WO2014201767A1 - 一种熔融缩聚反应方法及其反应器和降膜管 - Google Patents

一种熔融缩聚反应方法及其反应器和降膜管 Download PDF

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Publication number
WO2014201767A1
WO2014201767A1 PCT/CN2013/082365 CN2013082365W WO2014201767A1 WO 2014201767 A1 WO2014201767 A1 WO 2014201767A1 CN 2013082365 W CN2013082365 W CN 2013082365W WO 2014201767 A1 WO2014201767 A1 WO 2014201767A1
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Prior art keywords
tube
falling film
shaped
bellows
melt
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PCT/CN2013/082365
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English (en)
French (fr)
Inventor
陈文兴
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浙江理工大学
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Priority to DE112013007170.3T priority Critical patent/DE112013007170T5/de
Publication of WO2014201767A1 publication Critical patent/WO2014201767A1/zh

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J10/00—Chemical processes in general for reacting liquid with gaseous media other than in the presence of solid particles, or apparatus specially adapted therefor
    • B01J10/02—Chemical processes in general for reacting liquid with gaseous media other than in the presence of solid particles, or apparatus specially adapted therefor of the thin-film type
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/18—Stationary reactors having moving elements inside
    • B01J19/1887—Stationary reactors having moving elements inside forming a thin film
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/24—Stationary reactors without moving elements inside
    • B01J19/247—Suited for forming thin films
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78—Preparation processes
    • C08G63/785—Preparation processes characterised by the apparatus used
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/20—General preparatory processes
    • C08G64/205—General preparatory processes characterised by the apparatus used
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/04—Preparatory processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00051—Controlling the temperature
    • B01J2219/00074—Controlling the temperature by indirect heating or cooling employing heat exchange fluids
    • B01J2219/00076—Controlling the temperature by indirect heating or cooling employing heat exchange fluids with heat exchange elements inside the reactor
    • B01J2219/00078—Fingers

Definitions

  • the invention relates to a melt polycondensation reaction method, a melt polycondensation reaction device and an out-of-tube falling film element. Background technique
  • the polycondensation reaction is carried out by melt polycondensation, solution polycondensation, solid phase polycondensation, and interfacial polycondensation.
  • melt polycondensation has obvious advantages in terms of product quality, economy, environmental protection and industrial implementation, so most polyesters are used.
  • polyamide, etc. are produced by melt polycondensation, such as polyethylene terephthalate (PET), polytrimethylene terephthalate (PTT), polybutylene terephthalate ( ⁇ ), poly Ethylene naphthalate (yttrium), polyamide, polycarbonate, and the like.
  • PET polyethylene terephthalate
  • PTT polytrimethylene terephthalate
  • ⁇ polybutylene terephthalate
  • yttrium poly Ethylene naphthalate
  • polyamide polycarbonate
  • the key to the implementation of the melt polycondensation process is the reactor.
  • the ideal polycondensation reactor requires good material flow and mixing
  • the first object of the present invention is to provide a melt polycondensation reaction method for the deficiencies of the prior art, which can ensure uniform reaction temperature, increase film formation area, enhance dispersion and mixing of the melt, and finally improve polycondensation efficiency. Rate and product quality.
  • the present invention adopts the following technical solutions:
  • the heat transfer medium is injected from the outside of the polycondensation reactor into the polycondensation reactor, and then flows out from one end of the falling film tube to the other end, and then flows out to the outside of the polycondensation reactor to be cyclically operated by external heating or cooling;
  • the falling film tube is u Type tube, vertical installation;
  • the molten monomer blend or prepolymer is continuously injected into the interior of the polycondensation reactor from the feed port, and after being distributed by the cloth distributor, the film is formed from the upper end of the U-shaped falling film tube along the outer wall by gravity;
  • the melt on each falling film tube was collected at the bottom of the polycondensation reactor, and further stirred with a stirrer, and the material was homogenized, and the melt after completion of the reaction was discharged from the discharge port at the bottom of the reactor.
  • Another object of the present invention is to provide a melt polycondensation reactor using the above method, which can improve the film forming efficiency and enhance the dispersion and mixing of the melt by rationally designing the key structure of the film damper and the falling film element, installing the agitator, Ultimately improve the polycondensation efficiency and product quality.
  • a melt polycondensation reactor comprising a vertical casing, a head connected to the upper end of the vertical casing and a bottom shell at the lower end, and a feed opening at the top of the head, vertical
  • the upper part of the casing is provided with a vacuum suction port, and the bottom of the bottom case is provided with a discharge port
  • the membrane is provided with a membrane device, and one or more outer tube falling film is vertically installed in the reactor.
