CN119508642A - A high-strength polypropylene reinforced composite pipe and preparation method thereof - Google Patents
A high-strength polypropylene reinforced composite pipe and preparation method thereof Download PDFInfo
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- CN119508642A CN119508642A CN202411649510.1A CN202411649510A CN119508642A CN 119508642 A CN119508642 A CN 119508642A CN 202411649510 A CN202411649510 A CN 202411649510A CN 119508642 A CN119508642 A CN 119508642A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/14—Copolymers of propene
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
- F16L57/00—Protection of pipes or objects of similar shape against external or internal damage or wear
- F16L57/04—Protection of pipes or objects of similar shape against external or internal damage or wear against fire or other external sources of extreme heat
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
- F16L9/00—Rigid pipes
- F16L9/12—Rigid pipes of plastics with or without reinforcement
- F16L9/127—Rigid pipes of plastics with or without reinforcement the walls consisting of a single layer
- F16L9/128—Reinforced pipes
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- C—CHEMISTRY; METALLURGY
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/18—Applications used for pipes
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Abstract
The invention relates to the field of composite pipes and discloses a high-strength polypropylene reinforced composite pipe and a preparation method thereof, wherein the composite pipe comprises a pipe and a profile plastic pipe, the profile plastic pipe is obtained by melt extrusion and cooling shaping of a pipe composition through a double-screw extruder, the pipe composition comprises polypropylene, composite filler, modified glass fiber, a high-molecular compatilizer, a lubricant and an antioxidant, the composite filler is prepared by attaching nano silicon dioxide particles on the surface of a layered vermiculite sheet through chemical reaction, the modified glass fiber is prepared by modifying an anti-aging component and a flame-retardant component on the surface of carboxylated glass fiber through chemical reaction, the anti-aging component is prepared by reacting glycidyl ether with p-phenylenediamine, and the flame-retardant component is prepared by reacting 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide with octenyl succinic anhydride.
Description
Technical Field
The invention belongs to the technical field of composite pipes, and particularly relates to a high-strength polypropylene reinforced composite pipe and a preparation method thereof.
Background
Industrial pipelines require long service life and heat resistance, especially in applications with constant temperature of 40-60 ℃ or temperature peak up to 80 ℃, such as large diameter pipelines, hot fluid conveying pipelines, geothermal pipelines and the like of power plants, which have higher requirements on materials. The polypropylene pipe has the advantages of light weight, corrosion resistance, long service life, convenient installation, reliable connection and the like, is more and more concerned in recent years, has higher occupancy in the market, but the existing polypropylene material has limited heat resistance and flame retardance, is sensitive to environmental stress, is greatly influenced by factors such as temperature, loading speed, loading time and the like, is easy to generate high-temperature aging phenomenon under a high-temperature environment, and seriously influences the safety of a pipeline in conveying high-temperature liquid.
Disclosure of Invention
In order to solve the defects in the background art, the invention aims to provide a high-strength polypropylene reinforced composite pipe and a preparation method thereof, and excellent heat resistance, flame retardance, high-temperature aging resistance and mechanical property are provided for the pipe through the addition of composite filler and modified glass fiber.
