CN102786782B - Biodegradable material and preparation method and application thereof - Google Patents
Biodegradable material and preparation method and application thereof Download PDFInfo
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- CN102786782B CN102786782B CN201210313364.6A CN201210313364A CN102786782B CN 102786782 B CN102786782 B CN 102786782B CN 201210313364 A CN201210313364 A CN 201210313364A CN 102786782 B CN102786782 B CN 102786782B
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Abstract
The invention discloses a biodegradable material which comprises, by weight, 10% -35% of a copolymer of 3-hydroxybutyric acid and 4-hydroxybutyric acid, 10% -35% of a copolymer of butylene adipate and butylene terephthalate, 0% -50% of polylactic acid, 5% -25% of natural vegetable oil, 1% -10% of a plasticizer and 0.02% -5% of a reaction promoter component. The invention also discloses a preparation method of the biodegradable material, which has the advantages of simple process, easy control, strong operability, easy industrial production, good economic benefit and wide application prospect.
Description
Technical field
The present invention relates to plastic material field, particularly a kind of biodegradable material and preparation method thereof and the application in preparing Biodegradable film.
Background technology
Since the thirties in 20th century, plastic material came into operation, with bright and clean attractive in appearance, corrosion-resistant, the excellent properties such as production technique is simple of its light weight, inexpensive, appearance, be widely used in each field of each department of national economy and people's lives.World's plastic raw materials output breaks through 100,000,000 tons for 1991 first, has approached 200,000,000 tons to world's plastics annual production in 2003, by volume calculates the summation that surpasses the metallic substance output such as iron and steel, aluminium, copper.Nineteen ninety-five to 2000, a year global plastics output average annual growth was 6.3%.According to prediction, within 2026, whole world plastics demand will reach 3.8 hundred million tons, and plastics industry has become genuine first material industry.
Due to the extensive application of plastics, waste plastic goods also grow with each passing day, and the most stable performance of plastics, therefore, has also occurred so-called white pollution simultaneously, to environment, has brought very large harm.In recent years, accumulate successful experience both domestic and external, people have taked positive defensive measure to the improvement of waste plastic, such as the minimizing of Plastic Packaging Materials, are repeatedly used and recycling etc.But for those, be difficult for the goods that reclaim or recovery value is little, recycling is difficult to operation economically, as shopping bag, disposable tableware etc., adopt degradative plastics more favourable.Other goods are as agricultural mulching, and medical plastic ware etc., are also the huge potential markets of degradative plastics.
The main suitable application area of degradative plastics is that life cycle is short, the more difficult product of waste treatment after use.But degradative plastics is in whole plastics extended family, is a quite young member, at present also in a growth, perfect stage.Although product section is commercialization, still immature, constantly improving cost ratio, reducing material cost and widen in market, all can run into a lot of stubborn problems.
International monopoly WO2007/134492A1 discloses the production method of a kind of fully biodegradable Plastic Resin and film based article, raw material mainly comprises starch, glycerine, talcum powder, ethylene acrylic acid co polymer etc., after mixing, through twin screw extruder, carries out granulation.But film prepared by the method, owing to there being the existence of mineral-type and starch filled material in film, therefore, this film can not keep the good transparency, and the mechanical property of this film is also undesirable, exists the defects such as technology.
Publication number is that the Chinese patent application of CN 101508830A discloses a kind of Biodegradable polyester composition, its composition comprises by weight percentage: 45% ~ 90% poly butylene succinate terpolymer, 5% ~ 50% poly(lactic acid), 1% ~ 2% softening agent and 1% ~ 5% weighting agent, and described poly butylene succinate terpolymer is at least a kind of in poly-succinic-tetramethylene adipate, poly-succinic-mutual-phenenyl two acid bromide two alcohol ester and poly-succinic-lactic acid butanediol ester; Described softening agent is at least a kind of in dimethyl phthalate, diethyl phthalate; Described weighting agent is at least a kind of in talcum powder, bamboo powder, nanometer grade calcium carbonate and Ti-Si nano recombiner.Although this Biodegradable polyester composition has biodegradability, owing to lacking the components such as expanding material and compatilizer, its mechanical property is not good, and the film class plastics of preparation are very easy to damaged.
Summary of the invention
The invention provides a kind of biodegradable material, not only there is biological degradability, and by the effect each other of each component, embody excellent mechanical property, keep the transparency preferably simultaneously.
A biodegradable material, is comprised of the component of following weight percent:
3-hydroxybutyrate and 4 hydroxybutyric acid copolymer 1 0% ~ 35%;
Tetramethylene adipate and mutual-phenenyl two acid bromide two alcohol ester's copolymer 1 0% ~ 35%;
Poly(lactic acid) 0 ~ 50%;
Crude vegetal 5% ~ 25%;
Softening agent 1% ~ 10%;
Reaction promotor 0.02% ~ 5%.
3-hydroxybutyrate and 4 hydroxybutyric acid multipolymer, tetramethylene adipate and mutual-phenenyl two acid bromide two alcohol ester's multipolymer, crude vegetal, softening agent and reaction promotor in the present invention, combine and embody good elongation at break and good tensile strength, whole mechanics better performances.
As preferably, described biodegradable material, is comprised of the component of following weight percent:
3-hydroxybutyrate and 4 hydroxybutyric acid copolymer 1 5% ~ 22%;
Tetramethylene adipate and mutual-phenenyl two acid bromide two alcohol ester's copolymer 1 5% ~ 22%;
Poly(lactic acid) 25% ~ 50%;
Crude vegetal 14% ~ 25%;
Softening agent 5% ~ 12%;
Reaction promotor 1% ~ 5%.
