CN114985016B - 一种含膦壳聚糖负载钯金属催化剂及其制备方法与应用 - Google Patents
一种含膦壳聚糖负载钯金属催化剂及其制备方法与应用 Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 79
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 74
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 229920001661 Chitosan Polymers 0.000 title claims abstract description 35
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 35
- 239000002184 metal Substances 0.000 title claims abstract description 35
- 229910052763 palladium Inorganic materials 0.000 title claims abstract description 32
- 229910000073 phosphorus hydride Inorganic materials 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 238000006069 Suzuki reaction reaction Methods 0.000 claims abstract description 22
- 150000003839 salts Chemical class 0.000 claims abstract description 10
- -1 aryl boric acid Chemical class 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 37
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 26
- 229910052757 nitrogen Inorganic materials 0.000 claims description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 5
- 229920000642 polymer Polymers 0.000 claims description 5
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 4
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims description 4
- 229910021605 Palladium(II) bromide Inorganic materials 0.000 claims description 4
- 229910002666 PdCl2 Inorganic materials 0.000 claims description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 4
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 4
- INIOZDBICVTGEO-UHFFFAOYSA-L palladium(ii) bromide Chemical compound Br[Pd]Br INIOZDBICVTGEO-UHFFFAOYSA-L 0.000 claims description 4
- 238000006555 catalytic reaction Methods 0.000 claims description 3
- 229940125782 compound 2 Drugs 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
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- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- 229910021606 Palladium(II) iodide Inorganic materials 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(II) nitrate Inorganic materials [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 claims description 2
- HNNUTDROYPGBMR-UHFFFAOYSA-L palladium(ii) iodide Chemical compound [Pd+2].[I-].[I-] HNNUTDROYPGBMR-UHFFFAOYSA-L 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims 2
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- 125000004185 ester group Chemical group 0.000 claims 1
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- QARVLSVVCXYDNA-UHFFFAOYSA-N phenyl bromide Natural products BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 29
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 22
