端叠氮基聚醚的合成及与多炔固化剂的交联反应

依据点击化学反应原理,以端羟基环氧乙烷-四氢呋喃共聚醚(PET4000)和NaN3为原料经叠氮化反应得到端叠氮基环氧乙烷-四氢呋喃共聚醚(N3PET4000).用FTIR、NMR、GPC对N3PET4000进行了表征.研究了N3PET4000与多炔化合物的固化反应,对不同R值的胶片力学性能进行了表征.结果表明,R值为1.0时,N3PET4000固化体系具有良好的力学性能;R值为1.1左右时形成的交联识络的交联密度最大.     

端炔基聚乙二醇的合成及固化

针对NEPE推进剂中端羟基聚醚和多异氰酸酯固化体系对水敏感的缺点,为获得新的固化体系,依据点击化学反应(click-chemistry)原理,以聚乙二醇400和丙炔溴为原料,四氢呋喃为溶剂,在催化剂叔丁醇钾存在下,温度30℃,反应时间24 h,分离产物并真空干燥后,得到黏稠状液态端炔基聚乙二醇,产率为86.1%。用红外、核磁共振和元素分析对端炔基聚乙二醇进行了表征。研究了端炔基聚乙二醇与叠氮类化合物的固化反应,表明其有望用作新的复合固体推进剂的固化体系。     

端叠氮基聚叠氮缩水甘油醚的合成与热性能

以不同多元醇为起始剂,环氧氯丙烷经阳离子开环聚合得到不同结构的端羟基聚环氧氯丙烷(PECH-OH),将其端羟基进行磺酰化改性得到端磺酸酯基聚环氧氯丙烷(PECH-OTS),随后的叠氮化反应中叠氮基同时取代PECH-OTS的端磺酸酯基和侧基中的氯得到目标产物。用IR、GPC、TG和DSC对不同结构的GAPA进行了表征。结果表明,GAPA-2、GAPA-3和GAPA-4的数均相对分子质量分别为810、830和1190,玻璃化转变温度分别为-67.5、-63.8和-58.6℃,端叠氮基聚叠氮缩水甘油醚(GAPA)的热分解可分为相对独立的叠氮基热分解(250℃)和聚醚主链热分解。     

高碘酸氧化法制备端氨基聚乙二醇的研究

单甲氧基聚乙二醇5000(m PEG5000)和对甲苯磺酰氯(p-Ts Cl)磺酸酯化,得到单甲氧基聚乙二醇对甲苯磺酸酯(m PEG5000-OTs),与乙醇胺亲核取代反应,获得末端具有β-氨基醇结构的聚乙二醇中间体,用高碘酸盐氧化,得相对分子质量5000的端氨基聚乙二醇(m PEG5000-NH2),总收率75.1%,产物结构通过IR和1H NMR进行表征。     

化学共混改善GAP黏合剂力学性能研究进展

总结了近年来国内外关于化学共混在聚叠氮缩水甘油醚(GAP)黏合剂的力学性能改良中的研究现状,包括聚乙二醇(PEG)、乙二醇/四氢呋喃共聚醚(PET)、3,3-双(叠氮甲基)氧丁环/四氢呋喃共聚物(BAMO/THF)、端羟基聚丁二醇(HTPB)、聚甲基丙烯酸甲酯(PMMA)在内的各种聚合物与GAP共混,通过调控反应条件得到化学交联网络,不同程度提高了黏合剂体系的力学性能。     

PDMS-PEG核壳结构复合粒子的制备北大核心

采用溶液聚合法制备了以轻度交联的聚二甲基硅氧烷(PDMS)弹性粒子为核芯、端异氰酸酯基聚乙二醇(NCO-PEG)为壳层的PDMS-聚乙二醇(PEG)核壳结构复合粒子,并表征了其结构。结果表明:最佳反应时间为6 h;PDMS弹性粒子表面的硅羟基与NCO-PEG的端异氰酸酯基确实发生了化学反应,PEG被成功接枝到PDMS弹性粒子表面,PDMS-PEG中Si,O,C,N元素含量与理论值基本相符;PDMS-PEG为两相结构,具有明显的核壳结构,壳层厚度在130 nm左右;PDMS-PEG的初始热分解温度在300℃以上,可以满足聚乳酸增韧改性研究要求。     

