CN101219573B - Supercritical fluid auxiliary polyalcohol contour machining equipment, implementing method and application thereof - Google Patents
Supercritical fluid auxiliary polyalcohol contour machining equipment, implementing method and application thereof Download PDFInfo
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- CN101219573B CN101219573B CN2007100325893A CN200710032589A CN101219573B CN 101219573 B CN101219573 B CN 101219573B CN 2007100325893 A CN2007100325893 A CN 2007100325893A CN 200710032589 A CN200710032589 A CN 200710032589A CN 101219573 B CN101219573 B CN 101219573B
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- 229920000642 polymer Polymers 0.000 claims abstract description 49
- 238000002347 injection Methods 0.000 claims abstract description 47
- 239000007924 injection Substances 0.000 claims abstract description 47
- 238000002156 mixing Methods 0.000 claims abstract description 28
- 238000012545 processing Methods 0.000 claims abstract description 15
- 238000001746 injection moulding Methods 0.000 claims abstract description 10
- 239000002131 composite material Substances 0.000 claims abstract description 9
- 238000009830 intercalation Methods 0.000 claims abstract description 8
- 230000002687 intercalation Effects 0.000 claims abstract description 8
- 238000001125 extrusion Methods 0.000 claims abstract description 5
- 239000000463 material Substances 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 19
- 230000004927 fusion Effects 0.000 claims description 15
- 238000005086 pumping Methods 0.000 claims description 13
- 230000006837 decompression Effects 0.000 claims description 11
- 238000003860 storage Methods 0.000 claims description 10
- 230000000694 effects Effects 0.000 claims description 9
- 238000000518 rheometry Methods 0.000 claims description 8
- 229920002959 polymer blend Polymers 0.000 claims description 7
- 229910052615 phyllosilicate Inorganic materials 0.000 claims description 5
- 150000004760 silicates Polymers 0.000 claims description 5
- 230000008859 change Effects 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
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- 238000009530 blood pressure measurement Methods 0.000 claims description 2
- 238000005259 measurement Methods 0.000 claims description 2
- 125000003003 spiro group Chemical group 0.000 claims description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 abstract description 6
- 238000000465 moulding Methods 0.000 abstract description 2
- 230000008569 process Effects 0.000 description 20
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Images
Classifications
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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
- B29C48/57—Screws provided with kneading disc-like elements, e.g. with oval-shaped elements
-
- 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
- B29C48/375—Plasticisers, homogenisers or feeders comprising two or more stages
- B29C48/385—Plasticisers, homogenisers or feeders comprising two or more stages using two or more serially arranged screws in separate barrels
-
- 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
- B29C48/50—Details of extruders
- B29C48/505—Screws
- B29C48/54—Screws with additional forward-feeding elements
-
- 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
- B29C48/55—Screws having reverse-feeding elements
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Extrusion Moulding Of Plastics Or The Like (AREA)
- Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
Abstract
本发明公开一种超临界流体辅助聚合物成型加工设备，包括具有特定结构螺杆的挤出机或注塑机、超临界流体输送系统、自锁式注气单向阀、压力传感器和抽真空泵。一种由上述设备实现的方法，步骤为：超临界流体输送系统控制气体处于超临界状态输出，经自锁式注气单向阀注入挤出机或注塑机机筒内；所注入的超临界流体与经特定结构螺杆塑化的聚合物熔体混合，形成均相体系；均相体系经特定结构螺杆进一步混炼后，超临界流体在低压下从均相体系中释出转化成气体，经过螺杆排气段时，由抽真空泵抽出。本方法可应用到聚合物成型加工设备实现超临界流体辅助多相聚合物共混挤出和注塑、聚合物/层状硅酸盐复合材料的熔融插层挤出和注塑。
The invention discloses supercritical fluid-assisted polymer forming processing equipment, which comprises an extruder or injection molding machine with a screw with a specific structure, a supercritical fluid delivery system, a self-locking gas injection one-way valve, a pressure sensor and a vacuum pump. A method realized by the above-mentioned equipment, the steps are: the supercritical fluid delivery system controls the gas output in a supercritical state, and injects it into the extruder or injection molding machine barrel through a self-locking gas injection check valve; the injected supercritical fluid The fluid is mixed with the polymer melt plasticized by a screw with a specific structure to form a homogeneous system; after the homogeneous system is further mixed by a screw with a specific structure, the supercritical fluid is released from the homogeneous system at low pressure and converted into a gas. When the screw is exhausted, it is drawn out by a vacuum pump. The method can be applied to polymer molding processing equipment to realize supercritical fluid-assisted multi-phase polymer blending extrusion and injection molding, and melt intercalation extrusion and injection molding of polymer/layered silicate composite materials.