3-hydroxybutyrate and 4 hydroxybutyric acid multipolymer, tetramethylene adipate and mutual-phenenyl two acid bromide two alcohol ester's multipolymer, poly(lactic acid), crude vegetal, softening agent and reaction promotor in the present invention, combine and embody good elongation at break and excellent tensile strength, excellent combination property.
Further preferably, described biodegradable material, is comprised of the component of following weight percent:
3-hydroxybutyrate and 4 hydroxybutyric acid copolymer 1 5% ~ 19%;
Tetramethylene adipate and mutual-phenenyl two acid bromide two alcohol ester's copolymer 1 5% ~ 19%;
Poly(lactic acid) 37% ~ 50%;
Crude vegetal 14% ~ 18%;
Softening agent 5% ~ 7%;
Reaction promotor 1% ~ 2%.
Biodegradable film prepared by the biodegradable material under this weight percent, has very excellent tensile strength and good elongation at break, is very suitable for the fields such as plastic shopping bag.
3-hydroxybutyrate and 4 hydroxybutyric acid multipolymer can adopt the commercially available general trade mark, and tetramethylene adipate and mutual-phenenyl two acid bromide two alcohol ester's multipolymer also can adopt the commercially available general trade mark.
Described poly(lactic acid) is L-type poly(lactic acid), D type poly(lactic acid) or LD mixed type poly(lactic acid), and poly(lactic acid) can adopt the commercially available general trade mark.Under the condition existing in poly(lactic acid), this biodegradable material intensity is better, has improved the intensity of this biodegradable material.
Described crude vegetal is one or more in rapeseed oil, Viscotrol C, soya-bean oil, peanut oil, Oleum Cocois, plam oil, oleum lini, Oleum Gossypii semen, Semen Maydis oil, sunflower seed oil, pine-seed oil, tung oil.Add crude vegetal, active function groups by the reaction active groups in crude vegetal and matrix resin (being 3-hydroxybutyrate and 4 hydroxybutyric acid multipolymer and tetramethylene adipate and mutual-phenenyl two acid bromide two alcohol ester's multipolymer) interacts, to reach increase-volume object.
Described softening agent is one or more in sorbyl alcohol, polyoxyethylene glycol, acetylize citric acid, glycerine.Add softening agent, improve the travelling performance of polymer chain, the plastic effect of biodegradable material is improved, reduce fragility, improve flexible.
Described reaction promotor is one or both in coupling agent, catalyzer.
Described coupling agent is one or both in silane compound, isocyanate compound, as preferably, what described coupling agent was γ-aminopropyl triethoxysilane (KH-550), diphenylmethanediisocyanate (MDI), poly-methyl in phenylisocyanate (polymeric MDI is called for short PMDI) is a kind of or two or more.
Described catalyzer is one or both in organic acid, inorganic proton acid.As preferably, described catalyzer is a kind of or two or more in citric acid, hexanodioic acid, succinic acid.
The present invention also provides a kind of preparation method of biodegradable material, and its technique is simple, is easy to control, workable.
The preparation method of described biodegradable material, comprises the following steps:
The poly(lactic acid) that 3-hydroxybutyrate and 4 hydroxybutyric acid multipolymer, tetramethylene adipate and mutual-phenenyl two acid bromide two alcohol ester's multipolymer, crude vegetal, softening agent, reaction promotor and selectivity are added mixes, and obtains mixed material; Mixed material is added to tie rod, pelletizing after melt blending in twin screw extruder, obtains particulate state hybrid resin; Particulate state hybrid resin drying obtains biodegradable material after processing.
3-hydroxybutyrate and 4 hydroxybutyric acid multipolymer and tetramethylene adipate and mutual-phenenyl two acid bromide two alcohol ester's multipolymer is used as last to be needed to be dried, and the weight percentage of its moisture is controlled to 1.0% with interior.
The screw slenderness ratio of described twin screw extruder is 35 ~ 45:1, and the temperature of melt blending is 140 ℃ ~ 175 ℃.
The application of described biodegradable material in preparing Biodegradable film, owing to having excellent elongation at break and tensile strength, and has kept the good transparency, is particularly suitable for preparing Biodegradable film.The biodegradable material of preparing by aforesaid method can be prepared Biodegradable film through single screw rod inflation film manufacturing machine blown film.The screw slenderness ratio of described single screw rod inflation film manufacturing machine is 25:1 ~ 35:1.
Compared with prior art, tool of the present invention has the following advantages:
In biodegradable material of the present invention, the poly(lactic acid) (a kind of bio-based materials) that main ingredient 3-hydroxybutyrate and 4 hydroxybutyric acid multipolymer, tetramethylene adipate and mutual-phenenyl two acid bromide two alcohol ester's multipolymer, crude vegetal and selectivity are used, due to four special molecular structures, all can be decomposed by microorganism under given conditions, belong to Wholly-degradable biomaterial.In addition, together with each combination of components of poly(lactic acid), softening agent and reaction promotor that 3-hydroxybutyrate and 4 hydroxybutyric acid multipolymer, tetramethylene adipate and mutual-phenenyl two acid bromide two alcohol ester's multipolymer, selectivity are used, each component can interact, there is certain synergy, compared with prior art, embody excellent elongation at break and tensile strength, and kept the good transparency, excellent combination property.
