CN101240086A - Total-biodegradation plastic film and preparation method thereof - Google Patents
Total-biodegradation plastic film and preparation method thereof Download PDFInfo
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- CN101240086A CN101240086A CNA2008100449759A CN200810044975A CN101240086A CN 101240086 A CN101240086 A CN 101240086A CN A2008100449759 A CNA2008100449759 A CN A2008100449759A CN 200810044975 A CN200810044975 A CN 200810044975A CN 101240086 A CN101240086 A CN 101240086A
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Abstract
A full-biodegradable plastic membrane, which uses thermoplastic starch with diameter of 1-9 mu m, biodegradable polymer and auxiliary component as raw material, processed by screw extruding apparatus and membrane producing apparatus. The raw material comprises 30-70 parts by weight of thermoplastic starch with diameter of 1-9 mu m, 10-40 parts by weight of biodegradable polymer, 5-10 parts by weight of compatible modified component, 3-5 parts by weight of complex plasticized component, 10-30 parts by weight of lubricant. These materials are mixed and processed by screw extruding apparatus and membrane producing apparatus, wherein the lubricant is at least adding into other materials for mixture before process by screw extruding apparatus and during melt blending, and the adding amount of lubricant before process by screw extruding apparatus is not more than 1/3 of the total amount thereof. By highly increasing dosage of lubricant and changing mixing way, thermoplastic degree of starch is increased, rheological property of the system and processing quality of product are dramatically improved, mechanical property of the product is enhanced.
Description
Technical field
The present invention relates to a kind of full-biodegradable plastic film, specifically is a kind of full-biodegradable plastic film that contains the thermoplastic starch meal component, and corresponding preparation method.
Background technology
The environmental problem that production and use brought of nondegradation plastics manifests day by day, and has caused the great attention of the whole society.
Provide starch/polyester plastics of a kind of fully biodegradable and preparation method thereof in the Chinese patent literature of publication number for CN1778833A.These plastics are raw material by thermoplastic starch, fat-fragrant block blending polyester, long-chain unsaturated carboxylic acid or anhydrides graft modification composition, organic peroxide evocating agent, polyol ester compounds softening agent, organic compound or polyalcohols stablizer and the lubricant of particle diameter 1～9 μ m, earlier starch is handled to said particle diameter through mechanical force-chemical modification processing and thermoplasticity, under 100 ℃ of-160 ℃ of temperature condition, melt extruded granulation with other raw material mixed milling and by spiral response type forcing machine again.
Notification number is for then providing a kind of full biological degradable composition and manufacture method and purposes in the Chinese patent literature of CN100338132C, it is the treated starch of particle diameter≤6.5 micron that its basic raw material is formed, biodegradable polymers, nanometer strengthener, softening agent, lubricant, reactive compatibilizer, linking agent, with biological decomposition promotor, be earlier the exsiccant native starch to be pulverized and handled equally with modifier modification, then with the softening agent that adds successively, biodegradable polymers material and lubricant thorough mixing, again with the linking agent of said proportional and reactive compatibilizer behind reciprocating type single screw extrusion machine melting mixing, continue again to extrude and granulation through the Electromagnetic Dynamic mixing extruder is further mixing with the nanometer strengthener of said proportional and biological decomposition promotor.
In the said products, all to have adopted through mechanical force-chemical modification and handled and the small particle size starch of thermoplasticity after handling, corresponding composition mixing with other and extrude through different screw extruder melting mixings obtains.It can both realize the complete biodegradable of plastics, and have better physical mechanical property and characteristics such as adaptability preferably, but discovery is still not ideal enough aspect processing characteristics in the practice, and therefore causes certain disadvantageous effect at the aspects such as mechanical property of product.
Summary of the invention
At above-mentioned situation, the application will provide a kind of improved can full-biodegradable plastic film, with and corresponding preparation method.
