CN114031822A - Starch-based biodegradable packaging bottle with high oxygen barrier property and preparation method thereof - Google Patents
Starch-based biodegradable packaging bottle with high oxygen barrier property and preparation method thereof Download PDFInfo
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- CN114031822A CN114031822A CN202111244926.1A CN202111244926A CN114031822A CN 114031822 A CN114031822 A CN 114031822A CN 202111244926 A CN202111244926 A CN 202111244926A CN 114031822 A CN114031822 A CN 114031822A
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- starch
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 239000001301 oxygen Substances 0.000 title claims abstract description 70
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 70
- 238000004806 packaging method and process Methods 0.000 title claims abstract description 46
- 229920002472 Starch Polymers 0.000 title claims abstract description 44
- 235000019698 starch Nutrition 0.000 title claims abstract description 44
- 239000008107 starch Substances 0.000 title claims abstract description 44
- 230000004888 barrier function Effects 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title description 27
- 239000012767 functional filler Substances 0.000 claims abstract description 29
- 239000003054 catalyst Substances 0.000 claims abstract description 25
- 239000004970 Chain extender Substances 0.000 claims abstract description 22
- 239000002994 raw material Substances 0.000 claims abstract description 16
- 229920006167 biodegradable resin Polymers 0.000 claims abstract description 13
- 239000003607 modifier Substances 0.000 claims abstract description 13
- 239000004014 plasticizer Substances 0.000 claims abstract description 13
- 239000000126 substance Substances 0.000 claims abstract description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 36
- 239000005062 Polybutadiene Substances 0.000 claims description 30
- 229920002857 polybutadiene Polymers 0.000 claims description 30
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 23
- 238000003756 stirring Methods 0.000 claims description 23
- 238000001746 injection moulding Methods 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 17
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 15
- 229920000747 poly(lactic acid) Polymers 0.000 claims description 14
- 239000004626 polylactic acid Substances 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 11
- 229920000881 Modified starch Polymers 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 10
- 238000000071 blow moulding Methods 0.000 claims description 10
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 229920002121 Hydroxyl-terminated polybutadiene Polymers 0.000 claims description 9
- 238000009775 high-speed stirring Methods 0.000 claims description 9
- 238000004321 preservation Methods 0.000 claims description 9
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 238000001125 extrusion Methods 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- 239000002002 slurry Substances 0.000 claims description 8
- 238000009210 therapy by ultrasound Methods 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- 229920001592 potato starch Polymers 0.000 claims description 7
- 229920005989 resin Polymers 0.000 claims description 7
- 239000011347 resin Substances 0.000 claims description 7
- 239000013067 intermediate product Substances 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 6
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 claims description 5
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 5
- 239000004593 Epoxy Substances 0.000 claims description 5
- KDMCQAXHWIEEDE-UHFFFAOYSA-L cobalt(2+);7,7-dimethyloctanoate Chemical compound [Co+2].CC(C)(C)CCCCCC([O-])=O.CC(C)(C)CCCCCC([O-])=O KDMCQAXHWIEEDE-UHFFFAOYSA-L 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000002347 injection Methods 0.000 claims description 5
- 239000007924 injection Substances 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- 239000000600 sorbitol Substances 0.000 claims description 5
- 235000012424 soybean oil Nutrition 0.000 claims description 5
- 239000003549 soybean oil Substances 0.000 claims description 5
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 4
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 4
- 230000004048 modification Effects 0.000 claims description 4
- 238000012986 modification Methods 0.000 claims description 4
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 4
- 239000011975 tartaric acid Substances 0.000 claims description 4
- 235000002906 tartaric acid Nutrition 0.000 claims description 4
- VNTDZUDTQCZFKN-UHFFFAOYSA-L zinc 2,2-dimethyloctanoate Chemical compound [Zn++].CCCCCCC(C)(C)C([O-])=O.CCCCCCC(C)(C)C([O-])=O VNTDZUDTQCZFKN-UHFFFAOYSA-L 0.000 claims description 4
- 239000000243 solution Substances 0.000 claims description 3
- 229920002261 Corn starch Polymers 0.000 claims description 2
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 claims description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- 239000004368 Modified starch Substances 0.000 claims description 2
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 2
