CN109535594B - Super-hydrophobic pipe and preparation method thereof - Google Patents
Super-hydrophobic pipe and preparation method thereof Download PDFInfo
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- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
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Abstract
The invention relates to a super-hydrophobic pipe, which is prepared from the following raw materials: polyvinyl chloride and powdered polytetrafluoroethylene composite. The invention also relates to a preparation method of the super-hydrophobic pipe. The super-hydrophobic pipe material disclosed by the invention is strong in hydrophobicity, high in strength and good in market prospect.
Description
Technical Field
The invention relates to the technical field of PVC (polyvinyl chloride) pipes, in particular to a super-hydrophobic pipe and a preparation method thereof.
Background
With the development of the fields of petroleum transportation, construction industry, mines, electricity and the like, PVC pipes are more and more widely used. In the specific use process, the PV pipe is required to have excellent toughness and impact resistance, and is expected to have better hydrophobic property, so that the service life of the pipe can be prolonged, and the application field of the pipe can be greatly expanded.
Therefore, the invention aims to improve the PVC pipe so as to obtain a novel PVC pipe with good hydrophobic property and high strength.
Disclosure of Invention
The invention discloses a super-hydrophobic pipe which is prepared from the following raw materials in parts by weight:
polyvinyl chloride 100
10-40 parts of a powdery polytetrafluoroethylene composite material;
preferably, the preparation raw materials comprise:
polyvinyl chloride 100
30 parts of powdery polytetrafluoroethylene composite material.
In one embodiment, the raw materials for preparing the powdered polytetrafluoroethylene composite material comprise:
polytetrafluoroethylene 100
Polysiloxane 35
Polymer modified nanofiller 18
Lubricant 12
77 parts of a solvent.
In one embodiment, the polysiloxane is prepared by the method comprising:
adding 10 g of 3-aminopropylmethyldimethoxysilane, 30 g of perfluorooctyltriethoxysilane, 55 g of 1,3,5, 7-tetramethylcyclotetrasiloxane, 5 g of low-sulfonation-degree graphene oxide and 0.2 g of tetramethylammonium hydroxide into a reactor, introducing nitrogen for protection, stirring, heating to 90 ℃ for reaction for 2 hours, and heating to 120 ℃ for reaction for 1 hour to obtain the polysiloxane.
In one embodiment, the polymer-modified nanofiller is prepared by:
(1) adding 1mol of 1, 2-propylene glycol, 1mol of terephthalic acid, 0.5 mol of trimethylolpropane and 0.01mol of monobutyltin oxide into a reactor, reacting for 2 hours under the protection of argon and heating to 90 ℃, then heating to 270 ℃, adjusting the vacuum degree to be less than 0.02 MPa, continuing to react for 6 hours, cooling to room temperature, then adding 1000ml of N, N-dimethylformamide, 0.2mol of beta-cyclodextrin and KH-5600.05 mol into the reactor, heating to 110 ℃, reacting for 10 hours, then pouring the reaction solution into water, washing the obtained solid with water for 3 times, and fully drying the solid to obtain cyclodextrin modified polyester;
(2) at room temperature, 20 g of the cyclodextrin modified polyester is dissolved in 1000ml of DMF, then 2 g of nano yttrium oxide (average particle size of 300 nm), 3 g of nano silicon dioxide (average particle size of 100 nm), 5 g of hydroxyapatite (average particle size of 1 micron) and 5 g of silane coupling agent KH-550 are added, the mixture is kept at room temperature and stirred for 2 hours, and then the mixture is filtered by suction and the obtained solid is fully dried to obtain the polymer modified nano filler.
In one embodiment, the lubricant is jet fuel.
In one embodiment, the solvent is selected from at least one of dimethyl sulfoxide, N-dimethylformamide, N-dimethylacetamide, acetone, ethanol, isopropanol; preferably a mixture of N, N-dimethylformamide and isopropanol; more preferably a 1:3 by weight mixture of N, N-dimethylformamide and isopropanol.
In one embodiment, the raw material for preparing the powdered polytetrafluoroethylene composite further comprises:
n-heptafluorobutyrylimidazole 1-10
1, 7-dibromoheptane 1-10.
The invention also provides a preparation method of the powdery polytetrafluoroethylene composite material, which comprises the following steps:
(1) stirring and fully mixing the raw materials in a stirrer to form a mixed material, and standing and curing the mixed material at normal temperature for 5 hours;
(2) calendering the mixed material into a base band by a calender at 60 ℃;
(3) stretching the base band longitudinally by 2 times and transversely by 2 times at 150 ℃ by using a spoke expanding machine, sintering and heat setting at 330 ℃ for 2 hours to obtain a polytetrafluoroethylene composite material;
(4) and grinding the polytetrafluoroethylene composite material in a grinder until the average particle size is 800 nanometers to obtain the powdery polytetrafluoroethylene composite material.
The invention also provides a preparation method of the super-hydrophobic pipe, which comprises the following steps:
the raw materials are fully mixed and then processed into the pipe.
