CN105873666B - 具有高酸含量和低偶氮含量的复合聚酰胺膜 - Google Patents
具有高酸含量和低偶氮含量的复合聚酰胺膜 Download PDFInfo
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- CN105873666B CN105873666B CN201480071410.3A CN201480071410A CN105873666B CN 105873666 B CN105873666 B CN 105873666B CN 201480071410 A CN201480071410 A CN 201480071410A CN 105873666 B CN105873666 B CN 105873666B
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- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01D67/0081—After-treatment of organic or inorganic membranes
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- 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
- B01D67/0081—After-treatment of organic or inorganic membranes
- B01D67/0093—Chemical modification
- B01D67/00931—Chemical modification by introduction of specific groups after membrane formation, e.g. by grafting
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01D67/0081—After-treatment of organic or inorganic membranes
- B01D67/0093—Chemical modification
- B01D67/00933—Chemical modification by addition of a layer chemically bonded to the membrane
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01D69/12—Composite membranes; Ultra-thin membranes
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- B01D69/1251—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction by interfacial polymerisation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01D—SEPARATION
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- B01D2323/40—Details relating to membrane preparation in-situ membrane formation
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Health & Medical Sciences (AREA)
- Transplantation (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Polyamides (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
一种薄膜复合聚酰胺膜，其包含多孔载体和薄膜聚酰胺层，所述膜的特征为具有：i)如热解气相色谱法所测量，0.30％到0.80％偶氮(‑N＝N‑)含量；以及ii)如RBS在pH 9.5下所测量，至少0.18mol/kg的解离羧酸根含量。
Description
技术领域
本发明大体上涉及复合聚酰胺膜以及其制造和使用方法。
背景技术
复合聚酰胺膜用于各种流体分离中。常见的一类膜包括用“薄膜”聚酰胺层涂布的多孔载体。此类膜通常被称为薄膜复合材料(TFC)。薄膜层可通过多官能胺(例如间苯二胺)单体与多官能酰基卤(例如均苯三甲酰氯)单体之间的界面缩聚反应来形成，所述单体依次由不可混溶的溶液涂布在载体上，参见例如卡多特(Cadotte)的US 4277344。卡多特的US4812270和US 4888116描述了此类膜用磷酸或亚硝酸后处理。(又见US2014/0231338、US2013/0256215、US2013/0126419、US2012/0305473、US2012/0261332和US2012/0248027)。US2013/0237946、US2013/0287944、US2013/0287945、WO2013/048765和WO2013/103666描述了包括羧酸及胺反应性官能团的各种单体的添加与如米克尔斯(Mickols)的US 6878278中所述的磷酸三烃酯化合物的添加组合。不断地搜索单体、添加剂和后处理的新颖组合，从而进一步提高聚酰胺膜性能。