The aim of the invention can be achieved by the following technical scheme:
The utility model provides a high strength polypropylene adds muscle composite pipe, includes tubular product and spiral winding bonding at the section bar plastic tubing of tubular product surface, the inside of section bar plastic tubing is hollow structure, the inside of section bar plastic tubing is equipped with two sheets of laminating each other, two sheet separates the section bar plastic tubing into two hollow tubes, the outer wall of tubular product and the terminal surface that section bar plastic tubing kept away from the tubular product outer wall all are equipped with embedded steel wire, just be equipped with the strengthening rib along the circumference direction equidistance of tubular product between the section bar plastic tubing;
The profile plastic pipe is obtained by carrying out melt extrusion and cooling shaping on a pipe composition by a double screw extruder, wherein the pipe composition comprises, by weight, 100 parts of polypropylene, 3-8 parts of a composite filler, 5-20 parts of modified glass fibers, 2-8 parts of a high polymer compatilizer, 1-3 parts of a lubricant and 0.05-5 parts of an antioxidant;
The composite filler is prepared by attaching nano silicon dioxide particles on the surface of a layered vermiculite sheet by a sol-gel method through 3-aminopropyl triethoxysilane, wherein the modified glass fiber is prepared by modifying an anti-aging component and a flame-retardant component on the surface of carboxylated glass fiber by chemical reaction, wherein the anti-aging component is prepared by utilizing glycidyl ether and p-phenylenediamine to perform ring opening reaction, and the flame-retardant component is prepared by utilizing 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and octenyl succinic anhydride to perform addition reaction.
Preferably, the macromolecular compatilizer is one or a combination of more of maleic anhydride grafted polyethylene, maleic anhydride grafted polypropylene, glycidyl methacrylate grafted polyethylene, acrylic acid grafted polyethylene, silane grafted polyethylene, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, ethylene-acrylic ester copolymer and ethylene acrylic acid copolymer.
Preferably, the lubricant is one of polyethylene wax and oxidized polyethylene wax, and the antioxidant is one or a combination of more of antioxidant DLTP, antioxidant 168, antioxidant 1010, antioxidant 1076, antioxidant 3114 and antioxidant 1024.
Preferably, the preparation method of the composite filler comprises the following steps:
(1) Uniformly dispersing expanded vermiculite in a mixed solution of concentrated sulfuric acid and concentrated nitric acid by ultrasonic, placing the mixed solution at 110-125 ℃ for reflux reaction for 4-6 hours, and washing, drying and grinding after the reaction is finished to prepare an acidized lamellar vermiculite sheet;
(2) And (3) taking acidified lamellar vermiculite flakes, ultrasonically dispersing the acidified lamellar vermiculite flakes in a mixed solution of ethanol and deionized water, adding ammonia water to adjust the pH value of the system to 8-9, obtaining a suspension, taking tetraethyl silicate to be dissolved in absolute ethanol, adding the absolute ethanol into the suspension, ultrasonically dispersing the mixture uniformly, stirring and mixing the mixture for 16-18 hours, obtaining a dispersion, taking 3-aminopropyl triethoxysilane to be dissolved in a mixed solution of ethanol and acetic acid, adding the mixture into the dispersion, stirring and reacting the mixture for 5-7 hours, and centrifuging, washing and drying the mixture after the reaction is completed, thus obtaining the composite filler.
Preferably, the preparation method of the modified glass fiber comprises the following steps:
A. Placing glycidyl ether and p-phenylenediamine in a reactor, adding a toluene solvent, stirring and reacting for 10-12 hours at 95-105 ℃, cooling to room temperature after the reaction is finished, and removing the solvent by rotary evaporation to prepare an anti-aging component;
B. Taking 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and octenyl succinic anhydride in a reactor, adding tetrahydrofuran solvent, stirring and reacting for 5-7 hours at 45-60 ℃, and performing rotary evaporation, washing and drying after the reaction is completed to prepare a flame retardant component;
C. Adding an anti-aging component and a flame-retardant component into a reactor, adding an N, N-dimethylformamide solvent, stirring at 60-85 ℃ for reaction for 6-12 hours, and filtering, washing and drying after the reaction is completed to prepare the functional modifier;
D. And (3) dispersing the carboxylated glass fiber in deionized water by ultrasonic, adding a functional modifier, stirring and mixing, regulating the pH value of the system to 7-9 by using a sodium carbonate solution, then adding 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and N-hydroxysuccinimide, stirring and reacting for 4-6 hours, and carrying out suction filtration and drying after the reaction is completed to obtain the modified glass fiber.
Preferably, the molar ratio of the glycidyl ether to the p-phenylenediamine in the step A is 1:3-3.4.