Description
Technical field
The present invention relates to the forming polymer process technology, particularly a kind of supercritical fluid auxiliary polyalcohol contour machining equipment and its implementation and application.
Background technology
Forming polymer processing mainly develops to low energy consumption, full recovery, zero-emission directions such as (being green manufacturing), and supercritical fluid auxiliary polyalcohol processing is a kind of new type of polymer processing method that developed recently gets up.Supercritical fluid presents a kind of character between liquids and gases, have character such as high diffusibility, highly dissoluble and low-viscosity, as a kind of solvent of uniqueness, can be incorporated in the processing and forming of polymer more conveniently, realize the function that usual vehicle can't be realized.
Blend and nano combined be two kinds of important method that improve the polymeric material performance at present.The multiphase polymer blend extrude or injection moulding process in, each viscosity ratio between mutually is one of important parameter that influences blend microscopic pattern and performance.For example: in the two-phase polymer blend, the viscosity ratio of two-phase was near 1 o'clock, and the dispersed phase size in the blend is less, and the dispersion of decentralized photo in continuous phase is more even.In actual blend, add compatilizer and can improve each alternate compatibility, promote the dispersion of decentralized photo in continuous phase, but the small-molecular weight compatilizer can reduce the mechanical property of material.In the various preparation methods of nano composite polymer/laminated silicate material, melt intercalated method has simply, the advantage of easy realization of industrialization, but this method difficulty is disperseed phyllosilicate and is formed good intercalation or the form of peeling off in polymeric matrix, especially also usually improve the polymer molecular chain intercalation by the graft that adds some polar functionalities or make the unilateral ability of peeling off of silicate for non-polar polymer, this is easy to generate the negative interaction that reduces material property equally.Above-mentioned blend and nano combined in introduce supercritical fluid and can overcome these shortcomings.Because after supercritical fluid is dissolved in the polymer, can make polymers swell, increase its free volume, reduce its vitrification point, make its strand that bigger activity space be arranged, supercritical fluid has played " lubricant " in polymer molecular chain, not only reduced the viscosity of polymer melt on the macroscopic view, has also strengthened the diffusivity of polymer molecular chain on the microcosmic.
Yet, in the forming polymer process, how in the limited time of staying, improve the meltage of supercritical fluid in polymer, it is dispersed in forms polymer/supercritical fluid homogeneous system in the polymer melt, these difficult problems hamper the application and the development of supercritical fluid auxiliary polyalcohol processing and forming.
The patent No. is equipment and the method that U.S.'s patent of invention of US 6521258 B1 discloses the auxiliary multiphase polymer blend of a kind of supercritical fluid, whole process is carried out in reactor, the process that belongs to the batch preparation blend polymer, manufacturing cycle is long, output is subjected to the reactor capacity limit, is unfavorable for industrial popularization.
The patent No. is equipment and the method that U.S.'s patent of invention of US 2005/0256242 A1 discloses the auxiliary fusion intercalation extruded polymer/laminated nm-silicate composite material of a kind of supercritical fluid, as shown in Figure 1; Preparation process has comprised the step of two sections feedings, from hopper feeding polymer, treat that polymer is heated the mixture that advances reinject behind the segment distance phyllosilicate and supercritical fluid to constitute, its injection mode has two kinds, wherein a kind of (1B) another kind (1C) more near hopper.Before phyllosilicate and supercritical fluid mixture injection extruder, silicate will mix a period of time with supercritical fluid earlier in high pressure (being higher than the fluid supercritical pressure) airtight container, make the high diffusibility of supercritical fluid utilization itself infiltrate the silicate plate interlayer and fully strut lamella, it is batch process that this preprocessing process causes the preparation process of whole polymer nanocomposites, do not have long-time continuous, and the output of a production cycle is determined by the high pressure sealing container capacity.