- 239000008120 corn starch Substances 0.000 claims description 2
- 235000019426 modified starch Nutrition 0.000 claims description 2
- STSDHUBQQWBRBH-UHFFFAOYSA-N n-cyclohexyl-1,3-benzothiazole-2-sulfonamide Chemical compound N=1C2=CC=CC=C2SC=1S(=O)(=O)NC1CCCCC1 STSDHUBQQWBRBH-UHFFFAOYSA-N 0.000 claims description 2
- 239000007921 spray Substances 0.000 claims description 2
- 238000005507 spraying Methods 0.000 claims description 2
- 235000011187 glycerol Nutrition 0.000 claims 2
- 238000006065 biodegradation reaction Methods 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 17
- 238000010521 absorption reaction Methods 0.000 description 10
- 230000008569 process Effects 0.000 description 10
- 239000002250 absorbent Substances 0.000 description 7
- 230000002745 absorbent Effects 0.000 description 7
- 230000000903 blocking effect Effects 0.000 description 5
- 235000013305 food Nutrition 0.000 description 5
- 239000005022 packaging material Substances 0.000 description 5
- 230000035699 permeability Effects 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 229920008262 Thermoplastic starch Polymers 0.000 description 4
- 239000003814 drug Substances 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- 239000004628 starch-based polymer Substances 0.000 description 4
- 229940123973 Oxygen scavenger Drugs 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 238000007664 blowing Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920001896 polybutyrate Polymers 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 239000002861 polymer material Substances 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- 238000009456 active packaging Methods 0.000 description 1
- 125000003289 ascorbyl group Chemical class [H]O[C@@]([H])(C([H])([H])O*)[C@@]1([H])OC(=O)C(O*)=C1O* 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000014633 carbohydrates Nutrition 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 229920000891 common polymer Polymers 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000009264 composting Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000002118 epoxides Chemical class 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000011185 multilayer composite material Substances 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- -1 on the other hand Substances 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- BHZRJJOHZFYXTO-UHFFFAOYSA-L potassium sulfite Chemical compound [K+].[K+].[O-]S([O-])=O BHZRJJOHZFYXTO-UHFFFAOYSA-L 0.000 description 1
- 235000019252 potassium sulphite Nutrition 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 230000002000 scavenging effect Effects 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L3/00—Compositions of starch, amylose or amylopectin or of their derivatives or degradation products
- C08L3/04—Starch derivatives, e.g. crosslinked derivatives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/06—Biodegradable
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/14—Gas barrier composition
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/10—Applications used for bottles
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Biological Depolymerization Polymers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Wrappers (AREA)
Abstract
The invention discloses a starch-based biodegradable packaging bottle with high oxygen barrier property, which can realize complete biodegradation and has good mechanical property, shape stability and excellent oxygen barrier property. The starch-based biodegradable packaging bottle with high oxygen barrier property is prepared from the following raw materials in parts by weight: 100 parts of starch, 15-50 parts of plasticizer, 0.5-3 parts of chemical modifier, 2-10 parts of functional filler, 0.05-0.15 part of catalyst, 0.5-2 parts of chain extender and 60-100 parts of biodegradable resin.
Description
Technical Field
The invention relates to a packaging bottle and a preparation method thereof, in particular to a starch-based biodegradable packaging bottle with high oxygen barrier property and a preparation method thereof.
Background
In the field of packaging, high polymer materials have already occupied a leading position due to light weight, excellent comprehensive performance and easiness in molding and processing. As a packaging material, the requirement for oxygen barrier property is high in some application fields, but when a common polyolefin material is used for packaging oxygen-sensitive foods/medicines, the shelf life of the material is relatively shortened, so that the material needs to be modified to enhance the barrier property, and the material has more applications in the packaging field. At present, a lot of solutions to this problem are to prepare a multilayer composite material, i.e., to add a high-barrier polymer material layer between two layers of common polymers, so as to achieve the effect of increasing barrier properties, but the preparation process of a packaging material with a multilayer structure is complicated, and the cost is high, so that it is a key to solve the problem to prepare a polymer composite material with a single-layer structure and high oxygen barrier properties.