The beneficial technical effects of the invention are as follows:
1. the hydrophobic property of the PVC pipe is improved by introducing the powdery polytetrafluoroethylene composite material into PVC, so that the service life of the pipe is prolonged.
2. The polymer is used for coating the filler, so that a better dispersion effect is obtained, and the crosslinking degree is improved so as to obtain better adhesion and a hydrophobic effect;
3. through the matching of fillers with different particle sizes, a better microstructure is obtained so as to improve the hydrophobicity;
4. the strength of the system can be improved by adding the low-sulfonation-degree graphene oxide;
5. better system dispersibility and hydrophobic effect improvement can be achieved by adjusting the solvent;
6. the N-heptafluorobutyrylimidazole and 1, 7-dibromoheptane can improve the crosslinking degree of the polytetrafluoroethylene composite material, thereby improving the strength of the polytetrafluoroethylene composite material.
Detailed Description
Raw materials:
the preparation method of the sulfonated graphene oxide comprises the following steps:
adding 1 part of graphene oxide, 10 parts of sodium chloroethyl sulfonate, 6 parts of potassium hydroxide and 300 parts of deionized water into a reactor according to parts by weight, then adding 3 parts of concentrated nitric acid, heating to 50 ℃ for reaction for 1-5 hours, pouring the reaction solution into ice water, washing the obtained solid with ice water for 3 times, and fully drying the solid to obtain sulfonated graphene oxide with different sulfonation degrees;
specifically, the reaction time is 1 hour, so that graphene oxide with a sulfonation degree of 10% is obtained, and the reaction time is 5 hours, so that graphene oxide with a sulfonation degree of 30% is obtained.
Other materials are commercially available.
Example 1
I. The preparation method of the powdery polytetrafluoroethylene composite material comprises the following steps:
(1) stirring 100 g of polytetrafluoroethylene, 20 g of polysiloxane, 10 g of polymer modified nano filler, 5 g of aviation kerosene and 60 g of solvent (a mixture of N, N-dimethylformamide and isopropanol in a weight ratio of 1: 3) in a stirrer and fully mixing to form a mixed material, and then standing and curing the mixed material at normal temperature for 5 hours;
(2) calendering the mixed material into a base band by a calender at 60 ℃;
(3) stretching the base band longitudinally by 2 times and transversely by 2 times at 150 ℃ by using a spoke expanding machine, sintering and heat setting at 330 ℃ for 2 hours to obtain a polytetrafluoroethylene composite material;
(4) grinding the polytetrafluoroethylene composite material in a grinding machine until the average particle size is 800 nanometers to obtain a powdery polytetrafluoroethylene composite material;
the preparation method of the polysiloxane comprises the following steps:
adding 10 g of 3-aminopropylmethyldimethoxysilane, 30 g of perfluorooctyltriethoxysilane, 55 g of 1,3,5, 7-tetramethylcyclotetrasiloxane, 5 g of low sulfonation degree graphene oxide (sulfonation degree of 10%) and 0.2 g of tetramethylammonium hydroxide into a reactor, introducing nitrogen for protection, stirring, heating to 90 ℃, reacting for 2 hours, and heating to 120 ℃ for reacting for 1 hour to obtain polysiloxane;
the preparation method of the polymer modified nano filler comprises the following steps:
(1) adding 1mol of 1, 2-propylene glycol, 1mol of terephthalic acid, 0.5 mol of trimethylolpropane and 0.01mol of monobutyltin oxide into a reactor, reacting for 2 hours under the protection of argon and heating to 90 ℃, then heating to 270 ℃, adjusting the vacuum degree to be less than 0.02 MPa, continuing to react for 6 hours, cooling to room temperature, then adding 1000ml of N, N-dimethylformamide, 0.2mol of beta-cyclodextrin and KH-5600.05 mol into the reactor, heating to 110 ℃, reacting for 10 hours, then pouring the reaction solution into water, washing the obtained solid with water for 3 times, and fully drying the solid to obtain cyclodextrin modified polyester;
(2) at room temperature, 20 g of the cyclodextrin modified polyester is dissolved in 1000ml of DMF, then 2 g of nano yttrium oxide (average particle size of 300 nm), 3 g of nano silicon dioxide (average particle size of 100 nm), 5 g of hydroxyapatite (average particle size of 1 micron) and 5 g of silane coupling agent KH-550 are added, the mixture is kept at room temperature and stirred for 2 hours, and then the mixture is filtered by suction and the obtained solid is fully dried to obtain the polymer modified nano filler.
II, preparing the PVC pipe by the following steps:
(1) putting 100 parts by weight of PVC resin and 30 parts by weight of the powdery polytetrafluoroethylene composite material into a high-speed mixer, stirring and mixing to obtain a mixed material, wherein the stirring speed of the high-speed mixer is 800 rpm, the stirring time is 20 minutes, and the stirring temperature is 120 ℃;
(2) and (3) extruding and molding the mixed material at 170 ℃ to prepare the PVC pipe with the wall thickness of 5mm and the outer diameter of 200 mm.
