大规模集成电路封装用联苯型环氧树脂合成工艺优化及结构表征

研究了联苯型环氧树脂(TMBP)的合成方法,通过正交实验法得到了联苯型环氧树脂合成的最佳工艺条件,即:相转移催化剂为18-冠-6-醚、反应温度为80℃、反应时间为8h、NaOH的用量为0.2mol,在此工艺条件下TMBP产率在83%左右。用1H NMR、FTIR对所制备的产物进行了结构表征,结果表明,合成产物为含联苯结构的环氧树脂。     

氧化法合成四甲基联苯二酚二缩水甘油醚的工艺研究

以3,3′,5,5′-四甲基联苯二酚(TMBP)为原料,通过溴代反应和氧化反应合成了3,3′,5,5′-四甲基联苯二酚二缩水甘油醚,采用红外和核磁对目标化合物结构进行了表征。考察了原料配比,碱盐种类及用量等因素对产物收率的影响,并通过正交实验的方法确定了其它因素的最佳值,经反复实验得出最佳工艺条件为n(碳酸钾)∶n(3-溴丙烯)∶n(TMBP)=2.5∶3∶1,溴代反应温度40℃,氧化反应温度30℃,氧化反应时间30h,n(间氯代过氧化苯甲酸)∶n(TMBP)=1.12∶1,产品产率和纯度分别可达85%和99%以上。     

3,3′,5,5′-四甲基联苯二酚二缩水甘油醚的合成与表征

以3,3′,5,5′-四甲基联苯二酚和环氧氯丙烷为原料两步法合成了3,3′,5,5′-四甲基联苯二酚二缩水甘油醚。探讨了催化剂体系、原料配比、碱用量对产物质量的影响,确定了最佳反应条件,最佳工艺条件为:n(TMBP)∶n(ECH)=1∶15;n(TMBP)∶n(NaOH)=1∶2.25,并用红外光谱对产物结构进行了表征,同时对产物分子质量、环氧值、有机氯含量、无机氯含量、熔点进行了测定。结果表明,它的分子质量为354,环氧值为0.54~0.57,有机氯<40 mg/100 g树脂、无机氯<20 mg/100 g树脂,熔程104~110℃。     

短切/连续碳纤维协同增强本征导热环氧树脂基复合材料研究

采用含有联苯介晶基元结构的3,3’,5,5’-四甲基联苯二酚二缩水甘油醚（TMBP）与含有芳香酰胺介晶基元结构的固化剂4,4-二氨基苯酰替苯胺（DABA）制备本征导热TMBP/DABA环氧树脂。结果表明,热导率高达0.33 W/（m·K）,比普通双酚A缩水甘油醚（DGEBA）/4,4’-二氨基二苯甲烷（DDM）环氧树脂的热导率高约50%,相应短切碳纤维（含量为75%,质量分数,下同）增强复合材料面外和面内热导率分别高约42.7%和40.2%。采用紫外臭氧氧化方法对短切碳纤维（SCF）和连续碳纤维（M55J）进行表面改性,发现能够明显改善纤维与基体树脂之间的界面结合强度,进而提高复合材料的导热性能。进一步采用SCF和M55J为增强纤维、本征导热TMBP/DABA环氧树脂为基体树脂制备出短切/连续碳纤维协同增强本征导热环氧树脂基复合材料SCF/M55J/TMBP/BADA。SCF的加入能够同时改善M55J/TMBP/DABA单向复合材料板沿X、Y、Z轴方向的热导率,分别最高达到98.07、48.23、9.40 W/（m·K）。为改善复合材料综合导热性能提供了一种新思路。     

含有联苯结构二缩水甘油醚型环氧树脂的合成与表征

研究并合成了一种含有联苯结构的环氧树脂 ,例如 ,采用二步法由 3,3′ ,5 ,5′—四甲基联苯二酚和环氧氯丙烷合成了 3,3′,5 ,5′—四甲基联苯二酚二缩水甘油醚。采用红外光谱、核磁共振氢谱和质谱对其结构进行了表征 ,同时用DSC和TG对其热性能进行了研究。结果表明 ,它在常温下为固体 ,Tm =10 2℃ ,熔程为 80～ 10 7℃ ,热失重 5 %时温度为 2 37℃ ,分子质量为 35 4 ,环氧值 0 5 6～ 0 5 9,是一种结晶性环氧树脂。在Tm以上、分解温度以下具有良好的流动性 ,可在 110～ 2 37℃间固化。     

