CN112430382A - Compostable full-degradable disposable tableware and preparation method thereof - Google Patents
Compostable full-degradable disposable tableware and preparation method thereof Download PDFInfo
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- CN112430382A CN112430382A CN202011210425.7A CN202011210425A CN112430382A CN 112430382 A CN112430382 A CN 112430382A CN 202011210425 A CN202011210425 A CN 202011210425A CN 112430382 A CN112430382 A CN 112430382A
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- 238000002360 preparation method Methods 0.000 title abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 28
- 239000000203 mixture Substances 0.000 claims abstract description 26
- 229920003023 plastic Polymers 0.000 claims abstract description 24
- 239000004033 plastic Substances 0.000 claims abstract description 24
- 239000008187 granular material Substances 0.000 claims abstract description 22
- 238000001746 injection moulding Methods 0.000 claims abstract description 13
- 239000004970 Chain extender Substances 0.000 claims abstract description 12
- 229920003232 aliphatic polyester Polymers 0.000 claims abstract description 11
- 239000000945 filler Substances 0.000 claims abstract description 10
- 239000004645 polyester resin Substances 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 238000000465 moulding Methods 0.000 claims abstract description 7
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 6
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- 238000007599 discharging Methods 0.000 claims abstract description 3
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- 229920000573 polyethylene Polymers 0.000 claims description 14
- 239000000155 melt Substances 0.000 claims description 13
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 12
- 239000000843 powder Substances 0.000 claims description 10
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical group O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 8
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 7
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 claims description 7
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 7
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 7
- 235000017166 Bambusa arundinacea Nutrition 0.000 claims description 6
- 235000017491 Bambusa tulda Nutrition 0.000 claims description 6
- 235000015334 Phyllostachys viridis Nutrition 0.000 claims description 6
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- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
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- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical compound C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 claims description 4
- 235000021355 Stearic acid Nutrition 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 4
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 4
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- 229920005692 JONCRYL® Polymers 0.000 claims description 3
- 238000005469 granulation Methods 0.000 claims description 3
- 230000003179 granulation Effects 0.000 claims description 3
- 235000003166 Opuntia robusta Nutrition 0.000 claims description 2
- 244000218514 Opuntia robusta Species 0.000 claims description 2
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- 239000000463 material Substances 0.000 abstract description 16
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- 241001330002 Bambuseae Species 0.000 description 5
- 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 description 5
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
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- 238000011161 development Methods 0.000 description 3
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- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
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- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
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- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
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- ZMKVBUOZONDYBW-UHFFFAOYSA-N 1,6-dioxecane-2,5-dione Chemical compound O=C1CCC(=O)OCCCCO1 ZMKVBUOZONDYBW-UHFFFAOYSA-N 0.000 description 1
- HGUFODBRKLSHSI-UHFFFAOYSA-N 2,3,7,8-tetrachloro-dibenzo-p-dioxin Chemical compound O1C2=CC(Cl)=C(Cl)C=C2OC2=C1C=C(Cl)C(Cl)=C2 HGUFODBRKLSHSI-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
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- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
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- 125000001931 aliphatic group Chemical group 0.000 description 1
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- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
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Classifications
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- 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
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/02—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polycarbonates or saturated polyesters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
-
- 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
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Abstract
A compostable full-degradable disposable tableware and a preparation method thereof relate to the field of biodegradable materials. The raw materials by mass ratio are as follows: 100 parts of aliphatic polyester resin, 0-40 parts of filler, 0.5-5 parts of compatilizer, 0.5-5 parts of chain extender, 0.01-1 part of initiator, 0.5-3 parts of grafting monomer, 1-4 parts of lubricant and 0.3-0.6 part of antioxidant. Preparing required filler and compatilizer, and mixing in a high-speed mixer at 50-90 ℃ for 10-30 min, and discharging; putting the mixture into a continuous internal mixer, carrying out internal mixing for 2-3 min at 90-140 ℃, falling into a cone double-forced feeding machine, feeding the mixture into a double-screw extruder, and granulating to obtain granules with the required formula; pressing into sheets by a sheet machine at 120-180 ℃, and performing plastic suction molding according to requirements to obtain finished products; or directly injection-molding the formula granules by an injection molding machine.
