CN112175292A - Wood fiber degradable plastic master batch and preparation method thereof - Google Patents

Wood fiber degradable plastic master batch and preparation method thereof Download PDF

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CN112175292A
CN112175292A CN202011108632.1A CN202011108632A CN112175292A CN 112175292 A CN112175292 A CN 112175292A CN 202011108632 A CN202011108632 A CN 202011108632A CN 112175292 A CN112175292 A CN 112175292A
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rice hull
master batch
hull powder
wood fiber
starch
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陈庆
曾军堂
司文彬
白涛
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Chengdu New Keli Chemical Science Co Ltd
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Abstract

The invention relates to the field of bioplastic, and discloses a wood fiber degradable plastic master batch and a preparation method thereof. The preparation method comprises the following preparation processes: (1) uniformly mixing starch and stearic acid, and micronizing to obtain micronized starch; (2) uniformly mixing rice hull powder with succinic anhydride, dimethylaminopyridine and stearic acid, and refining and modifying to obtain modified rice hull powder; (3) adding the nano inorganic substance and the micronized starch into the melted monoglyceride and the paraffin, and stirring the mixture at a high speed to form slurry; adding the modified rice hull powder into a stirring kettle, and performing microwave heat treatment while stirring to enable the modified rice hull powder to expand; then adding the slurry to enable the slurry to permeate and adhere to the rice hull powder to obtain a composite material; (4) and (3) mixing and dispersing the composite material obtained in the step (3) with a coupling agent, compatible resin and matrix resin, extruding and granulating to obtain a master batch product, comprehensively solving the heat resistance problem, the processing problem and the compatibility problem of rice hull powder, wherein the master batch is used for processing an injection molding product, and the obtained product is compact and smooth.

Description

Wood fiber degradable plastic master batch and preparation method thereof
Technical Field
The invention relates to the field of bioplastic, and particularly relates to a wood fiber degradable plastic master batch and a preparation method thereof.
Background
Because resources such as petroleum, coal and the like used as initial raw materials of organic chemical industry are limited in reserves, various plastics produced for the resources cause serious pollution. The replacement of traditional plastic articles with biomass materials has become a hotspot. The wood fiber is used as renewable biomass resource, has rich reserves, low cost and sustainable supply, and becomes a preferable raw material for biomass degradation plastic. And the wood fiber belongs to solid waste, so that waste can be changed into valuable.
The wood fiber plastic products have been widely used in the industries of automobile industry, decoration, building materials and the like due to the texture, environmental protection, low cost and the like of wood. With the continuous research and modification of wood fiber, wood fiber plastic products are used in the fields of daily necessities such as cups, bowls, knives and forks, various packaging and the like. With the advance of finish machining of wood fiber plastic products, the cost is low, the added value is greatly improved, and great benefits are brought to environment-friendly enterprises engaged in degrading plastics, so that the significance of deeply researching and developing wood fiber plastic products is great. The wood fiber is derived from various kinds, such as crushed wood, bamboo powder, rice hull, straw, coconut shell powder, peanut shell powder, bagasse powder and the like. The wood fiber biomass mainly comprises 3 natural polymers of cellulose, hemicellulose and lignin. Since wood fibers contain a large amount of hydroxyl groups, the use in degradable plastics is subject to problems of poor thermoplastic processability, poor flowability, and poor compatibility with polymers.
The Chinese patent CN00125375.1 discloses a composite material of thermoplastic plastic and wood (bamboo) powder and its application, wherein the composite material contains 90-40 wt% of thermoplastic plastic, 10-60 wt% of wood (bamboo) powder, the granularity of the wood (bamboo) powder is 60-120, the thermoplastic plastic can be rigid composite foaming non-foaming polyvinyl chloride (PVC), composite foaming or non-foaming Polystyrene (PS), or acrylonitrile-butadiene-styrene copolymer (ABS), and the composite material of thermoplastic plastic and wood (bamboo) powder and the extruded or co-extruded section of thermoplastic plastic can be used, the content of wood (bamboo) powder in the composite material can be used to control the performance of the composite material, such as improving rigidity, reducing the influence of temperature on material deformation, reducing thermal expansion coefficient, etc.
