CN106916251B - 聚合物及其制备方法 - Google Patents
聚合物及其制备方法 Download PDFInfo
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- CN106916251B CN106916251B CN201610078291.5A CN201610078291A CN106916251B CN 106916251 B CN106916251 B CN 106916251B CN 201610078291 A CN201610078291 A CN 201610078291A CN 106916251 B CN106916251 B CN 106916251B
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- 229920000642 polymer Polymers 0.000 title claims abstract description 69
- 238000004519 manufacturing process Methods 0.000 title description 4
- 238000002360 preparation method Methods 0.000 claims abstract description 27
- 239000001257 hydrogen Substances 0.000 claims abstract description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 15
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims abstract description 9
- 230000003252 repetitive effect Effects 0.000 claims description 55
- 239000000203 mixture Substances 0.000 claims description 18
- 239000000178 monomer Substances 0.000 claims description 16
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 14
- -1 cyclopenta Chemical group 0.000 claims description 14
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 10
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 10
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 10
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 10
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 10
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 10
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 9
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 8
- 238000006116 polymerization reaction Methods 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims 4
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims 4
- 150000002431 hydrogen Chemical group 0.000 claims 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 abstract description 4
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 abstract 2
- 238000006243 chemical reaction Methods 0.000 description 28
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 24
- 239000003011 anion exchange membrane Substances 0.000 description 22
- 150000001875 compounds Chemical class 0.000 description 12
- 239000002904 solvent Substances 0.000 description 12
- 229940125898 compound 5 Drugs 0.000 description 11
- 239000003431 cross linking reagent Substances 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 8
- 229940113088 dimethylacetamide Drugs 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 150000001768 cations Chemical class 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 7
- 229940125782 compound 2 Drugs 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 229920002521 macromolecule Polymers 0.000 description 6
- 238000005160 1H NMR spectroscopy Methods 0.000 description 5
- 238000005481 NMR spectroscopy Methods 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 230000008676 import Effects 0.000 description 5
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 5
- 125000003010 ionic group Chemical group 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 230000003595 spectral effect Effects 0.000 description 5
- 239000007858 starting material Substances 0.000 description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 4
- OKJPEAGHQZHRQV-UHFFFAOYSA-N Triiodomethane Natural products IC(I)I OKJPEAGHQZHRQV-UHFFFAOYSA-N 0.000 description 4
- 239000013557 residual solvent Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 125000005439 maleimidyl group Chemical group C1(C=CC(N1*)=O)=O 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 3
- 239000005518 polymer electrolyte Substances 0.000 description 3
- 229940125904 compound 1 Drugs 0.000 description 2
- 229940126214 compound 3 Drugs 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000005194 fractionation Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 238000007152 ring opening metathesis polymerisation reaction Methods 0.000 description 2
