CN101210101A - Composition containing polyhydroxy butyrate ester copolymer and polylactic acid for sheet, thin film, pipeline and fibrous material - Google Patents
Composition containing polyhydroxy butyrate ester copolymer and polylactic acid for sheet, thin film, pipeline and fibrous material Download PDFInfo
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Abstract
The invention discloses a polyhydroxybutyrate containing copolymer and a polylactic acid composition which are used in sheet, film, tubular product and fiber materials. The invention has stated tensile strength and breaking elongation as well as complete biodegradation, which can be widely applied in the field of packaging.
Description
Technical field
The invention belongs to technical field of macromolecules, more specifically, the invention discloses a kind of composition that is used for the biodegradable high molecular polymer of sheet material, film, tubing, filamentary material, can be widely used in packing articles.
Background technology
Plastic wrapping has series of advantages such as convenient, healthy, safe, has become inalienable part in people's productive life.But its non-degradable has also caused the aggravation of environmental pollution.Especially the present plastics of China do not have recovery system and garbage sorting system, and the rubbish severe contamination that arbitrarily abandons environment.China is faced with the problem of plastics serious environment pollution now, according to incomplete statistics in 2006, the article of 100 yuan of average every consumption just need 2～3 plastics bags in the areas of Beijing supermarket, a supermarket consumed nearly ten thousand plastics bags in average one day, Beijing consumed about 5,000,000,000 plastics bags in 1 year, was worth 5,000 ten thousand yuan/year.This does not also add the packing of goods itself and the plastic packing product of other field.
Now the starting material of the bio-degradable plastics packing articles that uses on the market mainly are goods such as polyethylene, polypropylene, polypropylene/starch blend, polyethylene blend, and these goods are any all can not to reach biological degradation becomes CO
2And H
2The purpose of O.As polyethylene only is that physical method is mixed starch in polyethylene polymer, really be not grafted on the polyethylene macromolecular chain, the still not degraded of polyethylene polymer though cause starch degradation, see on the macroscopic view that goods are broken, but be dwindling of polyethylene material geometrical dimension in essence, and fundamental change does not take place in the polyethylene macromole, quickens to influence the quality and the environmental pollution of soil so on the contrary.
Show other polyhydroxyalkanoate copolymer that polyhydroxy butyrate ester copolymer P (3HB-co-4HB) is better than having gone on the market (as PHBV, PHBHHx) through detection and documents and materials on some performance.Its principal feature is that snappiness increases, and in the intensive soil of physical environment such as seawater, sewage or bacterium the time through 3-6 month can be degraded into carbonic acid gas and water fully.This polymkeric substance is to utilize fermentation process production, and the production process cleaning does not pollute environment.
Because polyhydroxy butyrate ester copolymer P (3HB-co-4HB) is the thermoplastic poly ester cpds of hemicrystalline normally, have low degree of crystallinity and fusing point, the work in-process crystallization rate is slow, also can adhere to each other after the cooling simultaneously, influenced the normal collection and the production output of goods, and the cost of present this biological copolyesters is also higher relatively.
Therefore, how to utilize the biodegradable characteristic that polyhydroxy butyrate ester copolymer P (3HB-co-4HB) has and overcome its low-crystallinity and fusing point, obtain that cost is low, the market acceptable, and can produce the wrapping material of biological degredation plastic packing articles such as sheet material, film, tubing, filamentary material class in batches with existing conventional production equipment, be the problem that this area need solve thereby make it be widely used in packaging field always.
Summary of the invention
The objective of the invention is to disclose a kind of composition that contains polyhydroxy butyrate ester copolymer P (3HB-co-4HB) and poly(lactic acid) that can be used for sheet material, film, tubing and fiber, be used to produce Plastic Packaging Materials, substitute by the nondegradable plastic raw materials of petrochemical complex synthetic, alleviate non-degradable plastics environmental pollution, simultaneously also save petroleum-based energy, but utilization and exploitation bio-regeneration resource.