Preferably, in the step B, the molar ratio of the 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide to the octenyl succinic anhydride is 1:1-1.2.
Preferably, in the step C, the molar ratio of the anti-aging component to the flame retardant component is 1:2-2.5.
Preferably, the preparation method of the carboxylated glass fiber in the step D comprises the following steps:
Taking glass fibers, placing the glass fibers in an acetone solution, carrying out ultrasonic treatment and soaking, removing soaked substances on the surfaces of the glass fibers, drying, soaking in a mixed solution of concentrated sulfuric acid and hydrogen peroxide, and stirring for 8-12 hours to prepare pretreated glass fibers;
D2, immersing the pretreated glass fiber in a toluene solution of 3-aminopropyl triethoxysilane, condensing and refluxing for 8-12 hours at 105-115 ℃, repeatedly washing with toluene after the reaction is finished, and drying to obtain the aminated glass fiber;
And D3, taking the aminated glass fiber, ultrasonically dispersing the aminated glass fiber into N, N-dimethylformamide, adding succinic anhydride, stirring and mixing, placing the mixture at 55-70 ℃ for stirring and reacting for 20-24 hours, and washing and drying the mixture after the reaction is completed to obtain the carboxylated glass fiber.
The preparation method of the high-strength polypropylene reinforced composite pipe comprises the following steps:
s1, uniformly mixing polypropylene, composite filler, modified glass fiber, a macromolecular compatilizer, a lubricant and an antioxidant in parts by weight to obtain a pipe composition;
S2, the pipe composition is melted and extruded into a profile plastic pipe die through a double-screw extruder, and the profile plastic pipe is obtained after molding, cooling and shaping on the outer surface of the pipe;
s3, arranging embedded steel wires on the outer wall of the pipe and the end face, far away from the outer wall of the pipe, of the profile plastic pipe, and spirally winding and bonding the reinforcing ribs on the outer surface of the pipe along the profile plastic pipe to prepare the high-strength polypropylene reinforced composite pipe.
The invention has the beneficial effects that:
According to the invention, the polypropylene material is used as a base material, and the composite filler and the modified glass fiber functional component are added, so that excellent heat resistance, flame retardance, high-temperature aging resistance and mechanical properties are provided for the pipe. The invention uses concentrated sulfuric acid and concentrated nitric acid to acidify the expanded vermiculite, so that the surface groups of the expanded vermiculite are activated, then tetraethyl silicate is used as a silicon source, a mixed system of lamellar vermiculite sheets and nano silicon dioxide is obtained by a sol-gel method, then 3-aminopropyl triethoxysilane is used for coupling the nano silicon dioxide and the lamellar vermiculite sheets, nano silicon dioxide particles are attached to the surfaces of the lamellar vermiculite sheets, and the composite filler is prepared.
According to the invention, the glycidyl ether and the anti-aging agent P-phenylenediamine are utilized to carry out ring opening reaction to prepare the anti-aging component, wherein a plurality of epoxy groups in the glycidyl ether structure can be used for carrying out grafting reaction on the P-phenylenediamine to generate a plurality of anti-aging functional groups-NH, so that the aging protection effect of the anti-aging agent is enhanced, meanwhile, the P-H bond in the 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide structure and octenyl succinic anhydride are utilized to carry out addition reaction to prepare the flame-retardant component, then amino groups in the anti-aging component structure and anhydride groups in the flame-retardant component structure are utilized to carry out grafting reaction to prepare the functional modifier, in addition, concentrated sulfuric acid and hydrogen peroxide are utilized to fully expose silicon hydroxyl groups on the surface of the glass fiber, and then 3-aminopropyl triethoxysilane and succinic anhydride are utilized to prepare carboxylated glass fiber, the carboxylated glass fiber is modified, so that the carboxylated glass fiber is subjected to amidation reaction, after the surface of the glass fiber is modified by the 9, the surface of the anti-aging component and the flame-retardant component are subjected to surface modification reaction, then the surface-aging resistance performance of the glass fiber is improved, and the anti-aging performance of the glass fiber is well combined with the high-aging resistance performance of the glass fiber is guaranteed, and the problem that the anti-aging performance of the glass fiber is not well is well due to the long-term aging performance is overcome, and the problem of the aging resistance is also can be avoided.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described, and it will be obvious to those skilled in the art that other drawings can be obtained according to these drawings without inventive effort.
