CN114196220A - Preparation method of fully-degradable biomass fiber-based waterproof dinner plate - Google Patents
Preparation method of fully-degradable biomass fiber-based waterproof dinner plate Download PDFInfo
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- CN114196220A CN114196220A CN202111613521.0A CN202111613521A CN114196220A CN 114196220 A CN114196220 A CN 114196220A CN 202111613521 A CN202111613521 A CN 202111613521A CN 114196220 A CN114196220 A CN 114196220A
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- 239000002028 Biomass Substances 0.000 title claims abstract description 72
- 235000003166 Opuntia robusta Nutrition 0.000 title claims abstract description 33
- 244000218514 Opuntia robusta Species 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 229920000728 polyester Polymers 0.000 claims abstract description 48
- 239000002131 composite material Substances 0.000 claims abstract description 10
- 229920006238 degradable plastic Polymers 0.000 claims abstract description 9
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 38
- CHTHALBTIRVDBM-UHFFFAOYSA-N furan-2,5-dicarboxylic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)O1 CHTHALBTIRVDBM-UHFFFAOYSA-N 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 239000010902 straw Substances 0.000 claims description 18
- 238000005886 esterification reaction Methods 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 241000209140 Triticum Species 0.000 claims description 11
- 235000021307 Triticum Nutrition 0.000 claims description 11
- 239000003054 catalyst Substances 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 9
- 125000001931 aliphatic group Chemical group 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 238000005507 spraying Methods 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 235000007164 Oryza sativa Nutrition 0.000 claims description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 6
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 6
- 238000005352 clarification Methods 0.000 claims description 6
- 230000032050 esterification Effects 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 235000009566 rice Nutrition 0.000 claims description 6
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 6
- 235000017166 Bambusa arundinacea Nutrition 0.000 claims description 5
- 235000017491 Bambusa tulda Nutrition 0.000 claims description 5
- 235000015334 Phyllostachys viridis Nutrition 0.000 claims description 5
- 239000011425 bamboo Substances 0.000 claims description 5
- 238000005469 granulation Methods 0.000 claims description 5
- 230000003179 granulation Effects 0.000 claims description 5
- 238000002844 melting Methods 0.000 claims description 5
- 230000008018 melting Effects 0.000 claims description 5
- 229920002522 Wood fibre Polymers 0.000 claims description 4
- 238000006116 polymerization reaction Methods 0.000 claims description 4
- 239000002025 wood fiber Substances 0.000 claims description 4
- 239000001361 adipic acid Substances 0.000 claims description 3
- 235000011037 adipic acid Nutrition 0.000 claims description 3
- 239000003292 glue Substances 0.000 claims description 3
- 239000000155 melt Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims description 2
- 239000000654 additive Substances 0.000 claims description 2
- 150000001298 alcohols Chemical class 0.000 claims description 2
- 239000007822 coupling agent Substances 0.000 claims description 2
- 238000001125 extrusion Methods 0.000 claims description 2
- 239000001384 succinic acid Substances 0.000 claims description 2
- 240000007594 Oryza sativa Species 0.000 claims 2
- 229940043375 1,5-pentanediol Drugs 0.000 claims 1
- 244000082204 Phyllostachys viridis Species 0.000 claims 1
- WCVRQHFDJLLWFE-UHFFFAOYSA-N pentane-1,2-diol Chemical compound CCCC(O)CO WCVRQHFDJLLWFE-UHFFFAOYSA-N 0.000 claims 1
- 238000006731 degradation reaction Methods 0.000 abstract description 15
- 230000015556 catabolic process Effects 0.000 abstract description 14
- 238000000465 moulding Methods 0.000 abstract description 6
- 229920001131 Pulp (paper) Polymers 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 description 21
- 230000008859 change Effects 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 11
- 230000000694 effects Effects 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 229920002472 Starch Polymers 0.000 description 6
- 239000004033 plastic Substances 0.000 description 6
- 229920003023 plastic Polymers 0.000 description 6
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- 235000019698 starch Nutrition 0.000 description 6
- 239000011347 resin Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 241001330002 Bambuseae Species 0.000 description 4
- 241000209094 Oryza Species 0.000 description 4
- 239000006087 Silane Coupling Agent Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000005357 flat glass Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 239000000523 sample Substances 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 238000011049 filling Methods 0.000 description 3
- 235000013305 food Nutrition 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 235000012054 meals Nutrition 0.000 description 3
- 239000002023 wood Substances 0.000 description 3
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- 229940035437 1,3-propanediol Drugs 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 239000002361 compost Substances 0.000 description 2
- 210000003298 dental enamel Anatomy 0.000 description 2
