CN113754992A - Biodegradable plastic film and preparation method thereof - Google Patents
Biodegradable plastic film and preparation method thereof Download PDFInfo
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- CN113754992A CN113754992A CN202111146572.7A CN202111146572A CN113754992A CN 113754992 A CN113754992 A CN 113754992A CN 202111146572 A CN202111146572 A CN 202111146572A CN 113754992 A CN113754992 A CN 113754992A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2403/00—Characterised by the use of starch, amylose or amylopectin or of their derivatives or degradation products
- C08J2403/02—Starch; Degradation products thereof, e.g. dextrin
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2467/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
-
- 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
- C08K5/10—Esters; Ether-esters
- C08K5/101—Esters; Ether-esters of monocarboxylic acids
- C08K5/103—Esters; Ether-esters of monocarboxylic acids with polyalcohols
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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
- C08K5/14—Peroxides
Abstract
The invention is suitable for the field of full-biodegradable plastics, and provides a biodegradable plastic film and a preparation method thereof, wherein the biodegradable plastic film comprises the following components: 150-300 parts of modified starch, 50-300 parts of polylactic acid, 500-800 parts of polybutylene adipate terephthalate, 10-40 parts of compatilizer, 2-5 parts of antioxidant, 5-20 parts of lubricant, 10-40 parts of monoglyceride fatty acid ester and 1-4 parts of dicumyl peroxide; the method adopts DCP chemical crosslinking, not only improves the mechanical property of the film material, but also has simple operation and saves cost.
Description
Technical Field
The invention relates to the technical field of thermoplastic biodegradable plastics, in particular to a biodegradable plastic film and a preparation method thereof.
Background
Petroleum-based plastics have been widely used in various fields in recent years, and waste generated from the permeation of high molecular materials such as polyethylene, polypropylene, polyamide and the like in daily life also poses a serious environmental problem. In particular to plastic products such as a large amount of waste mulching films and the like in agricultural production, which seriously damage the soil structure, harm the growth of crops and influence the balance of a soil micro-ecosystem. With the improvement of environmental protection consciousness of people, biodegradable high polymer materials attract wide attention of people. Biodegradable plastics refer to a class of plastics that are degraded by the action of microorganisms such as bacteria, fungi, and algae that exist in nature. The thermoplastic biodegradable plastic described by us refers to plastic which can be completely degraded in a certain time under specific conditions, but the biodegradable plastic is extracted from organisms, so the mechanical use performance of the material per se can not meet our requirements, and therefore, the blending modification of the bio-based high polymer materials is needed.
Taking polylactic acid as an example, the material has good thermal stability, compatibility, solvent resistance and transparency, is easy to blend with other polymers, and can realize complete degradation. However, polylactic acid has relatively high brittleness, and has a large defect in the processing and use process, and polybutylene adipate terephthalate (PBAT) can be used for blending modification.
At present, most of the biodegradable plastics on the market are extrusion blended and then thermoplastic starch is added, and industrial production is realized. Biodegradable plastics of the PBAT/PLA/St (thermoplastic starch) class are popular but still leave much room for improvement, firstly the problem of cross-linking blending of PBAT and PLA and secondly the problem of filling improvement of thermoplastic corn starch.
Disclosure of Invention
The invention aims to provide a biodegradable plastic film and a preparation method thereof, aims to solve the problem of full compatibility of PBAT and PLA in the prior art, and improves the service performance of a blending material by adding a crosslinking agent dicumyl peroxide and a compatilizer PLA-g-MAH.
According to the embodiment of the invention, the biodegradable plastic film comprises the following components in parts by weight: 150-300 parts of modified starch, 50-300 parts of polylactic acid, 500-800 parts of polybutylene adipate terephthalate, 10-40 parts of compatilizer, 2-5 parts of antioxidant, 5-20 parts of lubricant, 10-40 parts of monoglyceride and 1-4 parts of dicumyl peroxide.