Biodegradable material of the present invention is highly suitable for preparing Biodegradable film, and the Biodegradable film of preparation, owing to having added after bio-based fully-degradable polylactic acid, has increased significantly the intensity of this Biodegradable film.This Biodegradable film not only can be used as repeatedly Reusability of shopping bag, and still can be used as refuse bag use after repeatedly using, and finally by the microorganism in soil, is decomposed quick absorption completely, and environmental pollution is little, has good environmental benefit.
The preparation method of biodegradable material of the present invention, preparation method is simple, be easy to control, workable, low production cost, and the biodegradable material of preparation just can be able to be obtained to Biodegradable film through simple processing again, and be easy to suitability for industrialized production and there is good economic benefit, have broad application prospects.
Embodiment
Following examples further describe the present invention, but the present invention is not limited to these embodiment.
Embodiment 1
Take the raw material of following weight part:
(weight percentage of moisture is 0.8% for dried 3-hydroxybutyrate and 4 hydroxybutyric acid multipolymer, Tianjin Green Biomaterial Co., Ltd., model is 2001 resins) 15 weight parts, (weight percentage of moisture is 0.8% to tetramethylene adipate and mutual-phenenyl two acid bromide two alcohol ester's multipolymer, the prosperous rich medicine company in Hangzhou, Biocosafe2003) 15 weight parts, poly(lactic acid) (Natureworks 2002D, LD mixed type poly(lactic acid)) 50 weight parts, polyoxyethylene glycol (Chinese traditional Chinese medicines, PEG 400) 5 weight parts, Viscotrol C 14 weight parts, diphenylmethanediisocyanate (Yantai ten thousand China, MDI, WANNATE 100) 1 weight part.
First raw material is carried out in premixing machine to pre-mixing, the initial temperature of mixing is 40 ℃, and the rotating speed of premixing machine is that 800 ~ 1200 turn/min(are slowly improved to high speed by low speed, mixes 30 minutes), after fully mixing, obtain mixed material; By mixed material be added to melt blending in twin screw extruder (mixed material is 145 ℃ through excess temperature successively, 150 ℃, 155 ℃, 160 ℃, 175 ℃, 165 ℃, 160 ℃, 150 ℃ of each intervals of melt blending) tie rod after, pelletizing, obtains particulate state hybrid resin; Particulate state hybrid resin, after the drying treatment that dewaters, obtains biodegradable material.The screw slenderness ratio of the twin screw extruder of selecting is 40:1.
Biodegradable material obtained above is added in single screw rod inflation film manufacturing machine and carries out blown film machine-shaping, obtain Biodegradable film, the biological plastics that belongs to Wholly-degradable, can meet U.S. ASTMD6400 and the EN13432 of European Union degraded standard, single screw slenderness ratio of single screw rod inflation film manufacturing machine is 25:1.
Embodiment 2
Take the raw material of following weight part:
(weight percentage of moisture is 0.8% for dried 3-hydroxybutyrate and 4 hydroxybutyric acid multipolymer, Tianjin Green Biomaterial Co., Ltd., model is 2001 resins) 15 weight parts, (weight percentage of moisture is 0.8% to tetramethylene adipate and mutual-phenenyl two acid bromide two alcohol ester's multipolymer, the prosperous rich medicine company in Hangzhou, Biocosafe2003) 15 weight parts, poly(lactic acid) (Natureworks 2002D, LD mixed type poly(lactic acid)) 40 weight parts, polyoxyethylene glycol (Chinese traditional Chinese medicines, PEG 400) 5 weight parts, Viscotrol C 14 weight parts, epoxidation silane coupling agent (KH-550, γ-aminopropyl triethoxysilane) 1 weight part.
First raw material is carried out in premixing machine to pre-mixing, the initial temperature of mixing is 40 ℃, and the rotating speed of premixing machine is that 800 ~ 1200 turn/min(are slowly improved to high speed by low speed, mixes 30 minutes), after fully mixing, obtain mixed material; By mixed material be added to melt blending in twin screw extruder (mixed material is 145 ℃ through excess temperature successively, 150 ℃, 155 ℃, 160 ℃, 175 ℃, 165 ℃, 160 ℃, 150 ℃ of each intervals of melt blending) tie rod after, pelletizing, obtains particulate state hybrid resin; Particulate state hybrid resin, after the drying treatment that dewaters, obtains biodegradable material.The screw slenderness ratio of the twin screw extruder of selecting is 40:1.
Biodegradable material obtained above is added in single screw rod inflation film manufacturing machine and carries out blown film machine-shaping, obtain Biodegradable film, the biological plastics that belongs to Wholly-degradable, can meet U.S. ASTMD6400 and the EN13432 of European Union degraded standard, single screw slenderness ratio of single screw rod inflation film manufacturing machine is 25:1.
Embodiment 3
Take the raw material of following weight part:
(weight percentage of moisture is 0.8% for dried 3-hydroxybutyrate and 4 hydroxybutyric acid multipolymer, Tianjin Green Biomaterial Co., Ltd., model is 2001 resins) 15 weight parts, (weight percentage of moisture is 0.8% to tetramethylene adipate and mutual-phenenyl two acid bromide two alcohol ester's multipolymer, the prosperous rich medicine company in Hangzhou, Biocosafe2003) 15 weight parts, poly(lactic acid) (Natureworks 2002D, LD mixed type poly(lactic acid)) 30 weight parts, glycerine 5 weight parts, Viscotrol C 14 weight parts, diphenylmethanediisocyanate (Yantai ten thousand China, MDI, WANNATE 100) 1 weight part.
