Synthesis and characterization of aniline-doped mixed copolymer resins. II

Copolymer resins were synthesized by the mixed condensation of resorcinol–CH₂O, resorcinol–aniline–CH₂O, resorcinol–aniline–thiourea–CH₂O, and resorcinol–aniline–urea–thiourea–CH₂O with a view to develop synthetic resins having improved properties and performance like toughness, mechanical properties, thermal resistance, chemical inertness, and adhesion. The resins were characterized by IR and TG analyses. The thermal analysis showed that the mixed copolymer resins have significantly better thermal stability than that of the simple phenol–CH₂O, aniline–CH₂O, urea–CH₂O, and thiourea–CH₂O resins. At 600°C, only a 50% weight loss is observed, and even at 800°C, the weight loss is about 70%. The resins are insoluble in most of the organic solvents including DMSO-d₆. They too are unaffected by diluted HNO₃, but dissolve in concentrated HNO₃. © 1996 John Wiley & Sons, Inc.     

Synthesis and characterization of some novel unsaturated polyester resins containing amide groups

Summary An ethylenically dibasic acid amide was prepared by reacting anthranilic acid with maleic anhydride and characterized by various methods. The unsaturated dibasic acid amide was used for preparing three novel unsaturated polyesters with ethylene glycol (EG), diethylene glycol (DG) and tetraethylene glycol (TG), respectively. The molecular weights of the prepared polyesters were determined by the end group analysis. These polyesters were diluted with styrene / acrylonitrile (AN) mixture to prepare curable resins with inhibited premature gelation. The effect of the structure of the resins on their curing behavior and mechanical properties has been investigated.     

Synthesis and characterization of novel dihydrobenzoxazine resins

Three dihydrobenzoxazines are synthesized from bisphenol A (BPA), 4,4′‐biphenol (BIP), and dicyclopentadiene phenol adduct (DCPD). Polydihydrobenzoxazine containing 4,4′‐biphenol (BIPDB) had the most rigid structure of the three and was found to possess the best mechanical and thermal properties. The glass transition temperature of BIPDB was 206°C, and that of BPA‐type polydihydrobenzoxazine (BPADB) and dicyclopentadiene type polydihydrobenzoxazine (DCPDDB) were 184 and 183°C, respectively. DCPDDB, with a rigid hydrophobic cycloaliphatic structure, was found to possess excellent properties such as low moisture absorption, low dielectric constant, low polarization. The resulted polymer from DCPDDB had a dielectric constant of 2.94U, which was better than that of polymers derived from BPA (3.31U), BIP (3.45U), and traditional phenolic resin (3.9–4.0U). © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 342–347, 2006     

一种新型聚降冰片烯类无规共聚物的合成与表征

降冰片烯衍生物的开环易位聚合具有反应条件温和、反应速率快及尺寸可控等优点,且因其独特的结构使得聚合物主链具有良好的热稳定性及耐酸碱性能。本文通过开环易位聚合法制备了降冰片烯基苯磺酰氯(NBSC)与5-降冰片烯-2,3-二羧酸二甲酯(DCNM)的新型二元无规共聚物。通过FT-IR、NMR表征了单体和共聚物的化学结构,并通过设计对比实验探究了最佳反应条件。GPC数据显示,当两单体配比1:1,催化剂用量为单体总物质的量1/450,反应时间30 min,反应温度40℃时,共聚物的相对分子质量最大,分子量分布较窄,产率最高,此条件为最佳反应条件。DSC表明,DCNM单体均聚物的T_g为60℃,与NBSC共聚后,T_g升高至80℃左右。TGA数据显示共聚物质量分解5%时对应的温度为145℃,最大分解速率时的温度为245℃,证明该聚合物具有良好的热稳定性。综合考虑其各项性能,这种新型的聚合物有望用于燃料电池质子交换膜领域的研究。     

Synthesis and characterization of some new chelating amphoteric ion-exchange resins

Some new chelating amphoteric ion exchange resins have been synthesized by condensing catechol, 8-hydroxyquinoline, hydroquinone, salicyclic acid, sulfosalicyclic acid, 3-hydroxy-2-naphthoic acid, p-hydroxybenzoic acid, β-resorcylic acid, and anthranilic acid with epichlorohydrin employing diethylenetriamine as a cross linking agent in a nonaqueous medium, toluene. These resins are characterized by their physicochemical properties such as moisture retention ability, true density, apparent density, void fraction, concentration of ionogenic groups, volume capacity, total ion exchange capacity, copper exchange capacity, rate of ion exchange, pH titration curves, apparent pK_a and pK_b values, isoionic point values, oxidative degradation, thermal stability, the effect of temperature of equilibration on the capacity of the resin, swelling behavior in various solvents, and absorption specificity towards certain bivalent metal cations in ammonium acetate–dimethylformamide media.     

