CN110283472B - Anti-aging impact-resistant modified wood-plastic composite material and preparation method thereof - Google Patents
Anti-aging impact-resistant modified wood-plastic composite material and preparation method thereof Download PDFInfo
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Abstract
The invention provides an anti-aging impact-resistant modified wood-plastic composite material and a preparation method thereof, wherein the wood-plastic composite material comprises the following raw materials in parts by weight: 20-50 parts of polyolefin, 30-70 parts of enzymatic hydrolysis lignin modified plant fiber, 1-3.5 parts of polymerized rosin, 0.1-10 parts of inorganic filler, 0.1-4 parts of antioxidant and 0.1-3 parts of uvioresistant agent, wherein the enzymatic hydrolysis lignin modified plant fiber is obtained by reacting the enzymatic hydrolysis lignin and the plant fiber through acid anhydride. The modified wood-plastic composite material prepared by the invention has high affinity between plant fibers and plastics, high dimensional stability, balanced rigidity and toughness and improved aging resistance; in the process of preparing the enzymatic hydrolysis lignin, a certain amount of ligninase is added, so that the impact resistance of the wood-plastic composite material prepared by modifying the plant fiber by the enzymatic hydrolysis lignin can be improved. The method for modifying the plant fiber by utilizing the lignin provided by the invention fully utilizes the lignin resource, changes waste into valuable and realizes the comprehensive utilization of the lignin resource.
Description
Technical Field
The invention belongs to the field of composite materials, and particularly relates to an anti-aging impact-resistant modified wood-plastic composite material and a preparation method thereof.
Background
Wood-Plastic Composites (WPC) are a new type of composite material which has been vigorously developed in recent years at home and abroad, and refer to a board or a profile which is produced by mixing polyethylene, polypropylene, polyvinyl chloride and the like instead of a common resin adhesive with more than 50% of waste plant fibers such as Wood flour, rice hulls, straws and the like to form a new Wood material, and then carrying out Plastic processing processes such as extrusion, die pressing, injection molding and the like. The method is mainly used in industries such as building materials, furniture, logistics packaging and the like. Wood-plastic composites have been vigorously developed, most of the prior art focuses on the types of plastic components, reinforcing and toughening fillers and weather-resistant agents, and the research on the reinforcement of modified plant fibers is rarely reported.
In the prior art, some documents exist, and lignin is added into a wood-plastic composite material. For example, patent CN201810148584.5 discloses a PVC-lignin-sulfate wood-plastic composite material and a preparation method thereof, wherein the formula of the wood-plastic composite material comprises the following components in parts by mass: 100 parts of PVC, 5-150 parts of plant fiber, 2-100 parts of lignin, 5-100 parts of sulfate, 2-15 parts of heat stabilizer, 0.1-10 parts of lubricant, 1-20 parts of impact modifier, 1-15 parts of foaming agent and 8-25 parts of foaming regulator. The patent CN201710659376.7 discloses a lignin-enhanced wood-plastic composite material and a preparation method thereof, wherein the wood-plastic composite material is prepared by one or more of plant fiber, lignin, regenerated thermoplastic plastics, mineral powder and processing aids and is processed by adopting a screw granulation extrusion process. The lignin and the plant fiber are added into the wood-plastic composite materials disclosed by the above patents to improve the mechanical property, the thermal stability or the anti-aging property of the composite materials, but the lignin and the plant fiber are poor in compatibility, and although the lignin and the plant fiber both contain hydroxyl groups, hydrogen bonds can be formed to generate certain affinity, but the lignin and the plant fiber are still weak in interface combination, so that the problems of poor impact resistance, poor dimensional stability, unbalanced rigidity and toughness and the like of the composite materials due to poor stress transmission of the formed wood-plastic furniture material interface exist. And the lignin is obtained by strong acid and strong alkali treatment, so that the active groups are fewer, and the interface bonding force is further reduced.
