CN107325397B - Mildew-proof and algae-resistant functional wood-plastic composite material and preparation method thereof - Google Patents
Mildew-proof and algae-resistant functional wood-plastic composite material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a mildew-proof and algae-resistant functional wood-plastic composite material which comprises the following raw materials: the material comprises, by mass, 100 parts of a thermoplastic plastic matrix, 40-140 parts of modified wood fiber powder, 0.2-6 parts of a mildew-proof active substance, 0.5-6 parts of an anti-algae active substance, 6-30 parts of activated calcium carbonate, 2-5 parts of a lubricant, 1-6 parts of a coupling agent and 2-15 parts of other processing aids; the modified wood fiber powder is wood fiber powder modified by ultraviolet irradiation. According to the invention, through ultraviolet irradiation modification of wood fibers and addition of the mildew-proof active substance and the anti-algae active substance, the mildew resistance and algae resistance of the wood-plastic composite material are effectively improved, so that the wood-plastic composite material has broad-spectrum and efficient mildew resistance and anti-algae performance.
Description
Technical Field
The invention belongs to the field of preparation of wood-plastic composite materials, and particularly relates to a mildew-proof and algae-resistant functional wood-plastic composite material and a preparation method thereof.
Background
With the increasing prominence of the problems of population growth, energy crisis, soaring petroleum price, global warming, environmental pollution and the like, concepts such as sustainable development, circular economy, ecological benefits, green environmental protection and the like are receiving more and more attention and attention of people. Under the background, a novel environment-friendly material, namely a wood-plastic composite material, is produced and draws wide attention of people. The wood-plastic composite material takes natural wood fiber and thermoplastic resin as main components, wherein the wood fiber can be woody plants, herbaceous plants, crops and wastes thereof, and the thermoplastic resin mainly comprises polyethylene, polypropylene, polyvinyl chloride and the like, can be new materials, and can also adopt reclaimed materials or leftover materials. Due to the characteristic of the wood-plastic composite material, the wood-plastic composite material has important significance in the aspects of environmental protection, white pollution reduction, forest resource shortage relief and the like. In addition, the wood-plastic composite material has the advantages of both wood and plastic, has the characteristics of low price, repeated recycling, biodegradability, rich raw material sources and the like, and is widely applied to the fields of outdoor buildings, garden landscapes, automobile industry, packaging transportation, storage and the like at present.
In the early development and application of the wood-plastic composite material, because the content of wood fiber is low and the variety is single, the wood fiber is effectively wrapped by a plastic matrix, and most people think that the material has enough fungal and algae resistance. However, with the increase of the fiber content in the wood-plastic composite material, the rapid development of the industry and the continuous expansion of the application field, people find that the wood-plastic product does not meet the requirements of long expected life and no need of maintenance, and in fact, the wood-plastic floor board with high wood filling amount is corroded and damaged by biological factors such as mildew-rot fungi, algae, termites and the like as the natural wood.
The mold harm can cause macroscopic mold spots on the surface of the material, and in severe cases, the material is integrally moldy, so that the appearance aesthetic feeling is influenced, and the water absorption performance of the material is increased; the increase in water absorption further exacerbates the degree of mildew in the material, ultimately resulting in a cyclic mildew-water absorption-mildew process. The harm of algae can cause the surface of the material to breed a large amount of algae cells, so that the surface of the material is discolored, and the appearance and aesthetic feeling of the wood-plastic material and the product are also affected.
Therefore, the problems of mold hazard and algae hazard in wood-plastic materials are urgently to be solved.
Disclosure of Invention
The invention aims to provide a mildew-proof and algae-resistant functional wood-plastic composite material aiming at the problems of algae harm and mold harm in the application process of the existing functional wood-plastic composite material and product.
The invention aims to provide a mildew-proof and algae-resistant functional wood-plastic composite material which comprises the following raw materials: the material comprises, by mass, 100 parts of a thermoplastic plastic matrix, 40-140 parts of modified wood fiber powder, 0.2-6 parts of a mildew-proof active substance, 0.5-6 parts of an anti-algae active substance, 6-30 parts of activated calcium carbonate, 2-5 parts of a lubricant, 1-6 parts of a coupling agent and 2-15 parts of other processing aids; the modified wood fiber powder is wood fiber powder modified by ultraviolet irradiation.
