CN1706883A - Hydrophobic fully biodegradable material and preparation method thereof - Google Patents
Hydrophobic fully biodegradable material and preparation method thereof Download PDFInfo
- Publication number
- 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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- China
- Prior art keywords
- starch
- biodegradable material
- polymer
- hydrophobic
- polyvinyl alcohol
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- 239000000463 material Substances 0.000 title claims abstract description 69
- 230000002209 hydrophobic effect Effects 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 229920002472 Starch Polymers 0.000 claims abstract description 76
- 235000019698 starch Nutrition 0.000 claims abstract description 74
- 239000008107 starch Substances 0.000 claims abstract description 74
- 238000000034 method Methods 0.000 claims abstract description 36
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 34
- 229920000642 polymer Polymers 0.000 claims abstract description 33
- 150000002596 lactones Chemical class 0.000 claims abstract description 29
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 27
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 27
- 239000003999 initiator Substances 0.000 claims abstract description 10
- 229920002988 biodegradable polymer Polymers 0.000 claims abstract description 8
- 239000004621 biodegradable polymer Substances 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 238000001125 extrusion Methods 0.000 claims abstract description 4
- 239000000654 additive Substances 0.000 claims abstract 3
- -1 rice starch Polymers 0.000 claims description 26
- 239000000178 monomer Substances 0.000 claims description 11
- 238000006116 polymerization reaction Methods 0.000 claims description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- 239000012752 auxiliary agent Substances 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 6
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 claims description 5
- 239000003899 bactericide agent Substances 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 3
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 3
- 229920001661 Chitosan Polymers 0.000 claims description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 3
- 125000002091 cationic group Chemical group 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
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- 238000000465 moulding Methods 0.000 claims description 3
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- 239000004631 polybutylene succinate Substances 0.000 claims description 3
- 229920002961 polybutylene succinate Polymers 0.000 claims description 3
- 229920001610 polycaprolactone Polymers 0.000 claims description 3
- 239000004632 polycaprolactone Substances 0.000 claims description 3
- 229920001592 potato starch Polymers 0.000 claims description 3
- 150000002910 rare earth metals Chemical class 0.000 claims description 3
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 2
- QUVMSYUGOKEMPX-UHFFFAOYSA-N 2-methylpropan-1-olate;titanium(4+) Chemical compound [Ti+4].CC(C)C[O-].CC(C)C[O-].CC(C)C[O-].CC(C)C[O-] QUVMSYUGOKEMPX-UHFFFAOYSA-N 0.000 claims description 2
- 229920002101 Chitin Polymers 0.000 claims description 2
- RZTOWFMDBDPERY-UHFFFAOYSA-N Delta-Hexanolactone Chemical compound CC1CCCC(=O)O1 RZTOWFMDBDPERY-UHFFFAOYSA-N 0.000 claims description 2
- 108010010803 Gelatin Proteins 0.000 claims description 2
- 244000017020 Ipomoea batatas Species 0.000 claims description 2
- 235000002678 Ipomoea batatas Nutrition 0.000 claims description 2
- 229920002752 Konjac Polymers 0.000 claims description 2
- 240000003183 Manihot esculenta Species 0.000 claims description 2
- 235000016735 Manihot esculenta subsp esculenta Nutrition 0.000 claims description 2
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 2
- 238000006136 alcoholysis reaction Methods 0.000 claims description 2
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 2
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- YQHLDYVWEZKEOX-UHFFFAOYSA-N cumene hydroperoxide Chemical compound OOC(C)(C)C1=CC=CC=C1 YQHLDYVWEZKEOX-UHFFFAOYSA-N 0.000 claims description 2
