光致脱羧型光产碱体系的制备及性能研究
（1.广东工业大学材料与能源学院，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】基于光致脱羧机理，合成了三种新型光产碱剂。以异丙基硫杂蒽酮（ITX）作为光敏剂，制备了一系列高效的光产碱体系，并系统探究了其光物理和光化学行为。研究结果表明：该光产碱体系在365 nm具有较强吸收，含N-苯基甘氨酸（NPG）结构的光产碱剂的光解效率较高，光解后释放超强碱1,5,7-三氮杂双环[4.4.0]癸-5-烯（TBD），溶液的pH由6.2跃迁至8.98；通过光热双重固化，ITX/NPG-TBD体系可高效引发巯基-环氧体系的阴离子聚合，巯基和环氧的转化率达90%以上，在光固化涂料、黏合剂等领域具有良好的应用前景。
【关键词】光产碱剂；巯基-环氧；光致脱羧；阴离子光聚合
张 阳，周雨琪，段文鹏，张国栋，王 腾，唐 波，孙春燕，孙妮娟
【摘 要】采用马来酸二乙酯（DEM）与1,6-己二胺（HDA）反应，合成了含巨大位阻作用的仲胺型扩链剂；再与异佛尔酮二异氰酸酯（IPDI）和聚己内酯二元醇（PCL 210N）合成的预聚物反应，制备出了含新型受阻脲键的高强度室温自修复聚氨酯。采用傅里叶变换红外光谱、热性能和力学性能测试等手段，对材料进行表征。研究结果表明：含新型受阻脲键的高强度室温自修复聚氨酯弹性体具备较高的拉伸强度（17.00 MPa）与良好的室温自修复性能（48 h室温自修复效率达到88.82%）。该聚氨酯体系还具备良好的可逆粘接性能与可重复加工性能，在智能材料、可穿戴电子皮肤、可拆卸粘接等领域具备广阔的应用前景。
（黑龙江省科学院石油化学研究院，黑龙江哈尔滨 150040）
【摘 要】通过改变含氟单体双酚AF(BPAF)与酚酞(PP)的物质的量之比，在碱催化条件下与2,6-二氯苯甲腈缩聚，合成了一系列不同氟含量的共聚型聚芳醚腈(FPEN)。对FPEN共聚物的分子结构、分子量及其分布、热性能、力学性能和介电性能进行了表征。研究结果表明：FPEN共聚物具有良好的溶解性，能溶解于二甲基乙酰胺（DMAc）、N,N-二甲基甲酰胺（DMF）等多种有机溶剂；FPEN的热学性能随氟含量出现规律性变化，其Tg均高于200 ℃，T5%也都超过了470 ℃；当含氟单体加入量为30%，即n(PP)∶n(BPAF)=7∶3时，FPEN薄膜的拉伸强度和断裂伸长率分别为82.8 MPa和3.47%，同时具有良好的介电性能。本研究制备的FPEN是一类综合性能优异的新型特种高分子材料，在树脂基复合材料和胶粘剂改性方面有较大的应用前景。
（1.东华大学化学与化工学院应用化学系，上海 201620；2.山东圣泉新材料股份有限公司，山东济南 250204）
【摘 要】以酚醛-酰亚胺树脂（HPMI-F树脂）和酚醛-酰胺酸树脂（HPMA-F树脂）为改性剂，端羧基丁腈橡胶为增韧剂，邻甲酚醛环氧和环氧E-51为基体树脂，再加入固化剂、促进剂和稀释剂，制备了两组新型酚醛-酰亚胺改性环氧胶粘剂（MIF-E）和酚醛-酰胺酸改性环氧胶粘剂（MAF-E）。探究了其黏度、凝胶时间、力学性能、介电性能和吸水率等。研究结果表明：MIF-E的黏度更低，拉伸剪切强度更优，施胶工艺性更好，吸水率低（最低可达1.52%），疏水性良好；MIF-E的表观活化能比MAF-E的表观活化能更高，固化反应速率更小，并且室温储存性良好；两种树脂改性环氧胶粘剂的介电性能优良，MAF-E的相对介电常数更低，1 MHz时为2.11；两种树脂改性环氧胶粘剂的介质损耗因子相近，1 MHz时均小于1.7%。制备的酚醛-亚胺-环氧胶粘剂的介电性能优良、室温储存性良好、工艺性较好、疏水性较好，对配方进一步优化后，在半导体封装材料领域有着良好的应用前景。
【关键词】酚醛-酰亚胺树脂；酚醛-酰胺酸树脂；酚醛-酰亚胺-环氧胶粘剂；酚醛-酰胺酸-环氧胶粘剂
李 洋1,2，方小龙3，张婕妤1,2，刘锦翔1,2，李希望1,2，谷 欢1,2，杨鹏昆1,2，于红卫1,2