The present inventor is through a large amount of experiments, in polyhydroxy butyrate ester copolymer P (3HB-co-4HB), add poly(lactic acid) and make blend composition to change its processing characteristics, obtain being applicable to the goods of wrapping material, make it can satisfy traditional diamond-making technique, and have normal use properties and biodegradable advantage.
More specifically, the invention discloses a kind of composition that can be used for sheet material, film, tubing and filamentary material, contain polyhydroxy butyrate ester copolymer P (3HB-co-4HB) and polylactic acid PLA;
The 4HB molar content is 5-95% in the above-mentioned composition disclosed by the invention, polyhydroxy butyrate ester copolymer P (3HB-co-4HB);
Composition disclosed by the invention, also contain organic and/or inorganic additives, these organic and/or inorganic additivess are nanometer～micron particles, wherein organic additive is an organic solid, can be one of starch, degradable lipid acid such as glyceride, protein, inorganic additives can be one of oxygen compound of talcum powder, lime carbonate, silicon, titanium;
Composition disclosed by the invention also contains other auxiliary agent, and other auxiliary agent can be one of stearic acid, calcium stearate;
Composition disclosed by the invention, wherein polyhydroxy butyrate ester copolymer P (3HB-co-4HB), poly(lactic acid), organic and or the ratio of quality and the number of copies of inorganic additives, other auxiliary agent be 100: 100～300: 0～60: 0～1.5;
A kind of preparation is used for the method for the above-mentioned composition of fiber, for utilizing fusion or solution electrospinning process preparation micron～a few nanometer non-woven fibre cloth;
Above-mentioned method, wherein voltage is 5kv～50kv, shower nozzle diameter 0.5mm～1.5mm, receiving range 5cm～35cm;
Above-mentioned method is the solution method of electrostatic spinning, and solvent is for can dissolve any solvent of said composition.
Above-mentioned method, wherein solvent is trichloromethane, N, one of dinethylformamide, the concentration of composition volume ratio by weight is 1%～20%.
Composition disclosed by the invention is a blend composition, and its composition is biodegradable a kind of polyhydroxy butyrate ester copolymer P (3HB-co-4HB) and biodegradable poly(lactic acid) (PLA).Polyhydroxy butyrate ester copolymer P disclosed by the invention (3HB-co-4HB) is 3 hydroxybutyric acids and 4 butyric ester Random copolymer RCP P (3HB-co-4HB), and molecular formula is:
Wherein, the 4HB molar content is 5-95%.
Biodegradable poly(lactic acid) (PLA) among the present invention has general formula:
The present inventor has carried out a large amount of experiments, obtained polyhydroxy butyrate ester copolymer P (3HB-co-4HB), poly(lactic acid), organic and or the ratio of quality and the number of copies of inorganic additives, other auxiliary agent be 100: 100～300: 0～60: 0～1.5.
The invention also discloses the method for utilizing preparation of compositions wrapping material of the present invention, can carry out processing by using traditional producing apparatus of extruding.At first raw material is prepared according to formula rate, dry mixed extrusion compositions pellet, in the product extrusion equipment, the control certain temperature melt extrudes then, by the various required goods of subsidiary engine typing becoming.Sheet material and film all adopt dull and stereotyped curtain coating or T word extruder head, or adopt the tubulose head, cool off on water cooling or the polishing metal roll, collect finished product.Tubing utilizes the garden shape head of forcing machine configuration extruding pipe material, the water cooling typing, and the traction rolling is cut into goods.
Above-mentioned sheet material disclosed by the invention, film, tubing, filamentary material based packaging material, by a series of mechanical strength experiments, experimental result shows that it has impact strength and different elongation at breaks, meets relevant national standard.In addition, these materials also have good snappiness, intensity, thermal insulation, anti-usual vehicle and characteristics such as waterproof, nontoxic, meet the actual service requirements of packaged products such as food Package and frozen food.Its processing molding method is simple, and shaping cycle is serialization production, and energy consumption is low, production benefit is high, and easy handling and industrialization penetration and promotion are produced.The finished product waste has biodegradability, can all be degraded to CO through the several months in microbial strains compact districts such as all backward, corrupt and reactionary things, soil, seawater
2And H
2O does not have secondary pollution to belong to environment-friendly material to environment.
