CN111100437B - Preparation method of degradable plastic master batch containing nanocellulose - Google Patents
Preparation method of degradable plastic master batch containing nanocellulose Download PDFInfo
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- CN111100437B CN111100437B CN201911162926.XA CN201911162926A CN111100437B CN 111100437 B CN111100437 B CN 111100437B CN 201911162926 A CN201911162926 A CN 201911162926A CN 111100437 B CN111100437 B CN 111100437B
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- 229920006238 degradable plastic Polymers 0.000 title claims abstract description 37
- 239000004594 Masterbatch (MB) Substances 0.000 title claims abstract description 36
- 229920001046 Nanocellulose Polymers 0.000 title claims description 14
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 229920002678 cellulose Polymers 0.000 claims abstract description 63
- 239000001913 cellulose Substances 0.000 claims abstract description 63
- 229920000747 poly(lactic acid) Polymers 0.000 claims abstract description 33
- 239000004626 polylactic acid Substances 0.000 claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 22
- 238000003756 stirring Methods 0.000 claims abstract description 20
- 239000006185 dispersion Substances 0.000 claims abstract description 19
- 239000007787 solid Substances 0.000 claims abstract description 17
- 238000001035 drying Methods 0.000 claims abstract description 16
- 238000010438 heat treatment Methods 0.000 claims abstract description 15
- 239000002245 particle Substances 0.000 claims abstract description 14
- 239000000126 substance Substances 0.000 claims abstract description 11
- 239000000203 mixture Substances 0.000 claims abstract description 9
- 239000007788 liquid Substances 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 239000004014 plasticizer Substances 0.000 claims abstract description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 23
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 21
- 239000000463 material Substances 0.000 claims description 15
- 229920001610 polycaprolactone Polymers 0.000 claims description 10
- -1 polybutylene adipate terephthalate Polymers 0.000 claims description 9
- 239000002202 Polyethylene glycol Substances 0.000 claims description 7
- 229920001223 polyethylene glycol Polymers 0.000 claims description 7
- 239000004629 polybutylene adipate terephthalate Substances 0.000 claims description 5
- 239000000835 fiber Substances 0.000 claims description 4
- 238000010907 mechanical stirring Methods 0.000 claims description 4
- 238000010297 mechanical methods and process Methods 0.000 claims description 3
- 239000004632 polycaprolactone Substances 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 238000005728 strengthening Methods 0.000 claims 1
- 239000002131 composite material Substances 0.000 abstract description 13
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 238000012545 processing Methods 0.000 abstract description 3
- 239000002904 solvent Substances 0.000 abstract description 3
- 230000003014 reinforcing effect Effects 0.000 abstract description 2
- 231100000331 toxic Toxicity 0.000 abstract description 2
- 230000002588 toxic effect Effects 0.000 abstract description 2
- UZBRNILSUGWULW-UHFFFAOYSA-N 3,8-dioxabicyclo[8.2.2]tetradeca-1(12),10,13-triene-2,9-dione;hexanedioic acid Chemical compound OC(=O)CCCCC(O)=O.O=C1OCCCCOC(=O)C2=CC=C1C=C2 UZBRNILSUGWULW-UHFFFAOYSA-N 0.000 abstract 1
- 229920001896 polybutyrate Polymers 0.000 description 25
- 229920002472 Starch Polymers 0.000 description 17
- 239000008107 starch Substances 0.000 description 17
- 235000019698 starch Nutrition 0.000 description 17
- 229920005610 lignin Polymers 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 235000011187 glycerol Nutrition 0.000 description 7
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 229920000704 biodegradable plastic Polymers 0.000 description 6
- 239000002121 nanofiber Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 5
- 239000000725 suspension Substances 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000010146 3D printing Methods 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 244000004281 Eucalyptus maculata Species 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000008118 PEG 6000 Substances 0.000 description 2
- 229920002584 Polyethylene Glycol 6000 Polymers 0.000 description 2
- 229920000331 Polyhydroxybutyrate Polymers 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000010096 film blowing Methods 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 238000007909 melt granulation Methods 0.000 description 2
- 239000002159 nanocrystal Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000005014 poly(hydroxyalkanoate) Substances 0.000 description 2
- 239000005015 poly(hydroxybutyrate) Substances 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920000903 polyhydroxyalkanoate Polymers 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 238000004537 pulping Methods 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 239000010902 straw Substances 0.000 description 2
- 241000609240 Ambelania acida Species 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 1
- 235000017491 Bambusa tulda Nutrition 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 description 1
- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 description 1