With the constant importance of consumers on the safety and quality of food/medicine, active packaging systems can become a new trend of packaging materials, and active oxygen absorption materials with oxygen scavenging capacity also become a hotspot of research. The active oxygen absorption means that an oxygen absorbent is added into a polymer matrix, and when oxygen permeates into the polymer matrix, the oxygen absorbent inside absorbs and consumes the oxygen, so that the purpose of slowing down the oxygen permeation rate is achieved. For example, a highly resolved strategy has been reported to be the addition of oxygen absorbers to polyester materials to absorb oxygen and extend the shelf life of food products. It is known in the art that sulfites, ascorbic acid derivatives, unsaturated olefins, transition metal catalysts, and the like can be molecularly oxidized and thus can be used as oxygen absorbers. U.S. Pat. No. 4,536,409 recommends the use of potassium sulfite as an oxygen scavenger, chinese patent 104,028,102 discloses an organic oxygen scavenger utilizing a porous carrier and a method of manufacture, U.S. Pat. No. 5,211,875 discloses the use of unsaturated olefins as oxygen scavengers in the packaging field, and U.S. Pat. No. 5,211,875 generally discloses a method of initiating oxygen removal. At present, unsaturated olefin such as polybutadiene and a transition metal catalyst are introduced into a commonly used oxygen absorption system in polyester materials, the oxygen absorption agent achieves the effect of oxygen absorption by utilizing the principle that an allyl carbon-hydrogen bond is easy to be oxidized and degraded to generate hydroperoxide and double bonds can be catalytically oxidized to form epoxide, although the oxygen absorption effect is good, certain defects exist, such as poor compatibility of a small-molecular oxygen absorption agent and a high-molecular substrate, poor dispersibility of the oxygen absorption agent and further low oxygen absorption efficiency; meanwhile, the catalyst is added in a large amount, and excessive metal ions can cause the color value of the material to be higher.
Most of the traditional packaging materials are petroleum-based plastics, and the production of the traditional packaging materials consumes a large amount of petroleum resources and discharges a large amount of carbon dioxide on one hand, and on the other hand, a plurality of waste high polymer materials also cause environmental pollution. With the implementation of 'plastic limit order' in new edition in 2020, the market demand for biodegradable packaging is also rising sharply, but common biodegradable materials such as PLA, PBAT and the like which are produced in a larger scale cannot meet the oxygen barrier performance of some food/drug storage packages with high performance demands. Meanwhile, compared with the traditional polyolefin material, the cost of the biodegradable material such as PLA, PBAT and the like is relatively high. Starch, as a renewable carbohydrate, has the advantages of low price, easy degradation, wide source and reproducibility. However, the product prepared by only using thermoplastic starch as a raw material is often poor in comprehensive performance, so that the product is often used as biomass and a biodegradable material is compounded with biodegradable materials such as PLA, PBAT and the like, and the cost of the material can be greatly reduced. Therefore, the development of a starch-based biodegradable packaging bottle with high oxygen barrier property and a preparation method thereof is imperative.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provide the starch-based biodegradable packaging bottle with high oxygen barrier property, which can realize complete biodegradation and has good mechanical property, shape stability and excellent oxygen barrier property.
Meanwhile, the invention also provides a preparation method of the starch-based biodegradable packaging bottle with high oxygen barrier property, raw material particles of the packaging bottle can be continuously produced through a double-screw extruder, and the packaging bottle can be prepared through traditional injection blowing equipment under certain process conditions, so that the preparation method is economical and efficient, and is easy to realize large-scale production.
