POSS grafted oxidized sodium alginate composite material prepared based on graft polymerization method and method
阅读说明：本技术 基于接枝聚合法制备的poss接枝氧化海藻酸钠复合材料及方法 (POSS grafted oxidized sodium alginate composite material prepared based on graft polymerization method and method ) 是由 高党鸽 程一铭 吕斌 马建中 叶梦玉 于 2020-12-15 设计创作，主要内容包括：本发明为一种基于接枝聚合法制备的POSS接枝氧化海藻酸钠复合材料及方法,其克服了现有技术中胶原改性剂制备过程中产生严重污染的问题,本发明制备过程绿色环保,方法简单,反应周期短。本发明采用下述原料制成：海藻酸钠3-6g,水30-50g,过硫酸铵1-2g,乙烯基笼型倍半硅氧烷0.2-0.8g,四氢呋喃2g,浓度为0.5g/ml的甲基丙烯酸水溶液10-25ml,浓度为0.2-0.5g/ml的高碘酸钠水溶液20ml。本发明首先利用接枝聚合制备POSS-SAG-MAA,然后将其与强氧化剂高碘酸钠反应,经透析冻干提纯后即得POSS-OSA-MAA。(The invention relates to a POSS grafted oxidized sodium alginate composite material prepared based on a graft polymerization method and a method thereof, which overcome the problem of serious pollution generated in the preparation process of a collagen modifier in the prior art. The invention is prepared by adopting the following raw materials: 3-6g of sodium alginate, 30-50g of water, 1-2g of ammonium persulfate, 0.2-0.8g of vinyl cage-type silsesquioxane, 2g of tetrahydrofuran, 10-25ml of methacrylic acid aqueous solution with the concentration of 0.5g/ml and 20ml of sodium periodate aqueous solution with the concentration of 0.2-0.5 g/ml. The preparation method comprises the steps of preparing POSS-SAG-MAA by graft polymerization, reacting the POSS-SAG-MAA with a strong oxidant sodium periodate, dialyzing, freeze-drying and purifying to obtain the POSS-OSA-MAA.)
1. A POSS grafting oxidized sodium alginate composite material prepared based on a grafting polymerization method is characterized in that: the material is prepared from the following raw materials: 3-6g of sodium alginate, 30-50g of water, 1-2g of ammonium persulfate, 0.2-0.8g of vinyl cage-type silsesquioxane, 2g of tetrahydrofuran, 10-25ml of methacrylic acid aqueous solution with the concentration of 0.5g/ml and 20ml of sodium periodate aqueous solution with the concentration of 0.2-0.5 g/ml.
2. A method for preparing a POSS grafted oxidized sodium alginate composite material based on a graft polymerization method is characterized by comprising the following steps: the method comprises the following steps:
the method comprises the following steps: preparing a POSS grafted sodium alginate composite material:
adding 3-6g of sodium alginate and 30-50g of water into a three-neck flask, heating to 50-70 ℃ in water bath, setting the rotating speed at 300-400 r/min, and stirring until the sodium alginate and the water are dissolved; adding 1-2g of ammonium persulfate into a three-neck flask, then dissolving 0.2-0.8g of vinyl cage-type silsesquioxane into 2g of tetrahydrofuran, pouring into the three-neck flask, slowly dropwise adding 10-25ml of methacrylic acid aqueous solution with the concentration of 0.5g/ml into the three-neck flask for graft polymerization reaction, reacting at constant temperature for 4-8h, naturally cooling to room temperature, and discharging to obtain the POSS grafted sodium alginate composite material;
step two: preparing POSS grafted oxidized sodium alginate:
and (3) reacting the POSS grafted sodium alginate composite material prepared in the step one with 20ml of sodium periodate aqueous solution with the concentration of 0.2-0.5g/ml for 10-24h in a dark place, dialyzing the product in deionized water for 48h, purifying, and freeze-drying the purified product to obtain the POSS grafted oxidized sodium alginate.
3. The method for preparing POSS grafted oxidized sodium alginate composite material based on the graft polymerization method as claimed in claim 2, wherein: the three-neck flask is a 100mL three-neck flask provided with a stirrer and a condensing device.
The technical field is as follows:
the invention belongs to the field of nano material preparation, and relates to a POSS grafted oxidized sodium alginate composite material prepared based on a graft polymerization method and a method thereof.
