CN1706883A - Completely biodegradable hydrophobic material and its prepn - Google Patents
Completely biodegradable hydrophobic material and its prepn Download PDFInfo
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- CN1706883A CN1706883A CN 200410025024 CN200410025024A CN1706883A CN 1706883 A CN1706883 A CN 1706883A CN 200410025024 CN200410025024 CN 200410025024 CN 200410025024 A CN200410025024 A CN 200410025024A CN 1706883 A CN1706883 A CN 1706883A
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Abstract
The present invention discloses one kind of completely biodegradable hydrophobic material and its preparation process. The starch-base biodegradable material is prepared through reaction and extrusion in extruder of the following material: starch, PVA, lactone polymer capable of reacting with hydroxy group, biodegradable polymer, initiator and other assistant. The present invention has the advantages of low cost, high hydrophobicity of the product, simple operation, complete biodegradation of the material to eliminate 'white pollution', etc. The present invention is suitable for continuous production.
Description
Technical field
The present invention relates to a kind of starch base hydrophobicity completely biodegradable material and preparation method thereof.
Technical background
As everyone knows, be used for preparing in the various materials of biological degradation goods in consideration, starch is the most potential a kind of raw material.Starch is as the potential advantages that exploitation has biodegradable plastic: (1) starch all possesses biodegradability completely in various environment; (2) after the starch molecule biological degradation, finally resolve into CO
2And H
2O can not produce any pollution to soil or air; (3) can reach the mechanical property that is used to make plastic material after taking suitable technology to make starch thermoplasticityization; (4) starch is renewable resources, and that gets is without cease; (5) the new Application Areas of developing starch helps rural economic development; (6) the starch cost is low, and the biodegradable material of preparation has price advantage.
In recent years, along with people to eliminating " white pollution " and to the raising day by day of environmental protection cry, starch-base biodegradation material arises at the historic moment.But present most of starch-base biodegradation material and product are not water-fast, or even the water dissolution type, cause its application in a lot of fields to be restricted.As Novon International, Inc. company is at US5,852, propose preparation in 114 and had a kind of method of the thermoplastic polymer blend matrix material of very fast biodegradation rate, this body of material composition: ethylene-acrylic acid copolymer (EAA), ethylene-vinyl acetate copolymer (EVA), polyvinyl alcohol (PVA) and starch, adopt extruding forming method, article shape is various, but does not solve the water-fast problem of material.
US 6,517,994 prepared (methyl) acrylate of a kind of containing, the repeated monomer unit is that structural formula is:
Or
Polylactone, wherein R1, R2 are H or methyl.
This synthesis route carries out in the aqueous solution, does not extrude at the forcing machine internal reaction to obtain, and is not suitable for large-scale production, the cost height.Polylactone after the polymerization does not have the active reaction center in addition, can not react with hydroxyl again.
US5,631, though 342 made structural formula and be:
Lactone polymer, wherein R1 is H or methyl, R2 is that carbonatoms is 1～10 group, X represents from lactone ring-opening reaction deutero-structural unit, its structural formula is
Ra, Rb are H or methyl.But this synthesis route also carries out in the aqueous solution, does not extrude at the forcing machine internal reaction to obtain, and is not suitable for large-scale production, the cost height.Polylactone after the polymerization does not have the active reaction center in addition, can not react with hydroxyl again.
US4,632,975 have made structural formula is
Polylactone, wherein R1 is H or methyl, and R2 is the lactone repeated structural unit, and m is the integer between 2～6, and n is the integer between 0～2, and m+n 〉=3, m＞n.But the polylactone of this structure does not have the active reaction center, can not react with hydroxyl again, and carry out in the aqueous solution, and complicated operation can not large-scale production.
US4504635 adopts aqueous solution approach to synthesize structural formula
Polylactone, R wherein, R1, R2, R3 is H or methyl; R4, R5 are that H or carbonatoms are 1～12 alkyl; X is the integer between 4～7.The polymerization in solution of this polylactone obtains, and its X resin is less, and the polylactone relative molecular mass that obtains is less.Not having in the molecular structure of this polylactone in addition can be again and the functional group of hydroxyl reaction.
