4,4′-二乙炔二苯甲烷与苯乙炔的共聚及共聚物的表征研究

 本文做了4,4′-二乙炔二苯甲烷的本体热均聚和催化均聚,并用(Ph₃P)₂PdCl₂为催化剂做了4,4′-二乙炔二苯甲烷与苯乙炔的共聚,对均聚和共聚物中的不溶不熔组分测定了密度、溶胀度、Huggins参数以及交联点间的平均分子量M_c。实验表明,该交联聚合物的最良溶剂是四氢呋喃,溶度参数为9.9ca1^0.5。cm^-1.5,当用四氢呋喃为溶剂时的Huggins参数为0.34,并且在单体摩尔比中4,4′-二乙炔二苯甲烷用量越多,溶胀度越小,交联度越大。红外光谱分析表明,所有均聚及共聚物都为反式结构。     

1,4-丁炔二醇与4,4′-二乙炔联苯共聚物的合成及表征研究

本文用(Ph_3P)_2PdCl_2为催化剂,合成了1,4-丁炔二醇(BD)与4,4-二乙炔联苯(DEBP)共聚物。对用不同比例的两种单体得到的共聚物测定了比重(d_4~(25)、溶胀度(θ_D)、最良溶剂及相邻两交联点之间的平均分子量(M_c)。实验表明,在两种单体摩尔比中,DEBP用量越多,共聚物中泡状微孔越多,颜色越淡,溶胀度和比重越小,交联度越大;DEBP/BD(摩尔比)大于1/5时,共聚物的最良溶剂为苯,溶度参数为9.15卡~(0.5)·cm~(-1.5),是1/10时,其最良溶剂为乙醇,溶度参数是12.7卡~0.5·cm~(-1.5)。对共聚物还做了红外光谱表征。     

耐高温交联侧基苯乙炔封端酰亚胺预聚体

合成了含有苯乙炔基的二胺单体 3,5-二氨基-4'-苯乙炔苯甲酮(DPEB), 并与3,3',4,4'-联苯四酸二酐(s-BPDA)和1,4-双(4'-氨基苯氧基)-2-(苯基)苯(p-TPEQ)进行了缩聚反应, 以4-苯乙炔苯酐作为封端剂, 合成了交联侧基苯乙炔封端酰亚胺预聚体(n=4). DSC测试结果表明, 引入交联侧基后预聚体依然保持着较宽的加工窗口. 利用所合成的预聚体在370℃热压1 h制备了热固性薄膜. DMA测试结果表明, 引入交联侧基的预聚体树脂具有更高的玻璃化转变温度, 并且其储存模量在玻璃化转变后有很好的保持.     

1,4-丁炔二醇与4,4′-二乙炔联苯共聚物的合成及表征研究

 本文用(Ph₃P)₂PdCl₂为催化剂,合成了1,4-丁炔二醇(BD)与4,4-二乙炔联苯(DEBP)共聚物。对用不同比例的两种单体得到的共聚物测定了比重(d₄²⁵、溶胀度(θ_D)、最良溶剂及相邻两交联点之间的平均分子量(M_c)。实验表明,在两种单体摩尔比中,DEBP用量越多,共聚物中泡状微孔越多,颜色越淡,溶胀度和比重越小,交联度越大;DEBP/BD(摩尔比)大于1/5时,共聚物的最良溶剂为苯,溶度参数为9.15卡^0.5·cm^-1.5,是1/10时,其最良溶剂为乙醇,溶度参数是12.7卡^0.5·cm^-1.5。对共聚物还做了红外光谱表征。     

苯乙炔封端的BTDA系列酰亚胺预聚体的研究

合成了具有苯侧基的二胺单体1,4-双(4'-氨基苯氧基)-2-(苯基)苯(p-TPEQ), 并与3,3',4,4'-苯酮四羧酸二酐(BTDA)进行缩聚反应, 分别以4-苯乙炔苯酐(PEPA)和4-苯乙炔-1,8-萘二甲酸酐(PENA)作为封端剂, 合成了两个系列的苯乙炔封端的酰亚胺预聚体. DSC测试结果表明, 此类预聚体具有比PETI-5更宽的加工窗口; 利用所合成的预聚体制成了具有较高热分解温度热固性交联PI薄膜. 结果表明, PI预聚体加工性能良好, 其交联后具有优异的力学和热学性能; 同时PEPA封端的预聚体树脂具有比PENA封端的树脂更为优异的综合性能.     

