高分子材料烧结成型研究进展

高分子材料烧结成型是借鉴粉末冶金技术而形成的一种特殊的成型加工方法,特别适合熔体粘度极大、高温易分解的高分子材料的成型加工。传统高分子材料的烧结成型温度在熔点以上,通过粉末的熔融和界面扩散将粉末烧结在一起。本文首先对聚四氟乙烯和超高分子量聚乙烯这两种常用于烧结成型的高分子材料的烧结成型工艺条件、成型机理及其多功能材料的制备等方面进行了系统的介绍;最后,重点分析了我们组最近针对立构复合型聚乳酸熔融稳定性差、熔融加工易降解的问题而提出的一种低温(低于立构复合晶体熔点)烧结成型新方法,即通过在粉末表面形成新立构复合晶体将粉末烧结在一起,并对其研究进展进行了综述。     

聚乳酸立构复合物的研究最新进展与应用展望

立构复合型聚乳酸(SC-PLA)由于聚左旋乳酸(PLLA)与聚右旋乳酸(PDLA)分子链之间强烈的相互作用,可以使熔点提高约50℃,改善了聚乳酸在耐热性上的不足,同时这种立构复合结构使聚乳酸的力学性能、结晶性能、耐水解性等也得到提升.立构复合型聚乳酸的合成新进展主要集中在嵌段型SC-PLA的制备,同时广泛采用X射线衍射...     

高耐热聚乳酸立体复合材料的制备

以等比例的聚L乳酸(PLLA)和聚D乳酸(PDLA)树脂为原料,先通过低温共混制备聚乳酸全立构粉末,然后将立构粉末与成核剂、玻璃纤维等混合,直接在注塑机中成型,注塑样品经热处理后,得到高耐热性能聚乳酸(PLA)样品,经测试,其维卡软化温度高达165 ℃以上,差示扫描量热分析(DSC)结果表明,处理后的样品富含立构物结晶,立构物结晶熔融焓高达27.6 J/g。 拉伸强度较纯PLA也有大幅提升,达到129 MPa。     

高耐热PLLA/PDLA共混物的热性能和结晶结构研究

通过熔融共混法制备了一系列等比例聚左旋乳酸(PLLA)/聚右旋乳酸(PDLA)共混试样,采用差示扫描量热法(DSC)、核磁共振(13C-NMR)及广角X射线衍射(WAXD)等方法对共混产物进行了表征和研究分析.结果表明,等比例PLLA和PDLA熔融共混生成了立构复合物(stereocomplex,sc),同时部分均聚物发生酯交换反应,生成了立体嵌段物(stereoblock,sb),从而在DSC升温曲线上sc晶体处出现特殊的熔融双峰现象;随着熔融共混温度升高,sc晶体的生成率和结晶度逐渐下降;聚乳酸立构复合物的加工稳定性较好,二次加工后,sc晶体熔点基本不变,生成率和结晶度提高;由于sc晶体的存在,PLLA/PDLA共混物的耐热性能提高,退火热处理后耐热性能得到进一步提高.这对于开发高耐热聚乳酸及其加工应用具有重要的应用价值.     

PLLA/PDLA立构复合晶体的结晶、熔融行为

以水为引发剂合成了两种构型不同的左旋聚乳酸和右旋聚乳酸,运用DSC研究了分子量较低的PLLA/PDLA立构复合聚乳酸晶体的多重熔融行为,观察到随着180℃等温时间的增加,PLLA/PDLA共混物的立构复合晶体的熔点和熔融峰面积呈现震荡性变化行为,进一步的DSC和在线X射线研究结果显示,聚乳酸立构复合晶体多重熔融峰的震荡行为来自于晶体中就近生长的过量异构体链段的调整过程。     

高分子材料动态加工新技术

介绍了振动力场作用下高分子材料动态挤出成型、动态注射成型以及动态混炼成型的技术及装备,简要阐述了动态挤出中动态固体输送、动态熔融塑化、动态熔体输送过程的机理及实验研究成果,分析了脉动压力对注射过程的影响以及动态混炼过程中强制混炼、强制分散的原理,对各种动态成型技术辅以相应的制品性能测试.研究结果表明振动力场的引入在产量相同并保证甚至改善制品综合性能的同时,可有效缩短成型历程,降低功率消耗,因此高分子材料动态成型加工方法是一种新型的低能耗成型加工技术.     

植物纤维增强聚乳酸可降解复合材料的研究

聚乳酸因具有优良的生物相容性、易降解、强度高,可塑性强,易加工成型等优点,近年来倍受高分子材料行业的青睐。但是由于存在脆性高、热性能较差、降解速度不易控制等缺陷,限制了使用效果,因此需进行改性研究。植物纤维质轻、价廉、比强度高并可降解,近年来作为增强材料发展迅速,用来增强聚乳酸,不但可以提高材料的性能,而且赋予复合材料...     

