CN107987107B - 钌卡宾催化剂及其催化的降冰片烯开环易位聚合反应 - Google Patents
钌卡宾催化剂及其催化的降冰片烯开环易位聚合反应 Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 82
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 title claims abstract description 47
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 title claims abstract description 43
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 title claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 title claims description 57
- 229910052707 ruthenium Inorganic materials 0.000 title claims description 13
- 238000007152 ring opening metathesis polymerisation reaction Methods 0.000 title abstract description 13
- 239000003446 ligand Substances 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 22
- 230000003197 catalytic effect Effects 0.000 claims abstract description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical group O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 42
- 238000005865 alkene metathesis reaction Methods 0.000 claims description 33
- 239000002904 solvent Substances 0.000 claims description 31
- 239000012327 Ruthenium complex Substances 0.000 claims description 23
- 238000003756 stirring Methods 0.000 claims description 23
- 239000002243 precursor Substances 0.000 claims description 19
- 229920000642 polymer Polymers 0.000 claims description 17
- 238000006116 polymerization reaction Methods 0.000 claims description 16
- 239000007787 solid Substances 0.000 claims description 16
- 229910052736 halogen Chemical class 0.000 claims description 15
- 150000002367 halogens Chemical class 0.000 claims description 15
- 238000001914 filtration Methods 0.000 claims description 14
- 150000001336 alkenes Chemical group 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 11
- 125000003118 aryl group Chemical group 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 11
- 238000002360 preparation method Methods 0.000 claims description 11
- 125000003545 alkoxy group Chemical group 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 9
- CSDSSGBPEUDDEE-UHFFFAOYSA-N 2-formylpyridine Chemical class O=CC1=CC=CC=N1 CSDSSGBPEUDDEE-UHFFFAOYSA-N 0.000 claims description 8
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 8
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical group [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 150000002431 hydrogen Chemical class 0.000 claims description 8
- -1 nitro, amino Chemical group 0.000 claims description 8
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 8
- 150000002081 enamines Chemical group 0.000 claims description 7
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 6
- 239000012295 chemical reaction liquid Substances 0.000 claims description 6
- 238000001953 recrystallisation Methods 0.000 claims description 6
