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2-氨基吡啶镍配合物[(2-PyCH2NAr)NiBr,Ar=2,6-二甲基苯基(a),2,6-二异丙基苯基(b),2,6-二氟苯基(c)]在助催化剂甲基铝氧烷(MAO)作用下能高活性催化β-蒎烯与降冰片烯共聚合,得到分子量分布较宽(PDI≈3.7~5.5)的共聚产物.在相同条件下,配体含F取代的配合物c对共聚合的催化活性最高.对共聚产物用CHCl3和四氢呋喃(THF)萃取分级,得到2个分子量分布较窄(PDI≈2.0)且组成差异较大的级分,其中仅溶于CHCl3而不溶于THF的级分的分子量较高,具有高降冰片烯含量(xN90%);而另一个溶于THF的级分的分子量较低,具有较高的β-蒎烯含量.结果表明,共聚合体系中存在2种不同催化性质的活性中心.TGA分析显示,共聚物有2个热分解温度,随着降冰片烯含量的增加,低温处的失重量逐渐减少. 相似文献
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以传统Ziegler-Natta催化体系TiCl4/Al(#em/em#-Bu)3催化降冰片烯(NBE)和异戊二烯(IP)的共聚合, 制得可溶于常规有机溶剂的共聚物, 其数均分子量为2.0 × 104~6.5 × 104, 分子量分布指数为1.5~2.9, 降冰片烯结构摩尔含量为26%~60%. 考察了助催化剂用量、 聚合温度及2种单体投料比对共聚合的影响. 结果表明, 当降冰片烯与异戊二烯的投料摩尔比为4∶6时, 于40 ℃聚合6 h, 得到的共聚物产率为96%, 数均分子量为6.5×104, 降冰片烯结构含量45%. 用 1H NMR, 13CNMR, GPC和DSC等方法表征了共聚产物的微观结构与热性能. 13C NMR DEPT结果表明, 共聚反应中降冰片烯单体以加成方式聚合. DSC结果显示, 共聚物只有一个玻璃化转变温度(Tg=20~40 ℃). 通过Kelen-Tüdös方法得到2种单体的竞聚率分别为rNBE=0.07, rIP=0.44. 相似文献
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双烷基钪配合物LSc(CH2SiMe3)2(L=(2,6-iPr2C6H3)NC(Me)CHPPh2N(2,6-Me2C6H3))在助催化剂[Ph3C][B(C6F5)4]的作用下能够高活性地催化乙烯和丙烯共聚.在反应温度30℃和乙烯与丙烯常压(1.0×105Pa)下聚合,共聚活性能够达到7.5×105g(PE)mol-1h-1(105Pa)-1.单体的竞聚率分别为rE=29.75和rP=0.015.13C-NMR和DSC分析表明所得到的乙丙共聚物是弹性体,且丙烯单体无规分布在共聚物链中. 相似文献
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在C5系列的综合利用中近年来倍受关注的环烯烃共聚物是最具有发展潜力的高端产品之一。本文评述了用于乙烯和降冰片烯类共聚合体系新型加成催化剂的最新进展,包括茂金属催化剂、非茂金属催化剂和后过渡金属催化剂三大类。开发新型半夹心型催化剂是茂金属研究领域的热点,目前主要有两类:1.限定几何构型催化剂(CGC);2. Cp’MX3和Cp’M(R)X2 (Cp’=茂基或取代茂基;M=Ti, Zr, Hf;X=卤素或烷基;R=OAr, NR2, NPR3)。非茂金属催化剂则具有亲电能力更强的活性中心及更开放的配位空间,通常具有更高的NB插入率,甚至在一定条件下具有类活性聚合的特征。而后过渡金属催化剂由于对氧(或Lewis酸)更不敏感,导致对极性基团有更好的耐受性。此外,重点围绕配体结构对催化特性的影响,如何提高分子量和环烯烃的有效插入率及其序列结构的调控等进行了对比和剖析,并展望其今后发展趋势。 相似文献
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用多组份改性钛系载体催化剂TiCl_4,Ti(OBu)_4/MgCl_2/Ethylbenzeate(EB)/φ_2SiCl_2/AlEt_3进行了乙烯-丙烯-1-丁烯三元共聚合的研究。考察了单体进料比、聚合温度,烷基铝浓度和催化剂浓度等条件对共聚合的影响。发现本催化剂对乙丙丁三元共聚合有极高的催化效率,聚合1h达8.6×10~4g共聚物/g-Ti。共聚合速率衰减符合动力学方程:R_s=R_s+(R_0—R_s)_e~(βs)。 相似文献
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Summary In a metabolic pathway from galactose to glucose-1-phosphate, there are three major enzymes, galactokinase, galactose-1-phosphate
uridyl transferase (GALT) and UDP-galactose-4-epimerase. The deficiency of one of these enzymes causes accumulation of galactose
in blood, which provides a pathognomonic marker. A new reversed-phase HPLC method with fluorescence detector has been developed
for the measurement of galactose in 50μL of blood on Guthrie filter paper using 8-amino-2-naphthalenesulfonic acid (8,2-ANS)
as derivatization reagent for the diagnosis of Galactosemia. Galactose was extracted from blood spotted on filter paper and