（1.浙江农林大学化学与材料工程学院，浙江杭州 311300；2.国家木质资源综合利用工程技术研究中心，浙江杭州 311300；3.江山欧派门业股份有限公司，浙江江山 324100）
【摘 要】为探究珍珠岩不同添加量对氯氧镁无机胶合板性能的影响，本研究采用单因素试验法，对制备胶合板的理化性能、内结合强度、阻燃性能等进行测试。研究结果表明：相较于未添加珍珠岩的空白样（P-0），添加珍珠岩后，制备胶合板的内结合强度均在0.5~0.6 MPa之间，表明珍珠岩添加量的增加对胶合板的内结合强度影响不大。当w(珍珠岩)=0.5%时(相对于总质量而言)，制备胶合板浸渍剥离长度最小，改性胶合板耐水性能最好；当w(珍珠岩)=1.5%时，制备胶合板的静曲强度、弹性模量、端面握钉力和侧面握钉力分别提高到56.1 MPa、7 178.4 MPa、1 863.41 N和1 521.31 N，均达到峰值；当w(珍珠岩)=2.5%时，制备胶合板的阻燃性能最佳为668 s，相较于P-0组，胶合板阻燃时间延长98 s。此外，添加不同量珍珠岩制备的胶合板试件表面均未出现明显的返卤泛霜情况。
高折率有机硼硅粘接促进剂的合成及其在封装胶中的应用
潘科学，梁广强，梁广伟，钟炜洪，周敏活，吴明华，梁广耀
（广东新翔星科技股份有限公司，广东佛山 528145）
【摘 要】以苯基三乙氧基硅烷（PTES）、二苯基二甲氧基硅烷（DPDMS）、乙烯基二甲基乙氧基硅烷（VDMES）、3-甲基丙烯酰氧基丙基三甲氧基硅烷（MPTMS）、3-环氧丙氧基丙基三甲氧基硅烷（GPTMS）和硼酸（BA）等为原料，通过分步水解缩聚法合成了高折率有机硼硅粘接促进剂（HBSA）。采用傅里叶变换红外光谱法（FT-IR）、核磁共振氢谱法（1H-NMR）、核磁共振硅谱法（29Si-NMR）和核磁共振硼谱法（11B-NMR）对HBSA的结构进行了表征。同时使用HBSA制备了自黏性高折率加成型有机硅封装胶，并对其性能进行了研究。研究结果表明：当HBSA的质量份数为1.5份时，封装胶的粘接剪切强度为2.24 MPa，比未加粘接促进剂时提高了3.2倍，拉伸强度为5.79 MPa，断裂伸长率为63%，邵氏D硬度为56，折射率为1.536，在450 nm处的透光率为91%，黏度为6 350 mPa·s，综合性能较佳，可以满足LED封装要求。
【关键词】高折率；有机硼硅粘接促进剂；有机硅封装胶；应用
（西安科技大学材料科学与工程学院，陕西西安 710054）
【摘 要】加入新型可再分散胶粉后，通过测试砂浆的原强度、耐水强度和耐热老化强度，研究了胶粉对瓷砖胶粘剂耐老化性能的影响。研究结果表明：当w(新型可再分散胶粉)=0.15%时，瓷砖粘接砂浆的拉伸强度比未掺入胶粉时提高了105%，热老化后拉伸强度提高了400%，浸水处理后拉伸强度提高了360%。新型可再分散胶粉的粘接效果非常优异，能有效提高瓷砖胶的拉伸强度和耐老化性能。
【关键词】可再分散胶粉；瓷砖胶；拉伸强度；耐老化性
(一汽-大众汽车有限公司，吉林 长春 130011)
【摘 要】结构胶广泛应用于白车身、电池包等结构增强及轻量化设计，其力学性能及失效机理对其合理应用具有重要指导意义。本文通过对两种材料、不同粘接长度接头的搭接剪切测试结果曲线分析，结合数字图像相关法（DIC），阐述了结构胶在搭接剪切过程中由弹性变形、内部损伤至最终破坏的过程，并证明在脆性结构胶中，应力分布的不均匀性。同时明确了搭接剪切试验曲线与BK本构模型的对应关系，形成模拟计算对应的材料卡片，能够很好地体现材料搭接剪切失效过程。
【关键词】结构胶；搭接剪切；失效过程；DIC；应力分布
(郑州圣莱特空心微珠新材料有限公司，河南郑州 450100)
