CN112724518A - Environment-friendly rubber pipe and preparation method thereof - Google Patents
Environment-friendly rubber pipe and preparation method thereof Download PDFInfo
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- CN112724518A CN112724518A CN202011579903.1A CN202011579903A CN112724518A CN 112724518 A CN112724518 A CN 112724518A CN 202011579903 A CN202011579903 A CN 202011579903A CN 112724518 A CN112724518 A CN 112724518A
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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
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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Abstract
The invention discloses an environment-friendly rubber pipe, which comprises a modified polypropylene resin pipe body and a TPE elastomer rear plug; the invention also discloses a preparation method of the environment-friendly rubber pipe. The rice straw fiber and the polypropylene are subjected to cross-linking polymerization to endow the composite material with degradable and reproducible environmental protection performance, and the-OH number on the surface of the fiber is reduced by modifying the rice straw fiber through the modified silane coupling agentThe hydrophobicity and lipophilicity of the composite material are increased, the compatibility of the fiber and a polymer matrix is improved, and the aluminum sol is thermally decomposed into nano Al2O3Nano Al2O3The rear plug shows a certain degree of lipophilicity, the lipophilicity of the plant fiber and the polypropylene is improved by the synergistic cooperation of the plant fiber and the polysiloxane, in addition, in the preparation process of the TPE elastomer rear plug, the feeding ratio of the SEBS elastomer to the polypropylene is strictly controlled to be 0.03:1, and the rear plug prepared according to the ratio has excellent light transmittance.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and relates to an environment-friendly rubber tube and a preparation method thereof.
Background
Polypropylene is a thermoplastic polymer polymerized from propylene as a monomer, abbreviated as PP. The polypropylene has rich material source, low cost, low relative density, excellent machining performance, high yield strength, high tensile strength, high elastic modulus, high chemical resistance and other excellent comprehensive performance, and the product is non-toxic, smell-less and bright and may be used widely in automobile, electric appliance, daily use article and furniture. At present, the industry is only concerned about the mechanical and physical properties of materials such as impact resistance and compression resistance, and is gradually interested in materials with special properties such as corrosion resistance, static resistance, aging resistance, environmental protection and degradability, and natural plant fiber materials have the advantages of wide sources, environmental friendliness, degradability, reproducibility, low price and the like, and are used as reinforcing materials to be blended with polypropylene to prepare polymer composite materials to meet the requirements of environmental protection, energy conservation, recoverability and the like.
Because the natural plant fiber with stronger polarity has poor compatibility with a nonpolar polymer matrix, the interface bonding between the natural fiber and the polymer matrix is poor, and the mechanical property of the composite material is finally influenced. The chemical modifier is used for modifying the natural plant fiber, and the main purposes are to reduce the polarity of the surface of the natural plant fiber and improve the compatibility of the fiber and a nonpolar polymer matrix, so that the interface bonding between the fiber and the polymer matrix is finally improved. The silane coupling agent is a common chemical modification mode for modifying the surface of natural plant fibers, but the hardness and the light transmittance of the synthetic polymer treated by the silane coupling agent are not obviously improved, so that a method for solving the problem is urgently needed.
Disclosure of Invention
The invention aims to provide an environment-friendly rubber tube and a preparation method thereof, rice straw fiber and polypropylene are subjected to cross-linking polymerization to endow a composite material with easily degradable and reproducible environment-friendly performance, the rice straw fiber is modified by a modified silane coupling agent, silanol groups generated by hydrolysis of the modified silane coupling agent can be subjected to dehydration condensation reaction with hydroxyl groups on the surface of the fiber to form-Si-O-C-covalent bonds, so that polysiloxane oligomers are grafted to the surface of the fiber, the hydrophobicity and lipophilicity of the fiber are increased due to the reduction of the-OH number on the surface of the fiber, the compatibility of the fiber and a polymer matrix is improved, and aluminum sol is thermally decomposed into nano Al2O3Nano Al2O3The modified TPE elastomer rear plug has the advantages that the modified TPE elastomer rear plug shows certain lipophilicity, the lipophilicity is improved by the synergistic cooperation of the modified TPE elastomer rear plug and polysiloxane, the feeding proportion of the SEBS elastomer and the polypropylene is strictly controlled to be 0.03:1, the rear plug prepared according to the proportion has excellent light transmittance, and the inorganic nano Al formed by pyrolysis of the modified coupling agent is inorganic nano Al2O3The regularity of the polypropylene main chain is destroyed, the crystallinity is reduced, the transparency of the polypropylene is also improved, and the light transmission function of the product is met2O3The regularity of the polypropylene main chain is destroyed, the crystallinity is reduced, and the transparency of the polypropylene is improved, so that the light transmission function of the product is realized.
