CN102164658A - 浇铸在针织品上的不对称和复合分离膜 - Google Patents

浇铸在针织品上的不对称和复合分离膜 Download PDF

Info

Publication number
CN102164658A
CN102164658A CN2009801375064A CN200980137506A CN102164658A CN 102164658 A CN102164658 A CN 102164658A CN 2009801375064 A CN2009801375064 A CN 2009801375064A CN 200980137506 A CN200980137506 A CN 200980137506A CN 102164658 A CN102164658 A CN 102164658A
Authority
CN
China
Prior art keywords
polymer
film
poly
asymmetric
coating
Prior art date
Legal status (The legal status 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 status listed.)
Pending
Application number
CN2009801375064A
Other languages
English (en)
Inventor
M-W·唐
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Honeywell UOP LLC
Universal Oil Products Co
Original Assignee
Universal Oil Products Co
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 Universal Oil Products Co filed Critical Universal Oil Products Co
Publication of CN102164658A publication Critical patent/CN102164658A/zh
Pending legal-status Critical Current

Links

Classifications

    • 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
    • B01D71/70—Polymers having silicon in the main chain, with or without sulfur, nitrogen, oxygen or carbon only
    • 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
    • B01D67/0006—Organic membrane manufacture by chemical reactions
    • 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
    • B01D69/10—Supported membranes; Membrane supports
    • B01D69/105—Support pretreatment
    • 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
    • B01D69/12—Composite membranes; Ultra-thin membranes
    • B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
    • 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
    • B01D71/08—Polysaccharides
    • B01D71/12—Cellulose derivatives
    • B01D71/14—Esters of organic acids
    • 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
    • B01D71/08—Polysaccharides
    • B01D71/12—Cellulose derivatives
    • B01D71/14—Esters of organic acids
    • B01D71/16—Cellulose acetate
    • 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
    • B01D71/58—Other polymers having nitrogen in the main chain, with or without oxygen or carbon only
    • B01D71/62—Polycondensates having nitrogen-containing heterocyclic rings in the main chain
    • B01D71/64—Polyimides; Polyamide-imides; Polyester-imides; Polyamide acids or similar polyimide precursors
    • B01D71/641—Polyamide-imides
    • 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
    • B01D71/58—Other polymers having nitrogen in the main chain, with or without oxygen or carbon only
    • B01D71/62—Polycondensates having nitrogen-containing heterocyclic rings in the main chain
    • B01D71/64—Polyimides; Polyamide-imides; Polyester-imides; Polyamide acids or similar polyimide precursors
    • B01D71/643—Polyether-imides
    • 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
    • B01D71/68—Polysulfones; Polyethersulfones
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/01—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural macromolecular compounds or derivatives thereof
    • D06M15/03—Polysaccharides or derivatives thereof
    • D06M15/05—Cellulose or derivatives thereof
    • D06M15/07—Cellulose esters
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/55—Epoxy resins
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/59—Polyamides; Polyimides
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/63—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing sulfur in the main chain, e.g. polysulfones
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/18—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with two layers of different macromolecular materials
    • D06N3/183—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with two layers of different macromolecular materials the layers are one next to the other
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N7/00—Flexible sheet materials not otherwise provided for, e.g. textile threads, filaments, yarns or tow, glued on macromolecular material
    • D06N7/0094—Fibrous material being coated on one surface with at least one layer of an inorganic material and at least one layer of a macromolecular material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2323/00—Details relating to membrane preparation
    • B01D2323/30—Cross-linking
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2323/00—Details relating to membrane preparation
    • B01D2323/34—Use of radiation
    • B01D2323/345—UV-treatment
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/23907—Pile or nap type surface or component
    • Y10T428/23957—Particular shape or structure of pile

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
  • Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)

