高分子药物研究——Ⅱ.主链含5-氟脲嘧啶聚酯的合成

本文报道主链含5-氟脲嘧啶聚酯的合成及抗动物肿瘤初步试验。将5-氟脲嘧啶在二甲基甲酰胺中与无水碳酸钾作用,所生成的5-氟脲嘧啶钾盐随即与双氯乙酸二醇酯进行共缩聚,得到了6种主链含5-氟脲嘧啶的聚酯。同时还合成了三种新的双氯代乙酸二醇酯单体。     

高分子药物研究Ⅸ.1,3-二羟烷基-5-氟尿嘧啶与二氯磷酸酯缩聚物的合成

<正> 核酸的抗代谢物是研究正常细胞和肿瘤细胞代谢、发展新的抗肿瘤药物的极好来源。近年来合成含核酸碱基、核酸碱基衍生物的聚合物引起了人们的极大兴趣。在这些聚合物中,核酸碱基及其衍生物均以侧基支载在聚合物上。我们将5-氟尿嘧啶引入不同化学结构的高分子主链上,合成了一系列高分子抗癌药物,经动物试验和一期临床观察     

CHLOROMETHYLATION OF POLYMERS MADE FROM TECHNICAL DIVINYLBENZENE AND PROPERTY OF THE CHLOROMETHYLATED POLYMERS

1. INTRODUCTIONMacroporous polymers of technical divinylbenzene are often used as polymeric adsorbents for adsorptive separation. These resins may be advantageous compared to other polymeric adsorbents due to the high specific surface area and high porosity. However, the ability of these resins to adsorb polar compounds is very weak because the resins are non-polar and the values of the swelling capacity in aqueous solution are relatively low, and thus these resins are limited for adsorpti…     

CHLOROMETHYLATION OF POLYMERS MADE FROM TECHNICAL DIVINYLBENZENE AND PROPERTY OF THE CHLOROMETHYLATED POLYMERS

The goal this paper was to reveal the feasibility of chloromethylation of polymers made from technical divinylbenzene so as to introduce functional groups into polymeric adsorbents.Forthis study,the factors,that effect the chloromethylation reaction,such as the pore structure of the polymer,the ratio of the reactants to catalyst,the reaction temperature and reaction time and so on were investigated.and the pore structure and property of the chloromethylated polymers were studied.The results showed that polymers of technical divinylbenzene could be chloromethylated successfully,and the adsorptive property of the chloromethylated resin was different from that of the initial resin.     

含5-氟脲嘧啶的聚硅氧烷的合成

5-氟脲嘧啶与α、ω双二乙胺基聚二取代基硅氧烷反应 可得含5-氟脲嘧啶的缩聚物。并以红外、核磁对缩聚物进行了研究。在室温将所得缩聚物在不同pH介质中,进行水解,以266.5nm处紫外吸收光度,定量测定所释放出来5-氟脲嘧啶。当缩聚物n值增大时,水解速度减慢,1、3结构则比2、4结构缩聚物为快。     

高分子药物研究——ⅩⅦ. 二羟烷基嘧啶与N,N’-双(2-氯乙基) 二氯磷酰胺缩聚物的合成及其抗肿瘤活性研究

本文通过七种二羟烷基嘧啶单体与N,N’一双(2-氯乙基)氯磷酰胺进行缩聚反应,制得了七种新的含核酸碱基或其类似物和氮芥的聚磷酸酯,用核磁、红外光谱及元素分析确定了单体和聚合物的结构。部分聚合物试验结果表明,既含氮芥又含5-氟尿嘧啶的聚合物具有较高的抗癌活性和较低的毒性,聚合物(Ⅲ_a)对小鼠艾氏腹水癌的抑制率可达66％。     

高分子药物研究——Ⅲ.主链含5-氟尿嘧啶聚酯的合成及其药效的初步测定

本文报道四种新的主链含5-氟尿嘧啶聚酯型高分子抗肿瘤药物的合成及其中一种聚酯PFuE-Ⅱ-4药效的初步测定。结果表明,它具有较好的抗肿瘤活性,毒副作用小和缓释长效的特点。     

聚苯乙烯基偶氮聚合物的合成研究

改进了聚苯乙烯的硝化、还原、重氮化和偶合反应路线 (NRDC) ,使每步反应都得到很高的产率 ,并利用大分子重氮盐 (MDS)分别与苯胺、N 烃基苯胺和酚等三类化合物偶合 ,得到相应的聚苯乙烯基偶氮聚合物 .核磁共振分析结果证明了产物的高偶联率 .通过对大分子重氮盐热稳定性的研究 ,发现偶合反应之后需要一步加热反应以消除残余重氮基团 .还研究了这些聚合物的紫外 可见吸收光谱性质 ,氨 (胺 )基偶氮产物的水溶液表现出了明显的pH敏感性     

