CN101519524B - Material capable of completely biodegrading and preparation method thereof - Google Patents
Material capable of completely biodegrading and preparation method thereof Download PDFInfo
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- CN101519524B CN101519524B CN2009101061764A CN200910106176A CN101519524B CN 101519524 B CN101519524 B CN 101519524B CN 2009101061764 A CN2009101061764 A CN 2009101061764A CN 200910106176 A CN200910106176 A CN 200910106176A CN 101519524 B CN101519524 B CN 101519524B
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Abstract
The invention relates to a material capable of completely biodegrading, containing the following parts by weight:100 of polyester resin, 5-100 of polylactic resin and the multipolymer thereof, 10-80 of compounding converted starch, 10-60 of inorganic fillers, 0.1-0.9 of resin acceptor and 0.1-1.5 of functional agent wherein the polyester resin is at least one of polybutylene succinate resin, polybutylene adipate resin and the multipolymer thereof. The invention also provides a preparation method of the material. The material capable of completely biodegrading can combine the advantages of each component and has high intensity, modules, elongation at break and toughness, good heat resistance, and the like, thereby meeting the property requirements of a plurality of plastic products in the market and in particular products, such as non-returnable containers, mess kits, agricultural films, and the like, which cause serious white pollution, retaining the complete biodegradability of the material and reducing the production cost under the precondition of no influence on the property requirement.
Description
[technical field]
The present invention relates to polymeric material field, relate in particular to a kind of completely biodegradable material and preparation method thereof.
[background technology]
Plastics because of its have in light weight, satisfactory mechanical property, water-fast, resistance to chemical attack; Good looking appearance, manufacturing and easy for installation, and lower-price characteristic have replaced metal to a great extent rapidly; Timber, glass even paper product are widely used in each department of national economy.It is a lot of convenient that the birth of plastics is come to the daily life band really.Yet along with plastics industry develops into certain degree, some hidden danger that itself exist also come out gradually.The chemicalstability of plastics makes plastics be degraded hardly at occurring in nature, and plastic garbage is more and more, and the residual film of abandoning in environment of plastic refuse sharply increases, almost to being seen everywhere the degree that exists everywhere.Plastic garbage not only influences environmental beauty, and has polluted water source and soil, jeopardizes fowl poultry and wildlife, has brought heavy burden to ball ecological environment.
At present to the processing of plastic refuse, the main employing reclaimed, and burns, and method such as bury, but effect is all undesirable.Thereby the research and development that increasing people advocates development and application degradative plastics, particularly biodegradable plastic have become one of research focus of attracting attention.In general, biodegradated polymer materal refers to: in biology or biochemical action process, or the polymer that can degrade in the coenocorrelation.Therefore, because it has biodegradability, the use of biodegradable plastic can reduce the pollution that plastic garbage brings to ecotope greatly.In biodegradated polymer materal, kind is more, wherein uses frequent have thermoplastic starch (TPS), polycaprolactone (PCL), POLYACTIC ACID (PLA), poly butylene succinate (PBS) or the like.Wherein, aspect the over-all properties of material, comparatively outstanding with PLA and PBS.
Early several years ago, the PCL of fully biodegradable, PLA; Polyester such as PBS are successful development, and the many companies on the Japan and the U.S. and other places have possessed sophisticated throughput; These several years domestic fewer companies also begin to produce, but because these several kinds of polyester are relatively more expensive on price, and partial properties is perfect not enough; POLYACTIC ACIDs etc. also need special requirement to machine-shaping device, and synthesis technique is also comparatively complicated, and all conditions make these several kinds of polyester generally to be accepted by market; So, must carry out modification to above resin material.At present, on the industry to the existing many achievements of the modification of resins such as PBS and PLA, but the modified product of part, in order to reach crucial performance index, completely biodegradable that can't retained product can; Most modified products are in the completely biodegradable ability of retained product, and its partial properties requires to compare with existing non-biodegradation plastic prod, also has a certain distance; Simultaneously, the product after the modification still can't reach on the price or approaching present general-purpose plastics product.So, up to the present can still can't obtain promoting and mass production by biological fully price reduction material product.
