MPEG端基官能团转化及其与MPP的反应

研究了聚乙二醇单甲醚(MPEG)的端羟基转化,通过端羟基与二异氰酸酯的反应将端羟基转化为端异氰酸酯基,通过端羟基与对甲苯磺酰和邻苯二甲酰亚胺钾的分步反应将端羟基转化为端胺基,由此比较了不同端基官能团MPEG与聚丙烯接枝马来酸酐(MPP)的反应。结果表明,端羟基向端胺基的转化率达到86%,向端异氰酸酯基的转化率达到92%;在相同反应条件下,端异氰酸酯基MPEG与MPP反应体系的接枝率最高,端胺基MPEG/MPP反应体系次之,端羟基MPEG/MPP反应体系最低,表明MPEG端基官能团与MPP的反应活性顺序为─NCO>─NH2>─OH。     

N-(4-马来酰亚胺基苯基)二缩水甘油胺的合成

以马来酸酐、对硝基苯胺及环氧氯丙烷为原料合成了N-(4-硝基苯基)马来酰亚胺(NPMI),再将其催化还原成N-(4-氨基苯基)马来酰亚胺(APMI),最后以APMI与环氧氯丙烷反应得到1种新型的含马来酰亚胺的环氧树脂固化剂N-(4-马来酰亚胺基苯基)二缩水甘油胺(MPDGA)。采用傅里叶红外光谱,元素分析及核磁共振氢谱确认了产物MPDGA的结构,探讨了合成反应的相关条件。所得MPDGA为黄色固体,产品收率为48.6%。     

新型加成型有机硅树脂的合成

采用对羟基苯基马来酰亚胺与氯硅烷反应合成马来酰亚胺基氯硅烷单体,然后与苯基三氯硅烷,二苯基二氯硅烷经水解,缩合反应合成苯基马来酰亚胺基有机硅树脂,并对合成的硅树脂进行表征,探讨了不同条件对合成的影响。合成硅树脂的红外图谱表明含有马来酰亚胺基。TG分析合成硅树脂的失重初始温度高于360℃,耐热性能优异。     

N-氨乙基萜品烯马来酰亚胺基酰胺化合物的合成及杀菌活性

以α-蒎烯为原料,在质子酸催化下发生重排得到α-萜品烯,再与马来酸酐发生Diels-Alder环加成反应得到α-萜品烯马来酸酐加成物3,然后与乙二胺反应制备N-氨乙基萜品烯马来酰亚胺4。在三乙胺(TEA)催化下,4与各种取代苯甲酰氯发生N-酰化反应,合成得到11个新型N-氨乙基萜品烯马来酰亚胺基酰胺化合物5a~5k。初步探索了合成条件,并利用1H-NMR、13C NMR、FT-IR、ESI-MS、UV-vis和元素分析等多种手段对目标产物作了分析和表征。初步的生物活性测试表明,目标化合物具有一定的杀菌活性,其中3-甲基苯基-N-氨乙基萜品烯马来酰亚胺基酰胺5g在50μg·m L-1浓度下对苹果轮纹病菌的抑制率达63.6%。     

最新专利

<正>●耐高温复合材料基体树脂及其制备方法(CN200910056510.x)该发明涉及一种耐高温复合材料基体树脂及其制备方法,其组分包括:马来酰亚胺基聚酰亚胺粉末、二烯丙基化合物和双马来酰亚胺树脂粉末;其制备包括:将1,4-双(2,4-二氨基苯氧基)苯和强极性非质子有机溶剂混合,加入马来酸酐等原料制备树脂溶液;然后加入脱水剂、催化剂及沉析剂,搅拌反应析出固体粉末;再将马来酰亚胺基聚酰亚胺     

含DA键自修复硅氧烷环氧树脂性能研究

将环氧氯丙烷与糠醇反应,合成糠基缩水甘油醚(FGE),再用含双烯体结构的糠胺,将环氧双封头两端连接FGE,得到端基为四元呋喃结构的中间体,与含亲双烯体结构的1,6–双马来酰亚胺基己烷(1,6–BMI)进行交联固化,得到含有Diels-Alder(DA)键的自修复硅氧烷环氧树脂(EP–DA).通过红外分析仪、差示扫描量热...     