FIG. 1 is a schematic cross-sectional view of a high strength polypropylene reinforced composite pipe of the present invention;
FIG. 2 is a schematic structural view of the high strength polypropylene reinforced composite pipe of the present invention.
In the figure, 1-pipe, 2-section plastic pipe, 3-sheet, 4-reinforcing rib, 5-hollow pipe and 6-embedded steel wire.
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.
The melt index of the polypropylene copolymer in the examples of the present invention and comparative examples was 0.5g/10min (230 ℃ C., 2.16 Kg).
As shown in fig. 1-2, a high-strength polypropylene reinforced composite pipe comprises a pipe 1 and profile plastic pipes 2 spirally wound and adhered to the outer surface of the pipe 1, wherein the inside of the profile plastic pipes 2 is of a hollow structure, two mutually-attached sheets 3 are arranged in the profile plastic pipes 2, the profile plastic pipes 2 are divided into two hollow pipes 5 by the two sheets 3, embedded steel wires 6 are arranged on the outer wall of the pipe 1 and the end surface of the profile plastic pipes 2 far away from the outer wall of the pipe 1, and reinforcing ribs 4 are arranged between the profile plastic pipes 2 along the circumferential direction of the pipe 1 at equal intervals.
Example 1a method of preparing a composite filler comprises the steps of:
(1) Taking 5g of expanded vermiculite, uniformly dispersing the expanded vermiculite in a mixed solution of 120mL of concentrated sulfuric acid and 40mL of concentrated nitric acid by ultrasonic, placing the mixture at 120 ℃ for reflux reaction for 5 hours, and washing, drying and grinding the mixture after the reaction is finished to prepare an acidized lamellar vermiculite sheet;
(2) Taking 5g of acidified lamellar vermiculite flakes, ultrasonically dispersing the acidified lamellar vermiculite flakes in a mixed solution of 750mL of ethanol and 250mL of deionized water, adding ammonia water to adjust the pH value of the system to 8, obtaining a suspension, taking 20mL of tetraethyl silicate to dissolve in 200mL of absolute ethanol, adding the mixture into the suspension, ultrasonically dispersing the mixture uniformly, stirring and mixing the mixture for 18 hours, obtaining a dispersion, taking 0.5g of 3-aminopropyl triethoxysilane to dissolve in a mixed solution of 10mL of ethanol and 10mL of acetic acid, adding the mixture into the dispersion, stirring and reacting the mixture for 7 hours, and centrifuging, washing and drying the mixture after the reaction is finished, thus obtaining the composite filler.
Example 2 a method of making a modified glass fiber includes the steps of:
A. Taking 2.6g of glycidyl ether and 3.3g of p-phenylenediamine in a reactor, adding 70mL of toluene solvent, stirring at 100 ℃ for reaction for 12 hours, cooling to room temperature after the reaction is completed, and removing the solvent by rotary evaporation to prepare an anti-aging component;
B. taking 6.5g of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and 6.9g of octenyl succinic anhydride in a reactor, adding 100mL of tetrahydrofuran solvent, placing the mixture at 50 ℃ for stirring reaction for 7h, and performing rotary evaporation, washing and drying after the reaction is completed to prepare a flame retardant component;
C. Taking 5.8g of an anti-aging component and 8.7g of a flame retardant component in a reactor, adding 100mLN, N-dimethylformamide solvent, placing the mixture at 75 ℃ for stirring reaction for 10 hours, and filtering, washing and drying the mixture after the reaction is finished to prepare the functional modifier;
D. 2g of carboxylated glass fiber is taken and ultrasonically dispersed in 120mL of deionized water, 2.5g of functional modifier is added for stirring and mixing, the pH value of the system is regulated to 8 by using sodium carbonate solution with the mass fraction of 10 percent, then 1.4g of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and 2.1g of N-hydroxysuccinimide are added for stirring and reacting for 5h, and after the reaction is finished, the modified glass fiber is prepared by suction filtration and drying.
