含X-型二维液晶基元和顺式-4,4′-双(4-羟基苯基偶氮)二苯并-14-冠-4冠醚环液晶共聚酯的合成与表征

以4,4′-(α,ω-辛二酰氧)二苯甲酰氯(M1)、2,5-二(对十二烷氧基苯甲酰氧基)对苯二酚(M2)和顺式-4,4′-双(4-羟基苯基偶氮)二苯并-14-冠-4(M3)为单体,通过溶液共缩聚反应,合成了一系列含X-型二维液晶基元和顺式-4,4′-双(4-羟基苯基偶氮)二苯并-14-冠-4冠醚环的主链型液晶共聚酯.单体1(M1)由对羟基苯甲酸和辛二酰氯,通过酯化和取代反应制备,单体2(M2)由2,5-二羟基苯醌和对十二烷氧基苯甲酰氯通过酯化和还原反应制备,单体3(M3)由顺式-二氨基二苯并-14-冠-4和苯酚通过重氮化和偶联反应制备.共聚酯的分子量不高,[η]在0·35~0·25dL/g之间.单体的化学结构通过IR、UV、1H-NMR、MS和元素分析等方法确证.共聚酯的外观为黄色粉状固体,除CP9外,室温下不溶于CHCl3和THF溶剂.共聚酯的性质采用GPC、[η]、DSC、TG、WAXD和POM等方法进行了研究.发现所有的共聚酯加热到各自的熔融温度以上都能形成液晶态,在液晶态可以观察到向列相的丝状织构或纹影织构.共聚酯的熔融温度(Tm)和各向同性温度(Ti)随共聚酯分子中顺式-4,4′-双(4-羟基苯基偶氮)二苯并-14-冠-4用量的改变呈规律性变化.WAXD研究进一步证实了共聚酯的液晶性.     

含X-型二维液晶基元和顺式-4,4′-双(4-羟基苯基偶氮)二苯并-18-冠-6冠醚环液晶共聚酯的合成与表征

以4,4-′(α,ω-辛二酰氧)二苯甲酰氯(M1)、2,5-双[4-′(对癸氧基苯基)苯甲酰氧基]对苯二酚(M2)和顺式-4,4′-双(4-羟基苯基偶氮)二苯并-18-冠-6(M3)为单体,通过溶液共缩聚反应,合成了一系列新的含X-型二维液晶基元和顺式-4,4′-双(4-羟基苯基偶氮)二苯并-18-冠-6冠醚环的主链型液晶共聚酯.单体1(M1)由对羟基苯甲酸和辛二酰氯,通过酯化和取代反应制备,单体2(M2)由2,5-二羟基苯醌和对癸氧基苯基苯甲酰氯通过酯化和还原反应制备,单体3(M3)由顺式-二氨基二苯并-18-冠-6和苯酚通过重氮化和偶联反应制备.共聚酯的分子量不高,[η]在0.30~0.39之间.单体的化学结构通过IR、UV1、H-NMR、MS和元素分析等方法确证.共聚酯的外观为黄色粉状固体,除共聚酯CP9外,室温下不溶于CHCl3和THF溶剂.共聚酯的性质采用GPC、[η]、DSC、TG、WAXD和POM等方法进行了研究,发现所有的共聚酯加热到各自的熔融温度以上都能形成液晶态,在液晶态可以观察到近晶相和向列相的典型织构.共聚酯的熔融温度(Tm)和各向同性温度(Ti)随共聚酯分子中顺式-4,4′-双(4-羟基苯基偶氮)二苯并-18-冠-6用量的改变呈规律性变化.WAXD研究进一步证实了共聚酯的液晶性.     

