CN114031914A - Bio-based plastic uptake material and preparation method thereof - Google Patents
Bio-based plastic uptake material and preparation method thereof Download PDFInfo
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- CN114031914A CN114031914A CN202111648417.5A CN202111648417A CN114031914A CN 114031914 A CN114031914 A CN 114031914A CN 202111648417 A CN202111648417 A CN 202111648417A CN 114031914 A CN114031914 A CN 114031914A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/06—Biodegradable
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Abstract
The invention discloses a bio-based plastic uptake material and a preparation method thereof, belonging to the technical field of degradable materials. The bio-based plastic uptake material comprises the following raw materials in parts by weight: 45-80 parts of starch, 5-9 parts of starch grafting agent, 150 parts of biodegradable polyester, 12-15 parts of plasticizer, 6-10 parts of chain extender and 8-12 parts of catalyst; the biodegradable polyester can be polylactic acid, PBAT or PBST, and the chain extender is composed of a phosphate chain extender and an epoxy chain extender; the preparation method of the bio-based plastic uptake material comprises the following steps: and (3) putting the raw materials in parts by weight into a mixing machine, uniformly mixing, putting into a double-screw extruder, and performing melt extrusion granulation to obtain the bio-based blister material. The invention has the advantages of low production cost, environmental protection and green, and the prepared degradable plastic has good mechanical property.
Description
Technical Field
The invention belongs to the technical field of degradable materials, and particularly relates to a bio-based plastic uptake material and a preparation method thereof.
Background
The establishment of a plastic meal box recycling system faces a huge challenge, how to realize the sustainable development of the industry and reduce the pollution of packages to the environment are the problems concerned by numerous scholars at present. More and more places have been put forward on "plastic forbidden" and "plastic limited" schedules for related products in the packaging field. The biobased materials are gradually becoming a new leading industry leading the scientific and technological innovation and the economic development of the modern world due to the characteristics of green, environment-friendly, resource saving and the like; the bio-based plastics are a large variety of bio-based materials, and can be divided into two categories according to the degradation performance, namely biodegradable bio-based plastics and non-biodegradable bio-based plastics. The biodegradable bio-based plastics comprise polylactic acid and the like, and the non-biodegradable bio-based plastics comprise polyethylene and a plurality of varieties. At present, from the technical research and industrialization progress of China, biodegradable plastics are mainly used. The bio-based material is plastic taking starch, soybean, cellulose, lignin, vegetable oil and other renewable resources as raw materials, and the emphasis is on the biogenesis and the renewability of the production raw materials. Such plastics include both degradable or compostable plastics and non-degradable plastics; both thermoplastic and thermosetting resins.
With the improvement of the economic living standard of people and the continuous improvement of related national regulations, the biodegradable polyester plays more and more important roles in the fields of fibers (non-woven fabrics), "disposable" packaging, household garbage bags, agricultural films, disposable medical devices, high-value-added human-affinity medical materials and the like, and the development of biodegradable polyester technology and industrialization is promoted just because of the continuous expansion of the application fields. Most of the biodegradable plastics on the market have some defects, such as adding plasticizers and inorganic fillers for improving the mechanical properties of the plastics, but the cost of the plastics is greatly increased. Therefore, the research on the bio-based blister material is very important.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a bio-based plastic uptake material and a preparation method thereof.
The purpose of the invention is realized by the following technical scheme: a bio-based plastic uptake material comprises the following raw materials in parts by weight: 45-80 parts of starch, 5-9 parts of starch grafting agent, 150 parts of biodegradable polyester, 12-15 parts of plasticizer, 6-10 parts of chain extender and 8-12 parts of catalyst; the biodegradable polyester can be polylactic acid, PBAT or PBST, and the chain extender is prepared from a phosphate chain extender and an epoxy chain extender in a weight ratio of 2: 1, wherein the PBAT is produced by Henan RayChett Co., Ltd, and has a model of RQT-CH; the PBS is produced by China petrochemical company Limited and has the model number of TS 159; the phosphate chain extender is produced by Germany winning and creating company, and has the model of EVONIK VESTAMIN A95, and the epoxy chain extender is produced by Yino chemical technology Co., Ltd, Guangzhou city, and has the model of 6902.