The preparation method of the carboxylated glass fiber comprises the following steps:
d1, placing 10g of glass fiber in an acetone solution, carrying out ultrasonic treatment, soaking for 10 hours, drying, soaking in a mixed solution of 280mL of concentrated sulfuric acid and 120mL of hydrogen peroxide, and stirring for 12 hours to prepare pretreated glass fiber;
d2, immersing the pretreated glass fiber in a toluene solution of 10% 3-aminopropyl triethoxysilane, condensing and refluxing for 10 hours at 110 ℃, repeatedly washing with toluene after the reaction is finished, and drying to prepare the aminated glass fiber;
and D3, taking 2g of the aminated glass fiber, dispersing the aminated glass fiber in 50mLN, N-dimethylformamide, adding 50mL0.5mol/L succinic anhydride, stirring and mixing, stirring and reacting at 65 ℃ for 24 hours, and washing and drying after the reaction is completed to prepare the carboxylated glass fiber.
Example 3a method for preparing a high strength polypropylene reinforced composite pipe comprises the steps of:
S1, uniformly mixing 100 parts of copolymerized polypropylene, 3 parts of the composite filler prepared in the embodiment 1, 7 parts of the modified glass fiber prepared in the embodiment 2, 3 parts of macromolecular compatilizer maleic anhydride grafted polypropylene, 1 part of lubricant polyethylene wax and 0.05 part of antioxidant 1010 to obtain a pipe composition;
S2, the pipe composition is melted and extruded into a profile plastic pipe die through a double-screw extruder, and the profile plastic pipe is obtained after molding, cooling and shaping on the outer surface of the pipe;
s3, spirally winding and bonding the reinforcing ribs on the outer surface of the pipe along the section plastic pipe to prepare the high-strength polypropylene reinforced composite pipe.
Example 4 a method for preparing a high strength polypropylene reinforced composite pipe comprising the steps of:
S1, uniformly mixing 100 parts of copolymerized polypropylene, 5 parts of the composite filler prepared in the embodiment 1, 12 parts of the modified glass fiber prepared in the embodiment 2, 5 parts of a macromolecular compatilizer ethylene-vinyl acetate copolymer, 2 parts of a lubricant polyethylene wax and 0.5 part of an antioxidant 168 to obtain a pipe composition;
S2, the pipe composition is melted and extruded into a profile plastic pipe die through a double-screw extruder, and the profile plastic pipe is obtained after molding, cooling and shaping on the outer surface of the pipe;
s3, spirally winding and bonding the reinforcing ribs on the outer surface of the pipe along the section plastic pipe to prepare the high-strength polypropylene reinforced composite pipe.
Example 5 a method for preparing a high strength polypropylene reinforced composite pipe comprising the steps of:
S1, uniformly mixing 100 parts of copolymerized polypropylene, 8 parts of the composite filler prepared in the embodiment 1, 17 parts of the modified glass fiber prepared in the embodiment 2, 7 parts of a macromolecular compatilizer maleic anhydride grafted polyethylene, 3 parts of a lubricant polyethylene wax and 3 parts of an antioxidant 3114 to obtain a pipe composition;
S2, the pipe composition is melted and extruded into a profile plastic pipe die through a double-screw extruder, and the profile plastic pipe is obtained after molding, cooling and shaping on the outer surface of the pipe;
s3, spirally winding and bonding the reinforcing ribs on the outer surface of the pipe along the section plastic pipe to prepare the high-strength polypropylene reinforced composite pipe.
