CN116041798A - Fiber reinforced thermoplastic starch plate and preparation method thereof - Google Patents
Fiber reinforced thermoplastic starch plate and preparation method thereof Download PDFInfo
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- CN116041798A CN116041798A CN202211665963.4A CN202211665963A CN116041798A CN 116041798 A CN116041798 A CN 116041798A CN 202211665963 A CN202211665963 A CN 202211665963A CN 116041798 A CN116041798 A CN 116041798A
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- 239000000835 fiber Substances 0.000 title claims abstract description 31
- 229920008262 Thermoplastic starch Polymers 0.000 title claims abstract description 29
- 239000004628 starch-based polymer Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims description 14
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 32
- 229920002472 Starch Polymers 0.000 claims abstract description 25
- 235000019698 starch Nutrition 0.000 claims abstract description 25
- 239000008107 starch Substances 0.000 claims abstract description 25
- 239000000463 material Substances 0.000 claims abstract description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229920000049 Carbon (fiber) Polymers 0.000 claims abstract description 16
- 229920003043 Cellulose fiber Polymers 0.000 claims abstract description 16
- 239000004917 carbon fiber Substances 0.000 claims abstract description 16
- -1 graphene modified carbon Chemical class 0.000 claims abstract description 16
- 239000004014 plasticizer Substances 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims abstract description 5
- 238000001704 evaporation Methods 0.000 claims description 14
- PEDCQBHIVMGVHV-UHFFFAOYSA-N glycerol group Chemical group OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 230000007935 neutral effect Effects 0.000 claims description 6
- 238000000967 suction filtration Methods 0.000 claims description 6
- 238000009210 therapy by ultrasound Methods 0.000 claims description 6
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 6
- 239000012498 ultrapure water Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 229920000856 Amylose Polymers 0.000 claims description 4
- 239000004809 Teflon Substances 0.000 claims description 4
- 229920006362 Teflon® Polymers 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- 238000012545 processing Methods 0.000 claims description 4
- 229920001685 Amylomaize Polymers 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 229920002678 cellulose Polymers 0.000 claims description 3
- 239000001913 cellulose Substances 0.000 claims description 3
- PRAHCKGOTFKWKD-UHFFFAOYSA-N dimethyl(propyl)azanium;chloride Chemical compound Cl.CCCN(C)C PRAHCKGOTFKWKD-UHFFFAOYSA-N 0.000 claims description 3
- 238000002844 melting Methods 0.000 claims description 3
- 230000008018 melting Effects 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 3
- 238000007493 shaping process Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- 235000017166 Bambusa arundinacea Nutrition 0.000 claims description 2
- 235000017491 Bambusa tulda Nutrition 0.000 claims description 2
- 244000025254 Cannabis sativa Species 0.000 claims description 2
- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 claims description 2
- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 claims description 2
- 229920002261 Corn starch Polymers 0.000 claims description 2
- 229920000742 Cotton Polymers 0.000 claims description 2
- 244000082204 Phyllostachys viridis Species 0.000 claims description 2
- 235000015334 Phyllostachys viridis Nutrition 0.000 claims description 2
- 229920000297 Rayon Polymers 0.000 claims description 2
- 240000004922 Vigna radiata Species 0.000 claims description 2
- 235000010721 Vigna radiata var radiata Nutrition 0.000 claims description 2
- 235000011469 Vigna radiata var sublobata Nutrition 0.000 claims description 2
- 239000011425 bamboo Substances 0.000 claims description 2
- 235000009120 camo Nutrition 0.000 claims description 2
- 235000005607 chanvre indien Nutrition 0.000 claims description 2
- 239000008120 corn starch Substances 0.000 claims description 2
- 239000011487 hemp Substances 0.000 claims description 2
- 229920001592 potato starch Polymers 0.000 claims description 2
- 238000012216 screening Methods 0.000 claims description 2
- 238000007738 vacuum evaporation Methods 0.000 claims 1
- 239000003063 flame retardant Substances 0.000 abstract description 13
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 abstract description 11
- 230000007613 environmental effect Effects 0.000 abstract description 4
- 230000002940 repellent Effects 0.000 abstract 1
- 239000005871 repellent Substances 0.000 abstract 1
- 239000002994 raw material Substances 0.000 description 8
- 238000001125 extrusion Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229920006238 degradable plastic Polymers 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 229920001131 Pulp (paper) Polymers 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012768 molten material Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
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