发明内容
本发明包括一种薄膜复合聚酰胺膜，其包含多孔载体和薄膜聚酰胺层，所述膜的特征为具有：
i)如热解气相色谱法所测量，0.30％到0.80％偶氮(-N＝N-)含量；以及
ii)如RBS在pH 9.5下所测量，至少0.18mol/kg的解离羧酸根含量。描述了包括此类膜的应用在内的许多实施例。
具体实施方式
本发明不受复合膜或应用的特定类型、构造或形状的特定限制。举例来说，本发明适用于多种应用中所用的平板、管状和中空纤维聚酰胺膜，包括正向渗透(FO)、反向渗透(RO)、纳米过滤(NF)、超滤(UF)、微滤(MF)和压力延迟流体分离。然而，本发明特别适用于被设计用于RO和NF分离的膜。RO复合膜相对不可渗透几乎全部的溶解盐并且通常阻挡超过约95％的单价离子盐，如氯化钠。RO复合膜也通常阻挡超过约95％的无机分子以及分子量大于约100道尔顿的有机分子。NF复合膜比RO复合膜可渗透并且通常阻挡小于约95％的单价离子盐，同时阻挡超过约50％(并且常常超过90％)的二价离子盐，这取决于二价离子的种类。NF复合膜也通常阻挡在纳米范围内的粒子以及分子量大于约200到500道尔顿(AMU)的有机分子。
复合聚酰胺膜的实例包括平板复合膜，所述复合膜包含非编织背衬网(例如PET纱布)的底层(背面)、典型厚度为约25μm到125μm的多孔载体的中间层以及包含厚度通常小于约1微米(例如0.01微米到1微米，但更通常为约0.01μm到0.1μm)的薄膜聚酰胺层的顶层(正面)。多孔载体通常是具有一定孔径的聚合材料，其孔径具有足以准许渗透物基本上不受限制地通过的尺寸，但并未大到足以干扰上面形成的薄膜聚酰胺层的桥接。举例来说，载体的孔径优选在约0.001到0.5μm范围内。多孔载体的非限制性实例包括由以下制成的多孔载体：聚砜、聚醚砜、聚酰亚胺、聚酰胺、聚醚酰亚胺、聚丙烯腈、聚(甲基丙烯酸甲酯)、聚乙烯、聚丙烯和各种卤化聚合物(如聚偏二氟乙烯)。对于RO和NF应用来说，多孔载体提供强度，但由于其相对较高的孔隙度而几乎无流体流动阻力。
由于其相对较薄，所以聚酰胺层常常依据其在多孔载体上的涂布覆盖率或负载量加以描述，例如每平方米多孔载体表面积约2到5000mg聚酰胺并且更优选约50到500mg/m2。如在US 4277344和US 6878278中所描述，聚酰胺层优选通过在多孔载体表面上多官能胺单体与多官能酰基卤单体之间的界面缩聚反应来制备。更确切地说，聚酰胺膜层可通过在多孔载体的至少一个表面上使多官能胺单体与多官能酰基卤单体(其中每个术语意指使用单一物质或多个物质)界面聚合而制备。如本文所用，术语“聚酰胺”是指酰胺键(-C(O)NH-)沿着分子链存在的聚合物。多官能胺和多官能酰基卤单体最常借助于涂布步骤由溶液施用到多孔载体，其中所述多官能胺单体通常由水基或极性溶液涂布并且所述多官能酰基卤由有机基或非极性溶液涂布。尽管涂布步骤无需遵循特定顺序，但多官能胺单体优选地首先涂布在多孔载体上，接着涂布多官能酰基卤。涂布可通过喷雾、涂膜、辊涂或通过使用浸渍罐连同其它涂布技术一起实现。过量溶液可通过气刀、干燥器、烘箱等从载体去除。
多官能胺单体包含至少两个伯胺基团并且可为芳香族(例如间苯二胺(mPD)、对苯二胺、1，3，5-三氨基苯、1，3，4-三氨基苯、3，5-二氨基苯甲酸、2，4-二氨基甲苯、2，4-二氨基苯甲醚和二甲苯二胺)或脂族(例如乙二胺、丙二胺、环己烷-1，3-二胺和三(2-二氨基乙基)胺)。一种特别优选的多官能胺是间苯二胺(mPD)。多官能胺单体可呈极性溶液形式施加到多孔载体。极性溶液可含有约0.1重量％到约10重量％并且更优选约1重量％到约6重量％的多官能胺单体。在一组实施例中，极性溶液包括至少2.5重量％(例如2.5重量％到6重量％)的多官能胺单体。涂布在多孔载体上之后，可去除过量溶液。
多官能酰基卤单体包含至少两个酰基卤基团并且优选无羧酸官能团，并且可由非极性溶剂涂布，但多官能酰基卤可替代地由气相传递(例如，对于具有足够蒸气压的多官能酰基卤)。多官能酰基卤不受特别限制并且可使用芳香族或脂环族多官能酰基卤以及其组合。芳香族多官能酰基卤的非限制性实例包括：均苯三甲酰基氯、对苯二甲酸酰基氯、间苯二甲酸酰基氯、联苯二甲酸酰基氯和萘二甲酸二氯化物。脂环族多官能酰基卤的非限制性实例包括：环丙烷三甲酸酰基氯、环丁烷四甲酸酰基氯、环戊烷三甲酸酰基氯、环戊烷四甲酸酰基氯、环己烷三甲酸酰基氯、四氢呋喃四甲酸酰基氯、环戊烷二甲酸酰基氯、环丁烷二甲酸酰基氯、环己烷二甲酸酰基氯和四氢呋喃二甲酸酰基氯。一种优选的多官能酰基卤为均苯三甲酰基氯(TMC)。多官能酰基卤可呈约0.01重量％到10重量％、优选地0.05重量％到3重量％的范围溶解于非极性溶剂中，并且可作为连续涂布操作的一部分传递。在多官能胺单体浓度小于3重量％的一组实施例中，多官能酰基卤小于0.3wt％。