Abstract

本发明涉及用于气体和液体分离的膜的制备，其中将聚合物层直接施加到代替常规布或玻璃或金属基底的针织品织物上。

Description

浇铸在针织品上的不对称和复合分离膜
发明背景
为开发用于超滤、纳滤、全蒸发、反渗透和气体分离的不对称和复合膜做出了大量的努力。溶剂浇铸转相方法通常用于制备平片膜。在该方法中，选择合适聚合物、溶剂和非溶剂(溶胀剂)并以合适比例混合以对膜提供所需形态。不对称膜通过使用刮刀将聚合物溶液(常称作“浇铸涂布漆”(casting dope))铺展到光滑基底顶上的薄膜中，随后在水性浴中沉淀并在升高的温度下干燥而形成。浇铸到光滑基底如玻璃、金属、金属板或层压有塑料如聚乙烯的金属或涂覆有试剂的基底上并随后从其剥离的膜称为“自支撑”(free-standing)膜。除了脆度外，由于干燥时不均匀收缩的起皱的问题处理也是在大规模生产“自支撑”膜时遇到的主要障碍。这类选择性膜可非常昂贵地开发和生产，因此它们具有高价格。浇铸在非剥离性基底上的膜称作“浇铸在布上”(cast-on-cloth)的膜，并且该“浇铸在布上”的膜的性能主要取决于需对整个膜提供适当机械强度和结构完整性的织物的性质。基底的选择因此对需要容许其操作中遇到且必要的跨膜压降，或者在预期操作环境中以完整材料保持合理寿命的膜种类来说尤其重要。
发明概述
本领域熟练技术人员熟知能够提供满足膜要求的该种性能的基底的有限选择。这是因为不对称或复合膜仅通过织物基底最佳预成型，该织物基底(1)将对膜提供适当机械强度和结构完整性；(2)呈现光滑、均匀、平坦的(平的)表面而不露出纤维，不对称膜可以在其上形成而具有最少量的针孔和其他缺陷；(3)对化学反应呈惰性，和(4)为多孔的且具有高渗透性，从而不降低整个膜的通量。通常合适的基底织物具有约100-125微米的厚度。优选使用由Nylon或
Figure BDA0000051839840000012
聚酯制成的织造布。可使用的其他织物包括：
Figure BDA0000051839840000021
增强纸和
Figure BDA0000051839840000022
非织造聚酯。本发明的目的是为选择性不对称或复合膜提供一种基底，其组合下列特征(1)可通过常规转相浇铸技术廉价地制备，(2)显示优异的渗透性和选择性，(3)在操作条件下维持膜的寿命，和(4)提高了螺旋缠绕型或板和框架模件构造的填充密度。
发明详述
本发明为一种制备不对称分离膜的方法，该不对称分离膜包括涂覆有在大于200℃的温度下交联的基于“双酚A”的环氧化物的针织品(tricot)支撑基底、在宽范围的温度和压力下提供高渗透性和选择性的聚合物涂布漆和通过用可热固化或可UV固化聚硅氧烷或其他合适涂料涂覆不对称膜表面的罩面漆。不对称或复合分离膜包括纤维素膜如乙酸-丁酸纤维素、丙酸纤维素、乙基纤维素、甲基纤维素、硝酸纤维素和由其他聚合物涂布漆如聚砜、聚醚砜、聚酰胺、聚酰亚胺、聚醚酰亚胺、聚酰胺/酰亚胺；聚醚酮；聚醚醚酮、聚亚芳基氧；聚(酯酰胺-二异氰酸酯)；聚氨酯；聚苯并苯并咪唑；聚酰肼；聚二唑(polyoxadiazoles)；聚三唑；聚苯并咪唑；聚碳二亚胺；聚膦嗪；微孔聚合物、聚碳酸酯、聚苯乙烯、聚丙烯、全氟聚合物、聚丙烯酸、多芳基化合物、聚对苯二甲酸乙二酯、聚硅氧烷、聚丙烯腈、聚甲基丙烯腈、聚乙烯醇、聚硫化物、聚苯并
Figure BDA0000051839840000024
唑、聚偏二氟乙烯及其混合物形成的膜。
更具体地，将形成膜的聚合物薄膜(film)直接浇铸到针织品织物层的光滑侧，其中使形成膜的聚合物薄膜永久且整体地粘合。通常用于制备本发明不对称和复合膜的针织品基底具有交联的环氧化物涂层，范围为10-50重量％的环氧树脂。优选20-30重量％的环氧化物涂层。针织品的透气性为1-20cm3/(sec.cm2)，在本实施方案中优选使用透气性为2-5cm3/(sec.cm2)的针织品。针织品基底的厚度应为100-500微米，优选250-400微米。针织品基底的密度应为50-200gm/平方米，优选100-150gm/平方米。由于针织品基底为细网眼针织物设计，其中纤维在采用交织成圈纱线模式的同时纵向编织，其中一侧特征为细罗纹以纵向模式编织，而另一侧的特征为罗纹以交叉方向编织，其在罗纹侧应具有5-30纵行/cm，优选10-15纵行/cm。此外，在针织品的光滑侧，它应具有5-40横列/cm，在本发明中优选15-25横列/cm。“浇铸在针织品上(cast-on-tricot)”的不对称或复合膜的总厚度应为400-800微米，优选500-650微米。根据本发明优选实施方案，“浇铸在针织品上”的膜通过在针织品基底上浇铸聚合物涂布漆从而形成溶液薄层，使该膜在0-25℃，通常优选0℃的低温或环境温度的水中沉淀，然后在25-90℃，通常优选86℃的高温水中退火而制备。干燥膜可通过在或大于上述的环境温度(范围为25-80℃，通常65-70℃)下蒸发水而实现。