含二氮杂萘酮结构环氧树脂胶粘剂的研制

以双氰胺 (DCDA)为固化剂 ,以咪唑 (MZ)为固化促进剂 ,研制了一种含二氮杂萘酮结构的环氧树脂 (ER)胶粘剂 ,其成分为ER∶DCDA∶MZ∶SiO2 ∶Al=10 0∶7∶1∶3∶60 ,固化工艺为 12 0℃下固化 40min时 ,拉伸剪切强度为 17.8MPa ,有良好耐热性     

固化温度及填料对文物环氧胶粘剂性能的影响

研究了固化温度和填料对文物用双组分环氧胶粘剂力学性能的影响.红外分析表明,目前文物界普遍使用的国产3A万能胶,其主要组分为双酚A环氧树脂和脂肪胺/聚酰胺固化剂.以其作为研究对象,确定了适当的固化温度和填料用量,使环氧胶粘剂具有较好的操作性和粘接强度.     

水性环氧树脂/双氰胺体系的研究

多官能团酚醛环氧树脂F-51与适量二乙醇胺反应,制得一种分子中含环氧基和亲水基团的改性F-51环氧树脂,该树脂成盐后具有良好亲水性。以双氰胺为固化剂,对体系的反应性及固化物主要性能进行研究,结果表明固化反应起始温度显著降低,固化膜的硬度达6H,并具有很强的附着力。     

纳米TiO2对环氧树脂胶粘剂性能影响的研究

制备了纳米TiO2／环氧树脂胶，研究了不同制备方法和纳米TiO2含量对环氧树脂胶力学、热力学性能的影响，并采用扫描电镜时纳米TiO2粒子的增韧机理进行了分析，初步探讨了纳米TiO2／环氧树脂胶微波固化。研究结果表明：超声波与均质高速分散机结合使用，可使纳米TiO2粒子均匀分散于环氧树脂中。当纳米粒子TiO2质量分数为3％时，性能最佳。     

Effect of Xylene Formaldehyde Resins on Epoxy Resin Adhesive

The effect of some types of xylene formaldehyde on epoxy resin adhesive is studied. Xylene formaldehyde resin or modified xylene formaldehyde resins are mixed into liquid epoxy resin and curing properties of the blends, their adhesive properties and the dispersion state of xylene formaldehyde resin in cured adhesive film are examined. The results obtained are as follows.

1) Generally, by the addition of xylene formaldehyde resins, the degree of curing of blends are decreased, but pot life is prolonged, and tensile shear strength of steel bonds is increased.

2) It is observed that effects of the amount of xylene formaldehyde resins and curing condition on tensile shear strength vary with the kind of xylene formaldehyde resin, because of the difference in chemical structure of xylene formaldehyde resins and their reactivity to epoxy resin.

3) It is found that a limited region of compatibility, between 80 and 100 phr, exists for 100% xylene formaldehyde resin in epoxy resin. It is also found that joint strength is reduced with higher viscosity and molecular weight of 100% xylene formaldehyde resin in the case of 80 phr blends, and that these results have some relation to the dispersion state of xylene formaldehyde resin in epoxy resin, judging from the cured adhesive film observed under a phase contrast microscope.     

Thermally curable adhesive tapes with complex catalyst system for fabricating semiconductor packages

Thermal curing of adhesive films was investigated to facilitate the fabrication of a reliable bonding for semiconductors. The formulated adhesive films contained acrylic polymer, epoxy resins, phenol resin, and an imidazole derivative that was the catalyst for curing the epoxy resins with phenol resin. The solubility, thermally latent characteristics, mechanical and adhesive properties of 2‐methylimidazole/boron trifluoride (2MZ/BF3), and 2MZ/aluminum trisacetylacetonate (AlAC) were investigated. It was found that 2MZ/BF3 and 2MZ/AlAC had excellent solubility in adhesive materials and they had excellent latent characteristics as thermal curing catalysts for epoxy resins, whereas conventional catalysts (2MZ and 2‐phenyl‐4, 5‐dihydroxymethylimidazole (2PHZ)) could not achieve both excellent solubility and thermally latent characteristics. The mechanical and adhesive properties of the post‐thermal‐cured adhesive film that contained 2MZ/BF3 or 2MZ/AlAC were comparable to those of the post‐thermal‐cured adhesive films that contained conventional catalysts. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

