CN114163696A - Preparation method of degradable bio-based film material with phase change function - Google Patents
Preparation method of degradable bio-based film material with phase change function Download PDFInfo
- Publication number
- CN114163696A CN114163696A CN202111489982.1A CN202111489982A CN114163696A CN 114163696 A CN114163696 A CN 114163696A CN 202111489982 A CN202111489982 A CN 202111489982A CN 114163696 A CN114163696 A CN 114163696A
- Authority
- CN
- China
- Prior art keywords
- chitosan
- phase change
- preparation
- film material
- degradable
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01G—HORTICULTURE; CULTIVATION OF VEGETABLES, FLOWERS, RICE, FRUIT, VINES, HOPS OR SEAWEED; FORESTRY; WATERING
- A01G13/00—Protecting plants
- A01G13/02—Protective coverings for plants; Coverings for the ground; Devices for laying-out or removing coverings
- A01G13/0256—Ground coverings
- A01G13/0262—Mulches, i.e. covering material not-pre-formed in mats or sheets
-
- 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
- C08J2305/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2301/00 or C08J2303/00
- C08J2305/08—Chitin; Chondroitin sulfate; Hyaluronic acid; Derivatives thereof
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/042—Graphene or derivatives, e.g. graphene oxides
-
- 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
- C08K5/04—Oxygen-containing compounds
- C08K5/06—Ethers; Acetals; Ketals; Ortho-esters
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental Sciences (AREA)
- Toxicology (AREA)
- General Health & Medical Sciences (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Biological Depolymerization Polymers (AREA)
Abstract
The invention provides a preparation method of a degradable bio-based film material with a phase change function, belonging to the technical field of high polymer polymerization and processing. The preparation method comprises the following steps: 2, 5-furandicarboxylic acid, chitosan, butanediol and succinic acid are used as raw materials to prepare a bio-based copolymer, and graphene and dibenzylidene sorbitol are added to realize melt molding and processing into a film. The film material compost is degraded for 90d, the decomposition rate is up to more than 88%, and the phase change enthalpy is between 130-180J/g.
Description
Technical Field
The invention relates to a preparation method of a degradable bio-based film material with a phase change function, belonging to the technical field of polymerization and processing of high polymer materials.
Background
At present, the ever increasing demand for energy by the increasing population and social activities leads to pollution and the emission of greenhouse gases into the atmosphere, which can lead to shortages of petroleum feedstocks. The development of a sustainable, reliable and efficient energy storage system as an energy reserve will alleviate and solve the related problems to some extent. The storage of thermal energy, which can enhance and maintain energy, is considered to be an effective method for improving the efficiency of heat resource utilization.
Polymer-based phase change materials are widely used with excellent mechanical properties, chemical resistance and good thermal stability. Such as polystyrene, polymethylmethacrylate, polyurethane, urea, melamine formaldehyde and like materials (UF and MF). However, it has been found that e.g. UF and MF release harmful formaldehyde during use. The elimination of formaldehyde has become another problematic issue that is difficult to solve.
Biodegradable polymeric materials, having acceptable physical and mechanical properties, non-toxicity, biodegradability, renewability and ease of processing, etc., and requiring less energy than petroleum-based polymers, can promote environmental ecological sustainability. The chitosan is an environment-friendly natural polymer material, and has the advantages of rich yield and low price. The decomposition temperature of the chitosan is lower than the melting temperature, so the chitosan cannot be melt-processed, and the application of the chitosan is limited.
Disclosure of Invention
The invention realizes the melt processing of the chitosan by the copolymerization reaction and the controllable processing method, expands the application range of the chitosan, and prepares the phase-change copolymer with excellent phase-change function and degradation performance so as to prepare the phase-change film with biodegradability, thereby solving the problems.
The technical scheme of the invention is as follows:
a preparation method of a degradable bio-based film material with a phase change function is characterized in that 2, 5-furandicarboxylic acid, chitosan, succinic acid and ethylene glycol are copolymerized, and graphene and dibenzylidene sorbitol are further added, so that a phase change degradable film with excellent performance is processed and prepared; the method comprises the following specific steps:
(1) controllable copolymerization reaction: firstly, reacting 2, 5-furandicarboxylic acid with chitosan, then adding succinic acid and ethylene glycol for reaction, and further carrying out polycondensation to obtain a degradable chitosan-based copolymer;
(2) controllable forming: and (3) blending the degradable chitosan-based copolymer obtained in the step (i), graphene and dibenzylidene sorbitol, and extruding and forming to obtain the degradable film material with the phase change function.
