CN113025009A - Ultraviolet aging resistant PBAT material and preparation method thereof - Google Patents
Ultraviolet aging resistant PBAT material and preparation method thereof Download PDFInfo
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- CN113025009A CN113025009A CN202110312574.2A CN202110312574A CN113025009A CN 113025009 A CN113025009 A CN 113025009A CN 202110312574 A CN202110312574 A CN 202110312574A CN 113025009 A CN113025009 A CN 113025009A
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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
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
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- 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
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- C08K5/20—Carboxylic acid amides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3472—Five-membered rings
- C08K5/3475—Five-membered rings condensed with carbocyclic rings
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Abstract
An ultraviolet aging resistant PBAT material and a preparation method thereof comprise the following substances in parts by weight: 100 parts of PBAT melt, 0.2-1.2 parts of ultraviolet absorbent, 0.1-0.4 part of antioxidant, 0.1-0.4 part of lubricant and 0-20 parts of inorganic filler. The PBAT modified material prepared by the invention has excellent ultraviolet aging resistance, the tensile strength can be kept above 85% after the PBAT modified material is irradiated by ultraviolet for 96 hours, the elongation at break is kept above 75%, and the PBAT modified material has good weather resistance. In addition, the online modification technology of the PBAT melt improves the defects of thermal oxygen degradation and performance reduction caused by melting modification of PBAT granules. Meanwhile, the modifier is directly added into the melt obtained after PBAT polymerization, so that the problem that the modifier and PBAT granules cannot be uniformly mixed and are not uniformly distributed in the melt in the conventional modification process can be solved.
Description
Technical Field
The invention belongs to the field of high polymer degradation materials, and particularly relates to an ultraviolet aging resistant PBAT material and a preparation method thereof.
Background
With the high development of the petrochemical industry, plastic packaging products bring great convenience to the production and life of people, such as shopping bags, preservative films, food packaging bags, agricultural mulching films, fruit and vegetable packaging bags and the like. However, these plastic products are convenient, and also cause a great amount of white pollution, which causes great damage to the natural environment and human health, so it is important to develop a plastic material that can be degraded in the natural environment.
The poly (butylene adipate terephthalate) (PBAT) is a copolymer of butylene adipate and butylene terephthalate, is a common biodegradable material, can be completely degraded into carbon dioxide and water, has excellent mechanical property, can be directly blown and injected, and is widely applied to products such as shopping bags, packaging bags, mulching films, bands, self-sealing strip frameworks and the like.
However, some special use scenarios will require the service life of the product, and the degradation cannot occur too early. The PBAT material as a biodegradable polyester is easily affected by ultraviolet light under the illumination condition, so that the product is aged, the service life is seriously affected, and the popularization and the application of the PBAT material in the fields of agricultural films, fruit and vegetable protection bags and the like are limited.
The current research on the ultraviolet aging resistance of PBAT materials is relatively less, and no relevant patent exists. The ultraviolet aging resistance of traditional high polymer materials such as polypropylene, polyethylene, nylon and the like is prepared by mixing an auxiliary agent such as an ultraviolet absorbent and the like with plastic particles in a double-screw mixing granulation mode. However, the PBAT material is very sensitive to thermal shear as a degradable polyester, and can be degraded by thermal oxidation after undergoing one-time melting modification, so that the mechanical property and the thermal property of the PBAT product are reduced, and the subsequent processing is not facilitated.
Disclosure of Invention
The invention provides an ultraviolet aging resistant PBAT material and a preparation method thereof, which are used for overcoming the defects in the prior art.
The invention is realized by the following technical scheme:
an ultraviolet aging resistant PBAT material comprises the following substances in parts by weight:
100 parts of PBAT melt, 0.2-1.2 parts of ultraviolet absorbent, 0.1-0.4 part of antioxidant, 0.1-0.4 part of lubricant and 0-20 parts of inorganic filler.
The PBAT material with the ultraviolet aging resistance is characterized in that the PBAT melt is polymerized by the following substances in a molar ratio:
the molar ratio of terephthalic acid to adipic acid is 6:4-2:8, and the ratio of the sum of the molar amounts of terephthalic acid and adipic acid to 1, 4-butanediol is 1:1-1: 2.
The ultraviolet ray aging resistant PBAT material is a mixture of one or more than two of benzophenones, salicylates, benzotriazoles, hydroxybenzotriazines and the like which are mixed according to any proportion.
The PBAT material with ultraviolet aging resistance is a mixture of one or more than two of amine antioxidant, phenol antioxidant, phosphite antioxidant and thioester antioxidant which are mixed in any proportion.