- 235000021186 dishes Nutrition 0.000 description 2
- 235000013399 edible fruits Nutrition 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical compound CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000004809 thin layer chromatography Methods 0.000 description 2
- 238000004078 waterproofing Methods 0.000 description 2
- 229920002261 Corn starch Polymers 0.000 description 1
- 241000219470 Mirabilis Species 0.000 description 1
- 241000033695 Sige Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical group [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000008120 corn starch Substances 0.000 description 1
- 229940099112 cornstarch Drugs 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000013074 reference sample Substances 0.000 description 1
- 239000011122 softwood Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000005303 weighing Methods 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
- C08L97/00—Compositions of lignin-containing materials
- C08L97/02—Lignocellulosic material, e.g. wood, straw or bagasse
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/66—Polyesters containing oxygen in the form of ether groups
- C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/672—Dicarboxylic acids and dihydroxy compounds
-
- 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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
- C08L2205/16—Fibres; Fibrils
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Materials Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a preparation method of a fully-degradable biomass fiber-based waterproof dinner plate, and belongs to the technical field of paper pulp molding. The invention provides a preparation method of a fully-degradable biomass fiber-based waterproof dinner plate, which comprises the following steps: s1, preparing biomass fibers; s2, preparing degradable polyester master batches; s3, preparing a biomass fiber/degradable plastic composite material; s4, preparing the dinner plate. The preparation method of the fully-degradable biomass fiber-based waterproof dinner plate provided by the invention can ensure that the product has excellent waterproof performance and strength, can realize full degradation, is environment-friendly and pollution-free, and has low cost.
Description
Technical Field
The invention discloses a preparation method of a fully-degradable biomass fiber-based waterproof dinner plate, and belongs to the technical field of paper pulp molding.
Background
The pulp molding is applied to various aspects in life, such as disposable lunch boxes, coffee trays, fruit dinner plates and the like, the existing pulp molding has the advantages of light weight, low price, simple production process, full biodegradation and the like, but the pulp molding has the problems of low strength, poor waterproofness, poor antibacterial property and the like. Various water-proofing agents are added in the preparation process of the pulp molding dinner plate to improve the water resistance, but the water-proofing effect is poor. In the prior art, plant fibers are usually crushed into particles, then non-degradable plastics such as PE, PVC and the like are added to prepare wood-plastic materials, and then the wood-plastic materials are processed into products, although the waterproofness and the strength are improved, because the plant fiber particles are in a dispersion state, a large amount of plastics are added to prepare master batches, and the use of a large amount of non-degradable plastics has potential influence on the environment. Therefore, the method has important significance for changing the form of the biomass material, reducing the use of non-degradable plastics and simultaneously improving the waterproof performance and strength of the product.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide the preparation method of the fully-degradable biomass fiber-based waterproof dinner plate, which can realize full degradation, environmental protection, no pollution and low cost while ensuring that the product has excellent waterproof performance and strength.
In order to realize the aim, the invention provides a preparation method of a fully-degradable biomass fiber-based waterproof dinner plate, which comprises the following steps:
s1, preparation of biomass fibers
S2, preparation of degradable polyester master batch
Putting aliphatic diacid, 2, 5-furandicarboxylic acid, dihydric alcohol and a catalyst into a reaction kettle for reaction, slowly heating under the protection of nitrogen, keeping the temperature at 160-200 ℃ for 1-3 hours until a clarification point is reached, continuing to react for 1-3 hours, finishing esterification, gradually heating to 230-240 ℃ after the esterification reaction is finished, and simultaneously carrying out vacuum polymerization for 1-5 hours to obtain degradable polyester master batches;
s3, preparation of biomass fiber/degradable plastic composite material
Dispersing the biomass fiber into fine fiber with the diameter of 0.1-2 mm by using a dry pulp dissociator, heating and melting the degradable polyester master batch, and spraying the melted degradable polyester master batch on the dispersed biomass fiber to prepare the biomass fiber/degradable plastic composite material, wherein the weight part ratio of the dispersed biomass fiber to the degradable polyester master batch is 60-80: 20-40;
s4, preparing the dinner plate.