- 229920002261 Corn starch Polymers 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 241000195493 Cryptophyta Species 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- 240000003183 Manihot esculenta Species 0.000 description 1
- 235000016735 Manihot esculenta subsp esculenta Nutrition 0.000 description 1
- 229920001410 Microfiber Polymers 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 244000082204 Phyllostachys viridis Species 0.000 description 1
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 1
- 229920001131 Pulp (paper) Polymers 0.000 description 1
- 244000061456 Solanum tuberosum Species 0.000 description 1
- 235000002595 Solanum tuberosum Nutrition 0.000 description 1
- 235000021307 Triticum Nutrition 0.000 description 1
- 244000098338 Triticum aestivum Species 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000010905 bagasse Substances 0.000 description 1
- 239000011425 bamboo Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- 235000009120 camo Nutrition 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 235000005607 chanvre indien Nutrition 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000008120 corn starch Substances 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
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- 235000013305 food Nutrition 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000011487 hemp Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229920002961 polybutylene succinate Polymers 0.000 description 1
- 239000004631 polybutylene succinate Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000005070 sampling Methods 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
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2303/00—Characterised by the use of starch, amylose or amylopectin or of their derivatives or degradation products
- C08J2303/02—Starch; Degradation products thereof, e.g. dextrin
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2397/00—Characterised by the use of lignin-containing materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2401/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2401/02—Cellulose; Modified cellulose
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2467/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2467/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2471/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
- C08J2471/02—Polyalkylene oxides
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Biological Depolymerization Polymers (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a method for preparing a degradable plastic master batch containing nano-cellulose, relates to the field of processing and preparation of degradable plastics, and particularly relates to a method for preparing a master batch of a nano-cellulose composite degradable plastic. Stirring and mixing degradable plastic particles and a plasticizer uniformly under the heating condition, adding a certain amount of nano-cellulose dispersion liquid obtained by mechanical or chemical treatment, and then drying the mixture under the room temperature or heating condition to obtain the nano-cellulose-containing master batch with the solid content of 99%. The method has simple operation steps, does not use toxic solvents, is green and environment-friendly, and the obtained master batch has a reinforcing effect and can be added into degradable plastics such as polylactic acid, poly adipic acid-butylene terephthalate and the like so as to reduce the consumption of degradable plastic particles and reduce the production cost.
Description
Technical Field
The invention relates to the field of processing and preparation of degradable plastics, in particular to a preparation method of a master batch of nano-cellulose composite degradable plastics.
Background
The plastic product has the characteristics of light weight, durability, safety, low cost and the like, and is widely applied to the fields of packaging, daily use, buildings and the like. While bringing convenience to people, the disadvantages of plastic products are gradually recognized, most of the currently commonly used petroleum-based polyolefins (polyethylene PE, polypropylene PP, polyvinyl chloride PVC, etc.) cannot be recycled, and the degradation time under natural conditions is very long, so that a large amount of garbage is generated, and a quite serious 'white pollution' is caused.
The biodegradable plastic refers to plastic which is degraded under natural conditions under the action of certain microorganisms in the nature, such as bacteria, fungi and algae, and comprises three major types, namely microbial synthetic biodegradable plastic (such as polyhydroxyalkanoates PHA and polyhydroxybutyrate PHB), chemical synthetic biodegradable plastic (such as polylactic acid PLA, polybutylene adipate-terephthalate PBAT, polybutylene succinate PBS, polycaprolactone PCL and the like) and natural biodegradable plastic (starch, cellulose and the like). The price of the current synthetic biodegradable plastics is generally higher, and even the polylactic acid which is industrially produced is almost twice as high as that of the common petroleum-based polyethylene, so that the application range of the synthetic biodegradable plastics is greatly limited.
