CN110903671A - Polyformaldehyde-based wood-plastic composite material and preparation method thereof - Google Patents
Polyformaldehyde-based wood-plastic composite material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a polyformaldehyde-based wood-plastic composite material and a preparation method thereof, wherein the wood-plastic composite material comprises the following components in percentage by weight: polyoxymethylene resin: 30% -60%; polytetrafluoroethylene micro powder: 2% -20%; glass beads: 2% -20%; plant fiber powder: 20% -60%; ultraviolet absorber: 0.5% -3%; light stabilizer: 0.5% -3%; compatibilizer: 0.5% -2%; a formaldehyde scavenger: 0.2% -1%; antioxidant: 0.5% -2%; lubricant: 0.2 to 1 percent. Meanwhile, a preparation method of the wood-plastic composite material is also provided. The molding shrinkage of the wood-plastic composite material can be reduced to 0.62-0.98%, and the friction coefficient is as follows: 0.16-0.36, the abrasion loss is: 1.3-3.4 mg, and the notch impact strength retention rate is between 90.6% and 97.3%.
Description
Technical Field
The invention relates to a preparation method of a wood-plastic composite material, in particular to a polyformaldehyde-based wood-plastic composite material and a preparation method thereof, and specifically relates to a modified wood-plastic composite resin of polyformaldehyde engineering plastics, belonging to the technical field of wood-plastic composite material preparation.
Background
The wood-plastic composite material is commonly known as a biomass and polymer composite material, and is called WPC in English, and is mainly formed by mixing a polymer and plant components, wherein the plant components mainly comprise wood flour, plant fibers, fruit shells and the like. WPC as a novel environment-friendly material, develops rapidly in the field of biomass composite materials, is a key development target in the next years, and is also an important field of biomass material development. The WPC has the advantages of low cost, no toxicity, no harm, biodegradability and the like, and can be applied to various fields of manufacturing tableware, daily necessities, toys, environment-friendly floors, external wall panels, internal doors and the like.
At present, the polymer matrix in the wood-plastic composite material is mainly general plastics such as PVC, PE, PLA or PP, and due to the fact that the mechanical property parameters of the general plastics are generally low, when the content of the added plant components is high, the tensile strength, the bending strength and the impact strength of the composite material are sharply reduced, the waterproof performance is also poor, and the problems that the wood-plastic product is easy to deform, low in strength and the like exist.
Compared with general plastics, engineering plastics can meet higher requirements in the aspects of mechanical property, durability, corrosion resistance, heat resistance and the like, however, most of engineering plastics have higher melting points (more than 220 ℃), and plant fibers can be gelatinized and decomposed at the temperature, so that the engineering plastic-based wood-plastic composite material is difficult to prepare. The melting point of the polyformaldehyde engineering plastic which is one of five engineering plastics is between 170 ℃ and 185 ℃, and the polyformaldehyde engineering plastic is relatively suitable for being mixed with plant fiber powder to prepare a wood-plastic composite material, but because the polyformaldehyde plastic has the defects of easy aging and decomposition, poor weather resistance, low notch impact strength, large molding shrinkage and the like when meeting ultraviolet light, related patents for preparing the polyformaldehyde-based wood-plastic composite material by taking polyformaldehyde as a polymer matrix are not seen at present.
Disclosure of Invention
The invention provides a modified polyformaldehyde engineering plastic wood-plastic composite resin and a preparation method thereof, aiming at a series of defects of the existing polyformaldehyde engineering plastic, wherein the resin has the advantages of high wear resistance, corrosion resistance, water resistance, ultraviolet aging resistance, strong notch impact, small molding shrinkage and the like.
The technical scheme of the invention is as follows:
the polyformaldehyde-based wood-plastic composite material comprises the following components in percentage by weight:
the polyformaldehyde resin refers to all polyformaldehyde brand products of copolyoxymethylene or homo-polyformaldehyde; the polytetrafluoroethylene micro powder has the average particle size of 3-5 microns and the water content of less than or equal to 0.1 percent; the glass beads comprise one or more of silicon dioxide, aluminum oxide, zirconium oxide, magnesium oxide and sodium silicate as main chemical components, and have an average particle size of 2-10 micrometers.
The plant fiber powdery substance comprises wood flour, shell powder or plant straw powder; the particle size of the plant fiber powder is between 100 and 200 meshes.
The wood flour includes but is not limited to: cedar wood flour, pine wood flour, birch wood flour or poplar wood flour; the shell powder includes but is not limited to: rice hulls, peanut shells, or walnut shells; the plant straw powder includes but is not limited to: rape straw powder, cotton straw powder, wheat straw powder or rice straw powder.
The ultraviolet absorbent refers to one of ultraviolet absorbents UV-329UV-327UV-326UV-531 UV-770; the light stabilizer is one of hydroxyl benzotriazole light stabilizers Tinuvin326 and Tinuvin328 and hindered phenol light stabilizers Tinuvin 770.