The purpose of the invention can be realized by the following technical scheme:
an environment-friendly rubber pipe comprises a modified polypropylene resin pipe body and a TPE elastomer rear plug;
the environment-friendly rubber tube is prepared by the following steps:
step A1, pouring polypropylene, rice straw powder, a modified coupling agent, active color master batch, a plasticizer, a dispersant and an antioxidant into a high-temperature reaction kettle, and fully mechanically stirring and mixing at the temperature of 120 ℃ and 130 ℃ to prepare a mixture;
step A2, feeding the mixture prepared in the step A1 into a screw extrusion granulator, setting the rotation speed of a screw and the temperature of each section, extruding and granulating the mixture through a double-thread screw, and then putting the granulated material into a dryer to be stirred and dried for 20-30 minutes at the temperature of 100-;
step A3, placing the modified polypropylene resin prepared in the step A2 into a feed inlet of an injection molding machine, melting, quickly injecting the melted modified polypropylene resin into a mold cavity at high pressure by means of the thrust of a screw, performing injection molding, and performing cooling forming to obtain a modified polypropylene resin tube body;
step A4, drying polypropylene and SEBS elastomers in a vacuum drying oven at the temperature of 80-85 ℃ for 6-8 hours, adding the dried polypropylene, SEBS elastomers and modified coupling agents into a high-speed stirrer, stirring and mixing, transferring to a mixing roll, adding a dispersing agent, mixing, transferring to an injection molding machine, injection molding, cooling, and preparing TPE elastomer rear plugs;
and step A5, assembling the TPE elastomer rear plug prepared in the step A4 into the modified polypropylene resin pipe body prepared in the step A3 through a cylinder, and thus obtaining the environment-friendly rubber pipe.
Further, the polypropylene, the rice straw powder, the modified coupling agent, the active color master batch, the plasticizer, the dispersant and the antioxidant in the step A1 are 30-35 parts of polypropylene, 20-25 parts of rice straw powder, 6-8 parts of modified coupling agent and 4-6 parts of active color master batch by weight, 1-3 parts of plasticizer, 1-3 parts of dispersant and 1-3 parts of antioxidant, wherein the plasticizer is one or more of dioctyl adipate, diisodecyl adipate, epoxy fatty acid butyl ester and epoxy tetrahydrodioctyl phthalate which are mixed according to any proportion, the dispersant is one or more of glyceryl tristearate, microcrystalline paraffin and polyethylene wax which are mixed according to any proportion, the antioxidant is one or more of polyacrylic acid vinegar, tert-butyl hydroquinone and diisodecyl phosphite which are mixed according to any proportion, and the stirring speed is 180-charge 200 rpm; the rotation speed of the screw in the step A2 is 180-210rpm, the temperature of each section is 130-150 ℃ at the first section, 160-180 ℃ at the second section and 220 ℃ at the third section; the melting temperature of the injection molding machine in the step A3 is 190-210 ℃; the polypropylene, the SEBS elastomer, the modified coupling agent and the dispersing agent in the step A4 account for 45-50 parts by weight of polypropylene, 1.35-1.5 parts by weight of SEBS elastomer, 3-5 parts by weight of modified coupling agent and 0.5-1 part by weight of dispersing agent, the dispersing agent is one of microcrystalline paraffin and polyethylene wax, and the melting temperature of an injection molding machine is 200-215 ℃.