溴化马来松香环氧树脂的制备及阻燃性

以马来松香和液溴为原料,合成了溴化马来松香;再与环氧氯丙烷发生酯化反应、闭环反应,合成了溴化马来松香环氧树脂。结果表明,在适宜的条件下,合成的环氧树脂的环氧值为0.30 mol·（100 g）^-1。 用红外光谱（FT-IR）、核磁共振谱（¹H NMR）和元素分析法对产物进行了表征。采用固化剂4,4′–二氨基二苯甲烷（DDM）对产物进行了固化。实验证明,溴化马来松香环氧树脂固化物具有较好的阻燃性。     

3′,4′,5′-三氟联苯-4-硼酸的合成及表征

使用工业上易得的原料通过3步反应合成标题化合物.苯硼酸与3,4,5-三氟溴苯作为起始原料,在K2CO3水溶液和甲苯体系中,Pd/C催化反应生成3,4,5-三氟联苯,产率80%.接着3,4,5-三氟联苯在CCl4中经过Fe+I2催化溴化得到4′-溴-3,4,5-三氟联苯,产率75%.4′-溴-3,4,5-三氟联苯与n-BuLi在-78 ℃下反应生成3′,4′,5′-三氟联苯-4-锂,然后与硼酸三正丁酯-78 ℃反应,最后在室温下酸性条件下水解生成目标产物,产率86%.合成路线的总收率达到51.6%.合成的化合物用元素分析、FT-IR、1HNMR和13CNMR等手段进行了表征.     

4-(6-氨基己氧基)-4′-氰基联苯的合成

以4-羟基-4′-氰基联苯(Ⅰ)为原料,在碳酸钾(水和乙醇作溶剂)溶液中与1,6-二溴己烷反应得到4-(6-溴己氧基)-4′-氰基联苯(Ⅱ),然后经过Gabriel反应、肼解反应制得4-(6-氨基己氧基)-4′-氰基联苯(Ⅳ)。与国外相似结构的合成工作相比,简化了反应步骤,且总收率由文献[2]的27.8%提高到55.2%。用IR、1HNMR和元素分析确证了目标产物的化学结构;经DSC测试,其液晶相转变温度为:Tm(熔点)83℃,Ti(清亮点)104℃。为了应用和贮存将其转变为相应的盐酸盐。     

4′-甲基2腈基联苯的合成

以邻氨基苯甲酸为起始原料,经重氮化、芳基化、取代和脱水等步骤合成药物中间体4′-甲基-2-腈基联苯.通过正交实验得到芳基化反应较佳条件为:10mol/L氢氧化钠15mL,甲苯30mL,反应温度5℃,反应时间5h,产物4′-甲基-2-联苯羧酸的产率为59.4%. 考察了脱水剂种类,脱水反应较佳的实验条件为氯化亚砜15mL,4′-甲基-2-联苯酰胺2.6g,反应8h,产物4′-甲基-2-腈基联苯的产率为67.7%.     

联苯类化合物4′-氯-2-硝基联苯的绿色合成新工艺与晶体结构

对4′-氯-2-硝基联苯的合成路线进行优化,以获得适合工业化生产的工艺路线。以对氯溴苯和邻溴硝基苯为原料,以Pd(dppf)Cl²为催化剂,依次经过格氏反应、Suzuki偶联两步反应合成4′-氯-2-硝基联苯。X-射线衍射测定了其晶体结构。在优化的反应条件下,4′-氯-2-硝基联苯的合成总收率≥82%,纯度98.8%;产物结构经IR、2为催化剂,依次经过格氏反应、Suzuki偶联两步反应合成4′-氯-2-硝基联苯。X-射线衍射测定了其晶体结构。在优化的反应条件下,4′-氯-2-硝基联苯的合成总收率≥82%,纯度98.8%;产物结构经IR、¹H NMR、MS确证。该工艺绿色环保,条件温和,适合工业化生产。     

Curing and Thermal Properties of PEPEB Liquid Crystalline Diepoxide/Aromatic Diamine

The liquid crystalline epoxy resin p-phenylene di[4-2-(2,3-epoxypropyl)ethoxy] benzoate (PEPEB) was synthesized. The curing behavior of the liquid crystalline epoxy resin (LCER) with 4,4-diaminodiphenylmethane (DDM) was studied by fourier transform infrared (FTIR), differential scanning calorimetry (DSC), and torsional braid analysis (TBA). Morphology of curing product was observed by polarized optical microscopy (POM) at different temperatures. Nonisothermal curing kinetics of this system were investigated by DSC. Results show that the PEPEB has a smectic liquid crystalline structure, and the melting point, T _m, is 119°C, the clearing point is 184°C. The cured-system's gel point, T _I , is 83.5°C; cure temperature, T _P , is 111.6°C; and the disposal temperature, T _f , is 145.8°C; activation energy of curing reaction is 4.84 KJ/mol. Observation by POM shows that with the upgrade of initial curing temperature, the filament structure of this system transferred from anisotropy to isotropy.     