Chinese patent CN201611096059.0 discloses a preparation method of bio-based plastic, which comprises the following steps: (1) crushing the mulberry branches by a crusher, and drying; (2) placing wood powder into a ball milling tank, adding zirconia grinding balls, and ball milling for later use; (3) putting the pretreated wood flour into a three-neck flask, swelling and dissolving the wood flour in an oil bath kettle until the wood flour is partially dissolved, and adding succinic anhydride and a catalyst into the three-neck flask together; (4) after the esterification modification is finished, acetone is used for separating out, standing and suction filtration are carried out, then acetone is used for repeatedly cleaning until the filtrate is colorless and transparent, and the filtrate is placed in a drying oven for further drying after air drying, thus finishing the preparation. According to the preparation method, DMAP is used as a catalyst, SAA is used as an esterification reagent, and the mulberry twig wood powder subjected to ball milling pretreatment is modified, so that the injection molding grade bio-based plastic with good mechanical property is successfully prepared, and the efficient utilization of all components of the wood fiber raw material is realized.
The Chinese patent CN201910932360.8 discloses a cross-linking reaction extruded wood-plastic section and a preparation method thereof, wherein the formula comprises the following raw materials in parts by weight: 30-50 parts of high-density polyethylene, 50-70 parts of wood powder, 30-50 parts of alkaline solution, 30-50 parts of acidic solution, 4-8 parts of coupling agent, 3-6 parts of cross-linking agent, 2-3 parts of calcium carbonate and 1-3 parts of lubricating agent. The wood flour is subjected to alkaline treatment and acidic treatment, so that esterification reaction is carried out on the wood flour, ester is produced from hydrophilic groups, esterification reaction is carried out by using various acids, the wood flour is modified by adding a coupling agent, the polarity of the modified wood flour is changed, the compatibility between the wood flour and resin is enhanced, the wood flour is uniformly dispersed in the resin, and carboxyl groups of the esterification reaction of the modified wood flour are similar to cross-linking agent groups, so that good compatibility between the resin and the wood flour and good fluidity during material processing are ensured, and the wood-plastic material with higher service performance is produced at lower production cost.
Chinese invention patent CN201410107887.4 discloses a preparation method and application of a wood-plastic material, the method is that wood flour is placed in a high-pressure reaction vessel after being modified by esterification or etherification, high-temperature and high-pressure steam is adopted to carry out blasting and puffing treatment on the modified wood flour, and microporous modified wood flour is obtained; dispersing the obtained microporous modified wood powder and thermoplastic plastic polymerization monomers in an organic solvent by heating and stirring, and adding an initiator for initiation to perform in-situ polymerization reaction; after the reaction is finished, stopping the reaction by using hot water, and cooling, washing, filtering and drying the product to obtain wood-plastic powder with uniform particles and no plastic agglomeration; the wood-plastic powder can be further dyed by disperse dyes to prepare dyed wood-plastic powder with uniform color and bright color, and can also be further used for preparing wood-plastic plates with rich colors or functional wood-plastic plates by a hot pressing method. The esterified or etherified modified wood flour is obtained by esterifying raw wood flour or degreased wood flour with acetic anhydride, propionic anhydride, phthalic anhydride or maleic anhydride, or etherifying with benzyl chloride, acrylonitrile, diethyl sulfate or epichlorohydrin.
The invention CN202010174553.4 discloses a colorful wood-plastic section, which comprises the following raw materials in parts by weight: 40-45 parts of etherified wood powder, 25-30 parts of polyethylene plastic particles, 5-10 parts of disperse dye, 4-6 parts of vitrified micro bubbles, 5-7 parts of activated carbon, 8-10 parts of reinforcing agent, 2-5 parts of lubricant, 2-5 parts of processing aid, 3-6 parts of ultraviolet absorbent and 1-3 parts of antioxidant; wherein the etherified wood flour is specifically modified wood flour modified by an etherifying reagent. The preparation method comprises the steps of firstly carrying out etherification modification on wood flour by using an etherification reagent, sealing hydroxyl hydrophilic groups in the wood to improve the hydrophobicity of the wood, then selecting an organic solvent to be dissolved and uniformly mixed with thermoplastic polyethylene plastic particles to prepare etherified wood-plastic powder, and adopting the modified wood flour modified by the etherification reagent to improve the compatibility between fibers and plastics.
