CN112266583A - Preparation method of high-strength low-cost full-biodegradable material and product thereof - Google Patents
Preparation method of high-strength low-cost full-biodegradable material and product thereof Download PDFInfo
- Publication number
- CN112266583A CN112266583A CN202011153908.8A CN202011153908A CN112266583A CN 112266583 A CN112266583 A CN 112266583A CN 202011153908 A CN202011153908 A CN 202011153908A CN 112266583 A CN112266583 A CN 112266583A
- Authority
- CN
- China
- Prior art keywords
- fiber
- shearing
- biodegradable material
- cost
- glass fiber
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000463 material Substances 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000000835 fiber Substances 0.000 claims abstract description 67
- 239000003365 glass fiber Substances 0.000 claims abstract description 46
- 239000004626 polylactic acid Substances 0.000 claims abstract description 40
- 229920000747 poly(lactic acid) Polymers 0.000 claims abstract description 39
- 238000000034 method Methods 0.000 claims abstract description 20
- 239000002994 raw material Substances 0.000 claims abstract description 17
- 229920000229 biodegradable polyester Polymers 0.000 claims abstract description 11
- 239000004622 biodegradable polyester Substances 0.000 claims abstract description 11
- 239000012763 reinforcing filler Substances 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 238000010008 shearing Methods 0.000 claims description 28
- 241000196324 Embryophyta Species 0.000 claims description 24
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 9
- UAUDZVJPLUQNMU-UHFFFAOYSA-N Erucasaeureamid Natural products CCCCCCCCC=CCCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-UHFFFAOYSA-N 0.000 claims description 6
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 6
- 244000269722 Thea sinensis Species 0.000 claims description 6
- 239000003963 antioxidant agent Substances 0.000 claims description 6
- 230000003078 antioxidant effect Effects 0.000 claims description 6
- 239000007822 coupling agent Substances 0.000 claims description 6
- UAUDZVJPLUQNMU-KTKRTIGZSA-N erucamide Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-KTKRTIGZSA-N 0.000 claims description 6
- 150000008442 polyphenolic compounds Chemical class 0.000 claims description 6
- 235000013824 polyphenols Nutrition 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
- 235000012424 soybean oil Nutrition 0.000 claims description 5
- 239000003549 soybean oil Substances 0.000 claims description 5
- 239000010902 straw Substances 0.000 claims description 5
- 229920002522 Wood fibre Polymers 0.000 claims description 3
- 239000002025 wood fiber Substances 0.000 claims description 3
- JQYSLXZRCMVWSR-UHFFFAOYSA-N 1,6-dioxacyclododecane-7,12-dione;terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1.O=C1CCCCC(=O)OCCCCO1 JQYSLXZRCMVWSR-UHFFFAOYSA-N 0.000 claims description 2
- ZMKVBUOZONDYBW-UHFFFAOYSA-N 1,6-dioxecane-2,5-dione Chemical compound O=C1CCC(=O)OCCCCO1 ZMKVBUOZONDYBW-UHFFFAOYSA-N 0.000 claims description 2
- CFWRDBDJAOHXSH-SECBINFHSA-N 2-azaniumylethyl [(2r)-2,3-diacetyloxypropyl] phosphate Chemical compound CC(=O)OC[C@@H](OC(C)=O)COP(O)(=O)OCCN CFWRDBDJAOHXSH-SECBINFHSA-N 0.000 claims description 2
- 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 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- TXQVDVNAKHFQPP-UHFFFAOYSA-N [3-hydroxy-2,2-bis(hydroxymethyl)propyl] octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(CO)(CO)CO TXQVDVNAKHFQPP-UHFFFAOYSA-N 0.000 claims description 2
- 238000005520 cutting process Methods 0.000 claims description 2
- 229920006242 ethylene acrylic acid copolymer Polymers 0.000 claims description 2
- 239000000314 lubricant Substances 0.000 claims description 2
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 claims description 2
- FATBGEAMYMYZAF-UHFFFAOYSA-N oleicacidamide-heptaglycolether Natural products CCCCCCCCC=CCCCCCCCC(N)=O FATBGEAMYMYZAF-UHFFFAOYSA-N 0.000 claims description 2
- 239000004014 plasticizer Substances 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 229940092258 rosemary extract Drugs 0.000 claims description 2
- 235000020748 rosemary extract Nutrition 0.000 claims description 2
- 239000001233 rosmarinus officinalis l. extract Substances 0.000 claims description 2
- 239000000600 sorbitol Substances 0.000 claims description 2
- 229940071182 stannate Drugs 0.000 claims description 2
- 125000005402 stannate group Chemical group 0.000 claims description 2
- 244000082204 Phyllostachys viridis Species 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 8
- 230000000052 comparative effect Effects 0.000 description 12
- 239000000203 mixture Substances 0.000 description 10
- 238000001125 extrusion Methods 0.000 description 8
- 239000004593 Epoxy Substances 0.000 description 6
- 125000000524 functional group Chemical group 0.000 description 6
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 6
- QRIMLDXJAPZHJE-UHFFFAOYSA-N 2,3-dihydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(O)CO QRIMLDXJAPZHJE-UHFFFAOYSA-N 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 241001330002 Bambuseae Species 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 238000005469 granulation Methods 0.000 description 4
- 230000003179 granulation Effects 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 241000209140 Triticum Species 0.000 description 3
- 235000021307 Triticum Nutrition 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000004310 lactic acid Substances 0.000 description 3
- 235000014655 lactic acid Nutrition 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 235000019198 oils Nutrition 0.000 description 3
- 230000003014 reinforcing effect Effects 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- -1 polybutylene terephthalate-adipate Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 description 1
- 240000005373 Panax quinquefolius Species 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229920000704 biodegradable plastic Polymers 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000002354 daily effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 230000003203 everyday effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 229920003192 poly(bis maleimide) Polymers 0.000 description 1
- 229920002961 polybutylene succinate Polymers 0.000 description 1
- 239000004631 polybutylene succinate Substances 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000002341 toxic gas Substances 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
- 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