Further conditions are:
in the step (1), the 2, 5-furandicarboxylic acid and the chitosan are kept at room temperature for 12h, and react for 30-50min under the protection of nitrogen at the temperature of 110-50 ℃, then the temperature is reduced to 20-50 ℃, succinic acid and excessive glycol are added, and the reaction is carried out at the temperature of 160-190 ℃ until the reaction rate reaches more than 93%. Further, the obtained product is decompressed to the vacuum degree of 100-.
The molar ratio of the 2, 5-furandicarboxylic acid to the chitosan to the succinic acid to the ethylene glycol is 5: 3-8: 3-3.5: 6-9, the mole fraction ratio of 2, 5-furandicarboxylic acid and chitosan is controlled, so that the addition amount of chitosan is increased, and the subsequent smooth realization of the melt processing of the system is ensured; the control of the relative weight part of the ethylene glycol is beneficial to controlling the phase change enthalpy of the system.
The addition amount of the ethylene glycol cannot exceed 50 wt% of the total mass of the controllable copolymerization reaction system at most.
The mass of the chitosan cannot exceed 10 wt% of the total mass of the controllable copolymerization reaction system at most.
Further conditions are:
the film is formed by melt molding of the chitosan copolymer through adding the graphene and the dibenzylidene sorbitol to form master batches and further processing, wherein the added graphene and the dibenzylidene sorbitol are respectively used as nucleating agents and form a dynamic network. Wherein the relative amount of the graphene is controlled to be 1-5 wt% of the total mass of the mixed system, and the relative amount of the dibenzylidene sorbitol is controlled to be 3-4 wt% of the total mass of the mixed system.
The invention adopts a mode of polymerization and blending, which is beneficial to realizing the melt molding processing of the chitosan and obtaining the phase change function and the degradability. If the mode of blending chitosan is adopted, the melting processing of the material can not be tested, and the material without adding graphene is not easy to improve the crystallization degree and the heat conduction degree, so that the phase change function and the state maintenance of the phase change material are weakened.
The modulus of the obtained chitosan copolymer is rapidly reduced under the action of shearing force, and the chitosan copolymer is easy to degrade when the temperature is increased, so that the chitosan copolymer is difficult to normally process.
The invention has the beneficial effects that:
(1) the degradable film has larger phase change enthalpy at 35-46 ℃, and the phase change enthalpy is between 130-180J/g.
(2) The highest puncture strength of the degradable film can reach 4.5N.
(3) The biological-based copolymer compost is degraded for 90 days, and the decomposition rate is up to more than 70%.
(4) The invention can provide feasible process conditions for the film forming processing of the chitosan copolymer, and can be used for agricultural mulching films and packaging films.
Detailed Description
The following non-limiting examples are presented to enable those of ordinary skill in the art to more fully understand the present invention and are not intended to limit the invention in any way.
Example 1
A method for preparing a chitosan copolymer film with excellent degradability and phase change function comprises the following steps:
the copolymerization reaction comprises the following steps: firstly, adding 2, 5-furandicarboxylic acid and chitosan into a reaction kettle, keeping the temperature at room temperature for 12 hours, reacting at 120 ℃ for 40 minutes under the protection of nitrogen, cooling to 30 ℃, adding succinic acid and excessive ethylene glycol, and reacting at 170 ℃ for 2 hours until the reaction degree reaches 95%; the molar ratio of the 2, 5-furandicarboxylic acid to the chitosan to the succinic acid to the ethylene glycol is 5: 5: 3: 6; the polycondensation reaction comprises the following steps: adding a catalyst, reducing the pressure to 40Pa within 90min, and reacting for 3h at 210 ℃ to obtain a yellowish copolymer;
the obtained chitosan copolymer, graphene and dibenzylidene sorbitol are formed into master batches according to the mass ratio of 2:1, and then the master batches are mixed with chitosan for processing.
GPC analysis showed that the chitosan copolymer had a number average molecular weight of 20500 and a molecular weight distribution of 2.80.