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 5
- 238000005649 metathesis reaction Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 238000006555 catalytic reaction Methods 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 4
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 4
- 239000003153 chemical reaction reagent Substances 0.000 claims description 3
- 150000002576 ketones Chemical class 0.000 claims description 3
- 125000005245 nitryl group Chemical group [N+](=O)([O-])* 0.000 claims description 3
- 238000005580 one pot reaction Methods 0.000 claims description 3
- 239000012044 organic layer Substances 0.000 claims description 3
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims description 3
- HLPAQSMZFXUGMU-UHFFFAOYSA-N [Ru]CC1=CC=CC=C1 Chemical group [Ru]CC1=CC=CC=C1 HLPAQSMZFXUGMU-UHFFFAOYSA-N 0.000 claims description 2
- 150000001298 alcohols Chemical class 0.000 claims description 2
- 239000003849 aromatic solvent Substances 0.000 claims description 2
- 238000009835 boiling Methods 0.000 claims description 2
- 150000002170 ethers Chemical class 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 125000003367 polycyclic group Chemical group 0.000 claims description 2
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims 1
- 229920000636 poly(norbornene) polymer Polymers 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- ADLVDYMTBOSDFE-UHFFFAOYSA-N 5-chloro-6-nitroisoindole-1,3-dione Chemical compound C1=C(Cl)C([N+](=O)[O-])=CC2=C1C(=O)NC2=O ADLVDYMTBOSDFE-UHFFFAOYSA-N 0.000 abstract 1
- 238000001308 synthesis method Methods 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 14
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 6
- 238000002425 crystallisation Methods 0.000 description 6
- 230000008025 crystallization Effects 0.000 description 6
- 239000012265 solid product Substances 0.000 description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 5
- 229910052731 fluorine Inorganic materials 0.000 description 5
- 239000011737 fluorine Substances 0.000 description 5
- 239000008096 xylene Substances 0.000 description 5
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000012074 organic phase Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 125000001153 fluoro group Chemical group F* 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- DHOZGVQOZATZGP-UHFFFAOYSA-N 3-methylpent-4-en-1-amine Chemical compound C=CC(C)CCN DHOZGVQOZATZGP-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000008098 formaldehyde solution Substances 0.000 description 2
- FICBXRYQMBKLJJ-UHFFFAOYSA-N hex-5-en-1-amine Chemical compound NCCCCC=C FICBXRYQMBKLJJ-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 2
