催化剂用量对醋酸纤维素接枝聚乙二醇单甲醚相变材料接枝率和性能的影响

以二月桂酸二丁基锡(DBTDL)作为催化剂,以醋酸纤维素(CDA)为基体材料、以聚乙二醇单甲醚(MPEG)为工作物质,利用溶液聚合法合成了纤维素接枝聚乙二醇单甲醚相变材料,研究了催化剂用量对MPEG接枝产物接枝率和性能的影响.结果表明,当催化剂用量为0.15%(质量分数,下同)时,MPEG1000和MPEG1500接枝产物的接枝率均达到最大值,分别为224.03%和189.30%;当催化剂用量为0.1%时,MPEG2000接枝产物的接枝率最大,达129.99%.此外,由不同分子量MPEG制备的接枝产物的相变温度和相变焓不同,不同产物在升温过程中均呈现较好的固-固相变调温性能.     

AB型两亲聚L-谷氨酸-苄酯-聚乙二醇嵌段共聚物的合成与表征

利用L 谷氨酸和苯甲醇反应制备了L 谷氨酸 苄酯 ,然后将其与三聚光气反应制备了N 羧基 L 谷氨酸 环内酸酐 (NCA) .以聚乙二醇单甲醚 (MPEG)为原料 ,制备了端氨基聚乙二醇单甲醚 (MPEG NH2 ) ,并以此作为引发剂 ,引发NCA开环聚合 ,合成了不同分子量的聚L 谷氨酸 苄酯 聚乙二醇单甲醚 (PBGM )嵌段共聚物 .利用IR、1 H NMR、DSC、GPC等方法对共聚物结构进行了表征 .结果表明 ,MPEG NH2 引发NCA开环聚合得到的是嵌段共聚物 ,通过1 H NMR谱得到共聚物组成及数均分子量 ;随着共聚物中MPEG含量的增高 ,聚L 谷氨酸 苄酯的亲水性有所改善     

含氟两亲性嵌段聚合物乳液的合成

以聚乙二醇单甲醚(MPEG)为原料,与2-溴异丁酰溴经酯化反应合成了端基为溴原子的MPEG-Br;以MPEG-Br为大分子引发剂,甲基丙烯酸十二氟庚酯经电子活化再生原子转移自由基乳液聚合法合成了新型的含氟两亲性嵌段聚合物(1)乳液,其结构经1H NMR,IR和X-射线光电子能谱(XPS)表征。接触角测量结果表明:1可改变岩心的润湿性,由强液湿转变为气湿。     

改进型聚丙烯酸系高效减水剂的合成

根据分子结构设计原理,合成了一种改进型聚丙烯酸系高效减水剂(PC-C),对影响减水剂性能的几个关键因素进行了探讨,并用红外光谱表征了其分子结构。通过正交实验获得了最佳的合成参数:乙烯基磺酸钠(SVS):丙烯酸(AA):丙烯酸聚乙二醇单酯(PEA)=1.5:5:3,过硫酸铵(APS)用量为单体总质量的3%;同时研究了减水剂侧链和掺量对分散性能的影响。结果表明:采用甲氧基聚乙二醇(MPEG)作为接枝侧链合成减水剂的分散能力优于采用聚乙二醇(PEG)合成的减水剂;PC-C低掺量即可发挥高分散性能,分散保持性能随掺量的增加而得以提高。     

聚乙二醇/羟基磷灰石纳米杂化材料的制备及表征

以聚乙二醇单甲醚(MPEG)为原料, 采用先磷酰化再水解的方法合成了聚乙二醇单甲醚磷酸酯(P-MPEG). 以P-MPEG为空间位阻剂, 采用共沉淀法合成了内核为纳米羟基磷灰石(nHA)、 壳层为MPEG链的纳米杂化材料. 用傅里叶变换红外光谱(FTIR)、 X射线衍射(XRD)、 透射电子显微镜(TEM)和激光粒度分析(LPSA)对材料结构进行了表征. 结果表明, 所合成的杂化材料不仅能在水中再分散, 而且可以在甲醇和二甲基甲酰胺(DMF)等有机溶剂中再分散.     

