CN115124776B - Natural bamboo fiber modified PE or PP composite material and preparation method thereof - Google Patents

Natural bamboo fiber modified PE or PP composite material and preparation method thereof Download PDF

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CN115124776B
CN115124776B CN202210598533.9A CN202210598533A CN115124776B CN 115124776 B CN115124776 B CN 115124776B CN 202210598533 A CN202210598533 A CN 202210598533A CN 115124776 B CN115124776 B CN 115124776B
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bamboo fiber
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composite material
mass
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CN115124776A (en
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曹选勇
张玉平
龙春光
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Hunan Xiecheng Pipe Industry Technology
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    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/06—Polyethene
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    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/045—Reinforcing macromolecular compounds with loose or coherent fibrous material with vegetable or animal fibrous material
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
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    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
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    • C08J2397/00—Characterised by the use of lignin-containing materials
    • C08J2397/02—Lignocellulosic material, e.g. wood, straw or bagasse
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    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2423/04—Homopolymers or copolymers of ethene
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    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2423/10—Homopolymers or copolymers of propene
    • C08J2423/12—Polypropene
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
    • C08J2451/04—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to rubbers
    • C—CHEMISTRY; METALLURGY
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    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
    • C08J2451/06—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
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    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2497/00—Characterised by the use of lignin-containing materials
    • C08J2497/02—Lignocellulosic material, e.g. wood, straw or bagasse
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
    • C08L2205/16—Fibres; Fibrils
    • C—CHEMISTRY; METALLURGY
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/06—Properties of polyethylene
    • C08L2207/062—HDPE
    • C—CHEMISTRY; METALLURGY
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/06—Properties of polyethylene
    • C08L2207/068—Ultra high molecular weight polyethylene

Abstract

The invention discloses a natural bamboo fiber modified PE or PP composite material which comprises the following raw materials in parts by weight: 30-70 parts of modified bamboo fiber, 25-65 parts of PE or PP mixed material, 3-10 parts of organic polymer treating agent and 0.55-1.2 parts of processing aid. The invention reduces the processing temperature of the composite material and improves the flow processability by optimizing the formula of the PE mixed material, thereby reducing the carbonization and damage of the bamboo fiber; through scientific design and structure optimization of the coupling agent, the surface treatment of the bamboo fiber is optimized, the surface tension is effectively reduced, the distribution uniformity of the bamboo fiber is improved, and the interface bonding strength between the bamboo fiber and a polymer matrix PE or PP is increased, so that the comprehensive performance of the composite material is improved. The composite material can be applied to obtaining various products such as pipes, profiles, plates, sheets and the like through various molding processes of extrusion, calendaring and die pressing.

Description

Natural bamboo fiber modified PE or PP composite material and preparation method thereof
Technical Field
The invention relates to the technical field of bamboo fiber modified PE or PP composite materials, and particularly relates to a natural bamboo fiber modified PE or PP composite material and a preparation method thereof.
Background
With the shortage of petroleum resources and the increasing prominence of environmental protection problems, the high-valued and ecological application of plant fibers has been increasingly paid attention, and becomes one of the key points of research and development of novel composite materials in recent years. The natural bamboo material has excellent mechanical property, has higher tensile strength than other natural materials except hemp, and is very suitable to be used as a reinforcing phase of a composite material. In addition, the bamboo has the characteristics of antibiosis, bacteriostasis, ultraviolet resistance, good air permeability and the like, and the bamboo grows rapidly, has fast yield and high yield, and is a renewable material with rich resources, short growth period and strong environmental protection function. Therefore, the invention aims to invent the environment-friendly bamboo fiber modified PE or PP composite material with good comprehensive performance.
CN 101880423A discloses a bamboo fiber or polypropylene composite material and a preparation method thereof, the method comprises the steps of adding polypropylene, bamboo fiber, compatilizer and plasticizer into a kneader, an internal mixer or a double-screw extruder according to a certain proportion, mixing to prepare the bamboo fiber and polypropylene composite material, and then carrying out post processes such as extrusion molding, calendaring molding and compression molding to prepare sheets, plates, pipes or sections of the bamboo fiber and polypropylene composite material, wherein the sheets, plates, pipes or sections can be used for manufacturing products such as structures, decorations and packages. The bamboo fiber is a by-product of bamboo oil squeezed from bamboo at high temperature, and has the advantages of low cost, abundant resources, capability of extruding, calendering and compression molding of bamboo fiber or polypropylene composite material, material properties adjustable by changing the content of each component, and improved processing fluidity of bamboo fiber and polypropylene composite material due to plasticizer. The bamboo fiber polypropylene composite material can replace wood and plastic to a certain extent, is beneficial to the protection of resource environment, but has poor compatibility between bamboo fiber and polypropylene and poor raw material combination effect, and the prepared product reduces the mechanical property on the contrary.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a natural bamboo fiber modified PE or PP composite material and a preparation method thereof, so as to solve the problems in the background art.
