CN114605684A - Preparation method of POSS polymer/bone glue composite film - Google Patents
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- CN114605684A CN114605684A CN202210344487.XA CN202210344487A CN114605684A CN 114605684 A CN114605684 A CN 114605684A CN 202210344487 A CN202210344487 A CN 202210344487A CN 114605684 A CN114605684 A CN 114605684A
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- C08J5/18—Manufacture of films or sheets
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- C08J2351/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2351/08—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2389/00—Characterised by the use of proteins; Derivatives thereof
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Abstract
The invention relates to a preparation method of a POSS polymer/bone glue composite film. The preparation method takes vinyl monomers and octavinyl POSS as raw materials, prepares POSS polymer containing epoxy groups, carboxyl groups and ester groups through free radical polymerization, then modifies bone glue with the POSS polymer, and finally prepares the bone glue base composite film through a solution casting method, wherein the film has excellent mechanical property, thermal stability, water resistance and degradability. The invention utilizes the POSS polymer side chain polyfunctional group to generate covalent crosslinking and hydrogen bond action with the reactive active group of the bone glue, thereby improving the plasticity and water resistance of the bone glue film; the nano characteristic of POSS is utilized to improve the mechanical property and the thermal stability of the bone glue film. The bone glue base film obtained by the invention is green and environment-friendly, is expected to replace the traditional non-degradable plastic film, and promotes the resource utilization of livestock and poultry bones.
Description
Technical Field
The invention relates to the technical field of membrane preparation, in particular to a preparation method of a POSS polymer/bone glue composite membrane.
Background
The plastic film product has the advantages of good chemical stability, corrosion resistance, light weight and the like, and plays an important role in the modern society. But the material is derived from the petrochemical industry, and the use of the material in large quantities not only leads to resource exhaustion, but also is difficult to degrade after being discarded, so that a large amount of micro-plastics or nano-plastics can be produced and ingested by organisms, and the biological health is harmed; meanwhile, the production of plastics and the incineration of plastic wastes generate a large amount of greenhouse gases such as carbon dioxide and the like, and bring a serious challenge to global sustainable development.
In order to meet the requirements of social sustainable development, bio-based materials derived from renewable resources are receiving wide attention due to the advantages of carbon reduction, sustainability and the like. Gelatin is a renewable resource with abundant reserves and good degradability, can be widely extracted from skins, bones and other parts of animals, and can form a film through intermolecular hydrogen bonds and electrostatic interaction. The development of environment-friendly bio-based films by using gelatin to replace traditional petrochemical plastic film products is one of ways for effectively solving the problems of white pollution and resource exhaustion. However, the gelatin-based biological film has the problems of poor mechanical property, water resistance and thermal stability, and is subjected to physical or chemical modification, so that the gelatin-based biological film is an effective means for improving the performance of the gelatin-based biological film in all aspects.
Researchers often add a plasticizer into a gelatin system, adjust acting force among gelatin molecular chains through physical hydrogen bond action, hydrophobic action or electrostatic action, improve the toughness of the gelatin film, but relatively reduce the strength of the film; the mechanical property and the barrier property of the gelatin film are improved by utilizing the reinforcing and toughening effect of the nano particles; the compound containing aldehyde group, epoxy group and the like is selected to react with the amino group on the gelatin for chemical crosslinking, so that a plurality of linear molecules are bonded and crosslinked into a net structure, the mechanical property, the thermal stability and the water resistance of the gelatin film are improved, the degradation rate is slowed down, and the like.
The cage-like silsesquioxane (POSS) is a novel nanoparticle with an inorganic framework Si-O-Si as a core and an organic group as a shell, has an organic/inorganic hybrid structure in a molecular level, and can integrate the advantages of inorganic materials and organic materials. The POSS retains the characteristics of inorganic components, has outstanding thermal stability and high mechanical property, and Si atoms on the top points of the cage-shaped structures can be connected with various organic groups through covalent bonds, so that the POSS is endowed with flexible designable structures and has the potential of wide application in various fields.
Disclosure of Invention
The invention aims to provide a preparation method of a POSS polymer/bone glue composite film, and the bone glue-based composite film with good mechanical property, water resistance and thermal stability is obtained, so that the pollution problem of the traditional petroleum-source plastic film is solved.