  • the outer falling film element is a U-shaped falling film tube, and a stirrer is installed under the U-shaped falling film tube;
  • the melt polycondensation reactor is provided with a heat transfer system, and the heat transfer system comprises: an upper tank, a u-shaped falling film tube, and a lower tank body sequentially connecting to form a heat transfer medium flow path, and the heat transfer medium inlet and the outlet are respectively connected thereto
  • the heat transfer system comprises: an upper tank, a u-shaped falling film tube, and a lower tank body sequentially connecting to form a heat transfer medium flow path, and the heat transfer medium inlet and the outlet are respectively connected thereto
  • the box body and the lower box body one end of the U-shaped falling film tube is connected to the upper box body and communicates with the upper box body, and the other end of the U-shaped falling film tube is connected to the bottom plate of the lower box body to communicate with the lower box body.
  • the film splicer is composed of a storage tray and a deflector, the bottom plate of the storage tray is provided with a hole, and the alignment hole of the deflector is installed under the bottom plate of the storage tray, and the hole between the lower end of the deflector and the falling film tube is left. There is the annular gap, and the holes, the deflector and the falling film tube on the bottom plate of the storage tray are kept concentric.
  • the agitator is a ribbon agitator, and the power of the agitator is introduced from the bottom of the bottom case.
  • the U-shaped falling film tube adopts a round tube; or the straight portion of the U-shaped falling film tube adopts a corrugated tube or a bellows; or the upper part of the straight portion of the u-shaped falling film tube is a corrugated tube or a bellows, and the lower part is a round tube.
  • the corrugated tube is composed of an arc segment and a straight pipe segment.
  • the difference between the crest diameter and the straight pipe diameter is longer than the arc segment.
  • the ratio of (Li) is 0.05 ⁇ 1.0; the bellows is selected as a circular bellows or a zoomed bellows or a circular tangential bellows or a sinusoidal bellows, the difference between the peak diameter and the trough diameter and the pitch (L)
  • the ratio is 0.05 1.0.
  • the U-shaped falling film tube has a maximum outer diameter of 5 to 100 mm, and the U-shaped falling film tube has a height of 0.5 to 30 m.
  • the periphery of the vertical casing has a jacket, and the lower part and the upper part of the jacket are respectively provided with a jacket insulation medium inlet and a jacket insulation medium outlet;
  • the bottom shell has a bottom shell jacket, and the lower shell and the upper part of the bottom shell jacket respectively It is provided with a bottom shell insulation medium inlet and a bottom shell insulation medium outlet.
  • the head and the vertical shell are connected by the head connecting flange and the connecting bolt.
  • the vertical shell and the bottom shell are connected by the bottom shell connecting flange and the bottom shell connecting bolt, which is convenient for disassembly, inspection and installation.
  • the inner wall of the vertical housing is provided with a bracket ring for supporting the box body with the falling film tube and the storage tray.
  • a third object of the present invention is to provide an out-of-pipe falling film element which can improve film forming efficiency, precisely control the reaction temperature, and has a simple structure. To this end, the present invention adopts the following technical solutions:
  • the falling film element outside the tube is a U-shaped falling film tube, and the inside of the tube is a heat medium passage; the U-shaped falling film tube adopts a round tube; or the straight portion of the U-shaped falling film tube adopts a corrugated tube or a bellows; or a U-shaped falling film
  • the upper part of the straight portion of the tube is a corrugated tube or a bellows, and the lower part is a round tube;
  • the ratio of the difference between the peak diameter and the diameter of the straight tube to the length of the curved section is 0.05 ⁇ 1.0; the bellows is selected as a circular bellows or a scaled bellows or a circular tangent bellows or a sinusoidal bellows, the peak diameter
  • the ratio of the difference between the diameter of the trough and the pitch (L) is 0.05 to 1.0.
  • the invention can be used for polyethylene terephthalate (PET), polytrimethylene terephthalate (PTT), polybutylene terephthalate ( ⁇ ), polyethylene naphthalate Melt polycondensation reaction of ( ⁇ ), polyamide, polycarbonate, and the like.
  • PET polyethylene terephthalate
  • PTT polytrimethylene terephthalate
  • ⁇ polybutylene terephthalate
  • ⁇ polyethylene naphthalate Melt polycondensation reaction of ( ⁇ ), polyamide, polycarbonate, and the like.
  • the invention adopts a U-shaped tube as an out-of-tube falling film element for melt polycondensation reaction, and has a pass in the U-shaped tube
  • the heat medium circulates and flows.
  • the reactor has a simple structure, a large film forming area, sufficient heat exchange, and a uniform reaction temperature.
  • a stirrer is disposed under the u-type falling film tube, so that the same falling film tube and different drops are formed.
  • the melt between the membrane tubes may be sufficiently mixed and dispersed, and further reacted under stirring to improve the quality stability and uniformity of the melt.