- 229910000104 sodium hydride Inorganic materials 0.000 description 2
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 1
- XLXCHZCQTCBUOX-UHFFFAOYSA-N 1-prop-2-enylimidazole Chemical compound C=CCN1C=CN=C1 XLXCHZCQTCBUOX-UHFFFAOYSA-N 0.000 description 1
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000003851 azoles Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 238000010382 chemical cross-linking Methods 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000000909 electrodialysis Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- JQOAQUXIUNVRQW-UHFFFAOYSA-N hexane Chemical compound CCCCCC.CCCCCC JQOAQUXIUNVRQW-UHFFFAOYSA-N 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 239000003014 ion exchange membrane Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
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- C07D233/58—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring nitrogen atoms
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Abstract
本发明公开了一种聚合物及其制备方法。该聚合物包含一第一重复单元及一第二重复单元，其中该第一重复单元是该第二重复单元是其中R+是 A‑是F‑、Cl‑、Br‑、I‑、OH‑、HCO3 ‑、HSO4 ‑、SbF6 ‑、BF4 ‑、H2PO4 ‑、H2PO3 ‑或H2PO2 ‑；X是i及j独立地为0或1‑6的整数，Y是为‑O‑、‑S‑、‑CH2‑或‑NH‑；R1独立地为C1‑8的烷基；以及，R2及R3独立地为氢或C1‑8的烷基。
Description
技术领域
本发明涉及一种聚合物及其制备方法。
背景技术
离子交换膜目前被广泛应用于电透析提纯、燃料电池以及其它电镀及食品工业中。
离子交换膜具有与构成膜本体的聚合物材料连接的带负电荷或正电荷的基团，可在电势或化学势下输送阳离子或阴离子。阳离子交换膜具有固定的负电荷和移动的正电荷离子。同样地，阴离子交换膜则具有固定的带正电荷的基团和移动的带负电荷的阴离子。离子交换膜的性质受固定的离子基团的数量、类型和分布控制。然而，传统作为阴离子交换膜的高分子材料，由于溶解度、机械强度及溶剂选择性较差，并不适用于离子交换膜燃料电池中。
发明内容
根据本发明一实施例，本发明提供一种聚合物，包含一第一重复单元及一第二重复单元，其中该第一重复单元是该第二重复单元是其中R+是 A-可为F-、Cl-、Br-、I-、OH-、HCO3 -、HSO4 -、SbF6 -、BF4 -、H2PO4 -、H2PO3 -或H2PO2 -；X是i及j可独立地为0或1-6的整数，Y可为-O-、-S-、-CH2-或-NH-；R1可独立地为C1-8的烷基；以及，R2及R3可独立地为氢或C1-8的烷基。
根据本发明其他实施例，本发明提供上述聚合物的制备方法，包含：对一组合物进行聚合反应。其中，该组合物包含具有式(I)的第一单体以及具有式(II)的第二单体
式(I)式(II)，其中R+可为 A-可为F-、Cl-、Br-、I-、OH-、HCO3 -、HSO4 -、SbF6 -、BF4 -、H2PO4 -、H2PO3 -或H2PO2 -；X可为i及j可独立地为0或1-6的整数，Y可为-O-、-S-、-CH2-或-NH-；R1可独立地为C1-8的烷基；以及，R2及R3可独立地为氢或C1-8的烷基。
