WO2016033726A1 - 一种聚四氟乙烯中空纤维膜双向拉伸装置及拉伸方法 - Google Patents

一种聚四氟乙烯中空纤维膜双向拉伸装置及拉伸方法 Download PDF

Info

Publication number
WO2016033726A1
WO2016033726A1 PCT/CN2014/085682 CN2014085682W WO2016033726A1 WO 2016033726 A1 WO2016033726 A1 WO 2016033726A1 CN 2014085682 W CN2014085682 W CN 2014085682W WO 2016033726 A1 WO2016033726 A1 WO 2016033726A1
Authority
WO
WIPO (PCT)
Prior art keywords
oven
tube
hollow fiber
fiber membrane
mandrel
Prior art date
Application number
PCT/CN2014/085682
Other languages
English (en)
French (fr)
Inventor
郭玉海
朱海霖
王峰
张华鹏
Original Assignee
浙江理工大学
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 浙江理工大学 filed Critical 浙江理工大学
Priority to US14/785,526 priority Critical patent/US10293537B2/en
Priority to PCT/CN2014/085682 priority patent/WO2016033726A1/zh
Publication of WO2016033726A1 publication Critical patent/WO2016033726A1/zh

Links

Classifications

    • 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
    • B29C48/001—Combinations of extrusion moulding with other shaping operations
    • B29C48/0018—Combinations of extrusion moulding with other shaping operations combined with shaping by orienting, stretching or shrinking, e.g. film blowing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0002—Organic membrane manufacture
    • B01D67/0023—Organic membrane manufacture by inducing porosity into non porous precursor membranes
    • B01D67/0025—Organic membrane manufacture by inducing porosity into non porous precursor membranes by mechanical treatment, e.g. pore-stretching
    • B01D67/0027—Organic membrane manufacture by inducing porosity into non porous precursor membranes by mechanical treatment, e.g. pore-stretching by stretching
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/08—Hollow fibre membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/30—Polyalkenyl halides
    • B01D71/32—Polyalkenyl halides containing fluorine atoms
    • B01D71/36—Polytetrafluoroethene
    • 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
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/05—Filamentary, e.g. strands
    • 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
    • B29C48/92—Measuring, controlling or regulating
    • 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
    • B29C48/94—Lubricating
    • 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
    • B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
    • B29C55/22—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of tubes
    • B29C55/26—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of tubes biaxial
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2323/00—Details relating to membrane preparation
    • B01D2323/08—Specific temperatures applied
    • B01D2323/081—Heating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2323/00—Details relating to membrane preparation
    • B01D2323/42—Details of membrane preparation apparatus
    • 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
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92504—Controlled parameter
    • B29C2948/9258—Velocity
    • 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
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92504—Controlled parameter
    • B29C2948/92704—Temperature
    • 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
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/09—Articles with cross-sections having partially or fully enclosed cavities, e.g. pipes or channels
    • B29C48/10—Articles with cross-sections having partially or fully enclosed cavities, e.g. pipes or channels flexible, e.g. blown foils
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2027/00—Use of polyvinylhalogenides or derivatives thereof as moulding material
    • B29K2027/12—Use of polyvinylhalogenides or derivatives thereof as moulding material containing fluorine
    • B29K2027/18—PTFE, i.e. polytetrafluorethene, e.g. ePTFE, i.e. expanded polytetrafluorethene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2022/00—Hollow articles