新型环氧树脂胶粘剂的固化动力学研究

在不同升温速率下采用非等温差示扫描量热（DSC）技术对一种新型改性环氧树脂胶粘剂的固化反应过程进行了跟踪,并利用Kissinger、crane方程以及Arrhenius方程对该固化反应进行了动力学分析。结果表明,该固化反应的活化能为59.18kJ／mol,反应级数为0．89;结合Dsc谱图确定其固化工艺为130℃／1h＋150℃／2h＋175℃／3h。     

Adhesives and coatings based on poly(vinyl acetal)s

Phenolic resins such as resole phenol– and cresol–formaldehyde, as well as low-molecular-weight epoxy resin based on bis(4-hydroxy phenol) cyclohexane were prepared and modified with various types of the prepared poly(vinyl acetal)s. Poly(vinyl formal), poly(vinyl isobutyral), and poly(vinyl propional) were used. This study indicated that the optimum conditions for curing phenolic or epoxy resin–poly(vinyl acetal)s adhesive compositions are of an equal weight ratio or a 2 : 1 weight ratio in the presence of phthalic anhydride (10 or 20 wt %) of resin content as a curing agent at 150°C for 20 or 60 min, respectively. The effect of acetal type on the tensile shear strength values of resin samples, cured under the previously mentioned optimum conditions for different times, was investigated. The effect of structure of cresol–formaldehyde and epoxy resins was also studied. Metallic and glass coatings from the previous pure resins and their formulated mixtures were also prepared and evaluated as varnishes or paints. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 70: 1769–1777, 1998     

Study on reaction kinetics of epoxy resin cured by a modified dicyandiamide

To improve the disadvantage of the low reactivity and reduce the high curing temperature of epoxy resin cured by dicyandiamide (DICY), DICY is chemically modified with phenyl hydrazine and a new curing agent, LB‐A, is developed in this research. The structure, the curing behavior, and reaction kinetics of LB‐A curing epoxy resin are investigated. Results show that the DICY is modified successfully and the well‐defined structure of DICY is destroyed after modification. Consequently, a new curing agent in a noncrystal form is resulted. Thereupon, the reactivity and compatibility between the epoxy resin and the curing agent are improved appreciably using LB‐A instead of DICY. Meanwhile, the curing temperature and activation energy of the curing reaction decrease outstanding, whereas the rate constant increases remarkably. In addition, the compressive strength and the adhesive strength in shear by tension loading of the resulting epoxy resins have been increased using LB‐A instead of DICY as the curing agent. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

输油管线用熔结环氧粉末涂料的制备

采用线型酚醛环氧树脂(ENR)、环氧树脂E-12、固化剂JECP-02B制备了输油管线用熔结环氧粉末涂料。考察了线型酚醛环氧树脂与环氧树脂E-12质量比对涂料性能的影响,以及固化剂JECP-02B、流平剂GLP588和固化促进剂2-甲基咪唑对固化行为的影响,用红外光谱分析了固化前后树脂的变化,m(ENR)/m(E-12)=(75/25)~(25/75)、m(固化剂)/m(环氧树脂)=1/4、m(流平剂)/m(环氧树脂)=2/100、m(2-甲基咪唑)/m(环氧树脂)=(0.1~0.15)/100时,涂层性能达到输油管线防腐指标(SY/T 0315-97)。长庆化工有限责任公司用该技术扩大生产约10 t环氧粉末涂料,用于长庆油田输油管线的防腐,产品满足了1.5 m in/230℃快速固化的施工要求。     

室温固化抗剥离耐温环氧胶粘剂

研究了一种室温固化,可在１２０℃下使用的环氧树脂胶粘剂。通过ＣＴＢＮ增韧改性,获得了较高的剥离强度和剪切强度,通过加入高官能度环氧树脂和改性芳胺及催化剂,使得该体系具有一定的耐温性和可室温固化性。     

端脂肪氨基聚醚改性环氧树脂的性能研究

用自制的一种既含聚醚柔性链段又含苯脂肪氨基刚性链段的端脂肪氨基聚醚(APPEG)作为固化剂对环氧树脂进行增韧改性。扫描电子显微镜和力学性能测试结果表明,固化剂对环氧树脂具有明显的增强、增韧效果,且改性的环氧树脂胶粘剂具有很好的填充性能,填充比高达50%。与羰基铁粉组成的涂层材料具有优异的力学性能和热稳定性能。     