【摘 要】使用不同分子量的含羟基物质制备了不同的成膜物质，使用不同用量的双(3-三甲氧基甲硅烷基丙基)胺制备了不同的粘接助剂。分别制备了不同成膜物质、不同粘接助剂、不同空心玻璃微珠的聚氨酯底涂剂，测试分析了含羟基物质、粘接助剂、空心玻璃微珠用量对底涂剂性能的影响。研究结果表明：当使用分子量较大的含羟基物质A制备成膜物质时，表干时间会有不利影响，同时对底涂剂的粘接性能也有不良影响；随着粘接助剂中双(3-三甲氧基甲硅烷基丙基)胺质量分数在一定范围内（40%~53%）增加时，表干时间逐渐减少，底涂剂与基材之间的粘接往好的方向发展；空心玻璃微珠在一定范围内（质量分数为0.45%~0.89%）用量不会对底涂剂粘接强度有影响，大比表面积的空心玻璃微珠对底涂剂表干速度的影响要优于小比表面积的微球。
（同济大学材料科学与工程学院，功能粘接与涂层技术创新中心，上海 201804）
【摘 要】阐述了UV光固化胶粘剂的发展历史、组成和特点，系统介绍了不同种类UV胶（自由基固化型、阳离子固化型、自由基/阳离子混杂型、延迟固化、UV/湿气双重固化、UV/热双重固化、UV热熔胶、UV压敏胶、UV减粘胶、可拆卸的UV胶、UV光学胶以及其他）的特点、固化机理、材料结构设计以及性能调控方法等。总结了近年来各种UV胶的最新研究进展，最后对UV胶在各个领域的应用、挑战和未来发展方向提出了展望。
Scientific Research Report
Preparation and properties of photobase generator system based on photo induced decarboxylation
Xiang Hong1, Huang Yaoxin1, Li Zhiquan1, Liu Xiaoxuan1,2
(1.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】Three new types of photobase generators were synthesized based on photo induced decarboxylation mechanism. A series of efficient photobase generator systems were prepared by using isopropylthioanthrone (ITX) as photosensitizer, and their photophysical and photochemical behaviors were systematically investigated. The research results showed that the photobase generator system had strong absorption at 365 nm, the photolysis efficiency of photobase generator containing N-phenylglycine (NPG) structure was high, it released the super-powerful base 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) after photolysis, and the solution pH jumped from 6.2 to 8.98. Through photothermal dual curing, the ITX/NPG-TBD system could efficiently initiate the anionic polymerization of thiol-epoxy system, with the conversion rate of over 90% for thiol and epoxy, which showed good application prospects in the field of photocuring coating and adhesive.