By adopting the scheme, the strength of the dinner plate can be greatly improved by adding the degradable polyester master batch, the biomass fiber prepared in the step S1 and the degradable polyester master batch synthesized by the esterification reaction of the aliphatic diacid, the 2, 5-furandicarboxylic acid, the dihydric alcohol and the catalyst in the step S2 can be fully degraded, so that the prepared dinner plate can be fully degraded and is very environment-friendly, the mass part ratio of the dispersed biomass fiber to the degradable polyester master batch is 60-80: 20-40, wherein the mass ratio of the dispersed biomass fiber is more, the mass ratio of the degradable polyester master batch is less, the dispersed biomass fiber still keeps the fiber state but is not in the particle state, the biomass fiber can be mutually crossed and overlapped to generate an interaction force, the prepared dinner plate has higher strength, and the adding amount of the degradable polyester master batch can be reduced, therefore, the cost is reduced, in addition, although the mass of the degradable polyester master batch is less, the degradable polyester master batch is matched with the biomass fiber for use, and the prepared dinner plate still has excellent waterproof performance and strength.
Preferably, in step S1, the biomass fiber is one or more of wheat straw fiber, rice straw fiber, bamboo fiber, and wood fiber.
Preferably, in step S1, the biomass fibers are preferably wheat straw fibers or rice straw fibers.
Preferably, in step S2, the aliphatic diacid is one or more of long-chain diacids such as succinic acid and adipic acid, and the dihydric alcohol is one or more of dihydric alcohols such as propylene glycol, butylene glycol and pentanediol.
Preferably, in step S2, the weight ratio of the aliphatic diacid, the 2, 5-furandicarboxylic acid, the diol and the catalyst is 0-0.6: 0.5-1: 2-10: 0.001-0.005.
Preferably, in step S2, the pressure parameter condition of the evacuation is evacuation to 100Pa or less.
Preferably, step S3 specifically includes: and (2) fully dissociating the biomass fiber obtained in the step (S1) to disperse the biomass fiber into fine fibers of 0.1-2 mm, heating and melting 20-40 parts of the degradable polyester master batch prepared in the step (S2), uniformly spraying the melt on 60-80 parts of the dispersed biomass fiber through a high-flow glue spraying system, then adding 1-5 parts of additives such as coupling agents and the like, fully stirring to obtain a mixture, and granulating and dicing the mixture to obtain the biomass fiber/degradable polyester composite material.
Preferably, in step S6, the granulation is completed in an extrusion granulator at a temperature of 160 to 180 ℃ and a screw rotation speed of 5 to 20 r/min.
Compared with the prior art, the invention has the following beneficial effects:
(1) the dinner plate produced by using the dispersed biomass fibers and the degradable polyester master batches as raw materials is characterized in that the biomass fibers in the dispersed biomass fibers still keep a fiber state but a particle state, and the biomass fibers can be mutually crossed and overlapped to generate an interaction force, so that the prepared dinner plate has high strength, and meanwhile, the adding amount of the degradable polyester master batches can be reduced, and the cost is reduced.
(2) The biomass fiber and the degradable polyester master batch synthesized by the esterification reaction of aliphatic diacid, 2, 5-furandicarboxylic acid, dihydric alcohol and a catalyst can be fully degraded, so that the prepared dinner plate can be fully degraded and is very environment-friendly.
(3) The intensity of dinner plate can be improved to the degradable polyester master batch that adds on the one hand, and on the other hand can improve the waterproof performance of dinner plate, compares with biomass fiber, and although the quality of degradable polyester master batch accounts for than less, but degradable polyester master batch uses with biomass fiber cooperation, and the dinner plate of preparing still possesses excellent waterproof performance and intensity.
