CN114316542B - High-strength biodegradable plastic and preparation method thereof - Google Patents
High-strength biodegradable plastic and preparation method thereof Download PDFInfo
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- CN114316542B CN114316542B CN202111631505.4A CN202111631505A CN114316542B CN 114316542 B CN114316542 B CN 114316542B CN 202111631505 A CN202111631505 A CN 202111631505A CN 114316542 B CN114316542 B CN 114316542B
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- 238000002360 preparation method Methods 0.000 title claims abstract description 96
- 229920000704 biodegradable plastic Polymers 0.000 title claims abstract description 65
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 179
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 156
- 239000004626 polylactic acid Substances 0.000 claims abstract description 108
- 229920000747 poly(lactic acid) Polymers 0.000 claims abstract description 107
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 84
- 239000002071 nanotube Substances 0.000 claims abstract description 80
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 78
- 239000000835 fiber Substances 0.000 claims abstract description 71
- 239000000203 mixture Substances 0.000 claims abstract description 66
- 239000005014 poly(hydroxyalkanoate) Substances 0.000 claims abstract description 65
- 229920000903 polyhydroxyalkanoate Polymers 0.000 claims abstract description 65
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 62
- 238000001035 drying Methods 0.000 claims abstract description 43
- 239000011787 zinc oxide Substances 0.000 claims abstract description 31
- 239000004594 Masterbatch (MB) Substances 0.000 claims abstract description 30
- 238000002156 mixing Methods 0.000 claims abstract description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000007822 coupling agent Substances 0.000 claims abstract description 22
- 239000008367 deionised water Substances 0.000 claims abstract description 16
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 16
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 14
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 14
- 239000000945 filler Substances 0.000 claims abstract description 13
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000004014 plasticizer Substances 0.000 claims abstract description 12
- 239000005543 nano-size silicon particle Substances 0.000 claims abstract description 9
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 8
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 8
- 239000011259 mixed solution Substances 0.000 claims abstract description 5
- 238000009987 spinning Methods 0.000 claims abstract description 5
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 25
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 24
- 229920002873 Polyethylenimine Polymers 0.000 claims description 19
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 16
- 239000007864 aqueous solution Substances 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 15
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 14
- 238000001914 filtration Methods 0.000 claims description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- 239000002994 raw material Substances 0.000 claims description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 8
- 238000010335 hydrothermal treatment Methods 0.000 claims description 8
- 108010073771 Soybean Proteins Proteins 0.000 claims description 7
- 229940071440 soy protein isolate Drugs 0.000 claims description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 6
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 6
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 239000004246 zinc acetate Substances 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- 239000010902 straw Substances 0.000 claims description 5
- 239000005995 Aluminium silicate Substances 0.000 claims description 4
- 235000012211 aluminium silicate Nutrition 0.000 claims description 4
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 claims description 4
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 4
- 229940098779 methanesulfonic acid Drugs 0.000 claims description 4
- 238000000967 suction filtration Methods 0.000 claims description 4
- 238000002137 ultrasound extraction Methods 0.000 claims description 4
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 3
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 3
- ZHDTXTDHBRADLM-UHFFFAOYSA-N hydron;2,3,4,5-tetrahydropyridin-6-amine;chloride Chemical compound Cl.NC1=NCCCC1 ZHDTXTDHBRADLM-UHFFFAOYSA-N 0.000 claims description 3
- 229940001941 soy protein Drugs 0.000 claims description 2
- XKKVXDJVQGBBFQ-UHFFFAOYSA-L zinc ethanol diacetate Chemical compound C(C)O.C(C)(=O)[O-].[Zn+2].C(C)(=O)[O-] XKKVXDJVQGBBFQ-UHFFFAOYSA-L 0.000 claims description 2
- WMYJOZQKDZZHAC-UHFFFAOYSA-H trizinc;dioxido-sulfanylidene-sulfido-$l^{5}-phosphane Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([S-])=S.[O-]P([O-])([S-])=S WMYJOZQKDZZHAC-UHFFFAOYSA-H 0.000 claims 1
- 230000015556 catabolic process Effects 0.000 abstract description 11
- 238000006731 degradation reaction Methods 0.000 abstract description 11
- 239000002861 polymer material Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 18
- 229920003023 plastic Polymers 0.000 description 11
- 230000003247 decreasing effect Effects 0.000 description 10
- 239000004033 plastic Substances 0.000 description 10
- -1 polyethylene Polymers 0.000 description 10
- 229920006238 degradable plastic Polymers 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 8
- 239000011701 zinc Substances 0.000 description 8
- 229910052725 zinc Inorganic materials 0.000 description 8
- 230000004048 modification Effects 0.000 description 7
- 238000012986 modification Methods 0.000 description 7
- 238000002844 melting Methods 0.000 description 6
- 230000008018 melting Effects 0.000 description 6
- 229920001432 poly(L-lactide) Polymers 0.000 description 6
- 239000000377 silicon dioxide Substances 0.000 description 6
- 238000004132 cross linking Methods 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 235000019710 soybean protein Nutrition 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 4
- 229920002472 Starch Polymers 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229920000573 polyethylene Polymers 0.000 description 4
- 239000008107 starch Substances 0.000 description 4
- 235000019698 starch Nutrition 0.000 description 4
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 4
- 229920001634 Copolyester Polymers 0.000 description 3
- 241000196324 Embryophyta Species 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 238000006065 biodegradation reaction Methods 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 229920006242 ethylene acrylic acid copolymer Polymers 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- 230000004580 weight loss Effects 0.000 description 3
- RNWHGQJWIACOKP-UHFFFAOYSA-N zinc;oxygen(2-) Chemical class [O-2].[Zn+2] RNWHGQJWIACOKP-UHFFFAOYSA-N 0.000 description 3
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N Formic acid Chemical compound OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000001066 destructive effect Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 238000007602 hot air drying Methods 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 229940057995 liquid paraffin Drugs 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- 230000001699 photocatalysis Effects 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- JJTUDXZGHPGLLC-IMJSIDKUSA-N 4511-42-6 Chemical compound C[C@@H]1OC(=O)[C@H](C)OC1=O JJTUDXZGHPGLLC-IMJSIDKUSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229920002261 Corn starch Polymers 0.000 description 1
- 241000195493 Cryptophyta Species 0.000 description 1
- JVTAAEKCZFNVCJ-UWTATZPHSA-N D-lactic acid Chemical compound C[C@@H](O)C(O)=O JVTAAEKCZFNVCJ-UWTATZPHSA-N 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 229920003232 aliphatic polyester Polymers 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000003064 anti-oxidating effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
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- 239000003054 catalyst Substances 0.000 description 1
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- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical group O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
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- 229920001485 poly(butyl acrylate) polymer Polymers 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
- Biological Depolymerization Polymers (AREA)
Abstract
The application relates to the field of high polymer materials, and particularly discloses a high-strength biodegradable plastic and a preparation method thereof. The high-strength biodegradable plastic comprises the following components: polylactic acid, modified polylactic acid/polyhydroxyalkanoate blend fiber, nano calcium carbonate master batch, a filler, an antioxidant, a plasticizer and a coupling agent; the modified polylactic acid/polyhydroxyalkanoate blend fiber is prepared by the following method: (1) drying polylactic acid, mixing the polylactic acid with polyhydroxyalkanoate and polyethylene glycol, and spinning to obtain nascent mixed fiber; (2) placing the nascent mixed fiber in n-hexane, and adding nano silicon dioxide to prepare blended fiber; (3) and (3) placing the blend fiber into a mixed solution containing a coupling agent, a zinc oxide doped titanium dioxide nanotube and deionized water, and performing ultrasonic treatment and drying to obtain the modified polylactic acid/polyhydroxyalkanoate blend fiber. The high-strength biodegradable plastic has the advantages of good toughness, strong heat resistance and high degradation speed.