The technical scheme adopted by the invention for solving the technical problems is as follows:
the invention provides a natural bamboo fiber modified PE or PP composite material, which comprises the following raw materials in parts by weight:
30 to 70 parts of modified bamboo fiber, 25 to 65 parts of PE or PP mixed material, 3 to 10 parts of organic polymer treating agent and 0.55 to 1.2 parts of processing aid.
Preferably, the PE or PP composite material comprises the following raw materials in parts by weight:
50 parts by mass of modified bamboo fiber, 45 parts by mass of PE or PP mixed material, 6.5 parts by mass of organic polymer treating agent and 0.90 part by mass of processing aid.
Preferably, the modification method of the modified bamboo fiber comprises the following steps:
s11: after the bamboo fiber with 60-100 meshes is treated by 5-10% of alkali, the bamboo fiber is washed by water, neutralized by acid washing and dried to obtain a bamboo fiber pretreatment material;
s12: then drying for 4-6 h at 90-110 ℃, carrying out spray treatment on the carbon nano tube coupling agent mixed solution at 60-80 ℃, bagging and sealing after proton irradiation, and activating for more than 20h to obtain the modified bamboo fiber.
Preferably, the base is NaOH or KOH, and the acid is 10% acetic acid;
the coupling agent is at least one of silane coupling agent, titanate coupling agent or aluminate coupling agent, and the using amount of the coupling agent is 1-3 wt% of the mass of the bamboo fiber.
Preferably, the specific operation steps of the spray treatment of the carbon nanotube coupling agent mixed solution are as follows:
s101: dispersing the carbon nano tube in 2-3 times of ethanol solvent to form suspension, adding 6-10% of tetrabutyl zirconate and 1-4% of pentadecyl phenol in the total amount of the carbon nano tube, stirring and reacting for 1-2h at 45-65 ℃, wherein the stirring speed is 450-550r or min, and after stirring, washing and drying to obtain a modified carbon nano tube;
s102: mixing chitosan and acetic acid according to the weight ratio of 1 to 5 to obtain a chitosan solution, then adding 1 to 5 percent of samarium chloride, 1 to 3 percent of coupling agent and 2 to 6 percent of modified carbon nano tube into the chitosan solution, and fully stirring and mixing to obtain a spray;
s103: spraying the spraying agent on a product of S12 according to the weight ratio of 1.
Preferably, the PE or PP blending material is as follows:
wherein the PE mixed ingredient is prepared by mixing 40-50 parts by mass of HDPE, 40-50 parts by mass of LLHDPE and 8-12 parts by mass of UHMWPE at high speed and drying; the HDPE melt index is 15-20 g/10min, the LLHDPE melt index is 20-40 g/10min, and the molecular weight of UHMWPE is 300-600 ten thousand;
wherein the PP mixed material is a PP pipeline material.
Preferably, the organic polymer treating agent is a polymer compatibilizer with a polar group graft chain (point) or a block chain, such as one or a combination of PE-G-MA, EPDM-G-MA, EVA-G-MA, PP-G-MA, a linear polymer hyperdispersant and a high polymer with high melt flow rate and low melting point, such as EVA.
Preferably, the processing aid comprises a lubricant, an antibacterial agent, an anti-aging agent, an ultraviolet absorber and an antioxidant, wherein the lubricant is at least one of PE wax or lacquer wax, and the content of the lubricant is 0.15-0.25%; the antibacterial agent is at least one of chitin, mustard and castor oil, and the content is 0.05-0.15%; the anti-aging agent is HS-622 or HS-962, and the content is 0.2-0.4%; the ultraviolet absorbent is UV328 or UV531:0.1 to 0.25 percent; the antioxidant is 225 or 215:0.05-0.15 percent.