  • the present invention provides different u-type falling film tubes on the basis of a full understanding of the characteristics of the polycondensation reaction process and the rheological properties of the polymer system.
  • Select the round tube as the falling film tube which is good for the flow of high-viscosity melt, avoiding the flow "dead zone", preventing coking and color yellowing;
  • selecting the corrugated tube or bellows as the falling film tube can increase the melt formation Membrane area, control melt flow rate, strengthen melt dispersion and mixing, improve film formation efficiency and surface renewal frequency, and improve polycondensation efficiency;
  • select corrugated tube or combination of bellows and round tube as falling film tube which can adapt to the reaction process The melt viscosity is continuously increased. In the upper section, the corrugated tube or bellows is used to adapt to the lower viscosity melt, and the lower section is used to adapt to the high viscosity melt.
  • the holes, the deflector and the falling film tube on the bottom plate of the storage tray are kept concentric, which facilitates the filming of the melt on the falling film element. Uniform and prevent the melt from forming a plate at the bottom of the stock tray.
  • Fig. 1 is a schematic view showing the structure of a first embodiment of the present invention.
  • Fig. 2 is a schematic view showing the structure of a second embodiment of the present invention.
  • Figure 3 is a schematic view showing the structure of Embodiment 3 provided by the present invention.
  • Figure 4 is a schematic view of the structure of the corrugated tube.
  • Figure 5a is a schematic structural view of a circular arc bellows.
  • Fig. 5b is a schematic structural view of a zoom type bellows.
  • Figure 5c is a schematic view of the structure of a circular arc tangential bellows.
  • Figure 5d is a schematic view of the structure of a sinusoidal bellows.
  • Figure 6 is a schematic view of the structure of the deflector.
  • Embodiment 1 Referring to Figures 1 and 6.
  • the U-shaped falling film tube is a round tube.
  • a molten polycondensation reactor provided in this embodiment, as shown in FIG. 1, comprises: a vertical casing 7, a head 1 connected to the upper end of the vertical casing 7, and a bottom casing 14 at the lower end, the head 1
  • the top is provided with a feed port 26, the upper part of the vertical casing 7 is provided with a vacuum suction port 19, the bottom of the bottom case 14 is provided with a discharge port 13, and the vertical casing 7 has a plurality of vertically mounted U-shaped falling film tubes 17
  • the U-shaped falling film tube 17 is equipped with a stirrer 27;
  • the molten polycondensation reactor has a heat transfer system, comprising: a heat transfer medium inlet or outlet 22, an upper tank 41, a U-shaped falling film tube 17, a lower tank 42, The heat transfer medium outlet or the inlet 21, the upper tank, the U-shaped falling film tube and the lower tank sequentially communicate to form a flow path of the heat transfer medium, that is, the heat transfer medium inlet or outlet 22 communicates with
  • the other end of the U-shaped falling film tube 17 is connected to the lower case bottom plate 5 and communicates with the lower case 42.
  • the lower case 42 and the heat transfer medium The outlet or the inlet 21 is connected; the U-shaped falling film tube 17 is provided with a cloth damper, and the film damper is composed of the storage tray 6 and
  • the flow unit 62 is composed of a storage tray bottom plate 61 having a hole 611, and the deflector 62 alignment hole 611 is installed under the storage tray bottom plate 61, and a space between the lower end wall 621 of the deflector 62 and the falling film tube 17 is left.
  • the annular gap 611, the deflector 62 and the falling film tube 17 on the bottom plate 61 of the storage pan 61 are kept concentric; the three adjacent holes on the bottom plate 61 of the storage pan are evenly arranged in an equilateral triangle.
  • the feed port 26 is outside the head 1 and the feed tube 2 passes through the spacer 25 in the box into the top of the stock tray 6.
  • the periphery of the vertical casing has a jacket 8 , and the lower portion and the upper portion of the jacket 8 are respectively provided with a jacket insulation medium inlet 9 and a jacket insulation medium outlet 18 .
  • the bottom of the bottom case 14 has a bottom case jacket 11.
  • the lower portion and the upper portion of the bottom case jacket 11 are respectively provided with a bottom case warming medium inlet 12 and a bottom case heat insulating medium outlet 15.
  • the head 1 and the vertical housing 7 are connected by a head connecting flange 23 and a head connecting bolt 24.
  • the vertical housing 7 and the bottom shell 14 are connected by a bottom shell connecting flange 10 and a bottom shell connecting bolt 16, which is convenient for disassembly. Overhaul, installation.
  • the inner wall of the vertical casing 7 is provided with a bracket ring 20 for supporting the casing 4 equipped with the falling film tube 17 and the storage tray 6, which is convenient for installation, ensures the verticality of the falling film tube, and improves the uniformity of the film.
  • the agitator 27 is a ribbon agitator and power is introduced from the bottom of the bottom case.