Detailed Description
In order to make the technical means, the creation characteristics, the achievement purposes and the effects of the invention easy to understand, the invention is further described with the specific embodiments.
Example 1
A preparation method of a full-degradable biomass fiber-based waterproof dinner plate comprises the following steps:
s1, preparation of biomass fibers
Adopting the method of the preparation process A in the paragraph [0049] - [0053] of the specification of Chinese patent 201910104694.6, replacing the needle-leaf wood chips with wheat straw, and fully drying the prepared slurry A to obtain wheat straw fibers;
s2, preparation of degradable polyester master batch
Putting 0.2 part by weight of succinic acid, 0.5 part by weight of 2, 5-furandicarboxylic acid, 2 parts by weight of 1, 4-butanediol and 0.001 part by weight of catalyst into a reaction kettle for reaction, wherein the reaction kettle is provided with a reflux condensing device, slowly raising the temperature under the protection of nitrogen, respectively keeping the temperature at 170 ℃, 180 ℃ and 190 ℃ for 1 hour until a clarification point is reached, continuing the reaction for 1 hour to finish esterification, after the esterification reaction is finished, gradually raising the temperature to 240 ℃, simultaneously vacuumizing to below 100Pa, and polymerizing for 4 hours to obtain the degradable polyester master batch, wherein the catalyst is tetrabutyl titanate;
s3, preparation of biomass fiber/degradable plastic composite material
Fully dissociating the wheat straw fiber obtained in the step S1 by using a dry pulp disintegrator, dispersing into fine fibers of 0.1-2 mm, heating and melting 20 parts of the degradable polyester master batch prepared in the step S2, uniformly spraying the melt on 80 parts of the dispersed wheat straw fiber through a high-flow glue spraying system, then adding 1 part of KH550 silane coupling agent, fully stirring to obtain a mixture, adding the mixture into a granulator, granulating and granulating at the temperature of 160 ℃ and the screw rotation speed of 10r/min to obtain a biomass fiber/degradable polyester composite material;
s4, preparing dinner plates
And (5) carrying out plastic suction on the biomass fiber/degradable polyester composite material obtained in the step (S3) according to a preset shape and size to prepare the disposable lunch box.
Example 2
Specifically, the present invention is the same as example 1, except that:
step S1 is: adopting the method of the preparation process A of the embodiment 1 in the paragraphs [0049] - [0053] of the specification of Chinese patent CN201910104694.6, replacing the needle-leaved wood chips with bamboo poles, and fully drying the prepared slurry A to obtain bamboo fibers;
in the step S2, 0.4 part of adipic acid, 1 part of 2, 5-furandicarboxylic acid, 2 parts of 1, 3-propanediol and 0.001 part of catalyst are added to react in a reaction kettle, the reaction kettle is provided with a reflux condensing device, the temperature is slowly raised under the protection of nitrogen, the temperature is 170 ℃, 180 ℃ and 190 ℃ are respectively kept for 1 hour until reaching the clarification point, the reaction is continued for 1 hour, the esterification is completed, after the esterification reaction is completed, the temperature is gradually raised to 240 ℃, meanwhile, the vacuum is pumped to below 100Pa, and the polymerization is carried out for 3 hours, so that the degradable polyester master batch is obtained;
in step S3, the addition amount of the degradable polyester master batch is 30 parts, the addition amount of the dispersed bamboo fiber is 70 parts, the addition amount of the KH550 silane coupling agent is 3 parts, the temperature is 170 ℃ during granulation, and the screw rotation speed is 5 r/min.