- JDYVLWWFVYNMTN-UHFFFAOYSA-N 3-methylpyridine-2-carbaldehyde Chemical compound CC1=CC=CN=C1C=O JDYVLWWFVYNMTN-UHFFFAOYSA-N 0.000 description 1
- SQLOVHBDMDXZPP-UHFFFAOYSA-N 3-phenylpyridine-2-carbaldehyde Chemical compound O=CC1=NC=CC=C1C1=CC=CC=C1 SQLOVHBDMDXZPP-UHFFFAOYSA-N 0.000 description 1
- NZLNQSUMFSPISS-UHFFFAOYSA-N 4-chloropyridine-2-carbaldehyde Chemical compound ClC1=CC=NC(C=O)=C1 NZLNQSUMFSPISS-UHFFFAOYSA-N 0.000 description 1
- WRKFEQUUQYBTPF-UHFFFAOYSA-N 4-fluoropyridine-2-carbaldehyde Chemical compound FC1=CC=NC(C=O)=C1 WRKFEQUUQYBTPF-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 229920001153 Polydicyclopentadiene Polymers 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- UVBBCQLPTZEDHT-UHFFFAOYSA-N pent-4-en-1-amine Chemical compound NCCCC=C UVBBCQLPTZEDHT-UHFFFAOYSA-N 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 125000005493 quinolyl group Chemical group 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000006798 ring closing metathesis reaction Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- WLPUWLXVBWGYMZ-UHFFFAOYSA-N tricyclohexylphosphine Chemical compound C1CCCCC1P(C1CCCCC1)C1CCCCC1 WLPUWLXVBWGYMZ-UHFFFAOYSA-N 0.000 description 1
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Substances C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 1
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- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/0046—Ruthenium compounds
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- C08G61/04—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms
- C08G61/06—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms prepared by ring-opening of carbocyclic compounds
- C08G61/08—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms prepared by ring-opening of carbocyclic compounds of carbocyclic compounds containing one or more carbon-to-carbon double bonds in the ring
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Abstract
本发明提供了一种新型氮杂环卡宾配体的合成方法以及用它来合成的钌金属卡宾催化剂并以之催化降冰片烯开环易位聚合(ROMP)得到聚降冰片烯聚合物产品。该钌金属催化剂结构简单、易于合成、催化活性高,为制备聚降冰片烯材料提供了一种新的高效的途径。
Description
技术领域
该发明涉及一种烯烃复分解催化剂的制备方法及应用,特别是一种钌金属催化剂的制备方法及其在催化降冰片烯聚合反应中的应用。
背景技术
近几十年来,烯烃复分解反应的研究因其合成产物在医药、农药及材料等领域的重大价值而获得了迅速的发展。开环易位聚合(Ring-opening metathesispolymerization,简称ROMP)反应是烯烃复分解反应的另一种重要类型。该领域的研究主要集中在合成高效的ROMP反应催化剂和基于ROMP反应制备多功能的新材料方面(Macromolecules,2012,45,4447-4453),研究者们利用ROMP反应已经研究出了一大批具有优异性能的新型高分子材料,比如聚双环戊二烯、聚降冰片烯和聚环辛烯等。
目前ROMP常用的催化剂有Grubbs系列催化剂,可用于烯烃复分解反应和ROMP反应等,现已研制出第三代Grubbs,反应活性较前两代明显提高。作为一种新兴的聚合方法,它已经受到人们的广泛关注。ROMP具有反应条件温和、反应速率快及尺寸可控等优点,是用来制备可控功能化聚合物的重要方法之一(Journal of Polymer Science Part A:PolymerChemistry,2009,47(5),1266-1273)。降冰片烯价格便宜,环张力较大,是ROMP聚合的常用单体。
发明内容
本发明旨在合成一类新型的钌金属烯烃复分解催化剂并将它应用于催化降冰片烯进行关环复分解反应中。
本发明提供了一种钌金属烯烃复分解催化剂,其特征在于,为如下结构所示的化合物:
其中,R1为吡啶环上任一或任几取代的氢、卤素、硝基、氨基、芳基、烷基、烷氧基;上述芳基可选自苯基,苄基,喹啉基、吡啶基、吡咯基等五元/六元/七元芳香基团,以及苯环上任一或任几个碳原子为卤素、羟基、烷基等取代的五元/六元/七元芳香基团;上述烷基优选自碳原子数不大于6的短链支链或直链烷基;上述烷氧基优选自碳链长度不大于6的支链或直链烷氧基;
上述R1基团优选为对位取代的氟、氯、溴、碘、甲基、乙基、甲氧基、苯基等基团;
R2为多元环上任一或任几取代的氢、卤素、硝基、氨基、芳基、烷基、烷氧基;
n为自然数;
L为含膦配体,如:PCy3、PPh3等。
进一步地,本发明还提供的一种钌金属烯烃复分解催化剂的制备方法,其特征在于:由含有末端烯烃的卡宾配体前体,取代Grubbs 1st催化剂上的一个配体L后,经易位交换反应生成目标钌卡兵催化剂;
其中,上述含有末端烯烃的卡宾配体前体为如下结构所示的化合物:
R1为吡啶环上任一或任几取代的氢、卤素、硝基、氨基、芳基、烷基、烷氧基;
R2为碳链上任一或任几取代的氢、卤素、硝基、氨基、芳基、烷基、烷氧基;一般末端烯烃上不进行基团的取代;
n为自然数;
X为卤素;优选为氯、溴、碘;
上述Grubbs 1st催化剂为如下结构所示的化合物:
L为含膦配体。
进一步地,本发明提供的一种钌金属烯烃复分解催化剂的制备方法,其具体的工艺步骤如下所示:
S1-1、将卡宾配体前体和Grubbs 1st催化剂在溶剂中加强碱进行反应;
在S1-1中,该卡宾配体前体和Grubbs 1st催化剂的摩尔比为1.5-2:1;
该强碱优选自甲醇钠、乙醇钠、叔丁醇钠、叔丁醇钾;
该强碱和卡宾配体前体的摩尔比为1.5-2:1。
该溶剂可以为液态烷烃、芳烃、醚、醇、酯等;优选为正戊烷、正己烷、正庚烷、苯、甲苯、二甲苯等等。
S1-2、反应结束后用酸洗涤有机层,经重结晶后得到新的氮杂卡宾取代的钌络合物;
上述反应中的有机层用稀酸搅拌洗涤至没有明显的无机杂质,该酸一般选用无机酸(如:盐酸、硫酸等),其质量百分比浓度一般不大于50%。
经上述萃取过程后,蒸干溶剂的混合物,采用重结晶的方案进行产品的纯化,该重结晶的试剂可选择醚、醇、酯、酮等高级性溶剂,或选择上述溶剂与液态烷烃、芳烃的复合溶剂。其所用的量一般是Grubbs 1st催化剂用量的1-2倍,该重结晶的温度一般为0-10℃。
S2-1、将氮杂卡宾取代的钌络合物经90℃以上的温度反应,使末端烯烃和苯甲基钌卡宾发生易位反应后,经重结晶获得目标产物。
在S2-1中,反应一般在沸点为70℃以上的芳香类溶剂中进行;如:甲苯、二甲苯等,该溶剂的用量为钌络合物总重量的1-20倍,优选为5-8倍左右。
该重结晶的试剂可选择醚、醇、酯、酮等高级性溶剂,或选择上述溶剂与液态烷烃、芳烃的复合溶剂。其所用的量一般是氮杂卡宾取代的钌络合物用量的1-10倍,该重结晶一般在低温条件下进行,如:温度为20-30℃。
进一步地,本发明提供的一种钌金属烯烃复分解催化剂的制备方法,还具有这样的特点:即、上述含有末端烯烃的卡宾配体前体由取代的2-吡啶甲醛、链状末端烯胺和甲醛,在氢卤酸的作用下,经一锅法反应获得;
该取代的2-吡啶甲醛、链状末端烯胺和甲醛的摩尔比为1:0.8-1.5:0.8-1.5。优选摩尔比为1:0.9-1.1:0.9-1.1。
进一步地,本发明提供的一种钌金属烯烃复分解催化剂的制备方法,还具有这样的特点:即、具体步骤为:
S0-1、向反应器中加入取代的2-吡啶甲醛、链状末端烯胺和甲醛水溶液在醇溶液中,经氢卤酸的催化下,于40-70℃的反应温度下,搅拌反应1-8小时;
该反应优选在醇类、醚类等极性溶剂中进行,该溶剂的用量一般为取代的2-吡啶甲醛的质量的5-6倍,该反应温度最优选为50-60℃,最优选反应时间为4-8小时。
S0-2、降温至室温,产物从反应液中析出固体,过滤烘干得到卡宾配体前体。上述反应完成后,降温析晶的温度优选为0-10℃,搅拌析晶时间为2-5小时。
上述合成反应过程和方程式如下所示:
步骤一、一锅法合成新型结构的卡宾配体的前体
步骤二、卡宾配体取代Grubbs 1st分子上的一个配体
步骤三、卡宾配体上的末端烯基和钌卡宾进行易位交换生成新的钌卡宾催化剂
此外,本发明还提供了一种催化降冰片烯聚合反应的方法,其特征在于:采用上述任一的一种钌金属烯烃复分解催化剂进行催化反应;
其中,上述钌金属烯烃复分解催化剂的用量为:每10克降冰片烯选用0.1-15毫克的钌金属烯烃复分解催化剂进行催化反应。具体反应式如下所示:
上述催化反应的具体方法如下所述:
S3-1、在搅拌的情况下将催化剂溶液滴入降冰片烯溶液中,室温下搅拌反应10-30分钟后;上述反应原料和催化剂均优选溶解于卤代烃、烷烃、芳烃等溶剂中进行。
S3-2、将聚合反应液倒入液态烷烃中析出聚合物固体,经过滤烘干得到目标聚合物。
本发明的作用和效果:
本发明提供的钌金属催化剂结构简单、易于合成、催化活性高,为制备聚降冰片烯材料提供了一种新的高效的途径。
具体实施方式
实施例1
钌金属烯烃复分解催化剂1#的制备方法
包含以下三个步骤:
向2L反应瓶中加入4-氟-2-吡啶甲醛100克、40%甲醛水溶液60克、4-戊烯-1-胺68克、浓盐酸10毫升,溶剂甲醇600mL。加热到60℃,搅拌反应3小时。降温至10℃,搅拌析晶2小时,将固体产品过滤出来烘干,得产品150克,产率78%。
B.将氟取代的卡宾盐和Grubbs 1st催化剂反应得到钌络合物
向1L反应瓶中加入氟取代的卡宾盐100克,Grubbs 1st催化剂228克和叔丁醇钾70克,加入溶剂正庚烷500毫升。70℃氮气保护下搅拌反应。反应完毕后用1M稀盐酸洗涤有机相两次,然后蒸除溶剂,加丙酮400mL,加热溶解降温到0℃搅拌析晶。过滤出固体烘干,得到钌络合物150克,产率73%。
C.钌络合物卡宾上的末端烯和钌卡宾发生烯烃复分解得到环装催化剂
将钌络合物100克加入1L反应瓶中,加入溶剂甲苯400mL,然后加热到90℃反应2小时。反应结束后,蒸除溶剂,再加入甲醇200mL在10℃搅拌析晶2小时。过滤后得到催化剂产品66克,产率76%。
1H NMR(300.18MHz,22℃,CDCl3,Me4Si):δ=11.17(s,1H),6.76(d,J=7.8Hz,1H),6.05(d,J=6.8Hz,1H)5.34(d,J=7.8Hz,1H),4.30(s,1H),2.65(m,2H),1.60(m,2H),1.44-1.40(m,33H),1.30(m,2H)ppm.