Simultaneously, because the unstable of the instability, particularly common composite modified starch of completely biodegradable material; And make modified product have many problems; Such as: weather resistance is bad, causes product producing the for some time of depositing after the completion, physical properties and mechanical property occur and changes; Unsettled situation such as such as the hardness change greatly, elongation at break decline is more obvious; Water tolerance is not strong, cause product and water Long contact time after, bad order appears, decrease of hardness, phenomenons such as product deliquescing.Above phenomenon has limited the practical value of modified product to a certain extent.
[summary of the invention]
Goal of the invention of the present invention provides a kind of completely biodegradable material and preparation method thereof, to overcome the white pollution problems that present general-purpose plastics goods can not be degraded or part is degraded and bring; Overcome the degradative plastics weathering resistance, the water tolerance defect of bad; Reduce the production cost of fully biodegradable plastics, improve its over-all properties; Improve the consistency and the processing characteristics of various materials in the biodegradable plastic, optimization production technology.
For reaching the foregoing invention purpose, the present invention proposes following technical scheme:
A kind of completely biodegradable material, form by following compositions in portion by weight:
Wherein said vibrin is at least a in poly butylene succinate resin, poly adipate succinic acid ester (PBSA) resin and the multipolymer thereof.
In the completely biodegradable material provided by the present invention, said composite modified starch is the substituted treated starch of hydroxyalkyl, and its substitution value is 0.05～0.1%; Also can be the cross-linking modified starch of hydroxyalkyl, its degree of crosslinking be 5～50%; The fineness of these composite modified starchs is 100～600 orders, moisture content≤8%.
In the completely biodegradable material provided by the present invention, the molecular weight of said poly butylene succinate resin, poly adipate succinic acid ester resin and multipolymer thereof is 5～200,000, and the molecular weight of said polylactic resin and multipolymer thereof is 5～300,000.
In the completely biodegradable material provided by the present invention, said mineral filler is to be selected from least a in talcum powder, polynite, kaolin, mica, lime carbonate or the permanent white of fineness more than 3000 orders.
In the completely biodegradable material provided by the present invention; Said coupling agent is a silane coupling agent, in preferred γ-An Bingjisanyiyangjiguiwan, γ-glycidyl ether oxygen propyl trimethoxy silicane or the γ-methacryloxypropyl trimethoxy silane one or more.
In the completely biodegradable material provided by the present invention, said functional agent is to be selected from least a in softening agent, dispersion agent, toughener, hydrolysis inhibitor agent, fire retardant, whipping agent, tinting material or the demoulding auxiliary agent.
In the completely biodegradable material provided by the present invention; Said softening agent is citrate, MO and glycerol acetate etc.; Said dispersion agent is amidess such as hard esteramides, oleylamide, and said toughener is spun glass, mestha and flax fiber etc., and said hydrolysis inhibitor is a carbodiimide compound; Said fire retardant is silicon-series five-retardants such as silicone oil, silicone resin and ZGK 5; Said whipping agent is Cellmic C 121 and zinc oxide, and said tinting material is environmental protection dyestuffs such as diamino-heterocyclic, natural plant dye, and said demoulding auxiliary agent is the two hard esteramides of vinyl etc.
The present invention also provides the preparation method of above-mentioned completely biodegradable material, may further comprise the steps:
The S1 pre-treatment: in drying plant respectively with each resin, composite modified starch and mineral filler, be dried to moisture oven dry;
S2 will be stirred under the normal temperature in stirring mixer in each starting material that predetermined ratio prepares and mix;
S3 puts into twin screw extruder with mixed raw material and carries out extruding pelletization, and extrusion condition is: 100～150 ℃ of feeding section temperature, 150～170 ℃ of compression section temperature, 150～180 ℃ of metering zone temperature, 160～180 ℃ of head temperatures; Screw speed: 90～150r/min;
The S4 aftertreatment: the pellet that in drying plant, will make is dried to the moisture oven dry and gets final product under 60～80 ℃.
Can find out employed macromolecular material (PBS/PBSA, PLA in the completely biodegradable material provided by the present invention from above technical scheme; Starch), comparing with traditional macromolecular material, all is environmentally friendly macromolecular material; Can be at complete biodegradable under the composting conditions; Be decomposed into water and carbonic acid gas, can not produce white pollution, and can not work the mischief environment.