抗冲共聚PP树脂的结构表征

采用红外光谱、核磁共振碳谱、差示扫描量热法、动态热机械分析以及扫描电子显微镜对抗冲共聚聚丙烯树脂SP179与进口专用基础树脂AW191进行了结构表征。结果表明：SP179和AW191的聚合工艺不同,但两者在分子链结构及相态结构上差异微小．因此它们的物理性能基本相近,都具有优异的抗冲击性能;由于助剂体系不同．两者的热性能表现出较大差异。     

Synthesis and characterization of resorcinol-cinnamaldehyde resins

The mechanisms and kinetics of the reaction between resorcinol and cinnamaldehyde were studied by means of ¹³C-NMR spectroscopy, HPLC, and GPC. In the first step the addition of resorcinol to the double bond and to the carbonyl group of cinnamaldehyde takes place. In the second step of reaction the lower molecular weight oligomers form compounds with groups with molecular weights between 1500 and 2500. The red coloured resin reacts at temperatures above 150°C with crosslinking agents to form an insoluble and highly crosslinked product.     

对苯二酚-果糖树脂的合成与表征

在碱性条件下,使用果糖代替甲醛与对苯二酚反应,成功地制备出环境友好型的对苯二酚-果糖树脂。利用红外、GPC、TGA等对所合成的树脂进行了表征。同时使用响应面优化法优化了反应条件,最优反应条件为:催化剂用量3.99%、反应温度69.97℃、反应时间9.03h、n果糖:n对苯二酚=9.29:1。最优条件时的黏度为222.808mPa?s,拉伸强度15.71～23.61MPa。     

氯乙烯-丙烯酸异辛酯共聚树脂的合成与表征

通过连续滴加预乳化丙烯酸异辛酯(EHA)单体,采用悬浮聚合方法合成了氯乙烯(VC)/EHA共聚树脂,对共聚树脂的颗粒特性、加工性能和力学性能等进行了研究。随着单体配比[m(EHA)∶m(VC)]的增加,共聚树脂颗粒的孔隙率、增塑剂吸收量和玻璃化温度降低,塑化时间和转矩缩短,加工性能逐渐变好,加工试片的硬度和拉伸强度降低,冲击强度略增大。     

乙烯-辛烯共聚物接枝苯乙烯-丙烯腈共聚物的合成及其表征

用苯乙烯(St)、丙烯腈(AN)2种单体和乙烯一辛烯共聚物(POE)进行溶液接枝共聚合反应,制备了乙烯-辛烯共聚物接枝苯乙烯-丙烯腈共聚物(POE-g-SAN),探讨了接枝共聚反应条件,并对POE-g-SAN进行了表征.结果表明,接枝共聚反应的接枝率(GR)和接枝效率(GE)均随着St/AN(质量比)的减小而稍有增大,当POE/St-AN(质量比)为50/50时,GR与GE达到最大值;增加BPO用量有利于接枝反应;当反应物POE与St-AN在甲苯中的质量分数为27.5%时,GR与GE达到最大值;在反应前10 h,随着反应时间的延长,GR增大,GE在4 h时达到最大值77.8%,在反应10 h后,接枝反应几乎不再进行;在POE与St-AN接枝共聚反应中,POE已接枝了SAN支链,且GR越大,SAN支链越多;POE-g-SAN有2个玻璃化转变温度(Tg),约为-50℃和110℃;随着GR的增大,POE-g-SAN中POE相的Tg升高,熔融温度和熔融热均降低;随着共单体中AN配比量的增加,POE-g-SAN中SAN相的Tg升高.     

Synthesis of some new cation-exchanger resins

Polystyrene–PEG crosslinked block copolymers were prepared from styrene copolymerization by either poly(ethylene glycol dimethymethacrylate) (PEG-DM) or macronomer initiators (MIM). M_w values of PEG of PEG-DM were 400, 600, 1000, 1500, 3000, 10,000, and 35,000, and of MIM, 400 and 1500. Swelling in H₂O or CHCl₃ of the sulfonated and unsulfonated block copolymers were determined under comparable conditions and found to be vary significantly. The ion-exchange capacity and selectivity coefficients of these ionexchange resins were investigated. The capacities of the obtained ion exchangers were varied between 0.4 and 2.9 meq/g. © 1996 John Wiley & Sons, Inc.     

官能化丁苯渐变嵌段共聚物树脂的合成与表征

采用溶液聚合法,以官能化偶联剂合成了带有HN-,HO-,HS-的官能化丁二烯-苯乙烯渐变嵌段共聚物.结果表明,该聚合物为单形态的三臂或四臂星形共聚物,具有良好的透光率和耐环境开裂性以及较好的耐氧化性、耐热性和表面粘接性,可应用于医疗器械、儿童玩具、食品容器等行业.     