The invention provides a preparation method of a natural bamboo fiber modified PE or PP composite material, which comprises the following steps:
the method comprises the following steps: weighing raw materials;
step two: mixing the modified bamboo fiber, the PE or PP mixed material, the organic polymer treating agent and the processing aid, performing melt extrusion and air drying granulation, and uniformly mixing and plasticizing to obtain a bamboo fiber modified PE or PP composite material;
the mixing, melt extrusion and granulation processes are completed by adopting a double-screw extruder, the melt extrusion process is divided into eleven working temperature zones, and the temperature is set as follows: first zone 120-140 ℃, second zone 135-150 ℃, first zone temperature: 130 to 140 ℃; the screw rotation speed in the melt extrusion process is 50-200 rpm. And air drying granulation is adopted in the granulation process. The processing temperature is obviously lower than that of the common PE or PP material.
The invention also provides a natural bamboo fiber modified PE or PP composite material which is suitable for various molding processes of extrusion, calendering and mould pressing and is applied to obtaining various products such as pipes, sectional materials, plates and sheets.
Compared with the prior art, the invention has the following beneficial effects:
the invention reduces the processing temperature of the composite material and improves the flow processability by optimizing the formula of the PE mixed material, thereby reducing the carbonization and damage of the bamboo fiber; through scientific design and structural optimization of the coupling agent, the surface treatment of the bamboo fiber is optimized, the surface tension is effectively reduced, and the interface bonding strength between the coupling agent and a polymer matrix PE is increased, so that the comprehensive performance of the composite material is improved; the dispersibility of the bamboo powder is effectively improved through the organic polymer treating agent, and the mechanical property of the composite material is improved; in addition, the reinforcement adopts natural high-strength bamboo fiber, so that the cost performance is high, the environmental burden is favorably reduced, and the local economy and the country joy are favorably promoted;
the bamboo fiber modification adopts alkali treatment, water washing and acid neutralization, the interface compatibility is improved through the surface modification treatment of a coupling agent, the mixing environment of the PE or PP mixed material and the bamboo fiber is established in a high-speed mixer, and the interface improvement is further improved through the spray treatment.
The spraying treatment adopts the carbon nano tube as a bearing material with high specific surface area after being modified, and the spraying agent consisting of the carbon nano tube, the samarium chloride and the coupling agent is improved under the environment of PE or PP mixed materials and bamboo fibers, so that the interface improvement effect of the product is obviously improved, the dispersion uniformity of the bamboo fibers is improved, and the mechanical property, the heat conduction property, the sand resistance and the corrosion resistance of the bamboo fiber reinforced PE or PP composite material are obviously improved.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below with reference to specific embodiments, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention of the embodiment provides a natural bamboo fiber modified PE or PP composite material, which comprises the following raw materials in parts by mass:
30-70 parts of modified bamboo fiber, 25-65 parts of PE or PP mixed material, 3-10 parts of organic polymer treating agent and 0.55-1.2 parts of processing aid.
The PE or PP composite material comprises the following raw materials in parts by mass:
50 parts by mass of modified bamboo fiber, 45 parts by mass of PE or PP mixed material, 6.5 parts by mass of organic polymer treating agent and 0.90 part by mass of processing aid.
The modification method of the modified bamboo fiber of the embodiment comprises the following steps:
s11: after the bamboo fiber with 60-100 meshes is treated by 5-10% of alkali, the bamboo fiber is washed by water, neutralized by acid washing and dried to obtain a bamboo fiber pretreatment substance;
s12: then drying for 4-6 h at 90-110 ℃, then carrying out spray treatment on the carbon nano tube coupling agent mixed solution at 60-80 ℃, bagging and sealing after proton irradiation, and activating for more than 20h to obtain the modified bamboo fiber.
In the embodiment, naOH or KOH is used as the alkali, and 10% acetic acid is used as the acid;
the coupling agent is at least one of silane coupling agent, titanate coupling agent or aluminate coupling agent, and the using amount of the coupling agent is 1-3 wt% of the mass of the bamboo fiber.
The operation steps of the spray treatment of the carbon nanotube coupling agent mixed solution in this embodiment are:
s101: dispersing the carbon nano tube in 2-3 times of ethanol solvent to form suspension, adding 6-10% of tetrabutyl zirconate and 1-4% of pentadecyl phenol in the total amount of the carbon nano tube, stirring and reacting for 1-2h at 45-65 ℃, wherein the stirring speed is 450-550r or min, and after stirring, washing and drying to obtain a modified carbon nano tube;
s102: mixing chitosan and acetic acid according to the weight ratio of 1 to 5 to obtain a chitosan solution, then adding 1 to 5 percent of samarium chloride, 1 to 3 percent of coupling agent and 2 to 6 percent of modified carbon nano tube into the chitosan solution, and fully stirring and mixing to obtain a spray;
s103: spraying the spraying agent on a product of S12 according to a weight ratio of 1.