具体实施方式
为让本发明的上述和其他目的、特征和优点能更明显易懂，下文特举出较佳实施例，作详细说明：
以下提供多个不同的实施例，以提供本发明的不同特征。当然，这些实施例仅为范例，而不用以限制本发明。本发明中所述的“一”表示“至少一”。
本发明提供一种聚合物及其制备方法。本发明所述聚合物可为一含阳离子基团(例如高稳定性环状共轭阳离子基团)及非离子基团(例如长键烷基)的聚合物。在聚合物的设计上，为增加聚合物的导电性，本发明所述聚合物导入具有阳离子基团的重复单元。此外，为避免聚合物因为具有阳离子基团的重复单元导致在溶剂中的可溶性下降，本发明所述聚合物进一步导入具有非离子基团的重复单元。根据本发明实施例，本发明所述的聚合物除了在溶剂中具有较高的溶解度外，亦具有改善的机械强度以及增加的溶剂选择性。
根据本发明一实施例，本发明所述聚合物包含一第一重复单元及一第二重复单元。该第一重复单元可为其中R+是 (例如： )或(例如： )；A-可为F-、Cl-、Br-、I-、OH-、HCO3 -、HSO4 -、SbF6 -、BF4 -、H2PO4 -、H2PO3 -或H2PO2 -；X是i及j可独立地为0或1-6的整数，Y可为-O-、-S-、-CH2-或-NH-；以及，R2及R3可独立地为氢或C1-8的烷基(例如：甲基(methyl)、乙基(ethyl)、丙基(propyl)、异丙基(isopropyl)、正丁基(n-butyl)、仲丁基(sec-butyl)、异丁基(isobutyl)、叔丁基(tert-butyl)、戊基(pentyl)、己基(hexyl)、环己基(cyclohexyl)、环戊基(cyclopentyl)、庚基(heptyl)或辛基(octyl))。此外，该第二重复单元可为其中R1独立地为C1-8的烷基(例如：甲基(methyl)、乙基(ethyl)、丙基(propyl)、异丙基(isopropyl)、正丁基(n-butyl)、仲丁基(sec-butyl)、异丁基(isobutyl)、叔丁基(tert-butyl)、戊基(pentyl)、己基(hexyl)、环己基(cyclohexyl)、环戊基(cyclopentyl)、庚基(heptyl)或辛基(octyl))。
根据本发明实施例，该第一重复单元可例如为 其中R+是 (例如：)或(例如：)；A-可为F-、Cl-、Br-、I-、OH-、HCO3 -、HSO4 -、SbF6 -、BF4 -、H2PO4 -、H2PO3 -或H2PO2 -；X是Y可为-O-、-S-、-CH2-或-NH-；i及j可独立地为0或1-6的整数；以及，R2及R3可独立地为氢或C1-8的烷基。
根据本发明实施例，本发明所述聚合物的分子量(例如数均分子量)可介于约100,000至250,000之间。
根据本发明实施例，该第二重复单元可例如为
根据本发明实施例，该聚合物的该第一重复单元与该第二重复单元的数量比例可依所需的聚合物性质来加以调整。举例来说，为增加聚合物的导电性及阴离子的交换能力，可增加聚合物中第一重复单元的数量。另一方面，为增加聚合物的溶解度、机械强度以及溶剂选择性，可增加聚合物中第二重复单元的数量。该第一重复单元与该第二重复单元的数量比例可介于约1∶99至99∶1之间，例如介于约10∶90至90∶10之间、介于约20∶80至80∶20之间或介于30∶70至70∶30之间。
根据本发明实施例，本发明所述的聚合物可更包含一第三重复单元，其中该第三重复单元可为该第一重复单元、第二重复单元或该第三重复单元是以此部份与其他第一重复单元、第二重复单元或该第三重复单元的部份相连。此外，该第一重复单元、第二重复单元或该第三重复单元是以无规则方式重复。举例来说，本发明所述聚合物包含具有结构的基团、具有结构的基团或是具有结构的基团。根据本发明实施例，该聚合物第三重复单元的数量与该第一重复单元及第二重复单元的数量总和的比可介于约0.1∶100至5∶100之间，例如：可介于约0.5∶100至4∶100之间或介于约0.5∶100至3∶100之间。导入该第三重复单元至该聚合物中，可使该聚合物借由结构中的双键可再行交联反应，使其交联度上升，进而提升其机械强度。此外，当第三重复单元的数量过高时，会导致该聚合物交联程度过大，而使得高分子分子量过高，无法回溶于后续加工用的溶剂。
根据本发明实施例，本发明亦提供上述聚合物的制备方法。该聚合物的制备方法包含对一组合物进行聚合反应，例如为开环移位聚合(ring opening metathesispolymerization、ROMP)反应。该组合物可包含具有式(I)的第一单体以及具有式(II)的第二单体
式(I)式(II)
