N-(4-羟基苯基)马来酰亚胺的合成研究

合成了N-(4-羟基苯基)马来酰亚胺，采用FT-IR对其进行结构表征，考察了合成过程中的多种影响因素，获得了最佳条件的工艺参数。     

Polychelates of poly[N-(4-carboxy-3-hydroxyphenyl)maleimide]

The reactions of the bidentate polymeric chelating ligand poly[N-(4-carboxy-3-hydroxyphenyl)maleimide] with Co(II), Ni(II), Cu(II), Zn(II) and UO₂(II) metal ions were investigated. Analytical, magnetic, spectral and thermal studies were used to characterize these polychelates. All these polychelates are stable, intensely coloured solids and insoluble in common organic solvents.     

Thermal polymerization and reactive blending of 2-(4-hydroxyphenyl)-1,3-oxazoline

Summary Upon heating above its melting temperature at 195°C, 2-(4-hydroxyphenyl)-1,3-oxazoline (HPO) was polymerized thermally in melt phase within a few minutes to produce a polymer with etheramide and N-4-hydroxybenzoyl-ethyleneimine repeat units. Polymerization in solution afforded only oligomers with 93% etheramide structure after several hours. Reactive blending, combining 2-phenyl-1,3-oxazoline (PO) grafting with in-situ HPO thermal polymerization in poly(ethene-co-methacrylic acid), was the key to novel self-reinforced multiphase ethene copolymer blends containing spherical dispersed poly(HPO) microphases. Poly(HPO) microstructures, blend morphologies, thermal and mechanical properties were investigated.     

1-乙酰基-4-(4-羟基苯基)哌嗪合成的新工艺

研究了以二乙醇胺为起始原料,经氯代、环化和酰化反应合成标题化合物的工艺,产品总收率达37.5%。经红外光谱分析及核磁共振氢谱分析确定产物为目的产物。通过此工艺路线合成的目标化合物,其产品总收率优于现行工艺,且该工艺操作简单,生产成本较低。     

2,2-二(3-氨基-4-羟基苯基)六氟丙烷的合成

以2,2-二(4-羟基苯基)六氟丙烷为原料,分别经硝化和还原反应合成出2,2-二(3-氨基-4-羟基苯基)六氟丙烷。并在实验室小试成功后,进行工厂中试研究,以确定中试的各个工艺参数。结果表明,对于第1步硝化反应,以乙醇做溶剂,用量为n(乙醇)/n〔2,2-二(4-羟基苯基)六氟丙烷〕=4,n(稀硝酸)/n〔2,2-二(4-羟基苯基)六氟丙烷〕=2.15,反应温度为60℃,反应时间为6 h的条件下,合成2,2-二(3-硝基-4-羟基苯基)六氟丙烷的产率达到最高值96%。对于第2步还原反应,采用自制FeCl3/活性炭为催化剂,乙醇做溶剂,n(水合肼)/n〔2,2-二(3-硝基-4-羟基苯基)六氟丙烷〕=0.2,m(FeCl3/活性炭)/m〔2,2-二(3-硝基4-羟基苯基)六氟丙烷〕=0.05,反应温度为85℃,反应时间为10 h的条件下,合成2,2-二(3-氨基-4-羟基苯基)六氟丙烷的产率达到最高值92%。该工艺条件在工厂已进行了中试研究,确定了工业实验的各个工艺参数和工艺条件。     

单体三(4-氟苯基)膦氧化物和三(4-羟基苯基)膦氧化物的新合成方法

以4-氟溴苯和三氯氧磷为起始原料,经格氏反应可直接合成三官能团单体三(4-氟苯基)膦氧化物(TFPPO),该单体进一步与氢氧化钾反应可得到三(4-羟基苯基)膦氧化物(TOHPPO)。该合成方法安全、简便,利于实际应用中扩大规模生产。     

Copolymerization of N-(4-carboxyphenyl)maleimide with acrylonitrile and the properties of its membrane

