稀土催化丁二烯-二烯共聚合过程中的原位环化反应

采用 Nd( naph) 3- Al( C2 H5) 3- ( t- C4 H9) Cl三组分稀土催化剂进行丁二烯 ( BD) -异戊二烯( IP)的顺式共聚合 ,在聚合过程中引入有机氯代烃 ( RCl) ,以与聚合液中的烷基铝作用生成阳离子活性种 ,引发已生成的共聚物的环化反应及单体的环聚反应 ,得到可溶性无凝胶且含有环聚成分的环化共聚合产物 .考察了 RCl用量、单体组成、稀土催化剂用量、反应温度等对原位环化反应的影响 .以红外光谱、核磁共振光谱对环化产物的结构进行了初步分析 ,确认了环化产物的生成     

用Co(naph)2-Al2(C2H5)3Cl3-P(OPh)3催化体系合成中乙烯基液体聚丁二烯

为获得适中乙烯基含量的液体聚丁二烯为目的, 对Co(naph)2-Al2(C2H5)3Cl3-P(OPh)3催化体系进行了较为系统的研究, 考察了该体系的催化剂配比、浓度及供电子试剂对分子量、微观结构和转化率的影响. 实验结果表明, 该体系在一定的条件下可以制备出分子量在700~3500、1,2结构含量在35%~40%且转化率高于55%的液体聚丁二烯.     

碘催化的2-炔基苯胺与二硒醚的亲电环化反应

研究了碘催化的2-炔基苯胺与二硒醚的亲电环化反应. 结果表明, 在碘单质(0.2 mmol)、 2-炔基苯胺(0.2 mmol)、 二硒醚(0.1 mmol)和甲苯(2 mL)共存体系中, 反应温度为110℃时, 2-炔基苯胺与二硒醚能发生亲电环化反应, 生成相应的3-硒取代吲哚化合物, 产率为中等到良好. 该反应在无金属催化的条件下进行, 为合成官能团吲哚提供了一种新途径.     

N-(2-苦胺基乙基)单氮杂冠醚的合成

研究并比较了氮支套索型生色冠醚1a和1b两条不同的合成路线, 结果表明, 由N-苦基乙二胺(2)与1,11-二碘-3,6,9-三氧杂十一烷进行N-烷基化环化反应, 可方便地制备N-(2-苦胺基乙基)单氮杂-12-冠-4(1a), 但按此法未能获得更大环的-15-冠-5(1b);若从N-对甲苯磺酰基乙二胺(6)或N-(2-对甲苯磺酰胺基乙基)二乙醇胺(7)出发, 经环化, 脱除对甲苯磺酰基而制得的N-(2-氨基乙基)单氮杂冠醚5a和5b分别与苦基氯反应, 则可获得高产率的生色生色冠醚11a和1b.     

三羟甲基丙烷烯丙基醚二辛酸酯改性硅油的合成

以低含氢硅油(SH)和三羟甲基丙烷单烯丙基醚二辛酸酯(AEDD)为原料,甲苯为溶剂,H2Pt Cl6为催化剂,合成了一种新型的有机酯改性硅油——三羟甲基丙烷烯丙基醚二辛酸酯改性硅油(SE),其结构经1H NMR和FT-IR表征。考察了甲苯用量、物料比r[n(AEDD)∶n(SH)]、反应温度、反应时间和H2Pt Cl6用量对SH转化率的影响。结果表明,在最优反应条件[AEDD 0.1 mol,r=1.1,甲苯90 m L,H2Pt Cl68 g,于100℃反应6 h]下,SH转化率85%。     

1,4,7,10—四氮杂环十二烷的制备

N,N′,N″—三(对—甲苯磺酰基)二亚乙基三胺与氢化钠反应生成二钠盐,然后与N,O,O'—三(对—甲苯磺酰基)双(2—羟乙基)胺进行缩合环化反应,得N—对甲苯磺酰化的四氮杂环十二烷。在浓H_2SO_4作用下,脱去对—甲苯磺酰基,最后得到了1,4,7,10—四氮杂环十二烷,总得率为44％。     

