CN102850743A - Biodegradable material, and preparation method and application thereof - Google Patents
Biodegradable material, and preparation method and application thereof Download PDFInfo
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- CN102850743A CN102850743A CN2012103788614A CN201210378861A CN102850743A CN 102850743 A CN102850743 A CN 102850743A CN 2012103788614 A CN2012103788614 A CN 2012103788614A CN 201210378861 A CN201210378861 A CN 201210378861A CN 102850743 A CN102850743 A CN 102850743A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0016—Plasticisers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0033—Additives activating the degradation of the macromolecular compound
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/101—Esters; Ether-esters of monocarboxylic acids
- C08K5/103—Esters; Ether-esters of monocarboxylic acids with polyalcohols
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
Abstract
The invention provides a biodegradable material which is prepared from the following raw materials in percentage by weight: 10-35% of 3-hydroxybutanoic acid-4-hydroxybutanoic acid copolymer, 10-35% of poly(butylene succinate), 0-50% of polylactic acid, 5-25% of vegetable oil, 1-10% of plasticizer and 0.02-5% of reaction promoter. The invention also provides a preparation method of the biodegradable material and application of the biodegradable material in preparation of a biodegradable film. The biodegradable material, which is a degradable biological material, has the advantages of excellent elongation at break, high tensile strength, favorable transparency and excellent comprehensive properties. The preparation method provided by the invention has the advantages of simple technique, strong operability and low production cost, and is easy to control; and the biodegradable material can be prepared into a biodegradable film after being subjected to simple processing, and thus, the invention can easily implement industrial production and has favorable economic benefit and wide application prospects.
Description
Technical field
The present invention relates to the composition of macromolecular compound, be specifically related to a kind of biodegradable material, and the preparation method and application of this biodegradable material.
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.Because the extensive application of plastics, the waste plastic goods grow with each passing day, and therefore the most stable performance of plastics so-called white pollution occurred, has brought very large harm to environment.In recent years, people have taked positive measure to the improvement of waste plastic, and for example, the minimizing of Plastic Packaging Materials is repeatedly used, and recycling etc.Yet, for those be difficult for to reclaim, recovery value is little or recycle and be difficult to economically the goods that move, such as shopping bag, disposable tableware, agricultural mulching, medical plastic ware etc., it is more favourable to adopt degradative plastics to make.
But degradative plastics be evening the material that grows up, also be in a growth, perfect stage at present.Although existing degradative plastics has biodegradability, is conducive to environment protection, mostly can not keep the good transparency, and/or mechanical property is not good, the goods of made particularly film based article are damaged easily.
Summary of the invention
Technical problem to be solved by this invention provides a kind of biodegradable material, and the preparation method and application of this biodegradable material, this biodegradable material not only has biological degradability, and has excellent mechanical property, and keeps the preferably transparency.The technical scheme that adopts is as follows:
A kind of biodegradable material is characterized in that being made by the raw material of following weight per-cent:
3-hydroxybutyrate and 4 hydroxybutyric acid copolymer 10 ~ 35%;
Poly butylene succinate 10 ~ 35%;
Poly(lactic acid) 0 ~ 50%;
Vegetables oil 5 ~ 25%;
Softening agent 1 ~ 10%;
Reaction promotor 0.02 ~ 5%.
Above-mentioned 3-hydroxybutyrate and 4 hydroxybutyric acid multipolymer, poly butylene succinate, vegetables oil, softening agent and reaction promotor are combined, and embody good elongation at break and good tensile strength, whole mechanics better performances.
Preferred above-mentioned biodegradable material is made by the raw material of following weight per-cent:
3-hydroxybutyrate and 4 hydroxybutyric acid copolymer 15 ~ 22%;
Poly butylene succinate 15 ~ 22%;
Poly(lactic acid) 25 ~ 50%;
Vegetables oil 14 ~ 25%;
Softening agent 5 ~ 10%;
Reaction promotor 1 ~ 5%.
The 3-hydroxybutyrate of above-mentioned weight proportion and 4 hydroxybutyric acid multipolymer, poly butylene succinate, poly(lactic acid), vegetables oil, softening agent and reaction promotor are combined, and embody good elongation at break and excellent tensile strength, excellent combination property.
Further preferred above-mentioned biodegradable material is made by the raw material of following weight per-cent:
3-hydroxybutyrate and 4 hydroxybutyric acid copolymer 15 ~ 19%;
Poly butylene succinate 15 ~ 19%;
Poly(lactic acid) 37 ~ 50%;
Vegetables oil 14 ~ 18%;
Softening agent 5 ~ 7%;
Reaction promotor 1 ~ 2%.
The 3-hydroxybutyrate of above-mentioned weight proportion and 4 hydroxybutyric acid multipolymer, poly butylene succinate, poly(lactic acid), vegetables oil, softening agent and reaction promotor are combined, have good elongation at break and very excellent tensile strength, be very suitable for making the goods such as plastic shopping bag.