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D7/00—Producing flat articles, e.g. films or sheets
- B29D7/01—Films or sheets
-
- 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
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/045—Reinforcing macromolecular compounds with loose or coherent fibrous material with vegetable or animal fibrous material
-
- 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
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/06—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous 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
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/06—Coating with compositions not containing macromolecular substances
-
- 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
- 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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/05—Alcohols; Metal alcoholates
- C08K5/053—Polyhydroxylic alcohols
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/06—Elements
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/02—Ingredients treated with inorganic substances
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
- Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to a fiber reinforced thermoplastic starch material, which comprises starch, a plasticizer, natural cellulose fibers and graphene modified carbon fibers, wherein a high-speed mixer is used, the natural cellulose fibers and the plasticizer are mixed, the high-direct-connection starch and the graphene modified carbon fibers are mixed, a double-screw machine is used for directly plasticizing and extruding the mixture, and the mixture is shaped by a mould, so that the graphene modified carbon fibers are added, the mechanical property of a plate is enhanced, the flame retardant property of the plate is improved, a graphene transparent layer is evaporated on the surface of the plate, the water repellent capability is enhanced, the flame retardant property is further enhanced, and the fiber reinforced thermoplastic starch material has the advantages of scientific and reasonable components, reproducibility, biodegradability, no pollution, environmental friendliness, wide application and the like.
Description
Technical Field
The invention relates to the technical field of natural environment-friendly degradable materials, in particular to a fiber-reinforced thermoplastic starch plate and a preparation method thereof.
Background
Compared with petrochemical raw materials, the starch has the characteristics of low cost, regeneration, biodegradability, small pollution and no toxicity in the production process. The development and utilization of starch in the field of bio-based degradable environment-friendly materials are attracting attention in many countries in the world, and the existing degradable plastics prepared by using starch-based and derivatives thereof account for more than 60% of the whole degradable plastics.
The existing thermoplastic starch material is mainly prepared by adopting two methods of chemical modification of starch and blending of adding water-resistant resin, and has the defects of pollution in the preparation process, incapability of realizing complete degradation, poor environmental protection effect and the like.
In the prior art, the research on thermoplastic starch materials focuses on adding natural fibers and chemical flame retardants to enhance mechanical properties and flame retardant properties, but natural fiber components are complex, if the natural fiber components are not processed and have poor compatibility with starch, the chemical flame retardant materials have poor safety, in the preparation means of the prior art, the starch is easy to yellow in the processing process, the transparency of the materials is seriously affected by the addition of cellulose and other additives, the environment is seriously polluted by the addition of the chemical flame retardants, and the prepared materials have poor moisture absorption and seriously affect the application properties of the materials.
In order to solve the problems, how to provide a thermoplastic starch board which has the advantages of easily degradable natural components, pollution-free preparation process, good mechanical property, flame retardant property and moisture resistance is a problem to be solved by the technicians in the field.
Disclosure of Invention
In view of the above, the invention provides a fiber reinforced thermoplastic starch board which is renewable, biodegradable, pollution-free, excellent in mechanical property, high in flame retardant level and good in moisture resistance.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the fiber reinforced thermoplastic starch plate comprises the following components in parts by weight: 110-120 parts of starch, 30-50 parts of plasticizer, 2-20 parts of natural cellulose fiber and 3-5 parts of graphene modified carbon fiber.
Preferably, the starch is high-amylose starch, in particular at least one of corn starch, potato starch, mung bean starch and pea starch with high amylose content separated by components, wherein the amylose content is 40-90%.
