邻(对)羟基苯乙烯酮的合成

介绍了邻（对）羟基苯乙烯酮的制备方法。该法采用丙酮和邻（对）羟基苯甲醛在稀碱存在下，于20℃-25℃进行醛酮缩合反应，合成工艺简单，收率高。用^1HNMR,^13CNMR分析，产品纯度高。     

天然产物(E)-4′-甲氧基-3,5-二羟基■的合成研究

以3,5-二羟基苯甲酸为原料,通过乙酰基保护、酰氯化,生成中间体3,5-二乙酰氧基苯甲酰氯,再与4-甲氧基苯乙烯经Heck反应、甲醇钠脱乙酰基保护,得到单一的■类天然产物标题化合物,产率66%。研究结果对于其他类化合物的合成具有指导意义。     

天然产物（E）-4＇-甲氧基-3,5-二羟基芪的合成研究

以3,5-二羟基苯甲酸为原料,通过乙酰基保护、酰氯化,生成中间体3,5-二乙酰氧基苯甲酰氯,再与4-甲氧基苯乙烯经Heck反应、甲醇钠脱乙酰基保护,得到单一的芪类天然产物标题化合物,产率66%.研究结果对于其他芪类化合物的合成具有指导意义.     

天然产物(E)-4''''-甲氧基-3,5-二羟基芪的合成研究

以3,5-二羟基苯甲酸为原料,通过乙酰基保护、酰氯化,生成中间体3,5-二乙酰氧基苯甲酰氯,再与4-甲氧基苯乙烯经Heck反应、甲醇钠脱乙酰基保护,得到单一的芪类天然产物标题化合物,产率66%.研究结果对于其他芪类化合物的合成具有指导意义.     

聚对羟基苯甲酸侧链液晶高分子的合成与表征

合成了对羟基苯甲酸二聚体，四聚体，并分别接枝到苯乙烯－马来酸酐无规共聚物（SMA）上，得到侧链工度均匀的液晶高分子；同时在N，N'－二环己基碳二亚胺催化下采用溶液缩聚法制备了SMA接枝聚对羟基苯侧链液晶高分子。用FT-IR,DSC，偏光显同镜等方法表征了产物的结构作性质，讨论了液晶侧链对聚合物形态和热性质的影响。     

白藜芦醇关键中间体的合成工艺研究

改进了合成白藜芦醇的关键中间体3,5-二羟基-4’-甲氧基-1,2-二苯乙烯(1.3)的合成工艺。3,5-二乙酰氧基苄基三苯基膦溴化盐(1)与茴香醛在DMF中以CH3ONa为碱会发生Wittig反应,当1与CH3ONa的摩尔比为1:1时,反应的主产物有3个,分别为3,5-二乙酰氧基-4’-甲氧基-1,2-二苯乙烯(1.1)、3-乙酰氧基-5-羟基-4’-甲氧基-1,2-二苯乙烯(1.2)和3,5-二羟基-4’-甲氧基-1,2-二苯乙烯(1.3);当1与CH3ONa的摩尔比在1:2~3时,反应主产物是1.3。3,5-二羟基苄基三苯基膦溴化盐(2)与茴香醛在DMF中以CH3ONa为碱也会发生同样的反应,且当2与CH3ONa的摩尔比为1:1时,主产物是1.3。当1与CH3ONa的摩尔比为1:5时,没有Wittig反应产物生成。因此,按上述反应条件制得1.3后再去掉其上的甲基保护基团即可得白藜芦醇,相比其他的合成白藜芦醇工艺,省去了去乙酰基团的反应步骤。     