Above-mentioned 3-hydroxybutyrate and 4 hydroxybutyric acid multipolymer, poly butylene succinate can improve the elongation at break of biodegradable material of the present invention.
Above-mentioned poly(lactic acid) can adopt L-type poly(lactic acid), D type poly(lactic acid) or LD mixed type poly(lactic acid).Poly(lactic acid) can improve the intensity of biodegradable material of the present invention.
Preferred above-mentioned vegetables oil is a kind of in rapeseed oil, Viscotrol C, soybean oil, peanut oil, Oleum Cocois, plam oil, oleum lini, Oleum Gossypii semen, Semen Maydis oil, sunflower seed oil, pine-seed oil and the tung oil or wherein multiple combination.Add vegetables oil, by the interaction of the active function groups in the reaction active groups in the vegetables oil and the matrix resin (being 3-hydroxybutyrate and 4 hydroxybutyric acid multipolymer and poly butylene succinate), to reach the increase-volume purpose.
Above-mentioned softening agent is a kind of in sorbyl alcohol, polyoxyethylene glycol, acetylize citric acid and the glycerine or wherein multiple combination.Add softening agent, can improve the travelling performance of polymer chain, the plastic effect of biodegradable material is improved, reduce the fragility of biodegradable material, improve the flexibility of biodegradable material.
Preferred above-mentioned reaction promotor is a kind of in coupling agent and the catalyzer or both combinations.
Preferred above-mentioned coupling agent is a kind of in silane compound and the isocyanate compound or both combinations.As preferably, above-mentioned coupling agent is γ-aminopropyl triethoxysilane (KH-550), diphenylmethanediisocyanate (MDI) and poly-methyl to a kind of in the phenylisocyanate (being called for short PMDI) or wherein multiple combination.
Preferred above-mentioned catalyzer is a kind of in organic acid and the inorganic proton acid or both combinations.As preferably, above-mentioned catalyzer is a kind of in citric acid, hexanodioic acid, Succinic Acid and the hydrochloric acid or wherein multiple combination.
Above-mentioned 3-hydroxybutyrate and 4 hydroxybutyric acid multipolymer, poly butylene succinate, poly(lactic acid), vegetables oil, softening agent, reaction promotor (comprising coupling agent, catalyzer) all can buy in market, and wherein 3-hydroxybutyrate and 4 hydroxybutyric acid multipolymer can be chosen P (3HB-co-4HB) copolyesters that Tianjin Green Biomaterial Co., Ltd. produces.
The present invention also provides a kind of preparation method of above-mentioned biodegradable material, it is characterized in that comprising the steps: 3-hydroxybutyrate and 4 hydroxybutyric acid multipolymer, poly butylene succinate, poly(lactic acid), vegetables oil, softening agent and reaction promotor are mixed, obtain mixture; Then mixture is joined melt blending in the twin screw extruder, form the material melt; The material melt carries out tie rod, pelletizing after the die head of twin screw extruder is extruded, obtain material particles; The material particles drying obtains biodegradable material after processing.The screw slenderness ratio of preferred twin screw extruder is 35 ~ 45:1, and the temperature of melt blending is 140 ~ 175 ℃.Above-mentioned tie rod, pelletizing belong to existing conventional agglomeration technique means.Need to carry out first drying treatment as above-mentioned 3-hydroxybutyrate and 4 hydroxybutyric acid multipolymer and poly butylene succinate use are last.
The application of above-mentioned biodegradable material in the preparation Biodegradable film through single screw rod inflation film manufacturing machine blown film, obtains Biodegradable film with described biodegradable material.The screw slenderness ratio of above-mentioned single screw rod inflation film manufacturing machine is 25 ~ 35:1.Because above-mentioned biodegradable material has excellent elongation at break and tensile strength, and keep the preferably transparency, thereby be particularly suitable for making Biodegradable film.
The present invention compared with prior art has following beneficial effect:
In the biodegradable material of the present invention, main ingredient 3-hydroxybutyrate and 4 hydroxybutyric acid multipolymer, poly butylene succinate, vegetables oil and poly(lactic acid) all can be decomposed by microorganism under given conditions, belong to the Wholly-degradable biomaterial.In addition, 3-hydroxybutyrate and 4 hydroxybutyric acid multipolymer, poly butylene succinate, poly(lactic acid), softening agent and reaction promotor are combined, can interact, has certain synergy, so that biodegradable material of the present invention embodies excellent elongation at break and tensile strength, and kept the preferably transparency, excellent combination property.
Preparation method's technique of biodegradable material of the present invention is simple, is easy to control, and is workable, low production cost; And biodegradable material again after simple processing, just can be obtained Biodegradable film, be easy to suitability for industrialized production and have good economic benefit, have broad application prospects.
