CN113736222A - Starch-based PBAT/PLA complete biodegradable material composition and particles and film prepared from same - Google Patents
Starch-based PBAT/PLA complete biodegradable material composition and particles and film prepared from same Download PDFInfo
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- CN113736222A CN113736222A CN202110728645.7A CN202110728645A CN113736222A CN 113736222 A CN113736222 A CN 113736222A CN 202110728645 A CN202110728645 A CN 202110728645A CN 113736222 A CN113736222 A CN 113736222A
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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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- 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
- C08J2429/00—Characterised by the use 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; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
- C08J2429/02—Homopolymers or copolymers of unsaturated alcohols
- C08J2429/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
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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
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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
- C08K5/05—Alcohols; Metal alcoholates
- C08K5/053—Polyhydroxylic alcohols
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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
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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
- C08K5/092—Polycarboxylic acids
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Abstract
The invention relates to the field of completely biodegradable materials, and discloses a starch-based PBAT/PLA completely biodegradable material composition and particles and films prepared from the composition, wherein the composition comprises the following components in parts by weight: 30-60 parts of PBAT, 3-10 parts of PLA, 3-8 parts of PVA, 10-30 parts of starch, 2-8 parts of plasticizer, 0.1-1 part of lubricant and 0.1-1 part of compatilizer. The starch-based PBAT/PLA completely biodegradable film provided by the invention has smooth surface and mechanical property, and can realize continuous production.
Description
Technical Field
The invention relates to the field of completely biodegradable materials, in particular to a starch-based PBAT/PLA completely biodegradable material composition and particles and a film prepared from the same.
Background
Currently, as industry develops, large quantities of petroleum-based synthetic polymers are introduced into ecosystems, large quantities of disposable plastic products are discarded into the natural environment, and the plastic waste deposited in landfills each year occupies more land and even threatens the sea, which causes many environmental problems. Thus, bio-based materials and degradable plastics have become the focus of social attention.
Currently, the biodegradable materials which are produced in large scale and widely used are polylactic acid (PLA) and polybutylene adipate terephthalate (PBAT). The PLA and the PBAT have good complementarity, and particularly have obvious reflection on the mechanical property. PLA has good transparency, biocompatibility, and biodegradability, but its industrial application is limited due to its short sheet with poor heat resistance, poor impact strength, and the like. PBAT has the advantages of good processability, biodegradability and the like, so PBAT is commonly used for toughening and modifying other biological polyesters.
Therefore, it is desirable to provide a PBAT/PLA degradable plastic film with an excellent combination of properties.
Disclosure of Invention
The invention aims to overcome the problems of poor surface smoothness and mechanical property of a film in the prior art, and provides a starch-based PBAT/PLA completely biodegradable material composition, and particles and a film prepared from the composition. The starch-based PBAT/PLA completely biodegradable film provided by the invention has smooth surface and mechanical property, and can realize continuous production.
In order to achieve the above objects, in a first aspect, the present invention provides a starch-based PBAT/PLA complete biodegradable material composition, comprising: 30-60 parts of PBAT, 3-10 parts of PLA, 3-8 parts of PVA, 10-30 parts of starch, 2-8 parts of plasticizer, 0.1-1 part of lubricant and 0.1-1 part of compatilizer.
In a second aspect, the invention provides a method for preparing PBAT/PLA starch-based fully biodegradable material particles, which comprises the following steps: the PBAT/PLA starch-based complete biodegradable material composition is mixed and stirred and then extruded and granulated by a parallel double-screw granulator set.
In a third aspect, the invention provides a starch-based PBAT/PLA complete biodegradable film prepared by blow molding of the starch-based PBAT/PLA complete biodegradable material particles prepared by the method.
Compared with the prior art, the invention has the following beneficial effects:
(1) the starch-based PBAT/PLA fully biodegradable material provided by the invention can be completely degraded;
(2) the starch-based PBAT/PLA fully biodegradable material provided by the invention can be continuously granulated and blow molded, so that the production efficiency is further improved;
(3) the film prepared by blowing the starch-based PBAT/PLA fully biodegradable material provided by the invention has smooth surface and excellent mechanical property.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The present invention will be described in detail below by way of examples. In the following examples, each material used was commercially available unless otherwise specified, and the method used was a conventional method in the art unless otherwise specified.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
In a first aspect, the present invention provides a starch-based PBAT/PLA complete biodegradable material composition, comprising: 30-60 parts of PBAT, 3-10 parts of PLA, 3-8 parts of PVA, 10-30 parts of starch, 2-8 parts of plasticizer, 0.1-1 part of lubricant and 0.1-1 part of compatilizer.
