萘环非共价改性石墨烯环氧纳米复合材料的制备及性能研究

翟宁辉，蔡喜庆，赵富贵，张军营，程  珏

（北京化工大学材料科学与工程学院，北京  100029）

【摘  要】探究了不同结构的分散液对石墨烯作用力的大小，并通过显微镜和拉曼光谱对石墨烯分散液进行了相关表征，发现2-羟基萘缩水甘油醚（2-NGE）与石墨烯之间具有最强的萘环π-π相互作用。然后在1,6-二羟基萘缩水甘油醚（1,6-DNGE）中引入2-NGE悬挂链，以4,4'-二氨基二苯甲烷（DDM）为固化剂，探究“内部抗塑化”作用和不同浓度的2-NGE石墨烯分散液对体系的影响。研究结果表明：1,6-DNGE/2-NGE-10%-G₅体系展现出了最优异的综合性能，与1,6-DNGE相比，拉伸强度、模量和冲击强度分别提高了12.74%、21.67%和55.74%。这些优异的性能是基于“内部抗塑化”体系的构建和石墨烯的良好分散性而共同实现的，证明了在极低石墨烯负载条件下（0.026 9%）实现了对高性能材料的高效利用。通过这种简便、实用的方法，实现了快速大规模制备高性能石墨烯环氧纳米复合材料。

【关键词】萘基环氧；石墨烯；内部抗塑化；萘环π-π相互作用

茂铁盐阳离子光引发剂在胶粘剂中的应用

罗逸骢¹，李治全^1,2，刘晓暄^1,2

（1.广东工业大学材料与能源学院，广东省功能软凝聚态物质重点实验室，广东广州 510006；2.化学与精细化工广东省试验室揭阳分中心，广东揭阳  522000）

【摘  要】以2种茂铁盐（I-261、I-262）作为阳离子光引发剂，成功在405 nm LED光源下实现了阳离子胶粘剂的固化。选择3种环氧类单体，即双酚A二缩水甘油醚（BADGE）、3,4-环氧环己基甲基-3,4环氧环己基甲酸酯（CE）、3,3’-[氧基双(亚甲基)]双(3-乙基氧杂环丁烷)（DOX），研究了它们在405 nm LED光源下的光固化动力学，并研究了不同阳离子光引发剂的光引发性能、茂铁盐对不同阳离子单体的引发效率、环氧树脂的热稳定性、阳离子光固化胶粘剂的拉伸剪切性能以及后固化时间对胶粘剂拉伸剪切强度的影响。研究结果表明：确定了茂铁盐作为可见光固化胶粘剂用光引发剂的实用性，在405 nm LED光源下的引发效率均强于碘鎓盐光引发剂I-250。以BADGE作为主要单体，研究了在添加不同含量的CE与DOX形成的光固化胶粘剂的拉伸剪切性能。发现在40%的添加量下，混入CE与DOX的胶粘剂比BADGE本体聚合而成的胶粘剂的拉伸剪切强度分别提高了2.19倍与1.38倍，并且后固化时间的增加能够大幅提升胶粘剂的拉伸剪切强度。本研究为可见光固化的阳离子胶粘剂提供了一种切实可行的方法。

【关键词】茂铁盐；可见光固化；阳离子胶粘剂；光固化动力学

含氟双氨基邻苯二甲腈树脂合成及性能研究

刘彩召，李帅杰，张  斌，孙明明，张绪刚，李坚辉

(黑龙江省科学院石油化学研究院，黑龙江哈尔滨  150040)