闭式十二顶双镍十硼烷簇合物[(μ-Cl)(Ph_2PC_6H_4)_2Ni_2B_(10)H_6Cl(PPh_3)]的合成与结构

研究了[NiX_2(PPh_3)_2](X=F, Cl, SCN)在二氯甲烷中与B_(10)H_(10)~(2-) 的反应,对形成的产物[(μ-Cl)(Ph_2PC_6H_4)_2-Ni_2B_(10)H_6Cl(PPh_3)]·0. 25CH_2Cl_2 (1)通过元素分析、红外光谱、飞行时间二次离子质谱等进行了表征, 并通过单晶X射线衍射测定了簇合物的结构。1的晶体学数据：单斜晶系,空间群 P2_1/c,a = 1.1703(2)nm, b = 2.1082(4) nm, c = 2.2068 (8) nm, β = 99.98 (2) °, V = 5.3622(2)nm~3, Z = 4, F(000) = 2274, D_(calcd)=1.373g/cm~3. R_1 = 0.0358, wR_2 = 0.0807. 1为闭式十二项双镍十硼烷簇合物,具有两个邻 位环化的Ni-P-C-C-B五元环,镍-镍之间还存在氯桥。结构分析表明：邻位环化增 强了镍与硼之间的成键作用。     

两个具有混合卤素桥的闭式十二顶双镍十硼烷簇合物的合成与结构

研究了[NiX_2(PPh_3)_2](X = Br, I)在二氯甲烷等溶剂中与B_(10)H_(10)~ (2-)的反应，对形成的族合物[(μ-Br_(0.85)Cl_(0.15)-(Ph_2PC_6H_4)_2Ni_2B_ (10)H_6Cl(PPh_3)]·0.5CH_2Cl_2(1), [(μ-I_(0.1)Cl_(0.9)(Ph_2PC_6H_4) _2Ni_2B_(10)H_6Cl(PPh_3)]·0.25CH_2Cl_2(2)进行了元素分析、红外光谱、飞行 时间二次离子质谱和X射线单晶结构分析等表征。两个族合物均为闭式十二顶双镍 十硼烷，镍、镍之间还分别存在Cl, Br和Cl，I桥且Cl，Br或I的占有率不同。簇合 物还具有两个邻位环化的Ni-P-C-C-B五元环。研究结果进一步证实：阴离子对反应 产物有影响，二氯甲烷参与了反应。     

裂解色谱法研究环化顺—1,4—丁二烯—异戊二烯无规共聚物

如同顺-1,4-聚丁二烯(PBd)和聚异戊二烯(PIP),在一定的催化条件下,顺-1,4-丁二烯-异戊二烯无规共聚物(PBI,简称丁戊无规共聚物)可生成环化顺-1,4-丁戊无规共聚物(CP-BI)。作者曾报道用裂解色谱法表征环化顺-1,4-聚丁二烯(CPBd),本文对不同组成的CPBI和PBI进行了裂解色谱比较研究。 表1所列试样由实验室合成。用CDS pyro-probe 190型裂解器,SP-2305E型气相色谱仪,FID。裂解温度700℃,裂解时间5秒,色谱柱4mm×3m不锈钢柱,填充20%SE-30固定相(101白色担体),柱温106℃,载气氮气40mL/min。试样量约30μg,放于石英管内,后者再插入     

锆氧杂环络合物合成方法探索

邻甲氧基苯基锂和 6,6-二甲基富烯 (或 6,6-二乙基富烯 )反应得配体锂盐 ( Cp′ Li) ,Cp′ Li直接和 Cp Zr Cl3· DME反应生成 2个新的锆络合物 Cp′ Cp Zr Cl2 。 BBr3和 Li Br分别用来使 Cp′ Cp Zr Cl2 环化 ,发现在相同条件下 BBr3比 Li Br3更有效。Cp′ Cp Zr Cl2 通过和 BBr3反应得到 2个新的锆氧杂环络合物。 4个新的锆络合物经元素分析、1 H NMR和 MS确证     