The invention also provides a preparation method of the biodegradable plastic film, which mainly comprises the following steps:
(1) adding polylactic acid, polybutylene adipate terephthalate, a compatilizer, a lubricant and dicumyl peroxide into a parallel double-screw extruder, and carrying out melt blending extrusion granulation to prepare a chemical crosslinking modified PBAT/PLA master batch, wherein the temperatures of all zones of the extruder are 170 ℃, 172 ℃, 175 ℃, 172 ℃, 171 ℃, and the head temperature is 170 ℃;
(2) pre-blending corn starch and a starch plasticizer, standing for a period of time, adding into a double-screw extruder, extruding and granulating, wherein the temperatures of all zones of the extruder are 147 ℃, 150 ℃, 152 ℃, 150 ℃ and 150 ℃, and the temperature of a machine head is 149 ℃, so as to prepare modified plasticized starch;
(3) stirring and mixing the irradiation crosslinking modified PBAT/PLA blending master batch prepared in the step (1) and the modified plasticized starch prepared in the step (2) with an antioxidant, a lubricant and a monoglyceride fatty acid ester uniformly through a high-speed mixer, wherein the heating temperature is 90 ℃, the rotating speed is 500rpm, and the mixing time is 10min;
(4) adding the mixed master batch prepared in the step (3) into a parallel double-screw extruder, and performing melt blending, extrusion and granulation, wherein the temperatures of all zones of the extruder are respectively 170 ℃, 172 ℃, 175 ℃, 172 ℃, 171 ℃ and the temperature of a machine head is 170 ℃, so as to prepare the biodegradable plastic film blowing material;
(5) and (3) blowing the film blowing material prepared in the step (4) by using a common high-pressure PE film blowing machine to obtain the biodegradable plastic film, wherein the film blowing temperature is controlled to be about 168 ℃.
Compared with the existing biodegradable plastic film, the invention has the innovation points that: 1. by adding the cross-linking agent dicumyl peroxide, the mechanical property of the biodegradable plastic can be improved, and the application and the production become easier.
2. The modified biodegradable plastic has excellent performance, and can be filled with a large amount of thermoplastic starch, so that the effects of reducing cost and generating economic benefit are achieved.
Detailed Description
Example 1
A biodegradable plastic film comprises the following components in parts by weight: 220 parts of modified starch, 60 parts of polylactic acid, 600 parts of polybutylene adipate terephthalate, 20 parts of compatilizer, 4 parts of antioxidant, 6 parts of lubricant, 20 parts of monoglyceride and 2 parts of dicumyl peroxide.
The invention also provides a preparation method of the biodegradable plastic film, which mainly comprises the following steps:
(1) adding 60g of polylactic acid, 600g of polybutylene adipate terephthalate, 20g of compatilizer, 6g of lubricant and 2g of dicumyl peroxide into a parallel double-screw extruder, and carrying out melt blending extrusion granulation to prepare a chemically cross-linked modified PBAT/PLA master batch, wherein the temperatures of all zones of the extruder are 170 ℃, 172 ℃, 175 ℃, 172 ℃, 171 ℃, and the temperature of a machine head is 170 ℃;
(2) pre-blending corn starch and a starch plasticizer, standing for a period of time, adding into a double-screw extruder, extruding and granulating, wherein the temperatures of all zones of the extruder are 147 ℃, 150 ℃, 152 ℃, 150 ℃ and 150 ℃, and the temperature of a machine head is 149 ℃, so as to prepare modified plasticized starch;
(3) uniformly stirring and mixing the irradiation crosslinking modified PBAT/PLA blending master batch prepared in the step (1) and 200g of modified plasticized starch prepared in the step (2) with an antioxidant, a lubricant and monoglyceride by a high-speed mixer, heating to 90 ℃, rotating at 500rpm, and mixing for 10min;
(4) adding the mixed master batch prepared in the step (3) into a parallel double-screw extruder, and performing melt blending, extrusion and granulation, wherein the temperatures of all zones of the extruder are respectively 170 ℃, 172 ℃, 175 ℃, 172 ℃, 171 ℃ and the temperature of a machine head is 170 ℃, so as to prepare the biodegradable plastic film blowing material;
(5) and (3) blowing the film blowing material prepared in the step (4) by using a common high-pressure PE film blowing machine to obtain the biodegradable plastic film, wherein the film blowing temperature is controlled to be about 168 ℃.
