CN111138786A - Preparation method and application of chitosan PLGA nano essence - Google Patents
Preparation method and application of chitosan PLGA nano essence Download PDFInfo
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- CN111138786A CN111138786A CN202010030516.6A CN202010030516A CN111138786A CN 111138786 A CN111138786 A CN 111138786A CN 202010030516 A CN202010030516 A CN 202010030516A CN 111138786 A CN111138786 A CN 111138786A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L29/00—Compositions 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; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
- C08L29/02—Homopolymers or copolymers of unsaturated alcohols
- C08L29/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
- C11B9/00—Essential oils; Perfumes
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
- D21H19/10—Coatings without pigments
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
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- C08L2205/00—Polymer mixtures characterised by other features
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
- Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics
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Abstract
The invention provides a preparation method of chitosan PLGA nano essence and a preparation method of humidity-responsive PLGA nano sweet orange essence scented paper. Dissolving PLGA and orange essence in ethyl acetate to serve as an oil phase; dissolving chitosan and polyvinyl alcohol in distilled water to serve as a water phase; slowly dropping the oil phase into the water phase under the condition of mechanical stirring and continuously stirring to form a mixed solution, carrying out ultrasonic emulsification by a cell disruption instrument under the condition of ice bath to form a uniform emulsion, removing ethyl acetate, and uniformly spraying the nano essence on the upper part of the paper to be perfumed to obtain the perfumed paper. Meanwhile, the HY-4021 type lotus leaf hydrophobing agent is added to effectively control the water absorption rate of the scented paper in a humid environment, the scented paper is applied to the humid environment, and the orange essence embedded in the nanoparticles is slowly released through different PLGA hydrolysis rates under different humidity conditions, so that the purpose of long-acting slow release is achieved. The nano essence prepared by the invention has high loading capacity, can be used for the perfuming research of different essences, and has better slow release effect and wide applicability.
Description
Technical Field
The invention belongs to the field of fine chemical engineering, and particularly relates to chitosan PLGA nano essence and a preparation method and application thereof.
Background
The scented paper is a functional paper which is prepared by adding spices, essences or other scented products and can continuously emit fragrance for a period of time on the basis of not influencing the basic use performance of the scented paper. Along with the improvement of the life quality of people and the enhancement of the awareness of consumers on environmental protection, the biodegradable material has huge application space.
The essence is deeply loved by consumers because of the special fragrance, but the essence contains a large amount of alkene terpenes and polyphenols, so the essence is easily influenced by environmental factors such as temperature, humidity, pH and the like, and the problem can be well solved through microencapsulation of the essence. On the other hand, the microcapsule essence cannot meet the requirements of people to a certain extent due to large particle size and low loading capacity. The nano essence prepared by PLGA has small grain size, high loading capacity and good stability. Meanwhile, the prepared nano sweet orange essence scented paper is applied to life in consideration of the characteristic of easy hydrolysis of PLGA. When the moisture content in the air reaches a certain degree, the PLGA nano essence can be released in a large quantity, and other bad smells in the air are masked.
Disclosure of Invention
The invention aims to provide a chitosan PLGA nano essence and a preparation method and application thereof.
In order to achieve the aim, the invention provides a preparation method of chitosan PLGA nano essence, which is characterized by comprising the following steps:
step 1: dissolving PLGA and essence in ethyl acetate to obtain oil phase;
step 2: dissolving chitosan and polyvinyl alcohol in 1% glacial acetic acid solution to serve as a water phase;
and step 3: slowly injecting the oil phase into the water phase by a micro-injection pump under magnetic stirring, and continuously stirring for 0.5-1 h; carrying out ultrasonic emulsification on the mixed solution by an ultrasonic cell disruption instrument under the ice bath condition to obtain nano emulsion; stirring the nano emulsion for 1-3h at the temperature of 40 +/-2 ℃, removing ethyl acetate, and centrifuging for 15-40min at the rotating speed of 12000-18000rpm by an ultracentrifuge; collecting nanoparticles, washing with distilled water for multiple times, and filtering with 0.22 μm filter membrane to remove nanospheres with larger particle size; and (5) carrying out freeze drying to obtain the chitosan PLGA nano essence.