The prepared film is subjected to mechanical property test, and the tensile strength is 32MPa, the elongation at break is 800%, and the highest puncture strength can reach 4.0N.
DSC test is carried out on the prepared film, and the phase change enthalpy is 166.5J/g, and the maximum phase change value is 38 ℃.
The chitosan copolymer prepared above was composted and degraded for 90 days according to the method provided in us ASTM6400 to obtain a biodegradability of 92%.
The film prepared above was composted and degraded for 90d according to the method provided in ASTM6400 of the united states, to give a biodegradation rate of 88%.
Example 2
A method for preparing a chitosan copolymer film with excellent degradability and phase change function comprises the following steps:
the copolymerization reaction comprises the following steps: firstly, adding 2, 5-furandicarboxylic acid and chitosan into a reaction kettle, keeping the temperature at room temperature for 12 hours, reacting at 120 ℃ for 40 minutes under the protection of nitrogen, cooling to 30 ℃, adding succinic acid and excessive ethylene glycol, and reacting at 190 ℃ for 2 hours until the reaction degree reaches 96%; the molar ratio of the 2, 5-furandicarboxylic acid to the chitosan to the succinic acid to the ethylene glycol is 5: 8: 3.5: 9; the polycondensation reaction comprises the following steps: adding a catalyst, reducing the pressure to 40Pa within 90min, and reacting for 3h at 210 ℃ to obtain a yellowish copolymer;
the obtained chitosan copolymer, graphene and dibenzylidene sorbitol are formed into master batches according to the mass ratio of 2:1, and then the master batches are mixed with chitosan for processing.
GPC analysis showed that the chitosan copolymer had a number average molecular weight of 21400 and a molecular weight distribution of 2.90.
The prepared film is subjected to mechanical property test, so that the tensile strength is 33.5MPa, the elongation at break is 700%, and the highest puncture strength can reach 4.5N.
DSC test is carried out on the prepared film, and the phase change enthalpy is 160.5J/g, and the maximum phase change value is 38 ℃.
The chitosan copolymer prepared above was composted and degraded for 90 days according to the method provided in us ASTM6400 to obtain a biodegradability of 92%.
The film prepared above was composted and degraded for 90d according to the method provided in ASTM6400 of the united states, to give a biodegradation rate of 88%.
Example 3
A method for preparing a chitosan copolymer film with excellent degradability and phase change function comprises the following steps:
the copolymerization reaction comprises the following steps: firstly, adding 2, 5-furandicarboxylic acid and chitosan into a reaction kettle, keeping the temperature at room temperature for 12 hours, reacting at 120 ℃ for 40 minutes under the protection of nitrogen, cooling to 30 ℃, adding succinic acid and excessive ethylene glycol, and reacting at 180 ℃ for 2 hours until the reaction degree reaches 95%; the molar ratio of the 2, 5-furandicarboxylic acid to the chitosan to the succinic acid to the ethylene glycol is 5: 3: 3: 6; the polycondensation reaction comprises the following steps: adding a catalyst, reducing the pressure to 40Pa within 90min, and reacting for 3h at 210 ℃ to obtain a yellowish copolymer;
the obtained chitosan copolymer, graphene and dibenzylidene sorbitol are formed into master batches according to the mass ratio of 2:1, and then the master batches are mixed with chitosan for processing.
GPC analysis showed that the chitosan copolymer obtained above had a number average molecular weight of 20000 and a molecular weight distribution of 2.95.
The prepared film is subjected to mechanical property test, and the tensile strength is 31MPa, the elongation at break is 850%, and the highest puncture strength can reach 3.8N.
DSC test is carried out on the prepared film to obtain that the phase change enthalpy is 160.0J/g, and the maximum phase change value is 38 ℃.
The chitosan copolymer prepared above was composted and degraded for 90 days according to the method provided in us ASTM6400 to obtain a biodegradability of 92%.
The film prepared above was composted and degraded for 90d according to the method provided in ASTM6400 of the united states, to give a biodegradation rate of 88%.