SYNTHESIS AND CHARACTERIZATION OF TRIAZOLE CONTAINING LIQUID CRYSTALLINE POLYMERS THROUGH 1,3-DIPOLAR CYCLOADDITION POLYMERIZATION

Liquid crystalline polymers containing 1,2,3-triazole units as linking groups have been synthesized from the monomers containing triad ester diazide and flexible dialkyne ester by 1,3-cycloaddition reaction and were characterized. Click reaction of azide and alkyne functionals catalyzed by Cu(I) yielded target polyesters with 1,2,3-triazole groups.The structure of the polymer was confirmed by spectral techniques.GPC analysis reveals that the polymers have moderate molecular weight with narrow distributio...     

SYNTHESIS OF POLYMERS CONTAINING N-N LINKAGES

The N-N linkage in hydrazine is thermally stable when it is tetrasubstituted and there are electron-withdrawinggroups attached to the nitrogen atoms. Our research on the synthesis of polymers contaning N--N linkages is reviewed. TheN,N-bisimide structure has been introduced in the backbone of polymers as well as a pendant group in poly(aryl ether)s togive very thermoxidatively stable polymers with very high glass transition temperatures. Most of the polymers form tough,flexible films. N-Aminotriazoles also form stable imides by reaction with anhydrides and these N-imidotriazole groups havebeen introduced as pendent groups on poly(aryl ether)s. The polymers are highly fluorescent materials. Three methods for thesynthesis of polymers containing the tetrasubstituted-azine structure will be discussed: (1) oxidative coupling of bisimines;(2) condensation of bishydrazones with diketones; (3) poly(aryl ether azines) from the azine formed from 4-fluorobenzo-phenone by reaction with salts of bisphenols.     

膜渗透计测定低分子量聚合物

本文用小体积膜渗透计及动态渗透压法测定了聚苯乙烯标准样品(分子量1000—17000)和一系列主链含-5氟尿嘧啶聚酯的分子量(低于9000)。同时研究了再生纤维素玻璃纸制备的半透膜的渗透性和选择性。该膜在丙酮中具有较高的选择性,可测定1000分子量。 低分子量聚苯乙烯的第二维利系数A_2依从A_2=常数·(?)关系。     

MULTIFUNCTIONAL HYDROPHILIC POLYMERS

ABSTRACT

Different types of multifunctional hydrophilic polymers were synthesized and characterized in view of their possible biomedical application. Several poly(amide)s and poly(ester-amide)s containing oligo(oxyethylene) segments and tartaric or succinic acid residues were prepared by activated polycondensation methods. New functional derivatives of β-cyclodextrin were obtained by reaction with glycidyl ether of protected polyols. The mechanism of β-cyclodextrin polymerization with epichlorohydrine was investigated by ¹³C-NMR spectroscopy.     

重氮偶合反应合成超支化偶氮聚合物的光响应性能研究

利用重氮偶合反应和后重氮偶合反应制备了主链和端基含有不同假芪型偶氮苯生色团的超支化偶氮聚合物.利用氢核磁共振、紫外光谱、红外光谱等分析手段确定了合成聚合物的结构、玻璃化转变温度和光谱特性等.研究了聚合物光致二向色性的性能,此聚合物的取向有序度为0.063.用两束相干的P偏振Ar+激光对聚合物膜进行光加工,得到形状规则的正弦波形表面起伏光栅,末端偶氮苯基团的引入极大地增加了超支化偶氮聚合物的光响应速度.     

含噻唑偶氮苯生色团环氧树脂类聚合物的合成与表征

合成了2-氨基-4-氯-5-甲酰基噻唑和2-氨基-4-氯-5-二氰乙烯基噻唑.分别将其与亚硝酰硫酸反应配制成重氮盐,通过在极性溶剂中与含苯胺残基的环氧树脂类前体聚合物BP-AN进行重氮偶合反应,得到了两种含噻唑偶氮苯生色团的环氧树脂类聚合物BP-1A-T-F和BP-1A-T-2CN.利用仪器分析手段对其结构、光谱特性和热性能进行了表征,BP-1A-T-F和BP-1A-T-2CN的最大吸收波长分别为579nm和650nm;玻璃化转变温度152℃和149℃.     