聚羧酸系减缩剂的制备及应用性能研究

在水溶液中以过硫酸铵为引发剂、次亚磷酸钠为链转移剂,丙烯酸、二乙二醇单丁醚马来酸单酯为反应单体,合成聚羧酸减缩剂。研究在反应温度为75℃时,引发剂用量、链转移剂用量、单体质量分数对水溶液表面张力的影响。结果表明,聚合的最佳反应条件为:过硫酸铵用量为0.7%,次亚磷酸钠用量为5%,单体质量分数为24%。采用红外光谱对聚合物的结构进行表征,研究其对水溶液表面张力,溶液的蒸发速率,砂浆的干燥收缩、抗折、抗压强度的影响。研究发现,当聚合物的掺量为6%时,在水溶液中表面张力降低了40%,溶液的蒸发速率降低了15.3%。聚合物的掺量为3%时,与空白样相比水泥砂浆的28d干燥收缩率降低了18.9%,抗压强度与抗折强度有所降低。     

甲氧基聚乙二醇-b-聚L-半胱氨酸两亲性嵌段共聚物的合成与表征

首先以聚乙二醇单甲醚(mPEG-OH)为单体,采用经典的盖布瑞尔伯胺合成法合成了端氨基聚乙二醇单甲醚(mPEG-NH_2);然后以mPEG-NH_2为引发剂,S-苄基L-半胱氨酸N-羧酸内酸酐(BCys-NCA)为原料,通过N-羧酸内酸酐(NCA)开环聚合反应和液氨/钠处理脱除侧链上的保护基团,合成了两亲性嵌段共聚物甲氧基聚乙二醇-b-聚L-半胱氨酸(mPEG-b-PCys)。采用傅里叶变换红外光谱、核磁共振氢谱对聚合物的结构和组成进行了表征。结果表明:成功制备了侧链具有还原性巯基的两亲性嵌段共聚物mPEG-b-PCys,并且其聚合度可控性良好。     

马来酸酐类聚羧酸盐减水剂的合成与性能研究

目前聚羧酸减水剂大多由甲基丙烯酸合成,而马来酸酐因其结构对称、活性较低等特点而合成工艺简单、易于控制。本文研究以马来酸酐、甲氧基聚乙二醇、乙烯基磺酸钠、甲基丙烯酸为原料采用先酯化再共聚的方法合成出了含有羧酸基、磺酸基、聚氧乙烯基的马来酸酐类聚羧酸减水剂。酯化反应是极其关键的一步,通过研究表明马来酸酐甲氧基聚乙二醇单酯最佳合成条件为:酸醇比为1.15:1、催化剂用量为MPEG质量的6%,、反应时间4h,反应温度为110℃;马来酸酐聚羧酸减水剂的最佳合成配比为n(MPEG-MA):n(SVS):n(MAA)=1:0.75:5。马来酸酐聚羧酸减水剂最佳掺量为0.5%,与市场上的减水剂最佳掺量时的效果相当。     

聚乙二醇类单体的制备及其生物相容性测定

聚乙二醇类单体是合成功能性高分子材料的重要单体。直接酯化法是合成此类单体的主要方法,但利用该法所制备产物的双键保留率偏低。针对这一问题,本文以聚乙二醇单甲醚-200和丙烯酸为原料,在携水剂存在的同时,向反应体系中引入变色硅胶,提高了直接酯化法去除生成水的效率,制备出了高双键保留率、高产率的聚乙二醇单甲醚-200丙烯酸酯(MPEGA-200),并采用红外光谱、1H NMR对产物进行了表征,采用过氧化氢酶评价了产物的生物相容性。通过正交实验确定了最佳合成条件为:醇酸摩尔比1:2,催化剂对甲苯磺酸和阻聚剂对苯二酚加量均为2%,变色硅胶占醇酸总质量的12%,携水剂石油醚60~90加量为18%,反应温度120℃,反应时间6h。在此条件下,酯化率可达95.47%,MPEGA-200的双键保留率为95.45%,产率为87.68%。另外,本文还采用单因素法研究了各反应条件对酯化反应的影响规律。     

