CN115124776A - 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 PDFInfo
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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 by mass of modified bamboo fiber, 25-65 parts by mass of PE or PP mixed material, 3-10 parts by mass of organic polymer treating agent and 0.55-1.2 parts by mass 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 mixing material, thereby reducing the carbonization and damage of 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
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 has excellent mechanical property, has higher tensile strength than other natural materials except hemp, and is very suitable for being 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 firstly adding polypropylene, bamboo fiber, a compatilizer and a plasticizer into a kneader, an internal mixer or a twin-screw extruder according to a certain proportion, mixing to prepare the bamboo fiber and polypropylene composite material, and then carrying out subsequent processes such as extrusion molding, calendaring molding, compression molding and the like to prepare a sheet, a plate, a pipe or a section of the bamboo fiber and polypropylene composite material, wherein the sheet, the plate, the pipe or the section can be used for manufacturing products such as structures, decorations, packages and the like. 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 technology.
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:
30-70 parts by mass of modified bamboo fiber, 25-65 parts by mass of PE or PP mixed material, 3-10 parts by mass of organic polymer treating agent and 0.55-1.2 parts by mass 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: treating 60-100-mesh bamboo fibers with 5-10% of alkali, then washing with water, neutralizing with acid washing, and drying to obtain a bamboo fiber pretreatment material;
s12: and then drying at 90-110 ℃ for 4-6 h, 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 pentadecylphenol of the total amount of the carbon nano tube, stirring and reacting for 1-2h at 45-65 ℃ at the stirring speed of 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 1:5 to obtain a chitosan solution, then adding 1-5% of samarium chloride, 1-3% of coupling agent and 2-6% of modified carbon nano tube, and stirring and mixing fully to obtain a spray;
s103: spraying the spraying agent on the product of S12 according to the weight ratio of 1:4, and then irradiating with proton at 100-500W for 1-5 min.
Preferably, the PE or PP blending material is as follows:
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 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.
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 hyper-dispersant 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 UV 531: 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: 120-140 ℃ in the first zone, 135-150 ℃ in the second-tenth zone, and the temperature in the first zone: 130-140 ℃; the rotating speed of the screw in the melt extrusion process is 50-200 rpm. The granulation process adopts air drying granulation. 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, calendaring 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 mixing material, thereby reducing the carbonization and damage of 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 is modified by alkali treatment, water washing and acid neutralization, the interface compatibility is improved by surface modification treatment of a coupling agent, and the interface improvement is further improved by establishing a PE or PP mixed material and bamboo fiber mixing environment in a high-speed mixer and spraying treatment.
The spraying treatment adopts the carbon nano tube as a bearing material with high specific surface area after being modified, and the carbon nano tube, the chitosan solution, the samarium chloride and the coupling agent form a spraying agent which 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 by mass of modified bamboo fiber, 25-65 parts by mass of PE or PP mixed material, 3-10 parts by mass of organic polymer treating agent and 0.55-1.2 parts by mass 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: treating 60-100-mesh bamboo fibers with 5-10% of alkali, then washing with water, neutralizing with acid washing, and drying to obtain a bamboo fiber pretreatment substance;
s12: and then drying at 90-110 ℃ for 4-6 h, spraying 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 pentadecylphenol of the total amount of the carbon nano tube, stirring and reacting for 1-2h at 45-65 ℃ at the stirring speed of 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 1:5 to obtain a chitosan solution, then adding 1-5% of samarium chloride, 1-3% of coupling agent and 2-6% of modified carbon nano tube, and stirring and mixing fully to obtain a spray;
s103: spraying the spraying agent on the product of S12 according to the weight ratio of 1:4, and then irradiating with proton at 100-500W for 1-5 min.
