基于烯烃复分解反应的高乙烯基聚丁二烯橡胶酯基官能化及其羧酸型离聚体的阻尼性能（英文）

以高乙烯基聚丁二烯橡胶(HVBR)为基体,采用过氧甲酸法制备环氧化高乙烯基聚丁二烯(EHVBR)及第1代Grubbs催化剂,以甲基丙烯酸甲酯(MMA)为改性剂,利用交叉烯烃复分解对EHVBR酯基官能化,得到酯基化的EHVBR(EHVBR-g-MMA),并与Na OH皂化反应制备EHVBR羧酸型钠离聚体。结果表明,EHVBR的环氧化反应发生在主链双键,官能度为13.0%;EHVBR-g-MMA的酯基官能度最高可达1.4%。该方法既可保证HVBR基体在烯烃复分解反应过程中相对分子质量不降低,又可弥补其他接枝方法导致凝胶含量升高的缺点。     

端羟基聚丁二烯液体橡胶制备技术的研究进展

对端羟基聚丁二烯（HTPB）液体橡胶的性能特点和应用领域等进行了概述,综述了HTPB的制备方法及其特点,同时对各类方法进行了对比,并提出了利用烯烃复分解法制备HTPB的优势以及烯烃复分解反应的特点,对其未来的发展方向进行了展望。     

腰果酚功能化液体1,2-聚丁二烯橡胶的制备及其对丁苯橡胶/白炭黑复合材料界面作用的增强

采用烯烃复分解法将生物基腰果酚（CA）接枝到1,2-聚丁二烯橡胶（1，2-PB）上制备了苯酚官能化的液体1，2-PB（1，2-PB-g-CA）。结果表明，CA成功接枝到聚丁二烯上，并且在开放体系下可得到官能度大于10%的接枝产物。将1，2-PB-g-CA作为白炭黑填充的丁苯胶轮胎胎面胶配方体系的增塑剂可提高白炭黑在基体中的分散性。同时，此改性低聚物羟基的存在有利于增加白炭黑和橡胶基体的相互作用。且该硫化胶具有较低的滚动阻力和生热性能。     

液体橡胶的研究进展Ⅱ.端基聚丁二烯液体橡胶的合成

概述了端基聚丁二烯液体橡胶的常见种类和特性,主要介绍了端羟基聚丁二烯液体橡胶、端羧基聚丁二烯液体橡胶和端羟羧基聚丁二烯液体橡胶的合成技术,包括自由基乳液聚合法、自由基溶液聚合法、负离子聚合法等.     

专利202212

一种同时生产橡胶促进剂TMTM和润滑油添加剂TPPT的方法；一种基于轮胎曲线的曲线拟合方法、装置及介质；一种防爆轮胎支撑装置及防爆轮胎和防爆轮胎胎面的更换方法；一种取向型高导热石墨烯/硅橡胶复合材料及其制备方法；一种基于3D点云的轮胎气泡缺陷检测方法及系统；端基官能化液体天然橡胶及其制备方法和应用；一种肩部曲线改良的半鼓式成型机及其机头和轮胎成型方法；一种耐磨耐腐蚀橡胶软管及其制备方法     

官能化液体橡胶制备技术及应用

官能化液体橡胶作为应用于国防、航天及其他特殊领域的核心材料之一,其突出的材料性能使其在各个应用领域表现优异。目前官能化液体橡胶的市场前景日新月异,故其存在的技术难点需要深入研究与探讨。本文通过官能化液体橡胶的发展历程,对官能化液体橡胶的材料特性、合成技术以及其在具有代表性领域的相关应用进行了讨论。分析表明,因官能化液体橡胶中活性官能团的存在,多样化的新型材料可依托官能团反应进行开发,其应用领域也将因此进一步拓宽。并指出在绿色、清洁、安全及应用梯度化发展方向的应用值得在下一阶段的研究工作中深耕。     

Synthesis of end group functionalized styrene-butadiene-styrene three block copolymer using lithumamide as initiator

用氮锂引发剂合成端基官能化苯乙烯-丁二烯-苯乙烯三嵌段共聚物王强,廖明义,王玉荣,张雪涛,张春庆(大连理工大学化工学院,辽宁大连116012)研究了六亚甲基亚胺基锂、氮锂和正丁基锂引发剂引发苯乙烯的聚合速率,合成了端基官能化苯乙烯-丁二烯-苯乙烯三嵌段聚合物(SBS)。结果表明,在设计相对分子质量相同的情况下,随着四氢呋喃加入量的增加,端基官能化SBS的1,2-结构质量分数增加,顺式-1,4-结构和反式-1,4-结构质量分数下降,但两者比值基本不变。相同条件下,用氮锂引发剂制备的端基官能化SBS的1,2-结构质量分数要略高于用正丁基锂引发剂制备的SBS。     

