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CN116622180B - Fireproof high-strength plastic pipe and preparation method thereof - Google Patents

Fireproof high-strength plastic pipe and preparation method thereof Download PDF

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CN116622180B
CN116622180B CN202310363437.0A CN202310363437A CN116622180B CN 116622180 B CN116622180 B CN 116622180B CN 202310363437 A CN202310363437 A CN 202310363437A CN 116622180 B CN116622180 B CN 116622180B
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CN116622180A (en
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戴美玲
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Hebei Tongtao Pipe Group Co ltd
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Abstract

The invention discloses a fireproof high-strength plastic pipe and a preparation method thereof, and relates to the technical field of plastic pipes. The invention firstly reacts 2-butenyl triethoxysilane, p-isopropenyl acetophenone and p-isopropenyl acetophenone to prepare heat-resistant polyolefin, and the heat-resistant effect of the plastic pipe is achieved by improving the heat stability and the crosslinking degree; the antibacterial agent is prepared from 4-butyl-2-nitroaniline, sodium nitrite, 3-tertiary butyl-4-hydroxybenzaldehyde and perfluorocabastine, and the bacteria are killed by electrostatic adsorption and the penetration of alkyl chains, and the adhesion of the bacteria is reduced by utilizing the surface energy of the low plastic tube, so that the plastic tube has an antibacterial effect; the heat-resistant polyolefin is mixed with other additives to prepare a plastic pipe with the diameter of 120mm, and the plastic pipe is finished by an antibacterial agent to prepare the fire-resistant high-strength plastic pipe. The plastic pipe prepared by the invention has heat-resistant and antibacterial effects.

Description

Fireproof high-strength plastic pipe and preparation method thereof
Technical Field
The invention relates to the technical field of plastic pipes, in particular to a fireproof high-strength plastic pipe and a preparation method thereof.
Background
The plastic pipe is generally made by extrusion processing of synthetic resin in a pipe making machine, and is mainly used as a pipeline for a tap water supply system of a building construction, a sanitary pipe for drainage, exhaust and pollution discharge, an underground drainage pipe system, a rainwater pipe, a threading pipe for wire installation and application, and the like. The plastic pipe has the main advantages of good corrosion resistance, light weight, convenient molding, easy processing, and poor antibacterial, strength and fire resistance.
The improvement of the fire resistance of the plastic pipe is mainly to improve the heat resistance of the synthetic resin and add substances with strong heat resistance (such as ceramic powder and the like), the resin with high heat resistance and the substances with strong heat resistance which gradually melt the sealing plastic under the action of high temperature, and the firmness and most of the strength of the plastic pipe are maintained to inhibit the expansion of fire. Meanwhile, the addition of the nanoscale high-temperature-resistant substance can greatly improve the strength of the plastic pipe. In addition, the plastic pipe used in a humid environment for a long time is extremely easy to grow microorganisms, and forms a dirt layer along with the continuous growth of the microorganisms, so that the service performance of the plastic pipe is seriously affected. In view of the above, the invention utilizes the heat-resistant polyolefin and the nanoscale high temperature resistant substance to be mixed to prepare the fireproof high-strength plastic pipe, and simultaneously endows the fireproof high-strength plastic pipe with antibacterial effect so as to meet market demands.
Disclosure of Invention
The invention aims to provide a fireproof high-strength plastic pipe and a preparation method thereof, which are used for solving the problems in the prior art.
In order to solve the technical problems, the invention provides the following technical scheme:
a refractory high-strength plastic pipe is prepared from heat-resistant polyolefin and other additives through mixing, and antibacterial finishing.
Further, the heat-resistant polyolefin is prepared by reacting 2-butenyl triethoxysilane, p-isopropenyl acetophenone, 2-methylacrolein and 4,4 '-dihydroxy-3, 3' -glyoxal biphenyl.
Further, the other additives comprise an ultraviolet resistant agent, carbon nanofibers, a fire retardant agent and a dispersing agent.
Further, the anti-ultraviolet agent is nano titanium dioxide; the refractory agent is a mixture of antimony trioxide, zinc borate and ceramic powder; the dispersing agent is dibutyl phthalate.
Further, the antibacterial agent is prepared from 4-butyl-2-nitroaniline, sodium nitrite, 3-tertiary butyl-4-hydroxybenzaldehyde and perfluor cabastine.