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- 229910052723 transition metal Inorganic materials 0.000 description 4
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- PQCXFUXRTRESBD-UHFFFAOYSA-N (4-methoxycarbonylphenyl)boronic acid Chemical compound COC(=O)C1=CC=C(B(O)O)C=C1 PQCXFUXRTRESBD-UHFFFAOYSA-N 0.000 description 2
- VOAAEKKFGLPLLU-UHFFFAOYSA-N (4-methoxyphenyl)boronic acid Chemical compound COC1=CC=C(B(O)O)C=C1 VOAAEKKFGLPLLU-UHFFFAOYSA-N 0.000 description 2
- BIWQNIMLAISTBV-UHFFFAOYSA-N (4-methylphenyl)boronic acid Chemical compound CC1=CC=C(B(O)O)C=C1 BIWQNIMLAISTBV-UHFFFAOYSA-N 0.000 description 2
- QSSXJPIWXQTSIX-UHFFFAOYSA-N 1-bromo-2-methylbenzene Chemical compound CC1=CC=CC=C1Br QSSXJPIWXQTSIX-UHFFFAOYSA-N 0.000 description 2
- WJIFKOVZNJTSGO-UHFFFAOYSA-N 1-bromo-3-methylbenzene Chemical compound CC1=CC=CC(Br)=C1 WJIFKOVZNJTSGO-UHFFFAOYSA-N 0.000 description 2
- ZBTMRBYMKUEVEU-UHFFFAOYSA-N 1-bromo-4-methylbenzene Chemical compound CC1=CC=C(Br)C=C1 ZBTMRBYMKUEVEU-UHFFFAOYSA-N 0.000 description 2
- QJPJQTDYNZXKQF-UHFFFAOYSA-N 4-bromoanisole Chemical compound COC1=CC=C(Br)C=C1 QJPJQTDYNZXKQF-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
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- 230000015572 biosynthetic process Effects 0.000 description 2
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- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 125000006539 C12 alkyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229920002101 Chitin Polymers 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
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- 239000012300 argon atmosphere Substances 0.000 description 1
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- QARVLSVVCXYDNA-IDEBNGHGSA-N bromobenzene Chemical group Br[13C]1=[13CH][13CH]=[13CH][13CH]=[13CH]1 QARVLSVVCXYDNA-IDEBNGHGSA-N 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
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- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 150000002940 palladium Chemical class 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
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- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
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- 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
- B01J31/2409—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring with more than one complexing phosphine-P atom
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Abstract
本发明属于有机化学技术领域，具体涉及一种含膦壳聚糖负载钯金属催化剂及其制备方法。本发明应用化学合成手段将化合物与钯盐Pd(X)2反应而得。本发明所提供的含膦壳聚糖与钯金属盐形成催化剂后，可用于卤代芳烃和芳基硼酸的Suzuki偶联反应，且表现出较高的催化活性和循环性，具有实用价值。