In order to achieve the purpose, the invention adopts the technical scheme that:
the method comprises the following steps: preparation of P (POSS-AA-AGE-BA) hybrid material:
(1) adding 0.0400g of vinyl cage-like silsesquioxane (POSS-Vi) and 0.1875g of Sodium Dodecyl Sulfate (SDS) into a 100mL three-neck flask, adding 20g of deionized water, and stirring for 1h at 70 ℃ under the conditions of a condensing device and the rotating speed of 350r/min to uniformly disperse;
(2) 2.4600-7.4600g of Acrylic Acid (AA) and 2.0000-5.5000g of Allyl Glycidyl Ether (AGE) as monomers, as well as 1.4000g of Ammonium Persulfate (APS) and 0.4667g of sodium bisulfite (RH) as redox initiators were dissolved in 18g of deionized water and poured into the three-neck flask in (1) three times respectively, and the reaction was stirred at constant temperature at intervals of 30 min;
(3) after the oil-phase monomer and the water-phase redox initiator are added for the third time in the step (2), slowly dropwise adding 0.5000-3.0000g of Butyl Acrylate (BA) into the three-neck flask, controlling the dropwise addition to be finished for about 30min, and stirring at constant temperature for reaction;
(4) and after all the monomers are added into the system, stirring at constant temperature for reaction for 5 hours, and cooling to obtain a sample.
Step two: preparing a POSS polymer/bone glue composite film:
(1) weighing 2.000g of bone glue, adding the bone glue into 18g of deionized water, swelling for 2h, and magnetically stirring and dissolving in a water bath kettle at 40 ℃ to obtain a bone glue solution with the mass fraction of 10%;
(2) adding 2.0000g of POSS polymer prepared in the first step into the bone glue solution, adjusting the pH of the system to 6, magnetically stirring the mixture in a water bath kettle at the temperature of 40 ℃ for 3 hours, and standing the mixture until no bubble exists to obtain a film forming solution;
(3) and (3) casting the film forming liquid obtained in the step (2) onto a polytetrafluoroethylene film forming plate, wherein the film forming temperature is 30 ℃, and the film forming time is 20-24 hours, so as to obtain a film forming substance, namely the POSS polymer/bone glue composite film.
The invention has the following advantages:
1. the used base material bone glue is green and environment-friendly, has wide sources, is cheap and easy to obtain, and can promote the resource utilization of the livestock and poultry bones;
2. the preparation method is simple and easy to implement, has low requirements on experimental equipment, and the obtained film has good thickness uniformity, improved mechanical property and thermal stability and good biodegradability.
3. The POSS polymer can realize the multi-aspect modification of the bone glue, the introduced active functional group can perform cross-linking and plasticizing modification on the bone glue, and the introduction of the nano particles can realize the system reinforcement.
Drawings
FIG. 1 is a stress-strain curve diagram of a pure bone glue film and a POSS polymer/bone glue composite film.
Detailed Description
The patent proposes to design and synthesize POSS polymer containing carboxyl, epoxy group and ester group, and utilizes the ring-opening addition reaction between the epoxy group in the side chain of the POSS polymer and the amino group of bone glue to generate covalent bond combination, and the carboxyl group and the hydroxyl group of the bone glue generate hydrogen bond action, thereby forming a three-dimensional cross-linked network structure; the water resistance and the thermal stability of the bone-glue-based composite film are enhanced by utilizing the nanometer characteristic of POSS (polyhedral oligomeric silsesquioxane); the toughness of the gelatin film is improved by introducing soft segment ester groups. Thereby realizing the preparation of the high-performance bone glue-based composite film and being expected to replace the traditional non-degradable plastic; meanwhile, the resource utilization of the livestock and poultry bones can be promoted.
The invention relates to a preparation method of a POSS polymer/bone glue composite film, which is specifically realized by the following steps:
the method comprises the following steps: preparation of P (POSS-AA-AGE-BA) hybrid material
(1) Adding 0.0400g of vinyl cage-like silsesquioxane (POSS-Vi) and 0.1875g of Sodium Dodecyl Sulfate (SDS) into a 100mL three-neck flask, adding 20g of deionized water, and stirring for 1h at 70 ℃ under the conditions of a condensing device and the rotating speed of 350r/min to uniformly disperse;
(2) 2.4600-7.4600g of Acrylic Acid (AA) and 2.0000-5.5000g of Allyl Glycidyl Ether (AGE) as monomers, as well as 1.4000g of Ammonium Persulfate (APS) and 0.4667g of sodium bisulfite (RH) as redox initiators were dissolved in 18g of deionized water and poured into the three-neck flask in (1) three times respectively, and the reaction was stirred at constant temperature at intervals of 30 min;
(3) after the oil-phase monomer and the water-phase redox initiator are added for the third time in the step (2), slowly dropwise adding 0.5000-3.0000g of Butyl Acrylate (BA) into the three-neck flask, controlling the dropwise addition to be finished for about 30min, and stirring at constant temperature for reaction;
(4) and after all the monomers are added into the system, stirring at constant temperature for reaction for 5 hours, and cooling to obtain a sample.
