CN103087484B - Biodegradable composite film material that degradation rate is controlled and preparation method thereof - Google Patents
Biodegradable composite film material that degradation rate is controlled and preparation method thereof Download PDFInfo
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- CN103087484B CN103087484B CN201310009025.3A CN201310009025A CN103087484B CN 103087484 B CN103087484 B CN 103087484B CN 201310009025 A CN201310009025 A CN 201310009025A CN 103087484 B CN103087484 B CN 103087484B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/07—Flat, e.g. panels
- B29C48/08—Flat, e.g. panels flexible, e.g. films
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/04—Particle-shaped
Abstract
The object of this invention is to provide a kind of good mechanical property, degraded more rapidly, thoroughly, can not to controlled Biodegradable composite film material of the degradation rate of environmental danger and preparation method thereof.Does it comprise polylactic acid PLA? 80.0 weight parts, 3-hydroxybutyrate-3-hydroxycaproic acid copolyesters PHBH? 20.0 weight parts, poly-succinic fourth two (alcohol) ester PBS? 20.0 weight parts, 4,4 '-thiobis-(the 6-tertiary butyl-3-methylphenol) 0.8 weight part, talcum powder 1.0 weight part, glycidyl methacrylate 5.0 weight part, stearic acid 2.0 weight part, amine hydroxybenzene 1.5 weight part.
Description
Technical field
The present invention relates to controlled Biodegradable composite film material of a kind of degradation rate and preparation method thereof.
Background technology
In recent years, researchist attempts to work out eco-friendly thin-film material on the basis of conventional plastic, such as, disclose a kind of by starch and polyethylene and the direct blended rear obtained thin-film material of auxiliary agent in CN1931905A, but the tensile strength of this film is on the low side, and starch is while raising plastics degradability, its physical and mechanical properties can be caused as declines such as tensile strengths on the one hand, make its processing difficulties, also there is wetting ability on the other hand too strong, and the consistency between most of resins for universal use is very poor, the mechanical property of material is caused to decline to a great extent.In addition, although plasticity-starch content can be higher in this material, because the matrixes such as PE itself do not have biological degradability.Although plastics prepared by these technology can be easier to because of the degraded of starch subside, undegradable polymer fragment still can cause environmental pollution.
Summary of the invention
For solving the problems of the technologies described above, the invention provides a kind of good mechanical property, degraded more rapidly, thoroughly, can not to the degraded of environmental danger rapidly, Biocomposite material and preparation method thereof thoroughly.Adopt the present invention to degrade rapidly, the film made of Biocomposite material thoroughly, there is good mechanical property, and controlled biological decomposition composite material film of degradation rate and preparation method thereof; The material adopting the present invention to prepare possesses good processing characteristics, higher tear strength, elongation at break and tensile strength, and can be controlled the degradation time of material by the adjustment of each component ratio.
The Biodegradable composite film material that degradation rate of the present invention is controlled, it comprises
Described matrix resin is mixed to get according to often kind of 20-80 weight ratio poly(lactic acid) (PLA) and 3-hydroxybutyrate-3-hydroxycaproic acid copolyesters (PHBH);
Described other biological decomposing copolymer is: at least one in poly-succinic fourth two (alcohol) ester (PBS), polypropylene carbonate (PPC), 3-hydroxybutyrate-3 hydroxypentanoic acid copolyesters (PHBV), terephthalic acid-butyleneglycol-hexanodioic acid copolyesters (PBAT);
Described thermo-stabilizer is: four (β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester, 2,2 '-methylene-bis (4-methyl-6-tert-butylphenol), 4, at least one in 4 '-thiobis-(the 6-tertiary butyl-3-methylphenol);
Described nucleator is: at least one in talcum powder, boron nitride, terephthalic acid, dibenzylidene sorbitol;
Described compatilizer is: at least one in polyoxyethylene poly-oxygen propylene aether segmented copolymer, benzoyl peroxide, ethene and glycidyl methacrylate copolymer;
Described softening agent is: at least one in glycerine, stearic acid, ethyl lactate, polyoxyethylene glycol, epoxy soybean oil, triethyl citrate, acetyl tributyl citrate;
Described opening agent is: at least one in amine hydroxybenzene, silicon-dioxide, erucicamide.