Further, the preparation method of the refractory high-strength plastic pipe comprises the following preparation steps:
(1) Mixing 30% sodium hydroxide solution, dichlorotoluene and polyolefin according to a mass ratio of 130:50:27-130:50:31, stirring for 20-30 min at 0-5 ℃ and 200-300 rpm, adding 4,4 '-dihydroxy-3, 3' -glyoxal biphenyl with the mass of 0.3-0.5 times of the polyolefin, reacting for 3-5 h at 200-300 rpm, adding hydrochloric acid until the pH value of the solution is 1, filtering, and vacuum drying for 24h at-0.08 MPa and 60 ℃ to obtain heat-resistant polyolefin;
(2) Mixing heat-resistant polyolefin, an anti-ultraviolet agent, carbon nanofibers, a refractory agent and a dispersing agent according to a mass ratio of 40:1:5:7:1-50:3:15:9:1, stirring for 12h at 100-200 rpm and 180-200 ℃ with a mass ratio of 3:1:6-5:1:8 of antimony trioxide, zinc borate and ceramic powder in the refractory agent, pouring into a mould for molding, extruding and sizing to obtain a plastic pipe with a diameter of 120 mm;
(3) Mixing perfluorocabastine and absolute ethyl alcohol according to a mass ratio of 11:100-13:100, stirring for 5-10 min at 200-300 rpm, and adding acetic acid until the pH value of the solution is 6 to obtain a treatment solution; mixing the plastic pipe and the treatment fluid according to the mass ratio of 1:10-1:20, carrying out reflux reaction for 6-8 hours at the temperature of 40-80 ℃ at 100-200 rpm, adding benzotriazole cyclized product with the mass of 1.5-2.5 times of that of perfluorocabastine, continuing to react for 6-8 hours, washing for 3-5 times by absolute ethyl alcohol, and drying for 1-2 hours at room temperature to obtain the fire-resistant high-strength plastic pipe.
Further, the polyolefin production process in the step (1) is as follows: mixing 2-butenyl triethoxysilane, p-isopropenyl acetophenone, 2-methylacrolein and dibenzoyl peroxide according to the mass ratio of 7:5:2:0.01-9:7:4:0.01, stirring for 1-2 h at 100-200 rpm, reacting for 6-8 h under nitrogen atmosphere and at 100-200 rpm and 80-100 ℃, adding deionized water with 2 times of 2-butenyl triethoxysilane and triethylamine with 0.002 times of 2-butenyl triethoxysilane, continuously reacting for 6-8 h, cooling to 60 ℃, adding trichlorotrifluoroethane with 2 times of 2-butenyl triethoxysilane, standing for 1-3 h, taking the lower layer mixed solution, and vacuum drying for 12h at-0.08 MPa and 50-60 ℃ to obtain polyolefin.
Further, the preparation method of the benzotriazole cyclized product in the step (3) comprises the following steps: mixing an intermediate product 2, deionized water, absolute ethyl alcohol and sodium hydroxide according to a mass ratio of 4:20:25:2-6:25:35:2, stirring for 10-20 min at 200-300 rpm and 80-100 ℃, adding sodium hydrosulfite with a mass 1.1-1.3 times of that of sodium hydroxide, continuing to react for 2-3 h, adding deionized water at 0-5 ℃ until precipitation is complete, adding hydrochloric acid until the pH value of the solution is 5-6, filtering, washing for 3-5 times by absolute ethyl alcohol, and drying for 6-8 h at a vacuum degree of-0.085 MPa and a temperature of 60-80 ℃ to obtain a benzotriazole cyclized product.
Further, the preparation method of the intermediate product 2 comprises the following steps: mixing the intermediate product 1, 3-tertiary butyl-4-hydroxybenzaldehyde, sodium dodecyl benzene sulfonate and methanol according to the mass ratio of 22:22:2:70-50:24:3:70, carrying out reflux reaction for 4-6 hours at the temperature of 60-70 ℃ at 200-300 rpm, filtering, washing 3-5 times with deionized water, and drying at the temperature of 60-80 ℃ at the vacuum degree of-0.085 MPa for 6-8 hours to obtain an intermediate product 2.
Further, the preparation method of the intermediate product 1 comprises the following steps: mixing concentrated sulfuric acid, deionized water and 4-butyl-2-nitroaniline according to a mass ratio of 1:25:1.1-1:35:1.3, stirring for 30-60 min at a temperature of 0-5 ℃ and a speed of 200-300 rpm, adding sodium nitrite with a mass of 0.2-0.4 times that of the concentrated sulfuric acid, continuing to react for 2-3 h, adding sulfamic acid with a mass of 0.003-0.005 times that of the concentrated sulfuric acid, filtering, and taking a solution to obtain an intermediate product 1.
