CN111004406A - Preparation method of novel anti-ultraviolet and anti-oxidation film - Google Patents
Preparation method of novel anti-ultraviolet and anti-oxidation film Download PDFInfo
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- CN111004406A CN111004406A CN201911390781.9A CN201911390781A CN111004406A CN 111004406 A CN111004406 A CN 111004406A CN 201911390781 A CN201911390781 A CN 201911390781A CN 111004406 A CN111004406 A CN 111004406A
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2329/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
- C08J2329/02—Homopolymers or copolymers of unsaturated alcohols
- C08J2329/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
- C08K5/3415—Five-membered rings
- C08K5/3417—Five-membered rings condensed with carbocyclic rings
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Abstract
The invention discloses a preparation method of a novel anti-ultraviolet and anti-oxidation film compounded by microbial melanin and PVA plastic. The process comprises 1) selecting microorganism secreting melanin for amplification culture and extracting melanin; 2) dissolving PVA in NaOH solution to prepare PVA solution; 3) adding melanin into a PVA solution to obtain a melanin/PVA mixed solution, fully mixing under a water bath condition, and ultrasonically removing bubbles to obtain a bubble-free melanin/PVA mixed solution; 4) pouring a certain amount of melanin/PVA mixed solution into a mould, and drying at room temperature to prepare the anti-ultraviolet and anti-oxidation film. The preparation method of the novel anti-ultraviolet and anti-oxidation film provided by the invention combines the excellent anti-ultraviolet and anti-oxidation characteristics of the microbial melanin and the good physical and mechanical properties of the PVA plastic, has the advantages of degradability, environmental friendliness and the like, can obviously prolong the service life of the plastic film, and can be used for ultraviolet protection of buildings, automobiles and the like.
Description
Technical Field
The invention belongs to the technical field of materials, and particularly relates to a preparation method of a novel anti-ultraviolet and anti-oxidation film prepared by compounding microorganism melanin and PVA plastic.
Background
With the increasing global temperature rise and the increasing energy shortage and the large application of glass in buildings and automobiles, plastic films which are easy to oxidize and turn yellow at high temperature and even have poor cracking oxidation resistance in the market at present cannot meet the daily requirements of people, and functional protective films such as ultraviolet-proof films become more and more important. The ultraviolet-proof film mainly plays roles in reflecting and absorbing infrared and ultraviolet rays in sunlight, and correspondingly blocks solar energy according to different visible light transmittances. The prior art ultraviolet-proof film is generally prepared by using a PET (polyethylene terephthalate) material as a base material and then coating a coating material on the surface of the PET. The method has the advantages of complex process steps, low production efficiency, poor film quality and short service life.
The microbial melanin has excellent ultraviolet resistance and oxidation resistance, has the advantages of environmental friendliness, reproducibility, degradability and the like, and can be well combined with PVA plastic with good biocompatibility. The invention mixes and compounds the uvioresistant and anti-oxidation microorganism melanin and PVA plastic with excellent physical and mechanical properties through a film forming process to prepare a novel biodegradable film with uvioresistant and anti-oxidation functions.
Disclosure of Invention
The invention provides a method for preparing a novel ultraviolet-resistant and oxidation-resistant film by blending and compounding microorganism melanin and PVA plastic, which aims to extract the microorganism melanin and prepare PVA solution, mix the microorganism melanin and the PVA solution in a bath together by utilizing the good biocompatibility of the melanin, remove bubbles, pour the mixture into a mould and dry the mixture to obtain the ultraviolet-resistant and oxidation-resistant film. The preparation method of the novel anti-ultraviolet and anti-oxidation film combines the excellent anti-ultraviolet and anti-oxidation characteristics of the microbial melanin and the good physical and mechanical properties of the PVA plastic, has the advantages of degradability, environmental friendliness and the like, can obviously prolong the service life of the plastic film, and can be used for ultraviolet protection of buildings, automobiles and the like.