Example 2
A biodegradable plastic film comprises the following components in parts by weight: 300 parts of modified starch, 100 parts of polylactic acid, 600 parts of polybutylene adipate terephthalate, 20 parts of compatilizer, 4 parts of antioxidant, 6 parts of lubricant, 20 parts of monoglyceride and 2 parts of dicumyl peroxide.
The invention also provides a preparation method of the biodegradable plastic film, which mainly comprises the following steps:
(1) adding 100g of polylactic acid, 600g of polybutylene adipate terephthalate, 20g of compatilizer, 6g of lubricant and 2g of dicumyl peroxide into a parallel double-screw extruder, and carrying out melt blending extrusion granulation to prepare a chemically cross-linked modified PBAT/PLA master batch, wherein the temperatures of all zones of the extruder are 170 ℃, 172 ℃, 175 ℃, 172 ℃, 171 ℃, and the temperature of a machine head is 170 ℃;
(2) pre-blending corn starch and a starch plasticizer, standing for a period of time, adding into a double-screw extruder, extruding and granulating, wherein the temperatures of all zones of the extruder are 147 ℃, 150 ℃, 152 ℃, 150 ℃ and 150 ℃, and the temperature of a machine head is 149 ℃, so as to prepare modified plasticized starch;
(3) uniformly stirring and mixing the irradiation crosslinking modified PBAT/PLA blending master batch prepared in the step (1) and 300g of modified plasticized starch, antioxidant, lubricant and monoglyceride prepared in the step (2) by a high-speed mixer, heating to 90 ℃, rotating at 500rpm, and mixing for 10min;
(4) adding the mixed master batch prepared in the step (3) into a parallel double-screw extruder, and performing melt blending, extrusion and granulation, wherein the temperatures of all zones of the extruder are respectively 170 ℃, 172 ℃, 175 ℃, 172 ℃, 171 ℃ and the temperature of a machine head is 170 ℃, so as to prepare the biodegradable plastic film blowing material;
(5) and (3) blowing the film blowing material prepared in the step (4) by using a common high-pressure PE film blowing machine to obtain the biodegradable plastic film, wherein the film blowing temperature is controlled to be about 168 ℃.
Example 3
A biodegradable plastic film comprises the following components in parts by weight: 350 parts of modified starch, 300 parts of polylactic acid, 600 parts of polybutylene adipate terephthalate, 20 parts of compatilizer, 4 parts of antioxidant, 6 parts of lubricant, 20 parts of monoglyceride and 2 parts of dicumyl peroxide.
The invention also provides a preparation method of the biodegradable plastic film, which mainly comprises the following steps:
(1) adding 300g of polylactic acid, 600g of polybutylene adipate terephthalate, 20g of compatilizer, 6g of lubricant and 2g of dicumyl peroxide into a parallel double-screw extruder, and carrying out melt blending extrusion granulation to prepare a chemically cross-linked modified PBAT/PLA master batch, wherein the temperatures of all zones of the extruder are 170 ℃, 172 ℃, 175 ℃, 172 ℃, 171 ℃, and the temperature of a machine head is 170 ℃;
(2) pre-blending corn starch and a starch plasticizer, standing for a period of time, adding into a double-screw extruder, extruding and granulating, wherein the temperatures of all zones of the extruder are 147 ℃, 150 ℃, 152 ℃, 150 ℃ and 150 ℃, and the temperature of a machine head is 149 ℃, so as to prepare modified plasticized starch;
(3) uniformly stirring and mixing the irradiation crosslinking modified PBAT/PLA blending master batch prepared in the step (1) and 350g of modified plasticized starch prepared in the step (2) with an antioxidant, a lubricant and monoglyceride by a high-speed mixer, heating to 90 ℃, rotating at 500rpm, and mixing for 10min;
(4) adding the mixed master batch prepared in the step (3) into a parallel double-screw extruder, and performing melt blending, extrusion and granulation, wherein the temperatures of all zones of the extruder are respectively 170 ℃, 172 ℃, 175 ℃, 172 ℃, 171 ℃ and the temperature of a machine head is 170 ℃, so as to prepare the biodegradable plastic film blowing material;
(5) and (3) blowing the film blowing material prepared in the step (4) by using a common high-pressure PE film blowing machine to obtain the biodegradable plastic film, wherein the film blowing temperature is controlled to be about 168 ℃.