The lubricant is one or a mixture of more than two of white oil, stearic acid, mesonic acid amide, vinyl bis stearamide and oleamide which are mixed in any proportion.
The ultraviolet aging resistant PBAT material is a mixture of one or more than two of talcum powder, calcium carbonate, titanium dioxide, barium sulfate, solid glass beads, kaolin and montmorillonite mixed in any proportion.
A preparation method of a PBAT material with ultraviolet aging resistance comprises the following steps:
the method comprises the following steps: adding terephthalic acid, adipic acid and 1, 4-butanediol into a PBAT polymerization device, and polymerizing under the action of a catalyst to obtain a PBAT melt;
step two: continuously conveying the PBAT melt prepared in the step two to a second area of the double-screw extruder through a PBAT melt conveying pipeline and a melt metering pump under the action of a melt booster pump;
step three: continuously inputting the ultraviolet absorbent, the antioxidant and the lubricant into a third area in the double-screw extruder 1 through a weightlessness scale, continuously inputting the inorganic filler into a fifth area in the double-screw extruder through the weightlessness scale, uniformly mixing the inorganic filler with the unmodified PBAT melt, cooling and granulating to obtain the ultraviolet aging resistant PBAT material prepared by the melt online modification process.
In the above PBAT material with ultraviolet aging resistance, the catalyst in the second step is one or more of antimony catalyst and titanium catalyst, such as: antimony trioxide, antimony acetate, n-butyl titanate (TBOT), tetraisopropyl titanate and the like, wherein the addition amount of the catalyst is 0.1-0.5%.
The invention has the advantages that: the PBAT modified material prepared by the invention has excellent ultraviolet aging resistance, the tensile strength can be kept above 85% after the PBAT modified material is irradiated by ultraviolet for 96 hours, the elongation at break is kept above 75%, and the PBAT modified material has good weather resistance. In addition, the online modification technology of the PBAT melt improves the defects of thermal oxygen degradation and performance reduction caused by melting modification of PBAT granules. Meanwhile, the modifier is directly added into the melt obtained after PBAT polymerization, so that the problem that the modifier and PBAT granules cannot be uniformly mixed and are not uniformly distributed in the melt in the conventional modification process can be solved.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed to be used in the description of the embodiments or the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 is a flow chart of the preparation of the present invention;
FIG. 2 is a drawing of a tensile test run of the product of the present invention;
FIG. 3 is a tensile test report for example 2 of the present invention;
figure 4 is a tensile test report for comparative example 1 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Step 1: 54.2kg of terephthalic acid, 39kg of adipic acid and 106.8kg of 1, 4-butanediol are weighed and added into a PBAT polymerization device, and the PBAT melt is obtained by polymerization under the action of a specific catalyst.
Step 2: continuously conveying the PBAT melt to a second area of a double-screw extruder 1 through a PBAT melt conveying pipeline 2 and a melt metering pump 4 under the action of a melt booster pump 3, wherein the addition amount of the PBAT melt is 100 kg;
and step 3: continuously inputting 0.2kg of ultraviolet absorbent UV-326, 0.1kg of antioxidant and 0.2kg of calcium stearate into a third zone of a double-screw extruder 1 through a weight loss scale 5, uniformly mixing with unmodified PBAT melt, cooling and granulating to obtain the ultraviolet aging resistant PBAT material prepared by the melt online modification process.
Example 2
Step 1: 54.2kg of terephthalic acid, 39kg of adipic acid and 106.8kg of 1, 4-butanediol are weighed and added into a PBAT polymerization device, and the PBAT melt is obtained by polymerization under the action of a specific catalyst.
Step 2: continuously conveying the PBAT melt to a second area of a double-screw extruder 1 through a PBAT melt conveying pipeline 2 and a melt metering pump 4 under the action of a melt booster pump 3, wherein the addition amount of the PBAT melt is 100 kg; and step 3: continuously inputting 0.4kg of ultraviolet absorbent UV-329, 0.1kg of antioxidant and 0.2kg of vinyl bis stearamide into a third zone of a double-screw extruder 1 through a weightlessness scale 5, uniformly mixing with unmodified PBAT melt, cooling and granulating to obtain the ultraviolet aging resistant PBAT material prepared by the melt online modification process.
Example 3
Step 1: 54.2kg of terephthalic acid, 39kg of adipic acid and 106.8kg of 1, 4-butanediol are weighed and added into a PBAT polymerization device, and the PBAT melt is obtained by polymerization under the action of a specific catalyst.