含X-型二维液晶基元和反式-4,4′-双(4-羟基苯基偶氮)二苯并-18-冠-6冠醚环的液晶共聚酯的合成与表征

以4,4-′(α,ω己二酰氧)二苯甲酰氯(M1)、2,5-二(对辛氧基苯甲酰氧基)氢醌(M2)和反式4,4′-双(4羟基苯基偶氮)二苯并18冠6(M3)为单体,通过溶液共缩聚反应,合成了一系列含X型二维液晶基元和反式4,4′双(4羟基苯基偶氮)二苯并18冠6冠醚环的主链型液晶共聚酯.共聚酯的分子量不高,[η]在0.37～0.25dL g之间.单体的化学结构通过IR、UV、H NMR、MS和元素分析等方法确证.共聚酯的外观为黄色粉状固体,除CP9外,室温下不溶于CHCl3和THF溶剂.共聚酯的性质采用GPC、[η]、DSC、TG、WAXD和POM等方法进行了研究.发现所有的共聚酯加热到各自的熔融温度以上都能形成液晶态,在液晶态可以观察到近晶相的镶嵌织构或焦锥织构或破扇型织构和向列相的球粒织构或丝状织构或纹影织构.共聚酯的熔融温度(Tm)和各向同性温度(Ti)随共聚酯分子中反式4,4′双(4-羟基苯基偶氮)二苯并18冠6用量的改变呈规律性变化.WAXD研究进一步证实了共聚酯的液晶性.     

SYNTHESIS OF LIQUID CRYSTALLINE COPOLYESTERS WITH T-SHAPED TWO-DIMENSIONAL MESOGENIC UNIT AND CROWN ETHER CYCLE

A novel series of liquid crystalline copolyesters with T-shaped two-dimensional mesogenic unit and crown ether cycle of cis-4,4′-bis(4-hydroxyphenylazo)dibenzo-18-crown-6 was prepared via solution condensation polymerization from 4,4′-(α,ω-hexanedioyloxy)dibenzoyl dichloride(M_1),2-(4′-ethoxyphenyl)hydroquinone(M_2)and cis-4,4′-bis(4- hydroxyphenylazo)dibenzo-18-crown-6(M_3).The molecular weights of copolyesters are not high,and the intrinsic viscosity [η]of copolyesters ranges from 0.29-0.43.The monomer...     

含X-型二维液晶基元和冠醚环的液晶共聚酯的研究

合成了一系列新的含X-型二维液晶基元和反式-4,4'-双(4-羟基苯基偶氮)二苯并-14-冠-4冠醚环的主链型液晶共聚酯. 通过GPC, [η], DSC, TG, WAXD和POM对其液晶性研究发现, 所有的共聚酯都呈现出向列相的丝状织构或纹影织构. 共聚酯的熔融温度(T_m)和各向同性温度(T_i)随共聚酯分子中反式-4,4'-双(4-羟基苯基偶氮)二苯并-14-冠-4用量的改变呈规律性变化.     

含二苯并-18-冠-6冠醚环的主链型液晶共聚酯的设计与合成(英文)

以4,4′-(α,ω-亚烷基二酰氧)二联苯甲酰氯(M1)、顺式-4,4′-双(4-羟基苯基偶氮)二苯并-18-冠-6(M2)、反式-4,4′-双(4-羟基苯基偶氮)二苯并-18-冠-6(M3)和1,10-癸二醇(M4)为单体,通过溶液共缩聚反应,合成了两个系列新的含联苯型液晶基元和偶氮型冠醚环的主链型液晶共聚酯.共聚酯的[η]在0·25～0·35和0·27～0·38之间.单体的化学结构通过IR、UV-Vis、1H-NMR、MS和元素分析等方法确证.共聚酯的性质采用[η]、DSC、TGA、WAXD和POM等方法进行了研究.发现所有的共聚酯加热到各自熔融温度以上都能形成向列相液晶态,可以观察到向列相的丝状织构或纹影织构或球粒织构.共聚酯的熔融温度(Tm)和各向同性温度(Ti)随共聚酯分子中柔性间隔基长度的增加而有规律地降低,含反式冠醚环的共聚酯的Tm和Ti均高于相应含顺式冠醚环的共聚酯的Tm和Ti.     