Compared with the prior art, the invention has the following beneficial effects:
the invention prepares the fire-resistant high-strength plastic pipe by mixing the heat-resistant polyolefin with other additives and finishing the plastic pipe by the antibacterial agent, thereby having heat-resistant and antibacterial effects.
Firstly, the heat-resistant polyolefin is prepared by reacting 2-butenyl triethoxysilane, p-isopropenyl acetophenone, 2-methylacrolein and 4,4 '-dihydroxy-3, 3' -glyoxal biphenyl; 2-butenyl triethoxysilane, p-isopropenyl acetophenone and 2-methylacrolein are polymerized to prepare polyolefin, and siloxane can be hydrolyzed and polymerized to form a silicon dioxide net, so that the plastic pipe has heat resistance under the heat barrier effect, high temperature resistance and motion restriction effect on polyolefin molecular chains of the silicon dioxide net; the aldehyde group in the 4,4 '-dihydroxyl-3, 3' -glyoxal biphenyl reacts with the ketone group in the p-isopropenyl acetophenone to form a chalcone structure, so that the polyolefin is crosslinked, the crosslinking density of the polyolefin is improved, and meanwhile, the chalcone structure can react with free radicals generated by the pipe under the high temperature effect to prevent the pipe from damaging the thermal decomposition of the pipe, and the heat-resistant effect is improved.
Secondly, the antibacterial agent is prepared from 4-butyl-2-nitroaniline, sodium nitrite, 3-tertiary butyl-4-hydroxybenzaldehyde and perfluor cabastine; the benzotriazole cyclized product is prepared by reacting 4-butyl-2-nitroaniline, sodium nitrite and 3-tertiary butyl-4-hydroxybenzaldehyde, and can kill bacteria through electrostatic adsorption of triazole structure and puncturing of alkyl chain in 4-butyl-2-nitroaniline, so that the plastic pipe has antibacterial effect; the aldehyde group in the benzotriazole cyclized product and the aldehyde in the plastic tube are based on amino reaction in the perfluorocarbuncle, so that the antibacterial agent is combined with the plastic tube to form a Schiff base structure, the antibacterial effect is further improved, the surface energy of the plastic tube is reduced by utilizing a fluorine chain, the adhesion of bacteria to the tube wall is reduced, and the antibacterial effect is improved.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
For more clear description, the method provided by the invention is described in detail by the following examples, and the method for testing each index of the refractory high-strength plastic pipe manufactured in the following examples is as follows:
heat-resistant effect: taking the examples and the comparative examples with the same length, drying at 60 ℃ for 12 hours, and testing the 5% thermal decomposition temperature of the plastic pipe by using a thermogravimetric analyzer under the nitrogen atmosphere, the flow rate of 50mL/min and the heating rate of 10 ℃/min;
antibacterial effect: the bacteriostasis rate was measured according to GB/T31402 using the same length examples and comparative examples.
Example 1
(1) Mixing 2-butenyl triethoxysilane, p-isopropenyl acetophenone, 2-methylacrolein and dibenzoyl peroxide according to the mass ratio of 7:5:2:0.01, stirring for 1h at 100rpm, reacting for 6h at 80 ℃ under nitrogen atmosphere at 100rpm, adding deionized water with 2 times of the mass of the 2-butenyl triethoxysilane and triethylamine with 0.002 times of the mass of the 2-butenyl triethoxysilane, continuing to react for 6h, cooling to 60 ℃, adding trichlorotrifluoroethane with 2 times of the mass of the 2-butenyl triethoxysilane, standing for 1h, taking down the mixed solution, and vacuum drying for 12h at 50 ℃ under-0.08 MPa to obtain polyolefin;
(2) Mixing 30% sodium hydroxide solution, dichlorotoluene and polyolefin according to a mass ratio of 130:50:27, stirring at 0 ℃ and 200rpm for 20min, adding 4,4 '-dihydroxy-3, 3' -glyoxal biphenyl with the mass of 0.3 times of the polyolefin, reacting at 200rpm for 3h, adding hydrochloric acid until the pH of the solution is 1, filtering, and vacuum drying at-0.08 MPa and 60 ℃ for 24h to obtain heat-resistant polyolefin;