适合溶剂为能够溶解多官能酰基卤并且与水不可混溶的溶剂；例如烷烃(例如己烷、环己烷、庚烷、辛烷、十二烷)、异烷烃(例如ISOPARTML)、芳香族化合物(例如SolvessoTM芳族流体、VarsolTM非脱芳香族流体、苯、烷基化苯(例如甲苯、二甲苯、三甲苯异构体、二乙苯))和卤化烃(例如FREONTM系列、氯苯、二氯苯和三氯苯)或其混合物。优选的溶剂包括对臭氧层几乎不造成威胁并且在闪点和可燃性方面安全到足以在不采用特殊防护措施的情况下进行常规加工的溶剂。一种优选溶剂为可购自埃克森化学公司(Exxon Chemical Company)的ISOPARTM。非极性溶液可包括额外成分，包括共溶剂、相转移剂、增溶剂、络合剂以及除酸剂，其中个别添加剂可提供多个功能。代表性共溶剂包括：苯、甲苯、二甲苯、均三甲苯、乙苯、二乙二醇二甲醚、环己酮、乙酸乙酯、丁基卡必醇TM乙酸酯(butyl carbitolTM acetate)、月桂酸甲酯和丙酮。代表性除酸剂包括N，N-二异丙基乙胺(DIEA)。非极性溶液还可包括少量水或其它极性添加剂，但浓度优选低于其在非极性溶液中的溶解度极限。
极性和非极性溶液中的一者或两者另外包括如由式I表示的磷酸三烃酯化合物。
式(I)：
其中“P”为磷，“O”为氧并且R1、R2和R3独立地选自氢和包含1到10个碳原子的烃基，其限制条件为R1、R2和R3中至多一者为氢。R1、R2和R3优选独立地选自脂肪族基和芳香族基。适用的脂肪族基包括分支与未分支种类，例如甲基、乙基、丙基、异丙基、丁基、异丁基、戊基、2-戊基、3-戊基。适用的环状基团包括环戊基和环己基。适用的芳香族基包括苯基和萘基。环状基团和芳香族基可借助于例如甲基、乙基等脂肪族键联基团键联到磷原子。以上提及的脂肪族和芳香族基团可以是未被取代或被取代的(例如被甲基、乙基、丙基、羟基、酰胺、醚、砜、羰基、酯、氰化物、腈、异氰酸酯、氨基甲酸酯、β-羟基酯等取代)；然而，具有3到10个碳原子的未被取代的烷基是优选的。磷酸三烃酯化合物的特定实例包括：磷酸三乙酯、磷酸三丙酯、磷酸三丁酯、磷酸三戊酯、磷酸三己酯、磷酸三苯酯、磷酸丙酯联苯酯、磷酸二丁酯苯酯、磷酸丁酯二乙酯、磷酸氢二丁酯、磷酸氢丁酯庚酯和磷酸丁酯庚酯己酯。所选特定化合物应在其施加之溶液中至少部分可溶。此类化合物的其它实例在US 6878278、US6723241、US 6562266和US 6337018中描述。
当组合在非极性溶液内时，溶液优选包括0.001重量％到10重量％并且更佳0.01重量％到1重量％的磷酸三烃酯化合物。在另一个实施例中，非极性溶液包括与多官能酰基卤单体呈1∶5到5∶1并且更优选1∶1到3∶1摩尔(化学计量)比的磷酸三烃酯化合物。当组合在非极性溶液内时，溶液优选包括0.001重量％到10重量％并且更佳0.1到1重量％的磷酸三烃酯化合物。添加到极性相中的一种优选物质包括磷酸三乙酯。
在一子组优选的实施例中，非极性溶液进一步包含含酸单体，所述含酸单体包含被至少一个羧酸官能团或其盐和至少一个选自酰基卤、磺酰基卤和酸酐的胺反应性官能团取代的C2-C20烃部分，其中所述含酸单体与所述多官能酰基卤单体不同。在一组实施例中，含酸单体包含芳烃部分。非限制性实例包括以上提及的包括两个到三个酰基卤基团的多官能酰基卤单体的单水解和二水解对应物以及包括至少四个胺反应性部分的多官能卤化物单体的单水解、二水解和三水解对应物。一种优选的物质包括3，5-双(氯羰基)苯甲酸(即单水解均苯三甲酰氯或“mhTMC”)。单体的其它实例描述于WO 2012/102942和WO 2012/102943中(参见式III，其中所述胺反应性基团(“Z”)选自酰基卤、磺酰基卤和酸酐)。包括芳烃部分和单个胺反应性基团的特定物质包括：3-羧基苯甲酰氯、4-羧基苯甲酰氯、4-羧基邻苯二甲酸酐和5-羧基邻苯二甲酸酐和其盐。其它实例由式II表示：
式(II)：
其中A选自：氧(例如-O-)；胺基(-N(R)-)，其中R选自具有1到6个碳原子的烃基，例如被取代或未被取代的芳基、环烷基、烷基，但优选是具有或不具有如卤素和羧基等取代基的具有1到3个碳原子的烷基；酰胺(-C(O)N(R)-)，其碳或氮连接到芳环上并且其中R如先前所定义；羰基(-C(O)-)；磺酰基(-SO2-)；或不存在(例如，如在式III中所表示)；n是1到6的整数，或整个基团是芳基；Z是选自酰基卤、磺酰基卤和酸酐(优选地，酰基卤)的胺反应性官能团；Z′选自由Z所描述的官能团以及氢和羧酸。Z和Z′可独立地位于环上A取代基的间位或邻位。在一组实施例中，n是1或2。在又一组实施例中，Z和Z′均相同(例如均是酰基卤基团)。在另一组实施例中，A选自具有1到3个碳原子的烷基和烷氧基。