CN103881338B - A kind of antistatic biodegradation material of novel flame-retardant and preparation method thereof - Google Patents

A kind of antistatic biodegradation material of novel flame-retardant and preparation method thereof Download PDF

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CN103881338B
CN103881338B CN201210554523.1A CN201210554523A CN103881338B CN 103881338 B CN103881338 B CN 103881338B CN 201210554523 A CN201210554523 A CN 201210554523A CN 103881338 B CN103881338 B CN 103881338B
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parts
agent
retardant
acid
biodegradation material
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CN103881338A (en
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侯连龙
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Xiao Tongjian
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SHANGHAI ZAIHE INDUSTRIAL INVESTMENT Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/74—Mixing; Kneading using other mixers or combinations of mixers, e.g. of dissimilar mixers ; Plant
    • B29B7/7461—Combinations of dissimilar mixers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
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    • B29B7/80—Component parts, details or accessories; Auxiliary operations
    • B29B7/88—Adding charges, i.e. additives
    • B29B7/90—Fillers or reinforcements, e.g. fibres
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    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B29B9/14—Making granules characterised by structure or composition fibre-reinforced
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    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
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    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
    • B29C48/50—Details of extruders
    • B29C48/505—Screws
    • B29C48/625—Screws characterised by the ratio of the threaded length of the screw to its outside diameter [L/D ratio]
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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    • C09K21/00—Fireproofing materials
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    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00—Making granules
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    • B29B2009/125—Micropellets, microgranules, microparticles
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    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29B7/00—Mixing; Kneading
    • B29B7/02—Mixing; Kneading non-continuous, with mechanical mixing or kneading devices, i.e. batch type
    • B29B7/06—Mixing; Kneading non-continuous, with mechanical mixing or kneading devices, i.e. batch type with movable mixing or kneading devices
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29B7/00—Mixing; Kneading
    • B29B7/30—Mixing; Kneading continuous, with mechanical mixing or kneading devices
    • B29B7/34—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices
    • B29B7/38—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary
    • B29B7/46—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with more than one shaft
    • B29B7/48—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with more than one shaft with intermeshing devices, e.g. screws
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
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    • B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
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    • B29C2948/92561—Time, e.g. start, termination, duration or interruption
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29C2948/00—Indexing scheme relating to extrusion moulding
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B29C2948/00—Indexing scheme relating to extrusion moulding
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    • B29C2948/92504—Controlled parameter
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29C2948/00—Indexing scheme relating to extrusion moulding
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    • B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
    • B29C2948/92885—Screw or gear
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29C2948/00—Indexing scheme relating to extrusion moulding
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    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
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Abstract

The invention belongs to biodegradation material field, it is related to a kind of flame-retardant and anti-static biodegradation material and preparation method thereof.The biodegradation material is made of the component including following parts by weight：5 ~ 90 parts of Biodegradable resin, 0 ~ 10 part of reactivity agent, 5 ~ 90 parts of flame-retardant and anti-static starch masterbatch.The compounding that the present invention passes through organic antistatic agents and inorganic antistatic agent, the lasting antistatic property of biodegradation material is not given only, and reduce dependence of the antistatic property to ambient humidity, addition effectively improves the flammability problems of biodegradation material using starch as the expansion type flame retardant of carbon source simultaneously.The antistatic agent and expansion type flame retardant of the present invention is all environmental-friendly, and the excellent mechanical property and processing performance that maintain biodegradation material itself.

Description

A kind of antistatic biodegradation material of novel flame-retardant and preparation method thereof
Technical field
The invention belongs to biodegradation material field, it is related to a kind of flame-retardant and anti-static biodegradation material and its preparation side Method.
Background technology
Biodegradation material is widely used in all trades and professions, mainly include environment-friendly materials, packaging material and medical material, Conventional plastic can partly be replaced.But biodegradation material has excellent electrical insulating property, resistivity as conventional plastic Height is easy accumulation electrostatic charge in production and application and generates electrostatic phenomenon, causes some harm or accident.Therefore, life is eliminated The electrostatic of object degradable material, reduction resistivity are imperative.The inflammability of biodegradable plastic also largely limits simultaneously It is safely and effectively applied.
In order to eliminate material electrostatic, the generally method by adding antistatic agent.Patent CN200480003880.2 passes through Add diglycerine fatty acid ester poly- succinic acid fourth diester is carried out it is antistatic modified, 20 DEG C of the temperature, humidity 65%RH the case where Under, the surface resistivity for measuring poly- succinic acid fourth diester is 2 × 109Ω, antistatic property is more excellent, but such antistatic Material only just can effectively play antistatic effect in the environment of high humility, this is because the antistatic agent of addition is surface Activating agent adsorbs the moisture in air by hydrophilic group, and forming a monomolecular conductive layer in material surface reveals electrostatic Lotus plays antistatic property, therefore its anlistatig effect is strongly depend on ambient humidity, in addition, antistatic agent is in material table Face is simple physical absorption, is easy to be lost because of washing or friction the effects that.Patent CN201010513302.0 is provided The additive amount of a kind of short carbon fiber reinforced antistatic poly-lactic acid material and preparation method thereof, short carbon fiber is 10 ~ 40%, patent CN200780100909.2 is prepared for a kind of electrically conductive composition including adhesive and conductive filler granule, the addition of conductive filler Amount is 40% or more, although anti-static material antistatic property prepared by the above method is excellent, the additive amount of inorganic antistatic agent Too big, difficulties in dispersion in the material deteriorates the performance of product.It has been reported that through organic antistatic agents and inorganic antistatic agent Compounding, can be effectively improved above two method there are the problem of, compounded if Guo waits person's polyethylene glycol and zinc oxide quietly, it is right Polypropylene fibre progress is antistatic modified, improves fibre hue difference, antistatic effect durability difference and antistatic effect The problems such as being strongly depend on envionmental humidity, if Lee's cinnabar et al. is compounded with carbon nanotube and organic antistatic agents, with poly- third Alkene is blended to be prepared for antistatic fibre, significantly reduces the fricting static charge of polypropylene fiber.It is anti-quiet by preparing according to another report Then goddess of lightning's material adds again, can be effectively improved the antistatic property of material, be processed twice this is because antistatic agent have passed through, Dispersion evenly, is more conducive to performance antistatic effect, as patent 87107694.2 provides a kind of polypropylene antistatic mother The preparation method of material blends the polypropylene fibre of this antistatic master batch spinning, and spinnability and fibre property are substantially better than directly Connect the polypropylene fibre of addition antistatic agent spinning.
In biodegradation material flame-retardant modified document and patent, a kind of expansion type flame retardant, such as patent are provided 200510095368, patent 200910117485, patent 201010534448, patent 201010534450, the expansion type flame-retarding Agent is using starch as carbon source, by the way that acid source, air source are added in process, can be effectively improved the inflammability of biodegradation material Problem.
Document antistatic modified about biodegradation material at present and patent are fewer, and are all that addition is single and resist Electrostatic agent, such as patent CN200580046939.8, patent CN201110394987.6, fresh there are two types of antistatic agent compounding preparation is anti- The document and patent of electrostatic biodegradation material.
Invention content
It is an object of the invention to overcome the insufficient defect that biodegradation material is antistatic modified in the prior art and Using the advantage of advantage and antistatic master batch that organic antistatic agents and inorganic antistatic agent compound, provide a kind of fire-retardant anti- Electrostatic biodegradation material and preparation method thereof.
