WO2015024286A1 - 一种木塑复合材料及其制备方法 - Google Patents

一种木塑复合材料及其制备方法 Download PDF

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WO2015024286A1
WO2015024286A1 PCT/CN2013/084012 CN2013084012W WO2015024286A1 WO 2015024286 A1 WO2015024286 A1 WO 2015024286A1 CN 2013084012 W CN2013084012 W CN 2013084012W WO 2015024286 A1 WO2015024286 A1 WO 2015024286A1
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Prior art keywords
wood
powder
hollow silica
plastic
content
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PCT/CN2013/084012
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English (en)
French (fr)
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薛杨
张冬海
武晓峰
陈运法
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中国科学院过程工程研究所
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Publication of WO2015024286A1 publication Critical patent/WO2015024286A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L97/00—Compositions of lignin-containing materials
    • C08L97/02—Lignocellulosic material, e.g. wood, straw or bagasse

Definitions

  • Wood plastic composite material and preparation method thereof Wood plastic composite material and preparation method thereof
  • the present invention relates to the field of composite materials, and in particular, to a wood plastic composite material and a method of preparing the same. Background technique
  • Wood-plastic composite material combines the advantages of wood and plastic. It has the advantages of light weight, high strength, low cost, green environmental protection and obvious benefits. With the dual advantages of cost book and performance, it has been obtained in many countries in the world in recent years. Especially in developed countries such as Europe, America and Japan, the researchers in various countries are actively carrying out research and development work on wood-plastic composite materials and their processing equipment. The field of wood-plastic composites is expanding, and it is increasingly replacing other traditional materials. Although wood-plastic composite materials have the above advantages, in practical applications, due to the poor compatibility of polar wood fibers and non-polar plastics, mechanical and other performance defects are caused to the materials.
  • wood-plastic materials have become more and more widely used, and have shown good application prospects in many functional fields, but at the same time, they have exposed the performance defects of materials themselves, and need further optimization, such as heat insulation performance, sound insulation performance, etc. .
  • Conventionally used foamed wood-plastic materials tend to have problems of dimensional instability and poor thermal stability, and ⁇ can cause a constant increase in material decay constant.
  • the use of inorganic particles allows the acoustic wave to be refracted, scattered and diffracted multiple times to increase the propagation path, and the hollow particles have a very low thermal conductivity and superior sound insulation properties to achieve good thermal insulation and sound insulation.
  • a biomass nano-silica and ammonium polyphosphate synergistic flame-retardant wood-plastic composite material is disclosed, which is made of the following raw materials by weight: 30 ⁇ 50% plant fiber, 50 ⁇ 70% plastic, 2 ⁇ 8 % biomass nano silica, 8 to 12 % ammonium polyphosphate, 1 to 2 % lubricant.
  • the invention also relates to a method for preparing the ignited wood-plastic composite material: the plant fiber, the plastic, and the biomass nanometer
  • the silicon oxide, ammonium polyphosphate, and the lubricant are initially mixed and dried, and then the dried premix is placed in a twin-screw granulator for granulation to obtain wood-plastic granules, and the wood-plastic granules are molded by various molds. , cooling, made of flame retardant wood-plastic composite material.
  • one of the objects of the present invention is to provide a functional wood-plastic composite material which is modified by a multi-scale nano-silica hollow sphere on the basis of wood powder and plastic.
  • the product Made of pellet blending, the product has excellent mechanical properties and waterproof properties, as well as excellent thermal insulation and sound insulation.
  • the wood-plastic composite material comprises the following raw material components in parts by weight: wood flour 60-90, plastic 10 40, hollow silica 1 -15 and modifier 0.1-10.
  • the wood flour is one or a combination of at least two of tree powder, sawdust powder, wood waste powder, nut shell powder or crop powder.
  • the wood flour has a weight fraction of from 65 to 87, particularly preferably 70 85.
  • the plastics have a weight fraction of from 12 to 35, particularly preferably from 15 to 30.
  • the hollow silica has a weight fraction of from 3 to 10, particularly preferably from 5 to 8.
  • the modifier has a weight fraction of 0.23, particularly preferably 0.3-0.6.
  • the wood-plastic composite material comprises the following raw material components in parts by weight: wood flour 65-87, plastic 12-35, hollow silica 340 and modifier 0.2-3
  • the wood plastic composite material comprises the following raw material components in parts by weight: wood powder 70 85, Plastic 15-30, hollow silica 5-8 and modifier 0.3-0.6.
  • the plastic is polyethylene (PE), polypropylene (PP), polystyrene (PS:), polyethylene terephthalate (PET) or acrylonitrile-styrene-butadiene copolymerization.
  • PE polyethylene
  • PP polypropylene
  • PS polystyrene
  • PET polyethylene terephthalate
  • ABS acrylonitrile-styrene-butadiene copolymerization.
  • ABS acrylonitrile-styrene-butadiene copolymerization
  • the hollow silica is hollow silica particles, further preferably silica hollow sphere particles, and particularly preferably agglomerated, monodisperse, submicron silica hollow sphere particles.
  • the hollow silica has a hollow inner diameter of 100 to 720 nm and an outer wall thickness of 50 to 100 ⁇ .
  • the hollow silica has a hollow inner diameter of from 100 to 500 nm, particularly preferably 150 to 300 ⁇ .
  • the hollow silica particles have an outer wall thickness of 50 to 75 nm.
  • the average particle size of the monodisperse polystyrene colloidal particles ranges from 112 757 legs; (2) ffi silane coupling agent surface modification of silica hollow sphere particles: 0.5 ⁇ lg step (1) is obtained
  • the silica hollow sphere particles were added to a lOOg acetone solution containing 1 to 2 g of a silicon germanium coupling agent, and after ultrasonication, stirred at room temperature for 12 hours, separated and washed with acetone 2-3 times, and then vacuum dried.
  • the silicon germanium coupling agent may be 3-aminopropyltriethoxysilane, ⁇ -shrinkage T-oleyloxypropyltrimethoxysilane, ⁇ -(methacryloyloxy)propyltrimethoxy Silane, ⁇ -( ⁇ -aminoethyl) Aminopropyltrimethoxysilane, ⁇ -aminopropyltrimethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, vinyltris( ⁇ -methoxyethoxy)silicone, 3 Aminopropyltrimethoxysilane, ⁇ -mercaptopropyltriethoxysilane, preferably ⁇ -(methacryloyloxy)propyltrimethoxysilane.
  • the centrifugal separation in the above step (1) is to classify the silica hollow granules by a centrifuge, and the specific operation is as follows: 1 set the rotation speed of 1000-2000 rpm, the centrifugation time 15mm-30 mm, and separate the 500nni-900nm 2; set the rotation speed of 2000 ⁇ 3000rpni, centrifuge time 15niin-30iiiin, separate 300nm 500nm particles; 3 set the rotation speed of 3000-4000rpm, centrifuge time 20 hidden 40 hidden, separate 100 legs 300 brain particles.
  • the hollow silica having a particle diameter of 100 nm to 300 nm has a content of 15 to 40 vol%
  • the hollow silica having a particle diameter of 300 nni to 500 nm has a content of 50 70 voi%
  • -72011 ⁇ 1 has a hollow silica content of 5 30 vol%; further preferably, a hollow silica content of from 100 nm to 300 nm is from 20 to 35 vol%, and a hollow silica content of from 500 nm to 500 nm is 55 65 vol%.
  • the content of the hollow silica having a particle diameter of 500 720 nm is 15-25 vol%; particularly preferably, the hollow silica having a particle diameter of 100 nm to 300 nm is 20 to 30 vol%, and the hollow silica having a particle diameter of 300 nm to 500 nm is contained.
  • the content of hollow silica having a particle diameter of 500 720 nm is from 2.0 to 25 vol%, which is from 60 to 65 vol%.