Employed composite modified starch is to replace through hydroxyalkyls such as hydroxypropyl or hydroxyethyls in the completely biodegradable material provided by the present invention; Part and process are cross-linking modified; With PLA; Or the chemical lyotropy of matrix resin such as PBS is better, and comparing with other composite modified starchs has unique advantage; And employed mineral filler and other auxiliary agents all are the low molecule non-toxic substances that on the industry, has used for many years, add the biodegradability that can not influence product in the product, and also can not work the mischief to human and environment.
Completely biodegradable material provided by the present invention is the modification that PBS/PBSA and multipolymer thereof are carried out, and has not only increased the multiple intensity of material, rigidity; Outward appearance, and machine-shaping property have also improved the thermotolerance of PBS; Make that the use temperature of product can be above 100 ℃; So, aspect over-all properties, can compare mutually with present general plastic prod; Simultaneously,, added the cheap material (like starch, mineral filler) of great amount of cost in this biodegradable material, made its cost reduce greatly, near the general-purpose plastics that uses in the market with respect to pure PBS product; In addition; The weathering resistance and the water resistance of the finished product of this biodegradable material are better, test in the actual environment for use of simulation (soak in the water of normal temperature laboratory and the air ambient of normal temperature and pressure in place the several months etc.); Tangible degradation problem all do not occur, have more practicality and public demand.
[description of drawings]
Shown in Figure 1 is the preparation and the modified technique schema of completely biodegradable material provided by the invention.
[embodiment]
Completely biodegradable material provided by the present invention can be widely used in various plastics; When as the injection moulding proprietary material, form: 00 part of PBS/PBSA and copolymer 1 thereof, 5～100 parts of PLA and multipolymers thereof by following composition and content; 10～80 parts of composite modified starchs; 20～60 parts of mineral fillers, 0.3～0.9 part of coupling agent, 0.5～1.5 part of functional agent.Above material usage by weight.
When as the plastic uptake proprietary material, form: 00 part of PBS/PBSA and copolymer 1 thereof, 5～50 parts of PLA and multipolymers thereof by following composition and content; 10～15 parts of composite modified starchs; 10～15 parts of mineral fillers, 0.1～0.3 part of coupling agent, 0.1～0.5 part of functional agent.Above material usage by weight.
When as the blowing proprietary material, form: 00 part of PBS/PBSA and copolymer 1 thereof, 5～100 parts of PLA and multipolymers thereof by following composition and content; 10～20 parts of composite modified starchs; 15～25 parts of mineral fillers, 0.2～0.4 part of coupling agent, 0.1～1.0 part of functional agent.Above material usage by weight.
When as the hollow proprietary material, form: 00 part of PBS/PBSA and copolymer 1 thereof, 5～50 parts of PLA and multipolymers thereof by following composition and content; 10～15 parts of composite modified starchs; 10～20 parts of mineral fillers, 0.1～0.3 part of coupling agent, 0.1～1.0 part of functional agent.Above material usage by weight.
With reference to accompanying drawing 1, the preparation of completely biodegradable material provided by the present invention and modified technique process are:
1. raw-material pre-treatment:
(1) drying: in drying plants such as hot-air oven, PBS/PBSA (molecular weight is 5～200,000), the drying temperature of PLA (molecular weight is 5～300,000) is 60～80 ℃, the time is 3～4 hours; Composite modified starch and mineral filler are 100～110 ℃, and the time is 3～4 hours, if raw-material water content is lower, then the time can foreshorten to 1～2 hour.
(2) mix: each starting material that will prepare stirred 1～3 minute in the stirring mixer high speed, and the stirring at low speed time is 1～4 minute, and temperature gets final product (20～30 ℃) at normal temperature, to mixing.
2. double-screw extruding pelletizing:
(1) each section of forcing machine temperature: 100～150 ℃ of feeding sections, 150～170 ℃ of compression sections, 150～180 ℃ of metering zones, 160～180 ℃ of heads;
(2) screw speed: 90～150r/min;
(3) granulation aftertreatment: in drying plants such as hot-air oven, under 60～80 ℃, drying 2～4 hours is till with the moisture content oven dry with the pellet of making.