Even if biodegradation material prepared by the present invention still can effectively play antistatic effect in the case of low humidity Fruit, and antistatic effect is lasting, while the antistatic agent added is environmental-friendly, and biodegradation material itself can be kept excellent Mechanical property and processing performance；For using starch as the advantage of the expansion type flame retardant of carbon source, the present invention also add simultaneously with Starch is the expansion type flame retardant of carbon source, effectively improves the flammability problems of biodegradation material.
To achieve the above object, the present invention uses following technical scheme：
A kind of biodegradation material is made of the component including following parts by weight：
5 ~ 90 parts of Biodegradable resin,
0 ~ 10 part of reacting movable agent,
5 ~ 90 parts of flame-retardant and anti-static starch masterbatch.
Preferably, the reacting movable agent is 1-10 parts.
The Biodegradable resin is selected from polylactic acid, polyglycolide, poly (glycolide-lactide), polycaprolactone, polyvinyl alcohol, gathers Esteramide copolymers, polyhydroxyalkanoate, polyhydroxybutyrate valerate, poly butylene succinate, polydioxanone, Carbon dioxide-ethylene oxide copolymer, carbon dioxide-epoxy propane copolymer, polyadipate-butylene terephthalate or fourth One or more in diacid-adipic acid-butanediol ester copolymer.
The flame-retardant and anti-static starch masterbatch, is made of the component comprising following parts by weight：
The vector resin is preferably 1-50 parts.
The reacting movable agent is preferably 1-20 parts.
The starch be selected from cornstarch, wheaten starch, tapioca, potato starch, sweet potato starch, starch from sweet potato, One or more in water caltrop starch or Rhizoma Nelumbinis starch.
The plasticizer is selected from glycerine, urea, ethylene glycol, propylene glycol, butanediol, xylitol, sorbierite, ethanol amine, first One or more in amide, polyethylene glycol, tristerin, dibutyl adipate or tributyl citrate.
The expansion type flame retardant is made of carbon source, acid source and air source, and the weight ratio of three is preferably 1:3:1.
The carbon source is starch, one kind or one in further preferred cornstarch, wheaten starch or potato starch Kind or more.
One or more of the acid source in ammonium polyphosphate, ammonium magnesium phosphate or zinc borate.
The air source is selected from urea, melamine, dicyandiamide, melamine, hexamethylenetetramine, polyaminoacid ester, azo One or more in bis-isobutyronitrile, glycine or wood powder.
The organic antistatic agents are selected from glycerol monolaurate, glyceryl oleate, palmitin, glycerol stearate Ester, polyglyceryl laurate, Unigly GO 102S, polyglyceryl palmitate, polyglycerol stearate, polyethylene glycol lauric acid One or more in ester, polyethylene glycol (PEG) oleate, polyethylene glycol palmitate or polyethylene glycol stearate.
The inorganic antistatic agent is selected from carbon black, carbon fiber, expanded graphite, carbon nanotube, silica, aluminium oxide or oxygen Change the one or more in zinc.
The vector resin is selected from polylactic acid, polyglycolide, poly (glycolide-lactide), polycaprolactone, polyvinyl alcohol, polyesteramide Copolymer, polyhydroxyalkanoate, polyhydroxybutyrate valerate, poly butylene succinate, polydioxanone, titanium dioxide Carbon-ethylene oxide copolymer, carbon dioxide-epoxy propane copolymer, polyadipate-butylene terephthalate or succinic acid- One or more in adipic acid-butanediol ester copolymer.
The reacting movable agent is epoxy-activated agent, carbodiimide substance, acid anhydrides substance or isocyanates One or more in substance, the further preferably acrylic ester compound, Glycidyl methacrylate of epoxy group Glyceride type compound, epoxy soybean oils compound, dicyclohexylcarbodiimide, diisopropylcarbodiimide, two（2,6- bis- Isopropyl phenyl）Carbodiimide, 1- ethyls-（3- dimethylaminopropyls）Phosphinylidyne diimmonium salt hydrochlorate, activator Stabaxol-P（German Rhine chemical company）, activator Stabaxol-P200（German Rhine chemical company）, activator Stabaxol-100（German Rhine chemical company）, activator Stabaxol-I（German Rhine chemical company）, maleic anhydride, first Base glycidyl acrylate, 1,6- cyclohexylene diisocyanates, 4,4 '-di-2-ethylhexylphosphine oxides（Cyclohexyl isocyanate）, lysine first One or more in base ester diisocyanate or butane diisocyanate.
Preferably, the reacting movable agent is the molecular weight containing at least three epoxy group/segment less than 5,000 Oligomer or prepolymer, preferably one is specifically BASF AG of the U.S. suitable for the activator of system of the present invention （BASF）The JoncrylTM series of products of production.
The processing aid is selected from heat stabilizer, light stabilizer, lubricant, coupling agent, filler, colorant or foaming agent In one or more.
One or more of the heat stabilizer in phosphite ester kind antioxidant or Hinered phenols antioxidant, it is excellent It is selected as trialkyl phosphites, mixed alkyl/aryl phosphate ester, alkyl aryl phosphate ester, sterically hindered aryl phosphate ester, fat Spirocyclic phosphites, steric-hindrance phenyl, steric-hindrance bisphosphate or one kind in hydroxy-phenylpropionic acid ester or one kind More than；Further preferably antioxidant 1010, irgasfos 168, trisnonyl phenyl phosphite（TNPP）, heat stabilizer Irgafos168, heat stabilizer Ultranox626, heat stabilizer Cyanox2777, heat stabilizer Irganox B, heat stabilizer Irganox LC, heat stabilizer IrganoxLM, heat stabilizer IrganoxHP, heat stabilizer IrganoxXP, heat stabilizer Ultranox815A, heat stabilizer Ultranox817A, heat stabilizer Ultranox875A, heat stabilizer Naugard900 or heat One or more in stabilizer CyanoxXS4.
The light stabilizer be selected from carbon black, zinc oxide, titanium dioxide, zinc barium or benzophenone stabilizer, described two Benzophenone class stabilizer be more preferably light stabilizer UV400, light stabilizer UV9 or one kind in light stabilizer UV531 or More than one.
The lubricant be selected from stearic acid, butyl stearate, oleamide, glyceryl tristearate, ethylene bis stearamide, One or more in natural paraffin wax, white oil, microcrystalline wax, barium stearate, zinc stearate or calcium stearate.
The coupling agent is selected from silane coupling agent, titanate coupling agent, aluminate coupling agent, bimetallic coupling agent, phosphoric acid One or more in ester coupling agent, boric acid ester coupler, chromium complex, zirconium coupling agent or rare-earth coupling agent.
Preferably, the silane coupling agent is selected from γ-neon propyl front three nitrogen base silane, vinyl trichlorosilane, ethylene Ethyl triethoxy silicane alkane, vinyltrimethoxysilane, vinyl three ('beta '-methoxy ethyoxyl) silane, γ-(methacryls Oxygroup) propyl trimethoxy silicane, β-(3,4- epoxy cyclohexyl) ethyl trimethoxy silanes or γ-(2,3- glycidoxy) One or more in propyl trimethoxy silicane.