Description
Technical Field
The application relates to the technical field of high polymer materials, in particular to high-strength biodegradable plastic and a preparation method thereof.
Background
Biodegradable plastics are plastics degraded by the action of microorganisms existing in the nature, such as bacteria, molds and algae, and can be divided into safe biodegradable plastics and destructive biodegradable plastics, wherein the destructive biodegradable plastics mainly comprise starch modified polyethylene and the like, the biodegradable plastics can only degrade large plastics into smaller plastics, the components of plastic molecules are not completely disappeared, and the degradation degree is limited; the completely biodegradable plastic can be completely degraded, is mainly prepared by fermenting or synthesizing natural macromolecules or agricultural and sideline products through microorganisms, and mainly comprises PCL, PLA, PBS, PHA and the like.
The production process of polylactic acid (PLA) is low-carbon and environment-friendly, pollution is less, and the cost is lower than that of other common degradable plastics such as PBAT, PBA and PHA, so that the PLA becomes a degradable material which is most actively developed and fastest developed in recent years, but the polylactic acid has the defects of hard texture, poor toughness and poor heat resistance, and the application of the polylactic acid material is greatly restricted.
In the prior art, Chinese patent application No. CN200610086212.2 discloses a heat-resistant polylactic acid copolymer, which is prepared by ring-opening polymerization of a mixture of D-lactide and L-lactide under the action of a chiral catalyst, wherein the melting point of the polylactic acid copolymer is 180-225 ℃, and the molar ratio of the amount of the poly-D-lactic acid to the amount of the poly-L-lactic acid in the polylactic acid copolymer is 20: 80-80: 20.
In the prior art, chinese patent application No. CN200610097261.5 discloses a method for toughening and modifying polylactic acid, which comprises mixing polylactic acid and toughening modifier in proportion, drying to make the water content lower than 50ppm, and then molding into products by melt extrusion. The toughening modifier is copolyester with a melting point of 125-200 ℃, and is especially copolyester obtained by modifying PET (polyethylene terephthalate) by using isophthalic acid, hexamethylene diamine, 1, 4-butanediol and the like as a third monomer. When blending, the dosage of the copolyester accounts for 1-20 Wt% of the dosage of the polylactic acid, and the processing temperature of melt extrusion is 180-240 ℃.
In view of the above-mentioned related technologies, the inventors found that both the heat-resistant modification and the toughening modification of the polylactic acid are performed singly, and the toughening modification and the heat-resistant modification are not completed simultaneously, so that the application of the polylactic acid is limited.
Disclosure of Invention
In order to synchronously improve the heat resistance and the toughness of polylactic acid, the application provides a high-strength biodegradable plastic and a preparation method thereof.
In a first aspect, the present application provides a high-strength biodegradable plastic, which adopts the following technical scheme:
a high-strength biodegradable plastic comprises the following components in parts by weight:
50-70 parts of polylactic acid, 10-20 parts of modified polylactic acid/polyhydroxyalkanoate blend fiber, 20-40 parts of nano calcium carbonate master batch, 10-30 parts of filler, 5-10 parts of antioxidant, 10-20 parts of plasticizer and 5-10 parts of coupling agent;
the modified polylactic acid/polyhydroxyalkanoate blend fiber is prepared by the following method:
(1) drying polylactic acid, mixing the polylactic acid with polyhydroxyalkanoate and polyethylene glycol, and spinning to obtain nascent mixed fiber;
(2) placing the nascent mixed fiber in n-hexane, adding nano silicon dioxide, performing ultrasonic extraction, drying with hot air, and drafting to obtain blended fiber;
(3) and (3) placing the blend fiber into a mixed solution containing a coupling agent, a zinc oxide doped titanium dioxide nanotube and deionized water, and performing ultrasonic treatment and drying to obtain the modified polylactic acid/polyhydroxyalkanoate blend fiber.
By adopting the technical scheme, the biodegradable material is prepared by using the components such as the nano calcium carbonate master batch, the modified polylactic acid/polyhydroxyalkanoate blend fiber and the like, the polylactic acid and the modified polylactic acid/polyhydroxyalkanoate blend fiber have better compatibility, the mechanical strength of the biodegradable plastic is improved, and the heat resistance of the biodegradable plastic is improved; polylactic acid and polyhydroxyalkanoate belong to aliphatic polyester together, and the molecular weight of the two is similar, polyhydroxyalkanoate can be dispersed in a polylactic acid matrix more uniformly, polyethylene glycol is used as a micromolecule lubricant, so that the slippage between macromolecular chains is easier, the movement capacity is increased, meanwhile, hydroxyl on polyethylene glycol molecules is combined with hydrogen bonds between polylactic acid molecules, the hydrogen bonds between polylactic acid molecules are damaged, the intermolecular acting force of polylactic acid is reduced, the polylactic acid molecular chains are easier to move, a better plasticizing effect is achieved, polyhydroxyalkanoate has better toughness and lower crystallization rate, the polyethylene glycol breaks the hydrogen bonds of polylactic acid, the intermolecular spacing is increased, the molecular chain flexibility is increased, and the elongation at break of blended fibers is increased.
The nano silicon dioxide particles reach nano-scale dispersion in the primary mixed fiber, are used as crystallization crystal nuclei during stretching and drying, have strong interaction with polylactic acid and polyhydroxyalkanoate, play a role in cross-linking points, play a role in promoting further crystallization of the fiber, form a plurality of small crystal grains in the primary mixed fiber, improve crystallinity and improve heat resistance, and in addition, when the modified polylactic acid/polyhydroxyalkanoate blended fiber is stretched by external force, nano silicon dioxide ions generate a stress concentration effect to excite a surrounding matrix to generate micro cracks and absorb certain deformation force, so that a strong toughening effect is generated; the coupling agent can form a layer of coupling molecule interface on the surface of the zinc oxide doped titanium dioxide nanotube, so that the compatibility and the dispersibility of the coupling molecule interface with the blended fiber are improved, the specific surface area of the titanium dioxide nanotube is large, the zinc oxide is easily adsorbed, the antibacterial property is improved, the impact strength is improved, and the degradable plastic has biodegradability and photodegradability.