Example 2
I. The preparation method of the powdery polytetrafluoroethylene composite material comprises the following steps:
(1) stirring 100 g of polytetrafluoroethylene, 30 g of polysiloxane, 15 g of polymer modified nano filler, 10 g of aviation kerosene and 70 g of solvent (a mixture of N, N-dimethylformamide and isopropanol in a weight ratio of 1: 3) in a stirrer and fully mixing to form a mixed material, and then standing and curing the mixed material at normal temperature for 5 hours;
(2) calendering the mixed material into a base band by a calender at 60 ℃;
(3) stretching the base band longitudinally by 2 times and transversely by 2 times at 150 ℃ by using a spoke expanding machine, sintering and heat setting at 330 ℃ for 2 hours to obtain a polytetrafluoroethylene composite material;
(4) grinding the polytetrafluoroethylene composite material in a grinding machine until the average particle size is 800 nanometers to obtain a powdery polytetrafluoroethylene composite material;
the preparation method of the polysiloxane comprises the following steps:
adding 10 g of 3-aminopropylmethyldimethoxysilane, 30 g of perfluorooctyltriethoxysilane, 55 g of 1,3,5, 7-tetramethylcyclotetrasiloxane, 5 g of low sulfonation degree graphene oxide (sulfonation degree of 10%) and 0.2 g of tetramethylammonium hydroxide into a reactor, introducing nitrogen for protection, stirring, heating to 90 ℃, reacting for 2 hours, and heating to 120 ℃ for reacting for 1 hour to obtain polysiloxane;
the preparation method of the polymer modified nano filler comprises the following steps:
(1) adding 1mol of 1, 2-propylene glycol, 1mol of terephthalic acid, 0.5 mol of trimethylolpropane and 0.01mol of monobutyltin oxide into a reactor, reacting for 2 hours under the protection of argon and heating to 90 ℃, then heating to 270 ℃, adjusting the vacuum degree to be less than 0.02 MPa, continuing to react for 6 hours, cooling to room temperature, then adding 1000ml of N, N-dimethylformamide, 0.2mol of beta-cyclodextrin and KH-5600.05 mol into the reactor, heating to 110 ℃, reacting for 10 hours, then pouring the reaction solution into water, washing the obtained solid with water for 3 times, and fully drying the solid to obtain cyclodextrin modified polyester;
(2) at room temperature, 20 g of the cyclodextrin modified polyester is dissolved in 1000ml of DMF, then 2 g of nano yttrium oxide (average particle size of 300 nm), 3 g of nano silicon dioxide (average particle size of 100 nm), 5 g of hydroxyapatite (average particle size of 1 micron) and 5 g of silane coupling agent KH-550 are added, the mixture is kept at room temperature and stirred for 2 hours, and then the mixture is filtered by suction and the obtained solid is fully dried to obtain the polymer modified nano filler.
II, preparing the PVC pipe by the following steps:
(1) putting 100 parts by weight of PVC resin and 30 parts by weight of the powdery polytetrafluoroethylene composite material into a high-speed mixer, stirring and mixing to obtain a mixed material, wherein the stirring speed of the high-speed mixer is 800 rpm, the stirring time is 20 minutes, and the stirring temperature is 120 ℃;
(2) and (3) extruding and molding the mixed material at 170 ℃ to prepare the PVC pipe with the wall thickness of 5mm and the outer diameter of 200 mm.
Example 3
I. The preparation method of the powdery polytetrafluoroethylene composite material comprises the following steps:
(1) stirring and fully mixing 100 g of polytetrafluoroethylene, 35 g of polysiloxane, 18 g of polymer modified nano filler, 12 g of aviation kerosene and 77 g of solvent (a mixture of N, N-dimethylformamide and isopropanol in a weight ratio of 1: 3) in a stirrer to form a mixed material, and then standing and curing the mixed material at normal temperature for 5 hours;
(2) calendering the mixed material into a base band by a calender at 60 ℃;
(3) stretching the base band longitudinally by 2 times and transversely by 2 times at 150 ℃ by using a spoke expanding machine, sintering and heat setting at 330 ℃ for 2 hours to obtain a polytetrafluoroethylene composite material;
(4) grinding the polytetrafluoroethylene composite material in a grinding machine until the average particle size is 800 nanometers to obtain a powdery polytetrafluoroethylene composite material;
the preparation method of the polysiloxane comprises the following steps:
adding 10 g of 3-aminopropylmethyldimethoxysilane, 30 g of perfluorooctyltriethoxysilane, 55 g of 1,3,5, 7-tetramethylcyclotetrasiloxane, 5 g of low sulfonation degree graphene oxide (sulfonation degree of 10%) and 0.2 g of tetramethylammonium hydroxide into a reactor, introducing nitrogen for protection, stirring, heating to 90 ℃, reacting for 2 hours, and heating to 120 ℃ for reacting for 1 hour to obtain polysiloxane;
the preparation method of the polymer modified nano filler comprises the following steps:
(1) adding 1mol of 1, 2-propylene glycol, 1mol of terephthalic acid, 0.5 mol of trimethylolpropane and 0.01mol of monobutyltin oxide into a reactor, reacting for 2 hours under the protection of argon and heating to 90 ℃, then heating to 270 ℃, adjusting the vacuum degree to be less than 0.02 MPa, continuing to react for 6 hours, cooling to room temperature, then adding 1000ml of N, N-dimethylformamide, 0.2mol of beta-cyclodextrin and KH-5600.05 mol into the reactor, heating to 110 ℃, reacting for 10 hours, then pouring the reaction solution into water, washing the obtained solid with water for 3 times, and fully drying the solid to obtain cyclodextrin modified polyester;
(2) at room temperature, 20 g of the cyclodextrin modified polyester is dissolved in 1000ml of DMF, then 2 g of nano yttrium oxide (average particle size of 300 nm), 3 g of nano silicon dioxide (average particle size of 100 nm), 5 g of hydroxyapatite (average particle size of 1 micron) and 5 g of silane coupling agent KH-550 are added, the mixture is kept at room temperature and stirred for 2 hours, and then the mixture is filtered by suction and the obtained solid is fully dried to obtain the polymer modified nano filler.