In addition, with the rise of outdoor activities, especially outdoor furniture, such as plastic tables, beach chairs and the like, which are easy to clean and store products are generally popular with people, but the problems of long-term sunlight irradiation influence, material aging, continuous reduction of mechanical properties, yellowing of the surfaces of white or light-colored products and the like are increasingly prominent, which directly leads to the continuous shortening of the service life of the products and seriously influences the use value of the products. In the prior art, the ageing resistance of the wood-plastic composite material is poor due to weak interface bonding force of lignin and plant fiber. Therefore, the problem of simultaneously improving the mechanical property and the aging resistance of the product needs to be solved urgently.
Disclosure of Invention
The invention aims to solve the problem that the impact resistance, the dimensional stability and the aging resistance of a wood-plastic composite material in the prior art cannot meet the actual requirements, and aims to provide an anti-aging impact-resistant modified wood-plastic composite material which has excellent comprehensive performance, can greatly improve the anti-aging performance, the impact resistance and the dimensional stability of outdoor wood-plastic furniture, ensures the balance of the rigidity and the toughness of the composite material, ensures the attractiveness of the outdoor furniture, and prolongs the service life.
In order to achieve the purpose, the invention adopts the technical scheme that:
an anti-aging impact-resistant modified wood-plastic composite material comprises the following raw materials in parts by weight: 20-50 parts of polyolefin, 30-70 parts of enzymatic hydrolysis lignin modified plant fiber, 1-3.5 parts of polymerized rosin, 0.1-10 parts of inorganic filler, 0.1-4 parts of antioxidant and 0.1-3 parts of uvioresistant agent;
the enzymatic hydrolysis lignin modified plant fiber is obtained by reacting enzymatic hydrolysis lignin and plant fiber through acid anhydride.
The enzymolysis lignin is obtained by separating and extracting the straw and other lignocellulose-rich raw materials after enzymolysis by microbial enzymes, is not subjected to alkali-acid treatment in the preparation process, has low ash content in the enzymolysis lignin, and well retains the chemical activity and molecular structure of the enzymolysis lignin.
The microbial enzyme is at least one of cellulase, hemicellulase and ligninase, and the amount of the microbial enzyme is 2-5 wt% of the straw.
According to the invention, the enzymatic hydrolysis lignin is adopted to modify the plant fiber, so that a large amount of polar groups contained in the plant fiber are consumed, the polarity of the plant fiber is reduced, the compatibility with non-polar polyolefin resin is improved, and on the other hand, the enzymatic hydrolysis lignin and the plant fiber are macromolecular substances with net structures, and are connected and wound to a certain extent through anhydride to form a composite net structure. Finally, the enzymatic hydrolysis lignin well retains active groups, effectively improves the bonding force of an interface, and is beneficial to fixing various additives and auxiliaries of the composite material, so that the strength of the composite material is improved, the aging resistance of the composite material is improved, and the problem of unattractive appearance caused by precipitation is reduced.
Specifically, the preparation method of the enzymatic hydrolysis lignin comprises the following steps:
crushing plant straws to obtain a plant straw pulp mixture, adding microbial enzyme for full enzymolysis, filtering, drying and grinding an enzymolysis product to obtain residue powder, fully dissolving the residue powder by using an organic solvent for extraction, filtering while hot to obtain a filtrate, adding water, standing to separate out an enzymolysis lignin precipitate, and filtering, washing and drying to obtain the enzymolysis lignin.
The conditions for the preparation of the enzymatic lignin by extraction are well known in the art, and in the above method, the organic solvent is not particularly limited as long as the target reagent has a certain solubility and the solvent does not adversely affect the raw material, the product, or the reaction, and examples thereof include, but are not limited to, one or more selected from dioxane, tetrahydrofuran, chloroform, dichloromethane, dimethylformamide, cyclohexanone, ethanol, isopropanol, and acetone.
The enzymolysis temperature is controlled at 20-50 deg.C, pH is controlled at 4-6, and the enzymolysis time is 2-6h, preferably 30-40 deg.C, pH is controlled at 4.5-6.3, and the enzymolysis time is 3-5 h.