【摘  要】采用2,2-双(3-氨基-4-羟基苯基)六氟丙烷和4-硝基邻苯二甲腈为原料，通过亲核取代反应制备了一种含氟元素的双氨基邻苯二甲腈树脂(FPN-p)。通过傅里叶红外光谱(FT-IR)和核磁氢谱(¹H-NMR)对其化学结构进行表征，通过差示扫描量热法(DSC)和FT-IR考察了树脂的固化行为，并研究了树脂的热稳定性、热机械性能以及耐湿热性能。研究结果表明：FPN-p树脂在不加促进剂的情况下可实现自催化聚合，产物结构以三嗪环和酞菁环为主；树脂的玻璃化转变温度和质量分数5%热分解温度均超过400 ℃，耐温等级较高；树脂的耐湿热性能良好，高温水煮168 h后吸水率小于1%。该树脂有望用于耐高温涂层、树脂基复合材料以及高性能胶粘剂等领域。

【关键词】双氨基；邻苯二甲腈；树脂；热性能；吸水率

农业机械维修用环氧树脂胶粘剂的研制

王东霖，李守忠

(中国农业大学工学院，北京  100083)

【摘  要】以端氨基液体丁腈橡胶(ATBN)和表面硅烷偶联化处理的铝粉为改性剂，制备了用于农业机械快速修复的环氧树脂胶粘剂。考察了铝粉用量、ATBN用量对胶粘剂粘接性能的影响。研究结果表明：环氧树脂胶粘剂的适用期随着铝粉的增多不断延长，随着铝粉用量或ATBN用量的不断增加，胶粘剂对铝合金的粘接强度呈现先升高后降低的趋势。当改性铝粉和ATBN用量分别为20和15份(相对于环氧树脂质量100份而言)时，环氧树脂胶粘剂的综合性能相对较好，其适用期为37 min，拉伸剪切强度和浮辊剥离强度分别为29.5 MPa和5.4 kN/m。该胶粘剂具有优异的耐介质性能和耐热性能，不仅可用于农业机械的日常维修保养，还可用于其他领域多种金属材料和非金属材料的结构粘接。

【关键词】环氧树脂；胶粘剂；室温固化；农业机械；维修

耐溶剂乳液型丙烯酸酯压敏胶的制备与性能研究

（浙江理工大学，浙江杭州  310020）

【摘  要】采用环氧树脂和丙烯酸酯类单体为原料，通过种子乳液聚合法制备了丙烯酸酯压敏胶。研究探讨了硬单体种类及含量、软单体配比、功能单体含量、引发剂含量、种子乳液含量等因素对压敏胶粘接性能的影响。研究结果表明：8种硬单体中，环氧树脂E-20的性能相对最优；当其添加量为质量分数2.5%（相对于总质量而言），软单体为丙烯酸异辛酯（2-EHA）且质量分数为35%，功能单体β-丙烯酰氧基丙酸（β-CEA）质量分数为10%，引发剂质量分数为0.5%，种子乳液质量分数为5%，缓冲剂质量分数为0.5%时，制备出的压敏胶性能较优，剥离强度为15.10 N/25 mm，持粘性大于48 h，耐溶剂性优异。

【关键词】丙烯酸酯；压敏胶；乳液聚合

Zhai Ninghui, Cai Xiqing, ZhaoFugui, Zhang Junying, Cheng Jue

(College of Materials Science and Engineering, Beijing University of Chemical Technology, Beijing 100029, China)

【Abstract】The force of dispersion with different structures on graphene was investigated, and the graphene dispersion was characterized by microscope and Raman spectroscopy. It was found that 2-hydroxynaphthalene glycidyl ether (2-NGE)  had the strongest naphthalene ring π-π interaction with graphene. Then, 2-NGE suspension chain was introduced into 1,6-dihydroxynaphthalene glycidyl ether (1,6-DNGE), and 4,4'-diaminodiphenylmethane (DDM) was used as curing agent, the effect of "internal anti-plasticization" and the effect of 2-NGE graphene dispersion with different concentrations on the system were investigated. The research results showed that 1,6-DNGE/2-NGE-10%-G₅ system exhibited the best comprehensive performance. Compared with 1,6-DNGE, the tensile strength, modulus and impact strength increased by 12.74%, 21.67% and 55.74%, respectively. These excellent properties were achieved based on the construction of the "internal anti-plasticization" system and the good dispersion of graphene, demonstrating that the efficient utilization of high-performance materials was realized under the condition of extremely low graphene loading (0.026 9%). Through this simple and practical method, the rapid and large-scale preparation of high performance graphene epoxy nanocomposites was achieved.