Chinese invention CN201110222635.2 discloses bagasse polypropylene bio-based plastic and a preparation method thereof. The bio-based plastic is prepared by mixing and processing bagasse, polypropylene, an inorganic nano reinforcing agent, a coupling agent, a plasticizer, a heat stabilizer, a lubricant, a dispersing agent and the like, and the bio-based plastic contains 20-40% of the bagasse, 20-40% of the polypropylene and 10-30% of the inorganic nano reinforcing agent; the pretreated bagasse is modified by an aluminate coupling agent, raw materials are mixed step by an internal mixer, the dispersion uniformity and the homogeneous phase step by step composite reaction of the raw materials are enhanced, and the filling amount and the dispersibility of the bagasse are improved.
At present, the modification of wood fiber is mainly chemical modification through esterification, etherification, allylation and other modes; or modified by physical coupling. Chemical modification such as deep esterification, etherification, allylation and the like is carried out on the wood fiber, so that on one hand, the reaction process is complex, the environment is polluted, and the cost is high; on the other hand, the fiber structure is damaged too much. Since wood fibers are a fibrous structure, it is difficult for coupling modification to fundamentally achieve good compatible bonding of the fibers to the polymer. In addition, wood fiber has problems such as easy water absorption and unsusceptibility to repeated heat treatment.
Disclosure of Invention
The rice hull powder is used as a plant fiber material with excellent quality, has rich sources, is stable in supply, healthy and sanitary, and is an excellent biomass material; when the rice hull powder is used for processing degradable plastics, the problems of poor heat fluidity, poor heat resistance, poor polymer dispersion compatibility and the like exist. Aiming at the defects, the invention provides a preparation method of wood fiber degradation plastic master batch, which is characterized in that nano inorganic powder and fine starch are permeated in micropores of rice hull powder to modify the heat resistance of the rice hull powder and the interweaving adhesion of the rice hull powder and a polymer; the obtained wood fiber degradable plastic master batch is used for processing injection molding products, and the obtained injection molding products are compact and smooth.
The invention achieves the above purpose by the following technical scheme:
a preparation method of wood fiber degradation plastic master batch is characterized by comprising the following steps: the preparation method comprises the following steps:
(1) uniformly mixing starch and stearic acid in a mass ratio of 100:1-2, and micronizing to 90% with particle size below 2 μm to obtain micronized starch for later use;
(2) mixing rice hull powder, succinic anhydride, dimethylaminopyridine and stearic acid in a mass ratio of 100: 1-3:0.02-0.05: 1-3, uniformly mixing, and carrying out refinement modification to 200-400 meshes to obtain modified rice hull powder for later use;
(3) adding the nano inorganic substance and the micronized starch into the melted monoglyceride and paraffin, and stirring at a high speed at 80 ℃ to form slurry; adding the modified rice hull powder into a stirring kettle, and performing microwave heat treatment while stirring to enable the modified rice hull powder to expand; then adding the slurry to enable the slurry to permeate and adhere to the rice hull powder to obtain a composite material;
(4) and (4) mixing and dispersing the composite material obtained in the step (3) with a coupling agent, compatible resin and matrix resin, conveying the mixture into a screw extruder for extrusion, and carrying out air-cooling die surface grain cutting to obtain the wood fiber degradable plastic master batch.
Preferably, the starch in step (1) is selected from at least one of corn starch, tapioca starch and pea starch, and further preferably pea starch, selected from Ci brand pea starch produced in Gansu province (provided by Gansu province starch food Co., Ltd.) or double-tower brand pea starch produced in Shandong tobacco stage (provided by tobacco stage double-tower food Co., Ltd.).
Preferably, the stearic acid in the step (1) is 1801 stearic acid;
preferably, a vortex airflow refiner is adopted for refining in the step (1), the rotating speed of a main machine is controlled to be 1200-1400rpm, and the grading rotating speed is controlled to be 900-1000 rpm; the obtained micronized starch has 90% particle diameter of 2 μm or less.
Preferably, the refining in the step (2) adopts a vortex airflow refining machine, the rotating speed of a main machine is controlled to be 400rpm in 300-; the obtained modified rice hull powder is 200-400 meshes. The rice hull powder is a plant fiber material, has rich sources, is stable in supply, healthy and sanitary, and is an excellent biomass material. The bioplastic used in the method has defects in the aspects of hot workability, fluidity, compatibility and adhesiveness with polymers and the like; the stable product appearance of the rice hull powder can be ensured by mechanical force refinement, and the surface of the rice hull powder is quickly esterified under the action of succinic anhydride and catalyst dimethylaminopyridine by mechanical force chemical treatment so as to increase the hot workability; compared with the prior esterification treatment in a reaction vessel, the method is more suitable for batch high-efficiency production.
