低分子量PAA的制备与纳米二氧化硅颗粒分散性能研究

刘  宁¹，孙  健²，夏浙安¹，李欣欣¹

[1.华东理工大学特种功能高分子材料及相关技术教育部重点实验室，上海  200237；2.海隆石油产品技术服务（上海）有限公司，上海  200941]

【摘  要】采用恒流滴定法，以高效液相色谱跟踪聚丙烯酸(PAA)水溶液聚合反应过程，系统研究了单体浓度、体系pH值、链转移剂量、加料时间、引发剂量及反应温度等对PAA分子量的影响，获得了低分子量PAA的可控合成方法。以所制的PAA为超分散剂，利用正交试验研究了pH值、PAA分子量及其质量分数等因素对纳米二氧化硅颗粒分散性能的影响。研究结果表明：单体丙烯酸浓度不宜过大，控制在小于30%为宜；若要获得低分子聚合物，单体pH值应该小于4.5；随着链转移剂异丙醇量的增加，PAA分子量下降，当异丙醇/丙烯酸质量比为2.9：1.0时，PAA分子量降为3 000左右；随着加料时间的延长，PAA分子量逐渐下降并趋缓，综合考虑，加料时间控制在120 min为宜；随着引发剂量增大或反应温度增加，PAA的动力学链长减小，分子量相应减小。多因素方差分析表明，pH值对分散效果影响最大。同时确定了纳米二氧化硅的最优分散条件为：pH值为7，PAA分子量为5 210，质量分数为2.0%。

【关键词】聚丙烯酸；超分散剂；低分子量；纳米二氧化硅

高性能聚酰亚胺-环氧胶粘剂的研制

徐晓清，虞鑫海

(东华大学化学与化工学院，上海  201620)

【摘 要】本研究通过改变环氧增韧剂（SRTEM-C21）、固化剂（ECA-30、2E4MI）和促进剂（B-30）的比例，经过系列化学反应，制备了8种不同配方的聚酰亚胺-环氧胶粘剂。对其黏度性能、力学性能、电学性能、吸水性能、热学性能、凝胶化时间以及表观活化能性能进行了综合分析。对8种环氧胶粘剂体系的力学、电学、热学性能等综合分析得出，J-3-2胶粘剂的各项性能比其他配方均要优异，是较合理的配方，有较宽广的应用前景。

【关键词】双马来酰亚胺；环氧树脂；环氧胶粘剂；胶粘剂制备；胶粘剂性能

高分子量聚氨酯丙烯酸酯的制备及其在PET基材用UV胶粘剂中的性能调变

郑可心^1,2，凌丽霞¹，吴建兵²，王宝俊¹

[1.太原理工大学化学工程与技术学院，山西 太原  030024；2.山西省应用化学研究所(有限公司)，山西 太原  030024]

【摘  要】针对聚对苯二甲酸乙二醇酯(PET)基材表面张力低，UV胶粘剂粘接强度低，采用聚己二酸新戊二醇酯(PNA)、甲苯二异氰酸酯(TDI)、小分子二元醇和甲基丙烯酸羟乙酯(HEMA)为原料，通过分子结构设计、分子量控制合成了一系列低黏度、高分子量聚氨酯丙烯酸酯低聚物(PUA)。分别采用傅里叶变换红外光谱、凝胶渗透色谱对PUA的结构、分子量进行了表征。然后以低聚物、单体、光引发剂和磷酸酯为原料，配制了用于PET基材的UV胶粘剂，考察了初始n(NCO)/n(OH)值(R值)、扩链剂种类及比例、软硬单体种类对UV胶粘剂的黏度、力学性能、体积收缩率和耐高低温等性能的影响。研究结果表明：当初始R值为1.6，扩链剂为丙二醇且与PNA的物质的量比为5∶10时，PUA的分子量和黏度均衡，UV胶的粘接强度最大，达到4.09 MPa。以丙烯酸异冰片酯(IBOA)为硬单体、四氢呋喃丙烯酸酯(THFA)为软单体按照一定比例配制UV胶时，得到的UV胶性能最优，拉伸强度达到8.38 MPa，断裂伸长率达到948.94%，固化体积收缩率为4.38%，耐高低温性能相对最好。