According to the invention, after ultraviolet irradiation pretreatment is carried out on wood fibers, mildew-proof active substances and anti-algae active substances are added into the wood fibers, so that the mildew and algae resistance of the wood-plastic composite material is improved, and thus the mildew-proof and anti-algae functional wood-plastic composite material is obtained.
According to the invention, the mildew inhibitor and the algaecide are added, so that the mould and algae resistance of the wood-plastic composite material can be effectively improved, the wood-plastic composite material is endowed with good mould and algae resistance, and various losses caused by the harm of the mould and the algae are reduced or avoided. In addition, the improvement of the mildew resistance and the algae resistance of the wood-plastic composite material is beneficial to expanding the application range of the wood-plastic composite material, can also improve the overall performance of the wood-plastic composite material, and is beneficial to reducing the later maintenance cost and prolonging the service life of the wood-plastic composite material.
The modified wood fiber powder is prepared by the following method: after being crushed, cleaned and dried, the wood fiber powder is placed under an ultraviolet lamp with the wavelength of 200-450nm and the power of 30-300W for irradiation treatment for 2-20h, and then the modified wood fiber powder is obtained. The specific surface area of the wood fiber can be increased by ultraviolet irradiation, and a certain active oxygen-containing functional group is introduced to the surface of the wood fiber, so that the wood fiber is stably combined with the mildew-proof active substance and the anti-algae active substance through chemical bonding reaction, and the wood-plastic composite material is endowed with more broad-spectrum and efficient mildew-proof performance and anti-algae performance.
Preferably, the mildew-proof active substance is selected from more than one of 2,4,5, 6-tetrachlorodicyanobenzene, 3-iodo-2-propynyl butylcarbamate, copper naphthenate, 8-hydroxyquinoline copper, tebuconazole, propiconazole, 2-chloro-N- (4' -chlorobenzen-2-yl) nicotinamide, N-allyl-4, 5-dimethyl-2-trimethylsilyl thiophene-3-carboxamide and didecyldimethyl ammonium chloride.
Preferably, the anti-algae active substance is selected from more than one of 3-p-cumyl-1, 1-dimethyl urea, 2-methylthio-4-ethylamino-6-tert-butylamino-1, 3, 5-triazine, ammonia-soluble quaternary ammonium copper, ethanolamine copper and N- (7-fluoro-3, 4-dihydro-3-oxo- (2-propynyl) -2H-1, 4-benzoxazine-6-yl) cyclohex-1-ene-1, 2-dicarboximide.
Preferably, the thermoplastic plastic matrix is selected from one or more of polyvinyl chloride (PVC), Polyethylene (PE), polypropylene (PP) and Polystyrene (PS). The thermoplastic matrix in the present invention may be virgin or recycled.
Preferably, the wood fiber powder is selected from more than one of wood powder, bamboo powder and crop straw powder, and the particle size is 40-160 meshes.
Preferably, the lubricant is selected from one or more of stearic acid, PE wax and paraffin wax.
Preferably, the coupling agent is selected from more than one of bisaminosilane, vinylsilane, methacryloxysilane, and maleic anhydride grafted polypropylene.
Preferably, the other processing aids are selected from one or more of light stabilizers, heat stabilizers, toners, plasticizers, impact modifiers and foaming agents.
The second purpose of the invention is to provide a preparation method of the mildew-proof and algae-resistant functional wood-plastic composite material.
