CN110509388B - Preparation method of high-strength weather-resistant colored sheet based on ramie bones - Google Patents

Preparation method of high-strength weather-resistant colored sheet based on ramie bones Download PDF

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CN110509388B
CN110509388B CN201910893662.9A CN201910893662A CN110509388B CN 110509388 B CN110509388 B CN 110509388B CN 201910893662 A CN201910893662 A CN 201910893662A CN 110509388 B CN110509388 B CN 110509388B
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epoxy resin
ramie
water
bones
emulsion
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CN110509388A (en
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吴庆定
宋喜艳
霍皓灵
唐小杰
杜沐青
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Central South University of Forestry and Technology
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Central South University of Forestry and Technology
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
    • B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
    • B27K3/02—Processes; Apparatus
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
    • B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
    • B27K3/16—Inorganic impregnating agents
    • B27K3/20—Compounds of alkali metals or ammonium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
    • B27K5/00—Treating of wood not provided for in groups B27K1/00, B27K3/00
    • B27K5/02—Staining or dyeing wood; Bleaching wood
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
    • B27K9/00—Chemical or physical treatment of reed, straw, or similar material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27N—MANUFACTURE BY DRY PROCESSES OF ARTICLES, WITH OR WITHOUT ORGANIC BINDING AGENTS, MADE FROM PARTICLES OR FIBRES CONSISTING OF WOOD OR OTHER LIGNOCELLULOSIC OR LIKE ORGANIC MATERIAL
    • B27N1/00—Pretreatment of moulding material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27N—MANUFACTURE BY DRY PROCESSES OF ARTICLES, WITH OR WITHOUT ORGANIC BINDING AGENTS, MADE FROM PARTICLES OR FIBRES CONSISTING OF WOOD OR OTHER LIGNOCELLULOSIC OR LIKE ORGANIC MATERIAL
    • B27N1/00—Pretreatment of moulding material
    • B27N1/02—Mixing the material with binding agent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27N—MANUFACTURE BY DRY PROCESSES OF ARTICLES, WITH OR WITHOUT ORGANIC BINDING AGENTS, MADE FROM PARTICLES OR FIBRES CONSISTING OF WOOD OR OTHER LIGNOCELLULOSIC OR LIKE ORGANIC MATERIAL
    • B27N3/00—Manufacture of substantially flat articles, e.g. boards, from particles or fibres
    • B27N3/02—Manufacture of substantially flat articles, e.g. boards, from particles or fibres from particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27N—MANUFACTURE BY DRY PROCESSES OF ARTICLES, WITH OR WITHOUT ORGANIC BINDING AGENTS, MADE FROM PARTICLES OR FIBRES CONSISTING OF WOOD OR OTHER LIGNOCELLULOSIC OR LIKE ORGANIC MATERIAL
    • B27N3/00—Manufacture of substantially flat articles, e.g. boards, from particles or fibres
    • B27N3/08—Moulding or pressing

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Forests & Forestry (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Dry Formation Of Fiberboard And The Like (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

The invention discloses a preparation method of a high-strength weather-resistant colored sheet based on ramie bones, which comprises five steps of ramie bone pretreatment, deep monochromatic dyeing, color mixing and sizing, warm-pressing forming and post-treatment.

Description

Preparation method of high-strength weather-resistant colored sheet based on ramie bones
Technical Field
The invention belongs to the field of new materials and green manufacturing, and particularly relates to a preparation method of a high-strength weather-resistant colored sheet material based on ramie bones.
Background
The ramie which is called Chinese grass has wide planting range, compared with cotton fiber, the fiber has the characteristics of high Young modulus, high polymerization degree, high single fiber strength and the like, and the components and the performance of the harvested remainder of the ramie are not inferior to those of common woody plants. Unfortunately, in vast rural areas, ramie bones are directly burned off or used as a burning material for cooking rice and pig food by farmers at home, so that the economic value of the ramie bones is not fully and efficiently utilized.
The preparation of high-cost-performance wood composite (functional) materials by high-value clean utilization of cheap woody, liana, herbaceous plants and harvesting/processing residues thereof has become one of the important concerns of new material developers. The ramie bones can be used for preparing a wood composite (functional) board with high cost performance.
Through patent retrieval, the following related and relatively close patent technical schemes are inquired.