  • the modifiers of the present invention may employ modifiers commonly used or commonly used in the art, such as silicon germanium coupling agents, titanate coupling agents, maleic anhydride grafts, such as vinyl ethoxysilane. , 3 aminopropyltriethoxysilane, i,4-diphenylisocyanate, methylene diphenyl isocyanate, triethoxychlorosilane, tetraethoxysilane, specific products such as Dow Corning Z-6518 , Z ⁇ 6172, WCO's A ⁇ 172, Shin-Etsu's KBM 1003, Degussa's Si-69, Kenrich Petroleum's KR-TTS, KR-38S, KR-12; Du Pont's TYZOR TPT , TYZOR TnBT, MANALOX 360 of FedChem, etc., preferably i or at least Z-6518, KR 'ITS or K.BM 1003 A combination of 2 kinds.
  • a second object of the present invention is to provide a method for preparing the wood-plastic composite material, comprising the following steps:
  • the wood powder of the step (1) has a particle diameter of 10 to 150 mesh, more preferably 15 to 120 mesh, particularly preferably 20400 mesh; and if the particle size of the wood flour is larger than the size, It needs to be crushed beforehand.
  • the wood powder has a water content of ⁇ 3%, such as 2, 9 wt%, 2.8 wt%, 2.5 wt%, 2 wt:%, 1.8 wt%, 1.5 wt%, 1.2 wt%, ⁇ wt :%, 0.8 wt%, 0.5 wt%, 0.2 wt%, 0.1 wt% or 0.05 wt%, etc.; if the water content is 3 wt%, it is required to be dried before mixing with the modifier solution; preferably,
  • the drying temperature is 50 to 130 ⁇ , more preferably 70 to 120 ⁇ , and particularly preferably 80 to 110 ° C.
  • the drying time is at least 0.5 h, further preferably 0.8 to 6 h, particularly preferably ⁇ 4 h.
  • the drying is carried out in an oven.
  • the volume fraction of the modifier in the modifier solution is from 5 to 50%, more preferably from 8 to 45%, particularly preferably 1040%.
  • the solvent of the modifier solution may be an alcohol such as ethanol or butanol, a ketone such as acetone, butanone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, toluene, xylene or the like.
  • Aromatic hydrocarbons such as toluene, esters such as ethoxyethyl acetate and ethyl acetate, hydrazine, hydrazine-dimethylformamide, hydrazine, hydrazine-dimethyl diol
  • a nitrogen-containing solvent such as an amide or N-methylpyrrolidone.
  • the above solvents may be used singly or in combination of two or more kinds.
  • the solvent of the modifier solution is ethanol and/or acetone.
  • the mixing according to the step (1) comprises: spraying the wood powder with the modifier solution at a rotation speed of 300 to 2000 rpm, and then performing premixing in a high speed mixer; preferably, the rotation speed is 400-1800 ipm Particularly preferred is 500-1500 rpm; preferably, the time for premixing in a high speed mixer is at least 0.5 h, such as 0.8 hours, 1 hour, 1.5 hours, 2 hours, 2.5 hours, 2.9 hours, 3,1 Hour, 3.5 hours, 3.8 hours, 4 hours, 4.5 hours, 4.8 hours, 4.9 hours, 5.1 hours, 5.5 hours, 6 hours, 8 hours or 10 hours, etc., preferably 0.5-5 h, particularly preferably 0.5 3 h; preferably The temperature at which the premixing is carried out in a high speed mixer is 30,400 'C, more preferably 35 90 Torr, and particularly preferably 40 to 80 Torr.
  • the step (2) is carried out in a high speed mixer.
  • the mixing temperature in the step (2) is 50 to 100 ° C, more preferably 60 9 CTC, and particularly preferably 70 80 °.
  • the mixing time of the step (2) is at least 10 mm, further preferably from 12 to 50 mm, particularly preferably from 15 to 20 min.
  • the step (3) is performed by using a double-screw extruder.
  • the extrusion temperature in the step (3) is 125 270 ⁇ :, more preferably 135-260 Torr, and particularly preferably 145-250 Torr.
  • the forming of the step (3) comprises sequential hot pressing and cold pressing; preferably, the hot pressing temperature is 150 to 220 Torr, further preferably 160 200 ⁇ , particularly preferably 170 90: preferably, the cold The press is at least 5 min, further preferably 8 50 mm, particularly preferably 10-25 min.
  • the method for preparing the wood plastic composite material comprises the following steps:
  • step (2) sequentially adding the wood powder, plastic powder and hollow silica obtained in step (1) to a high-speed mixer, the temperature is controlled at 50 100 ° C, and the high-speed mixing is at least 10 min;
  • the wood plastic composite material of the invention has simple preparation process, the thermal conductivity (room temperature) of the product is less than 0.15 W/[m, the average sound insulation of the low frequency 200-2000HZ is greater than 25 dB, and the intermediate frequency is 2500-4000HZ. The average sound insulation is greater than 30dB, and the average sound insulation of the high frequency 5000 6300HZ is greater than 38dB.
  • the performance of the wood-plastic composite material of the present invention is determined by the following method: The thermal insulation performance is performed by a Physical Property Measurement System (PPMS-9, US A), and the scanning temperature range is 298K-358K;
  • PPMS-9 Physical Property Measurement System
  • the sawdust powder was pulverized by a mill to a particle size of 100 mesh, and then the wood flour was placed in a 60 Torr air oven for 4 hours (water content ⁇ 3%), and then cooled to 30 Torr.
  • 0.6 parts of ⁇ -6518 was diluted with acetone to 20% 0 ⁇ , and the diluted mixture was sprayed to process 85 parts of wood powder at a speed of 500 ⁇ ⁇ , and then forced into a high-speed mixer for premixing for 0.5 h at a temperature of 50 ° C.
  • silica hollow spherical particles according to the method described in detail in the patent CN200810 12232.0, which is a mixture having a hollow inner diameter of 100 nm to 300 nm of 5 vol%, a 300 nm to 500 nm content of 55 vol%, and a 500-720 nm content of 30 vol%, and an outer wall The thickness is 75mn.
  • the pretreated wood powder, 15 parts of bismuth plastic powder, and 8 parts of silica hollow sphere granules were sequentially added to the high-speed mixer in proportion, the temperature was controlled at 80 ⁇ , the high-speed mixing was 20 mm, and the mixture was placed in a 220 ⁇ double snail.
  • the mixture was extruded in a crucible extruder, cooled and pelletized, and then passed through a hot press at 170. C-molded, and then cold pressed 25 mm to prepare a hot-pressed wood-plastic composite product.
  • the obtained composite has a tensile strength of 56.2 MPa, an impact strength of 12.9 kj7 m2, a hardness of 96.3, a thermal conductivity (room temperature) of 0.0512 W, / m, an average sound insulation of a low frequency of 200-2000 Hz of 35.9 dB, and an average of an intermediate frequency of 2500 4000 Hz.
  • the sound insulation is 39.6dB, and the average sound insulation of the high frequency 5000-6300HZ is 44.8dB.
  • the wood waste powder was pulverized by a mill to have a particle size of 20 mesh, and then the wood powder was placed in a 90 Torr air oven for 2 hours (water content ⁇ 3%), and then cooled to 40 Torr.
  • 0.3 parts of Z 6172 was diluted with acetone to 10% (V/V), and the diluted mixture was treated with 60 parts of wood powder at a rotation speed of llOO rpm, and then added to a high-speed mixer for pre-mixing 2 b.
  • the temperature was in accordance with the patent.
  • silica hollow spherical particles which is a mixture having a hollow inner diameter of 100 nm to 300 nm of 40 vol%, a 30 () nm 500 mn content of 50 voi%, and a 500 720 nm content of 10 vol%.
  • the outer wall thickness is 50 ⁇ .
  • the pretreated wood powder, 40 parts of bismuth plastic powder, and 5 parts of silica hollow sphere granules were added to the high-speed mixer in proportion, the temperature was controlled at 70 ⁇ , the high-speed mixing was 15 mm, and the mixture was placed in a 210 ⁇ double snail.
  • the mixture was extruded in a crucible extruder, cooled and pelletized, and then passed through a hot press at 180. C compression molding, and then cold pressing] 5 mm to prepare hot-pressed wood-plastic composite products.
  • the obtained composite material has a tensile strength of 67.1 MPa, an impact strength of 13.7 kJ/m2, a hardness of 104.2, a thermal conductivity (room temperature) of 0.0828 W./[m, an average sound insulation of a low frequency of 200 2000 Hz of 25.1 dB, and an intermediate frequency of 25004000 Hz.
