CN109096600B - Preparation method of polymer nanosphere modified straw fiber reinforced wood-plastic composite material and obtained product - Google Patents
Preparation method of polymer nanosphere modified straw fiber reinforced wood-plastic composite material and obtained product Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
- C08L2205/16—Fibres; Fibrils
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
- C08L2205/18—Spheres
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- Chemical & Material Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
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- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Dry Formation Of Fiberboard And The Like (AREA)
Abstract
The invention discloses a preparation method of a polymer nanosphere modified straw fiber reinforced wood-plastic composite material and an obtained product, and the preparation method comprises the following steps: straw skins are used as raw materials, PVA and glutaraldehyde are adopted to perform surface modification on the straws, and then modified straw fibers, PP, a lubricant and an antioxidant are uniformly mixed and extruded to form the product. According to the invention, the hydrophobic polymer nanospheres with stable chemical structures are formed on the surfaces of the straw fibers by surface modification of glutaraldehyde and PVA for the first time, and a new path is found for application of the crop straw fibers in the application of wood-plastic composite materials by applying a straw fiber surface crosslinking modification technology. The interfacial compatibility of the straw fiber modified by the polymer nanosphere and the PP matrix is greatly improved, so that the doping amount of the straw fiber in the wood-plastic composite material is increased, and the recycling rate of the straw fiber is improved.
Description
Technical Field
The invention relates to a preparation method of a modified straw fiber reinforced wood-plastic composite material, in particular to a preparation method of a polymer nanosphere modified straw fiber reinforced PP wood-plastic composite material and an obtained product, and belongs to the technical field of wood-plastic composite materials.
Technical Field
The wood-plastic composite material is a nontoxic and recyclable environment-friendly material, and is mainly prepared by using thermoplastic plastics such as polyethylene, polypropylene, polyvinyl chloride and the like and wood fibers in a certain proportion as main raw materials and then carrying out processing technologies such as extrusion, mould pressing, injection molding and the like. The wood-plastic composite material has wide attention due to excellent comprehensive performance, particularly has properties of moth prevention, corrosion resistance, water resistance, moisture resistance and the like, and has great development space in the field of furniture manufacturing as a novel environment-friendly material.
As a big agricultural country, China can generate abundant straw resources in agricultural production activities every year. Crop straws are a precious renewable resource, but for a long time, due to the influence of consumption concept and life style, the rural straw resources in China are completely in the conditions of high consumption, high pollution and low yield, and a considerable part of crop straws are abandoned or incinerated and are not reasonably developed and utilized. The method utilizes rich regional raw materials, namely straws, researches and develops the environment-friendly recyclable wood-plastic building material, replaces materials such as wood, steel, cement and the like to the maximum extent, and is one of important directions for the development of building material industry. At present, artificial boards, decorative boards, composite wallboards, straw bricks, straw blocks and the like prepared by straws can be used as civil furniture, office furniture, doors, ceilings, partition walls and the like indoors; the composite material can be used as a high-strength heat-insulation light steel straw house, a high-strength heat-insulation outer wall and a roof of various buildings and the like outdoors, and has the characteristics of light weight, high strength, waste recycling, heat insulation, fire prevention, sound insulation, greenness, energy conservation, environmental protection and the like.
The crop straws contain rich fibers, as many plant fibers, a large number of hydroxyl groups exist on the surfaces of the crop straws, intermolecular hydrogen bonds are formed among the hydroxyl groups, so that the straw fibers are not easy to be uniformly dispersed in a nonpolar polymer matrix, the straw fibers are easy to mutually gather in the preparation process of the wood-plastic composite material, even fiber clusters are formed, stress concentration is caused, the interface combination condition between the fibers and the matrix is poor, and the mechanical property of the material is easily reduced. Therefore, improving the interface bonding between the polymer matrix and the straw fiber is the key to develop the application of the straw fiber in the wood-plastic composite material.
In order to solve the interfacial bonding condition between the straw fiber and the polymer matrix, the most conventional operation is to pre-treat the straw fiber. For example, patent CN104448728A and patent CN104761818A disclose methods for preparing wood-plastic composite material from straw fiber reinforced PBS and PP treated with sodium hydroxide solutions of different concentrations, respectively. The alkali treatment can increase the roughness of the fiber surface and improve the engagement between the fiber and the matrix, thereby improving the processing performance and the related mechanical property of the wood-plastic composite material. However, the subsequent treatment of the alkali waste liquid is not good, water pollution is easy to cause, and the environmental protection property is poor. Therefore, the development of a wood-plastic composite material capable of improving the compatibility between the fibers and the matrix is of great significance in the art.