Patent 1: patent application No. CN201711391972.8, a preparation method and application of ramie fiber/epoxy resin composite material. In the preparation method, the ramie fibers are cut into sections, placed in a die cavity and then placed in a mechanical vibration table, the vibration power is set to be 1.2-1.8 KW, the vibration frequency is set to be 300-600 HZ, the amplitude is set to be 1-5 mm, and the vibration time is set to be 10-30 min; uniformly mixing liquid epoxy resin, a curing agent and a silane coupling agent in a mass ratio of (1-1.2) to 1 to (0.01-0.066) to obtain an epoxy resin glue solution; taking the mold cavity out of the mechanical vibration table, and injecting epoxy resin glue solution into the mold cavity to soak ramie fibers; and (3) drying the ramie fibers subjected to the impregnation treatment at room temperature, then pressing and forming, and finally curing to obtain the ramie fiber/epoxy resin composite material. The patent adds silane coupling agent, utilizes ramie fiber, and has high economic cost.
Patent 2: application No. CN201810675026.4, a method for preparing a ramie fiber/epoxy resin composite material with the assistance of supercritical CO, which comprises the steps of dispersing ramie fibers in ethanol, then placing the ethanol into a supercritical CO treatment device, and treating for 30-60 min at the temperature of 60-80 ℃ and under the pressure of 20-30 MPa; releasing the pressure to normal pressure after the treatment is finished, taking out the ramie fibers, and carrying out heat treatment on the ramie fibers at 200-300 ℃ in an N atmosphere for 40-60 min; putting the ramie fibers subjected to heat treatment into a supercritical CO treatment device again, adding SiC particles, nano silicon dioxide and a curing agent into epoxy resin, uniformly mixing, pouring the uniformly mixed materials into the supercritical CO treatment device, soaking the ramie fibers, and treating for 30-60 min at 40-60 ℃ under 20-30 MPa; and (3) after the treatment is finished, releasing the pressure to normal pressure, taking out the ramie fibers, airing at room temperature, pressing for forming, and curing to obtain the ramie fiber/epoxy resin composite material. The patent uses ramie fiber in the supercritical CO treatment device, and has high economic cost.
In the 89 th year in 1989, the process flow of the ramie fiber board comprises the steps of cutting, screening, hot grinding, fine grinding, preparing coarse pulp by a hot grinding method, fine pulp treatment, molding, hot pressing and edge cutting, wherein ramie bones are subjected to hot grinding and fine grinding, and the ramie fiber board is soaked in water for two hours, and has a thickness expansion rate of 8% at a water temperature of 18 ℃. The technology to the product of the ramie core fiber board has the problem of environmental pollution, and the product of the ramie core fiber board is a conventional fiber board which is gradually replaced by a high-strength board.
Neither the above-mentioned patent solutions nor the above-mentioned papers disclose the contents of the present invention, and those skilled in the art can not derive the technical teaching of the present invention from the combination of the above-mentioned solutions.
Disclosure of Invention
The invention aims to open up a new way for high-value clean utilization of ramie bones, provide a preparation method of a colorful plate with bright color, high strength, abrasion resistance and good weather resistance, and enable people to enjoy the beautiful life accompanied by expensive and inexpensive high-grade wood products.
A preparation method of a high-strength weather-resistant colored sheet material based on ramie bones comprises the following steps:
step 1: pretreating ramie bones: soaking the dried ramie bones in a 2-5% NaOH solution for 10-12 h at room temperature, washing with water, and drying;
step 2: deep monochromatic dyeing: carrying out monochromatic dyeing treatment on the ramie bones pretreated in the step 1 for 45-60 min, wherein the dye solution comprises 2-4% of water-based dye, 2-3% of salt and the balance of soft water in percentage by weight, and the water-based dye is at least one of seven monochromatic dyes of red, orange, yellow, green, cyan, blue and purple; the monochromatic dyeing treatment is carried out in a vacuum environment with the temperature of 50-70 ℃ and the vacuum degree of 0.05-0.08 MPa; the deep monochromatic dyeing is essentially a process of dyeing the ramie bones from the outside to the inside after the ramie bones are fully soaked in NaOH solution and then the pits are opened, washed and dried in the step 1;
and step 3: color mixing and sizing: mixing and bundling at least one ramie bone deeply dyed in the step 2, wherein the weight of each ramie bone bundle is 3-5 kg, and soaking water-based epoxy resin adhesive by using the ramie bone bundles as an operation unit;
the waterborne epoxy resin adhesive is prepared by epoxy resin composite emulsion and a water-soluble curing agent in real time according to the volume ratio of 1:1, wherein the epoxy resin composite emulsion is uniform mixed emulsion of epoxy resin emulsion and coating emulsion of epoxy resin-organic nano montmorillonite, the volume ratio of the epoxy resin to the epoxy resin emulsion in the epoxy resin composite emulsion is 1: 9-1: 3, and the content of the organic nano montmorillonite in the epoxy resin composite emulsion is 4-6 wt%;
and 4, step 4: warm-pressing and forming: paving the ramie bones subjected to color mixing and sizing in the step 3 in time in a four-side top forming die to perform warm-pressing forming to prepare a color plate blank, wherein the forming pressure is 200-300 MPa, the forming temperature is 80-120 ℃, and the heat preservation and pressure maintaining time is 30-60 min;
and 5: and (3) post-treatment: and (4) performing edge cutting, sanding and waxing treatment on the color plate blank to finally obtain the high-strength weather-resistant color plate based on the ramie bones.