In the present invention, preferably, the composition comprises: 50-60 parts of PBAT, 5-8 parts of PLA, 5-6 parts of PVA, 20-30 parts of starch, 3-6 parts of plasticizer, 0.5-0.8 part of lubricant and 0.5-0.8 part of compatilizer.
In the present invention, it is preferable to use PBAT having a melt flow rate of 2.99g/10min of raw material from the Higherkinson HighTech Co., Ltd in the embodiment of the present invention.
In the present invention, preferably, PLA having a melt flow rate of 10.52g/10min, which is manufactured by Nature Works, is used in the embodiment of the present invention.
In the present invention, the PVA is a partially alcoholysis type PVA, preferably, the PVA has an alcoholysis degree of 88% and a polymerization degree of 500-.
In the invention, the starch is one or more of corn starch, cassava starch, sweet potato starch, wheat starch, water chestnut starch and lotus root starch, and preferably, the corn starch is selected in the invention.
In the present invention, preferably, the plasticizer is one or more of ethylene glycol, glycerin, sorbitol, mannitol, neopentyl glycol, trimethylolpropane, tetramethylolpropane, diethylene glycol, polyethylene glycol 200, polyethylene glycol 400, diethanolamine, triethanolamine, diglycerin, triglycerol, pentaglycerol, decaglycerol, and diethylene glycol.
In the present invention, preferably, the lubricant is one or more of paraffin wax, polyethylene wax, oxidized polyethylene wax, hardened oil, triglycerol monostearate, pentaerythritol stearate, stearic acid, and calcium stearate.
In the invention, preferably, the compatilizer is one or more of aluminate coupling agent, titanate coupling agent, SEBS-g-GMA, SEBS-g-MAH, olefin-GMA, POE-g-GMA, St-AN-GMA, anhydrous citric acid, E-MA-GMA and E-BA-GMA.
In a second aspect, the invention provides a method for preparing PBAT/PLA starch-based fully biodegradable material particles, which comprises the following steps: mixing and stirring the PBAT/PLA starch-based complete biodegradable material composition, and then extruding and granulating by using a parallel double-screw granulator set.
In a third aspect, the invention provides a starch-based PBAT/PLA complete biodegradable film prepared by blow molding of the starch-based PBAT/PLA complete biodegradable material particles prepared by the method. In the specific embodiment of the invention, the raw material components are mixed and extruded and granulated by a parallel double-screw granulator set to prepare the particles of the starch-based PBAT/PLA complete biodegradable film capable of being blow molded, and finally, the particles are blown to form the film. Wherein, the mixing and stirring conditions comprise:
firstly, adding starch and plasticizer into a stirrer to stir for 5-8min at 300r/min of 200-.
In one embodiment of the invention, the preparation is carried out according to the following steps:
(1) stirring all the components in a high-speed mixer for 10-20 minutes;
(2) extruding and granulating by using a parallel double-screw granulator set to obtain particles of the starch-based PBAT/PLA complete biodegradable film capable of being subjected to blow molding; finally, preparing a film by blow molding;
wherein the temperature of each section of the double-screw granulator unit is 75-165 ℃, and the rotating speed of the screws is 300-400 rpm.
The present invention will be described in detail below with reference to examples, but the present invention is not limited to the following examples.
Example 1
A starch-based PBAT/PLA complete biodegradable material composition comprises the following raw materials in parts by weight:
56 parts of PBAT, 8 parts of PLA, 05884 parts of starch, 3 parts of glycerol, 0.5 part of stearic acid and 0.5 part of anhydrous citric acid.
Example 2
A starch-based PBAT/PLA complete biodegradable material composition comprises the following raw materials in parts by weight:
56 parts of PBAT, 8 parts of PLA, 05885 parts of starch, 3 parts of glycerol, 0.5 part of stearic acid and 0.5 part of anhydrous citric acid.