The invention is realized by the following technical scheme:
the starch-based biodegradable packaging bottle with high oxygen barrier property is prepared from the following raw materials in parts by weight:
the starch-based biodegradable packaging bottle with high oxygen barrier property has the further technical scheme that the functional filler is one or the combination of talcum powder and mesoporous silica, and is graft-modified by polybutadiene. Still further, the polybutadiene is a mixture of hydroxyl-terminated polybutadiene and epoxy-terminated polybutadiene, wherein the ratio of the hydroxyl-terminated polybutadiene to the epoxy-terminated polybutadiene is 1:1-1: 5; the size of the talcum powder and the size of the mesoporous silica are both below 500 nanometers. Still further technical scheme can be that the preparation method of the polybutadiene graft modified functional filler is as follows:
1) carrying out ultrasonic treatment on the dried functional filler in anhydrous toluene, adding toluene diisocyanate and a catalyst dibutyltin dilaurate at 40-70 ℃, reacting under the protection of a nitrogen atmosphere, and drying the slurry after the reaction is finished to obtain an intermediate product;
2) carrying out ultrasonic treatment on the intermediate product obtained in the step 1) and anhydrous toluene under the protection of nitrogen, adding polybutadiene diluted by the anhydrous toluene and a catalyst dibutyltin dilaurate, reacting at 50-75 ℃, and drying slurry after the reaction to obtain the polybutadiene graft modification functional filler.
The starch-based biodegradable packaging bottle with high oxygen barrier property has the further technical scheme that the starch is one or a combination of modified corn starch and modified potato starch. The further technical proposal is that the modification method of the modified corn starch or the modified potato starch comprises the following steps:
(1) taking 0.5-3 parts of N-cyclohexyl-2-benzothiazole sulfonamide and 0.5-3 parts of silane coupling agent KH560, and reacting with 10 parts of glycerol for 1-3 hours at the temperature of 60-90 ℃ under the protection of nitrogen;
(2) stirring 100 parts of dried corn starch or potato starch in a high-speed mixer at 60-90 ℃, spraying the solution obtained in the step (1) into the mixer in a spray shape, and stirring at a constant temperature and a high speed for 1-3 hours;
(3) slowly stirring, and cooling to room temperature to obtain the modified starch.
The starch-based biodegradable packaging bottle with high oxygen barrier property has the further technical scheme that the plasticizer can be one or the combination of glycerol, sorbitol and epoxidized soybean oil; the chemical modifier is one or the combination of tartaric acid and citric acid; the catalyst is one or the combination of zinc neodecanoate and cobalt neodecanoate; the chain extender is one or the combination of isocyanate chain extender and epoxy chain extender; the biodegradable resin is one or the combination of polylactic acid and itaconic anhydride grafted polylactic acid.
The preparation method of the starch-based biodegradable packaging bottle with high oxygen barrier property comprises the following steps:
1) taking 100 parts of starch, adding a plasticizer and a chemical modifier, and stirring at a high speed for the first time in a high-speed mixer at 40-60 ℃;
2) heating to 60-90 ℃, adding functional filler, chain extender, biodegradable resin and the like, and carrying out secondary high-speed stirring;
3) slowly stirring and carrying out heat preservation treatment;
4) adding the starch mixture after heat preservation into a double-screw extruder, extruding, air cooling and granulating;
5) extruding the dried resin particles, mixing the resin particles with a catalyst uniformly, performing injection molding by using an injection molding machine to form a bottle blank, and performing blow molding by using a bottle making machine to form the biodegradable packaging bottle.
The preparation method of the starch-based biodegradable packaging bottle with high oxygen barrier property has the further technical scheme that the first high-speed stirring speed is 600-1000 revolutions per minute, and the time is 5-10 minutes; the second high-speed stirring speed is 800-; the slow stirring speed is 50-100 r/min, and the heat preservation time is 2-4 hours.
The preparation method of the starch-based biodegradable packaging bottle with high oxygen barrier property further adopts the technical scheme that the double-screw extruder is melt extrusion, and the length-diameter ratio of the double-screw extruder is 44: 1-60: 1, the temperature range is 110-; the injection temperature range of the injection molding machine is 140-180 ℃; the blow molding temperature range of the bottle making machine is 60-90 ℃, and the blow-up ratio is 3: 1-5: 1.
