用作光致抗蚀剂的环化橡胶

介绍了环化聚异戊二烯和环化聚丁二烯橡胶的研究发展状况、合成方法、结构表征及在光刻胶中的应用,提出了环化橡胶的发展趋势。环化反应是按阳离子型机理进行的;分子结构由含不饱和双键的线形高分子链转变成含特殊多环结构的线形高子分链;由单体直接生产环化橡胶是研究的发展方向。     

环化丁苯橡胶的表征

在ＳＢＲ中加入环化试剂ＡｌＥｔ２Ｃｌ－Ｃ６Ｈ５ＣＨ２Ｃｌ,在１２０℃,２０ｍｉｎ条件下制备了环化ＳＢＲ,并借助ＩＲ,＾１Ｈ－ＮＭＲ,ＤＳＣ,ＧＰＣ等方法对产物性能进行了表征。结果表明,二国本溶剂参与了环化反应,且随环化度增加,参与反应的二甲苯量也逐渐增加,并确定了环结构的形成。利用＾１Ｈ－ＮＭＲ谱图导出了环化ＳＢＲ的环化度和溶剂参与量的计算公式。     

环化氯丁橡胶的表征

在氯丁橡胶中加入环化试剂AlEt2 Cl-C6H5CH2 Cl,在 12 0℃× 2 0min条件下 ,可制备环化氯丁橡胶。借助IR ,1H -NMR ,DSC ,GPC和裂解色谱测试方法对产物进行了表征。结果表明 ,二甲苯溶剂参与了环化反应 ,且随环化度增加 ,参与反应的溶剂二甲苯的数目也逐渐增加 ,并确定了环结构的形成     

聚酰胺酸的化学环化与微纤的成形

采用化学环化方法制备不同酰亚胺化程度的聚酰胺酸-聚酰亚胺(PAA-PI),通过红外光谱、热失重分析对其结构和性能进行了表征,发现产物的环化程度与理论值相符合。PAA-PI液滴在非溶剂中经过牵伸、变形、取向、凝固,沉析出不同环化程度的PAA-PI微纤,通过宏观照片和扫描电子显微镜(SEM)研究了聚合物的环化程度与微纤成形的相互关系,结果表明:相对于没有环化的纯PAA,经过化学环化的PAA-PI制备出的微纤微观上具有更规则的形貌,表面光洁,手感柔软。     

1,3—双烯聚合物的环化

采用AlEt2Cl－C6H5CH2Cl体系成功地对聚异戊二烯、聚了二烯、聚氯丁二烯3种1,3—双烯聚合物进行了环化,并对环化过程进行了比较。     

合成环化聚异戊二烯的新方法

在二甲苯中，以氯化钕异丙醇配合物－三乙基铝为催化剂异二烯顺式聚合，在转 小于２０％时，引入烯丙基氯，当Ｃｌ／Ａｌ摩尔比为１．０－６．０时，可制得环化度为６６－１００％，Ｔ６为６０－７０℃的环化聚异戊二烯（ＣＰＩｐ），实验结果表明，随Ｃｌ／Ａｌ摩尔比的增加，ＩＰ转化率升高，产物「η」降低。同时，用ＩＲ，Ｈ＿ＮＭＲ，ＤＳＣ等测试方法对环化产物的结构和性能进行了表征。     

稀土催化合成反式,环化和顺反立构嵌段聚异戊二烯

采用新型稀土催化体系Ｌ３－ｎＬｎＸｎ－Ｒ３Ａｌ－ＲＸ，研究了催化体系各组分、室温下再陈沦时间、ＲＸ和Ｒ３Ａ种类及用量、溶剂种类等因素对异戊二烯聚合的影响。在此基础上，经经环化聚合合成出环化聚异戊二烯，并尝试了异戊二 立构癌段聚合，用Ｉ动态力学测试等方法表片了聚合物的结构，合成出含１，４－结构６８．１％含环化结构的２８．９％，顺－１，４和反－１，４链段的Ｔｇ分别为－２９℃和７０℃的顺反立嵌段聚异戊二     

