CN113416319A - Ultraviolet light blocking type hydrogel containing immobilized nanoparticles and preparation method thereof - Google Patents

Ultraviolet light blocking type hydrogel containing immobilized nanoparticles and preparation method thereof Download PDF

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CN113416319A
CN113416319A CN202110569215.5A CN202110569215A CN113416319A CN 113416319 A CN113416319 A CN 113416319A CN 202110569215 A CN202110569215 A CN 202110569215A CN 113416319 A CN113416319 A CN 113416319A
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hydrogel
ultraviolet light
light blocking
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CN113416319B (en
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张玲
于健
兰巧巧
毛小雨
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Dragon Totem Technology Hefei Co ltd
Hanzhong Shuobong Medical Technology Co ltd
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Lishui University
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Abstract

本发明属于功能型水凝胶材料技术领域，公开了一种含固定化纳米粒子的紫外光阻隔型水凝胶及其制备方法。采用零价铁粒子氧化成的纳米氧化铁与过硫酸盐形成的氧化还原型引发剂在水凝胶中引发含紫外光阻隔功能的单体和含羧基单体的微乳液聚合形成具有紫外光阻隔性能的纳米粒子，再利用EDC/NHS实现纳米粒子在水凝胶中的固定化。本发明利用零价纳米铁粒子氧化后可缓慢提供Fe2+作为缓释剂与过硫酸盐形成氧化还原体系，保证含有光阻隔效果的纳米粒子在水凝胶中以较为温和条件形成，而下一步的固化条件也是较为温和不易破坏水凝胶结构。本发明通过EDC/NHS将具有紫外光阻隔性能的纳米粒子固定于水凝胶体系中，解决了长期使用后纳米粒子外溢和团聚的问题。

Figure 202110569215

The invention belongs to the technical field of functional hydrogel materials, and discloses an ultraviolet light blocking hydrogel containing immobilized nanoparticles and a preparation method thereof. Using the oxidation-reduction initiator of nano-iron oxide formed by the oxidation of zero-valent iron particles and persulfate to initiate microemulsion polymerization of monomers with UV light blocking function and carboxyl group-containing monomers in hydrogels to form microemulsion polymerization with UV light blocking Nanoparticles with high performance, and then use EDC/NHS to achieve the immobilization of nanoparticles in hydrogels. The invention utilizes zero-valent nano-iron particles to be oxidized and can slowly provide Fe 2+ as a slow-release agent to form a redox system with persulfate, so as to ensure that nanoparticles with light blocking effect are formed in a hydrogel under relatively mild conditions, and The one-step curing conditions are also milder and less likely to damage the hydrogel structure. The invention fixes the nanoparticles with ultraviolet light blocking performance in the hydrogel system through EDC/NHS, and solves the problems of overflow and agglomeration of the nanoparticles after long-term use.

Figure 202110569215

Description

Ultraviolet light blocking type hydrogel containing immobilized nanoparticles and preparation method thereof
The technical field is as follows:
the invention belongs to the technical field of functional hydrogel materials, and particularly relates to an ultraviolet light blocking type hydrogel containing immobilized nanoparticles and a preparation method thereof.
Background art:
the polymer hydrogel can be applied to the fields of corneal contact angle, artificial tissue and the like. When the hydrogel is applied to a corneal contact lens, the hydrogel with functions of blocking ultraviolet rays and releasing drug has higher popularization value and application prospect, but the traditional light blocking water-proof gel is prepared by adding a light blocking agent of micromolecule or inorganic nanoparticles into a hydrogel raw material through a physical blending method, and the raw material is remained in the hydrogel after reaction. The problems of overflow, phase separation and agglomeration can exist when the catalyst is used for a long time. In addition, the preparation method and the defects of the hydrogel with the function of releasing the medicine by wrapping the nano particles are basically the same, which not only influences the light transmittance of the hydrogel, but also causes biological toxicity.
In the preparation of functionalized hydrogel, the in-situ generation of nanoparticles has been a difficult problem, because the special structure and chemical composition of hydrogel make the preparation process of nanoparticles loaded therein need mild reaction conditions, which also becomes a difficult point for developing such materials. Therefore, the development of a reasonable process for effectively improving the application value of the hydrogel is significant.
The invention content is as follows:
in order to overcome the defects mentioned in the background technology, the invention provides a preparation method of ultraviolet light blocking type hydrogel, and the invention uses a reducing agent and Fe3+The solution introduces zero-valent iron particles into hydrogel grids, and generates Fe through oxidation2+When persulfate is added, the system can form a redox system, and the pre-emulsion containing light barrier can be initiated to polymerize under mild conditions, because of Fe2+The ions are supplied by the oxidized nano-iron particles, compared with the direct preparation of Fe2+The reaction speed of the ions is not too fast, and Fe can be controlled by adjusting oxygen supply2+The generated ions and the generated nanoparticles with the light blocking effect contain reactive active functional group carboxyl, and the nanoparticles can react with the active functional group amino of the hydrogel after being activated by EDC/NHS, so that the nanoparticles are fixed.
