CN108274555B - Modified phenolic resin adhesive, preparation method and application thereof, and preparation method of bamboo-wood composite board - Google Patents

Modified phenolic resin adhesive, preparation method and application thereof, and preparation method of bamboo-wood composite board Download PDF

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Publication number
CN108274555B
CN108274555B CN201810130148.5A CN201810130148A CN108274555B CN 108274555 B CN108274555 B CN 108274555B CN 201810130148 A CN201810130148 A CN 201810130148A CN 108274555 B CN108274555 B CN 108274555B
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China
Prior art keywords
bamboo
phenolic resin
wood
resin adhesive
modified phenolic
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CN108274555A (en
Inventor
侯伦灯
俞艳
吴黄贵
郑忠福
郑志伟
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Fujian Heqizu Forestry Technology Co ltd
Fujian Agriculture and Forestry University
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Fujian Heqizu Forestry Technology Co ltd
Fujian Agriculture and Forestry University
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Priority to CN201810130148.5A priority Critical patent/CN108274555B/en
Publication of CN108274555A publication Critical patent/CN108274555A/en
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    • 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
    • B27D—WORKING VENEER OR PLYWOOD
    • B27D1/00—Joining wood veneer with any material; Forming articles thereby; Preparatory processing of surfaces to be joined, e.g. scoring
    • B27D1/04—Joining wood veneer with any material; Forming articles thereby; Preparatory processing of surfaces to be joined, e.g. scoring to produce plywood or articles made therefrom; Plywood sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27D—WORKING VENEER OR PLYWOOD
    • B27D1/00—Joining wood veneer with any material; Forming articles thereby; Preparatory processing of surfaces to be joined, e.g. scoring
    • B27D1/04—Joining wood veneer with any material; Forming articles thereby; Preparatory processing of surfaces to be joined, e.g. scoring to produce plywood or articles made therefrom; Plywood sheets
    • B27D1/08—Manufacture of shaped articles; Presses specially designed therefor
    • 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
    • B27K3/04—Impregnating in open tanks
    • 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
    • B27K3/34—Organic impregnating agents
    • B27K3/36—Aliphatic compounds
    • 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
    • B27K5/04—Combined bleaching or impregnating and drying of 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
    • B27K9/002—Cane, bamboo

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

Abstract

The invention provides a modified phenolic resin adhesive and a preparation method thereof. The phenolic resin adhesive prepared by the method has high viscosity, can realize quick impregnation of bamboo wood, has high bonding strength, can realize firm bonding of bamboo boards and wood boards, does not need to prolong impregnation time in order to improve the adhesive absorption amount, and is beneficial to reducing energy consumption. The results of the embodiment show that when the modified phenolic resin adhesive is used for preparing bamboo-wood composite boards, the moisture content of bamboo is only controlled within the range of 25-45%, and the moisture content of bamboo is not required to be dried to be below 6%, so that the composite boards meeting the corresponding performance requirements can be obtained. The invention also provides a preparation method of the bamboo-wood composite board, which takes the modified phenolic resin adhesive as the impregnation liquid, adopts a centrifugal impregnation mode, dries the bamboo while impregnating, can realize impregnation in a high-humidity state, and saves the drying energy consumption of the bamboo.

Description

Modified phenolic resin adhesive, preparation method and application thereof, and preparation method of bamboo-wood composite board
Technical Field
The invention belongs to the technical field of composite board preparation, and particularly relates to a modified phenolic resin adhesive, a preparation method and application thereof, and a preparation method of a bamboo-wood composite board.
Background
The container is a general name of a group tool for transporting packaged goods or unpacked goods, and the bottom plate of the container is an important component and a main bearing accessory of the container, so that the transportation safety and the quality of goods are influenced. The traditional container bottom plate mainly adopts wood plywood made of tropical hard broad-leaved wood. Due to the reduction of the resources of the hard broad-leaved wood in the world and the implementation of the protection measures of natural forests, the countries in the world gradually adopt alternative materials to reduce the usage amount of tropical broad-leaved wood. The bamboo-wood container bottom plate adopts a bamboo-wood composite structure production mode, the mechanical processing characteristics of bamboo and eucalyptus are comprehensively utilized to optimize the product structure, the surface layer of the bottom plate is coated with phenolic resin impregnated paper, the surface layer is coated with a bamboo mat and a bamboo curtain, the core layer is formed by gluing and hot-pressing the bamboo curtain/eucalyptus veneer by phenolic resin. The bamboo wood raw material utilization rate is high in the processing process of the bamboo wood composite board, and the problem of wood board resource shortage is effectively solved.
The bamboo-wood composite board is prepared through the conventional preparation process including the steps of processing bamboo and wood into semi-finished product, drying, soaking the semi-finished product in glue, drying, assembling the semi-finished product and pressing. The water content of the dried board is clearly limited, the water content of the dried bamboo board is required to be lower than 6%, and if the board with the water content not meeting the requirement is directly used for gum dipping, the smooth proceeding of gum dipping is influenced, and the gum sucking amount in the gum dipping process is insufficient. In order to increase the glue absorption amount, the glue dipping time can be prolonged, so that more water is absorbed in the glue dipping process, the glue drying time after glue dipping can be correspondingly prolonged, and the energy consumption can be increased by the requirement of lower water content after drying and the prolongation of the glue drying time. Furthermore, phenolic resin glue is a common adhesive used nowadays, and is a general name of resin formed by taking phenols and derivatives thereof and aldehydes as raw materials under the action of an alkaline or acidic catalyst, and is widely used in the production of artificial boards due to excellent weather resistance and bonding performance, but harmful substances such as free phenol are accompanied in the production and use processes, and the release of the harmful substances is aggravated when the glue drying time is too long.
