CN111841626B - 一类树脂材料负载的聚醚功能化离子液体催化剂及其制备方法 - Google Patents
一类树脂材料负载的聚醚功能化离子液体催化剂及其制备方法 Download PDFInfo
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- 239000002608 ionic liquid Substances 0.000 title claims abstract description 115
- 239000004721 Polyphenylene oxide Substances 0.000 title claims abstract description 93
- 229920000570 polyether Polymers 0.000 title claims abstract description 93
- 239000000463 material Substances 0.000 title claims abstract description 59
- 239000003054 catalyst Substances 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 229920005989 resin Polymers 0.000 title claims description 15
- 239000011347 resin Substances 0.000 title claims description 15
- HBAHZZVIEFRTEY-UHFFFAOYSA-N 2-heptylcyclohex-2-en-1-one Chemical compound CCCCCCCC1=CCCCC1=O HBAHZZVIEFRTEY-UHFFFAOYSA-N 0.000 claims abstract description 84
- 229920001367 Merrifield resin Polymers 0.000 claims abstract description 84
- 238000000034 method Methods 0.000 claims abstract description 10
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 44
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 39
- 239000011734 sodium Substances 0.000 claims description 26
- 239000003446 ligand Substances 0.000 claims description 22
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 239000008367 deionised water Substances 0.000 claims description 16
- 229910021641 deionized water Inorganic materials 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 14
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 12
- 229910052708 sodium Inorganic materials 0.000 claims description 12
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 12
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 9
- 150000007530 organic bases Chemical class 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 8
- 150000001450 anions Chemical class 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 238000005342 ion exchange Methods 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 9
- 238000005470 impregnation Methods 0.000 abstract description 8