Definitions

  • the present invention relates to a hollow fiber membrane stretching apparatus and a stretching method, and in particular to a polytetrafluoroethylene hollow fiber membrane biaxial stretching apparatus and a stretching method.
  • Hollow fiber membranes are widely used in the field of membrane separation such as reverse osmosis, ultrafiltration, microfiltration, membrane contactors and membrane reactors.
  • Common hollow fiber membrane materials include cellulose acetate, polyvinyl chloride, polypropylene, polyethylene, polyacrylonitrile, polysulfone, polyethersulfone, polyvinylidene fluoride and the like.
  • Different applications require different requirements for hollow fiber membranes, including membrane pore size, porosity, mechanical properties, and corrosion resistance.
  • PTFE has excellent properties such as acid and alkali resistance, oxidation resistance, microbial resistance, high temperature resistance, etc.
  • PTFE hollow fiber membranes have high strength. The advantages of large flux have important application value in the fields of special filtration, membrane contactor and membrane reactor.
  • a processing method of the polytetrafluoroethylene hollow fiber membrane is to use a polytetrafluoroethylene resin to perform paste extrusion under the action of a lubricant to obtain a polytetrafluoroethylene tube blank, and to remove the lubricant (degreasing).
  • a polytetrafluoroethylene hollow fiber membrane having micropores in the hollow fiber wall is obtained by stretching and sintering. The stretching step is the key to achieving micropore production, micropore size control and hollow fiber membrane structure control. There are not many reports and patents in this area.
  • the PTFE tube blank is generally extruded by a pusher, and the push mold consists of a cone mold, a die and a core mold (eg, Qian Zhijun, Bao Yongzhong, editor, fluoroplastic processing and application). , Chemical Industry Press, July 2010, Beijing, the first edition of the first printing, pages 152-154), the structure is shown in Figure 1.
  • the push mold consists of a cone mold, a die and a core mold (eg, Qian Zhijun, Bao Yongzhong, editor, fluoroplastic processing and application).
  • the mandrel is generally 1 to 3 mm longer than the lower end of the die.
  • ZL201010185858.1 An expanded polytetrafluoroethylene tube extrusion molding die, which discloses a device for simultaneously extruding a plurality of tube blanks.
  • the patents disclosed at home and abroad include, in U.S. Patent No. 4,250,138, a PTFE hollow fiber drawing device is provided, which adopts a similar seamless metal pipe stretching device, using a round hole die and a mandrel. The way to achieve the stretch of PTFE.
  • U.S. Patent No. 4,496, 051 discloses a slotted hot roll stretching apparatus which is employed in the apparatus.
  • the heating roller performs temperature control, and one hollow fiber is stretched at a time, and problems such as breakage of hollow fibers and collapse of hollow fibers are likely to occur during stretching.
  • Patent ZL201010508798.2 a polytetrafluoroethylene hollow fiber drawing device, discloses a degreasing and stretching device consisting of a guide roll, a stretching roll and a cooling roll.
  • Patent ZL201010504784.3 A method for controlling the pore diameter of a polytetrafluoroethylene hollow fiber membrane, which discloses coating a surface of a polytetrafluoroethylene hollow fiber membrane with a water-dispersible fluorine-containing dispersion concentrate to control the pore diameter.
  • An object of the present invention is to provide a biaxial stretching device for a polytetrafluoroethylene hollow fiber membrane and a stretching method for achieving biaxial stretching (lateral and longitudinal), thereby increasing the porosity of the polytetrafluoroethylene hollow fiber membrane.
  • a biaxial stretching device for a polytetrafluoroethylene hollow fiber membrane 1.
  • the invention comprises a degreasing oven and a tube heating oven which are sequentially installed at the outlet end of the pressing die;
  • the invention comprises a mandrel extension extending linearly from the mandrel in the pressing die, the mandrel extension extending into the degreasing oven and the tube raising oven, and the diameter of the mandrel extension in the tube raising oven is increased for forming a transversely stretched mandrel;
  • the utility model comprises a speed control guide wheel for longitudinal stretching installed at the outlet of the tube blank heating oven, and the speed control guide wheel is located below the bottom of the core mold extension.
  • the tube blank is extruded by a pusher on the extension of the core mold through a degreasing oven for degreasing, heated by a tube blanking oven, and transversely stretched by the expanded mandrel, and the tube blank is detached.
  • the longitudinal extension of the tube blank is performed by adjusting the rotation speed.
  • the expanded mandrel is increased by 10% to 300% compared to the diameter of the mandrel of the pressing die.
  • the tube blank is a polytetrafluoroethylene tube blank.
  • a biaxial stretching method for a polytetrafluoroethylene hollow fiber membrane comprising the following steps:
  • the degreasing temperature of the tube blank in the degreasing oven is 120 to 300 ° C, and the degreasing residence time is 3 seconds to 5 minutes.
  • the heating temperature of the tube blank in the tube billet raising oven is 150 to 360 ° C, and the heating residence time is 3 seconds to 5 minutes.
  • the diameter of the tube blank after the transverse stretching is increased by 10% to 300%.
  • the length of the tube blank after longitudinal stretching is increased by 100% to 300%.
  • the invention can realize the transverse stretching and the longitudinal stretching of the polytetrafluoroethylene tube blank, and overcomes the defects that the conventional processing equipment can only stretch longitudinally. Due to the realization of biaxial stretching, the porosity of the polytetrafluoroethylene hollow fiber membrane can be greatly improved.
  • Fig. 1 is a schematic view showing the structure of a conventional pressing die.
  • Figure 2 is a schematic view of the structure of the present invention.
  • the present invention comprises a core mold extension section, a degreasing oven 5, a tube billet raising oven 6 and a speed control guide wheel 9 in a pressing die of a push press, and the pressing die comprises a cone die 1 and a die die.