4,4′-二苯甲烷二胺与碳酸二甲酯合成4,4′-二苯甲烷二氨基甲酸甲酯反应过程分析

对碳酸二甲酯(DMC)与4,4′-二苯甲烷二胺(MDA)合成4,4′-二苯甲烷二氨基甲酸甲酯(MDC)的反应过程进行了研究,采用质谱、元素分析、红外光谱以及核磁共振氢谱等手段,对反应中间产物和最终产物进行了分离、组成结构分析和确认。研究结果表明,该反应是一个经过中间产物的串联反应,主产物为MDC,中间产物结构为4-(4′-氨苯基)苯甲烷氨基甲酸甲酯。     

4-苯乙炔苯酐封端聚酰亚胺树脂的合成与性能研究

使用3,3′,4,4′-二苯醚四酸二酐(ODPA)、3,3′,4,4′-联苯四酸二酐(BPDA)、1,3-双(4-氨基苯氧基)苯(1,3,4-APB)、3,4′-二氨基二苯醚(3,4′-ODA)和反应性封端剂4-苯乙炔苯酐(4-PEPA)合成了设计分子量为5000的系列苯乙炔基封端的聚酰亚胺低聚物,并使用XRD、DSC、TGA、FT-IR、DMA和流变仪等对低聚物的化学结构、热性能和熔体性能,固化后树脂的热性能和力学性能进行了测试.研究结果表明基于ODPA的低聚物具有低的熔体粘度和良好的熔体粘度稳定性,固化后的树脂具有很高的热失重温度,较高的玻璃化转变温度以及良好的力学性能尤其是高的断裂伸长率(>10%);基于BPDA的低聚物具有一定的结晶性,其结晶熔融温度与苯乙炔基固化交联温度相近,影响了材料的成型工艺性能.     

4-苯乙炔基苯胺封端聚酰亚胺树脂的合成与性能研究

使用4-苯乙炔基苯胺(4-PEA)作为反应性封端剂,和3,3′,4,4′-二苯醚四酸二酐(ODPA),3,3′,4,4′-联苯四酸二酐(BPDA),1,4-双(4′-氨基-2′-三氟甲基苯氧基)苯(BTPB)和3,4′-二氨基二苯醚(3,4-′ODA)反应合成了系列4-苯乙炔基苯基封端的聚酰亚胺低聚物,对低聚物的化学结构、热性能和熔体粘度以及固化后树脂的热性能等进行了研究.实验结果表明,低聚物均具有一定的结晶性,含有ODPA的聚酰亚胺低聚物较之含有BPDA的低聚物具有更低的熔体粘度,且出现最低熔体粘度的温度更低;固化后的树脂表现出良好的热性能,含有BPDA的树脂具有更高的玻璃化转变温度;系列低聚物中二胺单体的比例对于低聚物的熔体粘度和固化后树脂的热稳定性有一定影响.     

二氯二茂钛引发二苯乙炔聚合的研究

在高温下 ,二氯二茂钛受光照引发二苯乙炔聚合 ,得到结晶度为 95 %的聚二苯乙炔 .经红外、质谱、热分析、X光衍射、元素分析等方法 ,确定其结构为顺顺式螺旋刚性棒状结构 ,形成假六方晶系堆积 ,螺旋柱直径即螺旋轴间距为 1 46nm ,其特征红外吸收峰位于 1179cm-1和 115 6cm-1.在聚合引发阶段中止反应 ,分离出聚合中间体六苯基苯 .根据不同温度时聚合转化率与时间的关系曲线 ,测得聚合活化能为 2 6× 10 5J/mol.热分析表明 ,结晶聚二苯乙炔在 493K至 5 73K比较稳定 ;在 713K的吸热峰显示出破坏晶格的能量 .根据聚合反应诱导期长、中间体和聚合物的结构以及阻聚反应 ,推断聚合过程中二氯二茂钛受光照产生二氯化钛 ,催化二苯乙炔进行均相定向聚合 .结晶聚二苯乙炔电导率小于 10 -12 (Ωcm) -1.     