The compatibilizer is a mixture of a coupling agent and a diluent, and the mass ratio of the coupling agent to the diluent is 0.1-0.3;
in the compatibilizer, the coupling agent is one of a silane coupling agent KH550, a silane coupling agent KH560, a titanate coupling agent, a phosphate coupling agent or an aluminate coupling agent, and the diluent is one of white oil, propylene glycol and isoamyl alcohol.
The formaldehyde catching agent is one of dicyandiamide, urea, polyamide or melamine; the antioxidant is one of antioxidant 264, antioxidant 245 and antioxidant 1010; the lubricant is one of calcium stearate, zinc stearate, magnesium stearate, ethylene bis-stearamide or oleic acid diethanolamide.
The preparation method of the polyformaldehyde-based wood-plastic composite resin comprises the following steps:
(1) pretreatment of plant fiber powder: soaking plant fiber powder in sodium hydroxide solution for 1-2 hr, heating and boiling for 30-60min, filtering to obtain plant fiber powder, washing with water to neutrality, drying in oven at 60-80 deg.C for 1-2 hr;
(2) grinding polyformaldehyde into powder with particle size of 50-60 μm;
(3) putting polyformaldehyde powder, polytetrafluoroethylene micro powder, glass beads, ultraviolet absorbent, light stabilizer, formaldehyde scavenger, antioxidant and lubricant into a high-speed mixer, and fully stirring for 20-60 min;
(4) putting the uniformly mixed blend into a double-screw extruder, extruding, drawing wires and cutting into granules, wherein the processing temperature is 170-190 ℃;
(5) putting the cut modified material into an oven for drying, and then removing powder and particles by a screening machine;
(6) putting the granules, the treated plant fiber powder and the compatibilizer into a high-speed mixer for blending for 20-60min, putting the mixture into a bin of an extruder for 2 times of extrusion, drawing wires and cutting into granules, wherein the processing temperature is 170-190 ℃;
(7) and (3) putting the prepared granules into an injection molding machine, and carrying out spline injection molding by adopting different molds, wherein the injection molding temperature is 170-190 ℃, and finally obtaining the polyformaldehyde-based wood-plastic composite resin.
The mass fraction of the sodium hydroxide solution in the step (1) is 10-20%; the mass ratio of the plant fiber powder to the sodium hydroxide is 1: 10.
The method has the beneficial effects that:
the wood-plastic composite material has the advantages of ultraviolet aging resistance, high wear resistance, difficult deformation, good thermal stability, strong notch impact, corrosion resistance, water resistance and the like. Wherein, the molding shrinkage can be reduced to 0.62-0.98%, and the friction coefficient is as follows: 0.16-0.36, the abrasion loss is: 1.3mg-3.4mg, water absorption rate is 0.12% -0.25%; the corrosion rate (1500h) was: 1.79 g/(m)2·h)-2.78g/(m2H); ultraviolet irradiation (1500 h): the retention rate of the notch impact strength is between 90.6 and 97.3 percent.
The invention takes polyformaldehyde engineering plastics as main raw materials in the preparation process. Meanwhile, in order to better prepare the polyformaldehyde-based wood-plastic composite resin, secondary extrusion is adopted in the experiment, firstly, the polyformaldehyde resin, polytetrafluoroethylene micro powder and glass beads are blended to prepare polyformaldehyde alloy resin, then the polyformaldehyde alloy resin is blended with plant fiber powder, and a compatibilizer is added to be fully mixed for secondary extrusion, so that the polyformaldehyde-based wood-plastic composite resin is finally obtained.
The polytetrafluoroethylene micro powder is added in the formula in a corresponding proportion, so that the wear resistance, the water resistance and the corrosion resistance of the polyformaldehyde-based wood-plastic composite resin are improved.
The glass beads are added in the formula according to the corresponding proportion, so that the toughness of the polyformaldehyde wood-plastic composite resin is improved, and the notch impact strength and the elongation of the product are improved. The dimensional stability of the product is improved, and shrinkage and warpage can be reduced.
The ultraviolet absorber and the light stabilizer are added in the formula according to the corresponding proportion, so that the ultraviolet resistance and the aging resistance of the polyformaldehyde-based wood-plastic composite resin are improved.
In addition, the compatibilizer with a corresponding proportion is added into the modified material, so that the dispersion and mixing effects of the polyformaldehyde and the plant fiber powder are improved.
Detailed Description
The present invention will be described in detail with reference to specific examples.
The invention relates to a polyformaldehyde-based wood-plastic composite material which comprises the following components in percentage by weight:
polyoxymethylene resin: 30 to 60 percent
Polytetrafluoroethylene micro powder: 2 to 20 percent of
Glass beads: 2 to 20 percent of
Plant fiber powder: 20 to 60 percent
Ultraviolet absorber: 0.5 to 3 percent of
Light stabilizer: 0.5 to 3 percent of
Compatibilizer: 0.5 to 2 percent
A formaldehyde scavenger: 0.2 to 1 percent
Antioxidant: 0.5 to 2 percent
Lubricant: 0.2 to 1 percent
The polyformaldehyde resin refers to all polyformaldehyde brand products of copolyoxymethylene or homo-polyformaldehyde. .