  • the U-shaped falling film tube 17 has an outer diameter of 5 to 100 mm and a height of 0.5 to 30 m.
  • the melt polycondensation reaction method using the above polycondensation reactor is:
  • the heat transfer medium enters from the outside of the polycondensation reactor to the upper tank inside the polycondensation reactor, flows from one end of the U-shaped falling film tube and flows out from the other end, and flows out to the outside of the polycondensation reactor after the lower tank is concentrated, passing through the outside Circulating after heating or cooling;
  • the melt is continuously injected from the upper feed port and transported to the storage tray through the feed pipe.
  • the melt flows out from the annular gap between the wall of the deflector and the falling film tube, and forms a film along the outer wall of the falling film tube by gravity.
  • the straight portion of the U-shaped falling film tube 17 is a bellows or a bellows.
  • the corrugated tube is composed of an arc segment and a straight pipe segment alternately, with a peak diameter D 2 and a straight pipe diameter.
  • the bellows can be selected as an arc-shaped bellows, that is, the longitudinal profile of the bellows is a continuous wave of tangent to the size arc.
  • the bellows can be selected as a scaled bellows, that is, the bellows is alternately composed of an expanded section and a contracted section.
  • the bellows can be selected as a circular tangential bellows, that is, the longitudinal contour of the bellows is a continuous wave of alternating arc and tangent.
  • the bellows can be selected from a sinusoidal bellows, that is, the longitudinal profile of the bellows is a sine wave.
  • the ratio of the difference between the peak diameter D 2 and the trough diameter to the pitch L (D ⁇ D /I ⁇ O.OS l .0; the pitch is the distance between adjacent peaks.
  • the peak diameter of the U-shaped falling film tube 17 is. 2 is 5 ⁇ 100mm, and the height is 0.5 ⁇ 30m.
  • Other parts and implementation methods of this embodiment are the same as those of Embodiment 1, in FIG. 2, reference numerals and figures