非限制性代表性物质包括：2-(3，5-双(氯羰基)苯氧基)乙酸、3-(3，5-双(氯羰基)苯基)丙酸、2-((1，3-二氧代-1，3-二氢异苯并呋喃-5-基)氧基)乙酸、3-(1，3-二氧代-1，3-二氢异苯并呋喃-5-基)丙酸、2-(3-(氯羰基)苯氧基)乙酸、3-(3-(氯羰基)苯基)丙酸、3-((3，5双(氯羰基)苯基)磺酰基)丙酸、3-((3-(氯羰基)苯基)磺酰基)丙酸、3-((1，3-二氧代-1，3-二氢异苯并呋喃-5-基)磺酰基)丙酸、3-((1，3-二氧代-1，3-二氢异苯并呋喃-5-基)氨基)丙酸、3-((1，3-二氧代-1，3-二氢异苯并呋喃-5-基)(乙基)氨基)丙酸、3-((3，5-双(氯羰基)苯基)氨基)丙酸、3-((3，5-双(氯羰基)苯基)(乙基)氨基)丙酸、4-(4-(氯羰基)苯基)-4-氧代丁酸、4-(3，5-双(氯羰基)苯基)-4-氧代丁酸、4-(1，3-二氧代-1，3-二氢异苯并呋喃-5-基)-4-氧代丁酸、2-(3，5-双(氯羰基)苯基)乙酸、2-(2，4-双(氯羰基)苯氧基)乙酸、4-((3，5-双(氯羰基)苯基)氨基)-4-氧代丁酸、2-((3，5-双(氯羰基)苯基)氨基)乙酸、2-(N-(3，5-双(氯羰基)苯基)乙酰胺基)乙酸、2，2′-((3，5-双(氯羰基)苯基氮烷二基)二乙酸、N-[(1，3-二氢-1，3-二氧代-5-异苯并呋喃基)羰基]-甘胺酸、4-[[(1，3-二氢-1，3-二氧代-5-异苯并呋喃基)羰基]氨基]-苯甲酸、1，3-二氢-1，3-二氧代-4-异苯并呋喃丙酸、5-[[(1，3-二氢-1，3-二氧代-5-异苯并呋喃基)羰基]氨基]-1，3-苯二甲酸和3-[(1，3-二氢-1，3-二氧代-5-异苯并呋喃基)磺酰基]-苯甲酸。另一实施例由式III表示。
式(III)：
其中羧酸基可位于苯环上的间位、对位或邻位。
烃部分为脂肪族基的代表性实例由式IV表示。
式(IV)：
其中X为卤素(优选是氯)并且n是1到20的整数，优选是2到10。代表性物质包括：4-(氯羰基)丁酸、5-(氯羰基)戊酸、6-(氯羰基)己酸、7-(氯羰基)庚酸、8-(氯羰基)辛酸、9-(氯羰基)壬酸、10-(氯羰基)癸酸、11-氯-11-氧代十一酸、12-氯-12-氧代十二酸、3-(氯羰基)环丁烷甲酸、3-(氯羰基)环戊烷甲酸、2，4-双(氯羰基)环戊烷甲酸、3，5-双(氯羰基)环己烷甲酸和4-(氯羰基)环己烷甲酸。虽然酰基卤和羧酸基团显示在末端位置，但一者或两者可位于沿着脂肪族链的替代位置。虽然式(IV)中未显示，但含酸单体可包括其它羧酸和酰基卤基团。
含酸单体的代表性实例包括至少一个酸酐基团和至少一个羧酸基团，包括：3，5-双(((丁氧基羰基)氧基)羰基)苯甲酸、1，3-二氧代-1，3-二氢异苯并呋喃-5-甲酸、3-(((丁氧基羰基)氧基)羰基)苯甲酸和4-(((丁氧基羰基)氧基)羰基)苯甲酸。
含酸单体的上限浓度范围可受其在非极性溶液内的溶解性限制并且取决于磷酸三烃酯化合物的浓度，即磷酸三烃酯化合物被认为充当含酸单体在非极性溶剂内的增溶剂。在大部分实施例中，浓度上限小于1重量％。在一组实施例中，含酸单体以至少0.01重量％、0.02重量％、0.03重量％、0.04重量％、0.05重量％、0.06重量％、0.07重量％、0.08重量％、0.1重量％或甚至0.13重量％的浓度提供于非极性溶液中，同时保持在溶液中可溶。在另一组实施例中，非极性溶液包含0.01重量％到1重量％、0.02重量％到1重量％、0.04重量％到1重量％或0.05重量％到1重量％的含酸单体。在多官能胺与酰基卤单体之间的界面聚合期间包括含酸单体产生性能改进的膜。并且，与在薄膜聚酰胺层表面上可能进行的水解后反应不同，认为在界面聚合期间包括含酸单体产生在整个薄膜层中有益地改性的聚合物结构。
一旦彼此接触，多官能酰基卤单体和多官能胺单体即在其表面界面处反应，形成聚酰胺层或膜。此层常常称为聚酰胺“辨别层”或“薄膜层”，给复合膜提供了其用于使溶质(例如盐)与溶剂(例如水性进料)分离的主要构件。多官能酰基卤和多官能胺单体的反应时间可小于一秒，但是接触时间通常介于约1秒到60秒范围内。可通过用水冲洗膜并且接着在例如约40℃到约120℃的高温下干燥实现过量溶剂的去除，不过可使用在环境温度下的空气干燥。然而，出于本发明的目的，优选地不使膜干燥，仅用水冲洗(例如浸渍)并且任选地储存在湿润状态中。一旦形成，使聚酰胺层暴露于亚硝酸。多种技术描述于US 4888116中并且US 4888116以引用的方式并入本文中。相信亚硝酸与聚酰胺辨别层中存在的残余伯胺基团反应，形成重氮盐基团。这些重氮盐基团的至少一部分水解形成酚基或经由重氮偶合而偶氮交联。尽管水溶液可包括亚硝酸，但是其优选包括当场形成亚硝酸的试剂，例如含碱金属亚硝酸盐的酸溶液或亚硝酰硫酸。由于亚硝酸是挥发性的并且易分解，所以其优选地通过含碱金属亚硝酸盐的酸性溶液与聚酰胺辨别层接触的反应而形成。一股来说，如果水溶液的pH值小于约7(优选地小于约5)，那么碱金属亚硝酸盐将反应，释放亚硝酸。亚硝酸钠在水溶液中与盐酸或硫酸反应是形成亚硝酸尤其优选的。水溶液可另外包括湿润剂或表面活性剂。亚硝酸在水溶液中的浓度优选地是0.01重量％到1重量％。一股来说，亚硝酸在5℃下比在20℃下可溶性更高，并且略微较高浓度的亚硝酸可在较低温度下操作。只要膜不受有害影响并且可以安全地操纵溶液，较高浓度是可操作的。一股来说，亚硝酸浓度高于约二分之一(0.5)百分比由于操纵这些溶液困难而并非优选的。优选地，亚硝酸由于其在大气压下的有限溶解度而以约0.1重量百分比或更小的浓度存在。膜接触时的温度可在宽范围变化。由于亚硝酸并非特别稳定，所以一股需要使用在约0℃到约30℃范围内的接触温度，其中在0℃到约20℃范围内的温度是优选的。高于这一范围的温度会增加处理溶液上方通风或超大气压的需要。低于优选范围的温度一股导致反应速率和扩散速率降低。