II, preparing the PVC pipe by the following steps:
(1) putting 100 parts by weight of PVC resin and 30 parts by weight of the powdery polytetrafluoroethylene composite material into a high-speed mixer, stirring and mixing to obtain a mixed material, wherein the stirring speed of the high-speed mixer is 800 rpm, the stirring time is 20 minutes, and the stirring temperature is 120 ℃;
(2) and (3) extruding and molding the mixed material at 170 ℃ to prepare the PVC pipe with the wall thickness of 5mm and the outer diameter of 200 mm.
Example 4
I. The preparation method of the powdery polytetrafluoroethylene composite material comprises the following steps:
(1) stirring 100 g of polytetrafluoroethylene, 35 g of polysiloxane, 18 g of polymer modified nano filler, 12 g of aviation kerosene, 77 g of solvent (a mixture of N, N-dimethylformamide and isopropanol in a weight ratio of 1: 3), 5 g of N-heptafluorobutyrylimidazole and 5 g of 1, 7-dibromoheptane in a stirrer, fully mixing to form a mixed material, and standing and curing the mixed material at normal temperature for 5 hours;
(2) calendering the mixed material into a base band by a calender at 60 ℃;
(3) stretching the base band longitudinally by 2 times and transversely by 2 times at 150 ℃ by using a spoke expanding machine, sintering and heat setting at 330 ℃ for 2 hours to obtain a polytetrafluoroethylene composite material;
(4) grinding the polytetrafluoroethylene composite material in a grinding machine until the average particle size is 800 nanometers to obtain a powdery polytetrafluoroethylene composite material;
the preparation method of the polysiloxane comprises the following steps:
adding 10 g of 3-aminopropylmethyldimethoxysilane, 30 g of perfluorooctyltriethoxysilane, 55 g of 1,3,5, 7-tetramethylcyclotetrasiloxane, 5 g of low sulfonation degree graphene oxide (sulfonation degree of 10%) and 0.2 g of tetramethylammonium hydroxide into a reactor, introducing nitrogen for protection, stirring, heating to 90 ℃, reacting for 2 hours, and heating to 120 ℃ for reacting for 1 hour to obtain polysiloxane;
the preparation method of the polymer modified nano filler comprises the following steps:
(1) adding 1mol of 1, 2-propylene glycol, 1mol of terephthalic acid, 0.5 mol of trimethylolpropane and 0.01mol of monobutyltin oxide into a reactor, reacting for 2 hours under the protection of argon and heating to 90 ℃, then heating to 270 ℃, adjusting the vacuum degree to be less than 0.02 MPa, continuing to react for 6 hours, cooling to room temperature, then adding 1000ml of N, N-dimethylformamide, 0.2mol of beta-cyclodextrin and KH-5600.05 mol into the reactor, heating to 110 ℃, reacting for 10 hours, then pouring the reaction solution into water, washing the obtained solid with water for 3 times, and fully drying the solid to obtain cyclodextrin modified polyester;
(2) at room temperature, 20 g of the cyclodextrin modified polyester is dissolved in 1000ml of DMF, then 2 g of nano yttrium oxide (average particle size of 300 nm), 3 g of nano silicon dioxide (average particle size of 100 nm), 5 g of hydroxyapatite (average particle size of 1 micron) and 5 g of silane coupling agent KH-550 are added, the mixture is kept at room temperature and stirred for 2 hours, and then the mixture is filtered by suction and the obtained solid is fully dried to obtain the polymer modified nano filler.