In the preparation method of the enzymatic hydrolysis lignin, the mass ratio of the raw materials is 15-25:10-20:1-3 of cellulase, hemicellulase and ligninase. The inventors have unexpectedly found that when the ratio of cellulase, hemicellulase and ligninase in the formulated microbial enzyme is within the above range, the prepared enzymatic lignin-modified plant fiber has the best affinity with resin and other components, and the impact performance and dimensional stability of the composite material can be effectively improved.
Preferably, the plant fiber is not particularly limited and is preferably a hemp fiber, and examples of the hemp fiber include, but are not limited to, one or more of ramie, flax, jute, hemp, kenaf, coconut fiber, palm fiber and bamboo fiber.
The anhydride is selected from at least one of maleic anhydride, alkylene succinic anhydride, methyl tetrahydrophthalic anhydride, glutaric anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride and dodecenyl succinic anhydride.
The mass ratio of the enzymatic hydrolysis lignin to the plant fiber to the acid anhydride is 10-15:8-12: 2-4.
The preparation method of the enzymatic hydrolysis lignin modified plant fiber comprises the following steps:
(1) adding an organic solvent into 8-12 parts of plant fiber powder for fully swelling;
(2) adding 10-15 parts of enzymatic hydrolysis lignin into the system swelled in the step (1), stirring uniformly, gradually dropwise adding an organic solvent solution dissolved with 1-10 parts of catalyst and 2-4 parts of anhydride, and reacting at constant temperature for 2-6 h;
(3) and (3) filtering the mixed system in the step (2), washing with deionized water, drying, and performing vacuum drying again, wherein the water content is controlled to be 0.01-3%, so as to obtain the enzymatic hydrolysis lignin modified plant fiber powder.
The catalyst is p-dimethylaminopyridine or ammonium polyfluorobutyl sulfonate.
The organic solvent is one or more selected from dioxane, tetrahydrofuran, chloroform, dichloromethane, dimethylformamide, cyclohexanone, ethanol, isopropanol and acetone.
Preferably, the particle size of the plant fiber powder in the step (1) is 50-100 meshes, the swelling temperature is 40-90 ℃, and the swelling time is 2-6 h.
The polyolefin used in the present invention is not particularly limited, and polyolefins commonly used in wood-plastic composites are within the scope of the present invention, and examples of the polyolefin include, but are not limited to, polyethylene, polypropylene or ethylene-propylene copolymer, and the molecular weight thereof is 10 to 100 ten thousand.
The polymerized rosin is mainly dimer and has the characteristics of light color, low acid value, high viscosity, no crystallization, high softening point, good compatibility, excellent oxidation resistance, strong durability and the like, and the particle size of the polymerized rosin used in the invention is preferably 10-50 meshes.
The inorganic filler is at least one of nano silicon dioxide, nano titanium dioxide and nano calcium carbonate, the inorganic filler is modified by a coupling agent, and the coupling agent for modifying the nano silicon dioxide and the nano titanium dioxide is an amino-hydrocarbyl silane coupling agent, such as KH-550 or A-1110 or a mixture of the two; the modifier for the nano calcium carbonate is titanate coupling agent, such as tri (dioctyl phosphoryloxy) isopropyl titanate, tri (dioctyl, pyrophosphyloxy) isopropyl titanate and di (dioctyl phosphoryloxy) ethylene titanate; preferably, the inorganic filler is a compound of nano calcium carbonate and at least one of nano silicon dioxide and nano titanium dioxide, wherein the mass ratio of the nano silicon dioxide and/or the nano titanium dioxide to the nano calcium carbonate is 1: 1-3.
The anti-ultraviolet agent is a hindered amine organic compound, and includes but is not limited to at least one of 622, 770, 944, 783, 791, 3853, 292 and a light stabilizer 123; and/or the antioxidant comprises p-alkoxy phenol and hindered phenol organic matter, including but not limited to at least one of p-alkoxy phenol, antioxidant 1010, antioxidant 1098, antioxidant 264 and antioxidant 300.
