Synthesis of copolymers of 3-acryloyloxymethyl-3′-methyloxetane and 3-(2-(2-(2-methoxyethylenoxy)ethylenoxy)ethylenoxy)-3′-methyloxetane and their ionic conductivity properties

An oxetane-derived monomer, 3-acryloyloxy-methyl-3′-methyloxetane (AMO) was prepared from the reaction of 3-hydromethyl-3-methyloxetane with acryloyl chloride. The cationic ring-opening copolymerization of AMO with another oxetane-derived monomer, 3-(2-(2-(2-methoxyethylenoxy)ethylenoxy)ethylenoxy)-3′-methyloxetane (MEMO) was conducted in CH₂Cl₂ solution using BF₃ · OEt₂/1,4-butanediol as a co-initiator. The resulting copolymers were characterized by FTIR, ¹H NMR and Gel Permeation Chromatography (GPC) analyses, and it was found that the enchained ratio of AMO in the copolymers is far lower than its feed ratio. They were crosslinked in situ via the radical polymerization of the vinyl group initiated by BPO after doping with lithium trifluoromethanesulfonimide (LiTFSI) to give rise to tough polymeric electrolyte films. The ionic conductivity was measured at varying content of AMO and different concentration of lithium salt LiTFSI by AC impedance, and a maximum ion conductivity of 1.44 × 10⁻⁵ S/cm at 30°C or 1.25 × 10⁻⁴ S/cm at 80°C was attained in the sample PAM 33 at the mole ratio of O: Li = 20. The DSC results indicated that T _g decreases with the increase of the proportion of AMO in the copolymer, well consistent with the ion conductivity trend. The TGA (thermogravimetric analysis) measurement revealed that this kind of copolymer electrolytes is more thermostable than their liquid counterparts. __________ Translated from Transactions of Beijing Institute of Technology, 2006, 26(12): 1098–1103 [译自: 北京理工大学学报]     

氯化N-[3-长链烷氧(双)乙烯氧-2-羟]丙基-N,N,N-三甲基铵的合成及性质

以溴代烷和乙二醇或一缩二乙二醇为原料合成长链烷基（双）氧乙烯醇（收率为７５％ ）,然后在相转移催化条件下和环氧氯丙烷反应得到长链烷基（双）氧乙烯缩水甘油醚（收率为９０％ ）,后者和三甲胺盐酸盐反应得到氯化Ｎ［３长链烷氧（双）乙烯氧２羟］丙基Ｎ,Ｎ,Ｎ三甲基铵（收率为９１％ ）,其结构通过红外光谱、核磁共振氢谱和元素分析结果得以证实,测定了产物的γｃｍ 及ｃｍ ｃ     

含硅聚酰亚胺的合成及性能研究

合成了一类含硅二胺双氨丙基四甲基二硅氧烷,并将其与芳族二胺和芳族四酸二酐共聚,得到了一系列不同配比的含硅聚酰亚胺。通过差热分析(DSC)和热重分析(TGA),表明引入有机硅链段能有效地改善聚酰亚胺的性能。共聚物的玻璃化转变温度(Tg)符合Kwei方程。     

Synthesis and electrical properties of poly[2-(2-(4-trifluoromethyl)phenyl)ethenyl-1,4-phenylenevinylene] and PPV copolymers

Summary Poly[2-(2-(4-(trifluoromethyl)phenyl)ethenyl)-5-methoxy-1,4-phenylenevinylene] (PFEMPV) and a series of PPV copolymers containing 1,4-phenylenevinylene (PV) units were synthesized through a water-soluble precursor route, and their electrical and third-order nonlinear optical properties were studied. The PFEMPV films could not be doped with I₂, but FeCl₃-doped films showed an electrical conductivity of 5.0x10^-4 S/cm. The conductivities of FeCl₃-doped copolymer films ranged from 2.0x10^-3 to 2.0 S/cm depending on their copolymer compositions. The third-order nonlinear optical susceptibility, ⁽³⁾(–;,,–), was also investigated by the degenerate four wave mixing technique at 602 nm. The ⁽³⁾ value of PFEMPV was 6.9x10^-11 esu. The photoluminescence spectrum of PFEMPV shows its emission maximum at 550 nm.     

