WO2018188257A1

WO2018188257A1 - Preparation method for environment-friendly biomass plastic material and application thereof

Info

Publication number: WO2018188257A1
Application number: PCT/CN2017/100475
Authority: WO
Inventors: 屠志豪
Original assignee: 苏州轩朗塑料制品有限公司
Priority date: 2017-04-12
Filing date: 2017-09-05
Publication date: 2018-10-18
Also published as: CN107057188A

Abstract

A preparation method for an environment-friendly biomass plastic material and application thereof. The process comprises: using a specific biomass material for powdering and activation treatment; polymerizing raw materials such as polypropylene, high density polyethylene, acrylonitrile, kaolin, and maleic anhydride polyolefin together; improving the performance of a composite material by heating and roasting with a muffle furnace and by adding ingredients such as a coupling agent, a defoaming agent, a curing agent, and a flexibilizer; and then, obtaining a composite plastic material by means of a series of operations such as mold pouring, surface activation treatment, demolding, and drying. The prepared environment-friendly biomass plastic material features high strength, environmental friendliness and no harm, can be recycled, and has a better application prospect. Also disclosed is application of the environment-friendly biomass plastic material prepared using the preparation method in plastic films, disposable medical materials, and latex gloves.

Description

Preparation method and application of environment-friendly biomass plastic material

Technical field

The invention relates to the technical field of plastic materials, in particular to a preparation method and application of environment-friendly biomass plastic materials.

Background technique

With the continuous growth of the population and the improvement of material life brought about by the progress of human civilization, it is putting more and more pressure on the global environment. In this contradictory process, chemistry and chemists are in a very embarrassing position. On the one hand, they have made great contributions to human civilization, but at the same time they have an unshirkable responsibility for environmental destruction. Chemical workers should be brave enough to take on the responsibility of history, that is, to minimize pollution while building a modern society of advanced technology. This requires the creation and improvement of an emerging marginal discipline.)) Environmental materials science, theoretically discusses and summarizes the impact of materials on the environment, the ability of the environment to absorb substances, the influence of the environment on ecological balance, and the environment on humans. The ability to bear, and how to monitor environmental factors and establish judgments

Due to the large amount of plastic materials used, the use period is short, the waste volume is large, and the environmental impact is obvious. Plastics and environmental issues are not just plastic/white pollution problems, they also include important issues such as the adaptability of plastic materials to the environment. Broadly speaking, plastic materials that are durable, cost-effective, easy to clean, recyclable, environmentally acceptable, etc. should be classified as environmentally friendly plastic materials. Environment-friendly plastic materials that can be environmentally absorbed should have environmentally degradable, incintable, and compostable properties. It is characterized by harmless or relatively less harmful to the natural environment, humans, and biosphere. From this definition, the following two types of substances are added to plastic formulations and processing, which contribute to environmental protection. One is inorganic minerals that can be returned to nature, and the other is protein, starch, fiber, etc. derived from photosynthesis and environmentally acceptable. Therefore, the ultra-fine technology of minerals and coupling, compatibilization technology, starch grafting and dehydration Processing technology, fiber reinforcement technology is one of the technical support for the development of environmentally friendly plastic materials, and should be vigorously supported. It can be seen that most plastic research institutes and product R&D and production companies are working hard in this regard, and they are also contributing to environmental protection.

Summary of the invention

In order to solve the above technical problems, the present invention provides a method for preparing an environmentally-friendly biomass plastic material, which utilizes a specific biomass material for powdering and activation treatment, and uses polypropylene, high-density polyethylene, acrylonitrile, kaolin, The raw materials such as maleic anhydride polyolefin are polymerized together, and the properties of the composite material are improved by heating and calcining in a muffle furnace, adding a coupling agent, a defoaming agent, a curing agent, a toughening agent and the like, and then passing through a casting mold, surface activation treatment, A series of operations such as demoulding and drying obtain a composite plastic material. The prepared environmentally-friendly biomass plastic material has high strength, environmental protection, and can be recycled, and has a good application prospect. At the same time, the application of the environment-friendly biomass plastic material prepared by the preparation method in plastic film, disposable medical material and latex glove is also disclosed.