Example 3
Specifically, the present invention is the same as example 1, except that:
step S1 is: adopting the method of the preparation process A of the embodiment 1 in the paragraphs [0049] - [0053] of the specification of Chinese patent 201910104694.6, taking softwood chips as raw materials, and fully drying the prepared slurry A to obtain wood fibers;
in the step S2, adding 0.4 part of succinic acid, 1 part of 2, 5-furandicarboxylic acid, 5 parts of 1, 3-propanediol and 0.002 part of catalyst into a reaction kettle for reaction, wherein the reaction kettle is provided with a reflux condensing device, slowly raising the temperature under the protection of nitrogen, keeping the temperature at 170 ℃, 180 ℃ and 190 ℃ for 1 hour respectively until reaching a clarification point, continuing the reaction for 2 hours to complete esterification, after the esterification reaction is completed, gradually raising the temperature to 230 ℃, simultaneously vacuumizing to below 100Pa, and polymerizing for 1 hour to obtain the degradable polyester master batch;
in step S3, the addition amount of the degradable polyester master batch is 30 parts, the addition amount of the dispersed wood fiber is 70 parts, the addition amount of the KH550 silane coupling agent is 3 parts, the temperature is 180 ℃ during granulation, and the screw rotation speed is 20 r/min.
Example 4
Specifically, the present invention is the same as example 1, except that:
step S1 is: adopting the method of the preparation process A of the embodiment 1 in the paragraphs [0049] to [0053] of the specification of Chinese patent 201910104694.6, replacing the needle-leaf wood chips with wheat straw and rice straw in the mass ratio of 1:1, and fully drying the prepared slurry A to obtain a mixture of rice straw fibers and wheat straw fibers;
in the step S2, 0.8 part of 2, 5-furandicarboxylic acid, 10 parts of pentanediol and 0.005 part of catalyst are added to react in a reaction kettle, the reaction kettle is provided with a reflux condensing device, the temperature is slowly raised under the protection of nitrogen, the temperature is kept at 160 ℃ and 200 ℃ for 1 hour respectively until the clarification point is reached, the reaction is continued for 3 hours, the esterification is completed, after the esterification reaction is completed, the temperature is gradually raised to 235 ℃, meanwhile, the vacuum pumping is carried out until the pressure is lower than 100Pa, and the polymerization is carried out for 5 hours, so that the degradable polyester master batch is obtained;
in step S3, the addition amount of the degradable polyester master batch is 40 parts, the addition amount of the dispersed mixture of the straw fiber and the wheat straw fiber is 60 parts, the addition amount of the KH550 silane coupling agent is 5 parts, the temperature is 180 ℃ during granulation, and the screw rotation speed is 20 r/min.
With the preparation method of examples 1-4, dishes in the form of fruit dishes, egg trays, etc. can also be prepared.
Example 5
Specifically, the present invention is the same as example 1, except that:
in step S3, the weight ratio of the dispersed biomass fiber to the degradable polyester masterbatch is 90: 20.
Example 6
Specifically, the present invention is the same as example 1, except that:
in step S3, the weight portion ratio of the dispersed biomass fiber to the degradable polyester masterbatch is 50: 40.
Example 7
Specifically, the present invention is the same as example 1, except that:
in step S3, the biomass fibers are discretized to a length of less than 0.08 millimeters.
Example 8
Specifically, the present invention is the same as example 1, except that:
in step S3, the biomass fiber is dispersed to make the length of the biomass fiber less than 0.08 mm, and the weight portion ratio of the dispersed biomass fiber to the degradable polyester master batch is 80: 40.
The disposable lunch boxes prepared in examples 1-8 were 1000mL capacity four-grid lunch boxes.
Comparative example 1 is a commercial disposable starch lunch box, specifically a disposable lunch box made of cornstarch of the Mirabilis brand, with a capacity of 1000mL and a product number of 100023415826.
Comparative example 2 is a commercial disposable resin lunch box, specifically a disposable Sige lunch box made of PP material, Mirabi brand, with a capacity of 1000mL and a product number of 100011468130.
Test example 1 Performance test of the disposable lunch boxes prepared in examples 1 to 4 and the disposable lunch boxes of comparative examples 1 to 2
(1) Weight bearing test
Test equipment: two pieces of flat glass 200mm x 150mm x 3mm, 3kg weight, metal ruler with 1mm accuracy.