3. goods machine-shaping:
(1) injection-molded item:
On general injection moulding machine, process injection-molded item, like heavy wall goods such as disposable tableware cutter, fork, spoons.Wherein, begin each section temperature from the injection moulding machine spout and be 120～190 ℃ and raise gradually, different according to injecting products prescription and type, injection pressure is 50～100MPa, and injection moulding speed is a middling speed or fast slightly, and shaping cycle is 6～40 seconds.In the time of suitable,, can carry out anneal to it in order to guarantee the quality of product.
(2) Blister product:
The processing Blister product carries out in two steps; Earlier that granulation is good plastic uptake proprietary material extrusion sheet on the general-purpose plastics sheet extruder; Wherein, Each section temperature is 140～170 ℃ of feeding sections, 170～185 ℃ of compression sections, 180～195 ℃ of metering zones, 180～200 ℃ of heads, and three roll temperatures are: 50～60 ℃ of top rolls, 70～80 ℃ of central rolls, 40～50 ℃ of lower rolls; The sheet material that will squeeze again is processed into disposable product, like thin-gage goods such as bowl, cup, dish, boxes on general plastic suction forming apparatus.
(3) blow-molded article:
Processing blown film goods on general plastic film blowing machine; Like packing film, refuse bag, food bag etc.; Wherein, The blown film temperature is: 140～155 ℃ of die heads, 135～145 ℃ of threeways, 120～135 ℃ of barrel leading portions, 110～125 ℃ in barrel stage casing, 90～110 ℃ of barrel back segments, and blow-up ratio is: 1.5～2.5, ratio of drawing is: 4～6.
(4) hollow piece:
Machine-shaping hollow piece on general blow moulding machine is like the container bottle of different shape.Wherein, extrusion temperature is 120～170 ℃, and die temperature is 20～50 ℃, and blow-up ratio is 1.5～2.5, and blowing pressure is at 0.3～0.5MPa, and screw speed is 40～50r/min.
With concrete embodiment completely biodegradable material provided by the present invention and preparation and modification are described below, and with the performance test and the comparison of current material.
Embodiment 1 (injection-molded item):
(1) composition and content are formed: 100 parts of PBS (Anqing and Xinghua worker produce, injection grade), and (NatureWork produces PLA; Trade mark 3051D) 40 parts, 40 parts of complex denaturation tapioca(flour)s (100 orders, hydroxypropyl substitution value 0.06-0.07%); Mineral filler (talcum powder; 5000 orders) 30 parts, 0.5 part of coupling agent (silane coupling agent KH560), 1.0 parts of the two hard esteramides (EBS) of functional agent vinyl.Above material usage by weight.
(2) raw-material pre-treatment:
1. dry: in drying plants such as hot-air oven, PBS, the drying temperature of PLA are 80 ℃, and the time is 4 hours; Starch and mineral filler are 105 ℃, and the time is 4 hours;
2. mix: each starting material that will prepare stirred 2 minutes in the stirring mixer high speed, and the stirring at low speed time is 3 minutes, and temperature gets final product (20～30 ℃) at normal temperature, to mixing.
(3) double-screw extruding pelletizing:
1. each section of forcing machine temperature (totally 7 sections) is: one section 120 ℃, and two sections 140 ℃, three sections 155 ℃, four sections 160 ℃, five sections 165 ℃, six sections 160 ℃, seven sections 165 ℃, 170 ℃ of heads;
2. screw speed: 100r/min;
3. granulation aftertreatment: in drying plants such as hot-air oven, under 70 ℃, drying 3 hours is till with the moisture content oven dry with the pellet of making.
(4) above pellet machine-shaping injection-molded item (like heavy wall goods such as disposable tableware cutter, fork, spoons) on general injection moulding machine:
1. beginning each section temperature (totally 4 sections) from the injection moulding machine spout is: one section 120 ℃, and two sections 160 ℃, three sections 175 ℃, four sections 180 ℃;
2. injection pressure is: 80～100MPa;
3. injection moulding speed: 50～60 (middling speed is up to 99);
4. shaping cycle is 30 seconds.