Further, the water content of the ramie before and after the pretreatment in the step 1 is 12-15%.
Further, the soft water in the step 2 is natural soft water, and is river water, river water or fresh water lake water containing no or less than 550mg/L soluble calcium and magnesium compounds.
Further, the four-side top forming die in the step 4 is a three-dimensional bidirectional forming die for performing warm-pressing forming by using four parallel surfaces of every two of six surfaces of the die, wherein the forming pressure is 250MPa, the forming temperature is 100 ℃, and the heat preservation and pressure maintaining time is 55 min.
Further, the epoxy resin emulsion in the step 3 is an emulsion prepared from epoxy resin, maleic anhydride and polyethylene glycol according to a molar ratio of 2:2: 1-3: 3: 1.
Further, the organic nano montmorillonite in the step 3 is obtained by organically modifying inorganic montmorillonite by using octadecyl trimethyl ammonium bromide as an intercalating agent.
Further, the water-soluble curing agent in the step 3 comprises triethylene tetramine, epoxy resin, allyl glycidyl ether and a diluent, wherein the triethylene tetramine, the epoxy resin and the allyl glycidyl ether are prepared according to the molar ratio of 2:1: 2-5: 2:4, and the diluent is acetone and distilled water.
The invention has the beneficial effects that:
1. the ramie bones are used as a base material, and the forming technology and the method of the wood composite material are innovated by comprehensively applying the forming theories of powder metallurgy and powder engineering, composite materials and engineering, wood science and technology and other interdisciplinary materials through the processes of pretreatment, deep dyeing, color mixing and sizing, warm-pressing forming, post-treatment and the like.
2. The ramie bones are fully soaked in the NaOH solution, and the ramie bones are dyed from the outside to the inside after the ramie bones open the pits, so that the dyeing uniformity and completeness are ensured, and the ramie bones are not easy to fade to a certain extent.
3. The components of the waterborne epoxy resin adhesive are all environment-friendly preparations, so that the problem of environmental pollution is solved; the preparation method is simple, the epoxy group of the epoxy resin reacts with the groups of other additives to realize bonding, and the durability of the material is improved; acetone and water are used as diluents, so that the removal from the system is convenient, the energy consumption is reduced, the heat generated in the reaction is taken away, and the stable and mild reaction is facilitated.
4. According to the invention, the four-side top forming die is used for performing four-side extrusion warm-pressing forming on the ramie core after the mixed color sizing, so that the obvious defect that the plate blank has inevitable internal defects due to the fact that the conventional artificial board is extruded in the upper and lower directions is overcome, and the manufactured color plate blank is extruded through four sides, has no internal defects compared with two-side extrusion, and is bright in color, high in strength, wear-resistant and good in weather resistance.
5. Compared with the patent application No. CN201711391972.8, the invention carries out drying and dyeing pretreatment on ramie, and does not add a coupling agent in the process of color mixing and sizing, thereby achieving the same adhesive force and weather resistance in a wet state; vacuum dyeing can enable the water-based fuel to achieve good dispersibility; the method selects the xylem of the ramie, namely the waste of the ramie as a raw material, and prepares the wood composite (functional) material with high cost performance by utilizing the processing residues, thereby having great significance for energy conservation and emission reduction.
6. Compared with the patent application No. CN201810675026.4, the invention accurately controls the formula of the waterborne epoxy resin adhesive, accurately controls the temperature, pressure and time of the warm-pressing forming process, does not need to dry at room temperature, and directly performs color mixing and gluing to achieve the same effect; the method selects the xylem of the ramie, namely the waste of the ramie as a raw material, and prepares the wood composite (functional) material with high cost performance by utilizing the processing residues, thereby having great significance for energy conservation and emission reduction.