Comparative example 1 a method for preparing a high-strength polypropylene reinforced composite pipe, comprising the steps of:
S1, uniformly mixing 100 parts of copolymerized polypropylene, 5 parts of nano silicon dioxide, 12 parts of modified glass fiber prepared in the embodiment 2,5 parts of high molecular compatilizer ethylene-vinyl acetate copolymer, 2 parts of lubricant polyethylene wax and 0.5 part of antioxidant 168 to obtain a pipe composition;
S2, the pipe composition is melted and extruded into a profile plastic pipe die through a double-screw extruder, and the profile plastic pipe is obtained after molding, cooling and shaping on the outer surface of the pipe;
s3, spirally winding and bonding the reinforcing ribs on the outer surface of the pipe along the section plastic pipe to prepare the high-strength polypropylene reinforced composite pipe.
Comparative example 2a method for preparing a high strength polypropylene reinforced composite pipe comprising the steps of:
S1, uniformly mixing 100 parts of copolymerized polypropylene, 5 parts of the composite filler prepared in the embodiment 1, 12 parts of glass fiber, 5 parts of a macromolecular compatilizer ethylene-vinyl acetate copolymer, 2 parts of a lubricant polyethylene wax and 0.5 part of an antioxidant 168 to obtain a pipe composition;
S2, the pipe composition is melted and extruded into a profile plastic pipe die through a double-screw extruder, and the profile plastic pipe is obtained after molding, cooling and shaping on the outer surface of the pipe;
s3, spirally winding and bonding the reinforcing ribs on the outer surface of the pipe along the section plastic pipe to prepare the high-strength polypropylene reinforced composite pipe.
Performance detection
The high-strength polypropylene reinforced composite pipes prepared in examples 3 to 5 and comparative examples 1 to 2 were injection molded into standard dumbbell-shaped test pieces having a thickness of 4mm, and performance test was performed:
a. the tensile properties of the materials were tested at a tensile rate of 50mm/min by referring to GB/T1040.2-2022 standard, the flame retardant properties of the samples were evaluated by referring to the limiting oxygen index of GB/T2406.2-2009 test materials, the samples were placed in a TGA-103 thermogravimetric analyzer under nitrogen protection, the temperature rising rate of 5 ℃ per min was increased from room temperature to 800 ℃, the initial decomposition temperature of the materials was recorded, the heat resistance of the samples was evaluated, and the data results were shown in Table 1.
Table 1 results of testing the properties of the samples
As can be seen from the data results in Table 1, the pipes prepared in examples 3 to 5 of the present invention have high tensile strength, are not easily broken, and have excellent heat resistance and flame retardance. The fact that the composite filler is replaced by nano silicon dioxide in equivalent manner in comparative example 1, the measured tensile property and initial thermal decomposition temperature of the composite filler are reduced compared with those of examples 3-5 shows that the addition of the composite filler can improve the mechanical property and heat resistance of the pipe, the glass fiber is not modified in comparative example 2, the measured tensile property and limiting oxygen index of the composite filler are reduced compared with those of examples 3-5, and the flame retardant property of the composite filler is reduced due to the fact that the anti-aging component and the flame retardant component are not modified on the surface of the glass fiber, and the mechanical property of the pipe is reduced due to the agglomeration phenomenon of the glass fiber.
B. The samples are placed in an air thermal aging test box for 100 ℃ high temperature thermal oxidation aging, the aging period is divided into four test periods of 3, 6, 12 and 24 days, 5 samples are taken in each period, each sample is subjected to oxidation induction time test, the high temperature aging resistance of the pipe is evaluated, and the data results are shown in table 2.
