熔融-拉伸法制备亲水聚丙烯/聚乙烯醇缩丁醛中空纤维膜

以聚丙烯(PP)为基材,聚乙烯醇缩丁醛(PVB)为亲水改性剂,聚丙烯接枝马来酸酐(PP-g-MAH)为增容剂,通过熔融-拉伸法(MS-S)制备亲水PP/PVB中空纤维膜.采用差示扫描量热(DSC)和水接触角(WCA)测试考察了PVB添加量对PP/PVB共混物结晶行为及亲水性的影响;采用广角X射线衍射(WAXD)和小角X射线散射(SAXS)研究了PP/PVB中空纤维热处理后片晶微观结构;采用场发射扫描电镜(FESEM)观察了PP/PVB中空纤维膜内表面孔结构的变化,测试了PP/PVB中空纤维膜的孔隙率及纯水通量.研究结果表明,随着PVB含量的增加,PP/PVB共混物的WCA从103°降低到76°,表明PP/PVB共混物亲水性得到明显改善.同时,PVB可以起到异相成核作用,但由于MAH与PVB发生键合作用,过量添加PVB会阻碍PP分子链段运动,导致晶体结构不完善,这与WAXD和SAXS分析结果相同.PP/PVB2.5(PVB质量分数为2.5%)中空纤维膜热处理后结晶度、片晶取向度、厚度及Shish-kebab结构完善度均高于纯PP样品.对应膜孔隙率为66%,纯水通量达到320 L/(m2·h),比纯PP膜提高了76.8%.     

PVDF/PVB共混物的非等温结晶动力学

采用差示扫描量热法测试了在不同降温速率下的聚偏氟乙烯(PVDF),以及不同配比的聚偏氟乙烯(PVDF)/聚乙烯醇缩丁醛(PVB)共混物的DSC曲线,采用Jeziorny法和莫志深法分析了各组样品的非等温结晶动力学。结果表明:在同一降温速率下,PVB含量的增加使得结晶温度范围先减小后增加,峰值温度先升高后降低,结晶度先增大后减小,说明PVB的加入对共混物的结晶起到先促进后抑制的作用;而且随着PVB含量的增加,共混物的n值增大,说明其晶体生长方式从接近二维片晶生长向三维球晶生长转变,PVB的加入促进共混物生成多维复杂晶体。     

PP/PP-g-MAH/PA6共混物结构与可纺性研究

运用DSC、SEM、纺丝成形等手段研究了增容剂聚丙烯接枝马来酸酐 (PP g MAH)对聚丙烯 聚酰胺 6(PP PA6 )共混物结构和性能的影响 .结果表明 ,共混物呈典型海岛型两相结构 ;增容剂PP g MAH与PA6之间的在位反应改善了PP PA6共混体系的相容性 ,使共混物中PA6的热结晶峰消失 ,PP的结晶生长速率和成核速率降低 ,可纺性提高     

聚甲醛与热塑性酚醛树脂相容性研究

考察了聚甲醛(POM)与热塑性酚醛树脂(Novolak)的相容性;浊点法研究结果表明,POM/Novolak共混物存在一个低位临界相转变温度.DSC测试表明,POM与Novolak共混后,共混物的熔点下降;通过DSC测试得到数据,采用Hoffman-Weeks平衡熔点外推法和Flory熔点下降方程推算出POM与Novolak的相互作用参数(χ)约为-0.032.FTIR研究表明,Novolak的羟基能够与POM的醚氧基形成氢键,导致共混物中Novolak的羟基峰向高频偏移.研究结果表明,POM与Novolak能够达到热力学相容.     

聚乙烯醇-羧甲基纤维素钠共混膜的制备与性能

用溶液共混法制备聚乙烯醇-羧甲基纤维素钠(PVA-CMC)共混膜.用SEM、FT-IR、DSC对其进行表征,并测试了膜的性能、交联速率和凝胶分数.结果表明:共混膜组分之间相容性良好,综合力学性能比单一组分有所提高.利用磷酸和氯化钙溶液可以有效地对共混膜进行交联,使其在醇水混合溶液中稳定存在;且交联过程未引入有毒物质,这种共混膜材料有望用作软骨修复材料的基体.     