The invention is realized by the following technical scheme:
a preparation method of an ultraviolet light blocking type hydrogel containing immobilized nanoparticles comprises the following steps:
the method comprises the following steps: mixing 20-100ml of the mixture in a volume ratio of 1-4: adding the mixed solvent of water and glycol of 1 into a beaker, adding 10-50g of the monomer mixture 1, performing ultrasonic dispersion at low temperature for 10-30min, adding 0.05-1g of initiator, performing ultrasonic dispersion at low temperature for 15-50min, pouring into a mold after the ultrasonic dispersion is finished, standing for 8-18h at 30-60 ℃, heating to 50-90 ℃, and keeping for 12-36h to obtain an intermediate product;
step two: putting the intermediate product obtained in the step one into a three-neck flask, adding 100-500ml deionized water to soak for 1-3 days, replacing the deionized water every 8h, introducing nitrogen for 20-60min, then transferring the whole system into an oscillating table at an oscillating speed of 20-300rpm/min, firstly adding 10-150ml reducing agent, and then dropwise adding 5-100ml Fe3+Continuously oscillating the solution for 0.5-12h after the dropwise adding is finished to obtain hydrogel 1;
step three: adding 15-30g of monomer mixture 2 (containing vinyl ultraviolet absorbent, carboxyl acrylate and n-butyl acrylate), 1-15g of 1-pentanol and 0.01-1.5g of emulsifier into a three-neck flask filled with 50-300ml of distilled water, and stirring for 20-60min to obtain a pre-emulsion; placing the hydrogel 1 prepared in the step two into a three-neck flask, adding 20-200ml of deionized water, placing on an oscillating shaker, oscillating at the speed of 20-50rpm/min and introducing oxygen, placing 5-40ml of the pre-emulsion into a micro-sample injector, placing 5-50ml of 0.01-1g/ml persulfate aqueous solution for later use, under the oscillation at the speed of 20-100rpm/min, dropwise adding persulfate aqueous solution into the diluted hydrogel and simultaneously injecting the pre-emulsion, maintaining the oscillation at the speed of 20-100rpm/min for 10-24h after the dropwise adding and sample introduction are finished, and stopping oxygen supply to obtain a hydrogel 2;
step four: and (3) putting the hydrogel 2 obtained in the third step into an erlenmeyer flask filled with 50-200ml of PBS aqueous solution with the pH value of 4.5-7, respectively adding (1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride) (EDC) and N-hydroxysuccinimide (NHS), moving the erlenmeyer flask into a shaking table, shaking for 0.5-24h at the speed of 50-300rpm/min, and washing for 1-3 times by using deionized water to obtain the target hydrogel.
Wherein, in the first step, the monomer mixture 1 is prepared by mixing the following components in a mass ratio of 1: 0.01-0.1:0.01-0.2 of hydroxyethyl methacrylate, ethylene glycol dimethacrylate and amino group-containing monomer; wherein the amino-containing monomer is one or a mixture of more of 1-allyl piperazine, N-ethyl methyl allylamine, N-methyl allylamine and diallyl amine.
Wherein, the initiator in the first step is persulfate or azobisisobutyronitrile;
and in the second step, the reducing agent is sodium borohydride or glucose, and the concentration of the reducing agent solution is 0.2-0.5 g/ml.
Wherein, Fe in the second step3+The solution is ferric trichloride hexahydrate, ferric chloride or ferric nitrate aqueous solution, and the concentration of the solution is 0.1-0.9 g/ml.
Wherein, the vinyl-containing ultraviolet absorbent in the third step is one or more of 2- (2 '-hydroxy-5' -2- (methacryloyloxy) ethyl) phenyl) -2H-benzotriazole, 2- [3- (2H-benzotriazole-2-yl) -4-hydroxyphenyl ] ethyl 2-methacrylate, and 2- (4-benzoyl-3-hydroxyphenoxy) ethyl 2-acrylate.
Wherein the mass ratio of the vinyl-containing ultraviolet absorbent, the carboxyl-containing acrylate and the n-butyl acrylate in the third step is 1:50-150: 100-300.
Wherein the emulsifier in the third step is one or a mixture of more of an op-10 emulsifier, sodium dodecyl sulfate, sodium dodecyl benzene sulfonate and octadecyl trimethyl ammonium chloride.