用催化剂1#催化降冰片烯聚合的具体操作步骤如下:
用20mL的三氯甲烷溶解降冰片烯10g,然后用0.5mL的二氯甲烷溶解催化剂1#1mg后,在搅拌的情况下将催化剂溶液滴入降冰片烯中,室温下搅拌反应30分钟。
然后将聚合反应液倒入200mL正己烷中析出聚合物固体,然后将聚合物固体过滤烘干得到聚降冰片烯固体产品8.5g,产率85%。经过GPC测定聚合物的数均分子量Mn=1.24×104,分子量分布为Mw/Mn=1.22。
实施例2
钌金属烯烃复分解催化剂2#的制备方法
包含以下三个步骤:
向2L反应瓶中加入4-氯-2-吡啶甲醛140克、40%甲醛水溶液120克、5-己烯-1-胺100克、浓盐酸12毫升,溶剂甲醇600mL。加热到70℃,搅拌反应3小时。降温至10℃,搅拌析晶2小时,将固体产品过滤出来烘干,得产品200克,产率74%。
B.将氯取代的卡宾盐和Grubbs 1st催化剂反应得到钌络合物
向1L反应瓶中加入氟取代的卡宾盐100克,Grubbs 1st催化剂250克和叔丁醇钠70克,加入溶剂甲苯500毫升。70℃氮气保护下搅拌反应。反应完毕后用1M稀盐酸洗涤有机相两次,然后蒸除溶剂,加丙酮300mL,加热溶解降温到10℃搅拌析晶。过滤出固体烘干,得到钌络合物180克,产率67%。
C.钌络合物卡宾上的末端烯和钌卡宾发生烯烃复分解得到环装催化剂
将钌络合物100克加入1L反应瓶中,加入溶剂二甲苯500mL,然后加热到100℃反应2小时。反应结束后,蒸除溶剂,再加入甲醇250mL在10℃搅拌析晶2小时。过滤后得到催化剂产品76克,产率80%。
1H NMR(300.18MHz,22℃,CDCl3,Me4Si):δ=11.17(s,1H),6.76(d,J=7.8Hz,1H),6.05(d,J=6.8Hz,1H)5.34(d,J=7.8Hz,1H),4.30(s,1H),2.65(m,2H),1.60(m,2H),1.44-1.40(m,33H),1.30(m,4H)ppm.