The technical scheme of the invention comprises the following process steps:
1) selecting fungi secreting melanin such as aspergillus niger, alternaria alternata, aspergillus nidulans, globisporus cacao or aureobasidium pullulans, sequentially cutting agar columns with mycelia along the edges of colonies by using a sterile perforator with the inner diameter of 10mm in a super-clean workbench, transplanting the agar columns into a PDA culture medium by using a needle, carrying out amplification culture for 7-15 days by using a constant temperature and humidity box under the conditions that the temperature is 25-35 ℃ and the humidity is 75-90%, and inoculating the agar columns into the PDA culture medium for amplification culture. Preparing 60-90% ethanol as a pigment dissolving agent, soaking the pigment-containing fungus cake after the expanded culture in the pigment dissolving agent, fully shaking, extracting and extracting for 1-2 times at 2 h/time in a water bath environment at the temperature of 25-100 ℃, centrifuging for 5-10 min at 5000-10000 r/min to obtain ethanol pigment supernatant, and directly drying the ethanol pigment supernatant to constant weight in a vacuum environment at the temperature of 25-40 ℃, and at-60 KPa to-90 KPa to obtain dry melanin;
2) adding 0.5-1.5 mol/L NaOH solution into a mixture of PVA 17-88 and PVA 17-99, a mixture of PVA 17-99 and PVA 17-99 or a mixture of PVA 17-88 and PVA 17-99 according to a ratio of 10: 1-20: 1, and completely dissolving in a water bath at 80-100 ℃ to prepare a PVA solution;
3) and adding the melanin into the dissolved PVA solution to obtain a melanin/PVA mixed solution with the melanin content of 0.5-5%. Fully mixing the melanin/PVA mixed solution for 30-60 min under the water bath condition of 80-100 ℃, putting the mixture into an ultrasonic cell crusher, and ultrasonically treating the mixture for 10-30 min at the frequency of 10-40 kHz and the ultrasonic power of 100-800W under the environment of 60-80 ℃ to remove air bubbles in the mixed solution to obtain a bubble-free melanin/PVA mixed solution;
4) pouring the melanin/PVA mixed solution into a flat-bottom glass container, controlling the film forming amount of the melanin/PVA mixed solution in the flat-bottom container to be 30-60 mg/cm2, and drying for one week at room temperature to prepare the anti-ultraviolet and anti-oxidation film with the film thickness of 0.02-0.20 mm.
Detailed Description
Example 1: selecting Aspergillus niger as melanin-producing fungus, PVA mixture is PVA 17-88 and PVA 17-99 mixture, and melanin content of the melanin/PVA mixed solution is 1%
Step 1) selecting Aspergillus niger, sequentially cutting agar columns with mycelia along the edges of Aspergillus niger bacterial colonies by using a sterile perforator with the inner diameter of 10mm in a superclean bench, picking the agar columns by using a needle, transplanting the agar columns into a PDA culture medium, performing amplification culture for 10 days in a constant-temperature and constant-humidity box under the conditions that the temperature is 30 ℃ and the humidity is 85%, and inoculating the agar columns into the PDA culture medium for amplification culture. Preparing 80% ethanol as pigment dissolving agent, soaking the pigment-containing fungus cake after enlarged culture in the pigment dissolving agent, sufficiently shaking, extracting for 2 times at 2 h/time in a water bath environment at 100 ℃, centrifuging for 10min at 8000r/min to obtain ethanol pigment supernatant, and directly vacuum drying at 40 ℃, -90KPa to constant weight to obtain dry melanin;
step 2) adding 1mol/L NaOH solution into the mixture of PVA 17-88 and PVA 17-99 according to the proportion of 10:1, and completely dissolving in water bath at 100 ℃ to prepare PVA solution;
and 3) adding melanin into the dissolved PVA solution to obtain a melanin/PVA mixed solution with the melanin content of 1%. Fully mixing the melanin/PVA mixed solution for 60min under the water bath condition of 100 ℃, putting the mixture into an ultrasonic cell crusher, and ultrasonically treating the mixture for 30min at the frequency of 40kHz and the ultrasonic power of 600W under the environment of 70 ℃ to remove bubbles in the mixed solution to obtain a bubble-free melanin/PVA mixed solution;
step 4) pouring the melanin/PVA mixed solution into a flat-bottom glass container, and controlling the film forming amount of the melanin/PVA mixed solution in the flat-bottom container to be 60mg/cm2Drying at room temperature for one week to obtain an anti-ultraviolet and anti-oxidation film with a film thickness of 0.20 mm.