Preferably, the titanate coupling agent is selected from isopropyl thirdly (isostearoyl base) titanate esters, (the burnt phosphorus of isopropyl three Dioctyl phthalate) titanate esters, the oxygen-containing acetic acid esters titanium of two (dioctyl pyrophosphoryl bases), tetra isopropyl two (phosphorous acid dilauryl) metatitanic acid Ester, isopropyl three（Dioctyl pyrophosphoryl base) titanate esters, two（Dioctyl pyrophosphoryl base）Ethylene titanate esters, pyrophosphoric acid type list alcoxyl Base class titanate esters, plant acid type monoalkoxy class titanate esters, phosphatic type monoalkoxy class titanate esters, two (metering system of isopropyl Acyl group) isostearoyl base titanate esters, isopropyl three (dioctyl phosphoryl) titanate esters, isopropyl three（Dodecyl benzenesulfonyl） One or more in titanate esters or isopropyl three (positive ethylamino-ethylamino) titanate esters.
The filler is selected from calcium carbonate, calcium sulfate, montmorillonite, talcum powder, chitosan, chitin, glass microballoon, stone It is cotton, mica, silica, wood powder, shell powder, concave convex rod, clay, carbon black, clay, cellulose, glass fibre, carbon fiber, inorganic One or more in fiber, organic fiber, whisker or metal powder.
The colorant is selected from titanium dioxide, carbon black, lithopone, chrome yellow, barba hispanica, iron oxide yellow, silver powder, brass powder, pigment scarlet powder, idol Yellowish, phthalocyanine blue, quinacridone, cinnabar, laterite, realgar, peacock green, calcium carbonate, wollastonite, blanc fixe, talcum powder, mica Powder, kaolin etc..
The foaming agent is selected from chemical foaming agent or physical blowing agent.
The chemical foaming agent is selected from azo compound, N- nitroso compounds, sulfonyl hydrazines compound, urea groups One or more in compound, carbonate, nitrite, further preferably Azodicarbonamide, azoformic acid Diisopropyl ester, azodiisobutyronitrile, two ammonium carbonate of azo, barium azodicarboxylate, N, N'- dinitrosopentamethlyene tetramines, N, N'- dinitrosoterephthalamines, sodium nitrite-ammonium chloride, urea, unifor, phenylSulphon hydrazine, to diphenyl One or more in sulfohydrazide acid, sodium bicarbonate or ammonium hydrogen carbonate.
One or more of the physical blowing agent in low-boiling alkane or fluorocarbons, further One preferably in pentane, n-hexane, normal heptane, petroleum ether, Arcton 11, dicholorodifluoromethane or dichlorotetra-fluoroethane Kind or more than one.
A kind of preparation method of above-mentioned biodegradation material, includes the following steps：
（1）Prepare flame-retardant and anti-static starch masterbatch：
Weigh 10 ~ 90 parts of starch, 5 ~ 50 parts of plasticizer, 5 ~ 90 parts of expansion type flame retardants, 5 ~ 40 parts of organic antistatic agents, 1 ~ 20 parts of inorganic antistatic agent, 0 ~ 50 part of vector resin, 0 ~ 20 part of reacting movable agent and 0 ~ 60 part of other processing aid are first just mixed, mix After closing uniformly, remelted blending is granulated finally by comminutor, obtains flame-retardant and anti-static starch masterbatch.It is spare；
（2）By step（1）5 ~ 90 parts of flame-retardant and anti-static starch masterbatch, 0 ~ 10 part of reacting movable agent and 5 ~ 90 of middle preparation Part Biodegradable resin is first just mixed, and remelted blending is granulated finally by comminutor, you can biodegradation material is made.
The step（1）In it is just mixed used in equipment be high mixer, just do time as 1 ~ 20min；
The step（1）Equipment used in middle melt blending is selected from double screw extruder, the twin-screw extrusion The screw speed of machine is 50 ~ 150rpm, and screw slenderness ratio L/D is 15 ~ 50, and the temperature of melt blending is 60 ~ 200 DEG C, and melting is altogether The mixed time is 1 ~ 15min.
The step（2）In it is just mixed used in equipment be high mixer, just do time as 1 ~ 10min；
The step（2）Equipment double screw extruder used in middle melt blending, the double screw extruder Screw speed is 50 ~ 150rpm, and screw slenderness ratio L/D is 15 ~ 50, and the temperature of melt blending is 60 ~ 250 DEG C, melt blending Time is 1 ~ 10min.
Compared with prior art, the present invention has the following advantages：
（1）The present invention passes through the compounding of organic antistatic agents and inorganic antistatic agent, the antistatic biodegradable material of preparation Not only antistatic property is lasting for material, but also is influenced by ambient humidity smaller, and greatly expand biodegradation material uses model It encloses；
（2）The present invention effectively improves biodegradation material by adding the expansion type flame retardant using starch as carbon source Flammability problems；
（3）The antistatic agent and expansion type flame retardant that the present invention adds are nontoxic, and the biodegradation material of preparation does not also pollute Environment；
（4）The method comprises the steps of firstly, preparing flame-retardant and anti-static starch masterbatch, then modification biological degradable material, are conducive to antistatic agent With the dispersion of fire retardant, antistatic and flame retardant effect is improved；
（5）Biodegradation material prepared by the present invention maintains the excellent mechanical property of biodegradation material itself and processing Performance.
Specific implementation mode
It is further illustrated the present invention with reference to embodiment.
In following embodiment, the standard and method of dependence test are：
The test equipment of mechanical property is microcomputer controlled electronic universal tester, and testing standard is ASTM D638, stretches speed Degree is 500mm/min, tests 5 times and is averaged；
Antistatic property test uses Insulation Resistance Tester, test condition：Environment temperature is 25 ± 2 DEG C, ambient humidity 30 ± 5%RH and 60 ± 5%RH is tested 3 times and is averaged.
Flame retardant property test use oxygen index (OI) tester and Vertical combustion instrument, testing standard be respectively GB2406-80 and GB4609-1984。
In the following example, unless otherwise instructed, the dosage of each raw material is in parts by weight.
Embodiment 1
（1）The preparation of flame-retardant and anti-static starch masterbatch：By 35 parts of cornstarch, 15 parts of plasticizer glycerine, 25 parts of intumescents Fire retardant（Cornstarch：Ammonium polyphosphate：Melamine=1:3:1）, 8 parts of organic antistatic agents glyceryl oleates, 2 parts it is inorganic anti- Electrostatic agent aluminium oxide, 7 parts of vector resin polyadipate-butylene terephthalates, 4 parts of activator 1,6- cyclohexylene diisocyanates It is added to high-speed mixer and mixing 5min with 4 parts of heat stabilizer Irgafos168 sequences, is then added to 120 DEG C of twin-screw extrusion Extruding pelletization in machine obtains flame-retardant and anti-static starch masterbatch, spare, and wherein screw speed is 50rpm, and screw slenderness ratio L/D is 15, the time of melt blending is 5min；
（2）Take 30 parts of steps（1）In flame-retardant and anti-static starch masterbatch, 70 parts of Biodegradable resin polyadipates-are to benzene Dioctyl phthalate fourth diester is added to high-speed mixer and mixing 4min, is then added to extruding pelletization in 140 DEG C of double screw extruder, obtains To flame-retardant and anti-static biodegradation material, wherein screw speed is 50rpm, and screw slenderness ratio L/D is 15, the time of melt blending For 5min.