一种侧链型液晶聚合物与环氧树脂共混改性研究

设计并合成了一种侧链型液晶聚合物（SLCP），用红外光谱（FTIR），差示扫描量热分析（DSC）和偏光显微镜（POM）对聚合物结构和液晶性能进行表征，探讨其对环氧树脂共混物力学性能的影响，并分析共混物的微相分离结构，结果表明，用T31作固化剂时SLCP对环氧树脂有较好的增强增韧效果，在强度和玻璃化温度不降低的情况下断裂伸长度比未改性固化物最大提高2．6倍，但用三乙醇胺作固化剂时SLCP对环氧树脂改性效果不明显。     

Reaction kinetics,thermal properties of tetramethyl biphenyl epoxy resin cured with aromatic diamine

Epoxy resins, 4, 4′‐diglycidyl (3, 3′, 5, 5′‐tetramethylbiphenyl) epoxy resin (TMBP) containing rigid rod structure as a class of high performance polymers has been researched. The investigation of cure kinetics of TMBP and diglycidyl ether of bisphenol‐A epoxy resin (DGEBA) cured with p‐phenylenediamine (PDA) was performed by differential scanning calorimeter using an isoconversional method with dynamic conditions. The effect of the molar ratios of TMBP to PDA on the cure reaction kinetics was studied. The results showed that the curing of epoxy resins contains different stages. The activation energy was dependent of the degree of conversion. At the early of curing stages, the activation energy showed the activation energy took as maximum value. The effects of rigid rod groups and molar ratios of TMBP to PDA for the thermal properties were investigated by the DSC, DMA and TGA. The cured 2/1 TMBP/PDA system with rigid rod groups and high crosslink density had shown highest T_g and thermal degradation temperature. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Effect of backbone moiety in epoxies on thermal conductivity of epoxy/alumina composite

We chose two commercial epoxies, bisphenol A diglycidyl ether (DGEBA) and 3,3′,5,5′‐tetramethyl‐4,4′‐biphenol diglycidyl ether (TMBP), and synthesized one liquid crystalline epoxy (LCE), 4′4′‐bis(4‐hydroxybenzylidene)‐diaminophenylene diglycidyl ether (LCE‐DP) to investigate the effect of backbone moiety in epoxies on the thermal conductivity of epoxy/alumina composite. The DGEBA structure shows an amorphous state and the TMBP structure displays a crystal phase, whereas the LCE‐DP structure exhibits a liquid crystalline phase. The curing behaviors of them were examined employing 4,4′‐diaminodiphenylsulfone (DDS) as a curing agent. The heat of curing of epoxy resin was measured with dynamic differential scanning calorimetry (DSC). Alumina (Al₂O₃) of commercial source was applied as an inorganic filler. Thermal conductivity was measured by laser flash method and compared with value predicted by two theoretical models, Lewis‐Nielsen and Agari‐Uno. The results indicated that the thermal conductivity of the LCE‐DP structure was larger than that of the commercial epoxy resins such as TMBP and DGEBA and the experimental data fitted quite well in the values estimated by Agari‐Uno model. POLYM. COMPOS., 2013. © 2013 Society of Plastics Engineers     

PET／60PABA 热致型液晶共聚酯的合成与表征

将对羟基苯甲酸（PHB）的乙酰化产物对乙酰氧基苯甲酸（PABA）引入聚酯（PET）分子主链结构中,成功制备出共聚酯 PET /60PABA,研究了聚合温度和催化剂浓度对共聚酯合成的影响。通过差示扫描量热（DSC）、X 射线衍射（XRD）、超导核磁共振（NMR）、凝胶渗透色谱（GPC）、偏光显微镜（POM）和毛细管流变仪等手段对共聚酯的分子结构与液晶形态进行表征,结果表明,共聚酯 PET /60PABA 几乎为完全无规共聚,熔融状态下具有向列型热致液晶聚合物的典型特征。     

Synthesis,characterization, and thermomechanical properties of liquid crystalline epoxy resin containing ketone mesogen