II, preparing the PVC pipe by the following steps:
(1) putting 100 parts by weight of PVC resin and 30 parts by weight of the powdery polytetrafluoroethylene composite material into a high-speed mixer, stirring and mixing to obtain a mixed material, wherein the stirring speed of the high-speed mixer is 800 rpm, the stirring time is 20 minutes, and the stirring temperature is 120 ℃;
(2) and (3) extruding and molding the mixed material at 170 ℃ to prepare the PVC pipe with the wall thickness of 5mm and the outer diameter of 200 mm.
Comparative example 1
I. The preparation method of the powdery polytetrafluoroethylene composite material comprises the following steps:
(1) stirring 100 g of polytetrafluoroethylene, 35 g of polysiloxane, 18 g of polymer modified nano filler, 12 g of aviation kerosene, 77 g of solvent (a mixture of N, N-dimethylformamide and isopropanol in a weight ratio of 1: 3), 5 g of N-heptafluorobutyrylimidazole and 5 g of 1, 7-dibromoheptane in a stirrer, fully mixing to form a mixed material, and standing and curing the mixed material at normal temperature for 5 hours;
(2) calendering the mixed material into a base band by a calender at 60 ℃;
(3) stretching the base band longitudinally by 2 times and transversely by 2 times at 150 ℃ by using a spoke expanding machine, sintering and heat setting at 330 ℃ for 2 hours to obtain a polytetrafluoroethylene composite material;
(4) grinding the polytetrafluoroethylene composite material in a grinding machine until the average particle size is 800 nanometers to obtain a powdery polytetrafluoroethylene composite material;
the preparation method of the polysiloxane comprises the following steps:
adding 10 g of 3-aminopropylmethyldimethoxysilane, 30 g of perfluorooctyltriethoxysilane, 55 g of 1,3,5, 7-tetramethylcyclotetrasiloxane, 5 g of low sulfonation degree graphene oxide (sulfonation degree of 30%) and 0.2 g of tetramethylammonium hydroxide into a reactor, introducing nitrogen for protection, stirring, heating to 90 ℃, reacting for 2 hours, and heating to 120 ℃ for reacting for 1 hour to obtain polysiloxane;
the preparation method of the polymer modified nano filler comprises the following steps:
(1) adding 1mol of 1, 2-propylene glycol, 1mol of terephthalic acid, 0.5 mol of trimethylolpropane and 0.01mol of monobutyltin oxide into a reactor, reacting for 2 hours under the protection of argon and heating to 90 ℃, then heating to 270 ℃, adjusting the vacuum degree to be less than 0.02 MPa, continuing to react for 6 hours, cooling to room temperature, then adding 1000ml of N, N-dimethylformamide, 0.2mol of beta-cyclodextrin and KH-5600.05 mol into the reactor, heating to 110 ℃, reacting for 10 hours, then pouring the reaction solution into water, washing the obtained solid with water for 3 times, and fully drying the solid to obtain cyclodextrin modified polyester;
(2) at room temperature, 20 g of the cyclodextrin modified polyester is dissolved in 1000ml of DMF, then 2 g of nano yttrium oxide (average particle size of 300 nm), 3 g of nano silicon dioxide (average particle size of 100 nm), 5 g of hydroxyapatite (average particle size of 1 micron) and 5 g of silane coupling agent KH-550 are added, the mixture is kept at room temperature and stirred for 2 hours, and then the mixture is filtered by suction and the obtained solid is fully dried to obtain the polymer modified nano filler.
II, preparing the PVC pipe by the following steps:
(1) putting 100 parts by weight of PVC resin and 30 parts by weight of the powdery polytetrafluoroethylene composite material into a high-speed mixer, stirring and mixing to obtain a mixed material, wherein the stirring speed of the high-speed mixer is 800 rpm, the stirring time is 20 minutes, and the stirring temperature is 120 ℃;
(2) and (3) extruding and molding the mixed material at 170 ℃ to prepare the PVC pipe with the wall thickness of 5mm and the outer diameter of 200 mm.