【Keywords】naphthyl epoxy; graphene; internal anti-plasticization; π-π interaction of naphthalene ring

Application of ferrocenium salt as cationic photoinitiator in adhesive

Luo Yicong¹, Li Zhiquan^1,2, Liu Xiaoxuan^1,2

（1.Guangdong Provincial Key Laboratory of Functional Soft Condensed Matter, School of Materials and Energy, Guangdong University of Technology, Guangzhou  510006, Guangdong, China; 2.Guangdong Laboratory of Chemistry and Fine Chemical Industry Jieyang Center, Jieyang  522000, Guangdong, China)

【Abstract】Two types of ferrocenium salt (I-261 and I-262) were used as cationic photoinitiators, the cationic adhesive was successfully cured under 405 nm LED light source. Three types of epoxy monomers were selected, namely bisphenol-A diglycidyl ether (BADGE), 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate (CE), 3,3’-[Oxybis(methylene)]bis(3-ethyloxetane) (DOX), their photo curing kinetics were studied under 405 nm LED light source. The photoinitiation properties of different cationic photoinitiators, the initiation efficiency of ferrocenium salt on different cationic monomers, the thermal stability of epoxy resin, the tensile shear properties of cationic light-curing adhesive and the effects of post-curing time on tensile shear strength of adhesive were also investigated. The research results showed that the practicality of ferrocenium salts as photoinitiator for visible light curing adhesive was determined, their initiation efficiency was stronger than that of iodonium salt photoinitiator I-250 under 405 nm LED light source. Using BADGE as the main monomer, the tensile shear properties of photo curing adhesive formed by adding different contents of CE and DOX were studied. It was found that with the adding amount of 40%, the tensile shear strength of the adhesive mixed with CE and DOX was 2.19 times and 1.38 times respectively higher than that of the adhesive polymerized by BADGE, and the tensile shear strength of the adhesive could be significantly improved with the increase of post-curing time. This study provided a practical method for visible light curable cationic adhesive.

【Keywords】ferrocenium salt; visible light curable; cationic adhesive; photo curing kinetics

Synthesis and properties of fluorine-containing diaminophthalonitrile resin

Liu Caizhao, Li Shuaijie, Zhang Bin, Sun Mingming, Zhang Xugang, Li Jianhui

(Institute of Petrochemistry Heilongjiang Academy of Sciences, Harbin 150040, Heilongjiang, China)

【Abstract】A kind of fluorine-containing diaminophthalonitrile resin (FPN-p) was prepared by nucleophilic substitution reaction using 2,2-bis(3-amino-4-hydroxyphenyl) hexafluoropropane and 4-nitrophthalonitrile as raw materials. Its chemical structure was characterized by Fourier infrared spectroscopy (FT-IR) and nuclear magnetic resonance spectroscopy (¹H-NMR), the curing behavior of the resin was investigated by differential scanning calorimetry (DSC) and FT-IR, and the thermal stability, thermal mechanical properties and moisture heat resistance of the resin were also studied. The research results showed that FPN-p resin could realize autocatalytic polymerization without accelerator, and the product structure was mainly composed of triazine ring and phthalocyanine ring. The glass transition temperature and thermal decomposition temperature with 5% mass fraction of the resin both exceeded 400 ℃, indicating a high temperature resistance level. The resin had good moisture heat resistance, the water absorption rate was less than 1% after 168 hours of high-temperature water boiling. The resin was expected to be used in fields such as high-temperature resistance coatings, resin based composites, and high performance adhesive.