  • the upper portion of the straight portion of the U-shaped falling film tube 17 is a bellows tube or a bellows 172, and the lower portion is a round tube 171.
  • the upper portion and the lower portion are coaxial, and the length of the upper portion is determined according to the viscosity of the feed melt. If the viscosity is high, the length is short, and vice versa.
  • the length of the lower section is determined according to the viscosity of the melt of the discharge, and the viscosity is high, the length is long, and vice versa; the structure of the corrugated tube and the bellows is the same as that of the second embodiment.
  • the peak diameter 1) 2 of the U-shaped falling film tube 17 is 5 to 100 mm, and the height is 0.5 to 30 m.
  • the falling film tube has different structural characteristics in the pre- and post-stage of the polycondensation reaction, and the upper section adopts a corrugated tube or a bellows to adapt to the lower viscosity melt.
  • the lower section adopts a round tube to adapt to the high viscosity melt.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Polyesters Or Polycarbonates (AREA)

Abstract

本发明公开一种熔融缩聚反应方法，熔融单体共混物或预聚物沿着 U型管外壁滑落进行缩聚反应，U型管内有传热介质循环流动，各根 U型管上的熔体汇聚到缩聚反应器下部进一步进行搅拌反应和混合均化，反应完毕出料。实施本方法的缩聚反应器，包括立式壳体、上端的封头、下端的底壳、U型管、传热系统、布膜器、螺带搅拌器等。本反应器具有结构简单、热交换充分、成膜面积大、反应温度均匀、缩聚效率高、过程满足平推流等优点，可用于聚对苯二甲酸乙二醇酯、聚对苯二甲酸丙二醇酯、聚对苯二甲酸丁二醇酯、聚萘二甲酸乙二醇酯、聚酰胺、聚碳酸酯等的熔融缩聚反应。

Description

说明书 一种熔融缩聚反应方法及其反应器和降膜管 技术领域
本发明涉及一种熔融縮聚反应方法及熔融縮聚反应设备和管外降膜元件。 背景技术
縮聚反应实施方法有熔融縮聚、溶液縮聚、 固相縮聚以及界面縮聚等， 其中 熔融縮聚不论从产品的质量、经济性、环保性以及工业化实施来看都具有明显的 优势， 因此绝大部分聚酯和聚酰胺等都采用熔融縮聚法生产， 如聚对苯二甲酸乙 二醇酯（PET)、聚对苯二甲酸丙二醇酯（PTT)、聚对苯二甲酸丁二醇酯（ΡΒΤ)、 聚萘二甲酸乙二醇酯 （ΡΕΝ)、 聚酰胺、 聚碳酸酯等。 熔融縮聚过程的实施关键 在于反应器， 理想的縮聚反应器要求物料流动和混合状态好， 传热传质效率高， 过程满足平推流， 以便获得品质均一的聚合产品， 同时实现较高的縮聚效率。
目前， 工业上终縮聚反应器常用卧式搅拌反应器， 主要有圆盘式和笼框式。 这类反应器受熔体网架桥限制， 圆盘或网片必须保持较大距离， 致使单位体积熔 体拥有的表面积有限； 受反应器结构限制， 反应温度不够均匀； 熔池内的熔体停 留时间长且受静压头影响， 对縮聚过程不利； 反应器内部依靠熔池液位差流动， 釜壁处流动状况不佳，存在较多死区；且受大量熔体粘附，搅拌轴产生相当绕度， 进一步增黏的设备改进空间不大。特别是对于制备高黏熔体的场合， 其过多的死 区、夹带、有限的成膜与表面更新以及过长停留时间造成的严重降解限制了这类 反应器的应用。
发明内容
本发明的第一个目的是针对现有技术的不足， 提供一种熔融縮聚反应方法， 能保证反应温度均匀， 提高成膜面积， 强化熔体的分散和混合， 最终提高縮聚效 率和产品品质。 为此， 本发明采用以下技术方案：
传热介质从縮聚反应器外部注入到縮聚反应器内，再从降膜管的一端流入另 一端流出，然后流出到縮聚反应器外部通过外加热或冷却后循环运行； 所述降膜 管为 u型管， 垂直安装；