Description
Technical Field
The invention relates to the field of biodegradable materials, in particular to compostable fully-degradable disposable tableware and a preparation method thereof.
Background
General-purpose plastics are widely applied to various fields due to excellent comprehensive performance, and are parallel to steel, wood and cement to be four major supporting column materials, so that the annual usage amount is continuously increased. The recovery rate of general-purpose plastics such as polyethylene, polypropylene, polyvinyl chloride, polystyrene, etc. is very low. They are stable in nature for a long period of time, so that they are difficult to degrade by nature after disposal. If incinerated, harmful gases are generated. Can cause serious pollution to the environment, which prompts the research and development of degradable materials to replace general plastics. A large amount of disposable tableware is consumed in the world every year, and the development of degradable material tableware is undoubtedly of great significance.
At least 67 countries and regions around the world have adopted restrictive measures for disposable plastic articles. 2020.1.19 Ministry of development and improvement of the State and development Commission and the department of ecological Environment, which promulgated the "improved version restriction regulations" about the further enhancement of plastics pollution control, the "non-degradable disposable tableware" was prohibited in the regulations.
Degradable materials (or degradable plastics) can be divided into two categories: biodegradation and photodegradation. The conventional biodegradable plastic is mostly a blend of polyethylene and starch or other biomass (namely starch-based biodegradable plastic), the biodegradable plastic is only partially degraded but not completely degraded in the true sense, and although the starch is eaten by bacteria, a large amount of residual polyethylene is in a microsphere shape or a flake shape and exists in soil or enters a water body of rivers, lakes and seas and cannot be discharged, so that irreversible permanent pollution is caused.
According to the standard of 'definition, classification, marking and degradation performance requirement of degradable plastics' in 2006 in China, controllable compost materials are regulated to be broken into fragments of which more than 90 percent can pass through a 22mm screen mesh within 12 weeks at the longest under the aerobic composting condition, and finally the fragments are completely converted into carbon dioxide, water and mineral substances, and developed countries in the world have similar standards.
According to 2020.9.8, under the guidance of the relevant ministry of the nation, the China Union of light industry establishes and prints the 'classification and identification standard guideline of degradable plastic products', and the 'compostable degradation' class, which is the main one of six types of degradable plastics. Examples of material abbreviations listed in the guide explicitly include PBS and PBAT used in the present invention.
The compostable fully-degradable disposable tableware is compostable fully-degradable material prepared by adding a certain amount of filler into fully-degradable resin. The resin and the filler are compostable and completely biodegradable.
Disclosure of Invention
The invention aims to provide compostable fully-degradable disposable tableware which can be as firm as plastic when being used and can be fully degraded in natural environment after being discarded, and a preparation method thereof.
A compostable full-degradable disposable tableware comprises the following raw materials in percentage by mass: 100 parts of aliphatic polyester resin, 0-40 parts of filler, 0.5-5 parts of compatilizer, 0.5-5 parts of chain extender, 0.01-1 part of initiator, 0.5-3 parts of grafting monomer, 1-4 parts of lubricant and 0.3-0.6 part of antioxidant.
The aliphatic polyester resin can adopt at least one of PBS, PBAT, PLA and the like;
the aliphatic polyester resin is preferably 50-100 parts of PBS, 0-30 parts of PBAT and 0-20 parts of PLA.
The melt index MI value of the aliphatic polyester resin can be 3.0-18.0 g/10 min;
the aliphatic polyester resin has a melt index MI (190 ℃ C., 2160g) in the range of 3.0 to 18.0g/10 min.
The compatilizer is at least one of stearic acid, titanate, a silane coupling agent KH550 and a silane coupling agent KH 570.
The chain extender is one of BASF Joncryl ADR series and bolt holding chemical X-U series.
The initiator is at least one of dicumyl peroxide (DCP) and Methyl Ethyl Ketone Peroxide (MEKP).