As a preferred technical solution of the present invention, in addition to the above main components, the wood plastic composite of the present invention may further contain other auxiliary components, including but not limited to lubricants, compatibilizers, heat stabilizers, toughening agents; the dosage of the auxiliary agent is as follows by mass: 2-10 parts of lubricant, 1-8 parts of compatilizer, 1-10 parts of heat stabilizer and 3-6 parts of toughener; the lubricant comprises at least one of stearic acid, calcium stearate, zinc stearate or PE wax; and/or the compatibilizer is maleic anhydride graft modified polypropylene or maleic anhydride graft modified polyethylene or a combination of the maleic anhydride graft modified polypropylene and the maleic anhydride graft modified polyethylene; and/or the heat stabilizer is at least one of an organic tin heat stabilizer and a metal soap heat stabilizer; and/or the toughening agent is selected from at least one of ethylene-vinyl acetate copolymer, hydrogenated ethylene-butadiene-styrene copolymer, styrene-butadiene-styrene copolymer, hydrogenated styrene-butadiene-styrene copolymer, ethylene propylene diene monomer and polyurethane.
The invention also provides a preparation method of the anti-aging impact-resistant modified wood-plastic composite material, which comprises the following steps:
fully and uniformly mixing inorganic filler, an anti-ultraviolet agent, an antioxidant and enzymatic hydrolysis lignin modified plant fiber to obtain a mixed material 1; adding the polyethylene into a mixer to obtain a mixed material 2, and inputting the mixed material 2 into an internal mixing device for internal mixing; and carrying out cooling, granulation and drying on the material strips generated by banburying to obtain the anti-aging impact-resistant modified wood-plastic composite material.
Compared with the prior art, the invention has the advantages that:
according to the anti-aging impact-resistant modified wood-plastic composite material provided by the invention, the plant fiber is modified by adding the enzymatic hydrolysis lignin, so that the interface binding force of the plant fiber and the resin base material in the composite material is obviously improved, the formed wood-plastic furniture material has excellent comprehensive performance, and the characteristics of high affinity between the plant fiber and the plastic, good interface stress transfer, high dimensional stability, balanced rigidity and toughness and improved aging resistance are embodied. The composite material is used as furniture composite material, has beautiful surface, and is environment-friendly, durable and pollution-free.
The invention creatively utilizes the enzymatic hydrolysis lignin to modify the plant fiber, thereby effectively solving the problem of weak affinity between the plant fiber and the resin base material in the wood-plastic composite material, simultaneously, the introduced enzymatic hydrolysis lignin is a natural product and is non-toxic, and the obtained wood-plastic composite material is a green, environment-friendly and safe material, and meets the requirement of modern furniture on reducing the dosage of chemical additives. The enzymatic hydrolysis lignin modified plant fiber not only can improve and modify the fixation of inorganic matters, but also can reduce the migration of the inorganic matters and the problem of unattractive appearance caused by the migration.
Thirdly, the inventor unexpectedly discovers that the impact resistance and the dimensional stability of the wood-plastic composite material prepared by modifying the plant fiber by the enzymatic hydrolysis lignin can be improved by adding a certain amount of lignin enzyme in the process of preparing the enzymatic hydrolysis lignin.
And fourthly, the lignin is wide in source, rich in storage, low in price and easy to obtain. At present, the method for treating the straw crops rich in lignin in China mainly comprises incineration, which causes serious resource waste and environmental pollution problems. The method for modifying the plant fiber by utilizing the lignin provided by the invention fully utilizes the lignin resource, changes waste into valuable and realizes the comprehensive utilization of the lignin resource.
Detailed Description
The anti-aging impact-resistant modified wood-plastic composite material provided by the invention is further explained and illustrated by combining specific examples. The parts in the examples are by weight unless otherwise specified. The reagents are commercially available in the art unless otherwise specified.
It is particularly emphasized that the specific plant fibers and additives, such as antioxidants, uv-resistant agents, modifiers, lubricants, etc., used in the embodiments of the present invention are for exploring the effect of enzymatic lignin modification on the performance of the composite material, and therefore, the specific plant fibers and additives used in the embodiments should not be a limitation to the scope of the present invention.
