CN103087484A - Biodegradable composite film material of controllable degradation rate and preparation method thereof - Google Patents
Biodegradable composite film material of controllable degradation rate and preparation method thereof Download PDFInfo
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- CN103087484A CN103087484A CN2013100090253A CN201310009025A CN103087484A CN 103087484 A CN103087484 A CN 103087484A CN 2013100090253 A CN2013100090253 A CN 2013100090253A CN 201310009025 A CN201310009025 A CN 201310009025A CN 103087484 A CN103087484 A CN 103087484A
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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 invention aims to provide a biodegradable composite film material of controllable degradation rate with good mechanical property, faster and more through degradation and no environmental harm, and a preparation method thereof. The material comprises the following components in parts by weight: 100 parts of matrix resin, 0-40 parts of other biodegradable polymers, 0.5-1.5 parts of heat stabilizer, 0.3-5 parts of nucleating agent, 1-5 parts of compatilizer, 2-15 parts of plasticizer and 0.3-5 parts of opener. The matrix resin is obtained by mixing poly lactic acid (PLA) and 3-hydroxybutyrate-3-hydroxy acid copolyester (PHBH) with each 20-80 parts by weight. The other biodegradable polymers are poly butylenes succinate (PBS), poly propylene carbonate (PPC), 3-hydroxybutyrate-3-hydroxyvalerate copolyester (PHBV) and terephthalic acid-butanediol-adipic acid copolyester (PBAT).
Description
Technical field
The present invention relates to controlled biological decomposition composite film material of a kind of degradation rate and preparation method thereof.
Background technology
In recent years, the researchist attempts to work out eco-friendly thin-film material on the basis of conventional plastic, for example, disclose a kind of with prepared thin-film material after starch and polyethylene and the direct blend of auxiliary agent in CN1931905A, but the tensile strength of this film is on the low side, and starch is when improving the plastics degradability, can cause the declines such as its physical and mechanical properties such as tensile strength on the one hand, make its processing difficulties, also exist on the other hand wetting ability too strong, and the consistency between most of resins for universal use is very poor, causes the mechanical property of material to decline to a great extent.In addition, although in this material, the plasticity-starch content can be higher, because the matrixes such as PE itself do not have biological degradability.Although the plastics of these technology preparations 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, the degraded that can not produce harm to environment rapidly, Biocomposite material and preparation method thereof thoroughly.Adopt that the present invention degrades rapidly, the film made of Biocomposite material thoroughly, have mechanical property preferably, and the controlled biological decomposition composite material film of degradation rate and preparation method thereof; Adopt the material of the present invention's preparation to possess processing characteristics preferably, higher tear strength, elongation at break and tensile strength, and can control the degradation time of material by the adjustment of each component ratio.
The biological decomposition composite film material that degradation rate of the present invention is controlled, it comprises
Described matrix resin is that poly(lactic acid) (PLA) and 3-hydroxybutyrate-3-hydroxycaproic acid copolyesters (PHBH) are mixed to get according to every kind of 20-80 weight ratio;
Described other biological decomposing copolymer is: at least a 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, the 5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester, 2,2 '-methylene-bis (4-methyl-6-tert-butylphenol), 4,4 '-at least a in thiobis-(the 6-tertiary butyl-3-methylphenol);
Described nucleator is: at least a in talcum powder, boron nitride, terephthalic acid, dibenzylidene sorbitol;
Described compatilizer is: at least a in polyoxyethylene poly-oxygen propylene aether segmented copolymer, benzoyl peroxide, ethene and glycidyl methacrylate copolymer;
Described softening agent is: at least a in glycerine, stearic acid, ethyl lactate, polyoxyethylene glycol, epoxy soybean oil, triethyl citrate, acetyl tributyl citrate;
Described opening agent is: at least a in amine hydroxybenzene, silicon-dioxide, erucicamide.
The biological decomposition composite film material that degradation rate of the present invention is controlled, wherein said matrix resin are that poly(lactic acid) (PLA) and 3-hydroxybutyrate-3-hydroxycaproic acid copolyesters (PHBH) are mixed to get according to every kind of 30-60 weight ratio; Described other biological decomposing copolymer 5-30 weight part; Described thermo-stabilizer is the 0.8-1.2 weight part; Described nucleator is the 1-4 weight part; Described compatilizer is the 2-4 weight part; Described softening agent is the 5-10 weight part; Described opening agent is the 1-4 weight part.
