CN113897071B - Preparation method of resin-impregnated wood powder filled wood-plastic composite material - Google Patents

Preparation method of resin-impregnated wood powder filled wood-plastic composite material Download PDF

Info

Publication number
CN113897071B
CN113897071B CN202111156724.1A CN202111156724A CN113897071B CN 113897071 B CN113897071 B CN 113897071B CN 202111156724 A CN202111156724 A CN 202111156724A CN 113897071 B CN113897071 B CN 113897071B
Authority
CN
China
Prior art keywords
wood
wood powder
resin
plastic
impregnated
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202111156724.1A
Other languages
Chinese (zh)
Other versions
CN113897071A (en
Inventor
唐道远
邓梦德
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Anhui Sentai Wpc Technology Floor Co ltd
Original Assignee
Anhui Sentai Wpc Technology Floor Co ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Anhui Sentai Wpc Technology Floor Co ltd filed Critical Anhui Sentai Wpc Technology Floor Co ltd
Priority to CN202111156724.1A priority Critical patent/CN113897071B/en
Publication of CN113897071A publication Critical patent/CN113897071A/en
Application granted granted Critical
Publication of CN113897071B publication Critical patent/CN113897071B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L97/00—Compositions of lignin-containing materials
    • C08L97/02—Lignocellulosic material, e.g. wood, straw or bagasse
    • 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
    • B27K3/0207—Pretreatment of wood before impregnation
    • 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
    • B27K3/08—Impregnating by pressure, e.g. vacuum impregnation
    • 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
    • B27K3/15—Impregnating involving polymerisation including use of polymer-containing impregnating agents
    • 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
    • B27K3/15—Impregnating involving polymerisation including use of polymer-containing impregnating agents
    • B27K3/153—Without in-situ polymerisation, condensation, or cross-linking reactions
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
    • C08H8/00—Macromolecular compounds derived from lignocellulosic materials
    • 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
    • B27K2200/00—Wooden materials to be treated
    • B27K2200/15—Pretreated particles or fibres
    • 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
    • B27K2240/00—Purpose of the treatment
    • B27K2240/70—Hydrophobation treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/06—Properties of polyethylene
    • C08L2207/062—HDPE

Landscapes

  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Forests & Forestry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Biochemistry (AREA)
  • Dry Formation Of Fiberboard And The Like (AREA)
  • Chemical And Physical Treatments For Wood And The Like (AREA)

Abstract

The application relates to a preparation method of a resin-impregnated wood powder filled wood-plastic composite material, and belongs to the technical field of wood-plastic materials. The preparation method of the resin-impregnated modified wood powder filled wood-plastic composite material comprises the following steps: a) Providing wood powder; b) Immersing wood powder in the dispersion liquid of the low molecular weight resin to obtain immersed wood powder; c) Mixing the impregnated wood powder with high polymer resin, and granulating to obtain modified wood-plastic master batch; d) Extruding the modified wood-plastic master batch by using an extruder to prepare the resin-impregnated modified wood powder filled wood-plastic composite material. According to the application, the wood powder is firstly subjected to plasticizing modification by using the low molecular weight resin to impregnate the wood powder, so that not only can the hydrophobicity of the wood powder be improved, but also the compatibility of the wood powder and the resin can be obviously improved, and the effect of uniform mixing under microcosmic condition can be achieved by treating the wood powder by a high-speed mixer, so that the mechanical property of the wood-plastic composite board in a humid environment is improved.

