CN107746452A - 基于微‑介孔酚醛树脂的钯负载异相催化剂及其制备方法 - Google Patents
基于微‑介孔酚醛树脂的钯负载异相催化剂及其制备方法 Download PDFInfo
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- CN107746452A CN107746452A CN201711002509.XA CN201711002509A CN107746452A CN 107746452 A CN107746452 A CN 107746452A CN 201711002509 A CN201711002509 A CN 201711002509A CN 107746452 A CN107746452 A CN 107746452A
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 100
- 239000003054 catalyst Substances 0.000 title claims abstract description 44
- 229910052763 palladium Inorganic materials 0.000 title claims abstract description 32
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 229920001568 phenolic resin Polymers 0.000 title claims abstract description 30
- 239000005011 phenolic resin Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 40
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 20
- 238000006069 Suzuki reaction reaction Methods 0.000 claims abstract description 18
- 229910052751 metal Inorganic materials 0.000 claims abstract description 18
- 239000002184 metal Substances 0.000 claims abstract description 18
- 239000012298 atmosphere Substances 0.000 claims abstract description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 7
- 150000001642 boronic acid derivatives Chemical class 0.000 claims abstract description 5
- 150000004820 halides Chemical class 0.000 claims abstract description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 4
- 150000003003 phosphines Chemical class 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 33
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 22
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 17
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 11
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 10
- 239000003960 organic solvent Substances 0.000 claims description 10
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 9
- 238000010792 warming Methods 0.000 claims description 5
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 4
- 150000001924 cycloalkanes Chemical class 0.000 claims description 4
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 3
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 3
- -1 phenol Hydroxy compounds Chemical class 0.000 claims description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 claims 1
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 claims 1
- 238000002156 mixing Methods 0.000 claims 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims 1
