 3 parts of arginine, 178 parts of deionized water and 2959.6 parts of photoinitiator.
The preparation method comprises the following steps:
(1) Preparation of novel aqueous polyurethane prepolymer: 42 parts of pre-dehydrated 2000 molecular weight poly epsilon-caprolactone diol (PCL) and 3 Parts of Polypropylene Glycol (PPG) were charged into a 250ml four-necked flask equipped with a stirrer, reflux condenser and thermometer, heated to 80℃and stirred uniformly at 120 r/min. 18 parts of lysine ethyl ester diisocyanate (LDI) were added and reacted for 2.5 hours under the condition of 0.8 part of dibutyltin dilaurate catalyst. The temperature was raised to 85℃and 3 parts of 2, 2-dimethylolpropionic acid (DMPA) and 10 parts of butanone were added and reacted for 2 hours.
(2) Introduction of photo-curing groups: the temperature was lowered to 70℃and 4 parts of hydroxyethyl acrylate (HEA) as a small molecular monomer having a photo-curing group was added thereto and reacted for 5 hours under stirring at 120 r/min.
(3) Neutralization of carboxylic acid groups: the reaction temperature is reduced to 40 ℃, and triethylamine with the mass fraction of 4 parts is added for neutralization for 30min.
(4) Amino acid modification and preparation of aqueous polyurethane dispersion: 3 parts of arginine was dissolved in 178 parts of deionized water, and the mixture was slowly dropped into a three-necked flask, the solid content was adjusted to 30%, and the mixture was dispersed for 40 minutes under stirring of 1300 r/min.
(5) Adding a photoinitiator: 0.6 part of photoinitiator 2959 is added into the waterborne polyurethane and stirred uniformly.
(6) Butanone and triethylamine are removed through a rotary evaporator, and finally the finished product amino acid modified waterborne polyurethane acrylic ester is obtained.
Tensile test:
the tensile mechanical properties of the samples were tested by a universal materials tester (AGX-100 plus, shimadzu, japan). The amino acid modified aqueous urethane acrylate synthesized in example 1 was poured into a mold of polytetrafluoroethylene, dried at 35℃for 2d, and then cured by irradiation with ultraviolet lamp of 385nm,5W for 5-10min. The cured film was cut into 25mm (length) ×5mm (width) ×0.5mm (thickness) for convenience of testing. The films were tested for tensile properties at a tensile speed of 10 mm/min. The test method is shown in fig. 1, and the test result is shown in fig. 2.
As can be seen from fig. 2, the amino acid modified aqueous urethane acrylate synthesized in example 1 has excellent mechanical properties, and exhibits typical elastomer stretching behavior with the occurrence of yield points. The tensile strength reaches 7.1MPa, and the elongation at break reaches 350%.
Hydrolysis resistance test:
the prepared film (preparation method and tensile test) was cut to a size of 10X 10mm, weighed to obtain an initial weight, denoted w0, placed in 10ml of deionized water and placed in a constant temperature shaker at 30℃and 120 rpm. Samples were taken at specific times (7 d, 14d, 21d, 28d, 42d, 60 d) and dried in an oven at 35 ℃ for 2d, and re-weighed (w 1). Weight loss (%) = (w 0-w 1)/w0×100%, where w0 and w1 are dry weight before and after degradation of the sample, respectively. Three samples per group were tested and the end result was the average of these measurements. The results are shown in FIG. 3.
As a result, the amino acid modified aqueous polyurethane acrylate synthesized in the two examples has excellent hydrolysis resistance. The amino acid modified aqueous polyurethane acrylates synthesized in example 1 and example 2 degraded 15.51% and 14.42% after 60 days, respectively.
Biocompatibility testing:
the biocompatibility of the bacteria-carrying sample was evaluated by using a laser confocal scanning microscope, and the results are shown in fig. 4.