Preferably, in the step (3), the mass ratio of the nano inorganic substance to the micronized starch to the monoglyceride to the paraffin is as follows: 1-3: 30-50:3-5: 5-8; because the monoglyceride and the paraffin are heated and melted, the consumption is higher, and the monoglyceride and the paraffin are easy to form slurry state when being stirred at a high speed at 80 ℃, namely a smooth fluid state; meanwhile, monoglyceride is a nonionic surfactant which has both hydrophilic and lipophilic groups, so that starch and paraffin form fine slurry.
Preferably, the nano inorganic substance in the step (3) is at least one of nano talc powder, calcium carbonate and barium sulfate.
Preferably, the microwave heat treatment in the step (3) is carried out for 3-5min under the action of 20KW microwaves, and the moisture contained in the rice hull powder particles generates steam through the microwave treatment, so that the rice hull powder particles are expanded to be loose; the preferred advantage is that the formed porous pores are combined with the pulp, which is more permeable to adhering rice husk powder; the thermal stability of the nano inorganic matter in the slurry is good, so that the thermal stability of the rice hull powder processing is excellent; due to the better starch adhesiveness, the interweaving adhesion of the rice hull powder and the polymer is promoted.
Preferably, the mass ratio of the pulp to the modified rice hull powder in the step (3) is 1: 3.
Preferably, the mass ratio of the composite material, the coupling agent, the compatible resin and the matrix resin in the step (4) is 100:0.5-1.0:3-5: 10-15. Wherein the coupling agent is an aluminate coupling agent; the compatible resin is maleic anhydride grafted polypropylene; the matrix resin is selected from one of polypropylene and polyethylene.
The invention provides a preparation method of wood fiber degradable plastic master batch, compared with the prior art, the outstanding characteristics and excellent effects are as follows:
the rice hull powder is used as a plant fiber material with excellent quality, has rich sources, is stable in supply, healthy and sanitary, and is an excellent biomass material; the rice hull powder is used for processing degradable plastics and has great potential. However, since the rice hull powder is fibrous and has a polyhydroxy structure, the problems of heat resistance, processability and polymer dispersion compatibility in the prior art when the rice hull powder is used for plastic processing need to be solved. In order to comprehensively solve the heat resistance problem, the processing problem and the compatibility problem of the rice hull powder, the invention prepares the nano inorganic powder and the fine starch into fine slurry in advance; puffing the esterified and modified rice hull powder to form a loose shape; the slurry is easy to permeate and adhere to the rice hull powder, and the thermal stability of the nano inorganic matter in the slurry is good, so that the thermal stability of the rice hull powder processing is excellent; due to the better starch adhesiveness, the interweaving adhesion of the rice hull powder and the polymer is promoted. The obtained wood fiber degradable plastic master batch is used for processing injection molding products, and the obtained injection molding products are compact and smooth.
Drawings
FIG. 1 is a particle size distribution diagram of modified rice hull powder of example 1, having a uniform particle size distribution and an average particle size of about 400 mesh;
FIG. 2 is a photograph of the wood fiber-degradable plastic master batch obtained in example 1;
FIG. 3 is a photograph of an extruded sheet of example 1 and comparative examples 1 to 2, wherein 3-a is a sheet obtained by mixing the wood fiber-degradable plastic master batch obtained in example 1 with polyethylene HDPE6098 at a mass ratio of 3:1 and extruding the mixture at 220 ℃; 3-b is a sheet obtained by mixing the wood fiber degradable plastic master batch obtained in the comparative example 1 and polyethylene HDPE6098 in a mass ratio of 3:1 and extruding the mixture at 220 ℃; 3-c is a sheet obtained by mixing the wood fiber-degradable plastic master batch obtained in comparative example 2 with polyethylene HDPE6098 in a mass ratio of 3:1 and extruding the mixture at 220 ℃.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments, but it should not be construed that the scope of the present invention is limited to the following examples. Various substitutions and alterations can be made by those skilled in the art and by conventional means without departing from the spirit of the method of the invention described above.