Embodiment 2 (Blister product):
(1) composition and content are formed: 100 parts of PBSA (Mitsubishi Chemical produces, trade mark AD92W), and (NatureWork produces PLA; Trade mark 3051D) 5 parts, 10 parts of complex denaturation tapioca(flour)s (100 orders, hydroxypropyl substitution value 0.06-0.07%); Mineral filler (talcum powder; 5000 orders) 10 parts, 0.1 part of coupling agent (silane coupling agent KH560), 0.1 part of the two hard esteramides (EBS) of functional agent vinyl.Above material usage by weight.
(2) raw-material pre-treatment:
1. dry: equal in the dry equipment at hot-air oven, PBSA, the drying temperature of PLA are 80 ℃, and the time is 3 hours; Starch and mineral filler are 105 ℃, and the time is 3 hours;
2. mix: each starting material that will prepare stirred 1 minute in the stirring mixer high speed, and the stirring at low speed time is 2 minutes, and temperature gets final product (20～30 ℃) at normal temperature, to mixing.
(3) double-screw extruding pelletizing:
1. each section of forcing machine temperature (totally 7 sections): one section 120 ℃, two sections 140 ℃, three sections 155 ℃, four sections 160 ℃, five sections 165 ℃, six sections 160 ℃, seven sections 160 ℃, 165 ℃ of heads;
2. screw speed: 140r/min;
3. granulation aftertreatment: in drying plants such as hot-air oven, under 80 ℃, drying 3 hours is till with the moisture content oven dry with the pellet of making.
(4) above pellet machine-shaping Blister product, carry out in two steps:
1. earlier that granulation is good plastic uptake proprietary material extrusion sheet on the general-purpose plastics sheet extruder, wherein, each section temperature (totally 7 sections) is: one section 140 ℃; Two sections 150 ℃, three sections 160 ℃, four sections 170 ℃; Five sections 175 ℃, six sections 180 ℃, seven sections 185 ℃; 180～190 ℃ of heads, three roll temperatures are: 60 ℃ of top rolls, 70 ℃ of central rolls, 50 ℃ of lower rolls;
The sheet material that 2. will squeeze again is processed into disposable product, like thin-gage goods such as bowl, cup, dish, boxes on general plastic suction forming apparatus.
Embodiment 3 (blow-molded article):
(1) composition and content are formed: 100 parts of PBSA (Mitsubishi Chemical produces, trade mark AD92W), and (NatureWork produces PLA; Trade mark 3051D) 20 parts, 15 parts of complex denaturation tapioca(flour)s (100 orders, hydroxypropyl substitution value 0.06-0.07%); Mineral filler (talcum powder; 5000 orders) 20 parts, 0.2 part of coupling agent (silane coupling agent KH560), 0.5 part of the two hard esteramides (EBS) of functional agent vinyl.Above material usage by weight.
(2) raw-material pre-treatment:
1. dry: in drying plants such as hot-air oven, PBSA, the drying temperature of PLA are 80 ℃, and the time is 3 hours; Starch and mineral filler are 105 ℃, and the time is 3 hours;
2. mix: each starting material that will prepare stirred 2 minutes in the stirring mixer high speed, and the stirring at low speed time is 2 minutes, and temperature gets final product (20～30 ℃) at normal temperature, to mixing.
(3) double-screw extruding pelletizing:
1. each section of forcing machine temperature (totally 7 sections): one section 120 ℃, two sections 140 ℃, three sections 155 ℃, four sections 160 ℃, five sections 165 ℃, six sections 160 ℃, seven sections 165 ℃, 170 ℃ of heads;
2. screw speed: 120r/min;
3. granulation aftertreatment: in drying plants such as hot-air oven, under 70 ℃, drying 3 hours is till with the moisture content oven dry with the pellet of making.
(4) above pellet is processed blown film goods (like packing film, refuse bag, food bag etc.) on general plastic film blowing machine:
1. the blown film temperature is: 140～155 ℃ of die heads, 135～145 ℃ of threeways, 120～135 ℃ of barrel leading portions, 110～125 ℃ in barrel stage casing, 90～110 ℃ of barrel back segments;
2. blow-up ratio is: 1.5～2.5;
3. ratio of drawing is: 4～6.