Embodiment
Following examples, experimental example only further illustrate the present invention, should not be construed as limiting the invention.
Polyhydroxy butyrate ester copolymer P (3HB-co-4HB) is from Tianjin Green Biosciences Limited Company, other compositions as do not explain be commercially available.
The preparation method of film: extrude casting method, starting material are extruded by T word machine head and certain pressure, flow on the cooling roller and are pulled stretching, form film.Processing condition: 120 ℃～180 ℃ of temperature; Extrusion pressure 5～10Pa; 90～10 ℃ of subsidiary engine cooling temperatures; Film thickness 0.01～0.1mm.Transparent or semitransparent.
The preparation method of sheet material and sheet material: the same.Sheet material and sheet thickness 〉=0.1mm.
The tubing extrusion method, starting material pass through the garden pipe die, and are extruded under certain pressure condition, cool off and draw through typing cover, cooling trough to stretch shaping pipe.Pipe diameter 3mm～200mm.Processing condition: 120 ℃～180 ℃ of temperature; Extrusion pressure 5～10Pa; 10～90 ℃ of subsidiary engine cooling temperatures, tube wall thickness degree 1～100mm.
The preparation method of filamentary material (spinning processes): fusion or solution electrospinning process preparation micron～a few nanometer non-woven fibre cloth.
The preparation of embodiment sheet material
The sheet material formula is as follows:
According to the mass fraction, and be benchmark (100 mass parts) with main body composition polyhydroxy butyrate ester copolymer P (3HB-co-4HB), each component proportions is as follows:
100 parts of polyhydroxy butyrate ester copolymer P (3HB-co-4HB)
100～300 parts of poly(lactic acid) (PLA)
0～60 part of organic and/or inorganic additives
Other auxiliary agent: 0～1.5 part
Working method: with all raw material blend, extruding pelletization.Extrusion moulding sheet material then, temperature is controlled at 120 ℃～180 ℃, 20～150 rev/mins of screw speeds, water-cooled moulding.Sheet material again on the Packing Machine plastics sucking moulding be goods.
Embodiment 1:
According to the mass fraction, 100 parts of P (3HB-co-5mol%4HB), PLA300 part, 1.5 parts of starch; With all raw material blend extruding pelletizations; Extrusion sheet then; Plastics sucking moulding is goods again.
The moulded products processing condition: 150 rev/mins of screw speeds (n/min), the heating warm area is controlled to be 1 district: 150 ℃, 2 districts: 170 ℃, 3 districts: 160 ℃, 4 districts: 150 ℃.
Embodiment 2:
Select 100 parts of P (3HB-co-95mol%4HB) according to the mass fraction, PLA200 part, talcum powder is 1.0 parts, 0.2 part of calcium stearate; With all raw material blend extruding pelletizations; Extrusion sheet then; Plastics sucking moulding is goods again.The moulded products processing condition: 150 rev/mins of screw speeds (n/min), the heating warm area is controlled to be 1 district: 150 ℃, 2 districts: 170 ℃, 3 districts: 160 ℃, 4 districts: 150 ℃.
Embodiment 3:
According to the mass fraction, 100 parts of P (3HB-co-5mol%4HB), PLA100 part is with all raw material blend extruding pelletizations; Extrusion sheet then; Plastics sucking moulding is goods again.150 rev/mins of screw speeds (n/min), the heating warm area is controlled to be 1 district: 150 ℃, 2 districts: 170 ℃, 3 districts: 160 ℃, 4 districts: 150 ℃.