对苯醌二亚胺与对苯乙炔共聚物的金属配合物催化法合成与表征

在金属配合物的存在下,通过N,N′-二氯对苯醌二亚胺与1,4-二炔基-2,5-二（烷氧基）苯共聚,得到了一系列新型交替共聚物聚[N,N′-对苯醌二亚胺-1,4-二炔基-2,5-二（烷氧基）苯]（PAn-PPE）。采用FT-IR、1H-NMR、GPC、XRD、UV-Vis、PL、TGA等测试手段对共聚物的化学结构和性能进...     

1,4-丁炔二醇的均聚及与苯乙炔的共聚研究

<正> 炔类聚合物由于具有长链π体系的结构特点,理论上可作为结构型导电聚合物,这一领域的研究工作正在迅速展开。 1,4-丁炔二醇(BD)可用PdCl_2,ZnCl_2,(Ph_3P)_2PdCl_2等多种催化剂催化聚合,得到长链共轭的聚(1,4-丁炔二醇)(PBD)。苯乙炔(PA)可用热聚合,光聚合、电聚合、自由基聚合、等离子体聚合、催化聚合等聚合方法,得到长链共轭的聚苯乙炔     

Methoxycarbonylation of olefins catalyzed by palladium complexes bearing P,N-donor ligands

The methoxycarbonylation of alkenes catalyzed by palladium(II) complexes with P,N-donor ligands, 2-(diphenylphosphinoamino)pyridine (Ph2PNHpy), 2-[(diphenylphosphino)methyl]pyridine (Ph2PCH2py), and 2-(diphenylphosphino)quinoline (Ph2Pqn) has been investigated. The results show that the complex [PdCl(PPh3)(Ph2PNHpy)]Cl or an equimolar mixture of [PdCl2(Ph2PNHpy)] and PPh3, in the presence of p-toluensulfonic acid (TsOH), is an efficient catalyst for this reaction. This catalytic system promotes the conversion of styrene into methyl 2-phenylpropanoate and methyl 3-phenylpropanoate with nearly complete chemoselectivity, 98% regioselectivity in the branched isomer, and high turnover frequency, even at alkene/Pd molar ratios of 1000. Best results were obtained in toluene-MeOH (3 : 1) solvent. The Pd/Ph2PNHpy catalyst is also efficient in the methoxycarbonylation of cyclohexene and 1-hexene, although with lower rates than with styrene. Related palladium complexes [PdCl(PPh3)L]Cl (L = Ph2PCH2py and Ph2Pqn) show lower activity in the methoxycarbonylation of styrene than that of the 2-(diphenylphosphinoamino)pyridine ligand. Replacement of the last ligand by (diphenylphosphino)phenylamine (Ph2PNHPh) or 2-(diphenylphosphinoaminomethyl)pyridine (Ph2PNMepy) also reduces significantly the activity of the catalyst, indicating that both the presence of the pyridine fragment as well as the NH group, are required to achieve a high performing catalyst. Isotopic labeling experiments using MeOD are consistent with a hydride mechanism for the [PdCl(PPh3)(Ph2PNHpy)]Cl catalyst.     

Cp2Fe(PR2)2PdCl2 (R = i-Pr, t-Bu) complexes as air-stable catalysts for challenging Suzuki coupling reactions

[reaction: see text] The use of Cp(2)Fe(PR(2))(2)PdCl(2) (R = i-Pr and t-Bu) in Suzuki coupling reactions were illustrated using a high throughput screening approach. The di-tbpfPdCl(2) catalyst was shown to be the more active catalyst for unactivated and sterically challenging aryl chlorides. Comparison studies using the commercial catalysts dppfPdCl(2), (Ph(3)P)(2)PdCl(2), (Cy(3)P)(2)PdCl(2), DPEPhosPdCl(2), dppbPdCl(2), dppePdCl(2), Pd(t-Bu(3)P)(2), and [Pd(mu-Br)(t-Bu(3)P)](2) were also done for selected cases to demonstrate the superior activities of di-tbpfPdCl(2) and di-isoppfPdCl(2).     