Wherein, the persulfate in the third step is one or a mixture of more of ammonium persulfate, potassium persulfate and sodium persulfate.
Wherein the concentration range of (1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride) in the fourth step is 0.5-20mg/ml, and the dosage of the concentration is 0.05-0.2 percent of the total amount of the amino monomer and the carboxyl monomer; the concentration range of the N-hydroxysuccinimide is 0.1-15mg/ml, and the dosage of the N-hydroxysuccinimide accounts for 0.05% -0.2% of the total amount of the amino monomer and the carboxyl monomer.
The ultraviolet light blocking hydrogel loaded with the nano particles is prepared by the preparation method.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention uses reducing agent and Fe3+The solution introduces zero-valent iron particles into hydrogel grids, and generates Fe through oxidation2+The oxide of (2) forms a redox system after adding persulfate, and can initiate the polymerization of the pre-emulsion containing light barrier under mild conditions, because of Fe2+The ions are supplied by the oxidized nano-iron particles, compared with the direct preparation of Fe2+The reaction speed of ions is not too fast, the reaction is mild, the hydrogel structure is not easy to be damaged, and Fe can be controlled by supplying oxygen2+Ions are generated, thereby controlling the extent of the reaction. Solves the technical problem that the preparation process and reaction conditions of the hydrogel heavy-load nano particles need to be very mild. In addition, the mild and controllable reaction enables the nano ions to form slowly without agglomeration, so that the prepared hydrogel keeps good light transmittance.
2. According to the invention, the amino groups of the EDC/NHS activated hydrogel react with the carboxyl groups of the nanoparticles to fix the nanoparticles with ultraviolet light blocking performance in the hydrogel system, the reaction conditions are mild, and the problems of nanoparticle overflow and agglomeration after long-term use are solved.
Description of the drawings:
FIG. 1 shows the UV transmittance of hydrogels prepared in examples 1-5 of the present invention;
FIG. 2 shows the cumulative release of nanoparticles after 10 days for the hydrogels prepared in examples 1-5 of the present invention.
The specific implementation mode is as follows:
the present invention is described in detail below with reference to examples, which are provided for further illustration of the present invention and are not to be construed as limiting the scope of the present invention. It should be understood that various changes and modifications can be made by those skilled in the art after reading the disclosure of the present invention, and equivalents fall within the scope of the appended claims.
Example 1
The method comprises the following steps: 50ml of the mixture is mixed into a mixture with the volume ratio of 3: 1, adding a mixed solvent of water and ethylene glycol into a beaker, and adding 30g of a mixed solvent with the mass ratio of 1: 0.05:0.015 of a mixture of hydroxyethyl methacrylate, ethylene glycol dimethacrylate and 1-allylpiperazine, ultrasonically dispersing for 15min at low temperature, adding 0.1g of azobisisobutyronitrile, ultrasonically separating for 45min at low temperature, pouring into a mold after the ultrasonic dispersion is finished, standing for 9h at 40 ℃, heating to 60 ℃, and keeping for 12h to obtain an intermediate product;
step two: putting the intermediate product obtained in the first step into a three-neck flask, adding 200ml of deionized water, soaking for 2 days, replacing the deionized water every 8 hours, then introducing nitrogen for 30min, then transferring the whole system into an oscillating table, adjusting the oscillation speed to 200rpm/min, firstly adding 60mlm of 0.3g/ml sodium borohydride solution, then dropwise adding 55ml of 0.5g/ml ferric chloride solution, and continuing to oscillate for 5 hours after dropwise adding is finished to obtain hydrogel 1;
step three: adding 20g of 2- (2 '-hydroxy-5' -2- (methacryloyloxy) ethyl) phenyl) -2H-benzotriazole, a mixture of carboxyl-containing acrylate and n-butyl acrylate, 7g of 1-Pentanol (1-Pentanol) and 0.3g of op-10 emulsifier in a mass ratio of 1:100:210 into a three-neck flask filled with 120ml of distilled water, stirring for 35min to obtain a pre-emulsion, putting the hydrogel 1 into the three-neck flask, adding 60ml of deionized water, placing the hydrogel on a shaking table, shaking at a speed of 40rpm/min and introducing oxygen, putting 20ml of the pre-emulsion into a microsyringe, taking 30ml of 0.05g/ml of ammonium persulfate aqueous solution for standby, dropping the ammonium persulfate aqueous solution into the hydrogel and simultaneously injecting the pre-emulsion under shaking at a speed of 70rpm/min, after the dripping and the sample introduction are finished, maintaining the speed of 60rpm/min for oscillation for 16h, and stopping supplying oxygen to obtain hydrogel 2;
step four: placing the hydrogel 2 obtained in the third step into an erlenmeyer flask containing 120ml of PBS aqueous solution with the pH value of 7, adding 8ml of (1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride) (EDC) with the concentration of 1mg/ml and 4ml of N-hydroxysuccinimide (NHS) with the concentration of 2mg/ml respectively, moving the erlenmeyer flask into a shaking table, shaking for 1h at the speed of 100rpm/min, and washing for 3 times by using deionized water to obtain the target hydrogel.