- 230000007547 defect Effects 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 abstract description 2
- 239000012528 membrane Substances 0.000 abstract 1
- 238000001816 cooling Methods 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- 238000006555 catalytic reaction Methods 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 239000012876 carrier material Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 238000006352 cycloaddition reaction Methods 0.000 description 1
- 150000002118 epoxides Chemical class 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000007037 hydroformylation reaction Methods 0.000 description 1
- 230000003100 immobilizing effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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Abstract
本发明涉及一类Merrifield树脂材料负载的聚醚功能化离子液体催化剂及其制备方法，具体为通过化学键合法将聚醚功能化的离子液体固载到Merrifield树脂材料表面，由于聚醚功能化离子液体具有较高的分子量，而且醚键具有高的柔性和构象自由度，使得聚醚链能够在材料表面延展，有效形成离子液体膜层，无需再二次物理浸渍离子液体，不但降低了离子液体的用量，也解决了离子液体催化剂易流失的难题，同时制备方法简单，从而克服了现有技术中存在的缺陷，这种新型的Merrifield树脂材料负载的聚醚功能化离子液体催化剂具有应用于催化氢化、氢甲酰化和CO2催化转化反应的潜力。
Description
技术领域
本发明涉及化学化工技术领域，具体地涉及一类树脂材料负载的聚醚功能化离子液体催化剂及其制备方法。
背景技术
近年来，随着对绿色化学的日益重视以及对环境友好溶剂的需求，绿色溶剂离子液体吸引了人们的极大关注。与传统的有机溶剂不同，离子液体具有极低的饱和蒸气压、高的热和化学稳定性、对过渡金属催化剂良好的溶解性以及结构的可设计性等优点，因此应用离子液体作为催化剂载体成为一种分离、回收和循环过渡金属催化剂的有效手段。尽管离子液体用于负载和分离过渡金属催化剂取得了一些成功的应用，但一个难以调和的问题也显现出来，即为了抑制催化剂的流失，通常大量的溶剂离子液体被应用于催化反应中以充分地溶解和固载催化剂，这既不符合绿色化学的要求，也导致了资源的浪费。而且大量溶剂离子液体的应用也使得离子液体中难以除去的微量杂质对金属催化剂产生的负效应(如使催化剂中毒)变得更加显著，导致催化效率的降低。因此，如何环境友好和经济地应用离子液体以构建高效的离子液体催化体系是当前迫切需要解决的难题。
固载化离子液体是近年来出现的一类新型材料，基于固载化离子液体而发展的固载离子液体(相)催化的概念融合了离子液体优良的溶解性和载体材料的高比表面积的优点，不但减少了离子液体的用量，而且提高了催化反应的活性和选择性，是近年来离子液体领域的研究热点之一，并在催化加氢、氢甲酰化、二氧化碳与环氧化物环加成等反应中得到广泛的应用。目前，负载离子液体催化剂的制备方法主要包括：物理浸渍法、化学键合法和化学键合-物理浸渍组合法。
基于物理吸附原理的浸渍法是制备固载化离子液体的常用方法，其优点是简单、方便，但离子液体容易从载体表面流失；化学键合法固载离子液体改善了物理浸渍法的不足，由于离子液体的阳离子或阴离子通过共价键与载体材料表面的活性官能团偶联，离子液体不易从载体表面流失，更有利于催化剂的稳定，延长催化剂的使用寿命，但由于载体表面活性基团的数量有限以及通常负载的均是小分子离子液体，单纯的化学键合法往往难以使离子液体在载体表面有效形成离子液体液膜；化学键合-物理浸渍组合法在一定程度上克服了物理浸渍和化学键合法的不足，降低了离子液体的流失并能够在材料表面有效形成离子液体液膜，但制备步骤繁复，二次浸渍吸附的离子液体仍存在流失问题。
发明内容