The patent No. is equipment and the method that U.S.'s patent of invention of US 2005/0131126 A1 discloses the auxiliary fusion intercalation extruded polymer/laminated nm-silicate composite material of a kind of supercritical fluid, as shown in Figure 2; This equipment adopts two stepwises to extrude, the first rank extruder is with the abundant fusion plastification of polymer/laminated silicate mixture, inject supercritical fluid at the second rank single screw extrusion machine near the melt inlet position, and keep higher pressure in the machine barrel by regulating the second rank outlet of extruder size.This complete equipment complex structure, volume is bigger, operation is relative more loaded down with trivial details with control, and because the pump-down process operation is not set, the gained extrudate contains bubble, if not the preparation foaming product, then also need add this procedure of bubble of removing in the foaming extrudate in addition, can make overall structure further complicated like this.
Summary of the invention
The objective of the invention is to overcome the weak point of existing polyblend and nanometer composite technology, provide a kind of compact conformation, simple to operate, work flow rationally, supercritical fluid auxiliary polyalcohol contour machining equipment that the mechanism continuity is good.
Another object of the present invention is to provide a kind of supercritical fluid auxiliary polyalcohol method for processing forming of realizing by the said equipment.
A further object of the present invention is to provide the application of above-mentioned supercritical fluid auxiliary polyalcohol contour machining equipment and its implementation.
Purpose of the present invention is achieved through the following technical solutions: a kind of supercritical fluid auxiliary polyalcohol contour machining equipment comprises extruder or injection machine, supercritical fluid delivery system, pressure sensor and vacuum pumping pump with ad hoc structure screw rod; Described supercritical fluid delivery system comprises gas storage tank, high-pressure metering pump, high-pressure solenoid valve and self-locking air injection uni-direction, gas storage tank is connected with high-pressure metering pump, and high-pressure metering pump is connected with extruder or injection machine with the self-locking air injection uni-direction by high-pressure solenoid valve; Described self-locking air injection uni-direction, pressure sensor and vacuum pumping pump are connected with extruder with ad hoc structure screw rod or injection machine along extruding the direction order; The ad hoc structure of described screw rod can be divided into four sections by the function that the screw element combination is produced: fusion plastification section, supercharging section, decompression section and exhaust section; Described fusion plastification section is made up of forward delivery element and mixing elements; Described supercharging section is formed single screw rod is more shallow by screw channel and pitch is short delivery element and mixing elements, and twin-screw is made up of reverse delivery element and mixing elements; Described decompression section is made up of forward delivery element and mixing elements; Described exhaust section is made up of the forward delivery element; The spiral groove depth of the delivery element that described screw channel is more shallow is (0.01～0.07) D, and the pitch pitch of short delivery element is (0.5～1.0) D, and wherein D is a screw diameter.
Described delivery element comprises forward delivery element and reverse delivery element.The spiral shell rib lift angle of described forward delivery element is set to guarantee the mass transport direction and to extrude direction identical.The spiral shell rib lift angle of described reverse delivery element is opposite with the forward delivery element, and its mass transport direction is with to extrude direction opposite.
Described decompression section is made up of forward delivery element and mixing elements, and major function is to make the supercritical fluid that is dissolved in the polymer melt grow into bubble under the low pressure condition, discharges.
Described mixing elements comprises kneading disk element, pin mixing elements etc.Described kneading disk element is mediated by a plurality of oval kneading disk stagger arrangement and is formed, and the size at stagger arrangement angle, the number of kneading disk and axial length have determined the mixing behavior of kneading disk.Described pin mixing elements row has the pin of multiple row projection, and its shunting action of utilizing pin is to carry out mixing to material.
Described high-pressure metering pump adopts the twin-tub design, and the twin-tub alternation can guarantee the continuity of supercritical fluid generative process; Described high-pressure metering pump is provided with temperature control system, can control the temperature of the supercritical fluid of the high-pressure metering pump of flowing through.