Example 1
(1) Uniformly mixing pea starch (selected from Gansu Star brand pea starch provided by Gansu Star starch food Co., Ltd.) and 1801 stearic acid in a mass ratio of 100:1-2, micronizing with a vortex airflow micronizer, wherein the rotation speed of a host is controlled at 1200-1400rpm, the grading rotation speed is controlled at 900-1000rpm, and the micronized starch is obtained after micronization to 90% with particle size below 2 μm for later use;
(2) mixing rice hull powder, succinic anhydride, dimethylaminopyridine and stearic acid in a mass ratio of 100: 1: 0.05: 1, uniformly mixing, and carrying out refinement modification to 200-400 meshes to obtain modified rice hull powder for later use; refining modification is carried out by adopting a vortex airflow refining machine, the rotating speed of a main machine is controlled to be 400rpm, and the grading rotating speed is controlled to be 300 rpm;
(3) adding the nano inorganic substance and the micronized starch into the melted monoglyceride and paraffin, and stirring at a high speed at 80 ℃ to form slurry; adding the modified rice hull powder into a stirring kettle, performing microwave heat treatment while stirring, and treating for 3min under the action of 20KW microwave to enable the modified rice hull powder to expand; then adding the slurry to enable the slurry to permeate and adhere to the rice hull powder to obtain a composite material; the mass ratio of the nano inorganic substance to the micronized starch to the monoglyceride to the paraffin is 1:30:3: 5; the nano inorganic matter is nano talcum powder; the mass ratio of the pulp to the modified rice hull powder is 1: 3;
(4) mixing and dispersing the composite material obtained in the step (3) with a coupling agent, compatible resin and matrix resin, conveying the mixture into a screw extruder for extrusion, and carrying out air-cooling die surface dicing to obtain wood fiber degradable plastic master batch; the mass ratio of the composite material to the coupling agent to the compatible resin to the matrix resin is 100:0.5:3: 10; wherein the coupling agent is an aluminate coupling agent; the compatible resin is maleic anhydride grafted polypropylene; the matrix resin is polypropylene.
Example 2
(1) Uniformly mixing pea starch (locally, double-tower pea starch of Shangdong tobacco station, provided by tobacco station double-tower food products company Limited) and 1801 stearic acid in a mass ratio of 100:1-2, micronizing by using a vortex airflow refiner, wherein the rotating speed of a main machine is controlled at 1200-1400rpm, the grading rotating speed is controlled at 900-1000rpm, and the micronized starch is obtained after micronization to 90% with the particle size of below 2 mu m for later use;
(2) mixing rice hull powder, succinic anhydride, dimethylaminopyridine and stearic acid in a mass ratio of 100: 1.5: 0.045: 1.5, uniformly mixing, and carrying out refinement modification to 200-400 meshes to obtain modified rice hull powder for later use; refining modification is carried out by adopting a vortex airflow refining machine, the rotating speed of a main machine is controlled to be 400rpm, and the grading rotating speed is controlled to be 300 rpm;
(3) adding the nano inorganic substance and the micronized starch into the melted monoglyceride and paraffin, and stirring at a high speed at 80 ℃ to form slurry; adding the modified rice hull powder into a stirring kettle, performing microwave heat treatment while stirring, and treating for 3.5min under the action of 20KW microwave to enable the modified rice hull powder to expand; then adding the slurry to enable the slurry to permeate and adhere to the rice hull powder to obtain a composite material; the mass ratio of the nano inorganic substance to the micronized starch to the monoglyceride to the paraffin is 1.5: 35:3.5: 5.8; the nano inorganic matter is nano talcum powder; the mass ratio of the pulp to the modified rice hull powder is 1: 3;
(4) mixing and dispersing the composite material obtained in the step (3) with a coupling agent, compatible resin and matrix resin, conveying the mixture into a screw extruder for extrusion, and carrying out air-cooling die surface dicing to obtain wood fiber degradable plastic master batch; the mass ratio of the composite material to the coupling agent to the compatible resin to the matrix resin is 100: 0.62: 3.5: 11; wherein the coupling agent is an aluminate coupling agent; the compatible resin is maleic anhydride grafted polypropylene; the matrix resin is polypropylene.