In the above-mentioned document of mentioning, though have made the polylactone that contains unsaturated double-bond, all be to adopt the solution method preparation, prepared polylactone does not have and can carry out the reactive activity reactive center with hydroxyl.
Summary of the invention
The technical issues that need to address of the present invention are to disclose a kind of hydrophobicity completely biodegradable material and preparation method thereof, to overcome the above-mentioned defective that prior art exists.
As everyone knows, starch is the poly-hydroxy macromole, has a large amount of free hydroxyl on the starch polymer chain, makes it have very high wetting ability, if not to starch and have certain hydrophilic thermoplastic polymer and carry out modification, just can not obtain having the starch-base biodegradation material of better hydrophobic performance.Extrude by reaction, the present invention has successfully carried out modification to starch, hydroxyl polymer-containing and has obtained having the biodegradable material of better hydrophobic performance.
Another object of the present invention provides a kind of water-fast treatment process of biodegradable material.
A kind of starch-base biodegradation material of the present invention is prepared from by following materials of weight proportions: starch, polyvinyl alcohol, can with several composition the in the lactone polymer of hydroxyl reaction, initiator etc., its weight proportion is as follows:
Starch 30～70%
Polyvinyl alcohol 5～40%
Can with the lactone polymer 1～30% of hydroxyl reaction
Biodegradable polymers 1～30%
Initiator 0.01～1%
Other various auxiliary agents 10～45%
Said starch is selected from a kind of or its mixture in W-Gum, Starch rice, yam starch, wheat starch, konjak starch, tapioca (flour) or the sweet potato starch;
Said starch comprises treated starch, as esterification starch, etherification starch, graft starch, cationic starch or pasted starch;
Said polyvinyl alcohol is preferably the polymerization degree 1500～2200 and the polyvinyl alcohol of alcoholysis degree in 85～100% scopes, is PVA1788, PVA1799, PVA1792, PVA2099 etc. as trade names;
Used in the present invention can with the lactone polymer of hydroxyl reaction, be selected from by carbonatomss such as the monomer of lactone polymer such as δ caprolactone, ε caprolactone, γ-Wu Neizhi, gamma-butyrolactone, γ-Ren Neizhi, γ-Geng Neizhi be 3～15 lactone or contain substituting group and substituent carbonatoms be 1～12 etc. internal ester monomer the polymerization polylactone or the multipolymer that obtain, its weight-average molecular weight is 3000～100,000, and more excellent is 5000～80,000.
The length of polymerized segment can be controlled by proportioning raw materials, and this can regulate proportioning according to actual needs, obtains the polymkeric substance of desired molecule amount.
Used in the present invention can be the lactone polymer that the lactone polymer that contains unsaturated double-bond, particularly end group contain acrylate with the lactone polymer of hydroxyl reaction in starch or other polymkeric substance.This lactone polymer is a polymeric under the effect of catalyzer, and contain the active reaction center in the polymkeric substance, can with hydroxyl in the starch, hydroxyl in the polyvinyl alcohol or the hydroxyl reaction in other polymkeric substance, the molecular structure of reaction back starch changes, strong hydrogen bonding between the molecule interacts and obtains weakening, thereby the hydrophobic performance of material is improved.
In addition, lactone polymer can be opened two keys owing to contain unsaturated double-bond under action of evocating, it is partial cross-linked that lactone is taken place, thus the mechanical property of the lactone that has improved.
Biodegradable polymers used in the present invention is selected from polycaprolactone, polylactide, poly-butyrolactone, chitosan, Mierocrystalline cellulose, chitin, gelatin, poly-3-hydroxyl butyl ester, poly-3-hydroxyl pentyl ester, poly-3-hydroxyl butyl ester-3-hydroxyl pentyl ester multipolymer, poly butylene succinate and multipolymer thereof etc., and its weight-average molecular weight is 8000～100,000.
Said initiator is Diisopropyl azodicarboxylate, dibenzoyl peroxide, dilauroyl peroxide, isopropyl benzene hydroperoxide, dicumyl peroxide, 2,2-dimethoxy-2-phenyl methyl phenyl ketone, Alpha-hydroxy phenylcyclohexane ketone, 2-hydroxy-2-methyl phenyl-1-acetone, 2-methyl isophthalic acid-[4-(first coloured glaze base) benzene]-2-beautiful jade acetone-1 etc.