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 claims description 2
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- LZWQNOHZMQIFBX-UHFFFAOYSA-N lithium;2-methylpropan-2-olate Chemical compound [Li+].CC(C)(C)[O-] LZWQNOHZMQIFBX-UHFFFAOYSA-N 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims description 2
- 235000011150 stannous chloride Nutrition 0.000 claims description 2
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 2
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 2
- 229940100445 wheat starch Drugs 0.000 claims description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical group N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims 2
- 229920001577 copolymer Polymers 0.000 claims 2
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims 1
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical class C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 claims 1
- LGJCFVYMIJLQJO-UHFFFAOYSA-N 1-dodecylperoxydodecane Chemical compound CCCCCCCCCCCCOOCCCCCCCCCCCC LGJCFVYMIJLQJO-UHFFFAOYSA-N 0.000 claims 1
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 claims 1
- PUYFYIVIYQGKOF-UHFFFAOYSA-K 2,6-ditert-butyl-4-methylphenolate lanthanum(3+) Chemical compound [La+3].Cc1cc(c([O-])c(c1)C(C)(C)C)C(C)(C)C.Cc1cc(c([O-])c(c1)C(C)(C)C)C(C)(C)C.Cc1cc(c([O-])c(c1)C(C)(C)C)C(C)(C)C PUYFYIVIYQGKOF-UHFFFAOYSA-K 0.000 claims 1
- OALYTRUKMRCXNH-UHFFFAOYSA-N 5-pentyloxolan-2-one Chemical compound CCCCCC1CCC(=O)O1 OALYTRUKMRCXNH-UHFFFAOYSA-N 0.000 claims 1
- 244000247812 Amorphophallus rivieri Species 0.000 claims 1
- 235000001206 Amorphophallus rivieri Nutrition 0.000 claims 1
- 229920002261 Corn starch Polymers 0.000 claims 1
- VLSVVMPLPMNWBH-UHFFFAOYSA-N Dihydro-5-propyl-2(3H)-furanone Chemical compound CCCC1CCC(=O)O1 VLSVVMPLPMNWBH-UHFFFAOYSA-N 0.000 claims 1
- 229920000881 Modified starch Polymers 0.000 claims 1
- 239000004368 Modified starch Substances 0.000 claims 1
- 150000004703 alkoxides Chemical class 0.000 claims 1
- 239000003429 antifungal agent Substances 0.000 claims 1
- 229940121375 antifungal agent Drugs 0.000 claims 1
- 239000008120 corn starch Substances 0.000 claims 1
- 229940099112 cornstarch Drugs 0.000 claims 1
- 239000003431 cross linking reagent Substances 0.000 claims 1
- 229920006237 degradable polymer Polymers 0.000 claims 1
- GAEKPEKOJKCEMS-UHFFFAOYSA-N gamma-valerolactone Chemical class CC1CCC(=O)O1 GAEKPEKOJKCEMS-UHFFFAOYSA-N 0.000 claims 1
- 239000000252 konjac Substances 0.000 claims 1
- KJGLZJQPMKQFIK-UHFFFAOYSA-N methanolate;tributylstannanylium Chemical compound CCCC[Sn](CCCC)(CCCC)OC KJGLZJQPMKQFIK-UHFFFAOYSA-N 0.000 claims 1
- 235000019426 modified starch Nutrition 0.000 claims 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims 1
- 239000004014 plasticizer Substances 0.000 claims 1
- 229940116317 potato starch Drugs 0.000 claims 1
- 229940100486 rice starch Drugs 0.000 claims 1
- 241000894007 species Species 0.000 claims 1
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- 125000001424 substituent group Chemical group 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 27
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- 239000002253 acid Substances 0.000 description 13
- 239000000126 substance Substances 0.000 description 11
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 10
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 8
- IZUPBVBPLAPZRR-UHFFFAOYSA-N pentachlorophenol Chemical compound OC1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1Cl IZUPBVBPLAPZRR-UHFFFAOYSA-N 0.000 description 6
- BZJTUOGZUKFLQT-UHFFFAOYSA-N 1,3,5,7-tetramethylcyclooctane Chemical group CC1CC(C)CC(C)CC(C)C1 BZJTUOGZUKFLQT-UHFFFAOYSA-N 0.000 description 5
- 235000021355 Stearic acid Nutrition 0.000 description 5
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 5
- 238000006065 biodegradation reaction Methods 0.000 description 5
- 229910021538 borax Inorganic materials 0.000 description 5
- 235000011187 glycerol Nutrition 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 5
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 5
