CN100493885C - Supercritical fluid assistant high molecular material extrusion forming machine - Google Patents

Supercritical fluid assistant high molecular material extrusion forming machine Download PDF

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Publication number
CN100493885C
CN100493885C CNB2006101565917A CN200610156591A CN100493885C CN 100493885 C CN100493885 C CN 100493885C CN B2006101565917 A CNB2006101565917 A CN B2006101565917A CN 200610156591 A CN200610156591 A CN 200610156591A CN 100493885 C CN100493885 C CN 100493885C
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China
Prior art keywords
barrel
screw
screw rod
shaping machine
extrusion shaping
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Expired - Fee Related
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CNB2006101565917A
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Chinese (zh)
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CN101003174A (en
Inventor
刘亚青
谢江波
张艳君
付一政
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North University of China
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North University of China
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Priority to CNB2006101565917A priority Critical patent/CN100493885C/en
Publication of CN101003174A publication Critical patent/CN101003174A/en
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    • 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
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
    • B29C48/50—Details of extruders
    • B29C48/505—Screws
    • B29C48/535—Screws with thread pitch varying along the longitudinal axis
    • 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
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
    • B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
    • B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
    • B29C48/405—Intermeshing co-rotating screws

Abstract

A supercritical fluid added extrusion forming machine for high-molecular material, especially the high-viscosity polymer, is composed of material barrel, dual screw bolts in said material barrel, driver of said screw bolts, heating cooling system, electronic control system, metering feeder, output die, and supercritical CO2 fluid delivering unit communicated with said material barrel.