7. Compared with the ramie fiber board developed in 89 th of 1989 in Hunan academy of agricultural sciences, the process flow and the cost are increased, paraffin, phenolic resin, aluminum sulfate and dilute sulfuric acid are added in the pulp washing process, and urea-formaldehyde resin adhesive is required to be added in the forming process, compared with the method disclosed by the invention, the environment pollution problem exists from the process to the product, the product ramie fiber board is a conventional fiber board, the density is low, the strength is low, the water absorption expansion rate is high, and the weather resistance is poor, the process is short, environment-friendly, and the product density, the strength and the weather resistance are more than 1 time higher than those of the fiber board prepared by a comparison document.
8. The material density of the high-strength weather-resistant colored sheet material is as high as 1.2-1.3 g/cm3Water absorption less than or equal to 2.0%, water absorption volume expansion rate of 0.0%, static bending strength of more than or equal to 100MPa, hardness of more than or equal to 8000N/mm2The wear resistance is less than or equal to 0.05g/100r, and the high-performance wear-resistant plate has the characteristics of high weather resistance, high density, high strength, low water absorption expansion rate and better than the conventional plate, and is suitable for manufacturing various high-grade household products and artware.
Detailed Description
The present invention is described in detail below with reference to specific examples for better understanding technical solutions of the present invention, and the description of the present invention is only exemplary and explanatory and should not be construed as limiting the scope of the present invention in any way.
The following are specific examples
Example 1
A preparation method of a high-strength weather-resistant colored sheet material based on ramie bones comprises the following steps:
step 1: pretreating ramie bones: soaking the dried ramie bones in a 2% NaOH solution for 10 hours at room temperature, washing with water, and drying; the water content of the ramie before and after the pretreatment in the step 1 is 12-15%.
Step 2: deep monochromatic dyeing: carrying out monochromatic dyeing treatment on the ramie bones pretreated in the step 1 for 45min, wherein the dye solution comprises 2% of water-based dyes, 2% of salt and the balance of soft water in percentage by weight, and the water-based dyes are seven monochromatic dyes of red, orange, yellow, green, cyan, blue and purple respectively; the monochromatic dyeing treatment is carried out in a vacuum environment with the temperature of 50 ℃ and the vacuum degree of 0.05 MPa; the deep monochromatic dyeing is essentially a process of dyeing the ramie bones from the outside to the inside after the ramie bones are fully soaked in NaOH solution and then the pits are opened, washed and dried in the step 1; the soft water in the step 2 is natural soft water, and contains river water with soluble calcium and magnesium compounds less than 550 mg/L.
And step 3: color mixing and sizing: respectively binding 7 ramie bones deeply dyed in the step 2 and with different colors, binding 7 pure-color ramie bones, wherein the weight of each bundle is 3kg, and soaking water-based epoxy resin glue by taking the bundle as an operation unit; the waterborne epoxy resin adhesive is prepared by epoxy resin composite emulsion and a water-soluble curing agent in real time according to the volume ratio of 1:1, wherein the epoxy resin composite emulsion is uniform mixed emulsion of epoxy resin emulsion and coating emulsion of epoxy resin-organic nano montmorillonite, the volume ratio of the epoxy resin to the epoxy resin emulsion in the epoxy resin composite emulsion is 1:9, and the mass content of the organic nano montmorillonite in the epoxy resin composite emulsion is 4%; the epoxy resin emulsion in the step 3 is an emulsion prepared from epoxy resin, maleic anhydride and polyethylene glycol according to the molar ratio of 2:2: 1. The organic nano montmorillonite in the step 3 is obtained by organically modifying inorganic montmorillonite by taking octadecyl trimethyl ammonium bromide as an intercalating agent. The water-soluble curing agent in the step 3 comprises triethylene tetramine, epoxy resin, allyl glycidyl ether and a diluent, wherein the triethylene tetramine, the epoxy resin and the allyl glycidyl ether are prepared according to the molar ratio of 2:1:2, and the diluent is acetone and distilled water.