Disclosure of Invention
Aiming at the defects of the application of straw fibers in the field of wood-plastic composite materials, the invention provides a preparation method of a straw fiber reinforced wood-plastic composite material modified by polymer nanospheres, which modifies the straw fibers, prevents the straw fibers from gathering each other, improves the interface compatibility between the straw fibers and a polymer matrix, and ensures the mechanical property and the mechanical property of the obtained wood-plastic composite material.
The invention takes the straw fiber and the polypropylene as raw materials, and adopts the straw fiber to completely replace wood fiber, thereby greatly reducing the cost. Polypropylene (PP) is one of five general-purpose plastics, is one of synthetic resins with the fastest development speed, the largest yield, the largest brand and the widest application in general-purpose plastics, and is widely applied to various fields in industry. The PP has the advantages of rich raw material source, low price, easy molding and processing, small density, excellent mechanical property, good electrical insulation, small dielectric constant, stress cracking resistance, chemical drug resistance and the like. In addition, the polypropylene has high recycling efficiency and good processability, and provides a foundation for manufacturing a good wood-plastic composite material with high strength, good processability and environmental protection.
In order to ensure that the straw fiber and the polypropylene matrix have good interface compatibility, the invention adopts the polymer nanospheres to modify the straw fiber. The polymer nanosphere is formed by crosslinking polyvinyl alcohol (PVA) and glutaraldehyde under the action of a catalyst. Polyvinyl alcohol is a non-toxic and non-irritant hydrophilic polymer, has the advantages of good biocompatibility, film-forming property, fiber forming property, adhesion and the like, and has good mechanical properties. Glutaraldehyde is a commonly used bifunctional aldehyde in industry, and has wide application in the aspects of wood preservation, polymer synthesis and the like. The invention is based on the principle that glutaraldehyde and PVA can be effectively crosslinked, and adopts an in-situ polymerization method to perform reaction on MgCl2Under the catalytic action of the molecular sieve, aldehyde groups at two ends of glutaraldehyde and hydroxyl on the surface of PVA undergo an aldol condensation reaction (namely a cross-linking reaction), so that a large amount of hydrophilic hydroxyl in PVA is consumed, and the water-insoluble polymer nanospheres are formed. The polymer nanospheres can be uniformly coatedThe surface of the straw fiber is covered, so that the straw fibers are prevented from being gathered, and the straw fibers and the PP matrix are promoted to be wound with each other, so that the interface compatibility of the straw fibers and the PP matrix is improved, the interface bonding capability of the straw fibers and the PP is improved, and the mechanical property of the wood-plastic composite material are effectively improved.
The specific technical scheme of the invention is as follows:
a preparation method of a polymer nanosphere modified straw fiber reinforced wood-plastic composite material comprises the following steps:
(1) taking straw skin as a raw material, drying and crushing the straw skin to obtain straw powder;
(2) mixing the PVA aqueous solution with the straw powder, and stirring uniformly;
(3) dripping glutaraldehyde into the ethanol aqueous solution, stirring uniformly, then dripping the ethanol aqueous solution containing glutaraldehyde into the mixture in the step (2), adding a magnesium chloride catalyst after dripping, and stirring for carrying out a crosslinking reaction;
(4) after reaction, filtering, washing and drying to obtain the straw fiber modified by the polymer nanospheres;
(5) uniformly mixing the straw fiber modified by the polymer nanosphere, PP, a lubricant and an antioxidant:
(6) and (5) extruding and molding the uniformly mixed materials in the step (5) to obtain the straw fiber reinforced wood-plastic composite material modified by the polymer nanospheres.
Further, in the step (1), the straw skin is crushed and then is sieved by a 100-mesh sieve to obtain the straw powder. The straw can be at least one of corn straw, wheat straw and rice straw.
Further, in the step (2), the concentration of the PVA aqueous solution is 1-3 wt%. Mixing PVA and straw powder at 90-95 deg.c.
Further, the mass ratio of the glutaraldehyde to the PVA to the straw powder to the magnesium chloride catalyst is 0.2-0.6: 0.5-1.5: 1: 0.6-1.2.
Further, in the step (3), the concentration of the ethanol aqueous solution is 50-90 wt%, and the concentration of the glutaraldehyde in the ethanol aqueous solution is 2-6 wt%.
Further, in the step (3), after magnesium chloride is added, the reaction is carried out for 2 to 3 hours at the temperature of between 90 and 95 ℃.
Further, in the step (5), the content of the straw fiber modified by the polymer nanospheres is 25-30 wt%, the content of the PP is 69-74wt%, the content of the lubricant is 0.3-0.6wt%, and the content of the antioxidant is 0.4-0.7wt%, based on the total weight of the straw fiber modified by the polymer nanospheres, the PP, the lubricant and the antioxidant being 100%.