其中，R+是 A-是F-、Cl-、Br-、I-、OH-、HCO3 -、HSO4 -、SbF6 -、BF4 -、H2PO4 -、H2PO3 -或H2PO2 -；X是i及j独立地为0或1-6的整数，Y是-O-、-S-、-CH2-或-NH-；R1独立地为C1-8的烷基；以及，R2及R3独立地为氢或C1-8的烷基。此外，在进行聚合反应时，亦可添加催化剂，例如第一代或第二代格拉布斯(Grubb’s)催化剂。
根据本发明实施例，该第一单体可例如为 其中，R+可为 A-可为F-、Cl-、Br-、I-、OH-、HCO3 -、HSO4 -、SbF6 -、BF4 -、H2PO4 -、H2PO3 -或H2PO2 -；X是i及j独立地为0或1-6的整数，Y是-O-、-S-、-CH2-或-NH-；以及，R2及R3独立地为氢或C1-8的烷基(例如：甲基(methyl)、乙基(ethyl)、丙基(propyl)、异丙基(isopropyl)、正丁基(n-butyl)、仲丁基(sec-butyl)、异丁基(isobutyl)、叔丁基(tert-butyl)、戊基(pentyl)、己基(hexyl)、环己基(cyclohexyl)、环戊基(cyclopentyl)、庚基(heptyl)或辛基(octyl))。此外，该第二单体可例如为
根据本发明实施例，该第一单体与该第二单体的摩尔比可介于约1∶99至99∶1之间，例如介于约10∶90至90∶10之间、介于约20∶80至80∶20之间或介于约30∶70至70∶30之间。
此外，根据本申请的实施例，上述组合物更包含一第三单体，其中该第三单体可为且该第三单体与该第一单体及第二单体的总和的摩尔比介于约0.1∶100至5∶100之间，例如：可介于约0.5∶100至4∶100之间或介于约0.5∶100至3∶100之间。
根据本发明的实施例，本发明所述聚合物可进一步应用于制备一离子交换膜。该离子交换膜的制备方法可包含以下步骤：首先提供一组合物，该组合物包含上述聚合物以及一交联剂。此外，该组合物亦可包含一溶剂，使得该组合物的固含量介于约5wt％至50wt％之间。在该组合物中，该交联剂可具有一重量百分比介于约1wt％至30wt％之间(例如：介于约5wt％至30wt％之间或介于约5wt％至25wt％之间)，以该聚合物的总重为基准。接着，对该组合物进行混合及分散，将该组合物涂布于一基材(如玻璃基板)上形成一涂层薄膜，在高温下进行烘烤以除去大部分的溶剂后，再于高温烘箱内烘烤，除去剩余的残存溶剂。最后，将所得膜层依序以氢氧化钾水溶液与去离子水分别在室温下浸泡1-3小时。烘干后，得到本发明所述的离子交换膜。
上述交联剂可为具有至少二个马来酰亚胺官能团的化合物。举例来说，该交联剂可为具有二个马来酰亚胺官能团的化合物。根据本发明实施例，该具有二个马来酰亚胺官能团的化合物可为其中Z可为 其中Y1为单键、-O-、-S-、-CH2-或-NH-，R4独立地为氢或C1-4的烷基；以及，n≥1、x介于1至12之间、y和z独立地地介于1至5之间。举例来说，该交联剂可为
此外，根据本发明实施例，上述交联剂亦可为具有至少二个马来酰亚胺官能团的高分子型交联剂。该高分子型交联剂是起始物(a)与起始物(b)的反应产物，起始物(a)是其中Z为 R4独立地为氢或C1-4的烷基；以及，n≥1、x介于1至12之间、y和z独立地介于1至5之间；以及，该起始物(b)具有式(III)或式(IV)所示的化合物
式(III)式(IV)，其中R5为氢或C1-4的烷基，以及R6为氢或C1-4的烷基。该起始物(b)可例如为该高分子型交联剂可与该聚合物形成具化学交联的互穿结构，强化该离子交换膜的机械强度及尺寸稳定性。
以下借由下列实施例来说明本发明所述的聚合物的制备方法，用以进一步阐明本发明的技术特征。
具有阳离子基团的单体的制备
制备例1
将10mL的双环戊二烯(dicyclopentadiene)(0.074mmol)及20.15mL的1-烯丙基咪唑(1-allylimidazole)(0.186mmol)加入一高压反应瓶中。在180℃下搅拌八小时后，以减压分馏纯化及管柱层析法纯化(以乙酸乙酯(EA)及己烷(hexane)作为冲提液(乙酸乙酯∶己烷＝9∶1))，得到化合物1(无色透明黏稠液体)。上述反应的反应式如下所示：
利用核磁共振光谱分析化合物1，所得的光谱信息如下：1H NMR(300MHz，CDCl3)：δ7.46(d，J＝15.3，1H)，6.98(m，2H)，6.12(m，2H)，3.79(m，2H)，2.66(m，3H)，1.89(m，1H)，1.33(m，2H)，0.62(m，1H)。
