特种氢化双酚A型环氧树脂合成研究

氢化双酚A和环氧氯丙烷在催化剂作用下开环反应生成了氯醇醚,而后加碱进行闭环反应,制备了低分子质量氢化双酚A型环氧树脂,再将其进一步与氢化双酚A等进行加聚反应,得到高分子质量环氧树脂。通过对产物的环氧值、力学性能和电性能的测试,研究了环氧氯丙烷用量、碱用量、环化反应温度、时间、溶剂及催化剂对合成反应的影响。结果表明,最佳反应条件为:环氧氯丙烷与醇羟基的物质的量比为3.0~3.5∶1,n(NaOH)∶n(醇羟基)=1∶1.1~1.2,环化反应温度25~30℃、时间4 h,甲苯为溶剂,催化剂为自制EH-10。所得氢化双酚A环氧树脂质量稳定,可替代进口。     

氢化双酚A型环氧树脂问世

烟台奥利福化工有限公司日前研制成功一种新型氢化双酚A型环氧树脂。这种以氢化双酚A和环氧氯丙烷为主要原料制备的耐候性环氧树脂包括AL-3040、AL-3020、AL-3010等牌号,用其配制的耐候环氧浇注料与进口耐候浇注料相比,断裂韧性强、热变形温度高,电气性能和其它力学性能相当。     

氢化双酚A型环氧树脂的生产及性能

氢化双酚A型环氧树脂,是一种综合性化工物质,具有黏着度低、污染低、融合度高等优势,在社会化工资源开发中发挥着重要作用。基于此,结合氢化双酚A型环氧树脂材料、应用方面的理论,着重对氢化双酚A型环氧树脂的生产及性能进行解析,以达到提升社会资源利用率,实现绿色发展的目的。     

双酚A型环氧树脂的合成

研究了环氧氯丙烷与双酚A在催化剂氢氧化钠的作用下合成双酚A型环氧树脂的方法。考察了环氧氯丙烷的纯度、氢氧化钠的质量、原料环氧氯丙烷与双酚A的配比等对产品色泽及可水解氯的影响,确定了双酚A型环氧树脂的优化工艺条件:n(双酚A)∶n(环氧氯丙烷)=5.0∶1.0,工艺简单易于生产。     

四氯双酚A环氧树脂合成的研究

作者应用两步加碱法,并由含适量双酚A的四氯双酚A(TCBA)与环氧氯丙烷合成具有良好阻燃性的四氯双酚A环氧树脂。经由探索性实验与正交实验提出了合成的优化反应条件。结果表明,按此新工艺合成路线得到的产品收率达90％,含氯量为36％,环氧值为0.30～0.33,节省环氧氯丙烷的用量。具有良好的重现性。     

连续法制备氢化双酚A

本研究以双酚A为原料,开展了固定床加氢连续制备氢化双酚A产品试验,结果表明:90～110℃、5.0 Mpa、0.5 h~(-1)、氢酚摩尔比10,双酚A残余量≤1.0 ppm,产品选择性≥98.0%;分离后氢化双酚A产品纯度≥98.5%,产品质量高于进口优等品,催化剂连续运行3000 h,活性稳定性未见明显变化。开展了工业放大试验,产品纯度稳定≥98.6%,吨级产品经下游多家客户试用,可完全替代国外高端氢化双酚A产品。     

氢化双酚A型环氧树脂的生产及性能

以氢化双酚A和环氧氯丙烷为主要原料,生产了耐候性环氧树脂AL 3040,AL 3020和AL 3010,并达到了一定规模的生产能力,通过对产品的分子质量分布和固化反应热流的测定测量,证明AL 3040的内在质量和固化特性与国外同类产品一致。用AL 3040配制成耐候环氧浇注料,与进口耐候浇注料相比,断裂韧性高,热变形温度高,电气性能和其他力学性能相当。用AL 3040配制的耐候性固化物,经国家电线电缆质量监督检验中心1000h日光老化实验,其耐候性能符合GB14049—1993标准。     