Preferably, the modified polylactic acid/polyhydroxyalkanoate blend fiber is prepared from the following raw materials in parts by weight: 1-2 parts of polylactic acid, 1-2 parts of polyhydroxyalkanoate, 0.1-0.3 part of polyethylene glycol, 5-10 parts of n-hexane, 1-2 parts of nano silicon dioxide, 0.05-0.1 part of coupling agent, 0.8-1.6 parts of zinc oxide doped titanium dioxide nanotube and 2-4 parts of deionized water.
By adopting the technical scheme, the toughness of the blended fiber can be improved by adding the polyhydroxyalkanoate, meanwhile, the regularity of polylactic acid molecules is damaged by adding the polyethylene glycol, the cleanliness of the blended material is reduced, and the toughness of the blended material is improved.
Preferably, the preparation method of the zinc oxide doped titanium dioxide nanotube comprises the following steps:
ultrasonically dispersing anatase type titanium dioxide in a sodium hydroxide solution with the mass fraction of 0.2-1%, performing hydrothermal treatment at the temperature of 150-200 ℃ for 20-24h, filtering, washing and drying to prepare a titanium dioxide nanotube;
acidifying the titanium dioxide nanotube with a methanesulfonic acid aqueous solution, then adding the acidified titanium dioxide nanotube into a solution containing toluene, a silane coupling agent and deionized water, heating the acidified titanium dioxide nanotube to 80-100 ℃ in a water bath, preserving the heat for 4-6 hours, and drying the acidified titanium dioxide nanotube to obtain an aminopropylated titanium dioxide nanotube;
adding aminopropylated titanium dioxide nanotube and hexamethylenetetramine into 0.01-0.03moL/L zinc acetate ethanol solution, performing heat treatment at the temperature of 280-0.02 moL/L for 20-30min, cooling, centrifuging, adding the centrifuged substance into 0.01-0.02moL/L polyethyleneimine water solution, performing water bath at the temperature of 120-150 ℃, performing suction filtration, washing and drying.
By adopting the technical scheme, anatase type titanium dioxide is subjected to hydrothermal treatment to prepare titanium dioxide nanotubes, methane sulfonic acid aqueous solution is used for activating the titanium dioxide nanotubes to ensure that the surfaces of the titanium dioxide nanotubes have more hydroxyl groups, then silane coupling agent is combined with the hydroxyl groups, the silane coupling agent is grafted to the surface of silicon dioxide to prepare aminopropylated titanium dioxide nanotubes, the aminopropylated titanium dioxide nanotubes are used as a base layer, a zinc oxide nano array is deposited on the aminopropylated titanium dioxide nanotubes, finally the titanium dioxide nanotubes deposited with zinc oxide are mixed with polyethyleneimine solution, the polyethyleneimine can aminate the zinc oxide, the aminated zinc oxide can enhance the interface bonding force between the zinc oxide doped titanium dioxide nanotubes and the zinc oxide, the tensile strength is improved, and the aminated zinc oxide can serve as a physical cross-linking point to ensure that blended fibers are randomly wound, the modified polylactic acid/polyhydroxyalkanoate blend fiber is compact in arrangement, the mechanical strength of the modified polylactic acid/polyhydroxyalkanoate blend fiber is improved, the transparency of the modified polylactic acid/polyhydroxyalkanoate blend fiber can be improved by the aminated zinc oxide, and the degradation rate is improved; in addition, hydroxyl on the aminopropylated titanium dioxide nanotube can also carry out substitution reaction with polyethyleneimine to polymerize, so that the polyethyleneimine is grafted on the aminopropylated titanium dioxide nanotube, and the aminopropylated titanium dioxide nanotube modified by the polyethyleneimine has good scattering property, reduces agglomeration, increases specific surface area, improves the photocatalytic activity of the titanium dioxide nanotube, improves the light energy utilization rate and improves the degradation speed.
Preferably, the mass ratio of the zinc acetate to the aminopropylated titanium dioxide nanotube to the polyethyleneimine aqueous solution is 0.1-0.5:0.3-0.7: 1.
By adopting the technical scheme, the polyethyleneimine can be grafted to the aminopropylated titanium dioxide nanotube, and meanwhile, the polyethyleneimine can fully aminate zinc oxide.
Preferably, the nano calcium carbonate master batch comprises the following components in parts by weight: 1 to 5 portions of nano calcium carbonate and 0.1 to 0.5 portion of
Soy protein isolate, 1-2 parts of silica sol and 3-8 parts of maleic anhydride grafted EVA.
By adopting the technical scheme, the mechanical strength and the heat resistance of the degradable plastic can be enhanced by filling the nano calcium carbonate, the flexibility of the degradable plastic can be improved by the isolated soy protein and the silica sol, the tensile strength of the degradable plastic can be improved by the maleic anhydride grafted EVA, the compatibility of the maleic anhydride grafted EVA and the polylactic acid is good, and the dispersibility of the nano calcium carbonate in the polylactic acid can be improved.
Preferably, the nano calcium carbonate master batch is prepared by the following method:
adding nano calcium carbonate into a silane coupling agent aqueous solution, stirring for 5-10min, filtering, and drying to obtain modified nano calcium carbonate; mixing the soy protein isolate and the silica sol, adding ammonia water and deionized water, stirring for 3-4h, and mixing with the modified nano calcium carbonate uniformly to obtain a nano calcium carbonate mixture;
and (3) drying the nano calcium carbonate mixture and maleic anhydride grafted EVA in vacuum, extruding and granulating.
By adopting the technical scheme, firstly, silane coupling agent solution is used for processing, the compatibility of the nano calcium carbonate with the soybean protein isolate and the silica sol is enhanced, then the soybean protein isolate and the silica sol are connected through silica-alumina bond to form a cross-linked network structure, and further, when the nano calcium carbonate is combined with the hydroxyl of the maleic anhydride grafted EVA, the binding force is further improved from point to surface; in addition, the silicon dioxide ions in the silicon dioxide sol can be uniformly dispersed in the maleic anhydride grafted EVA and generate stronger intermolecular force with the maleic anhydride grafted EVA to form a large number of physical crosslinking points, so that the crosslinking density is increased, the maleic anhydride grafted EVA is in a net structure, the mechanical strength and flexibility of the maleic anhydride grafted EVA are enhanced, the heat-resistant effect of the maleic anhydride grafted EVA is improved, and the maleic anhydride grafted EVA is combined with the nano calcium carbonate, so that the dispersibility of components such as the nano calcium carbonate and polylactic acid can be enhanced, and the compatibility of the nano calcium carbonate and the polylactic acid is improved.
Preferably, the filler comprises straw biochar and kaolin in a mass ratio of 1: 2-3.