Taking two lunch boxes to be tested, reversely buckling the lunch boxes on a smooth desktop, placing plate glass at the bottom of the lunch boxes, and measuring the height H from the lower surface of the plate glass to the desktop by using a metal ruler0(mm), then a 3kg weight was placed at the center of the plate glass, and the height H (mm) was precisely measured immediately after loading for 1 min. And (3) calculating the load change rate of each tested lunch box by using the formula (1), and taking the arithmetic average of the load change rates of the two tested lunch boxes as the load change rate.
W＝(H0-H)/H0X 100 formula (1)
(2) Drop test
At normal temperature, the bottom of the test meal box at the height of 0.6, 0.8, 1.0 and 1.2m away from the flat ground is freely dropped downwards once, and whether the test meal box is intact or not is observed.
(3) Temperature resistance test
And filling the test lunch box with hot water at 95 +/-5 ℃, moving the test lunch box into a constant temperature box at 60 ℃, standing for 30min, and observing whether the test lunch box is deformed or not, whether the box bottom has leakage or not and the like.
(4) Test for Water resistance
Testing waterproof performance for 30min
A test method of a water leakage test in GB18006.1-2009 Universal technical requirements for plastic disposable tableware is adopted: and (3) placing two test lunch boxes on an enamel tray lined with filter paper, filling water at 23 +/-2 ℃, standing for 30min, observing whether the test lunch boxes deform or not, and observing whether the box bottom has signs of leakage or seepage.
② 4h waterproof performance test
And (3) placing two test lunch boxes on an enamel tray lined with filter paper, filling water at 45 +/-2 ℃, standing for 4 hours, observing whether the test lunch boxes deform or not, and observing whether the box bottom has signs of leakage or seepage.
(5) Test for degradation Rate
And testing by using the built controlled compost degradation device. By weighing CO2The mass of the absorption tube is calculated to obtain the accumulated discharged CO of the culture process of the meal box sample and the reference sample (thin-layer chromatography grade cellulose)2Mass m1(g) And CO discharged in the accumulation way of the blank compost sample2Mass m2(g) In that respect Theoretical CO of lunch box samples2Mass discharge m0(g) Mass m as determined by elemental analyser1(g) The C element content (C%) of the sample of (1) was calculated according to the formula (2). And (3) calculating the degradation rate of the lunch box sample in the degradation process according to the formula (3). Three replicates were required for each blank, reference (thin layer chromatography cellulose) and lunch box samples.
m0Formula (2) m × c% × 44/12
Degradation rate (m)1-m2)/m0X 100% formula (3)
The load change rate, the dropping performance, the temperature resistance, the waterproof performance and the degradation rate of the disposable lunch box prepared by the invention and the disposable lunch box sold in the market are detailed in tables 1-3.
Table 1 test results of load bearing performance, dropping performance and temperature resistance of the disposable lunch box prepared by the present invention and commercially available disposable lunch boxes
| Item | Weight change rate/%) | Drop performance | Temperature resistance |
| Example 1 | 0.9 | Without damage | No deformation and no leakage |
| Example 2 | 1.1 | Without damage | No deformation and no leakage |
| Example 3 | 1.5 | Without damage | No deformation and no leakage |
| Example 4 | 1.4 | Without damage | No deformation and no leakage |
| Example 5 | 4.4 | Has a breakage | With deformation and leakage |
| Example 6 | 0.8 | Without damage | No deformation and no leakage |
| Example 7 | 4.9 | Has a breakage | With deformation and leakage |
| Example 8 | 0.9 | Without damage | No deformation and no leakage |
| Comparative example 1 | 3.2 | Without damage | No deformation and no leakage |
| Comparative example 2 | 4.3 | Without damage | No deformation and no leakage |
As can be seen from the data in Table 1, the disposable food boxes prepared in examples 1-4 of the present invention have no difference in the drop property and temperature resistance from the commercially available disposable starch food boxes and disposable resin food boxes; the disposable lunch boxes prepared in examples 1 to 4 of the present invention have a smaller weight change rate than those of comparative examples 1 to 2, which shows that the disposable lunch boxes prepared in examples 1 to 4 of the present invention have more excellent weight bearing performance, i.e., the strength of the disposable lunch boxes prepared in examples 1 to 4 of the present invention is superior to that of the commercially available disposable starch lunch boxes and disposable resin lunch boxes.