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 abstract description 18
- 238000006555 catalytic reaction Methods 0.000 abstract description 7
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 238000010668 complexation reaction Methods 0.000 abstract description 3
- 239000012736 aqueous medium Substances 0.000 abstract description 2
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 26
- 239000012071 phase Substances 0.000 description 26
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 description 12
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 12
- 238000000034 method Methods 0.000 description 11
- 239000000376 reactant Substances 0.000 description 10
- 208000012839 conversion disease Diseases 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 238000004949 mass spectrometry Methods 0.000 description 8
- 239000012046 mixed solvent Substances 0.000 description 8
- 239000012074 organic phase Substances 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 6
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 6
- 229910000027 potassium carbonate Inorganic materials 0.000 description 6
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 5
- QOCQQHJSBRCCRA-UHFFFAOYSA-N (2-ethylphenoxy)boronic acid Chemical compound CCC1=CC=CC=C1OB(O)O QOCQQHJSBRCCRA-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- HVRUGFJYCAFAAN-UHFFFAOYSA-N 1-bromo-2-ethylbenzene Chemical compound CCC1=CC=CC=C1Br HVRUGFJYCAFAAN-UHFFFAOYSA-N 0.000 description 3
- HTDQSWDEWGSAMN-UHFFFAOYSA-N 1-bromo-2-methoxybenzene Chemical compound COC1=CC=CC=C1Br HTDQSWDEWGSAMN-UHFFFAOYSA-N 0.000 description 3
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- PYLWMHQQBFSUBP-UHFFFAOYSA-N monofluorobenzene Chemical compound FC1=CC=CC=C1 PYLWMHQQBFSUBP-UHFFFAOYSA-N 0.000 description 3
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 0 CC1*C*C1 Chemical compound CC1*C*C1 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- KKWDHUMYGILVHS-UHFFFAOYSA-N [K].C(=O)=O Chemical compound [K].C(=O)=O KKWDHUMYGILVHS-UHFFFAOYSA-N 0.000 description 2
- 239000003905 agrochemical Substances 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000007172 homogeneous catalysis Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- LUBNKNNXRUCCRO-UHFFFAOYSA-N phenol 1,3,5-trimethylbenzene Chemical compound C1(=CC(=CC(=C1)C)C)C.C1(=CC=CC=C1)O LUBNKNNXRUCCRO-UHFFFAOYSA-N 0.000 description 2