Biodegradable material of the present invention is highly suitable for preparing Biodegradable film, and the Biodegradable film of making has very high intensity; The shopping bag that this Biodegradable film is made is Reusability repeatedly, and still can be used as the refuse bag use after repeatedly using, and is decomposed quick absorption fully by the microorganism in the soil after discarding, and environmental pollution is little, has good environmental benefit.
Embodiment
Embodiment 1
At first, take by weighing the raw material of following weight part: 3-hydroxybutyrate and 4 hydroxybutyric acid copolymer 18 weight parts, poly butylene succinate 17 weight parts, poly(lactic acid) 42 weight parts, vegetables oil 16 weight parts (being Viscotrol C), softening agent 6 weight parts (being polyoxyethylene glycol), reaction promotor 1 weight part (being diphenylmethanediisocyanate).Above-mentioned 3-hydroxybutyrate and 4 hydroxybutyric acid multipolymer and poly butylene succinate carry out first drying treatment before using.
Then, prepare according to the following steps full-biodegradable material: above-mentioned all raw materials are mixed (all raw materials can be carried out pre-mixing in premixing machine, the initial temperature of mixing is 40 ℃, the rotating speed of premixing machine is 800 ~ 1200 rev/mins, mixed 30 minutes, the mixing process medium speed can improve gradually), obtain mixture; Then mixture is joined melt blending in the twin screw extruder (mixture is respectively each melt blending interval of 145 ℃, 150 ℃, 155 ℃, 160 ℃, 175 ℃, 165 ℃, 160 ℃, 150 ℃ successively through excess temperature), form the material melt; The material melt carries out tie rod, pelletizing after the die head of twin screw extruder is extruded, obtain material particles; The material particles drying obtains biodegradable material after processing.The screw slenderness ratio of twin screw extruder is 40:1.Above-mentioned tie rod, pelletizing belong to existing conventional agglomeration technique means, are not described in more detail at this.
Above-mentioned biodegradable material can meet U.S. ASTMD6400 and the EN13432 of European Union degraded standard.
Above-mentioned biodegradable material through single screw rod inflation film manufacturing machine blown film, is obtained Biodegradable film.The screw slenderness ratio of single screw rod inflation film manufacturing machine is 25:1.
Embodiment 2
At first, take by weighing the raw material of following weight part: 3-hydroxybutyrate and 4 hydroxybutyric acid copolymer 15 weight parts, poly butylene succinate 15 weight parts, poly(lactic acid) 50 weight parts, vegetables oil 14 weight parts (being Viscotrol C), softening agent 5 weight parts (being polyoxyethylene glycol), reaction promotor 1 weight part (being γ-aminopropyl triethoxysilane).Above-mentioned 3-hydroxybutyrate and 4 hydroxybutyric acid multipolymer and poly butylene succinate carry out first drying treatment before using.
Then, prepare according to the following steps full-biodegradable material: above-mentioned all raw materials are mixed (all raw materials can be carried out pre-mixing in premixing machine, the initial temperature of mixing is 40 ℃, the rotating speed of premixing machine is 800 ~ 1200 rev/mins, mixed 30 minutes, the mixing process medium speed can improve gradually), obtain mixture; Then mixture is joined melt blending in the twin screw extruder (mixture is respectively each melt blending interval of 145 ℃, 150 ℃, 155 ℃, 160 ℃, 175 ℃, 165 ℃, 160 ℃, 150 ℃ successively through excess temperature), form the material melt; The material melt carries out tie rod, pelletizing after the die head of twin screw extruder is extruded, obtain material particles; The material particles drying obtains biodegradable material after processing.The screw slenderness ratio of twin screw extruder is 40:1.
Above-mentioned biodegradable material can meet U.S. ASTMD6400 and the EN13432 of European Union degraded standard.
Above-mentioned biodegradable material through single screw rod inflation film manufacturing machine blown film, is obtained Biodegradable film.The screw slenderness ratio of single screw rod inflation film manufacturing machine is 25:1.
Embodiment 3
At first, take by weighing the raw material of following weight part: 3-hydroxybutyrate and 4 hydroxybutyric acid copolymer 19 weight parts, poly butylene succinate 18 weight parts, poly(lactic acid) 37 weight parts, vegetables oil 17 weight parts (being rapeseed oil), softening agent 7 weight parts (being glycerine), reaction promotor 2 weight parts (being diphenylmethanediisocyanate).Above-mentioned 3-hydroxybutyrate and 4 hydroxybutyric acid multipolymer and poly butylene succinate carry out first drying treatment before using.
Then, prepare according to the following steps full-biodegradable material: above-mentioned all raw materials are mixed (all raw materials can be carried out pre-mixing in premixing machine, the initial temperature of mixing is 40 ℃, the rotating speed of premixing machine is 800 ~ 1200 rev/mins, mixed 30 minutes, the mixing process medium speed can improve gradually), obtain mixture; Then mixture is joined melt blending in the twin screw extruder (mixture is respectively each melt blending interval of 145 ℃, 150 ℃, 155 ℃, 160 ℃, 175 ℃, 165 ℃, 160 ℃, 150 ℃ successively through excess temperature), form the material melt; The material melt carries out tie rod, pelletizing after the die head of twin screw extruder is extruded, obtain material particles; The material particles drying obtains biodegradable material after processing.The screw slenderness ratio of twin screw extruder is 45:1.