Disclosure of Invention
The invention aims to provide a modified phenolic resin adhesive, a preparation method and application thereof, and a preparation method of a bamboo-wood composite board.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a modified phenolic resin adhesive, which comprises the following steps:
(1) carrying out addition reaction on phenol, formaldehyde and tea polyphenol to obtain an addition product; the temperature of the addition reaction is 90-95 ℃, and the time of the addition reaction is 1-2 h;
(2) carrying out modification reaction on the addition product obtained in the step (1), the first modifier and the second modifier to obtain a modified phenolic resin adhesive;
the temperature of the modification reaction is 60-80 ℃, and the time of the modification reaction is 1-1.5 h;
the first modifier is resorcinol; the second modifier comprises propylene carbonate, epoxy resin or organic silicon resin.
Preferably, the molar ratio of phenol to formaldehyde in the step (1) is 1: 1.8-2; the mass of the tea polyphenol is 10-50% of that of phenol.
Preferably, in the step (2), the mass of the first modifier is 5-15% of that of the phenol for preparing the addition product; the mass of the second modifier is 2-6% of that of the phenol for preparing the addition product.
The invention provides the modified phenolic resin adhesive prepared by the preparation method in the technical scheme, and the density of the modified phenolic resin adhesive is 1.02-1.12 g/cm3The viscosity is 400-450 mPa.s, the curing time is 800-900 s, the curing temperature is 115-125 ℃, and the pH value is 9.5-11.5; the modified phenolic resin adhesive has a free phenol content of 0.6 to 1.0 wt.%.
The invention also provides the application of the modified phenolic resin adhesive in the technical scheme in an artificial board.
The invention provides a preparation method of a bamboo-wood composite board, which comprises the following steps:
(I) adopting the glue solution containing the modified phenolic resin adhesive in the technical scheme to centrifugally filter glue after centrifugally dipping the pre-assembled bamboo wood; drying the bamboo material subjected to centrifugal glue filtration to obtain a dipped bamboo material;
the moisture content of the pre-assembly bamboo is 25-45%;
the rotation speed of the centrifugal gumming is 100-200 rpm, and the time of the centrifugal gumming is 2-6 min;
the rotating speed of the centrifugal filter rubber is 250-500 rpm; the centrifugal glue filtering time is 2-5 min;
the water content of the impregnated bamboo wood is 10-18%;
(II) assembling the dipped bamboo wood obtained in the step (I) with a wood board to obtain a green body;
(III) sequentially heating, dehumidifying at low pressure, hot-pressing and cooling the green body obtained in the step (II) to obtain a bamboo-wood composite board;
the pressure of low-pressure moisture removal is 0.8-1.2 MPa.
Preferably, the mass fraction of the glue solution in the step (I) is 30-40%; the impregnation amount of the bamboo material after centrifugal impregnation is 135-150 Kg/m3。
Preferably, the low-pressure moisture removal time in the step (III) is 60-120 s; the temperature rise time in the step (III) is 10-20 min, and the temperature rises to 110-135 ℃.
Preferably, the pressure of hot pressing in the step (III) is 3.5-5.5 MPa; the hot pressing time is 0.8-1.6 min/mm based on the thickness of the plate to be hot pressed.
Preferably, the temperature of the bamboo-wood composite board cooled in the step (III) is 60-80 ℃.
The invention provides a preparation method of a modified phenolic resin adhesive, which comprises the steps of carrying out addition reaction on phenol, formaldehyde and tea polyphenol at 90-95 ℃, and carrying out modification reaction on the phenol, the formaldehyde and the tea polyphenol with a first modifier and a second modifier to obtain the modified phenolic resin adhesive; the temperature of the modification reaction is controlled to be 60-80 ℃, and the time of the modification reaction is 1-1.5 h, wherein the first modifier is resorcinol, and the second modifier comprises propylene carbonate, epoxy resin or organic silicon resin. According to the invention, tea polyphenol is used for replacing a part of phenol, and the two modifiers are combined, so that the obtained phenolic resin adhesive has high viscosity, can realize quick impregnation of bamboo wood, has high bonding strength performance, can realize firm bonding of bamboo boards and wood boards, and does not need to reduce the water content of the bamboo wood to below 6% so as to meet the requirement of the impregnation process on water; the gum dipping time does not need to be prolonged in order to improve the gum absorption amount, and the gum drying time does not need to be prolonged, so that the energy consumption is reduced; and the content of free phenol in the modified phenolic resin adhesive is low, and the release amount of the free phenol in the gum dipping process is small.
