CN111363206A - Full-degradable bio-based material for film and preparation method thereof - Google Patents
Full-degradable bio-based material for film and preparation method thereof Download PDFInfo
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- CN111363206A CN111363206A CN202010315162.XA CN202010315162A CN111363206A CN 111363206 A CN111363206 A CN 111363206A CN 202010315162 A CN202010315162 A CN 202010315162A CN 111363206 A CN111363206 A CN 111363206A
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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
- C08J2303/00—Characterised by the use of starch, amylose or amylopectin or of their derivatives or degradation products
- C08J2303/04—Starch derivatives
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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
- C08J2403/04—Starch derivatives
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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
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/04—Homopolymers or copolymers of ethene
- C08J2423/06—Polyethene
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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
- C08J2467/02—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
- 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
- C08K5/54—Silicon-containing compounds
- C08K5/544—Silicon-containing compounds containing nitrogen
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- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
A full-degradable bio-based material for films and a preparation method thereof, aiming at overcoming the defects that the common agricultural films in the prior art can not be completely degraded and are easy to pollute the environment, provides a full-degradable bio-based material for films, which comprises the following raw materials in parts by weight: PBAT 40-50%, starch 40-55%, PCL2-6%, and coupling agent 0.5-2%0.5-1% of dispersing agent, 1-4% of plasticizer and 0.5-1% of nucleating agent. The obtained material is a biodegradable material with controllable induction period, and the agricultural film prepared from the material can be degraded into CO with a degradation rate of more than 90% in 8 months2And H2O, does not pollute the environment, and is suitable for crops; the cost of the material obtained by the invention is lower than 1.55 ten thousand yuan/ton, the price is low, and the material is suitable for agriculture.
Description
Technical Field
The invention relates to the field of degradable materials, in particular to a fully-degradable bio-based material for a film and a preparation method thereof.
Background
In the aspect of agricultural production, the film is used for heat preservation and moisture preservation, the demand is large, but the film is used as a plastic, particularly under the situation of preventing and treating white pollution, the post-treatment aspect of the agricultural film is particularly important, and at present, the best method is to use a fully-degradable bio-based material to prepare the fully-degradable film. The degradation time of the bio-based material with the controllable induction period is adjustable and controllable, and the bio-based material is completely degraded into carbon dioxide and water in the controllable induction period, can be decomposed by soil, sunlight and microorganisms, and is finally absorbed by soil and plants, so that the air is not polluted, and the burden on the environment is not caused.
Disclosure of Invention
The invention overcomes the defects that the common agricultural film can not be completely degraded and is easy to pollute the environment, and provides a completely degradable bio-based material for the film and a preparation method thereof.
The invention adopts the technical scheme that the purpose of the invention is realized by: a full-degradable bio-based material for a film is prepared from the following raw materials in percentage by mass: 40-50% of PBAT, 40-55% of starch, 2-6% of PCL, 0.5-2% of coupling agent, 0.5-1% of dispersing agent, 1-4% of plasticizer and 0.5-1% of nucleating agent.
Further, the PBAT is standard TH-801T of Xinjiang blue Shantun river chemical industry.
Further, the starch is modified corn starch.
Further, the coupling agent is a coupling agent KH 550.
Further, the dispersing agent is polyethylene wax powder A-C-6A produced by United states Honeywell.
Further, the plasticizer is glycerol.
Further, the nucleating agent is produced by DuPont in the United states and is HPD3001 in model number.
A preparation method of a fully degradable bio-based material for a film comprises the following steps: step one, uniformly blending starch, a coupling agent and a plasticizer according to a formula ratio to obtain a standby material A; step two, mixing the PBAT, the PCL, the dispersing agent and the nucleating agent according to the formula proportion and uniformly stirring to obtain a standby material B; and step three, uniformly blending the spare material A and the spare material B obtained in the step one and the step two according to a formula ratio, and then putting the mixture into a double-screw machine for modification and granulation to obtain a finished product.
Further, the temperature control arrangement sequence in the twin-screw machine for modified granulation in the third step is as follows: 135 deg.C, 140 deg.C, 145 deg.C, 150 deg.C, 160 deg.C, 165 deg.C, 160 deg.C, 165 deg.C, and 170 deg.C.
The invention has the beneficial effects that: the main raw materials PBAT and starch of the invention are good biodegradable materials and can be degraded into CO2And H2O, no burden is caused to the environment; the material obtained by the invention is a biodegradable material with controllable induction period, the agricultural film prepared by the material can reach a degradation rate of more than 90% in 8 months, is suitable for crops, and can ensure that the agricultural film is not degraded in the growth period of the crops and is rapidly degraded after the growth period is finished; the material obtained by the invention has the advantages of high tensile strength, high elongation at break and the like, the cost is lower than 1.55 ten thousand yuan/ton, the price is low, and the material is suitable for agriculture.