含二苯并-18-冠-6席夫碱型液晶冠醚钾配合物的合成与表征

以顺(反)-4,4＇-双[4-(4＇-正烷氧基联苯基-4-羧基) 苯亚氨基] 二苯并-18-冠-6（I和II）为配体合成了2个系列席夫碱型液晶冠醚钾配合物,产率分别为85.5%~92.1%和88.7%~90.7%。配合物的结构通过元素分析、IR、UV-Vis和AAS等方法确证。液晶行为通过DSC、POM、XRD等方法表征。实验结果表明,所有配合物均具有热致液晶性,且随分子末端烷氧基碳原子数增加,其熔点和清亮点呈规律性变化。近晶相温度范围渐增,向列相温度范围递减。与配体相比,配合物液晶态温度范围变宽     

含二苯并-18-冠-6席夫碱型液晶冠醚钾配合物的液晶行为

以顺(反)-4,4′-双[4-(4′-正烷氧基联苯基-4-羧基)苯亚氨基]二苯并-18-冠-6(Ⅰ和Ⅱ)为配体合成了2种系列席夫碱型液晶冠醚钾配合物,产率分别为85.5%～92.1%和88.7%～90.7%。配合物的结构通过元素分析、IR、UV-Vis和AAS等测试技术确证。液晶行为通过DSC、POM、XRD等方法表征。实验结果表明,所有配合物均具有热致液晶性,且随分子末端烷氧基碳原子数增加,其熔点和清亮点呈规律性变化。近晶相温度范围渐增,向列相温度范围递减。与配体相比,配合物液晶态温度范围变宽。     

偶氮型液晶冠醚的合成与表征

以4'-正烷氧基联苯-4-甲酸和顺(反)-4,4'-双(4-羟基苯基偶氮)二苯并-14-冠-4为中间体, 通过溶液缩合反应, 合成了一系列偶氮型液晶冠醚. 并用元素分析、核磁共振、紫外可见分光光度计、红外光谱、基质辅助激光解析电离飞行时间质谱、示差扫描量热法和偏光显微镜对其进行了表征. 随分子末端烷氧基碳原子数增加, 化合物4I和4II的熔点(T_m)和液晶态的清亮点(T_i)逐渐降低, 液晶态温度范围较宽.     

New crown ether with indoxyl groups

Conclusions The reaction of diaminodibenzo-18-crown-6 with monochloroacetic anhydride in dioxane at room temperature gives 4,5-bis(chloroacetylamino)dibenzo-18-crown-6. The same reaction carried out in ethanol at reflux gives 4,5-bis(glycine hydrochloride)dibenzo-18-crown-6, which is converted in the presence of water to 8,9;17,18-bis(indoxyl)-18-crown-6.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 5, pp. 1160–1162, May, 1989.     

叔丁基取代二苯并-18-冠-6的合成

以二甘醇和邻苯二酚为原料制得二苯并-18-冠-6;以多聚磷酸为催化剂和溶剂,将二苯并-18-冠-6与叔丁醇反应实现叔丁基化;利用正庚烷重结晶对叔丁基化反应产物进行纯化,得到4,4′-二叔丁基二苯并-18-冠-6和4,5′-二叔丁基二苯并-18-冠-6两种对称的二叔丁基二取代苯并冠醚产品.利用红外光谱和核磁共振谱表征了二叔丁基二取代苯并冠醚产物的结构。     

Synthesis and characterization of new unsaturated polyesters and copolyesters containing azo groups in the main chain

A new interesting class of linear unsaturated polyesters based on dibenzylidenecycloalkanones have been synthesized by interfacial polycondensation of 4,4^′-azodibenzoyl chloride or 3,3^′-azodibenzoyl chloride with: 2,5-bis(p-hydroxybenzylidene)cyclopentanone I, 2,6-bis(p-hydroxybenzylidene)cyclohexanone II, 2,6-divanillylidenecyclohexanone III, or 2,7-bis(p-hydroxybenzylidene)cycloheptanone IV at ambient temperature. The copolyesters are also synthesized from the monomers I, II, III or IV with the diacid chlorides. The resulting polyesters and their copolyesters were characterized by elemental analyses, IR spectroscopy and solubility. Additionally, inherent viscosity of the polyesters in the range 0.32-0.86 dL g⁻¹ and the inherent viscosity of the copolyesters in the range 0.28-0.65 dL g⁻¹ were determined. The UV-visible spectra of certain polymers were measured in m-cresol solution and showed a characteristic absorption band at 435-473 nm due to n-π^* transition. The thermal properties of the polymers were evaluated by thermo gravimetric analysis and differential scanning calorimetry measurements and correlated with their structural units. The crystallinity of some polyesters and copolyesters were tested. In addition, the electrical properties of all polyesters and copolyesters were measured.     

