TWI652105B - 具有可相容強化物之中空絲膜 - Google Patents

具有可相容強化物之中空絲膜 Download PDF

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TWI652105B
TWI652105B TW101145316A TW101145316A TWI652105B TW I652105 B TWI652105 B TW I652105B TW 101145316 A TW101145316 A TW 101145316A TW 101145316 A TW101145316 A TW 101145316A TW I652105 B TWI652105 B TW I652105B
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史帝文 克里斯頓 沛德森
佩瑞 路西恩 柯提
白珍華
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美商Ｂｌ科技有限公司
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    • 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
    • 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
    • B01D69/082—Hollow fibre membranes characterised by the cross-sectional shape of the fibre
    • 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
    • B01D69/085—Details relating to the spinneret
    • 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
    • B01D69/087—Details relating to the spinning process
    • 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
    • B01D71/34—Polyvinylidene fluoride
    • 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
    • B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
    • 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
    • B29C48/03—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
    • B29C48/07—Flat, e.g. panels
    • B29C48/08—Flat, e.g. panels flexible, e.g. films
    • 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
    • B29C48/11—Articles with cross-sections having partially or fully enclosed cavities, e.g. pipes or channels comprising two or more partially or fully enclosed cavities, e.g. honeycomb-shaped
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/24—Formation of filaments, threads, or the like with a hollow structure; Spinnerette packs therefor