Example 2
The method comprises the following steps: mixing 60ml of the mixture in a volume ratio of 3: 1, adding a mixed solvent of water and ethylene glycol into a beaker, and adding 30g of a mixed solvent with the mass ratio of 1: 0.05:0.05 of mixture of hydroxyethyl methacrylate, ethylene glycol dimethacrylate and N-ethyl methyl acrylamide, ultrasonically dispersing for 25min at low temperature, then adding 0.07g of azodiisobutyronitrile, ultrasonically dispersing for 40min at low temperature, pouring into a mold after the ultrasonic dispersion is finished, standing for 10h at 50 ℃, heating to 60 ℃, and keeping for 24h to obtain an intermediate product;
step two: putting the intermediate product obtained in the first step into a three-neck flask, adding 200ml of deionized water, soaking for 3 days, replacing the deionized water every 8 hours, then introducing nitrogen for 50min, then transferring the whole system into an oscillating table, adjusting the oscillating speed to 200rpm/min, firstly adding 100ml of 0.3g/ml sodium borohydride solution, then dropwise adding 90ml of 0.6g/ml ferric chloride solution, and continuing to oscillate for 6 hours after dropwise adding is finished to obtain hydrogel 1;
step three: adding 25g of 2- (2 '-hydroxy-5' -2- (methacryloyloxy) ethyl) phenyl) -2H-benzotriazole, a mixture of carboxyl-containing acrylate and n-butyl acrylate, 10g of 1-Pentanol (1-Pentanol) and 1g of sodium dodecyl sulfate in a mass ratio of 1:120:200 into a three-neck flask filled with 100ml of distilled water, stirring for 60min to obtain a pre-emulsion, putting the hydrogel 1 into the three-neck flask, adding 100ml of deionized water, placing on a shaking table, shaking at a speed of 50rpm/min and introducing oxygen, taking 30ml of the pre-emulsion into a microsyringe, taking 40ml of 0.5g/ml ammonium persulfate aqueous solution for standby, dropping the ammonium persulfate aqueous solution into the hydrogel and simultaneously injecting the pre-emulsion under shaking at a speed of 80rpm/min, after the dripping and the sample introduction are finished, the speed of 70rpm/min is maintained for oscillation for 20h, and oxygen supply is stopped to obtain hydrogel 2;
step four: placing the hydrogel 2 obtained in the third step into an erlenmeyer flask containing 100ml of PBS aqueous solution with the pH value of 4.5, adding 10ml of (1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride) (EDC) with the concentration of 1mg/ml and 10ml of N-hydroxysuccinimide (NHS) with the concentration of 1.5mg/ml respectively, moving the erlenmeyer flask into a shaking table, shaking for 0.5h at the speed of 250rpm/min, and washing for 2 times with deionized water to obtain the target hydrogel.
Example 3
The method comprises the following steps: mixing 65ml of the mixture in a volume ratio of 4: 1, adding a mixed solvent of water and ethylene glycol into a beaker, and adding 45g of a mixed solvent with the mass ratio of 1: 0.05:0.015 of a mixture of hydroxyethyl methacrylate, ethylene glycol dimethacrylate and 1-allylpiperazine, ultrasonically dispersing for 30min at low temperature, adding 0.8g of azobisisobutyronitrile, ultrasonically dispersing for 50min at low temperature, pouring into a mold after the ultrasonic dispersion is finished, standing for 18h at 55 ℃, heating to 80 ℃, and keeping for 30h to obtain an intermediate product;
step two: putting the intermediate product obtained in the step one into a three-neck flask, adding 300ml of deionized water, soaking for 2 days, replacing the deionized water every 8 hours, then introducing nitrogen for 50 minutes, then transferring the whole system into an oscillating table, adjusting the oscillation speed to 250rpm/min, firstly adding 125ml of 0.3g/ml sodium borohydride solution, then dropwise adding 95ml of 0.6g/ml ferric chloride solution, and continuing to oscillate for 11 hours after dropwise adding is finished to obtain hydrogel 1;
step three: adding 30g of 2- (4-benzoyl-3-hydroxyphenoxy) ethyl 2-acrylate, a mixture of carboxyl-containing acrylate and n-butyl acrylate, 15g of 1-Pentanol (1-Pentanol) and 1.3 gp-10 emulsifier in a mass ratio of 1:100:200 into a three-neck flask filled with 300ml of distilled water, stirring for 60min to obtain a pre-emulsion, putting the hydrogel 1 into the three-neck flask, adding 180ml of deionized water, placing on a shaking table, shaking at a speed of 50rpm/min and introducing oxygen, taking 30ml of the pre-emulsion into a microsyringe, taking 50ml of 0.5g/ml sodium persulfate aqueous solution for standby, dropping the sodium persulfate aqueous solution into the hydrogel and simultaneously injecting the pre-emulsion under the shaking at a speed of 100rpm/min, maintaining the shaking speed of 100rpm/min for 24h after dropping and sample introduction, stopping supplying oxygen to obtain hydrogel 2;
step four: placing the hydrogel 2 obtained in the third step into an erlenmeyer flask containing 130ml of PBS aqueous solution with the pH value of 5, respectively adding 20ml of (1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride) (EDC) with the concentration of 1mg/ml and 10ml of N-hydroxysuccinimide (NHS) with the concentration of 2mg/ml, moving the erlenmeyer flask into a shaking table, shaking for 3 hours at the speed of 250rpm/min, and then washing for 3 times by using deionized water to obtain the target hydrogel.