【Keywords】diamino group; phthalonitrile; resin; thermal property;water absorption rate

Development of epoxy resin adhesive for agricultural machinery maintenance

Wang Donglin, Li Shouzhong

(College of Engineering, China Agricultural University, Beijing 100083, China)

【Abstract】With amino-terminated liquid acrylonitrile-butadiene rubber (ATBN) and silane coupling-treated aluminum powder as modifiers, epoxy resin adhesive for quick repair of agricultural machinery was prepared. The effects of aluminum powder and ATBN dosage on the bonding properties of adhesive were investigated. The research results showed that the pot life of epoxy resin adhesive was prolonged with the increase of aluminum powder using amount. With the continuous increase of aluminum powder dosage or ATBN dosage, the bonding strength of adhesive on aluminum alloy was increased first and then decreased. When the using amount of aluminum powder and ATBN was 20 and 15 phr respectively (relative to the mass of 100 phr epoxy resin), the comprehensive performance of epoxy resin adhesive was relatively good, its pot life was 37 min, tensile shear strength and floating roll peel strength were 29.5 MPa and 5.4 kN/m respectively. The adhesive had excellent medium resistance and heat resistance, which could be used not only for daily maintenance of agricultural machinery, but also for structural bonding of various metallic and non-metallic materials in other fields.

【Keywords】epoxy resin; adhesive; room temperature curing; agricultural machinery; maintenance

Preparation and properties of solvent-resistance emulsion-type acrylate pressure sensitive adhesive

Chen Jie, Pei Kemei

(Zhejiang Sci-Tech University, Hangzhou 310020, Zhejiang, China)

【Abstract】Acrylate pressure sensitive adhesive was prepared by seed emulsion polymerization using epoxy resin and acrylate monomer as raw materials. The effects of hard monomer type and content, soft monomer ratio, functional monomer content, initiator content and seed emulsion content on the bonding properties of pressure sensitive adhesive were studied. The research results showed that among 8 types of hard monomer, the performance of epoxy resin E-20 was relatively optimal. When its addition amount was 2.5% by mass (relative to the total mass), the soft monomer was 2-ethylhexyl acrylate (2-EHA) and the mass fraction was 35%, the mass fraction of functional monomer b-carboxyethyl acrylate (β-CEA) was 10%, the mass fraction of initiator was 0.5%, the mass fraction of seed emulsion was 5%, and the mass fraction of buffer agent was 0.5%, the prepared pressure sensitive adhesive had good performance, the peel strength was 15.10 N/25 mm, the holding power was greater than 48 h, and the solvent resistance was excellent.

【Keywords】acrylate; pressure sensitive adhesive; emulsion polymerization

Study on reinforcement performance of modified epoxy resin adhesive in underground steel frame structure of building

Zhao Hongmei, Zhang Shipin

(China Nuclear Industry Huawei Engineering Design and Research Co., Ltd., Nanjing 210000, Jiangsu, China)

【Abstract】The composite epoxy resin adhesive for building reinforcement was prepared with epoxy resin, curing compound, accelerator, filler and coupling agent as main preparation materials, mixed with different kinds or contents of them, and modified by self-made graphene oxide. 45# steel sheet specimen was prepared, and the mechanical indexes, gel time and other indexes of the specimen coated with adhesive were tested respectively, and the reinforcement effect of epoxy resin adhesive with different proportions in the underground steel frame structure of building was analyzed. The research results showed that the tensile, flexural and compressive strength of epoxy resin adhesive could be improved by selecting E-51 as main resin, and the tensile resistance of epoxy resin adhesive was the best when it was mixed with curing agent at the mass ratio of 75∶100. The mechanical properties of epoxy resin adhesive could be improved effectively when the mass addition amounts of curing agent, accelerator and filler were 30%, 4% and 80% respectively, and KH-570 was used as coupling agent. After adding 2.0% graphene oxide, the tensile strength and elongation at break of composite epoxy resin adhesive reached the maximum. In the humid environment, the composite epoxy resin adhesive could be fully cured after about 65 hours, and the shear bonding strength was stable at 20 MPa.