The PE or PP blending material of the embodiment is as follows:
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;
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 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 antiaging agent is HS-622 or HS-962, and the content is 0.2-0.4%; the ultraviolet absorbent is UV328 or UV 531: 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: 120-140 ℃ in the first zone, 135-150 ℃ in the second zone-ten zone, and the temperature in the first zone: 130-140 ℃; the rotating speed of the screw 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 of the embodiment 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: after the 60-mesh bamboo fiber is subjected to 5% alkali treatment, washing with water, neutralizing with acid washing, and drying to obtain a bamboo fiber pretreatment substance;
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 2 wt% 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 2 times of ethanol solvent to form suspension, adding 6 percent of tetrabutyl zirconate and 1 percent of pentadecylphenol of the total amount of the carbon nano tube, stirring and reacting for 1h at 45 ℃, wherein the stirring speed is 450r 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 1:5 to obtain a chitosan solution, then adding 1% of samarium chloride, 1% of hexadecyl trimethoxy silane and 2% of modified carbon nano tube into the chitosan solution, and stirring and mixing fully to obtain a spray;
s103: spraying the spray on the product of S12 according to the weight ratio of 1:4, and then irradiating with proton for 100W for 1 min.
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 comprises a lubricant, an antibacterial agent, an anti-aging agent, an ultraviolet absorber 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 UV 328: 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 to tenth zones 135 ℃, head zone temperature: 130 ℃; the screw rotation speed in the melt extrusion process is 50rpm, and the air drying granulation process 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: and 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 3 wt% 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 2-3 times of ethanol solvent to form suspension, adding tetrabutyl zirconate accounting for 10% of the total amount of the carbon nano tube and pentadecylphenol accounting for 4% 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 a weight ratio of 1:5 to obtain a chitosan solution, then adding samarium chloride accounting for 5% of the total amount of the chitosan solution, isopropyl dioleate acyloxy (dioctyl phosphate acyloxy) titanate accounting for 3% of the total amount of the chitosan solution and 6% of modified carbon nano tubes, and fully stirring and mixing to obtain a spray;
s103: spraying the spray on the product of S12 according to the weight ratio of 1:4, and then irradiating with protons for 500W for 1-5 min.
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 melt index of HDPE is 20g/10min, the melt index of LLHDPE is 40g/10min, and the molecular weight of 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 of the embodiment comprises a lubricant, an antibacterial agent, an anti-aging agent, an ultraviolet absorbent 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 a content of 0.15%; the anti-aging agent is HS-962, the content is 0.4%; the ultraviolet absorbent is UV 531: 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 150 ℃ to tenth zone, head zone temperature: 140 ℃; the screw speed during melt extrusion was 520 rpm. 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.
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: treating 80-mesh bamboo fiber with 7.5% alkali, then washing with water, neutralizing with acid wash, and drying to obtain bamboo fiber pretreatment;
s12: and then drying for 5h at 95 ℃, spraying the carbon nanotube coupling agent mixed solution at 70 ℃, bagging and sealing after proton irradiation, and finally activating for 20h 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 3 wt% 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 1:5 to obtain a chitosan solution, then adding 5% of samarium chloride, 3% of distearoyl isopropyl aluminate and 6% of modified carbon nano-tubes into the chitosan solution, and fully stirring and mixing to obtain a spray;
s103: spraying the spray on the product of S12 according to the weight ratio of 1:4, and then irradiating with protons for 500W for 5 min.
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 comprises a lubricant, an antibacterial agent, an anti-aging agent, an ultraviolet absorber 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 UV 531: 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 165 rpm. 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, calendering 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 is prepared by mixing the bamboo fiber and the PE mixed materials according to the embodiment 3 by weight.
Comparative example 2.
The difference from example 3 is that the PE blend stock is common PE pipe stock, and the rest is all according to 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;
standing the bamboo fiber, titanate coupling agent and water according to the weight ratio of 1:2:4 at 65-75 ℃ for reaction for 1-2h, and then washing and drying.