The composite processing of natural materials such as starch, lignin and cellulose with relatively low price and degradable plastics such as PLA, PBAT and the like is an effective way for reducing the production cost of the degradable plastics. The PBAT is filled with cassava starch and corn starch, and the comprehensive mechanical property of the material is better improved when the using amount of the starch is 5-10 parts; however, when the amount of the starch exceeds 10 parts, the performance is obviously reduced (Ningping et al, research on the structure and performance of starch-filled modified PBAT, novel chemical materials, 2010.7). The crepe snow is found that when the lignin content is 5 percent in a PBAT/PES polyester matrix, the crepe snow can be uniformly dispersed in a system, and the mechanical property of the material is not obviously reduced; and when the lignin content reaches 15%, the tensile strength is greatly reduced (Zhouyanxue, preparation and performance research of lignin/PBAT/PES composite material, Master thesis of southwest science and technology university, 2016). The 3D printing material is prepared by mixing and melting starch and PLA (polylactic acid) for the Lilingyu, and the mechanical property of the composite material shows an obvious decline trend along with the increase of the proportion of the starch, when the using amount of the starch is 40%, the tensile strength is reduced by 72-74%, the impact strength is reduced by 28%, and the bending strength is reduced by 30-34% (Lilingyu, the preparation and characterization of the polylactic acid/starch composite material applied to 3D printing, chemical technology and development, 2018.7). Previous researches show that starch, lignin and the like can be only added in a small amount in degradable plastics, otherwise, the mechanical property of the composite material is reduced.
The nano-cellulose is ultra-fine fiber with the diameter less than 100nm obtained by treating cellulose by a mechanical or chemical method, and is the smallest physical structural unit of the cellulose. Nanocellulose has many excellent characteristics compared to non-nanocellulose, such as high crystallinity, high purity, high young's modulus, high strength, high hydrophilicity, high transparency, and the like; and because of the characteristics of reproducibility, biodegradability, good biocompatibility, light weight and the like, the nano-cellulose has wide application prospect in the fields of paper making, shoe making, materials, buildings, automobiles, foods, cosmetics, electronic products, medicine and the like. The nano-cellulose is added into the degradable plastic, so that the strength of the material can be improved, the using amount of the degradable plastic is reduced, and the production cost is reduced.
Patent CN 105885367 a discloses a cellulose nanofiber/polylactic acid composite material and a preparation method thereof. According to the method, cellulose nanofiber dispersion liquid is subjected to organic solvent dehydration, toluene solvent replacement of acetone, acetic anhydride and pyridine addition reaction and the like in sequence to improve the dispersibility of the cellulose nanofiber dispersion liquid, then the cellulose nanofiber/polylactic acid composite material is obtained by dispersing the cellulose nanofiber dispersion liquid in solvents such as dichloromethane or chloroform and the like, adding polylactic acid, dissolving to obtain a mixed solution of nanocellulose and polylactic acid, and drying. The composite material can be directly used after being crushed, or can be used as reinforced master batch to be further compounded with polylactic acid through a melt extrusion method, an injection molding method and the like, so as to prepare the cellulose nanofiber reinforced polylactic acid composite material with lower fiber content, higher mechanical strength and higher crystallization speed. The method needs to use various organic solvents such as toluene, acetone, acetic anhydride, pyridine, chloroform, dichloromethane and the like, causes pollution to the environment and is not beneficial to the health of operators.
Patent CN104672825A discloses a polybutylene adipate-terephthalate/nanocellulose degradable composite material and a preparation method thereof. Respectively dispersing nano-cellulose and PBAT in chloroform to obtain a nano-cellulose suspension A and a PBAT solution B, then mixing A and B to obtain C, mixing with ethanol, purifying, and drying in vacuum to obtain the PBAT/nano-cellulose degradable composite material. The method also uses a large amount of organic solvent, and is not environment-friendly.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a method for preparing degradable plastic master batch containing nano cellulose.