【Keywords】epoxy resin adhesive; steel frame; reinforcement effect; graphene oxide; tensile resistance; shear bonding strength

Application of waterproof concrete in crack filling of tunnel secondary lining

Song Jianing, Zeng Qingwei, Wang Andong

(Shaanxi Railway Institute, Weinan 714000, Shaanxi, China)

【Abstract】Waterproof concrete samples were prepared by mixing cement, fly ash and waterproof agent in a certain ratio. The application effect of waterproof concrete in crack filling of tunnel secondary lining was tested,and various properties such as impermeability and crack resistance of waterproof concrete in crack filling of tunnel secondary lining were studied. At the same time, the microstructure of building materials in crack filling of tunnel secondary lining before and after drying was observed. The research results showed that in the application of crack filling of tunnel secondary lining, fly ash helped to increase the impermeability of concrete, and an excess replacement ratio between 15% and 25% was suitable. When the water cement ratio was high, adding an appropriate type of waterproof agent could improve the impermeability performance. When the water cement ratio was low, there was no need to add waterproof agent to the concrete. Under the same replacement ratio of fly ash, concrete with excessive replacement had good resistance to chloride ion diffusion. Fly ash could avoid early cracking of concrete, and concrete with different fly ash ratios had the characteristics of later cracking time and narrower crack width. The microstructure of the concrete added with fly ash exhibited dense fine needle bar ettringite crystals, the concrete had strong tensile strength after the drying test.

【Keywords】fly ash; concrete; waterproof agent; crack filling; water pressure impermeability; secondary lining; crack resistance

Simultaneous determination of multiple compounds in water-based adhesive

Yang Fei¹, Zhou Yun², Zhang Yupu³, Ju Huabo⁴, Yan Jun², Meng Dongling²,Deng Huimin¹, Tang Gangling¹, Chen Zhiyan¹

（1. China National Tobacco Quality Supervision & Test Center, Zhengzhou  450001, Henan, China; 2. China Tobacco Guangxi Industrial Co., Ltd., Nanning  530001, Guangxi, China; 3. Jilin Tobacco Quality Supervision & Test Station, Changchun  130062, Jilin, China; 5. Northwest Tobacco Quality Supervision & Test Station, Lanzhou  730030, Gansu, China)

【Abstract】A method was developed for the simultaneous determination of isothiazolinone fungicides and environmental hormones such as bisphenol A, nonylphenol, octylphenol and phthalate in water-based adhesive. After methanol extraction, the sample was directly analyzed by ultra-high performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) and quantified by isotope internal standard method. The research results showed that all compounds showed good linearity (R²≥0.998 3) within the concentration range of 20~500 ng/mL, and the limit of detection (LOD) and limit of quantification (LOQ) were in the range of 0.009~0.115 mg/kg and 0.029~0.382 mg/kg, respectively. At different concentration levels, the recovery rates of all analytes were in the range of 84.1% to 105.6%, the daytime relative standard deviation (RSD) was less than 8.0%. Sixty actual samples were tested, all samples detected isothiazolinone fungicides, and one sample each detected nonylphenol and dibutyl phthalate. This method had high detection efficiency and saved detection costs, especially suitable for routine detection of large batches of samples in the laboratory.