The preparation method of the mildew-proof and algae-resistant functional wood-plastic composite material comprises the following steps:
(1) crushing, cleaning and drying the wood fiber powder according to the formula amount, and then placing the wood fiber powder under an ultraviolet lamp with the wavelength of 200-450nm and the power of 30-300W for irradiation treatment for 2-20h to obtain modified wood fiber powder;
(2) dispersing the mildew-proof active substance and the algae-resistant active substance according to the formula ratio by using absolute ethyl alcohol or dimethyl sulfoxide respectively, spraying the dispersed mildew-proof active substance and algae-resistant active substance onto the surface of the modified wood fiber powder in the step (1), and stirring for 5-15min at the temperature of 50-100 ℃ and the speed of 600-1000rpm for uniformly mixing;
(3) adding the modified wood fiber powder sprayed with the mildew-proof active substance and the anti-algae active substance obtained in the step (2), the thermoplastic plastic matrix, the activated calcium carbonate, the coupling agent, the lubricant and other processing aids into a high-speed mixer according to the formula amount, and mixing for 10-20min at 100-140 ℃ and 800-1200rpm to obtain a premix;
(4) and putting the premix into a double-screw extruder, extruding and granulating at 150-200 ℃ and 30-120rpm, then putting the granules into an injection molding machine, and carrying out injection molding at 170-200 ℃ to obtain the mildew-proof and algae-resistant functional wood-plastic composite material.
The invention has the beneficial effects that:
(1) through ultraviolet irradiation modification of wood fibers and addition of the mildew-proof active substances and the anti-algae active substances, the mildew resistance and the algae resistance of the wood-plastic composite material are effectively improved, so that the wood-plastic composite material has broad-spectrum and efficient mildew resistance and anti-algae performance.
(2) The ultraviolet radiation can increase the specific surface area of the wood fiber and introduce a certain active oxygen-containing functional group to the surface of the wood fiber, so that the wood fiber is stably combined with the mildew-proof active substance and the anti-algae active substance through chemical bonding reaction, the wood-plastic composite material is endowed with more broad-spectrum and efficient mildew-proof performance and anti-algae performance, the problems of material mildew and discoloration and the like caused by growth and propagation of the mildew and algae are reduced, the improvement of the comprehensive performance and the expansion of the application field of the wood-plastic composite material are facilitated, and the reduction of the later maintenance cost of the material and the extension of the service life are facilitated.
Detailed Description
The present invention is described in detail by the following examples, which should be construed as merely illustrative and not limitative of the remainder of the disclosure in any way whatsoever, and which would enable those skilled in the art to make various changes and modifications within the spirit and scope of the invention.
Unless otherwise specified, the experimental materials and reagents in the invention are all conventional commercial products in the technical field.
Example 1
100 parts of pine wood powder with the grain size of 100 meshes are taken, crushed, cleaned and dried, and then the modified pine wood powder is obtained after the irradiation treatment for 16 hours under an ultraviolet lamp with the wavelength of 254nm and the power of 80W.
1 part of 2,4,5, 6-tetrachlorodicyanobenzene and 0.5 part of 3-p-cumyl-1, 1-dimethylurea are respectively and uniformly dispersed by absolute ethyl alcohol, sprayed on the surface of modified pine wood powder, and stirred and uniformly mixed in a high-speed mixer at 90 ℃ and 600rpm for 8 min.
Sequentially adding the pine wood powder, 100 parts of PP matrix, 15 parts of activated calcium carbonate, 2 parts of stearic acid, 2 parts of bisaminosilane, 4 parts of light stabilizer and 2 parts of toner into a high-speed mixer, and mixing at 120 ℃ and 800rpm for 15min to obtain the premix.
Adding the premix into a double-screw extruder, extruding and granulating at the temperature of 170 ℃, 175 ℃, 180 ℃, 185 ℃ and 190 ℃ in each zone of the extruder and the screw rotating speed of 120 rpm; and then injection molding is carried out at 190 ℃ to obtain the mildew-proof and algae-resistant functional wood-plastic composite material.
Example 2
100 parts of bamboo powder with the particle size of 80 meshes is taken, crushed, cleaned and dried, and then the bamboo powder is placed under an ultraviolet lamp with the wavelength of 365nm and the power of 250W for irradiation treatment for 10 hours to obtain the modified bamboo powder.
Taking 1.5 parts of copper naphthenate and 1 part of 3-p-cumyl-1, 1-dimethyl urea, respectively dispersing uniformly by absolute ethyl alcohol, spraying the mixture on the surface of the modified bamboo powder, and stirring and uniformly mixing in a high-speed mixer at 60 ℃ and 1000rpm for 8 min.