Further, the lubricant and the antioxidant may be selected from conventional components, for example, the lubricant may be selected from stearic acid, low molecular weight polyethylene, low molecular weight polypropylene, etc., and the antioxidant may be selected from phenolic antioxidants (BHT, 1010, 1076), sulfur-containing antioxidants (DSTDP, DLTDP), phosphorus-based antioxidants (168, 626), etc.
Further, in the step (6), the uniformly mixed materials are put into a double-screw extruder for extrusion molding. The extrusion temperature is 160-175 ℃, and the screw rotation speed is 30-50 rpm.
Further, in the step (6), the obtained straw fiber reinforced wood-plastic composite modified by the polymer nanospheres can be made into different shapes according to requirements, such as rectangular plate shapes and the like.
In order to improve the interface performance of the straw fiber and PP and increase the addition amount of the straw fiber, the polymer nanospheres with stable chemical structures are modified on the surface of the straw fiber through the cross-linking reaction of glutaraldehyde and PVA, on one hand, the polymer nanospheres improve the roughness of the surface of the fiber and are beneficial to the mechanical interlocking effect of the fiber in a polymer matrix, and on the other hand, the existence of the polymer nanospheres also improves the hydrophobicity of the surface of the fiber, so that the interface compatibility between the fiber and the matrix is improved. In addition, the straw fiber can play a role in stress transmission and energy consumption in the stress process of the wood-plastic composite material, so that the mechanical property of the wood-plastic composite material is effectively improved. The wood-plastic composite material obtained by the invention has excellent mechanical property and mechanical property, can be used in the fields of home furnishing, outdoor construction and the like, can be recycled and reused, and has wide application prospect, so that the straw fiber reinforced wood-plastic composite material modified by the polymer nanospheres prepared by the method is also in the protection range of the invention.
The invention has the following advantages:
1. according to the invention, the hydrophobic polymer nanospheres with stable chemical structures are formed on the surfaces of the straw fibers by surface modification of glutaraldehyde and PVA for the first time, and a new path is found for application of the crop straw fibers in the application of wood-plastic composite materials by applying a straw fiber surface crosslinking modification technology. The interface compatibility of the straw fiber modified by the polymer nanosphere and the PP matrix is greatly improved, so that the addition amount of the straw fiber in the wood-plastic composite material is increased, and the recovery utilization rate of the straw fiber is improved;
2. the preparation method disclosed by the invention is simple in process, the used raw materials are wide in source and low in price, and the wood-plastic composite material is economic and green, has excellent mechanical properties and mechanical properties, has a good application prospect in the fields of building decoration, landscape, automobiles and the like, and finds a new utilization value for agricultural wastes.
Drawings
FIG. 1 is an SEM photograph of straw fibers after surface modification in example 1;
FIG. 2 is an SEM image of straw fibers after surface modification in comparative example 3;
FIG. 3 is an SEM photograph of the straw fiber after surface modification in comparative example 4;
fig. 4 is an SEM image of comparative example 5.
Detailed Description
The present invention is further illustrated by the following specific examples, it being understood that the following description is illustrative only and is not intended to be in any way limiting.
In the following examples, the polyvinyl alcohol (PVA) used was 1797 type, and the degree of alcoholysis was 98-99% (mol/mol).
Example 1
The preparation method of the polymer nanosphere modified straw fiber reinforced wood-plastic composite material comprises the following steps:
1) surface modification of straw fiber
a. Placing corn straws in a forced air drying oven at 80 ℃ for drying for 24h, manually peeling to obtain straw skins, crushing by using an ultrafine crusher, and sieving by using a 100-mesh standard sieve to obtain straw powder;
b. dissolving 5g of PVA in 245mL of deionized water, mechanically stirring in a water bath at 95 ℃ at the rotating speed of 350rpm, adding 5g of straw powder after complete dissolution, and continuing stirring;
c.3g of glutaraldehyde (50 wt% aqueous glutaraldehyde solution) is added dropwise to 47mL of aqueous ethanol solution (anhydrous ethanol: water mass ratio =9: 1) and stirred uniformly, and then added dropwise to the system in the step b, and then 4.5 g of catalyst MgCl is weighed2•6H2Adding O into the system, continuously stirring for 2h, and keeping the reaction process at 95 ℃;
d. filtering the obtained product, washing the product for three times by using deionized water and absolute ethyl alcohol alternately, drying the product in a 75 ℃ blast drying oven, and fully grinding the product to obtain the straw fiber modified by the polymer nanospheres;
2) preparation of straw fiber reinforced wood-plastic composite material modified by polymer nanospheres
a. Uniformly mixing the straw fiber modified by the polymer nanosphere, PP, a lubricant and an antioxidant in a high-speed mixer to obtain a mixed material, wherein the content of the crosslinking modified straw fiber is 30wt%, the content of the PP is 69wt%, the content of the lubricant is 0.6wt% and the content of the antioxidant is 0.4 wt%;
b. and (3) putting the mixed material into a double-screw extruder for extrusion molding to obtain the cross-linked modified straw fiber/PP wood-plastic composite material, wherein the temperatures of four subareas of the extruder are respectively 160 ℃, 165 ℃ and 175 ℃, and the screw rotation speed is 40 rpm. The obtained wood-plastic composite material is a cuboid plate.