接着，将0.5g的化合物1(2.87mmol)及0.268mL的碘甲烷(methyl iodide)(4.30mmol)加入一反应瓶中。在室温下搅拌八小时后，抽干多余的碘甲烷，得到化合物2(黄色黏稠液体)。上述反应的反应式如下所示：
利用核磁共振光谱分析化合物2，所得的光谱信息如下：1H NMR(300MHz，CDCl3)：δ10.03(d，J＝12.0Hz，1H)，7.42(m，2H)，6.21(m，2H)，4.19(m，5H)，2.74(m，3H)，1.99(m，1H)，1.41(m，2H)，0.67(m，1H)。
制备例2
将15mL的二甲基甲酰胺(dimethylformamide、DMF)加入一反应瓶中。在0℃下，将1.7g的氢化钠(NaH)(0.00427mol)加入反应瓶中。接着，在0℃下加入2.122g的5-降冰片烯-2-甲醇(5-Norbornene-2-methanol)(0.0171mol)到反应瓶中。充分搅拌后，再加2g的1-甲基-2-氯甲基咪唑(0.0154mol)。搅拌12小时后，加入水进行中和反应后再以二氯甲烷进行萃取。移除溶剂后，经由减压分馏纯化得到化合物3。上述反应的反应式如下所示：
利用核磁共振光谱分析化合物3，所得的光谱信息如下：1H NMR(300MHz，CDCl3)：δ6.90(s，2H)，6.10-5.76(m，2H)，4.59-4.81(m，2H)，3.71(s，3H)，3.51-3.00(m，2H)，2.86-2.69(m，2H)，2.33(m，1H)，1.84-1.66(m，1H)，1.41-1.10(m，2H)，0.47-0.43(m，1H)。
接着，将2g的化合物3(9mmol)溶于二氯甲烷中。接着，加入1mL的碘甲烷(methyliodide)(17mmol)。在室温下搅拌12小时后，抽干多余的碘甲烷及溶剂，得到化合物4(黄色黏稠液体)。上述反应的反应式如下所示：
利用核磁共振光谱分析化合物4，所得的光谱信息如下：1H NMR(300MHz，CDCl3)：δ7.45(s，2H)，6.18-5.84(m，2H)，4.90(s，2H)，3.98(s，6H)，3.68-3.20(m，2H)，2.35(m，1H)，1.86-1.78(m，1H)，1.46-1.14(m，4H)，0.52-0.51(m，1H)。
具有非离子基团的单体的制备
制备例3
将13.4mL的双环戊二烯(dicyclopentadiene)(0.1mmol)及36mL的1-辛烯(1-octene)(0.23mmol)加入一高压反应瓶中。于240℃下搅拌12小时后，以中性氧化铝过滤掉黄色悬浮物。接着，以减压分馏进行纯化，得到化合物5(无色透明黏稠液体)。上述反应的反应式如下所示：
利用核磁共振光谱分析化合物5，所得的光谱信息如下：1H NMR(300MHz，CDCl3)：δ6.08(m，1H，endo)，6.04(m，1H，exo)，5.90(m，1H，endo)，2.67-2.77(m，2H)，2.48(m，1H，exo)，1.97(m，1H，endo)，1.80(m，1H，endo)，1.14-1.38(m，11H)，0.82-0.90(m，3H)，0.43-0.50(m，1H，endo)。
交联剂的制备
制备例4
将2.73g的以及0.37g的加入一反应瓶中，并加入97g二甲基乙酰胺(DMAc)中。充分搅拌后，在100-150℃下反应5-10小时，得到高分子型交联剂(1)。(与摩尔比例为2∶1)。
聚合物的制备
实施例1
在氮气环境下，将3.08g的化合物2(9.74mmole)与0.19g的化合物5(1.08mmole)置于一反应瓶中，并加入30mL的二氯甲烷加以溶解。接着，在30℃下将Grubb’s溶液(9.2mg、溶于6mL的二氯甲烷中)慢慢加入反应瓶中。搅拌4小时后，将所得溶液慢慢加入250mL的乙醚中。搅拌约30分钟后，将溶液移除，并以100mL的丙酮进行清洗，并将固体进行减压干燥，得到聚合物(1)(具有重复单元及重复单元其中重复单元及重复单元的数量比例约为9∶1)。经测量后，该聚合物(1)的数均分子量(Mn)约为110000、分子量分布值(PDI)约为1.4。
实施例2
如实施例1所述的方式进行，除了将化合物2及化合物5的摩尔比由约9∶1调整为约8∶2，得到聚合物(2)(其中重复单元及重复单元的数量比例约为8∶2)。
实施例3
如实施例1所述的方式进行，除了将化合物2及化合物5的摩尔比由约9∶1调整为约7∶3，得到聚合物(3)(其中重复单元及重复单元的数量比例约为7∶3)。
实施例4
如实施例1所述的方式进行，除了将化合物2及化合物5的摩尔比由约9∶1调整为约4∶6，得到聚合物(4)(其中重复单元及重复单元的数量比例约为4∶6)。