The object of the present invention can be achieved by the following technical solutions:

The preparation method and application of environmentally friendly biomass plastic materials are composed of the following steps:

(1) Washing 5-10 parts of wheat straw, 6-9 parts of corn stover, 5-8 parts of rice husk, 4-9 parts of pine bark, 3-8 parts of peat, 3-5 parts of peanut shell, respectively, washed together, together Adding to a pulverizing cutter for shearing;

(2) adding the biomass shearing product of step (1) to a high temperature and high pressure steam reaction pot for heat treatment, the reaction temperature is 450-500 ° C, the pressure is 5-10 MPa, and the reaction time is 20-35 min;

(3) adding the biomass mixed chips of the step (2) to a high-speed ball mill for ball milling, the ball milling time is 30-60 minutes, and a small amount of liquid nitrogen is added during the ball milling to completely pulverize the product, and the ball-milled product is collected and sieved;

(4) adding the biomass powder obtained in the step (3) to a 75% benzoyl solution for living Treatment, processing time is 60min;

(5) 10-15 parts of polypropylene, 2-5 parts of high-density polyethylene, 5-8 parts of acrylonitrile, 3-6 parts of kaolin, 1-4 parts of maleic anhydride polyolefin, and then added to the muffle furnace. Calcination, heating to 60 ° C preheating, while adding the biomass activator obtained in step (4), after stirring, add 1-3 parts of coupling agent, 1-4 parts of curing agent and 2-3 parts of toughening agent , the temperature is raised to 260-300 ° C, the reaction time is 4-5 h, then the temperature is naturally cooled to 160 ° C, 1-3 parts of antifoaming agent is added, and the reaction is kept for 30 min;

(6) The reaction liquid of the step (5) is naturally cooled to 70-80 ° C, 1-2 parts of the curing agent is added again, stirred uniformly, poured into a mold, and cured at room temperature for 24 hours;

(7) The mold of the step (6) is placed in a surfactant to be treated, soaked for 40-60 minutes, and then demolded;

(8) The mold release material of the step (7) is dried in a carbon dioxide drying oven to obtain a finished product.

Preferably, the ball milling power in the step (3) is 350W.

Preferably, the sieved pore size in the step (3) is 80 mesh.

Preferably, in the step (5), the coupling agent is selected from the group consisting of vinyl triethoxysilane, vinyl tris(β-methoxyethoxy)silane, γ-aminopropyltrimethoxysilane, 3- One or more of aminopropyltrimethoxysilane.

Preferably, the curing agent in the step (5) is selected from one or more of ethylenediamine, diethylenetriamine, m-xylene, and diaminodiphenylsulfone.

Preferably, the toughening agent in the step (5) is selected from one or more of methyl methacrylate, styrene-butadiene polymer, ethylene-vinyl acetate copolymer, and acrylonitrile.

Preferably, the antifoaming agent in the step (5) is selected from one or more of a high carbon alcohol, a phenyl oleic acid oleate, a lauryl phenylacetate, and a dimethyl silicone oil.

Preferably, the composition of the surfactant in the step (7) is 5 parts of sodium linear alkylbenzene sulfonate, 3 parts of fatty alcohol polyoxyethylene ether sulfate, 2 parts of sodium dodecyl benzene sulfonate, 1 part of p-toluenesulfonamide formaldehyde resin, 4 parts of hydroxypropyl cumene, 3 parts of terpineol acetate, 1-benzene 2 parts of cyclopentanecarboxylic acid, 3 parts of trichloroacetaldehyde, 15 parts of deionized water

The invention also provides the application of the environment-friendly biomass plastic material obtained by the above preparation method in plastic film, disposable medical material and latex glove.