Step two: preparation of POSS polymer/bone glue composite film
(1) Weighing 2.000g of bone glue, adding the bone glue into 18g of deionized water, swelling for 2h, and magnetically stirring and dissolving in a water bath kettle at 40 ℃ to obtain a bone glue solution with the mass fraction of 10%;
(2) adding 2.0000g of POSS polymer into the bone glue solution, adjusting the pH of the system to 6, magnetically stirring the mixture in a water bath kettle at the temperature of 40 ℃ for 3 hours, and standing the mixture until no bubbles exist to obtain a film forming solution;
(3) and (3) casting the film forming liquid obtained in the step (2) onto a polytetrafluoroethylene film forming plate, wherein the film forming temperature is 30 ℃, and the film forming time is 20-24 hours, so as to obtain a film forming material, namely the POSS polymer/bone glue composite film.
Example 1:
the first step is as follows: preparation of P (POSS-AA-AGE-BA) hybrid material
(1) Adding 0.0400g of POSS-Vi and 0.1875g of SDS into a 100mL three-neck flask, adding 20g of deionized water, and stirring for 1h to disperse uniformly at 70 ℃ under the conditions of a condensing device and the rotating speed of 350 r/min;
(2) dissolving oil phase 2.9600g AA and 5.0000g AGE, and water phase 1.4000g APS and 0.4667g RH in 18g deionized water, respectively pouring into the three-neck flask in the step (1) for three times at intervals of 30min, and stirring at constant temperature for reaction;
(3) after the AA, AGE, APS and RH are added for the third time, slowly dropwise adding 2.0000g of BA into the three-neck flask, controlling the dropwise adding to be finished for about 30min, and stirring at constant temperature for reaction;
(4) after all the monomers are added into the system, stirring and reacting for 5 hours at constant temperature, and cooling to obtain a yellow homogeneous polymer solution.
The second step: preparation of POSS polymer/bone glue composite film
(1) Weighing 2.000g of bone glue, adding the bone glue into 18g of deionized water, swelling for 2h, and magnetically stirring and dissolving in a water bath kettle at 40 ℃ to obtain a bone glue solution with the mass fraction of 10%;
(2) adding 2.0000g of POSS polymer into the bone glue solution, adjusting the pH of the system to 6, magnetically stirring the mixture in a water bath kettle at the temperature of 40 ℃ for 3 hours, and standing the mixture until no bubbles exist to obtain a film forming solution;
(3) and (3) casting the film forming liquid obtained in the step (2) onto a polytetrafluoroethylene film forming plate, wherein the film forming temperature is 30 ℃, and the film forming time is 20-24 hours, so as to obtain a film forming material, namely the POSS polymer/bone glue composite film.
Example 2:
the first step is as follows: preparation of P (POSS-AA-AGE-BA) hybrid material
(1) Adding 0.0400g of POSS-Vi and 0.1875g of SDS into a 100mL three-neck flask, adding 20g of deionized water, and stirring for 1h to disperse uniformly at 70 ℃ under the conditions of a condensing device and the rotating speed of 350 r/min;
(2) 7.4600g of AA and 2.000g of AGE in an oil phase, 1.4000g of APS and 0.4667g of RH in an aqueous phase are dissolved in 18g of deionized water and poured into the three-neck flask in the step (1) for three times respectively, and the reaction is stirred at constant temperature at intervals of 30 min;
(3) after the AA, AGE, APS and RH are added for the third time, 0.5000g of BA is slowly dripped into the three-neck flask, and the dripping is controlled to be finished for about 30min, and the mixture is stirred at constant temperature for reaction;
(4) after all the monomers are added into the system, stirring and reacting for 5 hours at constant temperature, and cooling to obtain a yellow homogeneous polymer solution.