The biological decomposition composite film material that degradation rate of the present invention is controlled, wherein said matrix resin are that poly(lactic acid) (PLA) and 3-hydroxybutyrate-3-hydroxycaproic acid copolyesters (PHBH) are mixed to get according to every kind of 40-50 weight ratio; Described other biological decomposing copolymer 10-20 weight part; Described thermo-stabilizer is the 0.9-1.1 weight part; Described nucleator is the 2-3 weight part; Described compatilizer is the 2.5-3.5 weight part; Described softening agent is the 6-8 weight part; Described opening agent is the 2-3 weight part.
The preparation method of the biological decomposition composite film material that degradation rate of the present invention is controlled comprises the steps:
A, the following raw material of preparation:
Matrix resin, other biological decomposing copolymer, thermo-stabilizer, nucleator, compatilizer, softening agent, opening agent;
Described matrix resin is that poly(lactic acid) (PLA) and 3-hydroxybutyrate-3-hydroxycaproic acid copolyesters (PHBH) are mixed to get according to every kind of 20-80 weight ratio; Increase 3-hydroxybutyrate-3-hydroxycaproic acid copolyesters (PHBH) consumption, can improve the degradation speed of the finished product, reduce the required time of degraded; Reduce 3-hydroxybutyrate-3-hydroxycaproic acid copolyesters (PHBH) consumption, can reduce the degradation speed of the finished product, increase the required time of degraded;
Described other biological decomposing copolymer is: at least a 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, the 5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester, 2,2 '-methylene-bis (4-methyl-6-tert-butylphenol) and 4,4 '-at least a in thiobis-(the 6-tertiary butyl-3-methylphenol);
Described nucleator is: at least a in talcum powder, boron nitride, terephthalic acid, dibenzylidene sorbitol;
Described compatilizer is: at least a in polyoxyethylene poly-oxygen propylene aether segmented copolymer, benzoyl peroxide, ethene and glycidyl methacrylate copolymer;
Described softening agent is: at least a in glycerine, stearic acid, ethyl lactate, polyoxyethylene glycol, epoxy soybean oil, triethyl citrate, acetyl tributyl citrate;
Described opening agent is: at least a in amine hydroxybenzene, silicon-dioxide, erucicamide;
Above-mentioned various raw materials are placed in drying oven, dry, drying temperature is 40 ℃-80 ℃, and be 6-10 hour time of drying;
After B, abundant drying, according to the matrix resin of 100 weight parts, 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, raw material is joined high-speed mixer, in high-speed mixer, raw material is mixed, mixing time is 5-10 minute;
C, with mixed raw material extruding pelletization, make the controlled biological decomposition composite film material of degradation rate of the present invention.
The preparation method of the biological decomposition composite film material that degradation rate of the present invention is controlled, wherein said matrix resin is that poly(lactic acid) (PLA) and 3-hydroxybutyrate-3-hydroxycaproic acid copolyesters (PHBH) are mixed to get according to every kind of 30-60 weight ratio; Described other biological decomposing copolymer 5-30 weight part; Described thermo-stabilizer is the 0.8-1.2 weight part; Described nucleator is the 1-4 weight part; Described compatilizer is the 2-4 weight part; Described softening agent is the 5-10 weight part; Described opening agent is the 1-4 weight part.
The preparation method of the biological decomposition composite film material that degradation rate of the present invention is controlled, wherein said matrix resin is that poly(lactic acid) (PLA) and 3-hydroxybutyrate-3-hydroxycaproic acid copolyesters (PHBH) are mixed to get according to every kind of 40-50 weight ratio; Described other biological decomposing copolymer 10-20 weight part; Described thermo-stabilizer is the 0.9-1.1 weight part; Described nucleator is the 2-3 weight part; Described compatilizer is the 2.5-3.5 weight part; Described softening agent is the 6-8 weight part; Described opening agent is the 2-3 weight part.