The PE or PP blending material of the embodiment is as follows:
wherein the PE mixed ingredient is prepared by mixing 40-50 parts by mass of HDPE, 40-50 parts by mass of LLHDPE and 8-12 parts by mass of UHMWPE at high speed and drying; the melt index of HDPE is 15-20 g/10min, the melt index of LLHDPE is 20-40 g/10min, and the molecular weight of UHMWPE is 300-600 ten thousand;
wherein the PP mixed material is a PP pipeline material.
The organic polymer treating agent of this embodiment is a polymer compatibilizer with a graft chain (point) or a block chain of a polar group, such as one or a combination of PE-G-MA, EPDM-G-MA, EVA-G-MA, PP-G-MA, a linear polymer hyperdispersant, and a high polymer having a high melt flow rate and a low melting point, such as EVA.
The processing aid of the embodiment comprises a lubricant, an antibacterial agent, an anti-aging agent, an ultraviolet absorber and an antioxidant, wherein the lubricant is at least one of PE wax or lacquer wax, and the content of the lubricant is 0.15-0.25%; the antibacterial agent is at least one of chitin, mustard and castor oil, and the content is 0.05-0.15%; the anti-aging agent is HS-622 or HS-962, and the content is 0.2-0.4%; the ultraviolet absorbent is UV328 or UV531:0.1 to 0.25 percent; the antioxidant is 225 or 215:0.05-0.15 percent.
The preparation method of the natural bamboo fiber modified PE or PP composite material comprises the following steps:
the method comprises the following steps: weighing raw materials;
step two: mixing the modified bamboo fiber, the PE or PP mixed material, the organic polymer treating agent and the processing aid, performing melt extrusion and air drying granulation, and uniformly mixing and plasticizing to obtain a bamboo fiber modified PE or PP composite material;
the mixing, melt extrusion and granulation processes are completed by adopting a double-screw extruder, the melt extrusion process is divided into eleven working temperature zones, and the temperature is set as follows: first zone 120-140 ℃, second zone 135-150 ℃, head zone temperature: 130 to 140 ℃; the screw rotation speed in the melt extrusion process is 50-200 rpm. And air drying granulation is adopted in the granulation process. The processing temperature is obviously lower than that of the common PE or PP material.
The natural bamboo fiber modified PE or PP composite material is suitable for various molding processes of extrusion, calendering and die pressing, and is applied to obtaining various products such as pipes, profiles, plates and sheets.
Example 1.
The invention provides a natural bamboo fiber modified PE or PP composite material, which comprises the following raw materials in parts by weight:
30 parts by mass of modified bamboo fiber, 65 parts by mass of PE or PP mixed material, 3 parts by mass of organic polymer treating agent and 0.55 part by mass of processing aid.
The modification method of the modified bamboo fiber of the embodiment comprises the following steps:
s11: treating 60-mesh bamboo fiber with 5% alkali, then washing with water, neutralizing with acid wash, and drying to obtain bamboo fiber pretreatment;
s12: and then drying at 90 ℃ for 4h, spraying the carbon nanotube coupling agent mixed solution at 60 ℃, bagging and sealing after proton irradiation, and activating for 20h to obtain the modified bamboo fiber.
In the embodiment, naOH is used as the alkali, and 10% acetic acid is used as the acid;
the coupling agent is a silane coupling agent, and the using amount of the silane coupling agent is 2wt% of the mass of the bamboo fiber.
The specific operation steps of the spray treatment of the carbon nanotube coupling agent mixed solution in this embodiment are as follows:
s101: dispersing carbon nano tubes in 2 times of ethanol solvent to form suspension, then adding 6 percent of tetrabutyl zirconate and 1 percent of pentadecylphenol based on the total amount of the carbon nano tubes, stirring and reacting for 1 hour at 45 ℃, wherein the stirring speed is 450r or min, and after stirring, washing and drying to obtain modified carbon nano tubes;
s102: mixing chitosan and acetic acid according to a weight ratio of 1;
s103: spraying the spraying agent on a product of S12 according to the weight ratio of 1.
The PE or PP blending material of the embodiment is as follows: the PE mixed material is prepared by mixing 40 parts by mass of HDPE, 40 parts by mass of LLHDPE and 8 parts by mass of UHMWPE at high speed and drying; the HDPE melt index is 15g/10min, the LLHDPE melt index is 20g/10min, and the molecular weight of UHMWPE is 300-600 ten thousand.