用氮锂引发剂合成端基官能化苯乙烯-丁二烯-苯乙烯三嵌段共聚物

研究了六亚甲基亚胺基锂、氮锂和正丁基锂引发剂引发苯乙烯的聚合速率,合成了端基官能化苯乙烯-丁二烯-苯乙烯三嵌段聚合物（SBS）。结果表明,在设计相对分子质量相同的情况下。随着四氢呋喃加入量的增加,端基官能化SBS的1,2-结构质量分数增加,顺式-1,4-结构和反式-1,4-结构质量分数下降,但两者比值基本不变。相同条件下,用氮锂引发剂制备的端基官能化SBS的1,2-结构质量分数要略高于用正丁基锂引发剂制备的SBS。     

用负离子原位聚合法合成链端氨基官能化集成橡胶

大连理工大学研究人员采用负离子原位聚合法，以N，N-二甲氨基苯甲醛缩苯胺为封端剂合成了链端氨基官能化集成橡胶，考察了封端剂用量、聚合物相对分子质量及大分子链活性端种类对分子官能化封端率的影响，并对聚合物进行了表征和性能测试。结果表明，N，N-二甲氨基苯甲醛缩苯胺封端剂可以与大分子活性端等摩尔反应，     

官能化溶聚丁苯橡胶研究进展

介绍了溶聚丁苯橡胶的发展历程,从官能化引发剂、官能化封端改性等方面详述了官能化溶聚丁苯橡胶的研究进展及溶聚丁苯橡胶的官能化技术在轮胎用橡胶方面的重要作用。将官能化技术和偶联技术结合而产生的官能化星型溶聚丁苯橡胶是丁苯橡胶研究的一个重要方面。     

Controlled synthesis of azobenzene functionalized homo and copolymers via direct acyclic diene metathesis polymerization

A powerful and efficient strategy for obtaining a series of azobenzene functionalized linear unsaturated polyolefins is described, which involves the first design and synthesis of three different α,ω-diene monomers with different reactivity of acrylates and terminal double bonds and their subsequent acyclic diene metathesis (ADMET) polymerization under mild reaction conditions. Different ruthenium based metathesis catalysts and conditions were tested to optimize the ADMET polymerization of these monomers. Besides, this polycondensation method is also reported allowing for the synthesis of alternating and diblock azobenzene-containing copolymers with molecular weight control by using the selectivity of olefin cross-metathesis between acrylates and terminal olefins. The resulting polymers showed well-defined molecular weights, reasonable polydispersity index, and reversible photoresponsive behavior. This special combination of the benefits of metathesis polymerization and azobenzene is a highly versatile system for materials in many applications.     

Liquid Phase Extraction and Separation of Noble Organometallic Catalysts by Functionalized Ionic Liquids

Abstract

The separation of two noble organometallic catalysts from a homogeneous organic phase was investigated using liquid phase extraction with functionalized ionic liquids. Thirteen functionalized ionic liquids containing amino, hydroxy, thioether, carboxylic, or olefin functional groups were prepared by a standard neutralization method. The extractions of Jacobsen's catalyst and Wilkinson's catalyst were conducted using the functionalized ionic liquids as the extraction phase without adding any other metal complexing extractant. The distribution factors between the ionic liquid (IL) phase and toluene (organic solution phase) demonstrated that the functional groups in ILs exhibited moderate to high affinity with the metal complexes. The influence of the ionic liquid structure on the distribution factors was also investigated.     

Salicylaldimine Ruthenium Alkylidene Complexes: Metathesis Catalysts Tuned for Protic Solvents

Tuning the electronic and steric environment of olefin metathesis catalysts with specialized ligands can adapt them to broader applications, including metathesis in aqueous solvents. Bidentate salicylaldimine ligands are known to stabilize ruthenium alkylidene complexes, as well as allow ring‐closing metathesis in protic media. Here, we report the synthesis and characterization of exceptionally robust olefin metathesis catalysts bearing both bidentate salicylaldimine and N‐heterocyclic carbene ligands, including a trimethylammonium‐functionalized complex adapted for polar solvents. NMR spectroscopy and X‐ray crystallographic analysis confirm the structures of the complexes. Although the N‐heterocyclic carbene–salicylaldimine ligand combination limits the activity of these catalysts in non‐polar solvents, this pairing enables efficient ring‐closing metathesis of both dienes and enynes in methanol and methanol/water mixtures under air.     