Description

Forming machine for extruding assistant high molecular material in supercritical fluid
Technical field
The present invention relates to the macromolecular material former, particularly relate to the double screw extruder of the polymer-extruded moulding of non-molten stream and molten fluidity difference.This extruder can be used for the moulding that melt extrudes of polymer (as ultra-high molecular weight polyethylene) of non-molten fluidity polymer (as polytetrafluoroethylene (PTFE)) and molten fluidity difference etc.
Background technology
Melt extruding is one of topmost forming method of macromolecular material, at present, has 50% thermoplastic articles to produce with extrusion by melting approximately, it be a kind of high speed, continuously, automation, high-quality macromolecular material forming method.But,,, its range of application is very limited because its fluidity of molten difference or not mobile causes it can easily not produce polytype goods with extrusion by melting for the engineering plastics of some excellent performances.
(Polytetrafluoroethylene PTFE) is example with " plastics king " polytetrafluoroethylene (PTFE).Because of having excellent chemical resistance, heat endurance, dielectric properties, non-viscosity, wearability and special performance such as aging hardly, PTFE becomes indispensable material in the commercial Application, having obtained widely using in industries such as national defence, machinery, electronics, chemical industry, light industry, medicine, is the kind of output and consumption figure maximum in the fluoroplastics.But because melt viscosity is too big, flowability is too poor, causes general processing method it is flowed and plasticizing, and PTFE is fluoridized inert material, does not have any conventional solvent and can dissolve it, thereby also be difficult to method processing and forming with dissolving.At present, the moulding of PTFE is adopted substantially is mold pressing and these two kinds of methods of extruding, and this not only makes the product type of PTFE be restricted, and makes troubles for painted, the modification etc. of PTFE; In addition, also there are problems such as hot-forming temperature height, temperature range pressure narrow, needs are very high, product properties difference in above-mentioned two kinds of forming methods.Therefore, the development priority of PTFE is to improve processing characteristics for a long time, and adapting to machining large product, thin-gage goods, and process automation, high speed, and it is easy to process and improve the needs of working (machining) efficiency to satisfy the user.
(Ultrahigh Molecular Weight Polyethylene UHMWPE) is example with ultra-high molecular weight polyethylene again.Because melt viscosity is big, mobile poor, therefore, melt extrudes the research focus that moulding becomes UHMWPE.For melt extruding of UHMWPE, present research emphasis concentrates on material modification and two aspects of equipment improvement, promptly improves the flowability of UHMWPE on the one hand, make it to melt extrude moulding, but this causes the decline of some physical and mechanical property of goods; On the other hand, design special extruder and head, though to adapt to this through modification but still the not too easily processing request of the material of extrusion molding.
The EP007851 patent has proposed the method that a kind of high viscosity low-density polymeric melt extrudes moulding, mainly is the overlay of coating low-friction coefficient at the feeding section of screw rod, as polytetrafluoroethylene (PTFE), and applies 101 alloys on barrel.Close patent also has JP53-6366, JP4-1832 etc.More than each patent mainly be by reducing the friction between high-viscosity material and screw rod, making material be able to advance along barrel.But these methods mainly are to solve linear low density of polyethylene in solid granulates shape or reinforced mobile poor, problem that transfer rate is low when Powdered, and the polymer that infusibilities such as ultra-high molecular weight polyethylene, polytetrafluoroethylene (PTFE) is flowed or melt the fluidity difference is not suitable.Because infusibility such as ultra-high molecular weight polyethylene, polytetrafluoroethylene (PTFE) stream or to melt the melt flow rate (MFR) of polymer of fluidity difference extremely low, its high viscosity shows under fusion or the critical molten condition.The designed double screw extruder of the present invention is just at these problems, reduces the melt temperature and the melt viscosity of the polymer of non-molten stream and molten fluidity difference significantly by the introducing of supercritical fluid, so that it can easily melt extrude moulding.
Supercritical fluid is the fluid that thermodynamic parameter is higher than its critical point (critical-temperature and critical pressure), and promptly reduced temperature (ratio of actual temperature and critical-temperature) and reduced pressure (ratio of actual pressure and critical pressure) are simultaneously greater than 1 fluid.It both had been different from gas, also was different from liquid, had the characteristics of gas and liquid concurrently: density and liquid are close, thereby have very strong solvent strength; Viscosity and gas are close, thereby mobile more much better than liquid, and mass tranfer coefficient is also much bigger than liquid.In addition, performances such as the density of supercritical fluid, solvent strength and viscosity can be regulated easily by the variation of pressure and temperature.
The more supercritical fluid of research has at present: CO 2, N 2, water, propane, methyl alcohol, ethene, ethane etc.CO 2Critical-temperature be 31.06 ℃, critical pressure is 7.39MPa, critical condition reaches easily comparatively speaking, and CO 2The chemical property torpescence, nontoxic, tasteless, cheap and easy to get, can be recycled, environmental protection, therefore, the present invention has selected supercritical carbon dioxide (SC-CO for use 2) as the process medium fluid.Solute molecule is at SC-CO 2In diffusion coefficient than big 1～2 order of magnitude in general liquid organic solvent, and, when pressure during up to 300～400atm, SC-CO 2The low order of magnitude of the general liquid organic solvent of ratio of viscosities, add its minimum surface tension, make that its infiltration in porous mass is easy especially.Therefore, SC-CO 2Can swelling most polymers, and polymer had very strong plasticization, can significantly reduce the viscosity of polymer melt, reduce the fusing point (T of crystalline polymer m) and the glass transition temperature (T of glassy polymers g).For example: the SC-CO that adds 0.5wt% in the low density polyethylene (LDPE) 2, its apparent viscosity can reduce by 25% at least; At SC-CO 2In, during P=2.5MPa, the T of polymethyl methacrylate gReduce to 60 ℃ from 110 ℃; During P=20.3MPa, the T of polystyrene gReduce to 35 ℃ from 100 ℃.