The organic polymer treating agent of this embodiment is a polymer compatibilizer having a graft chain (dot) or a block chain of a polar group, such as PE-G-MA.
The processing aid of the embodiment comprises a lubricant, an antibacterial agent, an anti-aging agent, an ultraviolet absorbent and an antioxidant, wherein the lubricant is PE wax, and the content of the PE wax is 0.15%; the antibacterial agent is chitin, and the content is 0.05%; the anti-aging agent is HS-622 with the content of 0.2 percent; the ultraviolet absorbent is UV328:0.1 percent; the antioxidant is 225:0.05 percent.
The preparation method of the natural bamboo fiber modified PE or PP composite material comprises the following steps:
the method comprises the following steps: weighing raw materials;
step two: mixing the modified bamboo fiber, the PE or PP mixed material, the organic polymer treating agent and the processing aid, performing melt extrusion and air drying granulation, and uniformly mixing and plasticizing to obtain a bamboo fiber modified PE or PP composite material;
the mixing, melt extrusion and granulation processes are completed by adopting a double-screw extruder, the melt extrusion process is divided into eleven working temperature zones, and the temperature is set as follows: first zone 120 ℃, second zone 135 ℃ to tenth zone, head zone temperature: 130 ℃; the rotating speed of a screw in the melting extrusion process is 50rpm, and air drying granulation is adopted in the granulation process.
The natural bamboo fiber modified PE or PP composite material is suitable for various molding processes of extrusion, calendering and die pressing, and is applied to obtaining various products such as pipes, profiles, plates and sheets.
Example 2.
The invention of the embodiment provides a natural bamboo fiber modified PE or PP composite material, which comprises the following raw materials in parts by weight:
70 parts by mass of modified bamboo fiber, 25 parts by mass of PE or PP mixed material, 10 parts by mass of organic polymer treating agent and 1.2 parts by mass of processing aid.
The modification method of the modified bamboo fiber of the embodiment comprises the following steps:
s11: treating 100-mesh bamboo fiber with 10% alkali, then washing with water, neutralizing with acid wash, and drying to obtain bamboo fiber pretreatment;
s12: then drying for 6h at 110 ℃, carrying out spray treatment on the carbon nano tube coupling agent mixed solution at 80 ℃, bagging and sealing after proton irradiation, and finally activating for 20h to obtain the modified bamboo fiber.
In the embodiment, naOH is used as the alkali, and 10% acetic acid is used as the acid;
the coupling agent is titanate coupling agent, and the dosage of the coupling agent is 3wt% of the bamboo fiber.
The specific operation steps of the spray treatment of the carbon nanotube coupling agent mixed solution in this embodiment are as follows:
s101: dispersing carbon nano tubes in 2-3 times of ethanol solvent to form suspension, then adding tetrabutyl zirconate accounting for 10% of the total amount of the carbon nano tubes and pentadecylphenol accounting for 4% of the total amount of the carbon nano tubes, stirring and reacting for 2 hours at 65 ℃, wherein the stirring speed is 550r or min, and after stirring, washing and drying to obtain modified carbon nano tubes;
s102: mixing chitosan and acetic acid according to a weight ratio of 1;
s103: spraying the spray on a product of S12 according to the weight ratio of 1.
The PE or PP blending material of the embodiment is as follows:
wherein the PE mixed material is prepared by mixing 50 parts by mass of HDPE, 50 parts by mass of LLHDPE and 12 parts by mass of UHMWPE at high speed and drying; the HDPE melt index is 20g/10min, the LLHDPE melt index is 40g/10min, and the molecular weight of the UHMWPE is 600 ten thousand.
The organic polymer treating agent of the present example is a polymer compatibilizer having a graft chain (dot) or a block chain of a polar group, EPDM-g-MA.
The processing aid comprises a lubricant, an antibacterial agent, an anti-aging agent, an ultraviolet absorber and an antioxidant, wherein the lubricant is lacquer wax, and the content of the lacquer wax is 0.25%; the antibacterial agent is mustard with content of 0.15%; the anti-aging agent is HS-962, the content is 0.4%; the ultraviolet absorbent is UV531:0.25 percent; the antioxidant is 215:0.15 percent.