Description

Preparation method of resin-impregnated wood powder filled wood-plastic composite material
Technical Field
The application relates to a preparation method of a resin-impregnated wood powder filled wood-plastic composite material, and belongs to the technical field of wood-plastic materials.
Background
The wood powder used for wood-plastic production is generally directly used as wood-plastic raw material for extrusion production after being dried and dehydrated. Since the compatibility of wood flour with plastics is not very good, the prior art generally requires mixing at high speed with a high speed mixer, then turning to low speed mixing, and then granulating; finally, extruding the wood-plastic master batch in an extruder with a die.
In order to enable the wood-plastic product to be more closely attached to wood, the filling proportion of wood powder is high and can reach 60% -70% at most. For example, the Chinese patent publication No. CN 103265768B discloses a method for producing wood-plastic floor. According to the method, 80-120 meshes of crushed, ground and dried wood powder with the water content less than or equal to 1% are selected, 10-15% of light calcium carbonate, 1.8-2.5% of stabilizer, 1.0-1.5% of modifier, 0.5-1.5% of coupling agent, 1.0-2.5% of lubricant, 2.5-3.5% of reinforcing agent, 1.5-2.0% of plastic processing aid, 0.5-1.0% of foaming agent and 0.8-2.0% of colorant are added into a high-low mixer to be fully mixed and reacted with waste plastic, and the required wood-plastic floor is obtained through an extruder, an extrusion die head, vacuum shaping, water cooling and automatic cutting. As described above, the wood flour is used in an amount of about 70%. Which also affects the quality of the wood-plastic panel to some extent.
Disclosure of Invention
The application aims to solve the technical problems, and provides a preparation method of a resin-impregnated wood powder filled wood-plastic composite material.
The method comprises the steps of firstly adopting resin to impregnate wood powder to modify the wood powder, then using the modified wood powder to blend with the resin to form raw materials, and finally forming the required plate or profile through an extruder, an extrusion die head, vacuum shaping and water cooling.
The technical scheme for solving the problems is as follows:
the preparation method of the resin-impregnated modified wood powder filled wood-plastic composite material comprises the following steps:
a) Providing wood powder;
b) Immersing the wood powder in a dispersion liquid of low molecular weight resin, taking out after immersing, and drying to obtain immersed wood powder;
c) And mixing the impregnated wood powder with a polymer resin in an amount of (1-5): 1, mixing and granulating to obtain modified wood-plastic master batch;
d) And carrying out melt extrusion on the modified wood-plastic master batch by using an extruder loaded with a wood-plastic extrusion die to prepare a plate blank, and cooling and shaping the plate blank to prepare the resin-impregnated modified wood powder filled wood-plastic composite material.
Although the degree of mixing of wood flour with resin can be significantly improved by the masterbatch technique. But from a microscopic point of view this degree of mixing is far from sufficient. The microphotograph of the section of the plate shows that the resin cannot completely wrap the wood powder, only a small part of the wood powder is uniformly dispersed, and most of the wood powder has a agglomeration phenomenon; the problems of poor dimensional stability, reduced mechanical property and the like of the wood-plastic plate after being used for a period of time are caused, and even the phenomenon of environmental stress cracking can be caused.
In the above technical solution of the present application, the inventor proposes the solution because the inventor finds that the structure of the existing wood-plastic panel in the microscopic state is very uneven. In the prior art, wood powder and resin powder (such as PE) are uniformly mixed by a high-speed mixer, or a granulator is used for preparing wood-plastic master batches; and then extruded with a die using an extruder. This operation is often considered to be a macroscopic (visual) mixing of wood flour with resin flour, i.e. whether microscopic mixing is negligible. The inventors believe that the deterioration of the properties of wood-plastic panels is often based on the microstructure of the panel being destroyed, such as the wood flour component becoming wet or absorbing water. Because the prior art shows that wood powder is added into resin to produce wood-plastic boards, the physical properties of the boards are obviously changed along with the addition amount of the wood powder, when the addition amount of the wood powder is about 5%, the boards have little influence, and the water absorption is equivalent to that of the boards without the wood powder; when the wood powder addition amount reaches 20%, the water absorption of the plate is increased, and the compressive strength after weight increment is also reduced; when the addition amount of wood plastic exceeds 50%, the above problems are highlighted. The analysis of the problems in the prior art is simply classified as the influence of the addition amount of wood powder on the wood-plastic panel, and the fact that the excessive addition amount of wood powder can cause adverse effect on the wood-plastic panel is considered fully by the person skilled in the art when producing the wood-plastic panel is suggested. Thus, one of the technological developments in the wood-plastic panel industry is to replace wood flour with other powders, a typical technical representative being SPC flooring. SPC floors are boards formed by a large amount of filling PVC resin with stone powder such as calcium carbonate.
In analyzing the cause of the above problems, the present inventors have proposed their new theories. The inventors believe that the filling amount of wood powder naturally has a negative effect on the water absorption of the wood-plastic panel, but this negative effect is not unilaterally caused by the addition amount factor of wood powder, and it is important that the wood powder is not uniformly mixed with the resin. I.e. the applicant believes that macroscopic mixing is often still not in the microscopic state. Based on this, the applicant carried out high magnification observation under a microscope on the existing wood-plastic panel. It was found that the dispersive distribution of wood flour pellets was seen in the existing wood-plastic panels at a magnification of 10 times. The wood powder aggregate is particles formed by a large amount of wood powder which are clustered together, the particles are small, the small particles can be seen to be uniformly dispersed in the resin component under the visual angle, and under the magnification of 10 times, the wood powder and the resin component can be seen to have low mixing degree, namely, in the 10 times visual field, partial areas are not distributed with wood powder, partial areas