室温固化长期耐300℃的高强度硅橡胶型胶黏剂的研制

选择甲基乙烯基硅橡胶(110-2)作为主要原料,以适量苯基马来酰亚胺基硅树脂、填料、催化剂、交联剂、乙烯基硅油等制备了室温固化的有机硅胶黏剂。研究了提高有机硅胶黏剂粘接性能和耐高温性能的方法,包括填料的表面处理、添加硅氮烷、耐热添加剂(氧化钛、二氧化锡、氧化铁)、苯基马来酰亚胺基硅树脂、高含氢硅树脂等。结果表明,填料经表面改性可提高胶黏剂的耐高温性能;耐热添加剂也可以有效提高胶黏剂的耐热性能,其中氧化铁、苯基马来酰亚胺基硅树脂和高含氢硅树脂耐热效果最佳。综上实验制备了一种室温剪切强度达7.8MPa,300℃剪切强度为3.2MPa,300℃老化24h后剪切强度达3.0MPa的高强度耐热有机硅胶黏剂。     

一种新型聚羧酸系减水剂的制备方法

<正>本发明公开了一种新型聚羧酸系减水剂的制备方法,采用如下步骤制备:1)不饱和酸小单体,胺类不饱和小单体在链转移剂,引发剂,还原剂作用下进行反应得到含胺基共聚产物;2)聚乙二醇单甲醚中滴加入过量的二异氰酸酯中,在催化剂的作用下反应得到聚乙二醇单甲醚单异氰酸酯;3)将得到的含胺基共聚产物加入聚乙二醇单甲醚单异氰酸酯反应     

聚乙二醇化壳聚糖的合成

对壳聚糖C(6)-OH进行聚乙二醇醚化接枝,制备聚乙二醇化壳聚糖衍生物,以提高其作为新型抗肿瘤药物载体对病理部位的选择性。实验中,壳聚糖C(2)-NH_2和聚乙二醇单甲醚(MPEG)分别用邻苯二甲酸酐保护氨基和利用Arbuzov重排实现聚乙二醇单甲醚碘化,而后C(6)-OH与碘代聚乙二醇单甲醚(MPEGI)醚化、脱保护,得到6-O-聚乙二醇单甲醚壳聚糖(CS-MPEG)。通过FTIR和1H NMR,确证了最终产物的结构,通过1H-NMR计算得MPEG接枝率为78%。     

含2-三氟甲基苯并咪唑的1,2,4-三唑的合成

2-三氟甲基苯并咪唑-1-乙酰肼在无水乙醇中分别与苯基异硫氰酸酯、对甲苯基异硫氰酸酯、对甲氧苯基异硫氰酸酯和邻甲苯基异硫氰酸酯反应,得到相应的酰氨基硫脲(Ⅲa~d),收率分别为73.3%、87.3%、85.5%和64.3%。再于115~120℃下,与w(NH2NH2.H2O)=85%的水合肼反应4 h,制得3-(2-三氟甲基苯并咪唑-1-亚甲基)-4-氨基-5-芳胺基-1,2,4-三唑(Ⅳa~d),收率分别为53.5%、56.1%、61.8%和50.7%。该方法反应时间短,处理简单,产率较高。目标化合物经元素分析,IR和1HNMR进行了结构确证。     

PEG分子量和温度对SiO2溶胶及光学增透膜的影响

本文研究了聚乙二醇(PEG)对TEOS-水-乙醇-碱催化剂溶胶体系的影响规律,通过TEM、SDP等分析手段,考察了分子量不同的PEG对SiO2溶胶粒度分布和簇团结构的变化以及对SiO2-PEG溶胶镀制光学膜增透效果的影响.结果表明:PEG改性后的SiO2溶胶形成有序的环状网络结构特征,而且分子量愈大,对溶胶的作用愈强,显著影响着膜层的光学增透性能.     

Thermodynamic Parameters and Interfacial Properties of Poly(ethylene glycol)-octyl Sulfosuccinates

Surface tension of a series of poly(ethylene glycol)-octyl sulfosuccinates at different temperatures was measured, and the interfacial properties were investigated in the absence and presence of inorganic salts. Surface tension results indicate that critical micelle concentration (CMC) values of five surfactants (C8-PEG200, C8-PEG400, C8-PEG600, C8-PEG800, and C8-PEG1000) decrease as the molecular weight of polyethylene glycol (PEG) segments and the experimental temperature increases. The surface activity of the C8-PEG series changes with temperature, and the surface tension at the CMC (γ_CMC) of the C8-PEG series decreases initially and then increases as the PEG molecular weight increases. This behavior may be attributed to the dehydration of the surfactant molecules, resulting in the change of hydrophile–lipophile balance for the different EO numbers in the surfactant molecules, which form a different surface energy film at the air–water interface. Negative ΔG_m indicates that the micellization process of these surfactants is spontaneous and an entropically driven process. For the water/alkane interface, these surfactants have low interfacial activity. The interfacial tension (IFT) between these surfactants and alkanes increases first and then decreases with the increase in the molecular weight of PEG segments. After the addition of salt, the interfacial activity of the investigated surfactants increases significantly. The IFT between C8-PEG800 and 10–12 alkanes and between C8-PEG1000 and 12–16 alkanes reaches a low IFT magnitude of 10⁻² mN m⁻¹ in the presence of 0.5% CaCl₂ or the mixed inorganic salts 0.5% NaCl+0.5% CaCl₂.     