Above-mentioned biodegradable material can meet U.S. ASTMD6400 and the EN13432 of European Union degraded standard.
Above-mentioned biodegradable material through single screw rod inflation film manufacturing machine blown film, is obtained Biodegradable film.The screw slenderness ratio of single screw rod inflation film manufacturing machine is 35:1.
Embodiment 4
At first; take by weighing the raw material of following weight part: 3-hydroxybutyrate and 4 hydroxybutyric acid copolymer 10 weight part; poly butylene succinate 35 weight parts; poly(lactic acid) 35 weight parts; vegetables oil 10 weight parts (wherein Oleum Cocois 5 weight parts, plam oil 5 weight parts); softening agent 7 weight parts (wherein acetylize citric acid 4 weight parts, glycerine 3 weight parts), reaction promotor 3 weight parts (wherein γ-aminopropyl triethoxysilane 1 weight part, hexanodioic acid 2 weight parts).Above-mentioned 3-hydroxybutyrate and 4 hydroxybutyric acid multipolymer and poly butylene succinate carry out first drying treatment before using.
Then, prepare according to the following steps full-biodegradable material: above-mentioned all raw materials are mixed (all raw materials can be carried out pre-mixing in premixing machine, the initial temperature of mixing is 40 ℃, the rotating speed of premixing machine is 800 ~ 1200 rev/mins, mixed 30 minutes, the mixing process medium speed can improve gradually), obtain mixture; Then mixture is joined melt blending in the twin screw extruder (mixture is respectively each melt blending interval of 145 ℃, 150 ℃, 155 ℃, 160 ℃, 175 ℃, 165 ℃, 160 ℃, 150 ℃ successively through excess temperature), form the material melt; The material melt carries out tie rod, pelletizing after the die head of twin screw extruder is extruded, obtain material particles; The material particles drying obtains biodegradable material after processing.The screw slenderness ratio of twin screw extruder is 35:1.
Above-mentioned biodegradable material can meet U.S. ASTMD6400 and the EN13432 of European Union degraded standard.
Above-mentioned biodegradable material through single screw rod inflation film manufacturing machine blown film, is obtained Biodegradable film.The screw slenderness ratio of single screw rod inflation film manufacturing machine is 30:1.
Embodiment 5
At first, take by weighing the raw material of following weight part: 3-hydroxybutyrate and 4 hydroxybutyric acid multipolymer 30 weight parts, poly butylene succinate 10 weight parts, poly(lactic acid) 30 weight parts, vegetables oil 15 weight parts (being pine-seed oil), softening agent 10 weight parts (wherein sorbyl alcohol 6 weight parts, polyoxyethylene glycol 4 weight parts), reaction promotor 5 weight parts (being citric acid).Above-mentioned 3-hydroxybutyrate and 4 hydroxybutyric acid multipolymer and poly butylene succinate carry out first drying treatment before using.
Then, prepare according to the following steps full-biodegradable material: above-mentioned all raw materials are mixed (all raw materials can be carried out pre-mixing in premixing machine, the initial temperature of mixing is 40 ℃, the rotating speed of premixing machine is 800 ~ 1200 rev/mins, mixed 30 minutes, the mixing process medium speed can improve gradually), obtain mixture; Then mixture is joined melt blending in the twin screw extruder (mixture is respectively each melt blending interval of 145 ℃, 150 ℃, 155 ℃, 160 ℃, 175 ℃, 165 ℃, 160 ℃, 150 ℃ successively through excess temperature), form the material melt; The material melt carries out tie rod, pelletizing after the die head of twin screw extruder is extruded, obtain material particles; The material particles drying obtains biodegradable material after processing.The screw slenderness ratio of twin screw extruder is 40:1.
Above-mentioned biodegradable material can meet U.S. ASTMD6400 and the EN13432 of European Union degraded standard.
Above-mentioned biodegradable material through single screw rod inflation film manufacturing machine blown film, is obtained Biodegradable film.The screw slenderness ratio of single screw rod inflation film manufacturing machine is 30:1.
Embodiment 6
At first; take by weighing the raw material of following weight part: 3-hydroxybutyrate and 4 hydroxybutyric acid multipolymer 20 weight parts; poly butylene succinate 20 weight parts; poly(lactic acid) 45 weight parts; vegetables oil 5 weight parts (being sunflower seed oil); softening agent 5 weight parts (being the acetylize citric acid), reaction promotor 5 weight parts (being poly-methyl to phenylisocyanate).Above-mentioned 3-hydroxybutyrate and 4 hydroxybutyric acid multipolymer and poly butylene succinate carry out first drying treatment before using.