γ-核酸碱基取代丙基甲基二乙氧基硅烷的合成及其聚合反应研究

本文以Υ-溴丙基甲基二乙氧基硅烷分别与尿嘧啶、胸腺嘧啶、腺嘌呤和5-氟尿嘧啶进行烷基化反应,制得了四种含有核酸碱基或5-氟尿嘧啶的新型有机硅单体。通过它们的缩聚反应,合成了六种侧基含核酸碱基或5-氟尿嘧啶的聚硅氧烷。     

STUDY ON CHIRAL LIQUID CRYSTALLINE POLYMERS WITH BIPHENYLENE AND AZOBENZENE AS THE MESOGENS

Chiral liquid crystalline polymers containing biphenylene and azobenzene as the mesogensand S(-)-2-methyl-1-butanol as the chiral end group were synthesized and characterized by DSC,POM and X-ray diffraction. These polymers show crystalline or glassy liquid crystalline phase atroom temperature. Most polymers show smectic A or highly ordered smectic phases abovemelting temperature.     

偶氮苯侧链结构对聚丙烯酸酯三阶非线性光学性能影响

设计合成了一系列含偶氮苯非线性生色团的丙烯酸酯,并采用溶液聚合法合成了功能化的聚丙烯酸酯,利用FTIR、NMR、UV等对化合物的结构进行了表征,证实得到了指定结构的化合物.利用Z扫描技术对合成的聚丙烯酸酯的非线性光学性能进行了研究,通过对聚合物的非线性光学吸收拟合,计算得到非线性吸收系数β和三阶非线性系数χ(3),并探讨了取代基生色团分子结构与高分子三阶非线性光学性能的关系,结果显示增大侧链生色团π电子离域长度或强DπA(推拉基团)结构均可有效提高聚合物的三阶非线性光学性能.     

CHEMOTHERAPEUTIC POLYMER ⅩⅦ. THE SYNTHESIS AND ANTITUMOR ACTIVITY OF POLYPHOSPHATES CONTAINING BOTH NUCLEIC ACID BASE AND NITROGEN MUSTARD

Seven new polyphosphates containing both nucleic acid base and nitrogen mustard were preparedby reacting the monomers, i.e. 1,3-dihydroxyalkyl-5-fluorouracil(II_(a.,b, g)), 1,3-dihydroxyalkyluracil(II_(c,d)) and 1, 3-dihydroxyalkylthymine (II_(e,f)) with W, N,N-bis(2-chloroethyl)phosphoramide dichlo-ride (I). The monomers and polymers were characterized by ~1H-NMR, IR spectra and elementalanalysis. All of the polymers obtained are soluble in water. The antitumor activity of some of thesepolymers were tested against Ehrlish Ascites in mice. The results showed that the polyphosphatescontaining both 5-fluorouracil and nitrogen mustard exhibit lower toxicity and higher antitumor ac-tivity. The inhibition ratio of the polymer (III_a) is 66%.     

STUDY ON SIDE REACTION IN THE SYNTHESIS OF HYPERCROSSLINKED POLYMERS

The systematical study about side reactions have revealed the formation mechanism of oxygen-containing groups of hypercrosslinked polymers. Surface chemistry and functionality of the polymers are characterized by Fourier-transform infrared spectroscopy （FT-IR）, solid state nuclear magnetic resonance （NMR） and contact angle. The results showed that the ether groups were from chloromethylated reaction, and the alcohol groups arose from partial hydrolysis of chloromethyl groups during the post-crosslinking reaction, and the carbonyl functionality was formed by further oxidation of the alcohol groups. Catalyst and solvent used in the postcrosslinking reaction would greatly influence the surface chemistry of the polymer.     

THE INVESTIGATION OF MONOMER SYNTHESIS METHODS FOR POLYSULFONES AND OTHER NEW CLASSES OF SULFUR-CONTAINING POLYMERS

Abstract

Polysulfones, the new promising class of sulfur-containing polymers, are produced by aromatic nucleophilic and electrophilic substitution reactions. The first way is based on 4,4′-dichlorodiphenylsulfone (DCDPS) application as one of the basic monomers, which can be produced by three technical methods, utilizing strong sulfonating and sulfonylating agents. The reaction of hydrocarbon sulfonylation with arylsulfochlorides in the presence of small quantities of Fe chloride (kinetics, mechanism, the reactivity of initial compounds) was investigated in detail. For the first time the competitive inhibiting by initial and final products was found in this reaction, and its quantitative evaluation was given. The data obtained allowed to explain the experimentally observed anomalous reactivity of arylsulfochlorides. The chemistry of sulfonylation reaction with stabilized liquid sulfuric anhydride and dimethylsulfate was thoroughly investigated. The peculiarities and application limits of substituted diphenylsulfones synthesis methods were discussed.