【Keywords】water-based adhesive; ultra-high performance liquid chromatography-tandem mass spectrometry; bisphenol A; alkylphenol; phthalate; isothiazolinone

Influence of weathering test on infrared spectrum of insulating glass sealants

Wang Longmei, Yao Yongxin, Zhou Lei, Huang Xinhang

(Shanghai Institute of Quality Inspection and Technical Research, Shanghai 201114, China)

【Abstract】The weathering test of insulating glass sealants was carried out under four conditions of high humidity, high and low temperature, climate and ultraviolet radiation. The attenuated total reflection (ATR) method was used to test the infrared spectrum of sealants before and after weathering test, the effects of different test conditions on the infrared spectrum of silicone sealant, polysulfide sealant and polyurethane sealant for insulating glass were analyzed. The research results showed that the position of infrared spectrum absorption peak of insulating glass sealants had no obvious change after four kinds of weathering test. After the high humidity test, the intensity of infrared absorption peak decreased, with silicone sealant showing the most significant decrease. After the high and low temperature test, the infrared spectrum remained basically unchanged. After the climate test and ultraviolet irradiation test, the infrared spectrum of silicone sealant did not change, the intensity of the main absorption peaks of polysulfide sealant decreased significantly, and the intensity of other absorption peaks of polyurethane sealant increased except for the decrease of intensity of the absorption peak near 1 407 cm^-1. The change of infrared spectrum of sealants after weathering test showed that three sealants had excellent high and low temperature resistance, among which silicone sealant had the worst moisture resistance and polyurethane sealant had the best, meanwhile silicone sealant had the best UV radiation resistance and polysulfide sealant had the worst.

【Keywords】weathering test; silicone sealant; polysulfide sealant; polyurethane sealant; infrared spectrum

Study on preparation  and properties of dealcoholized photovoltaic module sealant

Wen Renguang, Chu Saixia

（Shenzhen SISUN Silicone Technology Co., Ltd., Shenzhen    518107, Guangdong, China）

【Abstract】Using a,w-dihydroxypolydimethylsiloxane, dimethylpolysiloxane, reinforcing filler, thixotropic agent, coupling agent and catalyst as raw materials, adding self-made multifunctional telechelic oligosiloxane crosslinking agent and modified siloxane tackifier, a kind of dealcoholized silicone sealant suitable for durable bonding of photovoltaic module was prepared. Different types, structures and using amounts of tackifier and crosslinking agent on the properties of dealcoholized silicone sealant were studied. The research results showed that when the mass fraction of a,w-dihydroxypolydimethylsiloxane was 100 parts, the mass fraction of dimethylsiloxane was 10 parts, the mass fraction of multifunctional telechelic oligosiloxane crosslinking agent with  R of —(OCH₃) and m=4 was 5 parts, the mass fraction of reinforcing filler was 120 parts, the mass fraction of thixotropic agent was 5 parts, the mass fraction of modified siloxane tackifier with n=4 was 2 parts, the mass fraction of coupling agent was 3 parts, and the mass fraction of catalyst was 2 parts, the prepared dealcoholized silicone sealant had relatively optimal performance, with high deep curing and excellent adhesive strength. After multiple aging tests, it could still maintain excellent bonding strength, which could meet the continuous use of photovoltaic module in harsh environment, meeting the application requirements of photovoltaic module sealant.

【Keywords】dealcoholized sealant; photovoltaic module; tackifier; crosslinking agent; anti-aging

Research progress on low-temperature curing conductive silver paste system

Miao Xiangsen, Sun Ying, Zhang Xueqin

(School of Chemistry and Chemical Engineering, Southeast University, Nanjing 211189, Jiangsu, China)

【Abstract】Low-temperature curing conductive silver paste, as key functional material for the preparation of electronic components, has excellent properties such as electrical conductivity, hardness, adhesion and bending resistance after curing, and has been widely used in the field of electronic information industry. In this paper, the compounding of silver powder with different morphologies and sizes in low-temperature curing conductive silver paste system, the properties of organic resin, solvent and common additive on its properties were reviewed, some application of this system in the field of conductive adhesive was listed. The higher application requirements of low-temperature curing silver paste in future electronic information industry were prospected.

【Keywords】compounding of silver powder; nano silver powder; organic resin; conductive silver paste; conductive adhesive