Further, the modified coupling agent of step A1 is prepared by the following steps:
step S1, adding tetraethoxysilane, isopropanol, isobutanol and deionized water into a reaction kettle, mixing and stirring, adding a mixed solution of glacial acetic acid and hydrochloric acid, adjusting the pH to 4.5-5.5, magnetically stirring at normal temperature for 16-18 hours to form silica sol, adding KH-560, mixing and stirring for 2 hours to prepare the silica sol for later use;
step S2, refluxing and stirring aluminum isopropoxide and deionized water at 80-90 ℃ for 1-1.5 hours, adding nitric acid to adjust the pH value to 3-4, then heating to 100-105 ℃, refluxing and stirring to be clear, and cooling to obtain aluminum sol;
and step S3, adding the silica sol prepared in the step S1 into a flask, adding the aluminum sol prepared in the step S2, and magnetically stirring for 2-4 hours at the temperature of 40-45 ℃ to prepare the modified coupling agent.
Further, the dosage ratio of the ethyl orthosilicate, the isopropanol, the isobutanol, the deionized water and the KH-560 in the step S1 is 0.03-0.05 g: 2-4mL, 3-5 mL: 40-50 mL: 0.02-0.03g, the volume ratio of the glacial acetic acid to the hydrochloric acid is 2:1 to prepare a mixed solution, the concentration of the glacial acetic acid is 0.5g/L, the concentration of the hydrochloric acid is 0.5g/L, and the magnetic stirring speed is 160-180 rpm.
Further, the usage ratio of the aluminum isopropoxide and the deionized water in the step S2 is 0.06g-0.08 g: 35-45mL, and the volume fraction of the nitric acid is 45%.
Further, the mass ratio of the silica sol to the aluminum sol in the step S3 is 3:1, and the magnetic stirring speed is 200-220 rpm.
The specific preparation method of the environment-friendly rubber tube comprises the following steps:
step A1, pouring polypropylene, rice straw powder, a modified coupling agent, an active color master batch, a plasticizer, a dispersant and an antioxidant into a high-temperature reaction kettle, heating, and then fully mechanically stirring and mixing to obtain a mixture;
step A2, feeding the mixture prepared in the step A1 into a screw extrusion granulator, setting the rotation speed of a screw and the temperature of each section, extruding and granulating the mixture through a double-thread screw, and then putting the granulated material into a dryer to be stirred and dried for 20-30 minutes at the temperature of 100-;
step A3, placing the modified polypropylene resin prepared in the step A2 into a feed inlet of an injection molding machine, melting, quickly injecting the melted modified polypropylene resin into a mold cavity at high pressure by means of the thrust of a screw, performing injection molding, and performing cooling forming to obtain a modified polypropylene resin tube body;
step A4, drying the modified polypropylene resin and the SEBS elastomer in a vacuum drying oven at the temperature of 80-85 ℃ for 6-8 hours, adding the dried polypropylene and the SEBS elastomer into a high-speed stirrer, stirring and mixing, transferring to a mixing roll, adding a dispersing agent, mixing, transferring to an injection molding machine, injection molding, and cooling to obtain a TPE elastomer rear plug;
and step A5, assembling the TPE elastomer rear plug prepared in the step A4 into the modified polypropylene resin pipe body prepared in the step A3 through a cylinder, and thus obtaining the environment-friendly rubber pipe.
The invention has the beneficial effects that: the invention aims to provide an environment-friendly rubber tube and a preparation method thereof, rice straw fiber and polypropylene are subjected to cross-linking polymerization to endow a composite material with easily degradable and reproducible environment-friendly performance, the rice straw fiber is modified by a modified silane coupling agent, silanol groups generated by hydrolysis of the modified silane coupling agent can be subjected to dehydration condensation reaction with hydroxyl groups on the surface of the fiber to form-Si-O-C-covalent bonds, so that polysiloxane oligomers are grafted to the surface of the fiber, the hydrophobicity and lipophilicity of the fiber are increased due to the reduction of the-OH number on the surface of the fiber, the compatibility of the fiber and a polymer matrix is improved, and aluminum sol is thermally decomposed into nano Al2O3Nano Al2O3The modified silicone oil has certain lipophilicity, is cooperated with polysiloxane to enhance the phase affinity of plant fiber and polypropylene, forms an organic/inorganic composite structure by hydrolysis-polymerization reaction of silica sol, aluminum sol and polypropylene, has a basic framework composed of Si-O-Si, Si-O-Al and Al-O-Al, enhances the cross-linking strength between chains by forming Si-O-Al, enables the chains to exhibit excellent hardness, and simultaneously, in the preparation process of the TPE elastomer rear plug, the feeding proportion of the SEBS elastomer and the polypropylene is strictly controlled to be 0.03:1, the rear plug prepared at the ratio has excellent light transmittance, because the SEBS can effectively prevent polypropylene from crystallizing, refine crystal grains, when the crystal grain size of the crystal region is smaller than the wavelength of visible light, the transparency of the polymer is improved, and the inorganic nano Al formed by pyrolysis of the modified coupling agent is modified.2O3The regularity of the polypropylene main chain is destroyed, the crystallinity is reduced, the transparency of the polypropylene is also improved, and the light transmission function of the product is met.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the 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.