  • the degreasing oven 5 and the tube billet raising oven 6 are sequentially installed at the outlet end of the pressing mold, and the degreasing oven 5 and the tube billet raising oven 6 are closely connected to the outlet end of the pressing mold in turn, and the tube blank 4 is pushed.
  • the machine is extruded through a degreasing oven 5 for degreasing, and the tube blank 4 is heated by a tube billet raising oven 6, and the core mold extension in the pressing mold is located in the degreasing oven 5 and the tube billet raising oven 6, and the tube billet heating oven 6 is
  • the diameter of the extension of the mandrel is increased to form an expanded mandrel 7, and the tube blank 4 is transversely stretched by the expanded mandrel 7 to form an expanded tube blank 8.
  • the outlet of the tube raising temperature oven 6 is provided with a speed guiding guide for longitudinal stretching.
  • the wheel 9, the tube blank 4 is wound around the speed-regulating guide wheel 9 to achieve longitudinal stretching of the tube blank 4 by adjusting the rotational speed. As shown in FIG.
  • the tube blank 4 is wound around the 1/4 circumference of the speed control guide wheel 9, and the speed of the speed control guide wheel 9 is greater than the downward speed of the tube blank 4 in the degreasing oven 5 and the tube billet raising oven 6, The blank 4 is longitudinally stretched.
  • the expanded core mold 7 is increased by 10% to 300% in diameter compared to the core mold 3 of the push mold.
  • the tube blank 4 may be a polytetrafluoroethylene tube blank.
  • the method of the invention comprises the following steps:
  • the core mold is extended in a straight line extending from the core mold 3 by the pressing mold. Stretching the section and degreasing from the pressing die into the degreasing oven 5; the preferred degreasing temperature is 120 to 300 ° C, and the degreasing residence time is 3 seconds to 5 minutes.
  • heating from the degreasing oven 5 into the tube billet raising oven 6 is carried out, preferably at a heating temperature of 150 to 360 ° C and a heating residence time of 3 seconds to 5 minutes.
  • the transverse expansion is performed by the expansion core mold 7 in the degreasing oven 5, and the diameter of the tube blank 4 after the transverse stretching can be increased by 10% to 300%, and the expanded core mold 7 is heated by the core in the oven 6 The diameter of the die extension is increased;
  • the tube blank 4 is detached from the expanded mandrel 7 of the tube billet raising oven 6, and then wound around the speed regulating guide 9 at the exit of the tube billet raising oven 6, and longitudinally stretched by adjusting the speed of the speed regulating guide wheel 9,
  • the speed of the speed-regulating guide wheel 9 is greater than the speed of the tube blank 4 descending from the exit of the tube billet raising oven 6, and the length of the tube blank 4 after longitudinal stretching is increased by 100% to 300%, and finally the hollow fiber of the tube blank 4 is completed. Biaxial stretching of the film.
  • the invention prolongs the core mold in the original pressing mold, and the extended section is placed in two ovens.
  • the oven is divided into two parts, a degreasing and heating tube blank, and the oven separately degreases and heats the tube blank.
  • Embodiment 1 is a diagrammatic representation of Embodiment 1:
  • (1) Degreasing and transverse stretching of PTFE tube blank The PTFE tube blank is extruded by a pusher and enters the Teflon hollow fiber membrane biaxial stretching device shown in Figure 1. The first is Degreased oven, degreased in degreasing oven, temperature is 120 ° C, time is 5 minutes, then enter the tube billet heating oven, the temperature is 150 ° C, the time is 5 minutes, the tube blank passes through the expanded core in the tube billet heating oven After the mold is transversely stretched to form an expanded tube blank, the transverse stretch is 10%, that is, the expanded core mold 7 is increased by 10% compared with the diameter of the core mold 3 of the push mold;
  • biaxially stretched polytetrafluoroethylene hollow fiber membrane the expanded tubular blank is longitudinally stretched by 100% through a speed regulating guide wheel under the biaxial stretching device to form a biaxially stretched polytetrafluoroethylene hollow fiber membrane,
  • the porosity is 55%.
  • Embodiment 2 is a diagrammatic representation of Embodiment 1:
  • Degreasing and heating of PTFE tube blank The PTFE tube blank is extruded by a pusher and enters the Teflon hollow fiber membrane biaxial stretching device shown in Figure 1. The first is the degreasing oven. , degrease in a degreasing oven, the temperature is 300 ° C, the time is 3 seconds, then enter the tube billet heating oven, the temperature is 360 ° C, the time is 3 seconds, in the tube billet heating oven after the tube blank is expanded by the mandrel It is laterally expanded to form an expanded tube blank, and the transverse stretching is 300%, that is, the expanded core mold 7 is increased by 300% compared with the diameter of the core mold 3 of the pressing mold; (2) the biaxially stretched polytetrafluoroethylene hollow fiber membrane : The expanded tube blank is longitudinally stretched by 300% through the speed-regulating guide wheel under the biaxial stretching device to form a biaxially stretched PTFE hollow fiber membrane with a porosity of 90%.
  • Embodiment 3 (1) Degreasing and heating of PTFE tube blank: The PTFE tube blank is extruded by a pusher and enters the Teflon hollow fiber membrane biaxial stretching device shown in Figure 1. The first is the degreasing oven. Degrease in a degreasing oven at a temperature of 200 ° C for 1 minute, then enter the tube blanking oven at a temperature of 220 V for 1 minute. After the tube blank is passed through the expanded mandrel, the tube blank is The lateral expansion forms an expanded tube blank, and the transverse stretching is 150%, that is, the expansion of the core mold 7 is increased by 150% compared with the diameter of the core mold 3 of the pressing mold;
  • Biaxially stretched PTFE hollow fiber membrane The expanded tubular blank is longitudinally stretched by 200% through a speed regulating guide wheel under the biaxial stretching device to form a biaxially oriented PTFE hollow fiber membrane, porosity It is 82%.

