CN106179505B - 含膦微孔有机纳米管骨架负载钯催化剂及其合成和应用 - Google Patents
含膦微孔有机纳米管骨架负载钯催化剂及其合成和应用 Download PDFInfo
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- CN106179505B CN106179505B CN201610562966.3A CN201610562966A CN106179505B CN 106179505 B CN106179505 B CN 106179505B CN 201610562966 A CN201610562966 A CN 201610562966A CN 106179505 B CN106179505 B CN 106179505B
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- phosphine
- skeleton
- micropore
- organic nanotube
- containing phosphine
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- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 title claims abstract description 306
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 182
- 229910000073 phosphorus hydride Inorganic materials 0.000 title claims abstract description 138
- 239000002071 nanotube Substances 0.000 title claims abstract description 130
- 229910052763 palladium Inorganic materials 0.000 title claims abstract description 91
- 239000003054 catalyst Substances 0.000 title claims abstract description 89
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 27
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 66
- 239000000463 material Substances 0.000 claims abstract description 29
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000003446 ligand Substances 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 18
- 239000010970 precious metal Substances 0.000 claims abstract description 18
- 238000006161 Suzuki-Miyaura coupling reaction Methods 0.000 claims abstract description 15
- 238000004132 cross linking Methods 0.000 claims abstract description 15
- 238000010189 synthetic method Methods 0.000 claims abstract description 13
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 11
- 239000000178 monomer Substances 0.000 claims abstract description 8
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims abstract description 7
- 238000005859 coupling reaction Methods 0.000 claims abstract description 5
- 238000006555 catalytic reaction Methods 0.000 claims description 35
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 34
- 235000010290 biphenyl Nutrition 0.000 claims description 29
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 27
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 27