熔融单体共混物或预聚物从进料口连续注入到縮聚反应器内部，经布膜器分 配后， 从 U型降膜管上端沿着外壁成膜依靠重力下滑；
各根降膜管上的熔体汇聚到縮聚反应器底部， 用搅拌器进一步进行搅拌反 应， 并且均化物料， 完成反应后的熔体从反应器底部出料口排出。
本发明的另一个目的是提供一种运用上述方法的熔融縮聚反应器，通过合理 设计布膜器和降膜元件的关键结构， 安装搅拌器， 提高成膜效率， 强化熔体的分 散和混合， 最终提高縮聚效率和产品品质。 为此， 本发明采用以下技术方案： 一种熔融縮聚反应器，包括立式壳体， 连接于立式壳体上端的封头和下端的 底壳， 封头顶部设有进料口， 立式壳体上部设有真空抽气口， 底壳底部设有出料 口， 其特征在于： 所述反应器内设有布膜器， 所述反应器内还垂直安装有一根或 多根管外降膜元件， 管外降膜元件为 U型降膜管， U型降膜管下方安装有搅拌 器；
所述熔融縮聚反应器设有传热系统， 传热系统包括： 上箱体、 u型降膜管、 下箱体依次连通形成传热介质的流通路径，传热介质进口和出口分别连在上箱体 和下箱体上， U型降膜管的一端连接在上箱体底板上与上箱体相通， U型降膜管 的另一端连接在下箱体底板上与下箱体相通。
所述布膜器由贮料盘和导流器组成，贮料盘底板开有孔， 导流器对准孔安装 在贮料盘底板下方， 导流器下端孔壁与降膜管之间留有所述环形间隙， 贮料盘底 板上的孔、 导流器和降膜管三者保持同轴心。
当贮料盘底板上有三个以上孔时， 相邻的三个孔呈等边三角形均匀排布。 本发明中， 所述搅拌器为螺带搅拌器， 搅拌器的动力从底壳底部传入。 U型降膜管采用圆管； 或者 U型降膜管的笔直部分采用波节管或者波纹管； 或者 u型降膜管的笔直部分的上段为波节管或者波纹管， 下段为圆管。
波节管由弧形段和直管段交替构成， 波峰直径和直管直径之差与弧形段长
(Li)之比为 0.05~1.0； 波纹管选择圆弧型波纹管或者縮放型波纹管或者圆弧切 线型波纹管或者正弦型波纹管， 波峰直径和波谷直径之差与节距 （L) 之比为 0.05 1.0。
U型降膜管的最大外径为 5~100mm， U型降膜管的高为 0.5~30m。
立式壳体的外围有夹套，夹套的下部和上部分别设有夹套保温介质进口和夹 套保温介质出口；底壳的外围有底壳夹套，底壳夹套的下部和上部分别设有底壳 保温介质进口和底壳保温介质出口。
封头与立式壳体由封头连接法兰、连接螺栓连接， 立式壳体与底壳由底壳连 接法兰、 底壳连接螺栓连接， 便于拆卸检修、 安装。
立式壳体内壁设有支架环用于支撑装有降膜管、 贮料盘的箱体。
本发明的第三个目的是提供一种管外降膜元件， 能提高成膜效率， 精确控制 反应温度， 结构简单。 为此， 本发明采用以下技术方案：
管外降膜元件为 U型降膜管， 管内为传热介质通路； U型降膜管采用圆管； 或者 U型降膜管的笔直部分采用波节管或者波纹管； 或者 U型降膜管的笔直部 分的上段为波节管或者波纹管， 下段为圆管；
波峰直径和直管直径之差与弧形段长 （ )之比为 0.05~1.0； 波纹管选择圆 弧型波纹管或者縮放型波纹管或者圆弧切线型波纹管或者正弦型波纹管，波峰直 径和波谷直径之差与节距 （L) 之比为 0.05~1.0。
本发明可以用于聚对苯二甲酸乙二醇酯 （PET)、 聚对苯二甲酸丙二醇酯 (PTT)、聚对苯二甲酸丁二醇酯（ΡΒΤ)、聚萘二甲酸乙二醇酯（ΡΕΝ)、聚酰胺、 聚碳酸酯等的熔融縮聚反应。
本发明采用 U型管作为熔融縮聚反应的管外降膜元件， 并且 U型管内有传 热介质循环流动， 这种反应器具有结构简单、 成膜面积较大、 热交换充分、 反应 温度均匀； 同时， 在 u型降膜管的下方设置了搅拌器， 使得同一降膜管以及不 同降膜管之间有可能存在性质差异的熔体进行充分混合和分散，并在搅拌条件下 进行进一步反应， 提高熔体的质量稳定性和均匀性。
本发明在对縮聚反应过程特性和聚合物系的流变特性充分认识的基础上，提 供了不同的 u型降膜管。 选择圆管作为降膜管， 对于高黏熔体有利于流动， 避 免产生流动 "死区" ， 防止出现结焦和色泽变黄； 选择波节管或者波纹管作为降 膜管， 可增加熔体成膜面积， 控制熔体流速， 强化熔体的分散与混合， 提高成膜 效率和表面更新频率，提高縮聚效率； 选择波节管或者波纹管与圆管组合作为降 膜管， 可以适应反应过程中熔体黏度不断增加的变化， 上段采用波节管或者波纹 管适应较低黏度的熔体， 下段采用圆管适应高黏熔体。
进一步地， 本发明通过在贮料盘下方安装导流器， 贮料盘底板上的孔、 导流 器和降膜管三者保持同轴心， 这样有利于熔体在降膜元件上布膜均匀， 并且防止 熔体在贮料盘底板结板。
附图说明
图 1为本发明所提供的实施例 1的结构示意图。
图 2为本发明所提供的实施例 2的结构示意图。
图 3为本发明所提供的实施例 3的结构示意图。
图 4为波节管的结构示意图。
图 5a为圆弧型波纹管的结构示意图。
图 5b为縮放型波纹管的结构示意图。
图 5c为圆弧切线型波纹管的结构示意图。
图 5d为正弦型波纹管的结构示意图。
图 6为导流器的结构示意图。