Compared with examples 1-4, the disposable lunch box prepared in example 5 has significantly higher load change rate and poorer dropping performance and temperature resistance performance because the added biomass fiber accounts for a larger proportion. Compared with examples 1-4, the disposable lunch box prepared in example 6 has a lower load change rate due to the larger proportion of the added degradable polyester master batch. The weight part ratio of the dispersed biomass fibers to the degradable polyester master batches is 60-80: 20-40, and the prepared disposable lunch box has excellent load change rate, falling performance and temperature resistance.
Compared with the embodiment 1, the disposable lunch box prepared in the embodiment 7 has larger load change rate and poorer dropping performance and temperature resistance, because the biomass fiber with the length less than 0.08 mm is similar to powder, and cannot play a bridging role after being mixed with the degradable polyester master batch to provide enough strength for the prepared disposable lunch box.
The load change rate, the dropping performance and the temperature resistance of the disposable lunch box prepared in the embodiment 8 are the same as those of the embodiment 1, which shows that the biomass short fibers of 0.1-2 mm can be mutually crossed and overlapped to generate an interaction force in the embodiment 1 of the invention, and the addition amount of the degradable polyester master batch can be reduced while the prepared disposable lunch box is ensured to have higher strength by matching with the use of the degradable polyester master batch, so that the cost is reduced.
Table 2 waterproof performance test results of disposable lunch boxes prepared according to the present invention and commercially available disposable lunch boxes
| Item | Waterproof performance for 30min | 4h waterproof performance |
| Example 1 | No vaginal seepage and seepage | No vaginal seepage and seepage |
| Example 2 | No vaginal seepage and seepage | No vaginal seepage and seepage |
| Example 3 | No vaginal seepage and seepage | No vaginal seepage and seepage |
| Example 4 | No vaginal seepage and seepage | No vaginal seepage and seepage |
| Example 5 | Has the effects of yin leakage | Has the effects of yin leakage |
| Example 6 | No vaginal seepage and seepage | No vaginal seepage and seepage |
| Example 7 | Has the effects of yin leakage | Has the effects of yin leakage |
| Example 8 | No vaginal seepage and seepage | No vaginal seepage and seepage |
| Comparative example 1 | No vaginal seepage and seepage | Has the effects of yin leakage |
| Comparative example 2 | No vaginal seepage and seepage | No vaginal seepage and seepage |
As can be seen from the data in table 2, the disposable lunch boxes prepared in examples 1 to 4 of the present invention can satisfy GB18006.1-2009, general technical requirements for plastic disposable tableware, and in a 4h waterproof performance test, the phenomena of oozing and leakage appear in comparative example 1, which indicates that the 4h waterproof performance of the disposable lunch boxes prepared in examples 1 to 4 of the present invention is superior to that of the commercially available disposable starch lunch boxes.
The 30min waterproof performance and the 4h waterproof performance of the disposable lunch boxes prepared in examples 5 and 7 were poor, and the 30min waterproof performance and the 4h waterproof performance of the disposable lunch boxes prepared in examples 6 and 8 were the same as those of example 1. The water resistance of the disposable lunch box can be improved by increasing the dosage of the degradable polyester master batch under the condition of not changing the dosage of the biomass fiber.
Table 3 degradation rate test results of disposable lunch boxes prepared according to the present invention and commercially available disposable lunch boxes
| Item | Percent of degradation/%) |
| Example 1 | 93.5 |
| Example 2 | 94.6 |
| Example 3 | 97.4 |
| Example 4 | 99.6 |
| Example 5 | 94.1 |
| Example 6 | 92.8 |
| Example 7 | 93.6 |
| Example 8 | 93.2 |
| Comparative example 1 | 80.5 |
| Comparative example 2 | 3.5 |
As can be seen from table 3, the degradation rates of the disposable lunch boxes prepared in examples 1 to 4 of the present invention are all above 93%, and the degradation rate of the disposable lunch box prepared in example 4 is as high as 99.6%, while the degradation rate of the commercially available disposable resin lunch box is only 3.5%, and the degradation rate of the commercially available disposable starch lunch box is 80.5%, which indicates that the disposable lunch box prepared in example 4 of the present invention can be completely degraded, and is significantly more environment-friendly than the commercially available disposable resin lunch boxes and the commercially available disposable starch lunch boxes. The degradation rates of the disposable lunch boxes prepared in examples 5-8 were similar to those of example 1, indicating that the disposable lunch boxes prepared in examples 5-8 are all environmentally friendly.