This study focuses on the synthesis of a novel liquid crystalline epoxy resin (LCER) based on ketone mesogenic group. The chemical structure, melting range, and liquid‐crystalline phase transition behavior of the LCER were characterized using Fourier transform infrared spectroscopy, nuclear magnetic resonance spectroscopy, mass spectroscopy, differential scanning calorimetry (DSC), and polarized optical microscopy (POM). Two endothermal peaks and one exothermal peak appeared in the DSC curves. A birefringent liquid crystalline texture was observed with POM during heating. The curing reaction of the LCER was monitored by DSC using diaminodipheylmethane (DDM) and diaminodiphenylsulfone (DDS) as curing agents, respectively. The results showed that the curing reaction of LCER/DDM proceeded faster than that of LCER/DDS in the initial stage. Birefringence was observed with POM during the curing processes. The results of thermomechanical properties showed that the glass transition temperatures of the cured LCERs were higher than 230°C, and that the LCER crosslinked networks were thermally stable up to 360°C. The LCER crosslinked networks showed much higher glass transition temperature, storage modulus, and thermal conductivity, and a lower coefficient of thermal expansion both in the glassy region and the rubbery region compared to those of a common epoxy resin (diglycidyl ether of bisphenol A). POLYM. ENG. SCI., 57:424–431, 2017. © 2016 Society of Plastics Engineers     

真空辅助RTM用环氧树脂成型工艺研究

对环氧树脂LT-5078体系进行了粘度-温度、粘度-时间测试,研究了其粘度特性,通过动态DSC法测定了树脂的固化反应热,并通过外推法得到其特征固化温度和成型工艺条件。实验表明,LT-5078的凝胶温度、固化温度、后处理温度分别为42℃、102℃、185℃,固化工艺为25℃×24 h+120℃×4 h。该树脂25℃时由初始粘度250 mPa.s上升到800 mPa.s所用时间为170 min左右,常温下有较长的低粘度时长,适合真空辅助RTM成型。     

Novel adamantane‐containing epoxy resin

A novel adamantane‐containing epoxy resin diglycidyl ether of bisphenol‐adamantane (DGEBAda) was successfully synthesized from 1,3‐bis(4‐hydroxyphenyl)adamantane by a one‐step method. The proposed structure of the epoxy resin was confirmed with Fourier transform infrared, ¹H‐NMR, gel permeation chromatography, and epoxy equivalent weight titration. The synthesized adamantane‐containing epoxy resin was cured with 4,4′‐diaminodiphenyl sulfone (DDS) and dicyandiamide (DICY). The thermal properties of the DDS‐cured epoxy were investigated with differential scanning calorimetry and thermogravimetric analysis (TGA). The dielectric properties of the DICY‐cured epoxy were determined from its dielectric spectrum. The obtained results were compared with those of commercially available diglycidyl ether of bisphenol A (DGEBA), a tetramethyl biphenol (TMBP)/epoxy system, and some other associated epoxy resins. According to the measured values, the glass‐transition temperature of the DGEBAda/DDS system (223°C) was higher than that of the DGEBA/DDS system and close to that of the TMBP/DDS system. TGA results showed that the DGEBAda/DDS system had a higher char yield (25.02%) and integral procedure decomposition temperature (850.7°C); however, the 5 wt % degradation temperature was lower than that of DDS‐cured DGEBA and TMBP. Moreover, DGEBAda/DDS had reduced moisture absorption and lower dielectric properties. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Thermal Properties and Crystallite Morphology of Nylon 66 Modified with a Novel Biphenyl Aromatic Liquid Crystalline Epoxy Resin

In order to improve the thermal properties of important engineering plastics, a novel kind of liquid crystalline epoxy resin (LCER), 3,3′,5,5′-Tetramethylbiphenyl-4,4′-diyl bis(4-(oxiran-2-ylmethoxy)benzoate) (M1) was introduced to blend with nylon 66 (M2) at high temperature. The effects of M1 on chemical modification and crystallite morphology of M2 were investigated by rheometry, thermo gravimetric analysis (TGA), dynamic differential scanning calorimetry (DSC) and polarized optical microscopy (POM). TGA results showed that the initial decomposition temperature of M2 increased by about 8 °C by adding 7% wt M1, indicating the improvement of thermal stability. DSC results illustrated that the melting point of composites decreased by 12 °C compared to M2 as the content of M1 increased, showing the improvement of processing property. POM measurements confirmed that dimension of nylon-66 spherulites and crystallization region decreased because of the addition of liquid crystalline epoxy M1.