- 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
- C08L2205/03—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
- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
- C08L2205/16—Fibres; Fibrils
Abstract
The invention discloses a preparation method of a full-biodegradable material with high strength and low cost and a product thereof, wherein the preparation method takes biodegradable polyester as a base material and takes plant fiber and polylactic acid fiber as reinforcing fillers; the method specifically comprises the following steps: s1, blending all raw materials except the polylactic acid fiber and then adding the blended raw materials into an extruder from a main feeding port; s2: adding polylactic acid fiber into an extruder from a glass fiber hole, and extruding and granulating to obtain the high-strength low-cost fully biodegradable material. According to the preparation method disclosed by the invention, the plant fiber and the PLA fiber are simultaneously used as the reinforcing filler, and the material which is high in strength, low in cost and fully biodegradable is prepared by matching with specific process conditions.
Description
Technical Field
The invention belongs to the field of manufacturing of biodegradable materials, and particularly relates to a preparation method of a high-strength low-cost fully biodegradable material and a product thereof.
Background
With the acceleration of the industrial process and the improvement of the living standard, a large amount of plastic products are produced and consumed every day in daily life, however, the common plastic products are quite troublesome to treat after being discarded, and can generate toxic gas to pollute the atmosphere after being directly combusted; if a landfill treatment mode is adopted, the complete degradation needs one or two hundred years, and serious waste is caused to land resources.
Polylactic acid (PLA) is a novel biodegradable material, which is prepared by fermenting starch raw materials extracted from renewable plant resources and then synthesizing polymers. PLA has excellent biodegradability, complete degradability, and excellent mechanical properties, but is expensive. Poly (butylene adipate terephthalate) (PBAT) and poly (butylene succinate) (PBS) are polymers with good biodegradability, and have relatively low price compared with PLA, but have the problem of poor strength.
In order to combine the advantages of the two, the common method is to directly add PLA into the PBAT base material and/or the PBS base material, and to prepare the composite material through melting granulation after blending to play a role in enhancing, but when the adding part of PLA is small, the PLA is in particles and is dispersed in a system in a sea-island structure, the continuous phase is still PBAT and/or PBS, and the enhancing effect of the PLA cannot be really reflected; when the amount of PLA added is high, the strength is greatly improved, but the relative cost is high.
The plant fiber is a natural degradable material which is cheap and easy to obtain, and is usually used as a filler to be added into the degradable resin to reduce the cost, but the compatibility of the plant fiber and the degradable resin is poor due to the characteristics of a large amount of hydroxyl groups, strong hydrophilicity and the like in the plant fiber. The problem of poor compatibility is often solved by modifying the plant fibers or the matrix material in advance. However, even after the modification treatment, the enhancement effect is still not very obvious by simply adopting the plant fiber as the enhancement component.
Disclosure of Invention
Aiming at the problems in the prior art, the invention discloses a preparation method of a high-strength low-cost fully biodegradable material, and simultaneously, plant fibers and PLA fibers are used as reinforcing fillers, and the material which is high in strength, low in cost and fully biodegradable is prepared by matching with specific process conditions.
The specific technical scheme is as follows:
a preparation method of a full-biodegradable material with high strength and low cost takes biodegradable polyester as a base material and takes plant fiber and polylactic acid fiber as reinforcing fillers;
the method specifically comprises the following steps:
s1, blending all raw materials except the polylactic acid fiber and then adding the blended raw materials into an extruder from a main feeding port;
s2: adding polylactic acid fiber into an extruder from a glass fiber hole, and extruding and granulating to obtain the high-strength low-cost fully biodegradable material.
The invention firstly proposes that the plant fiber and the PLA fiber are used together as the reinforcing filler for compounding. The concept of the invention is different from the idea of using PLA as a base material in the prior art, but the PLA is spun into fibers and then used as a reinforcing filler, and tests show that the strength of the material can be greatly improved under the condition that the PLA accounts for a small amount.
The key point of the invention that the reinforcing functions of the lactic acid fiber and the lactic acid fiber can be fully exerted is that a specific processing technology is adopted, firstly, all raw materials except the lactic acid fiber are blended and then added into an extruder from a main feeding port, the extrusion temperature between the main feeding port and a glass fiber hole is controlled to be 140-150 ℃, and the screw combination is controlled to be strong shearing and strong dispersion; under the process condition, the plant fiber without any pretreatment can be fully dispersed and reacted in the biodegradable polyester; then blending and extruding with polylactic acid fiber added through glass fiber holes, setting the extrusion temperature between the glass fiber holes and a die head to be 110-120 ℃, and controlling screw combination to be medium shearing and strong dispersion; under the process conditions, the polylactic acid fiber cannot be fully melted, and most of the polylactic acid fiber is dispersed in the base material in a fiber shape with a certain length-diameter ratio, similar to the shape of the glass fiber reinforced resin. Through the design of the specific process flow and the process parameters, the fully-degradable composite material with high strength and low cost is prepared by one-step extrusion, and the reinforcing functions of the plant fiber and the PLA fiber are fully exerted.