Example 1
An environment-friendly rubber pipe comprises a modified polypropylene resin pipe body and a TPE elastomer rear plug;
the environment-friendly rubber tube is prepared by the following steps:
step A1, pouring 30 parts of polypropylene, 20 parts of rice straw powder, 6 parts of modified coupling agent, 4 parts of active color master batch, 1 part of dioctyl adipate, 1 part of glyceryl tristearate and 1 part of tert-butyl hydroquinone into a high-temperature reaction kettle, heating at 120 ℃, and then fully and mechanically stirring and mixing to obtain a mixture, wherein the stirring speed is 180 rpm;
step A2, feeding the mixture prepared in the step A1 into a screw extrusion granulator, setting the rotation speed of a screw and the temperature of each section, extruding and granulating the mixture through a double-thread screw, then putting the granulated material into a dryer, stirring and drying for 30 minutes at 105 ℃, and taking out the granulated material to obtain the modified polypropylene resin, wherein the rotation speed of the screw is 180rpm, the temperature of each section is 130 ℃ in the first section, 160 ℃ in the second section and 190 ℃ in the third section;
step A3, placing the modified polypropylene resin prepared in the step A2 into a feed inlet of an injection molding machine, melting, quickly injecting the melted modified polypropylene resin into a die cavity at high pressure by means of the thrust of a screw rod, performing injection molding, and cooling and forming to obtain a modified polypropylene resin tube body, wherein the melting temperature of the injection molding machine is 210 ℃;
step A4, drying polypropylene and SEBS elastomers in a vacuum drying oven at 80 ℃ for 6 hours, adding 45 parts of dried polypropylene, 1.35 parts of SEBS elastomers and 3 parts of modified coupling agents into a high-speed stirring machine, stirring and mixing, transferring to a mixing roll, adding 0.5 part of polyethylene wax for mixing, then transferring to an injection molding machine for injection molding, and cooling to obtain a TPE elastomer rear plug, wherein the melting temperature of the injection molding machine is 200 ℃;
and step A5, assembling the TPE elastomer rear plug prepared in the step A4 into the modified polypropylene resin pipe body prepared in the step A3 through a cylinder, and thus obtaining the environment-friendly rubber pipe.
Wherein, the modified coupling agent is prepared by the following steps:
step S1, adding 0.03g of ethyl orthosilicate, 2mL of isopropanol, 3mL of isobutanol and 40mL of deionized water into a reaction kettle, mixing and stirring, adding a mixed solution of glacial acetic acid and hydrochloric acid, adjusting the pH to 4.5, magnetically stirring at normal temperature for 16 hours to form silica sol, then adding 0.02gKH-560, mixing and stirring for 2 hours to prepare the silica sol for later use, wherein the glacial acetic acid and the hydrochloric acid are prepared into a mixed solution according to a volume ratio of 2:1, the concentration of the glacial acetic acid is 0.5g/L, the concentration of the hydrochloric acid is 0.5g/L, and the magnetic stirring speed is 180 rpm;
step S2, refluxing and stirring 0.06g of aluminum isopropoxide and 35mL of deionized water at 80 ℃ for 1.5 hours, adding nitric acid to adjust the pH value to 3, heating to 100 ℃, refluxing and stirring to clarify, and cooling to obtain aluminum sol, wherein the volume fraction of the nitric acid is 45%;
and S3, adding the silica sol prepared in the step S1 into a flask, adding the aluminum sol prepared in the step S2, controlling the temperature to be 40-45 ℃, and magnetically stirring for 2-4 hours to prepare the modified coupling agent, wherein the mass ratio of the silica sol to the aluminum sol is 3:1, and the magnetic stirring speed is 220 rpm.