Further, the bio-based plastic uptake material comprises the following raw materials in parts by weight: 52-70 parts of starch, 7-9 parts of a starch grafting agent, 134 parts of biodegradable polyester, 14-15 parts of a plasticizer, 7-9 parts of a chain extender and 10-12 parts of a catalyst, wherein the starch grafting agent is produced by Guangdong Hongxin biotechnology limited and is of the type YL 03M.
Further, the bio-based plastic uptake material also comprises 12-15 parts of natural degradable high polymer material.
Further, the natural degradable high polymer material is one or more of lignin, straw, chitosan and plant fiber.
Further, the bio-based plastic uptake material also comprises 4-8 parts of polyvinyl acetate.
Further, the plasticizer is one or more of tri-n-butyl citrate, epoxidized vegetable oil and isosorbide ester.
Further, the epoxidized vegetable oil is one or more of epoxidized soybean oil and rice bran oil.
Further, the catalyst is prepared from hydroxyethyl isobromobutyrate and iron powder according to the weight ratio of 3: 2, mixing the components.
A method for preparing the bio-based blister material comprises the following steps: and (2) putting the raw materials in parts by weight into a mixer, uniformly mixing, putting into a double-screw extruder, and performing melt extrusion granulation to obtain the bio-based blister material.
The invention has the beneficial effects that:
(1) according to the invention, a large amount of starch is added into the raw materials, the compatibility and stability of the starch in the plastic are improved through the starch grafting agent, and the relatively low price of the starch also reduces the production cost of the degradable material; the invention adopts the chain extender consisting of the phosphate chain extender and the epoxy chain extender, the phosphate chain extender has obvious increment effect on aliphatic and aliphatic-aromatic copolyester, and can improve the crystallization property; in contrast, the chain extender with polyepoxy groups in the epoxy group is relatively safe and low in cost.
(2) According to the invention, polylactic acid, PBAT or PBST is blended with lignin, straws, chitosan and plant fibers, so that the elastic modulus of the plastic can be effectively enhanced, the mechanical property of the plastic is improved, and meanwhile, the lignin, the straws, the chitosan and the plant fibers are natural degradable high polymer materials, so that the cost is low, and the natural degradable high polymer materials can be naturally degraded; in addition, the biodegradable polyester and the polyvinyl acetate are blended, so that the crystallization rate can be reduced, and the thermal stability of the plastic can be improved.
(3) According to the invention, tri-n-butyl citrate, epoxy vegetable oil and isosorbide ester are added as plasticizers, and the citrate plasticizers can effectively reduce the glass transition temperature of polylactic acid, improve the processing performance, reduce brittle fracture and improve the toughness of the product; the epoxy vegetable oil (epoxidized soybean oil and epoxy rice bran oil) is a biodegradable environment-friendly additive, can replace a biotoxic o-benzene plasticizer, and improves the processing performance of the material; the isosorbide ester has obvious plasticizing and modifying effects on the polylactic acid, and can also improve the crystallization performance of the polylactic acid.
Detailed Description
The technical solution of the present invention is further described in detail with reference to the following specific examples, but the scope of the present invention is not limited to the following.