And sequentially adding the obtained bamboo powder, 100 parts of PE matrix, 20 parts of active calcium carbonate, 5 parts of PE wax, 5 parts of vinyl silane, 3 parts of light stabilizer and 3 parts of toner into a high-speed mixer, and mixing at 110 ℃ and 900rpm for 15min to obtain the premix.
Adding the premix into a double-screw extruder, extruding and granulating at the temperature of 165 ℃, 170 ℃, 175 ℃, 180 ℃, 185 ℃ and the screw rotation speed of 100rpm in each zone of the extruder; and then injection molding is carried out at 185 ℃ to obtain the mildew-proof and algae-resistant functional wood-plastic composite material.
Example 3
Taking 120 parts of poplar wood powder with the particle size of 120 meshes, crushing, cleaning and drying the poplar wood powder, and placing the poplar wood powder under an ultraviolet lamp with the wavelength of 225nm and the power of 200W for irradiation treatment for 8 hours to obtain the modified poplar wood powder.
2 parts of 3-iodine-2-propynyl butyl carbamate and 1.5 parts of 2-methylthio-4-ethylamino-6-tert-butylamino-1, 3, 5-triazine are respectively dispersed uniformly by absolute ethyl alcohol, sprayed on the surface of modified poplar powder, stirred in a high-speed mixer at 100 ℃ and 800rpm for 8min and uniformly mixed.
Sequentially adding the obtained poplar powder, 100 parts of HDPE matrix, 10 parts of active calcium carbonate, 5 parts of PE wax, 4 parts of maleic anhydride grafted polyethylene, 2 parts of light stabilizer and 2 parts of toner into a high-speed mixer, and mixing at 100 ℃ and 800rpm for 12min to obtain the premix.
Adding the premix into a double-screw extruder, extruding and granulating at the temperature of 155 ℃, 165 ℃, 170 ℃, 175 ℃, 180 ℃ and the screw rotation speed of 60rpm in each zone of the extruder; and then injection molding is carried out at 180 ℃ to obtain the mildew-proof and algae-resistant functional wood-plastic composite material.
Example 4
60 parts of bagasse fiber with the particle size of 100 meshes is taken, crushed, cleaned and dried, and then the bagasse fiber is placed under an ultraviolet lamp with the wavelength of 370nm and the power of 30W for irradiation treatment for 20 hours, so that the modified bagasse is obtained.
Respectively dispersing 1 part of 8-hydroxyquinoline copper, 1 part of tebuconazole and 1 part of 2-methylthio-4-ethylamino-6-tert-butylamino-1, 3, 5-triazine with absolute ethyl alcohol uniformly, spraying the mixture onto the surface of the modified bagasse, and stirring and uniformly mixing the mixture in a high-speed mixer with the temperature of 50 ℃ and the rpm of 800 for 15 min.
And sequentially adding the obtained bagasse fiber, 100 parts of PVC matrix, 15 parts of active calcium carbonate, 3 parts of paraffin, 6 parts of methacryloxy silane, 3 parts of light stabilizer, 3 parts of toner, 5 parts of heat stabilizer and 4 parts of impact modifier into a high-speed mixer, and mixing at a high speed of 120 ℃ and 950rpm for 18min to obtain the premix.
Adding the premix into a double-screw extruder, extruding and granulating at the temperatures of 150 ℃, 165 ℃, 170 ℃, 160 ℃, 155 ℃ and the screw rotation speed of 30rpm in each zone of the extruder; and then injection molding is carried out at 170 ℃ to obtain the mildew-proof and algae-resistant functional wood-plastic composite material.
Example 5
Taking 140 parts of cypress powder with the grain size of 120 meshes, crushing, cleaning and drying the cypress powder, and placing the crushed cypress powder under an ultraviolet lamp with the wavelength of 450nm and the power of 200W for irradiation treatment for 2 hours to obtain the modified cypress powder.
Taking 1 part of propiconazole, 1 part of tebuconazole and 1.5 parts of ammonia-soluble quaternary ammonium copper, respectively uniformly dispersing by using dimethyl sulfoxide, spraying the mixture on the surface of modified cypress powder, and uniformly mixing in a high-speed mixer at 70 ℃ and 850rpm for 8 min.