Background art:
sodium alginate is a natural polysaccharide extracted from brown algae, and the molecule of the polysaccharide is formed by connecting beta-D-mannuronic acid and alpha-L-guluronic acid. The sodium alginate can be endowed with special functions by modifying the sodium alginate. The structure of the temporary diol on the sodium alginate can be reacted with a strong oxidant to be converted into aldehyde group, and the aldehyde group with high reactivity widens the application field of the sodium alginate. Meanwhile, under the action of an initiator, hydroxyl on the sodium alginate can be used as an active free radical to carry out graft polymerization with unsaturated vinyl monomers, so that different characteristics of the sodium alginate are endowed.
The cage type silsesquioxane (POSS) is a novel organic-inorganic composite material with a molecular general formula of (RSO)1.5)nN is generally 6, 8, 10, 12, etc., with n being the most typical of 8. The core of the composite material is an inorganic framework composed of Si-O-Si, the composite material has a highly symmetrical nanoscale cubic cage-shaped framework, each vertex has an active site capable of being freely modified, and the advantages of organic materials and inorganic materials can be effectively integrated. The POSS modified sodium alginate can endow the POSS modified sodium alginate with thermal stability and drug sustained release performance, researchers prepare the sodium alginate coated POSS microspheres through the electrostatic action of the POSS and the sodium alginate, and the POSS coated POSS microspheres have application potential in the field of drug release.
The existing collagen modifier uses micromolecular aldehyde in the preparation process, the reaction process is easy to cause environmental pollution, and the preparation process is complex.
The invention content is as follows:
the invention aims to provide a POSS grafted oxidized sodium alginate composite material prepared based on a graft polymerization method and a method thereof, which overcome the problem of serious pollution generated in the preparation process of a collagen modifier in the prior art, and have the advantages of green and environment-friendly preparation process, simple method and short reaction period.
In order to achieve the purpose, the invention adopts the technical scheme that:
a POSS grafting oxidized sodium alginate composite material prepared based on a grafting polymerization method is characterized in that: the material is prepared from the following raw materials: 3-6g of sodium alginate, 30-50g of water, 1-2g of ammonium persulfate, 0.2-0.8g of vinyl cage-type silsesquioxane, 2g of tetrahydrofuran, 10-25ml of methacrylic acid aqueous solution with the concentration of 0.5g/ml and 20ml of sodium periodate aqueous solution with the concentration of 0.2-0.5 g/ml.
A method for preparing a POSS grafted oxidized sodium alginate composite material based on a graft polymerization method is characterized by comprising the following steps: the method comprises the following steps:
the method comprises the following steps: preparing a POSS grafted sodium alginate composite material:
adding 3-6g of sodium alginate and 30-50g of water into a three-neck flask, heating to 50-70 ℃ in water bath, setting the rotating speed at 300-400 r/min, and stirring until the sodium alginate and the water are dissolved; adding 1-2g of ammonium persulfate into a three-neck flask, then dissolving 0.2-0.8g of vinyl cage-type silsesquioxane into 2g of tetrahydrofuran, pouring into the three-neck flask, slowly dropwise adding 10-25ml of methacrylic acid aqueous solution with the concentration of 0.5g/ml into the three-neck flask for graft polymerization reaction, reacting at constant temperature for 4-8h, naturally cooling to room temperature, and discharging to obtain the POSS grafted sodium alginate composite material;
step two: preparing POSS grafted oxidized sodium alginate:
and (3) reacting the POSS grafted sodium alginate composite material prepared in the step one with 20ml of sodium periodate aqueous solution with the concentration of 0.2-0.5g/ml for 10-24h in a dark place, dialyzing the product in deionized water for 48h, purifying, and freeze-drying the purified product to obtain the POSS grafted oxidized sodium alginate.
The three-neck flask is a 100mL three-neck flask provided with a stirrer and a condensing device.
Compared with the prior art, the invention has the following advantages and effects:
1. the POSS grafted oxidized sodium alginate composite material containing a large amount of aldehyde groups and carboxyl groups is prepared by taking natural high-molecular sodium alginate, methacrylic acid and vinyl POSS as raw materials through a graft polymerization method and a sodium periodate oxidation method, has a multi-branched structure, and has an application prospect in the field of collagen modification.