- 150000005207 1,3-dihydroxybenzenes Chemical class 0.000 description 1
- 150000004416 2,5-dihydroxy-1,4-benzoquinones Chemical class 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical class OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- OSCBARYHPZZEIS-UHFFFAOYSA-N phenoxyboronic acid Chemical class OB(O)OC1=CC=CC=C1 OSCBARYHPZZEIS-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000010148 water-pollination Effects 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
- B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
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- B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
- B01J2231/4205—C-C cross-coupling, e.g. metal catalyzed or Friedel-Crafts type
- B01J2231/4211—Suzuki-type, i.e. RY + R'B(OR)2, in which R, R' are optionally substituted alkyl, alkenyl, aryl, acyl and Y is the leaving group
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Abstract
本发明提供了一种基于微‑介孔酚醛树脂的钯负载异相催化剂及其制备方法。其制备步骤为:通过三(4‑醛基苯基)膦与酚羟基化合物聚合,得到具有大比表面积且富含羟基和三苯基膦的微‑介孔酚醛树脂,再通过钯金属和三苯基膦的配位反应,制备得到多孔酚醛树脂基负载钯金属的异相催化剂。该催化剂可在水介质中氮气或空气气氛下高效催化硼酸化合物与卤代物的Suzuki偶联反应,具有制备简单,催化产率高、催化剂易回收和可反复使用等优点。
Description
技术领域
本发明涉及一种具有大比表面积且富含羟基和三苯基膦的微-介孔酚醛树脂及其金属钯负载催化剂的制备方法,属于催化材料技术领域。由该方法合成的异相催化剂用于高效催化Suzuki偶联反应,可广泛应用于有机合成化学及医药和农药制造等工业领域。
背景技术
Suzuki偶联反应是金属钯催化下的卤代烃与有机硼酸化合物之间的反应。该反应是生成碳碳键的最重要的有机单元反应之一,具有操作简便等优点。但传统的钯均相催化体系存在诸多缺点,如反应产物的分离困难、催化剂不能重复使用等。将金属钯负载到不溶的固体介质载体上有可能克服钯均相催化体系的缺点。当前金属钯负载催化剂的制备主要有两种方法,其一是通过物理吸附将钯金属吸附在基体表面上,其二是首先在固体载体上引入可配位基团,再经由配位反应将钯固定在功能基团上。异相催化剂所使用的固体载体材料主要包括活性碳、金属氧化物、硅铝酸盐微孔分子筛、二氧化硅材料、活性粘土以及聚合物等。
采用金属钯负载的异相催化剂仍存在一些严重问题。例如,通过物理吸附法制备的钯负载催化剂,反应过程中或反应后产物分离过程中钯金属容易流失,导致催化剂再循环使用的催化效率大大下降,而将钯金属通过配位反应固定在载体表面,由于载体上可配位基团分布不均匀,使得所负载的钯金属含量较低且容易聚集,也大大影响了异相催化效率。
发明内容
本发明为解决现有技术中金属钯负载的异相催化剂存在配位基团分布不均、钯金属在分离过程中易流失导致异相催化效率低等问题,提供了一种具有大比表面积且富含羟基和三苯基膦的微-介孔酚醛树脂及其制备方法。
本发明采用如下技术方案:
具有大比表面积且富含羟基和三苯基膦的微-介孔酚醛树脂,其具有如式Ⅰ或式Ⅱ的结构:
其中:
R为
上述酚醛树脂的制备方法为:将三(4-醛基苯基)膦和酚羟基化合物在20-90℃溶解于有机溶剂中,用氮气充分置换高压反应釜中空气后,升温至150-250℃反应1-6天,降至室温后将所得固体在索氏提取器中抽提12-48小时,于50-120℃真空干燥;所述的酚羟基化合物为均三苯酚、间苯二酚或2,5-二羟基-1,4-苯醌,反应体系中醛基与羟基邻位氢原子的摩尔比为0.5:1—1:3。
上述制备步骤所用的有机溶剂为四氢呋喃、***、二氧六环、C4-C8的脂肪族烷烃或环烷烃中的一种或几种的混合物。
本发明另一个目的是请求保护采用上述微-介孔酚醛树脂制备负载金属钯的异相催化剂,其方法具体为:将微-介孔酚醛树脂与四(三苯基膦)钯置于有机溶剂中,在20-100℃下氮气下搅拌反应6-48小时,过滤后的固体用有机溶剂抽提后于25-100℃真空干燥;反应体系中磷和钯原子的摩尔比为1:0.5—1:3。
上述催化剂制备步骤所用的有机溶剂为苯、甲苯、二甲苯、四氢呋喃、***、二氧六环、C4-C8的脂肪族烷烃或环烷烃中的一种或几种的混合物。
本发明第三个目的是请求保护上述负载金属钯的微-介孔酚醛树脂异相催化剂的应用,该催化剂可用于硼酸化合物与卤代物的Suzuki偶联反应,且反应可在氮气或空气气氛下进行。
