CN105906787A - 一种钯催化剂及其制备方法和用途 - Google Patents
一种钯催化剂及其制备方法和用途 Download PDFInfo
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 83
- 239000003054 catalyst Substances 0.000 title claims abstract description 48
- 229910052763 palladium Inorganic materials 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000000178 monomer Substances 0.000 claims abstract description 13
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 23
- 238000006116 polymerization reaction Methods 0.000 claims description 20
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 15
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 150000001875 compounds Chemical class 0.000 claims description 15
- -1 2-bromo isobutyl acylbromide Chemical class 0.000 claims description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- VOCGYYOMSGYEJV-UHFFFAOYSA-N benzene cyanide Chemical class N#[C-].C1=CC=CC=C1 VOCGYYOMSGYEJV-UHFFFAOYSA-N 0.000 claims description 12
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- 239000012074 organic phase Substances 0.000 claims description 9
- 238000010898 silica gel chromatography Methods 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- 239000003208 petroleum Substances 0.000 claims description 6
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 5
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 5
- 239000003480 eluent Substances 0.000 claims description 5
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- 238000000034 method Methods 0.000 claims description 4
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- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
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- QWXYZCJEXYQNEI-OSZHWHEXSA-N intermediate I Chemical compound COC(=O)[C@@]1(C=O)[C@H]2CC=[N+](C\C2=C\C)CCc2c1[nH]c1ccccc21 QWXYZCJEXYQNEI-OSZHWHEXSA-N 0.000 claims description 3
- 150000002825 nitriles Chemical class 0.000 claims description 3
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- ASWXNYNXAOQCCD-UHFFFAOYSA-N dichloro(triphenyl)-$l^{5}-phosphane Chemical compound C=1C=CC=CC=1P(Cl)(C=1C=CC=CC=1)(Cl)C1=CC=CC=C1 ASWXNYNXAOQCCD-UHFFFAOYSA-N 0.000 claims description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 2
- 150000003863 ammonium salts Chemical class 0.000 claims 1
- 238000005660 chlorination reaction Methods 0.000 claims 1
- 239000012266 salt solution Substances 0.000 claims 1
- 229920006395 saturated elastomer Polymers 0.000 claims 1
- 150000002527 isonitriles Chemical class 0.000 abstract description 9
- 229920000642 polymer Polymers 0.000 abstract description 8