The hemicellulase used in the following embodiment of the invention is produced by Hubei Kangbao Tai Fine chemical Co., Ltd, and the enzyme activity is 350-; the enzyme activity of the used ligninase is 50-150 ten thousand u/kg, the enzyme activity of the cellulase is 100-300 ten thousand u/kg, and the ligninase is produced by Ningxia and Kyobi biotechnology limited company.
Preparation example preparation of enzymatic Lignin modified plant fiber
Preparation example 1
1) Preparation of enzymatic lignin
(1) Crushing the corn straws to obtain plant straw pulp;
(2) adding the powder slurry obtained in the step (1), the compound vitamin enzyme and a hexamethylenetetramine-hydrochloric acid buffer solution (pH is 5.4) into an enzymolysis chamber, and carrying out enzymolysis at 37 ℃ for 6 hours; the compound microbial enzyme is cellulase, hemicellulase and ligninase with the mass ratio of 15:20:1, and the dosage of the compound microbial enzyme is 5 wt% of the corn straw.
(3) Extruding, filtering, vacuum drying and grinding the enzymolysis product in the step (2) to obtain residue powder, and using the obtained filtrate for distilling and separating ethanol;
(4) heating with organic solvent under circulating microwave at 40 deg.C, dissolving residue powder sufficiently, extracting, filtering while hot to obtain filtrate, adding excessive deionized water, standing to precipitate enzymolysis lignin precipitate, filtering, washing, and drying to obtain enzymolysis lignin.
2) Preparation of enzymatic hydrolysis lignin modified plant fiber
(1) Adding 250 parts of dioxane into 80 parts of 10-30 meshes of ramie fiber powder, and fully swelling at the constant temperature of 60 ℃ for 6 hours;
(2) adding 100 parts of enzymatic hydrolysis lignin into the mixed system in the step (1), stirring uniformly, gradually dropwise adding a dioxane solution dissolved with 5 parts of catalyst p-dimethylaminopyridine and 20 parts of glutaric anhydride, and reacting for 5 hours at constant temperature;
(3) and (3) filtering the mixed system in the step (2), washing with deionized water, drying to obtain the enzymatic hydrolysis lignin modified ramie fiber, grinding to 50-200 meshes, drying in vacuum again, and controlling the water content to be 0.01-3% to obtain the enzymatic hydrolysis lignin modified ramie fiber powder to be used, which is called as modified fiber 1.
Preparation example 2
The rest is the same as the preparation example 1, except that the mass ratio of the cellulase, the hemicellulase and the ligninase in the compound microbial enzyme is 15:20:3, and the enzymatic hydrolysis lignin modified plant fiber, which is hereinafter referred to as modified fiber 2, is obtained.
Comparative preparation example 1
The rest is the same as the preparation example 1, except that no ligninase is added in the compound microbial enzyme, and the mass ratio of the cellulase to the hemicellulase is 15:20, so as to obtain the enzymatic hydrolysis lignin modified plant fiber, which is hereinafter referred to as modified fiber 3.
Preparation example 3
The rest is the same as the preparation example 1, except that the plant straw is flax, and enzymatic hydrolysis lignin modified plant fiber, hereinafter referred to as modified fiber 4, is obtained.
Comparative preparation example 2
The remainder was the same as in preparation example 1, except that the mass ratio of cellulase, hemicellulase and ligninase in the complex microbial enzyme was 15:20:0.5, to obtain an enzymatic lignin-modified plant fiber, hereinafter referred to as modified fiber 5.
Comparative preparation example 3
The rest is the same as the preparation example 1, except that the mass ratio of the cellulase, the hemicellulase and the ligninase in the compound microbial enzyme is 15:20:6, and the enzymatic hydrolysis lignin modified plant fiber, hereinafter referred to as modified fiber 6, is obtained.
Preparation example 4
The rest is the same as the preparation example 1, except that the dosage of the compound microbial enzyme is 2 wt% of the corn straw, which is hereinafter referred to as modified fiber 7.