Claims (4)
1. A biodegradable plastic film and a preparation method thereof are characterized by comprising the following components in parts by weight: 150-300 parts of modified starch, 50-300 parts of polylactic acid, 500-800 parts of polybutylene adipate terephthalate, 10-40 parts of compatilizer, 2-5 parts of antioxidant, 5-20 parts of lubricant, 10-40 parts of monoglyceride fatty acid ester and 1-4 parts of dicumyl peroxide;
the method comprises the following steps: (1) adding polylactic acid, polybutylene adipate terephthalate, a compatilizer, a lubricant and dicumyl peroxide into a parallel double-screw extruder, and performing melt blending extrusion granulation to prepare PBAT/PLA modified by chemical crosslinking;
(2) pre-blending corn starch and a starch plasticizer, standing for a period of time, adding the mixture into a double-screw extruder, and extruding and granulating to prepare modified plasticized starch;
(3) stirring and uniformly mixing the irradiation crosslinking modified PBAT/PLA blending master batch prepared in the step (1) and the modified plasticized starch prepared in the step (2) with an antioxidant, a lubricant and a monoglyceride through a high-speed mixer;
(4) adding the mixed master batch prepared in the step (3) into a parallel double-screw extruder, and performing melt blending, extrusion and granulation to prepare the biodegradable plastic film blowing material;
(5) blowing the film blowing material prepared in the step (4) by using a common high-pressure PE film blowing machine to obtain a biodegradable plastic film;
the temperatures of the 1-7 areas of the double-screw extruder in the step (1) are respectively 170 ℃, 172 ℃, 175 ℃, 172 ℃ and 171 ℃, and the temperature of a machine head is 170 ℃;
the temperatures of the zones 1-7 of the double-screw extruder in the step (2) are 147 ℃, 150 ℃, 152 ℃, 150 ℃ and 150 ℃ respectively, and the temperature of a machine head is 149 ℃;
the heating temperature of the high-speed mixer in the step (3) is 90 ℃, the rotating speed is 500rpm, and the mixing time is 10min;
the temperatures of the 1-7 areas of the double-screw extruder in the step (4) are respectively 170 ℃, 172 ℃, 175 ℃, 172 ℃ and 171 ℃, and the temperature of a machine head is 170 ℃;
the melting fusing temperature of the common high-pressure PE film blowing machine in the step (5) is 167 ℃, 168 ℃ and 169 ℃, the temperature of the machine head is 171 ℃, and the temperature of the film blowing nozzle is 172 ℃.
2. The biodegradable plastic film and the process for producing the same according to claim 1, wherein: the compatilizer in the step (1) is maleic anhydride grafted polylactic acid.
3. The biodegradable plastic film and the process for producing the same according to claim 1, wherein: the starch plasticizer in the step (2) is any one or more of glycerol, sorbitol, polyvinyl alcohol and acetyl tributyl citrate.
4. The biodegradable plastic film and the process for producing the same according to claim 1, wherein: the antioxidant in the step (3) is an antioxidant 1010 and an antioxidant 168; the lubricant is silicone master batch.