The preparation method of the natural bamboo fiber modified PE or PP composite material comprises the following steps:
the method comprises the following steps: weighing raw materials;
step two: mixing the modified bamboo fiber, the PE or PP mixed material, the organic polymer treating agent and the processing aid, performing melt extrusion and air drying granulation, and uniformly mixing and plasticizing to obtain a bamboo fiber modified PE or PP composite material;
the mixing, melt extrusion and granulation processes are completed by adopting a double-screw extruder, the melt extrusion process is divided into eleven working temperature zones, and the temperature is set as follows: first zone 140 ℃, second zone-ten zone 150 ℃, head zone temperature: 140 ℃; the screw speed during melt extrusion was 520rpm. And air drying granulation is adopted in the granulation process.
The natural bamboo fiber modified PE or PP composite material is suitable for various molding processes of extrusion, calendering and die pressing, and is applied to obtaining various products such as pipes, profiles, plates and sheets.
Example 3.
The invention of the embodiment provides a natural bamboo fiber modified PE or PP composite material, which comprises the following raw materials in parts by weight:
50 parts by mass of modified bamboo fiber, 45 parts by mass of PE or PP mixed material, 6.5 parts by mass of organic polymer treating agent and 0.90 part by mass of processing aid.
The modification method of the modified bamboo fiber of the embodiment comprises the following steps:
s11: after the bamboo fiber with the grain size of 80 meshes is treated by 7.5 percent of alkali, the bamboo fiber is washed by water, neutralized by acid washing and dried to obtain a bamboo fiber pretreatment substance;
s12: and then drying at 95 ℃ for 5 hours, spraying the carbon nano tube coupling agent mixed solution at 70 ℃, bagging and sealing after proton irradiation, and finally activating for 20 hours to obtain the modified bamboo fiber.
The base used in this example was KOH, and the acid used was 10% acetic acid;
the coupling agent is an aluminate coupling agent, and the dosage of the aluminate coupling agent is 3wt% of the mass of the bamboo fiber.
The specific operation steps of the spray treatment of the carbon nanotube coupling agent mixed solution in this embodiment are as follows:
s101: dispersing the carbon nano tube in 3 times of ethanol solvent to form suspension, adding tetrabutyl zirconate accounting for 10 percent of the total amount of the carbon nano tube and pentadecylphenol accounting for 4 percent of the total amount of the carbon nano tube, stirring and reacting for 2 hours at 65 ℃, wherein the stirring speed is 550r or min, and after stirring, washing and drying to obtain a modified carbon nano tube;
s102: mixing chitosan and acetic acid according to the weight ratio of 1;
s103: spraying the spray on a product of S12 according to the weight ratio of 1.
The PE or PP blending material of the embodiment is as follows: wherein the PP mixed material is a PP pipeline material.
The organic polymer treating agent of the present example is a polymer compatibilizer having a graft chain (dot) or a block chain of a polar group, EVA-g-MA.
The processing aid of the embodiment comprises a lubricant, an antibacterial agent, an anti-aging agent, an ultraviolet absorbent and an antioxidant, wherein the lubricant is PE wax, and the content of the PE wax is 0.20%; the antibacterial agent is castor oil, and the content is 0.10%; the anti-aging agent is HS-962, the content is 0.3%; the ultraviolet absorbent is UV531:0.16 percent; the antioxidant is 215:0.10 percent.
The preparation method of the natural bamboo fiber modified PE or PP composite material comprises the following steps:
the method comprises the following steps: weighing raw materials;
step two: mixing the modified bamboo fiber, the PE or PP mixed material, the organic polymer treating agent and the processing aid, performing melt extrusion and air drying granulation, and uniformly mixing and plasticizing to obtain a bamboo fiber modified PE or PP composite material;
the mixing, melt extrusion and granulation processes are completed by adopting a double-screw extruder, the melt extrusion process is divided into eleven working temperature zones, and the temperature is set as follows: first zone 130 ℃, second zone-ten zone 140 ℃, head zone temperature: 135 deg.C; the screw speed during melt extrusion was 165rpm. The granulation process adopts air drying granulation.
The natural bamboo fiber modified PE or PP composite material is suitable for various molding processes of extrusion, calendaring and die pressing, and is applied to obtaining various products such as pipes, profiles, plates and sheets.
Comparative example 1.
Different from the embodiment 3, the modified bamboo fiber adopts the bamboo fiber and the PE mixed material to be mixed according to the weight part of the embodiment 3.
Comparative example 2.
The difference from the example 3 is that the PE blending material adopts common PE pipe material, and the rest is all according to the example 3.
Comparative example 3.
The difference from the example 3 is that the modified bamboo fiber is not modified by spray treatment.
Comparative example 4.