用催化剂2#催化降冰片烯聚合的具体操作步骤如下:
用20mL的三氯甲烷溶解降冰片烯10g,然后用0.5mL的二氯甲烷溶解催化剂2#1mg后,在搅拌的情况下将催化剂溶液滴入降冰片烯中,室温下搅拌反应30分钟。
然后将聚合反应液倒入200mL正己烷中析出聚合物固体,然后将聚合物固体过滤烘干得到聚降冰片烯固体产品7.5g,产率75%。经过GPC测定聚合物的数均分子量Mn=1.35×104,分子量分布为Mw/Mn=1.33。
实施例3
钌金属烯烃复分解催化剂3#的制备方法
包含以下三个步骤:
向2L反应瓶中加入3-甲基-2-吡啶甲醛120克、40%甲醛水溶液140克、3-甲基-4-戊烯-1-胺80克、浓盐酸15毫升,溶剂甲醇600mL。加热到80℃,搅拌反应4小时。降温至5℃,搅拌析晶2小时,将固体产品过滤出来烘干,得产率71%。
B.将卡宾盐和Grubbs 1st催化剂反应得到钌络合物
向1L反应瓶中加入卡宾盐100克,Grubbs 1st催化剂210克和甲醇钠20克,加入溶剂甲苯500毫升。80℃氮气保护下搅拌反应。反应完毕后用1M稀盐酸洗涤有机相两次,然后蒸除溶剂,加丙酮300mL,加热溶解降温到10℃搅拌析晶。过滤出固体烘干,得到钌络合物产率66%。
C.钌络合物卡宾上的末端烯和钌卡宾发生烯烃复分解得到环装催化剂
将钌络合物110克加入1L反应瓶中,加入溶剂二甲苯500mL,然后加热到100℃反应2小时。反应结束后,蒸除溶剂,再加入乙醇250mL在10℃搅拌析晶2小时。过滤后得到催化剂产品产率81%。
m/z:652(100.0%).
用催化剂3#催化降冰片烯聚合的具体操作步骤如下:
用20mL的三氯甲烷溶解降冰片烯10g,然后用0.5mL的二氯甲烷溶解催化剂3#0.5mg后,在搅拌的情况下将催化剂溶液滴入降冰片烯中,室温下搅拌反应30分钟。
然后将聚合反应液倒入200mL正己烷中析出聚合物固体,然后将聚合物固体过滤烘干得到产率79%。
实施例4
钌金属烯烃复分解催化剂4#的制备方法
包含以下三个步骤:
向2L反应瓶中加入3-苯基-2-吡啶甲醛120克、40%甲醛水溶液160克、3-甲氧基-4-戊烯-1-胺120克、浓盐酸21毫升,溶剂甲醇600mL。加热到80℃,搅拌反应8小时。降温至0℃,搅拌析晶1.5小时,将固体产品过滤出来烘干,得产率63%。
B.将卡宾盐和Grubbs 1st催化剂反应得到钌络合物
向1L反应瓶中加入卡宾盐100克,Grubbs 1st催化剂180克和甲醇钠20克,加入溶剂甲苯500毫升。80℃氮气保护下搅拌反应。反应完毕后用1M稀盐酸洗涤有机相两次,然后蒸除溶剂,加丙酮/乙醚300mL,加热溶解降温到0℃搅拌析晶。过滤出固体烘干,得到钌络合物产率61%。
C.钌络合物卡宾上的末端烯和钌卡宾发生烯烃复分解得到环装催化剂
将钌络合物140克加入1L反应瓶中,加入溶剂二甲苯500mL,然后加热到120℃反应2小时。反应结束后,蒸除溶剂,再加入乙醇250mL在10℃搅拌析晶2小时。过滤后得到催化剂产品产率81%。
m/z:712(100.0%).