图中零部件、 部位及编号： 封头 1、 进料管 2、 上箱体底板 3、 箱体 4、 上箱 体 41、 下箱体 42、 下箱体底板 5、 贮料盘 6、 贮料盘底板 61、 孔 611、 导流器 62、 导流器下端孔壁 621、 立式壳体 7、 夹套 8、 夹套保温介质进口 9、 底壳连接 法兰 10、 底壳夹套 11、 底壳保温介质进口 12、 出料口 13、 底壳 14、 底壳保温 介质出口 15、底壳连接螺栓 16、 U型降膜管 17、 夹套保温介质出口 18、 真空抽 气口 19、 支架环 20、 传热介质出口或进口 21、 传热介质进口或出口 22、 封头连 接法兰 23、 封头连接螺栓 24、 隔套 25、 进料口 26、 螺带搅拌器 27。
具体实施方式
实施例 1， 参照附图 1、 6。
在本实施例中， U型降膜管采用圆管。
本实施例所提供的一种熔融縮聚反应器，如图 1所示， 它包括：立式壳体 7， 连接于立式壳体 7上端的封头 1和下端的底壳 14， 封头 1顶部设有进料口 26， 立式壳体 7上部设有真空抽气口 19， 底壳 14底部设有出料口 13， 立式壳体 7 内有多根垂直安装的 U型降膜管 17， U型降膜管 17下方安装有搅拌器 27; 熔 融縮聚反应器有传热系统， 包括： 传热介质进口或出口 22、 上箱体 41、 U型降 膜管 17、 下箱体 42、 传热介质出口或进口 21， 上箱体、 U型降膜管、 下箱体依 次连通形成传热介质的流通路径， 即传热介质进口或出口 22与上箱体 41相通， U型降膜管 17的一端连接在上箱体底板 3上与上箱体 41相通， U型降膜管 17 的另一端连接在下箱体底板 5上与下箱体 42相通，下箱体 42与传热介质出口或 进口 21相通； U型降膜管 17上设置有布膜器， 布膜器由贮料盘 6和导流器 62 组成， 贮料盘底板 61开有孔 611， 导流器 62对准孔 611安装在贮料盘底板 61 下方， 导流器 62下端孔壁 621与降膜管 17之间留有所述环形间隙； 贮料盘底板 61上的孔 611、 导流器 62和降膜管 17三者保持同轴心； 贮料盘底板 61上相邻 的三个孔呈等边三角形均匀排布。
进料口 26处于封头 1外面， 进料管 2穿过箱体中的隔套 25进入到贮料盘 6 的上方。 立式壳体 Ί的外围有夹套 8， 夹套 8的下部和上部分别设有夹套保温介质进 口 9和夹套保温介质出口 18。
底壳 14的外围有底壳夹套 11， 底壳夹套 11的下部和上部分别设有底壳保 温介质进口 12和底壳保温介质出口 15。
封头 1与立式壳体 7由封头连接法兰 23、 封头连接螺栓 24连接， 立式壳体 7与底壳 14由底壳连接法兰 10、 底壳连接螺栓 16连接， 便于拆卸检修、 安装。
立式壳体 7内壁设有支架环 20用于支撑装有降膜管 17、贮料盘 6的箱体 4， 既方便安装， 又确保降膜管的垂直度， 提高布膜均匀性。
作为优选， 搅拌器 27为螺带搅拌器， 动力从底壳底部传入。
作为优选， U型降膜管 17的外径为 5~100mm， 高度为 0.5~30m。
采用上述縮聚反应器的熔融縮聚反应方法为：
传热介质从縮聚反应器外部进入到处在縮聚反应器内部的上箱体， 再从 U 型降膜管的一端流入并从另一端流出， 在下箱体汇聚后流出到縮聚反应器外部， 通过外加热或冷却后循环运行；
熔体从上部进料口连续注入，通过进料管输送到贮料盘， 熔体从导流器孔壁 与降膜管之间的环形间隙中流出， 沿着降膜管外壁成膜依靠重力下滑；
各根降膜管上的熔体汇聚到縮聚反应器的底部，在底部中采用螺带搅拌器进 一步进行搅拌反应， 并且均化物料， 完成反应后的熔体从底部出料口排出。 实施例 2， 参照附图 2、 4、 5a、 5b、 5c、 5d、 6。
在本实施例中， U型降膜管 17的笔直部分为波节管或波纹管。
如图 4所示， 波节管由弧形段和直管段交替构成， 波峰直径 D2和直管直径
Di之差与圆弧段长 之比 (DrD /LFO.OS l.CL
如图 5a所示， 波纹管可选择圆弧型波纹管， 也即波纹管的纵切轮廓线为大 小圆弧相切的连续波。 如图 5b所示， 波纹管可选择縮放型波纹管， 也即波纹管由扩张段和收縮段 交替构成。
如图 5c所示， 波纹管可选择圆弧切线型波纹管， 也即波纹管的纵切轮廓线 为圆弧和切线交替的连续波。
如图 5d所示， 波纹管可选择正弦型波纹管， 也即波纹管的纵切轮廓线为正 弦波。
波纹管中，波峰直径 D2和波谷直径 之差与节距 L之比 (D^D /I^O.OS l .0; 所述节距为相邻波峰之间的距离。
作为优选， U型降膜管 17的波峰直径。2为 5~100mm， 高度为 0.5~30m。 本实施例的其它部分和实施方法与实施例 1相同，在图 2中， 附图标号和图
1相同的代表相同的含义。 实施例 3， 参照附图 3、 4、 5a、 5b、 5c、 5d、 6。
在本实施例中， U型降膜管 17的笔直部分的上段为波节管或者波纹管 172， 下段为圆管 171， 上段和下段同轴， 上段的长度根据进料熔体的黏度高低决定， 黏度高则长度短， 反之则长， 下段的长度根据出料熔体的黏度高低决定， 黏度高 则长度长， 反之则短； 波节管、 波纹管的结构与实施例 2 的相同。 U型降膜管 17的波峰直径 1)2为 5~100mm， 高度为 0.5~30m。