Example 2
The preparation method of the polymer nanosphere modified straw fiber reinforced wood-plastic composite material comprises the following steps:
1) surface modification of straw fiber
a. Drying wheat straws in a forced air drying oven at 80 ℃ for 24 hours, crushing by using an ultrafine crusher, and sieving by using a 100-mesh standard sieve to obtain straw powder;
b. dissolving 7.5g of PVA in 242.5mL of deionized water, mechanically stirring in a water bath at 95 ℃ at the rotating speed of 350rpm, adding 5g of straw powder after complete dissolution, and continuing stirring;
c.6 g of glutaraldehyde (50 wt% glutaraldehyde aqueous solution) is added dropwise into 44mL ethanol aqueous solution (anhydrous ethanol: water mass ratio =5: 5) and stirred uniformly, then added dropwise into the system in the step b, and then 6g of catalyst MgCl is weighed2•6H2Adding O into the system, continuously stirring for 3 hours, and keeping the reaction process at 95 ℃;
d. filtering the obtained product, washing the product for three times by using deionized water and absolute ethyl alcohol alternately, drying the product in a 75 ℃ blast drying oven, and fully grinding the product to obtain the straw fiber modified by the polymer nanospheres;
2) preparation of straw fiber reinforced wood-plastic composite material modified by polymer nanospheres
a. Uniformly mixing the straw fiber modified by the polymer nanosphere, PP, a lubricant and an antioxidant in a high-speed mixer to obtain a mixed material, wherein the content of the crosslinking modified straw fiber is 30wt%, the content of the PP is 69wt%, the content of the lubricant is 0.6wt% and the content of the antioxidant is 0.4 wt%;
b. and (3) putting the mixed material into a double-screw extruder for extrusion molding to obtain the cross-linked modified straw fiber/PP wood-plastic composite material, wherein the temperatures of four subareas of the extruder are respectively 160 ℃, 165 ℃ and 175 ℃, and the screw rotation speed is 30 rpm. The obtained wood-plastic composite material is a cuboid plate.
Example 3
The preparation method of the polymer nanosphere modified straw fiber reinforced wood-plastic composite material comprises the following steps:
1) surface modification of straw fiber
a. Drying rice straws in a forced air drying oven at 80 ℃ for 24 hours, crushing by using an ultrafine crusher, and sieving by using a 100-mesh standard sieve to obtain straw powder;
b. dissolving 2.5g of PVA in 247.5mL of deionized water, mechanically stirring in a water bath at 92 ℃ at the rotating speed of 350rpm, adding 5g of straw powder after complete dissolution, and continuing stirring;
c.2.5 g of glutaraldehyde (50 wt% glutaraldehyde aqueous solution) is added into 47.5mL of ethanol aqueous solution (anhydrous ethanol: water mass ratio =8: 2) dropwise, the mixture is stirred uniformly and added into the system in the step b dropwise, and then 3g of catalyst MgCl is weighed2•6H2Adding O into the system, continuously stirring for 2 hours, and keeping the reaction process at 92 ℃;
d. filtering the obtained product, washing the product for three times by using deionized water and absolute ethyl alcohol alternately, drying the product in a 75 ℃ blast drying oven, and fully grinding the product to obtain the straw fiber modified by the polymer nanospheres;
2) preparation of straw fiber reinforced wood-plastic composite material modified by polymer nanospheres
a. Uniformly mixing the straw fiber modified by the polymer nanosphere, PP, a lubricant and an antioxidant in a high-speed mixer to obtain a mixed material, wherein the content of the crosslinking modified straw fiber is 30wt%, the content of the PP is 69wt%, the content of the lubricant is 0.6wt% and the content of the antioxidant is 0.4 wt%;
b. and (3) putting the mixed material into a double-screw extruder for extrusion molding to obtain the cross-linked modified straw fiber/PP wood-plastic composite material, wherein the temperatures of four subareas of the extruder are respectively 160 ℃, 165 ℃ and 175 ℃, and the screw rotation speed is 50 rpm. The obtained wood-plastic composite material is a cuboid plate.