Synthesis and characterization of the epoxyfumarate resins

The synthesis and properties of the new epoxyfumarate and epoxymaleate resins obtained by the addition of acidic allyl maleate to the commercially available resin Epidian 5 are presented. The resins were synthesized in one‐ and two‐step procedures and properties of the obtained resins are compared. It should be noted that the use of allyl alcohol in the synthesis of unsaturated resins has an advantageous influence on their properties. Glass‐transition temperatures of the epoxyfumarate resins exceed 100°C, whereas those of epoxymaleates are higher than 70°C. The resins are also characterized by good chemical resistance. © 2002 John Wiley & Sons, Inc. J Appl Polym Sci 84: 716–722, 2002; DOI 10.1002/app.10067     

Synthesis and characterization of MQ silicone resins

MQ silicone resins, which represent a broad range of hydrolytic condensation products of monofunctional silane (M) and tetrafunctional silane (Q), were synthesized by reaction of water glass with hexamethyldisiloxane. The optimum reaction time and the optimal reaction temperature is 30 min and 30–40°C, respectively. Concentrated hydrochloric acid is the best one among those catalysts tested. In large-scale experiments (420–1680 mL), the favorable feeding order is catalyst first, and then water glass, the mixture of hexamethyldisiloxane and ethanol last and most MQ silicone resin was observed. The structure of MQ silicone resin was characterized by FT-IR and GPC spectra. The MQ silicone resin shows narrow molecular weight distribution and the number average molecular weight of MQ silicone resin is 2917. The silicone pressure sensitive adhesive prepared from as-synthesized MQ resin has good tack (29#) and 180° peel adhesion (5.630N/20 mm). © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Synthesis and characterization of a PE-g-LCP copolymer

The possibility of reinforcing polyethylene (PE) by blending it with a liquid crystalline polymer (LCP) rests on the successful improvement of phase compatibility and interfacial adhesion of these two structurally unlike polymers. The approach that is being considered in our laboratories consists of the synthesis of PE–LCP block or graft copolymers and of their use as compatibilizing agents for PE/LCP blends. In this work, the melt polycon-densation of sebacic acid (S), 4,4′-dihydroxybiphenyl (B), and 4-hydroxybenzoic acid (H) has been carried out at temperatures up to 280°C in the presence of an oxidized low molar mass PE sample containing free carboxylic groups (PEox), with the main scope of demonstrating that a PE-g-LCP copolymer may be synthesized by this route. The polycon-densation product has been fractionated by successive extractions with boiling toluene and xylene. The soluble fractions and the residues have been characterized by IR and NMR spectroscopy, differential scanning calorimetry (DSC), thermogravimetric analysis (TG, DTG), and scanning electron microscopy (SEM). The extractions and the analyses have been repeated on a PEox/LCP blend prepared by melt mixing PEox and preformed LCP (SBH 112, by Eniricerche). The results show that, whereas for the blend a fairly clean separation of PEox and SBH can be obtained by solvent extraction, this is not so for the polycondensation product. All analytical procedures concordantly show that a PEox-g-SBH copolymer has, in fact, been obtained. In effect, both PEox and SBH chain segments are present, with different relative ratios, in all fractions of the polycondensate. Moreover, a fairly quantitative esterification of the PEox carboxyl groups has been shown by IR analysis to take place in the adopted conditions. Preliminary morphological investigations carried out by SEM have shown that the addition of the synthesized graft copolymer into HDPE/SBH blends leads to an improvement of the interfacial adhesion. © 1996 John Wiley & Sons, Inc.     

NVF-DADMAC阳离子共聚物的合成与表征

以N-乙烯基甲酰胺(NVF)和二甲基二烯丙基氯化铵(DADMAC)为原料,通过水溶液聚合法合成了NVF-DADMAC阳离子共聚物。用FTIR和DSC-TG对共聚产物进行了表征,用胶体滴定法测定了共聚物的阳离子度,考察了引发剂浓度、反应温度对聚合过程中转化率以及聚合物的阳离子度和特性粘数的影响。研究结果表明:NVF与DADMAC发生了共聚,且该共聚物的热稳定性比NVF的均聚物高,DADMAC的转化率可达90%以上。     

丙烯酸酯-富马酸酯共聚乳液的合成及表征

采用半连续乳液聚合方法,以甲基丙烯酸甲酯（MMA）、富马酸二丁酯（DBF）为主单体,丙烯酸（AA）为功能单体,十二烷基硫酸钠（SDS）为乳化剂,过硫酸钾（KPS）为引发剂,合成了固含量为30%的共聚物乳液。探讨了单体配比、SDS用量、KPS用量对乳液及胶膜性能的影响。结果表明,乳胶粒子有核壳结构,当DBF/MMA比例为1/1.5,SDS为单体总质量的3%,KPS为0.4%时,乳液涂料综合性能达到最佳,涂膜光泽度、附着力良好,力学性能及耐化学试剂性能优良。     

Synthesis and characterization of vinyl silane modified imidazole copolymer as a novel corrosion inhibitor

For a novel corrosion inhibitor for copper, the free radical copolymerization of vinyl imidazole (VI) and vinyl trimethoxy silane (VTS) was carried out in benzene at 68 °C using azobisisobutyronitrile (AIBN) as an initiator. The reactivity ratios of the two monomers were determined from instantaneous composition diagram: r _VI = 3.22 and r _VTS = 0. Thermal stability of poly(VI-co-VTS) depended on VTS mole fraction in the feed rather than the molecular weight of the copolymer, due to the disiloxane bond linkages formed during heating. Received: 21 October 1996/Revised: 9 December 1996/Accepted: 12 December 1996