are distributed with wood powder aggregate, the wood powder aggregate is unevenly distributed in the visual field, and linear connection is formed among partial wood powder aggregate, so that most wood powder aggregate forms an intermittent network structure. Under the magnification of 40 times, the enlarged structure of the wood powder aggregate can be seen, and the wood powder aggregate and the surrounding resin are not well fused, and a narrow cavity exists between the wood powder aggregate and the surrounding resin. At a magnification of 100 times, almost all the visual field is occupied by the aggregates of wood powder, and the internal enlarged structure of the aggregates of wood powder can be seen, and no resin is impregnated into the interior of wood powder. Based on the above, the inventors have proposed a hypothesis that if all wood powder particles are uniformly mixed with resin without agglomeration, and some degree of fusion is generated (i.e., no narrow void is generated, and at least part of the interior of the wood powder is immersed in the resin), the addition amount of the wood powder can be further increased and the physical properties of the wood-plastic panel, especially various mechanical properties under a humid environment, are not significantly reduced. Because the inventors believe that in this ideal case, the wood powder aggregates are eliminated, the network structure formed by the aggregates is more unable to be constituted, the periphery of each wood powder is covered with the resin, and the resin and the wood powder form a fusion; the inventor also believes that in this case, the wood flour in the board itself does not come into contact with moisture, i.e. the wood-plastic board does not undergo significant weight gain in wet or even in a water-soaked environment, the board dimensions do not change significantly, and the mechanical properties do not significantly decrease. However, the inventors have not been able to mix wood flour and resin powder to an ideal state by any operation when mixing wood flour and resin powder by a high-speed mixer.
Based on the above factors, the inventors have conceived a solution for modifying wood flour. That is, the wood powder is resinated, whereby the mixing degree of the wood powder and the resin is improved.
However, the prior art reports on wood flour treatment, mainly comprising pretreatment of wood flour, mainly mechanical crushing, ultrasonic crushing and chemical reagent treatment. Wherein the mechanical crushing comprises mechanical shearing and ball milling treatment, so that the size of the raw material is obviously reduced, the crystalline structure of cellulose is destroyed, and the ball milling treatment is more common and has optimal effect. After ball milling treatment, the surface area of the wood powder is increased, the crystal structure of cellulose is damaged to a certain extent, so that the three-dimensional network structure is loose, intermolecular hydrogen bonds in microfibrils and inter-microfibril crystal areas are broken, and the compatibility of the wood powder and resin powder is improved to a certain extent. The chemical reagent treatment mainly comprises soaking wood powder with sodium hydroxide or dilute sulfuric acid; the alkali liquor soaking can break the ester bonds connected between cellulose, hemicellulose and lignin in the plant cell wall. Whereas dilute sulfuric acid hydrolyzes part of the cellulose.
The inventors believe that simple pretreatment does not improve the uniformity of wood flour in the resin and improve compatibility with the resin. Further modification of wood flour is required.
The present application adopts the scheme of impregnating wood powder with low molecular weight resin to pretreat wood powder. Tests show that the resin with low molecular weight can penetrate into wood powder, and the effect is better especially under the condition of pressurized impregnation. In the above-described embodiment of the present application, wood flour is first immersed in a dispersion of a low molecular weight resin. The grain diameter of the wood powder is 100-1 mm, and the size of wood cells is 10-100 mu m; that is, one wood powder is generally composed of several tens to several hundreds of wood cells. The process of impregnating the wood powder with the low molecular weight resin dispersion is also the process of entering the wood powder with the resin; since wood flour is composed of a large number of wood cells, impregnation of resin is practically divided into two cases, the first is that resin enters into the gaps between wood cells, such as pits, and fills in; alternatively, the low molecular weight resin penetrates the cell wall and fills the cell interior; however, in either case, the wood powder is filled therein. The impregnation operation described above impregnates some of the wood cells, on the one hand, and low molecular weight resin, on the other hand, into the pores between the wood cells. That is, by the operation of step b), not only some of the free organic matters in the wood powder can be released, but also the low molecular weight resin can be filled in the wood powder. More importantly, these low molecular weight resins tend to react with hydroxyl groups that the cells have, thereby allowing the low molecular weight resins to be immobilized within the wood flour and not readily leachable in the presence of water as some of the contents of the wood cells themselves. That is, through the operation of step b), the cells are permanently swollen and the wood flour is modified. The modified wood powder is difficult to show water absorption property because the internal gaps are occupied; and the compatibility of the modified wood powder and the high polymer resin is obviously improved. For example, after wood powder impregnated with the low-molecular-weight aqueous phenolic resin emulsion is prepared into wood-plastic boards, the dimensional stability of the boards is improved, for example, after the traditional wood-plastic boards are subjected to a 24-hour water soaking test, the wood weight gain rate reaches more than 10%, and the wood weight gain rate is within 2% of that of the wood-plastic boards prepared from the wood powder impregnated with the low-molecular-weight aqueous phenolic resin emulsion. Secondly, the strength is improved, and after 5 freeze thawing cycles are carried out, the bending modulus of the traditional wood plastic plate is reduced by 40 percent; and the bending modulus of the wood-plastic plate made of wood powder impregnated with the low molecular weight aqueous phenolic resin emulsion is reduced by less than 10 percent. The applicant speculates that these losses in properties before unmodified are most likely due to hygroscopicity and poor interfacial compatibility between wood flour and resins. Therefore, after wood powder is modified, the weight gain rate and the bending modulus reduction amplitude of the wood can be effectively controlled under the same test conditions.
