CN103842061A - 气体分离膜 - Google Patents
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- 125000006091 1,3-dioxolane group Chemical class 0.000 description 1
- JECYNCQXXKQDJN-UHFFFAOYSA-N 2-(2-methylhexan-2-yloxymethyl)oxirane Chemical compound CCCCC(C)(C)OCC1CO1 JECYNCQXXKQDJN-UHFFFAOYSA-N 0.000 description 1
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- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
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- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
- B01D53/228—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion characterised by specific membranes
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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Abstract
本发明涉及将相对于100mol氧亚甲基单元、氧亚烷基单元为1.5～10mol的聚缩醛作为主要成分的气体分离膜。本发明的气体分离膜的二氧化碳气体分离能以及透过速度高，适宜作为废气中的二氧化碳气体分离膜。
Description
技术领域
本发明涉及以特定的聚缩醛作为主要成分的气体分离膜。
背景技术
对于聚缩醛，优异的机械强度、耐化学试剂性、耐摩耗性等优异，此外成型加工性也良好，因此作为工程塑料、作为机械工业部件、汽车部件、电设备部件、其它产业用制品的成型材料而广泛使用。然而，现状是：其它的热塑性树脂在薄膜领域扩展其用途，而聚缩醛几乎不用作薄膜。作为期待的用途之一，可列举出聚缩醛的气体分离膜，过去，聚缩醛显示出高的相对于N2的CO2、NO2、SO2的分离能(气体透过系数的比)(例如，参照专利文献1、非专利文献1以及2)。
然而，为了在工业上使用，强烈要求进一步的气体分离能的提高、气体透过速度的提高。
现有技术文献
专利文献
专利文献1：日本特公昭64-9042号公报
非专利文献
非专利文献1：The Diffusion of Gases and Water Vapor Through GraftedPolyoxymethylene,Journal of Applied Polymer Science,Vol.14,pp.1949-1959(1970)
非专利文献2：Gaseous Transfer Coefficients in Membranes,SeparationScience,9(6),pp.461-478(1974)
发明内容
发明要解决的问题
本发明的目的在于提供包含CO2分离能以及透过速度高的聚缩醛的气体分离膜。
用于解决问题的方案
本发明人等着眼于聚缩醛的结构与作为气体分离膜的性能进行深入研究，结果，发现通过使用具有特定的结构的聚缩醛从而制成选择性地分离CO2的能力优异的品质良好的气体分离膜，从而完成本发明。