EXAMPLES preparation of Wood-Plastic composites
Example 1
The formula is as follows: 40 parts of polyethylene with the molecular weight of 50 ten thousand, 60 parts of modified fiber 1, 1 part of polymerized rosin, 0.5 part of hindered amine light stabilizer 622, 0.5 part of antioxidant 1010, 0.8 part of A-1110 modified nano silicon dioxide, 1 part of KH-550 modified nano titanium dioxide, 1 part of titanate coupling agent modified nano calcium carbonate, 0.5 part of p-alkoxy phenol, 3 parts of MA-g-PP compatilizer, 2 parts of calcium stearate and 3 parts of ethylene-vinyl acetate copolymer.
The preparation method comprises the following steps: mixing materials: a-1110 modified nano silicon dioxide, KH-550 modified nano titanium dioxide, titanate coupling agent modified nano calcium carbonate, antioxidant 1010, p-alkoxy phenol, hindered amine light stabilizer 622, calcium stearate and modified fiber 1 are added into a mixer, and are uniformly mixed at a high speed of 1000r/min at 90 ℃ for 15min to obtain a mixed material 1;
adding the polyethylene and the MA-g-PP compatilizer into a mixer, uniformly mixing at a high speed of 1500r/min, and uniformly mixing at a high speed of 120 ℃ for 30min to obtain a mixed material 2;
after mixing, inputting the mixed materials 1 and 2 into an internal mixing device through a spiral feeding pipe;
banburying: the mixture is smelted in an internal mixing device, and then strip-shaped materials are output through a die head;
pre-cooling: the strip-shaped material is conveyed along the length direction of the cooling groove under the action of traction equipment and a strip-shaped guide rail, and a precooling pipe arranged above the cooling groove is used for carrying out spraying primary cooling on the strip-shaped material;
and (3) cooling: the strip which is subjected to primary cooling enters a cooling pipe, the strip is wrapped and cooled by an expansion die for conveying coolant by a cooling tank pump in the cooling pipe, and the strip is extruded and compacted;
gradually cooling: the cooled strip material enters a gradually cooling pipe to be sprayed and cooled to normal temperature;
and (3) granulation: and inputting the gradually cooled material strips into a cutting machine for cutting to obtain the anti-aging impact-resistant modified wood-plastic composite material.
Example 2
The rest is the same as example 1, except that the modified fiber 1 is 80 parts in the formulation.
Example 3
The rest is the same as example 1, except that modified fiber 1 is 100 parts in the formulation.
Example 4
The other is the same as in example 2 except that the modified fiber 1 is replaced with modified fiber 2 in the formulation.
Example 5
The other is the same as in example 2 except that the modified fiber 1 is replaced with a modified fiber 4 in the formulation.
Example 6
The other is the same as in example 2 except that the modified fiber 1 is replaced with a modified fiber 7 in the formulation.
Comparative example 1
The other is the same as in example 2 except that the fiber used is a modified fiber 3.
Comparative example 2
The other steps are the same as the example 2, except that the nano silicon dioxide, the nano titanium dioxide and the titanium nano calcium carbonate in the formula are not modified by a coupling agent.
Comparative example 3
The rest is the same as example 2, except that the modified fiber 1 used in the formulation is replaced by 80 parts of 10-30 mesh ramie powder and 100 parts of enzymatic lignin.
Comparative example 4
The other is the same as in example 2 except that the fiber used is a modified fiber 5.
Comparative example 5
The other is the same as in example 2 except that the fiber used is a modified fiber 6.
The materials obtained in the above examples and comparative examples were subjected to mechanical property test, xenon accelerated aging test and dimensional stability test in the following detailed test methods, and the test results are shown in table 1.
Tensile Property test
Tensile Properties GB/T1040-.
Impact testing
The impact performance GB/T1043.1-2008 tests, and the impact energy of the pendulum is 2J, the impact speed is 2.9m/sec, the angle of the pendulum is 130 degrees, and the size of a sample is 80mm multiplied by 10mm multiplied by 4 mm.