Example 4
The method comprises the following steps: mixing 40ml of the mixture in a volume ratio of 2: 1, adding 20g of a mixed solvent of water and ethylene glycol into a beaker, wherein the weight ratio of the mixed solvent to the mixed solvent is 1: 0.06:0.1 of a mixture of hydroxyethyl methacrylate, ethylene glycol dimethacrylate and 1-allylpiperazine, ultrasonically dispersing for 15min at low temperature, adding 0.3g of azobisisobutyronitrile, ultrasonically dispersing for 20min at low temperature, pouring into a mold after the ultrasonic dispersion is finished, standing for 9h at 40 ℃, heating to 50 ℃, and keeping for 15h to obtain an intermediate product;
step two: putting the intermediate product obtained in the first step into a three-neck flask, adding 150ml of deionized water, soaking for 2 days, replacing the deionized water every 8 hours, then introducing nitrogen for 20min, then transferring the whole system into an oscillating table, adjusting the oscillating speed to 100rpm/min, firstly adding 80ml of 0.3g/ml sodium borohydride solution, then dropwise adding 60ml of 0.7g/ml ferric chloride hexahydrate solution, and continuing to oscillate for 5 hours after dropwise adding is finished to obtain hydrogel 1;
step three: adding 15g of 2- (4-benzoyl-3-hydroxyphenoxy) ethyl 2-acrylate, a mixture of carboxyl-containing acrylate and n-butyl acrylate, 6g of 1-Pentanol (1-Pentanol) and 1.3g of sodium dodecyl benzene sulfonate in a mass ratio of 1:150:200 into a three-neck flask filled with 200ml of distilled water, stirring for 50min to obtain a pre-emulsion, putting the hydrogel 1 into the three-neck flask, adding 150ml of deionized water, placing on a shaking table, shaking at a speed of 40rpm/min and introducing oxygen, taking 30ml of the pre-emulsion into a microsyringe, taking 20ml of 0.2g/ml of sodium persulfate aqueous solution for standby, dropping the sodium persulfate aqueous solution into the hydrogel and simultaneously injecting the pre-emulsion under shaking at a speed of 100rpm/min, maintaining shaking at a speed of 100rpm/min for 14h after dropping and sample injection, stopping supplying oxygen to obtain hydrogel 2;
step four: putting the hydrogel 2 obtained in the third step into an erlenmeyer flask containing 60ml of PBS aqueous solution with the pH value of 6, respectively adding 10ml of (1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride) (EDC) with the concentration of 1mg/ml and 7ml of N-hydroxysuccinimide (NHS) with the concentration of 1mg/ml, moving the erlenmeyer flask into a shaking table, shaking for 2 hours at the speed of 200rpm/min, and washing for 2 times by using deionized water to obtain the target hydrogel.