无水氨基酸类离子液体-聚乙二醇混合溶剂吸收CO2的动力学

以聚乙二醇400（PEG400）为溶剂,氨基酸类离子液体（AAILs）作为化学吸收剂的混合体系具有蒸汽压极低、热稳定性好、黏度和再生能耗低、CO₂吸收量和选择性高等优点,适用于燃烧前CO₂捕集过程的高温高压吸收条件。本文采用压降法,测定了以四正丁基膦（[P₄₄₄₄]⁺）为阳离子,甘氨酸（Gly）、丙氨酸（Ala）和脯氨酸（Pro）作为阴离子的3种氨基酸类离子液体的混合溶剂体系对CO₂的吸收速率,并建立了该无水体系的CO₂吸收动力学模型。对于反应速率而言,在333.15K时,[P₄₄₄₄][Gly]-PEG400 > [P₄₄₄₄][Pro]-PEG400 > [P₄₄₄₄][Ala]-PEG400,温度升高至373.15K时,[P₄₄₄₄][Pro]-PEG400 > [P4444][Gly]-PEG400 > [P₄₄₄₄][Ala]-PEG400;根据相关吸收动力学参数,推测出CO₂在AAILs-PEG400中的反应均为快反应。通过研究其吸收动力学,获得了关键的吸收动力学数据,为后续的工业开发设计提供基础数据和设计依据。     

PEG2000对MCM-22分子筛结构特性和催化性能的影响

以六亚甲基亚胺为模板剂,在动态水热合成MCM-22分子筛的过程中,加入有机辅助剂聚乙二醇2000(PEG2000),考察有机辅助剂PEG2000对MCM-22分子筛结构、酸性以及催化性能的影响。由X射线衍射谱图可以看出,合成时加入适量的PEG2000,可以得到结晶较好的MCM-22晶体,但结晶度稍微有些降低。由氮吸附脱附测试结果可以看出,适量助剂PEG2000的加入,改变了分子筛的最可几孔径分布,最可几孔径由0.556 nm提高至0.587 nm,孔容由0.35 m3/g增加到0.59 m3/g,BET比表面积由410 m2/g增加到456 m2/g。NH3-TPD方法测试样品的酸性结果显示,加入适量的PEG2000后,分子筛的强酸位得到加强。另外用合成的分子筛作为催化剂,以苯与丙烯烷基化为模型反应,考察了MCM-22分子筛的活性以及选择性,结果显示催化剂的活性有较大提高,然而对异丙苯的初始选择性降低,随着反应的进行,异丙苯的选择性却很快地增长。     

双水相中亮绿的萃取分离及测定

建立聚乙二醇-2000(PEG)-(NH4)2SO4双水相体系萃取光度法测定亮绿(BG)的新方法。测定了PEG相中亮绿吸收光谱和荧光光谱,研究了溶液酸度、盐用量、PEG用量及共存物质对体系测定的影响。结果表明,在溶液酸度pH=6,PEG用量5.0 mL,硫酸铵加入量2.0 g、测定波长630 nm时,PEG相中BG有最大吸光度。线性回归方程Y=0.005 83+0.054 53X,相关系数R=0.999 3,线性范围为0.01～0.17μg/mL。方法具有快速、灵敏、简便的优点,用于天然水中BG测定结果较好。用加入不同类型表面活性剂和光谱方法初步探讨了PEG与BG的相互作用。     

Specific rebinding of protein imprinted polyethylene glycol grafted calcium alginate hydrogel with different crosslinking degree