Full-biodegradable plastic film of the present invention, same is thermoplastic starch, biodegradable polymers and the complementary raw material that becomes to grade of 1～9 μ m with particle diameter, processes through spiral extrusion equipment and membrane equipment.The weight part composition form of said raw material is:
Particle diameter is thermoplastic starch 30-70 part of 1～9 μ m,
Biodegradable polymers 10-40 part,
Compatible altered contents 5-10 part,
Nano inorganic enhancing ingredients 3-5 part,
Compound plasticizer component 2-25 part,
Lubricated composition 10-30 part.
Said thermoplastic starch in the above-mentioned composition can be in the starch that comprises W-Gum, tapioca (flour), pea starch, wheat starch, potato starch, konjak starch, canna starch after adopting aforementioned documents report mode to do miniaturization modification and plasticising to handle any.
Said biodegradable polymers, can select at least a in synthesis type or the natural Biodegradable high-molecular polymkeric substance by the aforementioned documents mode equally, for example polyvinyl alcohol (PVA), poly(lactic acid) (PLA), poly butylene succinate (PBS), poly butyric ester (PHB), polyglycolic acid (PGA), polycaprolactone (PCL), poly-hydroxyalkyl polyester, poly-hydroxyl valerate, polyesteramide, urethane, and vegetable fibre etc.
Said compatible altered contents can be C
12At least a in above unsaturated carboxylic acid or the anhydrides compound, as octadecenic acid, dodecenylsuccinic acid acid anhydride, hendecene base Succinic anhydried etc., or these carboxylic acids or acid anhydrides and as the graft copolymer of poly(lactic acid) (PLA), poly butyric ester (PHB), poly-hydroxyl valerate (PHV), polycaprolactone (PCL), poly butylene succinate (PBS), polyglycolic acid biodegradable aliphatic polyesters such as (PGA).
Said compound plasticizer component can be selected polyvalent alcohol or its ester compound composition, at least a as in glycerine, ethylene glycol, propylene glycol, butyleneglycol, polyoxyethylene glycol, sorbyl alcohol, polypropylene glycol, hexanodioic acid two-(2-ethylhexyl) ester, Polycizer W 260, dibutyl phthalate, the acetate sorbitol ester.
Said nano inorganic enhancing ingredients nano level toughener can be selected as lime carbonate, clay, polynite, mica, vanadium oxide (V
2O
5), molybdenum oxide (MoO
3) wait at least a in the composition, wherein preferably at least one dimension be of a size of 50nm following lime carbonate, clay, polynite.These nano inorganic tougheners have enhancing and toughening effect to product, and mechanical property can be greatly enhanced.
Said lubricated composition can select to comprise at least a in the lubricated composition of fatty acid amide, fatty acid ester, soap composition, as compositions such as existing report and/or the stearic amide that uses, methylene bis stearylamide, ethylene bis stearamide, oxystearic acid, n-butyl stearate, calcium stearate, Magnesium Stearates, preferred compositions such as stearic amide, methylene bis stearylamide, ethylene bis stearamide wherein.
Form by the raw material of the above-mentioned full-biodegradable plastic film of the present invention and to be not difficult to find out that its distinguishing feature is to have adopted the lubricated composition of unconventional proportional.Though lubricant is the raw material a kind of commonly used in the present plastics-production, conventional amount used is 2～6% of a material total amount only generally, is used for improving the fluid property of course of processing composition, reduces machining load, improves the surface smoothness of goods.But a large amount of tests show, be subjected to factor affecting such as special rigidity of starch and high molecular and processibility be relatively poor, in the plastic working of starch-containing composition, adopt the lubricated composition of conventional amount used mode often to be difficult on its thermoplasticity and processibility, reach good effect, and can therefore have influence on the performance and the quality of goods.The present invention has adopted the lubricated composition of unconventional proportional in raw material is formed after, can significantly improve the thermoplasticity and the processibility of starch system, greatly improve the rheological property of system, improve the processing quality and the performance quality of goods by its mass effect.