The polytetrafluoroethylene micro powder is required to have an average particle size of 3-5 microns and a water content of less than 0.1%.
The polytetrafluoroethylene micro powder has the advantages that the polytetrafluoroethylene micro powder not only keeps the excellent waterproof, anti-corrosion and wear-resistant performances of polytetrafluoroethylene, but also can be well mixed with a polyformaldehyde resin matrix to prepare the polyformaldehyde alloy resin.
The glass beads comprise one or more of silicon dioxide, aluminum oxide, zirconium oxide, magnesium oxide and sodium silicate as main chemical components, and have an average particle size of 2-10 micrometers.
The glass beads have the advantages of ensuring the dimensional stability of the polyformaldehyde resin, reducing the molding shrinkage rate of the polyformaldehyde resin, improving the compression resistance and notch impact resistance, and simultaneously playing a certain role in improving the fire resistance, the sound insulation and heat insulation properties and the insulativity.
The plant fiber powdery substance comprises wood flour, shell powder or plant straw powder; the particle size of the plant fiber powder is between 100 and 200 meshes.
The ultraviolet absorbent refers to one of ultraviolet absorbents UV-329UV-327UV-326UV-531 UV-770.
The light stabilizer is one of hydroxyl benzotriazole light stabilizers Tinuvin326 and Tinuvin328 and hindered phenol light stabilizers Tinuvin 770.
The compatibilizer is a mixture of a coupling agent and a diluent, and the mass ratio of the coupling agent to the diluent is 0.1-0.3.
In the compatibilizer, the coupling agent can be one of a silane coupling agent KH550, a silane coupling agent KH560, a titanate coupling agent, a phosphate coupling agent or an aluminate coupling agent, and the diluent can be one of white oil, propylene glycol and isoamyl alcohol.
The formaldehyde catching agent is one of dicyandiamide, urea, polyamide or melamine.
The antioxidant is one of antioxidant 264, antioxidant 245 and antioxidant 1010.
The lubricant is one of calcium stearate, zinc stearate, magnesium stearate, ethylene bis-stearamide or oleic acid diethanolamide.
A preparation method of a polyformaldehyde-based wood-plastic composite resin comprises the following steps:
(1) pretreatment of plant fiber powder: the preparation method comprises the steps of soaking a certain amount of plant fiber powder in a sodium hydroxide solution (the mass fraction is 10% -20%) for 1-2h, heating and boiling for 30-60min (the mass ratio of the plant fiber powder to the sodium hydroxide is 1:10), filtering the plant fiber powder, washing the plant fiber powder with water to be neutral, and drying the plant fiber powder in an oven for later use (the temperature is 60-80 ℃ and the time is 1-2h).
(2) Grinding polyformaldehyde into powder with particle size of 50-60 μm
(3) Putting polyformaldehyde powder, polytetrafluoroethylene micro powder, glass beads, ultraviolet absorbent, light stabilizer, formaldehyde scavenger, antioxidant and lubricant into a high-speed mixer, and fully stirring for 20-60 min;
(4) putting the uniformly mixed blend into a double-screw extruder, extruding, drawing wires and cutting into granules, wherein the processing temperature is 170-190 ℃;
(5) putting the cut modified material into an oven for drying, and then removing powder and particles by a screening machine;
(6) putting the granules, the treated plant fiber powder and the compatibilizer into a high-speed mixer for blending for 20-60min, putting the mixture into a bin of an extruder for 2 times of extrusion, drawing wires and cutting into granules, wherein the processing temperature is 170-190 ℃;
(7) and (3) putting the prepared granules into an injection molding machine, and carrying out spline injection molding by adopting different molds, wherein the injection molding temperature is 170-190 ℃, and finally obtaining the polyformaldehyde-based wood-plastic composite resin.
Example 1
Weighing the following materials in percentage by weight:
polyoxymethylene (designation M270): 30 percent of
Polytetrafluoroethylene micro powder: 2 percent of
Glass beads: 2 percent of
Rape straw powder: 60 percent of
Ultraviolet absorber UV-329: 1.6 percent
Light stabilizer Tinuvin326: 1.5 percent
A compatibilizer (a mixture of a coupling agent and a diluent, wherein the mass ratio of the coupling agent to the diluent is 0.3, the coupling agent is a silane coupling agent KH550, and the diluent is propylene glycol): 2 percent of
Melamine: 0.2 percent of
Antioxidant 264: 0.5 percent
Calcium stearate: 0.2 percent of
The preparation method of the formaldehyde-based wood-plastic composite resin comprises the following steps:
(1) pretreatment of the rape straw powder: putting a certain mass of rape straw powder into a sodium hydroxide solution (the mass fraction is 20 percent), soaking for 2h, heating and boiling for 60min (the mass ratio of the rape straw powder to the sodium hydroxide is 1:10), filtering out the rape straw powder, washing the rape straw powder to be neutral, and putting the rape straw powder into an oven to dry for later use (80 ℃, 2h).