Claims (3)
1. A preparation method of a degradable bio-based film material with a phase change function is characterized by comprising the following steps:
controllable copolymerization reaction
Firstly, keeping 2, 5-furandicarboxylic acid and chitosan at room temperature for 12h, reacting for 30-50min under the protection of nitrogen at the temperature of 110-; reducing the pressure of the obtained product within 90-120min to the vacuum degree of 100-; wherein the molar ratio of the 2, 5-furandicarboxylic acid to the chitosan to the succinic acid to the ethylene glycol is 5: 3-8: 3-3.5: 6-9;
② controllable forming
Blending the degradable chitosan-based copolymer obtained in the step I, graphene and dibenzylidene sorbitol, and extruding and molding to obtain a degradable film material with a phase change function; wherein the relative amount of the graphene is controlled to be 1-5 wt% of the total mass of the mixed system, and the relative amount of the dibenzylidene sorbitol is controlled to be 3-4 wt% of the total mass of the mixed system.
2. The process according to claim 1, wherein the amount of ethylene glycol added in step (i) is not more than 50% by weight of the total mass of the controlled copolymerization reaction system at the maximum, and the mass of chitosan is not more than 10% by weight of the total mass of the controlled copolymerization reaction system at the maximum.
3. The preparation method according to claim 1 or 2, wherein in the step (II), the graphene and the dibenzylidene sorbitol are added to form master batches, and then the master batches are blended.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111489982.1A CN114163696B (en) | 2021-12-08 | 2021-12-08 | Preparation method of degradable bio-based film material with phase change function |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111489982.1A CN114163696B (en) | 2021-12-08 | 2021-12-08 | Preparation method of degradable bio-based film material with phase change function |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114163696A true CN114163696A (en) | 2022-03-11 |
| CN114163696B CN114163696B (en) | 2022-09-20 |
Family
ID=80484487
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111489982.1A Active CN114163696B (en) | 2021-12-08 | 2021-12-08 | Preparation method of degradable bio-based film material with phase change function |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114163696B (en) |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102282197A (en) * | 2008-11-06 | 2011-12-14 | 特瑞斯坦奥私人有限公司 | Biodegradable polymer composition |
| US20130230496A1 (en) * | 2012-02-23 | 2013-09-05 | Subhra Mohapatra | Graphene hydrogel and method for using the same |
| CN104292782A (en) * | 2014-05-13 | 2015-01-21 | 浙江大学 | Complete bio-based biodegradable polylactic acid composition and preparation method thereof |
| CN105315508A (en) * | 2015-11-17 | 2016-02-10 | 重庆理工大学 | Preparation method for modified graphene-chitosan composite thin film |
| CN106700046A (en) * | 2017-01-22 | 2017-05-24 | 大连工业大学 | Bio-based copolyester with excellent degradability and preparation method of bio-based copolyester |
| CN108610608A (en) * | 2018-04-21 | 2018-10-02 | 湖南辰砾新材料有限公司 | A kind of high-strength environment-friendly plastic material and preparation method thereof |
| CN109289094A (en) * | 2018-09-25 | 2019-02-01 | 湖南博隽生物医药有限公司 | A kind of vascular stent material and preparation method thereof |
| CN109575257A (en) * | 2018-11-16 | 2019-04-05 | 中国科学院宁波材料技术与工程研究所 | Poly- 2,5- furandicarboxylic acid -1,4- neopentyl glycol succinate and preparation method thereof, product |
| US20190375890A1 (en) * | 2017-01-26 | 2019-12-12 | Synvina C.V. | 2, 5-furandicarboxylic acid-based polyesters |
-
2021
- 2021-12-08 CN CN202111489982.1A patent/CN114163696B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102282197A (en) * | 2008-11-06 | 2011-12-14 | 特瑞斯坦奥私人有限公司 | Biodegradable polymer composition |
| US20130230496A1 (en) * | 2012-02-23 | 2013-09-05 | Subhra Mohapatra | Graphene hydrogel and method for using the same |
| CN104292782A (en) * | 2014-05-13 | 2015-01-21 | 浙江大学 | Complete bio-based biodegradable polylactic acid composition and preparation method thereof |