Then, prepare according to the following steps full-biodegradable material: above-mentioned all raw materials are mixed (all raw materials can be carried out pre-mixing in premixing machine, the initial temperature of mixing is 40 ℃, the rotating speed of premixing machine is 800 ~ 1200 rev/mins, mixed 30 minutes, the mixing process medium speed can improve gradually), obtain mixture; Then mixture is joined melt blending in the twin screw extruder (mixture is respectively each melt blending interval of 145 ℃, 150 ℃, 155 ℃, 160 ℃, 175 ℃, 165 ℃, 160 ℃, 150 ℃ successively through excess temperature), form the material melt; The material melt carries out tie rod, pelletizing after the die head of twin screw extruder is extruded, obtain material particles; The material particles drying obtains biodegradable material after processing.The screw slenderness ratio of twin screw extruder is 40:1.
Above-mentioned biodegradable material can meet U.S. ASTMD6400 and the EN13432 of European Union degraded standard.
Above-mentioned biodegradable material through single screw rod inflation film manufacturing machine blown film, is obtained Biodegradable film.The screw slenderness ratio of single screw rod inflation film manufacturing machine is 25:1.
Embodiment 7
At first, take by weighing the raw material of following weight part: 3-hydroxybutyrate and 4 hydroxybutyric acid multipolymer 30 weight parts, poly butylene succinate 25 weight parts, poly(lactic acid) 20 weight parts, vegetables oil 15 weight parts (being Viscotrol C), softening agent 8 weight parts (being glycerine), reaction promotor 2 weight parts (being diphenylmethanediisocyanate).Above-mentioned 3-hydroxybutyrate and 4 hydroxybutyric acid multipolymer and poly butylene succinate carry out first drying treatment before using.
Then, prepare according to the following steps full-biodegradable material: above-mentioned all raw materials are mixed (all raw materials can be carried out pre-mixing in premixing machine, the initial temperature of mixing is 40 ℃, the rotating speed of premixing machine is 800 ~ 1200 rev/mins, mixed 30 minutes, the mixing process medium speed can improve gradually), obtain mixture; Then mixture is joined melt blending in the twin screw extruder (mixture is respectively each melt blending interval of 145 ℃, 150 ℃, 155 ℃, 160 ℃, 175 ℃, 165 ℃, 160 ℃, 150 ℃ successively through excess temperature), form the material melt; The material melt carries out tie rod, pelletizing after the die head of twin screw extruder is extruded, obtain material particles; The material particles drying obtains biodegradable material after processing.The screw slenderness ratio of twin screw extruder is 40:1.
Above-mentioned biodegradable material can meet U.S. ASTMD6400 and the EN13432 of European Union degraded standard.
Above-mentioned biodegradable material through single screw rod inflation film manufacturing machine blown film, is obtained Biodegradable film.The screw slenderness ratio of single screw rod inflation film manufacturing machine is 25:1.
Embodiment 8
At first, take by weighing the raw material of following weight part: 3-hydroxybutyrate and 4 hydroxybutyric acid multipolymer 30 weight parts, poly butylene succinate 20 weight parts, poly(lactic acid) 25 weight parts, vegetables oil 18 weight parts (wherein oleum lini 10 weight parts, Oleum Gossypii semen 8 weight parts), softening agent 5 weight parts (being polyoxyethylene glycol), reaction promotor 2 weight parts (being diphenylmethanediisocyanate).Above-mentioned 3-hydroxybutyrate and 4 hydroxybutyric acid multipolymer and poly butylene succinate carry out first drying treatment before using.
Then, prepare according to the following steps full-biodegradable material: above-mentioned all raw materials are mixed (all raw materials can be carried out pre-mixing in premixing machine, the initial temperature of mixing is 40 ℃, the rotating speed of premixing machine is 800 ~ 1200 rev/mins, mixed 30 minutes, the mixing process medium speed can improve gradually), obtain mixture; Then mixture is joined melt blending in the twin screw extruder (mixture is respectively each melt blending interval of 145 ℃, 150 ℃, 155 ℃, 160 ℃, 175 ℃, 165 ℃, 160 ℃, 150 ℃ successively through excess temperature), form the material melt; The material melt carries out tie rod, pelletizing after the die head of twin screw extruder is extruded, obtain material particles; The material particles drying obtains biodegradable material after processing.The screw slenderness ratio of twin screw extruder is 40:1.
Above-mentioned biodegradable material can meet U.S. ASTMD6400 and the EN13432 of European Union degraded standard.
Above-mentioned biodegradable material through single screw rod inflation film manufacturing machine blown film, is obtained Biodegradable film.The screw slenderness ratio of single screw rod inflation film manufacturing machine is 25:1.