Accelerated aging test for xenon lamp
The energy distribution of the radiation spectrum of the xenon lamp is close to that of sunlight, and the working state is slightly influenced by the change of external conditions, so that the xenon lamp radiation spectrum energy distribution test method can be used for testing the ageing resistance of the wood-plastic composite material. The testing steps are as follows: the standard sample strips are put into a xenon lamp aging box for accelerated aging for four periods (one week isOne period), the experimental environment is air atmosphere, the cavity temperature is 55 ℃, the outer wall temperature is 38 ℃, the cavity humidity is 50 +/-5 percent, the lamp source is 10cm away from the sample, the wavelength of the xenon lamp is 290-800 mm, the power of the xenon lamp tube is 1800W, and the power density is 1.10W/m2。
Post heat dimensional change rate test
The degree of dimensional change after heating is characterized by the rate of dimensional change after heating, the standard length of the sample is 250mm, two marked lines with the distance of 200mm are marked on the specified visible surface of the sample, and the distance between each marked line and one end of the sample is 25 mm. The sample is placed vertically at a temperature (62 +/-1) and heated for 60min at a temperature of 100 ℃. The dimensional change rate after heating is given by the formula: standing at 24 + -0.5 h.
In the formula, R-dimensional change rate after heating,%;
L0-the distance between the two support points before heating, mm;
L1-distance between two points after heating, mm;
cold and hot cycle resistance test
Reference standard: GB/T245908-2009, sample sizes 40mm × 40mm × 5 mm. The test method comprises the following steps:
and (5) dipping a little of ethanol in absorbent gauze to wipe the surface of the test piece and drying the test piece in the air. A center line parallel to the longitudinal direction was drawn on each sample, and the center line length L was measured1。
The cycle test was performed by repeating the high and low temperatures 3 times. As follows:
then placing at (23 + -2) deg.C for more than 6 hr, testing appearance under natural light, and measuring center length L2。
The dimensional change deltal of each sample was calculated according to the formula,
△L＝L2-L1
in the formula:
Δ L-sample size change, mm;
l2-size of sample after test, mm;
l1-size of sample before test, mm;
TABLE 1
It can be seen from table 1 that the tensile strength, elongation at break and impact strength of the composite material modified by enzymatic hydrolysis lignin are all significantly improved, the phenomena of toughness improvement and rigidity sacrifice are not generated, and the composite material has good impact resistance, aging resistance and dimensional stability. The inventor unexpectedly finds that when lignin is subjected to enzymolysis, a certain amount of ligninase is added, the affinity between the lignin and plant fibers can be effectively improved, and the mechanical property and the ageing resistance of the wood-plastic composite material are obviously improved. The effect of optimizing the comprehensive performance of the wood-plastic composite material cannot be realized without adding the ligninase or with too much or too little adding amount of the ligninase. Meanwhile, the invention also modifies the inorganic filler by the coupling agent, and optimizes the proportion of the inorganic filler and the type of the coupling agent, so that the ageing resistance and the mechanical property of the composite material are improved. The ageing resistance and the impact resistance of the composite material prepared by the unmodified plant fiber are greatly reduced compared with those of the composite material prepared by the modified inorganic filler or the modified plant fiber. The dosage of the enzymatic hydrolysis lignin modified plant fiber has obvious influence on the anti-aging performance of the composite material.
The above detailed description is specific to one possible embodiment of the present invention, and the preferred embodiment is not intended to limit the scope of the present invention, and all equivalent implementations or modifications without departing from the scope of the present invention should be included in the technical scope of the present invention.