Homogeneous catalysts supported on soluble polymers: biphasic Sonogashira coupling of aryl halides and acetylenes using MeOPEG-bound phosphine-palladium catalysts for efficient catalyst recycling

The Sonogashira coupling of various aryl bromides and iodides with different acetylenes was studied under biphasic conditions with soluble, polymer-modified catalysts to allow the efficient recycling of the homogeneous catalyst. For this purpose, several sterically demanding and electron-rich phosphines of the type R(P)PR(2) were synthesised. They are covalently linked to a monomethyl polyethylene glycol ether with a mass of 2000 Dalton (R(P)=MeOPEG(2000)) R(P)PR(2): -PR(2)= -CH(2)C(6)H(4)CH(2)P(1-Ad)(2), -C(6)H(4)-P(1-Ad)(2), -C(6)H(4)-PPh(2). To couple aryl iodides and acetylenes, the catalyst [(MeCN)(2)PdCl(2)]/2 R(P)-C(6)H(4)-PPh(2) was used in CH(3)CN/Et(3)N/n-heptane (5/2/5). The combined yields of coupling product over five reaction cycles are between 80-95 percent. There is no apparent leaching of the catalyst into n-heptane, as evidenced by (1)H NMR spectroscopy. The new catalyst [(MeCN)(2)PdCl(2)]/2 (1-Ad)(2)PBn can be used for room-temperature coupling of various aryl bromides and acetylenes in THF with HNiPr(2) as a base. A closely related catalyst Na(2)[PdCl(4)]/2 R(P)-CH(2)C(6)H(4)CH(2)P(1-Ad)(2) linked to the polymer was used to couple aryl bromides and acetylenes in DMSO or DMSO/n-heptane at 60 degrees C with 0.5 mol percent Na(2)[PdCl(4)], 1 mol percent R(P)PR(2) and 0.33 mol percent CuI. The combined yield of coupling products over five cycles is always greater than 90 percent, except for sterically hindered aryl bromides. The determination of the turnover frequency (TOF) of the catalyst indicates only a small decrease in activity over five cycles. Leaching of the catalyst into the product containing n-heptane solution could not be detected by means of (1)H NMR and TXRF; this is indicative of >99.995 percent catalyst retention in the DMSO solvent.     

Synthesis of beta-P,N aminophosphines and coordination chemistry to Pd(II). X-ray structures of [PdCl2(Ph2PCH(Ph)NHPh-kappaP,kappaN)] and PdCl(eta3-C3H5)(Ph2PCH2CH(Ph)NHPh-kappaP)

The reaction of the C=N bond in PhCH=NPh with the carbanionic species Ph2PCH2-, leading to the N-phenyl beta-aminophosphine Ph2PCH2CH(Ph)NHPh, L1, is described. This molecule reacts with different organic electrophiles to afford related compounds Ph2PCH2CH(Ph)NPhX (X = SiMe3, L2; COPh, L4), [Ph2MePCH2CH(Ph)NHPh]+(I-), L3, and [Ph2PCH2CH(Ph)N(Ph)CO]2, L5, containing two amido and two phosphino functions. The coordination properties of L1, L2, and L4 have been studied in palladium chemistry. The X-ray structure of [PdCl2(Ph2PCH2CH(Ph)NHPh-kappaP,kappaN)] shows the bidentate coordination mode for the L1 ligand with equatorial C(Ph)-N(Ph) phenyl groups. [PdCl2(Ph2PCH2CH(Ph)NHPh-kappaP,kappaN)] crystallizes at 298 K in the space group P2(1)/n with cell parameters a = 10.689(2) A, b = 21.345(3) A, c = 12.282(2) A, beta = 90.294(12) degrees, Z = 4, D(calcd) = 1.526. The reaction between 2 equiv of L1 and [PdCl(eta3-C3H5)]2 affords the [PdCl(eta3-C3H5)(Ph2PCH2CH(Ph)NHPh-kappaP)] complex in which an unexpected N-H.Cl intramolecular interaction has been observed by an X-ray diffraction analysis. [PdCl(eta3-C3H5)(Ph2PCH2CH(Ph)NHPh-kappaP)] crystallizes at 298 K in the monoclinic space group Cc with cell parameters a = 10.912(1) A, b = 17.194(2) A, c = 14.169(2) A, beta = 100.651(9) degrees, Z = 4, D(calcd) = 1.435. Neutral and cationic alkyl or allyl palladium chloride complexes containing L1 are also reported as well as a neutral allyl palladium chloride complex containing L4. Variable-temperature 31P[1H] NMR studies on the allyl complexes show that the eta3/eta1 allyl interconversion is enhanced by a positive charge and also by a N-H.Cl intramolecular interaction.     