Moreover, the modified phenolic resin adhesive provided by the invention is low in free phenol content, and the modifier adopted in the preparation process has the effect of stabilizing formaldehyde and phenol, so that the release of harmful substances in the heating process is avoided. The results of the embodiment show that when the modified phenolic resin adhesive is used for preparing bamboo-wood composite boards, the moisture content of bamboo can be controlled within the range of 25-45% to obtain the composite boards meeting the corresponding performance requirements.
The invention also provides a preparation method of the bamboo-wood composite board, the bamboo-wood composite board takes the modified phenolic resin adhesive as the impregnation liquid, adopts a centrifugal impregnation mode, dries the bamboo wood while impregnating, can realize impregnation in a high-humidity state, does not need to reduce the moisture content of the impregnated bamboo wood to be lower than 6 percent for impregnation, and saves the drying energy consumption of the bamboo wood; and the mode of firstly pre-pressing, dehumidifying and re-pressing treatment is favorable for reducing the hot-pressing temperature and the hot-pressing time and reducing the hot-pressing consumption.
Detailed Description
The invention provides a preparation method of a modified phenolic resin adhesive, which comprises the following steps:
(1) carrying out addition reaction on phenol, formaldehyde and tea polyphenol to obtain an addition product; the temperature of the addition reaction is 90-95 ℃, and the time of the addition reaction is 1-2 h;
(2) carrying out modification reaction on the addition product obtained in the step (1), the first modifier and the second modifier to obtain a modified phenolic resin adhesive;
the temperature of the modification reaction is 60-80 ℃, and the time of the modification reaction is 1-1.5 h;
the first modifier is resorcinol; the second modifier comprises propylene carbonate, epoxy resin or organic silicon resin.
The invention carries out addition reaction on phenol, formaldehyde and tea polyphenol to obtain an addition product. In the present invention, the molar ratio of phenol to formaldehyde is preferably 1: 1.8-2, most preferably 1: 2; the mass of the tea polyphenol is preferably 10-50% of that of phenol, more preferably 15-45%, and even more preferably 20-30%.
In the present invention, the tea polyphenol is preferably provided in the form of a tea polyphenol solution; the invention has no special requirements on the mass concentration of the tea polyphenol solution, and the tea polyphenol solution can be used in any concentration. In the present invention, the method for preparing the tea polyphenol solution preferably comprises: mixing tea stems with an ethanol solution, and extracting under an ultrasonic condition to obtain a tea polyphenol solution. In the invention, the mass concentration of the ethanol solution is preferably 60-75%, more preferably 65-72%, and even more preferably 70%; the mass of the tea stem is 10-30% of that of the ethanol solution, preferably 15-25%, and more preferably 20%. In the invention, the particle size of the tea stems is preferably 0.5-2 mm; the invention has no special requirements on the source of the tea stem, and the tea stem can be prepared by adopting the method well known by the technical personnel in the field. The invention has no special requirement on the mixing mode of the tea stalks and the ethanol solution, and the material liquid mixing mode which is well known by the technical personnel in the field can be adopted.
The tea stem and the ethanol solution are mixed and then extracted under the ultrasonic condition to obtain the tea polyphenol solution. In the present invention, the frequency of the ultrasound is preferably 20 KHz; the extraction temperature is preferably 60-80 ℃, and more preferably 65-75 ℃; more preferably 70 ℃; the extraction time is preferably 20-40 min, more preferably 25-35 min, and even more preferably 30 min. The invention adopts an ultrasonic extraction mode to fully extract the tea polyphenol in the tea stem and improve the utilization rate.
The source of the phenol and formaldehyde is not particularly required in the present invention, and commercially available products well known to those skilled in the art may be used.
The phenol, the formaldehyde and the tea polyphenol are subjected to addition reaction to obtain an addition product. In the invention, the temperature of the addition reaction is 90-95 ℃, preferably 92-94 ℃, and more preferably 93 ℃; the time of the addition reaction is 1-2 h, preferably 1.5 h.
After the addition reaction, the obtained addition product, the first modifier and the second modifier are subjected to modification reaction to obtain the modified phenolic resin adhesive. In the invention, the first modifier is resorcinol; the mass of the first modifier is preferably 5 to 15%, more preferably 8 to 12%, and even more preferably 10% of the mass of the phenol for producing the addition product.
In the present invention, the second modifier includes propylene carbonate, epoxy resin or silicone resin. In the present invention, the epoxy resin is preferably one or more of epoxy resin E35, epoxy resin E42, epoxy resin E44 and epoxy resin E51; the organic silicon resin is preferably one or more of organic silicon resin W33-2, organic silicon resin W33-5 and organic silicon resin W35-1. The present invention has no particular requirement for the specific sources of the propylene carbonate, epoxy resin and silicone resin, and commercially available products well known to those skilled in the art can be used. In the present invention, the mass of the second modifier is preferably 2 to 6%, more preferably 3 to 5% of the mass of the phenol for producing the addition product.
In the invention, the temperature of the modification reaction is 60-80 ℃, preferably 65-75 ℃, and more preferably 70-72 ℃. In the invention, the time of the modification reaction is 1 to 1.5 hours, preferably 1.1 to 1.4 hours, and more preferably 1.2 to 1.3 hours. In the modification reaction process, the first modifier and formaldehyde are subjected to addition reaction, so that free aldehyde in the glue is reduced, and the bonding strength and the water resistance of the modified phenolic resin adhesive are improved; the second modifier and the phenolic resin adhesive which is an addition product are subjected to a crosslinking reaction, and the second modifier has good plasticity and can be subjected to crosslinking curing with the phenolic resin adhesive in the resin curing process, so that the benzene ring distance in the resin is increased, the flexibility of the resin is improved, and the deformation of the part can be absorbed or buffered in the hot pressing process of the plate, the deformation is reduced, and the size stability of the plate is improved.