Sequentially adding the obtained cypress powder, 100 parts of PS matrix, 30 parts of active calcium carbonate, 2 parts of PE wax, 2 parts of paraffin, 6 parts of maleic anhydride grafted polypropylene, 4 parts of light stabilizer, 2 parts of toner, 4 parts of heat stabilizer, 3 parts of impact modifier and 2 parts of foaming agent into a high-speed mixer, and mixing at 120 ℃ and 1000rpm for 20min to obtain the premix.
Adding the premix into a double-screw extruder, extruding and granulating at the temperatures of 155 ℃, 165 ℃, 160 ℃, 155 ℃ and 165 ℃ in all zones of the extruder at the screw rotating speed of 40 rpm; and then injection molding is carried out at 180 ℃ to obtain the mildew-proof and algae-resistant functional wood-plastic composite material.
Example 6
Taking 140 parts of rice bran fiber powder with the particle size of 40 meshes, crushing, cleaning and drying the rice bran fiber powder, and placing the rice bran fiber powder under an ultraviolet lamp with the wavelength of 200nm and the power of 40W for irradiation treatment for 12 hours to obtain the modified rice bran powder.
Taking 6 parts of 2-chloro-N- (4' -chlorodiphenyl-2-yl) nicotinamide and 6 parts of ethanolamine copper, respectively uniformly dispersing by using dimethyl sulfoxide, spraying the mixture on the surface of the modified rice bran powder, and stirring and uniformly mixing in a high-speed mixer at 100 ℃ and 600rpm for 5 min.
Sequentially adding the obtained rice chaff fiber powder, 100 parts of PP matrix, 30 parts of active calcium carbonate, 2 parts of PE wax, 2 parts of paraffin, 6 parts of vinyl silane, 3 parts of light stabilizer, 2 parts of toner and 4 parts of heat stabilizer into a high-speed mixer, and mixing at high speed of 120 ℃ and 1100rpm for 16min to obtain the premix.
Adding the premix into a double-screw extruder, wherein the temperature of each zone of the extruder is 170 ℃, 180 ℃, 190 ℃, 200 ℃, 195 ℃, and the screw rotation speed is 100rpm, and performing extrusion granulation; and then injection molding is carried out at 200 ℃ to obtain the mildew-proof and algae-resistant functional wood-plastic composite material.
Example 7
Taking 40 parts of pine wood powder with the particle size of 80 meshes, crushing, cleaning and drying the pine wood powder, and placing the pine wood powder under an ultraviolet lamp with the wavelength of 365nm and the power of 300W for irradiation treatment for 16h to obtain the modified pine wood powder.
Taking 0.2 part of N-allyl-4, 5-dimethyl-2-trimethylsilyl thiophene-3-formamide and 0.8 part of N- (7-fluoro-3, 4-dihydro-3-oxygen- (2-propynyl) -2H-1, 4-benzoxazine-6-yl) cyclohex-1-ene-1, 2-dicarboximide, dispersing the materials uniformly by absolute ethyl alcohol, spraying the materials onto modified pine powder, and stirring the materials in a high-speed mixer at 80 ℃ and 900rpm for 10min to uniformly mix.
Sequentially adding the pine wood powder, 100 parts of HDPE matrix, 15 parts of active calcium carbonate, 5 parts of PE wax, 2 parts of bisaminosilane, 3 parts of light stabilizer and 3 parts of toner into a high-speed mixer, and mixing at 120 ℃ and 1200rpm for 12min to obtain the premix.
Adding the premix into a double-screw extruder, extruding and granulating at the temperature of 165 ℃, 170 ℃, 175 ℃, 180 ℃, 185 ℃ and the screw rotation speed of 80rpm in each zone of the extruder; and then injection molding is carried out at 185 ℃ to obtain the mildew-proof and algae-resistant functional wood-plastic composite material.