叠氮化合物在杂环化合物合成中的应用

利用叠氨化合物合成杂环化合物的新方法，包括环化、环加成、扩环和缩环反应。共特点是方法简便，收率高，并可制备一些用其它方法难以合成的杂环化合物。     

环化橡胶共混物的热学性能和热力学参数

上世纪50年代以来,橡胶科学界一直在关注由天然橡胶（NR）、聚丁二烯橡胶（BR）和异戊二烯橡胶（IR）产生的环化橡胶。环化橡胶产品使用在粘合剂、涂料、油墨的配方中,也用于NR的配合来改善其力学性能,环化NR可加入到胎面胶胶料中来改善牵引性能、胎面耐磨性和耐撕裂性。更进一步的是,以这一发现为基础,环化IR可以与氯化丁基橡胶或NR共混,用于轮胎气密层胶料。     

异苯橡胶环化反应动力学研究及产物微细结构表征

本文采用红外光谱法研究了前无报导的聚异苯橡胶环化反应动力学，测定了标题反应的动力学参数：反应级数ｎ＝１；活化能Ｅ＿ａ＝５３．２ｋＪ·ｍｏｌ￣（－１）；指前因子Ａ＝２．２４×１０￣６ｍｉｎ￣（－１），确立了该反应速率常数ｋ＿ｔ与ｓ反应温度Ｔ之间的函数关系为：Ｌｎ（ｋ＿Ｔ／ｍｉｎ￣（－１））＝１４．６２—６．４０×１０￣３Ｋ／Ｔ并采用核磁共振法分析了标题反应的产物环化异苯橡胶的微细结构，提出了标题反应的可能机理，并对活化能及指前因子进行了分析讨论。     

Cationic cyclization of purified natural rubber in latex form with a trimethylsilyl triflate as a novel catalyst

Cyclization of deproteinized natural rubber (DPNR) or purified natural rubber latex was effectively performed in latex phase by using trimethylsilyl‐trifluoromethane sulfonate or trimethylsilyl triflate (TMSOTF) as a novel catalyst, which is still not reported in the case of natural rubber latex. Various cyclization conditions affecting the degree of cyclization were studied, such as dry rubber contents, temperature, TMSOTF concentrations, and time. The cyclized products were characterized by FTIR, Raman, ¹H‐, and ¹³C‐NMR spectroscopies, as well as DSC and TGA. The degree of cyclization was estimated by ¹H‐NMR spectrum. It was found that the degree of cyclization in NR was a function of cyclization conditions. The thermal stability of cyclized DPNR increased with the degree of cyclization. Solubility of the obtained rubber was good in chloroform, toluene, cyclohexanone, and cyclohexane, and bad in tetrahydrofuran. The average number molecular weight of cyclized DPNR with 76% degree of cyclization was about 4.2 × 10⁴ g/mol. On the basis of FTIR, Raman, ¹H‐, and ¹³C‐NMR, the C?C of cyclized DPNR dramatically decreased after prolonged reaction time. In addition, the topology of cyclization DPNR particles was rough on its rubber particle as analyzed by TEM. The mechanism for this reaction will also be discussed. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007.     

New photoresists of cyclized butadlene polymers

A new photoresist composed of cyclized cis-1, 4-polybutadiene has been developed. The resist has much higher sensitivity on exposure to ultraviolet light than the conventional resist from cyclized polyisoprene. This new resist has no resist-flow even at 250°C, and provides high resolution on baking at 200°C. Thermogravimetric analysis showed that the cyclized polybutadiene decomposes at temperature higher than cyclized polyisoprene.     

环化聚丁二烯的合成及其在光刻胶中的应用

本文扼要地阐述了国内外环化橡胶的研究发展状况,介绍了环化天然橡胶、环化聚异戊二烯橡胶和环化聚丁二烯橡胶的合成新方法及其结构表征技术。其中,重点介绍了环化聚丁二烯橡胶的合成新技术。由于环化橡胶负性光刻胶对金属及硅片的粘接性和耐酸性方面的优异性能以及其良好的热稳定性能,因此被广泛应用于硅、二氧化硅及铬不锈钢等材料的光刻,因而在高密度集成电路的生产与研制上得到了广泛应用。同时,本文还介绍了市场上常见的几种环化橡胶光刻胶产品。     

Conducting complexes of vacuum-cyclized polyacrylonitrile and iodine

Polyacrylonitrile, thermally cyclized in a vacuum, was found to form conducting complexes with iodine. These complexes would not form until the thermal treatment of polyacrylonitrile resulted in a certain minimum cyclicity, or number of cyclized rings per fused segment in the polymer chain, as measured by infra-red spectroscopy. Cyclized polyacrylonitrile-iodine complexes approaching two iodine atoms per cyclized six-member ring had a room-temperature conductivity of 10^?2 ohm^?1 cm^?1 with an activation energy of 0.60 eV.     