针对上述的制备负载离子液体催化剂的三种方法存在的局限性，本发明的目的旨在提供一类树脂材料负载的聚醚功能化离子液体催化剂。
本发明的另一目的旨在提供一种上述的一类树脂材料负载的聚醚功能化离子液体催化剂的制备方法。
本发明的一类Merrifield树脂材料负载的聚醚功能化离子液体催化剂，是在Merrifield树脂材料表面接枝有式1、式2、式3或式4所示的结构：
其中，n＝4–140，R1为C1–C16烷基或苯基；Y为-OMs，-OTs，-OAc，Br-，I-，BF4 -，PF6 -或具有以下结构的磺酸钠型水溶性膦配体阴离子：
式中1，2，3，4，5，6，7、8、9、10和11分别为不同的磺酸钠型水溶性膦配体的母体部分，m是膦配体上磺酸根的总数，m>1；R2为C6H4-3-SO3 -；o＝0，1，2；p＝0，1，2；q＝r＝0，1；s＝t＝0，1。
本发明的一类Merrifield树脂材料负载的聚醚功能化离子液体催化剂，Merrifield树脂材料表面接枝有式1、式2、式3或式4所示的结构：
其中，n＝4–45，R1为C1–C16烷基或苯基；Y为-OMs，-OTs，-OAc，Br-，I-，BF4 -，PF6 -或具有以下结构的磺酸钠型水溶性膦配体阴离子：
式中1，2，3，4，5，6，7、8、9、10和11分别为不同的磺酸钠型水溶性膦配体的母体部分，m是膦配体上磺酸根的总数，m>1；R2为C6H4-3-SO3 -；o＝0，1，2；p＝0，1，2；q＝r＝0，1；s＝t＝0，1。
一类Merrifield树脂材料负载的聚醚功能化离子液体催化剂的制备，在乙腈溶剂中将聚醚功能化的有机碱12、13、14或15键合到Merrifield树脂上，得到式5、式6、式7或式8所示的Merrifield树脂材料负载的聚醚功能化离子液体，然后在去离子水中通过与NamY进行离子交换反应得到式1、式2、式3或式4所示的Merrifield树脂材料负载的聚醚功能化离子液体：
其中，n＝4–140，R1为C1–C16烷基或苯基；当Y为-OMs，-OTs，-OAc，Br-，I-，BF4 -，PF6 -时，l＝1；当Y为具有以下结构的磺酸钠型水溶性膦配体阴离子时，l＝m，m是膦配体上磺酸根的总数，m>1：
式中1，2，3，4，5，6，7、8、9、10和11分别为不同的磺酸钠型水溶性膦配体的母体部分，m是膦配体上磺酸根的总数，m>1；R2为C6H4-3-SO3 -；o＝0，1，2；p＝0，1，2；q＝r＝0，1；s＝t＝0，1。
一类Merrifield树脂材料负载的聚醚功能化离子液体催化剂的制备，在乙腈溶剂中将聚醚功能化的有机碱12、13、14或15键合到Merrifield树脂上，得到式5、式6、式7或式8所示的Merrifield树脂材料负载的聚醚功能化离子液体，然后在去离子水中通过与NamY进行离子交换反应得到式1、式2、式3或式4所示的Merrifield树脂材料负载的聚醚功能化离子液体：
其中，n＝4–45，R1为C1–C16烷基或苯基；当Y为-OMs，-OTs，-OAc，Br-，I-，BF4 -，PF6 -时，l＝1；当Y为具有以下结构的磺酸钠型水溶性膦配体阴离子时，l＝m，m是膦配体上磺酸根的总数，m>1：
式中1，2，3，4，5，6，7、8、9、10和11分别为不同的磺酸钠型水溶性膦配体的母体部分，m是膦配体上磺酸根的总数，m>1；R2为C6H4-3-SO3 -；o＝0，1，2；p＝0，1，2；q＝r＝0，1；s＝t＝0，1。
一类Merrifield树脂材料负载的聚醚功能化离子液体催化剂的制备，将Merrifield树脂在乙腈中室温溶胀12-24h，然后加入聚醚功能化的有机碱，在惰性气氛下，80-100℃条件下反应24-48h，冷却至室温，过滤分离，用乙醇洗涤树脂，并干燥，得到表面接枝聚醚功能化离子液体催化剂的Merrifield树脂材料；将得到的表面接枝聚醚功能化离子液体催化剂的Merrifield树脂材料分散在去离子水中，然后加入NamY，在20-40℃进行离子交换反应24-48h，得到Merrifield树脂材料负载的聚醚功能化离子液体。
本发明的意义在于，通过化学键合法将聚醚功能化的离子液体固载到Merrifield树脂材料表面，由于聚醚功能化离子液体具有较高的分子量，而且醚键具有高的柔性和构象自由度，使得聚醚链能够在材料表面延展，有效形成离子液体膜层，无需再二次物理浸渍离子液体，不但降低了离子液体的用量，也解决了离子液体催化剂易流失的难题，同时制备方法简单，从而克服了现有技术中存在的缺陷。
具体实施方式
以下实施例旨在说明本发明而不是对本发明进一步限定。
实施例1
式5(n＝16；R1＝Ph)接枝聚醚功能化离子液体催化剂的Merrifield树脂材料的制备