The invention is further described below by means of specific embodiments.
Detailed Description
A full-degradable bio-based material for a film is prepared from the following raw materials in percentage by mass: 40-50% of PBAT, 40-55% of starch, 2-6% of PCL, 0.5-2% of coupling agent, 0.5-1% of dispersing agent, 1-4% of plasticizer and 0.5-1% of nucleating agent.
PBAT and poly (butylene adipate terephthalate) belong to thermoplastic biodegradable plastics and have excellent biodegradability. PBAT is a copolymer of butanediol adipate and butanediol terephthalate, has the characteristics of PBA and PBT, and has better ductility and elongation at break as well as better heat resistance and impact property. The PBAT preferred in the embodiment is standard TH-801T of Xinjiang blue Shantun river chemical industry.
The preferred starch for this embodiment is modified corn starch, modified corn starch. The modified corn starch is degradable and can not cause pollution to the environment. PCL, polycaprolactone and PCL with good biocompatibility, good organic polymer compatibility and good biological compatibilityDegradability, can be used as a cell growth supporting material, can be compatible with various conventional plastics, and can be completely degraded into CO in natural environment within 6-12 months2And H2O。
The preferred plasticizer in this embodiment is glycerol. Glycerol, namely glycerin, is used as a micromolecular plasticizer and is easy to form hydrogen bonds with starch, so that the hydrogen bonds among starch molecules are replaced, the high crystallinity of the starch is destroyed, and the starch has thermoplasticity. The preferred coupling agent of this example is coupling agent KH 550; the dispersing agent is polyethylene wax powder A-C-6A produced by United states Honeywell; the nucleating agent is the product of Dupont in USA with model number of HPD 3001.
The following are specific examples of the present invention.
Example 1
Step one, weighing 48% of starch, 0.5% of coupling agent and 2.5% of plasticizer in weight ratio, and uniformly blending to obtain a spare material A; weighing PBAT accounting for 45 percent of the total weight, PCL accounting for 3 percent of the total weight, diffusant accounting for 0.5 percent of the total weight and nucleating agent accounting for 0.5 percent of the total weight, and mixing and stirring uniformly to obtain a standby material B; and step three, uniformly blending the spare material A and the spare material B obtained in the step one and the step two according to a formula ratio, and then putting the mixture into a double-screw machine for modification and granulation to obtain a finished product.
Example 2
Step one, weighing 53% of starch, 0.5% of coupling agent and 2.5% of plasticizer in weight ratio, and uniformly blending to obtain a spare material A; weighing 40% of PBAT, 3% of PCL, 0.5% of diffusant and 0.5% of nucleating agent in parts by weight, mixing and uniformly stirring to obtain a standby material B; and step three, uniformly blending the spare material A and the spare material B obtained in the step one and the step two according to a formula ratio, and then putting the mixture into a double-screw machine for modification and granulation to obtain a finished product.
Example 3
Step one, weighing 43% of starch, 0.5% of coupling agent and 2.5% of plasticizer in weight ratio, and uniformly blending to obtain a spare material A; weighing 50% of PBAT, 3% of PCL, 0.5% of diffusant and 0.5% of nucleating agent in parts by weight, mixing and uniformly stirring to obtain a standby material B; and step three, uniformly blending the spare material A and the spare material B obtained in the step one and the step two according to a formula ratio, and then putting the mixture into a double-screw machine for modification and granulation to obtain a finished product.
In the above examples, the twin-screw extruder used for modification granulation was a 65-type twin-screw extruder having an aspect ratio L/D =48/1, and the first purpose of the relatively large length-diameter ratio of the screws was to ensure uniform plasticization and the second purpose was to generate heat and evaporate water for as much time as possible. The screw combination adopts 11 groups of shear block combination structures; the temperature control arrangement sequence in the double-screw machine is as follows: 135 deg.C, 140 deg.C, 145 deg.C, 150 deg.C, 160 deg.C, 165 deg.C, 160 deg.C, 165 deg.C, and 170 deg.C. The twin screw machine is provided with double vacuum exhaust facilities, which is beneficial to reducing the percentage of water in the material.
The samples obtained in examples 1 to 3 were subjected to the test and the cost calculation to obtain the following data.
| Cost/yuan/ton | Tensile Strength/M Pa | Elongation at break/% | 8 month compost degradation/%) | |
| Example 1 | 14480 | 5.6 | 284 | 92 |
| Example 2 | 13660 | 5.1 | 276 | 96 |
| Example 3 | 15276 | 5.7 | 293 | 90 |
Analyzing the above table, it can be seen that: the cost of the obtained bio-based material is not more than 1.55 ten thousand yuan/ton, and the bio-based material has the advantages of high tensile strength, high elongation at break and the like, and can be degraded by more than 90% in 8 months.