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 abstract description 3
- 238000009826 distribution Methods 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 230000002194 synthesizing effect Effects 0.000 abstract description 2
- 230000000379 polymerizing effect Effects 0.000 abstract 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- 239000000047 product Substances 0.000 description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000010560 atom transfer radical polymerization reaction Methods 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 101710141544 Allatotropin-related peptide Proteins 0.000 description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 5
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- 229910052757 nitrogen Inorganic materials 0.000 description 3
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- 238000000710 polymer precipitation Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000010948 rhodium Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical class [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 2
- 229910001914 chlorine tetroxide Inorganic materials 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 244000144992 flock Species 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Chemical compound [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 2
- SUSQOBVLVYHIEX-UHFFFAOYSA-N phenylacetonitrile Chemical compound N#CCC1=CC=CC=C1 SUSQOBVLVYHIEX-UHFFFAOYSA-N 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical group 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- 125000003006 2-dimethylaminoethyl group Chemical group [H]C([H])([H])N(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- MQWSHBCKOSWEFJ-UHFFFAOYSA-N CC[P] Chemical compound CC[P] MQWSHBCKOSWEFJ-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000005059 dormancy Effects 0.000 description 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- FOSDKQXKZPWNNK-UHFFFAOYSA-N isocyanoethene Chemical compound C=C[N+]#[C-] FOSDKQXKZPWNNK-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 150000002896 organic halogen compounds Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
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- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- 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
- C07F15/006—Palladium compounds
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
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- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/33—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain
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Abstract
本发明公开了一种钯催化剂及其制备方法和用途,其中钯催化剂的结构由如下通式表示:上式中R选自‑CH2CH3或‑Ph;本发明钯催化剂具有很好的催化异腈聚合能力,合成容易,稳定性好,可用于苯乙烯类,苯异腈类单体的活性/可控聚合,所得的聚合物具有较高的分子量和较窄的分子量分布。
Description
技术领域
本发明属于聚合物催化领域,具体涉及一种钯催化剂及其制备方法和用途,该催化剂可以用于催化苯乙烯及异腈类化合物活性聚合。
背景技术
聚异腈是第一个被报道的具有稳定螺旋构象的聚合物,在手性分子识别,不对称催化以及对映体分离等领域都有重要的研究意义和应用前景。如今异腈聚合最常用的催化剂是过渡金属络合物,如Ni(II),Pd(II)-Pt(II)或Rh(III)络合物。Ni(II)是最早发现用于异腈聚合的标准催化剂,主要有NiCl2·6H2O,Ni(ClO4)2·6H2O,Ni(acac)2等形式,其中NiCl2·6H2O,Ni(ClO4)2·6H2O对脂肪族异腈的活性聚合有效,而Ni(acac)2则是乙烯基异腈聚合的高效催化剂。而Pd(II)-Pt(II)络合物主要用于芳香族异腈的聚合,得到的聚合物具有分子量分布窄,单体转化率高等特性。然而,邻位连有大取代基的苯异腈不能被Ni(II)和Pd(II)–Pt(II)络合物引发聚合,Yamamoto等人通过不断实验最终得出这类邻位连有大取代基团的苯异腈的聚合可以通过有机铑络合物来实现。但是这些催化剂均有其不足之处,如二价镍盐催化的可控性差;Pd-Pt络合物的结构不易裁剪和修饰,聚合过程对氧气和水很敏感,并且金属Pt价格昂贵;铑络合物合成困难,且聚合过程中需要加入大量的配体添加剂等。
原子转移自由基聚合(atom transfer radicalpolymerization,ATRP)是一种强大且灵活的合成技术,由于其具有分子量可控、分子量分布窄、聚合物端基易修饰及分子设计能力强,因此被称为精确可控大分子结构的合成方法。如今ATRP技术已成功应用于接枝、嵌段、梳状、星型、超支化和端基官能团聚合物的制备,且具有较高的链端保真度和精确的结构可控性,也有研究者将其应用于无机、生物材料表面修饰。ATRP技术适用于多种单体的可控聚合,且操作方便,其核心是引发剂的使用。传统的ATRP是以简单的有机卤化物为引发剂、过渡金属配合物为卤原子载体,通过氧化还原反应,在活性种与休眠种之间建立可逆的动态平衡,从而实现对聚合反应加以控制,随着技术的成熟和研究的深入,大分子引发体系成为研究的热点。
因此,本领域的技术人员致力于开发一种新的催化活性高、性质稳定、合成容易的催化剂用于催化苯乙烯及异腈类化合物的活性聚合,从而为苯乙烯,苯异腈嵌段共聚物提供了一种新的聚合方法和聚合体系。
发明内容
本发明旨在:提供一种钯催化剂及其制备方法和用途,本发明钯催化剂用于苯乙烯类化合物和苯异腈类化合物聚合,催化活性高、性质稳定且合成容易。
一种钯催化剂,其结构由如下通式表示:
上式中R选自-CH2CH3或-Ph。
进一步地,所述的钯催化剂的制备方法,按以下步骤操作:
a、将2-溴代异丁酰溴和丙炔醇溶于二氯甲烷中,加入三乙胺为催化剂,在氮气气氛中于室温反应3-6h,加水淬灭、分离取有机相、洗涤、提纯、干燥后得到中间体I;
b、将二(三乙基磷)二氯化钯或二(三苯基磷)二氯化钯、氯化亚铜和中间体I加入到二乙胺中,在氮气气氛中于室温搅拌反应4-5h,旋蒸除去溶剂后将粗产品提纯、干燥后得到钯催化剂;
其中中间体I的结构式为:
优选地,所述的钯催化剂的制备方法,按以下步骤操作:
a、将42.9-50mmol的2-溴代异丁酰溴和38.6-42.9mmol的丙炔醇溶于30-50mL的二氯甲烷中,加入10-20mL的三乙胺为催化剂,在氮气气氛中于室温反应3-6h,加水淬灭、分离取有机相、洗涤、提纯、干燥后得到中间体I;
b、将0.63-0.70mmol的二(三乙基磷)二氯化钯或二(三苯基磷)二氯化钯、0.03-0.05mmol的氯化亚铜和0.52-0.63mmol的中间体I加入到10-20mL的二乙胺中,在氮气气氛中于室温搅拌反应4-5h,旋蒸除去溶剂后将粗产品提纯、干燥后得到钯催化剂;
其中中间体I的结构式为:
进一步地,步骤a中分离取有机相、提纯、干燥的具体过程如下:用二氯甲烷取有机相,依次用饱和氯化铵溶液、饱和碳酸氢钠溶液、饱和氯化钠溶液洗涤3-4次后,加入无水硫酸钠干燥,蒸发除去溶剂得到粗产品,粗产品用硅胶柱层析提纯,真空干燥得到中间体I,硅胶柱层析中的洗脱液按体积比:石油醚:乙酸乙酯=25:1。
进一步地,步骤b中提纯、干燥的具体过程如下:将粗产品用硅胶柱层析提纯,真空干燥得到钯催化剂,其中洗脱液按体积比:石油醚:乙酸乙酯=25:1。
进一步地,所述的钯催化剂在苯乙烯类单体和苯异腈类单体聚合反应时能够作为催化剂使用。
进一步地,所述的苯乙烯类单体的结构式为:
式中R1选自-H或-Cl;
所述的苯异腈类单体的结构式为:
式中R2为烷基,R3为-H或-CH3;R4为-H或-CH3。
优选地,所述的R2为C5-C10烷基。
与已有技术相比,本发明的有益效果体现在:
本发明钯催化剂在空气中具有很好的稳定性,容易合成,结构易于修饰和裁剪,聚合时单体转化率较高,可以一锅得到聚苯乙烯和聚苯异腈的嵌段共聚物,且聚合物分子量分布窄,表明该聚合反应具有活性可控的特性。
附图说明
图1是本发明实施例1得到的钯催化剂的红外吸收光谱图,图中,2179cm-1和2057cm-1是碳碳叁键的红外特征吸收峰,1729cm-1上碳氧双键的红外特征吸收峰。
图2是本发明实施例1得到的催化剂的1HNMR(600M Hz)谱图。