Step 2: continuously conveying the PBAT melt to a second area of a double-screw extruder 1 through a PBAT melt conveying pipeline 2 and a melt metering pump 4 under the action of a melt booster pump 3, wherein the addition amount of the PBAT melt is 100 kg;
and step 3: continuously inputting 0.2kg of ultraviolet absorbent UV-329, 0.4kg of ultraviolet absorbent UV-326, 0.1kg of antioxidant and 0.2kg of vinyl bis stearamide into a third zone of a double-screw extruder 1 through a weightlessness scale 5, uniformly mixing with an unmodified PBAT melt, cooling and granulating to obtain the ultraviolet aging resistant PBAT material prepared by the melt online modification process.
Comparative example 1
Step 1: 54.2kg of terephthalic acid, 39kg of adipic acid and 106.8kg of 1, 4-butanediol are weighed and added into a PBAT polymerization device, and the PBAT melt is obtained by polymerization under the action of a specific catalyst.
Step 2: continuously conveying the PBAT melt to a second area of a double-screw extruder 1 through a PBAT melt conveying pipeline 2 and a melt metering pump 4 under the action of a melt booster pump 3, wherein the addition amount of the PBAT melt is 100 kg;
and step 3: continuously inputting 0.1kg of antioxidant and 0.1kg of vinyl bis stearamide into a third zone of a double-screw extruder 1 through a weightlessness scale 5, uniformly mixing with unmodified PBAT melt, cooling and granulating to obtain the ultraviolet aging resistant PBAT material prepared by the melt online modification process.
Comparative example 2
Step 1: 100kg of PBAT resin particles are uniformly mixed with 0.2kg of ultraviolet absorbent UV-329, 0.4kg of ultraviolet absorbent UV-326, 0.1kg of antioxidant and 0.1kg of vinyl bis stearamide, and then the mixture is added into an extruder for melting and blending, and cooled and cut into particles to obtain the ultraviolet aging resistant PBAT material obtained by common modification.
The modified PBAT materials prepared in examples 1-3 and comparative examples 1-2 were used to prepare standard sample bars using an injection molding machine, and then irradiated with UV light having an illumination intensity of 0.51W/m2 and a wavelength of 340nm at 50 ℃ for 96 hours, and tested for tensile properties according to ISO 527-1,2 standard, with the test results shown in Table I.
Watch 1
As can be seen from the data in Table I, the tensile strength and elongation at break of the UV aging resistant PBAT materials prepared by the melt online modification technology in examples 1-3 can be maintained above 85% and above 75% after the UV lamp irradiation for 96 h. Wherein the tensile strength and the elongation at break retention in example 3 are both above 90%, and show good ultraviolet aging resistance compared with comparative examples 1 and 2.
This is mainly because: 1. the melt online modification technology avoids the problem that the performance of the PBAT material is deteriorated due to thermo-oxidative degradation in the secondary melting processing modification process. In addition, the ultraviolet absorbent and other additives are directly mixed with the PBAT melt for modification, so that the mixing uniformity is higher, the more uniform the additives are dispersed in the PBAT melt, and the ultraviolet aging resistance of the PBAT material is further enhanced. 2. Under the action of ultraviolet rays, C ═ O ester bonds in the PBAT are broken to generate alkyl free radicals, so that the PBAT molecular chains are further broken, and the mechanical properties of the product are reduced. After the ultraviolet absorbent is added, the ultraviolet absorbent such as UV-326 can absorb light energy to generate corresponding nitroxide free radicals, and the radicals can capture alkyl radicals generated in the light degradation process of PBAT, so that the alkyl radicals are quenched, and the fracture of PBAT molecular chains is further prevented, so that the PBAT material after ultraviolet-resistant modification has a higher mechanical property retention rate.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (8)
1. A PBAT material resistant to uv aging characterized by: the composition comprises the following substances in parts by weight:
100 parts of PBAT melt, 0.2-1.2 parts of ultraviolet absorbent, 0.1-0.4 part of antioxidant, 0.1-0.4 part of lubricant and 0-20 parts of inorganic filler, and is prepared by melt on-line modification technology.
2. The uv aging resistant PBAT material of claim 1, wherein: the PBAT melt is polymerized by the following substances in molar ratio:
the molar ratio of terephthalic acid to adipic acid is 6:4-2:8, and the ratio of the sum of the molar amounts of terephthalic acid and adipic acid to 1, 4-butanediol is 1:1-1: 2.