(2) Grinding polyformaldehyde into powder with particle size of 50 μm
(3) Putting polyformaldehyde powder, polytetrafluoroethylene micro powder, glass beads, an ultraviolet absorbent, a light stabilizer, a formaldehyde scavenger, an antioxidant and a lubricant into a high-speed mixer, and fully mixing and stirring for 60 min;
(4) putting the uniformly mixed blend into a double-screw extruder feeder, extruding, drawing wires and cutting into granules, wherein the processing temperature is 170 ℃;
(5) putting the cut modified material into an oven for drying, and removing powder and particles by a screening machine;
(6) putting the granules, the treated rape straw powder and the compatibilizer into a high-speed mixer, blending for 60min, putting into an extruder feeder, extruding for 2 times, drawing wires, and granulating, wherein the processing temperature is 170 ℃;
(7) and (3) putting the prepared granules into an injection molding machine, and carrying out spline injection molding by adopting different molds, wherein the injection molding temperature is 170 ℃, and finally obtaining the polyformaldehyde-based wood-plastic composite resin.
Respectively testing the molding shrinkage, water resistance, corrosion resistance, wear resistance and ultraviolet light resistance of various sample strips, and calculating to reduce the molding shrinkage to 0.74%; the detection and analysis result shows that: coefficient of friction μ: 0.36 abrasion loss: 3.3mg inhalationWater rate: 0.25 percent; corrosion rate (1500 h): 2.78 mg/(m)2H). Ultraviolet irradiation (1500 h): notched impact strength retention: 96.2 percent.
Example 2
Polyoxymethylene (designation M90): 46 percent
Polytetrafluoroethylene micro powder: 12 percent of
Glass beads: 12 percent of
Poplar powder: 25 percent of
Ultraviolet absorber UV-329: 1 percent of
Light stabilizer Tinuvin326: 1 percent of
A compatibilizer (a mixture of a coupling agent and a diluent, wherein the mass ratio of the coupling agent to the diluent is 0.2, the coupling agent is a silane coupling agent KH550, and the diluent is propylene glycol): 1 percent of
Melamine: 0.5 percent
Antioxidant 264: 1 percent of
Calcium stearate: 0.5 percent
The preparation method of the formaldehyde-based wood-plastic composite resin comprises the following steps:
(1) pretreating poplar powder: putting a certain mass of poplar wood powder into a sodium hydroxide solution (mass fraction is 15%) to be soaked for 1.5h, heating and boiling for 50min (mass ratio: poplar wood powder: sodium hydroxide is 1:10), filtering the poplar wood powder, washing the poplar wood powder with water to be neutral, and putting the poplar wood powder into an oven to be dried for later use (70 ℃, 1.5h).
(2) Grinding polyformaldehyde into powder with particle size of 60 μm
(3) Putting polyformaldehyde powder, polytetrafluoroethylene micro powder, glass beads, an ultraviolet absorbent, a light stabilizer, a formaldehyde scavenger, an antioxidant and a lubricant into a high-speed mixer, and fully mixing and stirring for 30 min;
(4) putting the uniformly mixed blend into a double-screw extruder feeder, extruding, drawing wires and cutting into granules, wherein the processing temperature is 180 ℃;
(5) putting the cut modified material into an oven for drying, and removing powder and particles by a screening machine;
(6) putting the granules, the treated poplar powder and the compatibilizer into a high-speed mixer, blending for 30min, putting the mixture into a feeder of an extruder, extruding for 2 times, drawing wires, and cutting into granules, wherein the processing temperature is 180 ℃;
(7) and (3) putting the prepared granules into an injection molding machine, and carrying out spline injection molding by adopting different molds, wherein the injection molding temperature is 185 ℃, and finally obtaining the polyformaldehyde-based wood-plastic composite resin.
Respectively testing the molding shrinkage, water resistance, corrosion resistance, wear resistance and ultraviolet light resistance of various sample strips, and calculating to reduce the molding shrinkage to 0.92%; the detection and analysis result shows that: coefficient of friction μ: 0.18 abrasion loss: 1.5mg water absorption: 0.2 percent; corrosion rate (1500 h): 2.56 mg/(m)2H). Ultraviolet irradiation (1500 h): notched impact strength retention: 92.4 percent.