By adopting the technical scheme, the straw biochar and the kaolin are porous materials, so that the high-temperature resistance of the degradable plastic can be improved, an environment is provided for microbial propagation, and the degradation rate is accelerated.
Preferably, the coupling agent is one or more of KH550, KH560 and KH 570.
By adopting the technical scheme, the coupling agent can increase the dispersibility of the filler and the nano calcium carbonate master batch equal to that of the polylactic acid, so that the filler and the nano calcium carbonate master batch can be uniformly dispersed in the polylactic acid, and the toughness of the biodegradable plastic is increased.
Preferably, the plasticizer is one or more of ethylene glycol, glycerol and propylene glycol; the antioxidant is one or more of 4, 4-diaminodiphenyl ether, dialkyl diphenylamine and dialkyl dithiophosphate.
In a second aspect, the present application provides a method for preparing a high-strength biodegradable plastic, which adopts the following technical scheme: a process for preparing high-strength biodegradable plastics includes such steps as adding filler and nano-class calcium carbonate mother material to solution of coupling agent, stirring, baking, cooling to ordinary temp, mixing with polylactic acid, antioxidizing agent, plasticizer and modified polylactic acid/polyhydroxy fatty acid ester fibres, extruding out and granulating.
By adopting the technical scheme, the filler and the nano calcium carbonate are treated by the coupling agent, so that the compatibility and the dispersibility of the filler, the nano calcium carbonate master batch, the polylactic acid and other components are improved, the interface bonding force is improved, and the mechanical strength of the biodegradable plastic is improved.
In summary, the present application has the following beneficial effects:
1. because the biodegradable plastic is prepared by adopting the raw materials such as the nano calcium carbonate master batch, the modified polylactic acid/polyhydroxyalkanoate blend fiber, the polylactic acid and the like, the nano calcium carbonate master batch can be fully dispersed in the polylactic acid, and the modified polylactic acid/polyhydroxyalkanoate blend fiber is prepared by mixing the components such as PHA, PLA, silicon dioxide, zinc oxide doped titanium dioxide nanotubes and the like, the PHA in the blend fiber can improve the toughness of the PLA in the blend fiber raw material, and the PLA in the blend fiber can enhance the compatibility of the blend fiber and the polylactic acid in the plastic raw material, so that the heat-resisting temperature of the biodegradable plastic is improved, and the mechanical properties such as the toughness, the tensile strength and the like are synchronously improved.
2. In the application, the aminopropylated titanium dioxide nanotube is preferably used as a base layer, zinc oxide is deposited on the surface of the aminopropylated titanium dioxide nanotube and then the aminopropylated titanium dioxide nanotube and the polyethyleneimine are mixed to prepare the zinc oxide doped titanium dioxide nanotube, the zinc oxide can be aminated, the transparency of plastics is improved, in addition, calcium can serve as a cross-linking point, the mechanical strength is improved, in addition, the polyethyleneimine can be grafted to the aminopropylated titanium dioxide nanotube, the agglomeration phenomenon of the titanium dioxide nanotube is reduced, the photocatalytic effect of the titanium dioxide nanotube is improved, and the degradation rate is improved.
3. In the application, nano calcium carbonate, soy protein isolate, silica sol and maleic anhydride grafted EVA are preferably adopted to prepare the nano calcium carbonate master batch, the compatibility of the maleic anhydride grafted EVA and polylactic acid is good, the bonding force of the nano calcium carbonate and the polylactic acid can be improved, and in addition, the heat resistance and the mechanical strength of the nano calcium carbonate master batch can be improved by adding the soy protein isolate and the silica sol, so that the prepared nano calcium carbonate master batch can be uniformly dispersed in the polylactic acid, and the heat resistance and the toughness of the polylactic acid are improved.
Detailed Description
Preparation examples 1 to 4 of Zinc oxide-doped titanium dioxide nanotubes
Preparation examples 1 to 4 the anatase type titanium dioxide was selected from Nanjing Hongde nanomaterial Co., Ltd, model number HDZY 13; the silane coupling agent is selected from Tokyo Changhe chemical industry Co., Ltd, and the model is KH 550; the polyethyleneimine is selected from Shandong Deno chemical Co., Ltd, and is PEI.
Preparation example 1: (1) ultrasonically dispersing 1kg of anatase titanium dioxide in 2kg of sodium hydroxide solution with the mass fraction of 0.2%, carrying out hydrothermal treatment at 150 ℃ for 20h, filtering, washing and drying to obtain a titanium dioxide nanotube;
(2) adding the titanium dioxide nanotube prepared in the step (1) into 3kg of methane sulfonic acid aqueous solution, heating the mixture to 80 ℃ in a water bath, acidifying the mixture for 4 hours, then adding the mixture into a solution prepared by mixing 0.2kg of toluene, 0.5kg of silane coupling agent and 1kg of deionized water, heating the mixture to 80 ℃ in a water bath, preserving the heat for 6 hours, and drying the mixture to obtain an aminopropylated titanium dioxide nanotube;
(3) adding 3kg of aminopropylated titanium dioxide nanotube and 0.5kg of hexamethylenetetramine into 1kg of ethanol solution in zinc acetate with the concentration of 0.01moL/L, carrying out heat treatment at 280 ℃ for 30min, cooling, centrifuging, adding the centrifuged substance into 10kg of polyethyleneimine aqueous solution with the concentration of 0.01moL/L, carrying out water bath at 120 ℃ for 5h, carrying out suction filtration, washing and drying.
Preparation example 2: the difference from preparation example 1 is that the mass ratio of the zinc acetate to the aminopropylated titanium dioxide nanotubes to the polyethyleneimine aqueous solution is 0.5:0.7: 1.
Preparation example 3: (1) ultrasonically dispersing 1kg of anatase titanium dioxide in 2kg of sodium hydroxide solution with the mass fraction of 0.2%, carrying out hydrothermal treatment at 150 ℃ for 20h, filtering, washing and drying to obtain a titanium dioxide nanotube;
(2) adding 3kg of titanium dioxide nanotube into 1kg of zinc acetate absolute ethanol solution, performing heat treatment at 280 ℃ for 30min, cooling, centrifuging, adding the centrifuged product into 10kg of polyethyleneimine aqueous solution with the concentration of 0.01moL/L, performing water bath at 120 ℃ for 5h, performing suction filtration, washing, and drying.
Preparation example 4: (1) ultrasonically dispersing 1kg of anatase titanium dioxide in 2kg of sodium hydroxide solution with the mass fraction of 0.2%, performing hydrothermal treatment at 150 ℃ for 20 hours, filtering, washing and drying to obtain a titanium dioxide nanotube;
(2) adding 3kg of titanium dioxide nanotube into 1kg of zinc acetate absolute ethanol solution, placing at 280 ℃ for heat treatment for 30min, cooling, centrifuging, washing and drying.