丁三醇三硝酸酯与高分子黏合剂的相互作用

运用半经验分子轨道理论PM3方法计算丁三醇三硝酸酯(BTTN)分别与聚乙二醇(PEG)、端羟基聚丁二烯(HTPB)、缩水甘油叠氮基聚醚(GAP)、3-叠氮甲基-3-甲基环氧丁烷聚合物(AMMO)和3,3-双(叠氮甲基)环氧丁烷聚合物(BAMO)等高分子黏合剂所形成的混合体系模型物,求得稳定几何构型.由色散能校正电子相关,求得其结合能.计算结果表明,高分子黏合剂HTPB、AMMO与BTTN的结合能(绝对值)随着高分子聚合度的增加而增大,而BAMO、GAP、PEG与BTTN间的结合能呈不同规律.GAP、AMMO和BAMO与BTTN的结合能略大于HTPB和PEG.     

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。     

PDMS-PEG核壳结构复合粒子的制备

采用溶液聚合法制备了以轻度交联的聚二甲基硅氧烷(PDMS)弹性粒子为核芯、端异氰酸酯基聚乙二醇(NCO-PEG)为壳层的PDMS-聚乙二醇(PEG)核壳结构复合粒子,并表征了其结构。结果表明:最佳反应时间为6 h;PDMS弹性粒子表面的硅羟基与NCO-PEG的端异氰酸酯基确实发生了化学反应,PEG被成功接枝到PDMS弹性粒子表面,PDMS-PEG中Si,O,C,N元素含量与理论值基本相符;PDMS-PEG为两相结构,具有明显的核壳结构,壳层厚度在130 nm左右;PDMS-PEG的初始热分解温度在300℃以上,可以满足聚乳酸增韧改性研究要求。     

八叠氮基聚倍半硅氧烷的合成及表征

以对羟基苯甲酸、八（二甲基硅氧基）聚倍半硅氧烷、叠氮化钠为原料,经酯化、醚化、水解、硅氢加成等反应制备了八叠氮基的六面体聚倍半硅氧烷[POSS-（N3）8],通过1H NMR、13C NMR、FT-IR对其进行了表征;并探讨了叠氮化反应温度对POSS-（N3）8产率的影响。结果表明,随着叠氮化反应温度的降低,POSS-（N3）8的产率逐渐增加;当叠氮化反应温度为70℃时,POSS-（N3）8的产率达到60%。     

亲和分配基质羟基二氯亚砜法活化工艺的改进

以二氯亚砜（SOCl₂）为羟基氯化试剂,聚乙二醇（PEG）为对象,对亲和配基合成中基质上羟基活化的常规方法进行了改进：通过在反应体系中引入三乙胺,使反应成为热力学上有利而大大提高了反应效率,减少了二氯亚砜的用量,并简化了工艺操作.考察了反应温度、反应时间、二氯亚砜和三乙胺加入量等因素对活化效果的影响,得到了活化程度较高的介质［1.54 mol Cl•（mol PEG)^-1］,并与常规二氯亚砜法和环氧氯丙烷法进行了比较.     

Synthesis and the Structure to Property Relationship of Monoperfluoroalkyl Polyethylene Glycol

Monoprotected polyethylene glycols (PEG) react with epichlorohydrin to furnish PEGylated epoxides. The latter were converted into the corresponding α-(2-F-alkylethyl)thiomethyl polyethylene glycols by treatment with 2-F-alkylethanethiol. Surface activity of the obtained surfactants was investigated by evaluation of PEG and perfluoroalkyl chains length on the critical micelle concentration (CMC), surface and interfacial tensions.     