Example 3
(1) (1) uniformly mixing pea starch (selected from Gansu Star brand pea starch provided by Gansu Star starch food Co., Ltd.) and 1801 stearic acid in a mass ratio of 100:1-2, micronizing by using a vortex airflow micronizer, wherein the rotating speed of a main machine is controlled at 1200-1400rpm, the grading rotating speed is controlled at 900-1000rpm, and the micronized starch is obtained for later use after being micronized until the particle size of 90% is below 2 μm;
(2) mixing rice hull powder, succinic anhydride, dimethylaminopyridine and stearic acid in a mass ratio of 100: 2: 0.04: 2, uniformly mixing, and carrying out refinement modification to 200-400 meshes to obtain modified rice hull powder for later use; refining modification is carried out by adopting a vortex airflow refining machine, the rotating speed of a main machine is controlled to be 400rpm, and the grading rotating speed is controlled to be 300 rpm;
(3) adding the nano inorganic substance and the micronized starch into the melted monoglyceride and paraffin, and stirring at a high speed at 80 ℃ to form slurry; adding the modified rice hull powder into a stirring kettle, performing microwave heat treatment while stirring, and treating for 4min under the action of 20KW microwave to enable the modified rice hull powder to expand; then adding the slurry to enable the slurry to permeate and adhere to the rice hull powder to obtain a composite material; the mass ratio of the nano inorganic substance to the micronized starch to the monoglyceride to the paraffin is 2: 40:4: 6.7; the nano inorganic matter is nano calcium carbonate; the mass ratio of the pulp to the modified rice hull powder is 1: 3;
(4) mixing and dispersing the composite material obtained in the step (3) with a coupling agent, compatible resin and matrix resin, conveying the mixture into a screw extruder for extrusion, and carrying out air-cooling die surface dicing to obtain wood fiber degradable plastic master batch; the mass ratio of the composite material to the coupling agent to the compatible resin to the matrix resin is 100:0.74:4: 12.4; wherein the coupling agent is an aluminate coupling agent; the compatible resin is maleic anhydride grafted polypropylene; the matrix resin is polypropylene.
Example 4
(1) Uniformly mixing corn starch and 1801 stearic acid according to a mass ratio of 100:1-2, micronizing by using a vortex airflow micronizer, wherein the rotating speed of a host is controlled at 1200-1400rpm, the grading rotating speed is controlled at 900-1000rpm, and the micronized starch is obtained after micronization until the particle size of 90% is less than 2 μm for later use;
(2) mixing rice hull powder, succinic anhydride, dimethylaminopyridine and stearic acid in a mass ratio of 100: 2.5:0.03: 2.5, uniformly mixing, and refining and modifying to 200-400 meshes to obtain modified rice hull powder for later use; refining modification is carried out by adopting a vortex airflow refining machine, the rotating speed of a main machine is controlled to be 400rpm, and the grading rotating speed is controlled to be 300 rpm;
(3) adding the nano inorganic substance and the micronized starch into the melted monoglyceride and paraffin, and stirring at a high speed at 80 ℃ to form slurry; adding the modified rice hull powder into a stirring kettle, performing microwave heat treatment while stirring, and treating for 4.5min under the action of 20KW microwave to enable the modified rice hull powder to expand; then adding the slurry to enable the slurry to permeate and adhere to the rice hull powder to obtain a composite material; the mass ratio of the nano inorganic substance to the micronized starch to the monoglyceride to the paraffin is 2.5: 45:4.5: 7.5; the nano inorganic matter is nano calcium carbonate; the mass ratio of the pulp to the modified rice hull powder is 1: 3;
(4) mixing and dispersing the composite material obtained in the step (3) with a coupling agent, compatible resin and matrix resin, conveying the mixture into a screw extruder for extrusion, and carrying out air-cooling die surface dicing to obtain wood fiber degradable plastic master batch; the mass ratio of the composite material to the coupling agent to the compatible resin to the matrix resin is 100:0.87:4.5: 13.7; wherein the coupling agent is an aluminate coupling agent; the compatible resin is maleic anhydride grafted polypropylene; the matrix resin is polyethylene.