立构复合PL(D) LA-TMC无规共聚物的制备、结构与性能

以辛酸亚锡为催化剂,通过开环聚合法制备了聚左旋乳酸-三亚甲基碳酸酯(PLLA-TMC)和聚右旋乳酸-三亚甲基碳酸酯(PDLA-TMC)无规共聚物.利用共聚物中PLLA/PDLA链段形成立构复合体,通过溶液浇注法制备了PLLA-TMC/PDLA-TMC立构复合聚乳酸材料(sc-PLA-TMC).研究结果表明,聚合物链中的柔性TMC单元可以增强L(D)LA链段的运动能力,有助于不同旋光性的LA链段形成立构复合晶体,但也使得L(D)LA链段的规整度和序列长度降低.即随着共聚物链段中柔性TMC单元摩尔含量的增加,sc-PLA-TMC中同质结晶能力降低.当TMC含量≥5%时,仅生成熔点200℃的PLLA/PDLA立构复合结晶,表明sc-PLA-TMC的耐热性有所提高.蛋白酶K降解实验表明,PL(D)LA-TMC共聚物的降解速率不但比PLLA高,而且可通过共聚物中TMC含量进行调控.     

界面立构复合化电活性聚乳酸纳纤膜的制备及高效过滤性能

聚乳酸纤维膜在可降解空气过滤材料领域具有巨大潜力,但低比例的电活性相导致纤维膜的介电性能较弱,难以满足高性能空气颗粒物(PMs)过滤材料的需要.本文利用聚L-乳酸(PLLA)和聚D-乳酸(PDLA)组成的立构复合物(SC)提供高比例电活性相,采用同轴静电纺丝策略构筑界面立构复合化的电活性聚乳酸纳纤膜.通过改变纺丝时的注射速度,调控纤维形貌以及羰基(C=O)偶极子、 β晶相和界面立构复合晶(SCs)的形成,得到的核壳(CS)结构纳纤膜具有改善的表面电势(9.3 kV)和介电常数(1.60 F/m).界面立构复合化的纤维膜力学性能提升显著,核部PLLA和壳部PDLA的注射速度分别为1.0和0.5 mL/h时获得的CS1.5纳纤膜的拉伸强度和杨氏模量分别达到17.2和351.1 MPa,明显优于纯聚乳酸纤维膜.更重要的是,提升的电活性显著增强了聚乳酸纳纤膜对PM0.3和PM2.5的过滤效率,界面立构复合化在应对高流速下捕尘时具有独特优势, CS1.5纳纤膜的过滤效率由10 L/min时的82.5%提升至85 L/min时的97.9%.本文提出了采用界面立构复合化激发聚乳酸电活性的策略,为解决...     

高分子加工制品的多层次结构控制——从传统加工到定构加工

现代高分子材料加工所倡导的高性能化、功能化、多用途性、节能低碳等对加工制品内部多层次结构控制提出了非常高的要求.与传统高分子加工方法所注重评价加工参数变量对形态结构的影响不同,本文提出的定构加工方法学是通过特殊外场作用使得形态结构更利于调控,其特点是由外场作用决定的多层次结构;所获得的加工制品具有比常规加工更优异的宏观性能.两个典型的定构加工实例,聚丙烯/β成核剂注塑制品中形成类似竹子的仿生结构以及嵌段共聚物SIS微相分离结构与宏观力学性能关系,表明定构加工在调控制品最终多层次结构上的突出优势.定构加工代表着未来高分子加工发展的重要方向.     

二氧化碳和丙烯直接合成甲基丙烯酸的NiPMo/TiO2催化剂的研究

用溶胶-凝胶法以磷钼酸(MPA)的镍盐溶液水解钛酸四丁酯制备了NiPMo/TiO2催化剂.使用ICP、 XRD、 TG-DTA、 IR、 TPD-MS和微反应技术研究了催化剂的化学组成、热稳定性、化学吸附性质和催化反应性能.杂多钼酸盐与TiO2通过O2-在TiO2表面发生了键合.在623 K下,杂多阴离子仍保持原有的Keggin结构.CO2在Lewis酸位Ni(Ⅱ)和Lewis碱位Ni-O-Mo的桥氧协同作用下生成CO2卧式吸附态Ni(Ⅱ)←O-(CO)←(O--Ni).丙烯有多种吸附态在催化剂上吸附.在563 K、 1 MPa和空速1500 h-1的反应条件下,丙烯的摩尔转化率为3.2%,产物MAA选择性为95%.     

Synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives

Different approaches for the synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives from simple amino acids have been investigated. A library of 33 precursors for the preparation of N-hydroxy pyrazinones was obtained in moderate to good yields.     

Toward new camptothecins. Part 6: Synthesis of crucial ketones and their use in Friedländer reaction

In the context of the preparation of camptothecin and luotonin A analogs, the synthesis of some key keto-precursors and their use in Friedländer condensation are described. This paper also focuses on the stability of these keto intermediates and emphasizes the major differences between indolizinones and pyrroloquinazolinones series. Noteworthy is also the report of some original structures isolated as by-products of some experiments.     