氢化双酚A型环氧树脂问世

烟台奥利福化工有限公司日前研制成功一种新型氧化双酚A型环氧树脂。这种以氰化双酚A和环氧氯丙烷为主要原料制备的耐候性环氧树脂包括AL-3040、AL-3020、AL-3010等牌号，用其配制的耐候环氧浇注料与进口耐候浇注料相比，断裂韧性强、热变形温度高，电气性能和其他力学性能相当。     

双酚A型环氧树脂合成技术进展

介绍了双酚A型环氧树脂的合成机理和工业生产方法,综述了一步法和两步法双酚A型环氧树脂（BADGE）合成技术的研究进展,一步法包括添加催化剂、固碱法、溶剂法、钠盐法、常减压共沸法,两步法包括两步法动力学、使用催化剂、降低水解氯,分析了其合成技术中存在的问题,提出了BADGE合成技术的未来发展方向。     

低分子量双酚A型环氧树脂的合成方法

介绍了用双酚A和环氧氯丙烷制造低分子量环氧树脂的各种合成工艺,并对各种方法的优缺点进行了分析比较。     

Preparation and curing kinetics of bisphenol A type novolac epoxy resins

A bisphenol A type novolac resin (Bis‐ANR) was synthesized from bisphenol A and formaldehyde; the resulting novolac was epoxidized to generate a bisphenol A type novolac epoxy resin (Bis‐ANER). The chemical structures of Bis‐ANR and Bis‐ANER were confirmed by ¹H‐NMR spectroscopy and IR spectroscopy; the molecular weights and molecular weight distributions were determined by gel permeation chromatography. In addition, the curing process of Bis‐ANER with 4,4′‐diaminodiphenyl sulfone was studied in both dynamic and isothermal modes with differential scanning calorimetry. The dynamic curing kinetic analysis was evaluated with both the Kissinger and Flynn–Wall–Ozawa methods, and the curing activation energy values were obtained. The isothermal curing reaction exhibited autocatalytic behavior, and the curing kinetics were described with the Kamal kinetics model, which accounted for both the autocatalytic and diffusion‐control effects. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 858–868, 2006     

E-51环氧树脂改性双酚A型氰酸酯树脂的研究

采用示差扫描量热法(DSC)、傅里叶变换红外光谱(FTIR)研究了E-51环氧树脂改性双酚A型氰酸酯树脂(BADCy)体系的反应活性、反应机理及固化工艺,通过TGA分析了不同含量E-51环氧树脂改性BADCy后固化物的热性能,并测定了体系的吸水率及力学性能。结果表明,随着E-51环氧树脂用量的增加,BADCy改性体系的反应活性逐渐提高,固化温度逐渐降低;用环氧树脂改性BADCy生成了恶唑烷酮等芳杂环结构,降低了氰酸酯树脂体系的三嗪环交联密度,增加了体系的韧性;改性后材料的起始热分解温度均在380℃以上,吸水率均低于2%。     

亲水性聚醚嵌段环氧树脂的合成及其工艺研究

采用PEG2000与环氧树脂E51以物质的量比为1:2制备了嵌段亲水性聚醚型环氧树脂,通过凝胶色谱和粘度测试研究了催化剂的添加量、催化剂的滴加速率对体系粘度的影响及分子质量分布与体系粘度的关系。结果表明,当体系粘度在800～1600mPa·s时,产物产率达90%以上。     

Synthesis of bisphenol a novolac epoxy resins for coating applications

Bisphenol A novolacs were synthesized in both melting and solution processes using p‐formaldehyde and formalin solution in presence of oxalic acid catalyst, respectively. Hydrogen nuclear magnetic resonance, ¹H NMR, investigations show a high methylene bridge contents in the novolacs synthesized in a melting process. These novolacs were analyzed by gel permation chromatography (GPC) and fourier transform infrared spectroscopy (FTIR). The bisphenol A novolac was cured with 1‐(2‐amino ethyl) piprazine (AEP) as a curing agent for epoxy resins. The cured resins were evaluated as organic coating for steel. The mechanical properties of the cured epoxy resins were evaluated. The chemical resistances of the cured resins were evaluated through salt spray resistance, hot water, solvents, acid and alkali resistance measurements. The data indicate that the cured epoxy resins have excellent chemical resistances as organic coatings among other cured resins. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