The invention provides the modified phenolic resin adhesive prepared by the preparation method in the technical scheme. In the invention, the density of the modified phenolic resin adhesive is 1.02-1.12 g/cm3Preferably 1.1 to 1.12g/cm3. In the invention, the viscosity of the modified phenolic resin adhesive is 400-450 mPa.s, preferably 420-440 mPa.s; the modified phenolic resin adhesive disclosed by the invention is low in viscosity, has excellent permeability and wettability on a plate, and is convenient for efficient permeation of the modified phenolic resin adhesive in the plate.
In the invention, the curing time of the modified phenolic resin adhesive is 800-900 s, preferably 820-880 s, and more preferably 850 s; the curing temperature is 115-125 ℃, and is further preferably 120-123 ℃. The curing temperature of the modified phenolic resin adhesive disclosed by the invention is far lower than that of the traditional phenolic resin at about 145 ℃, so that the hot pressing time period in the process of gluing plates is favorably shortened, and the energy consumption is reduced.
In the present invention, the content of free phenol in the modified phenolic resin adhesive is 0.6 to 1.0 wt.%, preferably 0.75 to 0.85 wt.%, and more preferably 0.8 wt.%.
In the invention, the pH value of the modified phenolic resin adhesive is 9.5-10.5, and more preferably 10-10.2; the modified phenolic resin adhesive is stable in the pH value range, excessive alkalinity is avoided, white alkaline spots are easy to appear on the surface of a produced product, appearance quality is affected, too low alkalinity is also avoided, the phenolic resin adhesive is not easy to permeate, and the absorption amount of bamboo wood to the adhesive is affected, so that the overall quality of the board is affected. In the invention, the solid content of the modified phenolic resin adhesive is preferably 42.2-45.6%, more preferably 43-45%, and more preferably 44-44.5%; the requirement of the adhesive on solid content is met.
The invention also provides the application of the modified phenolic resin adhesive in the technical scheme in the preparation of artificial boards. The invention has no special requirements on the application mode of the modified phenolic resin adhesive, and can be realized by adopting the application mode of the adhesive in the preparation of artificial boards, which is well known by the technical personnel in the field.
The invention provides a preparation method of a bamboo-wood composite board, which comprises the following steps:
(I) adopting glue solution containing the modified phenolic resin adhesive in the technical scheme to centrifugally dip pre-assembled bamboo wood and then centrifugally filter the glue; drying the bamboo material subjected to centrifugal glue filtration to obtain a dipped bamboo material;
the moisture content of the pre-assembly bamboo is 25-45%;
the rotation speed of the centrifugal gumming is 100-200 rpm, and the time of the centrifugal gumming is 2-6 min;
the rotating speed of the centrifugal filter rubber is 250-500 rpm; the centrifugal glue filtering time is 2-5 min;
the water content of the impregnated bamboo wood is 10-18%;
(II) assembling the dipped bamboo wood obtained in the step (I) with a wood board to obtain a green body;
(III) sequentially heating, dehumidifying at low pressure, hot-pressing and cooling the green body obtained in the step (II) to obtain a bamboo-wood composite board;
the pressure of low-pressure moisture removal is 0.8-1.2 MPa.
The glue solution containing the modified phenolic resin adhesive in the technical scheme is adopted to centrifugally filter glue after centrifugal gum dipping of pre-assembled bamboo materials; and drying the bamboo material subjected to centrifugal glue filtration to obtain the dipped bamboo material. In the invention, the moisture content of the pre-assembled bamboo is 25-45%, preferably 30-44%, and more preferably 35-40%. The invention has no special requirements on the size of the pre-assembled bamboo material, and the size which is well known by the technical personnel in the field can be adopted. In the invention, the pre-assembled bamboo is preferably one or more of bamboo boards, veneers, bamboo curtains and bamboo mats. The invention has no special requirements on the source of the pre-assembled bamboo material, and the method can be realized by adopting the method which is well known by the technical personnel in the field.
In the invention, the mass fraction of the glue solution of the modified phenolic resin adhesive is preferably 30-40%, and more preferably 32-38%; in the invention, the solid content of the modified phenolic resin adhesive is slightly higher, and the modified phenolic resin adhesive needs to be diluted by water to obtain the glue solution of the modified phenolic resin adhesive, so that the subsequent glue dipping is convenient to use. In the invention, the rotation speed of the centrifugal gumming is 100-120 rpm, preferably 120-150 rpm, and more preferably 125-135 rpm; the centrifugal gum dipping time is 2-6 min, and the preferable time is 3-5 min. In the present invention, the centrifugal gumming is preferably performed by immersing the pre-assembled bamboo in a modified phenolic resin adhesive, and gumming is performed under a rotating and centrifugal condition to obtain a glued bamboo. The centrifugal impregnation method is adopted, the bamboo is dewatered while being impregnated, the moisture content of the impregnated bamboo is not required to be reduced to be lower than 6%, impregnation can be realized in a high-humidity state, the drying energy consumption of the bamboo is saved, the cost is saved, the drying time is also reduced, and the labor intensity of workers is reduced. The invention has no special requirement on the dosage of the modified phenolic resin adhesive liquid cement in the centrifugal gumming process, so as to ensure that the liquid cement submerges the plate in the centrifugal gumming process.