N-(4-Carboxyphenyl)maleimide (N-4-CPMI, M₁) was copolymerized with acrylonitrile (AN, M₂) to prepare the copolymer. The monomer reactivity ratios and Alfrey-Price Q, e values were determined as r₁ = 0.56, r₂ = 0.84, Q ₁ = 2.0, Q ₂ = 0.6 and e ₁ = 2.06, e ₂ = 1.2. The membrane of copolymer containing 0.25% CPMI had a good tensile property (67.3 MPa). The 0.75 mole% membrane had an excellent selectivity factor (α = 45.3).     

N-(p-Bromophenyl)maleimide and its copolymers with alkyl methacrylates

Copolymers of methyl, ethyl, butyl, pentyl, or octyl methacrylate with N-(p-bromophenyl)maleimide were synthesized by free-radical bulk polymerization using benzoyl peroxide as initiator. N-(p-bromophenyl)maleimide was prepared from maleic anhydride and p-bromoaniline in a two-step reaction. Thermal stability, chemical resistance, hardness, and Vicat softening point of the copolymers have been measured. The influence of N-(p-bromophenyl)maleimide content in the copolymers and the length of alkyl groups in methacrylates on their properties is discussed.     

2,2-双(3-苯基-4-羟基苯基)丙烷的合成研究

以邻苯基苯酚和丙酮为原料,盐酸为催化剂,巯基丙磺酸为助催化剂,通过缩合反应合成了2,2-双(3-苯基-4羟基苯基)丙烷(双OPP-A),研究了原料配比、催化剂用量、反应温度、反应时间等因素对反应的影响,通过实验确定了合成双OPP-A的最优条件为:n(邻苯基苯酚):n(丙酮):n(盐酸):n(巯基丙磺酸)=8:2:4:1,反应温度为60℃,反应时间24h,双OPP-A收率达到78.5%,经重结晶纯度达99.2%。产物通过红外光谱和核磁共振等进行了确证。     

Modification of surface properties of polypropylene films by blending with poly(ethylene-b-ethylene oxide) and its application

The possibility of improving the interfacial adhesion between polypropylene (PP) and polyamide layers (PA) has been investigated by means of addition of commercially available amphiphilic poly(ethylene-b-ethylene oxide) (P(E-b-EO)) block copolymers. These block copolymers were added to the PP matrix polymer in a twin screw extruder as integral additive. The change in surface properties of PP films upon incorporating P(E-b-EO) was investigated in model studies of blends prepared by casting PP/P(E-b-EO) solutions in 1,2-dichlorobenzene onto glass and Teflon Petri dishes, by melt pressing of PP/P(E-b-EO) blends between Teflon foils and glass substrates, or by melt extrusion of PP/P(E-b-EO) mixtures. The surfaces of the blend films were analyzed by attenuated total reflection Fourier transform infrared spectroscopy and water contact angle measurements. It was shown that an enrichment of the block copolymer at the surface of the blend depends highly on the conditions of film preparation and is driven by reducing the interfacial energy between the blend and the contacting medium. Effects of shear rate and residence time during normal processing conditions were also revealed. Blown film experiments with PP/P(E-b-EO) blends and PA were carried out for evaluating the effect of the integral P(E-b-EO) additive on the interfacial adhesion.     

Linear polyesters products of interfacial polycondensation of bis(4-hydroxyphenyl)ether with some aliphatic acid dichlorides

New polyesters were obtained by interfacial polycondensation of bis(4-hydroxyphenyl)ether with succinyl, adipolyl, suberoyl, or sebacoyl chlorides. To define the optimal conditions of the process, the polyesters of diol and adipoyl or sebacoyl chlorides were chosen as a model system. Yield for all reaction products and reduced viscosity were found. The following factors were studied: organic phase, contribution of catalyst, concentration and molar ratio of reagents, rate of addition of acid chloride, temperature of reaction and concentration of hydrochloride acceptor. The structure of all polyesters was determined by means of elementary analysis, infrared spectra, and X-ray. Initial decomposition and initial intensive decomposition temperatures were defined by the curves of thermogravimetric analysis. Thermal and electrical properties of polyesters from diol and adipoyl or sebacoyl chlorides were studied. The molecular weights for these polymers were also determined by gel chromatography.     