  • the average sound insulation is 32. IdB, and the average sound insulation of the high frequency 5000-6300HZ is 39.2dB c
  • the rice husk powder was pulverized by a mill to have a particle size of 60 mesh, and then the wood powder was placed in a 80 Torr air oven for 3 hours (water content ⁇ 3%), and then cooled to 30 Torr.
  • 3 parts of ⁇ 472 was diluted with acetone to 30% (V/V), and the diluted mixture was sprayed to treat 75 parts of wood powder at a speed of 1300 rpm, and then premixed for 1 h in a high-speed mixer at a temperature of 40;
  • the silica hollow sphere particles were prepared by the method described in detail in C 200810112232.0, which was a mixture having a hollow inner diameter of 100 nm to 300 nm of 20 vol%, a 300 rmi 500 nm content of 60 voI%, and a 500 720 nm content of 20 vol%, and an outer wall thickness of 60 mn.
  • the pretreated wood powder, 25 parts of PVC plastic powder and 8 parts of silica hollow sphere particles were sequentially added to the high-speed mixer in proportion, the temperature was controlled at 70 ⁇ , the high-speed mixing was 18 mm, and the mixture was placed at 160 ⁇ twin-screw extrusion. After being mixed and extruded in the machine, after cooling and granulating, it was molded by a hot press at 190 Torr, and then cold pressed at 10 mm to prepare a hot-pressed wood-plastic composite product.
  • the obtained composite material has a tensile strength of 67.8 MPa, an impact strength of 10.5 ld/m2, a hardness of 85.4, a thermal conductivity (room temperature) of 0.0717 W/K.rn, an average sound insulation of a low frequency of 200-2000 Hz of 27.4 dB, and an intermediate frequency of 2,500.
  • the average sound insulation of 4000HZ is 32.3dB, and the average sound insulation of high frequency 5000-6300HZ is 8,5 1B
  • the straw powder was pulverized by a mill with a particle size of 80 mesh, and then the wood powder was placed in a 110 Torr air oven for 1 h (water content ⁇ 3%), and then cooled to 40 °C.
  • 0.2 parts of KBM-1003 was diluted with acetone to 40% (VA, the diluted mixture was sprayed with 70 parts of wood powder, the rotation speed was 900 rpm, and then premixed for 3 h in a high-speed mixer, the temperature was in accordance with the patent CN200810112232.0
  • the silica hollow sphere particles were prepared by the method described in detail, and were a mixture having a hollow inner diameter of 100 nni-300 nm of 30 vol%, a 300 nm-500 mn content of 50 voi%, and a 500-720 nm content of 20 voi%, and an outer wall thickness of 55 ⁇ [dish.
  • the pretreated wood powder, 30 parts of PS plastic powder, 7.6 parts: silica hollow sphere particles were added to the high-speed mixer in proportion, the temperature was controlled at 70 ° C, the high-speed mixing was 16 mm, and the mixture was placed at 200 ⁇ .
  • the mixture was extruded and extruded in a double-screw extruder, and after cooling and granulating, it was molded by a hot press at 170 Torr, and then cold pressed at 10 mm to prepare a hot-pressed wood-plastic composite product.
  • the tensile strength of the obtained composite material is 86.9 MPa, the impact strength is 15.3 kJ/m2, the hardness is 113.6, the thermal conductivity (room temperature) is 0.0703 W/Km, and the average sound insulation of the low frequency 200-2000HZ is 28. 9 dB, the intermediate frequency is 2500- The average sound insulation of 4000HZ is 34.6dB, and the average sound insulation of high frequency 5000-6300HZ is 40,7clB o
  • the birch powder is crushed and sieved by a mill, the particle size is 50 mesh, and then the wood powder is placed in '70 Dry 2.5b in a C air oven (water content ⁇ 3%), then cool to 30 ⁇ .
  • silica hollow sphere particles were prepared by the method described in detail in the patent CN200810112232.0, which was a mixture having a hollow inner diameter of 100 nm and a 300 nm content of 30 vol%, a content of 300 nm to 500 nm of 65 voi%, and a content of 500 to 720 nm of 5 voi%, and an outer wall thickness of 65 nm.
  • Pre-treated wood powder 35 parts of PET plastic powder, 5.3 parts in order
  • the silica hollow sphere particles were added to a high speed mixer and the temperature was controlled at 80.
  • C high-speed mixing 19 mm
  • the mixture is placed in a 250-inch double-screw extruder and mixed and extruded. After cooling and granulating, it is molded by a hot press at 180 Torr, and then cold pressed at 10 mm to prepare a hot-pressed wood.
  • Plastic composite products 35 parts of PET plastic powder, 5.3 parts in order
  • the silica hollow sphere particles were added to a high speed mixer and the temperature was controlled at 80.
  • C high-speed mixing 19 mm
  • the mixture is placed in a 250-inch double-screw extruder and mixed and extruded. After cooling and granulating, it is molded by a hot press at 180 Torr, and then cold pressed at 10 mm to prepare a hot-pressed wood.
  • Plastic composite products 35 parts of PET plastic powder,
  • the obtained composite material has a tensile strength of 75.2 MPa, an impact strength of 16.8 kJ7 m2, a hardness of 95.4, a thermal conductivity (room temperature) of 0.0939 W/m, an average sound insulation of a low frequency of 200-2000 HZ of 27.2 dB, and an average sound insulation of an intermediate frequency of 2,500,4000 Hz.
  • the amount is 32.6dB, and the average sound insulation of the high frequency 5000-6300HZ is 38.7clB.
  • the coconut shell powder was pulverized by a mill with a particle size of 40 mesh, and then the wood powder was placed in a 1001: blast oven for 1.5 h (water content ⁇ 3%), and then cooled to 40 °C.
  • 8 parts of KR-38S was diluted to 30% with acetone (V:, the diluted mixture was sprayed with 60 parts of wood powder, the rotation speed was 1000 rpm, and then premixed for 1.5 h in a high speed mixer at a temperature of 50 ° C ;
  • Silica hollow sphere particles are prepared according to the method described in detail in the patent CN200810112232.0, which is a mixture having a hollow inner diameter of 100 nm to 300 nm of 15 voi%, a content of 300 nm to 500 nm of 55 vol%, and a content of 500 to 720 nm of 30 w>l%.
  • the thickness of the outer wall is 45 nm.
  • the pretreated wood powder, 40 parts of ABS plastic powder, and 5 parts of silica hollow sphere particles are sequentially added to the high-speed mixer in proportion, the temperature is controlled at 80 ⁇ , the high-speed mixing is 20 mm, and the mixture is placed.
  • the 230-inch twin-screw extruder was mixed and extruded, cooled and granulated, and then hot-pressed at 190 Torr, and then cold pressed at 15 mm to prepare a hot-pressed wood-plastic composite product.
  • the tensile strength of the obtained composite material is 8'7 2MPa, the impact strength is 7.1kJ/rn2, the hardness is 138.5, the thermal conductivity (room temperature) is 0.1010W/Km, and the average sound insulation of low frequency 200-2000HZ is 30.4dB.
  • the average sound insulation of 2500-4000HZ is 35.8dB, and the average sound insulation of high frequency 5000 6300HZ is 41.4dB.
  • Example 7 First, the maple powder was pulverized by a mill with a particle size of 70 mesh, and then the wood powder was placed in a 1101: blast oven for 2 hours (water content ⁇ 3%), and then cooled to 30 Torr. 3.7 parts of MANALOX 360 ⁇ acetone was diluted to 40% (V / V), the diluted mixture was sprayed with 90 parts of wood powder, the rotation speed was 1500 rpm, and then premixed for 0.5 h in a high-speed mixer, the temperature was 80 ⁇ ; The silica hollow sphere particles are prepared according to the method described in detail in the patent CN200810112232.0, which is a mixture having a hollow inner diameter I00nni-300nm content of 25 vol%, a 300 nm-500 nni content of 60 vol%, a 500-720 ⁇ content of 15 voi%, and an outer wall thickness.