Example 8
Taking 80 parts of flax fiber powder with the particle size of 160 meshes, crushing, cleaning and drying the flax fiber powder, and placing the flax fiber powder under an ultraviolet lamp with the wavelength of 254nm and the power of 120W for irradiation treatment for 8 hours to obtain the modified flax powder.
Taking 1 part of didecyl dimethyl ammonium chloride and 1 part of 3-p-cumyl-1, 1-dimethyl urea, respectively dispersing uniformly by absolute ethyl alcohol, spraying the mixture on modified flax powder, and stirring and uniformly mixing the mixture in a high-speed mixer at 50 ℃ and 1000rpm for 12 min.
Sequentially adding the obtained flax fiber powder, 100 parts of PP matrix, 6 parts of active calcium carbonate, 3 parts of stearic acid, 2 parts of PE wax, 6 parts of methacryloxy silane, 1 part of light stabilizer and 1 part of toner into a high-speed mixer, and mixing at 140 ℃ and 900rpm for 10min to obtain the premix.
Adding the premix into a double-screw extruder, wherein the temperature of each zone of the extruder is 175 ℃, 185 ℃, 190 ℃, 195 ℃, 185 ℃, and the screw rotation speed is 100rpm, and performing extrusion granulation; and then injection molding is carried out at 190 ℃ to obtain the mildew-proof and algae-resistant functional wood-plastic composite material.
Example 9
Taking 60 parts of cotton straw fiber powder with the particle size of 80 meshes, crushing, cleaning and drying the cotton straw fiber powder, and placing the cotton straw fiber powder under an ultraviolet lamp with the wavelength of 312nm and the power of 40W for irradiation treatment for 15 hours to obtain the modified cotton straw powder.
Taking 0.2 part of 2,4,5, 6-tetrachlorodicyanobenzene, 0.5 part of 8-hydroxyquinoline copper and 1 part of ammonia soluble quaternary ammonium copper, respectively dispersing the components uniformly by absolute ethyl alcohol, spraying the components on modified cotton straw powder, stirring the mixture in a high-speed mixer at 80 ℃ and 1000rpm for 10min, and uniformly mixing the components.
Sequentially adding the obtained cotton straw fiber powder, 100 parts of PVC matrix, 20 parts of active calcium carbonate, 5 parts of PE wax, 3 parts of bisaminosilane, 2 parts of light stabilizer, 2 parts of toner, 4 parts of heat stabilizer and 4 parts of impact modifier into a high-speed mixer, and mixing at 140 ℃ and 900rpm for 12min at high speed to obtain the premix.
Adding the premix into a double-screw extruder, extruding and granulating at the temperatures of 155 ℃, 165 ℃, 160 ℃, 155 ℃ and 165 ℃ in all zones of the extruder at the screw rotating speed of 40 rpm; and then injection molding is carried out at 175 ℃ to obtain the mildew-proof and algae-resistant functional wood-plastic composite material.
The invention takes the functional wood-plastic composite material which is prepared without ultraviolet irradiation or treatment of mildew-proof active substances and anti-algae active substances as a comparative example.
Comparative example 1
Pine wood powder which is not treated by ultraviolet irradiation and mildew-proof active substances and anti-algae active substances is used as filling wood fiber, and other formula components and processing and forming methods are the same as those of the example 1, so that the comparative example 1 is prepared.
Comparative example 2
Pine wood powder which is not treated by ultraviolet irradiation is used as filling wood fiber, and other formula components and processing and forming methods are the same as those of the example 1, so that the comparative example 2 is prepared.
Comparative example 3
The comparative example 3 was prepared by using bamboo powder without being treated with ultraviolet irradiation and anti-mold active substance and anti-algae active substance as the filling wood fiber, and the other formulation components and the processing and forming method were the same as those of example 2.
Comparative example 4
The comparative example 4 was prepared by using bamboo powder without ultraviolet irradiation treatment as the filler wood fiber, and the other formulation components and the processing method were the same as those of example 2.
The mildew resistance test method used in the invention is as follows:
the mould used in the mildew resistance test of the invention is as follows: aspergillus niger (Aspergillus niger), Trichoderma viride (Trichoderma viride), Penicillium funiculosum (Penicillium funiculosum), Aureobasidium pullulans (Aureobasidium pullulans), Gliocladium virens (Gliocladium virens) and Chaetomium globosum (Chaetomium globosum).