Example 5
The method comprises the following steps: mixing 35ml of the mixture in a volume ratio of 3: 1, adding a mixed solvent of water and ethylene glycol into a beaker, and adding 1g of a mixed solvent of water and ethylene glycol in a mass ratio of 1: 0.06:0.05 of a mixture of hydroxyethyl methacrylate, ethylene glycol dimethacrylate and N-ethyl methyl acrylamide, ultrasonically dispersing for 15min at low temperature, then adding 0.25g of azobisisobutyronitrile, ultrasonically dispersing for 20min at low temperature, pouring into a mold after the ultrasonic dispersion is finished, standing for 12h at 35 ℃, heating to 65 ℃ and keeping for 20h to obtain an intermediate product;
step two: putting the intermediate product obtained in the first step into a three-neck flask, adding 150ml of deionized water, soaking for 2 days, replacing the deionized water every 8 hours, then introducing nitrogen for 30min, then transferring the whole system into an oscillating table, adjusting the oscillation speed to 150rpm/min, firstly adding 55ml of sodium borohydride solution with the concentration of 0.3g/ml, then dropwise adding 40ml of ferric chloride solution with the concentration of 0.7g/ml, and continuing to oscillate for 8 hours after dropwise adding is finished to obtain hydrogel 1;
step three: adding 15g of 2- (4-benzoyl-3-hydroxyphenoxy) ethyl 2-acrylate, a mixture of acrylic ester containing carboxyl and n-butyl acrylate, 6g of 1-Pentanol (1-Pentanol) and 1g of sodium dodecyl benzene sulfonate in a mass ratio of 1:150:200 into a three-neck flask filled with 100ml of distilled water, stirring for 35min to obtain a pre-emulsion, putting the hydrogel 1 into the three-neck flask, adding 120ml of deionized water, placing on a shaking table, shaking at a speed of 30rpm/min and introducing oxygen, taking 25ml of the pre-emulsion into a microsyringe, taking 35ml of 0.6g/ml ammonium persulfate aqueous solution for standby, adding the ammonium persulfate aqueous solution into the hydrogel dropwise and injecting the pre-emulsion simultaneously under the speed of 80rpm/min, keeping the dropping and sample injection speeds of 800rpm/min for 16h, stopping supplying oxygen to obtain hydrogel 2;
step four: placing the hydrogel 2 obtained in the third step into an erlenmeyer flask containing 90ml of PBS aqueous solution with pH 7, adding 8ml of (1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride) (EDC) with the concentration of 1mg/ml and 5ml of N-hydroxysuccinimide (NHS) with the concentration of 2mg/ml respectively, moving the erlenmeyer flask into a shaking table, shaking for 0.5h at the speed of 200rpm/min, and washing with deionized water for 2 times to obtain the target hydrogel.
The attached figure 1 in the description shows the ultraviolet transmittance of the hydrogel prepared in the embodiment 1-5 of the invention, and the ultraviolet transmittance of the ultraviolet-blocking hydrogel prepared in the embodiment 1-5 is 63% -70%.
Fig. 2 in the specification is a condition of nanoparticle cumulative release after 10 days of the hydrogel prepared in the embodiments 1 to 5, and the cumulative release rates of the nanoparticles after 10 days of the ultraviolet light blocking hydrogel prepared in the embodiments 1 to 5 are respectively 11%, 9%, 9%, 10% and 8%, which shows that in the ultraviolet light blocking hydrogel prepared in the embodiments of the present invention, the nanoparticles with ultraviolet light blocking performance are fixed in the hydrogel system and are not easy to overflow.

Claims (10)