  • the pretreated wood powder, 10 parts of PE plastic powder, and 8 parts of silica hollow sphere particles were sequentially added to the high-speed mixer in proportion, the temperature was controlled at 70' ⁇ , the high-speed mixing was 20 mm, and the mixture was placed at 190 ⁇ . After being mixed and extruded in a screw extruder, after cooling and granulating, it was molded by a hot press at 170 Torr, and then cold pressed at 20 mill to prepare a hot-pressed wood-plastic composite product.
  • the obtained composite material has a tensile strength of 50.6 MPa, an impact strength of 9.7 kJ/m2, a hardness of 83.4, a thermal conductivity (room temperature) of 0.0495 W/Km, an average sound insulation of a low frequency of 200-2000 HZ of 37.9 dB, and an intermediate frequency of 2500-4000 HZ.
  • the average sound insulation is 45.2dB, and the average sound insulation of the high frequency 5000 6300HZ is 49.9dB.
  • the maple powder was pulverized by a mill with a particle size of 10 mesh, and then the wood powder was placed in a 130 Torr air oven for drying for 5 hours (water content ⁇ 3%), and then cooled to 35 Torr.
  • the method described in detail in CN200810112232.0 prepares silica hollow spherical particles having a hollow inner diameter of 100 nm to 300 nm of 18 vol%, a 300 nm to 500 nm content of 64 vol%, and a 500-720 nm content of 18 vol%, and an outer wall thickness of 55 nm.
  • the pretreated wood powder, 25 parts of PE plastic powder, and 3 parts of silica hollow sphere particles are added to the high-speed mixer in turn, and the temperature is controlled at 50 ° C, high.
  • the speed mixing 50 nu mix is placed at 270.
  • the mixture was extruded and extruded in a twin-screw extruder of C. After cooling and granulating, it was molded by a hot press at 220 Torr, and then cold pressed at 5 miii to prepare a hot-pressed wood-plastic composite product.
  • the obtained composite has a tensile strength of 43.7 MPa, an impact strength of 9.4 kJ/m2, a hardness of 71.4, a thermal conductivity (room temperature) of 0.1395 W/Km, a low frequency of 200-20001 IZ of an average sound insulation of 27.9 dB, and an intermediate frequency of 2500-
  • the average sound insulation of 4000HZ is 35,5dB, and the average sound insulation of high frequency 5000 6300HZ is 39.2dB o
  • the rice husk powder was pulverized by a mill to have a particle size of 150 mesh, and then the wood powder was placed in a 50 Torr air oven for 6 hours (water content ⁇ 3%), and then cooled to 40 Torr.
  • 2 parts of A- 172 ffi acetone was diluted to 5% (V/V), and the diluted mixture was sprayed to treat 82 parts of wood powder at a speed of 2000 rpm, and then added to a high-speed mixer for premixing for 0.5 h at a temperature of lOCTC; prepared according to the method detailed in the patent CN200810112232X), which is a mixture having a hollow inner diameter of 100 nm to 300 nm of 35 vol%, a content of 300 nm to 500 nm of 56 vol%, and a content of 500 720 nm of 9 vol%, and an outer wall thickness.
  • the obtained composite has a tensile strength of 39.8 MPa, an impact strength of 8.1 kJ/m2, a hardness of 75.1, a thermal conductivity (room temperature) of 0 1417 W./[m, an average sound insulation of low frequency 200 2000 Hz of 27 dB, an intermediate frequency of 2500 4000 HZ.
  • the average sound insulation is 31.3dB, and the average sound insulation of the high frequency 5000-6300HZ is 38.4dB.
  • the present invention illustrates the detailed process equipment and process flow of the present invention by the above embodiments, but the present invention is not limited to the above detailed process equipment and process flow, that is, it does not mean that the present invention must rely on the above detailed process equipment and The process can only be implemented. It will be apparent to those skilled in the art that any modifications of the present invention, equivalent substitution of the various materials of the products of the present invention, addition of auxiliary components, selection of specific means, etc., are all within the scope of protection and disclosure of the present invention.