Compared with the prior art, the invention has the following beneficial effects:

(1) A method for preparing an environmentally-friendly biomass plastic material of the present invention uses a specific biomass material for powdering and activation treatment, and comprises polypropylene, high-density polyethylene, acrylonitrile, kaolin, maleic anhydride polyolefin, and the like. The raw materials are polymerized together, and the properties of the composite material are improved by heating and calcining in a muffle furnace, adding a coupling agent, a defoaming agent, a curing agent, a toughening agent, and the like, and then passing through a casting mold, a surface activation treatment, a mold release drying, and the like. A series of plastic materials are obtained after the series operation. The prepared environmentally-friendly biomass plastic material has high strength, environmental protection, and can be recycled, and has a good application prospect.

(2) The environment-friendly biomass plastic material of the invention is easy to obtain, has simple process, and is suitable for large-scale industrial application, and has strong practicability.

detailed description

The technical solution of the invention will be described in detail below with reference to specific embodiments.

Example 1

(1) 5 parts of wheat straw, 6 parts of corn stover, 5 parts of rice husk, 4 parts of pine bark, 3 parts of peat, 3 parts of peanut shell, respectively, washed and dried, and added together to a pulverizing cutter for shearing;

(2) adding the biomass shearing product of step (1) to a high temperature and high pressure steam reaction pot for heat treatment, the reaction temperature is 450 ° C, the pressure is 5 MPa, and the reaction time is 20 min;

(3) adding the biomass mixed chips of step (2) to a high speed ball mill for ball milling, The ball milling time is 30 minutes, the ball milling power is 350W, and a small amount of liquid nitrogen is added during ball milling to completely pulverize the product, and the ball mill product is collected and sieved, and the sieve diameter is 80 mesh;

(4) The biomass powder obtained in the step (3) is added to a 75% benzoyl solution for activation treatment, and the treatment time is 60 min;

(5) 10 parts of polypropylene, 2 parts of high-density polyethylene, 5 parts of acrylonitrile, 3 parts of kaolin, and 1 part of maleic anhydride polyolefin are uniformly mixed, added to a muffle furnace for calcination, and heated to a temperature of 60 ° C for preheating. At the same time, the biomass activator obtained in the step (4) is added, and after stirring uniformly, 1 part of vinyltriethoxysilane, 1 part of ethylenediamine and 2 parts of methyl methacrylate are added, and the temperature is raised to 260 ° C, and the reaction is carried out. After 4h, then the temperature is naturally cooled to 160 ° C, 1 part of high carbon alcohol is added, and the reaction is kept for 30 minutes;

(6) The reaction liquid of the step (5) is naturally cooled to 70 ° C, 1 part of ethylene diamine is added again, stirred uniformly, poured into a mold, and cured at room temperature for 24 h;

(7) The mold of the step (6) is placed in a surfactant to be treated, soaked for 40 minutes, and then demolded;

The performance test results of the prepared environmentally-friendly biomass plastic materials are shown in Table 1.

Example 2

(1) 7 parts of wheat straw, 7 parts of corn stover, 6 parts of rice husk, 5 parts of pine bark, 4 parts of peat, 4 parts of peanut shell, respectively, washed and dried, and added together to crushing and cutting machine for shearing;

(2) adding the biomass shear product of step (1) to a high temperature and high pressure steam reaction pot for heat treatment, the reaction temperature is 470 ° C, the pressure is 7 MPa, and the reaction time is 30 min;

(3) The biomass mixed chips of the step (2) are added to a high-speed ball mill for ball milling, the ball milling time is 40 minutes, the ball milling power is 350 W, and a small amount of liquid nitrogen is added during the ball milling to completely pulverize the product, and the ball milled product is collected and sieved. The sieve aperture is 80 mesh;

(5) 15 parts of polypropylene, 3 parts of high-density polyethylene, 6 parts of acrylonitrile, 4 parts of kaolin, 2 parts of maleic anhydride polyolefin is uniformly mixed, then calcined in a muffle furnace, preheated by heating to 60 ° C, and simultaneously added to the biomass activator obtained in step (4), stirred uniformly, and then added with vinyl tris(β-甲2 parts of oxyethoxy)silane, 2 parts of diethylenetriamine and 2 parts of styrene-butadiene polymer, the temperature is raised to 280 ° C, the reaction time is 4.5 h, then the temperature is naturally cooled to 160 ° C, and benzene is added. 1 part of ethanol oleate, heat preservation reaction for 30 min;