The Biodegradable composite film material that degradation rate of the present invention is controlled, wherein said matrix resin is mixed to get according to often kind of 30-60 weight ratio poly(lactic acid) (PLA) and 3-hydroxybutyrate-3-hydroxycaproic acid copolyesters (PHBH); Described other biological decomposing copolymer 5-30 weight part; Described thermo-stabilizer is 0.8-1.2 weight part; Described nucleator is 1-4 weight part; Described compatilizer is 2-4 weight part; Described softening agent is 5-10 weight part; Described opening agent is 1-4 weight part.
The Biodegradable composite film material that degradation rate of the present invention is controlled, wherein said matrix resin is mixed to get according to often kind of 40-50 weight ratio poly(lactic acid) (PLA) and 3-hydroxybutyrate-3-hydroxycaproic acid copolyesters (PHBH); Described other biological decomposing copolymer 10-20 weight part; Described thermo-stabilizer is 0.9-1.1 weight part; Described nucleator is 2-3 weight part; Described compatilizer is 2.5-3.5 weight part; Described softening agent is 6-8 weight part; Described opening agent is 2-3 weight part.
The preparation method of the Biodegradable composite film material that degradation rate of the present invention is controlled, comprises the steps:
A, prepare following raw material:
Matrix resin, other biological decomposing copolymer, thermo-stabilizer, nucleator, compatilizer, softening agent, opening agent;
Described matrix resin is mixed to get according to often kind of 20-80 weight ratio poly(lactic acid) (PLA) and 3-hydroxybutyrate-3-hydroxycaproic acid copolyesters (PHBH); Increase 3-hydroxybutyrate-3-hydroxycaproic acid copolyesters (PHBH) consumption, the degradation speed of the finished product can be improved, reduce the time needed for degraded; Reduce 3-hydroxybutyrate-3-hydroxycaproic acid copolyesters (PHBH) consumption, the degradation speed of the finished product can be reduced, increase the time needed for degraded;
Described other biological decomposing copolymer is: at least one in poly-succinic fourth two (alcohol) ester (PBS), polypropylene carbonate (PPC), 3-hydroxybutyrate-3-hydroxypentanoic acid copolyesters (PHBV), terephthalic acid-butyleneglycol-hexanodioic acid copolyesters (PBAT);
Described thermo-stabilizer is: four (β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester, 2,2 '-methylene-bis (4-methyl-6-tert-butylphenol) and 4, at least one in 4 '-thiobis-(the 6-tertiary butyl-3-methylphenol);
Described nucleator is: at least one in talcum powder, boron nitride, terephthalic acid, dibenzylidene sorbitol;
Described compatilizer is: at least one in polyoxyethylene poly-oxygen propylene aether segmented copolymer, benzoyl peroxide, ethene and glycidyl methacrylate copolymer;
Described softening agent is: at least one in glycerine, stearic acid, ethyl lactate, polyoxyethylene glycol, epoxy soybean oil, triethyl citrate, acetyl tributyl citrate;
Described opening agent is: at least one in amine hydroxybenzene, silicon-dioxide, erucicamide;
Be placed in drying oven by above-mentioned various raw material, dry, drying temperature is 40 DEG C-80 DEG C, and time of drying is 6-10 hour;
After B, fully drying, according to matrix resin, the other biological decomposing copolymer of 0-40 weight part, the thermo-stabilizer of 0.5-1.5 weight part, the nucleator of 0.3-5 weight part, the compatilizer of 1-5 weight part, the softening agent of 2-15 weight part, the ratio of 0.3-5 weight part opening agent of 100 weight parts, raw material is joined high-speed mixer, mix raw material in high-speed mixer, mixing time is 5-10 minute;
C, by mixed raw material extruding pelletization, make the Biodegradable composite film material that degradation rate of the present invention is controlled.
The preparation method of the Biodegradable composite film material that degradation rate of the present invention is controlled, wherein said matrix resin is mixed to get according to often kind of 30-60 weight ratio poly(lactic acid) (PLA) and 3-hydroxybutyrate-3-hydroxycaproic acid copolyesters (PHBH); Described other biological decomposing copolymer 5-30 weight part; Described thermo-stabilizer is 0.8-1.2 weight part; Described nucleator is 1-4 weight part; Described compatilizer is 2-4 weight part; Described softening agent is 5-10 weight part; Described opening agent is 1-4 weight part.
The preparation method of the Biodegradable composite film material that degradation rate of the present invention is controlled, wherein said matrix resin is mixed to get according to often kind of 40-50 weight ratio poly(lactic acid) (PLA) and 3-hydroxybutyrate-3-hydroxycaproic acid copolyesters (PHBH); Described other biological decomposing copolymer 10-20 weight part; Described thermo-stabilizer is 0.9-1.1 weight part; Described nucleator is 2-3 weight part; Described compatilizer is 2.5-3.5 weight part; Described softening agent is 6-8 weight part; Described opening agent is 2-3 weight part.