As a preferable mode of the above technical scheme, the wood flour is pretreated with acid or alkali before being impregnated with the low molecular weight resin, and then rinsed with water and dried.
The hydrophilic components in the wood powder can be separated out by treating with acid liquor or alkali liquor; these components are generally not free components and are difficult to remove without treatment with acid or lye. Then the wood powder is impregnated with the resin with low molecular weight, so that the impregnation effect of the resin with low molecular weight can be remarkably improved.
As a preferable mode of the technical scheme, 10-50 vol% of ethanol is added when the alkali liquor is adopted for pretreatment.
The alkali liquor soaking can break the ester bonds connected between cellulose, hemicellulose and lignin in the plant cell walls, so that the solubility of the cellulose in the ionic liquid can be improved. In addition to cellulose, hemicellulose and lignin, wood flour also contains free substances, which tend to have higher solubility in ethanol, and the addition of ethanol can further increase the dissolution rate and dissolution rate of these substances.
As a preferable mode of the technical scheme, the dispersion liquid with low molecular weight is water-soluble resin, the polymerization degree is 2-50, and the average molecular weight is not more than 6000.
In the technical scheme, the impregnating effect of the water-soluble resin on wood powder is obviously better than that of the fat-soluble resin; and the impregnation effect of the resin having a lower polymerization degree on wood flour is also better.
As a preferable mode of the above technical scheme, the solid content of the dispersion liquid of the low molecular weight resin is 20wt% to 45wt%.
In the technical scheme, the solid content is 20-45 wt% which indicates that the concentration of the resin dispersion liquid is low, and the rapid impregnation of the resin is facilitated.
Preferably, the low molecular weight dispersion is a water-soluble phenol resin or a melamine resin.
As a preferred option of the above technical scheme, step b) adopts vacuum pressurizing impregnation, placing wood powder in a vacuum impregnation tank to vacuumize, then injecting the dispersion liquid of the low molecular weight resin, taking out after impregnation, and drying to obtain impregnated wood powder.
As the optimization of the technical scheme, when vacuumizing, the vacuum degree is controlled to be-95 KPa to-10 KPa; the vacuumizing time is controlled to be 30-60 min.
Experiments show that the resin impregnation effect of wood powder can be obviously improved by the preliminary vacuum treatment.
Preferably, the above-mentioned technical solution is that, before step c), the impregnated wood flour is further post-treated with a diisocyanate. The NCO group of the diisocyanate can react with the bare OH group of the impregnated wood powder which is not coated by the low molecular weight resin, so that the hydrophobicity of the wood powder is further improved, the compatibility of the wood powder and the resin is improved, the mechanical strength and the hydrophobicity of the wood-plastic composite material are improved, and the service life of the wood plastic is prolonged.
Preferably, the polymer resin is a polyolefin resin.
As a further preferable aspect of the above-mentioned aspect, the polymer resin is HDPE.
In summary, the application has the following beneficial effects:
1. according to the application, the wood powder is firstly subjected to plasticizing modification by using the low molecular weight resin to impregnate the wood powder, so that not only can the hydrophobicity of the wood powder be improved, but also the compatibility of the wood powder and the resin can be obviously improved, and the effect of uniform mixing under microcosmic can be achieved by treating the wood powder by a high-speed mixer, so that the mechanical property of the wood-plastic composite board in a humid environment can be improved;
2. the application also pretreats the wood powder by acid liquor or alkali liquor before impregnating the wood powder with low molecular weight resin; the water absorption characteristic of wood powder is mainly caused by free hydrophilic substances and combined hydrophilic substances contained in the wood powder; free hydrophilic substances such as nutrient substances contained in wood flour, and bonded hydrophilic substances such as cellulose and hemicellulose; the hydrophilic substances can be removed under the acid-base condition, so that the impregnation effect of the low molecular weight resin can be improved, and the hydrophobicity of the modified wood powder can be improved;
3. the application also carries out post-treatment on the modified wood powder by using diisocyanate containing NCO groups, and the NCO groups of the modified wood powder after the post-treatment can react with bare OH groups to generate urethane or polyurethane with low molecular weight, which obviously improves the hydrophobicity of the wood powder.
Detailed Description
This detailed description is merely illustrative of the application and is not intended to be limiting. Any alterations, modifications, and variations which may be practiced by those of ordinary skill in the art after reading this disclosure are intended to be within the scope of the claims.
Example 1
The preparation method of the resin-impregnated modified wood powder filled wood-plastic composite material comprises the following steps:
a) Providing wood powder; making wood processing leftovers by using a superfine pulverizer, and passing through 80 meshes;
b) Immersing the wood powder in an aqueous phenolic resin emulsion, wherein the polymerization degree of the phenolic resin is 2-50, the average weight molecular weight is not more than 6000, and the solid content is about 30wt%; taking out after soaking, and drying to obtain impregnated wood powder;
c) Mixing and granulating the impregnated wood powder and HDPE in a mass ratio of 2:1 to obtain modified wood-plastic master batch;
d) And (2) melting and extruding the modified wood-plastic master batch, the processing aid calcium stearate (the dosage is 0.5 percent) and the filler superfine calcium carbonate (the dosage is 10.0 percent) by using an extruder loaded with a wood-plastic extrusion die to prepare a plate blank, and cooling and shaping the plate blank to prepare the resin-impregnated modified wood powder filled wood-plastic composite plate.
Example 2
The preparation method of the resin-impregnated modified wood powder filled wood-plastic composite material comprises the following steps:
a) Providing wood powder; making wood processing leftovers by using a superfine pulverizer, and passing through 80 meshes;
b) Pretreating the wood powder by adopting alkali liquor, wherein in the pretreatment process, the alkali liquor contains alkaline substance caustic soda and 20vol% of ethanol; then, the wood flour is immersed in an aqueous phenolic resin emulsion, the polymerization degree of the phenolic resin is 2-50, the average molecular weight is not more than 6000, and the solid content is about 30wt%; the dipping in the step adopts vacuum pressurizing dipping, firstly placing wood powder in a vacuum dipping tank for vacuumizing, then injecting the aqueous phenolic resin emulsion, taking out after dipping, and drying to obtain dipping wood powder; when vacuumizing, controlling the vacuum degree at-65 KPa to-50 KPa; the vacuumizing time is controlled to be 30min;