Embodiment 2
（1）The preparation of flame-retardant and anti-static starch masterbatch：By 35 portions of wheaten starches, 15 parts of plasticizer sorbierites, 28 parts of expansions Type fire retardant（Wheaten starch：Ammonium magnesium phosphate：Melamine=1:3:1）, 8 parts of organic antistatic agents polyglyceryl laurates, 2 parts it is inorganic Antistatic agent zinc oxide, 7 parts of vector resin polyadipate-butylene terephthalates and 5 parts of activator Stabaxol-P200 are suitable Sequence is added to high-speed mixer and mixing 10min, is then added to extruding pelletization in 100 DEG C of double screw extruder, obtains fire-retardant anti- Electrostatic starch masterbatch, spare, wherein screw speed is 100rpm, and screw slenderness ratio L/D is 20, and the time of melt blending is 10min, finally by comminutor；
（2）Take 40 parts of steps（1）In flame-retardant and anti-static starch masterbatch, 60 parts of Biodegradable resin polyadipates-are to benzene Dioctyl phthalate fourth diester is added to high-speed mixer and mixing 6min, is then added to extruding pelletization in 80 DEG C of double screw extruder, obtains To flame-retardant and anti-static biodegradation material, wherein screw speed is 100rpm, and screw slenderness ratio L/D is 25, melt blending when Between be 10min.
Embodiment 3
（1）The preparation of flame-retardant and anti-static starch masterbatch：By 35 parts of potato starch, 15 parts of plasticizer urea, 30 parts of expansions Type fire retardant（Potato starch：Zinc borate：Dicyandiamide=1:3:1）, 12 parts of organic antistatic agents polyethylene glycol stearates, 1 part Inorganic antistatic agent carbon black, 7 parts of vector resin polyadipates-butylene terephthalate sequence are added to high-speed mixer and mixing 8min is then added to extruding pelletization in 130 DEG C of double screw extruder, obtains flame-retardant and anti-static starch masterbatch, spare, wherein Screw speed is 150rpm, and screw slenderness ratio L/D is 25, and the time of melt blending is 8min；
（2）Take 45 parts of steps（1）In flame-retardant and anti-static starch masterbatch, 2 parts of reacting movable agent maleic anhydrides and 53 parts it is poly- Adipic acid-butylene terephthalate is added to high-speed mixer and mixing 3min, is then added in 180 DEG C of double screw extruder Extruding pelletization obtains flame-retardant and anti-static biodegradation material, and wherein screw speed is 150rpm, and screw slenderness ratio L/D is 20, is melted The time for melting blending is 10min.
Embodiment 4
（1）The preparation of flame-retardant and anti-static starch masterbatch：By 30 parts of cornstarch, 15 parts of plasticizer formamides, 25 parts of expansions Type fire retardant（Cornstarch：Ammonium polyphosphate：Wood powder=1:3:1）, 12 parts of organic antistatic agents polyethylene glycol laurate, 3 parts of nothings Machine antistatic agent zinc oxide, 5 parts of vector resin polycaprolactones, 2.5 parts of heat stabilizer TNPP, 2.5 parts of heat stabilizers Irgafos168,5 parts of n-hexanes（Foaming agent）, it is sequentially added to high-speed mixer and mixing 10min, is then added to 95 DEG C of double spiral shells Extruding pelletization in bar extruder obtains flame-retardant and anti-static starch masterbatch, spare, and wherein screw speed is 100rpm, screw rod major diameter It is 20 than L/D, the time of melt blending is 10min；
（2）Take 60 parts of steps（1）In flame-retardant and anti-static starch masterbatch, 40 parts of polycaprolactones be added to high-speed mixer and mixing 6min is then added to extruding pelletization in 120 DEG C of double screw extruder, obtains flame-retardant and anti-static biodegradation material, wherein Screw speed is 100rpm, and screw slenderness ratio L/D is 20, and the time of melt blending is 8min.
Embodiment 5
（1）The preparation of flame-retardant and anti-static starch masterbatch：By 30 portions of wheaten starches, 10 parts of polyethylene glycol, 30 parts of intumescent resistances Fire agent（Wheaten starch：Ammonium magnesium phosphate：Urea=1:3:1）, 12 parts of organic antistatic agents polyglyceryl palmitate, 4 parts it is inorganic anti-quiet Electric agent aluminium oxide, 6 parts of resin carrier polylactic acid, 8 parts of colorant titanium dioxides（Colorant）Sequence is added to high-speed mixer and mixing 8min is then added to extruding pelletization in 160 DEG C of double screw extruder, obtains flame-retardant and anti-static starch masterbatch, spare, wherein Screw speed is 150rpm, and screw slenderness ratio L/D is 20, and the time of melt blending is 7min；
（2）Take 30 parts of steps（1）In flame-retardant and anti-static starch masterbatch, 5 parts of reacting movable agent Glycidyl methacrylates it is sweet Grease, 65 parts of polylactic acid are added to high-speed mixer and mixing 5min, are then added to squeeze out in 200 DEG C of double screw extruder and make Grain obtains flame-retardant and anti-static biodegradation material, and wherein screw speed is 100rpm, and screw slenderness ratio L/D is 20, melt blending Time be 3min.
Embodiment 6
（1）The preparation of flame-retardant and anti-static starch masterbatch：By 30 parts of potato starch, 10 parts of tributyl citrate, 30 parts it is swollen Swollen type fire retardant（Potato starch：Zinc borate：Glycine=1:3:1）, 10 parts of organic antistatic agents stearine, 2 parts of nothings Machine antistatic agent carbon black, 8 parts of vector resin poly butylene succinates, 10 parts of talcum powder（Filler）, sequentially be added to it is high mixed 6min is mixed in machine, is then added to extruding pelletization in 130 DEG C of double screw extruder, obtains flame-retardant and anti-static starch masterbatch, Spare, wherein screw speed is 150rpm, and screw slenderness ratio L/D is 25, and the time of melt blending is 5min；
（2）Take 25 parts of steps（1）In flame-retardant and anti-static starch masterbatch, 75 parts of poly butylene succinates be added to it is high mixed 3min is mixed in machine, is then added to extruding pelletization in 130 DEG C of double screw extruder, obtains flame-retardant and anti-static biodegradation material Material, wherein screw speed are 150rpm, and screw slenderness ratio L/D is 25, and the time of melt blending is 6min.
Embodiment 7
（1）The preparation of flame-retardant and anti-static starch masterbatch：By 25 portions of tapiocas, 10 ethanol amines, 30 parts of expansion type flame retardants （Cornstarch：Ammonium polyphosphate：Melamine=1:3:1）, 8 parts of organic antistatic agents polyethylene glycol (PEG) oleates, 2 parts it is inorganic anti-quiet Electric agent carbon nanotube, 15 parts of vector resin succinic acid-adipic acid-butanediol ester copolymers, 6 parts of pentaerythritol esters（Thermostabilization Agent）, 4 parts of titanium dioxide（Light stabilizer）, it is sequentially added to high-speed mixer and mixing 8min, is then added to 110 DEG C of twin-screw Extruding pelletization in extruder obtains flame-retardant and anti-static starch masterbatch, spare, and wherein screw speed is 100rpm, screw slenderness ratio L/D is 20, and the time of melt blending is 5min；
（2）Take 20 parts of steps（1）In flame-retardant and anti-static starch masterbatch, 10 parts of Biodegradable resin polycaprolactones, 70 parts Biodegradable resin succinic acid-adipic acid-butanediol ester copolymer is added to high-speed mixer and mixing 5min, is then added to 140 DEG C double screw extruder in extruding pelletization, obtain flame-retardant and anti-static biodegradation material, wherein screw speed is 100rpm, spiral shell Bar draw ratio L/D is 20, and the time of melt blending is 3min.