Table 2 sample high temperature aging resistance test results
As can be seen from the data in Table 2, the pipes prepared in examples 3 to 5 of the present invention have longer oxidation induction time, and after 24 days of thermal oxidation aging process, still maintain longer oxidation induction time, and have excellent high temperature aging resistance. Wherein the glass fiber is not modified in comparative example 2, the oxidation induction time is significantly shortened compared with examples 3 to 5, because the anti-aging component is not modified on the surface of the glass fiber, resulting in poor high temperature aging resistance.
In the description of the present specification, the descriptions of the terms "one embodiment," "example," "specific example," and the like, mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiments or examples. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing has shown and described the basic principles, principal features and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, and that the above embodiments and descriptions are merely illustrative of the principles of the present invention, and various changes and modifications may be made without departing from the spirit and scope of the invention, which is defined in the appended claims.
Claims (10)
1. The high-strength polypropylene reinforced composite pipe is characterized by comprising a pipe and profile plastic pipes spirally wound and adhered to the outer surface of the pipe, wherein the inside of the profile plastic pipes is of a hollow structure, two mutually-attached sheets are arranged inside the profile plastic pipes, the profile plastic pipes are divided into two hollow pipes by the two sheets, embedded steel wires are arranged on the outer wall of the pipe and the end surface of the profile plastic pipes far away from the outer wall of the pipe, and reinforcing ribs are arranged between the profile plastic pipes at equal intervals along the circumferential direction of the pipe;
The profile plastic pipe is obtained by carrying out melt extrusion and cooling shaping on a pipe composition by a double screw extruder, wherein the pipe composition comprises, by weight, 100 parts of polypropylene, 3-8 parts of a composite filler, 5-20 parts of modified glass fibers, 2-8 parts of a high polymer compatilizer, 1-3 parts of a lubricant and 0.05-5 parts of an antioxidant;
The composite filler is prepared by attaching nano silicon dioxide particles on the surface of a layered vermiculite sheet by a sol-gel method through 3-aminopropyl triethoxysilane, wherein the modified glass fiber is prepared by modifying an anti-aging component and a flame-retardant component on the surface of carboxylated glass fiber by chemical reaction, wherein the anti-aging component is prepared by utilizing glycidyl ether and p-phenylenediamine to perform ring opening reaction, and the flame-retardant component is prepared by utilizing 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and octenyl succinic anhydride to perform addition reaction.
2. The reinforced polypropylene composite pipe of claim 1, wherein the polymeric compatibilizer is one or more of maleic anhydride grafted polyethylene, maleic anhydride grafted polypropylene, glycidyl methacrylate grafted polyethylene, acrylic acid grafted polyethylene, silane grafted polyethylene, ethylene vinyl acetate copolymer, ethylene vinyl alcohol copolymer, ethylene acrylic acid ester copolymer, ethylene acrylic acid copolymer.
3. The reinforced composite pipe of claim 1, wherein the lubricant is one of polyethylene wax and oxidized polyethylene wax, and the antioxidant is one or more of antioxidant DLTP, antioxidant 168, antioxidant 1010, antioxidant 1076, antioxidant 3114 and antioxidant 1024.
4. The high strength polypropylene reinforced composite pipe of claim 1, wherein the method of preparing the composite filler comprises the steps of:
(1) Uniformly dispersing expanded vermiculite in a mixed solution of concentrated sulfuric acid and concentrated nitric acid by ultrasonic, placing the mixed solution at 110-125 ℃ for reflux reaction for 4-6 hours, and washing, drying and grinding after the reaction is finished to prepare an acidized lamellar vermiculite sheet;
(2) And (3) taking acidified lamellar vermiculite flakes, ultrasonically dispersing the acidified lamellar vermiculite flakes in a mixed solution of ethanol and deionized water, adding ammonia water to adjust the pH value of the system to 8-9, obtaining a suspension, taking tetraethyl silicate to be dissolved in absolute ethanol, adding the absolute ethanol into the suspension, ultrasonically dispersing the mixture uniformly, stirring and mixing the mixture for 16-18 hours, obtaining a dispersion, taking 3-aminopropyl triethoxysilane to be dissolved in a mixed solution of ethanol and acetic acid, adding the mixture into the dispersion, stirring and reacting the mixture for 5-7 hours, and centrifuging, washing and drying the mixture after the reaction is completed, thus obtaining the composite filler.