The second step is that: preparation of POSS polymer/bone glue composite film
(1) Weighing 2.000g of bone glue, adding the bone glue into 18g of deionized water, swelling for 2h, and magnetically stirring and dissolving in a water bath kettle at 40 ℃ to obtain a bone glue solution with the mass fraction of 10%;
(2) adding 2.0000g of POSS polymer into the bone glue solution, adjusting the pH of the system to 6, magnetically stirring the mixture in a water bath kettle at the temperature of 40 ℃ for 3 hours, and standing the mixture until no bubbles exist to obtain a film forming solution;
(3) and (3) casting the film forming liquid obtained in the step (2) onto a polytetrafluoroethylene film forming plate, wherein the film forming temperature is 30 ℃, and the film forming time is 20-24 hours, so as to obtain a film forming material, namely the POSS polymer/bone glue composite film.
Example 3:
the first step is as follows: preparation of P (POSS-AA-AGE-BA) hybrid material
(1) Adding 0.0400g of POSS-Vi and 0.1875g of SDS into a 100mL three-neck flask, adding 20g of deionized water, and stirring for 1h to disperse uniformly at 70 ℃ under the conditions of a condensing device and the rotating speed of 350 r/min;
(2) 2.4600g of AA and 4.500g of AGE in an oil phase, 1.4000g of APS and 0.4667g of RH in an aqueous phase are dissolved in 18g of deionized water and poured into the three-neck flask in the step (1) for three times respectively at intervals of 30min, and the mixture is stirred and reacted at constant temperature;
(3) after the AA, AGE, APS and RH are added for the third time, slowly dropwise adding 3.0000g of BA into the three-neck flask, controlling the dropwise adding to be finished for about 30min, and stirring at constant temperature for reaction;
(4) after all the monomers are added into the system, stirring and reacting for 5 hours at constant temperature, and cooling to obtain a yellow homogeneous polymer solution.
The second step is that: preparation of POSS polymer/bone glue composite film
(1) Weighing 2.000g of bone glue, adding the bone glue into 18g of deionized water, swelling for 2h, and magnetically stirring and dissolving in a water bath kettle at 40 ℃ to obtain a bone glue solution with the mass fraction of 10%;
(2) adding 2.0000g of POSS polymer into the bone glue solution, adjusting the pH of the system to 6, magnetically stirring the mixture in a water bath kettle at the temperature of 40 ℃ for 3 hours, and standing the mixture until no bubbles exist to obtain a film forming solution;
(3) and (3) casting the film forming liquid obtained in the step (2) onto a polytetrafluoroethylene film forming plate, wherein the film forming temperature is 30 ℃, and the film forming time is 20-24 hours, so as to obtain a film forming material, namely the POSS polymer/bone glue composite film.
As shown in figure 1, the stress-strain curve of the film is shown, and the POSS polymer/bone glue composite film prepared by the method has the advantages that the breaking elongation is improved by 11.57 times compared with that of a pure bone glue film, and the water vapor transmission is reduced by 17.2%.
The invention is not limited to the examples, and any equivalent changes to the technical solution of the invention by a person skilled in the art after reading the description of the invention are covered by the claims of the invention.
Claims (3)
1. A preparation method of a POSS polymer/bone glue composite film is characterized by comprising the following steps:
the method comprises the following steps: preparing a P (POSS-AA-AGE-BA) hybrid material:
(1) adding 0.0400g of vinyl cage-like silsesquioxane (POSS-Vi) and 0.1875g of Sodium Dodecyl Sulfate (SDS) into a 100mL three-neck flask, adding 20g of deionized water, and stirring for 1h at 70 ℃ under the conditions of a condensing device and the rotating speed of 350r/min to uniformly disperse;
(2) 2.4600-7.4600g of Acrylic Acid (AA) and 2.0000-5.5000g of Allyl Glycidyl Ether (AGE) as monomers, as well as 1.4000g of Ammonium Persulfate (APS) and 0.4667g of sodium bisulfite (RH) as redox initiators were dissolved in 18g of deionized water and poured into the three-neck flask in (1) three times respectively, and the reaction was stirred at constant temperature at intervals of 30 min;
(3) after the oil-phase monomer and the water-phase redox initiator are added for the third time in the step (2), slowly dropwise adding 0.5000-3.0000g of Butyl Acrylate (BA) into the three-neck flask, controlling the dropwise adding to be finished for about 30min, and stirring at constant temperature for reaction;
(4) and after all the monomers are added into the system, stirring at constant temperature for reaction for 5 hours, and cooling to obtain a sample.