实施例5
如实施例1所述的方式进行，除了将化合物2及化合物5的摩尔比由约9∶1调整为约2∶8，得到聚合物(5)(其中重复单元及重复单元的数量比例约为2∶8)。
实施例6
在氮气环境下，将3.53g的化合物4(9.74mmole)与0.19g的化合物5(1.08mmole)置于一反应瓶中，并加入30mL的二氯甲烷加以溶解。接着，在30℃下将Grubb’s溶液(9.2mg、溶于6mL的二氯甲烷中)慢慢加入反应瓶中。搅拌4小时后，将所得溶液慢慢加入250mL的乙醚中。搅拌约30分钟后，将溶液移除，并以100mL的丙酮进行清洗，并将固体进行减压干燥，得到聚合物(6)(具有重复单元及重复单元其中重复单元及重复单元的数量比例约为9∶1)。
实施例7
如实施例6所述的方式进行，除了将化合物4及化合物5的摩尔比由约9∶1调整为约6∶4，得到聚合物(7)(其中重复单元及重复单元的数量比例约为6∶4)。
实施例8
如实施例6所述的方式进行，除了将化合物4及化合物5的摩尔比由约9∶1调整为约3∶7，得到聚合物(8)(其中重复单元及重复单元的数量比例约为3∶7)。
实施例9
在氮气系统下，将3.08g的化合物2(9.74mmole)、0.19g的化合物5(1.08mmole)以及12mg的双环戊二烯(dicyclopentadiene)(0.097mmole)置于一反应瓶中，并加入30mL的二氯甲烷加以溶解。接着，在30℃下将Grubb’s溶液(9.2mg、溶于6mL的二氯甲烷中)慢慢加入反应瓶中。搅拌4小时后，将所得溶液慢慢加入250mL的乙醚中。搅拌约30分钟后，将溶液移除，并以100mL的丙酮进行清洗，并将固体进行减压干燥，得到聚合物(9)(具有重复单元重复单元以及重复单元其中重复单元重复单元及重复单元的数量比例约为9∶1∶0.09)。
阴离子交换膜的制备
实施例10
将100重量份的聚合物(1)(由实施例1所制备)加入一反应瓶中，并加入667重量份的二甲基乙酰胺(dimethylacetamide、DMAc)加以溶解。接着，将10重量份的高分子交联剂(1)(由制备例4所制备)加入反应瓶中。接着，以高速均质机进行混合分散，并进行除泡，得到一溶液。接着，将该溶液以旋转涂布方式涂布于一玻璃基板上，形成一涂层。接着，在40～150℃下进行烘烤以除去大部分的溶剂。接着，再在120～200℃下烘烤1～6小时，以除去剩余的残存溶剂。接着，将所得膜层依序以氢氧化钾水溶液与去离子水各自分别在室温下处理1.5小时，去除残余溶剂。最后，得到阴离子交换膜(1)。测量该阴离子交换膜的离子导电率，结果如表1所示。
实施例11-14
实施例11-14如实施例10所述的方式进行，除了分别将聚合物(1)以聚合物(2)-(5)取代，得到阴离子交换膜(2)-(5)。接着，测量该阴离子交换膜(2)-(5)的离子导电率、尺寸变化率及抗张强度，结果如表1所示。
表1
由表1可知，本发明所述阴离子交换膜，随着离子性重复单元比例的增加，所得的阴离子交换膜也随之具有较高的离子导电率。
实施例15
实施例15如实施例12所述的方式进行，除了将所使用的高分子交联剂(1)由10重量份降低至7重量份，得到阴离子交换膜(6)。接着，测量该阴离子交换膜(6)的抗拉强度及破裂强度，结果如表2所示。抗拉强度及破裂强度测试方法参照ASTM D882进行。
实施例16
实施例16如实施例12所述的方式进行，除了将所使用的高分子交联剂(1)由10重量份增加至20重量份，得到阴离子交换膜(7)。接着，测量该阴离子交换膜(7)的抗拉强度及破裂强度，结果如表2所示。
实施例17
实施例17如实施例12所述的方式进行，除了将所使用的高分子交联剂(1)由10重量份增加至25重量份，得到阴离子交换膜(8)。接着，测量该阴离子交换膜(8)的抗拉强度及破裂强度，结果如表2所示。
表2
由表2可知，随着高分子型交联剂导入量的增加，膜材的机械强度(抗张强度，yield stress)与破裂强度(break stress)亦随之提升。因此，基于表1及表2可得知，本发明所述的离子交换膜具有良好的离子传导能力与机械强度。
实施例18
将100重量份的聚合物(6)(由实施例6所制备)加入一反应瓶中，并加入667重量份的二甲基乙酰胺(dimethylacetamide、DMAc)加以溶解。接着，将10重量份的高分子交联剂(1)(由制备例4所制备)加入反应瓶中。接着，以高速均质机进行混合分散，并进行除泡，得到一溶液。接着，将该溶液以旋转涂布方式涂布于一玻璃基板上，形成一涂层。接着，在40～150℃下进行烘烤以除去大部分的溶剂。接着，再在120～200℃下烘烤1～6小时，以除去剩余的残存溶剂。接着，将所得膜层依序以氢氧化钾水溶液与去离子水各自分别在室温下处理1.5小时，去除残余溶剂。最后，得到阴离子交换膜(9)。测量该阴离子交换膜的离子导电率及尺寸变化率，结果如表3所示。