The preparation of the above-mentioned full-biodegradable plastic film of the present invention, be with the above-mentioned raw materials behind the thorough mixing through spiral extrusion equipment melting mixing and extrude after, process by the membrane equipment blown film again.Material enters processing and the mixing before the spiral extrusion equipment carries out melting mixing, can carry out with reference to the mode of aforementioned pertinent literature.Wherein, lubricated composition in the said raw material is answered gradation and is entered before the spiral extrusion equipment at material at least respectively and is in melt blending stage adding mixing of materials with material, wherein enter the preceding lubricated composition of spiral extrusion equipment and add 1/3 of no more than its total amount of combined amount, the lubricated composition of its surplus added in the later stage of material melting mixing.
Influence the plasticizing of material system and mixing owing in starch plastic processing, add lubricated composition regular meeting in advance, and also can make the lubricant effect discount.For solving common " plasticising " in these starch plastic processing, " flowability ", contradiction between performance such as " lubricate ", the present invention is on the basis of the above-mentioned lubricated composition that has adopted unconventional proportional, in preparation process, again further to lubricated composition and the mode that mixing of material has adopted gradation to add step by step, make material fully plasticizing and mixing earlier under the system of low lubricant content, and then add the lubricated composition of unconventional consumption, the rheological property of further improvement system, thereby realized not only having improved the processibility of system, also improved the physicochemical property of system, the mechanical property of goods is promoted significantly, obtain having the complete biodegradable starch plastic goods of better quality, reached the performance identical with conventional plastic.
When carrying out melting mixing with screw extruder, can not adopt conventional twin screw extrusion equipment to finish although do not get rid of yet, but preferably banburying formula three-screw extruder, can be respectively more than 43 times and 15000 times of twin screw extruder to the extruding of material/rub to carry in its superpower compression ratio and the identical residence time, all be higher than the common double screw extrusion press far away.Experiment shows that after the present invention was applied to the field of starch plastic first, crystalline structure and the comparable common double screw extrusion press of thermoplastic general effect of handling starch improved more than 40%, have produced extremely significant effect.
When carrying out melting mixing in screw extruders such as above-mentioned banburying formula three-screw extruder, making the processing temperature in Qi Ge district adopt the mode setting increase progressively gradually in 100 ℃～180 ℃ scopes is a kind of better choice.Test shows, adopts the processing mode of elevated temperature gradually, can avoid heat up the rapidly degraded that causes and the second half section cooling of material under the technology of falling after rising of conventional temperature to cause system crystallization velocity and degree of crystallinity to reduce and the problem that affects the mechanical properties.For example a kind of can be for reference the temperature set-up mode can for:
100 ℃-130 ℃ in one to three district, 130 ℃-150 ℃ in four to six districts, 150 ℃-165 ℃ in seven to nine districts, ten to 165 ℃-180 ℃ of No.12 Districts.
The routine operation pressure of material in the spiral extrusion equipment is normally below 10MPa.Test shows, on the basis of above-mentioned temperature setting and routine operation pressure, if the pressure in material melting mixing stage in screw extruders such as above-mentioned banburying formula three-screw extruder improved and maintain under the condition of high voltage of 20-30Mpa, handle the starch double-spiral structure by this high pressure of setting up at barrel, more help improving the Thermoplasticity of Starch degree.For example, the melt pressure of material in above-mentioned banburying formula three screw extruders can adopt the following manner setting generally speaking:
One to three district 3～5Mpa, four to nine district 20～30Mpa, ten to No.12 District 10～5MPa.
Through the material that above-mentioned screw extruder melting mixing is extruded, can further make corresponding film product by membrane equipment.