5. The high strength polypropylene reinforced composite pipe of claim 1, wherein the method of making the modified glass fiber comprises the steps of:
A. Placing glycidyl ether and p-phenylenediamine in a reactor, adding a toluene solvent, stirring and reacting for 10-12 hours at 95-105 ℃, cooling to room temperature after the reaction is finished, and removing the solvent by rotary evaporation to prepare an anti-aging component;
B. Taking 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and octenyl succinic anhydride in a reactor, adding tetrahydrofuran solvent, stirring and reacting for 5-7 hours at 45-60 ℃, and performing rotary evaporation, washing and drying after the reaction is completed to prepare a flame retardant component;
C. Adding an anti-aging component and a flame-retardant component into a reactor, adding an N, N-dimethylformamide solvent, stirring at 60-85 ℃ for reaction for 6-12 hours, and filtering, washing and drying after the reaction is completed to prepare the functional modifier;
D. And (3) dispersing the carboxylated glass fiber in deionized water by ultrasonic, adding a functional modifier, stirring and mixing, regulating the pH value of the system to 7-9 by using a sodium carbonate solution, then adding 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and N-hydroxysuccinimide, stirring and reacting for 4-6 hours, and carrying out suction filtration and drying after the reaction is completed to obtain the modified glass fiber.
6. The high-strength polypropylene reinforced composite pipe according to claim 5, wherein the molar ratio of the glycidyl ether to the p-phenylenediamine in the step A is 1:3-3.4.
7. The reinforced composite pipe of claim 5, wherein the molar ratio of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide to octenyl succinic anhydride in step B is 1:1-1.2.
8. The high-strength polypropylene reinforced composite pipe according to claim 5, wherein the molar ratio of the anti-aging component to the flame retardant component in the step C is 1:2-2.5.
9. The reinforced composite pipe of claim 5, wherein the method for preparing carboxylated glass fibers in step D comprises the steps of:
Taking glass fibers, placing the glass fibers in an acetone solution, carrying out ultrasonic treatment and soaking, removing soaked substances on the surfaces of the glass fibers, drying, soaking in a mixed solution of concentrated sulfuric acid and hydrogen peroxide, and stirring for 8-12 hours to prepare pretreated glass fibers;
D2, immersing the pretreated glass fiber in a toluene solution of 3-aminopropyl triethoxysilane, condensing and refluxing for 8-12 hours at 105-115 ℃, repeatedly washing with toluene after the reaction is finished, and drying to obtain the aminated glass fiber;
And D3, taking the aminated glass fiber, ultrasonically dispersing the aminated glass fiber into N, N-dimethylformamide, adding succinic anhydride, stirring and mixing, placing the mixture at 55-70 ℃ for stirring and reacting for 20-24 hours, and washing and drying the mixture after the reaction is completed to obtain the carboxylated glass fiber.
10. A method of making a high strength polypropylene reinforced composite pipe according to claim 1, comprising the steps of:
s1, uniformly mixing polypropylene, composite filler, modified glass fiber, a macromolecular compatilizer, a lubricant and an antioxidant in parts by weight to obtain a pipe composition;
S2, the pipe composition is melted and extruded into a profile plastic pipe die through a double-screw extruder, and the profile plastic pipe is obtained after molding, cooling and shaping on the outer surface of the pipe;
s3, arranging embedded steel wires on the outer wall of the pipe and the end face, far away from the outer wall of the pipe, of the profile plastic pipe, and spirally winding and bonding the reinforcing ribs on the outer surface of the pipe along the profile plastic pipe to prepare the high-strength polypropylene reinforced composite pipe.
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