Example 2
An environment-friendly rubber pipe comprises a modified polypropylene resin pipe body and a TPE elastomer rear plug;
the environment-friendly rubber tube is prepared by the following steps:
step A1, pouring 33 parts of polypropylene, 23 parts of rice straw powder, 7 parts of modified coupling agent, 5 parts of active color master batch, 2 parts of diisodecyl adipate, 2 parts of microcrystalline paraffin and 2 parts of diisodecyl phosphite into a high-temperature reaction kettle, heating at 125 ℃, and then fully and mechanically stirring and mixing to obtain a mixture, wherein the stirring speed is 190 rpm;
step A2, feeding the mixture prepared in the step A1 into a screw extrusion granulator, setting the rotation speed of a screw and the temperature of each section, extruding and granulating the mixture through a double-thread screw, then putting the granulated material into a dryer, stirring and drying for 30 minutes at 105 ℃, and taking out the granulated material to obtain the modified polypropylene resin, wherein the rotation speed of the screw is 190rpm, the temperature of each section is 140 ℃ in the first section, 160 ℃ in the second section and 180 ℃ in the third section;
step A3, placing the modified polypropylene resin prepared in the step A2 into a feed inlet of an injection molding machine, melting, quickly injecting the melted modified polypropylene resin into a die cavity at high pressure by means of the thrust of a screw rod, performing injection molding, and cooling and forming to obtain a modified polypropylene resin tube body, wherein the melting temperature of the injection molding machine is 200 ℃;
step A4, drying polypropylene and SEBS elastomers in a vacuum drying oven at 85 ℃ for 8 hours, adding 45 parts of dried polypropylene, 1.35 parts of SEBS elastomers and 4 parts of modified coupling agents into a high-speed stirring machine, stirring and mixing, transferring to a mixing roll, adding 1 part of polyethylene wax for mixing, then transferring to an injection molding machine for injection molding, and cooling to obtain a TPE elastomer rear plug, wherein the melting temperature of the injection molding machine is 210 ℃;
and step A5, assembling the TPE elastomer rear plug prepared in the step A4 into the modified polypropylene resin pipe body prepared in the step A3 through a cylinder, and thus obtaining the environment-friendly rubber pipe.
Wherein, the modified coupling agent is prepared by the following steps:
step S1, adding 0.04g of ethyl orthosilicate, 3mL of isopropanol, 4mL of isobutanol and 45mL of deionized water into a reaction kettle, mixing and stirring, adding a mixed solution of glacial acetic acid and hydrochloric acid, adjusting the pH to 4.5, magnetically stirring at normal temperature for 16 hours to form silica sol, then adding 0.025gKH-560, mixing and stirring for 2 hours to prepare the silica sol for later use, wherein the glacial acetic acid and the hydrochloric acid are prepared into a mixed solution according to a volume ratio of 2:1, the concentration of the glacial acetic acid is 0.5g/L, the concentration of the hydrochloric acid is 0.5g/L, and the magnetic stirring speed is 170 rpm;
step S2, refluxing and stirring 0.07g of aluminum isopropoxide and 40mL of deionized water at 90 ℃ for 1 hour, adding nitric acid to adjust the pH to 4, heating to 100 ℃, refluxing and stirring to clarify, and cooling to obtain aluminum sol, wherein the volume fraction of the nitric acid is 45%;
and S3, adding the silica sol prepared in the step S1 into a flask, adding the aluminum sol prepared in the step S2, controlling the temperature to be 40-45 ℃, and magnetically stirring for 2-4 hours to prepare the modified coupling agent, wherein the mass ratio of the silica sol to the aluminum sol is 3:1, and the magnetic stirring speed is 210 rpm.