Preferably, the plasticizer is glycerol or a mixture of glycerol and water.
Preferably, the natural cellulose fiber is viscose fiber pulp of wood pulp, cotton pulp, hemp pulp or bamboo pulp with the cellulose content of 98-100 percent, and is obtained by crushing by a rotary screening crusher with the aperture of 2 mm.
Preferably, the graphene modified carbon fiber is prepared by the following means:
1) Placing the carbon fiber in acetone, refluxing for 70 hours, filtering, drying in a vacuum drying oven at 60 ℃, then carrying out ultrasonic treatment in a concentrated nitric acid medium at 60 ℃ for 1.5 hours, washing with pure water after filtering, carrying out suction filtration to be neutral, and drying;
2) Dispersing graphene in polydialkenyl propyl dimethyl ammonium chloride solution with the mass fraction of 0.5wt%, carrying out ultrasonic treatment for 0.5h, and then carrying out suction filtration, washing to be neutral and drying;
3) Uniformly dispersing the carbon fiber treated in the step 1) and the graphene treated in the step 2) into ultrapure water, wherein the mass ratio of the carbon fiber to the ultrapure water is as follows: and (3) continuously stirring graphene=50:1 for 12-24 hours to obtain the graphene modified carbon fiber.
The invention also provides a preparation method of the fiber reinforced thermoplastic starch board, which comprises the following steps:
(1) Weighing starch, plasticizer, natural cellulose fiber and graphene modified carbon fiber according to the parts by weight for standby;
(2) Placing the natural cellulose fibers and the plasticizer weighed in the step (1) into a high-speed mixer for fully mixing, then sequentially adding the graphene modified carbon fibers and the starch, and continuously mixing for 15-20min to obtain a mixed material;
(3) And (3) adding the mixed material prepared in the step (2) into a hopper of a double-screw extruder, and extruding the mixed material to a die for shaping through high-temperature melting, blending, plasticizing and extruding to obtain the fiber reinforced thermoplastic starch plate.
Further, the method also comprises the step (4) of evaporating the graphene layer on the surface of the fiber reinforced thermoplastic starch plate, wherein the evaporating temperature is 100-120 ℃, non-vacuum evaporating is adopted, the evaporating time is controlled to be 0.5-3h, and then the evaporating layer is dried at 80-100 ℃ for 1-3 h.
Preferably, the rotating speed of the high-speed mixer in the step (2) is 500-1000r/min, and the mixing time of the natural cellulose fiber and the plasticizer is 5-10min.
Preferably, the processing temperature of the twin-screw extruder in the step (3) is 190-235 ℃, the rotating speed of the feeding machine is 13-16 Hz, and the rotating speed of the host machine is 9-12 Hz.
Preferably, both the screw and the die surface of the twin screw extruder are coated with a teflon coating.
In summary, compared with the prior art, the technical scheme of the invention has the following technical effects:
a) The raw materials selected by the invention are natural and environment-friendly, and the invention is degradable and has no pollution to the environment;
b) The natural cellulose fiber and the high amylose starch adopted by the invention have the same monomer glucose, are easy to plasticize by the same plasticizer, are easy to be compatible when being blended, so that the cellulose fiber is uniformly dispersed, and the transparency of the thermoplastic starch is maintained;
c) According to the invention, a small amount of graphene-treated carbon fibers are added into the plate, so that the mechanical property of the plate is enhanced, the flame retardant property and the heat conducting property of the plate are improved, the transparency of the plate is not affected, and the flame retardant component is safe and nontoxic;
d) According to the invention, the graphene layer is evaporated on the surface of the plate, and the graphene is a hydrophobic material, so that the flame retardant property of the plate and the moisture resistance of the plate are further enhanced;
e) According to the invention, the Teflon coating is coated in the double-screw extrusion device, so that the adhesion of the molten material is reduced, the waste is avoided, more importantly, the surface of the processed plate is smooth, and the overall performance is improved;