First raw material is carried out in premixing machine to pre-mixing, the initial temperature of mixing is 40 ℃, and the rotating speed of premixing machine is that 800 ~ 1200 turn/min(are slowly improved to high speed by low speed, mixes 30 minutes), after fully mixing, obtain mixed material; By mixed material be added to melt blending in twin screw extruder (mixed material is 145 ℃ through excess temperature successively, 150 ℃, 155 ℃, 160 ℃, 175 ℃, 165 ℃, 160 ℃, 150 ℃ of each intervals of melt blending) tie rod after, pelletizing, obtains particulate state hybrid resin; Particulate state hybrid resin, after the drying treatment that dewaters, obtains biodegradable material.The screw slenderness ratio of the twin screw extruder of selecting is 40:1.
Biodegradable material obtained above is added in single screw rod inflation film manufacturing machine and carries out blown film machine-shaping, obtain Biodegradable film, the biological plastics that belongs to Wholly-degradable, can meet U.S. ASTMD6400 and the EN13432 of European Union degraded standard, single screw slenderness ratio of single screw rod inflation film manufacturing machine is 25:1.
Embodiment 4
Take the raw material of following weight part:
(weight percentage of moisture is 0.8% for dried 3-hydroxybutyrate and 4 hydroxybutyric acid multipolymer, Tianjin Green Biomaterial Co., Ltd., model is 2001 resins) 15 weight parts, (weight percentage of moisture is 0.8% to tetramethylene adipate and mutual-phenenyl two acid bromide two alcohol ester's multipolymer, the prosperous rich medicine company in Hangzhou, Biocosafe2003) 15 weight parts, poly(lactic acid) (Natureworks 2002D, LD mixed type poly(lactic acid)) 30 weight parts, glycerine 5 weight parts, Viscotrol C 14 weight parts, epoxidation silane coupling agent (KH-550, γ-aminopropyl triethoxysilane) 1 weight part.
First raw material is carried out in premixing machine to pre-mixing, the initial temperature of mixing is 40 ℃, and the rotating speed of premixing machine is that 800 ~ 1200 turn/min(are slowly improved to high speed by low speed, mixes 30 minutes), after fully mixing, obtain mixed material; By mixed material be added to melt blending in twin screw extruder (mixed material is 145 ℃ through excess temperature successively, 150 ℃, 155 ℃, 160 ℃, 175 ℃, 165 ℃, 160 ℃, 150 ℃ of each intervals of melt blending) tie rod after, pelletizing, obtains particulate state hybrid resin; Particulate state hybrid resin, after the drying treatment that dewaters, obtains biodegradable material.The screw slenderness ratio of the twin screw extruder of selecting is 40:1.
Biodegradable material obtained above is added in single screw rod inflation film manufacturing machine and carries out blown film machine-shaping, obtain Biodegradable film, the biological plastics that belongs to Wholly-degradable, can meet U.S. ASTMD6400 and the EN13432 of European Union degraded standard, single screw slenderness ratio of single screw rod inflation film manufacturing machine is 25:1.
Embodiment 5
Take the raw material of following weight part:
(weight percentage of moisture is 0.8% for dried 3-hydroxybutyrate and 4 hydroxybutyric acid multipolymer, Tianjin Green Biomaterial Co., Ltd., model is 2001 resins) 15 weight parts, (weight percentage of moisture is 0.8% to tetramethylene adipate and mutual-phenenyl two acid bromide two alcohol ester's multipolymer, the prosperous rich medicine company in Hangzhou, Biocosafe2003) 15 weight parts, poly(lactic acid) (Natureworks 2002D, LD mixed type poly(lactic acid)) 30 weight parts, glycerine 5 weight parts, Viscotrol C 14 weight parts, poly-methyl is to phenylisocyanate (Yantai ten thousand China, PMDI, PM-200) 1 weight part.
First raw material is carried out in premixing machine to pre-mixing, the initial temperature of mixing is 40 ℃, and the rotating speed of premixing machine is that 800 ~ 1200 turn/min(are slowly improved to high speed by low speed, mixes 30 minutes), after fully mixing, obtain mixed material; By mixed material be added to melt blending in twin screw extruder (mixed material is 145 ℃ through excess temperature successively, 150 ℃, 155 ℃, 160 ℃, 175 ℃, 165 ℃, 160 ℃, 150 ℃ of each intervals of melt blending) tie rod after, pelletizing, obtains particulate state hybrid resin; Particulate state hybrid resin, after the drying treatment that dewaters, obtains biodegradable material.The screw slenderness ratio of the twin screw extruder of selecting is 40:1.
Biodegradable material obtained above is added in single screw rod inflation film manufacturing machine and carries out blown film machine-shaping, obtain Biodegradable film, the biological plastics that belongs to Wholly-degradable, can meet U.S. ASTMD6400 and the EN13432 of European Union degraded standard, single screw slenderness ratio of single screw rod inflation film manufacturing machine is 25:1.
