CN109458498B - High-strength PTFE composite pipe and preparation method thereof - Google Patents

High-strength PTFE composite pipe and preparation method thereof Download PDF

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Publication number
CN109458498B
CN109458498B CN201811591938.XA CN201811591938A CN109458498B CN 109458498 B CN109458498 B CN 109458498B CN 201811591938 A CN201811591938 A CN 201811591938A CN 109458498 B CN109458498 B CN 109458498B
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ptfe
fiber
inorganic fiber
pipe
tube
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CN109458498A (en
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宋朋泽
李刚
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Zhejiang Hongsheng New Material Technology Group Co ltd
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Zhejiang Hongsheng New Material Technology Group Co ltd
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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C67/00—Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00
    • B29C67/02—Moulding by agglomerating
    • B29C67/04—Sintering
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
    • B29C70/28—Shaping operations therefor
    • B29C70/30—Shaping by lay-up, i.e. applying fibres, tape or broadsheet on a mould, former or core; Shaping by spray-up, i.e. spraying of fibres on a mould, former or core
    • B29C70/34—Shaping by lay-up, i.e. applying fibres, tape or broadsheet on a mould, former or core; Shaping by spray-up, i.e. spraying of fibres on a mould, former or core and shaping or impregnating by compression, i.e. combined with compressing after the lay-up operation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L95/00—Compositions of bituminous materials, e.g. asphalt, tar, pitch
    • 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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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Structural Engineering (AREA)
  • Materials Engineering (AREA)
  • Civil Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Composite Materials (AREA)
  • Laminated Bodies (AREA)
  • Rigid Pipes And Flexible Pipes (AREA)

Abstract

The invention provides a high-strength PTFE composite pipe, which comprises a PTFE inner pipe, an inorganic fiber net woven and wound on the outer surface of the PTFE inner pipe and a PTFE outer pipe compounded on the surface of the inorganic fiber net; the inorganic fiber net is obtained by weaving and sintering inorganic fibers on the outer surface of the PTFE inner tube; the inorganic fiber is one or more of glass fiber, special glass fiber, basalt fiber, perlite fiber, high silica fiber and high silica modified fiber; the diameter of the inorganic fiber is 3.5-6 mu m. According to the invention, the inorganic fiber net is adopted to form a net-shaped mosaic structure between two layers of PTFE pipelines, so that the compression resistance and the dimensional stability of the PTFE pipe wall material are effectively enhanced, and the bursting pressure of the PTFE composite pipe is remarkably improved compared with that of a pure PTFE pipe, and the PTFE composite pipe is more suitable for high-temperature, high-pressure and certain strong corrosion environments. The invention also provides a preparation method of the high-strength PTFE composite pipe.

Description

High-strength PTFE composite pipe and preparation method thereof
Technical Field
The invention belongs to the technical field of building pipes, and particularly relates to a high-strength PTFE composite pipe and a preparation method thereof.
Background
The pipeline transportation (Pipeline transport) is a transportation mode for long-distance transportation of liquid and gas materials by using pipelines as transportation means, is a transportation mode for transporting petroleum, coal and chemical products to markets by production places, and is a special component of dry line transportation in a unified transportation network. The pipeline transportation is large in transportation quantity, continuous, rapid, economical, safe, reliable, stable, small in investment, small in occupied area and low in cost, and can realize automatic control. Besides being widely used for long-distance transportation of petroleum and natural gas, the device can also be used for transporting ores, coal, building materials, chemicals, grains and the like. The pipeline transportation can omit a middle damaged section of water transportation or land transportation, shortens the transportation period, reduces the transportation cost and improves the transportation efficiency.
The PTFE (polytetrafluoroethylene) tube has the advantages of extremely strong chemical stability, ageing resistance, non-tackiness, incombustibility and the like, and is suitable for conveying strong acid, strong alkali and various corrosive media relative to other pipeline materials, and the use temperature range of the PTFE tube can reach-180 ℃ to 260 ℃ under normal pressure. In addition, PTFE has small friction coefficient and self-lubricating effect, and can greatly reduce the conveying resistance of pipeline media. The PTFE pipe is widely used in many fields such as petroleum, chemical industry, food, national defense industry, advanced technology, medicine and the like. However, in practical applications, PTFE tubes still have problems such as poor antiknock capability and poor dimensional stability, and particularly, for some fields requiring higher service pressure, further improvements in pressure resistance, tensile strength, and the like have been desired.
Disclosure of Invention
The invention aims to provide a high-strength PTFE composite pipe and a preparation method thereof.
The invention provides a high-strength PTFE composite pipe, which comprises a PTFE inner pipe, an inorganic fiber net woven and wound on the outer surface of the PTFE inner pipe and a PTFE outer pipe compounded on the surface of the inorganic fiber net;
the inorganic fiber net is obtained by weaving and sintering inorganic fibers on the outer surface of the PTFE inner tube;
the inorganic fiber is one or more of glass fiber, special glass fiber, basalt fiber, perlite fiber, high silica fiber and high silica modified fiber;
the diameter of the inorganic fiber is 3.5-6 mu m.
Preferably, the inorganic fiber web has a weave density of 1 to 30 pieces/cm.
Preferably, the inorganic fiber web has a thickness of 0.1 to 0.3mm.
Preferably, the total thickness of the high-strength PTFE composite pipe is 0.4-2.0 mm.
The invention provides a preparation method of a high-strength PTFE composite pipe, which comprises the following steps:
a) Winding and braiding inorganic fibers on the outer surface of the PTFE inner tube to obtain the PTFE inner tube covered with the inorganic fiber net;
the inorganic fiber is one or more of glass fiber, special glass fiber, basalt fiber, perlite fiber, high silica fiber and high silica modified fiber;
the diameter of the inorganic fiber is 3.5-6 mu m;
b) And (3) nesting and compositing the PTFE outer tube and the PTFE inner tube covered with the inorganic fiber net, degreasing and sintering to form the PTFE composite tube.
Preferably, the inorganic fiber is woven on the surface of the PTFE inner tube after being subjected to presintered treatment;
the temperature of the presintered is 300-600 ℃;
the presintering time is 5-20 min.
Preferably, the PTFE inner tube and the PTFE outer tube are prepared according to the following steps:
and mixing polytetrafluoroethylene resin and an auxiliary agent, standing, sequentially prepressing, pushing, pressing, molding and sintering to obtain the PTFE inner tube or the PTFE outer tube.
Preferably, the auxiliary agent comprises aviation kerosene and a silane coupling agent;
the mass ratio of aviation kerosene to polytetrafluoroethylene is (15-35): 1, a step of;
the mass ratio of the silane coupling agent to the polytetrafluoroethylene is (0.1-1.5): 100.
preferably, the aviation kerosene is high flash point aviation kerosene;
the silane coupling agent is one or more of vinyl trimethoxy silane, vinyl triethoxy silane, gamma-glycidol ether oxygen propyl trimethoxy silane and gamma-aminopropyl triethoxy silane.
Preferably, the sintering molding temperature in the step B) is 325-355 ℃;
and B), sintering and forming for 5-30 min.
The invention provides a high-strength PTFE composite pipe, which comprises a PTFE inner pipe, an inorganic fiber net woven and wound on the outer surface of the PTFE inner pipe and a PTFE outer pipe compounded on the surface of the inorganic fiber net; the inorganic fiber net is obtained by weaving and sintering inorganic fibers on the outer surface of the PTFE inner tube; the inorganic fiber is one or more of glass fiber, special glass fiber, basalt fiber, perlite fiber, high silica fiber and high silica modified fiber; the diameter of the inorganic fiber is 3.5-6 mu m. The inner layer and the outer layer of the PTFE pipeline are made of polytetrafluoroethylene, the inorganic fiber net reinforcing layer is a core layer of the composite pipe and is made of inorganic fibers through a special braiding process, and a tightly nested composite structure is formed between the inner layer and the outer layer of the PTFE pipeline. According to the invention, a net-shaped mosaic structure is formed between the inner layer and the outer layer of the PTFE pipeline by adopting the inorganic fiber net subjected to special pretreatment, so that the compression resistance and the dimensional stability of the PTFE pipeline wall material are effectively enhanced, and the bursting pressure of the PTFE composite pipe is remarkably improved compared with that of a pure PTFE pipe, so that the PTFE composite pipe is more suitable for being used in high-temperature, high-pressure and certain strong corrosion environments. Experimental results show that the pressure resistance of the composite pipe with the outer diameter of 6mm is 8.3MPa, and the pressure resistance is improved by 180%; the molding shrinkage is 3%, the tensile strength is 25-50 MPa, the thermal deformation temperature is 150 ℃, and the flexural modulus is 5400-9000 MPa.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required to be used in the embodiments or the description of the prior art will be briefly described below, and it is obvious that the drawings in the following description are only embodiments of the present invention, and that other drawings can be obtained according to the provided drawings without inventive effort for a person skilled in the art.
FIG. 1 is a schematic side view of a high strength PTFE composite pipe according to the present invention;
FIG. 2 is a schematic cross-sectional view of a high strength PTFE composite pipe according to the present invention;
wherein 1 is an outer PTFE tube, 2 is an inorganic fiber net, and 3 is an inner PTFE tube.
Detailed Description
The invention provides a high-strength PTFE composite pipe, which comprises a PTFE inner pipe, an inorganic fiber net woven and wound on the outer surface of the PTFE inner pipe and a PTFE outer pipe compounded on the surface of the inorganic fiber net;
the inorganic fiber net is obtained by weaving and sintering inorganic fibers on the outer surface of the PTFE;
the inorganic fiber is one or more of glass fiber, special glass fiber, basalt fiber, perlite fiber, high silica fiber and high silica modified fiber;
the diameter of the inorganic fiber is 3.5-6 mu m.
The high-strength PTFE composite pipe consists of a three-layer nested composite structure, which sequentially comprises a PTFE inner pipe, an inorganic fiber net and a PTFE outer pipe, wherein the inorganic fiber net is a reinforced core layer of the composite pipe.
In the present invention, the material of the PTFE inner tube is polytetrafluoroethylene, and the thickness of the PTFE inner tube is preferably 0.2 to 0.5mm, and specifically, in the embodiment of the present invention, may be 0.25mm, 0.3mm or 0.4mm. The invention is not particularly limited to the outer diameter of the tube material of the PTFE inner tube.
In the present invention, the material of the PTFE outer tube is polytetrafluoroethylene, and the thickness of the PTFE outer tube is preferably 0.2 to 0.5mm, and specifically, in the embodiment of the present invention, may be 0.25mm, 0.3mm or 0.4mm. Preferably, the PTFE outer tube is of uniform thickness as the PTFE inner tube. The inner diameter and the outer diameter of the PTFE outer tube are not particularly limited, and the PTFE outer tube can be matched with the inner tube and the inorganic fiber net to form a good nested composite structure.
In the invention, the inorganic fiber net is wound and woven on the outer surface of the PTFE inner pipe and is compounded with the inner wall of the PTFE outer pipe to form a three-layer nested compound structure.
The inorganic fiber net is obtained by weaving and sintering inorganic fibers on the outer surface of the PTFE, wherein the inorganic fibers are preferably one or more of glass fibers, special glass fibers, basalt fibers, perlite fibers, high silica fibers and high silica modified fibers; the diameter of the fibers is preferably 3.5-6 μm, namely, the fibers are preferably woven by monofilament fine denier fibers, and the invention is preferably cross-woven, crisscross grid woven or spirally wound and woven along the pipe wall, and more preferably cross-woven; the density of the weave is preferably 1 to 30, more preferably 5 to 25, and in particular, may be 6, 10 or 20 in embodiments of the invention. The weaving angle of the inorganic fibers is preferably 30 to 60 °, more preferably 45 °.
The thickness of the inorganic fiber web is preferably 0.1 to 3mm, more preferably 0.1 to 2mm, most preferably 0.2 to 1mm, and in particular, may be 0.1mm or 0.2mm in embodiments of the present invention.
In the present invention, the total thickness of the high-strength PTFE composite pipe is preferably 0.4 to 2.0mm, more preferably 0.6 to 1.0mm, and in particular, in the embodiment of the present invention, may be 0.6mm, 0.8mm or 1.0mm.
The invention also provides a preparation method of the high-strength PTFE composite pipe, which comprises the following steps:
a) Winding and braiding inorganic fibers on the outer surface of the PTFE inner tube to obtain the PTFE inner tube covered with the inorganic fiber net;
the inorganic fiber is one or more of glass fiber, special glass fiber, basalt fiber, perlite fiber, high silica fiber and high silica modified fiber;
the diameter of the inorganic fiber is 3.5-6 mu m;
b) And (3) nesting and compositing the PTFE outer tube and the PTFE inner tube covered with the inorganic fiber net, degreasing and sintering to form the PTFE composite tube.
The PTFE inner tube is preferably prepared according to the following steps,
and mixing polytetrafluoroethylene resin and an auxiliary agent, standing, and sequentially prepressing, pushing, pressing and sintering to obtain the PTFE inner tube.
In the invention, the auxiliary agent preferably comprises aviation kerosene and a silane coupling agent, wherein the aviation kerosene is preferably high-flash aviation kerosene, and the mass ratio of the aviation kerosene to the polytetrafluoroethylene resin is preferably (15-35): 100, more preferably (20 to 30): 100, most preferably (25 to 30): 100;
the silane coupling agent is preferably one or more of vinyl trimethoxy silane, vinyl triethoxy silane, gamma-glycidol ether oxygen propyl trimethoxy silane and gamma-aminopropyl triethoxy silane; the mass ratio of the silane coupling agent to the polytetrafluoroethylene resin is preferably (0.1-1.5): 100, more preferably (0.5 to 1): 100.
in the present invention, the addition of the auxiliary agent is more advantageous in promoting the bonding between the PTFE inner and outer tubes and the inorganic fiber web.
According to the invention, the polytetrafluoroethylene resin and the auxiliary agent are mixed, and the uniform distribution of the polytetrafluoroethylene resin and the auxiliary agent is realized by the double functions of the stirrer and the container rotation, so that the subsequent processing is facilitated;
after the mixing is completed, the obtained mixture is subjected to standing and material awakening so as to promote the fusion of the polytetrafluoroethylene raw material and the auxiliary agent. The temperature of the standing is preferably a constant temperature of 22-26 ℃, more preferably 25+ -1 ℃; the time for the standing is preferably 8 to 16 hours, more preferably 10 to 15 hours.
After the static is finished, the mixture after static is pre-pressed and formed, wherein the pressure of the pre-pressing and forming is preferably 0.35-0.40 MPa, and the pre-pressing and forming method is preferably carried out by adopting a pre-pressing machine.
After the prepressing is finished, the prepressing blank is extruded by pushing and pressing to prepare a PTFE inner tube with uniform structure, wherein the pressure of pushing and pressing is preferably 0.40-0.45 MPa;
after pushing and pressing, the formed PTFE inner tube is sintered and shaped to obtain the PTFE inner tube, wherein the sintering and shaping temperature is preferably 325-355 ℃, more preferably 330-340 ℃; the sintering and shaping time is preferably 10-20 min, specifically, in the embodiment of the invention, may be 10min, 15min or 20min.
The preparation method of the PTFE outer tube is consistent with that of the PTFE inner tube, and different extrusion tube diameters are adjusted, so that the invention is not repeated here.
After the PTFE inner tube and the PTFE outer tube are obtained, the inorganic fiber is wound and woven on the outer surface of the PTFE inner tube, and then the inorganic fiber and the PTFE outer tube are subjected to nested compounding, degreasing and sintering molding to obtain the high-strength PTFE composite tube.
The invention preferably carries out pre-sintering treatment on the inorganic fibers, and aims to remove impregnating compound residues on the surfaces of the fibers and ensure better and firmer combination of the inorganic fiber woven layer and the PTFE tube. The temperature of the pre-sintering is preferably 300-600 ℃, more preferably 300-450 ℃, and in particular, in the embodiment of the invention, the temperature can be 300 ℃, 400 ℃ or 450 ℃; the pre-sintering time is preferably 5 to 30 minutes, more preferably 8 to 12 minutes.
In the present invention, the kind of the inorganic fiber, the weaving method of the inorganic fiber and the weaving density are identical to those described above, and are not described here again.
The nested composite process in the invention is to combine the inner tube and the outer tube together through the operation of sucking vacuum, and the vacuum degree is preferably-0.01 to-0.04 MPa.
The composite pipe after nested and compounded is introduced into an oil removing system for removing oil, and the oil removing process is an oil removing technology known to those skilled in the art and is not repeated here.
The composite pipe is sintered and shaped after oil removal, wherein the temperature of the sintering and shaping is preferably 325-355 ℃, more preferably 330-340 ℃, and in particular, in the embodiment of the invention, the temperature can be 330 ℃, 340 ℃ or 355 ℃; the sintering and shaping time is preferably 5 to 30min, more preferably 9 to 12min.
The invention provides a high-strength PTFE composite pipe, which comprises a PTFE inner pipe, an inorganic fiber net woven and wound on the outer surface of the PTFE inner pipe and a PTFE outer pipe compounded on the surface of the inorganic fiber net; the inorganic fiber net is obtained by weaving and sintering inorganic fibers on the outer surface of the PTFE; the inorganic fiber is one or more of glass fiber, special glass fiber, basalt fiber, perlite fiber, high silica fiber and high silica modified fiber; the diameter of the inorganic fiber is 3.5-6 mu m. The inner layer and the outer layer of the PTFE pipeline are made of polytetrafluoroethylene, the inorganic fiber net reinforcing layer is a core layer of the composite pipe and is made of inorganic fibers through a special braiding process, and a tightly nested composite structure is formed between the inner layer and the outer layer of the PTFE pipeline. According to the invention, a net-shaped mosaic structure is formed between the inner layer and the outer layer of the PTFE pipeline by adopting the inorganic fiber net subjected to special pretreatment, so that the compression resistance and the dimensional stability of the PTFE pipeline wall material are effectively enhanced, and the bursting pressure of the PTFE composite pipe is remarkably improved compared with that of a pure PTFE pipe, so that the PTFE composite pipe is more suitable for being used in high-temperature, high-pressure and certain strong corrosion environments. Experimental results show that the pressure resistance of the composite pipe with the outer diameter of 6mm is 8.3MPa, and the pressure resistance is improved by 180%; the molding shrinkage is 3%, the tensile strength is 25-50 MPa, the thermal deformation temperature is 150 ℃, and the flexural modulus is 5400-9000 MPa.
In order to further illustrate the present invention, the following examples are provided to describe in detail a high strength PTFE composite tube and a method for preparing the same, but should not be construed to limit the scope of the present invention.
Example 1
1000g of polytetrafluoroethylene resin, 150g of aviation kerosene and 1g of vinyl trimethoxy silane are uniformly distributed through the dual actions of a stirrer and a container, so that the subsequent processing is facilitated. The evenly mixed raw materials are kept stand for 12 hours at a constant temperature of 25+/-1 ℃ to promote the fusion of the polytetrafluoroethylene raw materials and the auxiliary agent.
After standing and awakening, the premix is put into a preformer for pressing, and the pressure value is preferably 0.35MPa, so as to prepare a blank.
The pre-pressed blank is introduced into a push press and extruded under the pressure of 0.40MPa to form the inner PTFE pipe with uniform structure and 0.25mm wall thickness.
And (3) conveying the inner PTFE pipe into a sintering machine, and sintering and shaping at 330+/-2 ℃ for 20min.
The fine denier special glass fiber is presintered at 300 ℃ to remove the impregnating compound residues on the surface of the fiber. The fine denier special glass fiber is woven and wound on the surface of the sintered inner PTFE tube by a warp knitting machine, the weaving density is 10 pieces/cm, the weaving angle is 45 degrees, the winding thickness is 0.1mm, and the fine denier special glass fiber weaving layer and the PTFE tube are better and more firmly combined in the weaving process.
The outer layer PTFE tube was subjected to the same manufacturing process as the inner layer PTFE tube in order to obtain an outer layer PTFE tube having a wall thickness of 0.25 mm. The inner layer PTFE tube and the outer layer PTFE tube which are woven and wound with fine denier special glass fiber on the surface are nested and compounded, the PTFE composite tube after the compounding processing is introduced into an oil removing system to remove auxiliary oil, and the PTFE composite tube enters a sintering machine after oil removal, and is sintered and shaped at the temperature of 330+/-2 ℃. The inner layer PTFE tube, the fine denier special glass fiber winding braid and the outer layer PTFE tube are tightly combined together through nested composite processing and sintering shaping, and the high-strength special glass fiber/PTFE composite tube with the wall thickness of 0.6mm is manufactured. And finally, rolling, checking, packaging and warehousing.
The pressure resistance of the PTFE composite tube obtained in example 1 is shown in table 1,
TABLE 1 pressure resistance of PTFE composite pipe obtained in example 1
Example 2
1000g of polytetrafluoroethylene resin, 280g of aviation kerosene and 6g of vinyl triethoxysilane are uniformly distributed through double functions of a stirrer and a container, so that subsequent processing is facilitated. The evenly mixed raw materials are stood for 16 hours at a constant temperature of 22+/-1 ℃ to promote the fusion of the polytetrafluoroethylene raw materials and the auxiliary agent.
After standing and awakening, the premix is put into a preformer to be pressed into a blank under the pressure of 0.38 MPa.
The pre-pressed blank is introduced into a push press and extruded under the pressure of 0.43MPa to form the inner PTFE pipe with uniform structure and 0.3mm wall thickness.
And (3) conveying the inner PTFE pipe into a sintering machine, and sintering and shaping at 340+/-2 ℃ for 15min.
The fine denier basalt fiber is presintered at 400 ℃ to remove impregnating compound residues on the surface of the fiber. The fine denier basalt fiber is woven and wound on the surface of the inner PTFE pipe formed by sintering through a warp knitting machine, the weaving density is 6 pieces/cm, the weaving angle is 45 degrees, the thickness is 0.2mm, and the fine denier basalt fiber weaving layer and the PTFE pipe are better and more firmly combined in the weaving process.
The outer layer PTFE tube is sequentially subjected to the same manufacturing procedure as the inner layer PTFE tube to prepare the outer layer PTFE tube with the wall thickness of 0.3mm. The inner PTFE tube and the outer PTFE tube which are woven and wound with fine denier basalt fibers on the surfaces are nested and compounded, the PTFE composite tube after compounding processing is introduced into an oil removing system to remove auxiliary oil, and the PTFE composite tube enters a sintering machine after oil removal and is sintered and shaped at the temperature of 340+/-2 ℃. The inner layer PTFE tube, the fine denier basalt fiber winding braid and the outer layer PTFE tube are tightly combined together through nested composite processing and sintering shaping, and the high-strength basalt fiber/PTFE composite tube with the wall thickness of 0.8mm is manufactured. And finally, rolling, checking, packaging and warehousing.
The pressure resistance of the PTFE composite tube obtained in example 2 is shown in table 2,
TABLE 2 pressure resistance of PTFE composite pipe obtained in example 2
Example 3
1000g of polytetrafluoroethylene resin, 350g of aviation kerosene and 10g of gamma-glycidol ether oxypropyl trimethoxy silane are uniformly distributed through the dual actions of a stirrer and a container rotation, so that the subsequent processing is facilitated. The evenly mixed raw materials are kept stand for 8 hours at a constant temperature of 26+/-1 ℃ to promote the fusion of the polytetrafluoroethylene raw materials and the auxiliary agent.
After standing and awakening, the premix is put into a preformer to be pressed into a blank under the pressure of 0.4 MPa.
The pre-pressed blank is introduced into a push press and extruded under the pressure of 0.45MPa to form the inner PTFE pipe with uniform structure and 0.4mm wall thickness.
And (3) conveying the inner PTFE pipe into a sintering machine, and sintering and shaping at 355+/-2 ℃ for 10min.
The fine denier high silica (modified) fiber is pre-sintered at 450 ℃ to remove the sizing agent residue on the fiber surface. The fine denier high silica (modified) fiber is woven and wound on the surface of the inner PTFE tube formed by sintering through a warp knitting machine, the weaving density is 20 pieces/cm, the weaving angle is 45 degrees, the thickness is 0.2mm, and the fine denier high silica (modified) fiber weaving layer and the PTFE tube are better and more firmly combined in the weaving process.
The outer layer PTFE tube is sequentially subjected to the same manufacturing procedure as the inner layer PTFE tube to prepare the outer layer PTFE tube with the wall thickness of 0.4mm. The inner layer PTFE tube and the outer layer PTFE tube which are woven and wound with fine denier high silica (modified) fiber on the surface are nested and compounded, the PTFE composite tube after the compounding processing is introduced into an oil removing system to remove auxiliary oil, and the PTFE composite tube enters a sintering machine after oil removal, and is sintered and shaped at 355+/-2 ℃. The inner layer PTFE tube, the fine denier high silica (modified) fiber winding braid and the outer layer PTFE tube are tightly combined together through nested composite processing and sintering shaping, and the high strength high silica (modified) fiber/PTFE composite tube with the wall thickness of 1mm is manufactured. And finally, rolling, checking, packaging and warehousing.
The pressure resistance of the PTFE composite tube obtained in example 3 is shown in table 3,
TABLE 3 pressure resistance of PTFE composite pipe obtained in example 3
Comparative example 1
The PTFE composite tube was prepared according to the preparation method in example 1, except that only polytetrafluoroethylene resin was used as the raw material for the PTFE inner tube and the PTFE outer tube in the present comparative example, and aviation kerosene and a silane coupling agent auxiliary agent were not used.
The pressure resistance of the obtained PTFE composite pipe is shown in Table 4.
TABLE 4 pressure resistance of PTFE composite pipe obtained in comparative example 1
Comparative example 2
A PTFE composite tube was prepared according to the preparation method in example 1, except that the inorganic fibers in this comparative example were used directly for braiding an inorganic fiber web without pre-sintering.
The pressure resistance of the obtained PTFE composite pipe is shown in Table 5.
TABLE 5 pressure resistance of PTFE composite pipe obtained in comparative example 2
TABLE 6 comparison of the Performance of PTFE composite tubes and pure PTFE tubes in example 3 and comparative examples 1-2
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.

Claims (7)

1. The preparation method of the high-strength PTFE composite pipe comprises the following steps:
a) After the inorganic fiber is subjected to presintered treatment, winding and braiding the inorganic fiber on the outer surface of the PTFE inner tube to obtain the PTFE inner tube covered with the inorganic fiber net;
the inorganic fiber is one or more of glass fiber, special glass fiber, basalt fiber, perlite fiber, high silica fiber and high silica modified fiber;
the diameter of the inorganic fiber is 3.5-6 mu m;
the temperature of the pre-sintering is 300-600 ℃; the presintering time is 5-20 min;
b) The PTFE outer tube and the PTFE inner tube covered with the inorganic fiber net are subjected to nested compounding, degreasing and sintering molding in sequence, so that a high-strength PTFE composite tube is obtained;
the PTFE inner tube and the PTFE outer tube are prepared according to the following steps:
mixing polytetrafluoroethylene resin and an auxiliary agent, standing, sequentially prepressing, pushing, forming and sintering to form a PTFE inner tube or a PTFE outer tube; the auxiliary agent comprises aviation kerosene and a silane coupling agent;
the mass ratio of aviation kerosene to polytetrafluoroethylene is (15-35): 100; the mass ratio of the silane coupling agent to the polytetrafluoroethylene is (0.1-1.5): 100.
2. the method of claim 1, wherein the aviation kerosene is a high flash point aviation kerosene;
the silane coupling agent is one or more of vinyl trimethoxy silane, vinyl triethoxy silane, gamma-glycidol ether oxygen propyl trimethoxy silane and gamma-aminopropyl triethoxy silane.
3. The method according to claim 1, wherein the sintering temperature in the step B) is 325-355 ℃;
and B), sintering and forming for 5-30 min.
4. The high-strength PTFE composite pipe prepared by the preparation method according to claim 1 comprises a PTFE inner pipe, an inorganic fiber net woven and wound on the outer surface of the PTFE inner pipe and a PTFE outer pipe compounded on the surface of the inorganic fiber net;
the inorganic fiber net is obtained by weaving and sintering inorganic fibers on the outer surface of the PTFE inner tube;
the inorganic fiber is one or more of glass fiber, special glass fiber, basalt fiber, perlite fiber, high silica fiber and high silica modified fiber;
the diameter of the inorganic fiber is 3.5-6 mu m.
5. The high strength PTFE composite pipe of claim 4 wherein the inorganic fiber web has a braid density of 1 to 30 roots/cm.
6. The high strength PTFE composite pipe of claim 4 wherein the inorganic fiber web has a thickness of 0.1 to 0.3mm.
7. The high strength PTFE composite pipe of claim 6, wherein the high strength PTFE composite pipe has an overall thickness of 0.4 to 2.0mm.
CN201811591938.XA 2018-12-25 2018-12-25 High-strength PTFE composite pipe and preparation method thereof Active CN109458498B (en)

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