2. The invention compounds POSS and sodium alginate through covalent bond. The POSS grafted sodium alginate composite material prepared by the method has the conversion rate of 90 percent, contains a large number of active functional groups capable of reacting with collagen on the multi-side chain structure of the POSS grafted oxidized sodium alginate composite material prepared by oxidizing the POSS grafted sodium alginate composite material, and has application prospect in the field of collagen modification.
3. The preparation process does not use micromolecular aldehyde, and the reaction process is green and efficient; the preparation method has the advantages of simple preparation process, mild conditions, short reaction period, easy control of reaction and good repeatability.
The specific implementation mode is as follows:
the present invention will be described in detail with reference to specific embodiments. These examples are intended to illustrate the invention and are not intended to limit the scope of the invention. The implementation conditions used in the examples can be further adjusted according to the specific experimental environment, and the implementation conditions not mentioned are generally the conditions in routine experiments.
The invention relates to a POSS grafted oxidized sodium alginate composite material based on a graft polymerization method and a method thereof, which comprises the steps of firstly preparing POSS-SAG-MAA by using graft polymerization, then reacting the POSS-SAG-MAA with a strong oxidant sodium periodate, dialyzing, freeze-drying and purifying to obtain the POSS-OSA-MAA, wherein the reaction route is shown as the following formula:
the invention is prepared by adopting the following raw materials: 3-6g of sodium alginate, 30-50g of water, 1-2g of ammonium persulfate, 0.2-0.8g of vinyl cage-type silsesquioxane, 2g of tetrahydrofuran, 10-25ml of methacrylic acid aqueous solution with the concentration of 0.5g/ml and 20ml of sodium periodate aqueous solution with the concentration of 0.2-0.5 g/ml.
The preparation method comprises the following steps:
the method comprises the following steps: preparation of POSS grafted sodium alginate
Adding 3-6g of Sodium Alginate (SAG) and 30-50g of water into a 100mL three-neck flask provided with a stirrer and a condensing device, heating the mixture in a water bath to 60 ℃, setting the rotating speed at 350r/min, stirring until the mixture is dissolved, adding 1-2g of ammonium persulfate into the three-neck flask, then dissolving 0.2-0.8g of vinyl cage-type silsesquioxane (POSS-Vi) into 2g of tetrahydrofuran, pouring the mixture into the three-neck flask, slowly dropwise adding 10-25mL of methacrylic acid (MAA) aqueous solution with the concentration of 0.5g/mL into the three-neck flask for graft polymerization, naturally cooling to room temperature after constant temperature reaction for 4-8h, and discharging to obtain the POSS graft sodium alginate composite material (POSS-SAG-MAA).
Step two: preparation of POSS grafted oxidized sodium alginate
And (2) reacting the POSS-SAG-MAA prepared in the step one with 20ml of sodium periodate aqueous solution with the concentration of 0.2-0.5g/ml for 10-24h in a dark place, dialyzing the product in deionized water for 48h, purifying, and freeze-drying the purified product to obtain the POSS grafted oxidized sodium alginate (POSS-OSA-MAA).
Example 1:
the method comprises the following steps: preparation of POSS grafted sodium alginate
Adding 3g of SAG and 30g of water into a 100mL three-neck flask provided with a stirrer and a condensing device, heating the water bath to 60 ℃, setting the rotating speed to be 350r/min, stirring until the mixture is dissolved, adding 1g of ammonium persulfate into the three-neck flask, then dissolving 0.2g of POSS-Vi into 2g of tetrahydrofuran, pouring the mixture into the three-neck flask, slowly dropwise adding 10mL of MAA aqueous solution with the concentration of 0.5g/mL into the three-neck flask for graft polymerization reaction, reacting at constant temperature for 4h, naturally cooling to room temperature, and discharging to obtain POSS-SAG-MAA.
Step two: preparation of POSS grafted oxidized sodium alginate
And (3) reacting the POSS-SAG-MAA prepared in the step one with 20ml of sodium periodate aqueous solution with the concentration of 0.2g/ml for 10 hours in a dark place, dialyzing the product in deionized water for 48 hours, purifying, and freeze-drying the purified product to obtain the POSS-OSA-MAA.