两亲性二嵌段共聚物MPEG_(44)-b-Phe的合成及其在水溶液中的自组装

利用光气法,以三光气和苯丙氨酸为原料,合成了苯丙氨酸酸酐(b-Phe-NCA).用端氨基聚乙二醇单甲醚(MPEG-NH2)作大分子引发剂,引发b-Phe-NCA开环聚合,合成了不同分子量的聚乙二醇单甲醚-聚(L-苯丙氨酸)(MPEG44-b-Phe)AB型二嵌段共聚多肽.利用IR1、H-NMR、GPC对共聚物结构进行了表征.利用TEM研究了二嵌段共聚多肽MPEG44-b-Phe50及MPEG44-b-Phe7在水溶液中的自组装形态,结果表明合成出的两亲性二嵌段共聚物在水溶液中自组装形成胶束,随着嵌段共聚物中亲水嵌段含量的增高,共聚物溶水性增强,其在水溶液中的自组装形态更加均一.     

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.     

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.     

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.     

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.     

α-Amino acid derived enaminones and their application in the synthesis of N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates and other heterocycles

A new and simple synthesis of novel N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates, which exist in equilibrium with their 4-oxo tautomers, has been developed in two steps starting from N-protected α-amino acids. The key intermediates are enaminones, which can also be isolated, characterized, and used for the construction of other functionalized heterocycles, before they spontaneously decompose to pyrrole products. 4-Hydroxypyrroles are prone to partial aerial oxidation but can be efficiently alkylated or reduced to stable polysubstituted pyrrolidine derivatives.     

Specific intramolecular aromatic CH insertion of diazosulfonamides

The chemoselectivity in the intramolecular CH insertion of various diazosulfonamides has been experimentally studied. The results reveal that the aliphatic 1,4-, 1,5-, or 1,6-C(sp³)?H insertions of diazosulfonamides are not accessible, while the aromatic 1,5-C(sp²)?H insertion can be realized specifically by adjusting the diazo-adjacent group. In addition, the general chemoselectivities in the intramolecular CH insertions of diazosulfonyl compounds are summarized. Generally, diazosulfones undergo both aromatic 1,5-C(sp²)?H and aliphatic 1,5- and 1,6-C(sp³)?H insertions, while diazosulfonates undergo aliphatic 1,5- and 1,6-C(sp³)?H insertions. However, diazosulfonamides only undergo aromatic 1,5-C(sp²)?H insertion.     

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.     

Microwave-assisted copper-catalyzed stereoselective ring expansion of three-membered heterocycles with α-diazo-β-dicarbonyl compounds

Microwave-assisted copper-catalyzed ring expansions of three-membered heterocycles with α-diazo-β-dicarbonyl compounds were investigated. Thiiranes generated 3-acyl-5,6-dihydro-1,4-oxathiines in the presence of copper sulfate and trans-3-acyl-5,6-dihydro-1,4-oxathiines as stereospecific products for 1,2-disubstituted cis-thiiranes through an intramolecular S_N2 process. Oxiranes gave rise to 2-acyl-5,6-dihydro-1,4-dioxines under the catalysis of copper hexafluoroacetylacetonate and cis-3-acyl-5,6-dihydro-1,4-dioxines as stereospecific products for 1,2-disubstituted cis-oxiranes via an intimate ion-pair mechanism. The current method provides a direct and simple strategy in efficient preparation of 3-acyl-5,6-dihydro-1,4-oxathiines and 2-acyl-5,6-dihydro-1,4-dioxines, important agents in medicinal and agricultural chemistry, from readily available thiiranes and oxiranes, respectively.     

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.