Said other auxiliary agent can take the circumstances into consideration to add according to the needs of material application scenario demand or others, and addible auxiliary agent has: softening agent, linking agent, lubricant, mould inhibitor, transparent base, weedicide, sterilant etc.
The softening agent of being addressed is selected from glycerine, ethylene glycol, water, sorbyl alcohol, hexanolactam, vegetables oil, soybean wet goods, is used for the occasion of plastification material;
The linking agent of being addressed is selected from the acid that contains aldehyde radical, preferred oxoethanoic acid, borax, di-carboxylic acid, as Succinic Acid, hexanodioic acid, sebacic acid, nonane diacid etc., acid anhydrides, as diacetyl oxide, propionic anhydride, Succinic anhydried, maleic anhydride, Tetra hydro Phthalic anhydride etc., need to be used to the mechanical property such as the higher occasion of tensile strength of material;
Lubricant can be selected stearic acid, calcium stearate, Magnesium Stearate, aluminum stearate, whiteruss, native paraffin, microcrystalline wax, polyethylene wax, higher fatty acid etc. for use, be used to reduce between polymer melt and the processor (as cylindrical shell, screw rod) and friction and adhesion that melt is inner mutual, improve fluidity of molten, promote machine-shaping, improve the occasion of throughput and products appearance quality and smooth finish;
Mould inhibitor can be selected pentachlorophenol, lauric ester of pentachlorophenol, salicylanilide, tributyl tin acetate, tributyl-tin fumarate, N-(trichloromethylthio) phthalic diamide, N-(trichloromethylthio)-4-tetrahydrobenzene-1 for use, 2-diformamide, N-(fluorine dichloromethyl sulfo-) phthalic diamide, 2-(4-thiazole benzene)-benzoglyoxaline etc. are used for preventing occasions such as various mould erosions;
Transparent base can be selected for use two-(right-ethyl dibenzylidene sec.-propyl) sorbyl alcohol, 1,3,2,4-two (4-methyl-benzal) sorbyl alcohols etc. are used to prepare the occasion of transparent material;
Weedicide can be selected mefenacet, alkoxylated triglyceride class weedicide, citric acid alkyl oxide ester herbicide, the polyoxyethylene fatty acid class that methylates weedicide etc. for use, is used for agricultural mulching to prevent occasions such as weed growth;
Sterilant can be selected inorganic fungicide for use, as the silver ions series bactericidal agent; Organic bactericide such as Vanillin, methoxyl group penicillin, chitosan, quaternary ammonium salts sterilant, season phosphonium salt series bactericidal agent, organic tin sterilant etc.; Be used for variously needing the applying biological degradable material but requiring this material to have the occasion of sterilizing function; All reactions are all finished in forcing machine, and hydrophobization and moulding process are finished simultaneously, and technology is simple, are convenient to large-scale industrialization production, and production cost is low, strong operability.
Preparation method of the present invention comprises the steps:
Behind starch, polyvinyl alcohol, initiator and other auxiliary agent uniform mixing from the main charging opening charging of forcing machine, extrude, can with lactone polymer, biodegradable polymers and the catalyzer of hydroxyl reaction from the charging of side direction charging opening, catalyzed polymerization, polymkeric substance after the polymerization after the melt thorough mixing of the fusion homogenizing zone of forcing machine and starch etc., reaction, the per os mold forming;
Or with starch, polyvinyl alcohol, initiator, can with lactone polymer, biodegradable polymers, catalyzer and other auxiliary agent uniform mixing of hydroxyl reaction after in forcing machine, react and extrude, straight forming, as extrusion-blown modling etc., be processed into needed shape, or granulation after extruding, be processed into masterbatch, and then adopt inject, extrude, method moulding such as blowing or add other component after reshaping, the temperature that reaction is extruded is 110～190 ℃, die head temperature is 165～185 ℃, and screw speed is 50～140rpm;
Can preferably adopt eight conventional twin screw extruders, the temperature of each is respectively:
110～140℃、140～155℃、155～165℃、165℃～175℃、175℃～185℃、175℃～185℃、185～195℃。
Said catalyzer is selected from the metal alkoxide compound, as aluminium isopropoxide, triethyl aluminum, dichloro methoxy basic ring pentadiene titanium, tetrabutyl titanate, iso-butyl titanate, metatitanic acid tetrapropylene acid hydroxyl ethyl ester, metatitanic acid tetrapropylene acid hydroxypropyl acrylate, metatitanic acid tetrapropylene acid methyl esters, the positive butyl ester of aluminic acid, tributyl methoxyl group tin, dibutyl tin, stannous octoate, tin protochloride, tert-butoxy potassium, the tert-butoxy lithium, the rare earth alkoxylation compound, three (2,6-di-t-butyl-4-methylphenoxy) lanthanum, rare earth acetylacetonates etc., catalyst levels is 0.001～1% of a raw material gross weight.