The method comprises the following specific steps:
(1) the nano-cellulose dispersion is prepared by treating fiber raw materials by a chemical method or a mechanical method.
(2) And (3) uniformly mixing the degradable plastic particles and a certain amount of plasticizer under mechanical stirring, and keeping the mixture at 65-100 ℃ for 10-50 min.
(3) And (3) adding a certain amount of the nano-cellulose obtained in the step (1) into the mixed system in the step (2), mechanically stirring uniformly, and keeping for 30-120 min.
(4) And (4) drying the mixture obtained in the step (3) at room temperature or under a heating condition, and intermittently or continuously stirring the mixture during the drying process to uniformly dry the upper part and the lower part of the material to obtain the master batch containing the nano-cellulose with the solid content of 99 percent.
The fiber raw material is wood pulp, cotton pulp, hemp pulp, bamboo pulp, bagasse, wheat straw, rice straw, potato stalks or corncobs and the like, and can contain lignin or not contain lignin.
The chemical method can adopt sulfuric acid, hydrochloric acid or mixed acid thereof, and the mechanical method adopts a colloid mill, a homogenizer, a high-pressure micro-jet machine and the like.
The nano-cellulose comprises nano-cellulose and microfibrillated cellulose, the solid content of the cellulose nano-crystal dispersion is about 1%, and the diameter of the cellulose nano-crystal dispersion is 5-100 nm; the solid content of the microfibrillated cellulose dispersion can reach about 5 percent, and the diameter is 10-500 nm.
The degradable plastic particles comprise polylactic acid, polybutylene adipate terephthalate and the like.
The plasticizer comprises polyethylene glycol, ethylene glycol, glycerin and the like, and the amount of the plasticizer is 1-50% of the mass of the degradable plastic.
The mechanical stirring device may be a high speed mixer (self heating or heating) or a high speed stirrer.
The mass of the nano-cellulose is 1-30% of that of the degradable plastic.
The heating temperature of the mixture is 30-55 ℃.
Compared with the prior art, the method has the advantages of simple operation steps, no use of toxic solvent, environmental protection and obvious cost advantage, and the obtained degradable plastic master batch containing the nano-cellulose can be added into degradable plastics and processed by adopting melt granulation, extrusion, blow molding and the like to obtain materials such as films, plates and the like. Because the nano cellulose in the master batch can have the reinforcing effect, the dosage of the degradable plastic particles with high price can be reduced, thereby reducing the cost of the product.
Detailed Description
The above and further features and advantages of the invention are explained in more detail below with reference to examples and test data, without being limited thereto.
Example 1:
the lignin-free corncobs were ground with a grinder to give a nanocellulose dispersion (MFC) with a solid content of 3.9% and a nanocellulose diameter of about 300 nm. Weighing a certain amount of polylactic acid particles in a container, heating in a water bath, setting the temperature of a water bath kettle to be 98 ℃, and stirring by using a mechanical stirrer, wherein the rotating speed of the stirrer is 30 rpm; glycerol is added into the polylactic acid particle system, and the mass ratio of the glycerol to the polylactic acid is 5: 100. After 10min, adding the nano-cellulose dispersion liquid with the mass ratio of 1: 100 to the polylactic acid, and continuing stirring for 45 min. Placing the mixed system of the nano-cellulose, the polylactic acid and the glycerol into an oven, drying for 3h at 50 ℃, stirring for 1 time every 1h during the drying so as to uniformly heat and dry the materials up and down to obtain the nano-cellulose-containing polylactic acid master batch with the solid content of 98%. The master batch can be mixed with polylactic acid, starch and the like, and then is subjected to melt granulation, extrusion and film blowing, when the dosage of the granules is 2%, the dosage of the polylactic acid is reduced by 6%, the dosage of the starch is increased by 4%, and the strength of the film is basically kept unchanged.