After the pre-assembly bamboo wood is subjected to centrifugal gumming, obtaining a gummy bamboo wood; the dipping amount of the bamboo material after centrifugal dipping is preferably 135-150 Kg/m3More preferably 140 to 148Kg/m3More preferably 142 to 145Kg/m3。
After the centrifugal gum dipping, the centrifugal gum filtering is carried out on the glued bamboo wood to obtain the clean glued bamboo wood. After the centrifugal gumming, the method preferably separates the glue solution of the modified phenolic resin adhesive remaining on the bamboo wood from the gummed bamboo wood, and then performs centrifugal glue filtering on the gummed bamboo wood. In the invention, the centrifugal filtration is carried out under a rotating and centrifuging condition, and the rotating speed of the centrifugal filtration is 250-500 rpm, more preferably 275-450 rpm, and more preferably 350-400 rpm; the centrifugal glue filtering time is 2-5 min, preferably 2.5-4 min, and more preferably 2.5-3 min. In the glue filtering process, redundant glue on the surface of the bamboo and moisture in the bamboo are removed.
After the centrifugal glue filtration, the bamboo material after the centrifugal glue filtration is dried to obtain the dipped bamboo material. In the invention, the drying temperature is preferably 55-75 ℃, more preferably 60-70 ℃, and even more preferably 65-68 ℃. In the present invention, the drying time is preferably 80 to 120min, and more preferably 100 to 110 min. In the invention, the moisture content of the dried bamboo wood is preferably 10-18%, more preferably 12-16%, and even more preferably 14-15%.
After the impregnated bamboo wood is obtained, the impregnated bamboo wood and the wood board are assembled to obtain a green body. The invention has no special requirements on the size of the wood board, and the wood board for assembling the bamboo-wood composite board required by the technical personnel in the field can be adopted. The invention has no special requirements on the number of the impregnated bamboo wood and the wood board for assembly, and the number of the layers of the bamboo wood composite board is based on the number of the layers which are commonly used and are well known by the technical personnel in the field. The invention has no special requirements on the specific implementation mode of assembly, and the bamboo and wood plate assembly mode in the bamboo and wood composite plate, which is well known by the technical personnel in the field, can be adopted.
After the green body is obtained, the green body is sequentially subjected to temperature rise, low-pressure moisture removal, hot pressing and cooling to obtain the bamboo-wood composite board. In the invention, the heating mode is preferably that the assembly is placed in a hot press, and steam is started to heat after the hot press is closed; the temperature to be raised is preferably 110-135 ℃, more preferably 115-120 ℃, and even more preferably 118 ℃; the time for heating to the target temperature is preferably 10-20 min, more preferably 12-18 min, and even more preferably 15 min.
After the temperature is raised, the invention carries out low-pressure moisture removal on the green body. In the present invention, the pressure for low-pressure moisture removal is 0.8 to 1.2MPa, and more preferably 0.9 to 1.0 MPa. In the invention, the time for moisture removal is preferably 60 to 120s, more preferably 70 to 100s, and even more preferably 75 to 90 s. The invention can further remove moisture in the bamboo under the low pressure condition, and avoid bubble caused by high temperature when the bamboo is taken out of the plate. In the present invention, the low-pressure dehumidification is performed under the aforementioned target temperature condition to which the temperature is raised. Before the temperature is raised, the blank obtained by assembling is preferably pre-pressed, so that the thickness of the blank is reduced, and the blank is conveniently placed into a hot press. The prepressing mode of the invention has no special requirement, and the prepressing mode of the new assembly which is well known by the technical personnel in the field can be adopted.
After the low-pressure moisture removal, the obtained green body is subjected to hot pressing treatment to obtain a compressed green body. In the present invention, the pressure of the hot pressing is preferably 3.5 to 5.5MPa, and more preferably 4 to 5 MPa. In the invention, the hot pressing temperature is preferably 110-135 ℃, and more preferably 120-130 ℃; the temperature of the hot pressing is consistent with the temperature of low-pressure moisture removal. In the invention, the hot pressing time is preferably 0.8-1.6 min/mm, more preferably 1.0-1.4 min/mm, and even more preferably 1.2-1.3 min/mm based on the thickness of the plate to be hot pressed. In the invention, the hot pressing time is short, the hot pressing temperature is low, and the energy consumption is reduced.
In the invention, the blank compressibility of the hot pressing treatment is preferably 25-35%, and more preferably 28-30%.
After the hot pressing, the compressed green body is cooled to obtain the bamboo-wood composite board. In the invention, the temperature of the cooled bamboo-wood composite board is preferably 60-80 ℃, more preferably 65-78 ℃, and even more preferably 70-75 ℃. The cooling method of the present invention has no special requirement, and the cooling method known to those skilled in the art can be adopted.