Example 5
(1) Uniformly mixing cassava starch and 1801 stearic acid in a mass ratio of 100:1-2, micronizing by using a vortex airflow micronizer, wherein the rotating speed of a host is controlled at 1200-1400rpm, the grading rotating speed is controlled at 900-1000rpm, and the micronized starch is obtained until 90% of the particle size is less than 2 μm for later use;
(2) mixing rice hull powder, succinic anhydride, dimethylaminopyridine and stearic acid in a mass ratio of 100: 3:0.02: 3, uniformly mixing, and refining and modifying to 200-400 meshes to obtain modified rice hull powder for later use; refining modification is carried out by adopting a vortex airflow refining machine, the rotating speed of a main machine is controlled to be 400rpm, and the grading rotating speed is controlled to be 300 rpm;
(3) adding the nano inorganic substance and the micronized starch into the melted monoglyceride and paraffin, and stirring at a high speed at 80 ℃ to form slurry; adding the modified rice hull powder into a stirring kettle, performing microwave heat treatment while stirring, and treating for 5min under the action of 20KW microwave to enable the modified rice hull powder to expand; then adding the slurry to enable the slurry to permeate and adhere to the rice hull powder to obtain a composite material; the mass ratio of the nano inorganic substance to the micronized starch to the monoglyceride to the paraffin is 3: 50:5: 8; the nano inorganic matter is nano barium sulfate; the mass ratio of the pulp to the modified rice hull powder is 1: 3;
(4) mixing and dispersing the composite material obtained in the step (3) with a coupling agent, compatible resin and matrix resin, conveying the mixture into a screw extruder for extrusion, and carrying out air-cooling die surface dicing to obtain wood fiber degradable plastic master batch; the mass ratio of the composite material to the coupling agent to the compatible resin to the matrix resin is 100:01.0:5: 15; wherein the coupling agent is an aluminate coupling agent; the compatible resin is maleic anhydride grafted polypropylene; the matrix resin is polyethylene.
Comparative example 1
The same procedure as in example 1 was repeated except that the nano inorganic substance, the micronized starch, the monoglyceride, and the paraffin were added to the modified and expanded rice hull to pulverize the rice hull, instead of previously adding the nano inorganic substance and the micronized starch to the melted monoglyceride and the paraffin to prepare a fine slurry. Because the nano inorganic substance and the micronized starch are not added into the melted monoglyceride and paraffin to prepare fine slurry, the nano inorganic substance and the micronized starch have weak penetration on the expanded rice hull powder, and the bonding property of the inorganic powder and the micronized starch with the rice hull powder is influenced, so that the heat resistance and the bonding compatibility are influenced.
Comparative example 2
The modified rice hull powder was not subjected to puffing treatment, and the rest was the same as in example 1. Because the rice hull powder does not form loose micropores, the penetration of slurry prepared from the nano inorganic substance and the fine starch to the rice hull powder is weakened, the binding property of the fine starch of the inorganic powder and the rice hull powder is influenced, and the heat resistance and the binding compatibility are influenced.
And (3) performance testing:
1. melt index test: the melt index of the wood fiber-degradable plastic master batches obtained in example 1 and comparative examples 1 to 2 was measured at 175 ℃ under the condition of 2.16kg according to the method for measuring the melt flow index of GB/T3682-2000; as shown in table 1.
2. And (3) testing mechanical properties:
mixing the wood fiber degradable plastic master batch obtained in the example 1 and the comparative examples 1-2 with the polypropylene EPS30R in a mass ratio of 3:1, extruding and tabletting by using a 20-type double-screw extruder, wherein the extrusion temperature is 190 ℃, and obtaining a sheet with the thickness of 0.2 mm; testing the mechanical property by referring to the measurement of the tensile property of the GB/T1040-2018 plastic; the resulting sheet was soaked in water for 24h and tested for mechanical properties as shown in table 2.
3. Testing the thermal processing stability:
mixing the wood fiber degradable plastic master batch obtained in example 1 and comparative examples 1-2 with polyethylene HDPE6098 (Zibo product) in a mass ratio of 3:1, extruding and tabletting by using a 20-type double-screw extruder, and increasing the extrusion temperature to 220 ℃ to obtain a sheet with the thickness of 0.5 mm; the extruded sheet was observed for color. Referring to FIG. 3, a is the sheet of example 1, which is lighter in color and has no gelatinization or scorching; b is the sheet of comparative example 1, the color turned yellow; but not scorching; the sheet of comparative example 2, which had a large color change, was blurred and scorched.