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- 239000002904 solvent Substances 0.000 claims description 14
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- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical group N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 8
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- AISZNMCRXZWVAT-UHFFFAOYSA-N 2-ethylsulfanylcarbothioylsulfanyl-2-methylpropanenitrile Chemical compound CCSC(=S)SC(C)(C)C#N AISZNMCRXZWVAT-UHFFFAOYSA-N 0.000 claims description 7
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- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
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- OUMKBAHMPRLISR-UHFFFAOYSA-N 1-phenyl-4-(trifluoromethyl)benzene Chemical group C1=CC(C(F)(F)F)=CC=C1C1=CC=CC=C1 OUMKBAHMPRLISR-UHFFFAOYSA-N 0.000 description 1
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- SYWDWCWQXBUCOP-UHFFFAOYSA-N benzene;ethene Chemical group C=C.C1=CC=CC=C1 SYWDWCWQXBUCOP-UHFFFAOYSA-N 0.000 description 1
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- GPAYUJZHTULNBE-UHFFFAOYSA-N diphenylphosphine Chemical compound C=1C=CC=CC=1PC1=CC=CC=C1 GPAYUJZHTULNBE-UHFFFAOYSA-N 0.000 description 1
- JJKOGDFBIDMPLF-UHFFFAOYSA-N ethenyl(phenyl)phosphane Chemical compound C=CPC1=CC=CC=C1 JJKOGDFBIDMPLF-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
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- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 125000002346 iodo group Chemical group I* 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
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- 239000013335 mesoporous material Substances 0.000 description 1
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Classifications
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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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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J35/617—500-1000 m2/g
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- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/638—Pore volume more than 1.0 ml/g
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/32—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen
- C07C1/321—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen the hetero-atom being a non-metal atom
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
- C07C17/263—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by condensation reactions
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
- C07C41/30—Preparation of ethers by reactions not forming ether-oxygen bonds by increasing the number of carbon atoms, e.g. by oligomerisation
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
- C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F120/10—Esters
- C08F120/26—Esters containing oxygen in addition to the carboxy oxygen
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
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Abstract
本发明公开了一种含膦微孔有机纳米管骨架负载钯催化剂及其合成方法。首先合成含膦微孔有机纳米管大分子前驱体,再以二甲醇缩甲醛作为交联剂,无水三氯化铁作为催化剂对大分子前驱体进行傅‑克超交联反应,合成含膦微孔有机纳米管骨架材料。利用所述含膦微孔有机纳米管骨架作为载体,骨架内膦配体为锚点,将贵金属钯络合到骨架内,形成最终的可调控的所述含膦微孔有机纳米管骨架负载钯催化剂。本发明的方法具有合成简单、单体选择性广、结构调控多样的特点。本发明还公开了所述含膦微孔有机纳米管骨架负载钯催化剂在催化含水相氯代苯体系铃木-宫浦(Suzuki‑Miyaura)偶联反应中的应用,所述催化剂的催化效率高,可循环多次使用。
Description
技术领域
本发明属于高分子合成技术领域,涉及聚合物负载贵金属钯催化剂技术领域,具体涉及一种用于催化Suzuki-Miyaura偶联反应的含膦微孔有机纳米管骨架负载钯催化剂的合成及其应用。
背景技术
近年来,由于在气体储存、分离、固相(非均相)催化等领域的诸多应用,多孔材料的研发得到科研工作者的广泛关注。相比于传统的无机多孔材料(沸石、活性炭),一些新型的有机多孔材料,如金属有机骨架材料(MOFs)、共价有机骨架材料(COFs)和微孔有机聚合物材料(MOPs)等材料陆续出现并在实际中得到广泛应用。这些有机多孔材料不仅有类似无机多孔材料的大的比表面积,而且还能在分子水平上调控材料的结构与性能。与MOFs和COFs材料相比,MOPs由于其更低的骨架密度、更好的稳定性、以及极强的可修饰性,因而常被视为应用于催化领域理想的载体。在实际中,催化反应的速率不仅取决于催化活性位点的数目,在涉及到具体的催化应用时还关系到底物的扩散速率。然而,在一些无定型的MOPs催化剂材料中,微孔占据了绝大部分,这将会影响到实际催化应用的传质速率。作为一个有效的解决方案,在MOPs中引入一定的介孔、大孔结构将会很好的提升底物在材料中的传质速率,从而增强其催化应用。目前,尽管有许多方法可以用来引入介孔、大孔,但是开发出一种可以精确控制各种孔径比例的方法仍然具有挑战性。
钯催化的Suzuki-Miyaura偶联反应一直以来被视为进行碳-碳偶联生产联苯类产物最有效的手段之一,在有机合成、制药工程等领域有着非常重要的应用价值。在实际生产中,选择更加经济、更易获取的氯代苯作为底物,对工业生产具有非常重要的意义。然而,氯代苯相对于碘代、溴代的底物而言,催化活化难度更大,而目前报道的催化剂在此领域成功的案例相对较少。由于其与反应底物的相容性以及高度可调的催化位点,均相催化剂或许可以催化这样高难度的催化反应。然而,均相催化剂难以分离的缺点也阻碍了其在工业上的高效应用。随着对负载催化剂的深入研究,科研工作者们尝试将金属有机配体负载到高比表面积的载体上,来整合均相催化剂高活性与非均催化剂相易分离的优点。但是,一般的负载方法金属有机配体负载量少,分布不易控制,也会导致催化活性的降低。因此,研制出具有高比表面积、有机配体负载量、分布可控的非均相催化剂将要非常重要的意义。
发明内容
为了克服现有技术的上述缺陷,本发明提出了一种含膦微孔有机纳米管骨架及其合成方法。其中,含膦微孔有机纳米管骨架的微孔、介孔比例,膦配体的浓度及其分布都可以进行有效调控,同时具有大的比表面积、优良的化学稳定性。本发明还提出了由所述含膦微孔有机纳米管骨架制备含膦微孔有机纳米管骨架负载钯催化剂的合成方法,将所述含膦微孔有机纳米管骨架负载钯后形成所述含膦微孔有机纳米管骨架负载钯催化剂,所述催化剂用于催化含水体系氯代苯的Suzuki-Miyaura偶联反应,表现出优异的催化性能,与微孔材料负载钯催化剂、均相钯催化剂相比,本发明提出的新型催化剂含膦微孔有机纳米管骨架负载钯催化剂拥有更高的催化反应速率,较多的循环次数,较好的稳定性。因此,新型含膦微孔有机纳米管骨架材料的制备及其负载钯催化的研究,不仅可以拓宽有机多孔材料的研究领域,而且可以推动工业催化领域进一步的发展,对丰富多孔材料负载催化的研究,使其朝着功能化、稳定化、多样化、工业化的方向发展具有重要的意义。