Embodiment 4 (hollow piece):
(1) composition and content are formed: 100 parts of PBSA (Mitsubishi Chemical produces, trade mark AD92W), and (NatureWork produces PLA; Trade mark 3051D) 50 parts, 10 parts of complex denaturation tapioca(flour)s (100 orders, hydroxypropyl substitution value 0.06-0.07%); Mineral filler (talcum powder; 5000 orders) 20 parts, 0.2 part of coupling agent (silane coupling agent KH560), 0.2 part of the two hard esteramides (EBS) of functional agent vinyl.Above material usage by weight.
(2) raw-material pre-treatment:
1. dry: in drying plants such as hot-air oven, PBSA, the drying temperature of PLA are 80 ℃, and the time is 4 hours; Starch and mineral filler are 105 ℃, and the time is 4 hours;
2. mix: each starting material that will prepare stirred 2 minutes in the stirring mixer high speed, and the stirring at low speed time is 3 minutes, and temperature gets final product (20～30 ℃) at normal temperature, to mixing.
(3) double-screw extruding pelletizing:
1. each section of forcing machine temperature (totally 7 sections): one section 120 ℃, two sections 140 ℃, three sections 155 ℃, four sections 165 ℃, five sections 170 ℃, six sections 165 ℃, seven sections 170 ℃, 175 ℃ of heads;
2. screw speed: 100r/min;
3. granulation aftertreatment: in drying plants such as hot-air oven, under 70 ℃, drying 3 hours is till with the moisture content oven dry with the pellet of making.
(4) machine-shaping hollow piece (like the container bottle of different shape) on general blow moulding machine:
1. extrusion temperature is: 120～170 ℃, die temperature is: 20～50 ℃;
2. blow-up ratio is: 1.5～2.5;
3. blowing pressure: 0.3～0.5MPa;
4. screw speed is: 40～50r/min.
Embodiment 5 (injection-molded item):
(1) composition and content are formed: 50 parts of 50 parts of PBS (Anqing and Xinghua worker produce, injection grade) and PBSA (Mitsubishi Chemical produces, trade mark AD92W); 100 parts of PLA (NatureWork produces, trade mark 3051D), complex denaturation tapioca(flour) (100 orders; Hydroxypropyl substitution value 0.06-0.07%) 80 parts, 60 parts of mineral fillers (talcum powder, 5000 orders); 0.9 part of coupling agent (silane coupling agent KH560), 1.5 parts of the two hard esteramides (EBS) of functional agent vinyl.Above material usage by weight.
(2) raw-material pre-treatment:
1. dry: in drying plants such as hot-air oven, PBS, PBSA, the drying temperature of PLA are 80 ℃, the time is 4 hours; Starch and mineral filler are 105 ℃, and the time is 4 hours;
2. mix: each source material that will prepare stirred 2 minutes in the stirring mixer high speed, and the stirring at low speed time is 3 minutes, and temperature gets final product (20～30 ℃) at normal temperature, to mixing.
(3) double-screw extruding pelletizing:
1. each section of forcing machine temperature (totally 7 sections) is: one section 120 ℃, and two sections 140 ℃, three sections 155 ℃, four sections 160 ℃, five sections 165 ℃, six sections 160 ℃, seven sections 165 ℃, 170 ℃ of heads;
2. screw speed: 100r/min;
3. granulation aftertreatment: in drying plants such as hot-air oven, under 70 ℃, drying 3 hours is till with the moisture content oven dry with the pellet of making.
(4) above pellet machine-shaping injection-molded item (like heavy wall goods such as disposable tableware cutter, fork, spoons) on general injection moulding machine:
1. beginning each section temperature (totally 4 sections) from the injection moulding machine spout is: one section 120 ℃, and two sections 160 ℃, three sections 175 ℃, four sections 180 ℃;
2. injection pressure is: 80～100MPa;
3. injection moulding speed: 50～60 (middling speed is up to 99);
4. shaping cycle is 30 seconds.