The mildew resistance testing method comprises the following steps: respectively inoculating Aspergillus niger, Trichoderma viride, Penicillium funiculosum, Aureobasidium pullulans, Gliocladium virens and Chaetomium globosum, culturing on potato glucose agar culture medium for 7-10 days,washing the mold spores with sterile water, shaking thoroughly, filtering to obtain spore stock solution, and adjusting the concentration of the spore stock solution to 1 × 106-1×107And (5) after cfu/mL, uniformly mixing the mold spore solutions in the same volume to obtain a mixed mold spore solution. Uniformly spraying the mixed mould spore liquid on the surface of the sterilized wood-plastic sample by using a chromatography sprayer, then culturing the wood-plastic sample in an incubator at the temperature of 28 ℃ and the relative humidity of more than or equal to 85% for 28 days, and observing and recording the mildew condition of the sample. The mildew resistance of the sample is judged by referring to the table 1, and the lower the damage value is, the better the mildew resistance of the material is; the higher the damage value, the worse the mildew resistance of the material. The results of the tests for the mold-proof properties of the wood-plastic composites of examples 1 to 9 and comparative examples 1 to 4 are shown in table 3.
TABLE 1 evaluation index of the mildew resistance of wood-plastic composite material
The method for testing the algae resistance comprises the following steps:
the algae species used in the algae resistance test are: chlorella (Chlorella vulgaris), Dinophytrium (Ulothrix sp), Scenedesmus quadratus (Scenedesmus quadratus) and Oscillatoria (Oscilllaria sp).
The method for testing the algae resistance comprises the following steps: respectively inoculating chlorella, hyphomycete, Scenedesmus quadricaudatus and Oscillatoria into algae liquid culture medium, culturing in illumination culture box with temperature of 25 + -2 deg.C, 1000-3000 lx and RH greater than or equal to 80% for 10-14d, and adjusting the concentration of algae liquid to 1 × 106-9×106And after cfu/mL, uniformly mixing the four algae strains in equal volume to obtain a mixed algae strain. Melting the solid culture medium of algae, cooling to 45-50 deg.C, pouring into a sterile culture dish, and cooling to solidify at room temperature. And lightly putting the sterilized wood-plastic test sample and the standard blank sample into the solidified algae solid culture medium, then uniformly spraying the mixed algae liquid onto the surface of the sample by using a chromatographic sprayer, wherein the inoculation liquid needs to be uniformly distributed on the whole surface of the sample. And (3) placing the inoculated sample into a constant-temperature constant-humidity illumination incubator with the temperature of 25 +/-2 ℃, the RH of 1000-3000 lx and the light intensity of more than or equal to 80 percent and the illumination time of 14 hours per day for culturing for 21 d. Checking at 7dWhen the algae growth (green culture) was observed clearly on the surface of the medium in the dish, otherwise the test was not effective. During the test, the sample surface was kept wet and the growth of algae in the sample and the petri dish was recorded. After the test, the growth of algae on the surface of the sample was observed, and the algae resistance of the sample was evaluated with reference to table 2. The results of the anti-algae performance test of the wood plastic composite materials of examples 1 to 9 and comparative examples 1 to 4 are shown in table 3.
TABLE 2 evaluation table of algal growth grade on sample surface
The results of the tests for the mildewproof property and the algae resistance of examples 1 to 9 and comparative examples 1 to 4 of the present invention are shown in Table 3.
Table 3 results of tests on mildew resistance and algae resistance of wood-plastic composite materials of examples 1-9 and comparative examples 1-4
As can be seen from table 3, the wood-plastic composite material prepared by using the wood fiber powder treated by ultraviolet irradiation as the filled wood fiber and adding the mildew-proof active substance and the anti-algae active substance has significantly better mildew-proof property and anti-algae property than the wood-plastic composite material prepared by using the wood fiber powder not subjected to ultraviolet irradiation as the filled wood fiber.