Described self-locking air injection uni-direction can prevent that the polymer melt adverse current from entering gas pipeline, and it comprises: adapter sleeve, high temperature resistant elastic rubber fitting, ball and air guide screw.Described air guide screw is connected and fixed by external screw thread and adapter sleeve lower end internal thread; Described ball compresses by high temperature resistant elastic rubber fitting and connects the air guide screw.
Described supercritical fluid auxiliary polyalcohol contour machining equipment also can be connected linear flow and become system, with the rheological property of on-line measurement polymer melt, for the control of processing conditions provides indirect data support.This system is made up of online flow graph, computer and rheological data analysis software.
A kind of supercritical fluid auxiliary polyalcohol method for processing forming of realizing by the said equipment, comprise the steps: that (1) supercritical fluid delivery system control gas is in supercriticality and output, in the self-locking air injection uni-direction enters extruder or injection machine machine barrel; (2) the interior Mixing of Polymer Melt through the ad hoc structure spiro rod plasticizing of supercritical fluid that is entered and extruder or injection machine machine barrel forms homogeneous system; (3) homogeneous system is after the ad hoc structure screw rod is further mixing, and supercritical fluid under low pressure disengages from homogeneous system and changes into gas, during through the screw rod exhaust section, is extracted out by vacuum pumping pump.
Described step (1) specifically can be: the gas in the gas storage tank enters the high-pressure metering pump that has temperature control system through valve; The temperature and pressure of control high-pressure metering pump makes this gas reach supercriticality; Set high pressure measurement delivery side of pump flow rate, make supercritical fluid with constant compression force and flow output; The supercritical fluid of output injects in extruder or the injection machine machine barrel through high-pressure solenoid valve and self-locking air injection uni-direction.
Described step (2) specifically can be: material adds from the feeder of extruder or injection machine, make its fusion through the heating of machine barrel and the shear heat of screw rod rotation generation, more shallow through screw channel again and pitch is short delivery element or oppositely delivery element effect make melt be full of the screw channel of screw restriction section; Mix with the supercritical fluid of injection in this section pressurized melt, rotate under shearing, stretching and the extruding that produces at mixing elements, supercritical fluid dissolves in the polymer melt gradually, forms homogeneous system.
In the described step (2), pressure sensor is measured the pressure of screw restriction section material in real time.Guarantee to be dissolved in gas pressure in the polymer on supercritical pressure by the control processing conditions.
Described step (3) specifically can be: homogeneous system is through entering the decompression section after the supercharging section of screw rod, rapid depressurization, supercritical fluid under low pressure discharge from homogeneous system and change into gas, during through the screw rod exhaust section, is extracted out by vacuum pumping pump.
The type of described material can serve as reasons blend that two or more polymer constitutes and the mixture that constitutes by polymer and phyllosilicate.
This processing method also can generate real time data by the rheological property of the online detection polymer melt of online flow graph, is transferred to computer, draws rheological curve via the rheological data analysis software.Process has the height real-time and does not influence the continuity of production.
This supercritical fluid auxiliary polyalcohol contour machining equipment and implementation method may be used on comprising the equipment of single screw extrusion machine, double screw extruder and injection machine, and the auxiliary multiphase polymer blend of realization supercritical fluid is extruded with the fusion intercalation of injection moulding, polymer/laminated silicate composite and extruded and injection moulding.
Action principle of the present invention is: the supercritical fluid delivery system is connected with polyalcohol contour machining equipment by the self-locking air injection uni-direction, in the supercharging section of screw rod supercritical fluid injection of polymer melt, mix the formation homogeneous system with it, make polymer melt generation swelling, free volume increases, polymer molecular chain has bigger activity space and stronger diffusivity, thereby it is more even to impel decentralized photo in the material system to disperse in continuous phase, and size is littler.Then in the decompression section of screw rod, supercritical fluid under low pressure discharges from homogeneous system and changes into gas, during through the screw rod exhaust section, is extracted out by vacuum pumping pump.At last, the material of process exhaust section is extruded machine and extrudes or be injection molding machine injection mould.The decentralized photo of one or more polymer in interior material system that comprise through aforementioned effect has good dispersing uniformity and smaller szie.