- 239000004328 sodium tetraborate Substances 0.000 description 5
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- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- 239000005038 ethylene vinyl acetate Substances 0.000 description 3
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- 235000019359 magnesium stearate Nutrition 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000004200 microcrystalline wax Substances 0.000 description 1
- 235000019808 microcrystalline wax Nutrition 0.000 description 1
- 125000005474 octanoate group Chemical group 0.000 description 1
- 239000012785 packaging film Substances 0.000 description 1
- 229920006280 packaging film Polymers 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 229940049954 penicillin Drugs 0.000 description 1
- 150000004714 phosphonium salts Chemical class 0.000 description 1
- NAYYNDKKHOIIOD-UHFFFAOYSA-N phthalamide Chemical compound NC(=O)C1=CC=CC=C1C(N)=O NAYYNDKKHOIIOD-UHFFFAOYSA-N 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- WYVAMUWZEOHJOQ-UHFFFAOYSA-N propionic anhydride Chemical compound CCC(=O)OC(=O)CC WYVAMUWZEOHJOQ-UHFFFAOYSA-N 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- WKEDVNSFRWHDNR-UHFFFAOYSA-N salicylanilide Chemical compound OC1=CC=CC=C1C(=O)NC1=CC=CC=C1 WKEDVNSFRWHDNR-UHFFFAOYSA-N 0.000 description 1
- 229950000975 salicylanilide Drugs 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 239000012815 thermoplastic material Substances 0.000 description 1
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 description 1
- 239000012780 transparent material Substances 0.000 description 1
- 150000003626 triacylglycerols Chemical class 0.000 description 1
- PWBHRVGYSMBMIO-UHFFFAOYSA-M tributylstannanylium;acetate Chemical compound CCCC[Sn](CCCC)(CCCC)OC(C)=O PWBHRVGYSMBMIO-UHFFFAOYSA-M 0.000 description 1
- MWOOGOJBHIARFG-UHFFFAOYSA-N vanillin Chemical compound COC1=CC(C=O)=CC=C1O MWOOGOJBHIARFG-UHFFFAOYSA-N 0.000 description 1
- FGQOOHJZONJGDT-UHFFFAOYSA-N vanillin Natural products COC1=CC(O)=CC(C=O)=C1 FGQOOHJZONJGDT-UHFFFAOYSA-N 0.000 description 1
- 235000012141 vanillin Nutrition 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Landscapes
- Biological Depolymerization Polymers (AREA)
Abstract
本发明公开了一种疏水性可完全生物降解材料及其制备方法。本发明的淀粉基生物降解材料是由如下原料在挤出机中反应挤出制备而成的：淀粉，聚乙烯醇，可与羟基反应的内酯聚合物，可生物降解聚合物，引发剂和其它各种助剂。本发明具有成本低、制品疏水性高、操作简单、材料可完全生物降解等优点，可以解决白色污染问题。本发明采用反应挤出的方法，材料的改性和材料成型同时进行，简化了生产工艺，降低了生产成本，且便于连续化生产。The invention discloses a hydrophobic completely biodegradable material and a preparation method thereof. The starch-based biodegradable material of the present invention is prepared by reacting and extruding the following raw materials in an extruder: starch, polyvinyl alcohol, a lactone polymer that can react with a hydroxyl group, a biodegradable polymer, an initiator and Various other additives. The invention has the advantages of low cost, high hydrophobicity of products, simple operation, complete biodegradability of materials and the like, and can solve the problem of white pollution. The invention adopts the method of reaction extrusion, and the modification of the material and the shaping of the material are carried out simultaneously, which simplifies the production process, reduces the production cost, and is convenient 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)
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| CN103276473A (en) * | 2013-06-19 | 2013-09-04 | 东华大学 | Method for preparing celluloses and modified biodegradable polymer blend fibers |
| CN103289266A (en) * | 2013-06-24 | 2013-09-11 | 苏州新区佳合塑胶有限公司 | Water-soluble plastic packaging bag and preparation method thereof |
| CN103554857A (en) * | 2013-10-22 | 2014-02-05 | 江南大学 | Polyhydroxyalkanoate composite material and preparation method thereof |
| CN104761738A (en) * | 2014-12-26 | 2015-07-08 | 重庆联佰博超医疗器械有限公司 | Starch styptic powder as well as preparation method and application thereof |
| CN106069278A (en) * | 2016-06-22 | 2016-11-09 | 重庆工商大学 | Disposable degradable is from nutrition lightweight flowerpot and preparation method thereof |
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