Synthesis and characterization of new polyhydrazides based on 2,5-bis(mercapto-acetichydrazide)-1,3,4-thiadiazole moiety

New interesting class of novel polyhydrazides containing 1,3,4-thiadiazole moieties in the main chain was synthesized. A solution polycondensation technique was used in the synthesis of these polymers. The new monomer namely: 2,5-bis(mercapto-acetichydrazide)-1,3,4-thiadiazole III was synthesized from the nucleophilic replacement of 2,5-dimercapto-1,3,5-thiadiazole I with ethylchloroacetate, followed by hydrazinolysis. The model compound VII was synthesized from the monomer 2,5-bis(mercapto-acetichydrazide)-1,3,4-thiadiazole III with benzoyl chloride and characterized by ¹H- NMR, IR, and elemental analyses. The polyhydrazides were synthesized from the polymerization of monomer III with 4,4^′-biphenic, 3,3^′-azodibenzoyl, 4,4^′-azodibenzoyl dichlorides. These polymers were characterized by elemental and spectral analyses, viscometry and solubility. The thermal properties of these polymers were determined by thermal gravimetric analyses, and differential thermal analysis, and correlated with their structure. The crystallinity of some polymers was tested by X-ray analyses.     

新型手性近晶C相液晶共聚酯的设计与合成

以对苯二甲酰氯 ,2 ,5 二 [4 ((s) 2 甲基丁氧基 )苯甲酰氧基 ]对苯二酚和乙二醇、一缩乙二醇、二缩三乙二醇、三缩四乙二醇和聚乙二醇为单体 ,采用低温溶液缩聚方法 ,合成了一系列新的手性近晶C相串型液晶共聚酯 .共聚酯通过GPC、DSC、TG、WAXD、偏光显微镜和旋光仪等方法表征 .发现所有的共聚酯加热至各自的熔点以上都能形成液晶态 ,在液晶态可以观察到近晶相的焦锥织构 ,所有的手性化合物和共聚酯都有较高的旋光性 .通过变温X 射线衍射研究结合偏光显微镜观察和旋光分析证明它们为手性近晶C相 .所有共聚酯的熔融温度 (Tm)和各向同性温度 (Ti)随共聚酯中不同柔性链段长度的增加逐渐降低 ,液晶态温度范围变宽     

Synthesis,characterization, and complexing properties of a polymethacrylate bearing pendant macroheterocyclic structures

The synthesis of a polymerizable methacrylate bearing the dibenzo-18-crown-6 moiety ( 5 ) was effected in three steps by condensation of 3,4-dihydroxybenzaldehyde with 1,2-bis[2′-(2″-chloroethoxy)ethoxy]benzene ( 2 ), reduction of the resulting 4-formyldibenzo-18-crown-6 ( 3 ) to 4 and subsequent reaction of 4 with methacryloyl chloride. The methacrylate ( 5 ) was polymerized in solution using 2,2′-azobis(isobutyronitrile) (AIBN) as the initiator and gave a solid polymer ( 6 ) having a midrange T_g of 67°C. The polymethacrylate bearing pendant crown-ether structure ( 6 ) was found to effectively complex potassium ions and was clearly more effective in its complexing ability than dibenzo-18-crown-6 ( 7 ) or a polyurethane bearing the dibenzo-18-crown-6 moiety ( 8 ) in the polymer backbone. The subject polymer ( 6 ) was also found to complex and consequently solubilize several metal 7,7,8,8-tetracyanoquinodimethane (TCNQ) salts to give semiconducting compositions. Evidence is given that in the presence of the neutral acceptor molecule, 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ), the polymethacrylate ( 6 ) acting as a donor, gives rise to a charge-transfer (C/T) complex.     