derivatized with 8,2-ANS to produce Schiff bases, and reduced with sodium cyanoborohydride. Linear range was from 2 mg dL−1 to 20 mg dL−1 (r=0.9998). Detection limit (S/N=3) of this method was 90 ng dL−1. The mean recovery of galactose was 102.7% (SD =0.3%, n=14). The normal range of blood galactose in Korean neonates (specimen
collected within 7 days after birth) was below 6 mg dL−1 (n=5 for each gender) without any gender difference. When applied to 11 anonymous blood spots of heterogeneous genotypes
of GALT deficiency all of the patients' blood samples showed abnormal elevation of galactose.
The results indicate that the new method using 8,2-ANS yields consistent and correct galactose determination that is simple
and practical as a rapid first screening tool for patients with galactosemia. 相似文献
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《Journal of Coordination Chemistry》2012,65(21):3825-3838
A series of nickel complexes LNiCl2 (C1–C16), where L represents 2-benzoimidazol-8-alkylquinoline and its derivatives, were prepared as potential catalysts for the oligomerization of ethylene. The molecular structure of a representative complex C2·CH3CH2OH was determined by single-crystal X-ray diffraction. Upon treatment with diethylaluminium chloride (Et2AlCl), all nickel complex pre-catalysts exhibited good activities in the oligomerization of ethylene. Furthermore, in the presence of methylaluminoxane (MAO), the nickel pre-catalysts were suitable for vinyl polymerization of norbornene. 相似文献
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以8-羟基喹啉为原料,合成了5-(烯丙氧)甲基-8-羟基喹啉配体及其铝配合物,并通过红外光谱对配体和配合物进行了表征,通过荧光光谱研究了配合物的光致发光性能。 相似文献
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A novel cadmium(Ⅱ) complex with 8-quinolinyloxyacetate has been prepared and characterized by X-ray diffraction. The complex is a centrosymmetric [Cd2L2Cl4(MeOH)2] dinuclear structure and the Cd(Ⅱ) centre is in a distorted octahedron geometry. The crystal is in triclinic system, space group P1, with a=0.752 2(4) nm, b=1.043 1(5) nm, c=1.097 3(6) nm, α=66.11(2)°, β=72.48(2)°, γ=70.28(2)° and Z=1. The most striking feature of this complex is the formation of a 3D network bridged through the intermolecular N-H…O, O-H…O, C-H…O and C-H…Cl hydrogen bonds and stabilized via intermolecular π-π stacking interactions. CCDC: 224677. 相似文献
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采用简便的方法, 合成了Schiff碱钛配合物Ti(Salen)2Cl2[Salen为N,N-(3,5-di-tert-butylsalicylidene)anilinato]并与Al(i-Bu)3组成二元催化体系用于n-辛基联烯的聚合. 实验结果表明, 在单体与催化剂摩尔比为100, n(Al)/n(Ti)=50, 催化剂于80 ℃陈化时间1 h后, 于80 ℃本体聚合16 h得到聚n-辛基联烯, 转化率100%, 分子量Mw=1.1×105, MWD=1.77, 1,2聚合链节单元质量分数为50%. 相似文献
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Jolanta Polak Marcin Grz Kamila Wlizo Katarzyna Szaapata Justyna Kapral-Piotrowska Roman Paduch Anna Jarosz-Wilkoazka 《Molecules (Basel, Switzerland)》2022,27(2)