The preparation of embodiment thin-film material
Film formulation is as follows:
According to the mass fraction, and be benchmark (100 mass parts) with main body composition polyhydroxy butyrate ester copolymer P (3HB-co-4HB), each component proportions is as follows:
100 parts of polyhydroxy butyrate ester copolymer P (3HB-co-4HB)
100～300 parts of poly(lactic acid) (PLA)
0～60 part of organic and/or inorganic additives
Other auxiliary agent: 0～1.5 part
Extrude casting method, starting material are extruded by T word machine head and certain pressure, flow on the cooling roller and are pulled stretching, form film.Processing condition: 120 ℃～180 ℃ of temperature; Extrusion pressure 5～10Pa; Subsidiary engine cooling temperature 90～10; Film thickness 0.1～0.01mm.Transparent or semitransparent.
Embodiment 1:
According to the mass fraction, 100 parts of P (3HB-co-10mol%4HB), PLA300 part, 1.5 parts of starch; With all raw material blend extruding pelletizations; Extrusion film then.Moulded products processing condition: 100 rev/mins of screw speeds (n/min), forcing machine pressure: 8Pa.The heating warm area is controlled to be 1 district: 150 ℃, 2 districts: 170 ℃, 3 districts: 160 ℃, 4 districts: 170 ℃, and 5 districts: 180 ℃.50 ℃ of cylinder cooling temperatures, film thickness 0.1mm.
Embodiment 2:
According to the mass fraction, 100 parts of P (3HB-co-20mol%4HB), PLA100 part, 1.0 parts of calcium stearates; With all raw material blend extruding pelletizations; Extrusion sheet then; Plastics sucking moulding is goods again.Moulded products processing condition: 100 rev/mins of screw speeds (n/min), forcing machine pressure: 8Pa.The heating warm area is controlled to be 1 district: 150 ℃, 2 districts: 170 ℃, 3 districts: 160 ℃, 4 districts: 170 ℃, and 5 districts: 180 ℃.50 ℃ of cylinder cooling temperatures, film thickness 0.01mm.
Embodiment 3
According to the mass fraction, 100 parts of P (3HB-co-20mol%4HB), PLA100 part, 1.5 parts of stearic acid; 20 parts of talcum powder are with all raw material blend extruding pelletizations; Extrusion film then.Moulded products processing condition: 150 rev/mins of screw speeds (n/min), forcing machine pressure: 10Pa.The heating warm area is controlled to be 1 district: 150 ℃, 2 districts: 170 ℃, 3 districts: 160 ℃, 4 districts: 170 ℃, and 5 districts: 180 ℃.50 ℃ of cylinder cooling temperatures, film thickness 0.01mm.
Embodiment 4
According to the mass fraction, 100 parts of P (3HB-co-20mol%4HB), PLA100 part is with all raw material blend extruding pelletizations; Extrusion film then.Moulded products processing condition: 150 rev/mins of screw speeds (n/min), forcing machine pressure: 10Pa.The heating warm area is controlled to be 1 district: 150 ℃, 2 districts: 170 ℃, 3 districts: 160 ℃, 4 districts: 170 ℃, and 5 districts: 180 ℃.50 ℃ of cylinder cooling temperatures, film thickness 0.01mm.
The preparation of embodiment pipe material
According to the mass fraction, and be benchmark (100 mass parts) with main body composition polyhydroxy butyrate ester copolymer P (3HB-co-4HB), each component proportions is as follows:
100 parts of polyhydroxy butyrate ester copolymer P (3HB-co-4HB)
100～300 parts of poly(lactic acid) (PLA)
0～60 part of organic and/or inorganic additives
Other auxiliary agent: 0～1.5 part
Extrusion method, starting material pass through the garden pipe die, and are extruded under certain pressure condition, cool off and draw through typing cover, cooling trough to stretch shaping pipe.Pipe diameter 3mm～200mm.Processing condition: 120 ℃～180 ℃ of temperature; Extrusion pressure 5～10Pa; Subsidiary engine cooling temperature 90～10; Tube wall thickness degree 1～100mm.Transparent or semitransparent.