聚羟基苯乙烯在光致抗蚀剂中的应用及其合成

主要综述了聚羟基苯乙烯用作深紫外光致抗蚀剂主体成膜树脂的发展历程、应用现状以及一些最新的研究进展，并简要介绍了聚羟基苯乙烯的单体衍生物及其聚合物的制备方法。     

热压印方法构筑聚对羟基苯乙烯微米线条

聚合物薄膜微纳图案化是近年来研究热点。本文采用热压印方法构筑聚对羟基苯乙烯(PVPh)薄膜的微米线条图案。据原子力扫描结果显示,经过热压印处理后的聚合物薄膜表面较处理前规整且出现与模板特征尺寸具有高吻合度的周期性微米线条。这说明在聚对羟基苯乙烯薄膜上已成功构筑了微米线条。通过对聚合物薄膜微米线条的成功构筑,表明热压印是聚合物薄膜图案化的有效方法之一。     

一锅法合成乙酰化羟基肉桂酸衍生物

介绍了一种反应条件温和、产物纯度高、操作简便的从羟基苯甲醛衍生物一步直接合成乙酰氧基肉桂酸衍生物的方法,并考查不同催化剂和催化剂用量对产物的影响。     

248nm光致抗蚀剂成膜树脂研究进展

光致抗蚀剂(photoresist)是制造超大规模集成电路的关键性材料之一,随着集成电路集成度的不断增加,光致抗蚀剂由g线(436nm)胶、i线(365nm)胶,逐渐发展到深紫外(DUV)(248nmKrF与193 nm ArF)胶。成膜树脂作为光致抗蚀剂的主要成分之一,决定了抗蚀剂的主要性能,因此研究成膜树脂具有重要的意义。本文综述了248 nm KrF光致抗蚀剂成膜树脂的研究进展,重点介绍了聚对羟基苯乙烯及其衍生物,并简要介绍了其合成方法及成像机理。     

Darstellung von Poly-4-hydroxystyrol und dessen Umsetzung zu einem Chelataustauscher auf Basis o-(2-Hydroxyphenylazo)benzoesäure. Chelatbildende Austauscherharze,VIII

The radical pearl-copolymerization of 4-acetoxystyrene in the presence of divinylbenzene yields cross-linked poly-4-acetoxystyrene which can be carefully hydrolized to poly-4-hydroxystyrene. Poly-4-hydroxystyrene reacts with diazocompounds to chelate forming polymers with o,o′-disubstituted azo-groups. The synthesis of a chelating resin based on o-(2-hydroxyphenylazo)benzoic acid is described.     

Preparations of 4-(2-chloroethyl)styrene, 4-(2-chloroethyl) α-acetoxystyrene and 4-(3-bromopropyl)α-acetoxystyrene

Summary Functionalized styrenes such as 4-(2-chloroethyl)styrene, 4-(2-chloroethyl)-acetoxystyrene and 4-(3-bromopropyl)-acetoxystyrene have been synthesized in two steps from commercial products and a preliminary study of their polymerization and copolymerization has been carried out.     

Preparation of macroporous,monodisperse, functionalized styrene–divinylbenzene copolymer beads: Effect of the nature of the monomers and total porogen volume on the porous properties

The staged templated suspension polymerization method was used for the preparation of 5 μm beads from mixtures of styrene and several substituted styrene monomers, including 4-methylstyrene, 4-aminostyrene, 3-aminostyrene, 4-acetoxystyrene, and 4-tert-butoxycarbonyl oxystyrene, with divinylbenzene in the presence of various amounts of linear polystyrene and dibutyl phthalate as porogens. The nature of the monomer as well as the total percentage of porogenic compounds in the polymerization mixture have a large effect on the porous properties and surface morphology of the monodisperse beads. Beads with large pores can only be obtained once the percentage of porogen in the mixture exceeds a threshold value that varies with the type of monomers involved in the polymerization. The level of incompatibility of the functional polymer chains formed during the crosslinking polymerization with the linear polystyrene porogen that is present in the polymerization mixture is another variable that also affects both the porous properties and the morphology of the beads. Because better compatibility is achieved, this effect is less pronounced if unfunctionalized styrene is used as a monomer. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 67: 597–607, 1998     

Synthesis and characterization of amorphous octakis-functionalized polyhedral oligomeric silsesquioxanes for polymer nanocomposites