    • 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
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/40—Fibre reinforced membranes
    • 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
    • B29C48/88—Thermal treatment of the stream of extruded material, e.g. cooling
    • B29C48/919—Thermal treatment of the stream of extruded material, e.g. cooling using a bath, e.g. extruding into an open bath to coagulate or cool the material

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  • Separation Using Semi-Permeable Membranes (AREA)
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Abstract

一種製造一加強型中空絲膜之方法包含：使一膜原液流動通過一澆製頭同時牽引一或多個細絲紗線或細絲絲束通過該澆製頭。該等細絲在該澆製頭中散開，例如藉由迫使該等紗線或絲束繞過該澆製頭中之一彎頭或通過該澆製頭中之一狹窄間隙。該等細絲經調適以黏結至該膜原液或該膜壁。一種加強型中空絲膜包含個別地由該膜壁環繞且黏結至該膜壁之複數個細絲。

Description

具有可相容強化物之中空絲膜
本發明之領域為中空絲膜，例如用於藉由微濾或超濾提供水處理之中空絲膜。
中空絲膜可藉由不同方法由各種聚合物製造而成。一種方法包含如(例如)美國專利3,615,024、5,066,401及6,024,872中教示之非溶劑誘發之相分離(NIPS)。另一種方法包含如(例如)美國專利4,702,836及7,247,238中教示之熱誘發之相分離(TIPS)。膜在其內部表面或其外部表面上可具有分離層，且可用於(例如)微濾(MF)或超濾(UF)。
可藉由塗覆膜原液於預形成之管狀編織層上來增加中空絲膜之強度。Mahendran等人之美國專利5,472,607及6,354,444教示將膜塗覆於具有有限滲透之編織層的外部。Hayano等人之美國專利4,061,861、Lee等人之美國專利7,267,872及Shinada等人之美國專利7,306,105亦教示編織層支撐之膜。根據Mahendran等人之教示製造之中空絲膜已成功商業化。
已被建議用於製造加強型中空絲膜之另一途徑包含在澆鑄中空纖維的同時將纖維嵌入至中空纖維之壁中。Murase等人之美國專利申請公開案2002/0046970、Yoon等人之國際專利申請公開案WO 03/097221及Koenhen之美國專利6,454,943描述將單絲或多絲紗線縱向地嵌入至中空纖維之壁中之方法。該等方法均未生產出市售之膜。
本申請案發明者之新近國際專利申請公開案WO 2010/108285及WO 2010/148517教示在澆鑄中空纖維的同時在中空纖維之壁中形成籠狀加強結構。可藉由(例如)加熱、UV光或溶劑黏結經由經調適以用於該黏結方法之細絲之組分來將加強結構之細絲在接觸點處黏結在一起。
以下介紹旨在為讀者介紹以下詳細描述而非限制或界定申請專利範圍。
在用藉由縱向紗線加強之中空絲膜進行之實驗中，發明者觀測到其中紗線突破膜壁的破損模式。紗線最初包覆於膜壁中，但隨著膜在空氣吹拂期間搖動，紗線看來似乎戳穿膜壁。國際專利申請公開案WO 2010/108285及WO 2010/148517中描述之籠狀結構藉由增加螺旋形包裹之細絲或其他傾斜細絲而避免此問題。本說明書將描述替代性加強型膜及其製造方法。