The present invention has following advantage and effect with respect to prior art and equipment: (1) uses the supercritical fluid auxiliary polyalcohol molding process, if the multiphase polymer blend, supercritical fluid has promoted dispersion and the reducing of size of polymer dispersed in polymer continuous phase; If preparation polymer/laminated silicate composite, supercritical fluid has strengthened the polymer molecular chain intercalation and has entered ability between the silicate lamella, has promoted peeling off of silicate lamella.(2) utilize the present invention can on polyblend and nano combined equipment, realize the processing of supercritical fluid assistant formation, compact conformation, simple to operate, work flow is reasonable, has kept the continuity of process, therefore is easy to realize and promote.(3) at different material systems, can set up different flow fields by changing different screw elements, make it to adapt to the characteristic of material system, so applicability is better.(4) can detect the rheological property of material system by online rheology system in real time, optimize machined parameters, supercritical fluid is played a role in the forming polymer process to greatest extent.
Description of drawings
Fig. 1 is the equipment schematic diagram among existing patent US 2005/0256242 A1.
Fig. 2 is the equipment schematic diagram among existing patent US 2005/0131126 A1.
Fig. 3 is the structural representation of supercritical fluid auxiliary polyalcohol contour machining equipment of the present invention.
Fig. 4 is a kind of screw-rod structure schematic diagram of the present invention.
Fig. 5 is the structural representation of self-locking air injection uni-direction in the process equipment shown in Figure 3.
Fig. 6 is the auxiliary optical microscope photograph of extruding the two-phase polymer blend of preparation of supercritical fluid.
Fig. 7 is the auxiliary transmission electron microscope photo of extruding the polymer nanocomposites of preparation of supercritical fluid.
Fig. 8 is the auxiliary wide-angle x-ray diffraction pattern of extruding the polymer nanocomposites of preparation of supercritical fluid.
Symbol description is as follows among above-mentioned each figure: the A-double screw extruder; B-supercritical fluid delivery system; The C-vacuum pumping pump; The online rheology of D-system; E-fusion plastification section; F-supercharging section; G-reduce pressure the section; The H-exhaust section; The 1-temperature control system; The 2-high-pressure metering pump; The 3-high-pressure solenoid valve; 4-self-locking air injection uni-direction (4-1-adapter sleeve; The high temperature resistant elastic rubber fitting of 4-2-; The 4-3-ball; 4-4-air guide screw); The 5-valve; The 6-gas storage tank; The 7-feeder; The 8-machine barrel; The 9-pressure sensor; The online flow graph of 10-; The 11-computer; 12-forward delivery element; The 13-mixing elements; The reverse delivery element of 14-; The 15-spout; The 16-gas injection port; The 17-pressure tap; The 18-exhaust outlet; 19-high density polyethylene (HDPE) (HDPE); 20-ultra high molecular weight polyethylene (UHMWPE); 21-polypropylene (PP); The 22-nanoclay; The wide-angle x-ray diffraction pattern of 23-nanoclay; The wide-angle x-ray diffraction pattern of 24-PP/ nano clay composite material; The 25-supercritical CO
2The auxiliary wide-angle x-ray diffraction pattern of extruding the PP/ nano clay composite material of preparation; 26-d
(001)Diffraction maximum.
The specific embodiment
The present invention is described in further detail below in conjunction with embodiment and accompanying drawing, but embodiments of the present invention are not limited thereto.
Embodiment
It is the concrete structure of embodiment with the double screw extruder that Fig. 3～Fig. 5 shows the present invention, and as seen from Figure 3, this supercritical fluid auxiliary polyalcohol contour machining equipment comprises double screw extruder A, supercritical CO
2Induction system B, vacuum pumping pump C and the online rheology D of system; Supercritical CO
2Induction system B is connected with self-locking air injection uni-direction 4; Self-locking air injection uni-direction 4, pressure sensor 9, vacuum pumping pump C and the online rheology D of system are connected with double screw extruder A along extruding the direction order.Described double screw extruder A comprises feeder 7, machine barrel 8, screw rod (as shown in Figure 4) and pressure sensor 9, the rear end of machine barrel 8 links to each other with feeder 7, machine barrel 8 be peripherally equipped with temperature control heating collar (not shown), the screw rod that machine barrel 8 inside are provided with specific screw element combination is as shown in Figure 4.