Example 1
A preparation method of a bio-based plastic uptake material comprises the following process steps:
putting 45 parts of starch, 5 parts of starch grafting agent, 120 parts of polylactic acid, 4 parts of phosphate chain extender, 2 parts of epoxy chain extender, 12 parts of lignin and 4 parts of polyvinyl acetate into a high-speed stirrer, stirring at a high speed of 1200r/min for 3 minutes, and then dripping 12 parts of tri-n-butyl citrate while stirring; continuously stirring at a high speed (1200 r/min) for 2 minutes after dripping is finished, finally adding 5 parts of hydroxyethyl iso-bromobutyrate and 3 parts of iron powder, and stirring at a low speed of 600r/min for 5 minutes to obtain a primary mixed material; adding the primary mixed material into a double-screw extruder for melt blending, extruding and granulating to obtain a bio-based plastic uptake material product; wherein the length-diameter ratio of the double-screw extruder is 28.5, the rotating speed of the double-screw extruder is 90rpm, and the temperature of each section of the double-screw extruder is set as follows: the first heating zone is 150 ℃, the second heating zone is 160 ℃, the third heating zone is 165 ℃, the fourth heating zone is 175 ℃, the fifth heating zone is 185 ℃, the sixth heating zone is 175 ℃, the seventh heating zone is 175 ℃ and the head temperature is 170 ℃.
Example 2
A preparation method of a bio-based plastic uptake material comprises the following process steps:
putting 65 parts of starch, 7 parts of starch grafting agent, 135 parts of PBAT, 5 parts of phosphate chain extender, 3 parts of epoxy chain extender, 13 parts of straw and 6 parts of polyvinyl acetate into a high-speed stirrer, stirring at a high speed of 1200r/min for 3 minutes, and then dripping 13 parts of epoxidized soybean oil while stirring; continuously stirring at a high speed (1200 r/min) for 2 minutes after dripping is finished, finally adding 6 parts of hydroxyethyl iso-bromobutyrate and 4 parts of iron powder, and stirring at a low speed of 600r/min for 5 minutes to obtain a primary mixed material; adding the primary mixed material into a double-screw extruder for melt blending, extruding and granulating to obtain a bio-based plastic uptake material; wherein the length-diameter ratio of the double-screw extruder is 28.5, the rotating speed of the double-screw extruder is 90rpm, and the temperature of each section of the double-screw extruder is set as follows: the first heating zone is 150 ℃, the second heating zone is 160 ℃, the third heating zone is 165 ℃, the fourth heating zone is 175 ℃, the fifth heating zone is 185 ℃, the sixth heating zone is 175 ℃, the seventh heating zone is 175 ℃ and the head temperature is 170 ℃.
Example 3
A preparation method of a bio-based plastic uptake material comprises the following process steps:
placing 80 parts of starch, 9 parts of starch grafting agent, 150 parts of polylactic acid, 7 parts of phosphate chain extender, 3 parts of epoxy chain extender, 7 parts of chitosan, 8 parts of plant fiber and 8 parts of polyvinyl acetate in a high-speed stirring machine, stirring at a high speed of 1200r/min for 3 minutes, and then dropping 15 parts of isosorbide nitrate while stirring; continuously stirring at a high speed (1200 r/min) for 2 minutes after dripping is finished, finally adding 7 parts of hydroxyethyl iso-bromobutyrate and 5 parts of iron powder, and stirring at a low speed of 600r/min for 5 minutes to obtain a primary mixed material; adding the primary mixed material into a double-screw extruder for melt blending, extruding and granulating to obtain a bio-based plastic uptake material; wherein the length-diameter ratio of the double-screw extruder is 28.5, the rotating speed of the double-screw extruder is 90rpm, and the temperature of each section of the double-screw extruder is set as follows: the first heating zone is 150 ℃, the second heating zone is 160 ℃, the third heating zone is 165 ℃, the fourth heating zone is 175 ℃, the fifth heating zone is 185 ℃, the sixth heating zone is 175 ℃, the seventh heating zone is 175 ℃ and the head temperature is 170 ℃.