3. The uv aging resistant PBAT material of claim 1, wherein: the ultraviolet absorbent is a mixture of one or more than two of benzophenones, salicylates, benzotriazoles, hydroxybenzotriazines and the like which are mixed in any proportion.
4. The uv aging resistant PBAT material of claim 1, wherein: the antioxidant is a mixture of one or more than two of amine antioxidant, phenol antioxidant, phosphite antioxidant and thioester antioxidant which are mixed in any proportion.
5. The uv aging resistant PBAT material of claim 1, wherein: the lubricant is a mixture of one or more than two of white oil, stearic acid, mesonic acid amide, vinyl bis-stearamide and oleic acid amide mixed in any proportion.
6. The uv aging resistant PBAT material of claim 1, wherein: the inorganic filler is one or a mixture of more than two of talcum powder, calcium carbonate, titanium dioxide, barium sulfate, solid glass microspheres, kaolin and montmorillonite which are mixed in any proportion.
7. A preparation method of a PBAT material with ultraviolet aging resistance is characterized in that: the method comprises the following steps:
the method comprises the following steps: adding terephthalic acid, adipic acid and 1, 4-butanediol into a PBAT polymerization device, and polymerizing under the action of a catalyst to obtain a PBAT melt;
step two: continuously conveying the PBAT melt prepared in the step two to a second area of the double-screw extruder through a PBAT melt conveying pipeline and a melt metering pump under the action of a melt booster pump;
step three: continuously inputting the ultraviolet absorbent, the antioxidant and the lubricant into a third area in the double-screw extruder through a weightlessness scale, continuously inputting the inorganic filler into a fifth area in the double-screw extruder through the weightlessness scale, uniformly mixing the inorganic filler with the unmodified PBAT melt, cooling and granulating to obtain the ultraviolet aging resistant PBAT material prepared by the melt online modification process.
8. The uv aging resistant PBAT material of claim 1, wherein: the catalyst in the second step is one or more of antimony catalyst and titanium catalyst, such as: antimony trioxide, antimony acetate, n-butyl titanate (TBOT), tetraisopropyl titanate and the like, wherein the addition amount of the catalyst is 0.1-0.5%.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114133738A (en) * | 2021-12-18 | 2022-03-04 | 裴珂 | Ultraviolet aging resistant high polymer material and preparation method thereof |
| CN114806106A (en) * | 2022-04-29 | 2022-07-29 | 山东道恩高分子材料股份有限公司 | PBAT-based biodegradable mulch film special material |
| CN116285245A (en) * | 2023-02-28 | 2023-06-23 | 山东道恩高分子材料股份有限公司 | Ultraviolet aging-resistant and hydrolysis-resistant PBAT material and preparation method thereof |
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| US20150337129A1 (en) * | 2012-12-19 | 2015-11-26 | The Nippon Synthetic Chemical Industry Co., Ltd. | Resin composition and molded article of thereof |
| CN110003626A (en) * | 2019-04-28 | 2019-07-12 | 兰州鑫银环橡塑制品有限公司 | A kind of resistance to intensive ultraviolet whole life cycle design PP Pipe Compound and preparation method thereof |
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2021
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US20150337129A1 (en) * | 2012-12-19 | 2015-11-26 | The Nippon Synthetic Chemical Industry Co., Ltd. | Resin composition and molded article of thereof |
| CN105038083A (en) * | 2015-07-02 | 2015-11-11 | 吉林省弗迪奈仕生物环保科技有限公司 | Method for preparing PLA/PBAT/PPC composite modified material through reactive extrusion |
| CN105086383A (en) * | 2015-08-04 | 2015-11-25 | 上海弘睿化工产品有限公司 | PBAT composite film based on irradiation modification and preparation method thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114133738A (en) * | 2021-12-18 | 2022-03-04 | 裴珂 | Ultraviolet aging resistant high polymer material and preparation method thereof |
| CN114806106A (en) * | 2022-04-29 | 2022-07-29 | 山东道恩高分子材料股份有限公司 | PBAT-based biodegradable mulch film special material |
| CN116285245A (en) * | 2023-02-28 | 2023-06-23 | 山东道恩高分子材料股份有限公司 | Ultraviolet aging-resistant and hydrolysis-resistant PBAT material and preparation method thereof |
| CN116285245B (en) * | 2023-02-28 | 2024-04-16 | 山东道恩高分子材料股份有限公司 | Ultraviolet aging-resistant and hydrolysis-resistant PBAT material and preparation method thereof |
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