compared with prior art, beneficial effect of the present invention is: biological decomposition 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 biological decomposition composite film material that the degradation rate of producing is controlled, good mechanical property not only, degrade also rapider, thoroughly, adopt the prepared film of this material, possesses processing characteristics preferably, 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, under can 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 produce harm to environment.The controlled degradable polymer thin film composite material that the present invention is prepared on MD and TD both direction, all has high tensile, high anti-tearing strength and controlled degradation property, can widespread use in wrapping material and agripast film field.Adopt that the present invention degrades rapidly, the film made of Biocomposite material thoroughly, have mechanical property preferably, and the controlled biological decomposition composite material film of degradation rate; Prepared material possesses processing characteristics preferably, higher tear strength, elongation at break and tensile strength, and can control the degradation time of material by the adjustment of each component ratio.
Embodiment
The below is described in further detail the specific embodiment of the present invention.Following examples are used for explanation the present invention, but are not used for limiting the scope of the invention.
According to following methods, the controlled biological decomposition composite material film of the degradation rate that obtains is carried out Mechanics Performance Testing:
The tensile property test is carried out according to GB/T1040.3-2006, uses the dumbbell shape cutting knife to cut sample, and is die-cut from MD and TD both direction, specimen size: total length 120mm, narrow 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, cuts into standard test specimen, and die-cut from MD and TD both direction, wherein spacing jig is 60mm, draw speed 100mm/min, and test number (TN) n 〉=5 time, 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) with matrix resin, properties-correcting agent, in baking oven 40-80 ℃ dry 6-10 hour, then by each component raw material of proportioning weighing, and manually carry out premix, with pre-composition extruding pelletization on twin screw extruder.The Temperature Setting of twin screw extruder is: a district, 110-145 ℃; 2nd district, 120-160 ℃; 3rd district, 145-185 ℃; 4th district, 145-185 ℃; 5th district, 145-185 ℃; Head, 145-160 ℃.
(2) with above-mentioned composition polymer pellet through single Screw Extrusion Blown Film, the Temperature Setting of single screw extrusion machine is: a district, 110-130 ℃; 2nd district, 130-150 ℃; 3rd district, 140-170 ℃; 4th district, 140-185 ℃; 5th district, 140-185 ℃; 6th district, 140-160 ℃; Die temperature, 145-160 ℃.Screw speed 30-60rpm wherein, pulling speed 2-5m/min, curling speed 3-6m/min.
The resulting product performance is as shown in table 1.
Table 1: film thickness 18 μ m
Embodiment 2: take each component by following formula and weight part
Processing conditions and parameter are seen embodiment 1;
The resulting product performance sees Table 2.
Table 2: film thickness 19 μ m
Embodiment 3: take each component by following formula and weight part
Processing conditions and parameter are seen embodiment 1;
The resulting product performance sees Table 3.
Table 3: film thickness 35 μ m
Embodiment 4: take each component by following formula and weight part
Processing conditions and parameter are seen embodiment 1.
The resulting product performance sees Table 4.
Table 4: film thickness 25 μ m
Embodiment 5: take each component by following formula and weight part
Processing conditions and parameter are seen embodiment 1.
The resulting product performance sees Table 5.
Table 5: film thickness 31 μ m
Embodiment 6: take each component by following formula and weight part
Processing conditions and parameter are seen embodiment 1.
The resulting product performance sees Table 6.
Table 6: film thickness 29 μ m
Embodiment 7: take each component by following formula and weight part
Processing conditions and parameter are seen embodiment 1;
The resulting product performance sees Table 2.
Table 7: film thickness 22 μ m
Embodiment 8
The biological decomposition composite film material that degradation rate of the present invention is controlled, it comprises
Described matrix resin is that poly(lactic acid) (PLA) and 3-hydroxybutyrate-3-hydroxycaproic acid copolyesters (PHBH) are mixed to get according to every kind 20 or 30 or 40 or 50 or 60 or 70 or 80 weight ratios;
Described other biological decomposing copolymer is: a kind of 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, the 5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester, 2,2 '-methylene-bis (4-methyl-6-tert-butylphenol), 4,4 '-a kind of in thiobis-(the 6-tertiary butyl-3-methylphenol) or two kinds or three kinds;
Described nucleator is: a kind of in talcum powder, boron nitride, terephthalic acid, dibenzylidene sorbitol or two kinds or three kinds or four kinds;
Described compatilizer is: a kind of in polyoxyethylene poly-oxygen propylene aether segmented copolymer, benzoyl peroxide, ethene and glycidyl methacrylate copolymer or two kinds;
Described softening agent is: a kind of 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: a kind of in amine hydroxybenzene, silicon-dioxide, erucicamide or two kinds or three kinds.