Example 2: selecting alternaria alternata as melanin-producing fungus, wherein the PVA mixture is a mixture of PVA 17-99 and PVA 17-99, and the melanin content of the melanin/PVA mixed solution is 2%
The method comprises the following steps of 1) selecting alternaria alternate, sequentially cutting agar columns with mycelia along the edges of colonies of the alternaria alternate by using a sterile perforator with the inner diameter of 10mm in an ultra-clean workbench, picking the agar columns by using a needle, transplanting the agar columns into a PDA culture medium, performing amplification culture for 10 days in a constant temperature and humidity box under the conditions that the temperature is 30 ℃ and the humidity is 85%, and inoculating the agar columns into the PDA culture medium for amplification culture. Preparing 80% ethanol as pigment dissolving agent, soaking the pigment-containing fungus cake after enlarged culture in the pigment dissolving agent, sufficiently shaking, extracting for 2 times at 2 h/time in a water bath environment at 100 ℃, centrifuging for 10min at 8000r/min to obtain ethanol pigment supernatant, and directly vacuum drying at 40 ℃, -90KPa to constant weight to obtain dry melanin;
step 2) adding 1mol/L NaOH solution into the mixture of PVA 17-99 and PVA 17-99 according to the ratio of 20:1, and completely dissolving in water bath at 100 ℃ to prepare PVA solution;
and 3) adding melanin into the dissolved PVA solution to obtain a melanin/PVA mixed solution with the melanin content of 2%. Fully mixing the melanin/PVA mixed solution for 60min under the water bath condition of 100 ℃, putting the mixture into an ultrasonic cell crusher, and ultrasonically treating the mixture for 30min at the frequency of 40kHz and the ultrasonic power of 600W under the environment of 70 ℃ to remove bubbles in the mixed solution to obtain a bubble-free melanin/PVA mixed solution;
step 4) pouring the melanin/PVA mixed solution into a flat-bottom glass container, and controlling the film forming amount of the melanin/PVA mixed solution in the flat-bottom container to be 60mg/cm2Drying at room temperature for one week to obtain an anti-ultraviolet and anti-oxidation film with a film thickness of 0.20 mm.
Example 3: selecting Coccomydia cacao as melanin-producing fungus, PVA mixture is mixture of PVA 17-88 and PVA 17-99, and melanin content of the melanin/PVA mixed solution is 5%
Selecting the diplospora cacao, sequentially cutting agar columns with mycelia along the colony edges of the diplospora cacao in an ultraclean workbench by using an aseptic perforator with the inner diameter of 10mm, transplanting the agar columns into a PDA culture medium by using a needle, performing amplification culture for 10 days in a constant-temperature and constant-humidity box under the conditions that the temperature is 30 ℃ and the humidity is 85 percent, and inoculating the agar columns into the PDA culture medium for amplification culture. Preparing 80% ethanol as pigment dissolving agent, soaking the pigment-containing fungus cake after enlarged culture in the pigment dissolving agent, sufficiently shaking, extracting for 2 times at 2 h/time in a water bath environment at 100 ℃, centrifuging for 10min at 8000r/min to obtain ethanol pigment supernatant, and directly vacuum drying at 40 ℃, -90KPa to constant weight to obtain dry melanin;
step 2) adding 1mol/L NaOH solution into the mixture of PVA 17-88 and PVA 17-99 according to the ratio of 20:1, and completely dissolving in water bath at 100 ℃ to prepare PVA solution;
and 3) adding melanin into the dissolved PVA solution to obtain a melanin/PVA mixed solution with the melanin content of 5%. Fully mixing the melanin/PVA mixed solution for 60min under the water bath condition of 100 ℃, putting the mixture into an ultrasonic cell crusher, and ultrasonically treating the mixture for 30min at the frequency of 40kHz and the ultrasonic power of 600W under the environment of 70 ℃ to remove bubbles in the mixed solution to obtain a bubble-free melanin/PVA mixed solution;
step 4) pouring the melanin/PVA mixed solution into a flat-bottom glass container, and controlling the film forming amount of the melanin/PVA mixed solution in the flat-bottom container to be 60mg/cm2Drying at room temperature for one week to obtain an anti-ultraviolet and anti-oxidation film with a film thickness of 0.20 mm.
Example 4: selecting Aureobasidium pullulans as melanin-producing fungus, wherein the PVA mixture is a mixture of PVA 17-88 and PVA 17-99, and the melanin content of the melanin/PVA mixed solution is 5%
Step 1) selecting aureobasidium pullulans, sequentially cutting agar columns with mycelia along the edges of aureobasidium pullulans colonies by using a sterile perforator with the inner diameter of 10mm in an ultra-clean workbench, picking the agar columns by using a needle, transplanting the agar columns into a PDA culture medium, performing amplification culture for 10 days in a constant-temperature and constant-humidity box under the conditions that the temperature is 30 ℃ and the humidity is 85%, and inoculating the agar columns into the PDA culture medium for amplification culture. Preparing 80% ethanol as pigment dissolving agent, soaking the pigment-containing fungus cake after enlarged culture in the pigment dissolving agent, sufficiently shaking, extracting for 2 times at 2 h/time in a water bath environment at 100 ℃, centrifuging for 10min at 8000r/min to obtain ethanol pigment supernatant, and directly vacuum drying at 40 ℃, -90KPa to constant weight to obtain dry melanin;
step 2) adding 1mol/L NaOH solution into the mixture of PVA 17-88 and PVA 17-99 according to the ratio of 20:1, and completely dissolving in water bath at 100 ℃ to prepare PVA solution;
and 3) adding melanin into the dissolved PVA solution to obtain a melanin/PVA mixed solution with the melanin content of 5%. Fully mixing the melanin/PVA mixed solution for 60min under the water bath condition of 100 ℃, putting the mixture into an ultrasonic cell crusher, and ultrasonically treating the mixture for 30min at the frequency of 40kHz and the ultrasonic power of 600W under the environment of 70 ℃ to remove bubbles in the mixed solution to obtain a bubble-free melanin/PVA mixed solution;
step 4) pouring the melanin/PVA mixed solution into a flat-bottom glass container, and controlling the film forming amount of the melanin/PVA mixed solution in the flat-bottom container to be 60mg/cm2Drying at room temperature for one week to obtain an anti-ultraviolet and anti-oxidation film with a film thickness of 0.20 mm.