Example 2
The method comprises the following steps: preparation of POSS grafted sodium alginate
Adding 4g of SAG and 40g of water into a 100mL three-neck flask provided with a stirrer and a condensing device, heating the water bath to 60 ℃, setting the rotating speed to be 350r/min, stirring until the mixture is dissolved, adding 1.2g of ammonium persulfate into the three-neck flask, then dissolving 0.5g of POSS-Vi into 2g of tetrahydrofuran, pouring the mixture into the three-neck flask, slowly dropwise adding 15mL of MAA aqueous solution with the concentration of 0.5g/mL into the three-neck flask for graft polymerization reaction, carrying out constant temperature reaction for 4h, naturally cooling to room temperature, and discharging to obtain POSS-SAG-MAA.
Step two: preparation of POSS grafted oxidized sodium alginate
And (3) reacting the POSS-SAG-MAA prepared in the step one with 20ml of sodium periodate aqueous solution with the concentration of 0.5g/ml for 24 hours in a dark place, dialyzing the product in deionized water for 48 hours, purifying, and freeze-drying the purified product to obtain the POSS-OSA-MAA.
Example 3
The method comprises the following steps: preparation of POSS grafted sodium alginate
Adding 6g of SAG and 50g of water into a 100mL three-neck flask provided with a stirrer and a condensing device, heating the water bath to 60 ℃, setting the rotating speed to be 350r/min, stirring until the mixture is dissolved, adding 2g of ammonium persulfate into the three-neck flask, then dissolving 0.8g of POSS-Vi into 2g of tetrahydrofuran, pouring the mixture into the three-neck flask, slowly dropwise adding 25mL of MAA aqueous solution with the concentration of 0.5g/mL into the three-neck flask for graft polymerization reaction, reacting at constant temperature for 8h, naturally cooling to room temperature, and discharging to obtain POSS-SAG-MAA.
Step two: preparation of POSS grafted oxidized sodium alginate
And (3) reacting the POSS-SAG-MAA prepared in the step one with 20ml of sodium periodate aqueous solution with the concentration of 0.4g/ml for 24 hours in a dark place, dialyzing the product in deionized water for 48 hours, purifying, and freeze-drying the purified product to obtain the POSS-OSA-MAA.
Example 4
The method comprises the following steps: preparation of POSS grafted sodium alginate
Adding 5g of SAG and 45g of water into a 100mL three-neck flask provided with a stirrer and a condensing device, heating the water bath to 60 ℃, setting the rotating speed to be 350r/min, stirring until the mixture is dissolved, adding 1.8g of ammonium persulfate into the three-neck flask, then dissolving 0.6g of POSS-Vi into 2g of tetrahydrofuran, pouring the mixture into the three-neck flask, slowly dropwise adding 20mL of MAA aqueous solution with the concentration of 0.5g/mL into the three-neck flask for graft polymerization reaction, carrying out constant temperature reaction for 4-8h, naturally cooling to room temperature, and discharging to obtain POSS-SAG-MAA.
Step two: preparation of POSS grafted oxidized sodium alginate
And (3) reacting the POSS-SAG-MAA prepared in the step one with 20ml of sodium periodate aqueous solution with the concentration of 0.4g/ml for 18h in a dark place, dialyzing the product in deionized water for 48h, purifying, and freeze-drying the purified product to obtain the POSS-OSA-MAA.
Example 5
The method comprises the following steps: preparation of POSS grafted sodium alginate
Adding 4g of SAG and 35g of water into a 100mL three-neck flask provided with a stirrer and a condensing device, heating the water bath to 60 ℃, setting the rotating speed to be 350r/min, stirring until the mixture is dissolved, adding 1.2g of ammonium persulfate into the three-neck flask, then dissolving 0.4g of POSS-Vi into 2g of tetrahydrofuran, pouring the mixture into the three-neck flask, slowly dropwise adding 10mL of MAA aqueous solution with the concentration of 0.5g/mL into the three-neck flask for graft polymerization reaction, carrying out constant temperature reaction for 6h, naturally cooling to room temperature, and discharging to obtain POSS-SAG-MAA.
Step two: preparation of POSS grafted oxidized sodium alginate
And (3) reacting the POSS-SAG-MAA prepared in the step one with 20ml of sodium periodate aqueous solution with the concentration of 0.2g/ml for 16h in a dark place, dialyzing the product in deionized water for 48h, purifying, and freeze-drying the purified product to obtain the POSS-OSA-MAA.
The above embodiments are merely illustrative of the principles and effects of the present invention, and it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the inventive concept of the present invention, and the scope of the present invention is defined by the appended claims.