CN115710412A - High-barrier-property biaxially oriented degradable polyester film and preparation method thereof - Google Patents
High-barrier-property biaxially oriented degradable polyester film and preparation method thereof Download PDFInfo
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- CN115710412A CN115710412A CN202211347418.0A CN202211347418A CN115710412A CN 115710412 A CN115710412 A CN 115710412A CN 202211347418 A CN202211347418 A CN 202211347418A CN 115710412 A CN115710412 A CN 115710412A
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- polyester film
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- montmorillonite
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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 discloses a high-barrier property biaxially oriented degradable polyester film, which comprises the following raw materials: the modified montmorillonite is obtained by modifying the surface of montmorillonite by dipalmitoyl carboxyethyl hydroxyethyl methyl ammonium methyl sulfate, dodecyl bis hydroxyethyl methyl ammonium chloride and a silane coupling agent KH-550. The polyester film prepared by the invention has excellent degradability and mechanical property, has excellent barrier property, and can be well applied to the field of packaging materials.
Description
Technical Field
The invention relates to the technical field of film materials, in particular to a high-barrier-property biaxially oriented degradable polyester film and a preparation method thereof.
Background
The poly (butylene adipate/terephthalate) (PBAT) is a copolymer of butylene adipate and butylene terephthalate, has good mechanical property, heat resistance and impact resistance, has excellent biodegradability, and is a thermoplastic biodegradable material which attracts much attention. The polybutylene adipate/terephthalate also has good film forming property, so that the polybutylene adipate/terephthalate can be applied to the field of packaging film materials. In particular, the biaxial stretching process can endow the PBAT film with better mechanical property and puncture resistance, greatly improves the service performance of the PBAT film as a packaging film, and is beneficial to expanding the application prospect of the PBAT film in the field of high-end packaging materials. However, the barrier property of the polybutylene adipate/terephthalate material is poor, so that the effects of oxygen and water vapor barrier are not high, and the barrier protection effect on the packaged contents, especially on the water and oxygen of foods, medicines and the like is not good, which becomes an important factor for limiting the popularization and application of the biaxially oriented PBAT film in the field of packaging materials.
Disclosure of Invention
Based on the technical problems in the background art, the invention provides a high-barrier property biaxially oriented degradable polyester film and a preparation method thereof.
The invention provides a high-barrier property biaxially oriented degradable polyester film, which comprises the following raw materials: poly (butylene adipate-terephthalate), modified montmorillonite, a chain extender, a dispersant and an antioxidant; wherein the mass ratio of the poly (butylene adipate-terephthalate), the modified montmorillonite, the chain extender, the dispersant and the antioxidant is 100: (5-15): (1-2): (2-3): (0.5-2);
the modified montmorillonite is obtained by modifying the surface of montmorillonite with dipalmityl carboxyethyl hydroxyethyl methyl ammonium methyl sulfate, dodecyl bis-hydroxyethyl methyl ammonium chloride and a silane coupling agent KH-550.
Preferably, the preparation method of the modified montmorillonite comprises the following steps: dispersing montmorillonite in a proper amount of water, adding dipalmitoyl carboxyethyl hydroxyethyl methyl ammonium methyl sulfate and dodecyl bis hydroxyethyl methyl ammonium chloride, stirring and reacting for 2-3h at 50-60 ℃, centrifuging after the reaction is finished, washing and drying the obtained precipitate, dispersing in a proper amount of ethanol water solution, adding a silane coupling agent KH-550, stirring and reacting for 5-10h at 60-80 ℃, centrifuging after the reaction is finished, washing and drying the obtained precipitate, and obtaining the modified montmorillonite.
Preferably, the mass ratio of the montmorillonite to the dipalmitoyl carboxyethyl hydroxyethyl methyl ammonium methyl sulfate to the dodecyl bis hydroxyethyl methyl ammonium chloride to the silane coupling agent KH-550 is 1: (0.2-0.3): (0.1-0.2): (0.2-0.4).
Preferably, the polybutylene adipate-terephthalate has a weight average molecular weight of 110000-130000g/mol, a melt flow rate of 3.5-4.5g/10min at 2.16kg and 190 ℃ and a melting point of 110-120 ℃.
Preferably, the chain extender is a basf ADR 4468 chain extender, the dispersant is at least one of stearic acid, zinc stearate and calcium stearate, and the antioxidant is antioxidant 1010, antioxidant 168 or a combination thereof.