Claims (7)
1. A preparation method of a novel anti-ultraviolet and anti-oxidation film is characterized by comprising the following steps: the novel biodegradable film with the ultraviolet-resistant and oxidation-resistant functions is prepared by compounding the excellent ultraviolet-resistant and oxidation-resistant microbial melanin and the PVA plastic with good physical and mechanical properties through a film forming process.
2. A preparation method of a novel anti-ultraviolet and anti-oxidation film is characterized by comprising the following process steps:
1) pigment extraction: selecting a microorganism capable of secreting melanin for amplification culture, purifying the melanin secreted by the microorganism and drying for later use;
2) dissolving PVA: mixing 0.5-1.5 mol/L NaOH solution and PVA at a ratio of 10: 1-20: 1, and completely dissolving in water bath at 80-100 ℃ to prepare PVA solution;
3) adding melanin into the dissolved PVA solution to obtain a melanin/PVA mixed solution with the melanin content of 0.5-5%; fully mixing for 30-60 min under the condition of 80-100 ℃ water bath, and then carrying out ultrasonic treatment at the temperature of 60-80 ℃ to remove bubbles to obtain a bubble-free melanin/PVA mixed solution;
4) preparing a film: pouring the melanin/PVA mixed solution into a flat-bottomed glass container, and drying for one week at room temperature to prepare the anti-ultraviolet and anti-oxidation film.
3. The method for preparing a novel anti-ultraviolet and anti-oxidation film according to claim 2, which is characterized in that: the microorganism in the step 1) is mainly one of mould (aspergillus niger, alternaria alternate, aspergillus nidulans and the like) or fungus (staphyloccocus cacao, aureobasidium pullulans and the like).
4. The method for preparing a novel anti-ultraviolet and anti-oxidation film according to claim 2, which is characterized in that: the PVA plastic in the step 2) is PVA 17-88, PVA 17-99 or a mixture of PVA 17-88 and PVA 17-99.
5. The method for preparing a novel anti-ultraviolet and anti-oxidation film according to claim 2, which is characterized in that: and 3) the ultrasonic frequency is 10-40 kHz, and the ultrasonic time is 10-30 min.
6. The method for preparing a novel anti-ultraviolet and anti-oxidation film according to claim 2, which is characterized in that: the film forming amount of the melanin/PVA mixed solution in the step 4) in a flat-bottom container is 30-60 mg/cm2The thickness of the film is 0.02-0.20 mm.
7. The method for preparing a novel anti-ultraviolet oxidation-preventing film according to any one of claims 1 to 6, wherein: PVA plastic with good biocompatibility is taken as a matrix, biological melanin with excellent ultraviolet resistance and oxidation resistance is added for blending and compounding, and thus the novel film with the ultraviolet resistance and oxidation resistance is prepared.
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| CN103320332A (en) * | 2013-07-18 | 2013-09-25 | 新疆农业科学院微生物应用研究所 | Radiation-resistant fungus and its application in melanin separation and extraction |
| CN107325526A (en) * | 2017-07-10 | 2017-11-07 | 湖北大学 | A kind of ultraviolet compounded film of heat-resistant and preparation method thereof |
| WO2018201616A1 (en) * | 2017-05-02 | 2018-11-08 | 上海海洋大学 | Method for use in preparing intelligent chromogenic antibacterial anti-oxidation protective film |
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- 2019-12-30 CN CN201911390781.9A patent/CN111004406A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102604293A (en) * | 2012-02-27 | 2012-07-25 | 江南大学 | Thermoplastically processable polyvinyl alcohol composite and preparation method thereof |
| CN103320332A (en) * | 2013-07-18 | 2013-09-25 | 新疆农业科学院微生物应用研究所 | Radiation-resistant fungus and its application in melanin separation and extraction |
| WO2018201616A1 (en) * | 2017-05-02 | 2018-11-08 | 上海海洋大学 | Method for use in preparing intelligent chromogenic antibacterial anti-oxidation protective film |
| CN107325526A (en) * | 2017-07-10 | 2017-11-07 | 湖北大学 | A kind of ultraviolet compounded film of heat-resistant and preparation method thereof |
Non-Patent Citations (1)
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