聚氨酯改性环氧胶粘剂的合成及性能研究

合成了具有反应活性的端环氧基聚氨酯,对其进行了初步的结构定性分析,并且研究了用端环氧基聚氨酯对环氧胶粘剂的改性,考查了端环氧基聚氨酯与环氧树脂的配比、填充料与树脂的配比、固化剂用量、固化温度等因素对胶粘剂强度的影响。该胶对黄铜粘接的剪切强度达30 MPa。     

Effect of a reactive interfacial agent on the properties of a nitrile-rubber-modified epoxy film adhesive

Reactive interfacial agents are often used to homogenise the morphology of immiscible polymer blends and to improve the level of adhesion between the phases to achieve enhanced properties. This paper demonstrates the ability of hydroxyl methyl bisphenol A (HMBPA) to function as a reactive interfacial agent (compartibilizer) in a nitrile-epoxy film adhesive made from nitrile rubber (NBR) and solid epoxy resin blend. The curing of the adhesive film was achieved at 170° C by adding dicyandiamide, a latent curing agent for epoxy resin, and rubber vulcanising agents. Hydroxyl methyl bisphenol A resins with different hydroxyl methyl content, synthesised by the base-catalysed reaction of bisphenol A and formaldehyde in various mole ratios, were used to compatibilize a blend of nitrile rubber (NBR) and epoxy resin 50/50wt/wt. The effect of addition of HMBPA on the morphology, adhesive, thermal, and mechanical properties of the adhesive film was investigated. The nitrile-epoxy adhesive films were characterised by measurements of adhesive joint strength, stress-strain properties, DSC, TGA, TMA, DMA, and SEM. Results revealed that significant improvement in joint strength occurred at low levels of HMBPA, and the optimum strength was obtained at about 15 wt% of HMBPA in the blend. The hydroxyl methyl content in HMBPA was found to influence the properties of the adhesive film. The concept of strengthening the interphase between NBR and epoxy through the coupling reactions of HMBPA was used for interpreting the results. The effect of addition of silica, alumina, and aluminium fillers on the properties of the nitrile-epoxy adhesive film was also studied, and a comparison of properties with and without HMBPA is presented.     

Ultraviolet/heat dual‐curable film adhesives with pendant‐acryloyl‐functional‐group‐modified epoxy resin

To facilitate the fabrication of a reliable semiconductor package, the UV/heat dual curing of film adhesives was investigated. The curing system of the epoxy resin affected the film adhesive properties. As the UV/heat dual‐curable epoxy resin, a modified o‐cresol novolak epoxy resin, in which half of the glycidyl groups were substituted by acryloyl groups (OCN‐AE), was applied to the film adhesive. The formulated film adhesive contained acrylic copolymer, OCN‐AE, phenolic aralkyl resin as a heat‐curing agent of the glycidyl groups, and 1‐hydroxycyclohexyl phenyl ketone as a photoinitiator of the acryloyl groups. The formulated reference film adhesive contained unmodified o‐cresol novolak epoxy resin (OCN‐E) in place of OCN‐AE. Formulated film adhesives containing a mixture of OCN‐E and o‐cresol novolak epoxy acrylate were also used as references. The morphology and the film adhesive properties were investigated. In these investigations, the film adhesive of OCN‐AE showed better adhesive properties, lower modulus, and a better stress‐relaxation ability than the referenced adhesives. As a result, a reliable film adhesive for semiconductor packages was successfully developed. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

聚氨酯改性环氧树脂的研究

为提高环氧树脂的韧性和粘接强度,采用自制端异氰酸酯聚氨酯预聚体对环氧树脂进行了改性,利用傅里叶变换红外光谱(FT-IR)对聚氨酯预聚体、改性环氧树脂的结构进行了表征。采用示差扫描量热法(DSC)对改性环氧树脂的固化行为进行了分析,并测试了改性环氧的力学性能。结果表明:聚氨酯预聚体与环氧树脂发生了接枝反应,n(NCO)/n(OH)=0.75时,改性环氧树脂/双氰胺/2-甲基咪唑组成的胶膜的剥离强度(液晶显示器(LCD)玻璃与柔性印刷线路板(FPC)界面)达到15.8 N/cm,粘接力良好。     