Description
技术领域
本发明属于有机化学技术领域，具体涉及一种含膦壳聚糖负载钯金属催化剂及其制备方法。
背景技术
在现代有机合成化学中，碳-碳键的构建是一类非常重要的反应，该反应广泛应用于天然产物、药物、聚合物材料的合成中。钯催化卤代芳烃与芳基硼酸的Suzuki偶联反应因反应条件温和、官能团耐受性好、产物易于分离、选择性高和空间位阻低等优点而受到广泛关注。
均相催化Suzuki偶联反应体系在过去的几十年里报道较多，但是均相催化体系存在环境污染和催化剂无法回收再利用的问题，因此，非均相催化Suzuki偶联反应更加有利。将过渡金属催化剂有效负载在高聚物上不仅可以提高催化剂的稳定性，还不会影响均相催化剂的活性和选择性；且非均相催体系在催化剂的回收分离方面具有显著优势，因此更适合工业应用。
此外，催化剂回收往往需要相应的载体，近年来报道的催化剂大多数应用于有机聚合物载体和无机载体。受到自然界中容易获得的生物聚合物的启发，设计将生物聚合物作为载体应用于过渡金属催化。在生物聚合物上负载过渡金属催化剂，反应场所在催化剂孔隙中，大大提升反应速度，最重要的是该催化剂可循环使用，极其符合当下绿色环保的理念。壳聚糖作为一种可生物降解的、可再生的绿色材料，可以通过甲壳素脱乙酰化而制得，来源相对丰富，且壳聚糖的热稳定性、不溶性(在许多有机溶剂中)使其成为催化剂载体的理想材料。并且其含有大量的羟基和伯氨基，可用于结合各种金属离子，因此提供了各种化学修饰的可能性。
本发明通过设计合成了一种含膦配体修饰壳聚糖负载金属催化剂并将该催化剂应用于Suzuki偶联反应。虽然已有壳聚糖负载过渡金属催化Suzuki偶联反应的应用，但这些体系都存在着反应活性低，底物兼容性差和催化剂循环活性损失等问题。比目前发展的壳聚糖负载金属催化剂表现出高的催化活性，底物兼容性和催化剂循环性。
发明内容
有鉴于此，本发明的目的是提供一类含膦壳聚糖负载钯金属催化剂的制备方法及应用，为非均相催化Suzuki偶联反应反应增添一类新催化剂。
发明所述的一类含膦壳聚糖负载钯金属催化剂，具有如下结构通式Ι：
上通式中：R1、R2、R3、R4、R5、R6、R7、R8、R9、R10、R11、R12分别独立选自氢、磺酸基、卤素、腈基、C1～C12的烷烃基、C1～C10的烷氧基、C1～C10的酯基、C1～C10的磺酸酯基；
X分别独立选自OAc、Cl、Br、I、NO3和SO4。
上述一类含膦壳聚糖负载钯金属催化剂的制备方法，将反应通式1中聚合物1含膦壳聚糖含与钯金属盐Pd(X)2反应，得到负载钯金属催化剂Ι；反应通式1如下所示：
其中：
所述钯盐为Pd(OAc)2、PdCl2、PdBr2、PdI2、Pd(NO3)2和Pd(SO4)2中的一种；
且，聚合物1由化合物2与壳聚糖在硫酸催化作用下反应得到，反应通式2如下所示:
上述通式中的R1、R2、R3、R4、R5、R6、R7、R8、R9、R10、R11、R12的含义均如上所述。
本发明所述的一类含膦壳聚糖负载钯金属催化剂是一种应用，用于催化Suzuki偶联反应。
作为进一步优选方案，上述催化剂的制备包括如下步骤：在惰性气体下，将所述含膦壳聚糖与钯金属盐加入有机溶剂中，在0～100℃搅拌反应0.1～24小时，除去溶剂，得到含膦壳聚糖负载钯金属催化剂。
作为更进一步优选方案，所述含膦壳聚糖与所述钯金属盐的质量比为3:1～12:1。
作为更进一步优选方案，所述钯金属盐为Pd(OAc)2、PdCl2、PdBr2或PdI2。
作为更进一步优选方案，所述惰性气氛为氩气氛或氮气氛；所述有机溶剂选自苯、甲苯、二甲苯、三甲苯、乙醚、四氢呋喃、N,N-二甲基甲酰胺、N-甲基吡咯烷酮、甲基叔丁基醚、乙二醇二甲醚、氯仿、二氯甲烷。
作为进一步优选方案，向含有所述含膦壳聚糖负载钯金属催化剂的史莱克管中加入卤代芳烃和芳基硼酸底物，在0～200℃条件下进行Suzuki偶联反应；所述卤代芳烃底物为溴苯及其相关带有其他官能团的衍生物；所述芳基硼酸底物为苯硼酸及其相关带有其他官能团的衍生物；所述炔烃底物与所述催化剂中Pd的摩尔比为2:1～200:1。
其中，所述卤代芳烃包括氯代芳烃，溴代芳烃或碘代芳烃。
作为进一步优选方案，所述含膦壳聚糖负载金属催化剂选自如下结构：
与现有技术相比，本发明具有如下显著效果：
1.本发明提供的含膦壳聚糖负载钯金属催化剂，用于Suzuki偶联反应，具有高的催化活性和循环性。
2.本发明提供的含膦壳聚糖负载钯金属催化剂的制备方法简单、反应条件温和、收率高，适于规模化生产，具有实用价值。
具体实施方式
下面将对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
为更好地理解本发明，下面通过以下实施例对本发明作进一步具体的阐述，但不可理解为对本发明的限定，对于本领域的技术人员根据上述发明内容所作的一些非本质的改进与调整，也视为落在本发明的保护范围内。
实施例1
化合物1的合成：在冰水浴下，向史莱克管中加入壳聚糖(12mg)并滴加浓硫酸，将化合物2(75mg)溶于有机溶剂并逐滴入史莱克管中，缓慢恢复至室温反应36小时。反应完毕后，产物经H2O洗涤3次，阴干称重得淡黄色固体(73mg)。
实施例2
如下含膦壳聚糖1负载钯金属催化剂Ι的合成。
在氮气气氛下，向100mL的Schlenk管里分别加入含膦壳聚糖1(50mg)，Pd(OAc)2(5mg)和四氢呋喃(4mL)。在60℃下反应24h，用石油醚洗涤反应产物后离心分离，如此离心洗涤3次。最后减压旋蒸除去石油醚，再有油泵抽3h，得到催化剂Ι(60mg)。
实施例3
催化剂Ι催化溴苯和苯硼酸(底物:催化剂＝100)的Suzuki偶联反应
在氮气气氛下，向史莱克管中加入催化剂I(9mg)、溴苯(79mg)、苯硼酸(73mg)、碳酸钾(69mg)、乙醇(3mL)和水(1mL)。然后置换史莱克管内氮气三次，室温下搅拌反应24h。反应完成后，离心收集上清液测气相，收率为99％。核磁氢谱表征数据：1H NMR(400MHz,CDCl3):δ7.58-7.52(m,4H),7.48-7.41(m,4H),7.39-7.35(m,2H).