【关键词】聚氨酯丙烯酸酯；紫外光固化；PET基材；软硬段；胶粘剂

E-7高温结构胶的固化工艺性研究

赵雪婷^1,2，刘翔宇^1,2，张成祥^1,2，邹俊军^1,2，张跃峰^1,2

（1.上海复合材料科技有限公司，上海    201112；

2.上海航天树脂基复合材料工程技术研究中心，上海   201112）

【摘    要】为研究E-7高温结构胶（E-7胶）的特性以便于工程应用，采用非等温差示扫描量热分析（DSC）法研究了不同升温速率（β）下反应的放热行为及固化度（α）曲线，得到反应特征温度（T）。通过T-β外推法得到理论固化温度，运用Ozawa-Flynn-Wall法计算不同α下的活化能（E_a）。通过等温DSC测试，得到胶液在60、70和80 ℃下固化结束时间。研究结果表明：E-7胶的E_a随α增加而增加，反应的平均活化能为69 kJ/mol；胶液在60、70和80 ℃的等温DSC测试下分别于140、70和46 min反应放热结束，理论凝胶点为67 ℃。此外，结合胶液的凝胶时间测试、黏温特性和黏时特性，得出实际刷胶时可考虑将待胶接件预热至60 ℃，该温度下凝胶时间为40 min，黏度较低，便于实际的刷胶操作。超声波无损检测设备研究结果表明，胶接间隙应控制在(0.10±0.02) mm。

【关键词】固化温度；凝胶时间；黏度；活化能；胶接间隙

氯醚树脂/纳米SiO₂改性丙烯酸酯复合乳液的制备及其在水性油墨中的应用研究

张天祥，裴克梅

（浙江理工大学化学与化工学院，浙江 杭州 310018）

【摘    要】以氯醚树脂和乙烯基纳米SiO₂为共聚单体，采用半间歇种子乳液聚合方法制备了氯醚树脂/纳米SiO₂改性丙烯酸酯复合乳液，并制备了水性油墨，测定或表征了其性能。研究结果表明：⑴成功制备了复合乳液；⑵SiO₂粒子在乳胶膜中分散较为均匀，氯醚树脂/纳米SiO₂改性丙烯酸酯复合乳液性能稳定，与同类产品E0503丙烯酸酯乳液相比，复合乳液的固含率更高，黏度更小，固化后薄膜的柔韧性更强，在应用方面具有一定的优势；⑶将复合乳液与色浆按照10∶4的比例配制水性油墨，墨层性能可以达到行业内平均水平。与同类产品E0503丙烯酸酯乳液配制的水性油墨相比，复合乳液水性油墨墨层在附着牢度和抗光老化性能方面具有明显优势。

【关键词】氯醚树脂；纳米SiO₂；丙烯酸酯乳液；水性油墨

废锂电池粘结剂去除和回收研究进展

马 伊，曹世伟，邢 延，曹腾良，林立群，王家骏，王 红，卢 峰，姜立忠

（沧州旭阳化工有限公司，河北 沧州  061113）

【摘  要】双碳背景下，大规模动力电池退役潮即将到来，锂离子电池（LIBs）绿色回收成为必然趋势。其中正极材料中贵金属的提取是回收的主要目的，有效剥离正极材料中的集流体铝箔、粘结剂与乙炔黑，是真正实现正极材料的全流程绿色回收的关键。然而，有机粘结剂聚偏氟乙烯（PVDF）较强的结合力阻碍了正极材料与集流体的有效分离，进而影响金属的回收与提纯，且工业直接破碎焙烧，产生的HF气体对环境造成严重污染，因此对锂电池粘结剂PVDF进行去除和回收迫在眉睫。本文综述了PVDF的理化性质、作用和结合机理，着重介绍了PVDF的去除和回收技术，为后续PVDF和正极材料的绿色回收提供理论基础和技术支持。

【关键词】正极材料；集流体；PVDF；分离；回收

聚氨酯热熔胶的研究进展

徐佳宁¹，钱  博¹，王岳鹏¹，孙 巍¹，王 洁²，徐欣欣²，游正伟¹

（1.东华大学材料科学与工程学院，上海  201620；2.浙江禾欣科技有限公司，浙江 嘉兴 314003）

【摘  要】随着全球环保意识的增强，无溶剂型的绿色环保胶粘剂引起了人们的广泛关注。聚氨酯热熔胶作为环保型胶粘剂的一种，体量庞大且发展迅猛，其结构可设计性强，性能可调节范围宽，得到了广泛的研究与应用。本文重点阐述了聚氨酯热熔胶的分类及其分子结构、粘接机理和性能特点，综述了其近年来的研究进展，最后对其未来的发展方向作出了展望。