Embodiment 6
Take the raw material of following weight part:
(weight percentage of moisture is 0.8% for dried 3-hydroxybutyrate and 4 hydroxybutyric acid multipolymer, Tianjin Green Biomaterial Co., Ltd., model is 2001 resins) 15 weight parts, (weight percentage of moisture is 0.8% to tetramethylene adipate and mutual-phenenyl two acid bromide two alcohol ester's multipolymer, the prosperous rich medicine company in Hangzhou, Biocosafe2003) 15 weight parts, poly(lactic acid) (Natureworks 2002D, LD mixed type poly(lactic acid)) 30 weight parts, polyoxyethylene glycol (Chinese traditional Chinese medicines, PEG 400) 5 weight parts, Viscotrol C 14 weight parts, poly-methyl is to phenylisocyanate (Yantai ten thousand China, PMDI, PM-200) 1 weight part.
First raw material is carried out in premixing machine to pre-mixing, the initial temperature of mixing is 40 ℃, and the rotating speed of premixing machine is that 800 ~ 1200 turn/min(are slowly improved to high speed by low speed, mixes 30 minutes), after fully mixing, obtain mixed material; By mixed material be added to melt blending in twin screw extruder (mixed material is 145 ℃ through excess temperature successively, 150 ℃, 155 ℃, 160 ℃, 175 ℃, 165 ℃, 160 ℃, 150 ℃ of each intervals of melt blending) tie rod after, pelletizing, obtains particulate state hybrid resin; Particulate state hybrid resin, after the drying treatment that dewaters, obtains biodegradable material.The screw slenderness ratio of the twin screw extruder of selecting is 40:1.
Biodegradable material obtained above is added in single screw rod inflation film manufacturing machine and carries out blown film machine-shaping, obtain Biodegradable film, the biological plastics that belongs to Wholly-degradable, can meet U.S. ASTMD6400 and the EN13432 of European Union degraded standard, single screw slenderness ratio of single screw rod inflation film manufacturing machine is 25:1.
Embodiment 7
Take the raw material of following weight part:
(weight percentage of moisture is 0.8% for dried 3-hydroxybutyrate and 4 hydroxybutyric acid multipolymer, Tianjin Green Biomaterial Co., Ltd., model is 2001 resins) 15 weight parts, (weight percentage of moisture is 0.8% to tetramethylene adipate and mutual-phenenyl two acid bromide two alcohol ester's multipolymer, the prosperous rich medicine company in Hangzhou, Biocosafe2003) 15 weight parts, poly(lactic acid) (Natureworks 2002D, LD mixed type poly(lactic acid)) 20 weight parts, glycerine 5 weight parts, Viscotrol C 14 weight parts, diphenylmethanediisocyanate (Yantai ten thousand China, MDI, WANNATE 100) 1 weight part.
First raw material is carried out in premixing machine to pre-mixing, the initial temperature of mixing is 40 ℃, and the rotating speed of premixing machine is that 800 ~ 1200 turn/min(are slowly improved to high speed by low speed, mixes 30 minutes), after fully mixing, obtain mixed material; By mixed material be added to melt blending in twin screw extruder (mixed material is 145 ℃ through excess temperature successively, 150 ℃, 155 ℃, 160 ℃, 175 ℃, 165 ℃, 160 ℃, 150 ℃ of each intervals of melt blending) tie rod after, pelletizing, obtains particulate state hybrid resin; Particulate state hybrid resin, after the drying treatment that dewaters, obtains biodegradable material.The screw slenderness ratio of the twin screw extruder of selecting is 40:1.
Biodegradable material obtained above is added in single screw rod inflation film manufacturing machine and carries out blown film machine-shaping, obtain Biodegradable film, the biological plastics that belongs to Wholly-degradable, can meet U.S. ASTMD6400 and the EN13432 of European Union degraded standard, single screw slenderness ratio of single screw rod inflation film manufacturing machine is 25:1.
Embodiment 8
Take the raw material of following weight part:
(weight percentage of moisture is 0.8% for dried 3-hydroxybutyrate and 4 hydroxybutyric acid multipolymer, Tianjin Green Biomaterial Co., Ltd., model is 2001 resins) 15 weight parts, (weight percentage of moisture is 0.8% to tetramethylene adipate and mutual-phenenyl two acid bromide two alcohol ester's multipolymer, the prosperous rich medicine company in Hangzhou, Biocosafe2003) 15 weight parts, poly(lactic acid) (Natureworks 2002D, LD mixed type poly(lactic acid)) 20 weight parts, glycerine 5 weight parts, Viscotrol C 14 weight parts, epoxidation silane coupling agent (KH-550, γ-aminopropyl triethoxysilane) 1 weight part.
First raw material is carried out in premixing machine to pre-mixing, the initial temperature of mixing is 40 ℃, and the rotating speed of premixing machine is that 800 ~ 1200 turn/min(are slowly improved to high speed by low speed, mixes 30 minutes), after fully mixing, obtain mixed material; By mixed material be added to melt blending in twin screw extruder (mixed material is 145 ℃ through excess temperature successively, 150 ℃, 155 ℃, 160 ℃, 175 ℃, 165 ℃, 160 ℃, 150 ℃ of each intervals of melt blending) tie rod after, pelletizing, obtains particulate state hybrid resin; Particulate state hybrid resin, after the drying treatment that dewaters, obtains biodegradable material.The screw slenderness ratio of the twin screw extruder of selecting is 40:1.