即，本发明如以下所述：
[1]一种气体分离膜，其以聚缩醛作为主要成分，该聚缩醛中，相对于100mol氧亚甲基单元，具有2个以上的碳原子的氧亚烷基单元为1.5～10mol。
[2]根据上述[1]记载的气体分离膜，其特征在于，聚缩醛为由三聚甲醛以及如下化合物得到的共聚物，该化合物为能够与三聚甲醛共聚并能够赋予具有2个以上的碳原子的氧亚烷基单元的化合物。
[3]根据上述[2]记载的气体分离膜，其特征在于，能够与三聚甲醛共聚并能够赋予具有2个以上的碳原子的氧亚烷基单元的化合物为选自环状缩醛、环状醚、乙烯基醚以及烯丙基醚中的至少1种。
[4]根据上述[2]记载的气体分离膜，其特征在于，能够与三聚甲醛共聚并能够赋予具有2个以上的碳原子的氧亚烷基单元的化合物为选自1,3-二氧戊环、1,4-二氧杂环庚烷(1,4-Dioxepan)、烷基缩水甘油醚、乙烯基醚以及烯丙基醚中的至少1种。
[5]根据上述[1]记载的气体分离膜，其特征在于，还含有热塑性树脂。
[6]根据上述[5]记载的气体分离膜，其特征在于，热塑性树脂为聚酯或聚醚树脂。
[7]根据上述[5]记载的气体分离膜，其特征在于，热塑性树脂为选自聚乳酸、聚羟基丁酸、聚甘醇酸、聚二氧戊环、聚乙二醇、聚丙二醇以及聚四亚甲基二醇中的至少1种。
[8]根据上述[5]记载的气体分离膜，其特征在于，相对于100质量份作为主要成分的聚缩醛，含有1～80质量份热塑性树脂。
发明的效果
根据本发明，与以往的高分子气体分离膜相比，能够提供选择性地分离二氧化碳气体(CO2)的能力优异的气体分离膜。本发明的气体分离膜适宜作为特别是从火力发电所、工厂等大量地排出的废气中分离二氧化碳气体的分离膜。
具体实施方式
在本发明的气体分离膜中作为主要成分而使用的聚缩醛为包含氧亚甲基单元和具有2个以上的碳原子的氧亚烷基单元的共聚物，相对于100mol氧亚甲基单元，具有2个以上的碳原子的氧亚烷基单元为1.5～10mol。以下，将所述聚缩醛称为“本发明的聚缩醛”。
作为本发明的聚缩醛中具有2个以上的碳原子的氧亚烷基单元，优选具有2～6个碳原子的氧亚烷基单元、更优选具有2～4个碳原子的氧亚烷基单元、特别优选具有2或3个碳原子的氧亚烷基单元。具有2个以上的碳原子的氧亚烷基单元可以为1种、也可以为2种以上。
本发明的聚缩醛，例如，将1,3,5-三聚甲醛作为单体、而且将能够与1,3,5-三聚甲醛共聚并能够赋予具有2个以上的碳原子的氧亚烷基单元的化合物用作共聚单体，根据需要可以添加三氟化硼等阳离子聚合引发剂，通过本体聚合法而得到。作为那样的共聚单体，例如，可列举出环状缩醛、环状醚、乙烯基醚以及烯丙基醚等。作为环状缩醛，可列举出1,3-二氧戊环、1,4-二氧杂环庚烷以及它们的衍生物，特别优选1,3-二氧戊环。作为环状醚，可列举出环氧乙烷、环氧丙烷等具有2～6个碳原子的环氧烷烃、环氧化合物、缩水甘油醚化合物等，特别优选丁基缩水甘油醚、己基缩水甘油醚那样的具有4～10个的碳原子的烷基缩水甘油醚。乙烯基醚以及烯丙基醚意味着具有乙烯基醚结构(CH2=CH-O-)或烯丙基醚结构(CH2=CH-CH2-O-)的化合物，例如，可列举出单(乙二醇)单烷基醚、二(乙二醇)单烷基醚、三(乙二醇)单烷基醚或聚(乙二醇)单烷基醚的乙烯基醚或烯丙基醚等。从这些共聚单体之中选择1种以上，以具有2个以上碳原子的氧亚烷基单元为规定的范围内的方式导入到聚缩醛中。
本发明的聚缩醛中，在不损害CO2分离能以及透过速度的范围内，也可以导入与氧亚甲基单元以及氧亚烷基单元不同的单元。作为赋予这样的不同的单元的追加的共聚单体，例如，可列举出十甲基硅氧烷那样的环状硅氧烷。