本发明提出了一种含膦微孔有机纳米管骨架的合成方法,采用聚合物瓶状分子刷软模板制备含膦微孔有机纳米管骨架,所述方法包括:
(1)以甲基丙烯酸缩水甘油酯(GM)为单体,通过可逆加成-裂解-链转移(RAFT)聚合生成PGM主链(A);在采用酸将主链上的环氧基水解成羟基之后,在1,8-二氮杂二环[5,4,0]十一烯-7(DBU)的催化下引发D,L-丙交酯(LA)开环聚合,生成PLA聚乳酸降解层(B);随后,在羟基末端安装RAFT链转移剂之后,将二苯基膦(或称为对乙烯基苯基膦)(DPPS)与苯乙烯(S)共聚引入到外层用于交联、引入膦配体基团;最终,得到含膦微孔有机纳米管骨架材料前驱体(C);反应过程如下反应式(1)所示:
(2)将上述得到的含膦微孔有机纳米管骨架材料前驱体(C)用二甲醇缩甲醛,四氯化碳等交联剂与三氯化铁,三氯化铝等催化剂催化超交联,一步得到含膦微孔有机纳米管骨架,如式(a)所示;
本发明还提出了由上述方法制备得到的含膦微孔有机纳米管骨架,含膦微孔有机纳米管骨架结构可调控,其微孔孔壁内含有膦配体,网络骨架由苯乙烯和二苯基(对乙烯基苯基)膦共交联组成,微孔主要存在于聚[二苯基(对乙烯基苯基)膦/苯乙烯]骨架缝隙中,其结构组成可表示为DPPS/S,其中,DPPS既作为纳米管的骨架,又提供了膦配体基团。所述含膦微孔有机纳米管骨架的比表面积为542~763m2/g,孔体积0.73~1.21cm3/g;所述含膦微孔有机纳米管骨架的微孔孔径分布主要集中在1.28nm,介孔孔径分布通过调控聚乳酸核层的聚合度,主要集中在3.17和4.76nm之间。
其中,所述含膦微孔有机纳米管骨架的结构如以下式(a)所示:
本发明还提出了含膦微孔有机纳米管骨架负载钯催化剂的合成方法,其包括如下步骤:
(1)以甲基丙烯酸缩水甘油酯(GM)为单体,通过可逆加成-裂解-链转移(RAFT)聚合生成PGM主链(A),并采用酸将主链上的环氧基水解成羟基之后,;在1,8-二氮杂二环[5,4,0]十一烯-7(DBU)的催化下引发D,L-丙交酯(LA)开环聚合,生成PLA聚乳酸降解层(B);然后在羟基末端安装RAFT链转移剂之后,;接着,将二苯基(对乙烯基苯基)膦(DPPS)与苯乙烯(S)共聚引入到外层用于交联、引入膦配体基团;最终,得到含膦微孔有机纳米管骨架材料前驱体(C);
(2)将上述得到的含膦微孔有机纳米管骨架材料前驱体用二甲醇缩甲醛,四氯化碳等交联剂与三氯化铁,三氯化铝等催化剂催化超交联,一步得到含膦微孔有机纳米管骨架;
(3)将上述得到的含膦微孔有机纳米管骨架材料与氯化钯共混,使钯金属配位到含膦微孔有机纳米管骨架内,最终得到含膦微孔有机纳米管骨架负载钯催化剂。
本发明合成方法中,所述含膦微孔有机纳米管骨架前驱体的制备过程,以GM为单体,通过RAFT聚合,合成PGM主链(A),并将主链上的环氧基水解成羟基;在DBU的催化下引发D,L-丙交酯开环聚合,生成PLA聚乳酸降解层(B);然后在羟基末端安装RAFT链转移剂;接着,将二苯基(对乙烯基苯基)膦(DPPS)与苯乙烯(S)共聚引入到外层用于交联、引入膦配体基团;最终,得到含膦微孔有机纳米管骨架材料前驱体(C);所述含膦微孔有机纳米管骨架前驱体在二甲醇缩甲醛交联剂与三氯化铁催化剂的作用下发生交联,一步得到含膦微孔有机纳米管骨架;将上述得到的含膦微孔有机纳米管骨架材料与氯化钯共混,使钯金属配位到含膦微孔有机纳米管骨架内,最终得到含膦微孔有机纳米管骨架负载钯催化剂,如式(b)所示。反应过程如反应式(2)所示。
具体地,含膦微孔有机纳米管骨架负载钯催化剂的合成方法,包括:
(1)含膦微孔有机纳米管骨架大分子前驱体的合成
(a)聚甲基丙烯酸缩水甘油酯(PGM)主链的合成
以甲基丙烯酸缩水甘油酯(GM)为单体,通过可逆加成-裂解-链转移(RAFT)聚合,合成聚甲基丙烯酸缩水甘油酯(PGM)主链(A);
(b)PGM主链的水解
将PGM主链上的环氧基水解成羟基(OH);
(c)poly(GM-g-LA)的合成
在1,8-二氮杂二环十一碳-7-烯(DBU)的催化下引发D,L-丙交酯开环聚合,在PGM支链上生成聚乳酸(PLA)降解层(B);
(d)poly(GM-g-LA)-TC的合成
将RAFT链转移剂(TC)安装到上述的聚乳酸PLA降解层的羟基末端;
(e)poly(GM-g-LA-g-S/DPPS)的合成
将苯乙烯(S)/二苯基(对乙烯基苯基)膦(DPPS)共聚接枝到所述PGM-g-PLA-TC分子支链上,作为交联层用于交联;最终,得到含膦微孔有机纳米管骨架材料前驱体(C);
得到式(C)所示的含膦微孔有机纳米管骨架大分子的前驱体,其中各组分的聚合度可以通过改变不同的投料比来调控。
(2)傅-克超交联反应合成含膦微孔有机纳米管骨架
将上述得到的式(C)所示的一种含膦微孔有机纳米管骨架大分子的前驱体用交联剂与催化剂对聚[苯乙烯(S)/二苯基(对乙烯基苯基)膦(DPPS)]交联层进行傅-克超交联反应;
(3)含膦微孔有机纳米管骨架负载钯催化剂的合成
以贵金属盐氯化钯为金属源,将钯配位络合负载于微孔有机纳米管骨架孔内壁;最终得到式(b)所示的含膦微孔有机纳米管骨架负载钯催化剂。