We have synthesized the polyhedral oligomeric silsesquioxane (POSS) derivatives OS-POSS and OA-POSS through the hydrosilylation of styrene and 4-acetoxystyrene, respectively, with octakis(dimethylsiloxy)silsesquioxane (Q₈M₈^H). We then prepared OP-POSS through acetoxyl hydrazinolysis of OA-POSS with hydrazine monohydrate. The chemical structures of these POSS derivatives were characterized using FTIR and ¹H NMR spectroscopy and MALDI-TOF mass spectrometry. Unlike Q₈M₈^H, which is crystalline, these three hydrosilylated POSS derivatives are liquids at 25 °C. Through DSC and XRD analyses, we found that they exhibit polymer-like glass transitions and amorphous halos. These octakis-functionalized POSS derivatives can be regarded as amorphous glasses possessing low glass transition temperatures, the values of which depend on the intermolecular interactions of their outer organic groups. To investigate the dispersion of these POSS derivatives in polymer nanocomposites, we blended OS-POSS, OA-POSS, and OP-POSS with polystyrene, poly(4-acetoxystyrene), and poly(4-vinylpyridine), respectively, and investigated the effects of the resulting intermolecular aromatic hydrophobic, dipole-dipole, and hydrogen-bonding interactions, respectively. Dipole-dipole interactions provided the best dispersion of OA-POSS in poly(4-acetoxystyrene), in which the POSS-polymer intermolecular interactions were of similar strength to the POSS-POSS interactions.     

Preliminary analysis of the 1H-NMR and 13C-NMR spectra of poly(4-acetoxystyrene)

Summary The title polymer was synthesized via free radical initiation. The ¹H- and ¹³C-NMR spectra of the polymer were recorded and analyzed in terms of polymer tacticity. Many resonances showed a multiplicity indicative of sensitivity to stereochemistry. Those resonances that could be analyzed with a reasonable degree of accuracy showed poly(4-acetoxystyrene) to be an atactic polymer.     

Unperturbed dimension of poly(4-acetoxystyrene) measured in good and theta solvents

In order to obtain the additional data concerning the unperturbed dimension of poly-4-substituted styrene, light scattering measurements are performed on the twenty-two fractions with molecular weight of (0.91–352)·10⁴ of poly(4-acetoxystyrene) in dioxan at 25°C, from which the molecular weight obtained was found easily to be evaluated with the gel permeation chromatography using THF. Phase separation experiments for this polymer indicate that the theta state is attained in isopropyl acetate at 19.7°C and butyl acetate at 26.8°C. By making viscosity measurements at that state, the value of K_Θ is directly evaluated as 5.4·10^?4 dl g^?1. The limiting viscosity number is also obtained in good solvents, THF and dioxan, at 25°C and constants of the Mark-Houwink-Sakurada equation in each solvent are determined. Further, approximately the same K_Θ as above is obtained from these data with the Stockmayer-Fixman plot. The calculated value of steric factor, 2.37, on this polymer may be plausible, compared with those of polyvinylaromatic derivatives.     

Novel amphiphilic carbon black composite nanoparticles from TEMPO-terminated polymer and TEMPO-terminated block copolymer grafted carbon black