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  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
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  • Medicinal Chemistry (AREA)
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  • Compositions Of Macromolecular Compounds (AREA)

Abstract

本发明涉及一种隔热、隔音木塑复合材料及其制备方法。本发明采用对木粉预处理后，添加改性中空二氧化硅颗粒作为填料，与塑料挤出成型，得到的木塑复合材料具有优异的力学性能和隔热、隔音性能，且绿色环保。

Description

一种木塑复合材料及其制备方法
本发明涉及复合材料领域， 具体地， 本发明涉及一种木塑复合材料及其制 备方法。 背景技术
说
木塑复合材料集木材和塑料的优点于一身， 具有质量轻、 强度高、 成本低 和绿色环保、 效益明显的优点， 凭借成本书和性能上的双重优势， 近几年来得到 世界上许多国家， 特别是欧美及日本等发达国家的普遍重视， 各国的科研人员 都在积极地进行木塑复合材料及其加工设备的研究开发工作。 木塑复合材料的 应 ffi领域不断扩大， 越来越多地替代其它传统材料。 虽然木塑复合材料具有上述优点但是在实际应用中， 由于极性的木质纤维 和非极性的塑料相容性较差， 给材料造成力学及其它性能上的缺陷。 随着材料 技术的发展， 木塑材料应用日益广泛， 并在许多功能性领域展现出良好的应用 前景， 但同时也暴露出材料本身的性能缺陷， 需要进一步优化， 如隔热性能、 隔音性能等。 而常规采用的发泡木塑材料， 往往会存在尺寸不稳定和热稳定性 差的问题， 并] ΐ会导致材料衰减常数增力 Π。 而釆用无机粒子可使声波多次折射、 散射和绕射导致传播路径增加， 且中空粒子具有极低的导热系数和更优越的隔 声性能从而达到良好的隔热、 隔音效果。
CN 102702767 Α 公开了一种生物质纳米二氧化硅及聚磷酸铵协效阻燃木塑 复合材料， 按如下重量百分比的原料制成： 30〜50 %植物纤维、 50〜70 %塑料、 2〜8 %生物质纳米二氧化硅、 8〜12 %聚礴酸铵、 1〜2 %润滑剂。 该发明还涉及 该隠燃木塑复合材料的制备方法： 将称取好的植物纤维、 塑料、 生物质纳米二 氧化硅、 聚磷酸铵、 润滑剂进行初混、 干燥， 然后将干燥好的预混物置于双螺 杆造粒机中进行造粒， 得到木塑颗粒， 再将木塑颢粒经各种模具成型、 冷却， 制成阻燃木塑复合材料。 但是专利中采用将阻燃剂聚磷酸铵接枝到纳米二氧化 硅表面协同作用的方法来使木材达到隠燃效果， 而本发明中采用的中空二氧化 硅本身就具有优异的隔热性能， 因此本发明的方法更加简单易行。
因此， 开发一种具有优异的物理性能及优良的保温隔热和隔音效果的木塑 复合材料是所属领域的技术难题。
发明内容
针对现有技术的不足， 本发明的目的之一在于提供一种功能性木塑复合材 料， 其是在以木粉和塑料为基体的基础上， 通过改性的多尺度纳米二氧化硅中 空球颗粒共混挤出制成， 产品除具有优异的力学性能、 防水性能外， 还有优良 的保温隔热及隔音效果。
所述木塑复合材料按照重量份数包括如下原料组分：木粉 60-90、塑料 10 40、 中空二氧化硅 1 -15和改性剂 0.1~10。
优选地， 所述木粉为树木粉、 锯末粉、 木材废料粉、 果壳粉或农作物粉中 的 1种或至少 2种的组合。
优选地， 所述木粉的重量份数为 65-87 , 特别优选为 70 85。
优选地， 所述塑料的重量份数为 12~35， 特别优选为 15-30。
优选地， 所述中空二氧化硅的重量份数为 3- 10 , 特别优选为 5-8。
优选地， 所述改性剂的重量份数为 0.2 3， 特别优选为 0.3- 0.6。
优选地， 所述木塑复合材料按照重量份数包括如下原料组分： 木粉 65-87、 塑料 12-35、 中空二氧化硅 340和改性剂 0.2-3
优选地， 所述木塑复合材料按照重量份数包括如下原料组分： 木粉 70 85、 塑料 15-30、 中空二氧化硅 5-8和改性剂 0.3-0.6。
优选地， 所述塑料为聚乙烯 (PE)、 聚丙烯（PP)、 聚苯乙烯（PS：)、 聚对苯 二甲酸乙二醇酯 （PET ) 或丙烯腈-苯乙烯 -丁二烯共聚物 （ABS ) 中的 1种或至 少 2种的组合。
优选地， 所述中空二氧化硅为中空二氧化硅颗粒， 进一步优选为二氧化硅 中空球颗粒， 特别优选为无团聚、 单分散、 亚微米二氧化硅中空球颗粒。
优选地， 所述中空二氧化硅的中空内径为 100~720nm , 外壁厚度为 50 100誦。
优选地， 所述中空二氧化硅的中空内径为 100- 500nm， 特别优选为 150 300誦。
优选地， 所述中空二氧化硅颗粒的外壁厚度为 50~75nm。
所述的中空二氧化硅颗粒的制备方法在专利 CN101585954A中有详细描述， 现简述如下：
( 1 )将 0.2 0.5g单分散聚苯乙烯胶体颗粒分散在 94.5ml/5.5ml乙醇 /水的混 合溶液中， 超声处理后， 滴加 0.65- 2.3ml的浓氮水， 搅拌均匀后， 继续滴加硅酸 四乙酯 1.9 4.5ml， 反应后， 离心分离出固体并用乙醇洗涤后， 分离烘千； 之后， 以 1- 5O/mm升温速度， 升温至 550- 650'Ό并保温 1- 3h, 以除去作为模板剂的聚 苯乙烯胶体颗粒， 得到二氧化硅中空球颗粒。 所述的单分散聚苯乙烯胶体颢粒 的平均粒径范围在 112 757腿； （2) ffi硅烷偶联剂对二氧化硅中空球颗粒进行表 面改性：将 0.5~lg步骤（1 )得到的二氧化硅中空球颗粒加入到含有 l~2g硅垸偶 联剂的 lOOg丙酮溶液中， 超声后， 室温下搅拌 12h, 分离并用丙酮洗 2-3次， 之后抽真空烘干。其中， 硅垸偶联剂可采用 3 -氨基丙基三乙氧基硅垸、 γ-缩水†T 油醚氧丙基三甲氧基硅烷、 γ -(甲基丙烯酰氧）丙基三甲氧基硅烷、 Ν-(β-氨乙基)于 氨丙基三甲氧基硅烷， γ-氨丙基三甲氧基硅烷、 乙烯基三乙氧基硅烷、 乙烯基三 甲氧基硅烷、 乙烯基三 (β -甲氧基乙氧基）硅垸、 3氨丙基三甲氧基硅烷、 γ巯丙 基三乙氧基硅烷， 优选 γ- (甲基丙烯酰氧） 丙基三甲氧基硅烷。
其中在上述步骤 （1 ) 中的离心分离是采用离心机对二氧化硅中空颢粒进行 尺度分级， 具体操作为： ①设置转速为 1000- 2000rpm， 离心时间 15mm- 30mm， 分离出 500nni-900nm 的颗粒； ②设置转速为 2000~3000rpni , 离心时间 15niin-30iiiin, 分离出 300nm 500nm的颗粒； ③设置转速为 3000- 4000rpm， 离 心时间 20隱 40隱， 分离出 100腿 300腦的颗粒。
优选地， 所述中空二氧化硅中， 粒径为 lOOnm- 300nm的中空二氧化硅含量 为 15- 40vol%， 粒径为 300nni- 500nm的中空二氧化硅含量为 50 70voi%, 粒径为 500-72011Π1的中空二氧化硅含量为 5 30vol%;进一步优选，粒径为 lOOnm- 300nm 的中空二氧化硅含量为 20- 35vol%， 粒径为 300nm 500nm的中空二氧化硅含量 为 55 65vol%,粒径为 500 720nm的中空二氧化硅含量为 15-25vol%;特别优选， 粒径为 lOOnm- 300nm的中空二氧化硅含量为 20~30vol%, 粒径为 300nm- 500nm 的中空二氧化硅含量为 60-65vol%， 粒径为 500 720nm 的中空二氧化硅含量为 2.0- 25vol%。