In the invention, all the raw materials comprise the following components in percentage by weight:
the biodegradable polyester is selected from one or two of polybutylene terephthalate-adipate and polybutylene succinate. Further preferred is a lower cost PBAT.
The plant fiber is selected from one or more of the common types in the field, such as straw fiber, chaff fiber, wood fiber and bamboo fiber. Specifically, plant fiber powder with 80-400 meshes can be selected, such as 120 meshes of wheat straw produced by Dongxiangsheng corporation, 200 meshes of wood powder produced by Xian Youhou technology, 150 meshes of bamboo powder produced by Zhejiang Shengshi biotechnology, and the like.
Preferably, the diameter of the polylactic acid fiber is 10-30 μm, and specifically, a PLA fiber of Koele Japan or a Nantong Jiuding organism can be selected; more preferably, the polylactic acid fiber has an average diameter of 15 μm.
The epoxy functional group grafted methacrylic acid glyceride has the advantages that the epoxy functional group can be subjected to cross-linking reaction with an ester group in biodegradable plastics, the compatibility between biodegradable polyester and PLA fiber spinning is improved, and the degradation speed of the material after the material is buried can be accelerated while the plant fiber is degradable. The epoxy-functional grafted glyceryl methacrylate is commercially available, such as SG-20 from Seiko corporation.
The coupling agent is used for increasing the compatibility between the plant fiber and the biodegradable polyester, and common types in the field can be adopted, such as one or more of titanate coupling agent, silane coupling agent and stannate coupling agent.
The natural antioxidant is used for improving processing stability and product use stability, and is specifically selected from one or more of tea polyphenol, cephalin and rosemary extract.
The lubricant provides guarantee for smooth processing, and common types in the field, such as one or more of pentaerythritol stearate, erucamide, oleamide and ethylene acrylic acid copolymer, can be adopted.
The plasticizer is selected from one or more of polyethylene glycol, glycerol, epoxidized soybean oil and sorbitol.
Preferably, the length-diameter ratio of the extruder is 52-64, and the screw rotation speed is 200-500 rpm. Tests show that the length-diameter ratio of the extruder is too short, the plant fibers and the PLA fibers are not uniformly dispersed in the system, the mechanical property is reduced, and the biodegradable polyester is partially degraded due to too long retention time and the mechanical property is reduced due to too high length-diameter ratio.
Preferably, in step S1, the temperature of the extruder before the glass fiber holes is set to 140 to 150 ℃, and the requirements for the screw combination are as follows: the shearing device comprises 2-4 sections of shearing areas, wherein each section of shearing area at least consists of three continuous groups of shearing thread blocks, and each section of shearing area at least comprises one group of 60-degree shearing thread blocks; the last section of the cutting area is connected with a reverse rotation conveying block. Tests show that the screw combination can ensure that the plant fiber can be completely plasticized only by one-time blending extrusion without pretreatment, and is fully dispersed and reacted in the biodegradable polyester; and the problem of air vent flash can not occur. Preferably, the specific combination mode of the glass fiber hole front screw combination is as follows:
44/44A、80/80、80/80、80/80、64/64、64/64、56/56、44/44、30°/7/72、45°/5/56/、60°/4/44、90°/5/56、56/56、44/44、45°/5/56/、60°/5/44、90°/5/56、44/44、45°/5/44、60°/4/44、90°/5/56、44/22L、80/80；
or, 44/44a, 80/80, 80/80, 80/80, 80/80, 64/64, 64/64, 64/64, 56/56, 44/44, 30 °/7/72, 45 °/5/56/, 60 °/4/44, 90 °/5/56, 56/56, 44/44, 56/56, 44/44, 45 °/5/56/, 60 °/5/44, 90 °/5/56, 44/44, 45 °/5/44, 60 °/4/44, 90 °/5/56, 44/22L, 80/80;
or 44/44a, 80/80, 80/80, 80/80, 80/80, 64/64, 64/64, 56/56, 44/44, 30 °/7/72, 45 °/5/56/, 60 °/4/44, 90 °/5/56, 56/56, 44/44, 56/56, 44/44, 45 °/5/56/, 60 °/5/44, 90 °/5/56, 44/44, 56/56, 45 °/5/44, 60 °/4/44, 90 °/5/56, 44/22L, 80/80.
Preferably, in step S2, the temperature of the extruder after glass fiber hole is set to 110 to 120 ℃, and the requirements for screw combination are as follows: the shearing device comprises 3-5 sections of shearing areas, each section of shearing area is composed of at most 2 continuous groups of shearing thread blocks, the angle of each shearing thread block is 45 degrees and/or 60 degrees, and the last section of shearing area is connected with a 45-degree reverse rotation shearing thread block. Experiments show that the screw combination is matched with the screw combination before the glass fiber hole, so that the reinforcing functions of the plant fiber and the PLA fiber can be fully exerted, and the mechanical property of the finally prepared full-biodegradable material is ensured to be optimal.