Embodiment 9
At first; take by weighing the raw material of following weight part: 3-hydroxybutyrate and 4 hydroxybutyric acid multipolymer 27 weight parts; poly butylene succinate 30 weight parts; poly(lactic acid) 15 weight parts; vegetables oil 15 weight parts (being tung oil); softening agent 10 weight parts (being the acetylize citric acid), reaction promotor 3 weight parts (wherein γ-aminopropyl triethoxysilane 2 weight parts, Succinic Acid 1 weight part).Above-mentioned 3-hydroxybutyrate and 4 hydroxybutyric acid multipolymer and poly butylene succinate carry out first drying treatment before using.
Then, prepare according to the following steps full-biodegradable material: above-mentioned all raw materials are mixed (all raw materials can be carried out pre-mixing in premixing machine, the initial temperature of mixing is 40 ℃, the rotating speed of premixing machine is 800 ~ 1200 rev/mins, mixed 30 minutes, the mixing process medium speed can improve gradually), obtain mixture; Then mixture is joined melt blending in the twin screw extruder (mixture is respectively each melt blending interval of 145 ℃, 150 ℃, 155 ℃, 160 ℃, 175 ℃, 165 ℃, 160 ℃, 150 ℃ successively through excess temperature), form the material melt; The material melt carries out tie rod, pelletizing after the die head of twin screw extruder is extruded, obtain material particles; The material particles drying obtains biodegradable material after processing.The screw slenderness ratio of twin screw extruder is 45:1.
Above-mentioned biodegradable material can meet U.S. ASTMD6400 and the EN13432 of European Union degraded standard.
Above-mentioned biodegradable material through single screw rod inflation film manufacturing machine blown film, is obtained Biodegradable film.The screw slenderness ratio of single screw rod inflation film manufacturing machine is 35:1.
Embodiment 10
At first, take by weighing the raw material of following weight part: 3-hydroxybutyrate and 4 hydroxybutyric acid multipolymer 35 weight parts, poly butylene succinate 35 weight parts, poly(lactic acid) 10 weight parts, vegetables oil 11 weight parts (being Semen Maydis oil), softening agent 8 weight parts (being glycerine), reaction promotor 1 weight part (being hexanodioic acid).Above-mentioned 3-hydroxybutyrate and 4 hydroxybutyric acid multipolymer and poly butylene succinate carry out first drying treatment before using.
Then, prepare according to the following steps full-biodegradable material: above-mentioned all raw materials are mixed (all raw materials can be carried out pre-mixing in premixing machine, the initial temperature of mixing is 40 ℃, the rotating speed of premixing machine is 800 ~ 1200 rev/mins, mixed 30 minutes, the mixing process medium speed can improve gradually), obtain mixture; Then mixture is joined melt blending in the twin screw extruder (mixture is respectively each melt blending interval of 145 ℃, 150 ℃, 155 ℃, 160 ℃, 175 ℃, 165 ℃, 160 ℃, 150 ℃ successively through excess temperature), form the material melt; The material melt carries out tie rod, pelletizing after the die head of twin screw extruder is extruded, obtain material particles; The material particles drying obtains biodegradable material after processing.The screw slenderness ratio of twin screw extruder is 35:1.
Above-mentioned biodegradable material can meet U.S. ASTMD6400 and the EN13432 of European Union degraded standard.
Above-mentioned biodegradable material through single screw rod inflation film manufacturing machine blown film, is obtained Biodegradable film.The screw slenderness ratio of single screw rod inflation film manufacturing machine is 30:1.
Embodiment 11
At first, take by weighing the raw material of following weight part: 3-hydroxybutyrate and 4 hydroxybutyric acid multipolymer 35 weight parts, poly butylene succinate 35 weight parts, vegetables oil 20 weight parts (being Viscotrol C), softening agent 5 weight parts (being glycerine), reaction promotor 5 weight parts (being diphenylmethanediisocyanate).Above-mentioned 3-hydroxybutyrate and 4 hydroxybutyric acid multipolymer and poly butylene succinate carry out first drying treatment before using.
Then, prepare according to the following steps full-biodegradable material: above-mentioned all raw materials are mixed, obtain mixture and (all raw materials can be carried out pre-mixing in premixing machine, the initial temperature of mixing is 40 ℃, the rotating speed of premixing machine is 800 ~ 1200 rev/mins, mixed 30 minutes, the mixing process medium speed can improve gradually); Then mixture is joined melt blending in the twin screw extruder (mixture is respectively each melt blending interval of 145 ℃, 150 ℃, 155 ℃, 160 ℃, 175 ℃, 165 ℃, 160 ℃, 150 ℃ successively through excess temperature), form the material melt; The material melt carries out tie rod, pelletizing after the die head of twin screw extruder is extruded, obtain material particles; The material particles drying obtains biodegradable material after processing.The screw slenderness ratio of twin screw extruder is 40:1.
Above-mentioned biodegradable material can meet U.S. ASTMD6400 and the EN13432 of European Union degraded standard.