Example 2:
pulping bleached chemical eucalyptus pulp, and grinding with a grinder to obtain nanometer cellulose dispersion (MFC) with solid content of 1.7% and diameter of 100 nm. Dissolving polyethylene glycol PEG-6000 in water to obtain 40% of solid content; weighing a certain amount of polylactic acid particles, adding the polylactic acid particles into a polyethylene glycol solution, heating the polyethylene glycol solution and the polylactic acid solution in a water bath at 85 ℃, and stirring by using a mechanical stirrer at the rotating speed of 30 rpm. After 15min, adding the nano-cellulose dispersion liquid with the mass ratio of the nano-cellulose dispersion liquid to the polylactic acid being 15: 100, and continuing stirring for 70 min. And (3) drying the mixed system of the nano-cellulose, the polylactic acid and the polyethylene glycol at room temperature for 30h, and slowly and continuously stirring the mixed system to uniformly dry the mixed system from top to bottom to obtain the nano-cellulose-containing polylactic acid master batch with the solid content of 89%. The master batch, polylactic acid, additives and the like are mixed uniformly by a double-screw extruder, a paper sample is molded on a flat vulcanizing machine, a sample strip is cut on a universal sampling machine, when the master batch is used in an amount of 3%, the using amount of the polylactic acid can be reduced by 12%, and the strength of the sample strip is basically kept unchanged.
Example 3:
the lignin-containing corncobs were ground using a grinder to obtain a lignin-containing nanocellulose dispersion (LMFC) having a solid content of 4.3% and a nanocellulose diameter of about 390 nm. Weighing a certain amount of glycerol in a container, adding PBAT particles, heating in a water bath, setting the temperature of a water bath kettle at 90 ℃, and stirring by using a mechanical stirrer, wherein the rotating speed of the stirrer is 50rpm, and the mass ratio of the glycerol to the PBAT is 20: 100. After 10min, adding nano-cellulose dispersion with the mass ratio of 10: 100 to PBAT, and continuing stirring for 80 min. And (3) putting the mixed system of the nano-cellulose, the PBAT and the glycerol into an oven, drying for 5h at the temperature of 40 ℃, stirring for 1 time every 1h during the drying so as to uniformly heat and dry the materials up and down to obtain the PBAT master batch containing the nano-cellulose and the solid content of 85%. The master batch can be mixed with PBAT, starch, lignin and the like, melted and granulated, and then extruded and blown into a film, when the use amount of the master batch is 10 percent, the use amount of PBAT is reduced by 17 percent, the use amount of lignin is increased by 7 percent, and the strength of the material is basically kept unchanged.
Example 4:
treating bleached chemical softwood pulp by using a sulfuric acid solution with the mass concentration of 64%, wherein the mass-volume ratio of the pulp to the sulfuric acid is 1: 8.75, and preserving heat for 1.5 hours at the temperature of 45 ℃ to obtain a milky white suspension; the suspension is centrifuged for a plurality of times to remove acid, and the lower layer of nano-cellulose suspension is collected, wherein the solid content of the suspension is 1 percent, and the diameter of the nano-cellulose is about 20 nm. Weighing a certain amount of ethylene glycol in a container, adding PBAT particles, wherein the mass ratio of the ethylene glycol to the PBAT is 15: 100, heating in a water bath, setting the temperature of a water bath kettle at 90 ℃, and stirring by using a mechanical stirrer at the rotating speed of 70 rpm. After 20min, adding nano-cellulose dispersion with the mass ratio of 10: 100 to PBAT, and continuing stirring for 150 min. And (3) putting the mixed system of the nano-cellulose, the PBAT and the ethylene glycol into an oven, drying for 15h at 45 ℃, stirring for 1 time every 1h during the drying so as to uniformly heat and dry the materials up and down to obtain the PBAT master batch containing the nano-cellulose and having the solid content of 92%. Blending, extruding and film blowing the master batch with PBAT, PBS, starch and the like to prepare a biodegradable bag; when the adding amount of the PBAT master batch is 10%, the total using amount of PBAT and PBS can be reduced by 16%, and the tensile strength of the bag can be kept unchanged.