(6) The reaction liquid of the step (5) is naturally cooled to 72 ° C, 2 parts of diethylene triamine is added again, stirred uniformly, poured into a mold, and cured at room temperature for 24 h;

(7) putting the mold of step (6) into a surfactant, soaking for 50 minutes, and then releasing the mold;

Example 3

(1) Washing 9 parts of wheat straw, 8 parts of corn stover, 7 parts of rice husk, 8 parts of pine bark, 7 parts of peat, and 4 parts of peanut shell are respectively washed and dried, and added together to a pulverizing cutter for shearing;

(2) adding the biomass shear product of step (1) to a high temperature and high pressure steam reaction pot for heat treatment, the reaction temperature is 480 ° C, the pressure is 8 MPa, and the reaction time is 32 min;

(3) adding the biomass mixed chips of step (2) to a high-speed ball mill for ball milling, the ball milling time is 50 minutes, the ball milling power is 350 W, and a small amount of liquid nitrogen is added during ball milling to completely pulverize the product, and the ball mill product is collected and sieved. The sieve aperture is 80 mesh;

(5) 20 parts of polypropylene, 4 parts of high-density polyethylene, 7 parts of acrylonitrile, 5 parts of kaolin, and 3 parts of maleic anhydride polyolefin are uniformly mixed, added to a muffle furnace for calcination, and heated to a temperature of 60 ° C for preheating. At the same time, the biomass activator obtained in the step (4) is added, and after stirring uniformly, 2 parts of γ-aminopropyltrimethoxysilane, 3 parts of m-xylene, and 3 parts of ethylene-vinyl acetate copolymer are added, and the temperature is heated up to 290 ° C, reaction time 4.8h, then the temperature is naturally cooled to 160 ° C, adding phenylacetic acid month 3 parts of cassia ester, heat preservation reaction for 30 min;

(6) The reaction liquid of the step (5) is naturally cooled to 76 ° C, 2 parts of m-xylene is added again, stirred uniformly, poured into a mold, and cured at room temperature for 24 hours;

(7) The mold of the step (6) is placed in a surfactant to be treated, soaked for 55 minutes, and then demolded;

Example 4

(1) 10 parts of wheat straw, 9 parts of corn stover, 8 parts of rice husk, 9 parts of pine bark, 8 parts of peat, and 5 parts of peanut shell are respectively washed and dried, and added together to a pulverizing cutter for shearing;

(2) adding the biomass shear product of step (1) to a high temperature and high pressure steam reaction pot for heat treatment, the reaction temperature is 500 ° C, the pressure is 10 MPa, and the reaction time is 35 min;

(3) The biomass mixed chips of the step (2) are added to a high-speed ball mill for ball milling, the ball milling time is 60 minutes, the ball milling power is 350 W, and a small amount of liquid nitrogen is added during the ball milling to completely pulverize the product, and the ball milled product is collected and sieved. The sieve aperture is 80 mesh;

(5) 25 parts of polypropylene, 5 parts of high-density polyethylene, 8 parts of acrylonitrile, 6 parts of kaolin, and 4 parts of maleic anhydride polyolefin are uniformly mixed, added to a muffle furnace for calcination, and heated to a temperature of 60 ° C for preheating. At the same time, the biomass activator obtained in the step (4) is added, and after stirring, 3 parts of 3-aminopropyltrimethoxysilane, 4 parts of diaminodiphenyl sulfone and 3 parts of acrylonitrile are added, and the temperature is raised to 300 ° C. , the reaction time is 5h, then the temperature is naturally cooled to 160 ° C, 3 parts of dimethyl silicone oil is added, and the reaction is kept for 30 minutes;

(6) The reaction liquid of the step (5) is naturally cooled to 80 ° C, 2 parts of diaminodiphenyl sulfone is added again, stirred uniformly, poured into a mold, and cured at room temperature for 24 h;