c) Mixing and granulating the impregnated wood powder and HDPE in a mass ratio of 2:1 to obtain modified wood-plastic master batch;
d) And (2) melting and extruding the modified wood-plastic master batch, the processing aid calcium stearate (the dosage is 0.5 percent) and the filler superfine calcium carbonate (the dosage is 10.0 percent) by using an extruder loaded with a wood-plastic extrusion die to prepare a plate blank, and cooling and shaping the plate blank to prepare the resin-impregnated modified wood powder filled wood-plastic composite plate.
Example 3
The preparation method of the resin-impregnated modified wood powder filled wood-plastic composite material comprises the following steps:
a) Providing wood powder; making wood processing leftovers by using a superfine pulverizer, and passing through 80 meshes; ball milling and sieving with 200 meshes;
b) Pretreating the wood powder by adopting alkali liquor, wherein in the pretreatment process, the alkali liquor contains alkaline substance caustic soda and 20vol% of ethanol; then, the wood flour is immersed in an aqueous phenolic resin emulsion, the polymerization degree of the phenolic resin is 2-50, the average molecular weight is not more than 6000, and the solid content is about 30wt%; the dipping in the step adopts vacuum pressurizing dipping, firstly placing wood powder in a vacuum dipping tank for vacuumizing, then injecting the aqueous phenolic resin emulsion, taking out after dipping, and drying to obtain dipping wood powder; when vacuumizing, controlling the vacuum degree at-65 KPa to-50 KPa; the vacuumizing time is controlled to be 30min; then mixing and stirring the impregnated wood powder and the polymeric MDI, and fully mixing to obtain modified wood powder;
c) Mixing and granulating the modified wood powder and HDPE in a mass ratio of 2:1 to obtain modified wood-plastic master batches;
d) And (2) melting and extruding the modified wood-plastic master batch, the processing aid calcium stearate (the dosage is 0.5 percent) and the filler superfine calcium carbonate (the dosage is 10.0 percent) by using an extruder loaded with a wood-plastic extrusion die to prepare a plate blank, and cooling and shaping the plate blank to prepare the resin-impregnated modified wood powder filled wood-plastic composite plate.
Example 4
The preparation method of the resin-impregnated modified wood powder filled wood-plastic composite material comprises the following steps:
a) Providing wood powder; making wood processing leftovers by using a superfine pulverizer, and passing through 80 meshes;
b) Immersing the wood flour in a mixed liquid containing polyurethane prepolymer and diisocyanate monomer (MDI is adopted in the embodiment), wherein the solid content is about 35wt%; taking out after soaking, and drying to obtain impregnated wood powder;
c) Mixing and granulating the impregnated wood powder and HDPE in a mass ratio of 2:1 to obtain modified wood-plastic master batch;
d) And (2) melting and extruding the modified wood-plastic master batch, the processing aid calcium stearate (the dosage is 0.5 percent) and the filler superfine calcium carbonate (the dosage is 10.0 percent) by using an extruder loaded with a wood-plastic extrusion die to prepare a plate blank, and cooling and shaping the plate blank to prepare the resin-impregnated modified wood powder filled wood-plastic composite plate.
Example 5
The preparation method of the resin-impregnated modified wood powder filled wood-plastic composite material comprises the following steps:
a) Providing wood powder; making wood processing leftovers by using a superfine pulverizer, and passing through 80 meshes; ball milling and sieving with 200 mesh sieve
b) Pretreating the wood powder by adopting alkali liquor, wherein in the pretreatment process, the alkali liquor contains alkaline substance caustic soda and 20vol% of ethanol; the wood flour was then immersed in a mixed liquid containing polyurethane prepolymer and diisocyanate monomer (MDI is used in this example) with a solids content of about 35wt%; taking out after soaking, and drying to obtain impregnated wood powder; the dipping in the step adopts vacuum pressurizing dipping, firstly placing wood powder in a vacuum dipping tank for vacuumizing, then injecting the aqueous phenolic resin emulsion, taking out after dipping, and drying to obtain dipping wood powder;
c) Mixing and granulating the impregnated wood powder and HDPE in a mass ratio of 2:1 to obtain modified wood-plastic master batch;
d) And (2) melting and extruding the modified wood-plastic master batch, the processing aid calcium stearate (the dosage is 0.5 percent) and the filler superfine calcium carbonate (the dosage is 10.0 percent) by using an extruder loaded with a wood-plastic extrusion die to prepare a plate blank, and cooling and shaping the plate blank to prepare the resin-impregnated modified wood powder filled wood-plastic composite plate.
Comparative example 1
The preparation method of the wood-plastic composite board comprises the following steps:
a) Providing wood powder; making wood processing leftovers by using a superfine pulverizer, and passing through 80 meshes;
b) Mixing and granulating the wood powder and HDPE in a mass ratio of 2:1 to obtain wood-plastic master batches;
d) And (3) melting and extruding the wood-plastic master batch, the processing aid calcium stearate (the dosage is 0.5 percent) and the filler superfine calcium carbonate (the dosage is 10.0 percent) by using an extruder loaded with a wood-plastic extrusion die to prepare a plate blank, and cooling and shaping the plate blank to prepare the wood-plastic composite plate.
Comparative example 2
The preparation method of the wood-plastic composite board comprises the following steps:
a) Providing wood powder; making wood processing leftovers by using a superfine pulverizer, and passing through 80 meshes; ball milling and sieving with 200 meshes;
b) Mixing and granulating the wood powder and HDPE in a mass ratio of 2:1 to obtain wood-plastic master batches;
d) And (3) melting and extruding the wood-plastic master batch, the processing aid calcium stearate (the dosage is 0.5 percent) and the filler superfine calcium carbonate (the dosage is 10.0 percent) by using an extruder loaded with a wood-plastic extrusion die to prepare a plate blank, and cooling and shaping the plate blank to prepare the wood-plastic composite plate.
The boards of examples 1-5 and comparative examples 1-2 were tested for water absorption after 24h of water immersion test according to the method of GB/T17657-2013, and the flexural modulus of the wood-plastic boards after 3 freeze thawing cycles according to the method of GB/T24508-2009 wood-plastic floor 6.5.10 were tested, the results are shown in the following table:

Claims (3)

1. the preparation method of the resin-impregnated modified wood powder filled wood-plastic composite material comprises the following steps:
a) Providing wood powder;
b) Pretreating the wood powder by adopting alkali liquor, wherein in the pretreatment process, 20vol% of ethanol is added into the alkali liquor; then, immersing wood powder in the dispersion liquid of the low molecular weight resin, adopting vacuum pressurizing for immersing, firstly placing the wood powder in a vacuum immersing tank for vacuumizing, then injecting the dispersion liquid of the low molecular weight resin, taking out after immersing, and drying to obtain the immersed wood powder; then, carrying out post-treatment on the impregnated wood powder by diisocyanate to obtain modified wood powder;
c) Mixing the modified wood powder with high polymer resin according to a ratio of 2:1, mixing and granulating to obtain modified wood-plastic master batch;
d) Melting and extruding the modified wood-plastic master batch by using an extruder loaded with a wood-plastic extrusion die to prepare a plate blank, and cooling and shaping the plate blank to prepare the resin-impregnated modified wood powder filled wood-plastic composite material;
the dispersion liquid of the low molecular weight resin is water-soluble resin, the polymerization degree is 2-50, and the average molecular weight is not more than 6000;
the dispersion of the low molecular weight resin has a solids content of 30wt%;
the dispersion liquid of the low molecular weight resin is water soluble phenolic resin.
2. The method for preparing the resin-impregnated wood powder filled wood-plastic composite according to claim 1, wherein the method comprises the following steps: when vacuumizing, controlling the vacuum degree at-95 KPa to-10 KPa; the vacuumizing time is controlled to be 30-60 min.
3. The method for preparing the resin-impregnated wood powder filled wood-plastic composite according to claim 1, wherein the method comprises the following steps: the polymer resin is polyolefin resin.
CN202111156724.1A 2021-09-30 2021-09-30 Preparation method of resin-impregnated wood powder filled wood-plastic composite material Active CN113897071B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202111156724.1A CN113897071B (en) 2021-09-30 2021-09-30 Preparation method of resin-impregnated wood powder filled wood-plastic composite material

