CN109249599B - Polymer functional pipe with continuous gradual change spiral structure and preparation method thereof - Google Patents
Polymer functional pipe with continuous gradual change spiral structure and preparation method thereof Download PDFInfo
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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
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Abstract
The invention discloses a polymer functional pipe with a continuous gradual change spiral structure and a preparation method thereof, wherein the pipe is extruded and molded by a core rod or/and a neck ring of an extrusion head at a variable rotation speed, polymer molecular chains are spirally arranged and distributed in the axial direction or/and the radial direction of the wall thickness, and the spiral degree in the axial direction or/and the radial direction is increased or reduced along the axial direction. The tube can obtain the rigidity of the tube endowed by low rotation rate and the gradual change mechanical property of the flexibility of the tube endowed by high rotation rate, thereby filling a blank of a polymer functional tube and solving the problems of the existing medical interventional polymer catheter.
Description
Technical Field
The invention belongs to the technical field of polymer pipes and processing methods thereof, and particularly relates to a polymer functional pipe with a continuous gradually-changing spiral structure and a preparation method thereof.
Background
Interventional therapy is a revolutionary breakthrough in modern clinical medical treatment. Interventional catheters, such as central venous catheters, electrophysiological catheters, angiography catheters, and the like, are transmission channels for constructing various interventional treatment devices, have a drug administration function, and are important medical devices for realizing interventional treatment. However, due to great difference in quality of related products at home and abroad, high-end micro catheters mainly depend on import, for example, more than 10 hundred million medical catheters are imported in 2016, so that development of high and new industries in China and improvement of medical level are greatly restricted, and great economic burden is brought to users. Therefore, the realization of the localization of high-performance micro polymer catheters is a demand for the development of national economy.
The Medical interventional catheter is a small-section hollow product with small characteristic dimensions, such as a contrast PU catheter with a diameter less than or equal to 2mm and a wall thickness less than or equal to 500 μm, so that the strength is low and kinks easily under stress, and although the conventional micro-polymer catheter extrusion processing is simple, generally, polymer melt is extruded through an annular die, axially stretched by a tractor, and cooled and sized, the micro-polymer catheter cannot effectively regulate a multi-level and multi-scale structure, and a high-performance micro-polymer catheter satisfying requirements is difficult to be manufactured, in particular, during interventional therapy, doctors usually perform advancement and steering of the catheter through pushing, pulling, rotating and other operations, so that the catheter reaches a distal target lesion position along a non-regular and tortuous channel of a human body, which requires that the catheter have excellent pushability, kink resistance, torsion response and soft front end, but because of softness and pushability, axial push, stress response and radial stress response contradictory and thin-wall of the micro-polymer catheter are difficult to manufacture by simple extrusion processing, so that the interventional catheter having excellent resistance and response to multi-directional loads, and the characteristics of the axial tension of the catheter produced by the inner and outer layers of the catheter become fragile fibers are not easily damaged by the inner and outer fibers of the inner and outer layers of the catheter produced by the inner and outer layers of the catheter.
Disclosure of Invention
The invention aims to provide a polymer functional pipe with a continuously gradually-changed spiral structure and a preparation method thereof, aiming at the defects of the prior art.
In order to achieve the purpose, the invention firstly adopts the technical scheme consisting of the following technical measures to realize the polymer functional pipe with the continuous gradual spiral structure.
A functional polymer pipe with a continuously gradually-changed spiral structure is characterized in that polymer molecular chains in the pipe are distributed in a spiral arrangement in the axial direction, the spiral degree in the axial direction is increased or reduced along the axial direction or/and is distributed in a spiral arrangement in the radial direction of the wall thickness of the pipe, and the spiral degree in the radial direction is increased or reduced along the radial direction.
The above functional polymer pipe further comprises a filler having a fibrous structure, the filler being distributed in a helical arrangement in the axial direction, and the degree of helical arrangement in the axial direction being increased or decreased in the axial direction and/or being distributed in a helical arrangement in the radial direction of the wall thickness thereof, and the degree of helical arrangement in the radial direction being increased or decreased in the radial direction.
The polymer in the polymer functional pipe is a thermoplastically processable polymer, and specifically is any one of a polyolefin polymer, a polyamide polymer or polyurethane. Wherein the polyolefin-based polymer is preferably polyethylene, polypropylene or a polyolefin elastomer; the polyamide-based polymer is preferably polyamide 11, polyamide 12, polyamide 1212 or polyamide 6.
The polymer in the above polymer functional pipe is further preferably a polyolefin elastomer, polyamide 11, polyamide 12 or polyurethane.
The filler having a fibrous structure in the above polymer functional pipe is any one of carbon fiber, carbon nanotube, nanocellulose, whisker, metal nanowire, cotton fiber, hemp fiber, polyester fiber or aramid fiber, and further preferably carbon fiber, carbon nanotube and silver nanowire.
The method for preparing the polymer functional pipe with the continuous gradual change spiral structure is characterized in that in the process of processing and forming the polymer functional pipe, the core rod of an extruder head is used for extrusion processing and forming at a variable rotation rate or/and the neck ring of the extruder head is used for extrusion processing and forming at a variable rotation rate.
The preparation method of the polymer functional pipe with the continuous gradual change spiral structure comprises the following specific process steps:
adding a polymer or a polymer and a filler with a fibrous structure into a screw extruder according to a certain proportion, and extruding and processing the polymer or the polymer and the filler with the fibrous structure through an extrusion head with a variable speed rotation of a core rod or/and a die above the melting temperature of the polymer, or extruding and processing the polymer and the filler with a variable rotation speed of the set core rod or/and the set die, or extruding and processing the polymer and the filler with a variable rotation speed of the set core rod and the set die in the same direction, or extruding and processing the.
The proportion of the filler having a fibrous structure described in the above method is 0.1 to 20%, preferably 0.1 to 10%, more preferably 0.1 to 5%.
The extruder head described in the above method may specifically employ the apparatus described in applicant's prior-granted application 200810045785.9.
The core rod or the die is set in the above method, the rotation speed is changed to be unidirectional, and the rotation speed is increased or decreased linearly and increased or decreased non-linearly with time.
When the rotation rate increases or decreases linearly with time, the time is denoted as T, and the initial rotation rate of the core rod or die is denoted as a constant kαThe rotation rate of the core rod or die is denoted by k1The rate of change of the rate of rotation of the mandrel or die is recorded as X1The linear increase or decrease in the rotation rate of the core rod or die satisfies the formula: k is a radical of1＝kα±X1T, wherein k1In the range of 0 to 100rpm, X1The variation range is 1-500 rpm/min, and the constant kαIn the range of 0 to 100rpm, and k1≠kα。
When the rotation rate increases or decreases non-linearly with time, the time is recorded as T, and the initial rotation rate of the core rod or die is recorded as a constant kαThe rotation rate of the core rod or die being recordedk2The rate of change of the rate of rotation of the mandrel or die is recorded as X2The nonlinear increase or decrease of the rotation rate of the core rod or the die satisfies the following formula: k is a radical of2＝kα±X2·|T|n-1T, wherein k2In the range of 0 to 100rpm, X2The variation range is 1-500 rpm/min, and the constant kαIn the range of 0 to 100rpm, and k2≠kα，2≤n≤6。
The rotation rate of the core rod and the die which are arranged in the above method and are changed in the same direction or in the opposite direction is that the core rod and the die are rotated in the same direction or in the opposite direction, and the rotation rate is linearly increased or decreased along with time or simultaneously, or is nonlinearly increased or decreased simultaneously, or is not linearly increased or decreased simultaneously. The rotation rate variation in both ways also corresponds to the following formula and its definition.
When the rotation rate increases or decreases linearly with time, the time is denoted as T, and the initial rotation rate of the core rod or die is denoted as a constant kαThe rotation rate of the core rod or die is denoted by k1The rate of change of the rate of rotation of the mandrel or die is recorded as X1The linear increase or decrease in the rotation rate of the core rod or die satisfies the formula: k is a radical of1＝kα±X1T, wherein k1In the range of 0 to 100rpm, X1The variation range is 1-500 rpm/min, and the constant kαIn the range of 0 to 100rpm, and k1≠kα。
When the rotation rate increases or decreases non-linearly with time, the time is recorded as T, and the initial rotation rate of the core rod or die is recorded as a constant kαThe rotation rate of the core rod or die is denoted by k2The rate of change of the rate of rotation of the mandrel or die is recorded as X2The nonlinear increase or decrease of the rotation rate of the core rod or the die satisfies the following formula: k is a radical of2＝kα±X2·|T|n-1T, wherein k2In the range of 0 to 100rpm, X2The variation range is 1-500 rpm/min, and the constant kαIn the range of 0 to 100rpm, and k2≠kα，2≤n≤6。
It is worth mentioning that other processing aids such as antioxidants, stabilizers, plasticizers, etc. known in the art can be added during the melt blending process of the polymer or the polymer and the filler in the actual industrial production. However, it is a prerequisite that these processing aids do not adversely affect the achievement of the objects of the present invention and the achievement of the advantageous effects of the present invention.
The invention has the following advantages:
1. the pipe provided by the invention is extruded and processed by the core rod of the extruder head at a variable rotation rate or/and is extruded and processed by the neck ring of the extruder head at a variable rotation rate, so that the obtained pipe is a polymer functional pipe with a continuous gradually-changing spiral structure, a blank of the polymer functional pipe is filled, and the problems of the existing medical interventional polymer catheter can be solved.
2. The invention provides a preparation method which is characterized in that a continuously variable spiral structure is formed on an extruded pipe by means of a continuously variable shearing force which is controlled by a computer and can rotate at a variable rotation speed in an extruder head used for extruding polymers or polymers and fillers with fibrous structures along the axial direction or/and the radial direction, so that the prepared polymer functional pipe can obtain the rigidity of the pipe endowed with low rotation speed and the gradual change mechanical property of the flexibility of the pipe endowed with high rotation speed compared with the spiral pipe with more stable rotation speed.
3. The preparation method provided by the invention has the advantages of simple process, convenient operation and continuous production, so that compared with the traditional preparation process, the preparation method not only obtains the polymer functional pipe with a new structure, but also provides a manufacturing approach for meeting different requirements of the market on the pipe.
4. The method provided by the invention does not need to add extra equipment in the preparation process, so that the method meets the requirements of industrial large-scale production, has a wide application system, effectively overcomes the defects of single condition and single rotation in the existing preparation process of the polymer or the polymer and the filler pipe, has a wide application range and is convenient to popularize.
Drawings
FIG. 1 is a schematic view of a polarizing microscope photograph showing the arrangement distribution of fillers observed at intervals of 2cm at a starting point of 0cm in the axial direction of a 10cm long polymer functional pipe prepared in example 1 of the present invention and pipes having a continuously gradually changing helical structure drawn correspondingly based on these photographs. As shown, the orientation angle of the packing in the axial direction at different positions results differently: 0cm, 0 degree of deflection; 2cm, 7.8 degrees of deflection; deflection is 15.5 degrees at 4 cm; deflection at 6cm, 23.7 °; deflection is 31.5 degrees at 8 cm; at 10cm, the deflection is 39.1 deg.. The method of the invention can successfully prepare the functional polymer pipe with the axially continuous gradually-changed spiral structure.
FIG. 2 is a polarized light microscope photograph showing the arrangement distribution of fillers observed at an interval of 100 μm at an inner wall of 0 μm in the radial direction of a 500 μm thick polymer functional pipe prepared in example 2 of the present invention and a pipe having a continuously gradually changing helical structure drawn correspondingly based on these photographs. As shown, the orientation angle of the filler in the radial direction at different locations results differently: 0 μm, 0 ° deflection; deflection at 100 μm, 7.8 °; deflection at 200 μm, 15.3 °; 300 μm, deflection of 23.5 °; deflection at 400 μm, 31.3 °; at 500 μm, the deflection is 39.5 °. The method of the invention can successfully prepare the functional pipe of the polymer with the radial continuous gradual change spiral structure.
Detailed Description
The invention is further illustrated by the following examples. It should be noted that the examples given are not to be construed as limiting the scope of the invention, and that those skilled in the art, on the basis of the teachings of the present invention, will be able to make numerous insubstantial modifications and adaptations of the invention without departing from its scope.
Example 1
Firstly, polyamide 11 and carbon fiber are mixed according to a mass ratio of 98:2 into a screw extruder, melted at 210 ℃ and extruded through a die set so that the rotation rate of the die increases linearly with time. The set die rotation rate formula: k is a radical of1＝kα+X1In T, the initial rate of rotation k of the dieαAt 0rpm, rate of change of rotation X1At 100rpm/min, rotation rate k1Is 0 to 100 rpm.
Example 2
Polyamide 12 was initially introduced into a screw extruder, melted at 215 ℃ and extruded to give moldings by setting the rotation speed of the mandrel to increase linearly with time. The set core rod rotation rate formula is as follows: k is a radical of1＝kα+X1In T, initial rate of rotation k of the mandrelα5rpm, rate of change of rotation X1At 50rpm/min, rotation rate k15 to 100 rpm.
Example 3
Firstly, mixing a polyolefin elastomer and a carbon nano tube according to a mass ratio of 99.9: 0.1 into a screw extruder, melted at 110 ℃ and extruded through a die set so that the rotation rate decreases non-linearly with time. The set die rotation rate formula: k is a radical of2＝kα－X2·|T|n-1In T, the initial rate of rotation k of the dieαAt 0rpm, rate of change of rotation X2At 100rpm/min, rotation rate k2The number of revolutions is 0 to 100rpm, and the constant n is 2.
Example 4
Firstly, polyurethane is added into a screw extruder, melted at 180 ℃ and extruded and molded by the nonlinear reduction of the rotation speed of a set mandrel along with time. The set core rod rotation rate formula is as follows: k is a radical of2＝kα－X2·|T|n-1In T, initial rate of rotation k of the mandrelα100rpm, rate of change of rotation X2At 20rpm/min, rotation rate k2The number of revolutions is 0 to 100rpm, and the constant n is 2.
Example 5
Firstly, polyurethane and nano-cellulose are added into a screw extruder according to the mass ratio of 98:2, melted at 185 ℃, and extruded and molded by the rotation speed of a set neck ring die which increases in a nonlinear way along with time. The set die rotation rate formula: k is a radical of2＝kα+X2·|T|n-1In T, the initial rate of rotation k of the dieαAt 0rpm, rate of change of rotation X2At 5rpm/min, rotation rate k2The number of revolutions is 0 to 100rpm, and the constant n is 3.
Example 6
Firstly, adding a polyolefin elastomer and silver nanowires into a screw extruder according to the mass ratio of 95:5, melting at 115 ℃, and performing extrusion processing molding by linearly increasing the rotation speed of a set mandrel along with time. The set core rod rotation rate formula is as follows: k is a radical of1＝kα+X1In T, initial rate of rotation k of the mandrelαAt 20rpm, rate of change of rotation X1At 50rpm/min, rotation rate k1Is 20 to 100 rpm.
Example 7
The polyamide 11 and the whiskers are added into a screw extruder according to the mass ratio of 92:8, melted at 225 ℃ and extruded and molded by linearly reducing the rotation speed of a set neck ring die along with time. The set die rotation rate formula: k is a radical of1＝kα－X1In T, the initial rate of rotation k of the dieα50rpm, rate of change of rotation X1At 20rpm/min, rotation rate k1Is 0 to 50 rpm.
Example 8
The polyamide 12 and the silver nanowires are added into a screw extruder according to the mass ratio of 90:10, melted at 228 ℃, and extruded and molded by the linear increase of the rotation speed of a set core rod along with time. The set core rod rotation rate formula is as follows: k is a radical of1＝kα+X1In T, initial rate of rotation k of the mandrelα30rpm, rate of change of rotation X1At 70rpm/min, rotation rate k1Is 30 to 100 rpm.
Example 9
Firstly, adding a polyolefin elastomer into a screw extruder, melting at 100 ℃, linearly increasing the rotation speed of a set core rod along with time, and simultaneously carrying out equidirectional rotary extrusion processing and forming along with the linear increase of the rotation speed of a set neck ring die along with time. The set core rod rotation rate formula is as follows: k is a radical of1＝kα+X1In T, initial rate of rotation k of the mandrelαAt 0rpm, rate of change of rotation X1At 50rpm/min, rotation rate k 10 to 100 rpm; the set die rotation rate formula: k is a radical of1＝kα+X1In T, the initial rate of rotation k of the dieαAt 0rpm, rate of change of rotation X1At 50rpm/min, rotation rate k1Is 0 to 100 rpm.
Example 10
Firstly, adding a polyolefin elastomer and carbon fibers into a screw extruder according to the mass ratio of 95:5, melting at 120 ℃, and carrying out unidirectional rotary extrusion processing and forming by the rotation speed of a set neck ring die which is reduced in a nonlinear way along with time. The set core rod rotation rate formula is as follows: k is a radical of2＝kα－X2·|T|n-1In T, initial rate of rotation k of the mandrelα100rpm, rate of change of rotation X2At 500rpm/min, rotation rate k2Is 0 to 100rpm, and n is 2; the set die rotation rate formula: k is a radical of2＝kα－X2·|T|n-1In T, the initial rate of rotation k of the dieα100rpm, rate of change of rotation X2At 500rpm/min, rotation rate k2Is 0 to 100rpm, and n is 2.
Example 11
Firstly, polyurethane and carbon nano tubes are added into a screw extruder according to the mass ratio of 99.5:0.5, are melted at 190 ℃, and are subjected to non-linear increase along with time through the rotation rate of a set core rod, and are subjected to reverse-direction rotation extrusion processing and forming along with non-linear increase along with time through the rotation rate of a set neck ring die. The set core rod rotation rate formula is as follows: k is a radical of2＝kα+X2·|T|n-1In T, initial rate of rotation k of the mandrelα100rpm, rate of change of rotation X2At 20rpm/min, rotation rate k2Is 0 to 100rpm, and n is 3; the set die rotation rate formula: k is a radical of2＝kα+X2·|T|n-1In the case of T, the ratio of,initial rate of rotation k of dieα100rpm, rate of change of rotation X2At 20rpm/min, rotation rate k2Is 0 to 100rpm, and n is 3.
Example 12
Firstly, polyurethane and silver nanowires are added into a screw extruder according to the mass ratio of 85:15, are melted at 190 ℃, and are subjected to non-linear reduction along with time through the rotation rate of a set core rod, and are subjected to reverse-direction rotation extrusion processing and forming along with non-linear reduction along with time through the rotation rate of a set neck mold. The set core rod rotation rate formula is as follows: k is a radical of2＝kα－X2·|T|n-1In T, initial rate of rotation k of the mandrelα40rpm, rate of change of rotation X2At 2rpm/min, rotation rate k2Is 0 to 100rpm, and n is 3; the set die rotation rate formula: k is a radical of2＝kα－X2·|T|n-1In T, the initial rate of rotation k of the dieαAt 20rpm, rate of change of rotation X2At 1rpm/min, rotation rate k2Is 0 to 100rpm, and n is 3.
Example 13
Firstly, adding a polyolefin elastomer and carbon fibers into a screw extruder according to a mass ratio of 80:20, melting at 125 ℃, linearly increasing with time through the rotation speed of a set core rod, and carrying out equidirectional rotary extrusion processing and forming through the non-linear increase with time of the rotation speed of a set neck ring mold. The set core rod rotation rate formula is as follows: k is a radical of1＝kα+X1In T, initial rate of rotation k of the mandrelαAt 0rpm, rate of change of rotation X1At 20rpm/min, rotation rate k 10 to 100 rpm; the set die rotation rate formula: k is a radical of2＝kα+X2·|T|n-1In T, the initial rate of rotation k of the dieαAt 0rpm, rate of change of rotation X2At 5rpm/min, rotation rate k2Is 0 to 100rpm, and n is 2.
Example 14
Firstly, polyamide 11 and carbon nano tube are added into a screw extruder according to the mass ratio of 99.8:0.2The melt was melted at 210 ℃ and was subjected to a non-linear decrease with time by the rotation rate of the set core rod, and simultaneously to a unidirectional rotational extrusion molding by a linear decrease with time by the rotation rate of the set die. The set core rod rotation rate formula is as follows: k is a radical of2＝kα－X2·|T|n-1In T, initial rate of rotation k of the mandrelα100rpm, rate of change of rotation X2At 40rpm/min, rotation rate k 20 to 100 rpm; the set die rotation rate formula: k is a radical of1＝kα－X1In T, the initial rate of rotation k of the dieα100rpm, rate of change of rotation X1At 8rpm/min, rotation rate k1Is 0 to 100rpm, and n is 2.
Example 15
The polyamide 11 was first fed into a screw extruder, melted at 210 ℃ and subjected to counter-rotating extrusion molding by the rotation rate of a set mandrel increasing linearly with time and by the rotation rate of a set die increasing non-linearly with time. The set core rod rotation rate formula is as follows: k is a radical of1＝kα+X1In T, initial rate of rotation k of the mandrelαAt 0rpm, rate of change of rotation X1At 10rpm/min, rotation rate k1Is 0 to 100rpm, and n is 3; the set die rotation rate formula: k is a radical of2＝kα+X2·|T|n-1In T, the initial rate of rotation k of the dieαAt 0rpm, rate of change of rotation X2At 2rpm/min, rotation rate k2Is 0 to 100rpm, and n is 3.
Example 16
Firstly, polyamide 12 and carbon fiber are mixed according to a mass ratio of 98:2 into a screw extruder, melted at 215 c and subjected to a reverse-direction rotational extrusion process by setting the rotation rate of the mandrel to decrease linearly with time while the rotation rate of the die to decrease non-linearly with time. The set core rod rotation rate formula is as follows: k is a radical of1＝kα－X1In T, initial rate of rotation k of the mandrelα80rpm, change in rotation rateRate X1At 16rpm/min, rotation rate k1Is 0 to 80rpm, and n is 3; the set die rotation rate formula: k is a radical of2＝kα－X2·|T|n-1In T, the initial rate of rotation k of the dieα80rpm, rate of change of rotation X2At 4rpm/min, rotation rate k2Is 0 to 80rpm, and n is 2.
Example 17
Firstly, polyamide 1212 and aramid fiber are mixed according to the mass ratio of 99: 1 into a screw extruder, melted at 205 ℃ and extrusion-molded by setting the rotation rate of a mandrel to linearly increase with time. The set core rod rotation rate formula is as follows: k is a radical of1＝kα+X1In T, initial rate of rotation k of the mandrelα50rpm, rate of change of rotation X1At 10rpm/min, rotation rate k150 to 100 rpm.
Example 18
Firstly, polyamide 6 and polyester fiber are mixed according to the mass ratio of 98:2 into a screw extruder, melted at 235 ℃ and extruded through a die set to produce a shape with a non-linear decrease in the rotation rate over time. The set die rotation rate formula: k is a radical of2＝kα－X2·|T|n-1In T, the initial rate of rotation k of the dieα40rpm, rate of change of rotation X2At 2rpm/min, rotation rate k2Is 0 to 40rpm, and n is 4.
Example 19
Firstly, polyethylene and cotton fibers are mixed according to the mass ratio of 96: 4 into a screw extruder, melted at 210 ℃ and extruded through a die set to produce a shaped product whose rotation rate decreases non-linearly with time. The set die rotation rate formula: k is a radical of2＝kα－X2·|T|n-1In T, the initial rate of rotation k of the dieα30rpm, rate of change of rotation X2At 1rpm/min, rotation rate k 20 to 30rpm, and n is 6.
Example 20
Firstly, polypropylene and fibrilia are mixed according to the mass ratio of 97: 3 addition ofIn the screw extruder, the melt was melted at 210 ℃ and extrusion processing was performed by setting the rotation rate of the mandrel rod to linearly increase with time. The set core rod rotation rate formula is as follows: k is a radical of1＝kα+X1In T, initial rate of rotation k of the mandrelα60rpm, rate of change of rotation X1At 4rpm/min, rotation rate k1Is 60 to 100 rpm.
Example 21
Firstly, polypropylene and carbon nano tubes are mixed according to the mass ratio of 99: 1 is added into a screw extruder, melted at 200 ℃ and subjected to co-rotating extrusion processing forming by the rotation rate of a set core rod linearly increasing with time and by the rotation rate of a set neck ring die linearly increasing with time. The set core rod rotation rate formula is as follows: k is a radical of1＝kα+X1In T, initial rate of rotation k of the mandrelα70rpm, rate of change of rotation X1At 2rpm/min, rotation rate k160 to 100 rpm; the set die rotation rate formula: k is a radical of1＝kα+X1In T, the initial rate of rotation k of the dieα80rpm, rate of change of rotation X1At 1rpm/min, rotation rate k1Is 80 to 100 rpm.
Example 22
The polyamide 1212 was first fed into a screw extruder, melted at 195 ℃ and was shaped by counter-rotating extrusion with a set linear increase in the rotation speed of the mandrel and a non-linear increase in the rotation speed of the die. The set core rod rotation rate formula is as follows: k is a radical of1＝kα－X1In T, initial rate of rotation k of the mandrelα50rpm, rate of change of rotation X1At 5rpm/min, rotation rate k150 to 100 rpm; the set die rotation rate formula: k is a radical of2＝kα－X2·|T|n-1In T, the initial rate of rotation k of the dieαAt 0rpm, rate of change of rotation X2At 1rpm/min, rotation rate k2Is 0 to 100rpm, and n is 2.
To examine whether this method produces a tube having a continuously tapered helical structure, a tube having a length of 10cm and a thickness of 500 μm, which was produced under the processing conditions of example 1, was structurally characterized by taking a mass point every 2cm from the starting section in the axial direction under a polarization microscope, as shown in FIG. 1. As can be seen from the figure, the carbon fiber has a continuously graded helical structure in the axial direction. Meanwhile, a particle at 10cm is taken every 100 μm in the radial direction and is subjected to structural characterization under a polarization microscope, as shown in FIG. 2. As can be seen from the figure, the carbon fibers have a continuously graded helical structure in the radial direction. The results of figures 1 and 2 show that the process of the invention makes it possible to obtain pipes with a continuously graduated helix.
Secondly, whether the tube with the continuous gradual change spiral structure prepared by the method has the gradual change mechanical property that the tube is rigid at a low rotation rate and flexible at a high rotation rate is also examined. The specific investigation method comprises the following steps: the pipe having a length of 10cm and a thickness of 500 μm, which was prepared under the processing conditions of example 1, was divided into 5 sections on average in the axial direction in a length of 2cm, and the properties of each section of the pipe were measured by a universal drawing machine, respectively. The test results were as follows: the Young modulus of the pipe is 397MPa at a position of 0-2 cm; at the position of 2-4 cm, the Young modulus is 372 MPa; at the position of 4-6 cm, the Young modulus is 344 MPa; at the position of 6-8 cm, the Young modulus is 309 MPa; and the Young modulus is 282MPa at the position of 8-10 cm. The test result shows that the gradient mechanical property prepared by the method has the characteristics of high rigidity under the condition of low rotation rate and good flexibility at high rotation rate.
Claims (8)
1. A method for preparing functional tube of polymer with continuous gradually-changing spiral structure includes such steps as proportionally adding polymer or polymer and filler with fibrous structure to screw extruder, extruding out at speed-varying speed by core rod or/and die above the fusion temp of polymer, or at speed-varying speed by core rod or/and die, or at speed-varying speed by die, or at same direction or opposite direction, extruding out,
the rotation speed of the arranged core rod or the arranged neck ring die is changed into unidirectional rotation of the core rod or the neck ring die, the rotation speed is linearly increased or decreased and is nonlinearly increased or decreased along with time, or the rotation speed of the arranged core rod and the arranged neck ring die which are changed in the same direction or in the opposite direction is changed into the same direction or the opposite direction of the core rod and the neck ring die, the rotation speed is linearly increased or decreased along with time or at the same time, or is nonlinearly increased or decreased at different times,
when the rotation rate increases or decreases linearly with time, the time is denoted as T, and the initial rotation rate of the core rod or die is denoted as a constant kαThe rotation rate of the core rod or die is denoted by k1The rate of change of the rate of rotation of the mandrel or die is recorded as X1The linear increase or decrease in the rotation rate of the core rod or die satisfies the formula: k is a radical of1＝kα±X1T, wherein k1In the range of 0 to 100rpm, X1The variation range is 1-500 rpm/min, and the constant kαIn the range of 0 to 100rpm, and k1≠kα，
When the rotation rate increases or decreases non-linearly with time, the time is recorded as T, and the initial rotation rate of the core rod or die is recorded as a constant kαThe rotation rate of the core rod or die is denoted by k2The rate of change of the rate of rotation of the mandrel or die is recorded as X2The nonlinear increase or decrease of the rotation rate of the core rod or the die satisfies the following formula: k is a radical of2＝kα±X2·|T|n-1T, wherein k2In the range of 0 to 100rpm, X2The variation range is 1-500 rpm/min, and the constant kαIn the range of 0 to 100rpm, and k1≠kα，2≤n≤6，
So that the polymer molecular chains in the prepared polymer functional pipe are distributed in a spiral arrangement in the axial direction, the spiral degree in the axial direction is increased or reduced along the axial direction or/and is distributed in a spiral arrangement in the radial direction of the wall, and the spiral degree in the radial direction is increased or reduced along the radial direction.
2. A method for producing a functional pipe of a polymer having a continuously gradually varying helical structure according to claim 1, characterized in that the filler having a fibrous structure used in the method is also distributed in a helical arrangement in the axial direction, and the degree of helical arrangement in the axial direction is also increased or decreased in the axial direction or/and is also distributed in a helical arrangement in the radial direction of the wall, and the degree of helical arrangement in the radial direction is also increased or decreased in the radial direction.
3. The method for preparing the polymer functional pipe material with the continuous gradient spiral structure according to claim 1 or 2, characterized in that the polymer used in the method is any one of polyolefin polymer, polyamide polymer or polyurethane.
4. The method for preparing the polymer functional pipe material with the continuously gradually-changed spiral structure according to claim 1 or 2, wherein the filler with the fibrous structure used in the method is any one of carbon fiber, carbon nano tube, nano cellulose, whisker, metal nano wire, cotton fiber, hemp fiber, polyester fiber or aramid fiber.
5. The method for preparing the polymer functional pipe with the continuous gradual change spiral structure according to claim 3, wherein the filler with the fiber-shaped structure used in the method is any one of carbon fiber, carbon nano tube, nano cellulose, whisker, metal nano wire, cotton fiber, hemp fiber, polyester fiber or aramid fiber.
6. A method for producing a functional pipe of a polymer having a continuously gradually varying helical structure according to claim 1 or 2, characterized in that the proportion of the filler having a fibrous structure in the method is 0.1-20%.
7. The method for producing a functional pipe of a polymer having a continuously gradually varying helical structure according to claim 5, wherein the proportion of the filler having a fibrous structure is 0.1 to 20%.
8. A continuously graded helically structured polymeric functional pipe produced by the process of claim 1.
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| US6776945B2 (en) * | 2001-07-03 | 2004-08-17 | Scimed Life Systems, Inc. | Medical device with extruded member having helical orientation |
| CN2601817Y (en) * | 2002-08-07 | 2004-02-04 | 郑州大学国家橡塑模具工程研究中心 | Helically lining up long fiberglass head of circular plastic pipe extrusion machine |
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