本发明含膦微孔有机纳米管骨架和/或含膦微孔有机纳米管骨架负载钯催化剂的合成方法中,
所述步骤(1)中,用于水解主链环氧基的酸为乙酸、稀盐酸和硫酸等。优选地,为乙酸。
所述步骤(1)中,二苯基(对乙烯基苯基)膦的结构为
所述步骤(1)中,用于合成含膦微孔有机纳米管骨架负载钯催化剂的前驱体的方法为可逆加成-裂解-链转移(RAFT)聚合和从主链接枝法(graft from);其中,所述可逆加成-裂解-链转移(RAFT)也称可逆加成-断裂-链转移(RAFT)。
其中,步骤(a)的反应条件为溶剂为苯,引发剂为偶氮二异丁腈,反应温度为60摄氏度;
其中,步骤(b)的反应条件为溶剂为四氢呋喃,酸为乙酸,反应温度为60摄氏度;
其中,步骤(c)的反应条件为溶剂为干燥的二甲基甲酰胺,碱为DBU,酸为苯甲酸,反应温度为室温;
其中,步骤(d)的反应条件为溶剂为干燥的二氯甲烷,酰化剂为草酰氯,温度为室温;
其中,步骤(e)的反应条件为溶剂为甲苯,引发剂为偶氮二异丁腈,温度是60摄氏度;
所述步骤(2)中,用于交联聚[苯乙烯/二苯基(对乙烯基苯基)膦]的交联剂为二甲醇缩甲醛。
所述步骤(2)中,用于交联聚[苯乙烯/二苯基(对乙烯基苯基)膦]的催化剂为三氯化铁。
所述步骤(2)中,用于交联聚[苯乙烯/二苯基(对乙烯基苯基)膦]的交联剂,催化剂与原料的摩尔比为5:5:1,反应溶剂为干燥的二氯乙烷,反应温度为95摄氏度,反应时间为72h。
所述步骤(3)中,钯源氯化钯与含膦微孔有机纳米管骨架的摩尔比为2:1,反应溶剂为乙腈,反应温度为80摄氏度,回流反应时间为12h。。
本发明还提出了由上述方法制备得到的含膦微孔有机纳米管骨架负载钯催化剂,包括含膦微孔有机纳米管骨架和贵金属催化功能基团,微观形貌上其具有中空微孔有机纳米管网状结构,属于一种有机微介孔材料。含膦微孔有机纳米管骨架结构可调控,其微孔孔壁内含有膦配体,网络骨架由苯乙烯和二苯基(对乙烯基苯基)膦共交联组成,微孔主要存在于聚[二苯基(对乙烯基苯基)膦/苯乙烯]骨架缝隙中,其结构组成可表示为DPPS/S,其中,DPPS既作为纳米管的骨架,又提供了膦配体基团。所述贵金属催化功能基团来源为贵金属盐氯化钯,其与膦配体络合负载于微孔有机纳米管骨架的微孔孔壁内;所述含膦微孔有机纳米管骨架负载钯催化剂的比表面积为538~696m2/g,孔体积0.70~1.07cm3/g;所述含膦微孔有机纳米管骨架负载钯催化剂的微孔孔径分布主要集中在1.17nm,介孔孔径分布通过调控聚乳酸核层的聚合度,主要集中在3.17和4.76nm;其中,微孔孔径从1.28nm降为1.17nm主要源于钯金属部分占据微孔孔道所致。
其中,所述含膦微孔有机纳米管骨架负载贵金属钯催化剂的结构如以下式(b)所示:
本发明含膦微孔有机纳米管骨架负载钯催化剂可重复循环使用多次且催化活性基本不变。优选地,其可重复循环使用5次,催化活性基本保持不变。
本发明还提出了所述含膦微孔有机纳米管骨架负载钯催化剂在催化含水体系的有机反应中的应用。
本发明还提出了所述含膦微孔有机纳米管骨架负载钯催化剂在催化油溶性有机反应铃木-宫浦(Suzuki-Miyaura)偶联反应中的应用。
本发明还提出了含膦微孔有机纳米管骨架负载钯催化剂可催化含水体系氯代苯类Suzuki-Miyaura偶联反应,具体提出了含膦微孔有机纳米管骨架负载钯催化剂在催化氯苯与苯硼酸交叉偶联反应中的应用,所述应用的步骤包括:将负载有钯的含膦微孔有机纳米管骨架催化剂分散于乙醇和水的混合溶剂,加入催化底物氯苯和苯硼酸,如反应式(i)所示。在氮气保护下,80℃下反应3h,氯苯的转化率大于99%。反应体系通过离心方式将固体催化剂进行回收。重复循环5次,催化活性基本保持不变;
本发明还提出了所述含膦微孔有机纳米管骨架负载钯催化剂在催化其他不同取代基的氯代苯、不同取代基的苯硼酸发生交叉偶联的应用,具有较好的普适性,其结果如表1所示。
本发明还提出了所述含膦微孔有机纳米管骨架负载钯催化剂在催化其他不同取代基氯代苯与芳基硼酸交叉偶联反应中的应用,所述应用的步骤包括:将负载有钯的含膦微孔有机纳米管骨架催化剂分散于乙醇和水的混合溶剂,加入催化底物,在氮气保护下,80℃下反应到一定的时间,其结果如表1所示。
表1含膦微孔有机纳米管骨架负载贵金属钯催化剂催化其他不同取代基氯代苯与芳基硼酸Suzuki-Miyaura交叉偶联反应。
本发明公开了一种含膦微孔有机纳米管骨架负载钯催化剂及其合成方法。首先合成含膦微孔有机纳米管大分子前驱体(聚乳酸-聚[二苯基(对乙烯基苯基)膦/苯乙烯]核-壳瓶刷状大分子),再以二甲醇缩甲醛作为交联剂,无水三氯化铁作为催化剂对大分子前驱体进行傅-克超交联反应,一步合成出含膦微孔有机纳米管骨架材料。作为调控手段,可通过改变不同单体的投料比来调控大分子前驱体中核-壳组分的聚合度,进而来调控含膦微孔有机纳米管骨架的微、介孔体积的相对比例,膦配体的含量及其分布。具体地,本发明中大分子前驱体采用可降解的聚乳酸(PLA)为核层,聚合度分别为24和46;采用聚[二苯基(对乙烯基苯基)膦/苯乙烯为交联层,聚合度分别为7/88和15/106;如上两种不同比列的前驱体分别进行超交联,得到两种不同核-壳比例、不同膦配体含量的骨架材料;其中,PLA聚合度为24时,所得骨架介孔孔径主要为3.17nm;PLA聚合度为46时,所得骨架介孔孔径主要为4.76nm,如上从而达到调控骨架的目的。利用所述含膦微孔有机纳米管骨架作为载体,骨架内膦配体为锚点,将贵金属钯络合到骨架内,形成最终的可调控的所述含膦微孔有机纳米管骨架负载钯催化剂。本发明还公开了含膦微孔有机纳米管骨架负载钯催化剂在催化含水相氯代苯体系铃木-宫浦(Suzuki-Miyaura)偶联反应中的应用。