The outstanding feature of the present invention is: employing can with the lactone polymer of hydroxyl reaction in starch or other polymkeric substance, the hydroxyl in starch and the polyvinyl alcohol is fallen in sealing, free hydroxyl quantity in starch and the polyvinyl alcohol is reduced greatly, because the many hydroxyls in starch and the polyvinyl alcohol macromole are closed, change has taken place in the molecular structure of starch and polyvinyl alcohol, the degree of crystallinity of starch descends, become the amorphous state macromole by crystal form, become thermoplastic material, thereby make the tensile strength of material, elongation at break and hydrophobic performance are greatly improved simultaneously; This lactone polymer also can make between starch polymer, polyvinyl alcohol macromole and starch and the polyvinyl alcohol macromole and to take place partial cross-linkedly simultaneously, and crosslinked between starch and the polyvinyl alcohol also makes the consistency between starch and the polyvinyl alcohol two-phase be improved.The reaction that realizes in forcing machine is as follows:
Represent the starch polymer structure
The structure of catalyzer is example with the titanium propanolate:
1. the polymerization of lactone polymer (is example with the caprolactone)
Reaction formula (1)
Since this lactone polymer contain can with the titanium propanolate active centre of hydroxyl reaction, with the melt-mixing process of starch or other polymkeric substance in, the titanium propanolate active centre can react with the hydroxyl in starch or other polymkeric substance and seal hydroxyl, make the hydrophobic performance of material be improved, with with starch in hydroxyl reaction be example, react as follows:
Reaction formula (2)
N is an integer in the formula, 1≤n≤3.If n 〉=2, then abutment has been served as at the titanium active reaction center of lactone, and it is crosslinked that starch polymer is taken place, and the molecular structure of starch polymer changes, and the tensile strength of material, elongation, hydrophobic performance are improved.If the titanium active centre with starch polymer and other polymer macromolecule reaction has taken place simultaneously, reaction product then can be served as the interfacial compatibilizer of starch and this polymkeric substance, thereby has improved the interface compatibility of the two, and the mechanical property of material also can correspondingly improve.
In addition,, be opened at the following pair key of action of evocating because this lactone polymer contains unsaturated double-bond, the generation free radical, free radical can react with starch or other polymkeric substance, and it is as follows with starch to be that example is then reacted:
Reaction formula (3)
The generation of this type of reaction, partial destruction the molecular structure of starch, the part ripple hydroxyl of living is fallen in sealing, so the hydrophobic performance of material improves.
This patent adopts the functionalization catalyzer, obtained the polylactone that contains unsaturated double-bond and have the active reaction center by the reaction extrusion method, this chain carrier can react with the hydroxyl in starch or other polymkeric substance, thereby the free hydroxyl in starch or other polymer molecular chain is fallen in sealing, changed their molecular structure, strong interaction between its molecule is seriously undermined, thereby improved the material hydrophobic performance.Abutment also can be served as in this active centre, and it is partial cross-linked that starch or other hydroxyl polymer-containing are taken place, thereby has improved the mechanical property of goods.
Advantages such as the present invention has that cost is low, goods hydrophobicity height, simple to operate, material fully biodegradable can solve white pollution problems.The method that the present invention adopts reaction to extrude, the modification of material and forming materials carry out simultaneously, have simplified production technique, have reduced production cost, and are convenient to serialization production.