Preferably, the specific combination mode of the screw combination behind the glass fiber hole is as follows:
80/80、64/64、56/56、56/56、56/56、45°/5/56、45°/5/56、56/56、56/56、45°/5/44、45°/5/56、80/80、72/72、32/32、32/32、28/28、28/28、56/56、45°/5/56、45°/5/56、56/56、56/56、44/44、60°/4/44、45°/5/56、45°/5/56L、80/80、72/72、32/32、32/32、56/56、56/56、44/44、44/44、44/44；
or 80/80, 64/64, 56/56, 56/56, 56/56, 45 °/5/56, 45 °/5/56, 56/56, 56/56, 56/56, 45 °/5/44, 45 °/5/56, 80/80, 72/72, 32/32, 32/32, 32/32, 32/32, 28/28, 28/28, 56/56, 45 °/5/56, 45 °/5/56, 56/56, 56/56, 44/44, 56/56, 44/44, 60 °/4/44, 45 °/5/56, 45 °/5/56L, 80/80, 72/72, 32/32, 32/32, 56/56, 56/56, 45 °/3683, etc, 32/32, 56/56, 56/56, 44/44, 44/44, 44/44;
or 80/80, 64/64, 56/56, 56/56, 56/56, 45 °/5/56, 45 °/5/56, 56/56, 64/64, 56/56, 45 °/5/44, 45 °/5/56, 80/80, 72/72, 32/32, 32/32, 32/32, 32/32, 28/28, 28/28, 56/56, 45 °/5/56, 45 °/5/56, 56/56, 56/56, 44/44, 60 °/4/44, 45 °/5/56, 45 °/5/56L, 80/80, 72/72, 32/32, 32/32, 56/56, 56/56, 56/56, 56/56, 45 °/5/56, 3542, 56/56, 64/64, 56/56, and the like, 44/44, 44/44, 44/44, 44/44.
Preferably, the glass fiber openings are positioned in the sixth zone to the eighth zone.
Under the above preferred process parameters, further preferably, all the raw materials comprise, by weight:
still more preferably:
screw combination of the extruder: before glass fiber hole, the screw combination is 44/44A, 80/80, 80/80, 80/80, 64/64, 64/64, 56/56, 44/44, 30 °/7/72, 45 °/5/56/, 60 °/4/44, 90 °/5/56, 56/56, 44/44, 45 °/5/56/, 60 °/5/44, 90 °/5/56, 44/44, 45 °/5/44, 60 °/4/44, 90 °/5/56, 44/22L and 80/80. After glass fiber hole, the screw combination is 80/80, 64/64, 56/56, 56/56, 56/56, 45 °/5/56, 45 °/5/56, 56/56, 56/56, 45 °/5/44, 45 °/5/56, 80/80, 72/72, 32/32, 32/32, 28/28, 28/28, 56/56, 45 °/5/56, 45 °/5/56, 56/56, 56/56, 44/44, 60 °/4/44, 45 °/5/56, 45 °/5/56L, 80/80, 72/72, 32/32, 32/32, 56/56, 56/56, 44/44, 44/44, glass fiber hole, 44/44, respectively;
the length to diameter ratio of the extruder was 52.
The mass percentage of the biodegradable polyester, the plant fiber and the polylactic acid fiber is 40%: 25%: 30 percent.
Tests show that the fully biodegradable material prepared by adopting the further optimized raw material proportion and combining with a specific screw has the highest strength and greatly reduced cost.
The invention also discloses the high-strength low-cost fully biodegradable material prepared by the method. Through the design of the composition and the content of the formula and the further optimization of the processing technological parameters, the prepared composite material has complete biodegradation performance, does not cause any burden to the environment, not only has excellent mechanical properties, but also can ensure lower material cost on the premise of the same mechanical strength.
Compared with the prior art, the invention has the following beneficial effects:
the invention discloses a preparation method of a high-strength low-cost full-biodegradable material, which firstly proposes that plant fibers and PLA fibers are used together as a reinforcing filler for compounding. The invention can fully exert the enhancement functions of the plant fiber and the degradable resin by optimizing the processing technological parameters, does not need to carry out surface modification pretreatment on the plant fiber, and can solve the problem of poor compatibility with the degradable resin only by one-time blending extrusion.
The composite material prepared by the process has complete biodegradability and excellent mechanical property, and can ensure lower material cost on the premise of the same mechanical strength.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes and modifications can be made by those skilled in the art after reading the disclosure of the present invention, and equivalents also fall within the scope of the invention defined by the claims.
Example 1
Firstly, 25 wt% of wheat straw fiber (Dongxiangshen company, 200 meshes), 2 wt% of epoxidized soybean oil (Texas Longda oil), 2 wt% of erucamide, 40 wt% of PBAT (Lanshan Tunghe 801T), 0.2 wt% of epoxy functional group grafted glyceryl methacrylate (easy-to-use SG-20), 0.2 wt% of silane coupling agent KH5500.2 wt% and 0.2 wt% of natural antioxidant tea polyphenol are added into a stirrer and stirred for 10 minutes to obtain a mixture A, then the mixture A is added into a double-screw extruder through a main feeding port, and then 30 wt% of PLA fiber (the average diameter is 15 mu m) is added into the double-screw extruder from a glass fiber hole.