Embodiment 8
（1）The preparation of flame-retardant and anti-static starch masterbatch：By 35 parts of sweet potato starch, 10 parts of butanediols, 22 parts of expansion type flame-retardings Agent（Wheaten starch：Ammonium magnesium phosphate：Melamine=1:3:1）, 8 parts of organic antistatic agents polyglyceryl laurates, 5 parts it is inorganic anti- Electrostatic agent silica, 5 parts of vector resin polyhydroxyalkanoates, 12 parts of calcium carbonate（Filler）, 3 parts of vinyl trichlorosilanes （Coupling agent）, it is sequentially added to high-speed mixer and mixing 6min, is then added to extruding pelletization in 110 DEG C of double screw extruder, Flame-retardant and anti-static starch masterbatch is obtained, spare, wherein screw speed is 150rpm, and screw slenderness ratio L/D is 20, melt blending Time is 9min；
（2）Take 50 parts of steps（1）In flame-retardant and anti-static starch masterbatch, 50 parts of Biodegradable resin polyhydroxyalkanoates It is added to high-speed mixer and mixing 6min, blending extrusion in 150 DEG C of double screw extruder is then added to and is granulated, is obtained fire-retardant anti- Electrostatic biodegradation material, wherein screw speed are 150rpm, and screw slenderness ratio L/D is 20, and the time of melt blending is 5min.
Embodiment 9
（1）The preparation of flame-retardant and anti-static starch masterbatch：By 28 parts of Rhizoma Nelumbinis starch, 10 parts of plasticizer xylitols, 22 parts of intumescents Fire retardant（Potato starch：Zinc borate：Melamine=1:3:1）, 16 parts of organic antistatic agents palmitins, 6 parts it is inorganic Antistatic agent expanded graphite, 8 parts of vector resin polydioxanone, 10 parts of oleamides（Lubricant）, sequentially it is added to high mixed 9min is mixed in machine, is then added to extruding pelletization in 120 DEG C of double screw extruder, obtains flame-retardant and anti-static starch masterbatch, Spare, wherein screw speed is 100rpm, and screw slenderness ratio L/D is 20, and the time of melt blending is 9min；
（2）Take 20 parts of steps（1）In flame-retardant and anti-static starch masterbatch, 80 parts of Biodegradable resin polydioxanone It is added to high-speed mixer and mixing 6min, extruding pelletization in 150 DEG C of double screw extruder is then added to, obtains flame-retardant and anti-static Biodegradation material, wherein screw speed are 100rpm, and screw slenderness ratio L/D is 20, and the time of melt blending is 5min.
Embodiment 10
（1）The preparation of flame-retardant and anti-static starch masterbatch：By 20 portions of wheaten starches, 16 parts of butanediols, 16 parts of expansion type flame-retardings Agent（Wheaten starch：Zinc borate：Hexamethylenetetramine=1:3:1）, 8 parts of organic antistatic agents palmitins, 4 parts it is inorganic anti- Electrostatic agent expanded graphite, 6 parts of vector resin polylactic acid, 10 parts of carbon fibers（Filler）, 4 parts of cinnabar（Colorant）, 8 parts of white oils （Lubricant）, 8 parts of zinc oxide（Light stabilizer）, it is sequentially added to high-speed mixer and mixing 10min, is then added to 130 DEG C of pair Extruding pelletization in screw extruder obtains flame-retardant and anti-static starch masterbatch, spare, and wherein screw speed is 100rpm, and screw rod is long Diameter ratio L/D is 20, and the time of melt blending is 9min；
（2）Take 30 parts of steps（1）In flame-retardant and anti-static starch masterbatch, 3 parts of reacting movable agent 1,6- hexamethylene diisocyanates Ester, 67 parts of Biodegradable Material Polylactic Acids are added to high-speed mixer and mixing 2min, are then added to 220 DEG C of double screw extruder Middle extruding pelletization obtains flame-retardant and anti-static biodegradation material, and wherein screw speed is 100rpm, and screw slenderness ratio L/D is 20, The time of melt blending is 5min.
Embodiment 11
（1）The preparation of flame-retardant and anti-static starch masterbatch：By 35 parts of corn sweet potato starch, 15 parts of urea, 28 parts of expansion type flame-retardings Agent（Potato starch：Zinc borate：Dicyandiamide=1:3:1）, 12 parts of organic antistatic agents polyethylene glycol stearates, 2 parts it is inorganic anti- Electrostatic agent carbon black, 10 parts of reacting movable agent diisopropylcarbodiimide, 8 parts of vector resin polyadipate-terephthalic acid (TPA) fourths two Ester sequence is added to high-speed mixer and mixing 8min, is then added to extruding pelletization in 130 DEG C of double screw extruder, obtains fire-retardant Antistatic starch masterbatch, spare, wherein screw speed is 150rpm, and screw slenderness ratio L/D is 25, and the time of melt blending is 5min；
（2）Take 60 parts of steps（1）In flame-retardant and anti-static starch masterbatch, 10 parts of reacting movable agent butane diisocyanates, 40 parts of Biodegradable resin polyadipate-butylene terephthalates are added to high-speed mixer and mixing 3min, are then added to 160 DEG C double screw extruder in extruding pelletization, obtain flame-retardant and anti-static biodegradation material, wherein screw speed is 150rpm, spiral shell Bar draw ratio L/D is 20, and the time of melt blending is 3min.
Embodiment 12
（1）The preparation of flame-retardant and anti-static starch masterbatch：By 10 parts of cornstarch, 5 parts of plasticizer xylitols, 5 parts of intumescents Fire retardant（Potato starch：Zinc borate：Melamine=1:3:1）, 5 parts of organic antistatic agents palmitins, 20 parts it is inorganic Antistatic agent expanded graphite, 8 parts of polydioxanone, 20 parts of reacting movable agent 4,4 '-di-2-ethylhexylphosphine oxides（Cyclohexyl isocyanic acid Ester）, 5 parts of oleamides（Lubricant）, 5 portions of realgars（Colorant）, 5 parts of vinyltriethoxysilane（Coupling agent）, sequence addition To high-speed mixer and mixing 1min, it is then added to extruding pelletization in 60 DEG C of double screw extruder, obtains flame-retardant and anti-static starch Masterbatch, spare, wherein screw speed is 100rpm, and screw slenderness ratio L/D is 15, and the time of melt blending is 1min；
（2）Take 5 parts of steps（1）In flame-retardant and anti-static starch masterbatch, 90 parts of polydioxanone-be added to high mixer Middle mixing 1min, is then added to extruding pelletization in 200 DEG C of double screw extruder, obtains flame-retardant and anti-static biodegradation material Material, wherein screw speed are 100rpm, and screw slenderness ratio L/D is 50, and the time of melt blending is 10min.