【Keywords】photobase generator; thiol-epoxy; photo induced decarboxylation; anionic photopolymerization
Room temperature self-healing polyurethane with high strength containing hindered urea bonds
Zhang Yang, Zhou Yuqi, Duan Wenpeng, Zhang Guodong, Wang Teng, Tang Bo, Sun Chunyan, Sun Nijuan
(Aerospace Research Institute of Materials & Processing Technology, Beijing 100076, China)
【Abstract】A secondary amine-type chain extender with great steric hindrance was synthesized by the reaction of diethyl maleate (DEM) and 1,6-hexanediamine (HDA). Then, it reacted with the prepolymer synthesized from isophorone diisocyanate (IPDI) and polycaprolactone diol (PCL 210N), room temperature self-healing polyurethane with high strength containing novel hindered urea bonds was prepared. The material was characterized by Fourier transform infrared spectroscopy, thermal and mechanical performance testing method. The research results showed that high strength room temperature self-healing polyurethane elastomer containing novel hindered urea bonds had relatively high tensile strength (17.00 MPa) and good room temperature self-healing performance (room temperature self-healing efficiency reached 88.82% after 48 h). The polyurethane system also had good reversible bonding performance and repeatable processing performance, which had broad application prospects in the fields such as intelligent materials, wearable electronic skin, and detachable bonding.
【Keywords】hindered urea bond; high strength; room temperature self-healing; polyurethane
Synthesis and properties of fluorine-containing copolymerized polyarylene ether nitrile
He Yuhong, Liu Caizhao, Sun Mingming, Zhang Xugang, Zhang Bin
(Institute of Petrochemistry, Heilongjiang Academy of Sciences, Harbin 150040, Heilongjiang, China)
【Abstract】By changing the molar ratio of fluorinated monomer bisphenol AF (BPAF) and phenolphthalein (PP), and then condensing with 2,6-dichlorobenzonitrile under alkaline catalytic conditions, a series of copolymerized polyarylene ether nitrile (FPEN) with different fluorine contents were synthesized. The molecular structure, molecular weight and its distribution, thermal properties, mechanical properties and dielectric properties of FPEN copolymer were characterized. The research results showed that FPEN copolymer had good solubility and could be dissolved in various organic solvents such as dimethylacetamide (DMAc), N,N-dimethylformamide (DMF), etc. The thermal properties of FPEN exhibited regular changes with fluorine content, with Tghigher than 200 ℃ and T5%higher than 470 ℃. When the content of fluorinated monomer was 30%, i.e.n(PP)∶n(BPAF)=7∶3, the tensile strength and elongation at break of FPEN film were 82.8 MPa and 3.47% respectively, while also exhibiting good dielectric properties. The FPEN prepared in this study was a new type of special polymer material with excellent comprehensive performance, which had great application prospects in resin-based composite materials and adhesive modification.
【Keywords】phenolphthalein; polyarylene ether nitrile; copolymerization modification; mechanical property
Study on preparation and properties of novel phenolic-imine-epoxyadhesive
Wang Zhaohao1, Yu Xinhai1, Li Zhifang2
(1.Department of Applied Chemistry, College of Chemistry and Chemical Engineering, Donghua University, Shanghai 201620, China; 2.Shandong Shengquan New Materials Co., Ltd., Ji’nan 250204, Shandong, China)
【Abstract】Two groups of novel phenolic-imide modified epoxy adhesive (MIF-E) and phenolic-amidate modified epoxy adhesive (MAF-E) were prepared with phenolic-imide resin (HPMI-F resin) and phenolic-amidate resin (HPMA-F resin) as modifiers, carboxyl terminated nitrile rubber as toughening agent, and o-cresol formaldehyde epoxy and epoxy E-51 as matrix resins, followed by the addition of curing agent, accelerator and diluent agent. Their viscosity, gel time, mechanical properties, dielectric properties and water absorption were investigated. The research results showed that MIF-E had lower viscosity, better tensile shear strength, better sizing process, low water absorption rate (lowest to 1.52%), and good hydrophobicity. The apparent activation energy of MIF-E was higher than that of MAF-E, with lower curing reaction rate and good room temperature storage performance. The dielectric properties of two resin modified epoxy adhesive were excellent, and the relative dielectric constant of MAF-E was lower, which was 2.11 at 1 MHz. The dielectric loss factors of two resin modified adhesive were similar, which were less than 1.7% at 1 MHz. The prepared phenolic-imine-epoxy adhesive had excellent dielectric properties, good room temperature storage performance, good processability, and good hydrophobicity, which had good application prospects in the field of semiconductor packaging materials after further optimization of the formula.