Fig. 4 shows the screw rod of described ad hoc structure, and the function that is produced by the screw element combination can be divided into four sections: fusion plastification section E, supercharging section F, decompression section G and exhaust section H.Described fusion plastification section E mainly is made up of forward delivery element 12 and mixing elements 13; Described supercharging section F mainly is made up of reverse delivery element 14 and mixing elements 13; Described decompression section G mainly is made up of forward delivery element 12 and mixing elements 13; Described exhaust section H mainly is made up of forward delivery element 12.The spiral shell rib lift angle of described forward delivery element 12 is set to guarantee the mass transport direction and to extrude direction identical; The spiral shell rib lift angle of described reverse delivery element 14 is opposite with forward delivery element 12, and its mass transport direction is with to extrude direction opposite; Described mixing elements 13 comprises the kneading disk element; Described kneading disk element is mediated by a plurality of oval kneading disk stagger arrangement and is formed, and the size at stagger arrangement angle, the number of kneading disk and axial length have determined the mixing behavior of kneading disk.
Described supercritical CO
2Induction system B comprises gas storage tank 6, valve 5, high-pressure metering pump 2, high-pressure solenoid valve 3 and check valve 4, gas storage tank 6 is connected with high-pressure metering pump 2 by valve 5, and high-pressure metering pump 2 is connected with the machine barrel 8 of double screw extruder A with self-locking air injection uni-direction 4 by high-pressure solenoid valve 3.Described self-locking air injection uni-direction 4 can prevent that the polymer melt adverse current from entering gas pipeline; Described high-pressure metering pump 2 adopts the twin-tub design, and the twin-tub alternation can guarantee supercritical CO
2The continuity of generative process; The pump housing of described high-pressure metering pump 2 is provided with temperature control system 1, can be to the supercritical CO of the high-pressure metering pump 2 of flowing through
2Temperature control.
Described self-locking air injection uni-direction 4 comprises: adapter sleeve 4-1, high temperature resistant elastic rubber fitting 4-2, ball 4-3 and air guide screw 4-4.Described air guide screw 4-4 is connected and fixed by external screw thread and adapter sleeve 4-1 lower end internal thread; Described ball 4-3 compresses by high temperature resistant elastic rubber fitting 4-2 and connects air guide screw 4-4.
The described online rheology D of system is made up of online flow graph 10, computer 11 and rheological data analysis software (not shown).
The entire work process of this supercritical fluid auxiliary polyalcohol contour machining equipment is: open the valve 5 that is connected with gas storage tank 6, make CO
2Enter the high-pressure metering pump 2 that has temperature control system; The temperature and pressure of control high-pressure metering pump 2 makes CO
2Be in supercriticality; Set the outlet flow rate of high-pressure metering pump 2, open high-pressure solenoid valve 3 and make supercritical CO
2With constant compression force and flow process self-locking air injection uni-direction 4.Material adds from feeder 7, makes its fusion through the heating of machine barrel 8 and the shear heat of screw rod fusion plastification section E, through reverse delivery element 14 effects, makes melt be full of the screw channel of screw restriction section F again.The supercritical CO of this section pressurized melt and injection
2Mix, under shearing, stretching and the extruding of mixing elements 13, supercritical CO
2Dissolve in gradually in the polymer melt, form homogeneous system.This homogeneous system enters decompression section F, rapid depressurization, supercritical CO through after the reverse delivery element 14
2Under low pressure can from homogeneous system, discharge and change into gaseous state CO
2, during through screw rod exhaust section H, extract out by vacuum pumping pump C.At last, when the material of process exhaust section is extruded into billot, also can carries out online rheology and detect by the online rheology D of system, this process is: online flow graph 10 its rheological properties of online detection, generate real time data, be transferred to computer 11, draw rheological curve via the rheological data analysis software.Process has the height real-time and does not influence the continuity of production.