Comparative example 2
I. The preparation method of the powdery polytetrafluoroethylene composite material comprises the following steps:
(1) stirring and fully mixing 100 g of polytetrafluoroethylene, 35 g of polysiloxane, 18 g of polymer modified nano filler, 12 g of aviation kerosene, 77 g of solvent (a mixture of N, N-dimethylformamide and ethanol in a weight ratio of 1: 3), 5 g of N-heptafluorobutyrylimidazole and 5 g of 1, 7-dibromoheptane in a stirrer to form a mixed material, and standing and curing the mixed material at normal temperature for 5 hours;
(2) calendering the mixed material into a base band by a calender at 60 ℃;
(3) stretching the base band longitudinally by 2 times and transversely by 2 times at 150 ℃ by using a spoke expanding machine, sintering and heat setting at 330 ℃ for 2 hours to obtain a polytetrafluoroethylene composite material;
(4) grinding the polytetrafluoroethylene composite material in a grinding machine until the average particle size is 800 nanometers to obtain a powdery polytetrafluoroethylene composite material;
the preparation method of the polysiloxane comprises the following steps:
adding 10 g of 3-aminopropylmethyldimethoxysilane, 30 g of perfluorooctyltriethoxysilane, 55 g of 1,3,5, 7-tetramethylcyclotetrasiloxane, 5 g of low sulfonation degree graphene oxide (sulfonation degree of 10%) and 0.2 g of tetramethylammonium hydroxide into a reactor, introducing nitrogen for protection, stirring, heating to 90 ℃, reacting for 2 hours, and heating to 120 ℃ for reacting for 1 hour to obtain polysiloxane;
the preparation method of the polymer modified nano filler comprises the following steps:
(1) adding 1mol of 1, 2-propylene glycol, 1mol of terephthalic acid, 0.5 mol of trimethylolpropane and 0.01mol of monobutyltin oxide into a reactor, reacting for 2 hours under the protection of argon and heating to 90 ℃, then heating to 270 ℃, adjusting the vacuum degree to be less than 0.02 MPa, continuing to react for 6 hours, cooling to room temperature, then adding 1000ml of N, N-dimethylformamide, 0.2mol of beta-cyclodextrin and KH-5600.05 mol into the reactor, heating to 110 ℃, reacting for 10 hours, then pouring the reaction solution into water, washing the obtained solid with water for 3 times, and fully drying the solid to obtain cyclodextrin modified polyester;
(2) at room temperature, 20 g of the cyclodextrin modified polyester is dissolved in 1000ml of DMF, then 2 g of nano yttrium oxide (average particle size of 300 nm), 3 g of nano silicon dioxide (average particle size of 100 nm), 5 g of hydroxyapatite (average particle size of 1 micron) and 5 g of silane coupling agent KH-550 are added, the mixture is kept at room temperature and stirred for 2 hours, and then the mixture is filtered by suction and the obtained solid is fully dried to obtain the polymer modified nano filler.
II, preparing the PVC pipe by the following steps:
(1) putting 100 parts by weight of PVC resin and 30 parts by weight of the powdery polytetrafluoroethylene composite material into a high-speed mixer, stirring and mixing to obtain a mixed material, wherein the stirring speed of the high-speed mixer is 800 rpm, the stirring time is 20 minutes, and the stirring temperature is 120 ℃;
(2) and (3) extruding and molding the mixed material at 170 ℃ to prepare the PVC pipe with the wall thickness of 5mm and the outer diameter of 200 mm.
Comparative example 3
I. The preparation method of the powdery polytetrafluoroethylene composite material comprises the following steps:
(1) stirring 100 g of polytetrafluoroethylene, 35 g of polysiloxane, 18 g of polymer modified nano filler, 12 g of aviation kerosene, 77 g of solvent (a mixture of N, N-dimethylformamide and isopropanol in a weight ratio of 1: 3), 5 g of N-heptafluorobutyrylimidazole and 5 g of 1, 7-dibromoheptane in a stirrer, fully mixing to form a mixed material, and standing and curing the mixed material at normal temperature for 5 hours;
(2) calendering the mixed material into a base band by a calender at 60 ℃;
(3) stretching the base band longitudinally by 2 times and transversely by 2 times at 150 ℃ by using a spoke expanding machine, sintering and heat setting at 330 ℃ for 2 hours to obtain a polytetrafluoroethylene composite material;
(4) grinding the polytetrafluoroethylene composite material in a grinding machine until the average particle size is 800 nanometers to obtain a powdery polytetrafluoroethylene composite material;
the preparation method of the polysiloxane comprises the following steps:
adding 10 g of 3-aminopropylmethyldimethoxysilane, 85 g of 1,3,5, 7-tetramethylcyclotetrasiloxane, 5 g of graphene oxide with low sulfonation degree (sulfonation degree of 10%) and 0.2 g of tetramethylammonium hydroxide into a reactor, introducing nitrogen for protection, stirring, heating to 90 ℃ for reaction for 2 hours, and heating to 120 ℃ for reaction for 1 hour to obtain polysiloxane;
the preparation method of the polymer modified nano filler comprises the following steps:
(1) adding 1mol of 1, 2-propylene glycol, 1mol of terephthalic acid, 0.5 mol of trimethylolpropane and 0.01mol of monobutyltin oxide into a reactor, reacting for 2 hours under the protection of argon and heating to 90 ℃, then heating to 270 ℃, adjusting the vacuum degree to be less than 0.02 MPa, continuing to react for 6 hours, cooling to room temperature, then adding 1000ml of N, N-dimethylformamide, 0.2mol of beta-cyclodextrin and KH-5600.05 mol into the reactor, heating to 110 ℃, reacting for 10 hours, then pouring the reaction solution into water, washing the obtained solid with water for 3 times, and fully drying the solid to obtain cyclodextrin modified polyester;
(2) at room temperature, 20 g of the cyclodextrin modified polyester is dissolved in 1000ml of DMF, then 2 g of nano yttrium oxide (average particle size of 300 nm), 3 g of nano silicon dioxide (average particle size of 100 nm), 5 g of hydroxyapatite (average particle size of 1 micron) and 5 g of silane coupling agent KH-550 are added, the mixture is kept at room temperature and stirred for 2 hours, and then the mixture is filtered by suction and the obtained solid is fully dried to obtain the polymer modified nano filler. A
II, preparing the PVC pipe by the following steps:
(1) putting 100 parts by weight of PVC resin and 30 parts by weight of the powdery polytetrafluoroethylene composite material into a high-speed mixer, stirring and mixing to obtain a mixed material, wherein the stirring speed of the high-speed mixer is 800 rpm, the stirring time is 20 minutes, and the stirring temperature is 120 ℃;
(2) and (3) extruding and molding the mixed material at 170 ℃ to prepare the PVC pipe with the wall thickness of 5mm and the outer diameter of 200 mm.