A preparation method of the high-barrier property biaxially oriented degradable polyester film comprises the following steps:
s1, weighing raw materials according to the mass parts, uniformly mixing, adding the raw materials into a double-screw extruder for melt extrusion, casting by using a casting machine, and cooling to obtain a sheet;
and S2, stretching the sheet in a two-way mode, and then carrying out heat setting to obtain the high-barrier property polybutylene adipate-terephthalate film.
Preferably, in S1, the temperature of melt extrusion is 180-200 ℃, the temperature of casting is 180-200 ℃, and the temperature of cooling is 20-30 ℃.
Preferably, in S2, the biaxial stretching includes: firstly, longitudinal stretching is carried out, and transverse stretching is carried out, wherein the longitudinal stretching temperature is 95-110 ℃, the stretching ratio is 3-4, the transverse stretching temperature is 105-115 ℃, the stretching ratio is 3-5, and the heat setting temperature is 110-115 ℃.
The invention has the following beneficial effects:
the invention firstly adopts cation quaternary ammonium salt dipalmitoyl carboxyethyl methyl ammonium methyl sulfate and dodecyl bis hydroxyethyl methyl ammonium chloride to carry out combined intercalation modification on the montmorillonite, ester groups and hydroxyl groups are introduced into the montmorillonite, then silane coupling agent KH-550 is added, silanol formed by hydrolysis further reacts with the hydroxyl groups to graft the silane coupling agent active groups onto the surface of the montmorillonite, so that modified montmorillonite with ester groups, amino groups and other active groups and good hydrophobic property is formed, the modified montmorillonite is added into a polybutylene adipate-terephthalate matrix as an additive, and the polybutylene adipate-terephthalate film is prepared by bidirectional stretching in the presence of a chain extender.
Detailed Description
The technical solution of the present invention will be described in detail below with reference to specific examples.
Example 1
Preparing a high-barrier property biaxially oriented degradable polyester film:
s1, mixing the following components in a mass ratio of 100:10:1.5:2.5:1, weighing and uniformly mixing poly (butylene adipate terephthalate), modified montmorillonite, a Basff ADR 4468 chain extender, zinc stearate and an antioxidant 1010, adding the mixture into a double-screw extruder, carrying out melt extrusion at 180-200 ℃, casting at 180-200 ℃ by using a casting machine, and cooling at 25 ℃ to obtain a sheet;
the preparation method of the modified montmorillonite comprises the following steps: dispersing 1kg of montmorillonite in 20L of water, adding 0.25kg of dipalmitoyl carboxyethyl hydroxyethyl methyl ammonium methyl sulfate (model: solvatep-88) and 0.15kg of dodecyl bis hydroxyethyl methyl ammonium chloride, stirring and reacting for 2.5h at 55 ℃, centrifuging after the reaction is finished, washing and drying the obtained precipitate, dispersing the obtained precipitate in 20L of ethanol water solution (obtained by mixing absolute ethanol and water according to the volume ratio of 1:4), adding 0.3kg of silane coupling agent KH-550, stirring and reacting for 8h at 70 ℃, centrifuging after the reaction is finished, washing and drying the obtained precipitate to obtain modified montmorillonite;
the weight average molecular weight of the polybutylene adipate-terephthalate is 120000g/mol, the melt flow rate is 3.9g/10min at 2.16kg and 190 ℃, and the melting point is 115 ℃;
s2, longitudinally stretching the sheet, transversely stretching the sheet, wherein the longitudinal stretching temperature is 98 ℃, the stretching ratio is 3.5, the transverse stretching temperature is 108 ℃, the stretching ratio is 4, and then performing heat setting at 113 ℃ to obtain the high-barrier property poly (butylene adipate-terephthalate) film.
Example 2
Preparing a high-barrier property biaxially oriented degradable polyester film:
s1, mixing the following components in a mass ratio of 100:5:1:2:0.5 weighing and uniformly mixing poly (butylene adipate-terephthalate), modified montmorillonite, bass ADR 4468 chain extender, zinc stearate and an antioxidant 1010, adding the mixture into a double-screw extruder, performing melt extrusion at 180-200 ℃, casting by using a casting machine at 180-200 ℃, and cooling at 20 ℃ to obtain a sheet;
the preparation method of the modified montmorillonite comprises the following steps: dispersing 1kg of montmorillonite in 20L of water, adding 0.2kg of dipalmitoyl carboxyethyl hydroxyethyl methyl ammonium methyl sulfate (model: solvatep-88) and 0.1kg of dodecyl bis hydroxyethyl methyl ammonium chloride, stirring and reacting for 3h at 50 ℃, centrifuging after the reaction is finished, washing and drying the obtained precipitate, dispersing the obtained precipitate in 20L of ethanol aqueous solution (obtained by mixing absolute ethanol and water according to the volume ratio of 1:4), adding 0.2kg of silane coupling agent KH-550, stirring and reacting for 10h at 60 ℃, centrifuging after the reaction is finished, washing and drying the obtained precipitate to obtain modified montmorillonite;
the weight average molecular weight of the polybutylene adipate-terephthalate is 120000g/mol, the melt flow rate is 3.9g/10min at 2.16kg and 190 ℃, and the melting point is 115 ℃;
s2, longitudinally stretching the sheet, then transversely stretching the sheet, wherein the longitudinal stretching temperature is 95 ℃, the stretching ratio is 3, the transverse stretching temperature is 105 ℃, the stretching ratio is 3, and then performing heat setting at 110 ℃ to obtain the high-barrier property poly (butylene adipate-terephthalate) film.