(3) Mixing heat-resistant polyolefin, nano titanium dioxide, nano carbon fiber, refractory agent and dibutyl phthalate according to a mass ratio of 40:1:5:7:1, stirring for 12 hours at 100rpm and 180 ℃ with a mass ratio of 3:1:6 of antimony trioxide, zinc borate and ceramic powder in the refractory agent, pouring into a mould for molding, extruding and sizing to obtain a plastic pipe with a diameter of 120 mm;
(4) Mixing concentrated sulfuric acid, deionized water and 4-butyl-2-nitroaniline according to a mass ratio of 1:25:1.1, stirring at 0 ℃ and 200rpm for 30min, adding sodium nitrite with the mass of 0.2 times of the concentrated sulfuric acid, continuing to react for 2h, adding sulfamic acid with the mass of 0.003 times of the concentrated sulfuric acid, filtering, and taking a solution to obtain an intermediate product 1;
(5) Mixing the intermediate product 1, 3-tertiary butyl-4-hydroxybenzaldehyde, sodium dodecyl benzene sulfonate and methanol according to the mass ratio of 22:22:2:70, carrying out reflux reaction for 4 hours at 200rpm and 60 ℃, filtering, washing with deionized water for 3 times, and drying for 6 hours at the vacuum degree of-0.085 MPa and 60 ℃ to obtain an intermediate product 2;
(6) Mixing an intermediate product 2, deionized water, absolute ethyl alcohol and sodium hydroxide according to a mass ratio of 4:20:25:2, stirring for 10min at 200rpm and 80 ℃, adding sodium hydrosulfite with the mass 1.1 times of that of sodium hydroxide, continuing to react for 2h, adding deionized water at 0 ℃ until the solution is completely precipitated, adding hydrochloric acid until the pH value of the solution is 5, filtering, washing with absolute ethyl alcohol for 3 times, and drying at the vacuum degree of-0.085 MPa and the temperature of 60 ℃ for 6h to obtain a benzotriazole cyclized product;
(7) Mixing perfluorocabastine and absolute ethyl alcohol according to a mass ratio of 11:100, stirring for 5min at 200rpm, and adding acetic acid until the pH value of the solution is 6 to obtain a treatment solution; mixing the plastic pipe and the treatment fluid according to the mass ratio of 1:10, carrying out reflux reaction for 6 hours at 100rpm and 40 ℃, adding benzotriazole cyclized product with the mass 1.5 times that of perfluorocabastine, continuing to react for 6 hours, washing with absolute ethyl alcohol for 3 times, and drying for 1 hour at room temperature to obtain the fire-resistant high-strength plastic pipe.
Example 2
(1) Mixing 2-butenyl triethoxysilane, p-isopropenyl acetophenone, 2-methylacrolein and dibenzoyl peroxide according to a mass ratio of 8:6:3:0.01, stirring for 1.5 hours at 150rpm, reacting for 7 hours at 90 ℃ in a nitrogen atmosphere at 150rpm, adding deionized water with 2 times of the mass of the 2-butenyl triethoxysilane and triethylamine with 0.002 times of the mass of the 2-butenyl triethoxysilane, continuing to react for 7 hours, cooling to 60 ℃, adding trichlorotrifluoroethane with 2 times of the mass of the 2-butenyl triethoxysilane, standing for 2 hours, taking out a lower layer mixed solution, and vacuum drying for 12 hours at-0.08 MPa and 55 ℃ to obtain polyolefin;
(2) Mixing 30% sodium hydroxide solution, dichlorotoluene and polyolefin according to a mass ratio of 130:50:29, stirring at 3 ℃ and 250rpm for 25min, adding 4,4 '-dihydroxy-3, 3' -glyoxal biphenyl with a mass of 0.4 times of the polyolefin, reacting at 250rpm for 4h, adding hydrochloric acid until the pH of the solution is 1, filtering, and vacuum drying at-0.08 MPa and 60 ℃ for 24h to obtain heat-resistant polyolefin;
(3) Mixing heat-resistant polyolefin, nano titanium dioxide, nano carbon fiber, refractory agent and dibutyl phthalate according to a mass ratio of 45:2:10:8:1, stirring for 12 hours at 150rpm and 190 ℃ with a mass ratio of antimony trioxide, zinc borate and ceramic powder in the refractory agent of 4:1:7, pouring into a mould for molding, extruding and sizing to obtain a plastic pipe with a diameter of 120 mm;
(4) Mixing concentrated sulfuric acid, deionized water and 4-butyl-2-nitroaniline according to a mass ratio of 1:30:1.2, stirring at the temperature of 3 ℃ and the speed of 250rpm for 45min, adding sodium nitrite with the mass of 0.3 times of the concentrated sulfuric acid, continuing to react for 2.5h, adding sulfamic acid with the mass of 0.004 times of the concentrated sulfuric acid, filtering, and taking a solution to obtain an intermediate product 1;