In this example, the screw speed was 300rpm and the screw length-diameter ratio was 52. The double-screw extruder is divided into a first zone to a twelfth zone and a die head, the glass fiber holes are positioned in a sixth zone, the temperature of the first zone to the fifth zone is 140 +/-5 ℃ before the glass fiber holes, the temperature of the sixth zone to the 12 zones is 120 +/-5 ℃ after the glass fiber holes are formed, and the temperature of the die head is 125 ℃.
Before glass fiber hole, the screw combination is 44/44A, 80/80, 80/80, 80/80, 64/64, 64/64, 56/56, 44/44, 30 °/7/72, 45 °/5/56/, 60 °/4/44, 90 °/5/56, 56/56, 44/44, 45 °/5/56/, 60 °/5/44, 90 °/5/56, 44/44, 45 °/5/44, 60 °/4/44, 90 °/5/56, 44/22L and 80/80.
After glass fiber hole, the screw combination is 80/80, 64/64, 56/56, 56/56, 56/56, 45 °/5/56, 45 °/5/56, 56/56, 56/56, 45 °/5/44, 45 °/5/56, 80/80, 72/72, 32/32, 32/32, 28/28, 28/28, 56/56, 45 °/5/56, 45 °/5/56, 56/56, 56/56, 44/44, 60 °/4/44, 45 °/5/56, 45 °/5/56L, 80/80, 72/72, 32/32, 32/32, 56/56, 56/56, 44/44, 44/44, glass fiber hole, 44/44.
This example, extrusion granulation, resulted in a high strength low cost fully biodegradable material, with 10 replicates per sample of example (including all examples and comparative examples below), with the average mechanical properties listed in table 1 below.
Example 2
Firstly, 15 wt% of wood fiber (Sien's Excellent technology, 200-mesh wood flour), 3 wt% of epoxidized soybean oil (Dezhou Longda oil), 2 wt% of erucamide, 50 wt% of PBAT (blue mountain Tunghe 801T), 0.2 wt% of epoxy functional group grafted glyceryl methacrylate (easy-to-use SG-20), 0.2 wt% of silane coupling agent KH550and 0.2 wt% of natural antioxidant tea polyphenol are added into a stirrer and stirred for 10 minutes to obtain a mixture A, then the mixture A is added into a double-screw extruder through a main feeding port, and then 30 wt% of PLA fiber (with the average diameter of 15 mu m) is added into the double-screw extruder from a glass fiber hole.
In this example, the screw speed was 200rpm and the screw length-diameter ratio was 64. The double-screw extruder is divided into a first zone to a twelfth zone and a die head, the glass fiber holes are positioned in the eighth zone, the temperature of the first zone to the seventh zone is 140 +/-5 ℃ before the glass fiber holes, the temperature of the eighth zone to the sixteenth zone is 110 +/-5 ℃ after the glass fiber holes are formed, and the temperature of the die head is 125 ℃.
Before glass fiber hole, the screw combination is 44/44A, 80/80, 80/80, 80/80, 80/80, 64/64, 64/64, 64/64, 56/56, 44/44, 30 °/7/72, 45 °/5/56/, 60 °/4/44, 90 °/5/56, 56/56, 44/44, 56/56, 44/44, 45 °/5/56/, 60 °/5/44, 90 °/5/56, 44/44, 45 °/5/44, 60 °/4/44, 90 °/5/56, 44/22L, 80/80.
After glass fiber hole, the screw combination is 80/80, 64/64, 56/56, 56/56, 56/56, 45 °/5/56, 45 °/5/56, 56/56, 56/56, 56/56, 45 °/5/44, 45 °/5/56, 80/80, 72/72, 32/32, 32/32, 32/32, 32/32, 28/28, 28/28, 56/56, 45 °/5/56, 45 °/5/56, 56/56, 56/56, 44/44, 56/56, 44/44, 60 °/4/44, 45 °/5/56, 45 °/5/56L, 80/80, 72/72, 32/32, K, 32/32, 32/32, 56/56, 56/56, 44/44, 44/44, 44/44.
The high-strength low-cost fully biodegradable material obtained by extrusion granulation in this example has the mechanical properties listed in table 1 below.
Example 3
Firstly, 20 wt% of bamboo fiber (150-mesh bamboo powder in Sheng's Biotechnology, Zhejiang), 4 wt% of glycerol (bismaleimide chemical), 1 wt% of erucamide, 50 wt% of PBAT (blue mountain Tunghe 801T), 0.2 wt% of epoxy functional group grafted glyceryl methacrylate (easy-to-use SG-20), 0.2 wt% of silane coupling agent KH5500.2 wt% and 0.2 wt% of natural antioxidant tea polyphenol are added into a stirrer and stirred for 10 minutes to obtain a mixture A, then the mixture A is added into a double-screw extruder through a main feeding port, and then 25 wt% of PLA fiber (the average diameter is 15 mu m) is added into the double-screw extruder from a glass fiber hole.
In this example, the screw speed was 500rpm and the screw length-diameter ratio was 56. The double-screw extruder is divided into a first zone to a fourteen zone and a die head, the glass fiber hole is positioned in a seventh zone, the temperature of the first zone to the sixth zone is 150 +/-5 ℃ before the glass fiber hole, the temperature of the seventh zone to the fourteen zone is 120 +/-5 ℃ after the glass fiber hole, and the temperature of the die head is 125 ℃.