Chlorinating cleavage of silicon–naphthyl bonds of polycarbosilane,and introduction of poly(ethylene glycol) graft copolymer micelles

A new series of polycarbosilanes [(PhCH₂)SiCH₃Cl, Poly B] was designed by chlorinating cleavage reaction of silicon–naphthyl in polycarbosilane. The ¹H spectra of poly B revealed that the SiCH₂ and the SiCH₃ protons peak were up-field shifted compared with the type [(PhCH₂)SiCH₃Np, Poly A] polycarbosilane. Grafted polycarbosilane was synthesized with poly ethylene glycol (PEG) by nucleophilic substitution of the chloride substituents on the polycarbosilane. The aggregation behaviors of graft copolymers were investigated by dynamic light scattering and fluorescence at 25 °C in aqueous solutions of different polyethylene glycol (PEG) substituent.     

聚乙二醇的生产与应用

介绍了聚乙二醇的生产技术现状，并着重叙述了聚乙二醇在各个工业领域中的主要应用，对了解和指导聚乙二醇的生产及应用具有促进意义。     

Synthesis and characterization of polyurethanes containing arylene sulfone ether linkages

Polyurethanes containing arylene sulfone ether linkages were synthesized by solution polymerization of 4,4′-bis(4-isocyanatophenoxy)diphenylsulfone (SPI) and 4,4′-bis(3-isocyanatophenoxy)diphenylsulfone (SMI) with various aliphatic glycols such as ethylene glycol (EG), 1,2-propylene glycol (PG), 1,4-butylene glycol (BG), polyethylene glycol (PEG 300 and 1000), polypropylene glycol (PPG 300 and 1000) and polytetramethylene glycol (PTMG 1000. TERACOL) in dimethylacetamide (DMAC) at 120°C. The diisocyanates SPI and SMI were prepared from the corresponding diacid chlorides via Curtius rearrangement. The polyurethanes were obtained in high yields. The effect of structures of diisocyanate and aliphatic diols on the molecular weight and thermal properties of polyurethanes was also investigated. The polyurethanes prepared were characterized by infrared spectroscopy, solution viscosity, elemental analysis, thermogravimetric analysis and X-ray diffraction. Physical and thermal properties of polyurethanes prepared from SPI and various aliphatic glycols were compared with the polyurethanes from SMI and various aliphatic glycols.     

氨基叠氮聚乙二醇的制备

以聚乙二醇1500为起始原料,经两步官能团转化得到双叠氮基聚乙二醇(N_3-PEG_(1500)-N_3),该中间体经有机相还原、水相终止,实现双叠氮基的单侧还原。反应选择性及转化率经液质联用(组分中代表性准分子离子峰的液相积分面积比例)进行评价。利用单因素实验,确定氨基叠氮聚乙二醇(NH_2-PEG_(1500)-N_3)最佳液液两相反应条件如下:N_3-PEG_(1500)-N_3与三苯基膦的物质的量比为1.0∶1.1,有机相为V(甲苯)∶V(二氯甲烷)=3∶2的混合溶液,水相为2.0 mol/L盐酸溶液,两相体积比1∶1,35℃下反应12 h,经柱分离提纯得NH_2-PEG-N_3,收率72%,单侧叠氮基还原选择性达97%。实验结果表明,该法制备NH_2-PEG_(1500)-N_3具有纯度高、方法简便等特点。产物经~1HNMR、~(13)CNMR、IR和HRMS进行结构确证。利用NH_2-PEG-N_3实现了叠氮封端功能化磷脂的合成。     