Comparative example 4
I. The preparation method of the powdery polytetrafluoroethylene composite material comprises the following steps:
(1) stirring 100 g of polytetrafluoroethylene, 35 g of polysiloxane, 18 g of polymer modified nano filler, 12 g of aviation kerosene, 77 g of solvent (a mixture of N, N-dimethylformamide and isopropanol in a weight ratio of 1: 3), 5 g of N-heptafluorobutyrylimidazole and 5 g of 1, 7-dibromoheptane in a stirrer, fully mixing to form a mixed material, and standing and curing the mixed material at normal temperature for 5 hours;
(2) calendering the mixed material into a base band by a calender at 60 ℃;
(3) stretching the base band longitudinally by 2 times and transversely by 2 times at 150 ℃ by using a spoke expanding machine, sintering and heat setting at 330 ℃ for 2 hours to obtain a polytetrafluoroethylene composite material;
(4) grinding the polytetrafluoroethylene composite material in a grinding machine until the average particle size is 800 nanometers to obtain a powdery polytetrafluoroethylene composite material;
the preparation method of the polysiloxane comprises the following steps:
adding 10 g of 3-aminopropylmethyldimethoxysilane, 30 g of perfluorooctyltriethoxysilane, 55 g of 1,3,5, 7-tetramethylcyclotetrasiloxane, 5 g of low sulfonation degree graphene oxide (sulfonation degree of 10%) and 0.2 g of tetramethylammonium hydroxide into a reactor, introducing nitrogen for protection, stirring, heating to 90 ℃, reacting for 2 hours, and heating to 120 ℃ for reacting for 1 hour to obtain polysiloxane;
the preparation method of the polymer modified nano filler comprises the following steps:
(1) adding 1mol of 1, 2-propylene glycol, 1mol of terephthalic acid, 0.5 mol of trimethylolpropane and 0.01mol of monobutyltin oxide into a reactor, reacting for 2 hours under the protection of argon and heating to 90 ℃, then heating to 270 ℃, adjusting the vacuum degree to be less than 0.02 MPa, continuing to react for 6 hours, cooling to room temperature, then adding 1000ml of N, N-dimethylformamide, 0.2mol of beta-cyclodextrin and KH-5600.05 mol into the reactor, heating to 110 ℃, reacting for 10 hours, then pouring the reaction solution into water, washing the obtained solid with water for 3 times, and fully drying the solid to obtain cyclodextrin modified polyester;
(2) at room temperature, 20 g of the cyclodextrin modified polyester is dissolved in 1000ml of DMF, then 5 g of nano yttrium oxide (average particle size of 300 nm), 5 g of hydroxyapatite (average particle size of 1 micron) and 5 g of silane coupling agent KH-550 are added, the mixture is stirred for 2 hours at room temperature, and then the mixture is filtered by suction, and the obtained solid is fully dried to obtain the polymer modified nano filler.
II, preparing the PVC pipe by the following steps:
(1) putting 100 parts by weight of PVC resin and 30 parts by weight of the powdery polytetrafluoroethylene composite material into a high-speed mixer, stirring and mixing to obtain a mixed material, wherein the stirring speed of the high-speed mixer is 800 rpm, the stirring time is 20 minutes, and the stirring temperature is 120 ℃;
(2) and (3) extruding and molding the mixed material at 170 ℃ to prepare the PVC pipe with the wall thickness of 5mm and the outer diameter of 200 mm.
The performance of the pipes obtained in the above examples and comparative examples was tested and the results are given in table 1 below.