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202111156724.1A CN113897071B (en) 2021-09-30 2021-09-30 Preparation method of resin-impregnated wood powder filled wood-plastic composite material

Publications (2)

Publication Number Publication Date
CN113897071A CN113897071A (en) 2022-01-07
CN113897071B true CN113897071B (en) 2023-11-07

Family

ID=79189479

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202111156724.1A Active CN113897071B (en) 2021-09-30 2021-09-30 Preparation method of resin-impregnated wood powder filled wood-plastic composite material

Country Status (1)

Country Link
CN (1) CN113897071B (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114800763B (en) * 2022-05-23 2023-03-24 广西科学院 Preparation method of high-strength shaving board
CN115746577A (en) * 2022-11-24 2023-03-07 浙江瑞欣装饰材料有限公司 Flame-retardant wood-plastic plate and production process thereof

Citations (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB549335A (en) * 1940-05-14 1942-11-17 Bakelite Ltd Improvements in or relating to the impregnation of wood with resin
JPH01299006A (en) * 1988-05-26 1989-12-01 Matsushita Electric Works Ltd Preparation of modified wood
US4890795A (en) * 1987-09-30 1990-01-02 Fiat Auto S.P.A. Method for the production of wood flour based fillers for plastic materials
JPH09216208A (en) * 1996-02-09 1997-08-19 Hiroyuki Yano Manufacture of wooden material
JP2002337110A (en) * 2001-05-18 2002-11-27 Kotobuki Kako Kk Timber processing liquid by curable oligomer and its processing method
CN1970260A (en) * 2005-11-24 2007-05-30 东北林业大学 Manufacture method of reinforced wood ceramic
CN101186754A (en) * 2006-11-16 2008-05-28 滨州华晨新型建材有限公司 Method for producing macromolecule composite wood-plastic material by utilizing crop straw
KR100886838B1 (en) * 2008-07-03 2009-03-04 (주)간삼파트너스 종합건축사사무소 Woodchips and structural materials using prepreg of powder and chips of woods
CN101942138A (en) * 2010-09-21 2011-01-12 浙江金迪木塑型材有限公司 Fire-retardant wood plastic compound material and preparation method thereof
CN103586947A (en) * 2013-11-11 2014-02-19 中南林业科技大学 Method of in-situ self-assembly in solid wood to prepare polyurethane reinforced wood
JP2015113364A (en) * 2013-12-09 2015-06-22 パナソニックＩｐマネジメント株式会社 Production method of woody resin molding
CN106317924A (en) * 2016-08-18 2017-01-11 中南林业科技大学 Wood fiber reinforced polyvinyl chloride imitation solid-wood cabinet door panel and manufacturing method thereof
CN108818818A (en) * 2018-07-10 2018-11-16 四川农业大学 A kind of preparation method of timber-lactic acid composite material
CN113372654A (en) * 2021-05-19 2021-09-10 会通新材料股份有限公司 Low-odor plant fiber reinforced polypropylene composite material and preparation method thereof

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002038019A (en) * 2000-07-19 2002-02-06 Sumitomo Chem Co Ltd Woodflour-filled thermoplastic resin composition and its production method