C36二聚脂肪酸聚乙二醇聚酯硫酸酯盐的制备及性能表征

以C36二聚脂肪酸(简称二聚酸)和聚乙二醇为原料,缩聚后得到聚酯,再用氨基磺酸硫酸化,制备了新型的C36二聚脂肪酸聚乙二醇聚酯硫酸酯盐型两性高分子表面活性剂,并对其性能进行了研究。聚酯适宜的制备工艺条件是:在0.097 MPa下,n(二聚酸)∶n(聚乙二醇)=1∶1.2,催化剂w(SnC l2)=0.3%(相对于反应物总质量),反应温度200℃,反应时间6 h,酯化率达到98.11%。聚酯平均相对分子质量为613 5,相对分子质量分布系数为1.212。优化的C36二聚脂肪酸聚乙二醇聚酯硫酸酯盐的制备条件是:尿素为催化剂,n(二聚酸聚乙二醇聚酯)∶n(NH2SO3H)∶n(尿素)=1∶1.2∶1.2,反应温度130℃,反应时间2.8 h,聚酯端羟基硫酸酯酯化率达81.17%。表面性能分析结果为:产物γCMC(25℃)为3.021 mN/m,与十二烷基硫酸钠(K12)相当;CMC(25℃)为1.07 mmol/L,远低于K12;乳化性能和乳化稳定性与壬基酚聚氧乙烯醚(OP-10)相当。与K12相比,产物起泡性差但表现出很好的抑泡性能。该工作的新颖性已为河南省科学技术情报研究所2005年12月15日出具的第2005 c0006号《论文查新报告》所证实。     

The Effect of PEG on the Water Absorption Capacity and Rate of Superabsorbent Copolymers Based on Acrylic Acid

ABSTRACT

In this study, acrylic acid–based superabsorbent copolymers were synthesized with different comonomers (PEGs) by inverse suspension polymerization technique. The said superabsorbent copolymers were obtained from the aqueous solution of monomers dispersed in a continuous organic phase. The inverse suspension polymerization was accomplished by the use of aqueous solutions of partly neutralized acrylic acid with a predetermined crosslinker agent/monomer ratio in cyclohexane. Sorbitan monostearate was used as a surfactant, ethylene glycol dimethacrylate (EGDM) either as a comonomer or a crosslinking agent, potassium persulfate as the initiator, and polyethylene glycols (PEG 200, PEG 1000, PEG 4000) were used as pore-making agents. The copolymers (SAPs) were characterized by IR spectroscopy and SEM micrographs. Effect of PEGs on the water absorption capacity, rate of absorption to reach equilibrium, and the time needed to release the water absorbed from the gels were investigated. It was observed that the copolymer based on EGDM-Na acrylate + PEG4000 (A3) gave better results than the other copolyemrs.     

Copper electrocrystallization from acidic sulfate electrolyte containing MPS additive

Copper electrodeposition and nucleation on a glassy carbon electrode from acid sulfate electrolytes in the presence of 3-mercapto-1-propanesulfonate sodium salt (MPS) and its combinations with chloride ions (Cl) or/and polyethylene glycol (PEG) were investigated by utilizing cyclic voltammetry (CV), chronoamperometry (CA) and scanning electron microscopy (SEM). CV results indicate that MPS and MPS–PEG inhibit whereas MPS–Cl and MPS–PEG–Cl accelerate copper deposition. CA and SEM results suggest that copper nucleation follows an instantaneous nucleation mechanism with three-dimensional growth from all baths at the studied deposition potentials. The copper nucleation rate and nuclei number density are increased greatly in the MPS–Cl and MPS–PEG–Cl baths.     

Synthesis of fluorescent ABA triblock copolymer via click reaction

A hyperbranched–linear–hyperbranched (ABA) triblock copolymer containing poly(ethylene glycol) (PEG) as linear block and polyglycerol (hbPG) as hyperbranched blocks has been synthesized through a copper‐catalysed click reaction. In order to synthesize the hyperbranched block, propargyl alcohol‐initiated ring‐opening multibranching polymerization of glycidol was used to prepare hbPG with the propargyl segment in the focal point (CH?C? hbPG). Separately, PEG was functionalized at both ends using cyanuric chloride, and then the chloride groups of cyanuric chloride were substituted by azide groups. Finally, the azide‐functionalized PEG was conjugated to CH?C? hbPG via a click reaction. Substitution of the chlorine atoms of cyanuric chloride under different conditions together with click chemistry allows the synthesis of a variety of polymeric architectures. In the last step, fluorescein was attached to the block copolymer as a fluorescent probe in order to study the cell internalization of this copolymer. This type of triblock copolymer is a promising future nanomaterial for simultaneous drug delivery and cell imaging. © 2016 Society of Chemical Industry