用催化剂3#催化降冰片烯聚合的具体操作步骤如下:
用20mL的三氯甲烷溶解降冰片烯10g,然后用0.5mL的二氯甲烷溶解催化剂3#0.1mg后,在搅拌的情况下将催化剂溶液滴入降冰片烯中,室温下搅拌反应30分钟。
然后将聚合反应液倒入200mL正己烷中析出聚合物固体,然后将聚合物固体过滤烘干得到产率71%。
Claims (9)
1.一种钌金属烯烃复分解催化剂的制备方法,其特征在于:所述钌金属烯烃复分解催化剂由含有末端烯烃的卡宾配体前体,取代Grubbs 1st催化剂上的一个配体L后,经易位交换反应生成目标钌卡宾催化剂;
其中,所述目标钌卡宾催化剂为如下结构所示的化合物:
其中,R1为吡啶环上任一或任几取代的氢、卤素、硝基、氨基、芳基、烷基、烷氧基;
R2为多元环上任一或任几取代的氢、卤素、硝基、氨基、芳基、烷基、烷氧基;
n为自然数;
L为含膦配体;
所述含有末端烯烃的卡宾配体前体为如下结构所示的化合物:
R1为吡啶环上任一或任几取代的氢、卤素、硝基、氨基、芳基、烷基、烷氧基;
R2为碳链上除烯烃末端位的任一或任几取代的氢、卤素、硝基、氨基、芳基、烷基、烷氧基;
n为自然数;
X为卤素;
所述Grubbs 1st催化剂为如下结构所示的化合物:
L为含膦配体。
2.如权利要求1所述的一种钌金属烯烃复分解催化剂的制备方法,其特征在于,具体的工艺步骤如下:
S1-1、将卡宾配体前体和Grubbs 1st催化剂在溶剂中加强碱进行反应;
S1-2、反应结束后用酸洗涤有机层,经重结晶后得到氮杂卡宾取代的钌络合物;
S2-1、将氮杂卡宾取代的钌络合物经90℃以上的温度反应,使末端烯烃和苯甲基钌卡宾发生易位反应后,经重结晶获得目标产物。
3.如权利要求2所述的一种钌金属烯烃复分解催化剂的制备方法,其特征在于:
在S1-1中,所述卡宾配体前体和Grubbs 1st催化剂的摩尔比为1.5-2:1;
所述强碱选自甲醇钠、乙醇钠、叔丁醇钠、叔丁醇钾;
所述强碱和卡宾配体前体的摩尔比为1.5-2:1。
4.如权利要求2所述的一种钌金属烯烃复分解催化剂的制备方法,其特征在于:
在S2-1中,反应在沸点为70℃以上的芳香类溶剂中进行;
所述溶剂的用量为钌络合物总重量的1-20倍。
5.如权利要求2所述的一种钌金属烯烃复分解催化剂的制备方法,其特征在于:用于所述重结晶的试剂选自酮类、醚类、醇类、酯类中的一种或几种的混合物。
7.如权利要求6所述的一种钌金属烯烃复分解催化剂的制备方法,其特征在于:
S0-1、向反应器中加入取代的2-吡啶甲醛、链状末端烯胺和甲醛水溶液在醇溶液中,经氢卤酸的催化下,于40-70℃的反应温度下,搅拌反应1-8小时;
S0-2、降温至室温,产物从反应液中析出固体,过滤烘干得到卡宾配体前体。
8.如权利要求6所述的一种钌金属烯烃复分解催化剂的制备方法,其特征在于:所述的钌金属烯烃复分解催化剂能用于进行催化降冰片烯聚合反应;
在所述催化降冰片烯聚合反应中,所述钌金属烯烃复分解催化剂的用量为:每10克降冰片烯选用0.1-15毫克的钌金属烯烃复分解催化剂进行催化反应。
9.如权利要求8所述的一种钌金属烯烃复分解催化剂的制备方法,其特征在于:所述催化降冰片烯聚合反应的具体步骤如下所示:
S3-1、在搅拌的情况下将催化剂溶液滴入降冰片烯溶液中,室温下搅拌反应10-30分钟后;
S3-2、将聚合反应液倒入液态烷烃中析出聚合物固体,经过滤烘干得到目标聚合物。
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Denomination of invention: Ruthenium carbene catalyst and its catalytic ring opening and translocation polymerization of norbornene Effective date of registration: 20231218 Granted publication date: 20200320 Pledgee: Industrial Bank Co.,Ltd. Shanghai Jinshan Branch Pledgor: SHANGHAI COACHCHEM TECHNOLOGY CO.,LTD. Registration number: Y2023980071859 |