一旦亚硝酸已经扩散到膜中，亚硝酸与伯胺基团之间的反应将相对快速地发生。扩散和发生所要反应所需的时间将取决于亚硝酸的浓度、膜的任意预湿润、存在的伯胺基团的浓度和发生接触时的温度。接触时间可在数分钟到数天的范围内变化。对于特定膜和处理来说，可容易地凭经验确定最优反应时间。
一种优选的应用技术涉及使亚硝酸水溶液以连续流经过膜表面。这允许使用相对低浓度的亚硝酸。当亚硝酸从处理介质耗尽时，其可补充并且使介质再循环到膜表面以进行额外处理。分批处理也是可操作的。用于施用亚硝酸水溶液的特定技术不受特别限制并且包括喷雾、涂膜、辊涂或通过使用浸渍罐连同其它施用技术。一旦进行处理，膜可用水洗涤并且在使用前湿润或干燥储存。对于RO和NF应用来说，当使用NaCl水溶液(250ppm)在25℃和70psi下测试时，用亚硝酸处理的膜优选具有至少2％的NaCl阻挡率。
下文提供说明聚酰胺用亚硝酸处理的代表性反应流程。
标的膜的薄膜聚酰胺层优选具有低于0.80％、0.75％、0.70％和在一些实施例中低于0.65％的偶氮含量(-N＝N-)。在其它实施例中，薄膜层具有0.30％至0.80％或更优选0.40％至0.75％偶氮含量。如本文所用，术语「偶氮含量」係指由-N＝N-基团偶合的两种芳香族化合物产生的重氮盐偶合(重氮偶合和偶氮偶合)的量。芳香族胺经亚硝酸或更强无机酸处理所产生的重氮阳离子可作为亲电试剂参与亲电芳香族取代反应。亲电反应中心为与苯胺或苯酚的偶合反应中-N＝N+基团的末端氮。结果，两种芳香族化合物由-N＝N-基团偶合。所得反应称为重氮盐偶合，其中上文说明一种代表性反应流程。裂解气相色谱法是优选用于测量薄膜聚酰胺层的偶氮含量的技术。举例来说，薄膜聚酰胺层的偶氮含量可通过使用安装在安捷伦(Agilent)6890GC上的前线实验室(Frontier Lab)2020iD热解器测定，所述6890GC具有来自安捷伦的30m×0.32mm 10μm MolsievePLOT，连接于热导率检测器(TCD)。重铬酸铵(NH4Cr2O7)用作校准标准，其在600℃下热降解时产生一摩尔的N2。标准校准溶液通过将约10mg NH4Cr2O7溶解在10mL水中来制备。为了制备校准溶液，将2μL、3μL、4μL和5μL的标准溶液沉积到样品杯中并且线性最小平方程序用于发展响应因子。在标准品上的热解在600℃下执行6秒。将复合聚酰胺膜的背衬层和聚砜层去除(剥离)并且将200μg范围内的所得膜称量至样品杯中并且使用单脉冲方式在550℃下热解6秒。样品重量用于确定从膜释放的N2的重量％，其对应于膜中偶氮(-N＝N-)键的重量％。关于气相色谱法条件，柱维持在1.8mL/min恒定流速的氦气下，喷射器分流比为30∶1，在280℃下。烘箱程序经设定，在38℃下1分钟，以每分钟25℃，从38℃到200℃。TCD维持在150℃下，参考流量为14mL/min并且组合流量为7mL/min。此方法用于测定在实例部分中所描述的样品的偶氮含量。
在一个优选实施例中，薄膜聚酰胺层的特征在于如通过卢瑟福背散射(Rutherford Backscattering，RBS)测量技术所测量，在pH 9.5下每千克聚酰胺的解离羧酸根含量为至少0.18摩尔、0.20摩尔、0.3摩尔、0.4摩尔并且在一些实施例中至少0.45摩尔。在其它实施例中，薄膜层的解离羧酸根含量低于0.50摩尔/千克，例如0.18到0.50摩尔/千克。借助于RBS技术的具体实例，样品膜(1英寸×6英寸)在去离子水(800mL)中煮沸30分钟，接着放置在甲醇和水的50/50w/w溶液(800mL)中浸泡过夜。然后，将这些膜的1英寸×1英寸大小的样品浸没在pH值调节到9.5的20mL 1×10-4M AgNO3溶液中30分钟。用胶带缠绕含有银离子的容器以限制曝光。在用银离子溶液浸泡后，通过将膜浸泡在2个干净的20mL等分试样的无水甲醇中各5分钟来去除未结合的银。最后，使膜在氮气氛围中干燥最少30分钟。将膜样品安装在导热并导电的双面胶带上，然后安装到充当散热片的硅晶片。胶带优选是固美丽导热双面胶(Chromerics Thermattach)T410或3M铜胶带。RBS测量结果是使用范德格拉夫加速器(Van de Graff accelerator)(马萨诸塞州伯林顿的高电压工程公司(High Voltage Engineering Corp.，Burlington，MA))；直径3mm、入射角22.5°、出射角52.5°、散射角150°和40毫微安(nAmp)射束电流的2MeV He+室温射束而获得。将膜样品安装到在测量期间不断移动的可移动样品台上。此移动使得离子通量保持在3×1014He+/cm2下。使用市售模拟程序对从RBS获得的光谱进行分析。关于其用于由RO/NF膜的RBS分析推导元素组成的用途的描述是由康奈尔(Coronell)等人《膜科学杂志(J.of MembraneSci.)》2006，282，71-81和《环境科学与技术(Environmental Science&Technology)》2008，42(14)，5260-5266描述。可使用模拟程序获得数据以拟合两层系统(厚聚砜层在薄聚酰胺层下方)，并且拟合三层系统(聚砜、聚酰胺和表面涂层)可使用相同方法。