(5) Mixing the intermediate product 1, 3-tertiary butyl-4-hydroxybenzaldehyde, sodium dodecyl benzene sulfonate and methanol according to the mass ratio of 36:23:2.5:70, carrying out reflux reaction for 5 hours at the temperature of 65 ℃ at 250rpm, filtering, washing with deionized water for 4 times, and drying for 7 hours at the temperature of 70 ℃ at the vacuum degree of-0.085 MPa to obtain an intermediate product 2;
(6) Mixing an intermediate product 2, deionized water, absolute ethyl alcohol and sodium hydroxide according to a mass ratio of 5:23:30:2, stirring for 15min at the temperature of 90 ℃ at 250rpm, adding sodium hydrosulfite with the mass 1.2 times of that of sodium hydroxide, continuing to react for 2.5h, adding deionized water at the temperature of 3 ℃ until the solution is completely precipitated, adding hydrochloric acid until the pH value of the solution is 5.5, filtering, washing for 4 times by using absolute ethyl alcohol, and drying for 7h at the temperature of 70 ℃ at the vacuum degree of-0.085 MPa to obtain a benzotriazole cyclized product;
(7) Mixing perfluorocabastine and absolute ethyl alcohol according to a mass ratio of 12:100, stirring for 8min at 250rpm, and adding acetic acid until the pH value of the solution is 6 to obtain a treatment solution; mixing the plastic pipe and the treatment fluid according to the mass ratio of 1:15, carrying out reflux reaction for 7 hours at the temperature of 60 ℃ at 150rpm, adding benzotriazole cyclized product with the mass of 2 times that of perfluorocabastine, continuing to react for 7 hours, washing for 4 times by absolute ethyl alcohol, and drying for 1.5 hours at room temperature to obtain the fire-resistant high-strength plastic pipe.
Example 3
(1) Mixing 2-butenyl triethoxysilane, p-isopropenyl acetophenone, 2-methylacrolein and dibenzoyl peroxide according to the mass ratio of 9:7:4:0.01, stirring for 2 hours at 200rpm, reacting for 8 hours at 100 ℃ under nitrogen atmosphere at 200rpm, adding deionized water with 2 times of the mass of the 2-butenyl triethoxysilane and triethylamine with 0.002 times of the mass of the 2-butenyl triethoxysilane, continuing to react for 8 hours, cooling to 60 ℃, adding trichlorotrifluoroethane with 2 times of the mass of the 2-butenyl triethoxysilane, standing for 3 hours, taking down the mixed solution, and vacuum drying for 12 hours at 60 ℃ under-0.08 MPa to obtain polyolefin;
(2) Mixing 30% sodium hydroxide solution, dichlorotoluene and polyolefin according to a mass ratio of 130:50:31, stirring at 5 ℃ for 30min at 300rpm, adding 4,4 '-dihydroxy-3, 3' -glyoxal biphenyl with a mass which is 0.5 times of the polyolefin, reacting at 300rpm for 5h, adding hydrochloric acid until the pH of the solution is 1, filtering, and vacuum drying at-0.08 MPa and 60 ℃ for 24h to obtain heat-resistant polyolefin;
(3) Mixing heat-resistant polyolefin, nano titanium dioxide, nano carbon fiber, refractory agent and dibutyl phthalate according to a mass ratio of 50:3:15:9:1, stirring for 12 hours at 200rpm and 200 ℃ with a mass ratio of antimony trioxide, zinc borate and ceramic powder in the refractory agent of 5:1:8, pouring into a mould for molding, extruding and sizing to obtain a plastic pipe with a diameter of 120 mm;
(4) Mixing concentrated sulfuric acid, deionized water and 4-butyl-2-nitroaniline according to a mass ratio of 1:35:1.3, stirring at 5 ℃ and 300rpm for 60min, adding sodium nitrite with the mass of 0.4 times of the concentrated sulfuric acid, continuing to react for 3h, adding sulfamic acid with the mass of 0.005 times of the concentrated sulfuric acid, filtering, and taking a solution to obtain an intermediate product 1;
(5) Mixing the intermediate product 1, 3-tertiary butyl-4-hydroxybenzaldehyde, sodium dodecyl benzene sulfonate and methanol according to the mass ratio of 50:24:3:70, carrying out reflux reaction for 6 hours at 300rpm and 70 ℃, filtering, washing with deionized water for 5 times, and drying for 8 hours at 80 ℃ under the vacuum degree of-0.085 MPa to obtain an intermediate product 2;