Different from the embodiment 3 in that the modified bamboo fiber is modified by a different method;
and (2) standing the bamboo fiber, the titanate coupling agent and water at 65-75 ℃ for reaction for 1-2h according to the weight ratio of 1.
Comparative example 5.
Unlike example 3, no modified carbon nanotubes were added in the spray treatment.
Comparative example 6.
Different from the example 3, the spray treatment method is different;
s101: mixing chitosan and acetic acid according to a weight ratio of 1;
s102: spraying the spray on a product of S12 according to the weight ratio of 1;
comparative example 7
Unlike example 3, no organic polymer treatment agent was added.
The products of examples 1-3 and comparative examples 1-6 were subjected to a performance test;
the products obtained in examples 1-3 and comparative examples 1-6 were subjected to injection molding to prepare samples, and the properties were tested by the following specific test methods:
static bending strength is tested according to the measurement of the static bending strength of a hard fiberboard of GBT 12626.9-1990;
the tensile strength and the elastic modulus are tested according to the determination of the tensile property of GB/T1040-2008 plastics;
the impact strength is tested according to the determination of GB/T1043.1-2008 plastic simple support dye gap impact performance;
the thermal conductivity was tested according to the method for measuring the heat transfer characteristics of ASTM D5470 thermally conductive electrically insulating materials;
and (3) testing sand resistance: the sand and water abrasion resistance of the material is carried out by adopting a horizontal abrasion tester (self-prepared sand and water test fixture), the sand content in water is respectively 10wt%, 15wt%, 20wt%, 25wt% and 30wt%, and the test time is as follows: 2h; a load of 500N; rotating speed: 200rpm. The evaluation was carried out under the above conditions in order to evaluate the magnitude of the mass loss. The mass loss is excellent at 1% or less, the mass loss is 2 to 5%, the mass loss is generally 6 to 10%, and the mass loss >10% is poor.
And (3) corrosion resistance test: placing various material samples in glacial acetic acid, ethanol, solvent oil, 60% strong base, 20% saline solution, 30% sulfuric acid and aqua regia for more than 8h respectively, and observing the surface change condition of the samples.
The samples of examples 1-3 and comparative examples 1-7 were tested for their performance as follows:
TABLE 1 results of performance tests on the products obtained in examples 1 to 3
Figure BDA0003669041300000171
TABLE 2 results of testing the properties of the samples obtained in comparative examples 1 to 7
Figure BDA0003669041300000172
Figure BDA0003669041300000181
From the examples 1 to 3, the comprehensive performance of the example 3 is good, and the fluidity of the example 2 is greatly reduced because the content of the bamboo fiber is too high, and the mechanical property and the sand resistance are obviously reduced;
as can be seen from the comparative example 1 and the example 3, the product adopts the bamboo fiber and PE mixed material to be directly mixed and modified, and the mechanical property, the heat conductivity coefficient, the sand resistance and the corrosion resistance of the product are obviously reduced;
as can be seen from comparative example 2 and example 3, with the conventional PE material, the melt index was significantly decreased, indicating that the flowability was deteriorated;
it can be seen from comparative example 3 and example 3 that the modified bamboo fiber is different in modification method, the coupling agent treatment is adopted, the spray treatment is not carried out, the elastic modulus of the product is not changed greatly, but the mechanical property is remarkably reduced, the corrosion resistance and sand resistance are reduced, and the modification effect is poor;
as can be seen from comparative example 4 and example 3, the use of titanate coupling agent has better modification effect than silane coupling agent, and the mechanical property is improved;
as can be seen from comparative example 5 and example 3, the thermal conductivity is reduced and the mechanical properties are slightly reduced only by spraying the coupling agent without adding the carbon nanotube;
as can be seen from comparative example 6 and example 3, the mechanical properties are slightly reduced by different spray treatment methods;
it can be seen from comparative example 7 and example 3 that the mechanical properties are significantly reduced without adding an organic polymer treating agent, and the thermal conductivity, sand resistance and corrosion resistance are reduced.
The product improved by the modification method of the invention has the advantages that the mechanical property, the sand resistance, the heat conductivity and the corrosion resistance can be enhanced in a coordinated manner, and the improvement effect is not obvious like the improvement effect of the invention when the product is modified by other methods.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.