compared with the prior art, the invention has the following beneficial effects:
the invention adopts a strategy of combining active blocking and passive blocking to realize high oxygen blocking performance, grafting the functional filler and the oxygen absorbent to improve the dispersibility of the filler and the oxygen absorbent in a polymer matrix, on one hand, the filler can serve as a nucleating agent in the crystallization process to improve the blocking performance of a crystallinity reinforcing material, on the other hand, polybutadiene has good oxygen absorption capacity to play an active blocking effect, and through grafting of the inorganic filler and the oxygen absorbent, the dispersibility of the oxygen absorbent can be greatly improved, so that the addition amount of the oxygen absorbent can be reduced, the dosage of a corresponding transition metal catalyst can be greatly reduced, and the color value stability of a biodegradable material is maintained. In addition, the specially modified thermoplastic starch (TPS) and the PLA are blended, on one hand, stress induced crystallization is formed in the injection and blowing process of a packaging bottle, on the other hand, the interaction between the non-crystallized PLA molecular chain and the specially modified TPS is strong, the gas permeation path is lengthened due to the synergistic effect of the two, and further, the oxygen barrier performance is improved in a passive barrier mode. Finally, the oxygen barrier property of the biodegradable bottle is equivalent to that of a polyester PET bottle, the comprehensive performance is good, and the biodegradable bottle can be used in the field of food/medicine packaging.
Secondly, the starch-based biodegradable packaging bottle with high oxygen barrier property prepared by the invention takes starch as a main product, has low price of raw materials, easy degradation, wide sources and regeneration, is still a full biodegradable material after being prepared by blending with other biodegradable materials, can be recycled like conventional plastics after being discarded, and can also be degraded by composting.
The starch-based biodegradable packaging bottle with high oxygen barrier property can be prepared by traditional high-polymer extrusion and injection blowing equipment under certain process conditions, is economical and efficient, has clean production process and no pollution, and is easy to realize large-scale production.
Detailed Description
The present invention will be described below with reference to specific examples, but the present invention is not limited to these examples.
Example 1
100 parts of modified corn starch, 20 parts of glycerol as a plasticizer, 3 parts of tartaric acid as a chemical modifier, and 2 parts of talcum powder grafted by polybutadiene as a functional filler, wherein the ratio of hydroxyl-terminated polybutadiene to epoxy-terminated polybutadiene is 1:1, 0.05 part of zinc neodecanoate as a catalyst, 0.5 part of isocyanate chain extender as a chain extender, and 60 parts of polylactic acid as biodegradable resin.
The preparation method comprises the following steps:
1) preparing functional filler: carrying out ultrasonic treatment on the dried filler in anhydrous toluene, adding Toluene Diisocyanate (TDI) and a catalyst dibutyltin dilaurate (DBTDL) at 50 ℃, reacting under the protection of nitrogen atmosphere, and drying the slurry after the reaction to obtain an intermediate product; carrying out ultrasonic treatment on the product obtained in the step (1) and anhydrous toluene under the protection of nitrogen, then adding polybutadiene diluted by the anhydrous toluene and a catalyst DBTDL, carrying out reaction at the temperature of 60 ℃, and drying the slurry after the reaction to obtain a polybutadiene graft modification functional filler;
2) pre-mixing treatment of raw materials: firstly stirring starch, a plasticizer and a chemical modifier in specified amounts at a high speed of 600 revolutions per minute in a high-speed mixer at 40 ℃ for 5 minutes; heating to 60 ℃, adding a specified amount of functional filler, chain extender and biodegradable resin, and carrying out high-speed stirring for the second time, wherein the stirring speed is 800 revolutions per minute and the stirring time is 10 minutes; slowly stirring at the speed of 50 revolutions per minute, and carrying out heat preservation treatment for 2 hours;
3) raw material melt extrusion preparation: adding the mixture treated in the step (2) into a double-screw extruder, wherein the length-diameter ratio of the double-screw extruder is 44: 1, extruding, air cooling and granulating at the temperature of 110-180 ℃ and the screw rotating speed of 250 rpm;
4) bottle injection-blow preparation: mixing the extruded and dried resin particles with a catalyst, and then performing injection molding on the mixture to obtain a bottle blank by an injection molding machine, wherein the injection molding temperature range of the injection molding machine is 140-180 ℃, and then performing blow molding on the bottle blank by a bottle making machine to obtain a biodegradable packaging bottle, wherein the blow molding temperature range of the bottle making machine is 60-70 ℃, and the blow-up ratio is 3: 1.
the prepared starch-based biodegradable packaging bottle with high oxygen barrier property has the oxygen permeability coefficient of 1.7 multiplied by 10- 14cm3·cm/(cm2s.Pa), tensile strength of 39MPa, elongation at break of 36%.