The filler is one or a mixture of calcium carbonate, talcum powder, bamboo powder, straw powder and the like.
The lubricant is at least one of paraffin, white oil, polyethylene wax and Shanghai Zhuang Jing chemical industry STRUKTOL TPW 604.
The antioxidant is at least one of antioxidant 1010 and antioxidant MB.
The grafting monomer is maleic anhydride (MHA).
A method for preparing compostable fully-degradable disposable tableware comprises the following steps:
1) and (3) granulation: preparing required filler and compatilizer, and mixing in a high-speed mixer at 50-90 ℃ for 10-30 min, and discharging; putting the mixture into a continuous internal mixer, carrying out internal mixing for 2-3 min at 90-140 ℃, falling into a cone double-forced feeding machine, feeding the mixture into a double-screw extruder (120-160 ℃) for granulation, and obtaining granules with the required formula;
2) forming tableware: pressing the mixture into sheets by a sheet machine at 120-180 ℃, and then carrying out plastic suction forming according to requirements to obtain finished products, such as: disposable trays, plates, bowls, cups, etc.; or directly injection-molding the formula granules by an injection molding machine, such as: disposable knives, forks, spoons, and the like.
PBS (poly (butylene succinate)) is a thermoplastic biodegradable resin that is easily decomposed by various microorganisms or enzymes in animals and plants in the nature. The raw material source can be petroleum resources or can be obtained by fermentation of biological resources. The 20 th century and the 90 th century are in the research field, and the mass production is started in China in recent years. PBS not only can meet the use requirements of general plastics in terms of mechanical properties, but also can be degraded only under the condition that compost and other microorganisms are contacted, and the performance is very stable in the normal storage and use processes. The PBS can resist 100 ℃ of heat and can meet the heat-resisting requirement of daily supplies. It has a wide range of applications, such as packaging materials, disposables, etc. The disadvantage of PBS is that it is rigid, relatively hard and brittle.
PBAT is also a thermoplastic fully biodegradable resin, a terpolymer of 1, 4-butanediol, adipic acid and terephthalic acid. The aliphatic part provides good biodegradability, while the aromatic part provides good mechanical properties. Because of the copolymerization structure, the crystallinity of the material is lower than that of PBS, so that the material is softer and has good toughness. Its tear strength is 120% of that of polyethylene and its impact strength is 130% of that of polyethylene. PBS can also resist 100 ℃ and can meet the heat-resisting requirement of daily supplies.
PBS and PBAT are combined for use, and good comprehensive performance can be obtained by making up for deficiencies of each other.
Compared with the prior art, the three inventions have the following advantages:
(1) the compostable fully-degradable disposable tableware finished product can be completely biodegraded after being discarded, and is disintegrated into more than 90 percent of fragments which can pass through a 22mm screen mesh within the longest 12 weeks under the aerobic composting condition, and finally, the fragments are completely converted into carbon dioxide, water and mineral substances.
(2) The compostable fully-degradable disposable tableware product can be as firm as plastics such as polyethylene and polypropylene when used. Has similar service performance of general plastics.
(3) The prepared material does not contain harmful substances such as formaldehyde, plasticizer, organic solvent and the like, does not have the problem of dioxin generation by chloride, and has no toxicity, no irritation, high safety and environmental protection performance.
(4) The compostable fully-degradable disposable tableware finished product disclosed by the invention is cold-resistant and heat-resistant (at the temperature of between 50 ℃ below zero and 100 ℃), and can be used for containing cold drinks such as ice cream and the like and can also be used for containing hot drinks.
(5) Compared with polyethylene and polypropylene, the printing ink has very good printing performance.
(6) Due to the poor melt strength of aliphatic polyesters, problems such as melt fracture and material breakage are likely to occur during pulling and extrusion of the sheet. In addition to using chain extenders, the present invention also provides melt grafting of resins by direct twin screw extruder addition of free radical initiators and monomers.
(7) The preparation method can be directly used on a general plastic production line, does not increase the process flow, and is suitable for industrial production; the production improvement cost is reduced. The processing temperature is low (120-160 ℃), and the energy consumption is reduced by half.