Preparation examples 5 to 16 of modified polylactic acid/polyhydroxyalkanoate blend fibers
Preparation examples 5 to 16 Poly-L-lactic acid was selected from Shanghai-derived leaf Biotech Co., Ltd, cat # S25341; the polyhydroxyalkanoate is selected from Kaalizli plastic materials Co., Ltd, Dongguan city, with the product number of PHA 1010; the polyethylene glycol is selected from Shandong Yangtao Biotechnology Co., Ltd, and has a molecular weight of 2000; the nano silicon dioxide is selected from Aidelajon chemical industry Co., Ltd, the product number is A200.
Preparation example 5: (1) drying 1kg of polylactic acid at 80 ℃ for 4h, mixing with 0.2kg of polyhydroxyalkanoate and 0.1kg of polyethylene glycol, and spinning to obtain nascent mixed fiber, wherein the temperature of a first zone is 170 ℃, the temperature of a second zone is 180 ℃, the temperature of a third zone is 185 ℃, the temperature of a machine head is 185 ℃, the rotating speed is 27r/min, and the polylactic acid is poly-L-lactic acid;
(2) placing the nascent mixed fiber prepared in the step (1) in 5kg of normal hexane, adding 1kg of nano silicon dioxide, carrying out ultrasonic extraction for 2h at the power of 200W, then carrying out hot air drying for 10min at the temperature of 60 ℃, and drafting by 96 times to prepare blended fiber;
(3) placing the blended fiber prepared in the step (2) into a mixed solution of 0.05kg of coupling agent KH550, 0.8kg of zinc oxide doped titanium dioxide nanotube and 2kg of deionized water, performing ultrasonic treatment, and drying to obtain the modified polylactic acid/polyhydroxyalkanoate blended fiber, wherein the zinc oxide doped titanium dioxide nanotube is prepared by mixing 1kg of zinc oxide and 3kg of titanium dioxide nanotube, and the preparation method of the titanium dioxide nanotube comprises the following steps: ultrasonically dispersing 1kg of anatase titanium dioxide in 2kg of sodium hydroxide solution with the mass fraction of 0.2%, carrying out hydrothermal treatment at 150 ℃ for 20h, filtering, washing and drying to obtain the titanium dioxide nanotube.
Preparation example 6: (1) drying 2kg of polylactic acid at 80 ℃ for 4h, mixing with 0.6kg of polyhydroxyalkanoate and 0.3kg of polyethylene glycol, and spinning to obtain nascent mixed fiber, wherein the temperature of a first zone is 170 ℃, the temperature of a second zone is 180 ℃, the temperature of a third zone is 185 ℃, the temperature of a machine head is 185 ℃, the rotating speed is 27r/min, and the polylactic acid is poly L-lactic acid;
(2) placing the nascent mixed fiber prepared in the step (1) in 10kg of normal hexane, adding 2kg of nano-silica, carrying out ultrasonic extraction for 2h at the power of 200W, then carrying out hot air drying for 10min at the temperature of 60 ℃, and drafting by 96 times to prepare blended fiber;
(3) putting the blend fiber prepared in the step (2) into a mixed solution of 0.1kg of coupling agent KH550, 1.6kg of zinc oxide doped titanium dioxide nanotube and 4kg of deionized water, performing ultrasonic treatment, and drying to obtain the modified polylactic acid/polyhydroxyalkanoate blend fiber, wherein the zinc oxide doped titanium dioxide nanotube is prepared by mixing 1kg of zinc oxide and 3kg of titanium dioxide nanotube, and the preparation method of the titanium dioxide nanotube comprises the following steps: ultrasonically dispersing 1kg of anatase titanium dioxide in 2kg of sodium hydroxide solution with the mass fraction of 0.2%, carrying out hydrothermal treatment at 150 ℃ for 20h, filtering, washing and drying to obtain the titanium dioxide nanotube.
Preparation example 7: the difference from preparation example 5 is that the amount of the polyhydroxyalkanoate used in step (1) was 1 kg.
Preparation example 8: the difference from preparation example 5 was that the amount of the polyhydroxyalkanoate used in step (1) was 0.05 kg.
Preparation example 9: the difference from preparation example 5 is that no nanosilica was added in step (2).
Preparation example 10: the difference from preparation example 5 is that the zinc oxide-doped titanium dioxide nanotubes are not added in step (3).
Preparation example 11: the difference from preparation example 5 is that no polyhydroxyalkanoate was added in step (1).
Preparation example 12: the difference from preparation example 5 is that polyethylene glycol was not added in step (1).
Preparation example 13: the difference from preparation example 5 is that the zinc oxide-doped titanium dioxide nanotube was prepared in preparation example 1.
Preparation example 14: the difference from preparation example 5 is that the zinc oxide-doped titanium dioxide nanotube was prepared from preparation example 2.
Preparation example 15: the difference from preparation example 5 is that the zinc oxide-doped titanium dioxide nanotubes were prepared in preparation example 3.
Preparation example 16: the difference from preparation example 5 is that the zinc oxide-doped titanium dioxide nanotube was prepared in preparation example 4.
Preparation examples 17 to 21 of Nano calcium carbonate masterbatch
The nano calcium carbonate in preparation examples 17 to 21 was selected from Shanghai Jiang chemical Co., Ltd., Cat number 08418; the silane coupling agent is selected from Tochu Changhe chemical Co., Ltd, and the model is KH 550; the soybean protein isolate is selected from Jinhua city honest biological technology Co., Ltd, and has a model number of SD 100; the silica sol is selected from Suzhou zirconium nano material Co., Ltd, and the model is UG-S01A; the maleic anhydride grafted EVA was selected from Touchi Seikagaku polymer Co., Ltd, model number PX 1164.
Preparation example 17: (1) adding 1kg of nano calcium carbonate into a silane coupling agent aqueous solution with the mass fraction of 20%, stirring for 5min, filtering, and drying at 60 ℃ for 5h to obtain modified nano calcium carbonate;
(2) mixing 0.1kg of soy protein isolate and 1kg of silica sol, adding 0.05kg of ammonia water with the concentration of 1mol/L and 2kg of deionized water, stirring for 3 hours, and mixing with the modified nano calcium carbonate obtained in the step (1) uniformly to obtain a nano calcium carbonate mixture;
(3) and (3) drying the nano calcium carbonate mixture obtained in the step (2) and 3kg of maleic anhydride grafted EVA in vacuum at 100 ℃ for 4h, melting at 160 ℃, extruding and granulating.
Preparation example 18: (1) adding 5kg of nano calcium carbonate into a silane coupling agent aqueous solution with the mass fraction of 20%, stirring for 10min, filtering, and drying at 60 ℃ for 5h to obtain modified nano calcium carbonate;
(2) mixing 0.5kg of soybean protein isolate and 2kg of silica sol, adding 0.1kg of ammonia water with the concentration of 1mol/L and 3kg of deionized water, stirring for 4 hours, and mixing with the modified nano calcium carbonate obtained in the step (1) uniformly to prepare a nano calcium carbonate mixture;
(3) and (3) drying the nano calcium carbonate mixture obtained in the step (2) and 8kg of maleic anhydride grafted EVA in vacuum at 110 ℃ for 4h, melting at 180 ℃, extruding and granulating.