实施例19-20
实施例19-20如实施例18所述的方式进行，除了分别将聚合物(6)以聚合物(7)及(8)取代，得到阴离子交换膜(10)及(11)。接着，测量该阴离子交换膜(10)及(11)的离子导电率及尺寸变化率，结果如表3所示。
表3
由表3可得知，本发明所述阴离子交换膜，随着离子性重复单元比例的增加，所得的阴离子交换膜也随之具较高之离子导电率。此外，本发明所述的阴离子交换膜亦具有不错的尺寸稳定性。
基于上述内容，本发明所述聚合物除了具有稳定的阳离子基团来增加聚合物的离子传导能力外，亦在聚合物的设计上导入非离子基团，以提高聚合物的溶解度、机械强度以及溶剂选择性。
虽然本发明的实施例及其优点已披露如上，但应该了解的是，任何所属技术领域中具有通常知识者，在不脱离本发明的精神和范围内，当可作更动、替代与润饰。此外，本发明的保护范围并未局限于说明书内所述特定实施例中的工艺、机器、制造、物质组成、装置、方法及步骤，任何所属技术领域中具有通常知识者可从本发明揭示内容中理解现行或未来所发展出的工艺、机器、制造、物质组成、装置、方法及步骤，只要可以在此处所述实施例中实施大抵相同功能或获得大抵相同结果皆可根据本发明使用。因此，本发明的保护范围包括上述工艺、机器、制造、物质组成、装置、方法及步骤。另外，每一申请专利范围构成个别的实施例，且本发明的保护范围也包括各个申请专利范围及实施例的组合。
Claims (12)
1.一种聚合物，其特征在于，其包含一第一重复单元及一第二重复单元，其中该第一重复单元是该第二重复单元是其中该第一重复单元与该第二重复单元的比介于1:99至99:1之间；R+是 A-是F-、Cl-、Br-、I-、OH-、HCO3 -、HSO4 -、SbF6 -、BF4 -、H2PO4 -、H2PO3 -或H2PO2 -；X是i及j独立地为0或1-6的整数，Y是-O-、-S-、-CH2-或-NH-；R1独立地为C1-8的烷基、环己基、或环戊基；以及，R2及R3独立地为氢、或C1-8的烷基、环己基、或环戊基。
2.根据权利要求1所述的聚合物，其特征在于，其中R1是甲基、乙基、丙基、异丙基、正丁基、仲丁基、异丁基、叔丁基、戊基、己基、环己基、环戊基、庚基或辛基。
3.根据权利要求1所述的聚合物，其特征在于，其中R2及R3独立地为氢、甲基、乙基、丙基、异丙基、正丁基、仲丁基、异丁基、叔丁基、戊基、己基、环己基、环戊基、庚基或辛基。
4.根据权利要求1所述的聚合物，其特征在于，其中该第二重复单元是
5.根据权利要求1所述的聚合物，其特征在于，其中该聚合物更包含一第三重复单元，其中该第三重复单元是
6.根据权利要求1所述的聚合物，其特征在于，其中该第三重复单元与该第一重复单元及第二重复单元总和的比介于0.1:100至5:100之间。
7.一种聚合物的制备方法，其特征在于，包含：对一组合物进行聚合反应，其中该组合物包含具有式(I)的第一单体以及具有式(II)的第二单体
其中该第一单体与该第二单体的摩尔比介于1:99至99:1之间；
R+是 A-是F-、Cl-、Br-、I-、OH-、HCO3 -、HSO4 -、SbF6 -、BF4 -、H2PO4 -、H2PO3 -或H2PO2 -；X是i及j独立地为0或1-6的整数，Y是-O-、-S-、-CH2-或-NH-；R1独立地为C1-8的烷基、环己基、或环戊基；以及，R2及R3独立地为氢、或C1-8的烷基、环己基、或环戊基。
8.根据权利要求7所述的聚合物的制备方法，其特征在于，其中R1是甲基、乙基、丙基、异丙基、正丁基、仲丁基、异丁基、叔丁基、戊基、己基、环己基、环戊基、庚基或辛基。
9.根据权利要求7所述的聚合物的制备方法，其特征在于，其中R2及R3独立地为氢、甲基、乙基、丙基、异丙基、正丁基、仲丁基、异丁基、叔丁基、戊基、己基、环己基、环戊基、庚基或辛基。
10.根据权利要求7所述的聚合物的制备方法，其特征在于，其中该第二单体是
11.根据权利要求7所述的聚合物的制备方法，其特征在于，其中该组合物更包含一第三单体，其中该第三单体是
12.根据权利要求11所述的聚合物的制备方法，其特征在于，其中该第三单体与该第一单体及第二单体总和的摩尔比介于0.1:100至5:100之间。
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