C_(60)敏化的顺-1,4-聚丁二烯的光氧化

Ｃ６０敏化的顺 １，４ 聚丁二烯的光氧化周涛陈双基（信阳师范学院化学系河南４６４０００）（北京大学分校化学系北京１０００８３）李子臣周锡煌李福绵（北京大学化学系北京１００８７１）关键词Ｃ６０，顺 １，４ 聚丁二烯，光氧化自从能以宏观量制备Ｃ６０...     

以红外3100～2800cm-1谱分析聚丁二烯

研究了红外3100～2800cm^-1谱区的聚丁二烯图谱,它是聚丁二烯的顺-1,4,反-1,4和1,2微观结构信息叠加谱区。用因素分析技术对聚丁二烯的微观结构进行了定量分析,与传统的分析方法和其它谱区的因素分析进行比较,结果显示3100～2800cm^-1港区的因素分析为现用方法中最佳。     

钕-铝双金属配合物催化异戊二烯聚合的原位环化反应

环化聚异戊二烯 (CPIP)具有优良的光敏性、较好的耐热性和力学性能 ,在光刻胶、胶粘剂、橡胶改性等方面得到广泛应用 [1,2 ] .CPIP可按阳离子机理经单体环聚或聚合物环化两种方法合成 .我们 [3]最近提出一种直接从单体出发在稀土催化聚合过程中引入烯丙基氯原位合成 CPIP的方法 .本文在此基础上 ,以三异丙氧基钕 -三乙基铝 -一氯二乙基铝均相体系中分离出的钕 -铝双金属配合物作为单组分催化剂 ,简化聚合体系 ,以便直观地考察氯化物、烷基铝等的作用 ,揭示稀土催化 IP聚合原位环化反应的过程 .1　实验部分　　 CPIP的合成参见文献 […     

辐射交联顺1,4-聚丁二烯的NMR研究

用１３Ｃ ＮＭＲ方法,测定了辐射交联顺１,４ 聚丁二烯在室温下的自旋 晶格弛豫时间（Ｔ１）,核Ｏｖｅｒｈａｕｓｅｒ因子（ＮＯＥ）,和１３Ｃ ＮＭＲ线宽．以及凝胶本体１Ｈ ＮＭＲ的Ｔ１和Ｔ２弛豫时间,结果表明,辐射交联顺１,４ 聚丁二烯体系中,随着凝胶含量的增加各碳核质子的Ｔ１值变化很小,而—ＣＨ２—核的ＮＯＥ因子明显降低和１３Ｃ ＮＭＲ线宽增宽．以及１Ｈ ＮＭＲ的Ｔ１和Ｔ２表现的双指数弛豫特性反映了交联体系中大分子链段长程运动受阻以及饱和交联叔碳核—ＣＨ对链段运动的影响．     

Electronic spectroscopy and photochromic mechanism of bis-Schiff bases, N, N''''-bis(2-hydroxy-1-naphthylidene)-1,4-phenyldiamine

The steady state and transient state absorption spectra and fluorescence spectra of N,N'-bis(2-hy-droxy-1-napbthylidcne)-1,4-phenyldiamme ( BNP ) in cyclohexane and acetonitrile were determined.The pho-tochromic mechanism was discussed In nonpolar solvents,BNP exists mainly in the enol form and has the absorption maximum in the UV region In polar solvents,however,both the enol and proton transfer tautomer are formed,but the farmer is the main one Fluorescence emissions result from the excited state of proton transfer product.     