Example 2
100 parts of modified corn starch, 15 parts of glycerol and 10 parts of sorbitol as plasticizers, 3 parts of citric acid as a chemical modifier and 5 parts of talcum powder grafted by polybutadiene as a functional filler, wherein the ratio of hydroxyl-terminated polybutadiene to epoxy-terminated polybutadiene is 1:3, 0.09 part of cobalt neodecanoate as a catalyst, 1 part of isocyanate chain extender as a chain extender and 90 parts of polylactic acid as biodegradable resin are taken.
The preparation method comprises the following steps:
1) preparing functional filler: the reaction conditions were the same as in example 1;
2) pre-mixing treatment of raw materials: firstly stirring starch, a plasticizer and a chemical modifier in specified amounts at a high speed of 800 revolutions per minute in a high-speed mixer at 50 ℃ for 8 minutes; heating to 80 ℃, adding specified amounts of functional filler, chain extender and biodegradable resin, and carrying out second high-speed stirring at the stirring speed of 1000 revolutions per minute for 25 minutes; slowly stirring at the speed of 50 revolutions per minute, and carrying out heat preservation treatment for 3 hours;
3) raw material melt extrusion preparation: adding the mixture treated in the step (2) into a double-screw extruder, wherein the length-diameter ratio of the double-screw extruder is 52: 1, extruding, air cooling and granulating at the temperature of 110-180 ℃ and the screw rotating speed of 300 rpm;
4) bottle injection-blow preparation: mixing the extruded and dried resin particles with a catalyst, and then performing injection molding on the mixture to obtain a bottle blank by an injection molding machine, wherein the injection molding temperature range of the injection molding machine is 140-180 ℃, and then performing blow molding on the bottle blank by a bottle making machine to obtain a biodegradable packaging bottle, wherein the blow molding temperature range of the bottle making machine is 60-70 ℃, and the blow-up ratio is 3.5: 1.
the prepared starch-based biodegradable packaging bottle with high oxygen barrier property has the oxygen permeability coefficient of 9.8 multiplied by 10- 15cm3·cm/(cm2s.Pa), tensile strength of 45MPa, elongation at break of 42%.
Example 3
100 parts of modified potato starch, 15 parts of glycerol and 5 parts of epoxidized soybean oil as plasticizers, 3 parts of citric acid as a chemical modifier and 8 parts of talcum powder grafted by polybutadiene as a functional filler, wherein the ratio of hydroxyl-terminated polybutadiene to epoxy-terminated polybutadiene is 1:3, 0.1 part of cobalt neodecanoate as a catalyst, 1.5 parts of epoxy chain extender as a chain extender, and 90 parts of itaconic anhydride grafted polylactic acid as biodegradable resin are taken.
The preparation method comprises the following steps:
1) preparing functional filler: the reaction conditions were the same as in example 1;
2) pre-mixing treatment of raw materials: firstly stirring starch, a plasticizer and a chemical modifier in specified amounts at a high speed of 800 revolutions per minute for 10 minutes in a high-speed mixer at 50 ℃; heating to 80 ℃, adding specified amounts of functional filler, chain extender and biodegradable resin, and carrying out high-speed stirring for the second time, wherein the stirring speed is 1200 revolutions per minute and the stirring time is 30 minutes; slowly stirring at the speed of 100 revolutions per minute, and carrying out heat preservation treatment for 3 hours;
3) raw material melt extrusion preparation: the equipment and the process are the same as those of the example 2;
4) bottle injection-blow preparation: the equipment and process were the same as in example 2.
The prepared starch-based biodegradable packaging bottle with high oxygen barrier property has the oxygen permeability coefficient of 7.2 multiplied by 10- 15cm3·cm/(cm2s.Pa), tensile strength of 56MPa, elongation at break of 51%.