Compared with prior art, beneficial effect of the present invention is: Biodegradable composite film material that degradation rate of the present invention is controlled and preparation method thereof, adopt the distinctive composition and engineering step of the present invention, the Biodegradable composite film material that the degradation rate produced is controlled, not only good mechanical property, degrade also rapider, thoroughly, adopt the film prepared by this material, possesses good processing characteristics, higher tear strength, elongation at break and tensile strength, and it is rapider to degrade, thoroughly, it is after the time limit of service of setting, can under the microbial process in physical environment, within the very short time of (landfill) 3-6 month, just occur degradable, product is water, carbonic acid gas and organic matter, can not to environmental danger.Controlled degradable polymer thin film composite material prepared by the present invention, in MD and TD both direction, all has high tensile, high anti-tearing strength and controlled degradation property, can widespread use in wrapping material and agricultural plastic film field.Adopt the present invention to degrade rapidly, the film made of Biocomposite material thoroughly, there is good mechanical property, and the biological decomposition composite material film that degradation rate is controlled; Prepared material possesses good processing characteristics, higher tear strength, elongation at break and tensile strength, and can be controlled the degradation time of material by the adjustment of each component ratio.
Embodiment
Below the specific embodiment of the present invention is described in further detail.Following examples for illustration of the present invention, but are not used for limiting the scope of the invention.
The biological decomposition composite material film controlled to obtained degradation rate according to following methods carries out Mechanics Performance Testing:
Tensile property test is carried out according to GB/T1040.3-2006, uses dumbbell shape cutting knife to cut sample, die-cut from MD and TD both direction, specimen size: total length 120mm, narrow portion partial width 10mm, rate of extension 200mm/min, test number (TN) n >=5 time, result adopts mean value to represent.
Right-angle tearing test is carried out according to QB/T1130-1991, and cut into standard test specimen, die-cut from MD and TD both direction, wherein spacing jig is 60mm, draw speed 100mm/min, test number (TN) n >=5 time, and result adopts mean value to represent.
Embodiment 1: take each component by following formula and weight part
Preparation method and condition are set as:
(1) by matrix resin, properties-correcting agent, 40-80 DEG C of dry 6-10 hour, then weighs each component raw material by proportioning in an oven, and manually carries out premix, by pre-composition extruding pelletization on the twin screw extruder.The temperature of twin screw extruder is set as: a district, 110-145 DEG C; 2nd district, 120-160 DEG C; 3rd district, 145-185 DEG C; 4th district, 145-185 DEG C; 5th district, 145-185 DEG C; Head, 145-160 DEG C.
(2) by above-mentioned composition polymer pellet through Single screw extrusion Blown Film, the temperature of single screw extrusion machine is set as: a district, 110-130 DEG C; 2nd district, 130-150 DEG C; 3rd district, 140-170 DEG C; 4th district, 140-185 DEG C; 5th district, 140-185 DEG C; 6th district, 140-160 DEG C; Die temperature, 145-160 DEG C.Wherein screw speed 30-60rpm, pulling speed 2-5m/min, curling rate 3-6m/min.
Resulting product performance is as shown in table 1.
Table 1: film thickness 18 μm
Embodiment 2: take each component by following formula and weight part
Processing conditions and parameter are shown in embodiment 1;
Resulting product performance is in table 2.
Table 2: film thickness 19 μm
Embodiment 3: take each component by following formula and weight part
Processing conditions and parameter are shown in embodiment 1;
Resulting product performance is in table 3.
Table 3: film thickness 35 μm
Embodiment 4: take each component by following formula and weight part
Processing conditions and parameter are shown in embodiment 1.
Resulting product performance is in table 4.
Table 4: film thickness 25 μm
Embodiment 5: take each component by following formula and weight part
Processing conditions and parameter are shown in embodiment 1.
Resulting product performance is in table 5.
Table 5: film thickness 31 μm
Embodiment 6: take each component by following formula and weight part
Processing conditions and parameter are shown in embodiment 1.
Resulting product performance is in table 6.
Table 6: film thickness 29 μm
Embodiment 7: take each component by following formula and weight part
Processing conditions and parameter are shown in embodiment 1;
Resulting product performance is in table 2.