Bovine serum albumin imprinted polyethylene glycol 600 (PEG600) grafted Calcium alginate (CaA) hydrogel microspheres were prepared and characterized. The adsorption and recognition properties of PEG600 grafted calcium alginate (CaA-g-PEG600) microspheres were evaluated and the results showed that the crosslinking structure of CaA-g-PEG600 microspheres exerted an obvious effect on the adsorption capacity and imprinting properties for bovine serum albumin. The adsorption isotherms and recognition properties indicated that the imprinted modified microspheres had excellent rebinding affinity toward target proteins and the imprinting efficiency varied according to PEG600 grafting degree. The adsorption capacity and the imprinting factor were 5.5 mg g^?1 and 3.6, respectively. Adsorption kinetics of CaA-g-PEG600 microspheres in accordance with the molecular weight between crosslinks (Mc) was investigated and the structural influence on protein selective rebinding was discussed. Furthermore, the binary solution separation performance of CaA-g-PEG600 microspheres with different Mc was investigated by selective binding bovine serum albumin from protein mixture solution.     

Synthesis and characterization of macromolecular surface modifier PP-g-PEG for polypropylene

A novel macromolecular surface modifier, polypropylene-grafted-poly(ethylene glycol) copolymer (PP-g-PEG), was synthesized by coupling polypropylene containing maleic anhydride with monohydroxyl-terminated poly(ethylene glycol). The effects of the reaction condition on the graft reactions were studied. The copolymers were characterized by IR, ¹H NMR, thermogravimetry (TG) and differential scanning calorimetry (DSC). The results indicated that the graft reactions were hindered by increasing the molecular weight of PP or PEG. The graft copolymer was found to have a higher initial thermal degradation temperature and lower crystallization capacity as compared with pure PP, and the side chain of PEG hindered the PP chain from forming a perfect β crystal. The thermal stability of PP-g-PEG decreased with the increasing content or molecular weight of PEG. The copolymers were blended with polypropylene to modify the surface hydrophilicity of the products. The results of attenuated total reflectance FTIR spectroscopy (ATR-FTIR) showed that PP-g-PEG could diffuse preferably onto the surface of the blends and be suitable as an effectual macromolecular surface modifier for PP. __________ Translated from Acta Polymerica Sinica, 2007, (2): 203–208 [译自:高分子学报]     

Factors Influencing the Surface Morphology of Poly(γ-benzyl L-glutamate)-Block-(Random Coil Polymer) Aggregates Deposited from the Dilute Solution

Poly(γ-benzyl L-glutamate)-block-poly(ethylene glycol) (PBLG-block-PEG, PEG as random coil polymer) was synthesized by a standard N-carboxyl-γ-benzyl-L-glutamate anhydride method. The surface morphology of PBLG-block-PEG copolymer aggregates from the dilute solution was studied by scanning electron microscopy (SEM). The effects of precipitation temperature, precipitation time, various solvent systems, and copolymer solution concentration on the surface morphologies of the polypeptide block copolymer aggregates from the dilute solution were investigated.     

聚乙二醇接枝壳聚糖对涤纶织物性能的影响

以壳聚糖为原料,通过邻苯二甲酸酐封闭2位氨基,利用三聚氰氯将壳聚糖的6位羟基引入聚乙二醇(PEG2000)链上,得到水溶性较好的壳聚糖衍生物(TCSO-PEG2000)。用TCSO-PEG2000整理剂对涤纶织物进行处理,采用红外光谱和扫描电镜对整理剂及涤纶织物进行表征分析,研究整理剂的用量、焙烘时间、焙烘温度等对涤纶织物的强力、透气性、亲水性、抗静电等性能的影响。结果表明:在整理剂质量浓度为8 g/L、焙烘时间为5 min、焙烘温度为120℃时,涤纶织物具有较好的力学性能、亲水性能及抗静电性能。     

Synthesis and characterization of novel comb-type amphiphilic graft copolymers containing polypropylene and polyethylene glycol

Amphiphilic comb-type graft copolymers containing polypropylene (PP) and polyethylene glycol (PEG) have been prepared. Polypropylene-g-polyethylene glycol comb-type thermoplastic amphiphilic copolymers were synthesized by the reaction between chlorinated polypropylene and polyethylene glycol in the presence of a base via a “grafting to” technique. A series of graft copolymers containing PEGs with molecular weights of 600 and 2,000 Da in the range of 4–34 mol% PEG were obtained. The amphiphilic graft copolymers with PEG segments in range between 20 and 30 mol% PEG displayed good film properties with elongation at break 275–440%. The hydrophilicity of the amphiphilic copolymers increases with the increasing PEG content in the copolymer while the mechanical properties decrease. Therefore, PP-g-PEG2000 with PEG contents in the range of 20–30 mol% PEG should be useful for medical and industrial applications where good film properties are needed.