Landscapes

  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Manufacturing & Machinery (AREA)
  • Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)

Abstract

提供一种聚四氟乙烯中空纤维膜双向拉伸装置及拉伸方法。该装置包括由芯模延伸出的芯模延伸段，该芯模延伸段延伸到脱脂烘箱和管坯升温烘箱中，在管坯升温烘箱内的芯模延伸段的直径增大形成胀大芯模。该装置和方法可以实现聚四氟乙烯管坯的双向拉伸，提高聚四氟乙烯中空纤维膜的孔隙率。

Description

一种聚四氟乙烯中空纤维膜双向拉伸装置及拉伸方法 技术领域
本发明涉及一种中空纤维膜拉伸装置及拉伸方法， 具体地涉及一种聚四氟 乙烯中空纤维膜双向拉伸装置及拉伸方法。
背景技术
中空纤维膜在反渗透、 超滤、 微滤、 膜接触器和膜反应器等膜分离领域中 大量采用。 常见的中空纤维膜材料包括醋酸纤维素、 聚氯乙烯、 聚丙烯、 聚乙 烯、 聚丙烯腈、 聚砜、 聚醚砜、 聚偏氟乙烯等。 不同的应用场合对中空纤维膜 提出了不同的使用要求， 包括膜孔径、 孔隙率、 力学性能、 耐腐蚀性等方面的 要求。 聚四氟乙烯具有极强的耐酸碱、 耐氧化、 耐微生物侵蚀、 耐高低温等优 良特性， 聚四氟乙烯中空纤维膜除了具有聚四氟乙烯本身的优良特性外， 还具 有强度高、 通量大的优点， 在特种过滤、 膜接触器、 膜反应器等领域中具有重 要的应用价值。
聚四氟乙烯中空纤维膜的一种加工方法是， 采用聚四氟乙烯树脂， 在润滑 剂作用下， 进行糊料挤出， 得到聚四氟乙烯管坯， 脱除润滑剂 （脱脂） 后再通 过拉伸和烧结， 得到中空纤维壁上具有微孔的聚四氟乙烯中空纤维膜。 拉伸步 骤是实现微孔产生、 微孔尺寸控制和中空纤维膜结构控制的关键环节， 此方面 的报道和专利不多。
对于挤出环节， 聚四氟乙烯管坯一般是采用推压机挤出， 推压模具由锥体 模、 口模和芯模组成 （如， 钱知勉， 包永忠主编， 氟塑料加工与应用， 化学工 业出版社， 2010年 7月北京第一版第一次印刷， 第 152-154页） ， 结构示意图 见图 1。
在实际使用过程中， 芯模一般比口模下端长 1〜3毫米。
以上装置一个推压模具挤出一根管坯。 ZL201010185858.1 —种膨体聚四氟 乙烯管挤出成型模具， 公开了同时挤出多根管坯的装置。
对于拉伸环节， 国内外公开的专利包括， 美国专利 US4250138中给出了一 种聚四氟乙烯中空纤维拉伸装置， 该装置采用类似无缝金属管拉伸装置， 采用 圆孔模具和芯棒的方式， 实现聚四氟乙烯的拉伸。
美国专利 US4496507中给出了一种采用开槽热辊拉伸装置， 该装置中采用 加热辊筒进行温度控制， 一次拉伸一根中空纤维， 拉伸过程中易出现中空纤维 破裂、 中空纤维塌陷等问题。
专利 ZL201010508798.2—种聚四氟乙烯中空纤维拉伸装置， 公开了一种由 导辊、 拉伸辊和冷却辊组成的脱脂和拉伸装置。 专利 ZL201010504784.3—种聚 四氟乙烯中空纤维膜的孔径控制方法， 公开了一种采用水分散型含氟分散浓缩 液涂覆聚四氟乙烯中空纤维膜表面以控制孔径。
综合以上， 在拉伸过程中不论是采用何种拉伸装置和手段， 均是纵向拉 伸， 即沿着管坯长度方向上拉伸。
发明内容