1,3,5-三(4-羟基苯基)苯的合成

以对甲氧基苯乙酮 (Ⅰ )为原料 ,四氯化硅 (TCS)为催化剂 ,按n(Ⅰ )∶n(TCS) =4 3∶10的量比 ,在绝对乙醇中经缩合反应制得 1,3 ,5 三 ( 4 甲氧基苯基 )苯 (Ⅱ ) ,产率为 72 % ,以此为中间体与三溴化硼按n(Ⅱ )∶n(BBr3) =1∶4的量比在无水二氯甲烷中经脱甲基反应合成了 1,3,5 三 ( 4 羟基苯基 )苯 (Ⅲ ) ,产率为 81%。     

1,1-二(4-羟基苯基)环辛烷的合成

以环辛酮和苯酚为原料,β-巯基丙酸为助催化剂,通人干燥的氯化氢气体在常温常压下反应制得标题化合物,其结构经红外、核磁共振氢谱和质谱确认正确.研究表明:氯化氢气体催化效果明显好于其他酸催化剂,硫醇/酚类化合物是有效的助催化剂,加热对反应不利.最佳反应条件为:n(环辛酮)∶n(苯酚)∶n(β-巯基丙酸)=1∶5∶0.1,干燥氯化氢气氛,无溶剂条件下,室温常压反应5d,产率81.0％.     

Thermoplastic vulcanizates based on epoxidized natural rubber/polypropylene blends: Effect of compatibilizers and reactive blending

Epoxidized natural rubber (ENR) was prepared using the performic epoxidation method. TPVs based on ENR/PP blends were later prepared by melt‐mixing processes via dynamic vulcanization. The effects of blend ratios of ENR/PP, types of compatibilizers, and reactive blending were investigated. Phenolic modified polypropylene (Ph‐PP) and graft copolymer of maleic anhydride on polypropylene molecules (PP‐g‐MA) were prepared and used as blend compatibilizers and reactive blending components of ENR/Ph‐PP and ENR/PP‐g‐MA blends. It was found that the mixing torque, apparent shear stress and apparent shear viscosity increased with increasing levels of ENR. This is attributed to the higher viscosity of the pure ENR than that of the pure PP. Furthermore, there was a higher compatibilizing effect because of the chemical interaction between the polar groups in ENR and PP‐g‐MA or Ph‐PP. Mixing torque, shear flow properties (i.e., shear stress and shear viscosity) and mechanical properties (i.e., tensile strength, elongation at break, and hardness) of the TPVs prepared by reactive blending of ENR/Ph‐PP and ENR/PP‐g‐MA were lower than that of the samples without a compatibilizer. However, the TPVs prepared using Ph‐PP and PP‐g‐MA as compatibilizers exhibited higher values. We observed that the TPVs prepared from ENR/PP with Ph‐PP as a compatibilizer gave the highest rheological and mechanical properties, while the reactive blending of ENR/PP exhibited the lowest values. Trend of the properties corresponds to the morphology of the TPVs. That is, the TPV with Ph‐PP as a blend compatibilizer showed the smallest rubber particles dispersed in the PP matrix, while the reactive blending of ENR/PP‐g‐MA showed the largest particles. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 4729–4740, 2006     

Free Radical Copolymerization of Methyl Methacrylate and Styrene with N-(4-Carboxyphenyl)maleimide