Claims (7)
1. The anti-aging impact-resistant modified wood-plastic composite material is characterized by comprising the following raw materials in parts by weight: 20-50 parts of polyolefin, 30-70 parts of enzymatic hydrolysis lignin modified plant fiber, 1-3.5 parts of polymerized rosin, 0.1-10 parts of inorganic filler, 0.1-4 parts of antioxidant and 0.1-3 parts of anti-ultraviolet agent, wherein the enzymatic hydrolysis lignin modified plant fiber is obtained by reacting enzymatic hydrolysis lignin and plant fiber through acid anhydride, and the mass ratio of the enzymatic hydrolysis lignin to the plant fiber to the acid anhydride is 10-15:8-12: 2-4;
the plant fiber is fibrilia;
the anhydride is selected from at least one of maleic anhydride, alkenyl succinic anhydride, methyl tetrahydrophthalic anhydride, glutaric anhydride, tetrahydrophthalic anhydride and hexahydrophthalic anhydride;
the enzymatic hydrolysis lignin is obtained by a preparation method comprising the following steps:
crushing plant straws to obtain a plant straw pulp mixture, adding microbial enzyme for full enzymolysis, and filtering, drying and grinding an enzymolysis product to obtain residue powder;
fully dissolving residue powder by using an organic solvent for extraction, filtering while the residue powder is hot to obtain a filtrate, adding water, standing to separate out an enzymolysis lignin precipitate, filtering, washing and drying to obtain enzymolysis lignin;
the using amount of the microbial enzyme is 2-5 wt% of the straw; the microbial enzyme is a mixture of cellulase, hemicellulase and ligninase according to a mass ratio of 15-25:10-20: 1-3;
the inorganic filler is modified by a coupling agent and is at least one of nano silicon dioxide, nano titanium dioxide and nano calcium carbonate; the coupling agent for the nano-silica and/or the nano-titanium dioxide is selected from an amino-hydrocarbyl silane coupling agent, and the coupling agent for the nano-calcium carbonate is selected from a titanate coupling agent.
2. The modified wood-plastic composite material of claim 1, wherein the plant fiber is one or more of ramie, flax, jute, hemp and kenaf.
3. The modified wood-plastic composite of claim 1, wherein the anhydride is selected from the group consisting of dodecenyl succinic anhydride.
4. The modified wood-plastic composite of claim 1, wherein the polyolefin comprises at least one of polypropylene, polyethylene, and ethylene-propylene copolymer, and has a molecular weight of 10 to 100 ten thousand.
5. The modified wood-plastic composite material according to claim 1, wherein the inorganic filler is a compound of nano calcium carbonate and at least one of nano silicon dioxide and nano titanium dioxide, and the mass ratio of the nano silicon dioxide and/or the nano titanium dioxide to the nano calcium carbonate is 1: 1-3.
6. The modified wood-plastic composite of claim 1, further comprising 2-10 parts of a lubricant, 1-8 parts of a compatibilizer, 1-10 parts of a heat stabilizer, and 3-6 parts of a toughening agent.
7. A method of preparing a wood-plastic composite as claimed in any one of claims 1 to 6, comprising the steps of:
(1) fully and uniformly mixing inorganic filler, an anti-ultraviolet agent, an antioxidant, enzymatic hydrolysis lignin modified plant fiber and other auxiliary agents to obtain a mixed material 1; adding polyolefin into a mixer to be mixed to obtain a mixed material 2, and inputting the mixed material 1 and the mixed material 2 into an internal mixing device for internal mixing;
(2) and carrying out cooling, granulation and drying on the material strips generated by banburying to obtain the anti-aging impact-resistant modified wood-plastic composite material.
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| CN112662108B (en) * | 2020-12-23 | 2023-08-15 | 安徽绿之态秸秆制品有限公司 | Whisker reinforced straw fiber environment-friendly furniture material and furniture |
| CN112708257B (en) * | 2020-12-31 | 2022-06-17 | 宁波能之光新材料科技股份有限公司 | High-elasticity wear-resistant outdoor wood-plastic surface layer material and preparation method thereof |
| CN113480780B (en) * | 2021-06-07 | 2022-09-02 | 山东路德新材料股份有限公司 | Bio-based three-dimensional geotechnical net pad and preparation method thereof |
| CN113305959B (en) * | 2021-06-24 | 2022-02-25 | 东北林业大学 | Method for improving size stability of fast-growing wood by using lignin-based modified liquid medicine |
| CN118063873A (en) * | 2024-04-24 | 2024-05-24 | 泉州兴源新材料科技有限公司 | Composite anti-aging agent modified polyethylene material and preparation method thereof |
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