干燥的“浇铸在针织品上”的不对称膜可用含有2-15重量％，通常优选8-10重量％环氧硅氧烷(epoxy silicone)溶液的环氧硅氧烷溶液涂覆。该硅氧烷溶剂含有比例为1∶1-1∶5，通常优选1∶3的己烷和庚烷溶剂。然后使该环氧硅氧烷涂料在环境温度下暴露于UV源1-10分钟，通常优选2-4分钟，从而在硅氧烷溶剂蒸发生产环氧硅氧烷的同时，固化该涂料。得到的“浇铸在针织品上”的不对称和复合膜适用于水由反渗透脱盐、非水液体分离、超滤、纳滤、全蒸发和所有已知的气体分离终端用途。使用针织品作为背衬基底的其他优点包括降低了从进料到渗透侧的压降；增加了螺旋缠绕型模件的填充密度，最小化了在使用布织物中遇到的膜卷曲问题以及降低了制备该膜的材料成本。
与由Dutton US 0034294A1所教导的将针织品在螺旋缠绕型膜的模件设置中用作渗透隔板不同，在本发明中将针织品在转相方法中用作不对称膜的支撑织物。更重要地是，虽然针织品的光滑侧用于支撑不对称膜，但可将针织品的罗纹侧在螺旋缠绕型或板和框架型结构模件构造中用作渗透隔板。
下列实施例旨在说明本发明的一个或多个优选实施方案，但本发明不限于这些实施方案。可对下列实施例所做的众多变体均属于本发明范围。
实施例1
二乙酸纤维素(CA)&三乙酸纤维素(CTA)不对称膜
由包含(以近似重量百分数计)8％三乙酸纤维素，8％二乙酸纤维素，32％1，3-二氧杂环戊烷，2％NMP，24％丙酮，12％甲醇，2％马来酸和3％正癸烷的浇铸涂布漆制备乙酸纤维素/三乙酸纤维素不对称膜。将薄膜浇铸到针织品网上，然后通过在0℃的水浴中浸没10分钟而胶凝，然后在86℃的热水浴中退火5分钟。使得到的湿膜在70℃的温度下干燥以除去水。用含有2重量％环氧硅氧烷溶液的环氧硅氧烷溶液涂覆干燥的不对称纤维素膜。该硅氧烷溶剂含有比例为1∶3的己烷和庚烷。使该环氧硅氧烷涂料在环境温度下暴露于UV源2-4分钟，从而在该硅氧烷溶剂蒸发的同时，使该涂料固化，由此产生本发明的环氧硅氧烷涂覆膜。
在6.89MPa(1000psig)的进料压力和50℃下使用含有10体积％CO2和90体积％CH4的进料气体对环氧硅氧烷涂覆膜的气体传输性能进行评价。表1显示的是致密膜的CO2渗透性和选择性(α)(固有特性)与不对称膜性能的比较。
表1气体传输性能
  膜   CO2   CO2/CH4的选择性
  致密膜   7.2Barrers＊   21.9
  不对称膜   199(GPU＊＊)   14.2
＊Barrer＝10-10cm3(STP)cm/sec.cm3.cmHg
＊＊气体渗透单元(GPU)＝10-6em3(STP)/cm2sec.cmHg
实施例2
二乙酸纤维素(CA)&三乙酸纤维素(CTA)不对称膜
由包含(以近似重量百分数计)8％三乙酸纤维素，8％二乙酸纤维素，32％1，3-二氧杂环戊烷，2％NMP，24％丙酮，12％甲醇，2％马来酸和3％正癸烷的浇铸涂布漆制备乙酸纤维素/三乙酸纤维素不对称膜。将薄膜浇铸到针织品网上，然后通过在0℃的水浴中浸没10分钟而胶凝，然后在86℃的热水浴中退火5分钟。使得到的湿膜在70℃的温度下干燥以除去水。表2显示的是致密膜的CO2渗透性和选择性(α)(固有特性)与不对称膜性能的比较。
表2气体传输性能
  膜   CO2   CO2/CH4的选择性
  致密膜   7.2Barrers＊   21.9＊
  不对称膜   53GPU   14.9
＊致密膜在690kPa(100psig)，50℃和纯气体下测试。
实施例3
P84聚酰亚胺/聚醚砜共混的不对称膜
由包含(以近似重量百分数计)6.5％聚醚砜，12.2％P84聚酰亚胺，50.5％1，3-二氧杂环戊烷，24.3％NMP，3.7％丙酮和2.8％甲醇的浇铸涂布漆制备P84聚酰亚胺/聚醚砜共混的不对称膜。将薄膜浇铸到针织品网上，然后通过在0℃的水浴中浸没10分钟而胶凝，然后在86℃的热水浴中退火5分钟。使得到的湿膜在65-70℃的温度下干燥以除去水。用含有8重量％环氧硅氧烷溶液的环氧硅氧烷溶液涂覆干燥的不对称膜。该硅氧烷溶剂具有比例为1∶3的己烷和庚烷。使该环氧硅氧烷涂料在环境温度下暴露于UV源2-4分钟，在该硅氧烷溶剂蒸发同时，使该涂料固化，从而产生本发明的环氧硅氧烷涂覆膜。
在6.89MPa(1000psig)的进料压力和50℃下使用含有10体积％CO2和90体积％CH4的进料气体对环氧硅氧烷涂覆膜的气体传输性能进行评价。表3显示的是致密膜的CO2渗透性和选择性(α)(固有特性)与不对称膜性能的比较。表3显示的是致密膜的CO2渗透性和选择性(α)(固有特性)与不对称膜性能的比较。
表3气体传输性能
  膜   CO2   CO2/CH4的选择性
  致密膜   2.7Barrers＊   33.7＊
  不对称膜   51GPU   24.7
＊致密膜在690kPa(100psig)，50℃和纯气体下测试。