Example 3
Preparing a high-barrier property biaxially oriented degradable polyester film:
s1, mixing the following components in a mass ratio of 100:15:2:3:2 weighing and uniformly mixing the polybutylene adipate-terephthalate, the modified montmorillonite, the BASF ADR 4468 chain extender, the zinc stearate and the antioxidant 1010, adding the mixture into a double-screw extruder, carrying out melt extrusion at 180-200 ℃, casting at 180-200 ℃ by using a casting machine, and cooling at 30 ℃ to obtain a sheet;
the preparation method of the modified montmorillonite comprises the following steps: dispersing 1kg of montmorillonite in 20L of water, adding 0.3kg of dipalmitoyl carboxyethyl hydroxyethyl methyl ammonium methyl sulfate (model: solvatep-88) and 0.2kg of dodecyl bis hydroxyethyl methyl ammonium chloride, stirring and reacting for 2h at 60 ℃, centrifuging after the reaction is finished, washing and drying the obtained precipitate, dispersing the obtained precipitate in 20L of ethanol aqueous solution (obtained by mixing absolute ethanol and water according to the volume ratio of 1:4), adding 0.4kg of silane coupling agent KH-550, stirring and reacting for 5h at 80 ℃, centrifuging after the reaction is finished, washing and drying the obtained precipitate to obtain modified montmorillonite;
the weight average molecular weight of the polybutylene adipate-terephthalate is 120000g/mol, the melt flow rate is 3.9g/10min at 2.16kg and 190 ℃, and the melting point is 115 ℃;
s2, longitudinally stretching the sheet, transversely stretching the sheet, wherein the longitudinal stretching temperature is 110 ℃, the stretching ratio is 4, the transverse stretching temperature is 115 ℃, the stretching ratio is 5, and then performing heat setting at 115 ℃ to obtain the high-barrier property poly (butylene adipate-terephthalate) film.
Comparative example 1
Comparative example 1 differs from example 1 only in that: different modified montmorillonites are adopted.
The preparation method of the modified montmorillonite in the comparative example 1 comprises the following steps: dispersing 1kg of montmorillonite in 20L of water, adding 0.4kg of hexadecyltrimethylammonium chloride, stirring and reacting for 2.5h at 55 ℃, centrifuging after the reaction is finished, washing and drying the obtained precipitate, dispersing the obtained precipitate in 20L of ethanol aqueous solution (obtained by mixing absolute ethanol and water according to the volume ratio of 1:4), adding 0.3kg of silane coupling agent KH-550, stirring and reacting for 8h at 70 ℃, centrifuging after the reaction is finished, washing and drying the obtained precipitate, and obtaining the modified montmorillonite.
Test examples
The films obtained in examples 1 to 3 and comparative example 1 were subjected to a water vapor barrier property test according to the following method: GB 1037-88, the test results are shown in Table 1:
TABLE 1
Therefore, the barrier property of the film can be greatly improved, so that the application effect of the film in the field of packaging materials is improved.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered as the technical solutions and the inventive concepts of the present invention within the technical scope of the present invention.
Claims (8)
1. The high-barrier-property biaxially oriented degradable polyester film is characterized by comprising the following raw materials: poly (butylene adipate-terephthalate), modified montmorillonite, a chain extender, a dispersant and an antioxidant; wherein the mass ratio of the poly (butylene adipate-terephthalate), the modified montmorillonite, the chain extender, the dispersant and the antioxidant is 100: (5-15): (1-2): (2-3): (0.5-2);
the modified montmorillonite is obtained by modifying the surface of montmorillonite with dipalmitoyl carboxyethyl hydroxyethyl methyl ammonium methyl sulfate, dodecyl bis hydroxyethyl methyl ammonium chloride and silane coupling agent KH-550.