Structural characterization of polybutadiene synthesized via cationic mechanism

The microstructure of polybutadiene synthesized via cationic polymerization using TiCl₄‐based initiating systems has been investigated using 1D (¹Н, ²Н, and ¹³С) and 2D (HSQC and HMBC) NMR spectroscopy. It was found that trans‐1,4‐unit is predominant structure of unsaturated part of polymer chain. Besides, the small amount of 1,2‐structures was also detected, while cis‐1,4‐units were totally absent. The signals of carbon atoms of three types of head groups (trans‐1,4‐, 1,2‐, and tert‐butyl) and two types of end groups (trans‐1,4‐Cl and 1,2‐Cl) were identified for the first time in macromolecules of cationic polybutadiene. It was showed that tert‐butyl head groups were formed due to the presence in monomer of admixtures of isobutylene. The new methodology for calculation of the content of different structural units in polybutadiene chain as well as the head and end groups was proposed. It was established that main part of 1,2‐units distributed randomly along the polybutadiene chain as separate units between trans‐1,4‐structures. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 387–398     

Ozonation of hydrocarbon diene elastomers: A mechanistic study

A study of the effects of ozonation on polybutadiene, polyisoprene, and several related hydrocarbon elastomers has shown that elastomers containing di-substituted double bonds (e.g., cis-1,4-polybutadiene) give crosslinked products as well as chain scission products in nonpolar solvents, whereas those containing tri-substituted double bonds (e.g., cis-1,4-polyisoprene) give chain scission products only. Both types of elastomer, however, give only chain scission products in polar solvents. Further investigation of the ozonation of elastomers, including the effect of ozonides of monoolefins and the solvent effect has led us to postulate that the chain scission involves the attack of a second ozone molecule on the preformed ozonide, and, the crosslinking is due to the attack of the biradical carbonyl oxide on the rubber.     

裂解色谱法测定环化顺1,4聚丁二烯的环化度

用裂解色谱法研究了不同环化度的环化顺１，４聚丁二烯，建立了测定ＣＰＢｄ环化度方法，分析了不同实验条件下生成的ＣＰＢｄ的环化度，结果与ＮＭＲ测定值一致。     

TWENTY-TWO CARBON HOMOLOGUE OF 11-CIS RETINAL. PHOTOPHYSICAL AND PHOTOCHEMICAL PROPERTIES

Abstract— Results concerning absorption-emission spectra and fluorescence quantum yields at 77 and 298K. triplet absorption spectra, and quantum yields of intersystem crossing and photoisomerization at 298 K, are presented for 11- cis β-apo-14'-carotenal (C₂₂-Ald), the immediate higher homologue of 11- cis retinal. The absorption spectra are characterized by two band-systems with maxima at 390–400 and 270–280 nm, respectively. Upon cooling from 298 to 77 K, the intensities of these two band-systems undergo changes in opposite directions indicating 12-s- cis: 12- s-trans conformational changes. No intermediate band-system analogous to the one located at 270–310 nm in cis retinals is observed for 11- cis C₂₂-Ald. In nonpolar hydrocarbon solvents (e. g. cyclohexane) at room temperature, quantum yields of fluorescence (0.01), intersystem crossing (0.6) and photoisomerization (0.4) are all quite pronounced. The photophysical and photochemical properties of 11- cis C₂₂-Ald are discussed in the light of similarities and dissimilarities with those of all- trans C₂₂-Ald and 11- cis retinal under comparable conditions.     

InCl(3)-catalyzed domino reaction of aromatic amines with cyclic enol ethers in water: a highly efficient synthesis of new 1,2,3,4-tetrahydroquinoline derivatives

The tetrahydroquinoline moiety is a structural feature of many natural products. By using a domino reaction of aromatic amines and cyclic enol ethers or 2-hydroxy cyclic ether catalyzed by indium chloride in water, various tetrahydroquinoline derivatives were synthesized efficiently. Most cyclization products showed cis selectivity. The use of 2,3-dihydrofuran as the cyclic enol ether provided both higher reactivity and cis selectivity than the use of 3,4-dihydro-2H-pyran. The cis selectivity was tentatively rationalized due to chelation control in water.