Example 5
Pulping bleached chemical eucalyptus pulp, and grinding with a grinder to obtain nanometer cellulose dispersion (MFC) with solid content of 1.7% and diameter of 100 nm. Weighing a certain amount of ethylene glycol and PEG-6000 (with solid content of 50%) in a container, adding PCL particles, wherein the mass ratio of the total amount of the ethylene glycol and the polyethylene glycol to the PBAT is 12: 100, heating in a water bath at 50 ℃, and stirring by using a mechanical stirrer at the rotating speed of 60 rpm. After 20min, adding the nano-cellulose dispersion with the mass ratio of 5: 100 to PCL, and continuing stirring for 100 min. And (3) drying the mixed system containing the nano-cellulose at room temperature for 27h, and stirring for 1 time every 1h to uniformly heat and dry the materials up and down to obtain the PCL master batch containing the nano-cellulose with the solid content of 90%. And (3) further drying the master batch, PCL, starch and the like, mechanically blending in a high-speed stirrer, and then granulating by using a double-screw extruder and extruding and molding by using a single-screw extruder to obtain a strip sample. When the addition amount of the PCL master batch is 5%, the consumption of the PCL can be reduced by 8%, the consumption of the starch can be increased by 3%, and the strength of the sample can be kept unchanged.
Claims (8)
1. A method for preparing degradable plastic master batch containing nano cellulose is characterized by comprising the following specific steps:
(1) treating fiber raw materials by a chemical method or a mechanical method to prepare nano cellulose dispersion liquid;
(2) uniformly mixing degradable plastic particles and a certain amount of plasticizer under mechanical stirring, and keeping the mixture at 65-100 ℃ for 10-50 min;
(3) adding a certain amount of the nano-cellulose obtained in the step (1) into the mixed system obtained in the step (2), mechanically stirring uniformly, and keeping for 30-120 min;
(4) and (3) drying the mixture in the step (3) at room temperature or under a heating condition, and intermittently or continuously stirring the mixture during the drying process to uniformly dry the upper part and the lower part of the material to obtain the master batch containing the nano-cellulose with the solid content of up to 99 percent.
2. The method for preparing the degradable plastic master batch containing the nano-cellulose according to claim 1, is characterized in that: the degradable plastic particles comprise polylactic acid, polybutylene adipate terephthalate and polycaprolactone.
3. The method for preparing the degradable plastic master batch containing the nano-cellulose according to claim 1, is characterized in that: the plasticizer comprises polyethylene glycol, ethylene glycol and glycerol.
4. The method for preparing the degradable plastic master batch containing the nano-cellulose according to claim 1, is characterized in that: the dosage of the plasticizer is 1-50% of the mass of the degradable plastic.
5. The method for preparing the degradable plastic master batch containing the nano-cellulose according to claim 1, is characterized in that: the mechanical stirring device is a self-heating or heating high-speed mixer or a high-speed stirrer.
6. The method for preparing the degradable plastic master batch containing the nano-cellulose according to claim 1, is characterized in that: the mass of the nano-cellulose is 1-30% of that of the degradable plastic.
7. The method for preparing the degradable plastic master batch containing the nano-cellulose according to claim 1, is characterized in that: the heating temperature of the mixture is 30-55 ℃.
8. The method for preparing the degradable plastic master batch containing the nano-cellulose according to claim 1, is characterized in that: the degradable plastic master batch containing the nano-cellulose obtained by the method is uniformly mixed with polylactic acid, polybutylene adipate terephthalate and polycaprolactone degradable plastic in a molten state, and has the effects of strengthening, toughening and reducing cost.
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| CN113512280A (en) * | 2021-05-19 | 2021-10-19 | 青岛科技大学 | A kind of preparation method of nanocellulose-based plastic film |
| CN113278272A (en) * | 2021-06-04 | 2021-08-20 | 四川宽窄纸品有限责任公司 | Plant cellulose-based full-biodegradable material and preparation method thereof |
| CN113416324A (en) * | 2021-07-09 | 2021-09-21 | 苏州优矿塑新材料股份有限公司 | Biodegradable talcum powder master batch and preparation process thereof |
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