(7) Put the mold of step (6) into a surfactant, soak for 60 minutes, then Demolding;

Comparative example 1

(1) Washing 5 parts of wheat straw, 6 parts of corn stover, 5 parts of rice husk, and 3 parts of peanut shell, respectively, and adding them together to a pulverizing cutter for shearing;

(2) adding the biomass shear product of step (1) to a high temperature and high pressure steam reaction pot for heat treatment, the reaction temperature is 450 ° C, the pressure is 5 MPa, and the reaction time is 20 min;

(3) The biomass mixed chips of the step (2) are added to a high-speed ball mill for ball milling, the ball milling time is 30 minutes, the ball milling power is 350 W, and a small amount of liquid nitrogen is added during the ball milling to completely pulverize the product, and the ball milled product is collected and sieved. The sieve aperture is 80 mesh;

(5) 10 parts of polypropylene, 2 parts of high-density polyethylene, and 5 parts of acrylonitrile are uniformly mixed, added to a muffle furnace for calcination, and heated to a temperature of 60 ° C for preheating, while adding the biomass activator obtained in the step (4). After stirring evenly, 1 part of vinyltriethoxysilane, 1 part of ethylenediamine and 2 parts of methyl methacrylate were added, the temperature was raised to 260 ° C, the reaction time was 4 h, then the temperature was naturally cooled to 160 ° C, and then added. 1 part of high carbon alcohol, heat preservation reaction for 30 min;

Comparative example 2

(4) 25 parts of polypropylene, 5 parts of high-density polyethylene, 8 parts of acrylonitrile, 6 parts of kaolin, and 4 parts of maleic anhydride polyolefin are uniformly mixed, then added to a muffle furnace for calcination, and heated to a temperature of 60 ° C for preheating. At the same time, the biomass activator obtained in the step (3) is added, and after stirring uniformly, 3 parts of 3-aminopropyltrimethoxysilane, 4 parts of diaminodiphenyl sulfone and 3 parts of acrylonitrile are added, and the temperature is raised to 300 ° C by heating. , the reaction time is 5h, then the temperature is naturally cooled to 160 ° C, 3 parts of dimethyl silicone oil is added, and the reaction is kept for 30 minutes;

(5) The reaction solution of step (4) is naturally cooled to 80 ° C, 2 parts of diaminodiphenyl sulfone is added again, stirred uniformly, poured into a mold, and cured at room temperature for 24 h;

(6) placing the mold of the step (5) into a surfactant, soaking for 60 minutes, and then releasing the mold;

(7) The release material of the step (6) is dried in a carbon dioxide drying oven to obtain a finished product.

The environmentally-friendly biomass plastic materials prepared in Examples 1-4 and Comparative Examples 1-2 were subjected to several performance tests of impact strength, tensile strength, and weight loss rate.

Table 1

The preparation method of the environment-friendly biomass plastic material of the invention utilizes a specific biomass material for powdering and activation treatment, and polymerizes raw materials such as polypropylene, high density polyethylene, acrylonitrile, kaolin, maleic anhydride polyolefin, etc. Together, the muffle furnace is heated and calcined, a coupling agent, an antifoaming agent, a curing agent, a toughening agent and the like are added to improve the properties of the composite material, and then a series of operations such as casting mold, surface activation treatment, and demoulding drying are performed. A composite plastic material is obtained. The prepared environmentally-friendly biomass plastic material has high strength, environmental protection, and can be recycled, and has a good application prospect. The environment-friendly biomass plastic material of the invention is easy to obtain, has simple process, is suitable for large-scale industrial application, and has strong practicability.

The above is only the embodiment of the present invention, and is not intended to limit the scope of the invention, and the equivalent structure or equivalent process transformation made by using the content of the specification of the present invention, or directly or indirectly applied in other related technical fields, The same is included in the scope of patent protection of the present invention.