Claims (10)

1.一种制备膜的方法，包括将聚合物溶液施加到织物片材的一侧和在所述聚合物溶液施加之后从所述聚合物溶液中除去溶剂成分，其中所述织物包含一系列在一个方向上交联的线圈和在垂直方向上的线圈线。
2.根据权利要求1的方法，其中所述聚合物选自聚砜、聚醚砜、聚醚酰亚胺、纤维素聚合物、聚酰胺、聚酰亚胺、聚酰胺/酰亚胺、聚醚酮、聚醚醚酮、聚亚芳基氧、聚(酯酰胺-二异氰酸酯)、聚氨酯、聚苯并苯并咪唑、聚酰肼、聚
Figure FDA0000051839830000011
二唑、聚三唑、聚苯并咪唑、聚碳二亚胺、聚膦嗪、微孔聚合物、聚硅氧烷、聚丙烯腈、聚甲基丙烯腈、聚乙烯醇、聚硫化物、聚苯并
Figure FDA0000051839830000012
唑、聚偏二氟乙烯及其混合物。
3.根据权利要求1的方法，其中所述织物片材已经用水基环氧化物层涂覆且热交联。
4.根据权利要求3的方法，其中所述环氧化物为双酚A。
5.根据权利要求2的方法，其中所述纤维素聚合物包括二乙酸纤维素或三乙酸纤维素。
6.根据权利要求2的方法，其中所述聚合物包括聚酰亚胺。
7.根据权利要求6的方法，其中所述聚合物另外包括聚砜。
8.根据权利要求1的方法，其中所述织物片材为针织品织物。
9.根据权利要求1的方法，其另外包括施加可UV辐射交联涂料到所述聚合物上，然后使所述可UV辐射交联涂料交联。
10.一种由权利要求1-9中任一项的方法制备的不对称膜。
CN2009801375064A 2008-09-25 2009-08-04 浇铸在针织品上的不对称和复合分离膜 Pending CN102164658A (zh)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US12/237,685 US20100075101A1 (en) 2008-09-25 2008-09-25 Cast-on-Tricot Asymmetric and Composite Separation Membranes
US12/237,685 2008-09-25
PCT/US2009/052672 WO2010036452A2 (en) 2008-09-25 2009-08-04 Cast-on-tricot asymmetric and composite separation membranes