Fig. 6～Fig. 8 shows implementation result of the present invention.Fig. 6 shows high density polyethylene (HDPE) (HDPE)/ultra high molecular weight polyethylene (UHMWPE) of extruding preparation, and (mass ratio: the 80/20) light micrograph of blend, Fig. 6 (a) and Fig. 6 (b) are respectively the supercritical CO that does not add and add content 3%
2Under the situation of secondary process, the dispersion effect of UHMWPE 20 in HDPE 19.As seen, supercritical CO
2Reduced the size of decentralized photo UHMWPE 20 effectively; Fig. 7 shows polypropylene (PP)/nanoclay of extruding preparation, and (mass ratio: the 97/3) transmission electron microscope photo of nano composite material, Fig. 7 (a) and Fig. 7 (b) are respectively the supercritical CO that does not add and add content 4%
2Under the situation of secondary process, the dispersion effect of nanoclay 22 in PP 21.Supercritical CO
2Promoted peeling off of nanoclay 22 lamellas effectively, made that agglomeration nano clay 22 particles are littler; Fig. 8 shows the PP/ nanoclay (mass ratio: 97/3) the wide-angle x-ray diffraction pattern of nano composite material, supercritical CO of extruding preparation
2Make the d of nano composite material
(001)Diffraction maximum 26 is offset left, and d
(001)Diffraction peak intensity reduces, and illustrates that nanoclay 22 sheet interlayer spacings are bigger, and nanoclay 22 limellar strippings are more.
The foregoing description is a preferred implementation of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from change, the modification done under spiritual essence of the present invention and the principle, substitutes, combination, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (8)
1. a supercritical fluid auxiliary polyalcohol contour machining equipment is characterized in that: comprise extruder or injection machine, supercritical fluid delivery system, pressure sensor and vacuum pumping pump with ad hoc structure screw rod; Described supercritical fluid delivery system comprises gas storage tank, high-pressure metering pump, high-pressure solenoid valve and self-locking air injection uni-direction, gas storage tank is connected with high-pressure metering pump, and high-pressure metering pump is connected with extruder or injection machine with the self-locking air injection uni-direction by high-pressure solenoid valve; Described self-locking air injection uni-direction, pressure sensor and vacuum pumping pump are connected with extruder with ad hoc structure screw rod or injection machine along extruding the direction order;
The ad hoc structure of described screw rod is divided into four sections by the function that the screw element combination is produced: fusion plastification section, supercharging section, decompression section and exhaust section; Described fusion plastification section is made up of forward delivery element and mixing elements; Described supercharging section is formed single screw rod is more shallow by screw channel and pitch is short delivery element and mixing elements, and twin-screw is made up of reverse delivery element and mixing elements; Described decompression section is made up of forward delivery element and mixing elements; Described exhaust section is made up of the forward delivery element; The spiral groove depth of the delivery element that described screw channel is more shallow is 0.01D～0.07D, and the pitch pitch of short delivery element is 0.5D～1.0D, and wherein D is a screw diameter.
2. supercritical fluid auxiliary polyalcohol contour machining equipment according to claim 1 is characterized in that: described self-locking air injection uni-direction comprises adapter sleeve, high temperature resistant elastic rubber fitting, ball and air guide screw; Described air guide screw is connected and fixed by external screw thread and adapter sleeve lower end internal thread; Described ball compresses by high temperature resistant elastic rubber fitting and connects the air guide screw.
3. supercritical fluid auxiliary polyalcohol contour machining equipment according to claim 1 is characterized in that: be connected with online rheology system, the rheological property of on-line measurement polymer melt.
4. supercritical fluid auxiliary polyalcohol method for processing forming of realizing by each described equipment of claim 1～3, it is characterized in that comprising the steps: that (1) supercritical fluid delivery system control gas is in supercriticality and output, in the self-locking air injection uni-direction enters extruder or injection machine machine barrel; (2) in supercritical fluid that is entered and extruder or the injection machine machine barrel through the Mixing of Polymer Melt of ad hoc structure spiro rod plasticizing, form homogeneous system; (3) homogeneous system is after the ad hoc structure screw rod is further mixing, and supercritical fluid under low pressure disengages from homogeneous system and changes into gas, during through the screw rod exhaust section, is extracted out by vacuum pumping pump.