本发明的方法具有合成简单、单体选择性广、结构调控多样等优点,具有很好的工业应用前景。在此基础上,本发明所提出的含膦微孔有机纳米管骨架比表面积大,具有很好的应用前景。与现有负载催化剂相比,本发明含膦微孔有机纳米管骨架负载钯催化剂为中空微孔有机纳米管网络负载钯催化剂,具有分离简单快速,催化效率高,可循环多次使用等特点。本发明所提出的含膦微孔有机纳米管骨架,合成方法简单,结构可控,比表面积大,具有很好的应用前景。在应用上具有分离简单快速,催化效率高,可循环多次使用等特点。含膦微孔有机纳米管骨架负载贵金属钯催化剂的研究,对丰富多孔材料负载催化的研究,使其朝着功能化、稳定化、多样化、工业化的方向发展具有重要的意义。
附图说明
图1表示实施例1成的含膦微孔有机纳米管前驱体1HNMR图。
图2表示实施例1成的含膦微孔有机纳米管骨架负载贵金属钯催化剂负载前后的红外示意图;其中,(A)为负载前,(B)为负载后;结果显示负载前后在1437cm-1处的P-C峰保持,说明膦配体稳定存在材料中。
图3表示实施例1合成的含膦微孔有机纳米管骨架负载贵金属钯催化剂的TEM图;结果显示负载后含膦微孔有机纳米管骨架负载贵金属钯催化剂仍然保持中空管状形貌,说明其结构稳定。
图4表示实施例1合成的含膦微孔有机纳米管骨架负载贵金属钯催化剂催化不同取代基氯代苯与芳基硼酸Suzuki-Miyaura交叉偶联反应产物的1H NMR图;其中,(A)为联苯,(B)为乙酰基联苯,(C)为4-硝基联苯,(D)为4-甲基联苯,(E)为4-甲氧基联苯,(F)为4-三氟甲基联苯。
具体实施方式
结合以下具体实施例和附图,对本发明作进一步的详细说明,本发明的保护内容不局限于以下实施例。在不背离发明构思的精神和范围下,本领域技术人员能够想到的变化和优点都被包括在本发明中,并且以所附的权利要求书为保护范围。实施本发明的过程、条件、试剂、实验方法等,除以下专门提及的内容之外,均为本领域的普遍知识和公知常识,本发明没有特别限制内容。
本发明含膦微孔有机纳米管骨架负载贵金属钯催化剂的合成方法,包括以下步骤:
(1)以甲基丙烯酸缩水甘油酯(GM)为单体,通过可逆加成-裂解-链转移(RAFT)聚合生成PGM主链(A),并将主链上的环氧基水解成羟基;在1,8-二氮杂二环[5,4,0]十一烯-7(DBU)的催化下引发D,L-丙交酯(LA)开环聚合,生成PLA聚乳酸降解层(B);然后在羟基末端安装RAFT链转移剂;接着,将二苯基(对乙烯基苯基)膦(DPPS)与苯乙烯(S)共聚引入到外层用于交联、引入膦配体基团;最终,得到含膦微孔有机纳米管骨架材料前驱体(C);
如下反应式(1)所示:
(2)将上述得到的含膦微孔有机纳米管骨架材料前驱体用二甲醇缩甲醛交联剂与三氯化铁催化剂催化超交联,一步得到含膦微孔有机纳米管骨架材料;
(3)将上述得到的含膦微孔有机纳米管骨架材料与氯化钯共混,使钯金属配位到含膦微孔有机纳米管骨架内,最终得到含膦微孔有机纳米管骨架负载钯催化剂;其中,所述含膦微孔有机纳米管骨架负载钯催化剂应用于催化含水体系氯代苯类Suzuki-Miyaura偶联反应中。
所述步骤(1)包括以下步骤:
(a)合成PGM主链:
甲基丙烯酸缩水甘油酯(GM,1ml),偶氮二异丁腈(AIBN,1.2mg),RAFT试剂(18mg),苯(1ml)加入到反应试管中,冷冻循环3次除去氧气后在60℃下封管反应。反应结束后在甲醇中沉淀,用二氯甲烷溶解,沉淀溶解循环3次。核磁结果显示其聚合度为200。
(b)PGM主链的水解:
将步骤1中合成的主链(PGM,1g)溶于四氢呋喃(THF,20ml)中,冰醋酸(40ml),在60℃下慢慢加入60ml水。反应24h后在乙醚中沉淀,用甲醇溶解,沉淀溶解3次。
(c)合成poly(GM-g-LA):
将50mg水解后的PGM溶解在4.5ml干燥的N,N-二甲基甲酰胺(DMF)中,加入重结晶后的D,L-丙交酯1.8g,接着用微量进样器加入54ulDBU。在室温下反应1.5h。再往反应液中加入苯甲酸162mg,反应0.5h。反应结束后在甲醇与水1:1的混合溶剂中沉淀,用四氢呋喃溶解,沉淀溶解重复3次。
(d)合成poly(GM-g-LA)-TC:
在干燥的圆底烧瓶中用1.5ml干燥的二氯甲烷溶解0.8gRAFT试剂,加入2.1ml草酰氯,反应2h。反应完后在真空下将溶剂和未反应完的草酰氯抽去,再加入用4ml干燥二氯甲烷溶解好的poly(GM-g-LA)(0.85g),加入反应瓶中。反应24h。反应结束后沉淀在甲醇中,用二氯甲烷溶解,沉淀溶解重复3次。
(e)poly(GM-g-LA-g-S/DPPS)的合成
将poly(GM-g-LA)-TC(20mg)、苯乙烯(S)(1.38ml)和二苯基(对乙烯基苯基)膦(DPPS)(170mg)溶解于1.38ml甲苯中,以AIBN(0.32mg)为引发剂,冷冻循环3次除去氧气后在60℃下封管反应一定的时间。反应结束后在甲醇中沉淀,二氯甲烷中溶解,沉淀溶解循环3次。核磁结果见图1。
所述步骤(2)包括:
(f)含膦微孔有机纳米管骨架的合成