Before glass fiber hole, the screw combination is 44/44A, 80/80, 80/80, 80/80, 80/80, 64/64, 64/64, 56/56, 44/44, 30 °/7/72, 45 °/5/56/, 60 °/4/44, 90 °/5/56, 56/56, 44/44, 56/56, 44/44, 45 °/5/56/, 60 °/5/44, 90 °/5/56, 44/44, 56/56, 45 °/5/44, 60 °/4/44, 90 °/5/56, 44/22L, 80/80.
After glass fiber hole, the screw combination is 80/80, 64/64, 56/56, 56/56, 56/56, 45 °/5/56, 45 °/5/56, 56/56, 64/64, 56/56, 45 °/5/44, 45 °/5/56, 80/80, 72/72, 32/32, 32/32, 32/32, 32/32, 28/28, 28/28, 56/56, 45 °/5/56, 45 °/5/56, 56/56, 56/56, 44/44, 60 °/4/44, 45 °/5/56, 38745 °/5/56L, 80/80, 72/72, 32/32, 32/32, 56/56, K, 56/56, 44/44, 44/44, 44/44, 44/44.
The high-strength low-cost fully biodegradable material obtained by extrusion granulation in this example has the mechanical properties listed in table 1 below.
Comparative example 1
The raw materials and preparation process were substantially the same as in example 1 except that the screw combination was different. The comparative example uses a conventional screw combination, i.e. the same combination mode of medium strength is used before and after the glass fiber hole.
Before glass fiber hole, the screw combination is 44/44A, 80/80, 80/80, 80/80, 64/64, 64/64, 56/56, 44/44, 44/44, 30 °/7/72, 45 °/5/56/, 90 °/5/56, 56/56, 56/56, 44/44, 60 °/5/44, 90 °/5/56, 44/44, 44/44, 60 °/4/44, 90 °/5/56, 44/22L and 80/80.
After glass fiber hole, the screw combination is 80/80, 64/64, 56/56, 56/56, 56/56, 45 °/5/56, 45 °/5/56, 45 °/5/56, 56/56, 56/56, 28/28, 45 °/5/44, 45 °/5/56, 45 °/5/56, 80/80, 72/72, 32/32, 32/32, 28/28, 56/56, 45 °/5/56, 56/56, 44/44, 60 °/4/44, 45 °/5/56, 45 °/5/56L, 80/80, 72/72, 32/32, 32/32, 56/56, 56/56, 44/44, 44/44, 44/44.
The mechanical properties of the fully biodegradable material prepared in this comparative example are shown in table 1 below.
Comparative example 2
The raw materials and the preparation process are basically the same as those in the example 1, the difference is only that the length-diameter ratio of the screw is 48, and the screw combination adopts a similar rule as that in the example 1, and the specific rule is as follows:
before glass fiber hole, the screw combination is 44/44A, 80/80, 80/80, 80/80, 64/64, 64/64, 44/44, 30 °/7/72, 45 °/5/56/, 60 °/4/44, 56/56, 44/44, 45 °/5/56/, 60 °/5/44, 90 °/5/56, 44/44, 45 °/5/44, 60 °/4/44, 90 °/5/56, 44/22L, 80/80.
After glass fiber hole, the screw combination is 80/80, 64/64, 56/56, 56/56, 45 °/5/56, 45 °/5/56, 56/56, 56/56, 45 °/5/44, 45 °/5/56, 80/80, 72/72, 32/32, 32/32, 28/28, 45 °/5/56, 45 °/5/56, 56/56, 56/56, 44/44, 60 °/4/44, 45 °/5/56, 45 °/5/56L, 80/80, 72/72, 56/56, 44/44, 44/44, 44/44, 32/32.
The mechanical properties of the fully biodegradable material prepared in this comparative example are shown in table 1 below.
Comparative example 3
The raw materials were exactly the same as in example 1 except that all the raw materials were blended and then all were fed into the extruder through the main feeding port. The temperature, aspect ratio and screw composition of the extruder were also the same as in example 1.
The mechanical properties of the fully biodegradable material prepared in this comparative example are shown in table 1 below.
Comparative example 4
The raw materials and preparation process were substantially the same as in example 1, and the screw combination was the same as in example 1 except that the temperature in each zone was 140 ℃ before and after the glass fiber holes.
The mechanical properties of the fully biodegradable material prepared in this comparative example are shown in table 1 below.
Comparative example 5
25 wt% of wheat straw fiber (such as Dongxiang Sheng 200 meshes), 2 wt% of epoxidized soybean oil (Texas Longda oil), 2 wt% of erucamide, 40 wt% of PBAT (blue mountain Tunghe), 0.2 wt% of epoxy functional group grafted glyceryl methacrylate (easy SG-20), 0.2 wt% of silane coupling agent KH550, 0.2 wt% of natural antioxidant tea polyphenol and 30 wt% of PLA particles (Zhongliang 310X) are all added into a stirrer and stirred for 10 minutes to obtain a mixture, and the mixture is added into a double-screw extruder through a main feeding port.
The temperature, length to diameter ratio and screw combination in each zone of the extruder were the same as in example 1.