Example 4
100 parts of modified corn starch, 25 parts of sorbitol and 5 parts of epoxidized soybean oil as plasticizers, 2 parts of citric acid as a chemical modifier and 10 parts of talcum powder grafted with polybutadiene as a functional filler, wherein the ratio of hydroxyl-terminated polybutadiene to epoxy-terminated polybutadiene is 1:5, 0.15 part of cobalt neodecanoate as a catalyst, 2 parts of epoxy chain extender as a chain extender, and 100 parts of itaconic anhydride grafted polylactic acid as biodegradable resin are taken.
The preparation method comprises the following steps:
1) preparing functional filler: preparing functional filler: carrying out ultrasonic treatment on the dried filler in anhydrous toluene, adding Toluene Diisocyanate (TDI) and a catalyst dibutyltin dilaurate (DBTDL) at 70 ℃, reacting under the protection of nitrogen atmosphere, and drying the slurry after the reaction to obtain an intermediate product; carrying out ultrasonic treatment on the product obtained in the step (1) and anhydrous toluene under the protection of nitrogen, then adding polybutadiene diluted by the anhydrous toluene and a catalyst DBTDL, carrying out reaction at 75 ℃, and drying the slurry after the reaction to obtain a polybutadiene graft modification functional filler;
2) pre-mixing treatment of raw materials: the equipment and the process are the same as those in example 3;
3) raw material melt extrusion preparation: adding the mixture treated in the step (2) into a double-screw extruder, wherein the length-diameter ratio of the double-screw extruder is 56: 1, extruding, air cooling and granulating at the temperature range of 110-175 ℃ and the screw rotating speed of 300 rpm;
4) bottle injection-blow preparation: the equipment and process were the same as in example 2.
The prepared starch-based biodegradable packaging bottle with high oxygen barrier property has the oxygen permeability coefficient of 3.6 multiplied by 10- 15cm3·cm/(cm2s.Pa), tensile strength of 53MPa, elongation at break of 58%.
Example 5
100 parts of modified corn starch, 15 parts of glycerol, 25 parts of sorbitol and 10 parts of epoxidized soybean oil as plasticizers, 1.5 parts of tartaric acid as a chemical modifier, 4 parts of polybutadiene grafted mesoporous silica as a functional filler, wherein the ratio of hydroxyl-terminated polybutadiene to epoxy-terminated polybutadiene is 1:2, 0.1 part of zinc neodecanoate as a catalyst, 2 parts of epoxy chain extender as a chain extender, and 100 parts of itaconic anhydride grafted polylactic acid as biodegradable resin.
The preparation method comprises the following steps:
1) preparing functional filler: the reaction conditions were the same as in example 1;
2) pre-mixing treatment of raw materials: the equipment and the process are the same as those in example 3;
2) raw material melt extrusion preparation: the equipment and the process are the same as those in example 4;
4) bottle injection-blow preparation: mixing the extruded and dried resin particles with a catalyst, and then performing injection molding on the mixture to obtain a bottle blank by an injection molding machine, wherein the injection molding temperature range of the injection molding machine is 140-180 ℃, and then performing blow molding on the bottle blank by a bottle making machine to obtain a biodegradable packaging bottle, wherein the blow molding temperature range of the bottle making machine is 70-80 ℃, and the blow-up ratio is 5: 1. .
The prepared starch-based biodegradable packaging bottle with high oxygen barrier property has the oxygen permeability coefficient of 4.1 multiplied by 10- 15cm3·cm/(cm2s.Pa), tensile strength of 64MPa, elongation at break of 73%.
Claims (10)
1. A starch-based biodegradable packaging bottle with high oxygen barrier property is characterized by being prepared from the following raw materials in parts by weight:
2. the starch-based biodegradable packaging bottle with high oxygen barrier property according to claim 1, wherein the functional filler is one or a combination of talcum powder and mesoporous silica, and is a functional filler grafted and modified by polybutadiene.