Synthesis and properties of well-defined poly (dimethylsiloxane)-b-poly(2-hydroxyethyl methacrylate) copolymers

Block copolymers containing dimethyl siloxane and 2-hydroxyethyl methacrylate sequences were synthesized by group transfer polymerization (GTP) of 2-trimethylsilyloxyethyl methacrylate (TMS-HEMA) using silyl ketene acetal terminated poly(dimethylsiloxane) (PDMS) as macroinitiator, followed by hydrolysis of TMS-HEMA to HEMA. The block copolymers were obtained with controlled molecular weight and narrow molecular weight distribution. Trimethylsilyl groups in the P(TMS-HEMA) block could be selectively hydrolyzed without cleaving Si-O bond in PDMS block. The block copolymers formed micelles in methanol, the effective diameters (R_h) of which were in the range of 78 – 110 nm with narrow distribution by dynamic light scattering (DLS). The TEM image showed micelles with a spherical shape. Received: 10 May 2001/Revised version: 23 August 2001/Accepted: 24 August 2001     

1-(2-羟丙基磺基)-3-十二烷基咪唑内盐的合成与性能

以3-氯-2-羟基丙磺酸钠与n-十二烷基咪唑为原料,合成了两性型离子液体(IL)表面活性剂1-(2-羟丙基磺基)-3-十二烷基咪唑内盐(HPSDim),通过ESI-MS,FTIR及1HNMR表征其分子结构;分别用表面张力法和稳态荧光法测定了35℃时HPSDim在0.5 mol·L-1的NaCl水溶液中的临界胶束浓度(cmc)和平均胶束聚集数(Nm)等表面活性参数。结果表明,HPSDim的Krafft点高达(65.8±0.5)℃,但在室温下易溶于0.5 mol·L-1的NaCl水溶液中;表面张力法测得其cmc为0.98 mmol.L-1(荧光探针法为1.0 mmol·L-1);在6.0～8.0 mmol·L-1范围内,Nm随HPSDim浓度增加而线性增大,推算其临界胶束聚集数(Nm,c)为30.9;其堆积参数(Pc)为0.40,推测HPSDim胶束形状可能为柱状。     

聚丁二酸丁二醇酯基共聚物及其多嵌段共聚物的合成与性能

采用“一步法”,以丁二酸酐（SAA）和1,4–丁二醇（BDO）为单体、端羟基二元醇为共聚单体合成了聚丁二酸丁二醇酯（PBS）及一系列端羟基二元醇共聚物,同时使酚酞与SAA的缩聚产物参与SAA和BDO的共聚反应,并通过链段调节合成法制备兼具刚性链段和柔性链段的可生物降解三嵌段共聚聚酯热塑性弹性体聚(丁二酸丁二醇酯-共-酚酞丁二酸丁二醇酯)（SAA-PHE-PBS）,研究了PBS及其共聚物的分子量、化学结构组成、热性能和结晶性能,此外,使用南极假丝酵母脂肪酶B测试了PBS及其共聚物的生物降解性能。结果表明,端羟基二元醇共聚物的玻璃化转变温度变化幅度不大,熔融温度无明显改变,结晶度降低,亲水性有所改善,生物降解性能得到大幅度提升;三嵌段热塑性弹性体SAA-PHE-PBS的玻璃化转变温度升高,结晶度与PBS相差不大,疏水性更强,共聚合物的残重率有所增加,生物降解性能有不同程度的降低。     

Synthesis, characterization, and properties of poly(2- and 3-aminophenol) and poly(2- and 3-aminophenol)-Cu(II) materials

Summary Poly(2-aminophenol) and poly(3-aminophenol) were synthesized from the respective monomers by using CuCl₂ × 2H₂O and ammonium persulfate as oxidizing agents in HCl(aq). The materials were characterized by FT-IR, X- ray electron spectroscopy (XPS), electron spin resonance (ESR) and nuclear magnetic resonance (NMR) spectroscopy, elemental analysis, thermal stability, and electrical conductivity. The poly(2-aminophenol) presented a higher copper(II) content than that of poly(3-aminophenol), moreover as shown by ESR measurements, Cu appears homogeneously dispersed in the former, poly(2-amino phenol), while it seems not to be the case in the latter. The electrical conductivity did not depend on the conditions of synthesis as well as of the hydroxyl groups position. The results indicate that the polymers have several branched rings and their thermal stability increased by the presence of the copper ions into the polymer matrix. Received: 7 August 2002/Revised version: 8 November 2002/ Accepted: 12 November 2002 Correspondence to B. L. Rivas     