聚合物分散液晶单体4,4′-二[6-(丙烯酰氧基)己氧基]联苯的合成

利用丙烯酰氯代替丙烯酸钾与4,4′-二(6-溴己氧基)联苯反应改进了制备4,4′-二[6-(丙烯酰氧基)己氧基]联苯(BAB6)的合成路线。改进前的反应温度较高,中间产物溶解度小,产物呈淡黄色,收率仅12.4%;改进后在室温反应,中间产物溶解度较高,产物呈白色,收率达到46.8%。采用1HNMR、13CNMR和元素分析对中间体和BAB6结构进行了表征。由改进后合成的单体,制备了具有快速响应的聚合物分散液晶(PDLC)膜,响应时间约2ms。扫描电子显微镜观察的结果表明,PDLC中形成了聚合物网络结构。     

Regioselective synthesis and properties of novel [60]fullerene bisadducts containing a dibenzocrown ether moiety

The reactions of [60]fullerene with bis-o-quinodimethane precursors 3, 4, and 5 containing a dibenzo-18-crown-6, 24-crown-8 and 30-crown-10 moiety, respectively, were investigated. Both 3 and 4 provided trans-4 bisadducts 6a and 7a, respectively, as major product, though the selectivity in the latter was lower than that in the former. As minor product, 6b (cis-2) was produced from 3, while 7c (e) as well as 7b (cis-2) were produced from 4. Precursor 5 exclusively afforded e bisadduct 8 without any other regioisomers. These bisadducts showed different ionophoric properties from one another; for instance, 6a and 7b exhibited a high complexing ability toward the K+ ion, while 6b hardly showed complexation with any alkali metal ions. The selectivity coefficients (K(Na,K)(pot)) of 6a and 7b toward K+ over Na+ ion, determined with an ion-selective electrode, were much higher than that of dibenzo-18-crown-6.     

一种基于联苯二甲酸为介晶基元的含磷液晶共聚酯的合成与表征

以联苯二甲酸二甲酯、二甘醇和9,10-二氢-9-氧杂-10磷酰杂菲-对苯二酚二羟乙基醚(DOPO-HQ-HE)为单体,通过无规共聚合成了一种新型含磷液晶共聚酯(PDEBP).用1H-NMR对共聚酯的结构进行了表征,用TGA、DSC和POM对其热性能及液晶行为进行了研究.结果表明,阻燃单体DOPO-HQ-HE的引入不会降低共聚酯的热稳定性,含7.5 mol％ DOPO-HQ-HE的共聚酯PDEBP7.5在700℃的氮气氛中的残余物(Wt700R)可达31.9 wt％,并且具有很好的阻燃性.DOPO-HQ-HE含量的增加对共聚酯的结晶性有较大的破坏,5 mol％ DOPO-HQ-HE的共聚酯PDEBP5的清亮点温度为154.2℃,焓变为4.64 J/g,而PDEBP7.5在POM测试中在升温及降温过程中均难观察到液晶相的双折射现象.     

Silylation of 5′-O-DMT-2′-Deoxyncleosides Using Dibenzo [18] Crown-6 and PTC

3′O-silylated derivatives of 5′-O-DMT-2′deoxynucleoside (2) were synthesized in high yield by reaction of 5′-O-DMT-2′-deoxynucleosides (1) with tert-butyl dimethylsilylchloride using sodium hydride, benzyltriethylammonlum chloride [TEBA] and a catalytic amount of dibenzo-[18]-crown-6 [DB-18-C-6] or 15-crown-5 [15-C-51 under mild reaction conditions.     

Synthesis of Schiff Base-type Liquid Crystalline Crown Ethers Containing Dibenzo-18-Crown-6 Unit

The synthesis and characterization of novel Schiff base liquid crystalline crown ethers prepared from the intermediates 4-(4‘-alkoxylbiphenyl-4-carbonyl)benzaldehyde, cis- and trans-4,4‘-diaminodibenzo-18-crown-6 are described. The structure of these compounds have been well characterized by elemental analysis, IR, ^1H NMR and MS spectroscopy. The liquid-crystalline behavior of these compounds was also inverstigated by differential scanning calorimetry (DSC), polarizing optical microscopy (POM) with a heating stage and polarimetric analysis.