与现有技术相比,本发明利用高度交联的网络结构使得酚醛树脂不溶于任何反应介质中,适于作为异相催化反应载体;三苯基膦基团在三维网络中分布均匀;再利用所含的三苯基膦基团与金属钯配位,使得钯元素牢牢固定在酚醛树脂载体上,可有效防止钯元素的流失,使其作为异相催化剂可重复使用;微-介孔酚醛树脂大的比表面积有利于反应物与钯催化中心接触反应,而且,酚醛树脂大量的羟基使该异相催化剂具有很好的亲水性,有利于反应物在水介质中扩散进入催化剂孔道,提高催化效率。此外,本发明具有原料来源广泛,合成简单,催化产率高,催化剂易回收和可反复使用等优点,可广泛应用于有机合成化学及医药和农药制造等工业领域。
附图说明
图1为本发明实施例制备的三苯基膦基微-介孔酚醛树脂。
图2本发明异相催化剂Pd@PFN-P-3反复使用次数与反应转化率。
具体实施方式
下面通过具体实施例详述本发明,但不限制本发明的保护范围。如无特殊说明,本发明实施例中所采用的实验方法为常规方法,所用实验器材、材料、试剂等均可从化学公司购买。
实施例1:
大比表面积三苯基膦基微-介孔酚醛树脂(PFN-P-1)的合成:
在100毫升的三口瓶中加入1.92克均三苯酚、1.41克三(4-醛基苯基)膦和20毫升环己烷和二氧六环的混合溶剂(环己烷/二氧六环体积比为0.5/9.5)。该混合物升温到80℃并搅拌2小时得到透明的溶液。将得到的溶液转移到100毫升高压反应釜中在200℃反应6天。冷却后过滤,得到的固体在索氏提取器中用四氢呋喃用抽提24小时,120℃真空干燥至恒重,产率90%。BET比表面积655平方米/克,孔径0.9-28纳米。
实施例2:
大比表面积三苯基膦基微-介孔酚醛树脂(PFN-P-2)的合成:
在50毫升的三口瓶中加入1.22克间苯二酚、0.75克三(4-醛基苯基)膦和20毫升四氢呋喃和二氧六环的混合溶剂(四氢呋喃/二氧六环比为1/9)。该混合物升温到60℃并搅拌2小时得到透明的溶液。将得到的溶液转移到100毫升高压反应釜中在190℃反应5天。冷却后过滤,得到的固体用四氢呋喃在索氏提取器中抽提48小时,120℃真空干燥至恒重,产率95%。BET比表面积645平方米/克,孔径0.6-32纳米。
实施例3:
大比表面积三苯基膦基微-介孔酚醛树脂(PFN-P-3)的合成:
在50毫升的三口瓶中加入0.85克2,5-二羟基-1,4-苯醌、0.70克三(4-醛基苯基)膦和10毫升二氧六环。该混合物升温到90℃并搅拌1小时得到透明的溶液。将得到的溶液转移到100毫升高压反应釜中在220℃反应4天。冷却后过滤,得到的固体用四氢呋喃用索氏提取器抽提24小时,120℃真空干燥至恒重,产率95%。BET比表面积775平方米/克,孔径0.6纳米-23.8纳米。
实施例4:
基于微-介孔酚醛树脂(PFN-P-1)钯负载异相催化剂(Pd@PFN-P-1)的合成:
在干燥的500毫升烧瓶中,氮气保护下,加入0.62克PFN-P-1,0.75克四(三苯基膦)钯和120毫升干燥的二氧六环。25℃搅拌24小时后过滤,所得到固体用甲苯和***连续洗3次,在80℃真空干燥至恒重,产率92%。
实施例5:
基于微-介孔酚醛树脂(PFN-P-2)钯负载异相催化剂(Pd@PFN-P-2)的合成:
在干燥的500毫升烧瓶中,氮气保护下,加入0.75克PFN-P-2,1.86克四(三苯基膦)钯和100毫升干燥的苯和环己烷的混合溶剂(苯/环己烷为8/2)。室温搅拌48小时后过滤,所得到固体用苯和四氢呋喃连续洗3次,在60℃真空干燥至恒重,产率94%。
实施例6:
基于微-介孔酚醛树脂(PFN-P-3)钯负载异相催化剂(Pd@PFN-P-3)的合成:
在干燥的500毫升烧瓶中,氮气保护下,加入0.78克PFN-P-3,0.78克四(三苯基膦)钯和120毫升干燥的甲苯。室温搅拌24小时后过滤,所得到固体用甲苯和***连续洗3次,在80℃真空干燥至恒重,产率97%。
实施例7:
Pd@PFN-P-1氮气下催化苯硼酸与溴代苯的Suzuki偶联反应。
10毫升甲苯,4毫升水,0.182克对乙基苯硼酸,0.157克溴代苯,0.346克无水碳酸钾和异相催化剂Pd@PFN-P-1加入到干燥的带有搅拌器和冷凝管的100毫升三口烧瓶中,在反应体系中,钯元素占溴代苯的摩尔百分数为0.1%。反应混合物在氮气保护下90℃搅拌反应12小时,冷却到室温后,所得产物的有机相通过气相色谱质谱方法分析,反应转化率为98.9%。
实施例8:
Pd@PFN-P-2氮气下催化苯硼酸与溴代苯的Suzuki偶联反应。
10毫升甲苯,4毫升水,0.182克对乙基苯硼酸,0.157克溴代苯,0.346克无水碳酸钾和异相催化剂Pd@PFN-P-2加入到干燥的带有搅拌器和冷凝管的100毫升三口烧瓶中,在反应体系中,钯元素占溴代苯的摩尔百分数为0.1%。反应混合物在氮气保护下90℃搅拌反应12小时,冷却到室温后,所得产物的有机相通过气相色谱质谱方法分析,反应转化率为98.7%。
实施例9:
Pd@PFN-P-3在空气气氛中催化苯硼酸与溴代苯的Suzuki偶联反应。
10毫升的乙醇和水的混合溶剂(乙醇/水体积比为1/3),0.146克苯硼酸,0.157克溴代苯,0.346克无水碳酸钾和异相催化剂Pd@PFN-P-3加入到干燥的带有搅拌器和冷凝管的100毫升三口烧瓶中,在反应体系中,钯元素占溴代苯的摩尔百分数为0.1%。反应混合物在空气气氛中80℃搅拌反应6小时,冷却到室温后,所得产物用10毫升***萃取3次,有机相用无水硫酸镁干燥。通过气相色谱质谱方法分析,反应转化率为99.6%。
实施例10:
Pd@PFN-P-3在氮气气氛中催化苯硼酸与溴代苯的Suzuki偶联反应。
10毫升的乙醇和水的混合溶剂(乙醇/水体积比为1/3),0.146克苯硼酸,0.157克溴代苯,0.346克无水碳酸钾和异相催化剂Pd@PFN-P-3加入到干燥的带有搅拌器和冷凝管的100毫升三口烧瓶中,在反应体系中,钯元素占溴代苯的摩尔百分数为0.1%。反应混合物在氮气气氛中80℃搅拌反应6小时,冷却到室温后,所得产物用10毫升***萃取3次,有机相用无水硫酸镁干燥。通过气相色谱质谱方法分析,反应转化率为99.8%。