Biodegradable material obtained above is added in single screw rod inflation film manufacturing machine and carries out blown film machine-shaping, obtain Biodegradable film, the biological plastics that belongs to Wholly-degradable, can meet U.S. ASTMD6400 and the EN13432 of European Union degraded standard, single screw slenderness ratio of single screw rod inflation film manufacturing machine is 25:1.
Embodiment 9
Take the raw material of following weight part:
(weight percentage of moisture is 0.8% for dried 3-hydroxybutyrate and 4 hydroxybutyric acid multipolymer, Tianjin Green Biomaterial Co., Ltd., model is 2001 resins) 15 weight parts, (weight percentage of moisture is 0.8% to tetramethylene adipate and mutual-phenenyl two acid bromide two alcohol ester's multipolymer, the prosperous rich medicine company in Hangzhou, Biocosafe2003) 15 weight parts, poly(lactic acid) (Natureworks 2002D, LD mixed type poly(lactic acid)) 20 weight parts, glycerine 8 weight parts, peanut oil 10 weight parts, poly-methyl is to phenylisocyanate (Yantai ten thousand China, PMDI, PM-200) 3 weight parts.
First raw material is carried out in premixing machine to pre-mixing, the initial temperature of mixing is 40 ℃, and the rotating speed of premixing machine is that 800 ~ 1200 turn/min(are slowly improved to high speed by low speed, mixes 30 minutes), after fully mixing, obtain mixed material; By mixed material be added to melt blending in twin screw extruder (mixed material is 145 ℃ through excess temperature successively, 150 ℃, 155 ℃, 160 ℃, 175 ℃, 165 ℃, 160 ℃, 150 ℃ of each intervals of melt blending) tie rod after, pelletizing, obtains particulate state hybrid resin; Particulate state hybrid resin, after the drying treatment that dewaters, obtains biodegradable material.The screw slenderness ratio of the twin screw extruder of selecting is 40:1.
Biodegradable material obtained above is added in single screw rod inflation film manufacturing machine and carries out blown film machine-shaping, obtain Biodegradable film, the biological plastics that belongs to Wholly-degradable, can meet U.S. ASTMD6400 and the EN13432 of European Union degraded standard, single screw slenderness ratio of single screw rod inflation film manufacturing machine is 25:1.
Embodiment 10
Take the raw material of following weight part:
(weight percentage of moisture is 0.8% for dried 3-hydroxybutyrate and 4 hydroxybutyric acid multipolymer, Tianjin Green Biomaterial Co., Ltd., model is 2001 resins) 15 weight parts, (weight percentage of moisture is 0.8% to tetramethylene adipate and mutual-phenenyl two acid bromide two alcohol ester's multipolymer, the prosperous rich medicine company in Hangzhou, Biocosafe2003) 15 weight parts, poly(lactic acid) (Natureworks 2002D, LD mixed type poly(lactic acid)) 20 weight parts, glycerine 4 weight parts, Viscotrol C 18 weight parts, diphenylmethanediisocyanate (Yantai ten thousand China, MDI, WANNATE 100) 1 weight part.
First raw material is carried out in premixing machine to pre-mixing, the initial temperature of mixing is 40 ℃, and the rotating speed of premixing machine is that 800 ~ 1200 turn/min(are slowly improved to high speed by low speed, mixes 30 minutes), after fully mixing, obtain mixed material; By mixed material be added to melt blending in twin screw extruder (mixed material is 145 ℃ through excess temperature successively, 150 ℃, 155 ℃, 160 ℃, 175 ℃, 165 ℃, 160 ℃, 150 ℃ of each intervals of melt blending) tie rod after, pelletizing, obtains particulate state hybrid resin; Particulate state hybrid resin, after the drying treatment that dewaters, obtains biodegradable material.The screw slenderness ratio of the twin screw extruder of selecting is 40:1.
Biodegradable material obtained above is added in single screw rod inflation film manufacturing machine and carries out blown film machine-shaping, obtain Biodegradable film, the biological plastics that belongs to Wholly-degradable, can meet U.S. ASTMD6400 and the EN13432 of European Union degraded standard, single screw slenderness ratio of single screw rod inflation film manufacturing machine is 25:1.
Embodiment 11
Take the raw material of following weight part:
(weight percentage of moisture is 0.8% for dried 3-hydroxybutyrate and 4 hydroxybutyric acid multipolymer, Tianjin Green Biomaterial Co., Ltd., model is 2001 resins) 20 weight parts, (weight percentage of moisture is 0.8% to tetramethylene adipate and mutual-phenenyl two acid bromide two alcohol ester's multipolymer, the prosperous rich medicine company in Hangzhou, Biocosafe2003) 20 weight parts, glycerine 5 weight parts, Viscotrol C 14 weight parts, diphenylmethanediisocyanate (Yantai ten thousand China, MDI, WANNATE 100) 1 weight part.
First raw material is carried out in premixing machine to pre-mixing, the initial temperature of mixing is 40 ℃, and the rotating speed of premixing machine is that 800 ~ 1200 turn/min(are slowly improved to high speed by low speed, mixes 30 minutes), after fully mixing, obtain mixed material; By mixed material be added to melt blending in twin screw extruder (mixed material is 145 ℃ through excess temperature successively, 150 ℃, 155 ℃, 160 ℃, 175 ℃, 165 ℃, 160 ℃, 150 ℃ of each intervals of melt blending) tie rod after, pelletizing, obtains particulate state hybrid resin; Particulate state hybrid resin, after the drying treatment that dewaters, obtains biodegradable material.The screw slenderness ratio of the twin screw extruder of selecting is 40:1.