The mechanical properties of the fully biodegradable material prepared in this comparative example are shown in table 1 below.
TABLE 1
The above embodiments are merely illustrative of the technical ideas and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes or modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Claims (9)
1. A preparation method of a full biodegradable material with high strength and low cost is characterized in that biodegradable polyester is used as a base material, and plant fiber and polylactic acid fiber are used as reinforcing fillers;
the method specifically comprises the following steps:
s1, blending all raw materials except the polylactic acid fiber and then adding the blended raw materials into an extruder from a main feeding port;
s2: adding polylactic acid fiber into an extruder from a glass fiber hole, and extruding and granulating to obtain the high-strength low-cost fully biodegradable material.
2. The method for preparing the high-strength low-cost fully biodegradable material according to claim 1, wherein all raw materials comprise, by weight:
3. the method for preparing the high-strength low-cost fully biodegradable material according to claim 2, wherein the method comprises the following steps:
the biodegradable polyester is selected from one or two of poly (terephthalic acid) -butylene adipate and poly (butylene succinate);
the plant fiber is selected from one or more of straw fiber, chaff fiber, wood fiber and bamboo fiber;
the coupling agent is selected from one or more of titanate coupling agent, silane coupling agent and stannate coupling agent;
the natural antioxidant is selected from one or more of tea polyphenol, cephalin and rosemary extract;
the lubricant is selected from one or more of pentaerythritol stearate, erucamide, oleamide and ethylene acrylic acid copolymer;
the plasticizer is selected from one or more of polyethylene glycol, glycerol, epoxidized soybean oil and sorbitol.
4. The preparation method of the high-strength low-cost fully biodegradable material according to claim 1, wherein the diameter of the polylactic acid fiber is 10-30 μm.
5. The preparation method of the high-strength low-cost fully biodegradable material according to claim 1, wherein the length-diameter ratio of the extruder is 52-64, and the screw rotation speed is 200-500 rpm.
6. The method for preparing the high-strength low-cost full-biodegradable material according to claim 1, wherein in step S1, the temperature of the extruder before the glass fiber holes is set to 140-150 ℃;
screw rod combination before the glass fiber hole: the shearing device comprises 2-4 sections of shearing areas, wherein each section of shearing area at least consists of three continuous groups of shearing thread blocks, and each section of shearing area at least comprises one group of 60-degree shearing thread blocks; the last section of the cutting area is connected with a reverse rotation conveying block.
7. The method for preparing the high-strength low-cost fully biodegradable material according to claim 1, wherein in step S2, the temperature of the extruder after glass fiber holes is set to be 110-120 ℃;
screw rod combination behind the glass fiber hole: the shearing device comprises 3-5 sections of shearing areas, each section of shearing area is composed of at most 2 continuous groups of shearing thread blocks, the angle of each shearing thread block is 45 degrees and/or 60 degrees, and the last section of shearing area is connected with a 45-degree reverse rotation shearing thread block.
8. The method for preparing the full biodegradable material with high strength and low cost according to claim 1, wherein the glass fiber openings are located in the sixth area to the eighth area.
9. A high-strength low-cost fully biodegradable material prepared by the method of any one of claims 1 to 8.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011153908.8A CN112266583A (en) | 2020-10-26 | 2020-10-26 | Preparation method of high-strength low-cost full-biodegradable material and product thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011153908.8A CN112266583A (en) | 2020-10-26 | 2020-10-26 | Preparation method of high-strength low-cost full-biodegradable material and product thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112266583A true CN112266583A (en) | 2021-01-26 |
Family
ID=74341646
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011153908.8A Pending CN112266583A (en) | 2020-10-26 | 2020-10-26 | Preparation method of high-strength low-cost full-biodegradable material and product thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112266583A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113072754A (en) * | 2021-04-21 | 2021-07-06 | 广东广海大实业有限公司 | Degradable non-slip mat and preparation method thereof |
| WO2022175700A1 (en) * | 2021-02-16 | 2022-08-25 | Bobak Kalman | Biodegradable chaff-based raw material, finished product produced from this, their production and use |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1678777A (en) * | 2002-08-30 | 2005-10-05 | 东丽株式会社 | Polylactic acid fiber, yarn package, and textile product |
| WO2009024837A1 (en) * | 2007-08-22 | 2009-02-26 | Kimberly-Clark Worldwide, Inc. | Method for forming polylactic acid fibers |
| CN103665800A (en) * | 2012-09-18 | 2014-03-26 | 上海载和实业投资有限公司 | Continuous fiber reinforced polylactic resin composition and preparation method thereof |
| WO2017094851A1 (en) * | 2015-12-02 | 2017-06-08 | 王子ホールディングス株式会社 | Molded body and manufacturing method for molded body |