Example 4
The preparation method of the polymer nanosphere modified straw fiber reinforced wood-plastic composite material comprises the following steps:
1) surface modification of straw fiber
a. Placing corn straws in a forced air drying oven at 80 ℃ for drying for 24h, manually peeling to obtain straw skins, crushing by using an ultrafine crusher, and sieving by using a 100-mesh standard sieve to obtain straw powder;
b. dissolving 5g of PVA in 245mL of deionized water, mechanically stirring in a water bath at 90 ℃ at the rotating speed of 350rpm, adding 5g of straw powder after complete dissolution, and continuing stirring;
c.2g of glutaraldehyde (50 wt% aqueous glutaraldehyde solution) is added dropwise to 48mL of aqueous ethanol solution (anhydrous ethanol: water mass ratio =9: 1) and stirred uniformly, and then added dropwise to step bIn the system (2), 4 g of MgCl catalyst was weighed2•6H2Adding O into the system, continuously stirring for 2h, and keeping the reaction process at 90 ℃;
d. filtering the obtained product, washing the product for three times by using deionized water and absolute ethyl alcohol alternately, drying the product in a 75 ℃ blast drying oven, and fully grinding the product to obtain the straw fiber modified by the polymer nanospheres;
2) preparation of straw fiber reinforced wood-plastic composite material modified by polymer nanospheres
a. Uniformly mixing the straw fiber modified by the polymer nanosphere, PP, a lubricant and an antioxidant in a high-speed mixer to obtain a mixed material, wherein the content of the crosslinking modified straw fiber is 30wt%, the content of the PP is 69wt%, the content of the lubricant is 0.6wt% and the content of the antioxidant is 0.4 wt%;
b. and (3) putting the mixed material into a double-screw extruder for extrusion molding to obtain the cross-linked modified straw fiber/PP wood-plastic composite material, wherein the temperatures of four subareas of the extruder are respectively 160 ℃, 165 ℃ and 175 ℃, and the screw rotation speed is 40 rpm. The obtained wood-plastic composite material is a cuboid plate.
Comparative example 1
A wood-plastic composite was prepared according to the method of example 1, except that: the method adopts poplar powder fiber to replace straw fiber and comprises the following steps:
(1) drying the purchased poplar powder in a forced air drying oven at 80 ℃ for 24 hours, and sieving the dried poplar powder by a 100-mesh standard sieve to obtain the poplar powder;
(2) uniformly mixing dried poplar powder, PP, a lubricant and an antioxidant in a high-speed mixer to obtain a mixed material, wherein the content of the poplar powder is 30wt%, the content of the PP is 69wt%, the content of the lubricant is 0.6wt%, and the content of the antioxidant is 0.4 wt%;
(3) and (3) putting the mixed material into a double-screw extruder for extrusion molding to obtain the poplar powder/PP wood-plastic composite material, wherein the temperatures of four subareas of the extruder are respectively 160 ℃, 165 ℃ and 175 ℃, and the screw rotation speed is 40 rpm. The obtained wood-plastic composite material is a cuboid plate.
Comparative example 2
A wood-plastic composite was prepared according to the method of example 1, except that: the straw fiber is treated by NaOH with the concentration of 5wt%, and the steps are as follows:
1) alkali treatment modification of straw fiber
a. Placing corn straws in a forced air drying oven at 80 ℃ for drying for 24h, manually peeling to obtain straw skins, crushing by using an ultrafine crusher, and sieving by using a 100-mesh standard sieve to obtain straw powder;
b. soaking 5g of the straw powder in 5wt% NaOH alkaline solution (the straw powder is alkaline solution =1: 10), and soaking for 24 hours at room temperature;
c. washing the straw powder soaked in the step b with deionized water until the pH of the filtrate is = 7;
d. drying the alkali-treated straw fiber in a blast drying oven at 75 ℃ and fully grinding;
2) preparation of alkali-treated straw fiber reinforced wood-plastic composite material
a. Uniformly mixing the alkali-treated straw fiber, PP, a lubricant and an antioxidant in a high-speed mixer to obtain a mixed material, wherein the content of the cross-linked modified straw fiber is 30wt%, the content of the PP is 69wt%, the content of the lubricant is 0.6wt%, and the content of the antioxidant is 0.4 wt%;
b. and (3) putting the mixed material into a double-screw extruder for extrusion molding to obtain the crosslinked modified wood fiber/PP wood-plastic composite material, wherein the temperatures of four subareas of the extruder are respectively 160 ℃, 165 ℃ and 175 ℃, and the screw rotation speed is 40 rpm. The obtained wood-plastic composite material is a cuboid plate.