将poly(GM-g-LA-g-S/DPPS)溶解于干燥的1,2-二氯乙烷中,通氮气30分钟除氧后,用二甲醇缩甲醛交联剂与三氯化铁催化剂催化交联。结束后所得不溶固体分别用水与甲醇洗至上清液为无色。红外测试结果显示在1437cm-1处的P-C峰保持,说明膦配体稳定存在材料中。见图2。
所述步骤(3)包括:
(g)含膦微孔有机纳米管骨架负载钯催化剂的制备
将上述含膦微孔有机纳米管骨架分散于乙腈溶剂中,加入氯化钯后,80℃回流12h。所得固体用丙酮洗至上清液无色。
实施例1:
(1)含膦微孔有机纳米管骨架前驱体的合成
在反应试管中加入40mgpoly(GM-g-LA),182mg DPPS,1.44mlS,0.34mgAIBN,1.44ml甲苯,经过冷冻-泵-解冻的方法3次除氧后,在60℃下反应12h。反应结束后将反应液沉淀在甲醇中,经离心后,溶于二氯甲烷中,沉淀在甲醇中,重复3次。1HNMR in d-THF,n(DPPS)=7,n(S)=88。
(2)含膦微孔有机纳米管骨架负载贵金属钯催化剂的制备
在圆底烧瓶中,70mgpoly(GM-g-LA-g-S/DPPS)溶于干燥的5ml 1,2-二氯乙烷中,通氮气除氧后,加入224uL二甲醇缩甲醛与405mg三氯化铁,在95℃下反应72h。结束后所得不溶固体分别用水与甲醇洗至上清液为无色。50℃真空干燥24h。
(3)含膦微孔有机纳米管骨架负载钯催化剂催化含水体系氯代苯类Suzuki-Miyaura偶联反应:
在反应瓶中将20mg含膦微孔有机纳米管骨架负载钯催化剂分散于2ml乙醇和水(1.2:0.8)混合溶剂中,加入0.5mmol氯代苯,0.75mmol苯硼酸,1.5mmol碳酸钾。在氮气保护下80℃下反应一定时间。通过核磁计算其固体产率(数值如下),其中,图4为含膦微孔有机纳米管骨架负载贵金属钯催化剂催化不同取代基氯代苯与芳基硼酸Suzuki-Miyaura交叉偶联反应产物的1H NMR图;其中,(A)为联苯,(B)为乙酰基联苯,(C)为4-硝基联苯,(D)为4-甲基联苯,(E)为4-甲氧基联苯,(F)为4-三氟甲基联苯。
(A)联苯
1H NMR(500MHz,CDCl3):δ7.59(d,J=7.5Hz,4H);7.45(t,J=7.5Hz,4H);7.35(tt,2H).产率99%。
(B)乙酰基联苯
1H NMR(500MHz,CDCl3):δ8.04(d,J=8.5Hz,2H);δ7.69(d,J=8.5Hz,2H);δ7.64(d,J=8.5Hz,2H);δ7.44(m,3H);δ2.64(s,3H).产率95%。
(C)4-硝基联苯
1H NMR(500MHz,CDCl3):δ8.30(d,J=8.5Hz,2H);δ7.74(d,J=8.5Hz,2H);δ7.62(d,J=7.5Hz,2H);δ7.50(m,3H).产率93%。
(D)4-甲基联苯
1H NMR(500MHz,CDCl3):δ7.58(d,J=8.0Hz,2H);δ7.49(d,J=8.0Hz,2H);δ7.43(t,J=7.5Hz,2H);δ7.31(m,1H);δ7.25(d,J=8.0Hz,2H);δ2.39(s,3H).产率95%/91%,分别对应表1中反应4和反应7。
(E)4-甲氧基联苯
1H NMR(500MHz,CDCl3):δ7.55(m,4H);δ7.42(d,J=7.5Hz,2H);δ7.31(t,J=7.5Hz,1H);δ6.98(d,J=9.0Hz,2H);δ3.86(s,3H).产率87%。
(F)4-三氟甲基联苯
1H NMR(500MHz,CDCl3):δ7.70(s,4H);δ7.59(d,J=8.0Hz,2H);δ7.42(m,3H).产率97%。
实施例2:
(1)含膦微孔有机纳米管骨架前驱体的合成
在反应试管中加入40mg poly(GM-g-LA),364mg DPPS,1.44ml S,0.34mg AIBN,1.44ml甲苯,经过冷冻-泵-解冻的方法3次除氧后,在60℃下反应17h。反应结束后将反应液沉淀在甲醇中,经离心后,溶于二氯甲烷中,沉淀在甲醇中,重复3次。1HNMR in d-THF,n(DPPS)=15,n(S)=106。
(2)含膦微孔有机纳米管骨架负载贵金属钯催化剂的制备
在圆底烧瓶中,180mgpoly(GM-g-LA-g-S/DPPS)溶于干燥的36ml 1,2-二氯乙烷中,通氮气除氧后,加入623uL二甲醇缩甲醛与1.14g三氯化铁,在95℃下反应72h。结束后所得不溶固体分别用水与甲醇洗至上清液为无色。50℃真空干燥24h。
(3)含膦微孔有机纳米管骨架负载钯催化剂催化含水体系氯代苯类Suzuki-Miyaura偶联反应:
在反应瓶中将与实施例1相同钯含量的含膦微孔有机纳米管骨架负载钯催化剂分散于2ml乙醇和水(1.2:0.8)混合溶剂中,加入0.5mmol氯代苯,0.75mmol苯硼酸,1.5mmol碳酸钾。在氮气保护下80℃下反应一定时间。在使用相同钯含量的条件下,选用上述催化模型实验,实施例2所用的催化剂表现出更好的催化反应速率,反应时间缩短为2h。这是因为实施例2中的催化剂介孔孔径扩大,使得反应物及产物在与催化剂作用时传质速率得到进一步提高,从而加快催化反应速率。
本发明的保护内容不局限于以上实施例。在不背离发明构思的精神和范围下,本领域技术人员能够想到的变化和优点都被包括在本发明中,并且以所附的权利要求书为保护范围。