本說明書中描述之中空絲膜係藉由嵌入於流動通過澆製頭之膜原液中之一或多個多絲紗線或絲束而加強。細絲至少部分地由經調適以黏結至膜原液或固化的膜壁之聚合物製造。舉例而言，聚合物可溶於膜原液中、可熔融於膜原液中、或其表面可經處理以促進黏結。例如藉由迫使細絲繞過澆製頭中之彎頭或通過澆製頭中之狹窄間隙而使紗線或絲束之細絲散開。原液能滲透紗線或絲束，從而環繞並黏結至個別的細絲。因為實質上所有個別細絲皆黏附於膜壁，故細絲在膜壁中不可移動且在正常使用期間不會戳穿 膜。
一種製造加強型中空絲膜之方法包含：使膜原液流動通過澆製頭同時牽引一或多個細絲紗線或細絲絲束通過澆製頭。可迫使紗線或絲束繞過澆製頭中之彎頭或通過澆製頭中之狹窄間隙。細絲經調適以與膜原液或固化的膜壁黏結。
一種加強型中空絲膜包含一或多個紗線或絲束，其每一者包含個別地由該膜壁環繞且黏結至該膜壁之複數個細絲。
參看圖1，中空絲膜10具有膜壁16。膜10可具有任意大小，但膜10之結構尤其適用於製造相對於其他加強型膜而言為小型及薄壁的膜。舉例而言，膜10之外徑可為約1.5mm或更少，其壁厚度為約0.25mm或更少。展示之膜10具有約0.9mm之外徑及約0.7mm之內徑。
膜壁16具有嵌入於其中之細絲14之一或多個絲束12。細絲14為連續的長纖維，因此至少大部分或約80%或更多的細絲14具有至少一公尺之長度。當膜10之至少一公尺長之段嵌裝於膜模組中時，至少大部分細絲14沿著段之全長為連續的。較佳地，全部或基本上全部細絲14沿著段之全長為連續的。
圖1中展示之特定膜10具有一個絲束12，但可存在複數個絲束12，例如介於二與八之間。詞語「絲束」用於在複合材料行業中指示人造連續細絲之大體上無撚束，或至少 長的細絲段之大體上無撚束。然而，絲束12通常每絲束12具有少於約200根細絲14，而複合材料行業中之絲束可具有數千根細絲。詞語「絲束」亦可指由人造連續細絲或至少長的細絲段製成之細絲紗線，該等細絲聚集於一起但未經充分撚合以歸類為撚紗。亦可能使用其他類型之紗線或線，但其並非較佳的。
雖然絲束12為可自錠牽引且被牽拉通過澆製頭的紡織物單元，但細絲14至多僅鬆散地纏結於絲束12中。如圖1所示，可使細絲14相互散開，以使得膜原液可在至少大部分相鄰細絲14對之間流動。儘管細絲14可偶爾或隨機地彼此交叉，但細絲14沿著膜10之長度大體上彼此平行。絲束12可具有大體上為圓筒形之初始形狀，且具有大於壁16的厚度之直徑，但細絲14散開為配合於壁16內之橫截面。
細絲14可由聚合纖維製成，諸如聚乙烯、聚丙烯、聚酯、耐綸或PVDF。細絲可為雙組分細絲，其中第一部分(較佳為完整的外層或鞘)由經調適以黏結至膜形成原液之第一聚合物製成。黏結可藉由使用原液中的溶劑部分地溶解細絲14之外層或其他部分來進行。舉例而言，加強細絲14可具有由可溶於用於膜原液中之溶劑之聚合物製成的外層或其他部分。詳言之，外層或其他部分可包含亦存在於膜原液中之聚合物。雙組分細絲14之第二部分(例如，芯)由相容於第一聚合物之第二聚合物製成。第二聚合物可經選擇以提供較單獨使用第一聚合物之改良。舉例而言，相對於第一聚合物，第二聚合物可更牢固或較便宜，或二者 兼具。第一及第二聚合物中之任一者可為經選擇以增加其紡為雙組分細絲14之能力的共聚物。
圖1中所示之細絲14為雙組分纖維，其由為聚對苯二甲酸伸乙酯(PET)之一部分及為聚偏二氟乙烯(PVDF)之另一部分紡成。雙組分細絲14經組合為220丹尼爾(g/9000m)之絲束12。此絲束12由36根細絲14製成，每一根約為6丹尼爾。每一細絲14具有PET芯及PVDF鞘，芯約占橫截面積之70-90%。芯可由較低熔融溫度之co-PET製成以更緊密地匹配PVDF加工溫度。PVDF鞘層近似於1-2微米厚。絲束亦可由其他數目及重量之細絲製成。
基於聚偏二氟乙烯(PVDF)之膜原液相容於以上段落中所述之細絲14，且可用於使用NIPS方法形成膜壁16。可藉由溶解PVDF至熱NMP中並加入少量非溶劑來製備此原液。該原液可具有80-84重量%之NMP、14-16重量%之PVDF及2-4重量%之PVP k30。可改變聚合物濃度及溫度以調整原液黏度。