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 the weight ratio of 1:5 to obtain a chitosan solution, then adding 2% of sodium alginate and 5% of silica sol, and stirring and mixing fully to obtain a spray;
s102: spraying the spray on a product of S12 according to a weight ratio of 1:4, and then irradiating with protons for 500W for 5 min;
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;
and (3) carrying out injection molding and sample preparation on the products obtained in the examples 1-3 and the comparative examples 1-6, and testing the performance, wherein the specific test method comprises the following steps:
static bending strength is measured according to the measurement of the static bending strength of GBT 12626.9-1990 hard fiberboard;
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 measurement of GB/T1043.1-2008 plastic simple support dyeing notch 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 10 wt%, 15 wt%, 20 wt%, 25 wt% and 30 wt%, and the test time is as follows: 2 h; a load of 500N; rotating speed: 200 rpm. 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 is poor at > 10%.
And (3) corrosion resistance testing: placing various material samples in glacial acetic acid, ethanol, solvent oil, 60% strong base, 20% saline solution, 30% sulfuric acid and aqua regia respectively for more than 8h, 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 test of products obtained in examples 1 to 3
Table 2 results of performance test of samples obtained in comparative examples 1 to 7
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 (10)
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 by mass of modified bamboo fiber, 25-65 parts by mass of PE or PP mixed material, 3-10 parts by mass of organic polymer treating agent and 0.55-1.2 parts by mass of processing aid.
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 modification method of the modified bamboo fiber is as follows:
s11: after 5-10% alkali treatment is carried out on 60-100-mesh bamboo fibers, washing is carried out, and then neutralization treatment is carried out by acid washing, so as to obtain bamboo fiber pretreatment substances;
s12: and then drying for 4-6 h at 90-110 ℃, spraying the carbon nanotube 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.
4. The natural bamboo fiber modified PE or PP composite material as claimed in claim 3, 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.
5. The natural bamboo fiber modified PE or PP composite material as claimed in claim 3, wherein the specific operation steps of the spraying treatment of the carbon nanotube coupling agent mixed solution are as follows:
s101: dispersing carbon nano tubes in 2-3 times of ethanol solvent to form suspension, then adding 6-10% of tetrabutyl zirconate and 1-4% of pentadecylphenol based on the total amount of the carbon nano tubes, stirring and reacting for 1-2h at 45-65 ℃ with the stirring speed of 450-550r or min, and after stirring, washing and drying to obtain modified carbon nano tubes;
s102: mixing chitosan and acetic acid according to the weight ratio of 1:5 to obtain a chitosan solution, then adding 1-5% of samarium chloride, 1-3% of coupling agent and 2-6% of modified carbon nano tube, and stirring and mixing fully to obtain a spray;
s103: spraying the spray on the product of S12 according to the weight ratio of 1:4, and then irradiating with proton of 100-500W for 1-5 min.
6. The natural bamboo fiber modified PE or PP composite material as claimed in claim 3, wherein the PE or PP blend stock comprises:
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;
wherein the PP mixed material is a PP pipeline material.
7. The natural bamboo fiber modified PE or PP composite material as claimed in claim 1, wherein the organic polymer treating agent is a polymer compatibilizer with polar group graft chain (point) or block chain, such as one or combination of PE-G-MA, EPDM-G-MA, EVA-G-MA, PP-G-MA, linear polymer hyper-dispersant and high polymer with high melt flow rate and low melting point, such as EVA.
8. 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 antiaging agent is HS-622 or HS-962, and the content is 0.2-0.4%; the ultraviolet absorbent is UV328 or UV 531: 0.1 to 0.25 percent; the antioxidant is 225 or 215: 0.05 to 0.15 percent.
9. The preparation method of the environment-friendly bamboo fiber modified PE or PP composite material as claimed in any one of claims 1 to 8, characterized by comprising 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: 120-140 ℃ in the first zone, 135-150 ℃ in the second-tenth zone, and the temperature in the first zone: 130-140 ℃; the rotating speed of a screw 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.
10. The environment-friendly bamboo fiber modified PE or PP composite material as defined in any one of claims 1 to 8, which is suitable for various molding processes of extrusion, calendering and die pressing, and is used for obtaining various products such as pipes, profiles, plates and sheets.
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