Electrochemical preparation of epinephrine/Nafion chemically modified electrodes and their electrocatalytic oxidation of ascorbic acid and dopamine

Two types of epinephrine and cyclized epinephrine quinone films have been prepared using cyclic voltammetry from the epinephrine in the strong acidic solutions and neutral aqueous solutions over different scanning potential ranges. The cyclic voltammogram of the epinephrine film is characterized by one redox couple at about +0.5 V (versus Ag|AgCl) and cyclized epinephrine quinone film exhibits one redox couples at about −0.15 V (versus Ag|AgCl) .In addition to cyclic voltammetry and an electrochemical quartz crystal microbalance (EQCM) were used to study the growth mechanism of the epinephrine and cyclized epinephrine quinone molecules. The electrocatalytic oxidation of catecholamines (dopamine and norepinephrine) and also ascorbic acid were investigated in acidic aqueous solutions using epinephrine films. The rotating ring-disk electrode technique was used to investigate the mechanism of electrochemical oxidation of dopamine and ascorbic acid.     

Soap-based detergent formulations: XXI. Amphoteric derivatives of fatty amides of aminoethylethanolamine1

Amides and 2-alkyl-N-(2-hydroxyethyl)-imidazolines were converted into various types of sulfated or sulfonated amphoteric lime soap dispersants. The alkylimidazolines could be readily hydrolyzed to give amidoamines. The cyclized amphoteric surfactants were generally superior in detergency and lime soap dispersing ability to analogous surfactants derived from amidoamines. Some of the cyclized surfactants, when formulated with soap and silicate builder, washed about as well under the test conditions as a control containing 50% sodium tripolyphosphate.     

新型2-烷氧基-3-芳基-5-苯基亚甲基-4H-咪唑啉-4-酮衍生物的合成与杀菌活性研究(Ⅱ)

研究了应用烯基膦亚胺与芳基异氰酸酯、醇的串联aza-Wittig反应合成2-烷氧基-3芳基-5-苯基亚甲基-4H-咪唑啉-4-酮衍生物的新方法。探讨了反应进行的条件和产物的波谱性质,提出了可能的环化反应机理。生成的环化产物结构经元素分析、IR、1HNMR和MS确证。对这些新型杂环化合物的杀菌活性测试结果表明,部分化合物表现出较好的抑菌活性。     

Synthesis and properties of photosensitive rubbers. II. Photosensitivity of cyclized polydienes and polypentenamer with pendent cinnamate groups

Photosensitivity of cyclized polydienes such as cis-1,4-polybutadiene, 1,2-polybutadiene, and polypentenamer having pendent cinnamate groups has been studied in terms of the influence of polymer structure. The photosensitivity, which was based on the photodimerization of cinnamate groups in these polymers, was greatly affected by the mobility of the cinnamate groups. The observed rates (k) could be estimated by using the reciprocal of the difference between an irradiated temperature (T) and a standardized temperature (T_g – 50), at which the free volume of the polymer could be considered as zero by taking the glass transition temperature (T_g) of the polymer as a standard. Furthermore, the photosensitivity of the cyclized rubber decreased with an increase in the amount of the cyclized units in the polymer. The overall rate of the photodimerization did not linearly correlate with the amount of the incorporated cinnamate groups, because the glass transition temperature of the cyclized rubber was not dependent on the small amount of the incorporated cinnamate groups, but on the amount of the cyclized units in the polymer. Theoretical treatment of the photodimerization reaction in the solid polymer was carried out, which was consistent with experimental results.     

Fourier transform ir studies of the degradation of polyacrylonitrile copolymers—II: Acrylonitrile/methacrylic acid copolymers

The results of a Fourier transform IR study of the degradation of an acrylonitrile copolymer containing approx. 4 wt% of methacrylic acid, at 130°C under a reduced pressure of 5 × 10^?2 Torr, are presented. A mechanism is proposed for the degradation that is consistent with the IR spectral evidence. Additionally, we have determined from our experimental results that methacrylic acid is incorporated into the cyclized degraded structure and that, on average, three to four acrylonitrile acids are cyclized for each acid initiation.