While there have been shown and described what are at present considered the fundamental principles and essential features of the invention and its advantages, it will be apparent to those skilled in the art that the invention is not limited to the details of the foregoing exemplary embodiments, but is capable of other specific forms without departing from the spirit or essential characteristics thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.
Claims (8)
1. A preparation method of a full-degradable biomass fiber-based waterproof dinner plate is characterized by comprising the following steps:
s1, preparation of biomass fibers
S2, preparation of degradable polyester master batch
Putting aliphatic diacid, 2, 5-furandicarboxylic acid, dihydric alcohol and a catalyst into a reaction kettle for reaction, slowly heating under the protection of nitrogen, keeping the temperature at 160-200 ℃ for 1-3 hours until a clarification point is reached, continuing to react for 1-3 hours, finishing esterification, gradually heating to 230-240 ℃ after the esterification reaction is finished, and simultaneously carrying out vacuum polymerization for 1-5 hours to obtain degradable polyester master batches;
s3, preparation of biomass fiber/degradable plastic composite material
Dispersing the biomass fiber into fine fiber with the diameter of 0.1-2 mm by using a dry pulp dissociator, heating and melting the degradable polyester master batch, and spraying the melted degradable polyester master batch on the dispersed biomass fiber to prepare the biomass fiber/degradable plastic composite material, wherein the weight part ratio of the dispersed biomass fiber to the degradable polyester master batch is 60-80: 20-40;
s4, preparing the dinner plate.
2. The method for preparing a fully degradable biomass fiber-based waterproof dinner plate according to claim 1, wherein in step S1, the biomass fiber is one or more of wheat straw fiber, rice straw fiber, bamboo fiber and wood fiber.
3. The method for preparing a fully degradable biomass fiber-based waterproof dinner plate according to claim 1, wherein in step S1, the biomass fiber is preferably wheat straw fiber or rice straw fiber.
4. The method for preparing a full-degradable biomass fiber-based waterproof dinner plate according to claim 1, wherein in step S2, the aliphatic diacid is one or more of long chain diacids such as succinic acid and adipic acid, and the dihydric alcohol is one or more of dihydric alcohols such as propylene glycol, butylene glycol and pentylene glycol.
5. The preparation method of the fully degradable biomass fiber-based waterproof dinner plate according to claim 1, wherein in step S2, the weight part ratio of the aliphatic diacid, the 2, 5-furandicarboxylic acid, the dihydric alcohol and the catalyst is 0-0.6: 0.5-1: 2-10: 0.001-0.005.
6. The method for preparing a fully degradable biomass fiber-based waterproof dinner plate according to claim 1, wherein in step S2, the pressure parameter condition of evacuation is that evacuation is performed to below 100 Pa.
7. The method for preparing a fully degradable biomass fiber-based waterproof dinner plate according to claim 1, wherein the step S3 is specifically as follows: and (2) fully dissociating the biomass fiber obtained in the step (S1) to disperse the biomass fiber into fine fibers of 0.1-2 mm, heating and melting 20-40 parts of the degradable polyester master batch prepared in the step (S2), uniformly spraying the melt on 60-80 parts of the dispersed biomass fiber through a high-flow glue spraying system, then adding 1-5 parts of additives such as coupling agents and the like, fully stirring to obtain a mixture, and granulating and dicing the mixture to obtain the biomass fiber/degradable polyester composite material.
8. The preparation method of the fully degradable biomass fiber-based waterproof dinner plate according to claim 7, wherein in step S6, the granulation is completed in an extrusion granulator at a temperature of 160-180 ℃ and a screw rotation speed of 5-20 r/min.
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