在圖1之膜10中，由與膜壁16的材料化學上相容之外鞘層及較牢固的芯聚合物製成細絲14。舉例而言，PET為牢固材料，其可容易地形成為細絲14並具有適合於加強或支撐膜之機械特性。相較而言，PVDF為較不牢固之材料，其不易形成為紗線。然而，圖1之芯與鞘雙組分細絲14兩者皆很好地黏結至膜壁16且機械上牢固。
膜10之抗張強度主要由細絲14之芯的抗張強度之總和決定。舉例而言，上述220丹尼爾絲束12具有約7N之斷裂強 度，其主要由PET芯提供。具有1.0mm外徑及0.7mm內徑之PVDF膜亦具有按照設在膜10中之絲束12的約7N之斷裂強度。相較而言，相同大小之未加強纖維在少於2N時就斷裂。
在由TIPS方法形成之膜中，細絲之至少部分可具有允許細絲至少部分地熔融於經加熱膜原液中之熔融溫度。該等細絲變成熔融黏結至膜壁。舉例而言，雙組分細絲可由Eastman F61HC聚對苯二甲酸伸乙酯(PET)均聚物(熔點260℃)芯及Dupont 3632 coPET(熔點160℃)鞘紡成。此雙組分細絲可經組合成為絲束。芯可占橫截面積之50%至80%。當coPET鞘被嵌入於TIPS方法之經加熱原液中時，其部分地熔融並在紡絲期間變得熔融黏結至膜壁。
包括單聚合物細絲之細絲的表面亦可在膜原液經澆鑄於其周圍以促進與膜原液之黏結之前受到改質或處理。此等處理可包括(例如)電漿蝕刻或化學蝕刻。處理經選擇以適用於紗線及原液之材料。
包括雙組分細絲14之細絲14在嵌入於壁16中之前，可經預收縮或熱處理。可提供加熱器(例如使用熱空氣或經加熱導件)以在絲束12被運載至塗覆頭時加熱絲束12以預收縮或處理細絲14。或者，在細絲14經組合成為絲束12之前或在絲束12經纏繞於線軸上以用於饋送至塗覆頭之前，可在一或多個單獨的步驟中預收縮或熱處理絲束12或個別細絲14。
加熱區可包括4cm(直徑)x 60cm(長度)之管狀腔室，其 頂部及底部具有開口，因此加熱區之軸線可與絲束12或細絲14之行進方向對準。管狀腔室亦具有至鼓風機及加熱元件之側面連接。可藉由改變加熱元件之電流汲取來控制空氣溫度。
視加熱區中之時間及溫度與細絲14上之任何張力而定，細絲14將收縮或熱定型或二者兼具。然而，細絲14不應被加熱至可開始相互黏結之程度。空氣溫度可為(例如)在攝氏100度與攝氏200度之間。接觸時間可在約0.1秒與5.0秒之間。
較佳地，藉由使細絲14受到張力以延長細絲14同時將細絲14暴露至高於原液的溫度並高於膜10在使用中將遇到之任何溫度之溫度而將細絲14熱定型。隨後允許細絲14冷卻至大約室溫同時仍然保持於延長狀態。此情形有助於避免在製造膜10或在膜10投入使用時細絲14之組分之間的分離。
為了在製造膜10時處置絲束12，一或多個線軸(每一線軸纏有絲束12)被置於通常位於澆製頭旁或上方的紗架上。紗架由固定的線軸固持器、導引器及張緊裝置組成，如在習知紡織設備中所發現。絲束12通過分佈模具，該分佈模具具有均勻地環繞澆製頭之中心軸線的延伸而分佈之一系列對準小孔。
圖2A展示澆製頭20，或稱為塗覆頭或紡絲頭。澆製頭20可由三個主要部分製造：本體28、針座30及扣狀體32。扣狀體32附接至本體28之一側並具有模具34，通常為圓筒形 孔，從而形成澆製頭20之最終外部澆鑄表面。針座30固持針26並插入於本體28之相反側中，以使得針26進入模具34。針26之末端通常與模具34之末端齊平，然而一者亦可相對於另一者位移。針26與模具34產生膜原液及絲束12通過之環形圈。針26及模具34與孔流體及原液之流動速率相結合地確定所得膜10之內徑及外徑。
針26經壓入至針座30之中心孔24內。針26及中心孔24與澆製頭20之中心軸線或縱向軸線對準，並在形成膜10時提供用於將孔流體注入至膜10內之管道。針26及針座30之外徑亦提供一內部表面，原液及絲束12在通過塗覆頭20時沿該內部表面流動。
參看圖2A與圖2B，針座30具有用於將行進通過澆製頭20之每一絲束12之槽38。本體28具有一或多個絲束入口22，每一者對應於一槽38，該等絲束入口22用於接收所需數目之絲束12並轉移其至槽38。通常僅有一個絲束12通過每一絲束入口22並進入對應之槽38，但兩個或兩個以上絲束12可經合併通過一個絲束入口22及槽38。此外，可使用具有多個絲束入口22之澆製頭20而不經由每一可用之絲束入口22提供一絲束12。