Example 3
Weighing the following materials in percentage by weight:
polyoxymethylene (designation M270): 50 percent of
Polytetrafluoroethylene micro powder: 8 percent of
Glass beads: 8 percent of
Pine wood flour: 30 percent of
Ultraviolet absorbers UV-327: 1 percent of
Light stabilizer Tinuvin328: 0.5 percent
A compatibilizer (a mixture of a coupling agent and a diluent, wherein the mass ratio of the coupling agent to the diluent is 0.3, the coupling agent is a silane coupling agent KH560, and the diluent is isoamyl alcohol): 1 percent of
Urea: 0.5 percent
Antioxidant 245: 0.5 percent
Zinc stearate: 0.5 percent
The preparation method of the formaldehyde-based wood-plastic composite resin comprises the following steps:
(1) pretreating pine wood powder: soaking pine wood powder of a certain mass in a sodium hydroxide solution (the mass fraction is 20%) for 1h, heating and boiling for 40min (the mass ratio: pine wood powder: sodium hydroxide is 1:10), filtering the pine wood powder, washing the pine wood powder with water to be neutral, and drying the pine wood powder in an oven for later use (60 ℃, 1h).
(2) Grinding polyformaldehyde into powder with particle size of 55 micrometers;
(3) putting polyformaldehyde powder, polytetrafluoroethylene micro powder, glass beads, ultraviolet absorbent, light stabilizer, formaldehyde scavenger, antioxidant and lubricant into a high-speed mixer, and fully mixing and stirring for 50 min;
(4) putting the uniformly mixed blend into a double-screw extruder feeder, extruding, drawing wires and cutting into granules, wherein the processing temperature is 190 ℃;
(5) putting the cut modified material into an oven for drying, and removing powder and particles by a screening machine;
(6) putting the granules, the treated pine wood powder and the compatibilizer into a high-speed mixer, blending for 20min, putting into a feeder of an extruder, extruding for 2 times, drawing wires, and cutting into granules, wherein the processing temperature is 190 ℃;
(7) and (3) putting the prepared granules into an injection molding machine, and carrying out spline injection molding by adopting different molds, wherein the injection molding temperature is 190 ℃, and finally obtaining the polyformaldehyde-based wood-plastic composite resin.
The molding shrinkage is reduced to 0.78 percent by calculation; the detection and analysis result shows that: coefficient of friction μ: 0.25 abrasion loss: 2.1mg Water absorption: 0.16 percent; corrosion rate (1500 h): 2.38 mg/(m)2H). Ultraviolet irradiation (1500 h): notched impact strength retention: 90.6 percent.
Example 4
Weighing the following materials in percentage by weight:
polyoxymethylene (designation M270): 35 percent of
Polytetrafluoroethylene micro powder: 20 percent of
Glass beads: 20 percent of
Rice straw powder: 20 percent of
Ultraviolet absorbers UV-327: 0.5 percent
Light stabilizer Tinuvin328: 0.5 percent
A compatibilizer (a mixture of a coupling agent and a diluent, wherein the mass ratio of the coupling agent to the diluent is 0.1, the coupling agent is a silane coupling agent KH560, and the diluent is isoamyl alcohol): 0.5 percent
Urea: 0.5 percent
Antioxidant 245: 2 percent of
Zinc stearate: 1 percent of
The preparation method of the formaldehyde-based wood-plastic composite resin comprises the following steps:
(1) pretreatment of rice straw powder: soaking a certain mass of rice straw powder in a sodium hydroxide solution (the mass fraction is 10%) for 1h, heating and boiling for 30min (the mass ratio of the rice straw powder to the sodium hydroxide is 1:10), filtering the rice straw powder, washing the rice straw powder to be neutral by water, and drying the rice straw powder in an oven for later use (60 ℃ and 1h).
(2) Grinding polyformaldehyde into powder with a particle size of 50 micrometers;
(3) putting polyformaldehyde powder, polytetrafluoroethylene micro powder, glass beads, an ultraviolet absorbent, a light stabilizer, a formaldehyde scavenger, an antioxidant and a lubricant into a high-speed mixer, and fully mixing and stirring for 20 min;
(4) putting the uniformly mixed blend into a double-screw extruder feeder, extruding, drawing wires and cutting into granules, wherein the processing temperature is 185 ℃;
(5) putting the cut modified material into an oven for drying, and removing powder and particles by a screening machine;
(6) putting the granules, the treated rice straw powder and the compatibilizer into a high-speed mixer, blending for 20min, putting the mixture into an extruder feeder, extruding for 2 times, drawing wires, and granulating, wherein the processing temperature is 185 ℃;
(7) and (3) putting the prepared granules into an injection molding machine, and carrying out spline injection molding by adopting different molds, wherein the injection molding temperature is 185 ℃, and finally obtaining the polyformaldehyde-based wood-plastic composite resin.
The molding shrinkage is reduced to 0.62 percent by calculation; the detection and analysis result shows that: coefficient of friction μ: 0.16 abrasion loss: 1.3mg Water absorption: 0.14 percent; corrosion rate (1500 h): 1.89 mg/(m)2H). Ultraviolet irradiation (1500 h): notched impact strength retention: 93.8 percent.