Embodiment 6 (hollow piece):
(1) composition and content are formed: 35 parts of PBS (Anqing and Xinghua worker produce, the injection moulding rank) and PBSA65 (Mitsubishi Chemical produces, trade mark AD92W) part; 50 parts of PLA (NatureWork produces, trade mark 3051D), complex denaturation tapioca(flour) (100 orders; Hydroxypropyl substitution value 0.06-0.07%) 10 parts, 20 parts of mineral fillers (talcum powder, 5000 orders); 0.2 part of coupling agent (silane coupling agent KH560), 0.2 part of the two hard esteramides (EBS) of functional agent vinyl.Above material usage by weight.
(2) raw-material pre-treatment:
1. dry: in drying plants such as hot-air oven, PBS, PBSA, the drying temperature of PLA are 80 ℃, the time is 4 hours; Starch and mineral filler are 105 ℃, and the time is 4 hours;
2. mix: each starting material that will prepare stirred 2 minutes in the stirring mixer high speed, and the stirring at low speed time is 3 minutes, and temperature gets final product (20～30 ℃) at normal temperature, to mixing.
(3) double-screw extruding pelletizing:
1. each section of forcing machine temperature (totally 7 sections): one section 120 ℃, two sections 140 ℃, three sections 155 ℃, four sections 165 ℃, five sections 170 ℃, six sections 165 ℃, seven sections 170 ℃, 175 ℃ of heads;
2. screw speed: 100r/min;
3. granulation aftertreatment: in drying plants such as hot-air oven, under 70 ℃, drying 3 hours is till with the moisture content oven dry with the pellet of making.
(4) machine-shaping hollow piece (like the container bottle of different shape) on general blow moulding machine:
1. extrusion temperature is: 120～170 ℃, die temperature is: 20～50 ℃;
2. blow-up ratio is: 1.5～2.5;
3. blowing pressure: 0.3～0.5MPa;
4. screw speed is: 40～50r/min.
The The performance test results of the prepared completely biodegradable material of the foregoing description is seen shown in the table 1:
Table 1
| Test event | Unit | Embodiment (1) | Embodiment (2) | Embodiment (3) | Embodiment (4) |
| Tensile strength | MPa | ＞25 | ＞25 | ＞25 | ＞25 |
| Elongation at break | ％ | ＞20 | ＞100 | ＞100 | ＞20 |
| Flexural strength | MPa | ＞50 | ＞50 | ＞50 | ＞50 |
| Modulus in flexure | MPa | ＞1500 | ＞1500 | ＞1500 | ＞1500 |
| Notched Izod impact strength | kj/m 2 | ＞6 | ＞8 | ＞8 | ＞6 |
| Heat-drawn wire | ℃ | ＞95 | ＞95 | ＞95 | ＞95 |
| Biological degradation rate (90 days) | ％ | ＞90 | ＞90 | ＞90 | ＞90 |
The weathering resistance and the water tolerance contrast test result of the foregoing description 1 prepared completely biodegradable material and common biodegradable material see shown in table 2 and the table 3:
Table 2
Annotate: (1) testing method is: at normal temperature, and normal pressure, humidity is 40～70% indoor environment placement, every certain hour of crossing extracts experimental sample and goods and carries out Performance Detection;
(2) the External Observation method for testing is: after removing surface dirt, and range estimation, surface color, gloss and the shape variation degree of check goods.
Table 3
Annotate: (1) testing method is: at normal temperature, soak in the non-pressurized tap water, every certain hour of crossing extracts experimental sample and goods and carries out Performance Detection;
(2) the External Observation method for testing is: after removing surface-moisture, and range estimation, surface color, gloss and the shape variation degree of check goods.
In other optional embodiment, the mineral filler of being adopted can also be used the medium replacement talcum powder of the above polynite of 3000 orders, kaolin, mica, lime carbonate or permanent white; Silane coupling agent also can be selected γ-An Bingjisanyiyangjiguiwan, γ-glycidyl ether oxygen propyl trimethoxy silicane or γ-methacryloxypropyl trimethoxy silane etc. for use individually or simultaneously; Also the different purposes of visual goods and selectivity add one or more functional agents, like softening agent (citrate, MO and glycerol acetate etc.), dispersion agent (amidess such as hard esteramides, oleylamide), toughener (spun glass, mestha and flax fiber etc.), hydrolysis inhibitor (carbodiimide compound etc.), fire retardant (silicon-series five-retardants such as silicone oil, silicone resin and ZGK 5), whipping agent (Cellmic C 121 and zinc oxide etc.), tinting material (environmental protection dyestuffs such as diamino-heterocyclic, natural plant dye), demoulding auxiliary agent (the two esteramides firmly of vinyl etc.).