Claims (6)
1. The mildew-proof and algae-resistant functional wood-plastic composite material is characterized by comprising the following raw materials: the material comprises, by mass, 100 parts of a thermoplastic plastic matrix, 40-140 parts of modified wood fiber powder, 0.2-6 parts of a mildew-proof active substance, 0.5-6 parts of an anti-algae active substance, 6-30 parts of activated calcium carbonate, 2-5 parts of a lubricant, 1-6 parts of a coupling agent and 2-15 parts of other processing aids;
the modified wood fiber powder is wood fiber powder subjected to ultraviolet irradiation modification treatment; the wood fiber powder is selected from more than one of wood powder, bamboo powder and crop straw powder, and the particle size is 40-160 meshes; the modified wood fiber powder is prepared by the following method: after being crushed, cleaned and dried, the wood fiber powder is placed under an ultraviolet lamp with the wavelength of 200-450nm and the power of 30-300W for irradiation treatment for 2-20h to obtain modified wood fiber powder; the mildew-proof active substance is selected from more than one of 2,4,5, 6-tetrachlorodicyanobenzene, 3-iodine-2-propynyl butyl carbamate, copper naphthenate, 8-hydroxyquinoline copper, tebuconazole, propiconazole, 2-chlorine-N- (4' -chlorine diphenyl-2-yl) nicotinamide, N-allyl-4, 5-dimethyl-2-trimethylsilyl thiophene-3-formamide and didecyl dimethyl ammonium chloride; the anti-algae active substance is selected from more than one of 3-p-cumyl-1, 1-dimethyl urea, 2-methylthio-4-ethylamino-6-tert-butylamino-1, 3, 5-triazine, ammonia-soluble quaternary ammonium copper, ethanolamine copper and N- (7-fluoro-3, 4-dihydro-3-oxo- (2-propynyl) -2H-1, 4-benzoxazine-6-yl) cyclohex-1-ene-1, 2-dicarboximide.
2. The mold and algae resistant functional wood-plastic composite material according to claim 1, wherein the thermoplastic matrix is selected from one or more of polyvinyl chloride, polyethylene, polypropylene and polystyrene.
3. The mold and algae resistant functional wood-plastic composite according to claim 1, wherein the lubricant is one or more selected from stearic acid, PE wax and paraffin wax.
4. The mold and algae resistant functional wood-plastic composite material according to claim 1, wherein the coupling agent is selected from one or more of bisaminosilane, vinylsilane, methacryloxysilane, and maleic anhydride grafted polypropylene.
5. The mold and algae resistant functional wood-plastic composite material according to claim 1, wherein the other processing aids are one or more selected from light stabilizer, heat stabilizer, toner, plasticizer, impact modifier and foaming agent.
6. The preparation method of the mildew-proof and algae-resistant functional wood-plastic composite material as claimed in claim 1, which is characterized by comprising the following steps:
(1) crushing, cleaning and drying the wood fiber powder according to the formula amount, and then placing the wood fiber powder under an ultraviolet lamp with the wavelength of 200-450nm and the power of 30-300W for irradiation treatment for 2-20h to obtain modified wood fiber powder;
(2) dispersing the mildew-proof active substance and the algae-resistant active substance according to the formula ratio by using absolute ethyl alcohol or dimethyl sulfoxide respectively, spraying the dispersed mildew-proof active substance and algae-resistant active substance onto the surface of the modified wood fiber powder in the step (1), and stirring for 5-15min at the temperature of 50-100 ℃ and the speed of 600-1000rpm for uniformly mixing;
(3) adding the modified wood fiber powder sprayed with the mildew-proof active substance and the anti-algae active substance obtained in the step (2), the thermoplastic plastic matrix, the activated calcium carbonate, the coupling agent, the lubricant and other processing aids into a high-speed mixer according to the formula amount, and mixing for 10-20min at 100-140 ℃ and 800-1200rpm to obtain a premix;
(4) and putting the premix into a double-screw extruder, extruding and granulating at 150-200 ℃ and 30-120rpm, then putting the granules into an injection molding machine, and carrying out injection molding at 170-200 ℃ to obtain the mildew-proof and algae-resistant functional wood-plastic composite material.
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