Publications (1)

Publication Number Publication Date
CN102164658A true CN102164658A (zh) 2011-08-24

Family

ID=42037955

Family Applications (1)

Application Number Title Priority Date Filing Date
CN2009801375064A Pending CN102164658A (zh) 2008-09-25 2009-08-04 浇铸在针织品上的不对称和复合分离膜

Country Status (7)

Country Link
US (2) US20100075101A1 (zh)
EP (1) EP2334414A4 (zh)
JP (1) JP2012503542A (zh)
CN (1) CN102164658A (zh)
BR (1) BRPI0919083A2 (zh)
MY (1) MY157467A (zh)
WO (1) WO2010036452A2 (zh)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109071765A (zh) * 2016-04-11 2018-12-21 巴斯夫欧洲公司 热塑性多孔隔膜
CN110764720A (zh) * 2018-07-23 2020-02-07 佳能株式会社 打印设备、打印设备的控制方法和存储介质

Families Citing this family (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9095821B1 (en) * 2010-10-26 2015-08-04 Nagare Membranes, Llc Non-reactive process for fixing nanotubes in a membrane in through-passage orientation
US9475258B2 (en) 2012-06-15 2016-10-25 The Boeing Company Multiple-resin composite structures and methods of producing the same
GB201211309D0 (en) * 2012-06-26 2012-08-08 Fujifilm Mfg Europe Bv Process for preparing membranes
US20140183134A1 (en) * 2013-01-02 2014-07-03 Hydration Systems, Llc Forward osmosis and pressure retarded osmosis spacer
CA2940233A1 (en) 2013-02-21 2014-08-28 The Regents Of The University Of California Universal scalable and cost-effective surface modifications
KR20180023971A (ko) 2015-07-01 2018-03-07 쓰리엠 이노베이티브 프로퍼티즈 컴파니 중합체성 이오노머 분리막 및 사용 방법
WO2017004492A1 (en) 2015-07-01 2017-01-05 3M Innovative Properties Company Pvp- and/or pvl-containing composite membranes and methods of use
US10478778B2 (en) 2015-07-01 2019-11-19 3M Innovative Properties Company Composite membranes with improved performance and/or durability and methods of use
CN106914139A (zh) * 2015-12-24 2017-07-04 通用电气公司 制备膜的方法及相应的膜和过滤元件
CN107450977A (zh) * 2015-12-30 2017-12-08 北京典赞科技有限公司 基于yarn的面向gpgpu集群的资源管理调度方法
CA3045807A1 (en) 2016-12-01 2018-06-07 The Regents Of The University Of California Energy providing devices and applications thereof
CN111629816A (zh) * 2017-11-09 2020-09-04 加州大学评议会 非对称复合膜和其用途
KR20200128514A (ko) 2017-12-01 2020-11-13 더 리전트 오브 더 유니버시티 오브 캘리포니아 바이오파울링 저항성 코팅 및 이의 제조 및 사용 방법
CN110080006A (zh) * 2019-05-31 2019-08-02 南通东屹高新纤维科技有限公司 防水复合面料的制备方法
CN110158324A (zh) * 2019-05-31 2019-08-23 南通东屹高新纤维科技有限公司 超疏水棉麻纺织面料
CA3142797A1 (en) 2019-06-05 2020-12-10 The Regents Of The University Of California Biofouling resistant coatings and methods of making and using the same
CN112403839B (zh) * 2020-11-30 2022-08-12 天津大学 一种二氧化碳分离多层复合膜的规模化制备方法及装置
CN112774465B (zh) * 2020-12-25 2022-04-15 湖南澳维科技股份有限公司 一种聚酰胺复合膜、其制备方法及膜元件