Preferably, the PLGA in step 1 is lactic acid-glycolic acid 75:25(w/w), carboxyl end group, molecular weight 10000 Da.
Preferably, the essence in the step 1 is sweet orange essence or lily of the valley essence.
Preferably, the mass ratio of the essence to the PLGA in the step 1 is 1: 1.
preferably, the polymerization degree of the chitosan in the step 2 is more than or equal to 80.0, and the concentration is 0.2%.
Preferably, the alcoholysis degree of polyvinyl alcohol (PVA) in the step 2 is 87.0-89.0, and the concentration is 1%.
Preferably, the ultrasonic emulsification time of the ultrasonic cell disruptor in the step 3 in ice bath is 5min, the interval is 2s, the power is 100W, and the temperature is 15 ℃.
Preferably, the magnetic stirring speed in the step 3 is 800rpm/min, the temperature is 25 ℃, and the stirring time is 30 min.
Preferably, the particle size of the chitosan PLGA nano-essence in the step 3 is 240-300 nm.
The invention also provides the chitosan PLGA nano essence prepared by the method.
The invention also provides a preparation method of the humidity response type scented paper, which is characterized by comprising the following steps: fixing the blank paper on a splint of a coating machine, dissolving the chitosan PLGA nano essence in distilled water, adding HY-4021 type lotus leaf hydrophobing agent, sampling the blank paper through the coating machine, preparing scented paper, and naturally drying at room temperature to obtain humidity response type scented paper.
The invention also provides humidity response type scented paper prepared by the method.
Compared with the prior art, the invention has the beneficial effects that:
(1) the amphiphilic block copolymer PLGA belongs to biodegradable polymers, and has good biocompatibility, no toxicity, no pungent smell and good encapsulation property. The wide application in biomedicine indicates that the medicine has higher safety.
(2) The chitosan modified PLGA nano essence can well protect easily oxidized and volatile components in the essence, and has high loading capacity and stable property. When the PLGA essence is applied to the scented paper, the hydrolysis rate of PLGA is different along with the change of humidity in the environment, and the release degrees of the essence embedded by PLGA degraded in different degrees are different.
(3) Through adding PLGA nanometer essence, perfuming paper possesses the controllable release nature in the humidity environment, not only can release pleasing sweet orange fragrance, improves people's work efficiency, but also can have certain antibacterial effect. The whole preparation process is relatively simple, easy to operate and environment-friendly.
Drawings
Fig. 1 is a transmission electron microscope picture of the chitosan PLGA nano-essence prepared in example 1 of the present invention.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
The materials and equipment used in the present invention are either commercially available or can be synthesized.
Example 1
The embodiment provides a preparation method of chitosan PLGA nano orange flavor essence, which comprises the following specific steps:
step 1: accurately weighing 100mg of PLGA (lactic acid: glycolic acid 75:25) and 100mg of orange essence respectively, and sequentially dissolving in 5mL of ethyl acetate solution to obtain oil phase;
step 2: preparing 1% glacial acetic acid solution as a solvent of a water phase; accurately weighing 0.1g of chitosan, and dissolving the chitosan in 10mL of 1% glacial acetic acid solution to prepare a chitosan solution; accurately weighing 1g of polyvinyl alcohol, and easily dissolving the polyvinyl alcohol in 9mL of chitosan solution to be used as a water phase;
and step 3: adding the water phase obtained in the step 2 into a glass reagent bottle with a cover, and continuously stirring at room temperature at 800rpm/min by using a magnetic stirrer; slowly injecting the oil phase obtained in the step 1 into the water phase at the speed of 0.5mL/min by using a micro-injection pump, wherein the volume ratio of the water phase to the oil phase is 10:1, and continuously stirring for 30 min; performing ultrasonic treatment on the mixed solution in ice bath for 5min (ultrasonic treatment for 2s at an interval of 2s, power of 100W and temperature of 15 ℃); continuously stirring the emulsion after ultrasonic treatment for 2h at 40 ℃ on a magnetic stirrer to volatilize ethyl acetate serving as an oil phase solvent, and centrifuging for 30min at the rotating speed of 15000rpm through an ultracentrifuge; collecting nanoparticles, washing with distilled water for 3 times, and filtering with 0.22 μm filter membrane to remove nanospheres with larger particle size; and (5) carrying out freeze drying to obtain the dried chitosan PLGA nano orange fragrance essence.