Be to improve the quality of plastics film, said membrane equipment preferably uses is that the Electromagnetic Dynamic inflation film manufacturing machine of short length-to-diameter ratio 20～32 is good for avoiding material to take place to decompose or phenomenons such as coking, and reduces energy expenditure.Because Electromagnetic Dynamic blown film function is carried by DYNAMIC SOLID, make material when helix groove is carried, periodically be compressed, discharge.Transient pressure and vibration can impel the quick compacting of material, air that bulk material is brought into and various lower molecular weight volatile matter are discharged fast by means of dynamic compacting process, extruding repeatedly between the pellet has produced dissipation heat energy, also provide positive preparation for the plastics fusion plastification, solid conveying section is shortened dramatically, and the branch subsolution twine, is orientated easily under vibrational state, intermolecular easy slippage, make polymkeric substance generation self-enhancement, improved the performance of material.This extrusion way reduces the viscosity of melt and elasticity, and the melt flow resistance reduces relatively during helical feed, and extruding output increases, and the extrusion swelling phenomenon reduces, and has realized the dynamic melt Conveying of material.Because material required little energy of plastication and extrusion process under vibrational state adds that the screw rod of forcing machine is shorter, the residence time of material in machine is short, so extrusion temperature reduces, is very favourable concerning the material starch plastic of extruding the processing heat stability difference.Therefore adopt this equipment to can be implemented in when improving the extrusion moulding effect and reduce cost, shorten process period, and obviously improve the purpose of extruded product capability and performance.
Make the set-up mode of membrane operations condition optimization when adopting above-mentioned Electromagnetic Dynamic inflation film manufacturing machine preferably: 120 ℃～180 ℃ of temperature, engine speed 100～400r/min, vibrational frequency are increased to 30～50Hz, to guarantee and to improve the Physical Mechanical of goods.
Test shows that the above-mentioned full-biodegradable plastic film of the present invention can have excellent mechanical property, biological degradability and cheap cost.Said film article can be realized degrading fully in 3～12 months, met the composting requirement of ISO14855 standard.The mechanical property of goods can surpass more than 30% of common PE plastics, and the mechanical property that has solved present starch plastic does not reach the common problem of common plastics goods, and (tensile strength of present starch-type biodegradable plastic membrane product generally is lower than 15MPa.Because its starch content can reach 80%, therefore the cost of goods is greatly reduced, even can only be with about 50% of based article.The correlated performance comparison test of full-biodegradable plastic film of the present invention and similar articles of biodegradable plastics material and common PE film, and be all the performance comparison test of CN1778833A document and the corresponding goods of the application at 65% o'clock at starch content, respectively as shown in Table 1 and Table 2.
The correlated performance of table 1 full-biodegradable plastic film of the present invention and other degradable plastic product and common PE film relatively
| Goods of the present invention | Similar biological plastics | Common LDPE | Operative norm | |
| Biological degradability | 100% degraded, it is controlled to degrade, degraded in 3-12 month. | Degradation time＞3 year, the time is difficult to control. | Do not degrade | ISO14855 |
| Tensile strength | 〉=30MPa | 10-15MPa | 15-25MPa | GB/T 4456-1996 |
| Elongation at break | 〉=450% | About 300% | About 450% | GB/T 4456-1996 |
The performance comparison of the different starch plastic products of the identical starch content of table 2 (65%)
| The CN1778833A film product | Film product of the present invention | |
| Starch content | 65％ | 65％ |
| Mechanical property | ≤12MPa | ≥20MPa |
| Water resistance | Soak 24h water-intake rate 〉=50% | Soak 24h water-intake rate≤10% |
Embodiment by the following examples is described in further detail foregoing of the present invention again.But this should be interpreted as that the scope of the above-mentioned theme of the present invention only limits to following example.Do not breaking away under the above-mentioned technological thought situation of the present invention, various replacements or change according to ordinary skill knowledge and customary means are made all should comprise within the scope of the invention.