(8) The leftover materials can be recycled as feed back.
Detailed Description
The following examples further illustrate the invention.
Example 1:
a compostable fully degradable disposable tableware comprising the following raw materials prepared by weight: comprises 65 portions of PBS, 35 portions of PBAT, 20 portions of bamboo powder, 20 portions of calcium carbonate, 0.5 portion of stearic acid, 0.5 portion of chain extender, 4 portions of paraffin and 0.3 portion of antioxidant 1010.
PBS is selected from TH-803A of polyester Co., Ltd, blue Shantun river of Xinjiang, and the melt index is 15.0g/10 min. PBAT is selected from TH-801T of polyester Co., Ltd, blue Shantun, Xinjiang, and has a melt index of 4.5g/10 min. The chain extender was BASF Joncryl ADR 4468.
The preparation method comprises the following steps:
1) placing bamboo powder and calcium carbonate in a high-speed mixer, mixing at the rotating speed of 800rpm for 10min, drying, dehumidifying, adding stearic acid and antioxidant 1010, and continuously mixing and heating at the rotating speed of 800rpm for 5min to obtain mixed powder.
2) And putting the PBAT, the PBS, the chain extender and the paraffin into a high-speed mixer, and mixing for 8min at the rotating speed of 600rpm and the temperature of 70 ℃ to obtain mixed granules.
3) And (3) mixing the mixed powder obtained in the step 1) and the mixed granules obtained in the step 2) for 3min at the rotating speed of 500rpm of the high-speed mixer to obtain a mixture.
4) And (3) putting the mixture obtained in the step 3) into a continuous internal mixer, setting the rotating speed to be 220rpm, wherein the continuous internal mixer comprises a two-section internal mixing section, the first-section temperature is set to be 110, the second-section temperature is set to be 130, and the mixture falls into a conical double-forced feeding machine after internal mixing is finished and enters a double-screw extruder.
5) And (3) putting the blend into a double-screw extruder, extruding, bracing and granulating at the temperature of 135 ℃ and the rotating speed of 260rpm to obtain granules with the required formula.
6) Pressing the formula granules prepared in the step 5) into sheets by a sheet machine (at 120-180 ℃), and carrying out plastic suction molding to obtain finished products.
Example 2:
a compostable fully degradable disposable tableware comprising the following raw materials prepared by weight: comprises 50 portions of PBS, 35 portions of PBAT, 15 portions of PLA, 10 portions of straw powder, 15 portions of talcum powder, 5 portions of titanate, 0.01 portion of dicumyl peroxide (DCP), 0.5 portion of maleic anhydride (MHA), 0.6 portion of TPW6041 portion and 0.6 portion of antioxidant MB.
PBS is selected from TH-803A of polyester Co., Ltd, blue Shantun river of Xinjiang, and the melt index is 15.0g/10 min. PBAT is selected from TH-801T of polyester Co., Ltd, blue Shantun, Xinjiang, and has a melt index of 4.5g/10 min. The PLA was selected from NatureWorks2003D, and the melt index MI (210 ℃, 2160g) ranged from 6.0g/10 min.
The preparation method comprises the following steps:
1) placing the straw powder and the talcum powder in a high-speed mixer, mixing for 10min at the rotating speed of 800rpm, drying and dehumidifying, adding the titanate, the TPW604 and the antioxidant MB, and continuously mixing and heating for 5min at the rotating speed of 800rpm of the high-speed mixer to obtain mixed powder.
2) PBAT, PBS, PLA, dicumyl peroxide (DCP) and maleic anhydride (MHA) are put into a continuous internal mixer, are internally mixed at the rotating speed of 180rpm and the temperature of 120 ℃ and enter a single screw to be extruded and granulated to obtain mixed resin granules.
3) And (3) mixing the mixed powder obtained in the step 1) and the mixed granules obtained in the step 2) for 3min at the rotating speed of 500rpm of the high-speed mixer to obtain a mixture.