Synthesis and bulk properties of poly(tetrahydrofuran)-poly(2-methyl-2-oxazoline) ABA triblock copolymers

A series of linear triblock-copolymers of the ABA type in which the central B-block is poly(tetrahydrofuran) (polyTHF) and the A-segments are poly(2-methyl-2-oxazoline) (polyMeOX) were synthesized by a one-pot sequential monomer addition copolymerization, utilizing the living nature of the cationic ring-opening polymerization of both monomers. Films of the copolymers, casted from chloroform solutions, exhibit excellent mechanical properties in comparison with the homopolymers with comparable molecular weights, which was ascribed to the phase separation occurring between the two copolymer segments. Materials, in which the polyTHF B-segment have a molecular weight 13 000 g/mol or higher and each polyMeOX A-block a molecular weight 1500 g/mol, kept elastomeric properties up to 130 °C notwithstanding the fact that this temperature is considerably higher than the melting point of polyTHF and the glass transition temperature of polyMeOX. It was found that these triblock-copolymer materials show a shape memory effect. These observations are attributed to the high degree of phase separation between the two blocks and the strong polar interactions between the polyMeOX segments. Received: 20 March 1997/Revised: 5 September 1997/Accepted: 8 September 1997     

Poly(2‐) and (3‐aminobenzoic acids) and their copolymers with aniline: Synthesis,characterization, and properties

Poly(2‐aminobenzoic acid) and poly(3‐aminobenzoic acid) were synthesized by chemical polymerization of the respective monomers with aqueous 1M hydrochloric acid and 0.49M sodium hydroxide, using ammonium persulfate as an oxidizing agent. In addition, polymerization in an acid medium was carried out in the presence of metal ions, such as Cu(II), Ni(II), and Co(II). Poly(2‐aminobenzoic acid‐co‐aniline) and poly(3‐aminobenzoic acid‐co‐aniline) were synthesized by chemical copolymerization of aniline with 2‐ and 3‐aminobenzoic acids, respectively, in aqueous 1M hydrochloric acid. The copolymers were synthesized at several mole fractions of aniline in the feed and characterized by UV–visible and FTIR spectroscopy, the thermal stability, and the electrical conductivity. Metal ions, such as Cu(II), Ni(II), and Co(II), were incorporated into homo‐ and copolymers by the batch method. The percentage of metal ions in the polymers was higher in the copolymers than in the homopolymers. The thermal stability of the copolymers increased as the feed mole fraction of aniline decreased and varied with the incorporation of metal ions in the polymers. The electrical conductivity of the homo‐ and copolymers was measured, which ranged between 10^?3 and 10^?10 S cm^?1. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2641–2648, 2003     

反式-(2-乙氧基-2-氧代乙基)阿魏酸醚的合成

在相转移催化剂四丁基溴化铵和乙醇钠作用下,以无水四氢呋喃为溶剂,阿魏酸、溴乙酸乙酯为原料,合成了新化合物反式-(2-乙氧基-2-氧代乙基)阿魏酸醚,收率可达92%。     

(S)-4-(2-甲基丁基)-4'-(4-丙基环己基)-2-氟联苯的合成及性能研究

以(S)-(2-甲基丁基)苯为原料,经碘代和Suzuki偶联四步反应,合成了手性液晶(S)-4-(2-甲基丁基)-4'-(4-丙基环己基)-2-氟联苯,总收率11.4%,纯度99.2%,并采用IR、MS、1H NMR及元素分析对其结构进行了表征。结合差示扫描量热仪(DSC)和偏光显微镜(POM)研究了目标化合物的介晶性,并采用Cano’s wedge法测定了目标化合物的扭曲力。     