New bisphenol novolac epoxy resins for marine primer steel coating applications

Bisphenol derived from reaction of phenol with benzaldehyde was prepared in the presence of sulfuric acid as catalyst. Bisphenol novolacs were synthesized in both melting and solution processes using p-formaldehyde and formalin solution in the presence of oxalic acid catalyst. ¹H NMR analysis shows a high methylene bridge contents using the novolacs synthesized in a melting process. The bisphenol novolac epoxy resin was prepared by reaction with epichlorohydrine in the presence of sodium hydroxide as a catalyst. The prepared novolac epoxy resins were cured with 1,2-amino ethyl piperazine (AEP) as a curing agent. The cured resins were evaluated as organic coating for steel. The mechanical properties of the cured epoxy resins were evaluated by measuring both impact resistance and hardness. The chemical resistances of the cured resins were evaluated through salt spray resistance, hot water immersion, solvent resistance, acid and alkali resistance measurements. The data indicate that the cured epoxy resins have excellent chemical resistances as organic coatings among other cured resins.     

Synthesis of novolac on the basis of bisphenol A as curing agent for epoxy resins

Bisphenol A novolacs were synthesized in a melting process using paraformaldehyde, and in a solution process using a formalin solution and oxalic acid catalyst. ¹H-NMR investigations show a higher content of methylene bridges in the novolacs synthesized in a melting process. These novolacs were analysed by HPLC, GPC, DSC and FT-IR spectroscopy. The molecular masses were determined by vapour pressure osmometry. The results were shown to be related with the molar ratio of the components. The bisphenol A novolacs were used as curing agents for epoxy resins. There exists a dependence of the gel times on the content of methylene bridges; this dependence is influenced by temperature. The activation energy for gel formation is nearly the same in all curing reactions investigated. The networks synthesized were investigated by thermomechanical analysis.     

Degradable epoxy resins based on bisphenol A diglycidyl ether and silyl ether amine curing agents

A series of silyl ether amine curing agents were synthesized by selective substitution reactions of chloroalkylsilanes or the transetherification of alkoxysilanes. Crosslinked networks were prepared by mixing a stoichiometric ratio of bisphenol A diglycidyl ether (D.E.R 331) with the amine curing agents. The networks were characterized by ATR‐FTIR spectroscopy, TGA, DSC, and DMA. The onset of thermal degradation, glass transition temperatures, and storage moduli for the networks were 350 °C, 70–108 °C, and 5–25 MPa, respectively. The degradation behavior of the cured samples was monitored for 30 days in PBS, NaOH 5% (w/v), and HCl 5% (v/v) solutions and the degradation products were characterized by spectroscopic methods. The thermal, mechanical, and degradation studies indicated that crosslink density, T_g, storage modulus, and the rate of degradation were affected by the functionality of the amine curing agents and the number of hydrolyzable silyl ether bonds present per mole of curing agent. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44620.     

Epoxy resins VIII. Thermal properties of 4,4′-sulfonyldiphenol and bisphenol a epoxy resins

Epoxy resins of different molecular weights were prepared from epichlorohydrin and 4,4′-sulfonyldiphenol (SDP) and from epicholorohydrin and bisphenol A (BA). They were cured at high temperatures with four different crosslinking agents, including aliphatic and aromatic amines. The thermal behaviour of these cured epoxy resins was studied. From the IPDT and IDT data it was observed that sulfone epoxy resins were thermally more stable than bisphenol A epoxy resins. The activation energies of thermal degradation of the resins were calculated and the implications of these results are discussed.     

Polymerization of diglycidyl ether of bisphenol A/ diaminodiphenyl sulfone epoxy resins using radio frequency fields

Curing of diglycidyl ether of bisphenol A/diaminodiphenyl sulfone (DGEBA/DDS) epoxy resin has been effected by heating with radio frequency (RF) radiation at frequencies of 30–99 MHz. The epoxy resins can be cured rapidly at low RF power levels. Comparison of the kinetics of the RF curing with thermal curing while maintaining the same curing temperature revealed no differences. Previous differences in rates of thermal and microwave curing are believed to be due to lack of temperature control during microwave curing. For RF curing, the rate of cure, at constant power level, increases at lower RF frequency, thus emphasizing one of the principal advantages of RF curing over microwave curing. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 2917–2923, 1999