本发明所述改性剂可采用在该领域内常用的或者通用的改性剂， 如硅垸偶 联剂、 钛酸酯偶联剂、 马来酸酐接枝物， 如乙烯基 乙氧基硅烷、 3氨基丙基三 乙氧基硅烷、 i,4-二苯基异氰酸酯、 亚甲基二苯基异氰酸酯、 三乙氧基氯硅烷、 四乙氧基硅垸， 具体产品如道康宁的 Z- 6518、 Z~6172、 威科公司的 A~172、 信 越公司的 KBM 1003、 德固赛公司的 Si-69、 Kenrich 石油公司的 KR-TTS、 KR-38S 、 KR- 12 ; Du Pont公司的 TYZOR TPT、 TYZOR TnBT 、 FedChem公 司的 MANALOX 360等， 优选 Z- 6518、 KR 'ITS或 K.BM 1003中的 i种或至少 2种的组合。
本发明目的之二在于提供一种所述木塑复合材料的制备方法， 包括以下步 骤：
( 1 ) 将木粉和改性剂溶液混合， 得到预处理后的木粉；
( 2 ) 将步骤 （1 ) 得到的预处理后的木粉、 塑料粉料和中空二氧化硅混合， 得到混料；
(3 ) 将步骤 (2 ) 得到的混料挤出、 造粒， 并成型， 得到木塑复合材料制
1：：) 优选地， 步骤（1 )所述木粉的粒径为 10〜150目， 进一步优选为 15〜120目， 特别优选为 20400目； 如果木粉的粒径大于所述尺寸， 即需要预先对其进行粉 碎。
优选地， 步骤（1 )所述木粉含水量<3^%, 例如 2,9wt%、 2.8wt%、 2.5wt%、 2wt:%、 1.8wt%, 1.5wt%、 1.2wt%、 】wt:%、 0.8wt%, 0.5wt%, 0.2wt%、 0.1 wt% 或 0.05wt%等； 如果其含水量 3wt%, 那么就需要在与改性剂溶液混合前对其 进行干燥; 优选地， 所述干燥温度为 50〜130Ό， 进一步优选为 70〜120Ό， 特别 优选为 80〜110°C ; 优选地， 所述干燥时间为至少 0.5h, 进一步优选为 0.8〜6h， 特别优选为】〜4h ; 优选地， 所述干燥在烘箱中进行。
优选地， 所述改性剂溶液中改性剂的体积分数为 5-50%, 进一步优选为 8-45%, 特别优选为 1040%。
所述改性剂溶液的溶剂可以为乙醇、 丁醇等醇类， 丙酮、 丁酮、 甲基乙基 甲酮、 甲基异丁基甲酮、 环己酮等酮类， 甲苯、 二甲苯、 均三甲苯等芳香族烃 类， 乙氧基乙基乙酸酯、 醋酸乙酯等酯类， Ν,Ν-二甲基甲酰胺、 Ν,Ν-二甲基乙 酰胺、 N 甲基 吡咯垸酮等含氮类溶剂。 上述溶剂可以单独使用一种， 也可以 两种或者两种以上混合使用； 优选地， 所述改性剂溶液的溶剂为乙醇和 /或丙酮。
优选地， 歩骤 （1 ) 所述混合包括： 在 300~2000rpm的转速下用改性剂溶液 喷洒处理木粉， 然后在高速混合机中进行预混合； 优选地， 所述转速为 400-1800ipm, 特别优选为 500- 1500rpm; 优选地， 在高速混合机中进行预混合 的时间为至少 0.5h， 例如 0.8小时、 1小时、 1.5小日寸、 2小时、 2.5小时、 2.9小 时、 3,1小时、 3.5小时、 3.8小时、 4小时、 4.5小时、 4.8小时、 4.9小时、 5.1 小时、 5.5小时、 6小时、 8小时或 10小时等，优选为 0.5-5h，特别优选为 0.5 3h; 优选地，在高速混合机中进行预混合的温度为 30400'C，进一步优选为 35 90Ό， 特别优选为 40- 80 Ό。
优选地， 步骤 （2 ) 所述混合在高速混合机中进行。
优选地， 步骤 (2 ) 所述混合温度为 50- 100°C， 进一步优选为 60 9CTC , 特 别优选为 70 80Ό。
优选地， 步骤 （2 ) 所述混合时间为至少 10mm, 进一步优选为 12~50mm， 特别优选为 15- 20min。
优选地， 步骤 （3 ) 所述挤出采用双螺杼挤出机。
优选地， 步骤 （3 ) 所述挤出温度为 125 270τ：， 进一步优选为 135-260Ό , 特别优选为 145- 250Ό。
优选地， 步骤 （3 )所述成型包括依次热压和冷压； 优选地， 所述热压温度 为 150~220 Ό， 进一步优选为 160 200Ό， 特别优选为 170 90 : 优选地， 所述 冷压 间为至少 5min， 进一步优选为 8 50mm， 特别优选为 10- 25min。
优选地， 所述木塑复合材料的制备方法， 包括以下步骤：
( 1：)将体积分数为 5 50%的改性剂溶液喷洒处理木粉，转速为 300- 2000rpm， 然后加入高速混合机中进行预混合至少 0.5h， 温度 3( 00Ό ;
(2 ) 按照比例依次把步骤 （1 ) 得到的木粉、 塑料粉料和中空二氧化硅加 入高速混合机中， 温度控制在 50 100°C， 高速混合至少 lOmin;
( 3 ) 混料置于 125- 270 'Ό的双螺杆挤出机中混合挤出， 冷却造粒后， 经热 压机于 150 220 Ό模压成型， 然后再冷压至少 5mm制备出热压型木塑复合材料 口
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与现有技术相比， 本发明所述木塑复合材料制备工艺简单， 产品的导热系 数 (室温) 小于 0.15W/【m， 低频 200- 2000HZ的平均隔音量大于 25 dB， 中频 2500-4000HZ 的平均隔音量大于 30dB , 高频 5000 6300HZ 的平均隔音量大于 38dB。
下面结合实施例对本发明作进一步详细说明。 但下述的实施例仅仅是本发 明的简易例子， 并不代表或限制本发明的权利保护范围， 本发明的保护范围以 权利要求书为准。
具体实施方式
为便于理解本发明， 本发明列举实施例如下。 本领域技术人员应该明了， 所述实施例仅仅是帮助理解本发明， 不应视为对本发明的具体限制。
本发明的木塑复合材料的性能采用以下方法测定： 隔热性能采用 Physical Property Measurement System(PPMS-9， US A)进行，扫描温度范围为 298K-358K;
隔音性能： GB/T19889.1 -2005 , 建筑及建筑构件隔声测量；
拉伸性能： GB/T 1040 1992， 塑料拉伸性能试验方法；
硬度： GB9342- 88， 塑料洛氏硬度试验方法；
导热系数： GB3399-82 , 塑料导热系数实验方法护热平板法；
冲击性能： GB/T 1043 1993， 硬质塑料简支梁冲击试验方法。 下面的实施例可以使本专业技术人员更全面的理解本发明， 但不限于此。 实施例 1
首先对用磨粉机将锯末粉粉碎过筛， 粒径为 100 目， 然后将木粉放入 60Ό 鼓风烘箱中干燥 4h (含水量<3%)， 然后冷却至 30Ό。 将 0.6份 Ζ- 6518用丙酮 稀释至 20% 0 Α ， 稀释后的混合液喷洒处理 85份木粉， 转速为 500φΐη, 然后 力 Π入高速混合机中进行预混合 0.5 h，温度为 50°C ;按照专利 CN200810 12232.0 中详细描述的方法制备二氧化硅中空球颗粒， 为中空内径 100nm~300nm含量为 】5vol%， 300nm- 500nm含量为 55 vol%， 500- 720nm含量为 30vol%的混合物， 外壁厚度为 75mn。 按照比例依次把预处理的木粉、 15份 ΡΕ塑料粉料、 8份二 氧化硅中空球颢粒加入高速混合机中， 温度控制在 80Ό , 高速混合 20 mm， 混 料置于 220Ό的双螺杼挤出机中混合挤出， 冷却造粒后， 经热压机于 170。C模压 成型， 然后再冷压 25 mm制备出热压型木塑复合材料制品。
所得复合材料的拉伸强度为 56.2MPa, 冲击强度为 12.9kj7m2，硬度为 96.3， 导热系数 (室温)为 0.0512W,/ m， 低频 200-2000HZ的平均隔音量为 35.9 dB， 中频 2500 4000HZ的平均隔音量为 39.6dB， 高频 5000- 6300HZ的平均隔音量为 44.8dB。
实施例 2
首先对用磨粉机将木材废料粉粉碎过筛，粒径为 20目，然后将木粉放入 90Ό 鼓风烘箱中干燥 2h (含水量<3%)， 然后冷却至 40Ό。 将 0.3份 Z 6172用丙酮 稀释至 10% (V/V), 稀释后的混合液啧洒处理 60份木粉， 转速为 llOOrpm, 然 后加入高速混合机中进行预混合 2 b，温度为 按照专利 CN200810112232.0 中详细描述的方法制备二氧化硅中空球颗粒， 为中空内径 100nm~300mn含量为 40vol%, 30()nm 500mn含量为 50 voi%, 500 720nm含量为 10vol%的混合物， 外壁厚度为 50ιιπι。 按照比例依次把预处理的木粉、 40份 ΡΡ塑料粉料、 5份二 氧化硅中空球颢粒加入高速混合机中， 温度控制在 70Ό , 高速混合 15 mm， 混 料置于 210Ό的双螺杼挤出机中混合挤出， 冷却造粒后， 经热压机于 180。C模压 成型， 然后再冷压】5 mm制备出热压型木塑复合材料制品。