4) And (3) putting the mixture obtained in the step 3) into a continuous internal mixer, setting the rotating speed to be 220rpm, wherein the continuous internal mixer comprises a two-section internal mixing section, the first-section temperature is set to be 110, the second-section temperature is set to be 130, and the mixture falls into a conical double-forced feeding machine after internal mixing is finished and enters a double-screw extruder.
5) And (3) putting the blend into a double-screw extruder, extruding, bracing and granulating at the temperature of 135 ℃ and the rotating speed of 260rpm to obtain granules with the required formula.
6) Pressing the formula granules prepared in the step 5) into sheets by a sheet machine (at 120-180 ℃), and carrying out plastic suction molding to obtain finished products.
Comparative example 1:
the LDPE pellets are selected from northern Europe chemical MB958T, and have a melt index of 36g/10 min. The preparation method comprises the steps of directly pressing the materials into sheets by a sheet machine (at 120-180 ℃), and carrying out plastic suction molding to obtain finished products.
The sheet property measurement method is as follows: tensile strength and elongation at break were determined according to GB/T1040-1992 standard methods; the bending strength is measured according to the GB/T9341-2008 standard method; the impact strength is determined according to the GB/T1843-2008 standard method; the Vicat softening point is determined according to the GB/T1633-2000 standard method. The compostability test (Rhine TUV, Germany) was carried out according to DIN EN13432: 2000.
The results of the measurements of the compostable fully degradable disposable tableware sheet are shown in Table 1:
table 1: properties of the sheets of examples 1 and 2 and of comparative example 1
As can be seen from Table 1, the compostable fully degradable disposable tableware sheet has properties close to the combination of polyethylene and polypropylene, and combines the high toughness of polyethylene and the strength and hardness of polypropylene. The plastic uptake plastic is very suitable for replacing common plastic to be used for inner and outer packages of various plastic uptake products, such as cup covers, trays, food, toys, electronic products, electric appliances, gifts, cosmetics, stationery and the like, and can be buried underground together with crop straws and the like to be converted into organic fertilizer in farmland.
Example 3:
a compostable fully degradable disposable tableware comprising the following raw materials prepared by weight: comprises 100 portions of PBS, 20 portions of bamboo powder, 15 portions of calcium carbonate, KH 5502 portions of silane coupling agent, 3 portions of chain extender, 2 portions of polyethylene wax and 0.4 portion of antioxidant 1010.
PBS is selected from TH-803A of polyester Co., Ltd, blue Shantun river of Xinjiang, and the melt index is 15.0g/10 min. The chain extender is used for containing chemical X-U992.
The preparation method comprises the following steps:
1) placing bamboo powder and calcium carbonate in a high-speed mixer, mixing at 800rpm for 10min for drying and dehumidifying, adding silane coupling agent KH550 and antioxidant 1010, and continuously mixing and heating at 800rpm for 5min to obtain mixed powder.
2) And (3) putting the PBS, the chain extender and the polyethylene wax into a high-speed mixer, mixing for 8min at the rotating speed of 600rpm and the temperature of 70 ℃ to obtain mixed granules.
3) And (3) mixing the mixed powder obtained in the step 1) and the mixed granules obtained in the step 2) for 3min at the rotating speed of 500rpm of the high-speed mixer to obtain a mixture.
4) And (3) putting the mixture obtained in the step 3) into a continuous internal mixer, setting the rotating speed to be 220rpm, wherein the continuous internal mixer comprises a two-section internal mixing section, the first-section temperature is set to be 110, the second-section temperature is set to be 130, and the mixture falls into a conical double-forced feeding machine after internal mixing is finished and enters a double-screw extruder.
5) And (3) putting the blend into a double-screw extruder, extruding, bracing and granulating at the temperature of 135 ℃ and the rotating speed of 260rpm to obtain granules with the required formula.
6) And 5) molding the granules with the required formula prepared in the step 5) by using an injection molding machine to obtain a finished product.