CoFe2O4自形成磁性液体场致结构化对磁化的影响

The Langevin paramagnetic theory can’t describe the relation between magnetization of ferrofluids and applied magnetic field. The structuralization of ferrofluids, which is considered the main influence factor of the magnetization, is regarded. The part of magnetization works is deposited when the structure is forming. This action influences the magnetization of ferrofluids directly or indirectly. On the base of the “compressing” model, the Langevin function that usually describes the magnetization of ferrofluid is modified, and a well-fitted curve is obtained. An equation of the relation between the equivalent volume fraction after being “compressed” and the intensity of magnetic field is discovered, which approximately describes the process of magnetization. The relation between the approximate initial susceptibility and the volume fraction can be obtained from modified formula.     

Highly regioselective Buchwald–Hartwig amination at C-2 of 2,4-dichloropyridine enabling a novel approach to 2,4-bisanilinopyridine (BAPyd) libraries

The highly regioselective Buchwald–Hartwig amination at C-2 of the cheap and readily accessible reagent, 2,4-dichloropyridine with a range of anilines and heterocyclic amines is described. This new methodology is robust and provides a facile access to 4-chloro-N-phenylpyridin-2-amines on 0.25 mol scale. These intermediates undergo a further Buchwald–Hartwig amination at higher temperature to enable rapid exploration of the chemical space at C-4 and to provide a library of 2,4-bisaminopyridines.     

KMnO4-mediated oxidative CN bond cleavage of tertiary amines: Synthesis of amides and sulfonamides

KMnO₄-mediated oxidative CN bond cleavage of tertiary amines producing secondary amine was introduced, which was trapped by electrophiles (acyl chloride and sulfonyl chloride) to form amides and sulfonamides. The reaction could take place at mild condition, tolerating a wide range of function groups and affording products in moderate to excellent yields.     

Chemistry of heterocyclic compounds at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, over 50 years (Review)

The review contains a concise historical account and information on the most significant researches undertaken by the staff at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences on the Chemistry of Heterocyclic Compounds. Dedicated to Academician of the Russian Academy of Sciences B. A. Trofimov on his 70th jubilee. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1443–1502, October, 2008.     

A general and convenient synthesis of 4-(tosylmethyl)semicarbazones and their use in amidoalkylation of hydrogen,heteroatom, and carbon nucleophiles

A general synthesis of previously unknown semicarbazone-based α-amidoalkylating reagents, 4-(tosylmethyl)semicarbazones, has been developed. The synthesis involved three-component condensation of semicarbazones of aliphatic or aromatic aldehydes with the same or other aldehydes and p-toluenesulfinic acid. The scope and limitations of this reaction were investigated. The compounds obtained were demonstrated to be an efficient α-(4-semicarbazono)alkylating agents. They were reacted with H- (sodium borohydride), O- (sodium methylate), S- (sodium phenylthiolate), N- (pyrrolidine, sodium succinimide), P- (trialkyl phosphites), and C-nucleophiles (sodium diethyl malonate) to give the corresponding products of the tosyl group substitution, 4-substituted semicarbazones, including analogues of nitrofurazone. Among the prepared compounds tested in vitro for antibacterial and antifungal activity, three nitrofuryl-containing semicarbazones exhibited high biological activities with minimum inhibitory concentration (MIC) values of 8–32 μg/mL.     

Sulfur-directed metal-free and regiospecific methyl C(sp3)–H imidation of thioanisoles

Regiospecific and direct imidation of the methyl C(sp³)–H bond of thioanisoles is realized under mild and metal-free conditions with N-fluorobis(benzenesulfonyl)imide as an oxidant and nitrogen source. Proposed mechanism suggests that thionium ion intermediates and a Pummerer-type reaction are involved. The imidation has advantages such as high step-economy, excellent functionality tolerance, and regiospecificity, giving structurally diverse imidation products.     

Synthesis of novel chiral bidentate hydroxyalkyl-N-heterocyclic carbene ligands and their application in palladium-catalyzed Mizoroki–Heck couplings and asymmetric addition of diethylzinc to benzaldehyde

A small library of new chiral bidentate hydroxyalkyl-imidazolium salts 1 is conveniently synthesized on multi-gram scale from inexpensive and commercially available chiral pool amino acids. The corresponding carbenes, generated by deprotonation of imidazolium salts 1, in combination with palladium(II) chloride were tested in the Mizoroki–Heck coupling reaction. The most significant results in terms of yields and reactivities were achieved with low catalyst loading. The catalytic activities of these imidazolium salts were also investigated in the asymmetric addition of diethylzinc to benzaldehyde. The use of MgO nanoparticles as an additive in conjunction with these ligands played a crucial role in increasing the efficiency of these reactions.