Comparative example 3
A wood-plastic composite was prepared according to the method of example 1, except that: the crosslinking reaction temperature is 98 ℃,
the method comprises the following specific steps:
1) surface modification of straw fiber
a. Placing the straws in a forced air drying oven at 80 ℃ for drying for 24h, manually peeling to obtain straw skins, crushing by using an ultrafine crusher, and sieving by using a 100-mesh standard sieve to obtain straw powder;
b. dissolving 5g of PVA in 245mL of deionized water, mechanically stirring in a water bath at 98 ℃ at the rotating speed of 350rpm, adding 5g of straw powder after complete dissolution, and continuing stirring;
c.3g of glutaraldehyde (50 wt% aqueous glutaraldehyde solution) is added dropwise to 47mL of aqueous ethanol solution (anhydrous ethanol: water mass ratio =9: 1) and stirred uniformly, and then added dropwise to the system in the step b, and then 4.5 g of catalyst MgCl is weighed2•6H2Adding O into the solution, continuously stirring for 2 hours, and keeping the reaction process at 98 ℃;
d. filtering the obtained product, washing the product for three times by using deionized water and absolute ethyl alcohol alternately, drying the product in a 75 ℃ blast drying oven, and fully grinding the product to obtain the straw fiber modified by the polymer nanospheres;
2) preparation of straw fiber reinforced wood-plastic composite material modified by polymer nanospheres
a. Uniformly mixing the straw fiber modified by the polymer nanosphere, PP, a lubricant and an antioxidant in a high-speed mixer to obtain a mixed material, wherein the content of the crosslinking modified straw fiber is 30wt%, the content of the PP is 69wt%, the content of the lubricant is 0.6wt% and the content of the antioxidant is 0.4 wt%;
b. and (3) putting the mixed material into a double-screw extruder for extrusion molding to obtain the cross-linked modified straw fiber/PP wood-plastic composite material, wherein the temperatures of four subareas of the extruder are respectively 160 ℃, 165 ℃ and 175 ℃, and the screw rotation speed is 40 rpm. The obtained wood-plastic composite material is a cuboid plate.
Comparative example 4
A wood-plastic composite was prepared according to the method of example 1, except that: the catalyst is H2SO4The method comprises the following steps:
1) surface modification of straw fiber
a. Placing the straws in a forced air drying oven at 80 ℃ for drying for 24h, manually peeling to obtain straw skins, crushing by using an ultrafine crusher, and sieving by using a 100-mesh standard sieve to obtain straw powder;
b. dissolving 5g of PVA in 245mL of deionized water, mechanically stirring in a water bath at 95 ℃ at the rotating speed of 350rpm, adding 5g of straw powder after complete dissolution, and continuing stirring;
c.3 g of glutaraldehyde (50 wt% of glutaraldehyde aqueous solution) is added into 47mL of ethanol aqueous solution (the mass ratio of absolute ethanol to water is =9: 1) dropwise, the mixture is stirred uniformly and then added into the system in the step b, then 4.5 g of catalyst concentrated sulfuric acid is weighed and added into the solution, the stirring is continued for 2 hours, and the reaction process is kept at 95 ℃;
d. filtering the obtained product, washing the product for three times by using deionized water and absolute ethyl alcohol alternately, drying the product in a 75 ℃ blast drying oven, and fully grinding the product to obtain the straw fiber modified by the polymer nanospheres;
2) preparation of straw fiber reinforced wood-plastic composite material modified by polymer nanospheres
a. Uniformly mixing the straw fiber modified by the polymer nanosphere, PP, a lubricant and an antioxidant in a high-speed mixer to obtain a mixed material, wherein the content of the crosslinking modified straw fiber is 30wt%, the content of the PP is 69wt%, the content of the lubricant is 0.6wt% and the content of the antioxidant is 0.4 wt%;
b. and (3) putting the mixed material into a double-screw extruder for extrusion molding to obtain the cross-linked modified straw fiber/PP wood-plastic composite material, wherein the temperatures of four subareas of the extruder are respectively 160 ℃, 165 ℃ and 175 ℃, and the screw rotation speed is 40 rpm. The obtained wood-plastic composite material is a cuboid plate.
Comparative example 5
A nano-polymer was prepared according to the method of example 1, except that: the straw fiber is not added in the system,
the method comprises the following steps:
a. dissolving 5g of PVA in 250 mL of deionized water, and mechanically stirring in a water bath at 95 ℃ at the rotating speed of 350 rpm;
b.3g of glutaraldehyde (50 wt% aqueous glutaraldehyde solution) is added dropwise into 50mL of aqueous ethanol solution (anhydrous ethanol: water volume ratio =9: 1) and stirred uniformly, and then added dropwise into the system in the step b, and then 4.5 g of catalyst MgCl is weighed2•H2Adding O into the solution and continuously stirring for 2 hours;
c. and filtering the obtained product, washing the product for three times by using deionized water and absolute ethyl alcohol alternately, and drying the product in a 75 ℃ forced air drying box.