Table 7: film thickness 22 μm
Embodiment 8
The Biodegradable composite film material that degradation rate of the present invention is controlled, it comprises
Described matrix resin is mixed to get according to often kind 20 or 30 or 40 or 50 or 60 or 70 or 80 weight ratios poly(lactic acid) (PLA) and 3-hydroxybutyrate-3-hydroxycaproic acid copolyesters (PHBH);
Described other biological decomposing copolymer is: the one in poly-succinic fourth two (alcohol) ester (PBS), polypropylene carbonate (PPC), 3-hydroxybutyrate-3 hydroxypentanoic acid copolyesters (PHBV), terephthalic acid-butyleneglycol-hexanodioic acid copolyesters (PBAT) or two kinds or three kinds or four kinds;
Described thermo-stabilizer is: four (β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester, 2,2 '-methylene-bis (4-methyl-6-tert-butylphenol), 4, the one in 4 '-thiobis-(the 6-tertiary butyl-3-methylphenol) or two kinds or three kinds;
Described nucleator is: the one in talcum powder, boron nitride, terephthalic acid, dibenzylidene sorbitol or two kinds or three kinds or four kinds;
Described compatilizer is: the one in polyoxyethylene poly-oxygen propylene aether segmented copolymer, benzoyl peroxide, ethene and glycidyl methacrylate copolymer or two kinds;
Described softening agent is: the one in glycerine, stearic acid, ethyl lactate, polyoxyethylene glycol, epoxy soybean oil, triethyl citrate, acetyl tributyl citrate or two kinds or three kinds or four kinds or five kinds or six kinds or seven kinds;
Described opening agent is: the one in amine hydroxybenzene, silicon-dioxide, erucicamide or two kinds or three kinds.
As improvement of the present invention, above-mentioned matrix resin is mixed to get according to often kind of 30-60 weight ratio poly(lactic acid) (PLA) and 3-hydroxybutyrate-3-hydroxycaproic acid copolyesters (PHBH); Described other biological decomposing copolymer 5-30 weight part; Described thermo-stabilizer is 0.8-1.2 weight part; Described nucleator is 1-4 weight part; Described compatilizer is 2-4 weight part; Described softening agent is 5-10 weight part; Described opening agent is 1-4 weight part.
As a further improvement on the present invention, above-mentioned matrix resin is mixed to get according to often kind of 40-50 weight ratio poly(lactic acid) (PLA) and 3-hydroxybutyrate-3-hydroxycaproic acid copolyesters (PHBH); Described other biological decomposing copolymer 10-20 weight part; Described thermo-stabilizer is 0.9-1.1 weight part; Described nucleator is 2-3 weight part; Described compatilizer is 2.5-3.5 weight part; Described softening agent is 6-8 weight part; Described opening agent is 2-3 weight part.
The preparation method of the Biodegradable composite film material that degradation rate of the present invention is controlled, comprises the steps:
A, prepare following raw material:
Matrix resin, other biological decomposing copolymer, thermo-stabilizer, nucleator, compatilizer, softening agent, opening agent;
Described matrix resin is mixed to get according to often kind 20 or 30 or 40 or 50 or 60 or 70 or 80 weight ratios poly(lactic acid) (PLA) and 3-hydroxybutyrate-3-hydroxycaproic acid copolyesters (PHBH); Increase 3-hydroxybutyrate-3-hydroxycaproic acid copolyesters (PHBH) consumption, the degradation speed of the finished product can be improved, reduce the time needed for degraded; Reduce 3-hydroxybutyrate-3-hydroxycaproic acid copolyesters (PHBH) consumption, the degradation speed of the finished product can be reduced, increase the time needed for degraded;
Described other biological decomposing copolymer is: the one in poly-succinic fourth two (alcohol) ester (PBS), polypropylene carbonate (PPC), 3-hydroxybutyrate-3 hydroxypentanoic acid copolyesters (PHBV), terephthalic acid-butyleneglycol-hexanodioic acid copolyesters (PBAT) or two kinds or three kinds or four kinds;
Described thermo-stabilizer is: four (β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester, 2,2 '-methylene-bis (4-methyl-6-tert-butylphenol), 4, the one in 4 '-thiobis-(the 6-tertiary butyl-3-methylphenol) or two kinds or three kinds;
Described nucleator is: the one in talcum powder, boron nitride, terephthalic acid, dibenzylidene sorbitol or two kinds or three kinds or four kinds;
Described compatilizer is: the one in polyoxyethylene poly-oxygen propylene aether segmented copolymer, benzoyl peroxide, ethene and glycidyl methacrylate copolymer or two kinds;
Described softening agent is: the one in glycerine, stearic acid, ethyl lactate, polyoxyethylene glycol, epoxy soybean oil, triethyl citrate, acetyl tributyl citrate or two kinds or three kinds or four kinds or five kinds or six kinds or seven kinds;
Described opening agent is: the one in amine hydroxybenzene, silicon-dioxide, erucicamide or two kinds or three kinds;
Be placed in drying oven by above-mentioned various raw material, dry, drying temperature is 40 DEG C-80 DEG C, and time of drying is 6-10 hour;
After B, fully drying, according to matrix resin, the other biological decomposing copolymer of 0-40 weight part, the thermo-stabilizer of 0.5-1.5 weight part, the nucleator of 0.3-5 weight part, the compatilizer of 1-5 weight part, the softening agent of 2-15 weight part, the ratio of 0.3-5 weight part opening agent of 100 weight parts, raw material is joined high-speed mixer, mix raw material in high-speed mixer, mixing time is 5-10 minute;
C, by mixed raw material extruding pelletization, make the Biodegradable composite film material that degradation rate of the present invention is controlled.