Embodiment 1:
According to the mass fraction, 100 parts of P (3HB-co-14mol%4HB), PLA100 part, 0.5 part of stearic acid; With all raw material blend extruding pelletizations; Extruding pipe material then.Shaping pipe goods processing condition: 100 rev/mins of screw speeds (n/min), forcing machine pressure: 8Pa.The heating warm area is controlled to be 1 district: 150 ℃, 2 districts: 170 ℃, 3 districts: 160 ℃, 4 districts: 170 ℃, and 5 districts: 180 ℃.50 ℃ of typing cover cooling temperatures, tube wall thickness degree 2mm, pipe diameter 6mm.
Embodiment 2:
According to the mass fraction, 100 parts of P (3HB-co-5mol%4HB), PLA150 part, 1.2 parts of calcium stearates; With all raw material blend extruding pelletizations; Extruding pipe material then.Moulding tubing products processing condition: 120 rev/mins of screw speeds (n/min), forcing machine pressure: 8Pa.The heating warm area is controlled to be 1 district: 150 ℃, 2 districts: 170 ℃, 3 districts: 160 ℃, 4 districts: 170 ℃, and 5 districts: 180 ℃.50 ℃ of cylinder cooling temperatures, tube wall thickness degree 5mm, pipe diameter 15mm.
Embodiment 3:
According to the mass fraction, 100 parts of P (3HB-co-5mol%4HB), PLA150 part, 1.2 parts of stearic acid, 15 parts in lime carbonate is with all raw material blend extruding pelletizations; Extruding pipe material then.Moulding tubing products processing condition moulding tubing products processing condition: 150 rev/mins of screw speeds (n/min), forcing machine pressure: 10Pa.The heating warm area is controlled to be 1 district: 150 ℃, 2 districts: 170 ℃, 3 districts: 160 ℃, 4 districts: 170 ℃, and 5 districts: 180 ℃.50 ℃ of cylinder cooling temperatures, tube wall thickness degree 2.0mm, pipe diameter 8mm.
Embodiment 4:
According to the mass fraction, 100 parts of P (3HB-co-5mol%4HB), PLA100 part is with all raw material blend extruding pelletizations; Extruding pipe material then.Moulding tubing products processing condition moulding tubing products processing condition: 150 rev/mins of screw speeds (n/min), forcing machine pressure: 10Pa.The heating warm area is controlled to be 1 district: 150 ℃, 2 districts: 170 ℃, 3 districts: 160 ℃, 4 districts: 170 ℃, and 5 districts: 180 ℃.50 ℃ of cylinder cooling temperatures, tube wall thickness degree 2.0mm, pipe diameter 8mm.
The preparation of embodiment filamentary material
According to the mass fraction, and be benchmark (100 mass parts) with main body composition polyhydroxy butyrate ester copolymer P (3HB-co-4HB), each component proportions is as follows:
100 parts of polyhydroxy butyrate ester copolymer P (3HB-co-4HB)
100～300 parts of poly(lactic acid) (PLA)
0～60 part of organic and/or inorganic additives
Other auxiliary agent: 0～1.5 part
Spinning processes: fusion or solution electrospinning process preparation micron～a few nanometer non-woven fibre cloth.Processing method: under the dc high-voltage field action, make non-woven fabrics by shower nozzle ejection random fiber by Coulomb repulsion.Voltage is 5kv～50kv, and strength of solution 1%～20% solvent all can be as trichloromethane, N for any solvent that can dissolve said composition, dinethylformamide etc.Shower nozzle diameter 0.5mm～1.5mm, receiving range 5cm～35cm.
Embodiment 1:
According to the mass fraction, 100 parts of P (3HB-co-15mol%4HB), PLA300 part, 0.2 part of stearic acid; All raw material blend are prepared into solution; Under the dc high-voltage field action, voltage 8kv, in chloroform soln, strength of solution 1.5%, shower nozzle diameter 0.5mm, receiving range 15cm sprays random fiber by Coulomb repulsion by shower nozzle.