本发明的目的是提供一种聚四氟乙烯中空纤维膜双向拉伸装置及拉伸方 法， 实现双向拉伸 （横向和纵向） ， 从而提高了聚四氟乙烯中空纤维膜的孔隙 率。
本发明采用的技术方案是：
一、 一种聚四氟乙烯中空纤维膜双向拉伸装置：
包括依次安装在推压模具出口端的脱脂烘箱和管坯升温烘箱；
包括由推压模具中芯模直线延伸出的芯模延伸段， 芯模延伸段延伸到脱脂 烘箱和管坯升温烘箱中， 在管坯升温烘箱内的芯模延伸段的直径增大形成用于 横向拉伸的胀大芯模；
包括安装在管坯升温烘箱出口处的用于纵向拉伸的调速导轮， 调速导轮位 于芯模延伸段底部下方。
所述的管坯采用推压机挤出套在芯模延伸段上经过脱脂烘箱进行脱脂， 再 经过管坯升温烘箱进行加热， 并通过所述胀大芯模进行横向拉伸， 管坯脱离胀 大芯模后绕到调速导轮上通过调整转速进行管坯的纵向拉伸。
所述的胀大芯模相比推压模具的芯模的直径增大 10%〜300%。
所述的管坯为聚四氟乙烯管坯。
二、 一种聚四氟乙烯中空纤维膜双向拉伸方法， 包括以下步骤：
1 )管坯从推压机挤出后， 套在由推压模具中芯模直线延伸出的芯模延伸段 上， 并从推压模具进入脱脂烘箱进行脱脂；
2 )脱脂后， 从脱脂烘箱进入管坯升温烘箱进行加热， 并通过脱脂烘箱内的 胀大芯模进行横向拉伸， 胀大芯模由通过管坯升温烘箱内的芯模延伸段直径增 大形成；
3 )管坯从管坯升温烘箱的胀大芯模脱离， 然后绕到管坯升温烘箱出口处的 调速导轮上， 通过调整调速导轮转速进行纵向拉伸， 最终完成对管坯中空纤维 膜的双向拉伸。
所述的步骤 2 ) 中管坯在脱脂烘箱的脱脂温度为 120〜300°C， 脱脂停留时 间为 3秒〜 5分钟。
所述的步骤 2 ) 中管坯在管坯升温烘箱中的加热温度为 150〜360°C， 加热 停留时间为 3秒〜 5分钟。
所述的横向拉伸后的管坯直径增大 10%〜300%。
所述的纵向拉伸后的管坯长度增加 100%〜300%。
与现有技术相比， 本发明的有益效果是：
本发明可实现聚四氟乙烯管坯的横向拉伸和纵向拉伸， 克服了传统加工设 备仅能纵向拉伸的缺陷。 由于双向拉伸的实现， 可极大地提高聚四氟乙烯中空 纤维膜的孔隙率。
附图说明
图 1是现有推压模具的结构示意图。
图 2是本发明的结构示意图。
图中： 1、 锥体模， 2、 口模， 3、 芯模， 4、 管坯， 5、 脱脂烘箱， 6、 管坯 升温烘箱， 7、 胀大芯模， 8、 胀大管坯， 9、 调速导轮。
具体实施方式
下面结合附图和实施例对本发明作进一步说明。
如图 2所示， 本发明包括推压机的推压模具中芯模延伸段、 脱脂烘箱 5、 管 坯升温烘箱 6和调速导轮 9， 其推压模具包括锥体模 1、 口模 2或者芯模 3， 脱 脂烘箱 5和管坯升温烘箱 6依次安装在推压模具出口端， 脱脂烘箱 5和管坯升 温烘箱 6依次紧密连接在推压模具出口端上， 管坯 4采用推压机挤出经过脱脂 烘箱 5进行脱脂， 管坯 4经过管坯升温烘箱 6进行加热， 推压模具中的芯模延 伸段位于到脱脂烘箱 5和管坯升温烘箱 6内， 管坯升温烘箱 6内芯模延伸段直 径增大形成胀大芯模 7， 管坯 4经过胀大芯模 7横向拉伸形成胀大管坯 8， 管坯 升温烘箱 6出口处设有用于纵向拉伸的调速导轮 9， 管坯 4绕到调速导轮 9上通 过调整转速实现管坯 4的纵向拉伸。 如图 2所示， 管坯 4绕到调速导轮 9的 1/4 圆周上， 调速导轮 9的转速大于脱脂烘箱 5和管坯升温烘箱 6中管坯 4下行速 度时， 对管坯 4进行纵向拉伸。
胀大芯模 7相比推压模具的芯模 3的直径增大 10%〜300%。
管坯 4可采用聚四氟乙烯管坯。