1.一种含固定化纳米粒子的紫外光阻隔型水凝胶的制备方法，其特征在于：包括如下步骤：1. a preparation method of the ultraviolet light blocking type hydrogel containing immobilized nanoparticles, is characterized in that: comprise the steps: 步骤一：将20-100ml体积比为1-4：1的水和乙二醇混合溶剂加入到烧杯中，加入10-50g单体混合物1，在低温下超声分散10-30min，再加入0.05-1g引发剂并低温超声分散15-50min，超声分散完成后灌入模具中，在30-60℃下静置8-18h后，升温至50-90℃并保持12-36h得到中间产物；Step 1: Add 20-100ml of water and ethylene glycol mixed solvent with a volume ratio of 1-4:1 into the beaker, add 10-50g of monomer mixture 1, ultrasonically disperse at low temperature for 10-30min, and then add 0.05- 1g of initiator and ultrasonically dispersed at low temperature for 15-50min. After ultrasonic dispersion is completed, pour it into the mold. After standing at 30-60°C for 8-18h, the temperature is raised to 50-90°C and kept for 12-36h to obtain an intermediate product; 步骤二：将步骤一所得中间产物放入三口烧瓶中，加入100-500ml去离子水浸泡1-3天，期间每隔8h更换一次去离子水，再通氮气20-60min，然后将整个体系移入到振荡摇床中，振荡速度为20-300rpm/min，先加入10-150ml还原剂，再滴加5-100ml的Fe3+溶液，滴加完毕后继续振荡0.5-12h，得到水凝胶1；Step 2: Put the intermediate product obtained in step 1 into a three-necked flask, add 100-500ml of deionized water to soak for 1-3 days, replace the deionized water every 8h during the period, and then pass nitrogen for 20-60min, and then move the whole system into In the shaking shaker, the shaking speed is 20-300rpm/min, first add 10-150ml reducing agent, then dropwise add 5-100ml Fe 3+ solution, continue to shake for 0.5-12h after the dropwise addition, to obtain hydrogel 1 ; 步骤三：将15-30g单体混合物2（含乙烯基紫外吸收剂、含羧基丙烯酸酯、丙烯酸正丁酯）、1-15g1-戊醇和0.01-1.5g乳化剂加入到装有50-300ml蒸馏水的三口烧瓶中，搅拌20-60min得到预乳化液；将步骤二制得的水凝胶1放入三口烧瓶中加入20-200ml的去离子水，并置于振荡摇床上，以20-50rpm/min的速度振荡并通氧气，取5-40ml上述预乳化液于微量进样器中，并取5-50ml的0.01-1g/ml的过硫酸盐水溶液备用， 在20-100rpm/min速度振荡下，向稀释后的水凝胶中滴加过硫酸盐水溶液并同时注射预乳化液，滴加和进样完毕维持20-100rpm/min速度振荡10-24h，停止供氧得水凝胶2；Step 3: Add 15-30g of monomer mixture 2 (containing vinyl UV absorber, carboxyl-containing acrylate, n-butyl acrylate), 1-15g 1-pentanol and 0.01-1.5g emulsifier to 50-300ml distilled water In the three-necked flask, stir for 20-60min to obtain a pre-emulsion; put the hydrogel 1 obtained in step 2 into the three-necked flask, add 20-200ml of deionized water, and place it on a shaking shaker, at 20-50rpm/ Oxygen at the speed of 1 min, take 5-40ml of the above pre-emulsion into the micro-injector, and take 5-50ml of 0.01-1g/ml persulfate aqueous solution for use, and shake at 20-100rpm/min speed , drop the persulfate aqueous solution into the diluted hydrogel and inject the pre-emulsion at the same time, keep the speed of 20-100rpm/min vibration for 10-24h after the dripping and sample injection, stop the oxygen supply to obtain the hydrogel 2; 步骤四：将步骤三所得水凝胶2放入装有50-200ml的pH为4.5-7的PBS水溶液的锥形瓶中，分别加入(1-(3-二甲氨基丙基)-3-乙基碳二亚胺盐酸盐)（EDC）和N-羟基琥珀酰亚胺（NHS），将锥形瓶移入振荡摇床以50-300rpm/min的速度振荡0.5-24h，再用去离子水洗涤1-3次，得目标水凝胶。Step 4: Put the hydrogel 2 obtained in step 3 into a conical flask containing 50-200ml of a PBS aqueous solution with a pH of 4.5-7, add (1-(3-dimethylaminopropyl)-3- Ethylcarbodiimide hydrochloride) (EDC) and N-hydroxysuccinimide (NHS), the conical flask was moved to a shaking shaker and shaken at a speed of 50-300rpm/min for 0.5-24h, and then deionized Wash with water 1-3 times to obtain the target hydrogel. 2.根据权利要求1所述的一种负载纳米粒子的紫外光阻隔型水凝胶的制备方法，其特征在于：所述步骤一中单体混合物1是质量比为1：0.01-0.1:0.01-0.2的甲基丙烯酸羟乙酯、乙二醇二甲基丙烯酸酯以及含氨基单体；其中含氨基单体为1-烯丙基哌嗪、N-乙基甲基丙烯胺、N-甲基烯丙基胺和二烯丙基胺中一种或多种混合物。2. The preparation method of a nanoparticle-loaded ultraviolet light-blocking hydrogel according to claim 1, characterized in that: in the step 1, the monomer mixture 1 is a mass ratio of 1:0.01-0.1:0.01 -0.2 hydroxyethyl methacrylate, ethylene glycol dimethacrylate and amino-containing monomers; wherein amino-containing monomers are 1-allyl piperazine, N-ethyl methacrylamine, N-methyl methacrylate One or more mixtures of allylamine and diallylamine. 