将2g Merrifield树脂在15mL乙腈中室温下溶胀12h，然后加入3.6g聚醚功能化的有机碱12(n＝16；R1＝Ph)，在惰性气氛下，80℃条件下反应24h后，冷却至室温，过滤分离，用乙醇洗涤树脂，并干燥，得到表面接枝聚醚功能化离子液体催化剂的Merrifield树脂材料。
实施例2
式6(n＝16；R1＝Ph)接枝聚醚功能化离子液体催化剂的Merrifield树脂材料的制备
将2g Merrifield树脂在15mL乙腈中室温下溶胀12h，然后加入3.6g聚醚功能化的有机碱13(n＝16；R1＝Ph)，在惰性气氛下，80℃条件下反应24h后，冷却至室温，过滤分离，用乙醇洗涤树脂，并干燥，得到表面接枝聚醚功能化离子液体催化剂的Merrifield树脂材料。
实施例3
式7(n＝16；R1＝Ph)接枝聚醚功能化离子液体催化剂的Merrifield树脂材料的制备
将2g Merrifield树脂在15mL乙腈中室温下溶胀12h，然后加入3.8g聚醚功能化的有机碱14(n＝16；R1＝Ph)，在惰性气氛下，80℃条件下反应24h后，冷却至室温，过滤分离，用乙醇洗涤树脂，并干燥，得到表面接枝聚醚功能化离子液体催化剂的Merrifield树脂材料。
实施例4
式8(n＝16；R1＝Ph)接枝聚醚功能化离子液体催化剂的Merrifield树脂材料的制备
将2g Merrifield树脂在15mL乙腈中室温下溶胀12h，然后加入3.9g聚醚功能化的有机碱15(n＝16；R1＝Ph)，在惰性气氛下，80℃条件下反应24h后，冷却至室温，过滤分离，用乙醇洗涤树脂，并干燥，得到表面接枝聚醚功能化离子液体催化剂的Merrifield树脂材料。
实施例5
式6(n＝4；R1＝CH3)接枝聚醚功能化离子液体催化剂的Merrifield树脂材料的制备
将2g Merrifield树脂在15mL乙腈中室温下溶胀12h，然后加入2.2g聚醚功能化的有机碱13(n＝4；R1＝CH3)，在惰性气氛下，80℃条件下反应24h后，冷却至室温，过滤分离，用乙醇洗涤树脂，并干燥，得到表面接枝聚醚功能化离子液体催化剂的Merrifield树脂材料。
实施例6
式6(n＝4；R1＝n-C12H25)接枝聚醚功能化离子液体催化剂的Merrifield树脂材料的制备
将2g Merrifield树脂在15mL乙腈中室温下溶胀12h，然后加入1.7g聚醚功能化的有机碱13(n＝4；R1＝n-C12H25)，在惰性气氛下，80℃条件下反应24h后，冷却至室温，过滤分离，用乙醇洗涤树脂，并干燥，得到表面接枝聚醚功能化离子液体催化剂的Merrifield树脂材料。
实施例7
式6(n＝34；R1＝Ph)接枝聚醚功能化离子液体催化剂的Merrifield树脂材料的制备
将2g Merrifield树脂在15mL乙腈中室温下溶胀12h，然后加入6.9g聚醚功能化的有机碱13(n＝34；R1＝Ph)，在惰性气氛下，80℃条件下反应48h后，冷却至室温，过滤分离，用乙醇洗涤树脂，并干燥，得到表面接枝聚醚功能化离子液体催化剂的Merrifield树脂材料。
实施例8
式2(n＝16；R1＝Ph；X＝Br-)Merrifield树脂负载聚醚功能化离子液体的制备
将实施例2得到的式6(n＝16；R1＝Ph)表面接枝聚醚功能化离子液体催化剂的Merrifield树脂材料分散在20mL去离子水中，然后加入1.3g NaBr，在30℃条件下反应48h，得到式2(n＝16；R1＝Ph；X＝Br-)Merrifield树脂负载聚醚功能化离子液体。
实施例9
式2(n＝16；R1＝Ph；X＝-OMs)Merrifield树脂负载聚醚功能化离子液体的制备
将实施例2得到的式6(n＝16；R1＝Ph)表面接枝聚醚功能化离子液体催化剂的Merrifield树脂材料分散在20mL去离子水中，然后加入1.5g NaOMs，在30℃条件下反应48h，得到式2(n＝16；R1＝Ph；X＝-OMs)Merrifield树脂负载聚醚功能化离子液体。
实施例10
式2(X＝(SO3 -)m-1；l＝m＝3；n＝16；R1＝Ph)Merrifield树脂负载聚醚功能化离子液体的制备
将实施例2得到的式6(n＝16；R1＝Ph)表面接枝聚醚功能化离子液体催化剂的Merrifield树脂材料分散在30mL去离子水中，然后加入7.2g(SO3Na)3-1，在30℃条件下反应48h，得到式2(X＝(SO3 -)m-1；l＝m＝3；n＝16；R1＝Ph)Merrifield树脂负载聚醚功能化离子液体。
实施例11
式2(X＝(SO3 -)m-2；l＝m＝4；o＝p＝0；n＝16；R1＝Ph)Merrifield树脂负载聚醚功能化离子液体的制备
将实施例2得到的式6(n＝16；R1＝Ph)表面接枝聚醚功能化离子液体催化剂的Merrifield树脂材料分散在30mL去离子水中，然后加入7.0g(SO3Na)4-2，在30℃条件下反应48h，得到式2(X＝(SO3 -)m-2；l＝m＝4；o＝p＝0；n＝16；R1＝Ph)Merrifield树脂负载聚醚功能化离子液体。