Example 4:
a compostable fully degradable disposable tableware comprising the following raw materials prepared by weight: comprises 60 portions of PBS, 25 portions of PBAT, 15 portions of PLA, 30 portions of talcum powder, 1 portion of Methyl Ethyl Ketone Peroxide (MEKP), 3 portions of maleic anhydride (MHA), 1 portion of white oil and 10100.5 portions of antioxidant.
PBS is selected from TH-803A of polyester Co., Ltd, blue Shantun river of Xinjiang, and the melt index is 15.0g/10 min. PBAT is selected from TH-801T of polyester Co., Ltd, blue Shantun, Xinjiang, and has a melt index of 4.5g/10 min. The PLA was selected from NatureWorks2003D, and the melt index MI (210 ℃, 2160g) ranged from 6.0g/10 min.
The preparation method comprises the following steps:
1) placing talcum powder into a high-speed mixer, mixing for 10min at the rotating speed of 800rpm, drying, dehumidifying, adding silane coupling agent KH570, white oil and antioxidant 1010, and continuously mixing and heating for 5min at the rotating speed of 800rpm of the high-speed mixer to obtain mixed powder.
2) PBAT, PBS, PLA, Methyl Ethyl Ketone Peroxide (MEKP) and maleic anhydride (MHA) are put into a continuous internal mixer, are internally mixed at the rotating speed of 180rpm and the temperature of 120 ℃ and then enter a single screw to be extruded and granulated to obtain mixed resin granules.
3) And (3) mixing the mixed powder obtained in the step 1) and the mixed granules obtained in the step 2) for 3min at the rotating speed of 500rpm of the high-speed mixer to obtain a mixture.
4) And (3) putting the mixture obtained in the step 3) into a continuous internal mixer, setting the rotating speed to be 220rpm, wherein the continuous internal mixer comprises a two-section internal mixing section, the first-section temperature is set to be 110, the second-section temperature is set to be 130, and the mixture falls into a conical double-forced feeding machine after internal mixing is finished and enters a double-screw extruder.
5) And (3) putting the blend into a double-screw extruder, extruding, bracing and granulating at the temperature of 135 ℃ and the rotating speed of 260rpm to obtain granules with the required formula.
6) Molding the formula granules prepared in the step 5) by an injection molding machine to obtain a finished product.
Comparative example 2:
the LDPE pellet is Yanshan petrochemical LD450 with melt index of 41.9g/10 min. The preparation method is to directly form the product by an injection molding machine to obtain the finished product.
The properties of the injection-molded articles were determined as follows: tensile strength and elongation at break were determined according to GB/T1040-1992 standard methods; the bending strength is measured according to the GB/T9341-2008 standard method; the impact strength is determined according to the GB/T1843-2008 standard method; the Vicat softening point is determined according to the GB/T1633-2000 standard method.
The results of the measurements of the properties of the injection moldings of examples 2 and 4 are shown in Table 2.
Table 2: properties of the injection moldings of examples 3 and 4 and comparative example 2
It can be seen from Table 2 that the properties of the disposable tableware injection-molded article are close to the combination of the properties of polyethylene and polypropylene. Is suitable for replacing common plastics to be used for various injection molding products, such as tableware, stationery, toys, sanitary equipment, small household appliance accessories, gardening products and the like.
The invention provides compostable fully-degradable disposable tableware (including trays, dinner plates, bowls, cups, spoons and the like) and a preparation method thereof (including injection molding, plastic uptake and the like). The product has the similar service performance of general plastic when in use. Can be completely biodegraded after being discarded, and finally converted into carbon dioxide, water and mineral substances. The PBAT, PBS and PLA master batches can be completely biodegraded, the problem of low solution strength of biodegradable resin is solved by free radical grafting, the production process is simple, and the large-scale production can be realized. The product does not contain harmful substances, and is non-toxic and non-irritant. The product is cold-resistant and heat-resistant (at-50 ℃ to 100 ℃), can be directly produced on a general plastic production line, and does not increase process flows and equipment. The processing temperature is low, and the energy consumption is reduced by half. The leftover materials can be recycled as feed back.