Practical Olefin Metathesis in Protic Media under an Air Atmosphere

The discovery that efficient olefin metathesis reactions involving previously challenging terminal olefin substrates are possible using novel and readily available catalyst systems in non‐distilled, non‐degassed protic media in air is reported.     

The ROMP toolbox upgraded

This article features the current state of research in olefin metathesis polymerization techniques towards the synthesis of functional polymeric materials. Emphasis is laid on work making use of ring opening metathesis polymerization (ROMP) initiated by ruthenium complexes published in the last five years. Other techniques such as alternating diene metathesis polymerization (ALTMET) are only covered when appropriate. A survey on polymer architectures accessible via olefin metathesis is presented and illustrated with manifold examples from research fields like life science, optics and electronics, sensorics or energy storage. Important new developments such as end-group functionalization or stereoselective polymerization are addressed. A chapter on using alternative and green solvents in ROMP is disclosed as well as an overview on the use of olefin metathesis polymerization using sustainable substrates. Applications in material science such as porous, liquid crystal or self-healing materials close the work.     

Well‐Defined End‐Functionalized Conjugated Polymers/Oligomers Exhibiting Unique Emission Properties through the End Groups: The Exclusive Synthesis by Combined Olefin Metathesis with Wittig‐type Coupling

Acyclic diene metathesis polymerization using ruthenium–carbene catalysts affords defect‐free, high molecular weight poly(arylene vinylene)s containing all trans olefinic double bonds. The exclusive end‐functionalization in the resultant poly(fluorene vinylene)s or poly(phenylene vinylene)s can be attained by treating the vinyl end groups using a molybdenum–alkylidene catalyst/reagent (through olefin metathesis) followed by addition of various aldehydes (Wittig‐type coupling). Some of these end‐modified conjugated materials display unique emission properties, which are different from the original ones, through an interaction (energy transfer or structural change in the excited state) between the conjugated main chain and the end groups [oligo(thiophene)s, F‐BODIPY, etc.]. Exclusive synthesis of well‐defined, all‐trans end‐functionalized oligo(2,5‐dialkoxy‐1,4‐phenylene vinylene)s [(oligo(phenylene vinylene), alkoxy = O(CH₂)₂OSiⁱ Pr₃, up to 31 repeat units] is demonstrated by adopting a stepwise synthetic approach (olefin metathesis and the subsequent Wittig‐type cleavage). It is clearly demonstrated that their optical properties (especially the fluorescence spectra including photoluminescence quantum yields) are strongly affected by the end groups as well as the conjugation repeat units.     

A Ring‐Closing Metathesis Approach to Cyclic α,β‐Dehydroamino Acids

A comprehensive study on the synthesis and ring‐closing metathesis (RCM) of α,β‐dehydroamino acids is described. This sequence has led to the formation of a range of biologically relevant functionalized nitrogen heterocycles. The incorporation of chiral building blocks in the RCM precursors eventually resulted in the formation of optically active 4‐substituted cyclic dehydroamino acids. In addition, olefin isomerization under metathesis conditions was observed for a number of compounds, which could be successfully inhibited either by the introduction of allylic substituents or by the addition of a ruthenium hydride scavenger.     

不饱和油脂交叉易位合成生物煤油的研究

研究了一种将油脂转化为一种碳数类似煤油的轻质燃油的全新方法，其合成步骤主要是：首先将富含双键的油脂与甲醇酯交换得到脂肪酸甲酯；再将甲酯与3-己烯通过交叉易位合成一些列碳数在9到16的烯烃燃料油；最后通过精馏将烯烃燃料油与饱和脂肪酸甲酯分离即得所需轻质燃油（生物煤油）。     

离子液体在烯烃复分解反应中的应用

离子液体作为一种环境友好的催化剂和溶剂，受到了人们日益的关注。本文从离子液体作为溶剂、催化剂溶解于离子液体、离子液体的负离子作为催化剂配体三个方面，详细地介绍了离子液体在烯烃复分解反应中的应用，很好地解决了催化剂难储存、难循环利用和底物范围狭窄等问题。