| CN105315508A (en) * | 2015-11-17 | 2016-02-10 | 重庆理工大学 | Preparation method for modified graphene-chitosan composite thin film |
| CN106700046A (en) * | 2017-01-22 | 2017-05-24 | 大连工业大学 | Bio-based copolyester with excellent degradability and preparation method of bio-based copolyester |
| US20190375890A1 (en) * | 2017-01-26 | 2019-12-12 | Synvina C.V. | 2, 5-furandicarboxylic acid-based polyesters |
| CN108610608A (en) * | 2018-04-21 | 2018-10-02 | 湖南辰砾新材料有限公司 | A kind of high-strength environment-friendly plastic material and preparation method thereof |
| CN109289094A (en) * | 2018-09-25 | 2019-02-01 | 湖南博隽生物医药有限公司 | A kind of vascular stent material and preparation method thereof |
| CN109575257A (en) * | 2018-11-16 | 2019-04-05 | 中国科学院宁波材料技术与工程研究所 | Poly- 2,5- furandicarboxylic acid -1,4- neopentyl glycol succinate and preparation method thereof, product |
Non-Patent Citations (4)
| Title |
|---|
| SANTOSH KUMAR等: "Synthesis of 2,5-furandicarboxylic acid-enriched-chitosan for anti-inflammatory and metal ion uptake", 《INTERNATIONAL JOURNAL OF BIOLOGICAL MACROMOLECULES》 * |
| 刘跃军等: "丁二酸-1,4-丁二醇-尿素聚酯酰脲共聚物的制备与性能", 《高校化学工程学报》 * |
| 张健等: "石墨烯/壳聚糖抗菌膜的制备及其保鲜性能评价", 《造纸科学与技术》 * |
| 王艳等: "生物质呋喃二甲酸聚酯的合成工艺路线概述及其应用前景", 《塑料科技》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114163696B (en) | 2022-09-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| WO2009015577A1 (en) | Producing method for polylactic acid-based copolymer | |
| KR100701622B1 (en) | Biodegradable aliphatic/aromatic copolyester polymer and preparation thereof | |
| WO2022142512A1 (en) | Semi-aromatic polyester, and preparation method therefor and application thereof | |
| KR20240141680A (en) | Process for preparation of block copolymer | |
| CN111100269A (en) | Process for producing polyester and polyester mixture | |
| Wang et al. | Biodegradable aliphatic/aromatic copolyesters based on terephthalic acid and poly (L-lactic acid): Synthesis, characterization and hydrolytic degradation | |
| JP4200340B2 (en) | Resin composition and molded body | |
| CN114163696B (en) | Preparation method of degradable bio-based film material with phase change function | |
| CN113429762A (en) | Starch/polylactic acid/PBAT nano composite material and preparation method thereof | |
| JP2003171544A (en) | Lactic acid resin composition, peroxide-modified lactic acid resin composition, and their molded items | |
| CN114685958A (en) | Modified preparation method of polylactic acid material | |
| CN113004668A (en) | Preparation method of modified polylactic acid material | |
| CN114456565B (en) | Carbon dioxide-based polylactic acid copolymer modified cellulose material and preparation method thereof | |
| CN108250421B (en) | Degradable environment-friendly plastic film and preparation method thereof | |
| CN112852129A (en) | Preparation method of polylactic acid composite material | |
| JP5050610B2 (en) | Molded product of resin composition with excellent low-temperature characteristics | |
| JP4744675B2 (en) | Process for producing biodegradable aliphatic polyester | |
| EP4108702B1 (en) | Polylactide stereocomplex and preparation method therefor | |
| KR102598027B1 (en) | Copolymer and method for preparation thereof | |
| JP4318495B2 (en) | Resin composition and biodegradable film | |
| CN115427478B (en) | Polylactic acid stereocomplex and preparation method thereof | |
| CN113754871B (en) | Biodegradable block copolyesters based on lactide- (cycloaliphatic-co-aromatic) -lactide | |
| JP7486609B2 (en) | Copolymer and method for producing same | |
| CN116120532B (en) | Preparation method of poly (butylene succinate) and poly (butylene succinate) | |
| JP4165800B2 (en) | Biodegradable resin and film |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20221216 Address after: 116032 No. 2, floor 3, unit 2, No. 15, fanglinyuan, Southwest Road, Ganjingzi District, Dalian, Liaoning Province Patentee after: Dalian Haichuan Technology Co.,Ltd. Address before: 116032 No. 2, floor 3, unit 2, No. 15, fanglinyuan, Southwest Road, Ganjingzi District, Dalian, Liaoning Province Patentee before: Dalian Haichuan Technology Co.,Ltd. Patentee before: DALIAN POLYTECHNIC University |