3.根据权利要求1所述的一种负载纳米粒子的紫外光阻隔型水凝胶的制备方法，其特征在于：所述步骤一中引发剂为过硫酸盐或偶氮二异丁腈；3. The preparation method of a nanoparticle-loaded ultraviolet light-blocking hydrogel according to claim 1, wherein the initiator is persulfate or azobisisobutyronitrile in the step 1; 所述步骤二中还原剂为硼氢化钠或葡萄糖，还原剂溶液浓度为0.2-0.5g/ml。In the second step, the reducing agent is sodium borohydride or glucose, and the concentration of the reducing agent solution is 0.2-0.5 g/ml. 4.根据权利要求1所述的一种负载纳米粒子的紫外光阻隔型水凝胶的制备方法，其特征在于：所述步骤二中Fe3+溶液为六水三氯化铁、氯化铁或硝酸铁的水溶液，其溶液浓度为0.1-0.9g/ml。4. the preparation method of a kind of nanoparticle-loaded ultraviolet light blocking hydrogel according to claim 1, is characterized in that: in described step 2, Fe solution is ferric trichloride hexahydrate, ferric chloride Or an aqueous solution of ferric nitrate with a solution concentration of 0.1-0.9g/ml. 5.根据权利要求1所述的一种负载纳米粒子的紫外光阻隔型水凝胶的制备方法，其特征在于：所述步骤三中含乙烯基紫外吸收剂为2-（2ˊ-羟基-5ˊ-（2-（甲基丙烯酰氧）乙基）苯基）-2H-苯并三唑、2-[3-(2H-苯并三唑-2-基)-4-羟基苯基]乙基2-甲基丙烯酸酯、2-丙烯酸 2-(4-苯甲酰-3-羟基苯氧基)乙基酯中一种或多种混合物。5. the preparation method of a kind of nano-particle-loaded ultraviolet light blocking hydrogel according to claim 1, is characterized in that: in described step 3, the ultraviolet absorber containing vinyl is 2-(2'-hydroxyl-5' -(2-(Methacryloxy)ethyl)phenyl)-2H-benzotriazole, 2-[3-(2H-benzotriazol-2-yl)-4-hydroxyphenyl]ethyl One or more mixtures of 2-methacrylate and 2-(4-benzoyl-3-hydroxyphenoxy)ethyl 2-acrylate. 6.根据权利要求1所述的一种负载纳米粒子的紫外光阻隔型水凝胶的制备方法，其特征在于：所述步骤三中含乙烯基紫外吸收剂、含羧基丙烯酸酯和丙烯酸正丁酯的质量比为1:50-150:100-300。6. The preparation method of a nanoparticle-loaded ultraviolet light-blocking hydrogel according to claim 1, wherein in the step 3, a vinyl-containing ultraviolet absorber, a carboxyl group-containing acrylate and n-butyl acrylate are included. The mass ratio of the ester is 1:50-150:100-300. 7.根据权利要求1所述的一种负载纳米粒子的紫外光阻隔型水凝胶的制备方法，其特征在于：所述步骤三中乳化剂为op-10乳化剂、十二烷基硫酸钠、十二烷基苯磺酸钠和十八烷基三甲基氯化铵中一种或多种混合物。7. the preparation method of a kind of nanoparticle-loaded ultraviolet light blocking hydrogel according to claim 1, is characterized in that: in described step 3, emulsifier is op-10 emulsifier, sodium lauryl sulfate , one or more mixtures of sodium dodecylbenzenesulfonate and octadecyltrimethylammonium chloride. 8.根据权利要求1所述的一种负载纳米粒子的紫外光阻隔型水凝胶的制备方法，其特征在于：所述步骤三中过硫酸盐为过硫酸铵、过硫酸钾、过硫酸钠中一种或多种混合物。8. the preparation method of a kind of nanoparticle-loaded ultraviolet light blocking hydrogel according to claim 1, is characterized in that: in described step 3, persulfate is ammonium persulfate, potassium persulfate, sodium persulfate one or more mixtures. 9.根据权利要求1所述的一种负载纳米粒子的紫外光阻隔型水凝胶的制备方法，其特征在于：所述步骤四中(1-(3-二甲氨基丙基)-3-乙基碳二亚胺盐酸盐)的浓度范围为0.5-20mg/ml，其用量为氨基单体和羧基单体总量的0.05%-0.2%；N-羟基琥珀酰亚胺的浓度范围为0.1-15mg/ml，其用量为氨基单体和羧基单体总量的0.05%-0.2%。9. The preparation method of a nanoparticle-loaded ultraviolet light-blocking hydrogel according to claim 1, wherein in the step 4, (1-(3-dimethylaminopropyl)-3- The concentration range of ethylcarbodiimide hydrochloride) is 0.5-20mg/ml, and its dosage is 0.05%-0.2% of the total amount of amino monomers and carboxyl monomers; the concentration range of N-hydroxysuccinimide is 0.1-15mg/ml, and its dosage is 0.05%-0.2% of the total amount of amino monomers and carboxyl monomers. 10.一种根据权利要求1-9任一所述的制备方法制得的负载纳米粒子的紫外光阻隔型水凝胶。10. A nanoparticle-loaded ultraviolet light blocking hydrogel prepared according to any one of the preparation methods of claims 1-9.
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