As improvement of the present invention, above-mentioned matrix resin is that poly(lactic acid) (PLA) and 3-hydroxybutyrate-3-hydroxycaproic acid copolyesters (PHBH) are mixed to get according to every kind of 30-60 weight ratio; Described other biological decomposing copolymer 5-30 weight part; Described thermo-stabilizer is the 0.8-1.2 weight part; Described nucleator is the 1-4 weight part; Described compatilizer is the 2-4 weight part; Described softening agent is the 5-10 weight part; Described opening agent is the 1-4 weight part.
As a further improvement on the present invention, above-mentioned matrix resin is that poly(lactic acid) (PLA) and 3-hydroxybutyrate-3-hydroxycaproic acid copolyesters (PHBH) are mixed to get according to every kind of 40-50 weight ratio; Described other biological decomposing copolymer 10-20 weight part; Described thermo-stabilizer is the 0.9-1.1 weight part; Described nucleator is the 2-3 weight part; Described compatilizer is the 2.5-3.5 weight part; Described softening agent is the 6-8 weight part; Described opening agent is the 2-3 weight part.
The preparation method of the biological decomposition composite film material that degradation rate of the present invention is controlled comprises the steps:
A, the following raw material of preparation:
Matrix resin, other biological decomposing copolymer, thermo-stabilizer, nucleator, compatilizer, softening agent, opening agent;
Described matrix resin is that poly(lactic acid) (PLA) and 3-hydroxybutyrate-3-hydroxycaproic acid copolyesters (PHBH) are mixed to get according to every kind 20 or 30 or 40 or 50 or 60 or 70 or 80 weight ratios; Increase 3-hydroxybutyrate-3-hydroxycaproic acid copolyesters (PHBH) consumption, can improve the degradation speed of the finished product, reduce the required time of degraded; Reduce 3-hydroxybutyrate-3-hydroxycaproic acid copolyesters (PHBH) consumption, can reduce the degradation speed of the finished product, increase the required time of degraded;
Described other biological decomposing copolymer is: a kind of 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, the 5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester, 2,2 '-methylene-bis (4-methyl-6-tert-butylphenol), 4,4 '-a kind of in thiobis-(the 6-tertiary butyl-3-methylphenol) or two kinds or three kinds;
Described nucleator is: a kind of in talcum powder, boron nitride, terephthalic acid, dibenzylidene sorbitol or two kinds or three kinds or four kinds;
Described compatilizer is: a kind of in polyoxyethylene poly-oxygen propylene aether segmented copolymer, benzoyl peroxide, ethene and glycidyl methacrylate copolymer or two kinds;
Described softening agent is: a kind of 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: a kind of in amine hydroxybenzene, silicon-dioxide, erucicamide or two kinds or three or three kinds;
Above-mentioned various raw materials are placed in drying oven, dry, drying temperature is 40 ℃-80 ℃, and be 6-10 hour time of drying;
After B, abundant drying, according to the matrix resin of 100 weight parts, 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, raw material is joined high-speed mixer, in high-speed mixer, raw material is mixed, mixing time is 5-10 minute;
C, with mixed raw material extruding pelletization, make the controlled biological decomposition composite film material of degradation rate of the present invention.
As improvement of the present invention, above-mentioned matrix resin is that poly(lactic acid) (PLA) and 3-hydroxybutyrate-3-hydroxycaproic acid copolyesters (PHBH) are mixed to get according to every kind of 30-60 weight ratio; Described other biological decomposing copolymer 5-30 weight part; Described thermo-stabilizer is the 0.8-1.2 weight part; Described nucleator is the 1-4 weight part; Described compatilizer is the 2-4 weight part; Described softening agent is the 5-10 weight part; Described opening agent is the 1-4 weight part.