And 4, step 4: warm-pressing and forming: paving the ramie bones mixed and glued in the step 3 in time in a four-side top forming die to carry out warm-pressing forming to prepare a color plate blank, wherein the forming pressure is 200Mpa, the forming temperature is 80 ℃, and the heat preservation and pressure maintaining time is 30 min; the four-side top forming die in the step 4 is a three-dimensional bidirectional forming die for performing warm-pressing forming by using four parallel surfaces in pairs of six surfaces of the die.
And 5: and (3) post-treatment: and (4) performing edge cutting, sanding and waxing treatment on the color plate blank to finally obtain the high-strength weather-resistant color plate based on the ramie bones.
The epoxy resin described above is standard bisphenol a epoxy resin E-51.
The test analysis of the 7 pure-color high-strength weather-resistant color plates prepared in the embodiment is as follows: the density is up to 1.21g/cm3Water absorption of 1.1%, water absorption volume expansion of 0.0%, static bending strength of 101MPa, hardness of 9100N/mm2The abrasion was 0.05g/100 r.
Example 2
A preparation method of a high-strength weather-resistant colored sheet material based on ramie bones comprises the following steps:
step 1: pretreating ramie bones: soaking the dried ramie bones in a 4% NaOH solution for 11h at room temperature, washing with water, and drying; the water content of the ramie before and after the pretreatment in the step 1 is 13-14%.
Step 2: deep monochromatic dyeing: carrying out monochromatic dyeing treatment on the ramie bones pretreated in the step 1 for 55min, wherein the dye solution comprises 3% of water-based dye, 2.8% of salt and the balance of soft water in percentage by weight, and the water-based dye is orange, yellow and green monochromatic dye respectively; the monochromatic dyeing treatment is carried out in a vacuum environment with the temperature of 60 ℃ and the vacuum degree of 0.06 MPa; the deep monochromatic dyeing is essentially a process of dyeing the ramie bones from the outside to the inside after the ramie bones are fully soaked in NaOH solution and then the pits are opened, washed and dried in the step 1; the soft water in the step 2 is natural soft water, and river water containing soluble calcium and magnesium compounds of which the concentration is lower than 500 mg/L.
And step 3: color mixing and sizing: mixing and bundling the 3 colors of ramie bones deeply dyed in the step 2, bundling a plate of three colors of orange, yellow and green with the weight of each bundle of 4kg, and infiltrating aqueous epoxy resin glue by taking the bundle as an operation unit; the waterborne epoxy resin adhesive is prepared by epoxy resin composite emulsion and a water-soluble curing agent in real time according to the volume ratio of 1:1, wherein the epoxy resin composite emulsion is uniform mixed emulsion of epoxy resin emulsion and coating emulsion of epoxy resin-organic nano montmorillonite, the volume ratio of the epoxy resin to the epoxy resin emulsion in the epoxy resin composite emulsion is 1:6, and the content of the organic nano montmorillonite in the epoxy resin composite emulsion is 5 wt%; the epoxy resin emulsion in the step 3 is an emulsion prepared from epoxy resin, maleic anhydride and polyethylene glycol according to the molar ratio of 2.5:2.5: 1. The organic nano montmorillonite in the step 3 is obtained by organically modifying inorganic montmorillonite by taking octadecyl trimethyl ammonium bromide as an intercalating agent. The water-soluble curing agent in the step 3 comprises triethylene tetramine, epoxy resin, allyl glycidyl ether and a diluent, wherein the triethylene tetramine, the epoxy resin and the allyl glycidyl ether are prepared according to the mol ratio of 2.3:1:2, and the diluent is acetone and distilled water.
And 4, step 4: warm-pressing and forming: paving the ramie bones mixed and glued in the step 3 in time in a four-side top forming die to carry out warm-pressing forming to prepare a color plate blank, wherein the forming pressure is 250MPa, the forming temperature is 100 ℃, and the heat preservation and pressure maintaining time is 55 min; the four-side top forming die in the step 4 is a three-dimensional bidirectional forming die for performing warm-pressing forming by using four parallel surfaces in pairs of six surfaces of the die,
and 5: and (3) post-treatment: and (4) performing edge cutting, sanding and waxing treatment on the color plate blank to finally obtain the high-strength weather-resistant color plate based on the ramie bones.
The epoxy resin described above is standard bisphenol a epoxy resin E-51.
The high-strength weather-resistant color plate prepared in the embodiment is subjected to test analysis: the density was 1.26g/cm3Water absorption of 1.4%, water absorption volume expansion of 0.0%, static bending strength of 103MPa, and hardness of 9800N/mm2The abrasion was 0.04g/100 r.