本发明方法包括以下步骤：
1 )管坯 4从推压机挤出后， 套在由推压模具中芯模 3直线延伸出的芯模延 伸段上， 并从推压模具进入脱脂烘箱 5 进行脱脂； 优选的脱脂温度为 120〜 300°C， 脱脂停留时间为 3秒〜 5分钟。
2 )脱脂后， 从脱脂烘箱 5进入管坯升温烘箱 6进行加热， 优选的加热温度 为 150〜360°C， 加热停留时间为 3秒〜 5分钟。 并通过脱脂烘箱 5内的胀大芯 模 7进行横向拉伸， 横向拉伸后的管坯 4直径可增大 10%〜300%， 胀大芯模 7 由通过管坯升温烘箱 6内的芯模延伸段直径增大形成；
3 ) 管坯 4从管坯升温烘箱 6的胀大芯模 7脱离， 然后绕到管坯升温烘箱 6 出口处的调速导轮 9上， 通过调整调速导轮 9转速进行纵向拉伸， 调速导轮 9 转速大于管坯 4从管坯升温烘箱 6出口处下行的速度进而实现拉伸， 纵向拉伸 后的管坯 4长度增加 100%〜300%， 最终完成对管坯 4中空纤维膜的双向拉伸。
本发明将原有推压模具中的芯模延长， 延长段置于两个烘箱内， 烘箱分为 脱脂和升温管坯两部分， 烘箱分别进行脱脂和加热管坯。
本发明的实施例如下：
实施例一：
( 1 ) 聚四氟乙烯管坯的脱脂和横向拉伸： 聚四氟乙烯管坯采用推压机挤 出， 进入附图 1 所示的聚四氟乙烯中空纤维膜双向拉伸装置， 首先是脱脂烘 箱， 在脱脂烘箱中脱脂， 温度为 120°C， 时间为 5 分钟， 之后进入管坯升温烘 箱， 温度为 150°C， 时间为 5分钟， 在管坯升温烘箱中管坯经过胀大芯模后被横 向拉伸形成胀大管坯， 横向拉伸 10%， 即胀大芯模 7相比推压模具的芯模 3的 直径增大 10%;
(2 )双向拉伸聚四氟乙烯中空纤维膜： 所述胀大管坯经过双向拉伸装置下 方的调速导轮实现纵向拉伸 100%， 形成双向拉伸聚四氟乙烯中空纤维膜， 孔 隙率为 55%。
实施例二：
( 1 ) 聚四氟乙烯管坯的脱脂和升温： 聚四氟乙烯管坯采用推压机挤出， 进 入附图 1 所示的聚四氟乙烯中空纤维膜双向拉伸装置， 首先是脱脂烘箱， 在脱 脂烘箱中脱脂， 温度为 300°C， 时间为 3 秒， 之后进入管坯升温烘箱， 温度为 360°C， 时间为 3秒， 在管坯升温烘箱中管坯经过胀大芯模后被横向扩张形成胀 大管坯， 横向拉伸 300%， 即胀大芯模 7 相比推压模具的芯模 3 的直径增大 300%； (2 )双向拉伸聚四氟乙烯中空纤维膜： 胀大管坯经过双向拉伸装置下方 的调速导轮实现纵向拉伸 300%， 形成双向拉伸聚四氟乙烯中空纤维膜， 孔隙 率为 90%。
实施例三： ( 1 ) 聚四氟乙烯管坯的脱脂和升温： 聚四氟乙烯管坯采用推压机挤出， 进 入附图 1 所示的聚四氟乙烯中空纤维膜双向拉伸装置， 首先是脱脂烘箱， 在脱 脂烘箱中脱脂， 温度为 200 °C， 时间为 1分钟， 之后进入管坯升温烘箱， 温度为 220 V , 时间为 1分钟， 在管坯升温烘箱中管坯经过胀大芯模后被横向扩张形成 胀大管坯， 横向拉伸 150%， 即胀大芯模 7相比推压模具的芯模 3 的直径增大 150%；
( 2 )双向拉伸聚四氟乙烯中空纤维膜： 胀大管坯经过双向拉伸装置下方的 调速导轮实现纵向拉伸 200%， 形成双向拉伸聚四氟乙烯中空纤维膜， 孔隙率 为 82%。
上述具体实施例用来解释说明本发明， 而不是对本发明进行限制， 在本发 明的精神和权利要求的保护范围内， 对本发明作出的任何修改和改变， 都落入 本发明的保护范围。