Fungal laccase obtained from a Cerrena unicolor strain was used as an effective biocatalyst for the transformation of 8-anilino-1-naphthalenesulfonic acid into a green-coloured antibacterial compound, which can be considered as both an antimicrobial agent and a textile dye, simultaneously. The process of biosynthesis was performed in buffered solutions containing methanol as a co-solvent, allowing better solubilisation of substrate. The transformation process was optimised in terms of the buffer pH value, laccase activity, and concentrations of the substrate and co-solvent. The crude product obtained exhibited low cytotoxicity, antibacterial properties against Staphylococcus aureus and Staphylococcus epidermidis, and antioxidant properties. Moreover, the synthesised green-coloured compound proved non-allergenic and demonstrated a high efficiency of dyeing wool fibres. 相似文献
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A series of titanium phosphinimide complexes [Ph2P(2-RO-C6H4)]2TiCl2 (7, R = CH3; 8, R = CHMe2) and [PhP(2-Me2CHO-C6H4)][THF]TiCl3 (9) have been prepared by reaction of TiCl4 with the corresponding phosphinimines under dehalosilylation. The structure of complex 9 has been determined by X-ray crystallography, and a solvent molecule THF was found to be coordinated with the central metal and the Ti-O bond was consistent with the normal Ti-O (donor) bond length. The complexes 7 and 8 displayed inactive to ethylene polymerization, and the complex 9 displayed moderate activity in the presence of modified methylaluminoxane (MMAO) or i-Bu3Al/Ph3CB(C6F5)4, and this should be partly attributed to coordination of THF with titanium and the steric effect of two iso-propoxyl. And catalytic activity up to 32.2 kg-PE/(mol-Ti h bar) was observed. 相似文献
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Yuan-Biao Huang 《Journal of organometallic chemistry》2009,694(1):86-4940
The novel nickel (II) complexes (2a, 2b) bearing 1-pyridyl-(3-substituedimidazole-2-thione) ligands were synthesized by the reaction of the corresponding ligands with NiBr2(DME). 2a and 2b have been characterized by IR, NMR and elemental analysis. The nickel complexes show high catalytic activities for norbornene polymerization in the presence of MAO (methylaluminoxane), although low activities for ethylene polymerization. 相似文献
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镧与8-羟基喹啉配合物固相化学合成与表征 总被引:6,自引:0,他引:6
近年来,固相配位化学反应研究取得许多进展,但大多集中于Cu、Co、Ni、Zn、Fe等d电子组元素[1,2],用室温或低热温度下的固相化学反应合成稀土配合物尚未见报道,我国稀土资源丰富,稀土配合物在材料科学和生命科学中占有独特的地位,因此开展稀土配合物的室温及低热温度下的固相合成有重要意义.我们在60℃利用La(Ac)3·3/2H2O与8-羟基喹啉的固相反应合成了La(Oxine)3,并对产物进行了表征.1实验部分1.1试剂与仪器根据文献[3]用液相合成法制备出对照的标准样品La(Oxine)3。按文献[4]的方法合成La(Ac)3·3/2H2O.8-羟… 相似文献