Biodegradable material obtained above is added in single screw rod inflation film manufacturing machine and carries out blown film machine-shaping, obtain Biodegradable film, the biological plastics that belongs to Wholly-degradable, can meet U.S. ASTMD6400 and the EN13432 of European Union degraded standard, single screw slenderness ratio of single screw rod inflation film manufacturing machine is 25:1.
Embodiment 12
Take the raw material of following weight part:
(weight percentage of moisture is 0.8% for dried 3-hydroxybutyrate and 4 hydroxybutyric acid multipolymer, Tianjin Green Biomaterial Co., Ltd., model is 2001 resins) 20 weight parts, (weight percentage of moisture is 0.8% to tetramethylene adipate and mutual-phenenyl two acid bromide two alcohol ester's multipolymer, the prosperous rich medicine company in Hangzhou, Biocosafe2003) 20 weight parts, glycerine 5 weight parts, Viscotrol C 14 weight parts, epoxidation silane coupling agent (KH-550, γ-aminopropyl triethoxysilane) 1 weight part.
First raw material is carried out in premixing machine to pre-mixing, the initial temperature of mixing is 40 ℃, and the rotating speed of premixing machine is that 800 ~ 1200 turn/min(are slowly improved to high speed by low speed, mixes 30 minutes), after fully mixing, obtain mixed material; By mixed material be added to melt blending in twin screw extruder (mixed material is 145 ℃ through excess temperature successively, 150 ℃, 155 ℃, 160 ℃, 175 ℃, 165 ℃, 160 ℃, 150 ℃ of each intervals of melt blending) tie rod after, pelletizing, obtains particulate state hybrid resin; Particulate state hybrid resin, after the drying treatment that dewaters, obtains biodegradable material.The screw slenderness ratio of the twin screw extruder of selecting is 40:1.
Biodegradable material obtained above is added in single screw rod inflation film manufacturing machine and carries out blown film machine-shaping, obtain Biodegradable film, the biological plastics that belongs to Wholly-degradable, can meet U.S. ASTMD6400 and the EN13432 of European Union degraded standard, single screw slenderness ratio of single screw rod inflation film manufacturing machine is 25:1.
Embodiment 13
Take the raw material of following weight part:
(weight percentage of moisture is 0.8% for dried 3-hydroxybutyrate and 4 hydroxybutyric acid multipolymer, Tianjin Green Biomaterial Co., Ltd., model is 2001 resins) 20 weight parts, (weight percentage of moisture is 0.8% to tetramethylene adipate and mutual-phenenyl two acid bromide two alcohol ester's multipolymer, the prosperous rich medicine company in Hangzhou, Biocosafe2003) 20 weight parts, polyoxyethylene glycol (Chinese traditional Chinese medicines, PEG 400) 5 weight parts, Viscotrol C 14 weight parts, epoxidation silane coupling agent (KH-550, γ-aminopropyl triethoxysilane) 1 weight part.
First raw material is carried out in premixing machine to pre-mixing, the initial temperature of mixing is 40 ℃, and the rotating speed of premixing machine is that 800 ~ 1200 turn/min(are slowly improved to high speed by low speed, mixes 30 minutes), after fully mixing, obtain mixed material; By mixed material be added to melt blending in twin screw extruder (mixed material is 145 ℃ through excess temperature successively, 150 ℃, 155 ℃, 160 ℃, 175 ℃, 165 ℃, 160 ℃, 150 ℃ of each intervals of melt blending) tie rod after, pelletizing, obtains particulate state hybrid resin; Particulate state hybrid resin, after the drying treatment that dewaters, obtains biodegradable material.The screw slenderness ratio of the twin screw extruder of selecting is 40:1.
Biodegradable material obtained above is added in single screw rod inflation film manufacturing machine and carries out blown film machine-shaping, obtain Biodegradable film, the biological plastics that belongs to Wholly-degradable, can meet U.S. ASTMD6400 and the EN13432 of European Union degraded standard, single screw slenderness ratio of single screw rod inflation film manufacturing machine is 25:1.
Embodiment 14
Take the raw material of following weight part:
(weight percentage of moisture is 0.8% for dried 3-hydroxybutyrate and 4 hydroxybutyric acid multipolymer 20 weight parts, Tianjin Green Biomaterial Co., Ltd., model is 2001 resins), (weight percentage of moisture is 0.8% to tetramethylene adipate and mutual-phenenyl two acid bromide two alcohol ester's multipolymer, the prosperous rich medicine company in Hangzhou, Biocosafe2003) 20 weight parts, polyoxyethylene glycol (Chinese traditional Chinese medicines, PEG 400) 5 weight parts, Viscotrol C 14 weight parts, diphenylmethanediisocyanate (WANNATE 100 for Yantai ten thousand China, MDI) 1 weight part.
First raw material is carried out in premixing machine to pre-mixing, the initial temperature of mixing is 40 ℃, and the rotating speed of premixing machine is that 800 ~ 1200 turn/min(are slowly improved to high speed by low speed, mixes 30 minutes), after fully mixing, obtain mixed material; By mixed material be added to melt blending in twin screw extruder (mixed material is 145 ℃ through excess temperature successively, 150 ℃, 155 ℃, 160 ℃, 175 ℃, 165 ℃, 160 ℃, 150 ℃ of each intervals of melt blending) tie rod after, pelletizing, obtains particulate state hybrid resin; Particulate state hybrid resin, after the drying treatment that dewaters, obtains biodegradable material.The screw slenderness ratio of the twin screw extruder of selecting is 40:1.