Through tests, the wood fiber degradable plastic master batch has the advantages of good melt index, good heat resistance, excellent mechanical property with plastic products prepared from polymers and good compatibility. Comparative example 1 because the nano inorganic substance and the micronized starch are not added into the melted monoglyceride and paraffin to prepare fine slurry, the nano inorganic substance and the micronized starch have weaker penetration on the expanded rice hull powder and influence the associativity of the inorganic powder, the micronized starch and the rice hull powder, so that the heat resistance and the adhesive compatibility are influenced, the processability of the material is poorer, and the sheet material has a yellowing sign and poor heat resistance when being processed at a high temperature of 220 ℃; the starch does not fully permeate the rice hull powder, so that the compatibility of the rice hull powder and the polymer is poor, the mechanical property of the sheet is poor, and meanwhile, the rice hull powder and the polymer are poor in interweaving and bonding, so that an interface gap exists, water is easy to absorb when the sheet is soaked in water, and the mechanical property is reduced; comparative example 2 since the rice hull powder was not formed with loose micropores, the penetration of the slurry prepared from the nano inorganic substance and the fine starch to the rice hull powder was weakened, and the binding property of the inorganic micronized starch and the rice hull powder was affected, thereby affecting the heat resistance, adhesive compatibility and processability of the material.
Table 1:
Figure 896232DEST_PATH_IMAGE001
table 2:
Figure DEST_PATH_IMAGE003

Claims (10)

1. a preparation method of wood fiber degradation plastic master batch is characterized by comprising the following steps:
(1) uniformly mixing starch and stearic acid in a mass ratio of 100:1-2, and micronizing to 90% with particle size below 2 μm to obtain micronized starch for later use;
(2) mixing rice hull powder, succinic anhydride, dimethylaminopyridine and stearic acid in a mass ratio of 100: 1-3:0.02-0.05: 1-3, uniformly mixing, and carrying out refinement modification to 200-400 meshes to obtain modified rice hull powder for later use;
(3) adding the nano inorganic substance and the micronized starch into the melted monoglyceride and paraffin, and stirring at a high speed at 80 ℃ to form slurry; adding the modified rice hull powder into a stirring kettle, and performing microwave heat treatment while stirring to enable the modified rice hull powder to expand; then adding the slurry to enable the slurry to permeate and adhere to the rice hull powder to obtain a composite material;
(4) and (4) mixing and dispersing the composite material obtained in the step (3) with a coupling agent, compatible resin and matrix resin, conveying the mixture into a screw extruder for extrusion, and carrying out air-cooling die surface grain cutting to obtain the wood fiber degradable plastic master batch.
2. The method for preparing a wood fiber-degradable plastic master batch according to claim 1, wherein the starch in step (1) is at least one of corn starch, tapioca starch and pea starch.
3. The method for preparing a wood fiber degradable plastic master batch as claimed in claim 1, wherein the micronization in step (1) is performed by using a vortex air flow micronizer, the rotation speed of the main machine is controlled at 1200-1400rpm, and the classification rotation speed is controlled at 900-1000 rpm.
4. The method for preparing a wood fiber degradable plastic master batch as claimed in claim 1, wherein the step (2) of refining adopts a vortex air flow refiner, the rotation speed of a main machine is controlled at 400rpm and the classification rotation speed is controlled at 300rpm and 200 rpm.
5. The method for preparing a wood fiber degrading plastic master batch according to claim 1, wherein the mass ratio of the nano inorganic substance, the micronized starch, the monoglyceride and the paraffin in the step (3) is as follows: 1-3: 30-50:3-5:5-8.
6. The method for preparing a wood fiber-degradable plastic master batch according to claim 1, wherein the nano inorganic substance in the step (3) is at least one of nano talc powder, calcium carbonate and barium sulfate.
7. The method for preparing a wood fiber degrading plastic master batch according to claim 1, wherein the microwave heat treatment in the step (3) is treatment under the action of 20KW microwaves for 3-5 min.
8. The method for preparing a wood fiber-degradable plastic master batch according to claim 1, wherein the amount by mass ratio of the pulp to the modified rice hull powder in the step (3) is 1: 3.
9. The method for preparing the wood fiber degradable plastic master batch according to the claim 1, wherein the mass ratio of the composite material, the coupling agent, the compatible resin and the matrix resin in the step (4) is 100:0.5-1.0:3-5: 10-15; the coupling agent is an aluminate coupling agent; the compatible resin is maleic anhydride grafted polypropylene; the matrix resin is selected from one of polypropylene and polyethylene.
10. A wood fiber degrading plastic masterbatch prepared according to the method of any one of claims 1 to 9.
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