f) In the preparation process, the mixture is subjected to primary plasticizing extrusion molding by a double-screw extruder, so that the problem of starch yellowing in the secondary plasticizing process in the extrusion granulating process is avoided, and the transparency of the product plate is improved;
g) The preparation process is simple and convenient, is easy for large-scale production, has the advantages of environmental protection and no pollution in the production process, easily available and renewable raw materials, and the prepared plate is biodegradable, accords with the environmental protection concept of sustainable development, and has higher production application value.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The preparation of the modified carbon fiber adopts the following technical scheme:
1) Placing the carbon fiber in acetone, refluxing for 70 hours, filtering, drying in a vacuum drying oven at 60 ℃, then carrying out ultrasonic treatment in a concentrated nitric acid medium at 60 ℃ for 1.5 hours, washing with pure water after filtering, carrying out suction filtration to be neutral, and drying;
2) Dispersing graphene in polydialkenyl propyl dimethyl ammonium chloride solution with the mass fraction of 0.5wt%, carrying out ultrasonic treatment for 0.5h, and then carrying out suction filtration, washing to be neutral and drying;
3) Uniformly dispersing the carbon fiber treated in the step 1) and the graphene treated in the step 2) into ultrapure water, wherein the mass ratio of the carbon fiber to the ultrapure water is as follows: and (3) continuously stirring graphene=50:1 for 12-24 hours to obtain the graphene modified carbon fiber.
Example 2
The preparation method of the fiber reinforced thermoplastic starch plate comprises the following steps:
(1) Weighing 110-120 parts of starch, 30-50 parts of plasticizer, 2-20 parts of natural cellulose fiber and 3-5 parts of graphene modified carbon fiber according to parts by weight for standby;
(2) Placing the natural cellulose fibers and the plasticizer weighed in the step (1) into a high-speed mixer with the speed of 500-1000r/min for fully mixing for 5-10min, then adding the graphene modified carbon fibers and the starch in sequence, and continuously mixing for 15-20min to obtain a mixed material;
(3) And (3) adding the mixed material prepared in the step (2) into a hopper of a double-screw extruder, extruding the mixed material to a die for shaping through high-temperature melting, blending, plasticizing and extruding, wherein the processing temperature of the double-screw extruder is 190-235 ℃, the rotating speed of a feeding machine is 13-16 Hz, the rotating speed of a host machine is 9-12 Hz, and discharging to obtain the fiber reinforced thermoplastic starch plate.
In order to further optimize the technical scheme, the method further comprises the step (4) of evaporating the graphene layer on the surface of the fiber reinforced thermoplastic starch plate, wherein the evaporating temperature is 100-120 ℃, non-vacuum evaporating is adopted, the evaporating time is controlled to be 0.5-3h, and then the evaporating layer is dried at 80-100 ℃ for 1-3 h.
In order to further optimize the technical scheme, the screw and the die surface of the double-screw extruder are coated with a Teflon coating.
The technical scheme of the present invention will be described below using the specific raw material data of examples 3 to 7, and the preparation of the sheet material is performed according to the preparation scheme of example 2 using the modified carbon fiber raw material prepared in example 1, and the specific raw material components are as follows:
the sheets prepared in examples 3-7 above were subjected to performance testing, and the specific test data are shown in the following table:
note that: the vertical burning is mainly used for measuring the incombustibility of the plastic under the condition that the plastic plate is directly burnt by a specified fire source, and is used for judging the fire resistance grade of the refractory material, wherein the fire resistance grade is gradually increased from V-2 and V-1 to V-0. Typical thicknesses of the samples are 0.8mm, 1.6mm and 3.2mm, and the thinner the sample is, the higher the flame retardant property requirement of the sample is.
The test results show that the fiber reinforced starch board prepared by the invention has good mechanical property and good flame retardant property, and the raw materials are mainly prepared from natural raw materials, so that the fiber reinforced starch board has good biodegradability, is pollution-free to the environment and has high application value.