Claims

权 利 要 求 书
1. 一种聚四氟乙烯中空纤维膜双向拉伸装置， 其特征在于：
包括依次安装在推压模具出口端的脱脂烘箱 （5) 和管坯升温烘箱 （6) ； 包括由推压模具中芯模 （3)直线延伸出的芯模延伸段， 芯模延伸段延伸到 脱脂烘箱 （5) 和管坯升温烘箱 （6) 中， 在管坯升温烘箱 （6) 内的芯模延伸段 的直径增大形成用于横向拉伸的胀大芯模 （7) ；
包括安装在管坯升温烘箱 （6) 出口处的用于纵向拉伸的调速导轮 （9) ， 调速导轮 （9) 位于芯模延伸段底部下方。
2. 根据权利要求 1所述的一种聚四氟乙烯中空纤维膜双向拉伸装置， 其特 征在于： 所述的管坯 （4)采用推压机挤出套在芯模延伸段上经过脱脂烘箱 （5) 进行脱脂， 再经过管坯升温烘箱 （6) 进行加热， 并通过所述胀大芯模 （7) 进 行横向拉伸， 管坯 （4) 脱离胀大芯模 （7) 后绕到调速导轮 （9) 上通过调整转 速进行管坯 （4) 的纵向拉伸。
3. 根据权利要求 1所述的一种聚四氟乙烯中空纤维膜双向拉伸装置， 其特 征在于： 所述的胀大芯模 (7)相比推压模具的芯模 (3)的直径增大 10%〜300%。
4. 根据权利要求 1所述的一种聚四氟乙烯中空纤维膜双向拉伸装置， 其特 征在于： 所述的管坯 （4) 为聚四氟乙烯管坯。
5. 应用于权利要求 1〜4 任一所述装置的一种聚四氟乙烯中空纤维膜双向 拉伸方法， 其特征在于包括以下步骤：
1) 管坯 （4) 从推压机挤出后， 套在由推压模具中芯模 （3) 直线延伸出的 芯模延伸段上， 并从推压模具进入脱脂烘箱 （5) 进行脱脂；
2) 脱脂后， 从脱脂烘箱 （5) 进入管坯升温烘箱 （6)进行加热， 并通过脱 脂烘箱 （5) 内的胀大芯模 （7) 进行横向拉伸， 胀大芯模 （7) 由通过管坯升温 烘箱 （6) 内的芯模延伸段直径增大形成；
3) 管坯 （4) 从管坯升温烘箱 （6) 的胀大芯模 （7) 脱离， 然后绕到管坯 升温烘箱 （6) 出口处的调速导轮 （9) 上， 通过调整调速导轮 （9) 转速进行纵 向拉伸， 最终完成对管坯 （4) 中空纤维膜的双向拉伸。
6. 根据权利要求 5所述的一种聚四氟乙烯中空纤维膜双向拉伸方法， 其特 征在于： 所述的步骤 2)中管坯（4)在脱脂烘箱（5)的脱脂温度为 120〜300°C， 脱脂停留时间为 3秒〜 5分钟。
7. 根据权利要求 5所述的一种聚四氟乙烯中空纤维膜双向拉伸方法， 其特 征在于： 所述的步骤 2) 中管坯 （4) 在管坯升温烘箱中的加热温度为 150〜 360°C， 加热停留时间为 3秒〜 5分钟。
8. 根据权利要求 5所述的一种聚四氟乙烯中空纤维膜双向拉伸方法， 其特 征在于： 所述的横向拉伸后的管坯 （4 ) 直径增大 10%〜300%。
9. 根据权利要求 5所述的一种聚四氟乙烯中空纤维膜双向拉伸方法， 其特 征在于： 所述的纵向拉伸后的管坯 （4 ) 长度增加 100%〜300%。
PCT/CN2014/085682 2014-09-01 2014-09-01 一种聚四氟乙烯中空纤维膜双向拉伸装置及拉伸方法 WO2016033726A1 (zh)

Priority Applications (2)

Application Number Priority Date Filing Date Title
US14/785,526 US10293537B2 (en) 2014-09-01 2014-09-01 Device for biaxially-oriented stretching polytetrafluoroethylene hollow fiber membranes and method thereof
PCT/CN2014/085682 WO2016033726A1 (zh) 2014-09-01 2014-09-01 一种聚四氟乙烯中空纤维膜双向拉伸装置及拉伸方法

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/CN2014/085682 WO2016033726A1 (zh) 2014-09-01 2014-09-01 一种聚四氟乙烯中空纤维膜双向拉伸装置及拉伸方法

Publications (1)

Publication Number Publication Date
WO2016033726A1 true WO2016033726A1 (zh) 2016-03-10

Family

ID=55438976

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2014/085682 WO2016033726A1 (zh) 2014-09-01 2014-09-01 一种聚四氟乙烯中空纤维膜双向拉伸装置及拉伸方法

Country Status (2)

Country Link
US (1) US10293537B2 (zh)
WO (1) WO2016033726A1 (zh)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109603581A (zh) * 2018-12-28 2019-04-12 长园电子（东莞）有限公司 一种聚四氟乙烯中空纤维膜双向拉伸模具

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5490931A (en) * 1992-02-24 1996-02-13 Hoechst Celanese Corp. Fabrication of a fluoropolymer hollow fiber having a defect-free separation layer
CN102642304A (zh) * 2012-05-14 2012-08-22 贵州普利英吉科技有限公司 反渗透膜用浓水网的双向拉伸定型方法及装置
CN103100310A (zh) * 2013-01-29 2013-05-15 浙江理工大学 一种膜吸收用聚四氟乙烯中空纤维膜的制备方法
JP2014136183A (ja) * 2013-01-16 2014-07-28 Sekisui Chem Co Ltd 中空糸膜の製造方法
CN104190268A (zh) * 2014-09-01 2014-12-10 浙江理工大学 一种聚四氟乙烯中空纤维膜双向拉伸装置及拉伸方法