From fig. 4, it can be seen that the amino acid modified aqueous polyurethane acrylate bacteria-carrying sample synthesized in example 1 sequentially from left to right shows the survival condition of digestive bacteria at 0h,24h and 48h, and the material is beneficial to the growth of nitrifying bacteria, and has good biocompatibility.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, and various modifications and variations may be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (7)

1. The preparation method of the amino acid modified waterborne polyurethane acrylate is characterized by comprising the following steps of:
s1, taking 30-45 parts of polyol, 11-18 parts of diisocyanate and 0.5 part of catalyst, uniformly mixing, reacting for 2-4 hours in a nitrogen atmosphere at 70-80 ℃, then adding 2-3 parts of alcohol micromolecular chain extender with carboxylic acid groups and 5-10 parts of organic solvent, and reacting for 1-3 hours at 70-85 ℃ to obtain an aqueous polyurethane prepolymer;
s2, adding 2-6 parts of acrylic ester into the product obtained in the step S1, reacting for 3-8 hours at 70-80 ℃, and introducing a photo-curing group;
s3, adding 2-4 parts of neutralizing agent into the product obtained in the step S2, and reacting for 0.5-1 h at the temperature of 30-45 ℃ to neutralize carboxylic acid groups; removing the residual organic solvent under vacuum;
s4, adding 1-3 parts of an amino acid micromolecule chain extender and 90-200 parts of deionized water into the product obtained in the step S3, and reacting for 0.5-1 h under stirring at 30-45 ℃ and 1000-2000 rpm to obtain an aqueous polyurethane dispersion liquid with 25-45% of solid content;
s5, adding 0.4-2 parts of photoinitiator into the product obtained in the step S4, uniformly stirring, and removing the organic solvent and triethylamine by rotary evaporation to obtain the amino acid modified waterborne polyurethane acrylate;
the acrylic ester is hydroxyethyl methacrylate (HEMA) or hydroxyethyl acrylate (HEA); the photoinitiator is selected from 2959, LAP and VA-086;
the molecular weight of the polyol is 1000-2000;
the amino acid small molecule chain extender is diamine amino acid.
2. The method for producing an amino acid-modified aqueous urethane acrylate according to claim 1, wherein the polyol is one or more of polyepsilon caprolactone diol, polyethylene glycol (PEG), polypropylene glycol (PPG), and polydiacid glycol ester diol.
3. The method for preparing amino acid modified aqueous urethane acrylate according to claim 1, wherein said diisocyanate is one or more of isophorone diisocyanate (IPDI) and lysine ethyl ester diisocyanate (LDI).
4. The method for producing an amino acid-modified aqueous urethane acrylate according to claim 1, wherein the catalyst is one or both of dibutyltin dilaurate and stannous octoate.
5. The method for preparing the amino acid modified waterborne polyurethane acrylate according to claim 1, wherein the alcohol small molecule chain extender with carboxylic acid groups is 2, 2-dimethylolpropionic acid (DMPA).
6. An amino acid modified aqueous polyurethane acrylate prepared by the method of any one of claims 1 to 5.
7. Use of the amino acid modified aqueous polyurethane acrylate of claim 6 in biological immobilization materials.
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CN108219093A (en) * 2016-12-14 2018-06-29 乐凯华光印刷科技有限公司 A kind of cured alcohol-soluble polyurethane of ultraviolet light and preparation method thereof
CN110669188A (en) * 2019-10-21 2020-01-10 南京林业大学 Waterborne polyurethane coating capable of self-repairing through ultraviolet light and preparation method thereof
CN112745732A (en) * 2021-01-18 2021-05-04 万华化学集团股份有限公司 Preparation of environment-friendly formaldehyde-removing polymer latex and application of environment-friendly formaldehyde-removing polymer latex in coating

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CN1712423A (en) * 2004-06-25 2005-12-28 拜尔材料科学有限责任公司 Polyurethane dispersions with high acid content
CN101230125A (en) * 2008-02-29 2008-07-30 安徽大学 Water-soluble alcohol-soluble polyurethane and preparation method thereof
CN105461863A (en) * 2015-12-23 2016-04-06 中山大学惠州研究院 Acrylate modified waterborne polyurethane emulsion and preparation method thereof
CN108219093A (en) * 2016-12-14 2018-06-29 乐凯华光印刷科技有限公司 A kind of cured alcohol-soluble polyurethane of ultraviolet light and preparation method thereof
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