实施例12
式2(X＝(SO3 -)m-4；l＝m＝2；n＝16；R1＝Ph)Merrifield树脂负载聚醚功能化离子液体的制备
将实施例2得到的式6(n＝16；R1＝Ph)表面接枝聚醚功能化离子液体催化剂的Merrifield树脂材料分散在30mL去离子水中，然后加入7.0g(SO3Na)2-4，在30℃条件下反应48h，得到式2(X＝(SO3 -)m-4；l＝m＝2；n＝16；R1＝Ph)Merrifield树脂负载聚醚功能化离子液体。
实施例13
式2(X＝(SO3 -)m-6；l＝m＝2；o＝2,q＝r＝1,s＝t＝0；n＝16；R1＝Ph)Merrifield树脂负载聚醚功能化离子液体的制备
将实施例2得到的式6(n＝16；R1＝Ph)表面接枝聚醚功能化离子液体催化剂的Merrifield树脂材料分散在40mL去离子水中，然后加入8.2g(SO3Na)2-6，在30℃条件下反应48h，得到式2(X＝(SO3 -)m-6；l＝m＝2；o＝2,q＝r＝1,s＝t＝0；n＝16；R1＝Ph)Merrifield树脂负载聚醚功能化离子液体。
实施例13
式2(X＝(SO3 -)m-8；l＝m＝4；o＝p＝0；n＝16；R1＝Ph)Merrifield树脂负载聚醚功能化离子液体的制备
将实施例2得到的式6(n＝16；R1＝Ph)表面接枝聚醚功能化离子液体催化剂的Merrifield树脂材料分散在50mL去离子水中，然后加入8.4g(SO3Na)4-8，在30℃条件下反应48h，得到式2(X＝(SO3 -)m-8；l＝m＝4；o＝p＝0；n＝16；R1＝Ph)Merrifield树脂负载聚醚功能化离子液体。
实施例14
式2(X＝(SO3 -)m-9；l＝m＝2；o＝p＝2；n＝16；R1＝Ph)Merrifield树脂负载聚醚功能化离子液体的制备
将实施例2得到的式6(n＝16；R1＝Ph)表面接枝聚醚功能化离子液体催化剂的Merrifield树脂材料分散在40mL去离子水中，然后加入6.4g(SO3Na)2-9，在30℃条件下反应48h，得到式2(X＝(SO3 -)m-9；l＝m＝2；o＝p＝2；n＝16；R1＝Ph)Merrifield树脂负载聚醚功能化离子液体。
实施例15
式2(X＝(SO3 -)m-10；l＝m＝2；o＝p＝2；n＝16；R1＝Ph)Merrifield树脂负载聚醚功能化离子液体制备
将实施例2得到的式6(n＝16；R1＝Ph)表面接枝聚醚功能化离子液体催化剂的Merrifield树脂材料分散在40mL去离子水中，然后加入7.2g(SO3Na)2-10，在30℃条件下反应48h，得到式2(X＝(SO3 -)m-10；l＝m＝2；o＝p＝2；n＝16；R1＝Ph)Merrifield树脂负载聚醚功能化离子液体。
实施例16
式2(X＝(SO3 -)m-11；l＝m＝2；o＝p＝2；n＝16；R1＝Ph)Merrifield树脂负载聚醚功能化离子液体制备
将实施例2得到的式6(n＝16；R1＝Ph)表面接枝聚醚功能化离子液体催化剂的Merrifield树脂材料分散在40mL去离子水中，然后加入6.6g(SO3Na)2-11，在30℃条件下反应48h，得到式2(X＝(SO3 -)m-11；l＝m＝2；o＝p＝2；n＝16；R1＝Ph)Merrifield树脂负载聚醚功能化离子液体。
Claims (3)
1.一种Merrifield树脂材料负载的聚醚功能化离子液体催化剂的制备方法，其特征在于，在乙腈溶剂中将聚醚功能化的有机碱12、13、14或15键合到Merrifield树脂上，得到式5、式6、式7或式8所示的Merrifield树脂材料负载的聚醚功能化离子液体，然后在去离子水中通过与NalY进行离子交换反应得到式1、式2、式3或式4所示的Merrifield树脂材料负载的聚醚功能化离子液体催化剂：
其中，n＝4–140，R1为C1–C16烷基或苯基；当Y为-OMs，-OTs，-OAc，Br-，I-，BF4 -，PF6 -时，l＝1；当Y为具有以下结构的磺酸钠型水溶性膦配体阴离子时，l＝m，m是膦配体上磺酸根的总数，m>1：
式中1，2，3，4，5，6，7、8、9、10和11分别为不同的磺酸钠型水溶性膦配体的母体部分，m是膦配体上磺酸根的总数，m>1；R2为C6H4-3-SO3 -；o＝0，1，2；p＝0，1，2；q＝r＝0，1；s＝t＝0，1。
2.根据权利要求1所述的一种Merrifield树脂材料负载的聚醚功能化离子液体催化剂的制备方法，其特征在于，在乙腈溶剂中将聚醚功能化的有机碱12、13、14或15键合到Merrifield树脂上，得到式5、式6、式7或式8所示的Merrifield树脂材料负载的聚醚功能化离子液体，然后在去离子水中通过与NalY进行离子交换反应得到式1、式2、式3或式4所示的Merrifield树脂材料负载的聚醚功能化离子液体催化剂：