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4826725A (en) * 1982-08-23 1989-05-02 Carlisle Corporation Manufacture of low density, sintered polytetrafluorethylene articles
DE4003696C1 (zh) * 1990-02-07 1990-12-13 Petzetakis, George Aristovoulos, Piraeus, Gr
NL9400453A (nl) * 1994-03-22 1995-11-01 Wavin Bv Werkwijze en inrichting voor het vervaardigen van biaxiaal georiënteerde buis uit thermoplastisch kunststofmateriaal.
NL9400452A (nl) * 1994-03-22 1995-11-01 Wavin Bv Werkwijze en inrichting voor het vervaardigen van biaxiaal georiënteerde buis uit thermoplastisch kunststofmateriaal.
NL9400451A (nl) * 1994-03-22 1995-11-01 Wavin Bv Werkwijze en inrichting voor het vervaardigen van biaxiaal georiënteerde buis uit thermoplastisch kunststofmateriaal.
BR9610557A (pt) * 1995-09-20 1999-12-21 Uponor Bv Produtos poliméricos orientados
US5800512A (en) * 1996-01-22 1998-09-01 Meadox Medicals, Inc. PTFE vascular graft
NL1012032C2 (nl) * 1999-03-05 2000-09-06 Wavin Bv Werkwijze voor het vervaardigen van een buis van biaxiaal georiënteerd thermoplastisch kunststofmateriaal.
FR2806956B1 (fr) * 2000-03-29 2003-05-09 Alphacan Sa Procede et ligne de fabrication en continu de tubes en matiere plastique avec etirage bi-axial, et tube en matiere plastique obtenu
US8609249B2 (en) * 2011-02-09 2013-12-17 Phillips Scientific Inc. Thin wall expandable polymer tubes having improved axial and radial strength, and a method of manufacturing thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5490931A (en) * 1992-02-24 1996-02-13 Hoechst Celanese Corp. Fabrication of a fluoropolymer hollow fiber having a defect-free separation layer
CN102642304A (zh) * 2012-05-14 2012-08-22 贵州普利英吉科技有限公司 反渗透膜用浓水网的双向拉伸定型方法及装置
JP2014136183A (ja) * 2013-01-16 2014-07-28 Sekisui Chem Co Ltd 中空糸膜の製造方法
CN103100310A (zh) * 2013-01-29 2013-05-15 浙江理工大学 一种膜吸收用聚四氟乙烯中空纤维膜的制备方法
CN104190268A (zh) * 2014-09-01 2014-12-10 浙江理工大学 一种聚四氟乙烯中空纤维膜双向拉伸装置及拉伸方法

Also Published As

Publication number Publication date
US10293537B2 (en) 2019-05-21
US20160257049A1 (en) 2016-09-08

Similar Documents

Publication Publication Date Title
CN103386256B (zh) 微孔型聚四氟乙烯杂化平板膜包缠法制备中空纤维膜和管式膜的方法
CN101961609B (zh) 一种聚四氟乙烯中空纤维拉伸装置
CN107441962B (zh) 一种超疏水聚四氟乙烯膜的制备方法
CN104190268B (zh) 一种聚四氟乙烯中空纤维膜双向拉伸装置及拉伸方法
CN103055721B (zh) 高通量高强度聚四氟乙烯中空纤维膜的制备方法
CN104415672A (zh) 一种高过滤精度聚四氟乙烯微孔膜的制备方法
CN111231383B (zh) 一种医用薄壁管连续成型设备及聚乳酸薄壁管成型方法
CN107596925A (zh) 聚4‑甲基‑1‑戊烯径向异质中空纤维膜及其制备方法
CN103949165A (zh) 一种聚四氟乙烯非均相中空纤维膜的制备方法
WO2016033726A1 (zh) 一种聚四氟乙烯中空纤维膜双向拉伸装置及拉伸方法
CN110975638A (zh) 一种聚四氟乙烯中空纤维膜双向拉伸设备及应用其制备聚四氟乙烯中空纤维膜的方法
CN109550409B (zh) 一种聚四氟乙烯中空纤维膜及其无极拉伸制备方法
CN101612530B (zh) 基于LabView控制的双组份中空纤维复合膜熔纺及拉伸设备
KR20140073331A (ko) 다공성 ｐｔｆｅ 분리막 및 그 제조방법
JPH0218977B2 (zh)
JPS595037A (ja) 多孔質四弗化エチレン樹脂成型物の製造方法
KR102050859B1 (ko) 제트 패킹 몰딩 중합체 파이프라인을 위한 방법 및 장치
CN104415673A (zh) 一种包缠聚四氟乙烯杂化中空纤维膜及管式膜的制备方法
JP2017112081A5 (zh)
CN102825805B (zh) 聚丙烯微孔膜制备方法
CN111016235B (zh) 一种多孔ptfe拉伸管及其制造工艺与应用
CN107837691B (zh) 一种超疏水聚四氟乙烯膜的制备方法
CN101733927A (zh) 用芯棒式管膜双向拉伸装置生产收缩薄膜的方法及设备
CN104529151B (zh) 一种光纤预制棒的制备方法及制备设备
CN109603581A (zh) 一种聚四氟乙烯中空纤维膜双向拉伸模具

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 14785526

Country of ref document: US

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 14901132

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 14901132

Country of ref document: EP

Kind code of ref document: A1