Example 3
A preparation method of a high-strength weather-resistant colored sheet material based on ramie bones comprises the following steps:
step 1: pretreating ramie bones: soaking the dried ramie bones in a 4.5% NaOH solution for 11.5h at room temperature, washing with water, and drying; the water content of the ramie before and after pretreatment in the step 1 is 14%.
Step 2: deep monochromatic dyeing: carrying out monochromatic dyeing treatment on the ramie bones pretreated in the step 1 for 58min, wherein the dye solution comprises 3.5% of water-based dyes, 2.6% of salt and the balance of soft water in percentage by weight, and the water-based dyes are red, orange, yellow, green, cyan, blue and purple water-based dyes respectively; the monochromatic dyeing treatment is carried out in a vacuum environment with the temperature of 58 ℃ and the vacuum degree of 0.07 MPa; the deep monochromatic dyeing is essentially a process of dyeing the ramie bones from the outside to the inside after the ramie bones are fully soaked in NaOH solution and then the pits are opened, washed and dried in the step 1; the soft water in the step 2 is natural soft water, and the water of the fresh water lake containing soluble calcium and magnesium compounds less than 550 mg/L.
And step 3: color mixing and sizing: carrying out hybrid binding on 7-color ramie bones deeply dyed in the step 2 to obtain a bundle of 7-color ramie bones, wherein the weight of each bundle is 4.5kg, and the bundle is used as an operation unit to be soaked with water-based epoxy resin glue; the waterborne epoxy resin adhesive is prepared by epoxy resin composite emulsion and a water-soluble curing agent in real time according to the volume ratio of 1:1, wherein the epoxy resin composite emulsion is uniform mixed emulsion of epoxy resin emulsion and coating emulsion of epoxy resin-organic nano montmorillonite, the volume ratio of the epoxy resin to the epoxy resin emulsion in the epoxy resin composite emulsion is 1:7, and the content of the organic nano montmorillonite in the epoxy resin composite emulsion is 5.2 wt%; the epoxy resin emulsion in the step 3 is an emulsion prepared from epoxy resin, maleic anhydride and polyethylene glycol according to the molar ratio of 2.8:2.8: 1. The water-soluble curing agent in the step 3 comprises triethylene tetramine, epoxy resin, allyl glycidyl ether and a diluent, wherein the triethylene tetramine, the epoxy resin and the allyl glycidyl ether are prepared according to the mol ratio of 2.8:1:2, and the diluent is acetone and distilled water.
And 4, step 4: warm-pressing and forming: paving the ramie bones mixed and glued in the step 3 in time in a four-side top forming die to carry out warm-pressing forming to prepare a color plate blank, wherein the forming pressure is 280MPa, the forming temperature is 110 ℃, and the heat preservation and pressure maintaining time is 48 min; the four-side top forming die in the step 4 is a three-dimensional bidirectional forming die for performing warm-pressing forming by using four parallel surfaces in pairs of six surfaces of the die.
And 5: and (3) post-treatment: and (4) performing edge cutting, sanding and waxing treatment on the color plate blank to finally obtain the high-strength weather-resistant color plate based on the ramie bones.
The epoxy resin described above is standard bisphenol a epoxy resin E-51.
The high-strength weather-resistant seven-color plate prepared in the embodiment is subjected to test analysis: the density was 1.28g/cm3Water absorption of 1.08%, water absorption volume expansion of 0.0%, static bending strength of 105MPa, and hardness of 9200N/mm2The abrasion was 0.041g/100 r.
Example 4
A preparation method of a high-strength weather-resistant colored sheet material based on ramie bones comprises the following steps:
step 1: pretreating ramie bones: soaking the dried ramie bones in a 5% NaOH solution for 12h at room temperature, washing with water, and drying; the water content of the ramie before and after the pretreatment in the step 1 is 12-15%.
Step 2: deep monochromatic dyeing: carrying out monochromatic dyeing treatment on the ramie bones pretreated in the step 1 for 60min, wherein the dye solution comprises 4% of water-based dye, 3% of salt and the balance of soft water in percentage by weight, and the water-based dye is a yellow-green dye formed by mixing yellow and green monochromatic dyes; the monochromatic dyeing treatment is carried out in a vacuum environment with the temperature of 70 ℃ and the vacuum degree of 0.08 MPa; the deep monochromatic dyeing is essentially a process of dyeing the ramie bones from the outside to the inside after the ramie bones are fully soaked in NaOH solution and then the pits are opened, washed and dried in the step 1; the soft water in the step 2 is natural soft water, and contains river water with soluble calcium and magnesium compounds lower than 500 mg/L.