本实施例的其它部分和实施方法与实施例 1相同，在图 3中， 附图标号和图 1相同的代表相同的含义。
本实施例中，根据縮聚反应进程中熔体的黏度变化特点， 降膜管对应縮聚反 应的前期和后期的部位具有不同的结构特点，上段采用波节管或者波纹管适应较 低黏度的熔体， 下段采用圆管适应高黏熔体。

Claims

权利要求书
1、 一种熔融縮聚反应方法， 其特征在于所述的方法包括： 传热介质从縮聚 反应器外部注入到縮聚反应器内， 再从管外降膜元件的一端流入另一端流出， 然 后流出到縮聚反应器外部通过外加热或冷却后循环运行；所述管外降膜元件为 u 型管， 垂直安装；
熔融单体共混物或预聚物从进料口连续注入到縮聚反应器内部，经布膜器分 配后， 从 U型降膜管上端沿着外壁成膜依靠重力下滑；
各根降膜管上的熔体汇聚到縮聚反应器底部， 用搅拌器进一步进行搅拌反 应， 并且均化物料， 完成反应后的熔体从反应器底部出料口排出。
2、 应用权利要求 1所述方法的熔融縮聚反应器， 包括立式壳体 （7)， 连接 于立式壳体 （7)上端的封头 （1 )和下端的底壳 （14)， 封头 （1 )顶部设有进料 口 （26)， 立式壳体 （7) 上部设有真空抽气口 （19)， 底壳 （14) 底部设有出料 口 （13)， 其特征在于： 所述反应器内设有布膜器， 所述反应器内还垂直安装有 一根或多根管外降膜元件， 管外降膜元件为 U型降膜管（17)， U型降膜管（17) 的笔直部分的上部穿过布膜器并与布膜器之间形成环形间隙， U型降膜管 （17) 下方安装有搅拌器 （27);
熔融縮聚反应器设有传热系统， 传热系统包括： 上箱体 （41 )、 U型降膜管 ( 17 )、 下箱体 （42) 依次连通形成传热介质的流通路径， 传热介质进口和出口 分别连在上箱体 （41 )和下箱体（42) 上， U型降膜管 （17) 的一端连接在上箱 体底板 （3) 上与上箱体 （41 ) 相通， U型降膜管 （17) 的另一端连接在下箱体 底板 （5) 上与下箱体 （42) 相通。
3、 根据权利要求 2所述的熔融縮聚反应器， 其特征在于： 所述布膜器由贮 料盘 （6) 和导流器 （62) 组成， 贮料盘底板 （61 ) 开有孔 （611 )， 导流器 （62) 对准孔 （611 ) 安装在贮料盘底板 （61 ) 下方， 导流器 （62) 下端孔壁 （621 ) 与 降膜管 （17)之间留有所述环形间隙， 贮料盘底板（61 ) 上的孔 （611 )、 导流器 (62) 和降膜管 ( 17) 三者保持同轴心。
4、 如权利要求 2所述的熔融縮聚反应器， 其特征在于： 所述搅拌器 （27) 为螺带搅拌器， 搅拌器 （27) 的动力从底壳底部传入。
5、 根据权利要求 2或 3所述的熔融縮聚反应器， 其特征在于： U型降膜管 ( 17) 采用圆管； 或者 U型降膜管 （17) 的笔直部分采用波节管或者波纹管； 或者 U型降膜管 （17) 的笔直部分的上段为波节管或者波纹管 （172)， 下段为 圆管 （171 )。
6、 根据权利要求 5所述的熔融縮聚反应器， 其特征在于： 波节管由弧形段 和直管段交替构成，波峰直径和直管直径之差与弧形段长（ )之比为 0.05~1.0； 波纹管选择圆弧型波纹管或者縮放型波纹管或者圆弧切线型波纹管或者正弦型 波纹管， 波峰直径和波谷直径之差与节距 （L) 之比为 0.05~1.0。
7、 根据权利要求 1所述的熔融縮聚反应器， 其特征在于： U型降膜管（17) 的最大外径为 5~100mm; U型降膜管 （17) 的高为 0.5~30m。
8、 根据权利要求 2所述的熔融縮聚反应器， 其特征在于： 立式壳体（7) 的 外围有夹套 （8)， 夹套的下部和上部分别设有夹套保温介质进口 （9) 和夹套保 温介质出口 （18);
底壳 （14) 的外围有底壳夹套 （11 )， 底壳夹套的下部和上部分别设有底壳 保温介质进口 （12) 和底壳保温介质出口 （15)。
9、根据权利要求 3所述的熔融縮聚反应器，其特征在于：当贮料盘底板（61 ) 上有三个以上孔时， 相邻的三个孔呈等边三角形均匀排布。
10、用于权利要求 1所述方法的管外降膜元件， 其特征在于： 管外降膜元件 为 U型降膜管 （17)， 管内为传热介质通路； U型降膜管 （17) 采用圆管； 或者 U型降膜管 （17) 的笔直部分采用波节管或者波纹管； 或者 U型降膜管 （17) 的笔直部分的上段为波节管或者波纹管 （172)， 下段为圆管 （171 ); 波节管由弧形段和直管段交替构成， 波峰直径和直管直径之差与弧形段长
(Li)之比为 0.05~1.0； 波纹管选择圆弧型波纹管或者縮放型波纹管或者圆弧切 线型波纹管或者正弦型波纹管， 波峰直径和波谷直径之差与节距 （L) 之比为 0·05~1·0。
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