| CN107151427A (en) * | 2016-03-02 | 2017-09-12 | 黑龙江鑫达企业集团有限公司 | A kind of biodegradable toughness reinforcing heat-proof polylactic acid modified resin and preparation method thereof |
| US20200140187A1 (en) * | 2017-04-28 | 2020-05-07 | Ahlstrom-Munksjö Oyj | Compostable lid comprising an oxygen barrier layer for sealing a capsule and capsule sealed by the lid |
| CN111571987A (en) * | 2020-05-21 | 2020-08-25 | 南京科尔克挤出装备有限公司 | Energy-saving combined screw for PET bottle flake material |
| CN111621162A (en) * | 2020-06-19 | 2020-09-04 | 杭实科技发展(杭州)有限公司 | Full-biodegradable bamboo fiber high-filling polylactic acid material and preparation method thereof |
-
2020
- 2020-10-26 CN CN202011153908.8A patent/CN112266583A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1678777A (en) * | 2002-08-30 | 2005-10-05 | 东丽株式会社 | Polylactic acid fiber, yarn package, and textile product |
| WO2009024837A1 (en) * | 2007-08-22 | 2009-02-26 | Kimberly-Clark Worldwide, Inc. | Method for forming polylactic acid fibers |
| CN103665800A (en) * | 2012-09-18 | 2014-03-26 | 上海载和实业投资有限公司 | Continuous fiber reinforced polylactic resin composition and preparation method thereof |
| WO2017094851A1 (en) * | 2015-12-02 | 2017-06-08 | 王子ホールディングス株式会社 | Molded body and manufacturing method for molded body |
| CN107151427A (en) * | 2016-03-02 | 2017-09-12 | 黑龙江鑫达企业集团有限公司 | A kind of biodegradable toughness reinforcing heat-proof polylactic acid modified resin and preparation method thereof |
| US20200140187A1 (en) * | 2017-04-28 | 2020-05-07 | Ahlstrom-Munksjö Oyj | Compostable lid comprising an oxygen barrier layer for sealing a capsule and capsule sealed by the lid |
| CN111571987A (en) * | 2020-05-21 | 2020-08-25 | 南京科尔克挤出装备有限公司 | Energy-saving combined screw for PET bottle flake material |
| CN111621162A (en) * | 2020-06-19 | 2020-09-04 | 杭实科技发展(杭州)有限公司 | Full-biodegradable bamboo fiber high-filling polylactic acid material and preparation method thereof |
Non-Patent Citations (4)
| Title |
|---|
| 宋亚男，等: "植物纤维增强聚乳酸可降解复合材料的研究", 《高分子通报》 * |
| 张燕等: "可降解聚乳酸/天然植物纤维复合材料的研究进展", 《工程塑料应用》 * |
| 张雪姣等: "植物纤维增强生物塑料的研究进展", 《林产工业》 * |
| 蔡秀娣: "最新专利", 《合成技术及应用》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022175700A1 (en) * | 2021-02-16 | 2022-08-25 | Bobak Kalman | Biodegradable chaff-based raw material, finished product produced from this, their production and use |
| CN113072754A (en) * | 2021-04-21 | 2021-07-06 | 广东广海大实业有限公司 | Degradable non-slip mat and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103540111B (en) | A kind of high intensity, resistant to elevated temperatures fully-degradable polylactic acid sheet material and manufacture method thereof | |
| CN110655769A (en) | High-toughness fully-degradable composite material | |
| CN101942118B (en) | Plant fiber starch fully-biodegradable material and preparation method thereof | |
| CN1216101C (en) | Preparation method of toughness enhanced and reinforced polybutanediol terephthalate nanometer composition | |
| CN108929527B (en) | PBAT/modified starch full-biodegradable film with high ductility and high barrier property as well as preparation method and application thereof | |
| CN113956623B (en) | Full-biodegradable plastic composite modified material suitable for film bag and preparation method thereof | |
| US11732058B2 (en) | Thermoplastic starch and starch-based biodegradable film | |
| CN103571164A (en) | Polylactic acid/core-shell structure composite material and preparation method thereof | |
| CN110698822A (en) | Full-biodegradable composite material for tableware and preparation method and application thereof | |
| CN112266583A (en) | Preparation method of high-strength low-cost full-biodegradable material and product thereof | |
| CN1793229A (en) | Complete degradable material with polyalctic as carrier and preparation process thereof | |
| CN112358708A (en) | Biodegradable film blowing modified material with high starch content and preparation method thereof | |
| WO2021154335A1 (en) | Earth plant compostable biodegradable substrate and method of producing the same | |
| CN113234304A (en) | Biodegradable film material and preparation method of film | |
| CN101735583A (en) | Completely biodegraded polylactic acid nanometer composite material and preparation method thereof | |
| CN115418083A (en) | Low-cost PBAT biodegradable material for film bag and preparation method thereof | |
| CN102702655B (en) | Polyvinyl alcohol/high amylose biodegradable material and melting preparation method thereof | |
| CN112405931B (en) | Preparation method of nano-montmorillonite reinforced starch-based biodegradable blown film material, product and application thereof | |
| CN114133712A (en) | Fully biodegradable agricultural mulching film | |
| CN111763410B (en) | Biodegradable PBAT alloy with high starch content and preparation method thereof | |
| CN113831702A (en) | Degradable plastic lunch box composition and preparation method thereof | |
| CN114921069B (en) | Full-biodegradable film with high heat seal strength and preparation method and application thereof | |
| CN113683875B (en) | Degradable high-toughness heat-resistant polylactic acid-starch composite material and preparation method thereof | |
| CN114891331A (en) | Toughened polylactic acid/starch blending material and preparation method thereof | |
| CN112094487B (en) | Easily-cleaned high-temperature-resistant polylactic acid composite material for environment-friendly tableware |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210126 |