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3813334A (en) * 1973-04-09 1974-05-28 Desalination Systems Porous backing material for semipermeable membrane cartridges
US5236643A (en) * 1990-02-14 1993-08-17 Industrial Technology Research Institute Preparation of gas separation membrane and spiral wound gas separation module
US20030034294A1 (en) * 2001-05-25 2003-02-20 Dutton Floyd Greene Non-fouling epoxy resin system for permeate carrier reverse osmosis membrane
US20030134550A1 (en) * 2001-12-07 2003-07-17 Moo-Seok Lee Braid-reinforced hollow fiber membrane
CN1625435A (zh) * 2002-04-03 2005-06-08 环球油品公司 环氧硅氧烷涂覆膜
CN101035608A (zh) * 2004-08-11 2007-09-12 佛兰芒技术研究所 一体化的渗透通道膜
WO2007116072A2 (en) * 2006-04-10 2007-10-18 Vlaamse Instelling Voor Technologisch Onderzoek (Vito) Knitted support for tubular membranes
WO2008076599A1 (en) * 2006-12-18 2008-06-26 Uop Llc Asymmetric gas separation membranes with superior capabilities for gas separation

Family Cites Families (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3872014A (en) * 1974-03-11 1975-03-18 Aerojet General Co Membrane separation apparatus
US4033878A (en) * 1975-05-12 1977-07-05 Universal Oil Products Company Spiral wound membrane module for direct osmosis separations
DE3687419T2 (de) * 1985-01-25 1993-05-19 Asahi Chemical Ind Nichtgewobene stoffbahn, oel-wasser-trennungsfilter und verfahren zur oel-wasser-trennung.
US4802982A (en) * 1987-10-01 1989-02-07 Desalination Systems, Inc. Spiral-wound membrane with improved permeate carrier
US4902417A (en) * 1988-06-14 1990-02-20 Desalination Systems, Inc. Spiral-wound membrane cartridge with ribbed and spaced carrier layer
AU636754B2 (en) * 1990-06-29 1993-05-06 W.L. Gore & Associates, Inc. Protective materials
GR1002482B (el) * 1995-12-07 1996-12-03 Παρασκευη και δοκιμη πολυμερικων μεμβρανων απο μιγματα πολυσουλφονων και πολυιμιδιων για τον διαχωρισμο αεριων.
JP2000051671A (ja) * 1998-08-06 2000-02-22 Nitto Denko Corp スパイラル型分離膜エレメント
ATE306312T1 (de) * 1999-06-08 2005-10-15 Nitto Denko Corp Membranmodul zur trennung von flüssigkeiten und verfahren zu seiner herstellung
US6755970B1 (en) * 1999-06-22 2004-06-29 Trisep Corporation Back-flushable spiral wound filter and methods of making and using same
US6368382B1 (en) * 2000-07-27 2002-04-09 Uop Llc Epoxysilicone coated membranes
US7048855B2 (en) * 2000-12-22 2006-05-23 Ge Osmonics, Inc. Cross flow filtration materials and cartridges
US20030034293A1 (en) * 2001-08-16 2003-02-20 Pti Advanced Filtration, Inc. Method of treating filtration media to prevent lateral flow, blistering and de-lamination
DE10208278A1 (de) * 2002-02-26 2003-09-04 Creavis Tech & Innovation Gmbh Hybridmembran, Verfahren zu deren Herstellung und die Verwendung der Membran
JP5090017B2 (ja) * 2006-03-09 2012-12-05 日東電工株式会社 スパイラル型膜エレメント及びその製造方法
JP2008126199A (ja) * 2006-11-24 2008-06-05 Mitsubishi Rayon Co Ltd 中空状多孔質膜およびその製造方法