Biodegradable material obtained above is added in single screw rod inflation film manufacturing machine and carries out blown film machine-shaping, obtain Biodegradable film, the biological plastics that belongs to Wholly-degradable, can meet U.S. ASTMD6400 and the EN13432 of European Union degraded standard, single screw slenderness ratio of single screw rod inflation film manufacturing machine is 25:1.
The Biodegradable film of embodiment 1 ~ 10 and embodiment 11 ~ 14 preparations is carried out to the test of elongation at break and tensile strength according to GB1040-79, its test result as shown in Table 1 and Table 2.
Table 1
| Embodiment | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 |
| Elongation at break (%) | 241 | 258 | 248 | 257 | 233 | 230 | 290 | 297 | 283 | 291 |
| Tensile strength (MPa) | 33 | 34 | 30 | 29 | 29 | 32 | 26 | 27 | 28 | 25 |
Table 2
| Embodiment | 11 | 12 | 13 | 14 |
| Elongation at break (%) | 550 | 545 | 530 | 530 |
| Tensile strength (MPa) | 23.5 | 24 | 23 | 23 |
From embodiment 1 ~ 6 test data, the biodegradable material of embodiment 1 ~ 6 preparation is used in to be produced in Biodegradable film, and the Biodegradable film of production embodies excellent tensile strength and good elongation at break, is very suitable for the fields such as plastic shopping bag.The biodegradable material of embodiment 11 ~ 14 preparation is used in to be produced in Biodegradable film, and the Biodegradable film of production embodies excellent elongation at break and good tensile strength, is suitable for to the elongation at break field that has higher requirements, as preservative film.Embodiment 7 ~ 10, between between the two above-mentioned, is suitable for elongation at break and tensile strength there are certain requirements but require not high field, can select as the case may be.
Claims (6)
1. a biodegradable material, is characterized in that, the component of following weight percent, consists of:
Described crude vegetal is one or more in rapeseed oil, Viscotrol C, soya-bean oil, peanut oil, Oleum Cocois, plam oil, oleum lini, Oleum Gossypii semen, Semen Maydis oil, sunflower seed oil, pine-seed oil, tung oil;
Described reaction promotor is one or both in coupling agent, catalyzer, what described coupling agent was γ-aminopropyl triethoxysilane, diphenylmethanediisocyanate, poly-methyl in phenylisocyanate is a kind of or two or more, and described catalyzer is a kind of or two or more in citric acid, hexanodioic acid, succinic acid.
2. biodegradable material according to claim 1, is characterized in that, the component of following weight percent, consists of:
Described crude vegetal is one or more in rapeseed oil, Viscotrol C, soya-bean oil, peanut oil, Oleum Cocois, plam oil, oleum lini, Oleum Gossypii semen, Semen Maydis oil, sunflower seed oil, pine-seed oil, tung oil;
Described reaction promotor is one or both in coupling agent, catalyzer, what described coupling agent was γ-aminopropyl triethoxysilane, diphenylmethanediisocyanate, poly-methyl in phenylisocyanate is a kind of or two or more, and described catalyzer is a kind of or two or more in citric acid, hexanodioic acid, succinic acid.
3. according to the biodegradable material described in claim 1～2 any one, it is characterized in that, described softening agent is one or more in sorbyl alcohol, polyoxyethylene glycol, acetylize citric acid, glycerine.
4. according to the preparation method of the biodegradable material described in claim 1～3 any one, comprise the following steps:
The poly(lactic acid) that 3-hydroxybutyrate and 4 hydroxybutyric acid multipolymer, tetramethylene adipate and mutual-phenenyl two acid bromide two alcohol ester's multipolymer, crude vegetal, softening agent, reaction promotor and selectivity are added mixes, and obtains mixed material; Mixed material is added to tie rod, pelletizing after melt blending in twin screw extruder, obtains particulate state hybrid resin; Particulate state hybrid resin drying obtains biodegradable material after processing.
5. the preparation method of biodegradable material according to claim 4, is characterized in that, the screw slenderness ratio of described twin screw extruder is 35～45:1, and the temperature of melt blending is 140 ℃～175 ℃.
6. the application in preparing Biodegradable film according to the biodegradable material described in claim 1～3 any one.
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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 |
| CN111205602A (en) * | 2018-11-22 | 2020-05-29 | 中国石油化工股份有限公司 | Modified polyhydroxyalkanoate material and film for biodegradable mulching film, and preparation method and application thereof |
| CN111205604B (en) * | 2018-11-22 | 2023-01-24 | 中国石油化工股份有限公司 | Ultrathin high-strength high-toughness biodegradable mulch film material, film, preparation method and application |
| CN112341767A (en) * | 2020-11-02 | 2021-02-09 | 兰州鑫银环橡塑制品有限公司 | Full-biodegradable mulching film for flue-cured tobacco planting and preparation method thereof |
| CN115368715B (en) * | 2022-09-22 | 2024-04-09 | 广州碧嘉材料科技有限公司 | Completely biodegradable self-adhesive film material and preparation method thereof |
| CN115926400B (en) * | 2023-01-03 | 2024-05-24 | 深圳市鼎力盛科技有限公司 | Environment-friendly calabash film, preparation method and application thereof |
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