Embodiment 13
（1）The preparation of flame-retardant and anti-static starch masterbatch：By 90 portions of tapiocas, 50 parts of urea, 90 parts of expansion type flame retardants （Potato starch：Zinc borate：Dicyandiamide=1:3:1）, 40 parts of organic antistatic agents polyethylene glycol stearates, 10 parts it is inorganic anti- Electrostatic agent carbon black, 10 parts of reacting movable agent diisopropylcarbodiimide, 50 parts of vector resin polyadipate-terephthalic acid (TPA) fourths two Ester sequence is added to high-speed mixer and mixing 20min, is then added to extruding pelletization in 60 DEG C of double screw extruder, obtains fire-retardant Antistatic starch masterbatch, spare, wherein screw speed is 150rpm, and screw slenderness ratio L/D is 15, and the time of melt blending is 15min；
（2）Take 90 parts of steps（1）In flame-retardant and anti-static starch masterbatch, 5 parts of reacting movable agent butane diisocyanates, 5 Part Biodegradable resin polyadipate-butylene terephthalate is added to high-speed mixer and mixing 10min, is then added to 250 DEG C double screw extruder in extruding pelletization, obtain flame-retardant and anti-static biodegradation material, wherein screw speed is 150rpm, spiral shell Bar draw ratio L/D is 50, and the time of melt blending is 1min.
Comparative example 1
（1）The preparation of starch masterbatch：By 60 parts of cornstarch, 25 parts of glycerine, 15 parts of polyadipates-terephthalic acid (TPA) fourth two Ester sequence is added to high-speed mixer and mixing 5min, is then added to extruding pelletization in 120 DEG C of double screw extruder, obtains starch Masterbatch, spare, wherein screw speed is 50rpm, and screw slenderness ratio L/D is 15, and the time of melt blending is 5min；
（2）Take 30 parts of steps（1）In starch masterbatch, 70 parts of Biodegradable resin polyadipate-terephthalic acid (TPA) fourths two Ester is added to high-speed mixer and mixing 4min, is then added to extruding pelletization in 140 DEG C of double screw extruder, obtains biodegradation Material, wherein screw speed are 50rpm, and screw slenderness ratio L/D is 15, and the time of melt blending is 5min.
Comparative example 2
（1）The preparation of flame-proof starch masterbatch：By 42 parts of cornstarch, 34 parts of expansion type flame retardants（Cornstarch：Polyphosphoric acid Ammonium：Melamine=1:3:1）, 16 parts of glycerine, 8 parts of polyadipates-butylene terephthalate sequence be added in high mixer and mix Conjunction 5min, is then added to extruding pelletization in 120 DEG C of double screw extruder, obtains flame-proof starch masterbatch, spare, wherein screw rod Rotating speed is 50rpm, and screw slenderness ratio L/D is 15, and the time of melt blending is 5min；
（2）Take 30 parts of steps（1）In flame-proof starch masterbatch, 70 parts of polyadipate-butylene terephthalates are added to High-speed mixer and mixing 4min is then added to extruding pelletization in 140 DEG C of double screw extruder, obtains fire-retardant biodegradable material Material, wherein screw speed are 50rpm, and screw slenderness ratio L/D is 15, and the time of melt blending is 5min.
Comparative example 3
（1）The preparation of antistatic starch masterbatch：By 50 parts of cornstarch, 20 parts of glycerine, 16 parts of glyceryl oleates, 4 parts of oxygen Change aluminium, 10 parts of polyadipates-butylene terephthalate sequence and be added to high-speed mixer and mixing 5min, is then added to 120 DEG C Double screw extruder in extruding pelletization, obtain antistatic starch masterbatch, it is spare, wherein screw speed be 50rpm, screw rod major diameter It is 15 than L/D, the time of melt blending is 5min；
（2）Take 30 parts of steps（1）In antistatic starch masterbatch, 70 parts of polyadipates-butylene terephthalate are added To high-speed mixer and mixing 4min, it is then added to extruding pelletization in 140 DEG C of double screw extruder, obtains antistatic biodegradation Material, wherein screw speed are 50rpm, and screw slenderness ratio L/D is 15, and the time of melt blending is 3min.
Comparative example 4
（1）The preparation of flame-retardant and anti-static starch masterbatch：By 35 parts of cornstarch, 30 parts of expansion type flame retardants（Cornstarch： Ammonium polyphosphate：Melamine=1:3:1）, 14 glycerine, 14 parts of glyceryl oleates, 7 parts of polyadipate-butylene terephthalates it is suitable Sequence is added to high-speed mixer and mixing 5min, is then added to extruding pelletization in 120 DEG C of double screw extruder, obtains fire-retardant anti-quiet Electric starch masterbatch, spare, wherein screw speed is 50rpm, and screw slenderness ratio L/D is 15, and the time of melt blending is 5min；
（2）Take 30 parts of steps（1）In flame-retardant and anti-static starch masterbatch, 70 parts of polyadipate-butylene terephthalates It is added to high-speed mixer and mixing 4min, extruding pelletization in 140 DEG C of double screw extruder is then added to, obtains flame-retardant and anti-static Biodegradation material, wherein screw speed are 50rpm, and screw slenderness ratio L/D is 15, and the time of melt blending is 5min.
The biodegradation material compression moulding on vulcanizing press that will be prepared in embodiment 1 ~ 3 and comparative example 1 ~ 4, plate Material thickness is 1mm, and vulcanizing press temperature is set as 180 DEG C, maximum pressure 10MPa, dwell time 2min.
Concrete operations are：0MPa preheats 2min；10MPa hot pressing 2min；10MPa is cold-pressed 3min, then by compression moulding Sheet material sample preparation, test mechanical property, flame retardant property and antistatic property.Test result is as follows table 1, table 2 and table 4；
Simultaneously table 3 be the antistatic polyadipate-butylene terephthalate prepared in embodiment 1 surface resistivity with The test result of the variation of time.Table 1
Embodiment Tensile strength（MPa） Elongation at break（%）
Embodiment 1 19.2 932
Embodiment 2 18.7 952
Embodiment 3 18.5 920
Comparative example 1 19.1 908
Comparative example 2 18.8 972
Comparative example 3 18.6 909
Comparative example 4 18.3 889
As can be seen from Table 1：The tensile strength of polyadipate-butylene terephthalate of preparation reaches 19.2 ~ 18.3MPa, elongation at break are generally more than 800%, maintain the mechanical property of polyadipate-butylene terephthalate itself.
Table 2
As can be seen from Table 2, in high humility（60%±5%RH）In the case of, pass through in embodiment 1 ~ 3 and comparative example 3 Antistatic polyadipate-butylene terephthalate prepared by organic antistatic agents and inorganic antistatic agent compounding, sheet resistance Rate is in 107 Ω or so, and compared with the blank comparative example 1,2 of no addition antistatic agent, surface resistivity has dropped 7 quantity Grade, belongs to the excellent material of antistatic property, and comparative example 4 is the polyadipate-of the single organic antistatic agents preparation of addition to benzene Dioctyl phthalate fourth diester, surface resistivity is in 109 Ω or so, and compared with blank comparative example 1,2, surface resistivity has dropped 5 numbers Magnitude belongs to the more excellent material of antistatic property；In low humidity（30%±5%RH）In the case of, embodiment 1 ~ 3 and right Polyadipate-the butylene terephthalate prepared in ratio 3, surface resistivity still can play anti-quiet in 109 Ω or so Electric effect, and the polyadipate-butylene terephthalate prepared in comparative example 4, surface resistivity is in 1012 Ω or so, substantially Do not have antistatic effect.