The present invention passes through SC-CO 2To the plasticising of polymer in the processing formula, dissolve or be partly dissolved effect, reduce the melt temperature and the melt viscosity of moulding polymeric system, thereby make big, the mobile poor polymer of melt viscosity as UHMWPE, polyphenylene oxide, and as the polyformaldehyde to heat or shear sensitive polymer, also have the polymer of processing temperature narrow range as thermoplastic polyester can be easily with melt extruding the polytype goods of method moulding.In addition, another important feature of the present invention is to pass through SC-CO 2Introducing, can make the so non-molten stream material of polytetrafluoroethylene (PTFE) can melt extrude moulding, this obtains more extensive, deeper application to the fluoropolymer that makes performance the best in specific area, thereby the upgrading and the technological progress that drive other industry product have important function.
Summary of the invention
Purpose of the present invention just provides a kind of polymer that can be used for non-molten stream polymer, molten fluidity difference and the polymer of heat or shear sensitive polymer, processing temperature narrow range is melt extruded the double screw extruder of moulding.
For realizing purpose of the present invention, adopt following technical scheme: a kind of extrusion shaping machine, the screw rod that this extrusion shaping machine has barrel and is arranged in this barrel, be used for the drive unit that drive screw makes it to rotate, heating and cooling system, the electronic instrument control system, the metering feeding device, and the mouth mould that is used for moulded product, screw rod is homodromal twin-screw, this extrusion shaping machine also is provided with the supercritical carbon dioxide fluid conveying device, this supercritical carbon dioxide fluid conveying device is communicated with barrel by at least one gas injection port, thereby carries supercritical fluid to barrel.
In addition, on the basis of technique scheme, extrusion shaping machine of the present invention also can be in conjunction with one or more feature in following a plurality of preferred features.
Screw rod can be combined by a plurality of screw elements, and each screwing element angle that interlaces makes the screw thread on the whole screw rod discontinuous during combination.
Barrel can be for multi-section combined.
Gas injection port is at least three.
Gas injection port can be opened stifled as required, and every～gas injection port is equipped with check valve, in the check valve exit jet rose is installed.
The supercritical carbon dioxide fluid conveying device is from upstream to the downstream and is disposed with carbon dioxide memory, filter, condenser, flowmeter, metering conveyor, pressurized tank, constant temperature and pressure jar and flow control valve.
Screw element preferably adopts shallow spline to be connected with connected mode between the screw mandrel.
The screw rod material preferably adopts nitrated steel.
Feeding section at screw rod can be provided with one group of reverse thread.
In brief, the present invention is based on conventional extruder, and adopted assembled screw rod and barrel, increased the many places air admission hole at the barrel place to add supercritical fluid.
Because adopt such scheme, the present invention has following beneficial effect:
(1) the present invention utilizes SC-CO 2Can significantly reduce the melt temperature of forming polymer and the characteristics of melt viscosity, by double screw extruder and SC-CO 2The combination of conveying device takes place, with SC-CO 2Be incorporated into melt extruding in the forming process of polymer, thereby realized the moulding that melt extrudes of non-molten stream and infusibility stream polymer.
(2) the present invention is provided with air admission hole and check valve is installed in air admission hole by the appropriate location at screw rod feeding section, compression section, the pairing barrel of homogenizing zone, has realized SC-CO 2Be incorporated into the purpose of the polymer in the extruder barrel; And by having realized SC-CO at the terminal jet rose of installing of air admission hole 2With continuous one by one independently the form of bubble be incorporated into polymer purpose in the extruder barrel.
(3) height mixes, the screw rod of high shear forces by adopting in the present invention, and in the appropriate location of screw rod feeding section reverse thread etc. is set, and has avoided SC-CO 2Effusion, improved SC-CO 2Mixing efficiency and effect with polymer.
(4) the present invention also can reach by the simple transformation to existing extruder and pass through SC-CO 2Booster action melt extrude the purpose of the non-molten stream of moulding, infusibility stream polymer.
(5) the present invention is by adopting cordwood screw rod and barrel, and on the barrel air inlet the double effects of having realized that an extruder not only can carry out conventional twin-screw extrusion molding but also can carry out the auxiliary extrusion molding of supercritical fluid such as open, block up, expand the scope of application of extruder greatly, saved the input of equipment funds.
Below in conjunction with accompanying drawing, structure of the present invention, function and advantage are described further.
Description of drawings
Fig. 1 is the general illustration of the auxiliary extrusion shaping machine of supercritical fluid of the present invention;
Fig. 2 is the schematic diagram of the barrel of the auxiliary extrusion shaping machine of supercritical fluid of the present invention.
The specific embodiment
The auxiliary extrusion shaping machine of supercritical fluid of the present invention is by extruder and SC-CO 2Conveying device two parts taking place form, sees Fig. 1.
What the extruder of the auxiliary extrusion shaping machine of supercritical fluid of the present invention adopted is double screw extruder, closely similar with common double screw extruder, also is made up of transmission device, extrusion device and heating-cooling device three parts.Transmission device wherein is the same with common double screw extruder with heating-cooling device, only is on the extrusion device with the difference of common double screw extruder, therefore only partly is described with regard to extrusion device below.