EFFECT OF A REACTIVE INTERFACIAL AGENT ON THE PROPERTIES OF A NITRILE-RUBBER-MODIFIED EPOXY FILM ADHESIVE

Reactive interfacial agents are often used to homogenise the morphology of immiscible polymer blends and to improve the level of adhesion between the phases to achieve enhanced properties. This paper demonstrates the ability of hydroxyl methyl bisphenol A (HMBPA) to function as a reactive interfacial agent (compartibilizer) in a nitrile-epoxy film adhesive made from nitrile rubber (NBR) and solid epoxy resin blend. The curing of the adhesive film was achieved at 170° C by adding dicyandiamide, a latent curing agent for epoxy resin, and rubber vulcanising agents. Hydroxyl methyl bisphenol A resins with different hydroxyl methyl content, synthesised by the base-catalysed reaction of bisphenol A and formaldehyde in various mole ratios, were used to compatibilize a blend of nitrile rubber (NBR) and epoxy resin 50/50wt/wt. The effect of addition of HMBPA on the morphology, adhesive, thermal, and mechanical properties of the adhesive film was investigated. The nitrile-epoxy adhesive films were characterised by measurements of adhesive joint strength, stress-strain properties, DSC, TGA, TMA, DMA, and SEM. Results revealed that significant improvement in joint strength occurred at low levels of HMBPA, and the optimum strength was obtained at about 15 wt% of HMBPA in the blend. The hydroxyl methyl content in HMBPA was found to influence the properties of the adhesive film. The concept of strengthening the interphase between NBR and epoxy through the coupling reactions of HMBPA was used for interpreting the results. The effect of addition of silica, alumina, and aluminium fillers on the properties of the nitrile-epoxy adhesive film was also studied, and a comparison of properties with and without HMBPA is presented.     

公路路面超薄石脂面层胶黏剂拉伸性能及影响机理

超薄石脂面层具有轻薄、抗滑、施工效率高等特性,在路面铺装中已得到广泛应用.通过配合比试验制备了用于公路路面超薄石脂面层铺装的胶黏剂,通过树脂浇铸体拉伸试验研究了不同种类、不同用量的增韧剂、稀释剂和固化剂对胶黏剂拉伸性能的影响,并通过SEM和FTIR试验,探讨了各添加剂对拉伸性能的影响机理.结果表明:超薄石脂面层胶黏剂中A组分(环氧树脂及改性剂)最佳配比为:环氧树脂E-51:环氧树脂E-44:增韧剂F1:稀释剂D1:阻燃剂=50:50:20:10:8,B组分(固化剂及改性剂)最佳配比为:固化剂H1:促进剂:偶联剂=70:10:2;随增韧剂或稀释剂含量的增加,试件抗拉强度先升高后降低,弹性模量持续降低,断裂伸长率则不断升高;胶黏剂固化物抗拉强度为21.83 MPa,拉伸弹性模量为0.47 GPa,断裂伸长率为38.24％;增韧剂中聚氨酯与环氧树脂相互缠绕、贯穿成网络结构,出现互穿包容效应,起到增韧作用,稀释剂通过降低胶黏剂的交联密度来增进延展性,固化剂中氨基与环氧基发生固化反应.     

粘接聚苯硫醚膜室温固化耐高温环氧胶黏剂

以环氧E-51和环氧TDE-85为主体树脂,三乙烯四胺和三乙醇胺为固化剂,并加入双马来酰亚胺(BMI)、液体端羧基丁腈橡胶(CTBN)等试剂,研制了用于粘接聚苯硫醚膜(PPS)与石油输送管道的室温固化耐高温环氧胶黏剂。通过TG、DSC和耐介质性测试,结果表明:所研制的胶黏剂具有较好的热稳定性和优良的耐油性,适用于石油管道这种高温的油性环境,有望在石油工业中得到应用。     

硅烷单体改性环氧树脂的固化及性能

分别用苯基三甲氧基硅烷(PTMS)和3-缩水甘油醚氧丙基三甲氧基硅烷(KH560)单体对环氧树脂进行了化学改性,通过红外(FT-IR)、核磁(1H NMR)对其化学结构进行了表征。以聚酰胺650为固化剂,用差示扫描量热仪(DSC)研究了固化物的固化动力学。此外还研究了涂膜的热失质量(TGA)、吸水率、附着力等性能。结果表明:苯基三甲氧基硅烷和3-缩水甘油醚氧丙基三甲氧基硅烷接枝上环氧树脂,与纯环氧树脂相比,改性后的树脂具有更好的热稳定性和更低的吸水率。改性环氧树脂固化后形成两面性质不同的涂层,与底材接触的涂层底面保留了环氧树脂原有的附着力,而涂层表面则具有高憎水性,起到防腐等作用。