Example 5
Weighing the following materials in percentage by weight:
polyoxymethylene (designation M270): 50 percent of
Polytetrafluoroethylene micro powder: 5 percent of
Glass beads: 5 percent of
Wheat straw powder: 33 percent
Ultraviolet absorber UV-531: 2 percent of
2 percent of light stabilizer Tinuvin326
A compatibilizer (a mixture of a coupling agent and a diluent, wherein the mass ratio of the coupling agent to the diluent is 0.1, the coupling agent is a titanate coupling agent, and the diluent is white oil): 1 percent of
A polycyanate amine: 0.5 percent
Antioxidant 1010: 1 percent of
Magnesium stearate: 0.5 percent
The preparation method of the formaldehyde-based wood-plastic composite resin comprises the following steps:
(1) pretreatment of the wheat straw powder: soaking a certain mass of wheat straw powder in a sodium hydroxide solution (the mass fraction is 10%) for 1h, heating and boiling for 40min (the mass ratio of the wheat straw powder to the sodium hydroxide is 1:10), filtering the wheat straw powder, washing the wheat straw powder to be neutral by water, and drying the wheat straw powder in an oven for later use (65 ℃ and 1h).
(2) Grinding polyformaldehyde into powder with particle size of 60 micrometers;
(3) putting polyformaldehyde powder, polytetrafluoroethylene micro powder, glass beads, an ultraviolet absorbent, a light stabilizer, a formaldehyde scavenger, an antioxidant and a lubricant into a high-speed mixer, and fully mixing and stirring for 30 min;
(4) putting the uniformly mixed blend into a double-screw extruder feeder, extruding, drawing wires and cutting into granules, wherein the processing temperature is 190 ℃;
(5) putting the cut modified material into an oven for drying, and removing powder and particles by a screening machine;
(6) mixing the granules, the treated wheat straw powder and the compatibilizer in a high-speed mixer for 30min, then putting the mixture into an extruder feeder for 2 times of extrusion, drawing wires and cutting into granules, wherein the processing temperature is 190 ℃;
(7) and (3) putting the prepared granules into an injection molding machine, and carrying out spline injection molding by adopting different molds, wherein the injection molding temperature is 190 ℃, and finally obtaining the polyformaldehyde-based wood-plastic composite resin.
The molding shrinkage is reduced to 0.68 percent by calculation; the detection and analysis result shows that: coefficient of friction μ: 0.32 abrasion loss:2.8mg Water absorption: 0.12 percent; corrosion rate (1500 h): 1.79 mg/(m)2H). Ultraviolet irradiation (1500 h): notched impact strength retention: 95.3 percent.
Example 6
Weighing the following materials in percentage by weight:
polyoxymethylene (designation M90): 35 percent of
Polytetrafluoroethylene micro powder: 10 percent of
Glass beads: 10 percent of
Peanut shell powder: 38 percent of
UV absorber uv-770: 2 percent of
Light stabilizer Tinuvin328: 2%
A compatibilizer (a mixture of a coupling agent and a diluent, wherein the mass ratio of the coupling agent to the diluent is 0.2, the coupling agent is an aluminate coupling agent, and the diluent is white oil): 1.5 percent
Melamine: 0.5 percent
Antioxidant 245: 0.5 percent
Oleic acid diethanolamide: 0.5 percent
The preparation method of the formaldehyde-based wood-plastic composite resin comprises the following steps:
(1) pretreatment of peanut shell powder: putting a certain mass of peanut shell powder into a sodium hydroxide solution (mass fraction is 20%), soaking for 1.5h, heating and boiling for 50min (mass ratio: 1:10), filtering out the peanut shell powder, washing with water to be neutral, and putting the peanut shell powder into an oven to dry for later use (70 ℃, 1.5h).
(2) Grinding polyformaldehyde into powder with particle size of 60 micrometers;
(3) putting polyformaldehyde powder, polytetrafluoroethylene micro powder, glass beads, ultraviolet absorbent, light stabilizer, formaldehyde scavenger, antioxidant and lubricant into a high-speed mixer, and fully mixing and stirring for 50 min;
(4) putting the uniformly mixed blend into a double-screw extruder feeder, extruding, drawing wires and cutting into granules, wherein the processing temperature is 185 ℃;
(5) putting the cut modified material into an oven for drying, and removing powder and particles by a screening machine;
(6) putting the granules, the treated peanut shell powder and the compatibilizer into a high-speed mixer, blending for 50min, putting into a feeder of an extruder, extruding for 2 times, drawing wires and cutting into granules, wherein the processing temperature is 185 ℃;
(7) and (3) putting the prepared granules into an injection molding machine, and carrying out spline injection molding by adopting different molds, wherein the injection molding temperature is 190 ℃, and finally obtaining the polyformaldehyde-based wood-plastic composite resin.