Preparation example 19: (1) adding 5kg of nano calcium carbonate into a silane coupling agent aqueous solution with the mass fraction of 20%, stirring for 10min, filtering, and drying at 60 ℃ for 5h to obtain modified nano calcium carbonate;
(2) stirring 2kg of silica sol and 3kg of deionized water for 4 hours, and mixing the silica sol and the modified nano calcium carbonate obtained in the step (1) uniformly to obtain a nano calcium carbonate mixture;
(3) and (3) drying the nano calcium carbonate mixture obtained in the step (2) and 8kg of maleic anhydride grafted EVA in vacuum at 110 ℃ for 4h, melting at 180 ℃, extruding and granulating.
Preparation example 20: (1) adding 5kg of nano calcium carbonate into a silane coupling agent aqueous solution with the mass fraction of 20%, stirring for 10min, filtering, and drying at 60 ℃ for 5h to obtain modified nano calcium carbonate;
(2) mixing and stirring 0.5kg of soybean protein isolate, 0.1kg of ammonia water with the concentration of 1mol/L and 3kg of deionized water for 4 hours, and uniformly mixing with the modified nano calcium carbonate obtained in the step (1) to obtain a nano calcium carbonate mixture;
(3) and (3) drying the nano calcium carbonate mixture obtained in the step (2) and 8kg of maleic anhydride grafted EVA in vacuum at 110 ℃ for 4h, melting at 180 ℃, extruding and granulating.
Preparation example 21: the difference from preparation example 17 is that no maleic anhydride was added to graft the EVA.
Examples
The poly-L-lactic acid in the following examples is selected from Shanghai Ye Biotech Co., Ltd, cat # S25341; the maleic anhydride grafted EVA is selected from Touchi Shijing polymer Co., Ltd, model number is PX 1164; the nano calcium carbonate is selected from Shanghai Yangjiang chemical industry Co., Ltd, and the product number is 08418; the straw charcoal is selected from Henan Jiahe water purification material Co., Ltd, and has the model number of JH-1006.
Example 1: the raw material composition of the high-strength biodegradable plastic is shown in table 1, polylactic acid is poly-L-lactic acid, modified polylactic acid/polyhydroxyalkanoate blend fiber is prepared by preparation example 5, a nano calcium carbonate master batch is prepared by mixing and extruding nano calcium carbonate and maleic anhydride grafted EVA according to a mass ratio of 1:3, a filling agent comprises straw biochar and kaolin according to a mass ratio of 1:2, an antioxidant is 4, 4-diaminodiphenyl ether, a plasticizer is ethylene glycol, and a coupling agent is KH 560.
The preparation method of the high-strength biodegradable plastic comprises the following steps:
adding the filler and the nano calcium carbonate master batch into a coupling agent solution with the mass fraction of 8%, uniformly stirring, drying, cooling to normal temperature, uniformly mixing with polylactic acid, an antioxidant, a plasticizer and modified polylactic acid/polyhydroxyalkanoate blend fibers, extruding at 150 ℃, and granulating.
TABLE 1 raw material ratios of high-strength biodegradable plastics in examples 1 to 5
Examples 2 to 5: a high-strength biodegradable plastic was distinguished from example 1 in that the amounts of the raw materials used are shown in Table 1.
Examples 6 to 10: a high-strength biodegradable plastic is different from the biodegradable plastic in example 1 in that the preparation example of the modified polylactic acid/polyhydroxyalkanoate blend fiber is selected as shown in Table 2.
TABLE 2 raw material ratios of high-strength biodegradable plastics in example 1 and examples 6 to 10
| Examples | Sources of modified polylactic acid/polyhydroxyalkanoate blend fibers |
| Example 1 | Preparation example 5 |
| Example 6 | Preparation example 6 |
| Example 7 | Preparation example 7 |
| Example 8 | Preparation example 8 |
| Example 9 | Preparation example 13 |
| Example 10 | Preparation example 14 |
| Example 11 | Preparation example 15 |
| Example 12 | Preparation example 16 |
Examples 13 to 17: a high-strength biodegradable plastic, which is different from example 9 in that the source of the nano calcium carbonate master batch is shown in table 3.
Table 3 selection of preparation examples for nano calcium carbonate masterbatch in examples 13-17
| Examples | Source of nano calcium carbonate mother material |
| Example 13 | Preparation example 17 |
| Example 14 | Preparation example 18 |
| Example 15 | Preparation example 19 |
| Example 16 | Preparation example 20 |
| Example 17 | Preparation example 21 |
Comparative example
Comparative example 1: a high-strength biodegradable plastic, which is different from example 1 in that the modified polylactic acid/polyhydroxyalkanoate blend fiber is selected from preparation example 9.
Comparative example 2: a high-strength biodegradable plastic, which is different from example 1 in that the modified polylactic acid/polyhydroxyalkanoate blend fiber is selected from preparation example 10.
Comparative example 3: a high-strength biodegradable plastic, which is different from example 1 in that the modified polylactic acid/polyhydroxyalkanoate blend fiber is selected from preparation example 11.
Comparative example 4: a high-strength biodegradable plastic, which is different from example 1 in that the modified polylactic acid/polyhydroxyalkanoate blend fiber is selected from preparation example 12.
Comparative example 5: a high-strength biodegradable plastic is different from the biodegradable plastic prepared in example 1 in that no nano calcium carbonate master batch is added.
Comparative example 6: a high-strength and easily degradable master batch for plastic bags comprises the following raw materials: 50kg of ethylene-acrylic acid copolymer, 80kg of polyethylene, 20kg of polyvinyl alcohol, 10kg of polylactic acid, 30kg of pentaerythritol, 10kg of suberic acid, 5kg of diphenylmethane diisocyanate, 20kg of plant starch, 10kg of urea, 10kg of calcium carbonate, 5kg of titanium oxide, 10kg of liquid paraffin, 5kg of titanate coupling agent, 5kg of compatibilizer, 5kg of plasticizer and 3kg of surfactant. The plant starch adopts corn starch, the viscosity of polyethylene is 15000 Pa.s, the plasticizer is ethylene glycol, the cross-linking agent is formaldehyde, the titanate coupling agent adopts TC-114, the compatibilizer is ethylene acrylic acid copolymer, and the surfactant adopts sodium dodecyl sulfate. The preparation method comprises the following steps: mixing pentaerythritol, suberic acid and polylactic acid uniformly, carrying out polycondensation reaction for 3 hours at 170 ℃ in a nitrogen atmosphere, adding an ethylene-acrylic acid copolymer, polyethylene and polyvinyl alcohol, cooling, adding 2mol/L NaOH solution to wash reactants to be neutral, carrying out solid-liquid separation, uniformly mixing the obtained solid with diphenylmethane diisocyanate, plant starch, urea, calcium carbonate, titanium oxide, liquid paraffin, titanate coupling agent, compatibilizer, plasticizer and surfactant, putting the mixture into an extruder, controlling the rotating speed of a screw of the extruder at 45rpm, controlling the extrusion temperature at 145 ℃, and then carrying out granulation.
