Enantioselective Alternating Copolymerization of Propylene with Carbon Monoxide Using Cationic Palladium-Chiral Diphosphine Catalyst

Alternating copolymerization of (-olefins with carbon monoxide (CO) catalyzed by cationic palladium-chiral ligand complexes is of great interest due to the potential use of the resulting polymer as a new material1. Recently, enantioselective alternating copolymerization of CO with styrene has been reported by us using PdCl_2-CuCl2-chiral phosphine catalyst2. Here, we first report enantioselective alternating copolymerization of CO with propylene (P) using [(DDPPI)Pd(CH3CN)4](BF4)2 as …     

阳离子钯—手性二膦配体催化剂存在下1—辛烯与一氧化碳对映选择性交替共聚

用阳离子钯-手性配体DDPPI（1,4-3,6-dianhydro-2,5-dideoxy-2,5-dis(diphenylphosphino)-L-iditol)催化剂,实现了一氧化碳与1-辛烯的对映选择性交替共聚。实验证明,手性配体对共聚具有非常好的手性诱导效应。旋光度、元素分析、碳谱、氢谱、红外光谱分析证明,所合成的1-辛烯-一氧化碳共聚物具有旋光活性及全同、交替共聚（1,4-酮）结构。     

芳香醛亚胺与一氧化碳的交替共聚反应

以苯乙酰基四羰基钴作为催化剂,研究了对芳香醛亚胺与一氧化碳(CO)的交替共聚反应.采用6种芳香醛亚胺单体,分别与CO进行交替共聚反应,得到了6种新的多肽类聚合物.利用核磁共振谱、红外光谱、凝胶渗透色谱(GPC)及MALDI-TOF质谱等对聚合物的结构进行了表征.探讨了芳香醛亚胺苯环上取代基的位阻效应和电子效应对聚合反应的影响.结果表明,聚合物链终止端存在3种不同类型的端基,分别具有慕尼黑酮类结构、咪唑啉类结构以及酰胺类结构,对这些端基的形成机理进行了讨论.     

Enantioselective Alternating Terpolymerization of Styrene and Ethene with Carbon Monoxide. Preliminary communication

In spite of the higher reactivity of styrene with respect to ethene for the alternating copolymerization with carbon monoxide, catalyzed by chiral (dihydrooxazole)(phosphino)palladium complexes, ethene is preferentially (and randomly) enchained in terpolymerization experiments; enantioface selection for styrene is comparably high in both copolymerization and terpolymerization processes.     

钯配合物催化的α-烯烃与一氧化碳对映选择性

乙烯与一氧化碳交替共聚合成的聚酮是一类新型的热塑性高分子材料, 具有良好的机械加工性能.     

双膦Cu及不对称Pd催化剂的结构及其对烯烃-一氧化碳完全交替共聚的催化性能

 配体及配合物的结构对催化烯烃-CO完全交替共聚反应活性及稳定性具有重要的影响. IR和XPS实验结果表明,5-硝基-1,10-菲咯啉的钯配合物催化苯乙烯-CO共聚的高活性与其结构的不对称性有关; 揭示了廉价的Cu金属双膦螯合物作为新型乙烯-CO交替共聚催化剂具有一定的可行性,探讨了配合物结构对烯烃-CO共聚反应活性及稳定性的影响,同时通过IR,1H NMR和13C NMR确认了所得交替共聚物聚酮的结构.     

General Method for Evaluation of Alternating Tendency in Copolymerization

A new method for deriving expressions for the mole fractions of alternating n-ads and the average lengths of the alternating sequences of n-component copolymers (n > 2) was developed based on the apparatus of finite Markov chains. These characteristics are considered as indexes of alternating tendency forn-component copolymerization. A specific property of n-component copolymerization (n > 3) compared with binary copolymerization is the fact that alternating n-ads might be constructed by two, three, or more types of monomeric units. In order to express this specific property of three and multi-component copolymers the term, alternating order, is introduced. The method developed in the paper permits the alternating indexes to be determined differentially in dependence of alternating order. Expressions for the average lengths and the compositions of all possible alternating sequences starting with a given monomer unit and ending with unit found only at that position, are derived as well. The alternating indexes for binary radical copolymerization of styrene and methyl methacrylate and for ternary radical copolymerization of styrene, methyl methacrylate, and acrylonitrile were determined.     

Insertion of Imines into Palladium–Acyl Bonds: Towards Metal-Catalyzed Alternating Copolymerization of Imines with Carbon Monoxide To Form Polypeptides

From a methyl ligand, CO, and an imine a chelating amide ligand is formed by insertion of the C=N bond into the metal–acyl bond in cationic palladium(II ) complexes (see reaction below). The cationic acylpalladium complexes are obtained from CO and readily accessible palladium starting materials. LL=diphosphane ligand.     