The molding shrinkage is reduced to 0.75 percent by calculation; the detection and analysis result shows that: coefficient of friction μ: 0.21 abrasion loss: 1.8mg water absorption: 0.13 percent; corrosion rate (1500 h): 2.01 mg/(m)2H). Ultraviolet irradiation (1500 h): notched impact strength retention: 94.2 percent.
Example 7
Weighing the following materials in percentage by weight:
polyoxymethylene (designation M270): 40 percent of
Polytetrafluoroethylene micro powder: 5 percent of
Glass beads: 5 percent of
Fir wood powder: 43 percent
Ultraviolet absorbers UV-326: 2 percent of
2 percent of light stabilizer Tinuvin770
A compatibilizer (a mixture of a coupling agent and a diluent, wherein the mass ratio of the coupling agent to the diluent is 0.2, the coupling agent is a phosphate coupling agent, and the diluent is isoamyl alcohol): 1 percent of
A polycyanate amine: 0.5 percent
Antioxidant 1010: 1 percent of
Ethylene bis stearamide: 0.5 percent
The preparation method of the formaldehyde-based wood-plastic composite resin comprises the following steps:
(1) preprocessing Chinese fir powder: soaking a certain mass of Chinese fir wood powder in a sodium hydroxide solution (mass fraction is 20%) for 1.5h, heating and boiling for 50min (mass ratio: Chinese fir wood powder: sodium hydroxide is 1:10), filtering out the Chinese fir wood powder, washing with water to neutrality, and drying in an oven for later use (70 ℃, 1.5h).
(2) Grinding polyformaldehyde into powder with particle size of 60 micrometers;
(3) putting polyformaldehyde powder, polytetrafluoroethylene micro powder, glass beads, ultraviolet absorbent, light stabilizer, formaldehyde scavenger, antioxidant and lubricant into a high-speed mixer, and fully mixing and stirring for 50 min;
(4) putting the uniformly mixed blend into a double-screw extruder feeder, extruding, drawing wires and cutting into granules, wherein the processing temperature is 180 ℃;
(5) putting the cut modified material into an oven for drying, and removing powder and particles by a screening machine;
(6) placing the granules, the treated fir powder and the compatibilizer into a high-speed mixer, blending for 50min, placing into an extruder feeder, extruding for 2 times, drawing wires, and cutting into granules, wherein the processing temperature is 180 ℃;
(7) and (3) putting the prepared granules into an injection molding machine, and carrying out spline injection molding by adopting different molds, wherein the injection molding temperature is 185 ℃, and finally obtaining the polyformaldehyde-based wood-plastic composite resin.
The molding shrinkage is reduced to 0.98 percent by calculation; the detection and analysis result shows that: coefficient of friction μ: 0.36 abrasion loss: 3.4mg Water absorption: 0.12 percent; corrosion rate (1500 h): 2.47 mg/(m)2H). Ultraviolet irradiation (1500 h): notched impact strength retention: 94.8 percent.
Example 8
Weighing the following materials in percentage by weight:
polyoxymethylene (designation M270): 60 percent of
Polytetrafluoroethylene micro powder: 2 percent of
Glass beads: 2 percent of
Birch wood powder: 24 percent of
Ultraviolet absorbers UV-326: 3 percent of
Light stabilizer Tinuvin770: 3%
A compatibilizer (a mixture of a coupling agent and a diluent, wherein the mass ratio of the coupling agent to the diluent is 0.3, the coupling agent is an aluminate coupling agent, and the diluent is isoamyl alcohol): 2 percent of
A polycyanate amine: 1 percent of
Antioxidant 245: 2 percent of
Zinc stearate: 1 percent of
The preparation method of the formaldehyde-based wood-plastic composite resin comprises the following steps:
(1) pretreatment of birch wood powder: soaking birch powder in a sodium hydroxide solution (mass fraction is 10%) for 1h, heating and boiling for 30min (mass ratio: birch powder: sodium hydroxide is 1:10), filtering out birch powder, washing with water to neutrality, and drying in an oven for later use (60 ℃, 1h).
(2) Grinding polyformaldehyde into powder with particle size of 60 micrometers;
(3) putting polyformaldehyde powder, polytetrafluoroethylene micro powder, glass beads, an ultraviolet absorbent, a light stabilizer, a formaldehyde scavenger, an antioxidant and a lubricant into a high-speed mixer, and fully mixing and stirring for 30 min;
(4) putting the uniformly mixed blend into a double-screw extruder feeder, extruding, drawing wires and cutting into granules, wherein the processing temperature is 170 ℃;
(5) putting the cut modified material into an oven for drying, and removing powder and particles by a screening machine;
(6) mixing the granules, the treated birch wood powder and the compatibilizer in a high-speed mixer for 30min, then putting the mixture into a feeder of an extruder for 2 times of extrusion, drawing wires and cutting into granules, wherein the processing temperature is 170 ℃;
(7) and (3) putting the prepared granules into an injection molding machine, and carrying out spline injection molding by adopting different molds, wherein the injection molding temperature is 175 ℃, and finally obtaining the polyformaldehyde-based wood-plastic composite resin.