1-(2-氯苯基)-2-(4-氟苯基)-3-溴-1-丙烯的合成

1-(2-氯苯基)-2-(4-氟苯基)-3-溴-1-丙烯(2)是氟环唑的关键中间体。以1,2-二氯乙烷和水为溶剂,1-(2-氯苯基)-2-(4-氟苯基)-1-丙烯(1)在氢溴酸/双氧水体系中发生α-溴代反应得到该化合物。通过使用氢溴酸/双氧水代替溴素或N-溴代丁二酰亚胺,提高了溴的利用率及产品的收率,避免了烯烃的加成,减少了副反应的发生,减少了三废。通过实验获得了反应的优惠条件:二氯乙烷和水为溶剂,回流反应,n(1)∶n(HBr)∶n(H2O2)=1∶1.1∶2.5,氢溴酸和双氧水的滴加时间为6 h,在上述反应条件下,反应收率为90.6%,选择性90.6%。     

Synthesis of poly(oxyethylene-styrene-oxyethylene) triblock copolymers and their phase behavior

Interesting phenomena were observed in the polymerization of styrene and ethylene oxide into PEO-PSt-PEO triblock copolymers using potassium naphthalene as initiator and tolusene as a solvent. The relationship between the phenomena and molecular weight of the blocks was studied. The purified and characterized triblock copolymer showed mesomorphic behavior in toluene solution which depolarized polarized light increasingly as the concentration was increased. The structure of the triblock copolymer was also studied by small-angle laser light scattering and by electron microscopy.     

3-(2-甲基哌啶)丙醇的合成

以3-氯丙醇和2-甲基哌啶为主要原料合成3-(2-甲基哌啶)丙醇,反应常压下完成,收率92.3%,含量96%.     

2-（3-苯甲酰基苯基）丙腈的合成

以间甲基苯甲酸甲酯为原料,经溴化、氰化、甲基化、水解和付-克反应合成了2-(3-苯甲酰基苯基)丙腈,并考察了有关反应条件对溴化反应和甲基化反应的影响,获得了最佳的反应条件。在最佳反应条件下进行合成实验,所得产品2-(3-苯甲酰基苯基)丙腈的总收率为56·7%,熔点52~54℃,含量98·6%。     

2-(N-苯甲酰胺甲基)-3-氧代丁酸甲酯的合成研究

以三氯化铁为催化剂,乙酰乙酸甲酯与N-羟甲基苯甲酰胺反应,得到2-(N-苯甲酰胺甲基)-3-氧代丁酸甲酯,适宜的反应条件为:反应温度25℃,反应时间2 h,催化剂用量0.3 mol,收率达86%。     

Synthesis and properties of novel polyurethane acrylate containing 3-(2-hydroxyethyl) isocyanurate segment

Novel UV curable multi-functional polyurethane acrylate (PUA) containing 3-(2-hydroxyethyl) isocyanurate (THEIC) segment was synthesized through three step reactions, the ring-opened reaction of ?-caprolactone with THEIC under the catalysis of tetrabutyl titanate (TBT), the polyaddition reaction between formed hydroxyl compounds and isophorone diisocyanate (IPDI) and condensation reaction between the product of the second step and pentaerythritol triacrylate (PETA). The chemical structure of PUA oligomer and some influence factors in synthesis process were characterized with GPC, ¹H NMR and FTIR. And its photopolymerization process and properties of cured films were also investigated.     

N-甲基-N'-(2-羟基-3-乙酰氧基丙基)咪唑盐离子液体的合成

离子液体作为一种新型的绿色溶剂和催化剂已引起了化学家们的极大关注.以乙酸钠和环氧氯丙烷为起始原料首先合成了乙酸缩水甘油酯,并优化筛选了乙酸缩水甘油酯的合成条件;再与无机酸质子化的N-甲基咪唑反应,制备了四个N-甲基-N'-(2-羟基-3-乙酰氧基丙基)咪唑盐新型离子液体.采用1H NMR,IR和UV对新型离子液体的结构进行了表征.测定了新型离子液体的电导率及与常用有机溶剂之间的溶解性能.优化筛选试验结果表明,乙酸缩水甘油酯最佳的合成条件为:乙酸钠与环氧氯丙烷的摩尔投料比为1:1.5,甲苯作溶剂,四丁基溴化铵为催化剂,回流反应7h.