Synthesis and reactivity studies of palladium(II) complexes containing the N-phosphorylated iminophosphorane-phosphine ligands Ph2PCH2P{=NP(=O)(OR)2}Ph2 (R=Et, Ph): application to the catalytic synthesis of 2,3-dimethylfuran

Reactions of [PdCl2(COD)] with 1 equiv. of the iminophosphorane-phosphine ligands Ph2PCH2P{=NP(=O)(OR)2}Ph2 (R=Et, Ph) lead to the novel Pd(II) derivatives cis-[PdCl2(kappa2-(P,N)-Ph2PCH2P{=NP(=O)(OR)2}Ph2)] (R=Et, Ph). Pd-N bond cleavage readily takes place upon treatment of these species with a variety of two-electron donor ligands. By this way, complexes cis-[PdCl2(kappa1-(P)-Ph2PCH2P{=NP(=O)(OR)2}Ph2)(L)] (R=Et, L=CNtBu, CN-2,6-C6H3Me2, py, P(OMe)3, P(OEt)3; R=Ph, L=CNtBu, CN-2,6-C6H3Me2, py, P(OMe)3, P(OEt)3) have been synthesized in high yields. The addition of two equivalents of ligands to dichloromethane solutions of [PdCl2(COD)] results in the formation of complexes trans-[PdCl2(kappa1-(P)-Ph2PCH2P{=NP(=O)(OR)2}Ph2)2] (R=Et, Ph), which can be converted into the dicationic species [Pd(Ph2PCH2P{=NP(=O)(OR)2}Ph2)2][SbF6]2 (R=Et, Ph) by treatment with AgSbF6. Complex also reacts with CNtBu to afford trans-[Pd(kappa1(P)-Ph2PCH2P{=NP(=O)(OPh)2}Ph2)2(CNtBu)2][SbF6]2. The structures of and have been determined by single-crystal X-ray diffraction methods. In addition, the ability of these Pd(II) complexes to promote the catalytic cycloisomerization of (Z)-3-methylpent-2-en-4-yn-1-ol into 2,3-dimethylfuran has also been studied.     

Molecular triangle of palladium(II) and its anion binding properties

The ligand 4(3H)-pyrimidone (Hpm) forms the complexes trans-[PdCl(2)(Hpm)(2)] and [Pd(PP)(Hpm)(2)](CF(3)SO(3))(2) (PP = Ph(2)PCH(2)PPh(2) or Ph(2)P(CH(2))(3)PPh(2)), with the neutral ligand (Hpm), and a bowl-like molecular triangle, [(Pd(bu(2)bipy)(mu-pm))(3)](3+) (bu(2)bipy = 4,4'-di-tert-butyl-2,2'-bipyridine), with the deprotonated ligand (pm). This triangular complex acts as a host for binding of several anionic guests.     

Suzuki reaction of vinyl triflates from six- and seven-membered N-alkoxycarbonyl lactams with boronic acids and esters

The Pd(0)-catalyzed reaction of vinyl triflates from N-alkoxycarbonyl lactams with different boron compounds has been studied. The coupling reaction of alkenylboronates and arylboronic acids with six- and seven-membered lactam-derived N-alkoxycarbonyl vinyl triflates was feasible under very mild conditions in THF-water employing (Ph3P)2PdCl2 as a catalyst and Na2CO3 as a base, which provided in high yields the corresponding 6- or 7-substituted N-alkoxycarbonyl-3,4-dihydro-2H-pyridines and N-alkoxycarbonyl-2,3,4,5-tetrahydroazepines. Allylboronates reacted slower but, with vinyl triflates from delta-valerolactam, still gave acceptable yields of the coupling product. Alkylboronic acids required different reaction conditions, in particular the presence of Ag2O together with a base in anhydrous toluene and (dppf)PdCl2 as a catalyst, affording the corresponding 6-alkyl-N-alkoxycarbonyl-3,4-dihydro-2H-pyridines in high yields.