Patent Citations (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB549335A (en) * 1940-05-14 1942-11-17 Bakelite Ltd Improvements in or relating to the impregnation of wood with resin
US4890795A (en) * 1987-09-30 1990-01-02 Fiat Auto S.P.A. Method for the production of wood flour based fillers for plastic materials
JPH01299006A (en) * 1988-05-26 1989-12-01 Matsushita Electric Works Ltd Preparation of modified wood
JPH09216208A (en) * 1996-02-09 1997-08-19 Hiroyuki Yano Manufacture of wooden material
JP2002337110A (en) * 2001-05-18 2002-11-27 Kotobuki Kako Kk Timber processing liquid by curable oligomer and its processing method
CN1970260A (en) * 2005-11-24 2007-05-30 东北林业大学 Manufacture method of reinforced wood ceramic
CN101186754A (en) * 2006-11-16 2008-05-28 滨州华晨新型建材有限公司 Method for producing macromolecule composite wood-plastic material by utilizing crop straw
KR100886838B1 (en) * 2008-07-03 2009-03-04 (주)간삼파트너스 종합건축사사무소 Woodchips and structural materials using prepreg of powder and chips of woods
CN101942138A (en) * 2010-09-21 2011-01-12 浙江金迪木塑型材有限公司 Fire-retardant wood plastic compound material and preparation method thereof
CN103586947A (en) * 2013-11-11 2014-02-19 中南林业科技大学 Method of in-situ self-assembly in solid wood to prepare polyurethane reinforced wood
JP2015113364A (en) * 2013-12-09 2015-06-22 パナソニックＩｐマネジメント株式会社 Production method of woody resin molding
CN106317924A (en) * 2016-08-18 2017-01-11 中南林业科技大学 Wood fiber reinforced polyvinyl chloride imitation solid-wood cabinet door panel and manufacturing method thereof
CN108818818A (en) * 2018-07-10 2018-11-16 四川农业大学 A kind of preparation method of timber-lactic acid composite material
CN113372654A (en) * 2021-05-19 2021-09-10 会通新材料股份有限公司 Low-odor plant fiber reinforced polypropylene composite material and preparation method thereof

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
低分子量酚醛树脂处理对杉木细胞壁的改性机理研究;黄艳辉等;《光谱学与光谱分析》;20151215(第12期);全文 *
低分子量酚醛树脂浸渍人工林木材研究进展;左迎峰等;《材料导报》;20151210(第23期);全文 *
左迎峰等.低分子量酚醛树脂浸渍人工林木材研究进展.《材料导报》.2015,(第23期), *
木塑复合材料及其研究进展;刘建勇等;《合成材料老化与应用》;20040930(第03期);全文 *
木塑复合材料界面改性研究进展;赵敏等;《化工时刊》;20090825(第08期);全文 *

Also Published As

Publication number Publication date
CN113897071A (en) 2022-01-07

Similar Documents

Publication Publication Date Title
CN113897071B (en) Preparation method of resin-impregnated wood powder filled wood-plastic composite material
Ayrilmis et al. Flat-pressed wood plastic composite as an alternative to conventional wood-based panels
EP2953997B1 (en) Micro-structured composite material, method for producing same, mouldings made of same, and uses thereof
US7446138B2 (en) Wood particle filled polyvinyl chloride composites and their foams
Espinach et al. Flexural properties of fully biodegradable alpha-grass fibers reinforced starch-based thermoplastics
CN107641242B (en) Injection molding material
EP3406793A1 (en) Method for manufacturing porous moulds
EP2890539B1 (en) Method for manufacturing a composite product, and composite product so produced
JP7453711B2 (en) Pretreatment of cellulose
EP2890538B1 (en) Method for manufacturing a composite product comprising an organic natural fiber material
CN105131633A (en) Preparation method of wood-plastic composite material
Soulestin et al. Polyolefins–biofibre composites: A new way for an industrial production
Hietala Extrusion processing of wood-based biocomposites
CN107236204A (en) A kind of preparation technology of PVC wood plastic composite decorating board
CN105949807A (en) Polyvinyl alcohol-based wood-plastic composite and melting processing method thereof
CN109762283B (en) Recyclable water-soluble degradable foam material and preparation method thereof
CN114605747B (en) Preparation method of calcium carbonate modified plant fiber composite material
WO2008074310A2 (en) Material for the production of a molded body, and a molded body
EP1890855B1 (en) Method for applying functional additives, particularly an adhesion promoter, to a fibrous material and method for producing a fiber composite
KR100854506B1 (en) Lyocell method and device comprising a press water recirculation system
CN107177212A (en) A kind of dalle polyethylene based wood-plastic composite material and preparation method thereof
EP0648804B1 (en) Process for producing sheet moulding compounds (S.M.C.)
Ge et al. The effects of processing parameters and ac foaming agent on the mechanical properties and morphology of foamed wood-polylactic acid (PLA) composites
AU2018379384B2 (en) Methods for producing a viscose dope from microbial cellulose
CN105924748A (en) White carbon black/bast fiber/polymer composite material with block structure

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant