CN109249599A - A kind of polymers function tubing of continuous gradation helical structure and preparation method thereof - Google Patents
A kind of polymers function tubing of continuous gradation helical structure and preparation method thereof Download PDFInfo
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- CN109249599A CN109249599A CN201811020747.8A CN201811020747A CN109249599A CN 109249599 A CN109249599 A CN 109249599A CN 201811020747 A CN201811020747 A CN 201811020747A CN 109249599 A CN109249599 A CN 109249599A
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- rotation
- speed
- plug
- mouth mold
- tubing
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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
Abstract
The invention discloses polymers function tubing of a kind of continuous gradation helical structure and preparation method thereof, the tubing is the speed of rotation extrusion machine-shaping of plug or/and mouth mold to change by squeezing out head, in its axial direction or/and the radially helically arranged distribution of wall thickness, and axial upper or/and helix degree radially is along axially increased or reduce for polymer molecular chain therein.The tubing both can get the rigidity of low the assigned tubing of the speed of rotation, it can get the assigned tubing of high slew rate gradual change mechanical property flexible again, a kind of blank for not only having filled up polymers function tubing also solves the problems, such as that current medical intervention polymeric catheter exists.
Description
Technical field
The invention belongs to polymer pipe and its processing method technical fields, and in particular to a kind of continuous gradation helical structure
Polymers function tubing and preparation method thereof, which can be used as a kind of interventional therapy micro-polymer interposing catheter.
Background technique
Interventional therapy, which is that one of current clinical medicine treatment is revolutionary, to be broken through.Interposing catheter, such as central venous catheter, electricity
Electrophysiology catheter, angiography catheter etc. are the transmission channels for constructing various interventional therapy devices, have both administration effect, are to realize intervention
The important medical device for the treatment of.But since domestic and international Related product quality is there are larger difference, high-end microtubular rely primarily on into
Mouthful, such as China's import medical catheter in 2016 is more than 1,000,000,000, this not only greatly constrains development and the doctor of China's high technology industry
Horizontal raising is treated, biggish financial burden can be also brought to user.Therefore, the state of high-performance micro polymeric catheter is realized
Productionization is the demand of the national economic development.
Medical intervention polymeric catheter is small bore hollow product, and characteristic size is small, as radiography PU conduit diameter≤
2mm, wall thickness≤500 μm, thus its intensity is low, easily twists together under stress.And traditional micro-polymer conduit, which squeezes out, to be added
Although work simple process, usually polymer melt are squeezed out by annular die, it is axially stretched through dragger, cools down sizing and make
Micro-polymer conduit is obtained, but is unable to the multi-level multiple dimensioned structure of Effective Regulation, it is difficult to it is micro- that the high-performance met the requirements be made
Type polymeric catheter.Specifically, in interventional procedure, doctor usually will realize conduit by the operation such as pushing away, drawing, revolve
Advance and turn to, so that it be made to reach remote target lesion locations along the non-regular, tortuous passageway of human body, it is necessary that this requires conduits
With excellent pushability, kink resistance turns round control responsiveness and soft front end.But due to flexibility and easy pushability, axial direction
The relatively thin tube wall of the contradiction and micro-polymer conduit of push and circumference stress response, single high molecular material is by simply squeezing
Out difficult processing be made it is this to multi-load all have it is excellent resistance and response require interposing catheter (R.C.L.Feneley,
I.B.Hopley,P.N.T.Wells,Journal of Medical Engineering&Technology,2015,39,
459.).Currently, the technology of preparing of medical intervention microtubular mainly uses wire or polymer fiber to wind or weave, shape
At axially varying enhancement layer, interposing catheter each section different mechanical properties are assigned, thin-walled, high pushability, high torque are prepared
Conducting power and kink resistance interposing catheter (J.E.Castaneda, R.F.Graham, P.Soltesz, T.Trotta,
Intravascular catheter with kink resistant tip.1994,US 5279596.).But enhancement layer and poly-
It is weak to close the interaction of object interface layer, inside and outside interlayer is also easy to produce sliding in use, it is difficult to the effect of enhancement layer is played, and
Complex process, the microtubular of preparation is size-constrained in existing enhancement layer, cannot prepare some interventions applied to fine vascular
Conduit.Though in traditional extrusion process, polymerizeing in addition, the intensity of micro-polymer conduit can be improved in the reinforcing fiber introduced
Object melt axial direction extrusion/stretching, fiber is axially aligned, shows anisotropic character, i.e. longitudinal strength transverse strength greatly
It is small.Thus, limited to microtubular circumferential direction performance boost, " bamboo split point " easily occur destroys, and the addition of fiber can also deteriorate
Its toughness, easily generation brittle break, cause severe compromise.Therefore, there is an urgent need to develop new micro-polymer conduit to add
Work new technology, the efficient preparation to realize high-performance micro-pipe are drawn come the great demand for meeting Modern medical therapy to interposing catheter
Lead the fast development of China's medical device industry.
Summary of the invention
In view of the deficiencies of the prior art, it is an object of the present invention to provide a kind of polymers functions of continuous gradation helical structure
Tubing and preparation method thereof.
In order to achieve the above object, the present invention is wanted first using the technical solution being made of following technical measures to realize
A kind of polymers function tubing of the continuous gradation helical structure provided.
A kind of polymers function tubing of continuous gradation helical structure, the polymer molecular chain in the tubing is in its axial direction
Helically arranged distribution, and the helix degree in axial direction is in the radial direction along axially increased or reduction or/and in its wall thickness
Helical arrangement distribution, and helix degree radially radially increases or decreases.
Also comprising the filler with fibrous structure in the above polymers function tubing, the filler is in the axial direction also helically
Arranged distribution, and the helix degree in axial direction is also along axially increased or reduction or/and in its wall thickness in the radial direction also in spiral shell
Arranged distribution is revolved, and helix degree radially also radially increases or decreases.
Polymer in the above polymers function tubing is the polymer that can be thermoformed, and specially polyolefins polymerize
Any one of object, polyamide polymers or polyurethane.The wherein preferred polyethylene of polyolefin polymers, polypropylene or polyene
Olefin elastomer；Polyamide polymers preferred polyamide 11, polyamide 12, polyamide 1212 or polyamide 6.
The further preferred polyolefin elastomer of polymer, polyamide 11, polyamide 12 in the above polymers function tubing
Or polyurethane.
The filler with fibrous structure in the above polymers function tubing is carbon fiber, carbon nanotube, nanofiber
Element, whisker, metal nanometer line, cotton fiber, flaxen fiber, polyester fiber or aramid fiber it is any, further preferred carbon fiber,
Carbon nanotube and silver nanowires.
The method provided by the invention for preparing above-mentioned continuous gradation spiropolymer function tubing, this method are poly-
Close in object function tubular object extruding forming process, by squeeze out the plug of head with the speed of rotation that changes squeeze out machine-shaping or/
Machine-shaping is squeezed out with the speed of rotation changed with the mouth mold by squeezing out head.
The preparation method of the polymers function tubing of above-described continuous gradation helical structure, specific process step
Are as follows:
First polymer or polymer and filler with fibrous structure are added in screw extruder by a certain percentage,
Polymer melting temperature is able to carry out the extrusion head of speed-changing rotation above by plug or/and mouth mold, or with the plug of setting
Change the speed of rotation and squeeze out machine-shaping, or machine-shaping is squeezed out with the mouth mold variation speed of rotation of setting, or with the core of setting
Stick and the speed of rotation of the equidirectional variation of mouth mold squeeze out machine-shaping, or with the rotation of the plug of setting and mouth mold changing inversely
Rate squeezes out machine-shaping.
Have the proportion of filler of fibrous structure for 0.1-20%, preferably 0.1-10% described in above method, more preferably
0.1-5%.
Extrusion head described in above method specifically can be used in the prior authorization application 200810045785.9 of applicant
The equipment.
Plug or mouth mold the variation speed of rotation of setting described in above method are that plug or mouth mold one direction rotate, and revolve
Rotational speed rate is linearly increased or reduced at any time to be increased or decreased with non-linear.
When the speed of rotation is linearly increased or reduced at any time, the time is denoted as T, the rotation first rate note of plug or mouth mold
For constant kα, the speed of rotation of plug or mouth mold is denoted as k1, the change rate of plug or the mouth mold speed of rotation is denoted as X1, plug or mouth
The speed of rotation of mould, which is linearly increased or is reduced, to meet formula: k1=kα±X1T, wherein k1Range is 0~100rpm, X1Become
Change range is 1~500rpm/min, constant kαRange is 0~100rpm, and k1≠kα。
When the speed of rotation is in non-linear increase or decrease at any time, the time is denoted as T, the rotation first rate of plug or mouth mold
It is denoted as constant kα, the speed of rotation of plug or mouth mold is denoted as k2, the change rate of plug or the mouth mold speed of rotation is denoted as X2, plug or
The speed of rotation of mouth mold should meet formula in non-linear increase or decrease: k2=kα±X2·|T|n-1T, wherein k2Range is 0
~100rpm, X2Variation range is 1~500rpm/min, constant kαRange is 0~100rpm, and k2≠kα, 2≤n≤6.
The plug and mouth mold of setting described in above method be equidirectional or the speed of rotation of changing inversely is plug and mouth
Mould is equidirectional or opposite direction rotates, and the speed of rotation is linearly increased or reduced at any time or simultaneously, or is simultaneously in non-linear increasing
It adds deduct few, or does not linearly increase or reduce simultaneously, or do not increased or decreased simultaneously in non-linear.The rotation of both modes
Rate variation also complies with formula below and its definition.
When the speed of rotation is linearly increased or reduced at any time, the time is denoted as T, the rotation first rate note of plug or mouth mold
For constant kα, the speed of rotation of plug or mouth mold is denoted as k1, the change rate of plug or the mouth mold speed of rotation is denoted as X1, plug or mouth
The speed of rotation of mould, which is linearly increased or is reduced, to meet formula: k1=kα±X1T, wherein k1Range is 0~100rpm, X1Become
Change range is 1~500rpm/min, constant kαRange is 0~100rpm, and k1≠kα。
When the speed of rotation is in non-linear increase or decrease at any time, the time is denoted as T, the rotation first rate of plug or mouth mold
It is denoted as constant kα, the speed of rotation of plug or mouth mold is denoted as k2, the change rate of plug or the mouth mold speed of rotation is denoted as X2, plug or
The speed of rotation of mouth mold should meet formula in non-linear increase or decrease: k2=kα±X2·|T|n-1T, wherein k2Range is 0
~100rpm, X2Variation range is 1~500rpm/min, constant kαRange is 0~100rpm, and k2≠kα, 2≤n≤6.
It is worth noting that in the production of actual industrial metaplasia, it can also be in polymer or polymer and filler melt blending mistake
Other processing aids such as other antioxidant known in the art, stabilizer, plasticizer can be also added in journey.But on condition that this
A little processing aids are realized the purpose of the present invention and must not be adversely affected to the acquirement of excellent results of the present invention.
The present invention has the advantage that
1. since tubing provided by the invention is to be processed by squeezing out the plug of head with the speed of rotation extrusion changed
Type or/and the mouth mold by squeezing out head squeeze out machine-shaping with the speed of rotation that changes, thus can make tubing obtained
For a kind of polymers function tubing of continuous gradation helical structure, a kind of blank of polymers function tubing has not only been filled up,
It can solve the problems, such as that current medical intervention polymeric catheter exists.
2. since preparation method provided by the invention is by can be with change in the extrusion head used control by computer
Change the speed of rotation rotation plug or/and mouth mold, to melting extrusion processing polymer or polymer and have threadiness knot
The filler of structure along it is axial or/and radially apply can continuous variable shearing force, allow the tubing of extrusion molding to form a kind of company
The helical structure of continuous gradual change, thus make obtained polymers function tubing compared with the spiral pipe of the more stable speed of rotation,
Not only it can get the rigidity of low the assigned tubing of the speed of rotation, but also can get the assigned tubing of high slew rate gradual change mechanics flexible
Performance.
3. it is easy to operate due to preparation method simple process provided by the invention, it can be continuously produced, thus it is more traditional
For preparation process, a kind of polymers function tubing of new structure is not only obtained, while being also to meet market to tubing
Different demands provide a kind of manufacture approach.
4. since method provided by the invention is not required to increase additional equipment in preparation process, thus meeting the big rule of industrialization
The requirement of mould production, and applicable system is extensive, not only effective solution existing polymer or polymer and the preparation of filler tubing
Process condition is single, rotates single defect, also has the wider scope of application, convenient for promoting.
Detailed description of the invention
The polymers function tubing that Fig. 1 is 10cm long prepared by the embodiment of the present invention 1 is in axial direction with starting point
At 0cm, the petrographic microscope photo at interval of the 2cm filler arranged distribution observed and the tool according to the corresponding drafting of these photos
There is the schematic diagram of continuous gradation helical structure tubing.As shown, filler in axial direction orientation angles result at different location
It is different: at 0cm, to deflect 0 °；At 2cm, 7.8 ° are deflected；At 4cm, 15.5 ° are deflected；At 6cm, 23.7 ° are deflected；At 8cm, deflection
31.5°；At 10cm, 39.1 ° are deflected.Illustrate that the method for the present invention is can successfully to prepare to have gradual change helical structure continuously in axial direction
Polymers function tubing.
Fig. 2 is that the polymers function tubing of 500 μ m-thicks prepared by the embodiment of the present invention 2 is radially 0 μ with inner wall
At m, the petrographic microscope photo for the filler arranged distribution observed at interval of 100 μm and the tool according to the corresponding drafting of these photos
There is the schematic diagram of continuous gradation helical structure tubing.As shown, filler radially orientation angles result at different location
It is different: at 0 μm, to deflect 0 °；At 100 μm, 7.8 ° are deflected；At 200 μm, 15.3 ° are deflected；At 300 μm, 23.5 ° are deflected；400μm
Place deflects 31.3 °；At 500 μm, 39.5 ° are deflected.Illustrate that the method for the present invention can be successfully prepared with radially continuous gradual change
The polymers function tubing of helical structure.
Specific embodiment
Below by embodiment, the invention will be further described.It is worth noting that the embodiment provided cannot understand
For limiting the scope of the invention, person skilled in art's content according to the present invention makes the present invention some non-
The modifications and adaptations of essence still should belong to the scope of the present invention.
Embodiment 1
First polyamide 11 and carbon fiber 98:2 in mass ratio are added in screw extruder, melts and passes through at 210 DEG C
The speed of rotation of the mouth mold of setting linearly increases at any time carries out extrusion machine-shaping.The set mouth mold speed of rotation is public
Formula: k1=kα+X1In T, the rotation first rate k of mouth moldαFor 0rpm, the change rate X of the speed of rotation1For 100rpm/min, rotation
Rate k1For 0~100rpm.
Embodiment 2
First polyamide 12 is added in screw extruder, melts and pass through the speed of rotation of the plug of setting at 215 DEG C
It linearly increases at any time and carries out extrusion machine-shaping.Set Mandrel Rotating rate equation: k1=kα+X1In T, plug
Rotation first rate kαFor 5rpm, the change rate X of the speed of rotation1For 50rpm/min, speed of rotation k1For 5~100rpm.
Embodiment 3
First polyolefin elastomer and carbon nanotube 99.9:0.1 in mass ratio are added in screw extruder, at 110 DEG C
The speed of rotation for melting and passing through the mouth mold of setting decreases nonlinearly at any time carries out extrusion machine-shaping.Set mouth mold
Speed of rotation formula: k2=kα- X2·|T|n-1In T, the rotation first rate k of mouth moldαFor 0rpm, the change rate X of the speed of rotation2
For 100rpm/min, speed of rotation k2For 0~100rpm, constant n=2.
Embodiment 4
First will polyurethane be added screw extruder in, at 180 DEG C melt and by setting plug the speed of rotation with
Time, which decreases nonlinearly, carries out extrusion machine-shaping.Set Mandrel Rotating rate equation: k2=kα- X2·|T|n-1·T
In, the rotation first rate k of plugαFor 100rpm, the change rate X of the speed of rotation2For 20rpm/min, speed of rotation k2For 0~
100rpm, constant n=2.
Embodiment 5
First polyurethane and nano-cellulose 98:2 in mass ratio are added in screw extruder, melts and leads at 185 DEG C
The speed of rotation for crossing the mouth mold of setting is in that non-linear increase carries out extrusion machine-shaping at any time.The set mouth mold speed of rotation
Formula: k2=kα+X2·|T|n-1In T, the rotation first rate k of mouth moldαFor 0rpm, the change rate X of the speed of rotation2For 5rpm/
Min, speed of rotation k2For 0~100rpm, constant n=3.
Embodiment 6
First polyolefin elastomer and silver nanowires 95:5 in mass ratio are added in screw extruder, melted at 115 DEG C
And it is linearly increased at any time by the speed of rotation of the plug of setting and carries out extrusion machine-shaping.Set Mandrel Rotating speed
Rate formula: k1=kα+X1In T, the rotation first rate k of plugαFor 20rpm, the change rate X of the speed of rotation1For 50rpm/min,
Speed of rotation k1For 20~100rpm.
Embodiment 7
First polyamide 11 and whisker 92:8 in mass ratio are added in screw extruder, melted at 225 DEG C and by setting
The speed of rotation for the mouth mold set linearly reduces carry out extrusion machine-shaping at any time.Set mouth mold speed of rotation formula:
k1=kα- X1In T, the rotation first rate k of mouth moldαFor 50rpm, the change rate X of the speed of rotation1For 20rpm/min, rotation speed
Rate k1For 0~50rpm.
Embodiment 8
First polyamide 12 and silver nanowires 90:10 in mass ratio are added in screw extruder, melts and leads at 228 DEG C
The speed of rotation for crossing the plug of setting linearly increases at any time carries out extrusion machine-shaping.Set Mandrel Rotating rate is public
Formula: k1=kα+X1In T, the rotation first rate k of plugαFor 30rpm, the change rate X of the speed of rotation1For 70rpm/min, rotation
Rate k1For 30~100rpm.
Embodiment 9
First polyolefin elastomer is added in screw extruder, melts and pass through the rotation of the plug of setting at 100 DEG C
Rate linearly increases at any time, while being linearly increased at any time by the speed of rotation of the mouth mold of setting and carrying out equidirectional rotation
Turn to squeeze out machine-shaping.Set Mandrel Rotating rate equation: k1=kα+X1In T, the rotation first rate k of plugαFor
0rpm, the change rate X of the speed of rotation1For 50rpm/min, speed of rotation k1For 0~100rpm；The set mouth mold speed of rotation
Formula: k1=kα+X1In T, the rotation first rate k of mouth moldαFor 0rpm, the change rate X of the speed of rotation1For 50rpm/min, rotation
Rate k1For 0~100rpm.
Embodiment 10
First polyolefin elastomer and carbon fiber 95:5 in mass ratio are added in screw extruder, melted simultaneously at 120 DEG C
It is decreased nonlinearly at any time by the speed of rotation of the plug of setting, while at any time by the speed of rotation of the mouth mold of setting
It decreases nonlinearly and carries out equidirectional rotary extrusion machine-shaping.Set Mandrel Rotating rate equation: k2=kα- X2·|T
|n-1In T, the rotation first rate k of plugαFor 100rpm, the change rate X of the speed of rotation2For 500rpm/min, speed of rotation k2
For 0~100rpm, and n=2；Set mouth mold speed of rotation formula: k2=kα- X2·|T|n-1In T, the rotation of mouth mold
First rate kαFor 100rpm, the change rate X of the speed of rotation2For 500rpm/min, speed of rotation k2For 0~100rpm, and n=2.
Embodiment 11
First polyurethane and carbon nanotube 99.5:0.5 in mass ratio are added in screw extruder, melted simultaneously at 190 DEG C
The speed of rotation by the plug of setting is in non-linear increase at any time, while at any time by the speed of rotation of the mouth mold of setting
The machine-shaping of opposite direction rotary extrusion is carried out in non-linear increase.Set Mandrel Rotating rate equation: k2=kα+X2·|T
|n-1In T, the rotation first rate k of plugαFor 100rpm, the change rate X of the speed of rotation2For 20rpm/min, speed of rotation k2For
0~100rpm, and n=3；Set mouth mold speed of rotation formula: k2=kα+X2·|T|n-1In T, the rotation initial velocity of mouth mold
Rate kαFor 100rpm, the change rate X of the speed of rotation2For 20rpm/min, speed of rotation k2For 0~100rpm, and n=3.
Embodiment 12
First polyurethane and silver nanowires 85:15 in mass ratio are added in screw extruder, melts and passes through at 190 DEG C
The speed of rotation of the plug of setting decreases nonlinearly at any time, while being at any time in non-by the speed of rotation of the mouth mold of setting
Linear reduce carries out the machine-shaping of opposite direction rotary extrusion.Set Mandrel Rotating rate equation: k2=kα- X2·|T
|n-1In T, the rotation first rate k of plugαFor 40rpm, the change rate X of the speed of rotation2For 2rpm/min, speed of rotation k2It is 0
~100rpm, and n=3；Set mouth mold speed of rotation formula: k2=kα- X2·|T|n-1In T, the rotation initial velocity of mouth mold
Rate kαFor 20rpm, the change rate X of the speed of rotation2For 1rpm/min, speed of rotation k2For 0~100rpm, and n=3.
Embodiment 13
First polyolefin elastomer and carbon fiber 80:20 in mass ratio are added in screw extruder, melted simultaneously at 125 DEG C
It is linearly increased at any time by the speed of rotation of the plug of setting, while being at any time by the speed of rotation of the mouth mold of setting
Non-linear increase carries out equidirectional rotary extrusion machine-shaping.Set Mandrel Rotating rate equation: k1=kα+X1In T,
The rotation first rate k of plugαFor 0rpm, the change rate X of the speed of rotation1For 20rpm/min, speed of rotation k1For 0~100rpm；
Set mouth mold speed of rotation formula: k2=kα+X2·|T|n-1In T, the rotation first rate k of mouth moldαFor 0rpm, rotation speed
The change rate X of rate2For 5rpm/min, speed of rotation k2For 0~100rpm, and n=2.
Embodiment 14
First polyamide 11 and carbon nanotube 99.8:0.2 in mass ratio are added in screw extruder, melted at 210 DEG C
And it is decreased nonlinearly at any time by the speed of rotation of the plug of setting, while at any time by the speed of rotation of the mouth mold of setting
Between linearly reduce and carry out equidirectional rotary extrusion machine-shaping.Set Mandrel Rotating rate equation: k2=kα- X2·|T
|n-1In T, the rotation first rate k of plugαFor 100rpm, the change rate X of the speed of rotation2For 40rpm/min, speed of rotation k2For
0~100rpm；Set mouth mold speed of rotation formula: k1=kα- X1In T, the rotation first rate k of mouth moldαFor 100rpm,
The change rate X of the speed of rotation1For 8rpm/min, speed of rotation k1For 0~100rpm, and n=2.
Embodiment 15
First polyamide 11 is added in screw extruder, melts and pass through the speed of rotation of the plug of setting at 210 DEG C
It linearly increases at any time, while being at any time in that non-linear increase carries out opposite direction rotation by the speed of rotation of the mouth mold of setting
Squeeze out machine-shaping.Set Mandrel Rotating rate equation: k1=kα+X1In T, the rotation first rate k of plugαFor 0rpm,
The change rate X of the speed of rotation1For 10rpm/min, speed of rotation k1For 0~100rpm, and n=3；Set mouth mold rotates speed
Rate formula: k2=kα+X2·|T|n-1In T, the rotation first rate k of mouth moldαFor 0rpm, the change rate X of the speed of rotation2For 2rpm/
Min, speed of rotation k2For 0~100rpm, and n=3.
Embodiment 16
First polyamide 12 and carbon fiber 98:2 in mass ratio are added in screw extruder, melts and passes through at 215 DEG C
The speed of rotation of the plug of setting is linearly reduced at any time, while being at any time in non-thread by the speed of rotation of the mouth mold of setting
Property reduce carry out the machine-shaping of opposite direction rotary extrusion.Set Mandrel Rotating rate equation: k1=kα- X1In T, plug
Rotation first rate kαFor 80rpm, the change rate X of the speed of rotation1For 16rpm/min, speed of rotation k1For 0~80rpm, and n=
3；Set mouth mold speed of rotation formula: k2=kα- X2·|T|n-1In T, the rotation first rate k of mouth moldαFor 80rpm, rotation
The change rate X of rotational speed rate2For 4rpm/min, speed of rotation k2For 0~80rpm, and n=2.
Embodiment 17
First polyamide 1212 and aramid fiber 99:1 in mass ratio are added in screw extruder, melted simultaneously at 205 DEG C
It is linearly increased at any time by the speed of rotation of the plug of setting and carries out extrusion machine-shaping.Set Mandrel Rotating rate
Formula: k1=kα+X1In T, the rotation first rate k of plugαFor 50rpm, the change rate X of the speed of rotation1For 10rpm/min, rotation
Rotational speed rate k1For 50~100rpm.
Embodiment 18
First polyamide 6 and polyester fiber 98:2 in mass ratio are added in screw extruder, melts and passes through at 235 DEG C
The speed of rotation of the mouth mold of setting decreases nonlinearly at any time carries out extrusion machine-shaping.The set mouth mold speed of rotation is public
Formula: k2=kα- X2·|T|n-1In T, the rotation first rate k of mouth moldαFor 40rpm, the change rate X of the speed of rotation2For 2rpm/
Min, speed of rotation k2For 0~40rpm, and n=4.
Embodiment 19
First polyethylene and cotton fiber 96:4 in mass ratio are added in screw extruder, melted at 210 DEG C and by setting
The speed of rotation for the mouth mold set decreases nonlinearly at any time carries out extrusion machine-shaping.The set mouth mold speed of rotation is public
Formula: k2=kα- X2·|T|n-1In T, the rotation first rate k of mouth moldαFor 30rpm, the change rate X of the speed of rotation2For 1rpm/
Min, speed of rotation k2For 0~30rpm, and n=6.
Embodiment 20
First polypropylene and flaxen fiber 97:3 in mass ratio are added in screw extruder, melted at 210 DEG C and by setting
The speed of rotation for the plug set linearly increases at any time carries out extrusion machine-shaping.Set Mandrel Rotating rate equation:
k1=kα+X1In T, the rotation first rate k of plugαFor 60rpm, the change rate X of the speed of rotation1For 4rpm/min, the speed of rotation
k1For 60~100rpm.
Embodiment 21
First polypropylene and carbon nanotube 99:1 in mass ratio are added in screw extruder, melts and passes through at 200 DEG C
The speed of rotation of the plug of setting linearly increases at any time, while linear at any time by the speed of rotation of the mouth mold of setting
Increase and carries out equidirectional rotary extrusion machine-shaping.Set Mandrel Rotating rate equation: k1=kα+X1In T, plug
Rotate first rate kαFor 70rpm, the change rate X of the speed of rotation1For 2rpm/min, speed of rotation k1For 60~100rpm；It is set
Mouth mold speed of rotation formula: k1=kα+X1In T, the rotation first rate k of mouth moldαFor 80rpm, the change rate X of the speed of rotation1
For 1rpm/min, speed of rotation k1For 80~100rpm.
Embodiment 22
First polyamide 1212 is added in screw extruder, is melted at 195 DEG C and by the rotation of the plug of setting speed
Rate linearly increases at any time, while being at any time in that non-linear increase carries out opposite direction rotation by the speed of rotation of the mouth mold of setting
Turn to squeeze out machine-shaping.Set Mandrel Rotating rate equation: k1=kα- X1In T, the rotation first rate k of plugαFor
50rpm, the change rate X of the speed of rotation1For 5rpm/min, speed of rotation k1For 50~100rpm；The set mouth mold speed of rotation
Formula: k2=kα- X2·|T|n-1In T, the rotation first rate k of mouth moldαFor 0rpm, the change rate X of the speed of rotation2For 1rpm/
Min, speed of rotation k2For 0~100rpm, and n=2.
In order to investigate whether this method has been made the tubing with continuous gradation helical structure, item will be processed in embodiment 1
The length prepared under part in axial direction takes a particle to exist with a thickness of 500 μm of tubing for 10cm from the initial segment every 2cm
Structural characterization is carried out under petrographic microscope, as shown in Fig. 1.It can be seen that carbon fiber is in axial direction in continuous gradation
Helical structure.Radially a particle is taken to carry out structure under petrographic microscope every 100 μm at 10cm simultaneously
Characterization, as shown in Fig. 2.It can be seen that carbon fiber is radially in the helical structure of continuous gradation.Pass through 1 He of attached drawing
The result of attached drawing 2 can illustrate that the method for the present invention is can to obtain the tubing with continuous gradation helical structure.
Secondly, also investigating whether the tubing obtained by this method with continuous gradation helical structure has the low speed of rotation
In rigidity, high slew rate is in gradual change mechanical property flexible.Specific investigation method is: will be under 1 processing conditions of embodiment
The length of preparation is in axial direction divided into 5 sections by 2cm long, and pass through omnipotent drawing with a thickness of 500 μm of tubing for 10cm
Stretch the performance that machine tests every section of tubing respectively.Test result is as follows: tubing is at 0~2cm, Young's modulus 397MPa；2~
At 4cm, Young's modulus 372MPa；At 4~6cm, Young's modulus 344MPa；At 6~8cm, Young's modulus is
309MPa；At 8~10cm, Young's modulus 282MPa.It can illustrate having for the method for the present invention preparation by test result
Rigidity is high under the conditions of the low speed of rotation, the feature of the flexible gradual change mechanical property of high slew rate.
Claims (10)
1. a kind of polymers function tubing of continuous gradation helical structure, it is characterised in that the polymer molecular chain in the tubing exists
Helically arranged distribution in its axial direction, and the helix degree in axial direction along it is axially increased or reduce or/and its wall thickness radial direction
Helically arranged distribution on direction, and helix degree radially radially increases or decreases.
2. the polymers function tubing of continuous gradation helical structure according to claim 1, it is characterised in that the polymer
Also comprising the filler with fibrous structure in function tubing, the filler also helically arranged distribution in the axial direction, and in axial direction
Helix degree also along it is axially increased or reduce or/and its wall thickness also helically arranged distribution in the radial direction, and it is radial
On helix degree also radially increase or decrease.
3. the polymers function tubing of continuous gradation helical structure according to claim 1 or 2, it is characterised in that the polymerization
Polymer in object function tubing is the polymer that can be thermoformed, specially polyolefin polymers, polyamide-based polymerization
Any one of object or polyurethane.
4. the polymers function tubing of continuous gradation helical structure according to claim 1 or 2, it is characterised in that the polymerization
The filler with fibrous structure in property management material is carbon fiber, carbon nanotube, nano-cellulose, whisker, metal nanometer line, cotton
Fiber, flaxen fiber, polyester fiber or aramid fiber it is any.
5. the polymers function tubing of continuous gradation helical structure according to claim 3, it is characterised in that the polymer
The filler with fibrous structure in tubing is carbon fiber, carbon nanotube, nano-cellulose, whisker, metal nanometer line, cotton fibre
Dimension, flaxen fiber, polyester fiber or aramid fiber it is any.
6. a kind of method for the polymers function tubing for preparing continuous gradation helical structure described in claim 1, feature exist
It is that the speed of rotation changed by squeezing out the plug of head squeezes out during polymer pipe machine-shaping in this method to add
The speed of rotation extrusion machine-shaping of work molding or/and the mouth mold by squeezing out head to change.
7. the preparation method of the polymers function tubing of continuous gradation helical structure according to claim 6, feature exist
In the specific process step of this method are as follows:
Polymer or polymer and filler with fibrous structure are added in screw extruder by a certain percentage first, polymerize
Object melting temperature is able to carry out the extrusion head of speed-changing rotation above by plug or/and mouth mold, or is changed with the plug of setting
The speed of rotation squeezes out machine-shaping, or squeezes out machine-shaping with the mouth mold of the setting variation speed of rotation, or with the plug of setting and
The speed of rotation of the equidirectional variation of mouth mold squeezes out machine-shaping, or with the speed of rotation of the plug of setting and mouth mold changing inversely
Squeeze out machine-shaping.