As a further improvement on the present invention, above-mentioned matrix resin is that poly(lactic acid) (PLA) and 3-hydroxybutyrate-3-hydroxycaproic acid copolyesters (PHBH) are mixed to get according to every kind of 40-50 weight ratio; Described other biological decomposing copolymer 10-20 weight part; Described thermo-stabilizer is the 0.9-1.1 weight part; Described nucleator is the 2-3 weight part; Described compatilizer is the 2.5-3.5 weight part; Described softening agent is the 6-8 weight part; Described opening agent is the 2-3 weight part.
The above is only the preferred embodiment of the present invention; should be pointed out that for those skilled in the art, under the prerequisite that does not break away 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 (6)
1. the controlled biological decomposition composite film material of degradation rate, it is characterized in that: it comprises
Described matrix resin is that poly(lactic acid) (PLA) and 3-hydroxybutyrate-3-hydroxycaproic acid copolyesters (PHBH) are mixed to get according to every kind of 20-80 weight ratio;
Described other biological decomposing copolymer is: at least a 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, the 5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester, 2,2 '-methylene-bis (4-methyl-6-tert-butylphenol), 4,4 '-at least a in thiobis-(the 6-tertiary butyl-3-methylphenol);
Described nucleator is: at least a in talcum powder, boron nitride, terephthalic acid, dibenzylidene sorbitol;
Described compatilizer is: at least a in polyoxyethylene poly-oxygen propylene aether segmented copolymer, benzoyl peroxide, ethene and glycidyl methacrylate copolymer;
Described softening agent is: at least a in glycerine, stearic acid, ethyl lactate, polyoxyethylene glycol, epoxy soybean oil, triethyl citrate, acetyl tributyl citrate;
Described opening agent is: at least a in amine hydroxybenzene, silicon-dioxide, erucicamide.
2. the controlled biological decomposition composite film material of degradation rate according to claim 1, it is characterized in that: described matrix resin is that poly(lactic acid) (PLA) and 3-hydroxybutyrate-3-hydroxycaproic acid copolyesters (PHBH) are mixed to get according to every kind of 30-60 weight ratio; Described other biological decomposing copolymer 5-30 weight part; Described thermo-stabilizer is the 0.8-1.2 weight part; Described nucleator is the 1-4 weight part; Described compatilizer is the 2-4 weight part; Described softening agent is the 5-10 weight part; Described opening agent is the 1-4 weight part.
3. the controlled biological decomposition composite film material of degradation rate according to claim 2, it is characterized in that: described matrix resin is that poly(lactic acid) (PLA) and 3-hydroxybutyrate-3-hydroxycaproic acid copolyesters (PHBH) are mixed to get according to every kind of 40-50 weight ratio; Described other biological decomposing copolymer 10-20 weight part; Described thermo-stabilizer is the 0.9-1.1 weight part; Described nucleator is the 2-3 weight part; Described compatilizer is the 2.5-3.5 weight part; Described softening agent is the 6-8 weight part; Described opening agent is the 2-3 weight part.
4. the preparation method of the controlled biological decomposition composite film material of degradation rate, is characterized in that comprising the steps:
A, the following raw material of preparation:
Matrix resin, other biological decomposing copolymer, thermo-stabilizer, nucleator, compatilizer, softening agent, opening agent;
Described matrix resin is that poly(lactic acid) (PLA) and 3-hydroxybutyrate-3-hydroxycaproic acid copolyesters (PHBH) are mixed to get according to every kind of 20-80 weight ratio; Increase 3-hydroxybutyrate-3-hydroxycaproic acid copolyesters (PHBH) consumption, can improve the degradation speed of the finished product, reduce the required time of degraded; Reduce 3-hydroxybutyrate-3-hydroxycaproic acid copolyesters (PHBH) consumption, can reduce the degradation speed of the finished product, increase the required time of degraded;
The described other biological decomposing copolymer that can play the fine setting effect to composite material film mechanical property and degradation rate is: at least a 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, the 5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester, 2,2 '-methylene-bis (4-methyl-6-tert-butylphenol) and 4,4 '-at least a in thiobis-(the 6-tertiary butyl-3-methylphenol);
Described nucleator is: at least a in talcum powder, boron nitride, terephthalic acid, dibenzylidene sorbitol;
Described compatilizer is: at least a in polyoxyethylene poly-oxygen propylene aether segmented copolymer, benzoyl peroxide, ethene and glycidyl methacrylate copolymer;
Described softening agent is: at least a in glycerine, stearic acid, ethyl lactate, polyoxyethylene glycol, epoxy soybean oil, triethyl citrate, acetyl tributyl citrate;
Described opening agent is: at least a in amine hydroxybenzene, silicon-dioxide, erucicamide;
Above-mentioned various raw materials are placed in drying oven, dry, drying temperature is 40 ℃-80 ℃, and be 6-10 hour time of drying;
After B, abundant drying, according to the matrix resin of 100 weight parts, 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, raw material is joined high-speed mixer, in high-speed mixer, raw material is mixed, mixing time is 5-10 minute;
C, with mixed raw material extruding pelletization, make the controlled biological decomposition composite film material of degradation rate.