Performance test
The degradable plastics were prepared according to the methods in the examples and comparative examples, and the performance test was conducted with reference to the following methods, and the test results are recorded in table 4.
1. Tensile property: according to GB/T1040-2006 "determination of tensile Properties of plastics part 1: the tensile rate was 5mm/min in the measurement in general rules.
2. Impact properties: according to GB/T1043.1-2008, the part 1 of the determination of the impact property of the plastic simple supported beam: the impact method of the simple supported beam non-gap sample in the non-instrumental impact test is used for detection.
3. Microcard softening point: the measurement was carried out according to GB/T1633-2000 "measurement of thermoplastic microcard softening temperature (VST)" method B120.
4. Weight loss rate: and (3) placing 500g of biodegradable plastic in a natural environment, weighing the mass of the biodegradable plastic after 3 months, and calculating the weight loss rate to measure the degradation rate of the biodegradable plastic, wherein the larger the weight loss rate is, the faster the degradation rate is.
5. Haze: the biodegradable plastic is made into a film with the thickness of 70 μm, and the detection is carried out according to GB/T2410-2008 'determination of transparent plastic light transmittance and haze'.
TABLE 4 Performance test results for high-strength biodegradable plastics
As can be seen from the data in table 4, the biodegradable plastics prepared in examples 1 to 5 have tensile strength of 45.1MPa or more, elongation at break of 27.4% or more, a microcard softening point of 76.7 ℃ or more, and a biodegradability of 43.5% or more in 3 months, and have good flexibility and heat resistance, which indicates that the present application synchronously completes the heat-resistant modification and toughening modification of the polylactic acid biodegradable material, and obviously improves the flexibility and heat resistance of the polylactic acid biodegradable material.
In example 6, the modified polylactic acid/polyhydroxyalkanoate blend fiber prepared in preparation example 6 of the present application was used, wherein the zinc oxide doped titanium dioxide nanotube was prepared by mixing zinc oxide and titanium dioxide nanotube, and the preparation method of example 6 was the same as that of example 1, and it can be seen from the data in table 4 that the mechanical properties of the biodegradable plastics prepared in example 6 and example 1 were not much different, and the change of the microcard softening point was not significant.
In example 7 and example 8, the modified polylactic acid/polyhydroxyalkanoate blend fibers prepared in preparation example 7 and preparation example 8 were used, respectively, and compared to example 1, the amount of polyhydroxyalkanoate used in example 7 was increased, the amount of polyhydroxyalkanoate used in example 8 was decreased, the work at break was increased by creep action and the tensile strength was decreased in example 7, and the amount of polyhydroxyalkanoate used was decreased in example 8, so that the intermolecular hydrogen bonds of polylactic acid could not be broken and the tensile strength was decreased, the elongation at break was decreased, the crystallinity was decreased, and the heat resistance was decreased.
Example 9 is different from example 1 in that, by using the modified polylactic acid/polyhydroxyalkanoate blend fiber prepared in preparation example 13, in which the zinc oxide doped titanium dioxide nanotubes are prepared in preparation example 1, and the modified polylactic acid/polyhydroxyalkanoate blend fiber prepared in preparation example 14 in example 10, and the zinc oxide doped titanium dioxide nanotubes are prepared in preparation example 2, it can be seen from the comparison of the data in table 4 that, compared with example 1, the degradable plastics prepared in examples 9 and 10 have increased tensile strength, increased elongation at break, significantly improved impact strength, increased degradation speed, further reduced haze, and increased transparency, which indicates that the zinc oxide doped titanium dioxide nanotubes prepared in the present application can effectively improve the heat resistance, toughness and transparency of the degradable plastics.
Example 11 compared with example 1, using the modified polylactic acid/polyhydroxyalkanoate blend fiber prepared in preparation example 15, in which the zinc oxide-doped titanium dioxide nanotubes were prepared in preparation example 3, the titanium dioxide nanotubes were not aminopropylated, the data in table 4 shows that the toughness of the biodegradable plastic is reduced, which indicates that the aminopropylation of the titanium dioxide nanotubes can effectively improve the flexibility of the biodegradable plastic.
In example 12, the modified polylactic acid/polyhydroxyalkanoate blend fiber prepared in preparation example 16, in which the titanium dioxide nanotubes doped with zinc oxide were prepared in preparation example 4, the titanium dioxide nanotubes were not aminopropylated, and polyethyleneimine was not used, the biodegradable plastic prepared in example 12 had significantly decreased tensile strength and elongation at break, decreased degradation speed, increased haze, and decreased transparency, compared to example 11.
Compared with example 9, the data in table 4 show that the biodegradable plastics prepared in examples 13 and 14 have higher tensile strength and elongation at break than those of example 9, stronger toughness, higher microcard softening point, better heat resistance and reduced haze, but the biodegradation rate is reduced, but the degradation rate can still reach more than 80% within 3 months, which indicates that the nano calcium carbonate master batch prepared in the application can simultaneously improve the heat resistance, toughness and transparency of the biodegradable plastics.
Example 15 using the nano calcium carbonate master batch prepared in preparation example 19, no soy protein isolate was added to preparation example 19, compared to preparation example 17, and the data in table 4 shows that the biodegradable plastic prepared in example 15 has reduced tensile strength and elongation at break, insignificant improvement in heat resistance, and increased haze.
Example 16 using the nano calcium carbonate master batch prepared in preparation example 20, tensile strength and impact strength were reduced, the microcard softening point was reduced, and toughness and heat resistance were reduced because no silica sol was added, which indicates that the addition of the silica sol to the nano calcium carbonate master batch can improve both toughness and heat resistance of biodegradable plastics.
Example 17 using the nano calcium carbonate master batch prepared in preparation example 21, since maleic anhydride grafted EVA was not used, it is shown in table 4 that the biodegradable plastic prepared in example 17 has reduced mechanical properties such as tensile strength and increased biodegradation rate.
Comparative example 1 and comparative example 2 using the modified polylactic acid/polyhydroxyalkanoate blend fibers prepared in preparation examples 9 and 10, respectively, nano silica was not added in preparation example 9, and zinc oxide-doped titanium dioxide nanotubes were not added in preparation example 10, and the mechanical properties such as tensile strength, elongation at break, and the like of the biodegradable plastics in comparative example 1 and comparative example 2 were weakened, and heat resistance was lowered.