And step 3: color mixing and sizing: bundling the yellow-green ramie bones deeply dyed in the step 2, wherein the weight of each bundle is 5kg, and soaking water-based epoxy resin glue by taking the bundle as an operation unit; the waterborne epoxy resin adhesive is prepared by epoxy resin composite emulsion and a water-soluble curing agent in real time according to the volume ratio of 1:1, wherein the epoxy resin composite emulsion is uniform mixed emulsion of epoxy resin emulsion and coating emulsion of epoxy resin-organic nano montmorillonite, the volume ratio of the epoxy resin to the epoxy resin emulsion in the epoxy resin composite emulsion is 1:3, and the content of the organic nano montmorillonite in the epoxy resin composite emulsion is 6 wt%; the epoxy resin emulsion in the step 3 is an emulsion prepared from epoxy resin, maleic anhydride and polyethylene glycol according to a molar ratio of 3:3: 1. The organic nano montmorillonite in the step 3 is obtained by organically modifying inorganic montmorillonite by taking octadecyl trimethyl ammonium bromide as an intercalating agent. The water-soluble curing agent in the step 3 comprises triethylene tetramine, epoxy resin, allyl glycidyl ether and a diluent, the triethylene tetramine, the epoxy resin and the allyl glycidyl ether are prepared according to a molar ratio of 5:2:4, the diluent is prepared by acetone and distilled water according to a mass ratio of 1:1, and the triethylene tetramine and the diluent are prepared according to a mass ratio of 1: 2.
And 4, step 4: warm-pressing and forming: paving the ramie bones mixed and glued in the step 3 in time in a four-side top forming die to carry out warm-pressing forming to prepare a color plate blank, wherein the forming pressure is 300MPa, the forming temperature is 120 ℃, and the heat preservation and pressure maintaining time is 60 min; the four-side top forming die in the step 4 is a three-dimensional bidirectional forming die for performing warm-pressing forming by using four parallel surfaces in pairs of six surfaces of the die.
And 5: and (3) post-treatment: and (4) performing edge cutting, sanding and waxing treatment on the color plate blank to finally obtain the high-strength weather-resistant color plate based on the ramie bones.
The epoxy resin described above is standard bisphenol a epoxy resin E-51.
The high-strength weather-resistant yellow-green plate prepared in the embodiment is subjected to test analysis: the density was 1.29g/cm3Water absorption of 1.6%, water absorption volume expansion of 0.0%, static bending strength of 102MPa, hardness of 9600N/mm2And an abrasion of 0.045g/100 r.
Comparative example 1
The difference from example 1 is that: in the step (2), the temperature is kept at 0.1MPa in a vacuum environment at 50 ℃; otherwise, the same procedure as in example 1 was repeated.
The density of the color plate prepared in the comparative example is 1.0g/cm3Water absorption of 2.4%, water absorption volume expansion of 0.9%, static bending strength of 90MPa, hardness of 7800N/mm2The abrasion was 0.06g/100r。
Comparative example 2
The difference from example 1 is that: in the step (3), warm-pressing and forming: the ramie core mixed with the color and the glue is laid in a four-side top forming die in time and is subjected to warm-pressing forming to prepare a color plate blank, the forming pressure is 180MPa, the forming temperature is 60 ℃, and the heat preservation and pressure maintaining time is 55 min. Otherwise, the same procedure as in example 1 was repeated.
The density of the colored sheet prepared in this comparative example was 1.2g/cm3The water absorption rate is 2.8 percent, the water absorption volume expansion rate is 1.1 percent, the static bending strength is 70MPa, and the hardness is 7900N/mm2The abrasion was 0.06g/100 r.
TABLE 1 color sheet Property parameter Table for examples and comparative examples
Figure BDA0002209570240000121
Comparing the performance data of the colored sheets obtained in examples 1 to 4 and comparative examples 1 to 2, it is found that the performance of examples 1 to 4 is significantly better than that of comparative examples 1 to 2. The color properties obtained in examples 1-4 completely satisfy the material requirements, while the properties of the color plates obtained in comparative examples 1-2 are below the critical value. Hardness, static bending strength and water absorption volume expansion rate can not meet part of application requirements.