所得复合材料的拉伸强度为 67.1MPa，冲击强度为 13.7kJ/m2，硬度为 104.2， 导热系数 (室温) 为 0.0828W./【m， 低频 200 2000HZ的平均隔音量为 25.1dB， 中频 25004000HZ的平均隔音量为 32. IdB,高频 5000- 6300HZ的平均隔音量为 39.2dB c
实施例 3
首先对用磨粉机将稻壳粉粉碎过筛， 粒径为 60目， 然后将木粉放入 80Ό鼓 风烘箱中干燥 3h (含水量<3%) , 然后冷却至 30Ό。 将 3份 Α472用丙酮稀释 至 30% (V/V), 稀释后的混合液喷洒处理 75份木粉， 转速为 1300rpm， 然后加 入高速混合机中进行预混合 1 h， 温度为 40 ; 按照专利 C 200810112232.0中 详细描述的方法制备二氧化硅中空球颗粒， 为中空内径 lOOnm- 300nm 含量为 20vol%, 300rmi 500nm.含量为 60 voI%, 500 720nm含量为 20vol%的混合物， 外壁厚度为 60mn。 按照比例依次把预处理的木粉、 25份 PVC塑料粉料、 8份 二氧化硅中空球颗粒加入高速混合机中， 温度控制在 70Ό， 高速混合 18 mm, 混料置于 160Ό的双螺杆挤出机中混合挤出， 冷却造粒后， 经热压机于 190Ό模 压成型， 然后再冷压 10 mm制备出热压型木塑复合材料制品。
所得复合材料的拉伸强度为 67.8MPa, 冲击强度为 10.5ld/m2，硬度为 85.4， 导热系数 （室温） 为 0.0717W/K.rn， 低频 200-2000HZ的平均隔音量为 27.4dB , 中频 2500- 4000HZ的平均隔音量为 32.3dB , 高频 5000- 6300HZ的平均隔音量为 8,5 1B 实施例 4
首先对用磨粉机将秸 粉粉碎过筛， 粒径为 80 目， 然后将木粉放入 110Ό 鼓风烘箱中干燥 lh (含水量<3%) , 然后冷却至 40°C。将 0.2份 KBM- 1003用丙 酮稀释至 40% (VA ， 稀释后的混合液喷洒处理 70份木粉， 转速为 900rpm， 然 后加入高速混合机中进行预混合 3 h，温度为 按照专利 CN200810112232.0 中详细描述的方法制备二氧化硅中空球颗粒， 为中空内径 lOOnni- 300nm含量为 30vol%, 300nm- 500mn含量为 50 voi%, 500- 720nm含量为 20voi%的混合物， 外壁厚度为 55ι [皿。按照比例依次把预处理的木粉、 30份 PS塑料粉料、 7.6份:二 氧化硅中空球颗粒加入高速混合机中， 温度控制在 70。C， 高速混合 16 mm， 混 料置于 200Ό的双螺杼挤出机中混合挤出， 冷却造粒后， 经热压机于 170Ό模压 成型， 然后再冷压 10 mm制备出热压型木塑复合材料制品。
所得复合材料的拉伸强度为 86.9MPa，冲击强度为 15.3kJ/m2 ,硬度为 113.6， 导热系数 (室温)为 0.0703W/K.m， 低频 200- 2000HZ的平均隔音量为 28. 9dB， 中频 2500- 4000HZ的平均隔音量为 34.6dB , 高频 5000- 6300HZ的平均隔音量为 40,7clB o 首先对用磨粉机将桦木粉粉碎过筛， 粒径为 50目， 然后将木粉放入' 70 C鼓 风烘箱中干燥 2.5b (含水量<3%)， 然后冷却至 30Ό。 将 2份 KR~TTS用丙酮稀 释至 20% (VA , 稀释后的混合液喷洒处理 65份木粉， 转速为 700ipm, 然后加 入高速混合机中进行预混合 2.5 h, 温度为 60°C ; 按照专利 CN200810112232.0 中详细描述的方法制备二氧化硅中空球颗粒， 为中空内径 100nm 300nrn含量为 30vol%, 300nm- 500nm含量为 65voi%， 500~720nm含量为 5voi%的混合物， 外 壁厚度为 65nm。 按照比例依次把预处理的木粉、 35份 PET塑料粉料、 5.3份二 氧化硅中空球颗粒加入高速混合机中， 温度控制在 80。C， 高速混合 19 mm， 混 料置于 250Ό的双螺杼挤出机中混合挤出， 冷却造粒后， 经热压机于 180Ό模压 成型， 然后再冷压 10 mm制备出热压型木塑复合材料制品。
所得复合材料的拉伸强度为 75.2MPa, 冲击强度为 16.8kJ7m2，硬度为 95.4， 导热系数 （室温） 为 0.0939W/ m， 低频 200- 2000HZ的平均隔音量为 27.2dB , 中频 2500 4000HZ的平均隔音量为 32.6dB， 高频 5000- 6300HZ的平均隔音量为 38.7clB。
实施例 6
首先对用磨粉机将椰壳粉粉碎过筛， 粒径为 40 目， 然后将木粉放入 1001： 鼓风烘箱中干燥 1.5h (含水量<3%)， 然后冷却至 40°C。 将 8份 KR- 38S用丙酮 稀释至 30% ( V：， 稀释后的混合液喷洒处理 60份木粉， 转速为 1000rpm， 然 后加入高速混合机中进行预混合 1.5 h , 温度为 50 °C ; 按照专利 CN200810112232.0 中详细描述的方法制备二氧化硅中空球颗粒， 为中空内径 100nm-300nm含量为 15voi%， 300nm-500nm含量为 55 vol%, 500-720nm含量 为 30w>l%的混合物， 外壁厚度为 45nm。 按照比例依次把预处理的木粉、 40份 ABS塑料粉料、 5份二氧化硅中空球颗粒加入高速混合机中， 温度控制在 80Ό， 高速混合 20 mm, 混料置于 230Ό的双螺杆挤出机中混合挤出， 冷却造粒后， 经 热压机于 190Ό模压成型， 然后再冷压 15 mm制备出热压型木塑复合材料制品。
所得复合材料的拉伸强度为 8'7 2MPa，冲击强度为〗7.1kJ/rn2，硬度为 138.5， 导热系数 (室温) 为 0.1010W/K.m, 低频 200- 2000HZ的平均隔音量为 30.4dB， 中频 2500-4000HZ的平均隔音量为 35.8dB , 高频 5000 6300HZ的平均隔音量为 41.4dB。
实施例 7 首先对用磨粉机将枫木粉粉碎过筛， 粒径为 70 目， 然后将木粉放入 1101： 鼓风烘箱中干燥 2h (含水量 <3%), 然后冷却至 30Ό。 将 3.7份 MANALOX 360 ^丙酮稀释至 40% (V/V)，稀释后的混合液喷洒处理 90份木粉，转速为 1500rpm, 然后加入高速混合机中进行预混合 0.5 h， 温度为 80 Ό ; 按照专利 CN200810112232.0 中详细描述的方法制备二氧化硅中空球颗粒， 为中空内径 I00nni-300nm含量为 25vol%， 300nm~500nni含量为 60 vol%， 500~720ηπι含量 为 15voi%的混合物， 外壁厚度为 50nm。 按照比例依次把预处理的木粉、 10份 PE塑料粉料、 8份二氧化硅中空球颗粒加入高速混合机中， 温度控制在 70'Ό , 高速混合 20 mm, 混料置于 190Ό的双螺杆挤出机中混合挤出， 冷却造粒后， 经 热压机于 170Ό模压成型， 然后再冷压 20 mill制备出热压型木塑复合材料制品。
所得复合材料的拉伸强度为 50.6MPa， 冲击强度为 9.7kJ/m2, 硬度为 83.4， 导热系数 (室温) 为 0.0495W/K.m, 低频 200- 2000HZ的平均隔音量为 37.9dB， 中频 2500-4000HZ的平均隔音量为 45.2dB, 高频 5000 6300HZ的平均隔音量为 49.9dB。
实施例 8
首先对用磨粉机将枫木粉粉碎过筛， 粒径为 10 目， 然后将木粉放入 130Ό 鼓风烘箱中干燥 o.5h (含水量 <3%) ,然后冷却至 35 Ό。将 8.7份 MANALOX 360 用丙酮稀释至 50% (V/V 稀释后的混合液喷洒处理 80份木粉，转速为 300rpm， 然后加入高速混合机中进行预混合 5h , 温度为 30 τ:； 按照专利 CN200810112232.0 中详细描述的方法制备二氧化硅中空球颗粒， 为中空内径 lOOmn- 300nm含量为 18vol%, 300nm-500nm含量为 64vol%, 500-720nm含量为 18vol%的混合物， 外壁厚度为 55nm。 按照比倒依次把预处理的木粉、 25份 PE 塑料粉料、 3 份二氧化硅中空球颗粒加入高速混合机中， 温度控制在 50°C， 高 速混合 50 nu 混料置于 270。C的双螺杆挤出机中混合挤出， 冷却造粒后， 经热 压机于 220Ό模压成型， 然后再冷压 5 miii制备出热压型木塑复合材料制品。
所得复合材料的拉伸强度为 43.7MPa， 冲击强度为 9.4kJ/m2 , 硬度为 71.4， 导热系数 (室温) 为 0.1395W/K.m， 低频 200- 20001 IZ的平均隔音量为 27.9dB , 中频 2500-4000HZ的平均隔音量为 35,5dB , 高频 5000 6300HZ的平均隔音量为 39.2dB o