The same with the common double screw extruder, the extrusion device of the auxiliary extrusion shaping machine of supercritical fluid also mainly is made up of screw rod and barrel two parts.The screw rod material adopts the high-quality nitrated steel.In order to improve mixing efficiency and effect, what screw rod adopted is to mix the stronger engagement type co-rotating twin screw of shear action.Screw rod among the present invention is a building block system, be that screw rod is combined by a plurality of screw elements, each screw element angle that interlaces during combination, so that the screw thread on the whole screw rod is discontinuous, like this, the material in the leading portion screw channel is separated when rolling into a ball in entering follow-up screw thread, the core of material group comes out, become the material heart and the surface of fusion is synthesized one, therefore, material is keeping good plasticizing admixture in whole screw rod progradation.And, by changing the built-up sequence of screw element, can obtain the screw rod of different qualities, to adapt to the processing request of different material and different goods, enlarge the range of work of equipment.Different with common engagement type co-rotating twin screw is that screw rod of the present invention has one group of reverse thread at feeding section.This group reverse thread can prevent the backflow of material, thereby avoids CO 2Overflow from charge door.In order to improve the bearing capacity of screw rod, adopted the line style splined between screw element and the mandrel.
The barrel of the auxiliary extrusion shaping machine of supercritical fluid of the present invention as shown in Figure 2.In order to adapt with the building block system screw rod, barrel of the present invention has also adopted building block system, be that barrel is also combined by multistage, the difference of itself and common extruder barrel is: barrel of the present invention respectively is provided with an air admission hole that is used to carry supercritical fluid in the appropriate location of screw rod feeding section, compression section, homogenizing zone, feeds the purpose of supercritical fluid with feeding section, compression section, the homogenizing zone that is implemented in extruder.Excessive in order to prevent supercritical fluid, check valve is equipped with in the end of supercritical fluid air admission hole of the present invention; In order to prevent owing to the single port flow produces the supercritical fluid injection stream greatly, increase the difficulty of mixing subsequently, be unfavorable for the formation of polymer-supercritical fluid homogeneous system, so jet rose all is equipped with in supercritical fluid air admission hole of the present invention end, so that supercritical fluid is re-introduced in the molding materials system after being refined into a plurality of a fluid streams, thereby can enlarge the contact area of supercritical fluid and material, improve both mixing rate and effects.
The SC-CO of the auxiliary extrusion shaping machine of supercritical fluid of the present invention 2Conveying device takes place as shown in Figure 1.
Described SC-CO 2Generating means is by CO 2Memory 1, filter 2, condenser 3, flowmeter 4, metering conveyor 5, pressurized tank 6, constant temperature vacuum tank 7, flow control valve 8 are formed.Described CO 2Memory 1 is a high pressure CO 2Gas bomb, its outlet is connected with the import of filter 2.The outlet of described filter 2 is connected with the import of condenser 3.Described condenser 3 is tubular heat exchangers, and carbon dioxide flows in pipe, and cooling agent flows outside pipe, with the carbon dioxide in the cooling tube.The outlet of described condenser 3 is connected with the import of flowmeter 4.The outlet of described flowmeter 4 is connected with the import of metering conveyor 5.Described metering conveyor 5 can be selected from screw pump, gear pump or plunger displacement pump.Screw pump has resin and measures pulseless advantage, but measuring accuracy is not high; High-pressure gear pump has the advantage of resin metering pulse free, accurate measurement, but costs an arm and a leg; Plunger displacement pump has the high advantage of measuring accuracy, but is used for that pulsation is arranged when resin measures.The outlet of described metering conveyor 5 is connected with an import of pressurized tank 6.The outlet of described blender 6 is connected with the import of constant temperature vacuum tank 7.Described constant temperature vacuum tank 7 is a jacket type structure, can feed heat medium in the chuck.Described heat medium comprises superheated water, steam, deep fat etc.Described constant temperature vacuum tank 7 also can be single layer structure, by the outer wall heating of jar.Mode of heating can adopt electrical heating, infrared ray heating or heating using microwave etc.Described constant temperature vacuum tank 7 also can select for use other to have the equipment of high pressure heating function.The outlet of described constant temperature vacuum tank 7 is connected with flow control valve 8.
The operation principle of the auxiliary extrusion shaping machine of supercritical fluid is:
Polymer enters into the charging basket of extruder from hopper 9, and under the turning effort of screw rod 10, because the rubbing action of charging basket inwall and screw surface travels forward, screw rod is carried and compacting polymer.Still be in the effect of the material of solid state owing to strong frictional heat, the surface begins to be clamminess, and particularly by behind one group of reverse thread on the feeding section screw rod, the degree that material is compacted improves greatly.Coordinate mutually therewith, by adding pore 12 with the SC-CO that generates on the barrel 2Fluid with continuous one independently bubble form be injected in the polymeric system because SC-CO 2High diffusivity, add the screw rod of high shear, high immixture and give the mixed performance of the excellence of extruder, make SC-CO 2Be dissolved in very soon in the polymer, not only reduced the melt temperature of polymer, and reduced the viscosity of polymer melt, according to the difference of technology and forming polymer performance can also continue or just the pore 11,13 that adds from the barrel inject SC-CO 2To the melt zone end, polymer finally becomes viscous state.The polymer SC-CO of viscous state 2Fluid is by homogenizing zone, is further mixed plasticizing evenly under the back pressure effect that the resistance of machine head port mould 14 causes, and quantitatively extrudes from machine head port mould to level pressure.At the machine head port mould place, since abrupt pressure reduction, SC-CO 2Supersaturation is overflowed rapidly from polymeric system with gas form, and polymer becomes mouthful closely knit goods of mould institute figuration shape.
Though invention has been described by the specific embodiment, yet be understood that easily those skilled in the art can carry out various corrections and change to the present invention in the scope that does not break away from spiritual essence of the present invention.Thereby protection scope of the present invention ought to comprise these corrections and change.