絲束入口22較佳地設置成與澆製頭20之中心軸線成一角度，例如30度或更大。當絲束12自絲束入口22移動至槽38時，其必須彎曲繞過設在本體28上之拐角42或在插入於本體28中之可選的第一小孔44上彎曲。槽38較佳地亦由突出部分40中斷，突出部分40在絲束12行進通過澆製頭20時迫 使絲束12再次彎曲。當絲束12進入模具34或單獨的可選第三小孔36時，絲束再次彎曲。拐角42之上游邊緣、突出部分40及模具34或第三小孔36(在絲束12彎曲時支承絲束12的無論哪一表面)較佳地具有1mm或更大之半徑並經加工為平滑拋光。拐角42、突出部分40、模具34或第三小孔36中之一或多者使細絲14分散，以使得絲束12相對於其初始圓形橫截面變得更寬及更薄，如圖1所示。或者，可藉由在拐角42與槽38之底部之間、在可選第二小孔50與槽38之底部之間、及在模具34或第三小孔36與針26之間中之一或多處具有狹窄間隙來提供或增強細絲14之分散。
本體28亦包括原液注入口46及原液排出口48。一組一或多個第一口46a允許原液注入至槽38中。原液流動通過第一口46a之速率較佳地足以保持槽38充滿原液，以使得在細絲14接觸針26之前由原液浸濕。若通過第一口46a的原液不足，則細絲14將傾向於跌落至膜10之內腔中且膜10將有缺陷。經由第一口46a進入之一些原液將被迫在拐角42周圍向上游移動。此原液經由與絲束入口22中之每一者連通之原液出口48排出。額外的第二口46b容許原液進入模具34與針26之間的間隙。此額外的原液完成形成膜壁16所需之原液的所需總流量。可自用氮增壓之罐或使用正排量泵將原液注入至口46中。可在約攝氏15度至攝氏200度範圍內之溫度及約20kPa至400kPa範圍內之壓力下提供原液。
挾帶有細絲14之膜原液之管狀流離開塗覆頭20並滴落至 凝固浴中。凝固浴通常為對於膜凝固而言已知之底部及頂部處配備有滾筒之貯槽。頂部滾筒之後的拉緊捲繞器具有介於1m/min至30m/min之間的可調速度及橫動導紗器以均勻地將凝固膜填入至線軸。
參看圖4，依據掃描電子顯微法(SEM)像片對膜10之檢查展示基於PVDF之膜壁16很好地黏附於多細絲絲束12中之個別細絲14。圖4中可見，原液滲透到細絲14之間並內聚地黏結至細絲14之表面。證據顯示PVDF層與PET層之間的雙組分纖維中存在一些分層。此係由切割樣本導致。
相較而言，圖3展示膜原液亦可經製造以使用澆製頭20滲透於PET細絲之133丹尼爾絲束之細絲之間。然而，在此情況下之原液不黏結至細絲。取而代之，原液在固化時自細絲退縮開，從而使得細絲在膜捲曲時可自由地在膜內移動。
藉由使用相容於膜原液之鞘材料以使膜壁16黏附於細絲14，且藉由在塗覆頭20內分佈細絲14以使細絲14充分地散開以允許膜原液滲透於實質上所有細絲14之間，可生產堅韌的加強型中空絲膜10，其能經受常規使用中之撓曲運動。結果是更耐用及抗斷裂之膜過濾裝置。
細絲14本質上不增加膜成本。與此相對照，與將具有更厚的壁截面以試圖改良其強度之無支撐的膜相比，更薄壁但加強型的膜可在表面面積基礎上產生更低成本的模組。
可使用相容於選定之膜原液的單一組分細絲。然而，與用PET或另一牢固的紡織聚合物作為芯材料之雙組分紗線 相比較，此等細絲很可能更貴或更不牢固，或二者兼具。詳言之，PVDF及聚醚碸(PES)為較佳的膜材料但並不會製成好的加強紗線，因為其較PET更不牢固且貴得多。
實例
使用以28cc/min之速率供應至模具34與針26之間的間隙及以3cc/min之速率供應至槽38中之主要為PVDF/NMP混合物的原液製造圖1所示之膜10。澆製頭20如圖2A及圖2B所示，且經加熱至攝氏60度。使用具有鞘/芯類型之雙組分細絲14之一個絲束12。細絲14之組成為以重量計70%之PET芯(Eastman F61HC)及以重量計30%之PVDF鞘(Solef 1006)。絲束12包含36個無撚細絲14，其每一者重量為6丹尼爾。線速度為15m/min(50fpm)，空氣間隙為110mm且凝固浴為攝氏45度之水。
本書面描述使用實例以揭示本發明且亦使任何熟習此項技術者能夠實踐本發明。本發明之範疇由申請專利範圍界定，且可包括熟習此項技術者可想到之其他實例。