As improvement of the present invention, above-mentioned matrix resin is mixed to get according to often kind of 30-60 weight ratio poly(lactic acid) (PLA) and 3-hydroxybutyrate-3-hydroxycaproic acid copolyesters (PHBH); Described other biological decomposing copolymer 5-30 weight part; Described thermo-stabilizer is 0.8-1.2 weight part; Described nucleator is 1-4 weight part; Described compatilizer is 2-4 weight part; Described softening agent is 5-10 weight part; Described opening agent is 1-4 weight part.
As a further improvement on the present invention, above-mentioned matrix resin is mixed to get according to often kind of 40-50 weight ratio poly(lactic acid) (PLA) and 3-hydroxybutyrate-3-hydroxycaproic acid copolyesters (PHBH); Described other biological decomposing copolymer 10-20 weight part; Described thermo-stabilizer is 0.9-1.1 weight part; Described nucleator is 2-3 weight part; Described compatilizer is 2.5-3.5 weight part; Described softening agent is 6-8 weight part; Described opening agent is 2-3 weight part.
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the prerequisite not departing from the technology of the present invention principle; can also make some improvement and modification, these improve and modification also should be considered as protection scope of the present invention.
Claims (1)
1. the Biodegradable composite film material that degradation rate is controlled, is characterized in that: it comprises
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| CN103571165B (en) * | 2013-11-06 | 2016-06-08 | 江南大学 | Lactic acid composite material and preparation method thereof |
| CN104691067B (en) * | 2015-03-06 | 2018-04-03 | 北京工商大学 | A kind of adjustable biodegradable multilayer material of gas permeation rate and its production and use |
| CN106147157A (en) * | 2015-03-26 | 2016-11-23 | 汉达精密电子(昆山)有限公司 | Lactic acid composite material and products thereof |
| CN106189130A (en) * | 2016-07-11 | 2016-12-07 | 董晓 | A kind of Microbial Synthesis of Polyhydroxyalkanoates prepares the method for composite package film |
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| CN109486138A (en) * | 2018-11-01 | 2019-03-19 | 南京五瑞生物降解新材料研究院有限公司 | PHA modified PLA/PBAT biodegradable resin and preparation method thereof |
| CN110330773A (en) * | 2019-07-19 | 2019-10-15 | 深圳利琒环保材料有限公司 | A kind of controllable full-biodegradable mulch and preparation method thereof |
| CN111154243B (en) * | 2020-01-16 | 2021-06-25 | 南京大学 | Bio-based compostable degradable heat-resistant film composite material and preparation method thereof |
| CN113527765A (en) * | 2021-06-25 | 2021-10-22 | 浙江兴越材料技术有限公司 | Polylactic acid composition and additive composition thereof, plastic product and preparation method thereof |
| CN114763430A (en) * | 2021-12-08 | 2022-07-19 | 山东联欣环保科技有限公司 | Composite degradable polymer with strong ductility and preparation method thereof |
| CN114479398B (en) * | 2022-03-24 | 2022-10-18 | 北京工商大学 | Biodegradable material and preparation method and application thereof |
| CN114836012A (en) * | 2022-04-14 | 2022-08-02 | 水发信达(山东)再生资源科技有限公司 | Completely biodegradable garbage bag film material and preparation method of garbage bag film |
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