TABLE 1
| Examples of the present invention | Water contact angle ° | Tensile strength |
| Example 1 | 134 | 48Mpa |
| Example 2 | 129 | 49Mpa |
| Example 3 | 140 | 51Mpa |
| Example 4 | 136 | 53Mpa |
| Comparative example 1 | 113 | 43Mpa |
| Comparative example 2 | 115 | 38Mpa |
| Comparative example 3 | 120 | 40Mpa |
| Comparative example 4 | 122 | 45Mpa |
| Pure PVC pipe | 101 | 57Mpa |
Claims (7)
1. The super-hydrophobic pipe is characterized by comprising the following preparation raw materials in parts by weight:
polyvinyl chloride 100
10-40 parts of a powdery polytetrafluoroethylene composite material;
the preparation raw materials of the powdery polytetrafluoroethylene composite material comprise:
polytetrafluoroethylene 100
Polysiloxane 35
Polymer modified nanofiller 18
Lubricant 12
N-heptafluorobutyrylimidazole 1-10
1, 7-dibromoheptane 1-10
77 parts of a solvent;
the preparation method of the polymer modified nano filler comprises the following steps:
(1) adding 1mol of 1, 2-propylene glycol, 1mol of terephthalic acid, 0.5 mol of trimethylolpropane and 0.01mol of monobutyltin oxide into a reactor, reacting for 2 hours under the protection of argon and heating to 90 ℃, then heating to 270 ℃, adjusting the vacuum degree to be less than 0.02 MPa, continuing to react for 6 hours, cooling to room temperature, then adding 1000ml of N, N-dimethylformamide, 0.2mol of beta-cyclodextrin and KH-5600.05 mol into the reactor, heating to 110 ℃, reacting for 10 hours, then pouring the reaction solution into water, washing the obtained solid with water for 3 times, and fully drying the solid to obtain cyclodextrin modified polyester;
(2) at room temperature, 20 g of the cyclodextrin modified polyester is dissolved in 1000ml of DMF, then 2 g of nano yttrium oxide with the average particle size of 300 nm, 3 g of nano silicon dioxide with the average particle size of 100 nm, 5 g of hydroxyapatite with the average particle size of 1 micron and 5 g of silane coupling agent KH-550 are added, the mixture is stirred for 2 hours at room temperature, and then the mixture is subjected to suction filtration, and the obtained solid is fully dried to obtain the polymer modified nano filler.
2. The superhydrophobic tubing of claim 1, wherein the raw materials comprise, in parts by weight: polyvinyl chloride 100
30 parts of powdery polytetrafluoroethylene composite material.
3. The superhydrophobic tubing of claim 1, wherein the polysiloxane is prepared by:
adding 10 g of 3-aminopropylmethyldimethoxysilane, 30 g of perfluorooctyltriethoxysilane, 55 g of 1,3,5, 7-tetramethylcyclotetrasiloxane, 5 g of low-sulfonation-degree graphene oxide and 0.2 g of tetramethylammonium hydroxide into a reactor, introducing nitrogen for protection, stirring, heating to 90 ℃ for reaction for 2 hours, and heating to 120 ℃ for reaction for 1 hour to obtain the polysiloxane.
4. The superhydrophobic tubing of claim 1, wherein the lubricant is jet fuel.
5. The superhydrophobic tubing of claim 1, wherein the solvent is selected from at least one of dimethyl sulfoxide, N-dimethylformamide, N-dimethylacetamide, acetone, ethanol, and isopropanol.
6. The superhydrophobic tubing of claim 1, wherein: the preparation method of the powdery polytetrafluoroethylene composite material comprises the following steps:
(1) stirring and fully mixing the raw materials in a stirrer to form a mixed material, and standing and curing the mixed material at normal temperature for 5 hours;
(2) calendering the mixed material into a base band by a calender at 60 ℃;
(3) stretching the base band longitudinally by 2 times and transversely by 2 times at 150 ℃ by using a spoke expanding machine, sintering and heat setting at 330 ℃ for 2 hours to obtain a polytetrafluoroethylene composite material;
(4) and grinding the polytetrafluoroethylene composite material in a grinder until the average particle size is 800 nanometers to obtain the powdery polytetrafluoroethylene composite material.
7. The preparation method of the super-hydrophobic pipe is characterized by comprising the following steps:
the raw materials as claimed in any of claims 1 to 6 are thoroughly mixed and then processed into pipes.
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| CN1621434A (en) * | 2003-11-28 | 2005-06-01 | 中国科学院化学研究所 | Super-hydrophobic porous polyvinyl chloride film and its preparing process |
| CN103756460A (en) * | 2014-01-19 | 2014-04-30 | 深圳市九合伟业科技有限公司 | Nanoscale waterproof film and preparation method thereof |
| CN106221064A (en) * | 2016-08-12 | 2016-12-14 | 滁州市宏源喷涂有限公司 | A kind of high heat-resisting self-lubricating PVC NBR composite foamed plate and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1621434A (en) * | 2003-11-28 | 2005-06-01 | 中国科学院化学研究所 | Super-hydrophobic porous polyvinyl chloride film and its preparing process |
| CN103756460A (en) * | 2014-01-19 | 2014-04-30 | 深圳市九合伟业科技有限公司 | Nanoscale waterproof film and preparation method thereof |
| CN106221064A (en) * | 2016-08-12 | 2016-12-14 | 滁州市宏源喷涂有限公司 | A kind of high heat-resisting self-lubricating PVC NBR composite foamed plate and preparation method thereof |
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