The invention preferably carries out pressure relief on the cooled blank to discharge the blank; according to the invention, the glue solution of the modified phenolic resin adhesive is used in the glue dipping process, and the moisture in the blank is discharged in the low-pressure dehumidification process, so that bubbling and layering phenomena of the blank in high-temperature blank discharging are avoided.
The bamboo-wood composite board prepared by the method has the water content of less than or equal to 12.0 percent and the density of more than or equal to 0.75g.cm-3Strong static bendingThe degree (longitudinal) is more than or equal to 85.0MPa, the static bending strength (transverse) is more than or equal to 35.0MPa, the elastic modulus (longitudinal) is more than or equal to 10000MPa, and the elastic modulus (transverse) is more than or equal to 3500 MPa; dipping and stripping length of the glue layer: the cumulative length of the glue stripping of any glue layer on each side does not exceed 1/3 (less than 3 mm) of the length of the glue layer, and the formaldehyde emission is less than or equal to 0.12mg.m-3Bending load (longitudinal): 6900N, concentrated load (middle): not less than 48000N.
The bamboo-wood composite board prepared by the method has high dimensional stability (the dipping and peeling lengths of the glue layers are all 0), high static bending strength and environmental protection, and meets the requirements of the detection standards of GB/T19536-.
In the invention, the bamboo-wood composite board can be used as a board suitable for any bamboo-wood composite board; in the embodiment of the invention, the bamboo-wood composite board is specifically used as a container bottom board or an automobile compartment bottom board.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
(1) Ultrasonic-assisted extraction of a tea polyphenol solution: preparing 60% ethanol solution, adding tea stem powder according to the proportion of 10% of the total mass of the ethanol solution, limiting ultrasonic frequency to 20KHz, extracting at 60 deg.C for 20 min.
(2) Preparing a modified phenolic resin adhesive: weighing phenol and formaldehyde according to a molar ratio of 1:2, wherein the mass of tea polyphenol in the tea stem extracting solution is 10% of the mass of the phenol, the mass of the resorcinol modifier is 15% of the mass of the phenol, and the mass of the propylene carbonate is 6% of the mass of the phenol.
And (2) performing addition reaction on phenol, formaldehyde and tea polyphenol at 90 ℃ for 60min, cooling to 70 ℃ after the reaction is finished, adding resorcinol and propylene carbonate, and reacting for 1h to obtain the modified phenolic resin adhesive.
The main performance detection results of the obtained modified phenolic resin adhesive are as follows: the density was 1.02g/cm3Viscosity 400mpa.s, pH 9.5, solid content 42.2 wt.%, curing time 800s, curing temperature 125 ℃, free phenol content 0.6 wt.%.
(3) Dipping the bamboo wood by using the glue solution of the modified phenolic resin adhesive obtained in the step (2), wherein the mass fraction of the glue solution is 30%; directly performing centrifugal gumming on the bamboo wood in a state of 25% of water content, and controlling the rotating speed of a centrifugal machine to be 100rpm and the centrifugal gumming time to be 2 min; then controlling the centrifugal rotation speed to be 280rpm, and filtering the glue for 5 min;
drying the bamboo materials after glue filtration at medium and low temperature, controlling the drying temperature at 75 ℃ and the drying time for 120 min; the moisture content of the dried bamboo is about 18 percent, and the gum dipping amount of the phenolic resin is 135Kg/m3And a volatile content of 8%.
(4) And (4) assembling the bamboo wood dried in the step (3) with the wood board to obtain a green body. Putting the blank body into a hot press, heating to 135 ℃ through steam for 10min after the press is closed, and then carrying out pressure reduction and moisture removal for 60s under the temperature condition and the pressure of 0.8 MPa; and (3) carrying out hot pressing treatment on the blank after depressurization and dehumidification, controlling the hot pressing pressure to be 3.5MPa and the temperature to be 135 ℃, limiting the hot pressing time of unit thickness to be 1.1min according to the thickness of the blank, leading the compression ratio of the blank to be 25% in the hot pressing process, and then cooling to 80 ℃ to release the pressure and obtain the bamboo-wood composite board.
(5) The performance parameters of the obtained bamboo-wood composite board meet the requirements of the detection standards of GB/T19536-. The main performance indexes of the bamboo-wood composite board are as follows: water content of 8.5% and density of 0.88g.cm-394.6MPa of static bending strength (longitudinal direction), 38.6MPa of static bending strength (transverse direction), 10035MPa of elastic modulus (longitudinal direction), 3608MPa of elastic modulus (transverse direction), 0 impregnation stripping length of an adhesive layer, more than or equal to 8418N of bending load (longitudinal direction), more than or equal to 65031N of concentrated load (middle part), and 0.107mg.m of formaldehyde release amount-3。
Example 2
(1) Ultrasonic-assisted extraction of a tea polyphenol solution: preparing 70% ethanol solution, adding tea stem powder according to the proportion of 20% of the total mass of the ethanol solution, limiting ultrasonic frequency to 20KHz, extracting at 70 deg.C for 30 min.
(2) Preparing a modified phenolic resin adhesive: weighing phenol and formaldehyde according to a molar ratio of 1:2, wherein the mass of tea polyphenol in the tea stem extracting solution is 30% of that of the phenol, the mass of the resorcinol modifier is 10% of that of the phenol, and the mass of the propylene carbonate is 4% of that of the phenol.