The free radical copolymerization of methyl methacrylate (MMA) or styrene (St) with N-(4-carboxyphenyl)maleimide (CPMI) was carried with AIBN as an initiator in THF solvent at 80°C. A series of copolymers of MMA and St with CPMI were prepared using different feed ratios of comonomers. The values of monomer reactivity ratios (r₁, r₂) determined by Fineman-Ross and Kelen-Tudos methods are 0.26 and 2.51 in the CPMI/MMA system and 0.08 and 0.22 in the CPMI/St system. Alfrey–Price Q-e values for CPMI were calculated as Q = 1.05 and e = 0.41 in the CPMI/MMA system and Q = 1.21 and e = 0.91 in the CPMI/St system. The polymer samples have been characterized by solubility tests, intrinsic viscosity measurements, FT-IR and ¹H-NMR spectral analysis, and thermo-gravimetric analysis. It was found that the initial and final decomposition temperatures increased with increasing the amount of CPMI in the copolymer. The integral procedural decomposition temperature and energy of activation of thermal degradation have also been reported.     

双酚芴的合成及应用进展研究

简要概述了双酚芴的合成方法,依据所使用催化剂的不同可分为硫酸法,氯化氢法和巯基磺酸法,同时对双酚芴的应用进行了较全面地论述。     

Synthesis and characterization of poly-(methyl methacrylate-co-N-4-bromophenyl maleimide)

Radical copolymerization of methyl methacrylate (MMA, M1) and N-(4-bromophenyl) maleimide (N4BrPhMI, M2) in dioxane at 60 °C was performed with AIBN as initiator. Analysis of composition data points was carried out to a terminal model copolymerization. Using 1H, 13C and DEPT NMR measurements, the observed resonances were assigned. Glass transition temperatures were determined by DSC and a linear correlation was found between the Tg values and M2 content of the copolymers.     

磷钨酸催化合成侧链双酚-3,3-双(4-羟基苯基)丙烯的研究

以磷钨杂多酸为催化剂,巯基乙酸为助催化剂,苯酚和丙烯醛为原料,催化合成了3,3-双(4-羟基苯基)丙烯,研究了磷钨杂多酸和巯基乙酸的用量、苯酚与丙烯醛摩尔比、反应温度及反应时间对侧链双酚的收率的影响,得出反应的最佳条件为n(酚)n(醛)=71,反应温度为55℃,磷钨杂多酸质量分数0.5%巯基乙酸质量分数0.62%,反应时间为6h,收率达到53.0%,并通过傅里叶变换红外光谱和核磁共振分析了产物的结构.     

Preparation and properties of silicon-containing copolymers for near-UV resists,II. Poly[(N-(4-hydroxyphenyl)maleimide)-alt-(p-trimethylsilyl-α-methylstyrene)]

Poly[(N-(4-hydroxyphenyl)maleimide)-alt-(p-trimethylsilyl-α-methylstyrene)] (α-PHTMMS) and several N-(4-hydroxyphenyl)maleimide -alt-p-α-methylstyrene related copolymers were synthesized for novel positive near-UV resists containing diazonaphthoquinone sulfonate (DNS). The chain-stiffening effect of the maleimide group was responsible for high thermal resistance. Thus, a high glass transition temperature of 240°C and thermal decomposition temperature of 425°C were obtained. Lithographic positive images were obtained which resisted thermal deformation at 250°C. The prepared silicon-containing resists were also used as the top imaging layer of a bilayer resist for microlithographic application.     

1,1-双(4-羟基苯基)乙烷的制备及应用

介绍了以苯酚、乙醛,以苯酚、乙炔,和以苯酚、乙缩醛为原料制备1,1-双(4-羟基苯基)乙烷的方法,对比了各种方法的优缺点,指出以苯酚,乙缩醛为原料制备1,1-双(4-羟基苯基)乙烷的方法是适合工业化的生产方法。同时介绍了1,1-双(4-羟基苯基)乙烷的应用,指出了1,1-双(4-羟基苯基)乙烷工业化生产的必要性。