多壁碳纳米管/液晶高分子复合材料的制备及其对PP结晶行为的影响

首先通过原位聚合法合成了一种新型多壁碳纳米管/液晶高分子复合材料(MCNT/LCP),然后将其与聚丙烯共混,制备了一系列的共混样品。采用FT-IR、DSC与POM等表征了MCNT/LCP复合材料的结构与液晶性能,利用XRD与DSC研究了聚丙烯共混物的结晶结构与结晶动力学,探讨了MCNT/LCP含量与结晶温度对聚丙烯共混物结晶行为的影响。结果表明:所合成的MCNT/LCP呈现近晶相的扇形织构,当MCNT/LCP被引入到聚丙烯中后,不仅起到异相成核的作用,而且能诱导β晶的形成,同时,DSC降温曲线峰型也变得比较尖锐,结晶峰温度提高,结晶速度加快。     

POM/PBSA合金的分子间作用力与相容性及结晶行为研究

采用熔融共混的方法制备了聚甲醛(POM)/丁二酸丁二醇酯-己二酸丁二醇酯共聚物(PBSA)合金.利用FTIR、DMA、DSC、PLM及WAXD研究了POM与PBSA分子间相互作用、相容性及结晶行为.结果表明PBSA的羰基和POM的端羟基之间形成了氢键,这使得PBSA和POM具有一定的相容性,同时使POM的熔融与结晶温度降低;当POM含量为15%时对PBSA起到成核剂的作用,促进了PBSA的结晶,使其晶体结构变得致密.另外,POM与PBSA之间的相容性依赖于PBSA含量,随着PBSA含量的增大,两者的相容性变好,但是PBSA的加入并没有改变POM的晶型.     

BTF变色对其热安定性和与PVB等相容性的影响

通过光照制备了一定量的变色苯并三呋咱氧化物（BTF）,再分别采用差热（DTA）,差示扫描量热（DSC）,真空安定性试验（VST）等热分析方法,对变色前后的BTF进行了热安定性研究及与聚乙烯醇缩丁醛（PVB）等接触材料的相容性研究,并通过热重－红外等仪器分析手段,初步探讨了BTF与PVB之间的作用机理。     

PTW对PA1010/PP共混物的增容作用

为了增加聚酰胺1010/聚丙烯(PA1010/PP)共混物的相容性,提高共混物的力学性能,采用一种新型的反应型增容剂乙烯-丙烯酸丁酯-甲基丙烯酸缩水甘油酯共聚物(PTW)进行增容,通过扫描电镜(SEM)、力学性能、傅里叶变换红外光谱(FTIR)和差示扫描量热(DSC)测试,研究了PTW对PA1010/PP共混物的增容作用.结果表明,随着PTW的加入,共混物的相区尺寸明显变小,当PA1010/PP/PTW质量比为70∶30∶7时,分散相尺寸细小而均匀,表明PTW有较好的增容作用.FTIR结果表明,PTW上的环氧基团和PA1010在熔融共混中发生了化学反应.DSC研究结果表明,PA1010的结晶温度随PTW的加入而降低,说明PTW对PA1010结晶有抑制作用.另外,PTW的加入使PP的结晶温度下降,当PTW质量分数为5%时出现2个结晶峰,即出现异相成核结晶和均相成核结晶,PP均相成核结晶的出现从另一个方面说明,在PA1010基体中分散相PP尺寸非常细小.当PTW质量分数为7%时共混物的力学性能最佳,干态冲击强度达到13.93kJ/m2,是未加增容剂时的2倍,拉伸和弯曲性能基本不变.PTW的增容机理在于其分子链中的甲基丙烯酸缩水甘油酯能与PA1010发生化学反应,而乙烯链段与PP有较好的亲和性,从而降低界面张力,减少相区尺寸,大幅度提高力学性能.     

聚乙烯醇/单宁共混膜的制备及其抗菌性能

采用溶液共混浇膜法制备了不同单宁含量的聚乙烯醇/单宁共混膜材料,利用扫描电镜(SEM)、广角X-射线衍射(WAXD)及示差扫描量热分析(DSC)对共混膜的结构进行了表征.结果表明,单宁和聚乙烯醇具有良好的相容性,聚乙烯醇的结晶能力及熔点均随单宁的加入量增大而稍降低.少量戊二醛的轻度交联作用使单宁在共混膜中非常稳定,在水中浸泡24 h后也仅有不到1.8%的单宁(相对膜中单宁总质量)渗出.接触法抗菌试验表明,所制备的共混膜对大肠杆菌(E.coli,CMCC 44103)、金黄色葡萄球菌(S.aureus,ATCC6538)和表皮葡萄球菌(S.epidermidis,ATCC 12228)都具有良好的抗菌能力,且随着单宁含量的升高而增强.     

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.     

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.     

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.     

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.