Comparative example 3 is different from example 1 in that the tensile strength of the biodegradable plastic prepared in comparative example 3 is weakened and the heat resistance is lowered using the modified polylactic acid/polyhydroxyalkanoate blend fiber prepared in preparation example 11, in which polyhydroxyalkanoate is not added.
Comparative example 4 is different from example 1 in that the modified polylactic acid/polyhydroxyalkanoate blend fiber prepared in preparation example 12, in which polyethylene glycol is not added, is not able to break intermolecular hydrogen bonds of polylactic acid, is not able to reduce intermolecular forces of polylactic acid, and is weakened in mechanical properties.
The difference between the comparative example 5 and the example 1 is that the heat-resistant temperature of the biodegradable plastic prepared in the comparative example 4 is reduced and the mechanical strength is weakened without adding the nano calcium carbonate master batch.
Comparative example 6 is a biodegradable plastic prepared by the prior art, which has weak tensile strength, large brittleness, insufficient heat resistance and slow biodegradation speed.
The present embodiment is only for explaining the present application, and it is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.
Claims (9)
1. The high-strength biodegradable plastic is characterized by comprising the following components in parts by weight: 50-70 parts of polylactic acid, 10-20 parts of modified polylactic acid/polyhydroxyalkanoate blend fiber, 20-40 parts of nano calcium carbonate master batch, 10-30 parts of filler, 5-10 parts of antioxidant, 10-20 parts of plasticizer and 5-10 parts of coupling agent;
the modified polylactic acid/polyhydroxyalkanoate blend fiber is prepared by the following method:
(1) drying polylactic acid, mixing the polylactic acid with polyhydroxyalkanoate and polyethylene glycol, and spinning to obtain nascent mixed fiber;
(2) placing the nascent mixed fiber in n-hexane, adding nano silicon dioxide, performing ultrasonic extraction, drying with hot air, and drafting to obtain blended fiber;
(3) placing the blend fiber in a mixed solution containing a coupling agent, a zinc oxide doped titanium dioxide nanotube and deionized water, performing ultrasonic treatment, and drying to obtain a modified polylactic acid/polyhydroxyalkanoate blend fiber;
the nano calcium carbonate master batch comprises the following components in parts by weight: 1-5 parts of nano calcium carbonate, 0.1-0.5 part of isolated soy protein, 1-2 parts of silica sol and 3-8 parts of maleic anhydride grafted EVA.
2. The high strength biodegradable plastic according to claim 1, characterized in that: the modified polylactic acid/polyhydroxyalkanoate blend fiber is prepared from the following raw materials in parts by weight:
1-2 parts of polylactic acid, 0.2-0.6 part of polyhydroxyalkanoate, 0.1-0.3 part of polyethylene glycol, 5-10 parts of n-hexane, 1-2 parts of nano silicon dioxide, 0.05-0.1 part of coupling agent, 0.8-1.6 parts of zinc oxide doped titanium dioxide nanotube and 2-4 parts of deionized water.
3. The high-strength biodegradable plastic according to claim 1, wherein the preparation method of the zinc oxide doped titanium dioxide nanotube comprises the following steps:
ultrasonically dispersing anatase type titanium dioxide in a sodium hydroxide solution with the mass fraction of 0.2-1%, performing hydrothermal treatment at the temperature of 150-200 ℃ for 20-24h, filtering, washing and drying to prepare a titanium dioxide nanotube;
acidifying the titanium dioxide nanotube with a methanesulfonic acid aqueous solution, then adding the acidified titanium dioxide nanotube into a solution containing toluene, a silane coupling agent and deionized water, heating the solution to 80-100 ℃ in a water bath, preserving the temperature for 4-6 hours, and drying the solution to obtain an aminopropylated titanium dioxide nanotube;
adding aminopropylated titanium dioxide nanotube and hexamethylenetetramine into 0.01-0.03mol/L zinc acetate ethanol solution, performing heat treatment at the temperature of 280-0.02 ℃ for 20-30min, cooling, centrifuging, adding the centrifuged substance into 0.01-0.02mol/L polyethyleneimine water solution, performing water bath at the temperature of 120-150 ℃, performing suction filtration, washing and drying.
4. The high-strength biodegradable plastic according to claim 3, wherein the mass ratio of the zinc acetate to the aminopropylated titanium dioxide nanotubes to the polyethyleneimine aqueous solution is 0.1-0.5:0.3-0.7: 1.
5. The high-strength biodegradable plastic according to claim 1, wherein the nano calcium carbonate master batch is prepared by the following method:
adding nano calcium carbonate into a silane coupling agent aqueous solution, stirring for 5-10min, filtering, and drying to obtain modified nano calcium carbonate;
mixing the soy protein isolate and the silica sol, adding ammonia water and deionized water, stirring for 3-4h, and mixing with the modified nano calcium carbonate uniformly to obtain a nano calcium carbonate mixture;
and (3) drying the nano calcium carbonate mixture and maleic anhydride grafted EVA in vacuum, extruding and granulating.
6. The high-strength biodegradable plastic according to claim 1, wherein the filler comprises straw biochar and kaolin in a mass ratio of 1: 2-3.
7. The high-strength biodegradable plastic according to claim 1, wherein the coupling agent is one or more of KH550, KH560 and KH 570.
8. The high-strength biodegradable plastic according to claim 1, wherein the plasticizer is one or more of ethylene glycol, glycerol and propylene glycol; the antioxidant is one or more of 4, 4-diaminodiphenyl ether, dialkyl diphenylamine and dialkyl zinc dithiophosphate.
9. The method for preparing high-strength biodegradable plastic according to any one of claims 1 to 8, comprising the steps of:
adding the filler and the nano calcium carbonate master batch into the coupling agent solution, uniformly stirring, drying, cooling to normal temperature, uniformly mixing with the polylactic acid, the antioxidant, the plasticizer and the modified polylactic acid/polyhydroxyalkanoate blend fiber, extruding and granulating.
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| CN116144191A (en) * | 2022-09-09 | 2023-05-23 | 中科广化（重庆）新材料研究院有限公司 | Degradable plastic prepared from plant wood fibers and preparation method thereof |
| CN115418091B (en) * | 2022-09-29 | 2023-12-08 | 浙江首康生物科技有限公司 | Liquid-transferring gun head material, preparation method thereof and liquid-transferring gun head |
| CN115651376B (en) * | 2022-11-03 | 2023-08-18 | 青岛周氏塑料包装有限公司 | Compostable antibacterial material for recyclable packaging products and preparation method thereof |
| CN115627559B (en) * | 2022-11-18 | 2023-05-16 | 北京微构工场生物技术有限公司 | Degradable filament and special material thereof |
| CN116178919A (en) * | 2022-12-20 | 2023-05-30 | 山东道恩周氏包装有限公司 | Biodegradable plastic packaging bag and preparation method thereof |
| CN117126517B (en) * | 2023-08-24 | 2024-03-12 | 广东岭南大健康生态科技集团有限公司 | Environment-controllable degradable mulching film and application thereof in weeding |
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