首先通过XPS测量两层(在添加聚酰胺层之前的聚砜和最终TFC聚酰胺层的表面)的原子分数组成以提供拟合值的界限。由于XPS无法测量氢，所以使用聚合物的建议分子式的H/C比，聚砜使用0.667并且聚酰胺使用0.60-0.67的范围。虽然用硝酸银滴定的聚酰胺仅仅引入少量的银，但是银的散射横截面基本上高于其它低原子数元素(C、H、N、O、S)并且峰的大小相对于其它值不成比例地大，尽管是以低得多的浓度存在，因此提供了优良的敏感性。在中使用两层建模方法，通过固定聚砜的组成并且拟合银峰值，同时保持聚酰胺层(层2，使用XPS预先确定范围)的窄窗组成来确定银的浓度。由模拟确定聚酰胺层中元素(碳、氢、氮、氧和银)的摩尔浓度。银浓度是在测试条件pH值下可用于结合银的羧酸根摩尔浓度的直接反映。每单位面积膜的羧酸基团的摩尔数指示通过物质穿过膜可见的相互作用的数目，并且较大数目将因此有利地影响盐通过。此值可通过测量得到的羧酸根含量乘以测量得到的厚度并且乘以聚酰胺密度计算得到。或者，每单位面积膜的羧酸根数目(mol/m2)可通过测量已知面积内的全部络合金属的方法更直接地测定。使用乙酸铀酰和甲苯胺蓝O染料的方法描述于提拉费瑞(Tiraferri)等人，《膜科学杂志(Journal of MembraneScience)》，2012，389，499-508中。通过聚合物灰化测定膜中络合阳离子(钠或钾)含量的方法描述于(谢伟(Wei Xie)等人，《聚合物(Polymer)》，第53卷，第7期，2012年3月22日，第1581-1592页)中。在pH 9.5下测定薄膜聚酰胺膜的每单位面积膜的解离羧酸根数目的一种优选方法如下。膜样品在去离子水中煮沸30分钟，接着放置在甲醇的50重量％水溶液中浸泡过夜。然后，将膜样品浸没在pH值用NaOH调节到9.5的1×10-4M AgNO3溶液中30分钟。在银离子溶液中浸泡之后，通过将膜浸泡在无水甲醇中30分钟两次而去除未结合的银。每单位面积的银的量优选地如魏(Wei)所述通过灰化并且再溶解用于进行ICP测量来测定。在pH9.5下每平方米膜的解离羧酸根数目优选大于6×10-5、8×10-5、1×10-4、1.2×10-4、1.5×10-4、2×10-4或甚至3×10-4mol/m2。
在本发明的另一个实施例中，薄膜聚酰胺层优选具有如IR所测定，等于或大于0.13、0.15或0.16的羧酸官能团与酰胺基团(-COOH∶(-C(O)NH-))的比率。用于测定此比率的一种优选方法首先通过将聚酰胺层与首先从背板剥离的多孔载体分离而进行。然后剥离的膜浸没在适合于溶解多孔载体的溶剂(例如二甲基甲酰胺)中。在溶解多孔载体之后，不溶的聚酰胺通过过滤收集，用二甲基甲酰胺洗涤4次，用DI水洗涤3次并且用甲醇洗涤3次，然后在真空烘箱中在50℃下干燥20小时。剥离的聚酰胺层的红外光谱可用珀金埃尔默(Perkin Elmer)Spectrum One FT-IR和通用ATR抽样附件在4cm-1的标称分辨率下并扫描16次(约90秒的采集时间)来采集。通用ATR抽样附件优选配备有单反射金刚石/ZnSe晶体。测得羧酸峰高度在1706cm-1处，单点基线在1765cm-1处。测得酰胺峰高度在1656cm-1处，单点基线在1765cm-1处。该方法用于分析在实例部分中描述的样品。
在本发明的另一个实施例中，薄膜聚酰胺层优选具有至少0.13、0.18、0.19或甚至0.20的苯酚胺官能团与间苯二胺基团的比率。优选范围为0.13至0.30。根据前线实验室制造商条件，使用安装在安捷伦6890GC上的前线实验室2020iD热解器进行优选的热解方法。使用火焰离子化检测器(FID)检测峰面积。使用能够测量到0.001mg的梅特勒(Mettler)E20微天平将膜样品称量到前线实验室二氧化硅内衬的不锈钢杯中。样品重量目标为200μg+/-50μg。热解通过以单脉冲方式将样品杯放入设定在650℃下的热解烘箱中6秒来进行。使用来自瓦里安(Varian)的具有1μm 5％苯基甲基硅酮内相柱的30M X 0.25mm id进行分离(法科图福(FactorFour)VF-5MS CP8946)。气相色谱条件如下：安捷伦6890GC(SN：CN10605069)，使用30M×0.25mm、1μm 5％二甲基聚硅氧烷相(瓦里安法科图福VF-5MSCP8946)。注射端口320℃，检测端口：320℃，50∶1的分流注射器流动比率，GC烘箱条件：以每分钟5℃，40℃到110℃，以每分钟20℃，110℃到320℃，320℃下10分钟；氦气载气，0.6mL/min(17cm/sec)的恒定流速，提供8.0psi的背压。检测器气流：H2在40mL/min下，空气在400mL/min下，He补气在30mL/min下。
当在制备薄膜聚酰胺层中包括羧酸单体与磷酸三烃酯时，相信所得聚合物比对照膜更柔软(即更空)。当些类型的膜进行后处理时，所得重氮化胺和胺基苯酚基团(由重氮化胺水解产生)足够接近以便促进偶氮偶合的机率比后处理的对照膜低得多。因此，相比于对照膜，根据本发明的一个实施例制备的膜具有更低的偶氮含量和更高的胺基苯酚与mPD比率。为了使羧酸基团(由膜中并入羧酸单体产生)促进唐南排斥(Donnan exclusion)(即减少NaCl通过)，相信聚合物结构的结构空旷性必不可少。降低的偶氮含量和对应更高的胺基苯酚含量表明在重氮化之后维持聚合物结构的空旷性。结果，标的膜降低NaCl通过并且在一些情况下增加通量。