New Catalyst for the Copolymerization of Styrene with Carbon Monoxide

Carbonmonoxide(CO)witholefinscanbec0p0lymerizedwithfreeradicalinitiatorsorn0bletransitionmetalc0mpoundcatalystS.Thefreeradicalinitiatedcopolymerizationunderhighgaspressure(upt0l(X)Mpa)andl2O-l65oC',whereasthemostusednobletransitionmetalcompoundsf0rthec0polymerizati0nofcarbonmonoxidewitholefinsarepalladiumorrhodiumcompounds"'.In0urw0rk,theneodymiumcomp0undcatalystsystemswerefoundt0beactiveforthecopolymerizationofstyreneandcarbonm0noxide.Thecopolymerizationofstyreneandcarbonm0n0xidewascAned0u…     

Donor-Acceptor Complexes in Copolymerization. IV. Alternating Tendency in Free Radical Copolymerization. NMR Analyses of Alternating and Random Copolymers

An NMR investigation was carried out on variable composition, random and equimolar, alternating copolymers of acrylonitrile (A) with styrene (S), isoprene (I), and butadiene (B). The NMR spectra of the SA copolymers contained peaks at 3 τ (aromatic ring protons), 7.2-7.5 τ (CH protons of A), and 8.1 -8.5 τ (CH and CH₂ protons of S and CH₂ protons of A). All NM R peaks of the alternating SA copolymer were shifted to the higher field due to the shielding effect of S. The NMR spectra of the IA copolymers contained peaks at 4.72-4.91 τ (?CH protons of I), 7.27-7.4 τ (CH protons of A), 7.71-7.93 τ (CH₂ protons of I), and 8.35 τ (CH₃ protons of I and CH₂ protons of A). The peaks at 4.72 τ (?CH) and 7.72 τ (CH₂) were assigned to I in the I-A diad and the peaks at 4.91 τ (?CH) and 7.93 τ (CH₂) were assigned to I in the I-I diad. The NMR spectra of the BA copolymers contained peaks at 4.4-4.6 τ (?CH protons of B), 7.2-7.5 τ (CH protons of A), 7.71-7.97 T (CH₂ protons of B), and 8.0-8.4 τ (CH₂ protons of A). The peaks at 4.42 τ (?CH) and 7.71 τ (CH₂) were assigned to B in the B-A diad and the peaks at 4.6 τ (?CH) and 7.9 τ(CH₂) were assigned to B in the B-B diad. The alternating structure of the copolymers prepared through metal halide-activated complexes was confirmed by NMR analysis. The random copolymers prepared by free radical initiation contain a high concentration of alternating sequences, as anticipated from the values of r₁ and r₂ where r₁(S, I, and B) is 6-10 times higher than r₂ (A).     

Heterocycle/Heteroallene Ring-Opening Copolymerization: Selective Catalysis Delivering Alternating Copolymers

Heteroatom-containing polymers have strong potential as sustainable replacements for petrochemicals, show controllable monomer–polymer equilibria and properties spanning plastics, elastomers, fibres, resins, foams, coatings, adhesives, and self-assembled nanostructures. Their current and future applications span packaging, house-hold goods, clothing, automotive components, electronics, optical materials, sensors, and medical products. An interesting route to these polymers is the catalysed ring-opening copolymerisation (ROCOP) of heterocycles and heteroallenes. It is a living polymerization, occurs with high atom economy, and creates precise, new polymer structures inaccessible by traditional methods. In the last decade there has been a renaissance in research and increasing examples of commercial products made using ROCOP. It is better known in the production of polycarbonates and polyesters, but is also a powerful route to make N-, S-, and other heteroatom-containing polymers, including polyamides, polycarbamates, and polythioesters. This Review presents an overview of the different catalysts, monomer combinations, and polymer classes that can be accessed by heterocycle/heteroallene ROCOP.     

Catalytic Copolymerization of Ethene and Carbon Monoxide on Nickel Complexes

Can palladium be replaced by nickel? For the industrial copolymerization of carbon monoxide and ethene a palladium catalyst is used which cannot be recovered—a cheaper procedure would be desirable. The presented complex 1 is the first structurally characterized nickel compound which does not polymerize ethene but a mixture from carbon monoxide and ethene unter mild conditions to give a perfectly alternating polyketone.     

Mechanism of Alternating Copolymerization of Vinyl Acetate and Maleic Anhydride

Vinyl acetate and maleic anhydride are known to give 1:1 alternating copolymerization regardless of the monomer feed composition. The existence of a charge transfer complex between the comonomers has been shown and its equilibrium constant determined.

The mechanism has been discussed, starting from a study of the copolymerization rate when varying the solvent, the temperature, and the concentration of comonomers.     