Claims (4)

1. extrusion shaping machine, this extrusion shaping machine has barrel and is arranged in the screw rod of this barrel, is used for drive unit, heating and cooling system, electronic instrument control system, metering feeding device that drive screw makes it to rotate, and the mouth mould that is used for moulded product, and
Screw rod is homodromal twin-screw, and
This extrusion shaping machine also is provided with the supercritical carbon dioxide fluid conveying device, and this supercritical carbon dioxide fluid conveying device is communicated with barrel by at least one gas injection port, thereby carries supercritical fluid in barrel,
Barrel is provided with a plurality ofly can open stifled gas injection port as required, and each described gas injection port is equipped with check valve, in the check valve exit jet rose is installed,
The supercritical carbon dioxide fluid conveying device is from upstream to the downstream and is disposed with carbon dioxide memory, filter, condenser, flowmeter, metering conveyor, pressurized tank, constant temperature and pressure jar and flow control valve, and
Be provided with one group at the feeding section of screw rod and prevent CO 2Reverse thread from the charge door effusion.
2. extrusion shaping machine as claimed in claim 1 is characterized in that: screw rod is wherein combined by a plurality of screw elements, and each screwing element angle that interlaces makes the screw thread on the whole screw rod discontinuous during combination.
3. extrusion shaping machine as claimed in claim 1 is characterized in that: barrel wherein is multi-section combined.
4. extrusion shaping machine as claimed in claim 2 is characterized in that: screw element is that shallow spline is connected with connected mode between the screw mandrel.
CNB2006101565917A 2006-12-28 2006-12-28 Supercritical fluid assistant high molecular material extrusion forming machine Expired - Fee Related CN100493885C (en)

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Application Number Priority Date Filing Date Title
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Assignee: Foshan New Changsheng Plastic films Co., Ltd.

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Denomination of invention: Forming machine for extruding assistant high molecular material in supercritical fluid

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