Dissolving the prepared chitosan PLGA nano sweet orange flavor essence in distilled water, adding HY-4021 type lotus leaf hydrophobing agent, and mixing uniformly, wherein the mass concentration of the chitosan PLGA nano sweet orange flavor essence is 5-10 wt%, and the mass concentration of HY-4021 type lotus leaf hydrophobing agent is 0.1-0.5%. Refer to the coating method in patent CN102127879, i.e. using the existing blade coating or roller coating, uniformly coating the orange essence on the surface of the scented paper by a coating machine, and controlling the coating amount to be 2-20g/m2. Because the coating machine can apply a certain external force in the coating processThe nanoparticles thus prepared can be better bonded to paper fibers. The HY-4021 type lotus leaf hydrophobing agent is used for preventing the perfumed paper from absorbing a large amount of water in a humid environment, so that the degradation speed of PLGA is slower, the perfumed paper is not released too fast, and a better slow release effect can be achieved. The humidity response type scented paper prepared in the way has good slow release performance.
Example 2
The embodiment provides a preparation method of chitosan PLGA nano orange flavor essence, which comprises the following specific steps:
step 1: accurately weighing 200mg of PLGA (polylactic acid: glycolic acid 75:25) and 200mg of orange essence respectively, and sequentially dissolving in 5mL of ethyl acetate solution to obtain oil phase;
step 2: preparing 1% glacial acetic acid solution as a solvent of a water phase; accurately weighing 0.1g of chitosan, and dissolving the chitosan in 10mL of 1% glacial acetic acid solution to prepare a chitosan solution; accurately weighing 1g of polyvinyl alcohol, and easily dissolving the polyvinyl alcohol in 9mL of chitosan solution to be used as a water phase;
and step 3: adding the water phase obtained in the step 2 into a glass bottle with a cover, and continuously stirring at room temperature at 800rpm/min by using a magnetic stirrer; slowly injecting the oil phase obtained in the step 1 into the water phase at the speed of 0.5mL/min by using a micro-injection pump, wherein the volume ratio of the water phase to the oil phase is 10:1, and continuously stirring for 30 min; performing ultrasonic treatment on the mixed solution in ice bath for 5min (ultrasonic treatment for 2s at an interval of 2s, power of 100W and temperature of 15 ℃); continuously stirring the emulsion after ultrasonic treatment for 2h at 40 ℃ on a magnetic stirrer to volatilize ethyl acetate serving as an oil phase solvent, and centrifuging for 30min at the rotating speed of 15000rpm through an ultracentrifuge; collecting nanoparticles, washing with distilled water for 3 times, and filtering with 0.22 μm filter membrane to remove nanospheres with larger particle size; and (5) carrying out freeze drying to obtain the dried chitosan PLGA nano orange fragrance essence.
Dissolving the prepared chitosan PLGA nano sweet orange flavor essence in distilled water, adding HY-4021 type lotus leaf hydrophobing agent, and mixing uniformly, wherein the mass concentration of the chitosan PLGA nano sweet orange flavor essence is 5-10 wt%, and the mass concentration of HY-4021 type lotus leaf hydrophobing agent is 0.1-0.5%. Reference is made to the coating in patent CN102127879The method comprises uniformly coating orange essence on the surface of scented paper by conventional knife coating or roller coating, wherein the coating weight is controlled at 2-20g/m2. Because the coating machine can apply certain external force in the coating process, the prepared nano particles can be better combined with paper fibers. The HY-4021 type lotus leaf hydrophobing agent is used for preventing the perfumed paper from absorbing a large amount of water in a humid environment, so that the degradation speed of PLGA is slower, the perfumed paper is not released too fast, and a better slow release effect can be achieved. The humidity response type scented paper prepared in the way has good slow release performance.