薄膜聚酰胺层可任选地在其表面的至少一部分上包括吸湿聚合物。此类聚合物包括聚合物表面活性剂、聚丙烯酸、聚乙酸乙烯酯、聚氧化烯化合物、聚(噁唑啉)化合物、聚丙烯酰胺和如US 6280853、US 7815987、US 7918349和US 7905361中概述的相关反应产物。在一些实施例中，此类聚合物可掺合和/或反应并且可由常见溶液涂布或以其它方式施加到聚酰胺膜或依次施用。
已经描述了本发明的多个实施例并且在一些情况下已将某些实施例、选择、范围、成分或其它特征表征为“优选的”。“优选”特征的表征决不应解释为将这类特征视为对本发明来说所需的、必需的或至关重要的。
实例
实例1：使用中试规模的膜制造线制备样品膜。聚砜载体是由16.5重量％于二甲基甲酰胺(DMF)中的溶液浇铸并且随后浸没在间苯二胺(mPD)水溶液中。接着所得载体以恒定速度拉出反应台，同时施加一层薄的均一的非极性涂布溶液。非极性涂布溶液包括异烷烃溶剂(ISOPAR L)和均苯三甲酰氯(TMC)。在所选样品中，非极性涂布溶液进一步包括以与TMC 1∶1.5化学计量比提供的磷酸三丁酯(TBP)，并且在其它样品中TBP与0.03wt/vol％1-羧基-3，5-双(氯羰基)苯甲酸(mh-TMC)。去除过量非极性溶液并且使所得复合膜通过水冲洗槽和干燥烘箱。然后将样品膜薄片(i)储存于去离子水中直到测试为止；或(ii)通过在5℃-15℃下通过组合0.05％w/v NaNO2和0.1w/v％HCl而制备的溶液中浸没约15分钟来进行“后处理”，并且其后在室温下进行冲洗并储存于去离子水中直到测试为止。在室温、pH 8和150psi下，使用2000ppm NaCl溶液进行测试。平均通量以GFD表示。如表3中概述的测试结果所示，与类似的对照膜相比，使用三烃基化合物和羧酸单体产生的样品的后处理意外地提高通量。
表1(用于制备样品薄膜聚酰胺层的组分混合物)
| 单体含量 | 系列1-1 | 系列1-2 | 系列1-3 | 系列1-4 | 系列1-5 |
| mPD(wt/vol％) | 2.5 | 3.5 | 3.5 | 3.5 | 4.5 |
| TMC(wt/vol％)* | 0.15 | 0.15 | 0.19 | 0.23 | 0.15 |
*除其中TMC含量降低0.03wt/vol％并且包括0.03wt/vol％mh-TMC的系列“e”和“f”外。
表2
表3
进行亚硝酸后处理的样品设计成具有星号(*)。
实例2：除了mh-TMC替换为变化量的单水解异酞酰基氯(mh IPC)以外，样品膜以与实例1相同的方式制备和测试，并且对于所有操作，mPD都保持恒定在3.5重量％下并且总酰氯保持恒定在0.2wt/vol％下。结果概括于表4中。
表4：
Claims (7)
1.一种薄膜复合聚酰胺膜，其包含多孔载体和薄膜聚酰胺层，所述膜的特征为具有∶
i)如热解气相色谱法，使用重铬酸铵作为校准标准并在550℃下使所述聚酰胺层热解6秒所测量，0.30重量％到0.80重量％偶氮(-N＝N-)含量；
ii)如RBS在pH9.5下所测量，至少0.18mol/kg聚酰胺的解离羧酸根含量；以及
iii)通过热解气相色谱法(GC)在650℃下6秒所测定，至少0.19的胺基苯酚/间苯二胺比率。
2.根据权利要求1所述的膜，其中所述薄膜聚酰胺层的特征进一步在于具有0.40重量％到0.75重量％的偶氮含量。
3.根据权利要求1所述的膜，其中所述薄膜聚酰胺层的特征进一步在于具有如ATR IR所测量，等于或大于0.14的COOH/酰胺比率。
4.根据权利要求1所述的膜，其中所述薄膜聚酰胺层的特征进一步在于具有如ATR IR所测量，等于或大于0.15的COOH/酰胺比率。
5.根据权利要求1所述的膜，其中所述薄膜聚酰胺层的特征进一步在于具有如ATR IR所测量，等于或大于0.16的COOH/酰胺比率。
6.根据权利要求1所述的膜，其中所述薄膜聚酰胺层的特征进一步为具有至少0.20的胺基苯酚/间苯二胺比率。
7.根据权利要求1所述的膜，其中所述薄膜聚酰胺层的特征进一步在于具有：
i)0.40重量％到0.75重量％的偶氮含量；
ii)至少0.30mol/kg聚酰胺的解离羧酸根含量；
ⅲ)等于或大于0.14的COOH/酰胺比率；以及
iv)至少0.19的胺基苯酚/间苯二胺比率。
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| US8999449B2 (en) | 2013-03-27 | 2015-04-07 | Dow Global Technologies Llc | Composite polyamide membrane derived from aromatic monomer including anhydride and sulfonyl halide functional groups |
| US9808769B2 (en) | 2013-12-02 | 2017-11-07 | Dow Global Technologies Llc | Composite polyamide membrane post treated with nitrious acid |