8. the preparation method of the polymers function tubing of continuous gradation helical structure according to claim 7, feature exist
The ratio of the filler with fibrous structure described in this method is 0.1-20%.
9. according to right want any one of 6-8 described in continuous gradation helical structure polymers function tubing preparation side
Method, it is characterised in that plug or mouth mold the variation speed of rotation of setting described in this method are that plug or mouth mold one direction rotate,
And the speed of rotation is linearly increased or is reduced at any time and increases or decreases with non-linear,
When the speed of rotation is linearly increased or reduced at any time, the time is denoted as T, and the rotation first rate of plug or mouth mold is denoted as often
Number kα, the speed of rotation of plug or mouth mold is denoted as k1, the change rate of plug or the mouth mold speed of rotation is denoted as X1, plug or mouth mold
The speed of rotation, which is linearly increased or is reduced, to meet formula: k1=kα±X1T, wherein k1Range is 0~100rpm, X1Change model
It encloses for 1~500rpm/min, constant kαRange is 0~100rpm, and k1≠kα；
When the speed of rotation is in non-linear increase or decrease at any time, the time is denoted as T, and the rotation first rate of plug or mouth mold is denoted as
Constant kα, the speed of rotation of plug or mouth mold is denoted as k2, the change rate of plug or the mouth mold speed of rotation is denoted as X2, plug or mouth mold
The speed of rotation should meet formula in non-linear increase or decrease: k2=kα±X2·|T|n-1T, wherein k2Range be 0~
100rpm, X2Variation range is 1~500rpm/min, constant kαRange is 0~100rpm, and k1≠kα, 2≤n≤6.
10. according to right want any one of 6-8 described in continuous gradation helical structure polymers function tubing preparation side
Method, it is characterised in that the plug and mouth mold of setting described in this method be equidirectional or the speed of rotation of changing inversely be plug and
Mouth mold is equidirectional or opposite direction rotates, and the speed of rotation is linearly increased or reduced at any time or simultaneously, or simultaneously in non-linear
It increases or decreases, or does not linearly increase or reduce simultaneously, or do not increased or decreased simultaneously in non-linear,
When the speed of rotation is linearly increased or reduced at any time, the time is denoted as T, and the rotation first rate of plug or mouth mold is denoted as often
Number kα, the speed of rotation of plug or mouth mold is denoted as k1, the change rate of plug or the mouth mold speed of rotation is denoted as X1, plug or mouth mold
The speed of rotation, which is linearly increased or is reduced, to meet formula: k1=kα±X1T, wherein k1Range is 0~100rpm, X1Change model
It encloses for 1~500rpm/min, constant kαRange is 0~100rpm, and k1≠kα；
When the speed of rotation is in non-linear increase or decrease at any time, the time is denoted as T, and the rotation first rate of plug or mouth mold is denoted as
Constant kα, the speed of rotation of plug or mouth mold is denoted as k2, the change rate of plug or the mouth mold speed of rotation is denoted as X2, plug or mouth mold
The speed of rotation should meet formula in non-linear increase or decrease: k2=kα±X2·|T|n-1T, wherein k2Range be 0~
100rpm, X2Variation range is 1~500rpm/min, constant kαRange is 0~100rpm, and k1≠kα, 2≤n≤6.
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| 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 |
| US6776945B2 (en) * | 2001-07-03 | 2004-08-17 | Scimed Life Systems, Inc. | Medical device with extruded member having helical orientation |
| CN101269540A (en) * | 2007-12-29 | 2008-09-24 | 郑州大学橡塑模具国家工程研究中心 | Extrusion frame head for core rod rotating long glass fiber-reinforced plastics tube |
| CN102216729A (en) * | 2008-11-14 | 2011-10-12 | 诺思罗普·格鲁曼·利特夫有限责任公司 | Method for simulating the operating behaviour of a coriolis gyroscope |
| CN104500867A (en) * | 2014-12-09 | 2015-04-08 | 华瀚管道系统科技有限公司 | Pressure pipe structure and manufacturing method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN101269540A (en) * | 2007-12-29 | 2008-09-24 | 郑州大学橡塑模具国家工程研究中心 | Extrusion frame head for core rod rotating long glass fiber-reinforced plastics tube |
| CN102216729A (en) * | 2008-11-14 | 2011-10-12 | 诺思罗普·格鲁曼·利特夫有限责任公司 | Method for simulating the operating behaviour of a coriolis gyroscope |
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