Claims (13)
1.一种含膦微孔有机纳米管骨架负载钯催化剂的合成方法,其特征在于,包括以下步骤:
(1)含膦微孔有机纳米管骨架大分子前驱体的合成
(a)聚甲基丙烯酸缩水甘油酯(PGM)主链的合成
以甲基丙烯酸缩水甘油酯(GM)为单体,通过可逆加成-裂解-链转移(RAFT)聚合,合成聚甲基丙烯酸缩水甘油酯(PGM)主链(A);
(b)PGM主链的水解
将PGM主链上的环氧基水解成羟基(OH);
(c)poly(GM-g-LA)的合成
在1,8-二氮杂二环十一碳-7-烯(DBU)的催化下引发D,L-丙交酯(LA)开环聚合,在PGM支链上生成聚乳酸(PLA)降解层(B);
(d)poly(GM-g-LA)-TC的合成
将RAFT链转移剂TC安装到上述的聚乳酸PLA降解层的羟基末端;
(e)poly(GM-g-LA-g-S/DPPS)的合成
将苯乙烯(S)/二苯基(对乙烯基苯基)膦(DPPS)共聚接枝到所述PGM-g-PLA-TC分子支链上,作为交联层用于交联;最终,得到含膦微孔有机纳米管骨架材料前驱体(C);
上述反应过程如反应式(1)所示:
(2)傅-克超交联反应合成含膦微孔有机纳米管骨架
将步骤(1)得到的含膦微孔有机纳米管骨架大分子的前驱体用交联剂与催化剂对聚[苯乙烯(S)/二苯基(对乙烯基苯基)膦(DPPS)]交联层进行傅-克超交联反应;
(3)含膦微孔有机纳米管骨架负载钯催化剂的合成
以贵金属盐氯化钯为金属源,将钯配位络合负载于微孔有机纳米管骨架孔内壁,得到所述含膦微孔有机纳米管骨架负载钯催化剂,如式(b)所示;
所述方法如反应式(2)所示;
2.如权利要求1所述的方法,其特征在于,所述步骤(1)中,
步骤(a)的反应条件:溶剂为苯,引发剂为偶氮二异丁腈,反应温度为60摄氏度;
步骤(b)的反应条件:溶剂为四氢呋喃,酸为乙酸,反应温度为60摄氏度;
步骤(c)的反应条件:溶剂为干燥的二甲基甲酰胺,碱为DBU,酸为苯甲酸,反应温度为室温;
步骤(d)的反应条件:溶剂为干燥的二氯甲烷,酰化剂为草酰氯,温度为室温;
步骤(e)的反应条件:溶剂为甲苯,引发剂为偶氮二异丁腈,温度是60摄氏度;
3.如权利要求1所述的方法,其特征在于,所述步骤(2)的反应条件:干燥的二氯乙烷为溶剂,二甲醇缩甲醛为交联剂,三氯化铁为催化剂,95摄氏度反应72小时。
4.如权利要求1所述的方法,其特征在于,所述步骤(3)的反应条件:乙腈为溶剂,二氯化钯为钯源,80摄氏度回流12小时。
5.一种如权利要求1所述方法合成的含膦微孔有机纳米管骨架负载钯催化剂,其特征在于,其形貌为多孔网状结构,比表面积为538~696m2/g,孔体积0.70~1.07cm3/g。
6.如权利要求5所述的含膦微孔有机纳米管骨架负载钯催化剂,其特征在于,所述含膦微孔有机纳米管骨架材料的微孔孔壁内含有膦配体,网络骨架由苯乙烯和二苯基(对乙烯基苯基)膦共交联组成,微孔主要存在于聚[二苯基(对乙烯基苯基)膦/苯乙烯]骨架缝隙中。
7.如权利要求5所述的含膦微孔有机纳米管骨架负载钯催化剂,其特征在于,所述贵金属催化功能基团来源为贵金属盐氯化钯,其与膦配体络合负载于微孔有机纳米管骨架的微孔孔壁内。
8.一种含膦微孔有机纳米管骨架,其特征在于,含膦微孔有机纳米管骨架结构可调控,其微孔孔壁内含有膦配体,网络骨架由苯乙烯和二苯基(对乙烯基苯基)膦共交联组成,微孔主要存在于聚[二苯基(对乙烯基苯基)膦/苯乙烯]骨架缝隙中,其结构组成可表示为DPPS/S,其中,DPPS既作为纳米管的骨架,又提供了膦配体基团;所述含膦微孔有机纳米管骨架的比表面积为542~763m2/g,孔体积0.73~1.21cm3/g;所述含膦微孔有机纳米管骨架的合成方法如权利要求1中步骤(1)和(2)所述。
9.如权利要求5所述的含膦微孔有机纳米管骨架负载钯催化剂在催化有机反应中的应用。
10.如权利要求5所述的含膦微孔有机纳米管骨架负载钯催化剂在催化油溶性有机反应铃木-宫浦(Suzuki-Miyaura)偶联反应中的应用。
11.如权利要求5所述的含膦微孔有机纳米管骨架负载钯催化剂在催化含水体系氯代苯类Suzuki-Miyaura偶联反应中的应用。
12.如权利要求5所述的含膦微孔有机纳米管骨架负载钯催化剂在催化氯苯与苯硼酸交叉偶联反应中的应用。
13.如权利要求8所述的含膦微孔有机纳米管骨架在制备含膦微孔有机纳米管骨架负载钯催化剂中的应用。
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Publication number | Priority date | Publication date | Assignee | Title |
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Non-Patent Citations (1)
Title |
---|
Carboxyl-containing microporous organic nanotube networks as a platform for Pd catalysts;Yang Xu, et al;《RSC Adv.》;20160415;第6卷;第39933-39939页 * |
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