The above embodiment has only expressed several kinds of embodiments of the present invention, and it describes comparatively concrete and detailed, but can not therefore be interpreted as the restriction to claim of the present invention.Should be pointed out that for the person of ordinary skill of the art under the prerequisite that does not break away from the present invention's design, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be as the criterion with accompanying claims.
Claims (3)
1. a completely biodegradable material is characterized in that, is made up of following compositions in portion by weight:
The hydroxypropyl substitution value of said complex denaturation tapioca(flour) is at 0.06-0.07%.
2. completely biodegradable material according to claim 1 is characterized in that, the talcous fineness of said mineral filler is more than 3000 orders.
3. the preparation method of the described completely biodegradable material of claim 1 may further comprise the steps:
S1 pre-treatment: in drying plant, respectively resin, composite modified starch and mineral filler are dried to the moisture oven dry;
S2 will be stirred under the normal temperature in stirring mixer in each starting material that predetermined ratio prepares and mix;
S3 puts into twin screw extruder with mixed raw material and carries out extruding pelletization, and extrusion condition is: 100～150 ℃ of feeding section temperature, 150～170 ℃ of compression section temperature, 150～180 ℃ of metering zone temperature, 160～180 ℃ of head temperatures; Screw speed: 90～150r/min;
The S4 aftertreatment: the pellet that in drying plant, will make is dried to the moisture oven dry and gets final product under 60～80 ℃.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5844023A (en) * | 1992-11-06 | 1998-12-01 | Bio-Tec Biologische Naturverpackungen Gmbh | Biologically degradable polymer mixture |
| CN1434076A (en) * | 2003-02-26 | 2003-08-06 | 中国科学院上海有机化学研究所 | Inorganic matter filled biodegrading material, preparation method and use thereof |
| CN1858114A (en) * | 2006-04-25 | 2006-11-08 | 邓国权 | Preparation of biological degradation resin composite and modified special resin and product forming process |
| CN1931906A (en) * | 2005-09-16 | 2007-03-21 | 李小鲁 | Biodegradable composition and its prepn process and filming product |
| CN1948374A (en) * | 2006-09-28 | 2007-04-18 | 浙江华发生态科技有限公司 | Biomass full degradable material and its preparation technology |
| CN101245174A (en) * | 2008-03-18 | 2008-08-20 | 浙江华发生态科技有限公司 | Hydroted alumina-poly-succinic acid butanediol ester composite degradation material and preparation technique |
-
2009
- 2009-03-23 CN CN2009101061764A patent/CN101519524B/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5844023A (en) * | 1992-11-06 | 1998-12-01 | Bio-Tec Biologische Naturverpackungen Gmbh | Biologically degradable polymer mixture |
| CN1434076A (en) * | 2003-02-26 | 2003-08-06 | 中国科学院上海有机化学研究所 | Inorganic matter filled biodegrading material, preparation method and use thereof |
| CN1931906A (en) * | 2005-09-16 | 2007-03-21 | 李小鲁 | Biodegradable composition and its prepn process and filming product |
| CN1858114A (en) * | 2006-04-25 | 2006-11-08 | 邓国权 | Preparation of biological degradation resin composite and modified special resin and product forming process |
| CN1948374A (en) * | 2006-09-28 | 2007-04-18 | 浙江华发生态科技有限公司 | Biomass full degradable material and its preparation technology |
| CN101245174A (en) * | 2008-03-18 | 2008-08-20 | 浙江华发生态科技有限公司 | Hydroted alumina-poly-succinic acid butanediol ester composite degradation material and preparation technique |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI494323B (en) * | 2013-08-30 | 2015-08-01 | Ind Tech Res Inst | Modified starch compositions, starch composite foam materials and method for preparing the starch composite foam material |
| US9850362B2 (en) | 2013-08-30 | 2017-12-26 | Industrial Technology Research Institute | Modified starch compositions, starch composite foam materials and method for preparing the starch composite foam material |
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