Example 3
A starch-based PBAT/PLA complete biodegradable material composition comprises the following raw materials in parts by weight:
56 parts of PBAT, 8 parts of PLA, 05886 parts of starch, 20 parts of glycerol, 3 parts of stearic acid and 0.5 part of anhydrous citric acid.
Example 4
A starch-based PBAT/PLA complete biodegradable material composition comprises the following raw materials in parts by weight:
56 parts of PBAT, 8 parts of PLA, 05886 parts of starch, 20 parts of glycerol, 4 parts of stearic acid and 0.5 part of anhydrous citric acid.
Example 5
A starch-based PBAT/PLA complete biodegradable material composition comprises the following raw materials in parts by weight:
56 parts of PBAT, 8 parts of PLA, 05886 parts of starch, 20 parts of glycerol, 4 parts of stearic acid and 0.5 part of anhydrous citric acid.
Example 6
A starch-based PBAT/PLA complete biodegradable material composition comprises the following raw materials in parts by weight:
56 parts of PBAT, 8 parts of PLA, 05886 parts of starch, 20 parts of glycerol, 0.5 part of stearic acid and 0.5 part of anhydrous citric acid.
Comparative example 1
A starch-based PBAT/PLA complete biodegradable material composition comprises the following raw materials in parts by weight:
56 parts of PBAT, 8 parts of PLA, 05886 parts of starch, 20 parts of glycerol, 3 parts of calcium stearate and 0.5 part of aluminate coupling agent.
Comparative example 2
A starch-based PBAT/PLA complete biodegradable material composition comprises the following raw materials in parts by weight:
56 parts of PBAT, 8 parts of PLA, 05886 parts of starch, 20 parts of triglycerol, 2 parts of pentaglycerol, 0.5 part of calcium stearate and 0.5 part of aluminate coupling agent.
The above examples 1 to 6 and comparative examples 1 to 3 were prepared as follows:
(1) pouring 20 parts by weight of starch, 4 parts by weight of 0588 and 3 parts by weight of glycerol into a high-speed mixer, stirring at low speed for 5-8min, stirring at high speed for 5-10min, and finally discharging for later use; (2) pouring 56 parts by weight of PBAT, 8 parts by weight of PLA, 0.5 part by weight of stearic acid and 0.5 part by weight of anhydrous citric acid into the plasticized starch for 10-20min, and finally discharging for later use; (3) pouring the (2) into a granulator for granulation, and discharging for later use; (4) the pellets were poured into a blow molding machine and blown into films, and examples 2 to 6 and comparative examples 1 to 2 were formed into films S1 to S6 and D1 to D2 in the same manner, and the films were subjected to the following property tests, the results of which are shown in Table 1.
Wherein, tensile strength, heat seal strength, pendulum impact resistance and puncture strength are as follows: and testing according to a corresponding national standard testing method.
And (3) testing tensile property: according to the test of GB/T1040.3-2006, the sample adopts type 2, the length is 150mm, the width is 15mm, and the test speed is 200 mm/min. Detecting data of the sample in the longitudinal direction and the transverse direction;
testing the heat seal strength: the test speed was 300 mm/min. + -. 50mm/min, as tested by QB/T2358-1998.
Pendulum impact resistance: testing according to GB/T8809-2015 standard;
puncture strength: testing according to GB/T10004-2008 standard;
tensile strength in MPa, elongation at break in%, heat seal strength in N/15mm, pendulum impact resistance in J, and puncture strength in N.
TABLE 1
As can be seen from table 1: the starch-based PBAT/PLA completely biodegradable film provided by the invention has excellent performances and is suitable for various packaging bags or sealing bags.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (11)
1. A starch-based PBAT/PLA completely biodegradable material composition, comprising: 30-60 parts of PBAT, 3-10 parts of PLA, 8-8 parts of PVA3, 10-30 parts of starch, 2-8 parts of plasticizer, 0.1-1 part of lubricant and 0.1-1 part of compatilizer.
2. The starch-based PBAT/PLA biodegradable material composition of claim 1, wherein the composition comprises: 50-60 parts of PBAT, 5-8 parts of PLA, 78-6 parts of PVA5, 20-30 parts of starch, 3-6 parts of plasticizer, 0.5-0.8 part of lubricant and 0.5-0.8 part of compatilizer.
3. The starch-based PBAT/PLA biodegradable material composition of claim 1 or 2, wherein the PBAT has a melt flow rate of 2.99g/10 min.