Embodiment
Embodiment 1
Take by weighing W-Gum 45Kg, polyvinyl alcohol 178820Kg, polycaprolactone 2Kg, glycerine 15Kg, borax 0.4Kg, EVA 3Kg, stearic acid 0.4Kg, Succinic Acid 1Kg add in the high-speed mixer successively, stir 5min, discharging.
Above-mentioned mixed material is extruded, and the extruder barrel temperature is respectively: 130 ℃, 150 ℃, 160 ℃, 170 ℃, 180 ℃, 180,190 ℃, 190 ℃, die head temperature is 180 ℃, and screw speed is 100rpm.Side direction spout at forcing machine adds 6-caprolactone monomer 1.5kg, butyl methacrylate monomer 0.01kg, catalyzer metatitanic acid tetrapropylene acid hydroxyl ethyl ester 0.005kg, Alpha-hydroxy phenylcyclohexane ketone 0.01kg, the side direction screw speed is about 10rpm, and the material in material in the main charging opening and the side loading mouth almost uses up simultaneously.Extrusion-blown modling obtains film article, and adopt the method for GB1040-1979 regulation to detect: the tensile strength 16.1MPa of goods, elongation at break are 130%; Adopt the method for ASTMD5725-99 regulation to detect, the contact angle of material is 81 °, and hydrophobic performance is good; According to the method for GB/T 18006.2-1999 regulation to detecting 85%, 12 month fully biodegradable of 6 months degradables of this material.
Embodiment 2
Take by weighing W-Gum 50Kg, PVA 1788 20Kg, poly(lactic acid) 2Kg, glycerine 15Kg, borax 0.4Kg, EVA3Kg, stearic acid 0.4Kg, Succinic anhydried 1Kg adds in the high-speed mixer successively, stirs 5min, discharging.
Above-mentioned mixed material is extruded, and the extruder barrel temperature is respectively: 130 ℃, 150 ℃, 160 ℃, 170 ℃, 180 ℃, 180,190 ℃, 190 ℃, die head temperature is 180 ℃, and screw speed is 100rpm.Side direction spout at forcing machine adds lactide monomer 1.5kg, butyl methacrylate monomer 0.01kg, catalyzer metatitanic acid tetrapropylene acid methyl esters 0.005kg, Diisopropyl azodicarboxylate 0.01kg, the side direction screw speed is about 10rpm, and the material in material in the main charging opening and the side loading mouth almost uses up simultaneously.Extrude and obtain sheet material products, adopt the method for GB1040-1979 regulation to detect: the tensile strength 17.3MPa of goods, elongation at break are 140%; Adopt the method for ASTM D5725-99 regulation to detect, the contact angle of material is 77 °, and hydrophobic performance is good; According to the method for GB/T 18006.2-1999 regulation to detecting 91%, 12 month fully biodegradable of 6 months degradables of this material.
Embodiment 3
Take by weighing W-Gum 45Kg, polyvinyl alcohol 1799 20Kg, poly-3-hydroxyl butyl ester (PHB) 2Kg, glycerine 18Kg, borax 0.3Kg, EVA3 Kg, stearic acid 0.5Kg, hexanodioic acid 1Kg adds in the high-speed mixer successively, and 5min, discharging are stirred in start.
Above-mentioned mixed material is extruded, the extruder barrel temperature is respectively: 130 ℃, 150 ℃, 160 ℃, 170 ℃, 180 ℃, 180,190 ℃, 190 ℃, die head temperature is 180 ℃, screw speed is 100rpm, side direction spout at forcing machine adds lactide monomer 0.75kg, 6-caprolactone monomer 0.75kg, butyl methacrylate monomer 0.01kg, the inferior tin 0.005kg of octoate catalyst, 2,2-dimethoxy-2-phenyl methyl phenyl ketone 0.01kg, the side direction screw speed is about 10rpm, and the material in material in the main charging opening and the side loading mouth almost uses up simultaneously.Extrude and obtain goods, adopt the method for GB1040-1979 regulation to detect: the tensile strength 15.7MPa of goods, elongation at break are 120%; Adopt the method for ASTMD5725-99 regulation to detect, the contact angle of material is 80 °, and hydrophobic performance is good; According to the method for GB/T 18006.2-1999 regulation to detecting 83%, 12 month fully biodegradable of 6 months degradables of this material.