Above-mentioned biodegradable material through single screw rod inflation film manufacturing machine blown film, is obtained Biodegradable film.The screw slenderness ratio of single screw rod inflation film manufacturing machine is 25:1.
Embodiment 12
At first, take by weighing the raw material of following weight part: 3-hydroxybutyrate and 4 hydroxybutyric acid multipolymer 35 weight parts, poly butylene succinate 29.98 weight parts, vegetables oil 25 weight parts (wherein pine-seed oil 15 weight parts, tung oil 10 weight parts), softening agent 10 weight parts (wherein sorbyl alcohol 6 weight parts, polyoxyethylene glycol 4 weight parts), reaction promotor 0.02 weight part (being γ-aminopropyl triethoxysilane).Above-mentioned 3-hydroxybutyrate and 4 hydroxybutyric acid multipolymer and poly butylene succinate carry out first drying treatment before using.
Then, prepare according to the following steps full-biodegradable material: above-mentioned all raw materials are mixed (all raw materials can be carried out pre-mixing in premixing machine, the initial temperature of mixing is 40 ℃, the rotating speed of premixing machine is 800 ~ 1200 rev/mins, mixed 30 minutes, the mixing process medium speed can improve gradually), obtain mixture; Then mixture is joined melt blending in the twin screw extruder (mixture is respectively each melt blending interval of 145 ℃, 150 ℃, 155 ℃, 160 ℃, 175 ℃, 165 ℃, 160 ℃, 150 ℃ successively through excess temperature), form the material melt; The material melt carries out tie rod, pelletizing after the die head of twin screw extruder is extruded, obtain material particles; The material particles drying obtains biodegradable material after processing.The screw slenderness ratio of twin screw extruder is 45:1.
Above-mentioned biodegradable material can meet U.S. ASTMD6400 and the EN13432 of European Union degraded standard.
Above-mentioned biodegradable material through single screw rod inflation film manufacturing machine blown film, is obtained Biodegradable film.The screw slenderness ratio of single screw rod inflation film manufacturing machine is 30:1.
Embodiment 13
At first, take by weighing the raw material of following weight part: 3-hydroxybutyrate and 4 hydroxybutyric acid multipolymer 35 weight parts, poly butylene succinate 35 weight parts, vegetables oil 25 weight parts (being soybean oil), softening agent 1 weight part (being polyoxyethylene glycol), reaction promotor 4 weight parts (wherein diphenylmethanediisocyanate 3 weight parts, Succinic Acid 1 weight part).Above-mentioned 3-hydroxybutyrate and 4 hydroxybutyric acid multipolymer and poly butylene succinate carry out first drying treatment before using.
Then, prepare according to the following steps full-biodegradable material: above-mentioned all raw materials are mixed (all raw materials can be carried out pre-mixing in premixing machine, the initial temperature of mixing is 40 ℃, the rotating speed of premixing machine is 800 ~ 1200 rev/mins, mixed 30 minutes, the mixing process medium speed can improve gradually), obtain mixture; Then mixture is joined melt blending in the twin screw extruder (mixture is respectively each melt blending interval of 145 ℃, 150 ℃, 155 ℃, 160 ℃, 175 ℃, 165 ℃, 160 ℃, 150 ℃ successively through excess temperature), form the material melt; The material melt carries out tie rod, pelletizing after the die head of twin screw extruder is extruded, obtain material particles; The material particles drying obtains biodegradable material after processing.The screw slenderness ratio of twin screw extruder is 40:1.
Above-mentioned biodegradable material can meet U.S. ASTMD6400 and the EN13432 of European Union degraded standard.
Above-mentioned biodegradable material through single screw rod inflation film manufacturing machine blown film, is obtained Biodegradable film.The screw slenderness ratio of single screw rod inflation film manufacturing machine is 35:1.
Embodiment 14
At first, take by weighing the raw material of following weight part: 3-hydroxybutyrate and 4 hydroxybutyric acid multipolymer 30 weight parts, poly butylene succinate 30 weight parts, vegetables oil 25 weight parts (being peanut oil), softening agent 10 weight parts (being polyoxyethylene glycol), reaction promotor 5 weight parts (being hydrochloric acid).Above-mentioned 3-hydroxybutyrate and 4 hydroxybutyric acid multipolymer and poly butylene succinate carry out first drying treatment before using.
Then, prepare according to the following steps full-biodegradable material: above-mentioned all raw materials are mixed (all raw materials can be carried out pre-mixing in premixing machine, the initial temperature of mixing is 40 ℃, the rotating speed of premixing machine is 800 ~ 1200 rev/mins, mixed 30 minutes, the mixing process medium speed can improve gradually), obtain mixture; Then mixture is joined melt blending in the twin screw extruder (mixture is respectively each melt blending interval of 145 ℃, 150 ℃, 155 ℃, 160 ℃, 175 ℃, 165 ℃, 160 ℃, 150 ℃ successively through excess temperature), form the material melt; The material melt carries out tie rod, pelletizing after the die head of twin screw extruder is extruded, obtain material particles; The material particles drying obtains biodegradable material after processing.The screw slenderness ratio of twin screw extruder is 35:1.