实施例 9
首先对用磨粉机将稻壳粉粉碎过筛， 粒径为 150 目， 然后将木粉放入 50Ό 鼓风烘箱中干燥 6h (含水量 <3%)， 然后冷却至 40Ό。 将 0,2份 A- 172 ffi丙酮稀 释至 5%(V/V)， 稀释后的混合液喷洒处理 82份木粉， 转速为 2000rpm， 然后加 入高速混合机中进行预混合 0.5 h， 温度为 lOCTC ; 按照专利 CN200810112232X) 中详细描述的方法制备二氧化硅中空球颗粒， 为中空内径 l OOnm- 300nm含量为 35vol%, 300nm-500nm含量为 56vol%, 500 720nm含量为 9vol%的混合物， 外 壁厚度为 72nm„ 按照比例依次把预处理的木粉、 12份: PVC塑料粉料、 10份二 氧化硅中空球颗粒加入高速混合机中， 温度控制在 ΙΟθτ：， 高速混合 10 mm, 混 料置于 125Ό的双螺杼挤出机中混合挤出， 冷却造粒后， 经热压机于 150Ό模压 成型， 然后再冷压 50 mm制备出热压型木塑复合材料制品。
所得复合材料的拉伸强度为 39.8MPa， 冲击强度为 8.1kJ/m2, 硬度为 75.1 , 导热系数 (室温) 为 0 1417W./【m, 低频 200 2000HZ的平均隔音量为 27 d.B， 中频 2500 4000HZ的平均隔音量为 31.3dB， 高频 5000-6300HZ的平均隔音量为 38.4dB。
应该注意到并理解， 在不脱离后^的权利要求所要求的本发明的精神和范 围的情况下， 能够对上述详细描述的本发明做出各种修改和改进。 因此， 要求 保护的技术方案的范围不受所给出的任何特定示范教导的限制。
申请人声明， 本发明通过上述实施例来说明本发明的详细工艺设备和工艺 流程， 但本发明并不局限于上述详细工艺设备和工艺流程， 即不意味着本发明 必须依赖上述详细工艺设备和工艺流程才能实施。 所属技术领域的技术人员应 该明了， 对本发明的任何改进， 对本发明产品各原料的等效替换及辅助成分的 添加、 具体方式的选择等， 均落在本发明的保护范 和公开范围之内。

Claims

1、 一种木塑复合材料， 按照重量份数包括如下原料组分： 木粉 60-90、 塑 料 10-40、 中空二氧化硅 1-15和改性剂 0.1 -10 o
2、 如权利要求 1所述的木塑复合材料， 其特征在于， 所述木粉为树木粉、 锯末粉、 木材废料粉、 果壳粉或农作物粉中的 1种或至少 2种的组合；
优选地， 所述木粉的重量份数为 65-87 , 特别优选为 70-85 ;
优选地， 所述塑料的重量份数为 12 35， 特别优选为 15-30;
优选地， 所述中空二氧化硅的重量份数为 3 10 , 特别优选为 5-8;
优选地， 所述改性剂的重量份数为 0.2-3， 特别优选为 0.3- 0.6。
3、 如权利要求 1或 2所述的木塑复合材料， 其特征在于， 所述木塑复合材 料按照重量份数包括如下原料组分：木粉 65-87、塑料】2 35、中空二氧化硅 3-】0 和改性剂 0.2-3 ;
优选地， 所述木塑复合材料按照重量份数包括如下原料组分： 木粉 70-85、 塑料 15-30、 中空二氧化硅 5-8和改性剂 0.3-0.6。
4、 如权利要求 1~3任一项所述的木塑复合材料， 其特征在于， 所述塑料为 聚乙烯、 聚丙烯、 聚苯乙烯、 聚对苯二甲酸乙二醇酯或丙烯腈-苯乙烯-丁二烯共 聚物中的 1种或至少 2种的组合；
优选地， 所述中空二氧化硅为中空二氧化硅颗粒， 进一步优选为二氧化硅 中空球颗粒， 特别优选为无团聚、 草分散、 亚微米二氧化硅中空球颗粒；
优选地， 所述中空二氧化硅的中空内径为 100- 720nm , 外壁厚度为 50- lOOnm ;
优选地， 所述中空二氧化硅的中空内径为 100 500nrn， 特别优选为 150- 300誦；
优选地， 所述中空二氧化硅颗粒的外壁厚度为 50-75nrn。
5、 如权利要求 1-4任一项所述的木塑复合材料， 其特征在于， 所述中空二 氧化硅中， 粒径为 】00nm- 300ηηι 的中空二氧化硅含量为 】540vol%， 粒径为 300nm-500mn的中空二氧化硅含量为 50- 70voi%， 粒径为 500- 720nm的中空二 氧化硅含量为 5 30vol%; 进一步优选， 粒径为 lOOnm- 300nm的中空二氧化硅含 量为 20- 35voi%， 粒径为 300nm- 500nm的中空二氧化硅含量为 55 65vol%， 粒径 为 500- 720nm 的中空二氧化硅含量为 15 25vOi% ; 特别优选， 粒径为 100nm-300mn的中空二氧化硅含量为 20- 30voi%， 粒径为 300nm- 500nm的中空 二氧化硅含量为 60-65νο1% , 粒径为 500~720ηπι 的中空二氧化硅含量为 20~25vol%:
优选地， 所述改性剂为 Ζ- 6518、 KR-TTS或 KBM 1003中的 1种或至少 2 种的组合。
6、 一种如权利要求 1~5任一项所述木塑复合材料的制备方法， 包括以下步 骤：
( 1 ) 将木粉和改性剂溶液混合， 得到预处理后的木粉；
(2) 将步骤 （1 ) 得到的预处理后的木粉、 塑料粉料和中空二氧化硅混合， 得到混料；
( 3 ) 将步骤 ( 2 ) 得到的混料挤出、 造粒， 并成型， 得到木塑复合材料制 口
7、 如权利要求 6所述的方法， 其特征在于， 步骤 （1 ) 所述木粉的粒径为 10-150目， 进一步优选为 15-120目， 特别优选为 20〜100目；
优选地， 步骤 （1 ) 所述木粉含水量<3 1%；
优选地， 在与改性剂溶液混合前对木粉进行千燥； 优选地， 所述千燥温度 为 50〜130 "C， 进一步优选为 70〜120'Ό , 特别优选为 80'、·'110'Ό ; 优选地， 所述干 燥时间为至少 0.51ι, 进一步优选为 0.8〜6h， 特别优选为 l〜4h; 优选地， 所述干 燥在烘箱中进行；
优选地， 所述改性剂溶液中改性剂的体积分数为 55(0%， 进一步优选为 8-45%, 特别优选为 1040%;
优选地， 所述改性剂溶液的溶剂为乙醇和 /或丙酮。
8、 如权利要求 6或 7所述的方法， 其特征在于， 步骤 （1) 所述混合包括： 在 3002000rpm 的转速下 ffi改性剂溶液喷洒处理木粉， 然后在高速混合机中进 行预混合； 优选地， 所述转速为 400- 1800rpm, 特别优选为 500 1500rpm; 优选 地， 在高速混合机中进行预混合的时间为至少 0.5h， 优选为 0.55h， 特别优选为 0.5-311； 优选地， 在高速混合机中进行预混合的温度为 30~100°C， 进一步优选为 35- 90。C， 特别优选为 40- 80°C;
优选地， 步骤 （2) 所述混合在高速混合机中进行；
优选地， 步骤 （2) 所述混合温度为 50 100Ό, 进一步优选为 6090Ό， 特 别优选为 7080Ό;
优选地， 步骤 (2) 所述混合时间为至少 lOim 进一步优选为 1250mm， 特别优选为 15- 20mm。
9、 如权利要求 6- 8任一项所述的方法， 其特征在于， 步骤（3)所述挤出釆 用双螺秄挤出机；
优选地， 步骤 （3) 所述挤出温度为 125- 270Ό, 进一步优选为 135260τ：， 特别优选为 145-250Ό;
优选地， 步骤 （3)所述成型包括依次热压和冷压； 优选地， 所述热压温度 150-220 °C, 进一步优选为 160- 200Ό, 特别优选为 170-190 ; 优选地， 所述 冷压时间为至少 5mm， 进一步优选为 8- 50min， 特别优选为 1025rnm。
10、 如权利要求 6~10任一项所述的方法， 其特征在于， 所述方法包括以下 步骤：
( 1 )将体积分数为 5- 50%的改性剂溶液喷洒处理木粉，转速为 300~2000ipm， 然后力 Π入高速混合机中进行预混合至少 0.5h， 温度 30 100Ό ;
(2 ) 按照比例依次把步骤 （1 ) 得到的木粉、 塑料粉料和中空二氧化硅加 入高速混合机中， 温度控制在 50 100°C， 高速混合至少 lOnim;
(3 ) 混料置于 125- 270Ό的双螺杆挤出机中混合挤出， 冷却造粒后， 经热 压机于 150 220Ό模压成型， 然后再冷压至少 5min制备出热压型木塑复合材料 rvh
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CN108947573A (zh) * 2018-07-26 2018-12-07 苏州华龙化工有限公司 一种吸声玻璃棉纤维复合材料的制备方法
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