Embodiment
Embodiment 1
Raw material is formed: thermoplasticity W-Gum 60 (weight part, as follows)
Poly(lactic acid) 25
Octadecenic acid 8
Lime carbonate 4
Glycerine/ethylene glycol mixture (1: 1) 28
Stearic amide 22
With above-mentioned thermoplasticity W-Gum, poly(lactic acid), octadecenic acid, lime carbonate, glycerine/ethylene glycol mixture and less than the stearic amide of total amount 1/3 with reference to the described mode of CN1778833A carry out mixed and modified be treated as the thermoplastic starch powder material that particle diameter is 1～9 μ m after, melt extrude granulation with banburying formula three-screw extruder, add remaining stearic amide in the 9th district of banburying formula three-screw extruder.The temperature in each district of banburying formula three-screw extruder is set to:
100 ℃-130 ℃ in one to three district, 130 ℃-150 ℃ in four to six districts, 150 ℃-165 ℃ in seven to nine districts, ten to 165 ℃-180 ℃ of No.12 Districts;
The pressure in each district is set to: one to three district 3～5Mpa, and four to nine district 20～30Mpa, ten to No.12 District 10～5MPa.
Directly send into length-to-diameter ratio behind the above-mentioned material extruding pelletization and be blowing in 30 the Electromagnetic Dynamic inflation film manufacturing machine, promptly obtain full-biodegradable film.The working parameter of Electromagnetic Dynamic inflation film manufacturing machine is: 120 ℃～180 ℃ of temperature, engine speed 200r/min, vibrational frequency 40Hz.
Embodiment 2
Raw material is formed: thermoplastic wood sweet potato starch 45
Polyvinyl alcohol 40
Dodecenylsuccinic acid acid anhydride 7
Clay 4.5
Dibutyl phthalate 5
Methylene bis stearylamide 20
Mode by embodiment 1 is operated.Wherein the length-to-diameter ratio of Electromagnetic Dynamic inflation film manufacturing machine is 25, and working parameter is: 120 ℃～180 ℃ of temperature, engine speed 300r/min, vibrational frequency 50Hz.
Embodiment 3
Raw material is formed: thermoplasticity konjak starch 70
Polycaprolactone 35
Hendecene base Succinic anhydried 5
Polynite 5
Sorbyl alcohol 15
Ethylene bis stearamide 25
Operate by embodiment 1 described mode.Wherein the length-to-diameter ratio of Electromagnetic Dynamic inflation film manufacturing machine is 28, and working parameter is: 120 ℃～180 ℃ of temperature, engine speed 250r/min, vibrational frequency 35Hz.
Embodiment 4
Raw material is formed: thermoplasticity pea starch 65
Vegetable fibre 30
Octadecenic acid and PCL graft copolymer 8
Lime carbonate, clay 4
Glycerine 10
N-butyl stearate 12
Operate by embodiment 1 described mode.Wherein the length-to-diameter ratio of Electromagnetic Dynamic inflation film manufacturing machine is 20, and working parameter is: 120 ℃～180 ℃ of temperature, engine speed 400r/min, vibrational frequency 30Hz.
Embodiment 5
Raw material is formed: thermoplasticity W-Gum 50
Poly butylene succinate 12
Octadecenic acid 9
Mica 4
Polycizer W 260 20
Oxystearic acid 18
Operate by embodiment 1 described mode.Wherein the length-to-diameter ratio of Electromagnetic Dynamic inflation film manufacturing machine is that 25 working parameters are: 120 ℃～180 ℃ of temperature, engine speed 120r/min, vibrational frequency 40Hz.
Embodiment 6
Raw material is formed: thermoplastic wood sweet potato starch 30
Polyglycolic acid+urethane 20
Dodecenylsuccinic acid acid anhydride 6
Polynite 3
Ethylene glycol 25
Magnesium Stearate 30
Operate by embodiment 1 described mode.Wherein the length-to-diameter ratio of Electromagnetic Dynamic inflation film manufacturing machine is 30, and working parameter is: 120 ℃～180 ℃ of temperature, engine speed 200r/min, vibrational frequency 35Hz.