Table 3
Table 3 is the change of the surface resistivity of the polyadipate-butylene terephthalate prepared in embodiment 1 at any time Change, as can be seen from Table 3, in 100 days, the surface resistivity of polyadipate-butylene terephthalate is substantially 107Ω is left The right side, antistatic effect are lasting.
Table 4
Embodiment Oxygen index (OI)（%） Vertical combustion（UL94）
Embodiment 1 29.5 V-0
Embodiment 2 30.4 V-0
Embodiment 3 31.8 V-0
Comparative example 1 20.2 /
Comparative example 2 29.7 V-0
Comparative example 3 19.9 /
Comparative example 4 30.1 V-0
As can be seen from Table 4, the oxygen index (OI) of polyadipate-butylene terephthalate of fire retardant is not added 20% Left and right belongs to combustible material, and after adding fire retardant modification, the oxygen index (OI) of polyadipate-butylene terephthalate is increased to 30%, belong to nonflammable material, while vertical combustion grade is UL94V-0 grades.
The antistatic agent and expansion type flame retardant that the present invention adds are nontoxic, free from environmental pollution；The compounding of two kinds of antistatic agents Not only antistatic property is lasting for the biodegradation material of preparation, but also is influenced by ambient humidity smaller, while adding with starch For the expansion type flame retardant of carbon source, the flame retardant property of biodegradation material is effectively improved, biodegradation material is greatly expanded Use scope；It prepares flame-retardant and anti-static starch masterbatch first by two-step method, is conducive to the dispersion of antistatic agent and fire retardant, To improve antistatic and flame retardant effect；It is excellent that biodegradation material prepared by the present invention maintains biodegradation material itself Mechanical property and processing performance.
This hair can be understood and applied the above description of the embodiments is intended to facilitate those skilled in the art It is bright.Person skilled in the art obviously easily can make various modifications to these embodiments, and described herein General Principle is applied in other embodiment without having to go through creative labor.Therefore, the present invention is not limited to implementations here Example, those skilled in the art's announcement according to the present invention, improvement and modification made without departing from the scope of the present invention all should be Within protection scope of the present invention.

Claims (18)

1. a kind of biodegradation material, it is characterised in that：It is made of the component of following parts by weight：
5~90 parts of Biodegradable resin,
First 1~10 part of reacting movable agent,
5~90 parts of flame-retardant and anti-static starch masterbatch；
The Biodegradable resin is selected from polyester-amide copolymer, polyhydroxybutyrate valerate, polydioxanone, dioxy Change in carbon-ethylene oxide copolymer, carbon dioxide-epoxy propane copolymer or succinic acid-adipic acid-butanediol ester copolymer More than one；
The flame-retardant and anti-static starch masterbatch, is made of the component of following parts by weight：
The organic antistatic agents are selected from glycerol monolaurate, glyceryl oleate, palmitin, stearine, gather Glycerol monolaurate, Unigly GO 102S, polyglyceryl palmitate, polyglycerol stearate, polyethylene glycol laurate, poly- second One or more of glycol oleate, polyethylene glycol palmitate or polyethylene glycol stearate；
The inorganic antistatic agent is in carbon fiber, expanded graphite, carbon nanotube, silica, aluminium oxide or zinc oxide More than one；
The expansion type flame retardant is made of carbon source, acid source and air source；
The weight ratio of carbon source, acid source and air source is 1 in the expansion type flame retardant:3:1；
The carbon source is one or more of cornstarch, wheaten starch or potato starch；
The acid source is ammonium magnesium phosphate；
The air source is in urea, hexamethylenetetramine, polyaminoacid ester, azodiisobutyronitrile, glycine or wood powder More than one；
First reacting movable agent or the second reacting movable agent is selected from the acrylic ester compound of epoxy group, methyl-prop Olefin(e) acid glycidol esters compound, epoxy soybean oils compound, dicyclohexylcarbodiimide, diisopropylcarbodiimide, Two (2,6- diisopropyl phenyls) carbodiimides, 1- ethyls-(3- dimethylaminopropyls)-phosphinylidyne diimmonium salt hydrochlorate, activation Agent Stabaxol-P, activator Stabaxol-P200, activator Stabaxol-100, activator Stabaxol-I, maleic acid Acid anhydride, 1,6- cyclohexylene diisocyanates, 4,4 '-di-2-ethylhexylphosphine oxides (cyclohexyl isocyanate), relies ammonia at glycidyl methacrylate One or more of acid methyl ester diisocyanate or butane diisocyanate；
The processing aid is in heat stabilizer, light stabilizer, lubricant, coupling agent, filler, colorant or foaming agent More than one；
The light stabilizer is selected from carbon black, zinc oxide, titanium dioxide or benzophenone stabilizer；
The benzophenone stabilizer in light stabilizer UV400, light stabilizer UV9 or light stabilizer UV531 one Kind or more；
The lubricant is selected from stearic acid, butyl stearate, oleamide, glyceryl tristearate, ethylene bis stearamide, natural One or more of paraffin, white oil, microcrystalline wax, barium stearate, zinc stearate or calcium stearate；
The preparation method of the biodegradation material includes the following steps：
(1) flame-retardant and anti-static starch masterbatch is prepared：
Weigh 10~90 parts of starch, 5~50 parts of plasticizer, 5~90 parts of expansion type flame retardants, 5~40 parts of organic antistatic agents, 1 ~20 parts of inorganic antistatic agent, 1~50 part of vector resin, 1~20 part of second reacting movable agent and 60 parts of processing aids are first just mixed, After mixing, remelted blending, is granulated finally by comminutor, obtains flame-retardant and anti-static starch masterbatch, spare；
(2) 5~90 parts of flame-retardant and anti-static starch masterbatch, 1~10 part of first reacting movable agent and 5 that will be prepared in step (1) ~90 parts of Biodegradable resins are first just mixed, and remelted blending is granulated finally by comminutor, you can biodegradation material is made；
Just mixed used equipment is high-speed mixer in the step (1), and just the mixed time is 1~20min；
Equipment used in melt blending is selected from double screw extruder in the step (1), the double screw extruder Screw speed is 50rpm or 150rpm, and screw slenderness ratio L/D is 15:1~25:1, the temperature of melt blending is 60 DEG C, and melting is altogether The mixed time is 1~15min；
Just mixed used equipment is high-speed mixer in the step (2), and just the mixed time is 1~10min；
Equipment used in melt blending is selected from double screw extruder in the step (2), the double screw extruder Screw speed is 50rpm or 150rpm, and screw slenderness ratio L/D is 15:1~25:1 or 50:1, the temperature of melt blending is 80 DEG C Or 180~250 DEG C, the time of melt blending is 1~10min.
2. biodegradation material according to claim 1, it is characterised in that：The starch is selected from cornstarch, wheat forms sediment One or more of powder, tapioca, potato starch, sweet potato starch, starch from sweet potato, water caltrop starch or Rhizoma Nelumbinis starch.