It should be noted that, in this document, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
The principles and embodiments of the present invention are explained herein using specific examples, which are presented only to assist in understanding the method and its core concepts of the present invention. The foregoing is only a preferred embodiment of the present invention, and it should be noted that there are objectively infinite specific structures due to the limited character expressions, and it will be apparent to those skilled in the art that a plurality of modifications, decorations or changes may be made without departing from the principle of the present invention, and the technical features described above may be combined in a suitable manner; such modifications, variations, combinations, or adaptations of the invention using its spirit and scope, as defined by the claims, may be directed to other uses and embodiments.

Claims (6)

1. A preparation method of a high-strength weather-resistant colored sheet material based on ramie bones is characterized by comprising the following steps:
step 1: pretreating ramie bones: soaking the dried ramie bones in a 2-5% NaOH solution for 10-12 h at room temperature, washing with water, and drying; the water content of the ramie before and after pretreatment in the step 1 is 12% -15%;
step 2: deep monochromatic dyeing: carrying out monochromatic dyeing treatment on the ramie bones pretreated in the step 1 for 45-60 min, wherein the dye solution comprises 2-4% of water-based dye, 2-3% of salt and the balance of soft water in percentage by weight, and the water-based dye is at least one of seven monochromatic dyes of red, orange, yellow, green, cyan, blue and purple; the monochromatic dyeing treatment is carried out in a vacuum environment with the temperature of 50-70 ℃ and the vacuum degree of 0.05-0.08 MPa; the deep monochromatic dyeing is essentially a process of dyeing the ramie bones from the outside to the inside after the ramie bones are fully soaked in NaOH solution and then the pits are opened, washed and dried in the step 1;
and step 3: color mixing and sizing: mixing and bundling at least one ramie bone deeply dyed in the step 2, wherein the weight of each ramie bone bundle is 3-5 kg, and soaking water-based epoxy resin adhesive by using the ramie bone bundles as an operation unit;
the waterborne epoxy resin adhesive is prepared by epoxy resin composite emulsion and a water-soluble curing agent in real time according to the volume ratio of 1:1, wherein the epoxy resin composite emulsion is uniform mixed emulsion of epoxy resin emulsion and coating emulsion of epoxy resin-organic nano montmorillonite, the volume ratio of the epoxy resin to the epoxy resin emulsion in the epoxy resin composite emulsion is 1: 9-1: 3, and the content of the organic nano montmorillonite in the epoxy resin composite emulsion is 4-6 wt%;
and 4, step 4: warm-pressing and forming: paving the ramie bones subjected to color mixing and sizing in the step 3 in time in a four-side top forming die to perform warm-pressing forming to prepare a color plate blank, wherein the forming pressure is 200-300 MPa, the forming temperature is 80-120 ℃, and the heat preservation and pressure maintaining time is 30-60 min;
and 5: and (3) post-treatment: and (4) performing edge cutting, sanding and waxing treatment on the color plate blank to finally obtain the high-strength weather-resistant color plate based on the ramie bones.
2. The method according to claim 1, wherein the soft water obtained in step 2 is natural soft water, river water or river water containing no soluble calcium or magnesium compounds, or river water containing soluble calcium or magnesium compounds and less than 550 mg/L.
3. The method for preparing a high-strength weather-resistant colored sheet material based on ramie bones according to claim 1, wherein the four-side-top forming die in step 4 is a three-dimensional bidirectional forming die which performs warm-pressing forming by using four parallel surfaces of every two of six surfaces of the die, the forming pressure is 200-300 MPa, the forming temperature is 80-120 ℃, and the heat and pressure maintaining time is 30-60 min.
4. The method for preparing a high-strength weather-resistant colored sheet material based on ramie bones according to claim 1, wherein the epoxy resin emulsion in the step 3 is an emulsion prepared from epoxy resin, maleic anhydride and polyethylene glycol according to a molar ratio of 2:2: 1-3: 3: 1.
5. The method of claim 1, wherein the organic montmorillonite nanoparticles obtained in step 3 are prepared by organically modifying inorganic montmorillonite with octadecyl trimethyl ammonium bromide as an intercalating agent.
6. The method for preparing a high-strength weather-resistant colored sheet material based on ramie bones according to claim 1, wherein the water-soluble curing agent in step 3 comprises triethylene tetramine, epoxy resin, allyl glycidyl ether and a diluent, wherein the triethylene tetramine, the epoxy resin and the allyl glycidyl ether are prepared according to a molar ratio of 2:1: 2-5: 2:4, and the diluent is acetone and distilled water.
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