Claims (7)

1. A natural bamboo fiber modified PE or PP composite material is characterized by comprising the following raw materials in parts by mass:
30-70 parts of modified bamboo fiber, 25-65 parts of PE or PP mixed material, 3-10 parts of organic polymer treating agent and 0.55-1.2 parts of processing aid;
the modification method of the modified bamboo fiber comprises the following steps:
s11: after the bamboo fiber with 60-100 meshes is treated by 5-10% of alkali, the bamboo fiber is washed by water and then neutralized by acid washing to obtain a bamboo fiber pretreatment substance;
s12: then drying for 4-6 h at 90-110 ℃, then carrying out spray treatment on the carbon nano tube coupling agent mixed solution at 60-80 ℃, bagging and sealing after proton irradiation, and activating for more than 20h to obtain modified bamboo fibers;
the PE or PP mixed material comprises:
wherein the PE mixed material is prepared by mixing 40-50 parts by mass of HDPE, 40-50 parts by mass of LLHDPE and 8-12 parts by mass of UHMWPE at high speed and drying; the HDPE melt index is 15-20 g/10min, the LLHDPE melt index is 20-40 g/10min, and the molecular weight of UHMWPE is 300-600 ten thousand;
the PP mixed material is PP pipeline material, and the organic polymer treating agent is polymer compatibilizer with polar group grafted chain or block chain, linear polymer hyperdispersant and high polymer with high melt flow rate and low melting point.
2. The natural bamboo fiber modified PE or PP composite material as claimed in claim 1, wherein the PE or PP composite material comprises the following raw materials in parts by mass:
50 parts by mass of modified bamboo fiber, 45 parts by mass of PE or PP mixed material, 6.5 parts by mass of organic polymer treating agent and 0.90 part by mass of processing aid.
3. The natural bamboo fiber modified PE or PP composite material as claimed in claim 1, wherein the base is NaOH or KOH, and the acid is 10% acetic acid;
the coupling agent is at least one of silane coupling agent, titanate coupling agent or aluminate coupling agent, and the using amount of the coupling agent is 1-3 wt% of the mass of the bamboo fiber.
4. The natural bamboo fiber modified PE or PP composite material as claimed in claim 1, wherein the specific operation steps of the spray treatment of the carbon nanotube coupling agent mixed solution are as follows:
s101: dispersing the carbon nano tube in 2-3 times of ethanol solvent to form suspension, adding 6-10% of tetrabutyl zirconate and 1-4% of pentadecyl phenol in the total amount of the carbon nano tube, stirring and reacting for 1-2h at 45-65 ℃, wherein the stirring speed is 450-550r or min, and after stirring, washing and drying to obtain a modified carbon nano tube;
s102: mixing chitosan and acetic acid according to the weight ratio of 1 to 5 to obtain a chitosan solution, then adding 1 to 5 percent of samarium chloride, 1 to 3 percent of coupling agent and 2 to 6 percent of modified carbon nano tube into the chitosan solution, and stirring and mixing fully to obtain a spraying agent;
s103: spraying the spraying agent on a product of S12 according to the weight ratio of 1.
5. The natural bamboo fiber modified PE or PP composite material as claimed in claim 1, wherein the processing aid comprises lubricant, antibacterial agent, anti-aging agent, ultraviolet absorber, and antioxidant, wherein the lubricant is at least one of PE wax or lacquer wax, and the content is 0.15-0.25%; the antibacterial agent is at least one of chitin, mustard and castor oil, and the content is 0.05-0.15%; the anti-aging agent is HS-622 or HS-962, and the content is 0.2-0.4%; the ultraviolet absorbent is UV328 or UV531:0.1 to 0.25 percent; the antioxidant is 225 or 215:0.05-0.15 percent.
6. A method for preparing the natural bamboo fiber modified PE or PP composite material as claimed in any one of claims 1 to 5, comprising the steps of:
the method comprises the following steps: weighing raw materials;
step two: mixing the modified bamboo fiber, the PE or PP mixed material, the organic polymer treating agent and the processing aid, performing melt extrusion and air drying granulation, and uniformly mixing and plasticizing to obtain a bamboo fiber modified PE or PP composite material;
the mixing, melt extrusion and granulation processes are completed by adopting a double-screw extruder, the melt extrusion process is divided into eleven working temperature zones, and the temperature is set as follows: first zone 120-140 ℃, second zone 135-150 ℃, head zone temperature: 130 to 140 ℃; the rotating speed of a screw in the melt extrusion process is 50-200 rpm, air drying granulation is adopted in the granulation process, and the processing temperature is obviously lower than that of a general PE or PP material.
7. The natural bamboo fiber modified PE or PP composite material as claimed in any one of claims 1 to 6 is suitable for various molding processes of extrusion, calendaring and die pressing, and is applied to obtain various products such as pipes, profiles, plates and sheets.
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