实施例4
催化剂Ι催化对溴甲苯和苯硼酸(底物:催化剂＝100)的Suzuki偶联反应
在氮气气氛下，向史莱克管中加入催化剂I(9mg)、对溴甲苯(86mg)、苯硼酸(73mg)、碳酸钾(69mg)、乙醇(3mL)和水(1mL)。然后置换史莱克管内氮气三次，室温下搅拌反应24h。反应完成后，离心收集上清液测气相，收率为96％。
实施例5
催化剂Ι催化3-溴甲苯和苯硼酸(底物:催化剂＝100)的Suzuki偶联反应
在氮气气氛下，向史莱克管中加入催化剂I(9mg)、3-溴甲苯(86mg)、苯硼酸(73mg)、碳酸钾(69mg)、乙醇(3mL)和水(1mL)。然后置换史莱克管内氮气三次，室温下搅拌反应24h。反应完成后，离心收集上清液测气相，收率为95％。
实施例6
催化剂Ι催化2-溴甲苯和苯硼酸(底物:催化剂＝100)的Suzuki偶联反应
在氮气气氛下，向史莱克管中加入催化剂I(9mg)、2-溴甲苯(86mg)、苯硼酸(73mg)、碳酸钾(69mg)、乙醇(3mL)和水(1mL)。然后置换史莱克管内氮气三次，室温下搅拌反应24h。反应完成后，离心收集上清液测气相，收率为95％。
实施例7
催化剂Ι催化4-甲氧基溴苯和苯硼酸(底物:催化剂＝100)的Suzuki偶联反应
在氮气气氛下，向史莱克管中加入催化剂I(9mg)、4-甲氧基溴苯(94mg)、苯硼酸(73mg)、碳酸钾(69mg)、乙醇(3mL)和水(1mL)。然后置换史莱克管内氮气三次，室温下搅拌反应24h。反应完成后，离心收集上清液测气相，收率为96％。
实施例8
催化剂Ι催化溴苯和对甲基苯硼酸(底物:催化剂＝100)的Suzuki偶联反应
在氮气气氛下，向史莱克管中加入催化剂I(9mg)、溴苯(79mg)、对甲基苯硼酸(82mg)、碳酸钾(69mg)、乙醇(3mL)和水(1mL)。然后置换史莱克管内氮气三次，室温下搅拌反应24h。反应完成后，离心收集上清液测气相，收率为99％。
实施例9
催化剂Ι催化溴苯和对羟基苯硼酸(底物:催化剂＝100)的Suzuki偶联反应
在氮气气氛下，向史莱克管中加入催化剂I(9mg)、溴苯(79mg)、对羟基苯硼酸(83mg)、碳酸钾(69mg)、乙醇(3mL)和水(1mL)。然后置换史莱克管内氮气三次，室温下搅拌反应24h。反应完成后，离心收集上清液测气相，收率为98％。
实施例10
催化剂Ι催化溴苯和对甲氧基苯硼酸(底物:催化剂＝100)的Suzuki偶联反应
在氮气气氛下，向史莱克管中加入催化剂I(9mg)、溴苯(79mg)、对甲氧基苯硼酸(91mg)、碳酸钾(69mg)、乙醇(3mL)和水(1mL)。然后置换史莱克管内氮气三次，室温下搅拌反应24h。反应完成后，离心收集上清液测气相，收率为95％。
实施例11
催化剂Ι催化溴苯和对甲氧羰基苯硼酸(底物:催化剂＝100)的Suzuki偶联反应
在氮气气氛下，向史莱克管中加入催化剂I(9mg)、溴苯(79mg)、对甲氧羰基苯硼酸(108mg)、碳酸钾(69mg)、乙醇(3mL)和水(1mL)。然后置换史莱克管内氮气三次，室温下搅拌反应24h。反应完成后，离心收集上清液测气相，收率为96％。