4. The starch-based PBAT/PLA biodegradable material composition of claim 1 or 2, wherein the PLA has a melt flow rate of 10.52g/10 min.
5. The starch-based PBAT/PLA fully biodegradable material composition as claimed in claim 1 or 2, wherein the PVA has an alcoholysis degree of 88% and a polymerization degree of 500-2400.
6. The starch-based PBAT/PLA fully biodegradable material composition of claim 1 or 2, wherein the starch is one or more of corn starch, tapioca starch, sweet potato starch, wheat starch, water chestnut starch and lotus root starch.
7. The starch-based PBAT/PLA biodegradable material composition of claim 1 or 2, wherein the plasticizer is one or more of ethylene glycol, glycerol, sorbitol, mannitol, neopentyl glycol, trimethylolpropane, tetrahydroxymethyl propane, diethylene glycol, polyethylene glycol 200, polyethylene glycol 400, glycerol, diethanolamine, triethanolamine, diglycerol, triglycerol, pentaglycerol, decaglycerol, and diethylene glycol.
8. The starch-based PBAT/PLA biodegradable material composition of claim 1 or 2, wherein the lubricant is one or more of paraffin wax, polyethylene wax, oxidized polyethylene wax, hardened oil, triglycerol monostearate, pentaerythritol stearate, stearic acid, and calcium stearate.
9. The PBAT/PLA starch-based fully biodegradable material composition of claim 1 or 2, wherein the compatibiliser is one or more of AN aluminate coupling agent, a titanate coupling agent, SEBS-g-GMA, SEBS-g-MAH, alkene-GMA, POE-g-GMA, St-AN-GMA, anhydrous citric acid, E-MA-GMA and E-BA-GMA.
10. A preparation method of PBAT/PLA starch-based complete biodegradable material particles is characterized by comprising the following steps: the PBAT/PLA starch-based complete biodegradable material composition of any of claims 1-9 is mixed, stirred and extruded and granulated by a parallel twin-screw granulator set.
11. The starch-based PBAT/PLA complete biodegradable material particles prepared by the method of claim 10 are blown to prepare a starch-based PBAT/PLA complete biodegradable film.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114133712A (en) * | 2021-12-14 | 2022-03-04 | 军毅科技(武汉)有限责任公司 | Fully biodegradable agricultural mulching film |
| CN114806050A (en) * | 2022-05-26 | 2022-07-29 | 无锡贝特塑料电器有限公司 | Polyvinyl alcohol water-soluble film and preparation method thereof |
| CN115386202A (en) * | 2022-08-24 | 2022-11-25 | 新疆蓝山屯河高端新材料工程技术研究中心有限公司 | Full-biodegradable material special for melt-blowing and preparation method thereof |
| WO2023093736A1 (en) * | 2021-11-25 | 2023-06-01 | 山东兰德英科新材料科技有限公司 | Degradable special material for infusion set tubing, and method for preparing infusion set tubing by using same |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112111133A (en) * | 2020-08-17 | 2020-12-22 | 江苏碧升生物新材料有限公司 | Preparation method of polybutylene terephthalate adipate/polylactic acid/starch ternary blending film blowing resin |
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2021
- 2021-06-29 CN CN202110728645.7A patent/CN113736222A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112111133A (en) * | 2020-08-17 | 2020-12-22 | 江苏碧升生物新材料有限公司 | Preparation method of polybutylene terephthalate adipate/polylactic acid/starch ternary blending film blowing resin |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023093736A1 (en) * | 2021-11-25 | 2023-06-01 | 山东兰德英科新材料科技有限公司 | Degradable special material for infusion set tubing, and method for preparing infusion set tubing by using same |
| CN114133712A (en) * | 2021-12-14 | 2022-03-04 | 军毅科技(武汉)有限责任公司 | Fully biodegradable agricultural mulching film |
| CN114806050A (en) * | 2022-05-26 | 2022-07-29 | 无锡贝特塑料电器有限公司 | Polyvinyl alcohol water-soluble film and preparation method thereof |
| CN115386202A (en) * | 2022-08-24 | 2022-11-25 | 新疆蓝山屯河高端新材料工程技术研究中心有限公司 | Full-biodegradable material special for melt-blowing and preparation method thereof |
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Application publication date: 20211203 |