作为本发明的聚缩醛中的共聚单体导入量，将(主要来自三聚甲醛的)氧亚甲基单元设为100mol时，(来自共聚单体的)具有2个以上碳原子的氧亚烷基单元优选为1.5～10mol、特别优选为2～6mol。作为共聚单体，适宜使用1,3-二氧戊环或1,4-二氧杂环庚烷。共聚单体的导入量可以由单体以及共聚单体的投入量或者所得到的共聚物的NMR光谱数据等而算出。
本发明的聚缩醛优选熔体指数处于0.5～50g/10分钟的范围。
本发明的气体分离膜通过使本发明的聚缩醛或将其作为主要成分的组合物薄膜化而得到。所述组合物中，可以配合其它的热塑性树脂，也可以配合少量的抗氧化剂、热稳定剂、其它的必要的添加剂。需要说明的是，本发明中，“作为主要成分”意味着，所述组合物(或者本发明的气体分离膜)至少含有50质量%、优选为60质量%以上的本发明的聚缩醛。
作为所述组合物(或者，本发明的气体分离膜)可以含有的热塑性树脂，若不使气体分离膜的耐热性显著降低，而且不损害本发明的聚缩醛的CO2分离能以及透过速度则没有特别限制，例如，可列举出聚酯以及聚醚树脂等。作为聚酯树脂的例子，可列举出聚乳酸、聚羟基丁酸以及聚甘醇酸等。作为聚醚树脂的例子，可列举出聚二氧戊环、聚乙二醇、聚丙二醇以及聚四亚甲基二醇。作为热塑性树脂，适宜使用聚乳酸和/或聚二氧戊环。相对于100质量份本发明所述的聚缩醛，热塑性树脂的配合量优选为1～80质量份的范围。
本发明的气体分离膜可以从本发明的聚缩醛或将其作为主要成分的组合物由本领域技术人员根据公知的制造方法来制造。例如，作为本发明的气体分离膜，适宜地使用利用热压、熔融挤出成型法将本发明的聚缩醛或将其作为主要成分的组合物薄膜化而成的气体分离膜或者将其单轴或双轴拉伸而成的气体分离膜。
进而，也可以为使本发明的聚缩醛或将其作为主要成分的组合物溶解于恰当的溶剂，进行流延、使其干燥而薄膜化的气体分离膜。作为前述溶剂，可列举出六氟异丙醇、二甲基亚砜、二甲基甲酰胺、二甲基乙酰胺、N-甲基吡咯烷酮、苄醇那样的高沸点溶剂(在高于100℃的温度下溶解)等。
作为本发明的气体分离膜的形状，不限于薄膜，可以以管、中空纤维等公知的形状使用。
以下列举出实施例来说明本发明。需要说明的是，本发明中使用的单体、共聚单体、催化剂、热塑性树脂、溶剂等的任一种均可从试剂供应商处得到或者可以由本领域技术人员根据公知的方法来制备。
<实施例1～12以及比较例1、2>
作为聚合装置，使用在内部具有Z型叶片、可以循环温水的夹套结构的内容积1000cc的台式双轴混炼机，通过间歇式的聚合来实施聚缩醛的制造。
以使夹套循环70℃的温水、卸下盖的状态用热风器将混炼机内部加热干燥之后，安装盖，对体系内进行氮气置换。从原料投入口注入1,3,5-三聚甲醛200g以及下述表1记载的共聚单体的规定量，边高速运转边搅拌，然后添加催化剂量(相对于1mol1,3,5-三聚甲醛为0.04mmol)的三氟化硼乙醚(Borontrifluoride diethyl etherate)，进行20分钟聚合。然后，加入三乙基胺/苯溶液，停止反应，从体系内提取聚缩醛，用混合器进行粉碎，得到聚缩醛粗共聚物。以所得到的聚缩醛粗共聚物中的固体成分率作为收率来计算，结果均为90%以上。
接着，相对于100质量份由上述而得到的聚缩醛粗共聚物，添加0.3质量份三乙二醇-双[3-(3-叔丁基-5-甲基-4-羟基苯基)丙酸酯](BASF公司制造、商品名Irganox245)、0.1质量份三聚氰胺、0.05质量份氢氧化镁以及下述表1中记载的热塑性树脂的规定量，均匀地混合，然后，供给到小型混合器(株式会社东洋精机制作所制造、商品名Labo-Plast Mill)，在220℃下熔融混炼20分钟。对于如此操作而得到的组合物，使用加热到200℃的油压挤压机，制备100微米厚的薄膜，对于CO2以及N2的气体透过速度以及分离能进行评价。