The molding shrinkage is reduced to 0.89% by calculation; the detection and analysis result shows that: coefficient of friction μ: 0.24 abrasion loss: 2.7mg Water absorption: 0.19 percent; corrosion rate (1500 h): 2.42 mg/(m)2H). Ultraviolet irradiation (1500 h): notched impact strength retention: 97.3 percent.
The foregoing illustrates the general principles of the present invention, and its attendant advantages, as will be understood by those skilled in the art, and it will be understood that the invention is not limited to the details of the foregoing embodiments, but is intended to cover various changes and modifications within the scope of the invention, as defined by the appended claims, and their equivalents.
Claims (10)
1. The polyformaldehyde-based wood-plastic composite material is characterized by comprising the following components in percentage by weight:
2. the composite resin according to claim 1, wherein the polyoxymethylene resin is a polyoxymethylene brand product of all polyoxymethylene of copolyoxymethylenes or homo-formaldehydes; the polytetrafluoroethylene micro powder has the average particle size of 3-5 microns and the water content of less than or equal to 0.1 percent; the glass beads comprise one or more of silicon dioxide, aluminum oxide, zirconium oxide, magnesium oxide and sodium silicate as main chemical components, and have an average particle size of 2-10 micrometers.
3. The composite resin as claimed in claim 1, wherein the plant fiber powder includes wood flour, nut shell powder or plant straw powder; the particle size of the plant fiber powder is between 100 and 200 meshes.
4. The composite resin of claim 3, wherein the wood flour includes but is not limited to: cedar wood flour, pine wood flour, birch wood flour or poplar wood flour; the shell powder includes but is not limited to: rice hulls, peanut shells, or walnut shells; the plant straw powder includes but is not limited to: rape straw powder, cotton straw powder, wheat straw powder or rice straw powder.
5. The composite resin according to claim 1, wherein the ultraviolet absorber is one of ultraviolet absorbers UV-329UV-327UV-326UV-531 UV-770; the light stabilizer is one of hydroxyl benzotriazole light stabilizers Tinuvin326 and Tinuvin328 and hindered phenol light stabilizers Tinuvin 770.
6. The composite resin according to claim 1, wherein the compatibilizer is a mixture of a coupling agent and a diluent, and the mass ratio of the coupling agent to the diluent is 0.1 to 0.3.
7. The composite resin of claim 6, wherein the compatibilizer comprises one of a silane coupling agent KH550, a silane coupling agent KH560, a titanate coupling agent, a phosphate coupling agent, or an aluminate coupling agent, and the diluent comprises one of white oil, propylene glycol, and isoamyl alcohol.
8. The composite resin according to claim 1, wherein the formaldehyde scavenger is one of dicyandiamide, urea, polyamide and melamine; the antioxidant is one of antioxidant 264, antioxidant 245 and antioxidant 1010; the lubricant is one of calcium stearate, zinc stearate, magnesium stearate, ethylene bis-stearamide or oleic acid diethanolamide.
9. A method for preparing the polyoxymethylene-based wood-plastic composite resin of claim 1, comprising the steps of:
(1) pretreatment of plant fiber powder: soaking plant fiber powder in sodium hydroxide solution for 1-2 hr, heating and boiling for 30-60min, filtering to obtain plant fiber powder, washing with water to neutrality, drying in oven at 60-80 deg.C for 1-2 hr;
(2) grinding polyformaldehyde into powder with particle size of 50-60 μm;
(3) putting polyformaldehyde powder, polytetrafluoroethylene micro powder, glass beads, ultraviolet absorbent, light stabilizer, formaldehyde scavenger, antioxidant and lubricant into a high-speed mixer, and fully stirring for 20-60 min;
(4) putting the uniformly mixed blend into a double-screw extruder, extruding, drawing wires and cutting into granules, wherein the processing temperature is 170-190 ℃;
(5) putting the cut modified material into an oven for drying, and then removing powder and particles by a screening machine;
(6) putting the granules, the treated plant fiber powder and the compatibilizer into a high-speed mixer for blending for 20-60min, putting the mixture into a bin of an extruder for 2 times of extrusion, drawing wires and cutting into granules, wherein the processing temperature is 170-190 ℃;
(7) and (3) putting the prepared granules into an injection molding machine, and carrying out spline injection molding by adopting different molds, wherein the injection molding temperature is 170-190 ℃, and finally obtaining the polyformaldehyde-based wood-plastic composite resin.
10. The method as set forth in claim 9, characterized in that the mass fraction of the sodium hydroxide solution in the step (1) is 10% -20%; the mass ratio of the plant fiber powder to the sodium hydroxide is 1: 10.
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