Example 3
An environment-friendly rubber pipe comprises a modified polypropylene resin pipe body and a TPE elastomer rear plug;
the environment-friendly rubber tube is prepared by the following steps:
step A1, pouring 35 parts of polypropylene, 25 parts of rice straw powder, 8 parts of modified coupling agent, 6 parts of active color master batch, 3 parts of diisodecyl adipate, 3 parts of microcrystalline paraffin and 3 parts of diisodecyl phosphite into a high-temperature reaction kettle, heating at 130 ℃, and then fully and mechanically stirring and mixing to obtain a mixture, wherein the stirring speed is 200 rpm;
step A2, feeding the mixture prepared in the step A1 into a screw extrusion granulator, setting the rotation speed of a screw and the temperature of each section, extruding and granulating the mixture through a double-thread screw, then putting the granulated material into a dryer, stirring and drying for 20 minutes at the temperature of 110 ℃, and taking out the granulated material to obtain the modified polypropylene resin, wherein the rotation speed of the screw is 210rpm, the temperature of each section is 150 ℃ in the first section, 180 ℃ in the second section and 200 ℃ in the third section;
step A3, placing the modified polypropylene resin prepared in the step A2 into a feed inlet of an injection molding machine, melting, quickly injecting the melted modified polypropylene resin into a die cavity at high pressure by means of the thrust of a screw rod, performing injection molding, and cooling and forming to obtain a modified polypropylene resin tube body, wherein the melting temperature of the injection molding machine is 210 ℃;
step A4, drying polypropylene and SEBS elastomers in a vacuum drying oven at 85 ℃ for 8 hours, adding 50 parts of dried polypropylene, 1.5 parts of SEBS elastomers and 5 parts of modified coupling agents into a high-speed stirring machine, stirring and mixing, transferring to a mixing roll, adding 1 part of polyethylene wax for mixing, then transferring to an injection molding machine for injection molding, and cooling to obtain a TPE elastomer rear plug, wherein the melting temperature of the injection molding machine is 215 ℃;
and step A5, assembling the TPE elastomer rear plug prepared in the step A4 into the modified polypropylene resin pipe body prepared in the step A3 through a cylinder, and thus obtaining the environment-friendly rubber pipe.
Wherein, the modified coupling agent is prepared by the following steps:
step S1, adding 0.05g of ethyl orthosilicate, 4mL of isopropanol, 5mL of isobutanol and 50mL of deionized water into a reaction kettle, mixing and stirring, adding a mixed solution of glacial acetic acid and hydrochloric acid, adjusting the pH to 4.5, magnetically stirring at normal temperature for 16 hours to form silica sol, then adding 0.03gKH-560, mixing and stirring for 2 hours to prepare the silica sol for later use, wherein the glacial acetic acid and the hydrochloric acid are prepared into a mixed solution according to a volume ratio of 2:1, the concentration of the glacial acetic acid is 0.5g/L, the concentration of the hydrochloric acid is 0.5g/L, and the magnetic stirring speed is 170 rpm;
step S2, refluxing and stirring 0.08g of aluminum isopropoxide and 45mL of deionized water at 90 ℃ for 1 hour, adding nitric acid to adjust the pH value to 4, heating to 100 ℃, refluxing and stirring to clarify, and cooling to obtain aluminum sol, wherein the volume fraction of the nitric acid is 45%;
and S3, adding the silica sol prepared in the step S1 into a flask, adding the aluminum sol prepared in the step S2, controlling the temperature to be 40-45 ℃, and magnetically stirring for 2-4 hours to prepare the modified coupling agent, wherein the mass ratio of the silica sol to the aluminum sol is 3:1, and the magnetic stirring speed is 220 rpm.
Comparative example 1
A commercially available environment-friendly rubber tube.
Comparative example 2
Comparative example 2 preparation of eco-friendly hose referring to example 1, except for the preparation of TPE elastomer rear plug in step a4, without adding a modified coupling agent.