Claims (9)
1. The fully-degradable bio-based material for the film is characterized by being prepared from the following raw materials in percentage by mass: 40-50% of PBAT, 40-55% of starch, 2-6% of PCL, 0.5-2% of coupling agent, 0.5-1% of dispersing agent, 1-4% of plasticizer and 0.5-1% of nucleating agent.
2. The fully degradable bio-based material for film of claim 1, wherein the PBAT is a standard type TH-801T of tun river chemical industry in blue mountains of xinjiang.
3. The fully degradable biobased material for film of claim 1 wherein said starch is modified corn starch.
4. The fully degradable biobased material for films of claim 1 wherein said coupling agent is KH 550.
5. The fully degradable biobased material for films of claim 1 wherein said dispersing agent is polyethylene wax powder A-C-6A from Honeywell USA.
6. A fully degradable biobased material for films according to claim 1 wherein said plasticizer is glycerol.
7. The fully degradable biobased material for films of claim 1 wherein said nucleating agent is manufactured by dupont, model number HPD 3001.
8. A method for the preparation of a fully degradable bio-based material for films according to any of claims 1 to 7, characterized in that it comprises the following steps:
step one, uniformly blending starch, a coupling agent and a plasticizer according to a formula ratio to obtain a standby material A;
step two, mixing the PBAT, the PCL, the dispersing agent and the nucleating agent according to the formula proportion and uniformly stirring to obtain a standby material B;
and step three, uniformly blending the spare material A and the spare material B obtained in the step one and the step two according to a formula ratio, and then putting the mixture into a double-screw machine for modification and granulation to obtain a finished product.
9. The method for preparing fully degradable bio-based material for film as claimed in claim 8, wherein the sequence of temperature control in the twin screw machine for modified granulation in step three is: 135 deg.C, 140 deg.C, 145 deg.C, 150 deg.C, 160 deg.C, 165 deg.C, 160 deg.C, 165 deg.C, and 170 deg.C.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202010315162.XA CN111363206A (en) | 2020-04-21 | 2020-04-21 | Full-degradable bio-based material for film and preparation method thereof |
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| CN202010315162.XA CN111363206A (en) | 2020-04-21 | 2020-04-21 | Full-degradable bio-based material for film and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111825996A (en) * | 2020-07-14 | 2020-10-27 | 厦门朗纳科材料技术有限公司 | Formula of bio-based degradable material and preparation method and application thereof |
| CN114752084A (en) * | 2022-04-25 | 2022-07-15 | 东莞市冠亿新材料科技有限公司 | Production process of degradable master batch for blown film and degradable master batch |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103205021A (en) * | 2012-01-11 | 2013-07-17 | 上海杰事杰新材料(集团)股份有限公司 | Thermoplastic and PBAT blend and preparation method thereof |
| CN108559232A (en) * | 2017-12-11 | 2018-09-21 | 杭州鑫富科技有限公司 | A kind of starch plastics film and preparation method thereof that tearing-resistant performance is excellent |
| CN108948681A (en) * | 2017-05-18 | 2018-12-07 | 济宁明升新材料有限公司 | A kind of full biology base PBAT biodegradable plastic of starch conversion and preparation method thereof |
| CN110483841A (en) * | 2019-08-06 | 2019-11-22 | 寿光金远东变性淀粉有限公司 | A kind of starch base alloy material and preparation method thereof |
-
2020
- 2020-04-21 CN CN202010315162.XA patent/CN111363206A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103205021A (en) * | 2012-01-11 | 2013-07-17 | 上海杰事杰新材料(集团)股份有限公司 | Thermoplastic and PBAT blend and preparation method thereof |
| CN108948681A (en) * | 2017-05-18 | 2018-12-07 | 济宁明升新材料有限公司 | A kind of full biology base PBAT biodegradable plastic of starch conversion and preparation method thereof |
| CN108559232A (en) * | 2017-12-11 | 2018-09-21 | 杭州鑫富科技有限公司 | A kind of starch plastics film and preparation method thereof that tearing-resistant performance is excellent |
| CN110483841A (en) * | 2019-08-06 | 2019-11-22 | 寿光金远东变性淀粉有限公司 | A kind of starch base alloy material and preparation method thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111825996A (en) * | 2020-07-14 | 2020-10-27 | 厦门朗纳科材料技术有限公司 | Formula of bio-based degradable material and preparation method and application thereof |
| CN114752084A (en) * | 2022-04-25 | 2022-07-15 | 东莞市冠亿新材料科技有限公司 | Production process of degradable master batch for blown film and degradable master batch |
| CN114752084B (en) * | 2022-04-25 | 2024-02-23 | 东莞市冠亿新材料科技有限公司 | Production process of degradable master batch for blown film and degradable master batch |
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