5. the preparation method of the controlled biological decomposition composite film material of degradation rate according to claim 4, it is characterized in that: described matrix resin is that poly(lactic acid) (PLA) and 3-hydroxybutyrate-3-hydroxycaproic acid copolyesters (PHBH) are mixed to get according to every kind of 30-60 weight ratio; Described other biological decomposing copolymer 5-30 weight part; Described thermo-stabilizer is the 0.8-1.2 weight part; Described nucleator is the 1-4 weight part; Described compatilizer is the 2-4 weight part; Described softening agent is 510 weight parts; Described opening agent is the 1-4 weight part.
6. the preparation method of the controlled biological decomposition composite film material of degradation rate according to claim 5, it is characterized in that: described matrix resin is that poly(lactic acid) (PLA) and 3-hydroxybutyrate-3-hydroxycaproic acid copolyesters (PHBH) are mixed to get according to every kind of 40-50 weight ratio; Described other biological decomposing copolymer 10-20 weight part; Described thermo-stabilizer is the 0.9-1.1 weight part; Described nucleator is the 2-3 weight part; Described compatilizer is the 2.5-3.5 weight part; Described softening agent is the 6-8 weight part; Described opening agent is the 2-3 weight part.
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| CN201310009025.3A CN103087484B (en) | 2013-01-11 | 2013-01-11 | Biodegradable composite film material that degradation rate is controlled and preparation method thereof |
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| CN201310009025.3A CN103087484B (en) | 2013-01-11 | 2013-01-11 | Biodegradable composite film material that degradation rate is controlled and preparation method thereof |
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| CN103087484A true CN103087484A (en) | 2013-05-08 |
| CN103087484B CN103087484B (en) | 2016-03-02 |
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| CN103571165A (en) * | 2013-11-06 | 2014-02-12 | 江南大学 | Polylactic acid composite material and preparation method thereof |
| CN104691067A (en) * | 2015-03-06 | 2015-06-10 | 北京工商大学 | Biodegradable multilayer material with adjustable gas transmission rate and preparation method and applications thereof |
| 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 |
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| CN103571165A (en) * | 2013-11-06 | 2014-02-12 | 江南大学 | Polylactic acid composite material and preparation method thereof |
| CN104691067A (en) * | 2015-03-06 | 2015-06-10 | 北京工商大学 | Biodegradable multilayer material with adjustable gas transmission rate and preparation method and applications thereof |
| 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 |
| CN106221165A (en) * | 2016-08-31 | 2016-12-14 | 深圳市虹彩新材料科技有限公司 | A kind of whole life cycle design of high-barrier and preparation method thereof |
| WO2019011153A1 (en) * | 2017-07-13 | 2019-01-17 | 山东农业大学 | Mechanically mulchable fully biodegradable mulching film |
| CN108912631A (en) * | 2018-06-06 | 2018-11-30 | 安徽顺科包装制品有限公司 | A kind of high leakproofness method for manufacturing thin film for paper and plastics compound bag |
| CN109486129A (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 PPC/PBAT biodegradable resin and preparation method thereof |
| 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 |
| CN111154243A (en) * | 2020-01-16 | 2020-05-15 | 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 |
| WO2023104073A1 (en) * | 2021-12-08 | 2023-06-15 | 山东联欣环保科技有限公司 | Degradable composite polymer having high ductility, and preparation method therefor |
| US20230303829A1 (en) * | 2022-03-24 | 2023-09-28 | Beijing Technology And Business University | Biodegradable material, 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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