Embodiment 4
Take by weighing Starch rice 45Kg, polyvinyl alcohol 178820Kg, poly butylene succinate 2Kg, glycerine 15Kg, borax 0.4Kg, EVA3Kg, stearic acid 0.4Kg, Succinic Acid 1Kg, δ-methyl-6-caprolactone monomer 1.5kg, butyl methacrylate monomer 0.01kg, the positive butyl ester 0.005kg of catalyzer aluminic acid, dibenzoyl peroxide 0.01kg, add successively in the high-speed mixer, 5min, discharging are stirred in start.
Above-mentioned mixed material is extruded, the extruder barrel temperature is respectively: 130 ℃, 150 ℃, 160 ℃, 170 ℃, 180 ℃, 180,190 ℃, 190 ℃, die head temperature is 180 ℃, screw speed is 100rpm, extrude and obtain goods, adopt the method for GB1040-1979 regulation to detect: the tensile strength 14.5MPa of goods, elongation at break are 130%; Adopt the method for ASTM D5725-99 regulation to detect, the contact angle of material is 78 °, and hydrophobic performance is good; According to the method for GB/T 18006.2-1999 regulation to detecting 87%, 12 month fully biodegradable of 6 months degradables of this material.
Embodiment 5
Adopt method and the processing condition identical with embodiment 1, the employing trade names are raw material for the DF-A esterification starch, and add 1 kilogram of mould inhibitor lauric ester of pentachlorophenol, and goods are used for the occasion of agricultural mulching; Adopt the method for GB1040-1979 regulation to detect: the tensile strength 15.3MPa of goods, elongation at break are 130%; Adopt the method for ASTM D5725-99 regulation to detect, the contact angle of material is 77 °, and hydrophobic performance is good; According to the method for GB/T 18006.2-1999 regulation to detecting 86%, 12 month fully biodegradable of 6 months degradables of this material.
Embodiment 6
Adopt method and the processing condition identical with embodiment 1, the employing trade names are that the cationic starch of CCS-02 is a raw material, and add 0.8 kilogram of mould inhibitor N-(trichloromethylthio)-4-tetrahydrobenzene-1, and 2-diformamide, goods are used for the occasion of packaging film; Adopt the method for GB1040-1979 regulation to detect: the tensile strength 16MPa of goods, elongation at break are 120%; Adopt the method for ASTM D5725-99 regulation to detect, the contact angle of material is 79 °, and hydrophobic performance is good; According to the method for GB/T 18006.2-1999 regulation to detecting 83%, 12 month fully biodegradable of 6 months degradables of this material.
Embodiment 7
Adopt method and the processing condition identical with embodiment 1, the employing trade names are that the etherification starch of Modistar is a raw material, and add 0.7 kilogram of weedicide mefenacet, and goods are used for the occasion of agricultural mulching; Adopt the method for GB1040-1979 regulation to detect: the tensile strength 15.7MPa of goods, elongation at break are 130%; Adopt the method for ASTM D5725-99 regulation to detect, the contact angle of material is 81 °, and hydrophobic performance is good; According to the method for GB/T 18006.2-1999 regulation to detecting 86%, 12 month fully biodegradable of 6 months degradables of this material.
Claims (10)
1. a hydrophobicity completely biodegradable material is characterized in that, its weight proportion is as follows:
Starch 30～70%
Polyvinyl alcohol 5～40%
Can with the lactone polymer 1～30% of hydroxyl reaction
Biodegradable polymers 1～30%
Initiator 0.01～1%
Other various auxiliary agents 10～45%.
Said other auxiliary agent comprises a kind of in softening agent, linking agent, lubricant, mould inhibitor, transparent base, weedicide or the sterilant etc.
2. hydrophobicity completely biodegradable material according to claim 1, it is characterized in that said starch is selected from a kind of or its mixture in W-Gum, Starch rice, yam starch, wheat starch, konjak starch, tapioca (flour) or the sweet potato starch.