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3813334A (en) * 1973-04-09 1974-05-28 Desalination Systems Porous backing material for semipermeable membrane cartridges
US5236643A (en) * 1990-02-14 1993-08-17 Industrial Technology Research Institute Preparation of gas separation membrane and spiral wound gas separation module
US20030034294A1 (en) * 2001-05-25 2003-02-20 Dutton Floyd Greene Non-fouling epoxy resin system for permeate carrier reverse osmosis membrane
US20030134550A1 (en) * 2001-12-07 2003-07-17 Moo-Seok Lee Braid-reinforced hollow fiber membrane
CN1625435A (zh) * 2002-04-03 2005-06-08 环球油品公司 环氧硅氧烷涂覆膜
CN101035608A (zh) * 2004-08-11 2007-09-12 佛兰芒技术研究所 一体化的渗透通道膜
WO2007116072A2 (en) * 2006-04-10 2007-10-18 Vlaamse Instelling Voor Technologisch Onderzoek (Vito) Knitted support for tubular membranes
WO2008076599A1 (en) * 2006-12-18 2008-06-26 Uop Llc Asymmetric gas separation membranes with superior capabilities for gas separation

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109071765A (zh) * 2016-04-11 2018-12-21 巴斯夫欧洲公司 热塑性多孔隔膜
CN110764720A (zh) * 2018-07-23 2020-02-07 佳能株式会社 打印设备、打印设备的控制方法和存储介质
CN110764720B (zh) * 2018-07-23 2023-09-26 佳能株式会社 打印设备、打印设备的控制方法和存储介质

Also Published As

Publication number Publication date
US20120085697A1 (en) 2012-04-12
MY157467A (en) 2016-06-15
WO2010036452A2 (en) 2010-04-01
JP2012503542A (ja) 2012-02-09
BRPI0919083A2 (pt) 2015-12-15
WO2010036452A3 (en) 2010-05-14
EP2334414A2 (en) 2011-06-22
US20100075101A1 (en) 2010-03-25
EP2334414A4 (en) 2013-12-04

Similar Documents

Publication Publication Date Title
CN102164658A (zh) 浇铸在针织品上的不对称和复合分离膜
Wang et al. Ceramic tubular MOF hybrid membrane fabricated through in situ layer‐by‐layer self‐assembly for nanofiltration
JP6155347B2 (ja) 正浸透膜
WO2015041250A1 (ja) ガス分離膜、ガス分離モジュール、ガス分離装置、及びガス分離方法
Naik et al. Influence of support layer and PDMS coating conditions on composite membrane performance for ethanol/water separation by pervaporation
CN109414660A (zh) 复合半透膜及复合半透膜的制造方法
KR20150060732A (ko) 복합 반투막
JP6602502B2 (ja) ガス分離膜エレメント、ガス分離膜モジュール、及びガス分離装置
KR20160026070A (ko) 기체분리막의 제조 방법
JP2016503448A (ja) フッ素化エチレン‐プロピレンポリマーを含有するガス分離のためのブレンドポリマー膜
CA2300519C (en) Solvent-resistant microporous polybenzimidazole membranes
WO2018221684A1 (ja) ガス分離膜、ガス分離膜エレメント、ガス分離装置及びガス分離方法
KR102573508B1 (ko) 가스 분리막, 가스 분리막 엘리먼트, 및 가스 분리 방법
JPH09103663A (ja) ポリエーテルイミド膜
WO2018159563A1 (ja) 分離用複合膜、分離膜モジュール、分離装置、分離膜形成用組成物、及び分離用複合膜の製造方法
KR20190051879A (ko) 기체 분리막의 제조방법 및 이에 의하여 제조된 기체 분리막
JPH10309449A (ja) 有機物分離用高分子膜及びその製造方法
JP2002126479A (ja) 多孔質膜、ガス分離膜及びその製造方法
WO2014050226A1 (ja) 酸性ガス分離用複合体の製造方法、酸性ガス分離用複合体、及び酸性ガス分離モジュール
KR20180057630A (ko) 복합 반투막
JP6573650B2 (ja) ガス分離方法
KR102503547B1 (ko) 중공사막 코팅용 조성물, 이로부터 제조된 복합중공사막, 이의 제조방법 및 이를 포함하는 이산화탄소 분리막
WO2021132218A1 (ja) ガス分離膜、ガス分離膜エレメント及びガス製造方法
JP2021186762A (ja) ガス分離膜、ガス分離膜エレメント及びガス製造方法
JP2021186763A (ja) ガス分離膜、ガス分離膜エレメント及びガス製造方法

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
WD01 Invention patent application deemed withdrawn after publication

Application publication date: 20110824

WD01 Invention patent application deemed withdrawn after publication