实施例11:
Pd@PFN-P-3在空气气氛中催化苯硼酸与对乙基溴代苯的Suzuki偶联反应。
10毫升的乙醇和水的混合溶剂(乙醇/水体积比为1/3),0.146克苯硼酸,0.157克对乙基溴代苯,0.346克无水碳酸钾和异相催化剂Pd@PFN-P-3加入到干燥的带有搅拌器和冷凝管的100毫升三口烧瓶中,在反应体系中,钯元素占乙基溴代苯的摩尔百分数为0.1%。反应混合物在空气气氛中80℃搅拌反应6小时,冷却到室温后,所得产物用10毫升***萃取3次,有机相用无水硫酸镁干燥。通过气相色谱质谱方法分析,反应转化率为98.9%。
实施例12:
Pd@PFN-P-3氮气下催化对乙基苯硼酸与对甲氧基溴代苯的Suzuki偶联反应。
10毫升甲苯,4毫升水,0.182克对乙基苯硼酸,0.157克对甲氧基溴代苯,0.346克无水碳酸钾和异相催化剂Pd@PFN-P-3加入到干燥的带有搅拌器和冷凝管的100毫升三口烧瓶中,在反应体系中,钯元素占甲氧基溴代苯的摩尔百分数为0.1%。反应混合物在氮气保护下90℃搅拌反应12小时,冷却到室温后,所得产物的有机相通过气相色谱质谱方法分析,反应转化率为97.7%。
实施例13:
Pd@PFN-P-3氮气下催化苯硼酸与氯代苯的Suzuki偶联反应。
10毫升的乙醇和水的混合溶剂(乙醇/水体积比为1/3),0.146克苯硼酸,0.112克氯代苯,0.346克无水碳酸钾和异相催化剂Pd@PFN-P-3加入到干燥的带有搅拌器和冷凝管的100毫升三口烧瓶中,在反应体系中,钯元素占氯代苯的摩尔百分数为0.1%。反应混合物在氮气保护下80℃搅拌反应6小时,冷却到室温后,所得产物用10毫升***萃取3次,有机相用无水硫酸镁干燥。通过气相色谱质谱方法分析,反应转化率为91.1%。
实施例14:
Pd@PFN-P-3氮气下催化苯硼酸与氟代苯的Suzuki偶联反应。
10毫升的乙醇和水的混合溶剂(乙醇/水体积比为1/3),0.146克苯硼酸,0.097克氟代苯,0.346克无水碳酸钾和异相催化剂Pd@PFN-P-3加入到干燥的带有搅拌器和冷凝管的100毫升三口烧瓶中,在反应体系中,钯元素占氟代苯的摩尔百分数为0.1%。反应混合物在氮气保护下80℃搅拌反应6小时,冷却到室温后,所得产物用10毫升***萃取3次,有机相用无水硫酸镁干燥。通过气相色谱质谱方法分析反应转化率为88.5%。
如表1所示为实施例7-14采用本发明制备的异相催化剂Pd@PFN-P-1、Pd@PFN-P-2和Pd@PFN-P-3进行Suzuki偶联反应反应条件及转化率。
本发明异相催化剂用于硼酸化合物与卤代物的Suzuki偶联反应如下:
表1.使用负载金属钯的微-介孔酚醛树脂异相催化剂催化Suzuki偶联反应
如图2所示为本发明制备的异相催化剂Pd@PFN-P-3按实施例10的反应条件反复使用5次催化苯硼酸与溴代苯Suzuki偶联的反应转化率。反复使用5次反应转化率稳定。
本发明制备的异相催化剂用于硼酸化合物与卤代物的Suzuki偶联反应的转化率可高达99.8%,催化反应条件温和,可以在氮气或空气气氛下进行,具有显著的效果。
以上所述,仅为本发明创造较佳的具体实施方式,但本发明创造的保护范围并不局限于此,任何熟悉本技术领域的技术人员在本发明创造披露的技术范围内,根据本发明创造的技术方案及其发明构思加以等同替换或改变,都应涵盖在本发明创造的保护范围之内。
Claims (6)
1.一种微-介孔酚醛树脂,其特征在于,具有如式Ⅰ或Ⅱ所示的结构:
其中:
R为
2.一种如权利要求1所述酚醛树脂的制备方法,其特征在于,将三(4-醛基苯基)膦和酚羟基化合物在20-90℃溶解于有机溶剂中,在氮气条件下升温至150-250℃反应1-6天,降至室温后将所得固体抽提12-48小时,于50-120℃真空干燥;所述的酚羟基化合物为均三苯酚、间苯二酚或2,5-二羟基-1,4-苯醌中的一种,反应体系中醛基与羟基邻位氢原子的摩尔比为0.5:1—1:3。
3.根据权利要求2所述酚醛树脂的制备方法,其特征在于,所述的有机溶剂为四氢呋喃、***、二氧六环、C4-C8的脂肪族烷烃或环烷烃中的一种或几种的混合物。
4.一种利用权利要求1所述微-介孔酚醛树脂制备负载金属钯的异相催化剂,其特征在于,制备方法为:将微-介孔酚醛树脂与四(三苯基膦)钯置于有机溶剂中,在20-100℃下氮气下搅拌反应6-48小时,过滤后的固体用有机溶剂抽提后于25-100℃真空干燥;反应体系中磷和钯原子的摩尔比为1:0.5—1:3。
5.根据权利要求4所述异相催化剂的制备方法,其特征在于,所述的有机溶剂为苯、甲苯、二甲苯、四氢呋喃、***、二氧六环、C4-C8的脂肪族烷烃或环烷烃中的一种或几种的混合物。
6.一种如权利要求4所述负载金属钯的微-介孔酚醛树脂异相催化剂的应用,其特征在于,该催化剂用于硼酸化合物与卤代物的Suzuki偶联反应,且反应可在氮气或空气气氛下进行。
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CN114369240B (zh) * | 2021-11-10 | 2023-07-14 | 贵研铂业股份有限公司 | 卟啉基多孔有机聚合物、制备方法及其负载钯催化剂的制备方法与用途 |
CN114773489A (zh) * | 2022-05-19 | 2022-07-22 | 浙江三和食品科技有限公司 | 一种低粘度羧甲基纤维素钠的制备方法 |
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