3. hydrophobicity completely biodegradable material according to claim 2 is characterized in that said starch comprises treated starch, as esterification starch, etherification starch, graft starch, cationic starch or pasted starch.
4. hydrophobicity completely biodegradable material according to claim 1 is characterized in that, said polyvinyl alcohol is the polymerization degree 1500～2200 and the polyvinyl alcohol of alcoholysis degree in 85～100% scopes.
5. hydrophobicity completely biodegradable material according to claim 1, it is characterized in that, can be selected from δ caprolactone, ε caprolactone, γ-Wu Neizhi, gamma-butyrolactone, γ-Ren Neizhi, γ-Geng Neizhi with the polymerization single polymerization monomer of the lactone polymer of hydroxyl reaction or contain substituting group and substituent carbonatoms is a kind of in 1～12 the lactone, weight-average molecular weight is 3000～150,000.
6. hydrophobicity completely biodegradable material according to claim 1, it is characterized in that, biodegradable polymers is selected from polycaprolactone, polylactide, poly-butyrolactone chitosan, Mierocrystalline cellulose, chitin, gelatin, poly-3-hydroxyl butyl ester, poly-3-hydroxyl pentyl ester, poly-3-hydroxyl butyl ester-3-hydroxyl pentyl ester multipolymer or poly butylene succinate and multipolymer thereof, and its weight-average molecular weight is 800～100,000.
7. hydrophobicity completely biodegradable material according to claim 1, it is characterized in that, said initiator is selected from Diisopropyl azodicarboxylate, dibenzoyl peroxide, dilauroyl peroxide, isopropyl benzene hydroperoxide, dicumyl peroxide, 2, a kind of in 2-dimethoxy-2-phenyl methyl phenyl ketone, Alpha-hydroxy phenylcyclohexane ketone, 2-hydroxy-2-methyl phenyl-1-acetone or 2-methyl isophthalic acid-[4-(first coloured glaze base) benzene]-2-beautiful jade acetone-1.
8. hydrophobicity completely biodegradable material according to claim 1 is characterized in that,
Preparation method of the present invention comprise the steps: behind starch, polyvinyl alcohol, initiator and other auxiliary agent uniform mixing from forcing machine main charging opening charging, extrude, can with lactone polymer, biodegradable polymers and the catalyzer of hydroxyl reaction from the charging of side direction charging opening, catalyzed polymerization, the per os mold forming; Or with starch, polyvinyl alcohol, initiator, can with lactone polymer, biodegradable polymers, catalyzer and other auxiliary agent uniform mixing of hydroxyl reaction after in forcing machine, react and extrude, straight forming, the temperature that reaction is extruded is 110～190 ℃, die head temperature is 165～185 ℃, and screw speed is 50～140rpm.
9. method according to claim 8, it is characterized in that, said catalyzer is selected from the metal alkoxide compound, as aluminium isopropoxide, triethyl aluminum, dichloro methoxy basic ring pentadiene titanium, tetrabutyl titanate, iso-butyl titanate, metatitanic acid tetrapropylene acid hydroxyl ethyl ester, metatitanic acid tetrapropylene acid hydroxypropyl acrylate, metatitanic acid tetrapropylene acid methyl esters, the positive butyl ester of aluminic acid, tributyl methoxyl group tin, dibutyl tin, stannous octoate, tin protochloride, tert-butoxy potassium, the tert-butoxy lithium, the rare earth alkoxylation compound, three (2,6-di-t-butyl-4-methylphenoxy) lanthanum or rare earth acetylacetonate, catalyst levels is 0.001～1% of a raw material gross weight.
10. method according to claim 8 is characterized in that, adopts eight conventional twin screw extruders, and the temperature of each is respectively:
110～140℃、140～155℃、155～165℃、165℃～175℃、175℃～185℃、175℃～185℃、185～195℃。
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| CN112405931A (en) * | 2020-10-26 | 2021-02-26 | 苏州和塑美科技有限公司 | Preparation method of nano-montmorillonite reinforced starch-based biodegradable blown film material, product and application thereof |
| CN114716655A (en) * | 2020-12-22 | 2022-07-08 | 上海丽珠制药有限公司 | Preparation method of lactide-glycolide copolymer |
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