Claims (10)
1. full-biodegradable plastic film is that thermoplastic starch, biodegradable polymers and the complementary composition of 1～9 μ m is raw material by particle diameter, processes through spiral extrusion equipment and membrane equipment, it is characterized in that the weight part of said raw material consists of:
Particle diameter is thermoplastic starch 30-70 part of 1～9 μ m,
Biodegradable polymers 10-40 part,
Compatible altered contents 5-10 part,
Nano inorganic enhancing ingredients 3-5 part,
Compound plasticizer component 2-25 part,
Lubricated composition 10-30 part,
Wherein, said thermoplastic starch is any in the starch that comprises W-Gum, tapioca (flour), pea starch, wheat starch, potato starch, konjak starch, canna starch of miniaturization modification and plasticising processing;
Biodegradable polymers is at least a in synthesis type or the natural biodegradable high molecular polymer;
Compatible altered contents is the C that comprises octadecenic acid, dodecenylsuccinic acid acid anhydride, hendecene base Succinic anhydried
12At least a in above unsaturated carboxylic acid or the anhydrides compound, or the graft copolymer of itself and biodegradable aliphatic polyester;
Compound plasticizer component is polyvalent alcohol or its ester compound composition;
Lubricated composition is to comprise at least a in the lubricated composition of fatty acid amide, fatty acid ester, soap composition.
2. full-biodegradable plastic film as claimed in claim 1 is characterized in that said biodegradable polymers is to comprise at least a in the synthetic of polyvinyl alcohol, poly(lactic acid), poly butylene succinate, poly butyric ester, polyglycolic acid, polycaprolactone, poly-hydroxyalkyl polyester, poly-hydroxyl valerate, polyesteramide, urethane, vegetable fibre or the natural Biodegradable high-molecular polymkeric substance.
3. full-biodegradable plastic film as claimed in claim 1 is characterized in that said nano inorganic enhancing ingredients is at least a in the following lime carbonate of 50nm, clay, polynite, mica, vanadium oxide, the molybdenum oxide.
4. full-biodegradable plastic film as claimed in claim 1 is characterized in that said compound plasticizer component is at least a in glycerine, ethylene glycol, propylene glycol, butyleneglycol, polyoxyethylene glycol, sorbyl alcohol, polypropylene glycol, hexanodioic acid two-(2-ethylhexyl) ester, Polycizer W 260, dibutyl phthalate, the acetate sorbitol ester.
5. the method for preparing the said full-biodegradable plastic film of claim 1, with well-mixed said raw material spiral extrusion equipment and membrane equipment processing and manufacturing, it is characterized in that the lubricated composition gradation in the said raw material enters before the spiral extrusion equipment and material is in the melt blending stage and adds mixing of materials at material at least respectively, wherein enter the preceding lubricated composition of spiral extrusion equipment and add 1/3 of no more than its total amount of combined amount, the lubricated composition of its surplus added in the material melting mixing later stage.
6. preparation method as claimed in claim 5 is characterized in that said spiral extrusion equipment is banburying formula three screw extruders, and the temperature in Qi Ge district adopts the mode that increases progressively gradually in 100 ℃～180 ℃ scopes to be provided with.
7. preparation method as claimed in claim 6 is characterized in that said material is set in the temperature in banburying formula three screw extruder Zhong Ge districts:
100 ℃-130 ℃ of one to three district's temperature, 130 ℃-150 ℃ of four to six district's temperature, 150 ℃-165 ℃ of seven to nine district's temperature, ten to 165 ℃-180 ℃ of No.12 District temperature.
8. preparation method as claimed in claim 6 is characterized in that material is in melting mixing and keeps the 20-30Mpa pressure condition during stage simultaneously in banburying formula three screw extruders.
9. full-biodegradable plastic film as claimed in claim 8 is characterized in that the melt pressure in the melting mixing process of said material in banburying formula three screw extruders is set to:
One to three district 3～5Mpa, four to nine district 20～30Mpa, ten to No.12 District 10～5MPa.
10. as the described full-biodegradable plastic film of one of claim 5 to 9, it is characterized in that said membrane equipment is that length-to-diameter ratio is 20～32 Electromagnetic Dynamic inflation film manufacturing machine, operational condition is set to: 120 ℃～180 ℃ of temperature, engine speed 100～400r/min, vibrational frequency 30～50Hz.
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2008
- 2008-03-14 CN CN2008100449759A patent/CN101240086B/en not_active Expired - Fee Related
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