Comparative example 6
A wood-plastic composite was prepared according to the method of example 1, except that: the added straw fiber is not subjected to any treatment, and the steps are as follows:
1) preparation of straw fiber
Drying the straws in a forced air drying oven at 80 ℃ for 24h, manually peeling to obtain straw skins, crushing the straw skins by an ultrafine pulverizer, sieving the crushed straw skins by a 100-mesh standard sieve, and drying the crushed straw skins in a forced air drying oven at 75 ℃ to obtain straw powder;
2) preparation of straw fiber/PP composite material
a. Uniformly mixing 30wt% of the straw fiber obtained in the step 1), 69wt% of PP, 0.6wt% of lubricant and 0.4wt% of antioxidant in a high-speed mixer;
b. and (3) putting the mixed material into a double-screw extruder for extrusion molding to obtain the cross-linked modified straw fiber/PP wood-plastic composite material, wherein the temperatures of four subareas of the extruder are respectively 160 ℃, 165 ℃ and 175 ℃, and the screw rotation speed is 40 rpm. The obtained wood-plastic composite material is a cuboid plate.
The products obtained in the above examples and comparative examples were subjected to performance verification by the following method:
bending property test
The test of the sample refers to the relevant requirements of GB/T1447-.
Impact strength test
The impact strength was tested in accordance with GB/T3808-2002 using a pendulum impact tester (China underwriter gold Instrument Co.) and each group of samples was tested 5 times and the test results were recorded and averaged.
The product performance test data for each of the examples and comparative examples is as follows:
SEM tests are carried out on the straw fibers subjected to surface modification in example 1 and comparative examples 3-4 and the products obtained in comparative example 5 through crosslinking of glutaraldehyde and PVA, and the obtained SEM images are shown in figures 1-4.
Fig. 1 is an SEM image of example 1, and it can be seen from the image that after surface modification, a dense and uniform nano polymer ball is formed on the fiber surface, and the formation of the nano polymer ball improves the non-polarity of the straw fiber surface, improves the compatibility between the fiber and the PP matrix, and improves the mechanical properties of the PP composite material. FIG. 2 is an SEM image of comparative example 3, and it can be seen from the SEM image that too high crosslinking temperature causes the partial area of the fiber surface to cover with nano polymer balls with different sizes and uneven distribution, and the partial area forms a thicker polymer film to wrap the fiber surface, which causes the mechanical property of the PP composite material to be reduced. FIG. 3 is an SEM image of comparative example 4, and it can be seen that after sulfuric acid is used as a crosslinking catalyst, the surface of the fiber can not form nano polymer spheres, but is covered with a thick polymer layer, and the fiber is brittle, and has many pores on the surface, which results in poor mechanical properties of the PP composite material. FIG. 4 is an SEM image of comparative example 5, from which it can be seen that PVA and glutaraldehyde crosslink to form stacked multi-layer thick films with easy overlap stacking due to the lack of growth adhesion matrix of the nano-polymer microspheres without straw fiber addition.
And (4) conclusion:
(1) as can be seen from the comparative example 3 and FIG. 2, the generation of the nano polymer microspheres is not facilitated due to the excessively high temperature of the crosslinking reaction, the polymer nano microspheres with uneven sizes are easily covered on the surface of the fiber, the aggregation phenomenon is easily caused, and a part of the fiber is wrapped by a thicker polymer film, so that the mechanical property of the composite material is reduced.
(2) It can be seen from comparative example 4 and fig. 3 that when concentrated sulfuric acid is used as a catalyst, the crosslinking reaction speed is fast, polymer nanospheres cannot be formed, and fibers are completely wrapped into clusters, so that the dispersibility among the fibers is poor, and the mechanical property of the composite material is poor.
(3) As can be seen from comparative example 5 and FIG. 4, the system with the straw fiber can provide a growth substrate for the polymer nanospheres, and PVA and glutaraldehyde are finally crosslinked to form a thick film which is mutually overlapped under the condition without the straw fiber.
(4) As can be seen from the example 1 and the comparative examples 1 and 2, the mechanical property of the wood-plastic composite material prepared by the method is equivalent to that of wood powder reinforced PP, and the wood-plastic composite material prepared by the method has better effect than that of the wood-plastic composite material prepared by alkali treatment.