(6) Mixing an intermediate product 2, deionized water, absolute ethyl alcohol and sodium hydroxide according to a mass ratio of 6:25:35:2, stirring for 20min at 300rpm and 100 ℃, adding sodium hydrosulfite with the mass 1.3 times of that of sodium hydroxide, continuing to react for 3h, adding deionized water at 5 ℃ until the solution is completely precipitated, adding hydrochloric acid until the pH value of the solution is 6, filtering, washing with absolute ethyl alcohol for 5 times, and drying at 80 ℃ at a vacuum degree of-0.085 MPa for 8h to obtain a benzotriazole cyclized product;
(7) Mixing perfluorocabastine and absolute ethyl alcohol according to a mass ratio of 13:100, stirring for 10min at 300rpm, and adding acetic acid until the pH value of the solution is 6 to obtain a treatment solution; mixing the plastic pipe and the treatment fluid according to the mass ratio of 1:20, carrying out reflux reaction for 8 hours at 200rpm and 80 ℃, adding benzotriazole cyclized product with the mass of 2.5 times that of perfluorocabastine, continuing to react for 8 hours, washing for 5 times by absolute ethyl alcohol, and drying for 2 hours at room temperature to obtain the fire-resistant high-strength plastic pipe.
Comparative example 1
Comparative example 1 differs from example 2 only in that step (1) was different, and step (1) was changed to: mixing isopropenyl acetophenone, 2-methylacrolein and dibenzoyl peroxide according to the mass ratio of 6:3:0.01, stirring for 1.5 hours at 150rpm, reacting for 7 hours at 90 ℃ in a nitrogen atmosphere at 150rpm, adding deionized water with the mass of 2.6 times of the isopropenyl acetophenone and triethylamine with the mass of 0.0026 times of the isopropenyl acetophenone, continuously reacting for 7 hours, cooling to 60 ℃, adding trichlorotrifluoroethane with the mass of 2.6 times of the isopropenyl acetophenone, standing for 2 hours, taking out the lower mixed solution, and vacuum drying for 12 hours at-0.08 MPa and 55 ℃ to obtain the polyolefin. The rest of the procedure is the same as in example 2.
Comparative example 2
Comparative example 2 differs from example 2 only in that there is no step (2), and step (3) is changed to: mixing polyolefin, nano titanium dioxide, nano carbon fiber, refractory agent and dibutyl phthalate according to the mass ratio of 45:2:10:8:1, stirring the mixture for 12 hours at the temperature of 190 ℃ at 150rpm with the mass ratio of antimony trioxide, zinc borate and ceramic powder in the refractory agent of 4:1:7, pouring the mixture into a die for molding, extruding and sizing to obtain the plastic pipe with the diameter of 120 mm. The rest of the procedure is the same as in example 2.
Comparative example 3
Comparative example 3 differs from example 2 only in that there are no steps (4) to (6), and step (7) is changed to: mixing perfluorocabastine and absolute ethyl alcohol according to a mass ratio of 12:100, stirring for 8min at 250rpm, and adding acetic acid until the pH value of the solution is 6 to obtain a treatment solution; mixing the plastic pipe and the treatment fluid according to the mass ratio of 1:15, carrying out reflux reaction for 7 hours at the temperature of 60 ℃ at 150rpm, adding 3-tertiary butyl-4-hydroxybenzaldehyde with the mass of 2 times of that of perfluorocabastine, continuing to react for 7 hours, washing with absolute ethyl alcohol for 4 times, and drying for 1.5 hours at room temperature to obtain the fire-resistant high-strength plastic pipe. The rest of the procedure is the same as in example 2.
Comparative example 4
Comparative example 4 differs from example 2 only in the step (7), and the step (7) is changed to: mixing the benzotriazole cyclized product and absolute ethyl alcohol according to the mass ratio of 24:100, stirring for 8min at 250rpm, and adding acetic acid until the pH value of the solution is 6 to obtain a treatment solution; mixing the plastic pipe and the treatment fluid according to the mass ratio of 1:15, carrying out reflux reaction for 7 hours at the temperature of 60 ℃ at 150rpm, washing for 4 times by absolute ethyl alcohol, and drying for 1.5 hours at room temperature to obtain the refractory high-strength plastic pipe. The rest of the procedure is the same as in example 2.