The bio-based plastics-absorbing material prepared in the above example is made into plastic film samples to be tested for tensile strength, elongation at break and biodegradability, which are shown in the following table 1:
TABLE 1
| Example 1 | Example 2 | Example 3 | |
| Elongation at break,% | 460 | 472 | 467 |
| Tensile strength, MPa | 34 | 35 | 33 |
| Biodegradability% | 90 | 94 | 95 |
The test method of the tensile strength and the elongation at break comprises the following steps: GB/T1040.1-2018 determination of tensile property of plastics, the specific test method of elongation at break is as follows: after the prestress is set, installing a calibrated extensometer on the gauge length of a sample and adjusting, and recording the stretching length when the sample is damaged, wherein the ratio of the length to the length of the sample before stretching is the elongation at break; the tensile strength test method comprises the following steps: during the stretching process by an extensometer, the maximum observed initial stress is the tensile strength, and the value can also be the stress of the sample at the time of yielding or breaking;
the biodegradability test method comprises the following steps: biodegradability GB/T19277.1 (ISO 14855-1) determination of the ultimate aerobic biological decomposition and disintegration capacity of a material under controlled composting conditions.
The foregoing is illustrative of the preferred embodiments of this invention, and it is to be understood that the invention is not limited to the precise form disclosed herein and that various other combinations, modifications, and environments may be resorted to, falling within the scope of the concept as disclosed herein, either as described above or as apparent to those skilled in the relevant art. And that modifications and variations may be effected by those skilled in the art without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (9)
1. The bio-based plastic uptake material is characterized by comprising the following raw materials in parts by weight: 45-80 parts of starch, 5-9 parts of starch grafting agent, 150 parts of biodegradable polyester, 12-15 parts of plasticizer, 6-10 parts of chain extender and 8-12 parts of catalyst; the biodegradable polyester is polylactic acid, PBAT or PBST, and the chain extender is prepared from a phosphate chain extender and an epoxy chain extender in a weight ratio of 2: 1.
2. The bio-based blister material according to claim 1, comprising the following raw materials in parts by weight: 52-70 parts of starch, 7-9 parts of starch grafting agent, 134 parts of biodegradable polyester, 14-15 parts of plasticizer, 7-9 parts of chain extender and 10-12 parts of catalyst.
3. The bio-based blister material according to claim 1 or 2, further comprising 12 to 15 parts of natural degradable polymer material.
4. The bio-based blister material of claim 3, wherein the natural degradable polymer material is one or more of lignin, straw, chitosan and plant fiber.
5. The bio-based blister material according to claim 1 or 2, further comprising 4 to 8 parts of polyvinyl acetate.
6. The bio-based blister material of claim 1, wherein the plasticizer is one or more of tri-n-butyl citrate, epoxidized vegetable oil, and isosorbide esters.
7. The bio-based blister material according to claim 6, wherein the epoxidized vegetable oil is at least one of epoxidized soybean oil and rice bran oil.
8. The bio-based blister material according to claim 1, wherein the catalyst is prepared from hydroxyethyl iso-bromobutyrate and iron powder in a weight ratio of 3: 2, mixing the components.
9. A method of making the bio-based blister material of claim 1, comprising the steps of: and putting the raw materials in a mixing machine according to the parts by weight, uniformly mixing, and then carrying out melt extrusion granulation by a double-screw extruder to obtain the bio-based blister material.
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Cited By (2)
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| CN114524977A (en) * | 2022-03-30 | 2022-05-24 | 扬州锦晨生物科技有限公司 | Bio-based high-molecular temperature-resistant material and preparation method thereof |
| CN114989575A (en) * | 2022-05-24 | 2022-09-02 | 张明晨 | Degradable high-strength plastic packaging bag and preparation method thereof |
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| CN101343406A (en) * | 2008-08-18 | 2009-01-14 | 丹阳市华东工程塑料有限公司 | Heat-proof polylactic acid-starch alloy system full-biodegradation material and preparation thereof |
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| CN114989575A (en) * | 2022-05-24 | 2022-09-02 | 张明晨 | Degradable high-strength plastic packaging bag and preparation method thereof |
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