3. biodegradation material according to claim 1, it is characterised in that：The plasticizer is selected from glycerine, urea, second two Alcohol, propylene glycol, butanediol, xylitol, sorbierite, ethanol amine, formamide, polyethylene glycol, tristerin, two fourth of adipic acid One or more of ester or tributyl citrate.
4. biodegradation material according to claim 1, it is characterised in that：The vector resin is selected from polylactic acid, poly- second Lactide, poly (glycolide-lactide), polycaprolactone, polyvinyl alcohol, polyester-amide copolymer, polyhydroxybutyrate valerate, poly-succinic fourth Diol ester, polydioxanone, carbon dioxide-ethylene oxide copolymer, carbon dioxide-epoxy propane copolymer, gather oneself two One or more of acid-butylene terephthalate or succinic acid-adipic acid-butanediol ester copolymer.
5. biodegradation material according to claim 1, it is characterised in that：The heat stabilizer is anti-selected from phosphorous acid esters One or more of oxygen agent or Hinered phenols antioxidant.
6. biodegradation material according to claim 1, it is characterised in that：The heat stabilizer is selected from trialkyl phosphorous acid One or more of salt, mixed alkyl/aryl phosphate ester, alkyl aryl phosphate ester or hydroxy-phenylpropionic acid ester.
7. biodegradation material according to claim 1, it is characterised in that：The heat stabilizer be selected from antioxidant 1010, Irgasfos 168, trisnonyl phenyl phosphite, heat stabilizer Irgafos168, heat stabilizer Ultranox626, heat stabilizer Cyanox2777, heat stabilizer Irganox B, heat stabilizer Irganox LC, heat stabilizer IrganoxLM, heat stabilizer IrganoxHP, heat stabilizer IrganoxXP, heat stabilizer Ultranox815A, heat stabilizer Ultranox 817A, thermostabilization One or more of agent Ultranox 875A, heat stabilizer Naugard900 or heat stabilizer CyanoxXS4.
8. biodegradation material according to claim 1, it is characterised in that：The coupling agent is selected from silane coupling agent, titanium Acid esters coupling agent, aluminate coupling agent, bimetallic coupling agent, phosphate coupling agent, boric acid ester coupler, zirconium coupling agent or rare earth One or more of coupling agent.
9. biodegradation material according to claim 1, it is characterised in that：The filler be selected from calcium carbonate, calcium sulfate, Talcum powder, chitosan, chitin, glass microballoon, asbestos, mica, silica, wood powder, shell powder, clay, carbon black, cellulose, One or more of inorfil, organic fiber, whisker or metal powder.
10. biodegradation material according to claim 1, it is characterised in that：The colorant be selected from titanium dioxide, carbon black, Lithopone, chrome yellow, barba hispanica, iron oxide yellow, silver powder, brass powder, pigment scarlet powder, even yellowish, phthalocyanine blue, quinacridone, cinnabar, laterite, hero Huang, peacock green, calcium carbonate, wollastonite, blanc fixe, talcum powder, mica powder or kaolin.
11. biodegradation material according to claim 1, it is characterised in that：The foaming agent be selected from chemical foaming agent or Physical blowing agent.
12. biodegradation material according to claim 8, it is characterised in that：The silane coupling agent is selected from γ-neon third Base front three nitrogen base silane, vinyl trichlorosilane, vinyltriethoxysilane, vinyltrimethoxysilane, vinyl three ('beta '-methoxy ethyoxyl) silane, γ-(methacryloxy) propyl trimethoxy silicane, β-(3,4- epoxies cyclohexyl) second One or more of base trimethoxy silane or γ-(2,3- glycidoxies) propyl trimethoxy silicane.
13. biodegradation material according to claim 8, it is characterised in that：The titanate coupling agent is selected from isopropyl Base three (isostearoyl base) titanate esters, isopropyl three (dioctyl pyrophosphate) titanate esters, two (dioctyl pyrophosphoryl base) oxygen-containing second Acid esters titanium, tetra isopropyl two (phosphorous acid dilauryl) titanate esters, isopropyl three (dioctyl pyrophosphoryl base) titanate esters, two (two Octyl pyrophosphoryl base) ethylene titanate esters, pyrophosphoric acid type monoalkoxy class titanate esters, plant acid type monoalkoxy class titanate esters, phosphorus Acid type monoalkoxy class titanate esters, isopropyl two (methylacryloyl) isostearoyl base titanate esters, (the dioctyl phosphorus of isopropyl three Acyl group) titanate esters, (dodecyl benzenesulfonyl) titanate esters of isopropyl three or isopropyl three (positive ethylamino-ethylamino) titanate esters One or more of.
14. biodegradation material according to claim 11, it is characterised in that：The chemical foaming agent is selected from azo In compound, N- nitroso compounds, sulfonyl hydrazines compound, urea-based compound, carbonate or nitrite it is a kind of with On.
15. biodegradation material according to claim 11, it is characterised in that：The chemical foaming agent is selected from azo two Ammonium formate, diisopropyl azodiformate, azodiisobutyronitrile, two ammonium carbonate of azo, barium azodicarboxylate, N, bis- nitrous of N'- Five methine tetramine of base, N, N'- dinitrosoterephthalamines, sodium nitrite-ammonium chloride, urea, unifor, benzene Base sulfohydrazide, one or more of sour, sodium bicarbonate or ammonium hydrogen carbonate to diphenyl sulfohydrazide.
16. biodegradation material according to claim 11, it is characterised in that：The physical blowing agent is selected from low boiling point Alkane or one or more of fluorocarbons.
17. biodegradation material according to claim 11, it is characterised in that：The physical blowing agent is selected from positive penta One or more of alkane, n-hexane, normal heptane, petroleum ether, Arcton 11, dicholorodifluoromethane or dichlorotetra-fluoroethane.
18. a kind of preparation method according to claim 1-17 any one of them biodegradation materials, it is characterised in that：Including Following steps：
(1) flame-retardant and anti-static starch masterbatch is prepared：
Weigh 10~90 parts of starch, 5~50 parts of plasticizer, 5~90 parts of expansion type flame retardants, 5~40 parts of organic antistatic agents, 1 ~20 parts of inorganic antistatic agent, 1~50 part of vector resin, 1~20 part of second reacting movable agent and 60 parts of processing aids are first just mixed, After mixing, remelted blending, is granulated finally by comminutor, obtains flame-retardant and anti-static starch masterbatch, spare；
(2) 5~90 parts of flame-retardant and anti-static starch masterbatch, 1~10 part of first reacting movable agent and 5 that will be prepared in step (1) ~90 parts of Biodegradable resins are first just mixed, and remelted blending is granulated finally by comminutor, you can biodegradation material is made；
Just mixed used equipment is high-speed mixer in the step (1), and just the mixed time is 1~20min；
Equipment used in melt blending is selected from double screw extruder in the step (1), the double screw extruder Screw speed is 50rpm or 150rpm, and screw slenderness ratio L/D is 15：1~25:1, the temperature of melt blending is 60 DEG C, and melting is altogether The mixed time is 1~15min；
Just mixed used equipment is high-speed mixer in the step (2), and just the mixed time is 1~10min；
Equipment used in melt blending is selected from double screw extruder in the step (2), the double screw extruder Screw speed is 50rpm or 150rpm, and screw slenderness ratio L/D is 15:1~25:1 or 50:1, the temperature of melt blending is 80 DEG C Or 180~250 DEG C, the time of melt blending is 1~10min.
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