Step two: preparing a POSS polymer/bone glue composite film:
(1) weighing 2.000g of bone glue, adding the bone glue into 18g of deionized water, swelling for 2h, and magnetically stirring and dissolving in a water bath kettle at 40 ℃ to obtain a bone glue solution with the mass fraction of 10%;
(2) adding 2.0000g of POSS polymer prepared in the first step into the bone glue solution, adjusting the pH of the system to 6, magnetically stirring the mixture in a water bath kettle at the temperature of 40 ℃ for 3 hours, and standing the mixture until no bubble exists to obtain a film forming solution;
(3) and (3) casting the film forming liquid obtained in the step (2) onto a polytetrafluoroethylene film forming plate, wherein the film forming temperature is 30 ℃, and the film forming time is 20-24 hours, so as to obtain a film forming substance, namely the POSS polymer/bone glue composite film.
2. The method for preparing the POSS polymer/bone glue composite film as claimed in claim 1, wherein the method comprises the following steps:
the specific steps of the first step are as follows:
(1) adding 0.0400g of POSS-Vi and 0.1875g of SDS into a 100mL three-neck flask, adding 20g of deionized water, and stirring for 1h to disperse uniformly at 70 ℃ under the conditions of a condensing device and the rotating speed of 350 r/min;
(2) dissolving oil phase 6.9600g AA and 2.0000g AGE, dissolving water phase 1.4000g APS and 0.4667g RH in 18g deionized water, pouring into the three-neck flask in the step (1) for three times respectively, and stirring at constant temperature for reacting at intervals of 30 min;
(3) after the AA, AGE, APS and RH are added for the third time, slowly dropwise adding 1.0000g of BA into the three-neck flask, controlling the dropwise adding to be finished for about 30min, and stirring at constant temperature for reaction;
(4) after all the monomers are added into the system, stirring and reacting for 5 hours at constant temperature, and cooling to obtain a yellow homogeneous polymer solution.
3. The method for preparing the POSS polymer/bone glue composite film as claimed in claim 1, wherein the method comprises the following steps:
the second step comprises the following specific steps:
(1) weighing 2.000g of bone glue, adding the bone glue into 18g of deionized water, swelling for 2h, and magnetically stirring and dissolving in a water bath kettle at 40 ℃ to obtain a bone glue solution with the mass fraction of 10%;
(2) adding 2.0000g of POSS polymer into the bone glue solution, adjusting the pH of the system to 6, magnetically stirring the mixture in a water bath kettle at the temperature of 40 ℃ for 3 hours, and standing the mixture until no bubble exists to obtain a film forming solution;
(3) and (3) casting the film forming liquid obtained in the step (2) onto a polytetrafluoroethylene film forming plate, wherein the film forming temperature is 30 ℃, and the film forming time is 20-24 hours, so as to obtain a film forming material, namely the POSS polymer/bone glue composite film.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105940326A (en) * | 2014-01-29 | 2016-09-14 | 柯尼卡美能达株式会社 | Optical film |
| CN106118586A (en) * | 2016-06-28 | 2016-11-16 | 陕西科技大学 | A kind of preparation method of high tenacity Bone glue adhesive glued membrane |
| CN106883439A (en) * | 2017-03-08 | 2017-06-23 | 常州大学 | Modified anti-reflection optical thin film high of one kind and preparation method thereof |
| CN107033805A (en) * | 2017-04-25 | 2017-08-11 | 晶锋集团股份有限公司 | A kind of composite heat-conducting high-temperature insulation pressure-sensitive band of polyacrylate glass fabric and preparation method thereof |
| CN112521610A (en) * | 2020-12-15 | 2021-03-19 | 陕西科技大学 | POSS grafted oxidized sodium alginate composite material prepared based on graft polymerization method and method |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105940326A (en) * | 2014-01-29 | 2016-09-14 | 柯尼卡美能达株式会社 | Optical film |
| CN106118586A (en) * | 2016-06-28 | 2016-11-16 | 陕西科技大学 | A kind of preparation method of high tenacity Bone glue adhesive glued membrane |
| CN106883439A (en) * | 2017-03-08 | 2017-06-23 | 常州大学 | Modified anti-reflection optical thin film high of one kind and preparation method thereof |
| CN107033805A (en) * | 2017-04-25 | 2017-08-11 | 晶锋集团股份有限公司 | A kind of composite heat-conducting high-temperature insulation pressure-sensitive band of polyacrylate glass fabric and preparation method thereof |
| CN112521610A (en) * | 2020-12-15 | 2021-03-19 | 陕西科技大学 | POSS grafted oxidized sodium alginate composite material prepared based on graft polymerization method and method |
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