3. The starch-based biodegradable packaging bottle with high oxygen barrier property as claimed in claim 2, wherein the polybutadiene is a mixture of hydroxyl-terminated polybutadiene and epoxy-terminated polybutadiene, wherein the ratio of the hydroxyl-terminated polybutadiene to the epoxy-terminated polybutadiene is 1:1-1: 5; the size of the talcum powder and the size of the mesoporous silica are both below 500 nanometers.
4. The starch-based biodegradable packaging bottle with high oxygen barrier property according to claim 2, wherein the polybutadiene graft-modified functional filler is prepared by the following method:
1) carrying out ultrasonic treatment on the dried functional filler in anhydrous toluene, adding toluene diisocyanate and a catalyst dibutyltin dilaurate at 40-70 ℃, reacting under the protection of a nitrogen atmosphere, and drying the slurry after the reaction is finished to obtain an intermediate product;
2) carrying out ultrasonic treatment on the intermediate product obtained in the step 1) and anhydrous toluene under the protection of nitrogen, adding polybutadiene diluted by the anhydrous toluene and a catalyst dibutyltin dilaurate, reacting at 50-75 ℃, and drying slurry after the reaction to obtain the polybutadiene graft modification functional filler.
5. The starch-based biodegradable package bottle with high oxygen barrier property as claimed in claim 1, wherein the starch is one or a combination of modified corn starch and modified potato starch.
6. The starch-based biodegradable packaging bottle with high oxygen barrier property as claimed in claim 5, wherein the modified corn starch or modified potato starch is modified by the following method:
1) taking 0.5-3 parts of N-cyclohexyl-2-benzothiazole sulfonamide and 0.5-3 parts of silane coupling agent KH560, and reacting with 10 parts of glycerol for 1-3 hours at the temperature of 60-90 ℃ under the protection of nitrogen;
2) stirring 100 parts of dried corn starch or potato starch in a high-speed mixer at 60-90 ℃, spraying the solution obtained in the step 1) into the mixer in a spray manner, and stirring at a constant temperature and a high speed for 1-3 hours;
3) slowly stirring, and cooling to room temperature to obtain the modified starch.
7. The starch-based biodegradable packaging bottle with high oxygen barrier property as claimed in claim 1, wherein the plasticizer is one or a combination of glycerin, sorbitol and epoxidized soybean oil; the chemical modifier is one or the combination of tartaric acid and citric acid; the catalyst is one or the combination of zinc neodecanoate and cobalt neodecanoate; the chain extender is one or the combination of isocyanate chain extender and epoxy chain extender; the biodegradable resin is one or the combination of polylactic acid and itaconic anhydride grafted polylactic acid.
8. A method for preparing starch-based biodegradable packaging bottles with high oxygen barrier property as claimed in any of claims 1 to 7, characterized by comprising the following steps:
1) taking 100 parts of starch, adding a plasticizer and a chemical modifier, and stirring at a high speed for the first time in a high-speed mixer at 40-60 ℃;
2) heating to 60-90 ℃, adding functional filler, chain extender, biodegradable resin and the like, and carrying out secondary high-speed stirring;
3) slowly stirring and carrying out heat preservation treatment;
4) adding the starch mixture after heat preservation into a double-screw extruder, extruding, air cooling and granulating;
5) extruding the dried resin particles, mixing the resin particles with a catalyst uniformly, performing injection molding by using an injection molding machine to form a bottle blank, and performing blow molding by using a bottle making machine to form the biodegradable packaging bottle.
9. The method for preparing the starch-based biodegradable packaging bottle with high oxygen barrier property as recited in claim 8, wherein the first high-speed stirring speed is 600-1000 rpm for 5-10 min; the second high-speed stirring speed is 800-; the slow stirring speed is 50-100 r/min, and the heat preservation time is 2-4 hours.
10. The method for preparing the starch-based biodegradable packaging bottle with high oxygen barrier property as claimed in claim 8, wherein the twin-screw extruder is melt extrusion, and the length-diameter ratio of the twin-screw extruder is 44: 1-60: 1, the temperature range is 110-; the injection temperature range of the injection molding machine is 140-180 ℃; the blow molding temperature range of the bottle making machine is 60-90 ℃, and the blow-up ratio is 3: 1-5: 1.
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