In the present specification, each embodiment is described in a progressive manner, and each embodiment is mainly described in a different point from other embodiments, and identical and similar parts between the embodiments are all enough to refer to each other. For the device disclosed in the embodiment, since it corresponds to the method disclosed in the embodiment, the description is relatively simple, and the relevant points refer to the description of the method section.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. The fiber reinforced thermoplastic starch plate is characterized by comprising the following components in parts by weight: 110-120 parts of starch, 30-50 parts of plasticizer, 2-20 parts of natural cellulose fiber and 3-5 parts of graphene modified carbon fiber.
2. Fiber reinforced thermoplastic starch board according to claim 1, wherein the starch is a high amylose starch, in particular at least one of corn starch, potato starch, mung bean starch, pea starch with a high amylose content separated by components, wherein the amylose content is 40-90%.
3. A fibre reinforced thermoplastic starch board according to claim 1, wherein the plasticizer is glycerol or a mixture of glycerol and water.
4. The fiber reinforced thermoplastic starch board according to claim 1, wherein the natural cellulose fiber is viscose fiber pulp of pulp, cotton pulp, hemp pulp or bamboo pulp with cellulose content of 98% -100%, and is obtained by crushing by a rotary screening crusher with aperture of 2 mm.
5. The fiber reinforced thermoplastic starch board according to claim 1, wherein the graphene modified carbon fiber is prepared by the following means:
1) Placing the carbon fiber in acetone, refluxing for 70 hours, filtering, drying in a vacuum drying oven at 60 ℃, then carrying out ultrasonic treatment in a concentrated nitric acid medium at 60 ℃ for 1.5 hours, washing with pure water after filtering, carrying out suction filtration to be neutral, and drying;
2) Dispersing graphene in polydialkenyl propyl dimethyl ammonium chloride solution with the mass fraction of 0.5wt%, carrying out ultrasonic treatment for 0.5h, and then carrying out suction filtration, washing to be neutral and drying;
3) Uniformly dispersing the carbon fiber treated in the step 1) and the graphene treated in the step 2) into ultrapure water, wherein the mass ratio of the carbon fiber to the ultrapure water is as follows: and (3) continuously stirring graphene=50:1 for 12-24 hours to obtain the graphene modified carbon fiber.
6. The preparation method of the fiber reinforced thermoplastic starch plate is characterized by comprising the following steps of:
(1) Weighing starch, plasticizer, natural cellulose fiber and graphene modified carbon fiber according to the parts by weight for standby;
(2) Placing the natural cellulose fibers and the plasticizer weighed in the step (1) into a high-speed mixer for fully mixing, then sequentially adding the graphene modified carbon fibers and the starch, and continuously mixing for 15-20min to obtain a mixed material;
(3) And (3) adding the mixed material prepared in the step (2) into a hopper of a double-screw extruder, and extruding the mixed material to a die for shaping through high-temperature melting, blending, plasticizing and extruding to obtain the fiber reinforced thermoplastic starch plate.
7. The method for preparing a fiber reinforced thermoplastic starch plate according to claim 7, further comprising the step of (4) evaporating a graphene layer on the surface of the fiber reinforced thermoplastic starch plate, wherein the evaporating temperature is 100-120 ℃, non-vacuum evaporation is adopted, the evaporating time is controlled to be 0.5-3h, and then the evaporating layer is dried at 80-100 ℃ for 1-3 h.
8. The method for preparing a fiber reinforced thermoplastic starch board according to claim 7, wherein the high-speed mixer in the step (2) has a rotation speed of 500-1000r/min and mixing time of 5-10min for the natural cellulose fiber and the plasticizer.
9. The method for preparing a fiber reinforced thermoplastic starch board according to claim 7, wherein the processing temperature of the twin-screw extruder in the step (3) is 190-235 ℃, the rotating speed of the feeder is 13-16 Hz, and the rotating speed of the host is 9-12 Hz.
10. The method of producing a fiber reinforced thermoplastic starch sheet material as defined in claim 7 wherein both the screw and die surfaces of the twin screw extruder are coated with a teflon coating.
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