Effect example
The following table 1 shows the results of performance analysis of the refractory high-strength plastic pipes using examples 1 to 3 of the present invention and comparative examples 1 to 4.
TABLE 1
As can be seen from the comparison of the thermal decomposition temperatures of the examples in Table 1 and the comparative examples of 5%, the plastic pipe has good heat resistance, the polyolefin is prepared by polymerizing 2-butenyltriethoxysilane, p-isopropenylacetophenone and 2-methacrolein, the siloxane in the 2-butenyltriethoxysilane is hydrolyzed and polymerized to form a silicon dioxide network, the heat barrier effect, the high temperature resistance effect and the movement restriction effect on polyolefin molecular chains of the silicon dioxide network are improved, the plastic pipe has heat resistance, the further reaction of the polyolefin and 4,4 '-dihydroxy-3, 3' -glyoxal biphenyl forms a chalcone structure, the polyolefin is crosslinked, the proceeding of thermal oxidation reaction is inhibited while the crosslinking density of the polyolefin is improved, and the heat resistance of the pipe is further improved; as can be seen from comparison of the antibacterial rates of the examples and the comparative examples in Table 1, the antibacterial finished plastic pipe has excellent antibacterial performance, the benzotriazole cyclized product is prepared by the reaction of 4-butyl-2-nitroaniline, sodium nitrite and 3-tertiary butyl-4-hydroxybenzaldehyde, bacteria can be killed by the electrostatic adsorption effect of a triazole structure and the puncturing effect of an alkyl chain in the 4-butyl-2-nitroaniline, and the bacteria agent and the plastic pipe form a Schiff base structure when being combined by perfluorocarbuncle, and the adhesion of the bacteria to the pipe wall is reduced by utilizing the low surface energy of a fluorine chain, so that the antibacterial effect is improved.
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 characteristics 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. Any reference sign in a claim should not be construed as limiting the claim concerned.

Claims (2)

1. The preparation method of the refractory high-strength plastic pipe is characterized by comprising the following preparation steps:
(1) Mixing a 30% sodium hydroxide solution, dichlorotoluene and polyolefin according to a mass ratio of 130:50:27-130:50:31, stirring for 20-30 min at 0-5 ℃ and 200-300 rpm, adding 4,4 '-dihydroxy-3, 3' -glyoxal biphenyl with the mass of 0.3-0.5 times of the polyolefin, reacting for 3-5 h at 200-300 rpm, adding hydrochloric acid until the pH value of the solution is 1, filtering, and vacuum drying for 24h at-0.08 MPa and 60 ℃ to obtain heat-resistant polyolefin;
the preparation method of the polyolefin comprises the following steps: mixing 2-butenyl triethoxysilane, p-isopropenyl acetophenone, 2-methylacrolein and dibenzoyl peroxide according to the mass ratio of 7:5:2:0.01-9:7:4:0.01, stirring for 1-2 hours at 100-200 rpm, reacting for 6-8 hours at 80-100 ℃ in a nitrogen atmosphere, adding deionized water with 2 times of the mass of 2-butenyl triethoxysilane and triethylamine with 0.002 times of the mass of 2-butenyl triethoxysilane, continuously reacting for 6-8 hours, cooling to 60 ℃, adding trichlorotrifluoroethane with 2 times of the mass of 2-butenyl triethoxysilane, standing for 1-3 hours, taking a lower layer mixed solution, and vacuum drying at-0.08 MPa and 50-60 ℃ for 12 hours to obtain polyolefin;
(2) Mixing heat-resistant polyolefin, an anti-ultraviolet agent, carbon nanofibers, a refractory agent and a dispersing agent according to a mass ratio of 40:1:5:7:1-50:3:15:9:1, wherein the mass ratio of antimony trioxide, zinc borate and ceramic powder in the refractory agent is 3:1:6-5:1:8, stirring for 12h at 100-200 rpm and 180-200 ℃, pouring into a mould for molding, extruding and sizing to obtain a plastic pipe with a diameter of 120 mm;