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| CN202111146572.7A CN113754992A (en) | 2021-09-28 | 2021-09-28 | Biodegradable plastic film and preparation method thereof |
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Cited By (9)
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| CN114106526A (en) * | 2021-12-17 | 2022-03-01 | 惠州俊儿塑料科技有限公司 | Production process of degradable plastic bag |
| CN114393901A (en) * | 2021-12-14 | 2022-04-26 | 山东哈工生物科技有限公司 | Degradable fruit and vegetable preservative film and preparation method thereof |
| CN114479375A (en) * | 2022-01-20 | 2022-05-13 | 盘锦海兴科技股份有限公司 | Degradable polymer, degradable film and preparation method thereof |
| CN114507423A (en) * | 2022-03-09 | 2022-05-17 | 万华化学（宁波）有限公司 | Starch-based biodegradable PBAT modified material and preparation method thereof |
| CN114591582A (en) * | 2022-03-18 | 2022-06-07 | 深圳市明星盛包装集团有限公司 | Photo-biodegradable plastic film and preparation method thereof |
| CN114605710A (en) * | 2022-04-11 | 2022-06-10 | 江苏多上新材料科技有限公司 | Ultraviolet light cross-linked completely biodegradable plastic bag material and preparation method thereof |
| CN114806111A (en) * | 2022-06-15 | 2022-07-29 | 祝建东 | Degradable mulching film capable of maintaining water and increasing fertilizer for long time, preparation method and degradation method |
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| CN115948035A (en) * | 2023-03-15 | 2023-04-11 | 河北立亚包装科技有限公司 | Biodegradable particles, preparation method and application |
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- 2021-09-28 CN CN202111146572.7A patent/CN113754992A/en active Pending
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| CN114393901A (en) * | 2021-12-14 | 2022-04-26 | 山东哈工生物科技有限公司 | Degradable fruit and vegetable preservative film and preparation method thereof |
| CN114106526A (en) * | 2021-12-17 | 2022-03-01 | 惠州俊儿塑料科技有限公司 | Production process of degradable plastic bag |
| CN114479375B (en) * | 2022-01-20 | 2023-09-12 | 盘锦海兴科技股份有限公司 | Degradable polymer, degradable film and preparation method thereof |
| CN114479375A (en) * | 2022-01-20 | 2022-05-13 | 盘锦海兴科技股份有限公司 | Degradable polymer, degradable film and preparation method thereof |
| CN114507423A (en) * | 2022-03-09 | 2022-05-17 | 万华化学（宁波）有限公司 | Starch-based biodegradable PBAT modified material and preparation method thereof |
| CN114507423B (en) * | 2022-03-09 | 2023-10-17 | 万华化学（宁波）有限公司 | Starch-based biodegradable PBAT modified material and preparation method thereof |
| CN114591582A (en) * | 2022-03-18 | 2022-06-07 | 深圳市明星盛包装集团有限公司 | Photo-biodegradable plastic film and preparation method thereof |
| CN114605710A (en) * | 2022-04-11 | 2022-06-10 | 江苏多上新材料科技有限公司 | Ultraviolet light cross-linked completely biodegradable plastic bag material and preparation method thereof |
| CN114806111A (en) * | 2022-06-15 | 2022-07-29 | 祝建东 | Degradable mulching film capable of maintaining water and increasing fertilizer for long time, preparation method and degradation method |
| CN114806111B (en) * | 2022-06-15 | 2023-11-24 | 广东崇熙环保科技有限公司 | Degradable mulching film capable of keeping water and increasing fertilizer for long time, preparation method and degradation method |
| CN115785532A (en) * | 2022-12-23 | 2023-03-14 | 福建冠中科技有限公司 | Biodegradable composite material packaging film and preparation method thereof |
| CN115948035B (en) * | 2023-03-15 | 2023-06-30 | 河北立亚包装科技有限公司 | Biodegradable particles, preparation method and application |
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