The following performance tests were performed on the hoses obtained in examples 1 to 3 and comparative examples 1 and 2:
the pipes and the rear plugs obtained in examples 1 to 3 and comparative examples 1 and 2 were tested for their degradation performance by the following test methods: the hose was cut into 10mm × 40mm specimens and vacuum-dried at room temperature for 24 hours for use. Mixing and stirring soil and water according to a mass ratio of 1:10 for 2 hours, standing for 24 hours, taking supernatant as degradation liquid for later use, accurately weighing sample strips, putting the sample strips into the degradation liquid, standing for 30 days and 90 days respectively, washing the degraded sample strips with distilled water, drying in a vacuum drying oven at 30 ℃ to obtain a constant weight, accurately weighing, calculating the weight loss rate of the sample strips, taking 3 parallel samples from each group, and calculating the average value; carrying out light transmittance and haze test on the rear plug according to the national standard GB/T2410-2008, testing on a WGT-S light transmittance haze instrument, wherein the thickness of a sample is 1mm, and testing 3 points in an experiment to obtain an average value; at room temperature, the hardness of the tube body is measured by using a shore durometer, each sample is tested for 3 points, the average value is taken to calculate the hardness, and the test data is shown in table 1:
TABLE 1
As can be seen from table 1, the tube body and the rear plug of the hose prepared in examples 1 to 3 are excellent in degradability, exhibit environmental protection characteristics, and have better hardness than the comparative example, and the rear plug prepared in examples 1 to 3 has higher light transmittance and lower haze than the comparative example, which indicates that the examples have better transparency and meet the appearance requirements of the rear plug product.
The preferred embodiments of the invention disclosed above are intended to be illustrative only. The preferred embodiments are not intended to be exhaustive or to limit the invention to the precise embodiments disclosed. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best utilize the invention. The invention is limited only by the claims and their full scope and equivalents.
Claims (7)
1. An environment-friendly rubber hose is characterized by comprising a modified polypropylene resin hose body and a TPE elastomer rear plug;
the environment-friendly rubber tube is prepared by the following steps:
step A1, pouring polypropylene, rice straw powder, a modified coupling agent, active color master batch, a plasticizer, a dispersant and an antioxidant into a high-temperature reaction kettle, and fully mechanically stirring and mixing at the temperature of 120 ℃ and 130 ℃ to prepare a mixture;
step A2, feeding the mixture prepared in the step A1 into a screw extrusion granulator, setting the rotation speed of a screw and the temperature of each section, extruding and granulating the mixture through a double-thread screw, and then putting the granulated material into a dryer to be stirred and dried for 20-30 minutes at the temperature of 100-;
step A3, placing the modified polypropylene resin prepared in the step A2 into a feed inlet of an injection molding machine, melting, quickly injecting the melted modified polypropylene resin into a mold cavity at high pressure by means of the thrust of a screw, performing injection molding, and performing cooling forming to obtain a modified polypropylene resin tube body;
step A4, drying polypropylene and SEBS elastomers in a vacuum drying oven at the temperature of 80-85 ℃ for 6-8 hours, adding the dried polypropylene, SEBS elastomers and modified coupling agents into a high-speed stirrer, stirring and mixing, transferring to a mixing roll, adding a dispersing agent, mixing, transferring to an injection molding machine, injection molding, cooling, and preparing TPE elastomer rear plugs;
and step A5, assembling the TPE elastomer rear plug prepared in the step A4 into the modified polypropylene resin pipe body prepared in the step A3 through a cylinder, and thus obtaining the environment-friendly rubber pipe.
2. The environment-friendly hose according to claim 1, wherein: the weight parts of the polypropylene, the rice straw powder, the modified coupling agent, the active color master batch, the plasticizer, the dispersant and the antioxidant in the step A1 are 30-35 parts of polypropylene, 20-25 parts of rice straw powder, 6-8 parts of modified coupling agent, 4-6 parts of active color master batch, 1-3 parts of plasticizer, 1-3 parts of dispersant and 1-3 parts of antioxidant, the plasticizer is one or more of dioctyl adipate, diisodecyl adipate, epoxy fatty acid butyl ester and epoxy tetrahydrodioctyl phthalate which are mixed according to any proportion, the dispersant is one or more of glyceryl tristearate, microcrystalline paraffin and polyethylene wax which are mixed according to any proportion, the antioxidant is one or more of polyacrylic acid vinegar, tert-butyl hydroquinone and diisodecyl phosphite which are mixed according to any proportion, and the stirring speed is 180-200 rpm; the rotation speed of the screw in the step A2 is 180-210rpm, the temperature of each section is 130-150 ℃ at the first section, 160-180 ℃ at the second section and 220 ℃ at the third section; the melting temperature of the injection molding machine in the step A3 is 190-210 ℃; the polypropylene, the SEBS elastomer, the modified coupling agent and the dispersing agent in the step A4 account for 45-50 parts by weight of polypropylene, 1.35-1.5 parts by weight of SEBS elastomer, 3-5 parts by weight of modified coupling agent and 0.5-1 part by weight of dispersing agent, the dispersing agent is one of microcrystalline paraffin and polyethylene wax, and the melting temperature of an injection molding machine is 200-215 ℃.