Claims

A method for preparing an environmentally-friendly biomass plastic material, characterized in that it consists of the following steps:

(1) Washing 5-10 parts of wheat straw, 6-9 parts of corn stover, 5-8 parts of rice husk, 4-9 parts of pine bark, 3-8 parts of peat, 3-5 parts of peanut shell, respectively, washed together, together Adding to a pulverizing cutter for shearing;

(2) adding the biomass shearing product of step (1) to a high temperature and high pressure steam reaction pot for heat treatment, the reaction temperature is 450-500 ° C, the pressure is 5-10 MPa, and the reaction time is 20-35 min;

(3) adding the biomass mixed chips of the step (2) to a high-speed ball mill for ball milling, the ball milling time is 30-60 minutes, and a small amount of liquid nitrogen is added during the ball milling to completely pulverize the product, and the ball-milled product is collected and sieved;

(4) The biomass powder obtained in the step (3) is added to a 75% benzoyl solution for activation treatment, and the treatment time is 60 min;

(5) 10-15 parts of polypropylene, 2-5 parts of high-density polyethylene, 5-8 parts of acrylonitrile, 3-6 parts of kaolin, 1-4 parts of maleic anhydride polyolefin, and then added to the muffle furnace. Calcination, heating to 60 ° C preheating, while adding the biomass activator obtained in step (4), after stirring, add 1-3 parts of coupling agent, 1-4 parts of curing agent and 2-3 parts of toughening agent , the temperature is raised to 260-300 ° C, the reaction time is 4-5 h, then the temperature is naturally cooled to 160 ° C, 1-3 parts of antifoaming agent is added, and the reaction is kept for 30 min;

(6) The reaction liquid of the step (5) is naturally cooled to 70-80 ° C, 1-2 parts of the curing agent is added again, stirred uniformly, poured into a mold, and cured at room temperature for 24 hours;

(7) The mold of the step (6) is placed in a surfactant to be treated, soaked for 40-60 minutes, and then demolded;

(8) The mold release material of the step (7) is dried in a carbon dioxide drying oven to obtain a finished product.
The method for preparing an environment-friendly biomass plastic material according to claim 1, wherein The ball milling power in the step (3) is 350W.
The method for preparing an environment-friendly biomass plastic material according to claim 1, wherein the sieved pore size in the step (3) is 80 mesh.
The method for preparing an environment-friendly biomass plastic material according to claim 1, wherein the coupling agent in the step (5) is selected from the group consisting of vinyl triethoxysilane and vinyl tris (β-methoxy). One or more of ethoxy)silane, γ-aminopropyltrimethoxysilane, and 3-aminopropyltrimethoxysilane.
The method for preparing an environment-friendly biomass plastic material according to claim 1, wherein the curing agent in the step (5) is selected from the group consisting of ethylenediamine, diethylenetriamine, m-xylene, and diaminodiphenyl. One or more of the sulfones.
The method for preparing an environment-friendly biomass plastic material according to claim 1, wherein the toughening agent in the step (5) is selected from the group consisting of methyl methacrylate, styrene-butadiene polymer, and ethylene. One or more of a vinyl acetate copolymer and acrylonitrile.
The method for preparing an environment-friendly biomass plastic material according to claim 1, wherein the antifoaming agent in the step (5) is selected from the group consisting of high alcohol, phenylethyl oleate, lauryl phenylacetate, and One or more of methyl silicone oils.
The method for preparing an environment-friendly biomass plastic material according to claim 1, wherein the composition of the surfactant in the step (7) is 5 parts of sodium linear alkylbenzene sulfonate, and the fatty alcohol polyoxyethylene is used. 3 parts of sodium ether sulfate, 2 parts of sodium dodecylbenzene sulfonate, 1 part of p-toluenesulfonamide formaldehyde resin, 4 parts of cumene hydroperoxide, 3 parts of terpineol acetate, 1-phenylcyclopentane carboxylate 2 parts of acid, 3 parts of trichloroacetaldehyde, and 15 parts of deionized water.
The environmentally-friendly biomass plastic material obtained by the preparation method according to any one of claims 1-8 is applied to a plastic film, a disposable medical material, and a latex glove.