Claims (10)
1. A compostable full-degradable disposable tableware is characterized by comprising the following raw materials in percentage by mass: 100 parts of aliphatic polyester resin, 0-40 parts of filler, 0.5-5 parts of compatilizer, 0.5-5 parts of chain extender, 0.01-1 part of initiator, 0.5-3 parts of grafting monomer, 1-4 parts of lubricant and 0.3-0.6 part of antioxidant.
2. A compostable fully degradable disposable tableware according to claim 1 wherein said aliphatic polyester resin is at least one of PBS, PBAT, PLA; the melt index MI value of the aliphatic polyester resin can be 3.0-18.0 g/10 min;
the aliphatic polyester resin is preferably 50-100 parts of PBS, 0-30 parts of PBAT and 0-20 parts of PLA.
3. The compostable fully degradable disposable tableware according to claim 1, wherein said compatibility agent is at least one of stearic acid, titanate, silane coupling agent KH550, silane coupling agent KH 570.
4. A compostable fully degradable disposable tableware according to claim 1 wherein said chain extender is one of the BASF Joncryl ADR series, bolt hole X-U series.
5. The compostable fully degradable disposable tableware according to claim 1, wherein said initiator is at least one of dicumyl peroxide and methyl ethyl ketone peroxide.
6. The compostable fully degradable disposable tableware according to claim 1, wherein said filler is one or a mixture of calcium carbonate, talc, bamboo powder and straw powder.
7. The compostable fully degradable disposable tableware according to claim 1, wherein said lubricant is at least one of paraffin wax, white oil, polyethylene wax, and STRUKTOL TPW 604.
8. The compostable fully degradable disposable tableware according to claim 1, wherein said antioxidant is at least one of antioxidant 1010 and antioxidant MB.
9. The compostable fully degradable disposable tableware according to claim 1 wherein said graft monomer is maleic anhydride.
10. The method of making compostable fully degradable disposable tableware according to claim 1 comprising the steps of:
1) and (3) granulation: preparing required filler and compatilizer, and mixing in a high-speed mixer at 50-90 ℃ for 10-30 min, and discharging; putting the mixture into a continuous internal mixer, carrying out internal mixing for 2-3 min at 90-140 ℃, falling into a cone double-forced feeding machine, feeding the mixture into a double-screw extruder, and granulating at 120-160 ℃ to obtain granules with the required formula;
2) forming tableware: pressing into sheets by a sheet machine at 120-180 ℃, and performing plastic sucking molding according to requirements to obtain finished products of disposable trays, dinner plates, bowls and cups; or directly injection-molding the formula granules by an injection molding machine to obtain the disposable knife, fork and spoon.
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| CN113150521A (en) * | 2021-05-08 | 2021-07-23 | 汕头市春叶新材料环保有限公司 | High-toughness biodegradable composite material, and preparation device and method thereof |
| CN113583405A (en) * | 2021-07-23 | 2021-11-02 | 广东省华标科技有限公司 | High-performance fully-degradable composite material and preparation method thereof |
| CN115819847A (en) * | 2022-11-08 | 2023-03-21 | 环霆科技(宁波)有限公司 | Daily necessity ingredient for extrusion processing under household compost condition |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2019155398A1 (en) * | 2018-02-07 | 2019-08-15 | Csir | Biodegradable plastic |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2019155398A1 (en) * | 2018-02-07 | 2019-08-15 | Csir | Biodegradable plastic |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113150521A (en) * | 2021-05-08 | 2021-07-23 | 汕头市春叶新材料环保有限公司 | High-toughness biodegradable composite material, and preparation device and method thereof |
| CN113150521B (en) * | 2021-05-08 | 2022-01-25 | 江西昕禾生态科技有限公司 | High-toughness biodegradable composite material, and preparation device and method thereof |
| CN113583405A (en) * | 2021-07-23 | 2021-11-02 | 广东省华标科技有限公司 | High-performance fully-degradable composite material and preparation method thereof |
| CN115819847A (en) * | 2022-11-08 | 2023-03-21 | 环霆科技(宁波)有限公司 | Daily necessity ingredient for extrusion processing under household compost condition |
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