10‧‧‧中空絲膜
12‧‧‧絲束
14‧‧‧細絲
16‧‧‧膜壁
20‧‧‧塗覆頭/澆製頭
22‧‧‧絲束入口
24‧‧‧中心孔
26‧‧‧針
28‧‧‧本體
30‧‧‧針座
32‧‧‧扣狀體
34‧‧‧模具
36‧‧‧第三小孔
38‧‧‧槽
40‧‧‧突出部分
42‧‧‧拐角
44‧‧‧第一小孔
46‧‧‧原液注入口
46a‧‧‧第一口
48‧‧‧原液排出口
50‧‧‧第二小孔
圖1為藉由雙組分細絲加強之中空絲膜之橫截面的像片。
圖2A為塗覆頭之橫截面示意圖。
圖2B為圖2A之塗覆頭的針座及針之等角視圖。
圖3為具有聚酯細絲之中空絲膜之橫截面的像片。
圖4為以高於圖1中之放大倍率的放大倍率的藉由雙組分細絲加強之中空絲膜的橫截面之一部分的像片。

Claims (14)

  1. 一種中空絲膜，其包含：a)由一膜原液形成之一膜壁；及b)嵌入該膜壁中之一或多個細絲紗線或絲束；其中該等細絲至少部分地由經調適以黏結至該膜原液或該膜壁之一聚合物製造；其中嵌入該膜壁中之該一或多個紗線或絲束具有一橫截面形狀，其於垂直於該膜之一半徑量測時大於平行於該膜之該半徑量測時；及其中該等細絲之圓筒形紗線或絲束具有大於該膜壁的厚度之一直徑。
  2. 如請求項1之膜，其中在環繞該細絲之一芯的一鞘中提供該聚合物，且該鞘中之該聚合物可溶於一用於該膜原液中之溶劑中，且該芯由一不同於該鞘中之該聚合物的聚合物所製造。
  3. 如請求項1之膜，其中該聚合物為PVDF或PES。
  4. 如請求項1之膜，其中該聚合物具有一熔融溫度，其低於用於形成該膜壁之一TIPS原液之熔融溫度。
  5. 如請求項1之膜，其中該聚合物具有經處理以促進黏結之一表面。
  6. 如請求項3之膜，其中該等細絲具有一PET或co-PET芯。
  7. 如請求項1之膜，其中該膜壁環繞該等細絲並經黏結至該等細絲。
  8. 如請求項1之膜，其中至少大部分該等細絲連續性地自該膜之至少1公尺長的一段之一端延伸至另一端，且該等細絲大體上相互平行。
  9. 一種製造一加強型中空絲膜之方法，其包括以下步驟：a)使一膜原液流動通過一澆製頭；b)牽引一或多個細絲紗線或細絲絲束通過該澆製頭，其中該一或多個紗線或絲束在其進入該澆製頭之前具有一初始圓筒形橫截面及一初始直徑；及c)迫使該一或多個紗線或絲束繞過該澆製頭中之至少一個彎頭，或通過該澆製頭中之窄於該一或多個紗線或絲束之該初始直徑的至少一個間隙，從而使該一或多個紗線或絲束之橫截面相對於該初始圓筒形橫截面變得平坦。
  10. 如請求項9之方法，其中該等細絲包括一第一聚合物之一芯及一第二聚合物之一鞘。
  11. 如請求項10之方法，其在步驟b)之前包括熱定型該等細絲之一步驟。
  12. 如請求項9之方法，其中步驟a)包括在該澆製頭之一第一區域中提供原液，在該第一區域中一絲束在一模具上游之一槽中行進；及在與該模具連通之一第二區域中提供原液。
  13. 如請求項9之方法，其進一步包括提供一孔流體至該膜之一內腔的一步驟。
  14. 如請求項9之方法，其中該一或多個紗線或絲束之該初始直徑係大於該膜壁的厚度。
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DE112012005274T5 (de) 2014-10-09
CN103998118A (zh) 2014-08-20
US9321014B2 (en) 2016-04-26
KR101806600B1 (ko) 2018-01-10
US20130153490A1 (en) 2013-06-20
TW201334859A (zh) 2013-09-01
CN103998118B (zh) 2017-11-10
KR20170049610A (ko) 2017-05-10
HUP1400398A2 (en) 2015-03-02
HU231247B1 (hu) 2022-05-28
WO2013089971A1 (en) 2013-06-20

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