气体透过率的测定(单位：cm3·cm/cm2·s·cmHg)通过基于JIS K7126的压力差法来进行。详细而言，将气相色谱仪作为检测器，使用压力差式气体/蒸汽透过率测定装置(GTR-30XAD、G6800T·F(S))[GTR Tec Corporation·Yanako Technical Science Inc.制造]。试验压力差设为1atm，使用干燥状态的气体。试验温度设为23±2℃、透过面积设为1.52×10-3m2(φ4.4×10-2m)。
在表1中一并表示结果。
表1
<合成例：聚二氧戊环的制造>
在实施例10～12中作为热塑性树脂使用的聚二氧戊环如以下操作来制造。
作为聚合装置使用与聚缩醛的制造同样的装置。
以使夹套循环50℃的温水、卸下盖的状态用热风器将混炼机内部加热干燥之后，安装盖，对体系内进行氮气置换。从原料投入口注入200g1,3-二氧戊环，边以高速搅拌边添加相对于100质量份投入的1,3-二氧戊环为0.003质量份的磷钨酸，进行20分钟聚合。然后，加入三乙基胺/苯溶液停止反应。接着，向混合器添加相对于水：甲醇=4：1(容积比)为1wt%的三乙基胺的溶液，进而投入聚二氧戊环，边混合边使反应完全停止并且去除残存的单体。固体成分过滤后，用丙酮清洗后在常温下使其真空干燥。从所得到的固体成分计算收率，结果为75%。此外，在ASTM-D1238(2.16kg载荷下)下将测定温度变更为100℃，测定熔融指数(MI值)，结果为1.6。
产业上的可利用性
将以规定量包含源自共聚单体的具有2个以上的碳原子的氧亚烷基单元的本发明的聚缩醛作为主要成分的气体分离膜(实施例1～12)与以往的高分子气体分离膜(比较例1、2)相比，为透过速度也高、并且相对于氧气、氮气、尤其是氮气选择性地分离二氧化碳气体(CO2)的能力优异的气体分离膜。因此，期待本发明的气体分离膜用作从火力发电所、工厂等大量排出的废气中分离二氧化碳气体的分离膜。
Claims (8)
1.一种气体分离膜，其以聚缩醛作为主要成分，该聚缩醛中，相对于100mol氧亚甲基单元，具有2个以上的碳原子的氧亚烷基单元为1.5～10mol。
2.根据权利要求1所述的气体分离膜，其特征在于，聚缩醛为由三聚甲醛以及如下化合物得到的共聚物，该化合物为能够与三聚甲醛共聚并能够赋予具有2个以上的碳原子的氧亚烷基单元的化合物。
3.根据权利要求2所述的气体分离膜，其特征在于，能够与三聚甲醛共聚并能够赋予具有2个以上碳原子的氧亚烷基单元的化合物为选自环状缩醛、环状醚、乙烯基醚以及烯丙基醚中的至少1种。
4.根据权利要求2所述的气体分离膜，其特征在于，能够与三聚甲醛共聚并能够赋予具有2个以上的碳原子的氧亚烷基单元的化合物为选自1,3-二氧戊环、1,4-二氧杂环庚烷、烷基缩水甘油醚、乙烯基醚以及烯丙基醚中的至少1种。
5.根据权利要求1所述的气体分离膜，其特征在于，还含有热塑性树脂。
6.根据权利要求5所述的气体分离膜，其特征在于，热塑性树脂为聚酯或聚醚树脂。
7.根据权利要求5所述的气体分离膜，其特征在于，热塑性树脂为选自聚乳酸、聚羟基丁酸、聚甘醇酸、聚二氧戊环、聚乙二醇、聚丙二醇以及聚四亚甲基二醇中的至少1种。
8.根据权利要求4所述的气体分离膜，其特征在于，相对于100质量份作为主要成分的聚缩醛，含有1～80质量份热塑性树脂。
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