实施例12
催化剂Ι催化溴苯和对氰基苯硼酸(底物:催化剂＝100)的Suzuki偶联反应在氮气气氛下，向史莱克管中加入催化剂I(9mg)、溴苯(79mg)、对氰基苯硼酸(88mg)、碳酸钾(69mg)、乙醇(3mL)和水(1mL)。然后置换史莱克管内氮气三次，室温下搅拌反应24h。反应完成后，离心收集上清液测气相，收率为83％。
实施例13
催化剂I催化溴苯和苯硼酸(底物:催化剂＝100)的Suzuki偶联反应循环测试
在氮气气氛下，向史莱克管中加入催化剂I(9mg)、溴苯(79mg)、苯硼酸(73mg)、碳酸钾(69mg)、乙醇(3mL)和水(1mL)。然后置换史莱克管内氮气三次，室温下搅拌反应24h。反应完成后，离心收集上清液测气相。离心收集的催化剂悬干溶剂并真空干燥后以同样的反应条件循环4次。具体测试数据如下：
对所公开的实施例的上述说明，使本领域专业技术人员能够实现或使用本发明。对这些实施例的多种修改对本领域的专业技术人员来说将是显而易见的，本文中所定义的一般原理可以在不脱离本发明的精神或范围的情况下，在其它实施例中实现。因此，本发明将不会被限制于本文所示的这些实施例，而是要符合与本文所公开的原理和新颖特点相一致的最宽的范围。
Claims (5)
1.一种含膦壳聚糖负载钯金属催化剂，其特征在于，结构通式I为：
，
其中：
R1、R2、R3、R4、R5、R6、R7、R8、R9、R10、R11、R12分别选自氢、磺酸基、卤素、腈基、C1～C12的烷烃基、C1～C10的烷氧基、C1～C10的酯基、C1～C10的磺酸酯基；
X分别独立选自OAc、Cl、Br、I、NO3、SO4中的一种；
所述的含膦壳聚糖负载钯金属催化剂的制备方法，将反应通式1中聚合物1含膦壳聚糖与钯金属盐Pd(X)2反应，得到负载钯金属催化剂I；反应通式1如下所示：
；
其中：
所述钯金属盐为Pd(OAc)2、PdCl2、PdBr2、PdI2、Pd(NO3)2和Pd(SO4)2中的一种；
且，聚合物1由化合物2与壳聚糖在硫酸催化作用下反应得到，反应通式2如下所示:
；
所述含膦壳聚糖与所述钯金属盐的质量比为3:1~12:1。
2.根据权利要求1所述的一种含膦壳聚糖负载钯金属催化剂，其特征在于，所述催化剂的制备包括如下步骤：在惰性气体下，将所述含膦壳聚糖与钯金属盐加入有机溶剂中，在0～100 ℃搅拌反应0.1～24小时，除去溶剂，得到含膦壳聚糖负载钯金属催化剂。
3.根据权利要求2所述的一种含膦壳聚糖负载钯金属催化剂，其特征在于，所述钯金属盐为Pd(OAc)2、PdCl2、PdBr2或PdI2。
4.根据权利要求2或3所述的一种含膦壳聚糖负载钯金属催化剂，其特征在于，所述惰性气体为氩气或氮气；所述有机溶剂选自苯、甲苯、二甲苯、三甲苯、乙醚、四氢呋喃、N,N-二甲基甲酰胺、N-甲基吡咯烷酮、甲基叔丁基醚、乙二醇二甲醚、氯仿或二氯甲烷。
5.一种如权利要求1所述的含膦壳聚糖负载钯金属催化剂在催化Suzuki偶联反应中的应用。
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