5. supercritical fluid auxiliary polyalcohol method for processing forming according to claim 4 is characterized in that: the gas that described step (1) is specially in the gas storage tank enters the high-pressure metering pump that has temperature control system through valve; The temperature and pressure of control high-pressure metering pump makes this gas reach supercriticality; Set high pressure measurement delivery side of pump flow rate, make supercritical fluid with constant compression force and flow output; The supercritical fluid of output injects in extruder or the injection machine machine barrel through high-pressure solenoid valve and self-locking air injection uni-direction.
6. supercritical fluid auxiliary polyalcohol method for processing forming according to claim 4, it is characterized in that: described step (2) is specially the feeder adding of material from extruder or injection machine, make its fusion through the heating of machine barrel and the shear heat of screw rod, more shallow through screw channel again and pitch is short delivery element or oppositely delivery element effect make melt be full of the screw channel of screw restriction section; Mix with the supercritical fluid of injection in this section pressurized melt, under shearing, stretching and the extruding of mixing elements, supercritical fluid dissolves in the polymer melt gradually, forms homogeneous system; Described step (3) is specially homogeneous system through entering the decompression section after the supercharging section of screw rod, and rapid depressurization, supercritical fluid under low pressure discharge from homogeneous system and change into gas, during through the screw rod exhaust section, are extracted out by vacuum pumping pump.
7. supercritical fluid auxiliary polyalcohol method for processing forming according to claim 6 is characterized in that: the type of described material is blend that is made of two or more polymer and the mixture that is made of polymer and phyllosilicate.
8. the application of supercritical fluid auxiliary polyalcohol method for processing forming according to claim 4 is characterized in that: be applied to the equipment that comprises single screw extrusion machine, double screw extruder and injection machine and realize that the auxiliary multiphase polymer blend of supercritical fluid is extruded with the fusion intercalation of injection moulding, polymer/laminated silicate composite and extrude and injection moulding.
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| CN101445612B (en) * | 2008-12-22 | 2011-04-27 | 华南理工大学 | Method for preparing thermoplastic elastomer by supercritical fluid assisted dynamic vulcanization |
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| CN102601962A (en) * | 2012-02-28 | 2012-07-25 | 青岛科技大学 | Auxiliary polymer processing method and device by supercritical fluid |
| CN105670116B (en) * | 2016-03-02 | 2018-01-23 | 中国科学院宁波材料技术与工程研究所 | A kind of polypropylene blend and preparation method thereof |
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| CN105922538B (en) * | 2016-05-23 | 2022-03-29 | 上海译科实业有限公司 | Extruder screw for a process for foaming polymers and extruder with such a screw |
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| CN106541540A (en) * | 2016-10-25 | 2017-03-29 | 武汉理工大学 | A kind of microporous foam product with decoration outer film and processing method |
| CA3064767A1 (en) * | 2017-05-31 | 2018-12-06 | Nanoxplore Inc. | Methods of exfoliating and dispersing a graphitic material into polymer matrices using supercritical fluids |
| CN107353617B (en) * | 2017-06-29 | 2019-10-08 | 上海锦湖日丽塑料有限公司 | PC/ABS alloy with anti-acoustic capability and preparation method thereof |
| CN112762693A (en) * | 2021-02-02 | 2021-05-07 | 苏州璞佩珊科技有限公司 | Screw type continuous drying device |
| CN113388148B (en) * | 2021-06-08 | 2022-04-01 | 华中科技大学 | A kind of preparation method of supercritical carbon dioxide assisted thermally conductive composite material |
| CN114161682B (en) * | 2021-12-08 | 2023-11-24 | 广东粤港澳大湾区黄埔材料研究院 | Method for preparing medical absorbable polyester by supercritical fluid assisted twin-screw continuous extrusion, product and application |
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Application publication date: 20080716 Assignee: HUILONG PLASTICS MACHINERY Co.,Ltd. Assignor: South China University of Technology Contract record no.: 2015440000266 Denomination of invention: Supercritical fluid auxiliary polyalcohol contour machining equipment, implementing method and application thereof Granted publication date: 20110518 License type: Exclusive License Record date: 20150617 |
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