3. The environment-friendly hose according to claim 1, wherein: the modified coupling agent of the step A1 is prepared by the following steps:
step S1, adding tetraethoxysilane, isopropanol, isobutanol and deionized water into a reaction kettle, mixing and stirring, adding a mixed solution of glacial acetic acid and hydrochloric acid, adjusting the pH to 4.5-5.5, magnetically stirring at normal temperature for 16-18 hours to form silica sol, adding KH-560, mixing and stirring for 2 hours to prepare the silica sol for later use;
step S2, refluxing and stirring aluminum isopropoxide and deionized water at 80-90 ℃ for 1-1.5 hours, adding nitric acid to adjust the pH value to 3-4, then heating to 100-105 ℃, refluxing and stirring to be clear, and cooling to obtain aluminum sol;
and step S3, adding the silica sol prepared in the step S1 into a flask, adding the aluminum sol prepared in the step S2, and magnetically stirring for 2-4 hours at the temperature of 40-45 ℃ to prepare the modified coupling agent.
4. The environment-friendly hose according to claim 3, wherein: the dosage ratio of the ethyl orthosilicate, the isopropanol, the isobutanol, the deionized water and the KH-560 in the step S1 is 0.03-0.05 g: 2-4mL, 3-5 mL: 40-50 mL: 0.02-0.03g, the volume ratio of the glacial acetic acid to the hydrochloric acid is 2:1 to prepare a mixed solution, the concentration of the glacial acetic acid is 0.5g/L, the concentration of the hydrochloric acid is 0.5g/L, and the magnetic stirring speed is 160-180 rpm.
5. The environment-friendly hose according to claim 3, wherein: the dosage ratio of the aluminum isopropoxide to the deionized water in the step S2 is 0.06g-0.08 g: 35-45mL, and the volume fraction of the nitric acid is 45%.
6. The environment-friendly hose according to claim 3, wherein: the mass ratio of the silica sol to the aluminum sol in the step S3 is 3:1, and the magnetic stirring speed is 200-220 rpm.
7. A preparation method of an environment-friendly rubber hose is characterized by comprising the following steps: the preparation method comprises the following preparation steps:
step A1, pouring polypropylene, rice straw powder, a modified coupling agent, an active color master batch, a plasticizer, a dispersant and an antioxidant into a high-temperature reaction kettle, heating, and then fully mechanically stirring and mixing to obtain a mixture;
step A2, feeding the mixture prepared in the step A1 into a screw extrusion granulator, setting the rotation speed of a screw and the temperature of each section, extruding and granulating the mixture through a double-thread screw, and then putting the granulated material into a dryer to be stirred and dried for 20-30 minutes at the temperature of 100-;
step A3, placing the modified polypropylene resin prepared in the step A2 into a feed inlet of an injection molding machine, melting, quickly injecting the melted modified polypropylene resin into a mold cavity at high pressure by means of the thrust of a screw, performing injection molding, and performing cooling forming to obtain a modified polypropylene resin tube body;
step A4, drying the modified polypropylene resin and the SEBS elastomer in a vacuum drying oven at the temperature of 80-85 ℃ for 6-8 hours, adding the dried polypropylene and the SEBS elastomer into a high-speed stirrer, stirring and mixing, transferring to a mixing roll, adding a dispersing agent, mixing, transferring to an injection molding machine, injection molding, and cooling to obtain a TPE elastomer rear plug;
and step A5, assembling the TPE elastomer rear plug prepared in the step A4 into the modified polypropylene resin pipe body prepared in the step A3 through a cylinder, and thus obtaining the environment-friendly rubber pipe.
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