(5) As can be seen from examples 1-4, figure 1 and comparative example 6, the embodiment of the invention can form the polymer nanospheres on the surface of the straw fiber, the polymer nanospheres can uniformly cover the surface of the straw fiber, prevent the straw fibers from aggregating with each other, improve the interface compatibility of the straw fiber and the PP (polypropylene) of the polymer matrix, improve the bonding capability of the straw fiber and the PP interface, and effectively improve the mechanical property of the wood-plastic composite material. The bending strength, the bending modulus and the impact resistance of the composite material are increased along with the proportion of PVA to glutaraldehyde, and show a trend of increasing firstly and then decreasing when the ratio of PVA to glutaraldehyde is as follows: glutaraldehyde =1:0.3 is the optimal proportion, the modified fiber surface is loaded with polymer nanospheres with uniform size and good dispersibility, and the prepared composite material has excellent bending property and impact resistance.
Claims (10)
1. A preparation method of a polymer nanosphere modified straw fiber reinforced wood-plastic composite material is characterized by comprising the following steps:
(1) taking straw skin as a raw material, drying and crushing the straw skin to obtain straw powder;
(2) mixing the PVA aqueous solution with the straw powder, and stirring uniformly;
(3) dripping glutaraldehyde into the ethanol aqueous solution, stirring uniformly, then dripping the ethanol aqueous solution containing glutaraldehyde into the mixture in the step (2), adding a magnesium chloride catalyst after dripping, and stirring for carrying out a crosslinking reaction;
(4) after reaction, filtering, washing and drying to obtain the straw fiber modified by the polymer nanospheres;
(5) uniformly mixing the straw fiber modified by the polymer nanosphere, PP, a lubricant and an antioxidant:
(6) extruding and molding the uniformly mixed materials in the step (5) to obtain a straw fiber reinforced wood-plastic composite material modified by the polymer nanospheres;
in the step (3), after magnesium chloride is added, reaction is carried out at 90-95 ℃.
2. The method of claim 1, wherein: the mass ratio of the glutaraldehyde to the PVA to the straw powder to the catalyst is 0.2-0.6: 0.5-1.5: 1: 0.6-1.2.
3. The method according to claim 1 or 2, characterized in that: in the step (2), the concentration of the PVA aqueous solution is 1-3 wt%.
4. The method according to claim 1 or 2, characterized in that: in the step (3), the concentration of the ethanol water solution is 50-90 wt%, and the concentration of the glutaraldehyde in the ethanol water solution is 2-6 wt%.
5. The method according to claim 1 or 2, characterized in that: in the step (2), mixing PVA and the straw powder at the temperature of 90-95 ℃; in the step (3), after magnesium chloride is added, the reaction is carried out for 2 to 3 hours at the temperature of between 90 and 95 ℃.
6. The method of claim 1, wherein: in the step (1), the straw skin is crushed and then is sieved by a 100-mesh sieve to obtain the straw powder.
7. The method according to claim 1 or 6, wherein: the straw is at least one of corn straw, wheat straw and rice straw.
8. The method of claim 1, wherein: in the step (5), the total weight of the straw fiber modified by the polymer nanospheres, the PP, the lubricant and the antioxidant is 100%, the content of the straw fiber modified by the polymer nanospheres is 25-30 wt%, the content of the PP is 69-74wt%, the content of the lubricant is 0.3-0.6wt%, and the content of the antioxidant is 0.4-0.7 wt%.
9. The method of claim 1, wherein: in the step (6), the straw fiber reinforced wood-plastic composite material modified by the polymer nanospheres is a cuboid plate.
10. The polymer nanosphere-modified straw fiber-reinforced wood-plastic composite prepared according to the preparation method of the polymer nanosphere-modified straw fiber-reinforced wood-plastic composite of any one of claims 1 to 9.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101384654A (en) * | 2006-01-12 | 2009-03-11 | 太尔公司 | Polymer-aldehyde binding system for manufacture of wood products |
| CN101885231A (en) * | 2009-05-15 | 2010-11-17 | 上海交福新材料科技有限公司 | Preparation method of fully-degradable polymer wood plastic composite |
| CN106220325A (en) * | 2016-07-25 | 2016-12-14 | 合肥工业大学 | A kind of water-fast degradable plant nutrition slow-release material and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101384654A (en) * | 2006-01-12 | 2009-03-11 | 太尔公司 | Polymer-aldehyde binding system for manufacture of wood products |
| CN101885231A (en) * | 2009-05-15 | 2010-11-17 | 上海交福新材料科技有限公司 | Preparation method of fully-degradable polymer wood plastic composite |
| CN106220325A (en) * | 2016-07-25 | 2016-12-14 | 合肥工业大学 | A kind of water-fast degradable plant nutrition slow-release material and preparation method thereof |
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