And (2) performing addition reaction on phenol, formaldehyde and tea polyphenol at 95 ℃ for 70min, cooling to 65 ℃ after the reaction is finished, adding resorcinol and propylene carbonate, and reacting for 1h to obtain the modified phenolic resin adhesive.
The main performance detection results of the obtained modified phenolic resin adhesive are as follows: the density was 1.06g/cm3Viscosity 420mpa.s, pH 10.0, solids content 43.2 wt.%, cure time 850s, cure temperature 120 ℃, free phenol content 0.8 wt.%.
(4) Dipping the bamboo wood by using the glue solution of the modified phenolic resin adhesive obtained in the step (2), wherein the mass fraction of the glue solution is 35%; directly performing centrifugal gumming on the bamboo wood in a state of 35% of water content, and controlling the rotating speed of a centrifugal machine to be 200rpm and the centrifugal gumming time to be 4 min; subsequently, the centrifugal speed is controlled to be 400rpm, and the rubber filtration is carried out for 3 min.
Drying the bamboo materials after glue filtration at medium and low temperature, controlling the drying temperature to be 65 ℃ and the drying time to be 100 min; the moisture content of the dried bamboo is about 14 percent, and the gum dipping amount of the phenolic resin is 145Kg/m3And a volatile content of 6%.
(4) And (4) assembling the bamboo wood dried in the step (3) with the wood board to obtain a green body. Putting the green body into a hot press, closing the hot press, raising the temperature to 125 ℃ through steam for 15min, and then reducing the pressure and dehumidifying for 90s under the pressure condition of 1.0MPa at the temperature; and (3) carrying out hot pressing treatment on the blank after depressurization and dehumidification, controlling the hot pressing pressure to be 4.5MPa and the temperature to be 125 ℃, limiting the hot pressing time of unit thickness to be 1.2min according to the thickness of the blank, leading the compression ratio of the blank to be 30% in the hot pressing process, and then cooling to 70 ℃ to release the pressure and obtain the bamboo-wood composite board.
(5) The performance parameters of the obtained bamboo-wood composite board meet the requirements of the detection standards of GB/T19536-. The main performance indexes of the bamboo-wood composite board are as follows: water content of 10.1% and density of 0.90g.cm-3Static bending strength (longitudinal direction) 97.1MPa, static bending strength (transverse direction) 37.1MPa, elastic modulus (longitudinal direction) 10123MPa, elastic modulus (transverse direction) 3823MPa, glue line dip peel length 0, bending load (longitudinal direction): 8569N, concentrated load (middle): not less than 65209N, and formaldehyde emission of 0.102mg.m-3。
Example 3
(1) Ultrasonic-assisted extraction of a tea polyphenol solution: preparing 75% ethanol solution, adding tea stem powder according to the proportion of 30% of the total mass of the ethanol solution, limiting ultrasonic frequency to 20KHz, extracting at 80 deg.C for 40 min.
(2) Preparing a modified phenolic resin adhesive: weighing phenol and formaldehyde according to a molar ratio of 1:2, wherein the mass of the tea polyphenol in the tea stem extracting solution is 50% of the mass of the phenol, the mass of the resorcinol modifier is 5% of the mass of the phenol, and the mass of the propylene carbonate is 2% of the mass of the phenol.
And (2) performing addition reaction on phenol, formaldehyde and tea polyphenol at 93 ℃ for 110min, cooling to 60 ℃ after the reaction is finished, adding resorcinol and propylene carbonate, and reacting for 1h to obtain the modified phenolic resin adhesive.
The main performance detection results of the obtained modified phenolic resin adhesive are as follows: the density was 1.12g/cm3Viscosity 450mpa.s, pH 10.5, solid content 45.6 wt.%, curing time 900s, curing temperature 115 ℃, free phenol content 1.0 wt.%.
(5) Dipping the bamboo wood by using the glue solution of the modified phenolic resin adhesive obtained in the step (2), wherein the mass fraction of the glue solution is 40%; directly performing centrifugal gumming on the bamboo wood in a state of water content of 45%, and controlling the rotating speed of a centrifugal machine to be 200rpm and the centrifugal gumming time to be 6 min; subsequently, the centrifugal speed is controlled to be 500rpm, and the glue filtration is carried out for 2 min.
Drying the bamboo materials after glue filtration at medium and low temperature, controlling the drying temperature to be 55 ℃ and the drying time to be 120 min; the moisture content of the dried bamboo material is about 10 percent, and the gum dipping amount of the phenolic resin is 150Kg/m3And a volatile content of 4%.
(4) And (4) assembling the bamboo wood dried in the step (3) with the wood board to obtain a green body. Putting the green body into a hot press, closing the hot press, raising the temperature to 120 ℃ through steam for 20min, and then reducing the pressure and dehumidifying for 120s under the condition of 1.2MPa at the temperature; and (3) carrying out hot pressing treatment on the blank after depressurization and dehumidification, controlling the hot pressing pressure to be 5.5MPa and the temperature to be 115 ℃, limiting the hot pressing time of unit thickness to be 1.6min according to the thickness of the blank, leading the compression ratio of the blank to be 35% in the hot pressing process, and then cooling to 60 ℃ to release pressure and discharge the blank to obtain the bamboo-wood composite board.