Above-mentioned biodegradable material can meet U.S. ASTMD6400 and the EN13432 of European Union degraded standard.
Above-mentioned biodegradable material through single screw rod inflation film manufacturing machine blown film, is obtained Biodegradable film.The screw slenderness ratio of single screw rod inflation film manufacturing machine is 30:1.
The Biodegradable film of embodiment 1 ~ 14 preparation is carried out the test of elongation at break and tensile strength according to GB1040-79, and its test result is as shown in table 1.
Table 1
| Embodiment | Elongation at break (%) | Tensile strength (MPa) |
| 1 | 220 | 30 |
| 2 | 247 | 31 |
| 3 | 237 | 27 |
| 4 | 246 | 26 |
| 5 | 222 | 26 |
| 6 | 219 | 29 |
| 7 | 279 | 23 |
| 8 | 286 | 24 |
| 9 | 272 | 25 |
| 10 | 280 | 22 |
| 11 | 539 | 20.5 |
| 12 | 534 | 21 |
| 13 | 519 | 20 |
| 14 | 519 | 20 |
From the test result of table 1 as seen, the biodegradable material of embodiment 1 ~ 6 preparation is used in to be produced in the 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 the 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, such as preservative film; Embodiment 7 ~ 10 is between between the two above-mentioned, is suitable for elongation at break and tensile strength are had certain requirement but requires not high field.
Claims (10)
1. biodegradable material is characterized in that being made by the raw material of following weight per-cent:
3-hydroxybutyrate and 4 hydroxybutyric acid copolymer 10 ~ 35%;
Poly butylene succinate 10 ~ 35%;
Poly(lactic acid) 0 ~ 50%;
Vegetables oil 5 ~ 25%;
Softening agent 1 ~ 10%;
Reaction promotor 0.02 ~ 5%.
2. biodegradable material according to claim 1 is characterized in that being made by the raw material of following weight per-cent:
3-hydroxybutyrate and 4 hydroxybutyric acid copolymer 15 ~ 22%;
Poly butylene succinate 15 ~ 22%;
Poly(lactic acid) 25 ~ 50%;
Vegetables oil 14 ~ 25%;
Softening agent 5 ~ 10%;
Reaction promotor 1 ~ 5%.
3. biodegradable material according to claim 2 is characterized in that being made by the raw material of following weight per-cent:
3-hydroxybutyrate and 4 hydroxybutyric acid copolymer 15 ~ 19%;
Poly butylene succinate 15 ~ 19%;
Poly(lactic acid) 37 ~ 50%;
Vegetables oil 14 ~ 18%;
Softening agent 5 ~ 7%;
Reaction promotor 1 ~ 2%.
4. each described biodegradable material according to claim 1-3 is characterized in that: described vegetables oil is a kind of in rapeseed oil, Viscotrol C, soybean oil, peanut oil, Oleum Cocois, plam oil, oleum lini, Oleum Gossypii semen, Semen Maydis oil, sunflower seed oil, pine-seed oil and the tung oil or wherein multiple combination.
5. each described biodegradable material according to claim 1-3 is characterized in that: described softening agent is a kind of in sorbyl alcohol, polyoxyethylene glycol, acetylize citric acid and the glycerine or wherein multiple combination.
6. each described biodegradable material according to claim 1-3 is characterized in that: described reaction promotor is a kind of in coupling agent and the catalyzer or both combinations.
7. biodegradable material according to claim 6 is characterized in that: described coupling agent is γ-aminopropyl triethoxysilane, diphenylmethanediisocyanate and poly-methyl to a kind of in the phenylisocyanate or wherein multiple combination.
8. biodegradable material according to claim 6 is characterized in that: described catalyzer is a kind of in citric acid, hexanodioic acid, Succinic Acid and the hydrochloric acid or wherein multiple combination.
9. the preparation method of biodegradable material claimed in claim 1, it is characterized in that comprising the steps: 3-hydroxybutyrate and 4 hydroxybutyric acid multipolymer, poly butylene succinate, poly(lactic acid), vegetables oil, softening agent and reaction promotor are mixed, obtain mixture; Then mixture is joined melt blending in the twin screw extruder, form the material melt; The material melt carries out tie rod, pelletizing after the die head of twin screw extruder is extruded, obtain material particles; The material particles drying obtains biodegradable material after processing.
10. the application of biodegradable material claimed in claim 1 in the preparation Biodegradable film through single screw rod inflation film manufacturing machine blown film, obtains Biodegradable film with described biodegradable material.
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| PCT/CN2013/000973 WO2014056293A1 (en) | 2012-10-09 | 2013-08-21 | Biodegradable material, preparation method and use thereof |
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