Example 3
The embodiment provides a preparation method of chitosan PLGA nano convallaria type essence, which comprises the following specific steps:
step 1: accurately weighing 100mg of PLGA (lactic acid: glycolic acid: 75:25) and 100mg of lily of the valley essence respectively, and dissolving in 5mL of ethyl acetate solution sequentially to obtain oil phases;
step 2: preparing 1% glacial acetic acid solution as a solvent of a water phase; accurately weighing 0.1g of chitosan, and dissolving the chitosan in 10mL of 1% glacial acetic acid solution to prepare a chitosan solution; accurately weighing 1g of polyvinyl alcohol, and easily dissolving the polyvinyl alcohol in 9mL of chitosan solution to be used as a water phase;
and step 3: adding the water phase obtained in the step 2 into a glass bottle with a cover, and continuously stirring at room temperature at 800rpm/min by using a magnetic stirrer; slowly injecting the oil phase obtained in the step 1 into the water phase at the speed of 0.5mL/min by using a micro-injection pump, wherein the volume ratio of the water phase to the oil phase is 10:1, and continuously stirring for 30 min; performing ultrasonic treatment on the mixed solution in ice bath for 5min (ultrasonic treatment for 2s at an interval of 2s, power of 100W and temperature of 15 ℃); continuously stirring the emulsion after ultrasonic treatment for 2h at 40 ℃ on a magnetic stirrer to volatilize ethyl acetate serving as an oil phase solvent, and centrifuging for 30min at the rotating speed of 15000rpm through an ultracentrifuge; collecting nanoparticles, washing with distilled water for 3 times, and filtering with 0.22 μm filter membrane to remove nanospheres with larger particle size; and (5) carrying out freeze drying to obtain the dried chitosan PLGA nano lily of the valley fragrance type essence.
Dissolving the prepared chitosan PLGA nano orange fragrance essence in distilled waterAnd adding HY-4021 type lotus leaf hydrophobing agent, and mixing, wherein the weight concentration of the chitosan PLGA nanometer orange flavor essence is 5-10 wt%, and the weight concentration of HY-4021 type lotus leaf hydrophobing agent is 0.1-0.5%. Refer to the coating method in patent CN102127879, i.e. using the existing blade coating or roller coating, uniformly coating the orange essence on the surface of the scented paper by a coating machine, and controlling the coating amount to be 2-20g/m2. Because the coating machine can apply certain external force in the coating process, the prepared nano particles can be better combined with paper fibers. The HY-4021 type lotus leaf hydrophobing agent is used for preventing the perfumed paper from absorbing a large amount of water in a humid environment, so that the degradation speed of PLGA is slower, the perfumed paper is not released too fast, and a better slow release effect can be achieved. The humidity response type scented paper prepared in the way has good slow release performance.
Example 4
The embodiment provides a preparation method of chitosan PLGA nano convallaria type essence, which comprises the following specific steps:
step 1: accurately weighing 100mg of PLGA (lactic acid: glycolic acid: 75:25) and 200mg of lily of the valley essence respectively, and dissolving in 5mL of ethyl acetate solution sequentially to obtain oil phases;
step 2: preparing 1% glacial acetic acid solution as a solvent of a water phase; accurately weighing 0.1g of chitosan, and dissolving the chitosan in 10mL of 1% glacial acetic acid solution to prepare a chitosan solution; accurately weighing 1g of polyvinyl alcohol, and easily dissolving the polyvinyl alcohol in 9mL of chitosan solution to be used as a water phase;
and step 3: adding the water phase obtained in the step 2 into a glass bottle with a cover, and continuously stirring at room temperature at 800rpm/min by using a magnetic stirrer; slowly injecting the oil phase obtained in the step 1 into the water phase at the speed of 0.5mL/min by using a micro-injection pump, wherein the volume ratio of the water phase to the oil phase is 10:1, and continuously stirring for 30 min; performing ultrasonic treatment on the mixed solution in ice bath for 5min (ultrasonic treatment for 2s at an interval of 2s, power of 100W and temperature of 15 ℃); continuously stirring the emulsion after ultrasonic treatment for 2h at 40 ℃ on a magnetic stirrer to volatilize ethyl acetate serving as an oil phase solvent, and centrifuging for 30min at the rotating speed of 15000rpm through an ultracentrifuge; collecting nanoparticles, washing with distilled water for 3 times, and filtering with 0.22 μm filter membrane to remove nanospheres with larger particle size; and (5) carrying out freeze drying to obtain the dried chitosan PLGA nano lily of the valley fragrance type essence.