The purpose of this study was to modify the surface characteristics of CB so as to prevent the aggregation of CB to provide the dispersibilities in either H₂O or organic solvent. In this study, five kinds of hydrophilic TEMPO-terminated polymer, hydrophobic TEMPO-terminated polymer and amphiphilic TEMPO-terminated block copolymer were synthesized. The five kinds of TEMPO-terminated polymers were: (1) poly(4-acetoxystyrene) (PAS-T), (2) poly(4-hydroxystyrene) (PHS-T), (3) polystyrene (PS-T), (4) poly(4-acetoxystyrene)-block-polystyrene (PAS-b-PS-T), (5) poly(4-hydroxystyrene)-block-polystyrene (PHS-b-PS-T). These TEMPO-terminated polymers with desired molecular weights and specific structures were synthesized by using the method of living radical polymerization in the presence of 2,2,6,6-tetramethylpiperidinyl-1-oxy (TEMPO). These TEMPO-terminated polymers and TEMPO-terminated block copolymers were grafted onto the surface of CB through a reaction of polymer radicals trapped by CB, so as to obtain the TEMPO-terminated polymer/CB and TEMPO-terminated block copolymer/CB composite nanoparticles. Various variables such as reaction time, reaction temperature, amount of TEMPO-terminated polymer, molecular weight of TEMPO-terminated polymer and amount of CB all of which influenced the grafting efficiency were investigated. Besides, the stability of the composite nanoparticles, which dispersed in H₂O or organic solvent, was investigated by laser light scattering. The amphiphilic composite nanoparticles, PHS-T/CB and PHS-b-PS-T/CB, which dispersed well in both H₂O and organic solvent, were synthesized successfully in this work.     

UV reactive polymers for refractive index modulation based on the photo-Fries rearrangement

In this study we report on the synthesis and characterization of photoreactive polymers which display large changes in their refractive index upon UV irradiation. These polymers contain aromatic ester groups which undergo a photo-Fries rearrangement from aryl esters to hydroxyketones. The polymers under investigation were poly(4-acetoxystyrene) and two derivatives of polynorbornene, poly(bicyclo[2.2.1]hept-5-ene-2-carboxylic acid, phenyl ester) and poly(bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid, diphenyl ester). The kinetics of the photoreaction was studied by FTIR spectroscopy. Ellipsometric measurements of thin films showed that the photo-Fries rearrangement causes a large increase of the refractive indices in these polymers (between +0.03 and +0.05). The modulation of the refractive index is of interest for applications in the field of optics and data storage. The photoreaction also leads to an increase in surface energy as evidenced by contact angle measurements with water and diiodomethane as test liquids.     

Poly(p-maleimidostyrene) as a macromolecule initiator for polymerization of styrene-type monomers - Synthesis of block copolymers containing poly(p-maleimidostyrene) with highly reactive pendent maleimido groups

4-Substituted styrenes (substituent: methoxy, methyl, acetoxy, maleimido and none), were cationically polymerized with an initiator system involving poly(p-maleimidostyrene)(PMS) as a macroinitiator, having highly reactive pendent maleimide moieties and a α-chlorobenzyl structure at the polymer end. Using PMS/SnCl₄/tetra-n-butylammmonium chloride initiator system, block copolymers of 4-substituted styrenes onto PMS were obtained in CH₂Cl₂ at 0 °C. As for the polymerization of N-(4-vinylphenyl)maleimide and 4-acetoxystyrene, especially, PMS as the macroinitiator was almost completely utilized for initiation reaction and the polymers having PMS-b-poly(4-substituted styrene) platform with very narrow and unimodal molecular weight distribution were formed in contrast with the case of using 4-methoxystyrene and 4-methylstyrene with stronger electron releasing groups, in which the molecular weight distributions of the formed polymeric materials appeared to be bimodal.     

The catalytic characteristic and synthesis technique for 4-methyl-1-pentene over a potassium-supported superbase catalyst

The dimerization of propene to 4-methyl-1-pentene (4MP1) was studied in a fixed-bed reactor at 150?°C temperature, 8?MPa pressure, and 1?h^?1 liquid hourly space velocity (LHSV) in the presence of solid superbase with 20?wt% one-pass conversion to hexene and 88% selectivity toward 4MP1. Based on the reaction results, propene competes with 4MP1 for adsorption on the catalyst surface. A higher reaction pressure or a lower liquid rate of 4MP1, controlled by a suitable propene LHSV or reaction temperature, was beneficial to the adsorption of propene, which reduced the isomerization of 4MP1. Under optimized conditions, propene dimerization was stable for 200?h, and isomerization was limited to less than 5%, yielding products with about 19% one-pass conversion to hexene by weight and 87% selectivity toward 4MP1.