2. The high-barrier property biaxially oriented degradable polyester film according to claim 1, wherein the preparation method of the modified montmorillonite comprises: dispersing montmorillonite in a proper amount of water, then adding dipalmitoyl carboxyethyl hydroxyethyl methyl ammonium methyl sulfate and dodecyl bis hydroxyethyl methyl ammonium chloride, stirring and reacting for 2-3h at 50-60 ℃, centrifuging after the reaction is finished, washing and drying the obtained precipitate, dispersing the precipitate in a proper amount of ethanol water solution, adding a silane coupling agent KH-550, stirring and reacting for 5-10h at 60-80 ℃, centrifuging after the reaction is finished, washing and drying the obtained precipitate, and obtaining the modified montmorillonite.
3. The high-barrier property biaxially oriented degradable polyester film according to claim 1, wherein the mass ratio of montmorillonite, dipalmitoyl carboxyethyl hydroxyethyl methyl ammonium methyl sulfate, dodecyl bis hydroxyethyl methyl ammonium chloride and silane coupling agent KH-550 is 1: (0.2-0.3): (0.1-0.2): (0.2-0.4).
4. The high barrier property biaxially oriented degradable polyester film according to claim 1, wherein said polybutylene adipate-terephthalate has a weight average molecular weight of 110000-130000g/mol, a melt flow rate of 3.5-4.5g/10min at 2.16kg and 190 ℃, and a melting point of 110-120 ℃.
5. The high-barrier property biaxially oriented degradable polyester film according to claim 1, wherein the chain extender is a basf ADR 4468 chain extender, the dispersant is at least one of stearic acid, zinc stearate and calcium stearate, and the antioxidant is antioxidant 1010, antioxidant 168 or a combination thereof.
6. A method for preparing the high-barrier property biaxially oriented degradable polyester film according to any one of claims 1 to 5, which comprises:
s1, weighing raw materials according to the mass parts, uniformly mixing, adding the raw materials into a double-screw extruder for melt extrusion, casting by using a casting machine, and cooling to obtain a sheet;
and S2, stretching the sheet in a bidirectional mode, and then carrying out heat setting to obtain the high-barrier property polybutylene adipate-terephthalate film.
7. The method for preparing a high-barrier property biaxially oriented degradable polyester film according to claim 6, wherein in S1, the melt extrusion temperature is 180-200 ℃, the casting temperature is 180-200 ℃, and the cooling temperature is 20-30 ℃.
8. The method for preparing the high-barrier property biaxially oriented degradable polyester film according to claim 6, wherein in S2, the biaxial stretching comprises: firstly, longitudinal stretching is carried out, and transverse stretching is carried out, wherein the longitudinal stretching temperature is 95-110 ℃, the stretching ratio is 3-4, the transverse stretching temperature is 105-115 ℃, the stretching ratio is 3-5, and the heat setting temperature is 110-115 ℃.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004005376A2 (en) * | 2002-07-08 | 2004-01-15 | Mitsubishi Polyester Film Gmbh | Biaxial-oriented polyester film with improved barrier properties |
| CN105623209A (en) * | 2016-03-25 | 2016-06-01 | 江苏裕兴薄膜科技股份有限公司 | Method for preparing high-water vapor barrier polyester thin film by melt polymerization method |
| CN107033557A (en) * | 2017-03-16 | 2017-08-11 | 华南理工大学 | A kind of barrier PBAT laminated films and preparation method and application |
| CN107418163A (en) * | 2017-07-27 | 2017-12-01 | 上海弘睿生物科技有限公司 | The preparation method of water vapor rejection PBAT complete biodegradables resin combination and film |
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- 2022-10-31 CN CN202211347418.0A patent/CN115710412B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004005376A2 (en) * | 2002-07-08 | 2004-01-15 | Mitsubishi Polyester Film Gmbh | Biaxial-oriented polyester film with improved barrier properties |
| CN105623209A (en) * | 2016-03-25 | 2016-06-01 | 江苏裕兴薄膜科技股份有限公司 | Method for preparing high-water vapor barrier polyester thin film by melt polymerization method |
| CN107033557A (en) * | 2017-03-16 | 2017-08-11 | 华南理工大学 | A kind of barrier PBAT laminated films and preparation method and application |
| CN107418163A (en) * | 2017-07-27 | 2017-12-01 | 上海弘睿生物科技有限公司 | The preparation method of water vapor rejection PBAT complete biodegradables resin combination and film |
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