(3) Mixing perfluorocabastine and absolute ethyl alcohol according to a mass ratio of 11:100-13:100, stirring for 5-10 min at 200-300 rpm, and adding acetic acid until the pH value of the solution is 6 to obtain a treatment solution; mixing a plastic pipe and a treatment fluid according to a mass ratio of 1:10-1:20, carrying out reflux reaction at 100-200 rpm and 40-80 ℃ for 6-8 hours, adding benzotriazole cyclized product with the mass 1.5-2.5 times that of perfluorocabastine, continuing to react for 6-8 hours, washing for 3-5 times with absolute ethyl alcohol, and drying at room temperature for 1-2 hours to obtain a fireproof high-strength plastic pipe;
the preparation method of the benzotriazole cyclized product comprises the following steps: mixing an intermediate product 2, deionized water, absolute ethyl alcohol and sodium hydroxide according to a mass ratio of 4:20:25:2-6:25:35:2, stirring for 10-20 min at 200-300 rpm and 80-100 ℃, adding sodium hydrosulfite with a mass 1.1-1.3 times of that of sodium hydroxide, continuously reacting for 2-3 h, adding deionized water at 0-5 ℃ until precipitation is complete, adding hydrochloric acid until the pH of the solution is 5-6, filtering, washing for 3-5 times by absolute ethyl alcohol, and drying for 6-8 h at a vacuum degree of-0.085 MPa and a temperature of 60-80 ℃ to obtain a benzotriazole cyclized product;
the preparation method of the intermediate product 2 comprises the following steps: mixing the intermediate product 1, 3-tert-butyl-4-hydroxybenzaldehyde, sodium dodecyl benzene sulfonate and methanol according to the mass ratio of 22:22:2:70-50:24:3:70, carrying out reflux reaction for 4-6 hours at the temperature of 60-70 ℃ at 200-300 rpm, filtering, washing 3-5 times with deionized water, and drying at the temperature of 60-80 ℃ at the vacuum degree of-0.085 MPa for 6-8 hours to obtain an intermediate product 2;
the preparation method of the intermediate product 1 comprises the following steps: mixing concentrated sulfuric acid, deionized water and 4-butyl-2-nitroaniline according to a mass ratio of 1:25:1.1-1:35:1.3, stirring at the temperature of 0-5 ℃ and at the speed of 200-300 rpm for 30-60 min, adding sodium nitrite with the mass of 0.2-0.4 times of the concentrated sulfuric acid, continuing to react for 2-3 h, adding sulfamic acid with the mass of 0.003-0.005 times of the concentrated sulfuric acid, filtering, and taking a solution to obtain an intermediate product 1.
2. The method for preparing a refractory high-strength plastic pipe according to claim 1, wherein the anti-ultraviolet agent is nano titanium dioxide; the refractory agent is a mixture of antimony trioxide, zinc borate and ceramic powder; the dispersing agent is dibutyl phthalate.
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Publication number Priority date Publication date Assignee Title
CN1445270A (en) * 2002-03-15 2003-10-01 上海塑杰科技有限公司 Functional agglomerates of polyolefin as well as its preparing method and application
CN105331033A (en) * 2015-11-26 2016-02-17 广东达华节水科技股份有限公司 Anti-bacterial and ultraviolet irradiation-resistant PP (Propene Polymer)/PE (Poly Ethylene) pipe and preparation method thereof
CN108914564A (en) * 2018-07-29 2018-11-30 段小宁 Moisture absorption is breathed freely, the preparation method of the Synthetic Leather spunlace non-woven cloth of antibacterial
CN115652645A (en) * 2022-09-20 2023-01-31 李开 Thermal oxidation-resistant wood ceramic and preparation method thereof

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Publication number Priority date Publication date Assignee Title
JPH11292978A (en) * 1998-04-06 1999-10-26 Dainippon Ink & Chem Inc Production of resin powder and resin powder

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1445270A (en) * 2002-03-15 2003-10-01 上海塑杰科技有限公司 Functional agglomerates of polyolefin as well as its preparing method and application
CN105331033A (en) * 2015-11-26 2016-02-17 广东达华节水科技股份有限公司 Anti-bacterial and ultraviolet irradiation-resistant PP (Propene Polymer)/PE (Poly Ethylene) pipe and preparation method thereof
CN108914564A (en) * 2018-07-29 2018-11-30 段小宁 Moisture absorption is breathed freely, the preparation method of the Synthetic Leather spunlace non-woven cloth of antibacterial
CN115652645A (en) * 2022-09-20 2023-01-31 李开 Thermal oxidation-resistant wood ceramic and preparation method thereof

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