(5) The performance parameters of the obtained bamboo-wood composite board meet the requirements of the detection standards of GB/T19536-. The main performance indexes of the bamboo-wood composite board are as follows: water content of 10.5% and density of 0.92g.cm-3Static bending strength (longitudinal direction) 98.6MPa, static bending strength (transverse direction) 38.6MPa, elastic modulus (longitudinal direction) 10203MPa, elastic modulus (longitudinal direction) 3903MPa, glue line impregnation peel length 0, bending load (longitudinal direction): ≥ 8612N, concentrated load (middle part): not less than 65577N, and formaldehyde emission of 0.111mg.m-3。
The physical and chemical performance indexes (GB19536-2015 standard) of the bamboo-wood composite container bottom plate are shown in Table 3.
TABLE 3 physical and chemical performance indexes of bamboo-wood composite container bottom plate
Figure BDA0001574686290000131
As can be seen from comparison of the performance detection results of the above embodiments and the physicochemical performance indexes of the bamboo-wood composite board flooring in Table 3, the bamboo-wood composite board prepared by the method disclosed by the invention meets the performance requirements of the bamboo-wood container flooring, and both the performance requirements are far higher than the minimum index requirements.
According to the preparation method of the bamboo-wood composite board, the high-humidity impregnation of the bamboo wood is realized in a centrifugal impregnation mode, the drying energy consumption before impregnation is reduced, the cost is saved, the drying time is also reduced, the combination of the depressurization, dehumidification and hot pressing is combined, the hot pressing temperature is reduced, the plate inlet and outlet temperature is increased, the hot pressing time is shortened, the production efficiency and the energy-saving and consumption-reducing effects are obvious, no other additional pollutants are generated in the production organization process, and the product performance is obviously improved.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (6)

1. A preparation method of a bamboo-wood composite board comprises the following steps:
(I) centrifugally dipping the pre-assembled bamboo wood by using glue solution of the modified phenolic resin adhesive, and then centrifugally filtering the glue; drying the bamboo material subjected to centrifugal glue filtration to obtain a dipped bamboo material;
the moisture content of the pre-assembly bamboo is 25-45%;
the rotation speed of the centrifugal gumming is 100-200 rpm, and the time of the centrifugal gumming is 2-6 min;
the rotating speed of the centrifugal filter rubber is 250-500 rpm; the centrifugal glue filtering time is 2-5 min;
the water content of the impregnated bamboo wood is 10-18%;
(II) assembling the dipped bamboo wood obtained in the step (I) with a wood board to obtain a green body;
(III) sequentially heating, dehumidifying at low pressure, hot-pressing and cooling the green body obtained in the step (II) to obtain a bamboo-wood composite board;
the pressure of the low-pressure moisture removal is 0.8-1.2 MPa;
the hot pressing temperature is 110-135 ℃;
the density of the modified phenolic resin adhesive is 1.02-1.12 g/cm3The viscosity is 400-450 mPa.s, the curing time is 800-900 s, and the curing time isThe melting temperature is 115-125 ℃, and the pH value is 9.5-11.5; the content of free phenol in the modified phenolic resin adhesive is 0.6-1.0 wt.%;
the preparation method of the modified phenolic resin adhesive comprises the following steps:
(1) carrying out addition reaction on phenol, formaldehyde and tea polyphenol to obtain an addition product; the temperature of the addition reaction is 90-95 ℃, and the time of the addition reaction is 1-2 h;
(2) carrying out modification reaction on the addition product obtained in the step (1), the first modifier and the second modifier to obtain a modified phenolic resin adhesive;
the temperature of the modification reaction is 65-75 ℃, and the time of the modification reaction is 1-1.5 h;
the first modifier is resorcinol; the second modifier comprises propylene carbonate, epoxy resin or organic silicon resin;
the mass of the first modifier is 5-15% of that of the phenol for preparing the addition product; the mass of the second modifier is 2-6% of that of the phenol for preparing the addition product.
2. The method for preparing the bamboo-wood composite board according to claim 1, wherein the molar ratio of phenol to formaldehyde in the step (1) is 1: 1.8-2; the mass of the tea polyphenol is 10-50% of that of phenol.
3. The preparation method of the bamboo-wood composite board according to claim 1, wherein the mass fraction of the glue solution in the step (I) is 30-40%; the impregnation amount of the bamboo material after centrifugal impregnation is 135-150 Kg/m3。
4. The preparation method of the bamboo-wood composite board according to claim 1, wherein the time for low-pressure moisture removal in the step (III) is 60-120 s; the temperature rise time in the step (III) is 10-20 min, and the temperature rises to 110-135 ℃.
5. The preparation method of the bamboo-wood composite board according to claim 1 or 4, wherein the pressure of the hot pressing in the step (III) is 3.5-5.5 MPa; the hot pressing time is 0.8-1.6 min/mm based on the thickness of the plate to be hot pressed.
6. The preparation method of the bamboo-wood composite board according to claim 1 or 4, wherein the temperature of the bamboo-wood composite board after cooling in the step (III) is 60-80 ℃.
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