Dissolving the prepared chitosan PLGA nano sweet orange flavor essence in distilled water, adding HY-4021 type lotus leaf hydrophobing agent, and mixing uniformly, wherein the mass concentration of the chitosan PLGA nano sweet orange flavor essence is 5-10 wt%, and the mass concentration of HY-4021 type lotus leaf hydrophobing agent is 0.1-0.5%. Refer to the coating method in patent CN102127879, i.e. using the existing blade coating or roller coating, uniformly coating the orange essence on the surface of the scented paper by a coating machine, and controlling the coating amount to be 2-20g/m2. Because the coating machine can apply certain external force in the coating process, the prepared nano particles can be better combined with paper fibers. The HY-4021 type lotus leaf hydrophobing agent is used for preventing the perfumed paper from absorbing a large amount of water in a humid environment, so that the degradation speed of PLGA is slower, the perfumed paper is not released too fast, and a better slow release effect can be achieved. The humidity response type scented paper prepared in the way has good slow release performance.
Claims (10)
1. A preparation method of chitosan PLGA nano essence is characterized by comprising the following steps:
step 1: dissolving PLGA and essence in ethyl acetate to obtain oil phase;
step 2: dissolving chitosan and polyvinyl alcohol in 1% glacial acetic acid solution to serve as a water phase;
and step 3: slowly injecting the oil phase into the water phase by a micro-injection pump under magnetic stirring, and continuously stirring for 0.5-1 h; carrying out ultrasonic emulsification on the mixed solution by an ultrasonic cell disruption instrument under the ice bath condition to obtain nano emulsion; stirring the nano emulsion for 1-3h at the temperature of 40 +/-2 ℃, removing ethyl acetate, and centrifuging for 15-40min at the rotating speed of 12000-18000rpm by an ultracentrifuge; collecting nanoparticles, washing with distilled water for multiple times, and filtering with 0.22 μm filter membrane to remove nanospheres with larger particle size; and (5) carrying out freeze drying to obtain the chitosan PLGA nano essence.
2. The method for preparing the chitosan-PLGA nano-essence according to claim 1, wherein the PLGA in the step 1 is lactic acid-glycolic acid 75:25(w/w), carboxyl end group, and molecular weight is 10000 Da.
3. The method for preparing the chitosan PLGA nano-essence according to claim 1, wherein the essence in the step 1 is sweet orange essence or lily of the valley essence.
4. The method for preparing chitosan-PLGA nano essence according to claim 1, wherein the mass ratio of essence to PLGA in the step 1 is 1: 1.
5. the preparation method of chitosan PLGA nano essence of claim 1, wherein the chitosan polymerization degree in step 2 is not less than 80.0, and the concentration is 0.2%; the alcoholysis degree of the polyvinyl alcohol is 87.0-89.0, and the concentration is 1%.
6. The method for preparing chitosan-PLGA nano-essence according to claim 1, wherein in the step 3, the ultrasonic cell disruptor is ultrasonically emulsified in ice bath for 5min at an interval of 2s and at a power of 100W and a temperature of 15 ℃; the magnetic stirring speed is 800rpm/min, the temperature is 25 ℃, and the stirring time is 30 min.
7. The method for preparing the chitosan PLGA nano essence of claim 1, wherein the particle size of the chitosan PLGA nano essence in the step 3 is 240-300 nm.
8. Chitosan PLGA nanoperfume prepared according to the method of any one of claims 1 to 7.
9. A preparation method of humidity response type scented paper is characterized by comprising the following steps: fixing the blank paper on a splint of a coating machine, dissolving the chitosan PLGA nano essence of claim 8 in distilled water, adding HY-4021 type lotus leaf hydrophobing agent, sampling the blank paper through the coating machine to prepare scented paper, and naturally drying at room temperature to obtain humidity-responsive scented paper.
10. A moisture responsive scented paper made by the process of claim 9.
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CN114872222A (en) * | 2022-04-18 | 2022-08-09 | 苏州银锐环保材料有限公司 | Edible plastic agent production system and production method |
CN114872222B (en) * | 2022-04-18 | 2023-09-26 | 苏州银锐环保材料有限公司 | Plastic eating agent production system and production method |
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