Chemoselective Alternating Copolymerization of Limonene Dioxide and Carbon Dioxide: A New Highly Functional Aliphatic Epoxy Polycarbonate

The alternating copolymerization of biorenewable limonene dioxide with carbon dioxide (CO₂) catalyzed by a zinc β‐diiminate complex is reported. The chemoselective reaction results in linear amorphous polycarbonates that carry pendent methyloxiranes and exhibit glass transition temperatures (T_g) up to 135 °C. These polycarbonates can be efficiently modified by thiols or carboxylic acids in combination with lithium hydroxide or tetrabutylphosphonium bromide as catalysts, respectively, without destruction of the main chain. Moreover, polycarbonates bearing pendent cyclic carbonates can be quantitatively prepared by CO₂ insertion catalyzed by lithium bromide.     

一氧化碳与烯烃共聚及其功能高分子

本文综述了一氧化碳与烯烃共聚合成聚酮的方法，共聚反应机理以及聚酮在合成其他功能高分子方面的应用。     

钯-稀土催化一氧化碳和苯乙烯交替共聚反应

 利用稀土钇盐或钕盐和乙酸钯组成的催化体系催化一氧化碳和苯乙烯共聚,合成了聚(1-氧代-2-苯基丙撑). 用元素分析、红外光谱、示差扫描量热、热重分析及X射线光电子能谱(XPS)等方法对共聚产物进行了表征. 测试结果表明,共聚物为一氧化碳和苯乙烯的线性交替共聚产物,其玻璃化温度为235 ℃,熔点为250 ℃,分解温度为325 ℃,且用XPS未检测到聚合物中含有残留的金属. 同时考察了催化剂组分2,2′-联吡啶、对甲苯磺酸和对苯醌及溶剂甲醇等的用量对共聚反应的影响,并对聚合反应条件进行了优化. 在优化的反应条件下稀土与钯组成的复合催化剂对一氧化碳和苯乙烯交替共聚的催化活性可达1200 g/(g·h).     

手性钯(Ⅱ)配合物及BF3·Et2O助剂催化的丙烯与一氧化碳立体选择性交替共聚反应研究

BF3·Et2O助催化剂加速了[L2]Pd (OAC)2(L:手性双瞵配体)催化的丙烯与一氧化碳立体选择性交替共聚反应,在相对较短的时间里合成了手性聚酮高分子,13C NMR和1H NMR,及摩尔旋光度证实产物具有较高的区域规整度和立构规整度,红外光谱指出产物同时具有螺旋缩酮和交替聚酮结构,凝胶渗透色谱法测定产物具有较低的分子量和宽的聚合度。     

Co-syndiospecific Alternating Copolymerization of Functionalized Propylenes and Styrene by Rare-Earth Catalysts

The precise control of monomer sequence and stereochemistry in copolymerization is of much interest and importance for the synthesis of functional polymers, but studies toward this goal have met with only limited success to date. Now, the co-syndiospecific alternating copolymerization of methoxyphenyl- and N,N-dimethylaminophenyl-functionalized propylenes with styrene by half-sandwich rare-earth catalysts is reported. This reaction efficiently afforded the corresponding functionalized propylene-alt-styrene copolymers with a perfect alternating sequence and excellent co-syndiotacticity (rrrr >99 %), thus constituting the first example of co-stereospecific alternating copolymerization of polar and non-polar olefins.     

Highly Enantioselective Catalytic System for Asymmetric Copolymerization of Carbon Dioxide and Cyclohexene Oxide

A new ligand can be easily prepared, and its intramolecular dinuclear zinc complexes act as a high performance catalyst for the asymmetric alternating copolymerization of cyclohexene oxide and CO₂ under very mild conditions (1 atm CO₂, room temperature), affording completely alternating polycarbonates with up to 93.8 % enantiomeric excess (ee) and 98 % yield. A high M_n value of 28 600 and a relatively narrow polydispersity (M_w/M_n ratio) of 1.43 were also achieved.     

Alternating Copolymerization of Styrene and N-(4-Bromophenyl)Maleimide

Abstract

Free radical copolymerization of styrene (St) and N(4-bro-mophenyl)maleimide (4BPMI) in dioxane solution gave an alternating copolymer in all proportions of feed comonomer compositions. The monomer reactivity ratios were found to be r ₁, = 0.0218 ± 0.0064 (St) and r ₂, = 0.0232 ± 0.0112 (4BPMI), and the activation energy of the copolymerization reaction for the equimolar ratios of comonomer was E _a, = 51.1 kJ/mol. The molecular weights of the copolymers obtained are relatively high, the T _g's showed similar values (490 K), and the thermal stability is higher than that of polystyrene. The initial rate of copolymerization depends on the total concentration of the comonomers and the maximum occurred at higher 4BPMI mol fractions; however, the overall conversion is highest at equimolar comonomer composition. It has been shown that a charge-transfer complex participates in the process of copolymerization. The initial reaction rate was measured as a function of the monomer molar ratios, and the participation of the charge-transfer complex monomer and the free monomers was quantitatively estimated.