【Keywords】phenolic-imide resin; phenolic-amidate resin; phenolic-imide-epoxy adhesive; phenolic-amidate-epoxy adhesive
Development and Application
Effect of perlite on properties of magnesium oxychloride inorganic plywood
Li Yang1,2, Fang Xiaolong3, Zhang Jieyu1,2, Liu Jinxiang1,2, Li Xiwang1,2, Gu Huan 1,2,
Yang Pengkun1,2, Yu Hongwei1,2
(1.College of Chemistry and Materials Engineering, Zhejiang A&F University, Hangzhou 311300, Zhejiang, China; 2.National Engineering and Technology Research Center of Wood-Based Resources Comprehensive Utilization, Hangzhou 311300, Zhejiang, China; 3.Jiangshan Oupai Door Industry Co., Ltd., Jiangshan 324100, Zhejiang, China)
【Abstract】In order to explore the effect of different amounts of perlite on the properties of magnesium oxychloride inorganic plywood, the single factor experiment method was used to test the physical and chemical properties, internal bonding strength, flame retardancy of the prepared plywood. The research results showed that compared with the blank sample (P-0) without perlite, the internal bonding strength of plywood prepared with perlite was between 0.5 and 0.6 MPa, indicating that the increase of perlite addition had little effect on the internal bonding strength of plywood. When w(perlite)=0.5% (relative to the total mass), the immersion stripping length of the prepared plywood was the smallest, the modified plywood had the best water resistance. When w(perlite)=1.5%, the static bending strength, elastic modulus, end-face nail holding force and side-face nail holding force of plywood increased to 56.1 MPa, 7 178.4 MPa, 1 863.41 and 1 521.31 N, respectively, all reaching peak values. When w(perlite)=2.5%, the best flame retardancy of plywood was 668 s, which was 98 s longer than that of P-0 group.In addition, the surface of plywood specimens prepared by adding different amounts of perlite had no obvious halogenation and frost return phenomena.
【Keywords】magnesium oxychloride adhesive;inorganic plywood; perlite
Synthesis of organic borosilicone adhesion promoter with high refractive index and its application in packaging adhesive
Pan Kexue, Liang Guangqiang, Liang Guangwei, Zhong Weihong,Zhou Minhuo, Wu Minghua, Liang Guangyao
(Guangdong Sheensun Technology Co., Ltd., Foshan 528145, Guangdong, China)
【Abstract】The organic borosilicone adhesion promoter with high refractive index (HBSA) was synthesized by step hydrolysis-condensation reaction of phenyltriethoxysilane (PTES), diphenyldimethoxysilane (DPDMS), vinyl dimethylethoxylsilane (VDMES), 3-methylacryloxypropyl trimethoxysilane (MPTMS), 3-epoxypropyl trimethoxylsilane (GPTMS) and boric acid (BA) as raw materials. The structure of HBSA was characterized by Fourier transform infrared spectroscopy (FT-IR), nuclear magnetic resonance hydrogen spectroscopy (1H-NMR), nuclear magnetic resonance silicon spectroscopy (29Si-NMR) and nuclear magnetic resonance boron spectroscopy (11B-NMR). At the same time, HBSA was used to prepare self-adhesive addition-type organic silicon packaging adhesive with high refractive index, and its properties were studied. The research results showed that when the mass fraction of HBSA was 1.5 phr, the bonding shear strength of packaging adhesive was 2.24 MPa, which was 3.2 times higher than that without the adhesion promoter. The tensile strength was 5.79 MPa, the elongation at break was 63%, the Shore D hardness was 56, the refractive index was 1.536, the transmittance at 450 nm was 91%, and the viscosity was 6 350 mPa·s. The comprehensive performance was quite good, which could meet the requirements of LED packaging.