| CN106170333B (zh) | 2013-12-02 | 2019-02-15 | 陶氏环球技术有限责任公司 | 用二羟基芳基化合物和亚硝酸处理的复合聚酰胺膜 |
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| WO2015105632A1 (en) | 2014-01-07 | 2015-07-16 | Dow Global Technologies Llc | Separation of hydrocarbons from aqueous mixture using fouling resistant reverse osmosis membrane |
| CA2935685A1 (en) | 2014-01-07 | 2015-07-16 | Dow Global Technologies Llc | Desalination of aqueous mixture containing nano-sized particles using fouling resistant reverse osmosis membrane |
| US9555378B2 (en) | 2014-01-09 | 2017-01-31 | Dow Global Technologies Llc | Composite polyamide membrane having preferred azo content |
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| WO2015105639A1 (en) | 2014-01-13 | 2015-07-16 | Dow Global Technologies Llc | Highly swellable composite polyamide membrane |
| AU2015259613B2 (en) | 2014-05-14 | 2019-07-04 | Dow Global Technologies Llc | Composite polyamide membrane post treated with nitrous acid |
| JP6654576B2 (ja) | 2014-05-14 | 2020-02-26 | ダウ グローバル テクノロジーズ エルエルシー | 亜硝酸で後処理される複合ポリアミド膜 |
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2014
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- 2014-12-15 CN CN201480071410.3A patent/CN105873666B/zh active Active
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| US4888116A (en) * | 1987-01-15 | 1989-12-19 | The Dow Chemical Company | Method of improving membrane properties via reaction of diazonium compounds or precursors |
| CN102665881A (zh) * | 2009-12-24 | 2012-09-12 | 东丽株式会社 | 复合半透膜及其制造方法 |
| WO2013048765A1 (en) * | 2011-09-29 | 2013-04-04 | Dow Global Technologies Llc | Composite polyamide membrane derived from carboxylic acid containing acyl halide monomer |
Also Published As
| Publication number | Publication date |
|---|---|
| US20160317980A1 (en) | 2016-11-03 |
| CN105873666A (zh) | 2016-08-17 |
| EP3092061A1 (en) | 2016-11-16 |
| JP6612758B2 (ja) | 2019-11-27 |
| KR102289354B1 (ko) | 2021-08-12 |
| WO2015105637A1 (en) | 2015-07-16 |
| JP2017503646A (ja) | 2017-02-02 |
| KR20160106081A (ko) | 2016-09-09 |
| EP3092061B1 (en) | 2020-02-05 |
| ES2786928T3 (es) | 2020-10-14 |
| US9616392B2 (en) | 2017-04-11 |
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