Embodiment 2:
According to the mass fraction, 100 parts of P (3HB-co-25mol%4HB), PLA200 part, calcium stearate is 0.8 part; All raw material blend are prepared into solution; Under the dc high-voltage field action, voltage 15kv, in chloroform soln, strength of solution 15%, shower nozzle diameter 1.5mm, receiving range 25cm sprays random fiber by Coulomb repulsion by shower nozzle, makes non-woven fabrics.
Embodiment 3:
According to the mass fraction, 100 parts of P (3HB-co-25mol%4HB), PLA100 part is prepared into solution with all raw material blend; Under the dc high-voltage field action, voltage 15kv, in chloroform soln, strength of solution 15%, shower nozzle diameter 1.5mm, receiving range 25cm sprays random fiber by Coulomb repulsion by shower nozzle, makes non-woven fabrics.
Experimental example:
The product that the foregoing description obtains experimentizes respectively by following standard:
Sheet material standard: QB/T2471-2000. physical and mechanical properties: tensile yield strength (vertical/horizontal stroke) 〉=20.0MPa, longitudinal size velocity of variation≤60.0%
Tubing reaches standard: can bear operating pressure, at 20 ℃～50 ℃ of temperature, non-stop run pressure 0.25MPa, 0.4MPa, 0.6MPa, 1.0MPa, 1.6MPa, 2.0MPa.5 years the highest work-ing life.
Film reaches standard: food product pack can be used for, also the packing generation that environmental sanitation such as ight soil uses can be used for, and complete biodegradable.Tensile strength (vertical, horizontal) 〉=12MPa, elongation at break 〉=130, the film that is used for food product pack, medical packaging should meet the GB9687 regulation.
The film that filamentary material (non-woven fabrics) is used for food product pack, medical packaging should meet the GB9687 regulation.Tensile strength (vertical, horizontal) 〉=8MPa, elongation at break 〉=80, and have better ventilation property.
Experimental result shows: the product that the foregoing description obtains has reached above-mentioned standard-required respectively, has impact strength and different elongation at breaks; Meet the actual service requirements of packaged product.
The product that the foregoing description obtains has also carried out the biological degradation experiment in mud and seawater, in three to six months, and all degradeds.
Claims (9)
1. a composition that can be used for sheet material, film, tubing and filamentary material contains polyhydroxy butyrate ester copolymer P (3HB-co-4HB) and polylactic acid PLA.
2. the described composition of claim 1, wherein the 4HB molar content is 5-95% among the polyhydroxy butyrate ester copolymer P (3HB-co-4HB).
3. the described composition of claim 1, also contain organic and/or inorganic additives, wherein organic additive is an organic solid, can be one of starch, degradable lipid acid such as glyceride, protein, and inorganic additives can be one of oxygen compound of talcum powder, lime carbonate, silicon, titanium.
4. the described composition of claim 1 also contains other auxiliary agent, can be one of stearic acid, calcium stearate.
5. the arbitrary described composition of claim 1-4, wherein polyhydroxy butyrate ester copolymer P (3HB-co-4HB), poly(lactic acid), organic and or the ratio of quality and the number of copies of inorganic additives, other auxiliary agent be 100: 100～300: 0～60: 0～1.5.
6. one kind prepares the arbitrary described method for compositions of the claim 1-5 that is used for filamentary material, for utilizing the preparation of fusion or solution electrospinning process.
7. the described method of claim 6, wherein voltage is 5kv～50kv, shower nozzle diameter 0.5mm～1.5mm, receiving range 5cm～35cm.
8. the described method of claim 7 is the solution method of electrostatic spinning, and solvent is for can dissolve any solvent of said composition.
9. the described method of claim 8, wherein solvent is trichloromethane, N, one of dinethylformamide, composition concentration in solvent volume ratio by weight is 1%～20%.
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| CN112592569A (en) * | 2020-12-15 | 2021-04-02 | 浙江金晟环保股份有限公司 | High-thermal-stability modified PHA film and preparation method thereof |
| KR20230015022A (en) * | 2021-07-22 | 2023-01-31 | 도레이첨단소재 주식회사 | Biodegradable fiber having with excellent softness and Method for manufacturing the same |
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