其中，n＝4–45，R1为C1–C16烷基或苯基；当Y为-OMs，-OTs，-OAc，Br-，I-，BF4 -，PF6 -时，l＝1；当Y为具有以下结构的磺酸钠型水溶性膦配体阴离子时，l＝m，m是膦配体上磺酸根的总数，m>1：
式中1，2，3，4，5，6，7、8、9、10和11分别为不同的磺酸钠型水溶性膦配体的母体部分，m是膦配体上磺酸根的总数，m>1；R2为C6H4-3-SO3 -；o＝0，1，2；p＝0，1，2；q＝r＝0，1；s＝t＝0，1。
3.根据权利要求1或2所述的一种Merrifield树脂材料负载的聚醚功能化离子液体催化剂的制备方法，其特征在于，将Merrifield树脂在乙腈中室温溶胀12-24h，然后加入聚醚功能化的有机碱，在惰性气氛下，80-100℃条件下反应24-48h，冷却至室温，过滤分离，用乙醇洗涤树脂，并干燥，得到表面接枝聚醚功能化离子液体的Merrifield树脂材料；将得到的表面接枝聚醚功能化离子液体的Merrifield树脂材料分散在去离子水中，然后加入NalY，在20-40℃进行离子交换反应24-48h，得到Merrifield树脂材料负载的聚醚功能化离子液体催化剂。
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6723798B1 (en) * | 2000-08-28 | 2004-04-20 | Korean Research Institute Of Chemical Technology | Resins having vinyl ether linker for the solid phase organic synthesis |
| WO2007048943A1 (fr) * | 2005-10-28 | 2007-05-03 | Novalyst Discovery | Systeme catalytique heterogene et son utilisation |
| CN103483381A (zh) * | 2013-08-22 | 2014-01-01 | 青岛科技大学 | 一类膦功能化离子液体的制备及其在氢甲酰化反应中的应用 |
| CN103521147A (zh) * | 2013-09-30 | 2014-01-22 | 苏州国环环境检测有限公司 | 树脂负载咪唑基离子液体磁性微球的制备方法 |
| CN105017315A (zh) * | 2015-04-02 | 2015-11-04 | 青岛科技大学 | 一类膦功能化聚醚咪唑盐离子液体及其在烯烃氢甲酰化反应中的应用 |
-
2020
- 2020-06-12 CN CN202010535745.3A patent/CN111841626B/zh active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6723798B1 (en) * | 2000-08-28 | 2004-04-20 | Korean Research Institute Of Chemical Technology | Resins having vinyl ether linker for the solid phase organic synthesis |
| WO2007048943A1 (fr) * | 2005-10-28 | 2007-05-03 | Novalyst Discovery | Systeme catalytique heterogene et son utilisation |
| CN103483381A (zh) * | 2013-08-22 | 2014-01-01 | 青岛科技大学 | 一类膦功能化离子液体的制备及其在氢甲酰化反应中的应用 |
| CN103521147A (zh) * | 2013-09-30 | 2014-01-22 | 苏州国环环境检测有限公司 | 树脂负载咪唑基离子液体磁性微球的制备方法 |
| CN105017315A (zh) * | 2015-04-02 | 2015-11-04 | 青岛科技大学 | 一类膦功能化聚醚咪唑盐离子液体及其在烯烃氢甲酰化反应中的应用 |
Non-Patent Citations (1)
| Title |
|---|
| 固定化离子液体在有机合成中的应用;锅小龙 等;《化学通报》;20161231;第79卷(第1期);摘要、第18页右栏第2.4节高分子材料部分 * |
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