【Keywords】high refractive index; organic borosilicone adhesion promoter; silicone packaging adhesive; application
Study on the effect of new-type redispersible adhesive powder on the durability of ceramic tile adhesive
Peng Longgui, He Yugang,Yin Chenghui, Cheng Huanquan, Wang Rong, Ye Ruirui
(College of Materials Science and Engineering, Xi’an University of Science and Technology, Xi’an 710054, Shaanxi, China)
【Abstract】After adding new-type redispersible adhesive powder, the effect of adhesive powder on the aging resistance of ceramic tile adhesive was studied by testing the original strength, water resistance, and heat aging strength of the mortar. The research results showed that when w(new-type redispersible adhesive powder)=0.15%, the tensile strength of ceramic tile bonding mortar increased by 105% compared to that without the adhesive powder, the tensile strength increased by 400% after thermal aging, and the tensile strength increased by 360% after immersion treatment. The new-type redispersible adhesive powder had excellent bonding effect, which could effectively improve the tensile strength and aging resistance of ceramic tile adhesive.
【Keywords】redispersible adhesive powder; ceramic tile adhesive; tensile strength; aging resistance
Analysis and numerical simulation of lap shear curve of structural adhesive
Liu Lianbao, Wei Haibo, Li Shaoqian, Li Dapeng, Niu Dongyan
(FAW-Volkswagen Automotive Co., Ltd., Changchun 130011, Jilin, China)
【Abstract】Structural adhesive is widely used in structure reinforcement and lightweight design of body-in-white and battery pack, and its mechanical properties and failure mechanism have important guiding significance for its rational application. Based on the analysis of lap shear test results of two types of material and different bonding lengths of joint, combined with the digital image correlation method (DIC), the process of structural adhesive from elastic deformation, internal damage to final failure during the lap shear was described in this paper, and the non-uniformity of stress distribution in brittle structural adhesive was approved. At the same time, the corresponding relationship between the lap shear test curve and the BK constitutive structure model was clarified, and the material card corresponding to the simulation calculation was formed, which could well reflect the lap shear failure process of material.
【Keywords】structural adhesive; lap shear; failure process; DIC; stress distribution
Preparation and performance study of polyurethane primer
Zhang Yong, Lu Yuchong, Li Yao, Ma Yumin, Cai Yaowu, Wang Jianbin
(Zhengzhou Hollowlite Materials Co., Ltd., Zhengzhou450100, Henan, China)
【Abstract】Different film-forming substances were prepared by using hydroxyl-containing substances with different molecular weights, and different bonding auxiliaries were prepared by using different amounts of bis(3-trimethoxysilylpropyl) amine.Polyurethane primer with different film-forming substances, different bonding auxiliaries, and different hollow glass microspheres were prepared, and the effects of the amount of hydroxyl-containing substance, bonding auxiliary, and hollow glass microsphere on the performance of primer were tested and analyzed. The research results showed that when hydroxyl-containing substance A with larger molecular weight was used to prepare the film-forming substance, the surface drying time had adverse effects, and it also had adverse effects on the bonding performance of primer. As the mass fraction of bis(3-trimethoxysilylpropyl) amine in the bonding auxiliary increased within a certain range (40%-53%), the surface drying time gradually decreased, and the bonding between the primer and the substrate developed in a positive direction. The amount of hollow glass microsphere within a certain range (mass fraction 0.45%-0.89%) did not affect the bonding strength of primer, hollow glass microsphere with large specific surface area had a better effect on the surface drying speed of primer than microsphere with small specific surface area.
【Keywords】hollow glass microsphere; polyurethane; primer; film-forming substance
Special Topics and Review
Research progress on UV light-curing adhesive
(Innovation Center of Functional Adhesion and Coating Technology, School of Materials Science and Engineering, Tongji University, Shanghai 201804, China)
【Abstract】The development history, composition and characteristics of UV light-curing adhesive were elaborated. The characteristics, curing mechanism, material structure design and performance optimization of different kinds of UV adhesive (free-radical curing type, cationic curing type, free radical/cationic hybrid type, delayed curing, UV/moisture dual curing, UV/thermal dual curing, UV hot melt adhesive, UV pressure sensitive adhesive, UV viscosity-reducing adhesive, detachable UV adhesive, UV optical adhesive and others）were systematically introduced. The latest research progress of various UV adhesive in recent years was summarized, and finally, the application, challenges, and future development direction of UV adhesive in various fields were prospected.
【Keywords】adhesive; UV light-curing; development history; research progress
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