图3是本发明实施例2、3和4中聚合物的凝胶渗透色谱图。点线是凝胶渗透色谱测得实施例2聚苯异腈的曲线(Mn=2.06×104,PDI=1.22);实线是凝胶渗透色谱测得实施例3聚苯异腈的曲线(Mn=1.21×104×104,PDI=1.19);虚线是凝胶渗透色谱测得实施例4聚苯异腈的曲线(Mn=2.20×104,PDI=1.28)。
具体实施方式
实施例1:钯催化剂的制备方法
a、取丙炔醇42.9mmol(2.5mL)和2-溴异丁酰溴42.9mmol(5.3mL)溶于40mL二氯甲烷,加入15mL三乙胺,,在氮气气氛中于室温反应5h,加入20mL水淬灭反应。用30mL二氯甲烷取有机相,依次用饱和氯化铵溶液、饱和碳酸氢钠溶液、饱和氯化钠溶液洗涤3次,加入无水硫酸钠干燥,蒸发除去溶剂得到粗产品,粗产品用硅胶柱层析(洗脱液按体积比:石油醚:乙酸乙酯)提纯,真空干燥得无色油状液体即为中间体Ⅰ,结构式如下:
b、取中间体Ⅰ0.63mmol(0.128g)、氯化亚铜0.04mmol(4.0mg)和二(三乙基磷)二氯化钯0.63mmol(267mg)加入到干燥的15mL二乙胺中,然后在氮气氛围中于室温下搅拌反应4.5h,旋蒸除去溶剂后将粗产品用硅胶柱层析(洗脱液按体积比:石油醚:乙酸乙酯=25:1)提纯,真空干燥后得到275mg黄色液体即为钯催化剂,钯催化剂的结构式如下:
本发明钯催化剂的合成路线如下:
实施例2:引发苯异腈聚合反应
苯异腈聚合在无水无氧条件下进行,在10mL聚合瓶中加入实施例1制备的钯催化剂8.73mg(0.015mmol),苯异腈单体41.6mg(0.15mmol),抽真空充氮气重复3次,加入干燥的四氢呋喃0.7mL,在55℃回流反应8h后,加入10mL甲醇淬灭,使聚合物沉淀析出,用甲醇洗涤5次,经离心得到白色絮状沉淀,真空干燥至质量不变。得36.3mg聚异腈,其数均分子量为2.06×104,分子量分布指数为1.22。
本实施例中的苯异腈单体的结构式为:
所得产物结构式为:
实施例3:引发苯乙烯聚合反应
苯乙烯聚合在无水无氧条件下进行,在10mL聚合瓶中加入实施例1制备的钯催化剂35.5mg(0.06mmol),苯乙烯单体62.4mg(0.6mmol),氯化亚铜6mg(0.06mmol),三(2-二甲氨基乙基)胺34mL(0.12mmol)抽真空充氮气重复3次,加入干燥的四氢呋喃0.2mL,在55℃回流反应3h后,加入10mL甲醇淬灭,使聚合物沉淀析出,用甲醇洗涤5次,经离心得到黄色絮状沉淀,真空干燥至质量不变。得88.2mg大分子引发剂Ⅱ,其数均分子量为1.21×104,分子量分布指数为1.19。
本实施例中的苯异腈单体的结构式为:
所得产物结构式为:
实施例4:合成苯乙烯,苯乙腈嵌段共聚物
在10mL聚合瓶中加入实施例3制备的大分子引发剂Ⅱ21mg(3.4μmol),苯异腈单体50mg(0.17mmol),抽真空充氮气重复3次,加入干燥的四氢呋喃0.8mL,在55℃回流反应20h后,加入10mL甲醇淬灭,使聚合物沉淀析出,用甲醇洗涤5次,经离心得到白色絮状沉淀,真空干燥至质量不变。得39.5mg聚异腈,其数均分子量为2.20×105,分子量分布指数为1.28。
本实施例中的苯异腈单体的结构式为:
所得产物结构式为:
以上详细描述了本发明的较佳具体实施例。应当理解,本领域的普通技术无需创造性劳动就可以根据本发明的构思作出诸多修改和变化。因此,凡本技术领域中技术人员依本发明的构思在现有技术的基础上通过逻辑分析、推理或者有限的实验可以得到的技术方案,皆应在由权利要求书所确定的保护范围内。
Claims (8)
1.一种钯催化剂,其特征在于,其结构由如下通式表示:
上式中R选自-CH2CH3或-Ph。
2.一种如权利要求1所述的钯催化剂的制备方法,其特征在于:按以下步骤操作:
a、将2-溴代异丁酰溴和丙炔醇溶于二氯甲烷中,加入三乙胺为催化剂,在氮气气氛中于室温反应3-6h,加水淬灭、分离取有机相、洗涤、提纯、干燥后得到中间体I;
b、将二(三乙基磷)二氯化钯或二(三苯基磷)二氯化钯、氯化亚铜和中间体I加入到二乙胺中,在氮气气氛中于室温搅拌反应4-5h,旋蒸除去溶剂后将粗产品提纯、干燥后得到钯催化剂;
其中中间体I的结构式为:
3.如种权利要求2所述的钯催化剂的制备方法,其特征在于:按以下步骤操作:
a、将42.9-50mmol的2-溴代异丁酰溴和38.6-42.9mmol的丙炔醇溶于30-50mL的二氯甲烷中,加入10-20mL的三乙胺为催化剂,在氮气气氛中于室温反应3-6h,加水淬灭、分离取有机相、洗涤、提纯、干燥后得到中间体I;
b、将0.63-0.70mmol的二(三乙基磷)二氯化钯或二(三苯基磷)二氯化钯、0.03-0.05mmol的氯化亚铜和0.52-0.63mmol的中间体I加入到10-20mL的二乙胺中,在氮气气氛中于室温搅拌反应4-5h,旋蒸除去溶剂后将粗产品提纯、干燥后得到钯催化剂;
其中中间体I的结构式为:
4.如权利要求2所述的钯催化剂的制备方法,其特征在于:步骤a中分离取有机相、提纯、干燥的具体过程如下:用二氯甲烷取有机相,依次用饱和氯化铵溶液、饱和碳酸氢钠溶液、饱和氯化钠溶液洗涤3-4次后,加入无水硫酸钠干燥,蒸发除去溶剂得到粗产品,粗产品用硅胶柱层析提纯,真空干燥得到中间体I,硅胶柱层析中的洗脱液按体积比:石油醚:乙酸乙酯=25:1。
5.如权利要求2所述的钯催化剂的制备方法,其特征在于:步骤b中提纯、干燥的具体过程如下:将粗产品用硅胶柱层析提纯,真空干燥得到钯催化剂,其中洗脱液按体积比:石油醚:乙酸乙酯=25:1。
6.一种如权利要求1所述的钯催化剂的用途,其特征在于:所述的钯催化剂在苯乙烯类单体和苯异腈类单体聚合反应时能够作为催化剂使用。
7.如权利要求6所述的钯催化剂的用途,其特征在于:
所述的苯乙烯类单体的结构式为:
式中R1选自-H或-Cl;
所述的苯异腈类单体的结构式为:
式中R2为烷基,R3为-H或-CH3;R4为-H或-CH3。
8.如权利要求7所述的钯催化剂的用途,其特征在于:所述的R2为C5-C10烷基。
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