【关键词】绿色环保；聚氨酯；热熔胶

预制混凝土节段拼装用环氧胶粘剂标准研究

王先前¹，曾  兵^2,3，姚淑芳^2,3，安绍都^2,3

（1.深圳市市政设计研究院有限公司，广东深圳  518029；2.中国建筑科学研究院有限公司，北京  100013；3.建研院检测中心有限公司，北京  100013）

【摘  要】环氧胶粘剂是预制节段拼装结构接缝处的关键材料，影响着结构的安全性和耐久性。本文综述了国内外拼接胶产品相关标准的主要检测项目、技术指标、检测方法和适用范围，对比了标准间的差异。结合预制混凝土节段拼装用环氧胶粘剂产品新国标的制定，提出了标准编制的思路和重点要解决的问题。

【关键词】节段；环氧胶粘剂；标准

无溶剂聚氨酯复膜胶的研究进展

刘鹏程，胡  阳，李  星，付小芳

（中国胶粘剂和胶粘带工业协会，北京  100027）

【摘  要】无溶剂聚氨酯复膜胶凭借安全、环保等性能优势，已经经历了几代产品的更迭，性能更加优化，产品更加成熟，在复膜胶市场中占比不断增大。本文综述了无溶剂复膜胶的施工特点，包括通用型无溶剂单组分、双组分聚氨酯复膜胶，耐水煮型、耐蒸煮型双组分聚氨酯复膜胶和生物基双组分聚氨酯复膜胶的最新研究进展。对软包装用无溶剂聚氨酯复膜胶当前存在的问题及现状进行了分析，还对未来发展方向进行了展望。

【关键词】软包装；聚氨酯；无溶剂；复膜胶；双组分；耐蒸煮

Study on the preparation of low molecular weight PAA and dispersion performance of nano silica particles

Liu Ning¹, Sun Jian², Xia Zhean¹, Li Xinxin¹

(1.Key Laboratory of Specially Functional Polymeric Materials and Related Technology (Ministry of Education), East China University of Science and Technology, Shanghai  200237, China; 2. Hilong Petroleum Product Technology Services (Shanghai) Co., Ltd., Shanghai  200941, China)

【Abstract】The polymerization process of polyacrylic acid (PAA) aqueous solution was tracked by high-performance liquid chromatography with the constant current titration method. The effects of monomer concentration, system pH value, chain transfer agent amount, feeding time, initiator amount and reaction temperature on the molecular weight of PAA were systematically studied, and the controllable synthesis method for low molecular weight PAA was obtained. The effects of pH value, PAA molecular weight, and its mass fraction on the dispersion performance of nano silica particles were studied by orthogonal experiment with the prepared PAA as hyperdispersant. The research results showed that the concentration of monomer acrylic acid should not be too high and should be controlled at less than 30%. In order to obtain low molecular weight polymer, the monomer pH value should be less than 4.5. As the amount of chain transfer agent isopropanol increased, the molecular weight of PAA decreased. When the mass ratio of isopropanol to acrylic acid was 2.9 : 1.0, the molecular weight of PAA decreased to about 3 000. As the feeding time prolonged, the molecular weight of PAA gradually decreased and slowed down. Overall, it was advisable to control the feeding time at 120 minutes. As the initiator amount or reaction temperature increased, the kinetic chain length of PAA decreased, and the molecular weight correspondingly decreased. Multivariate analysis of variance showed that pH value had the greatest impact on dispersion effect. The optimal dispersion conditions for nano silica were determined as follows: the pH value was 7, the molecular weight of PAA was 5 210, and the mass fraction was 2.0%.

【Keywords】polyacrylic acid; hyperdispersant; low molecular weight; nano silica

Development of high performance polyimide-epoxy adhesive

Xu Xiaoqing, Yu Xinhai

(College of Chemistry and Chemical Engineering, Donghua University, Shanghai 201620)

【Abstract】In this study, 8 different formulations of polyimide-epoxy adhesive were prepared by changing the proportion of epoxy toughening agent (SRTEM-C21), curing agent (ECA-30, 2E4MI), and accelerator (B-30) through a series of chemical reactions. The viscosity properties, mechanical properties, electrical properties, water absorption properties, thermal properties, gelation time and apparent activation energy properties were comprehensively analyzed. The comprehensive analysis of mechanical, electrical, and thermal properties of 8 epoxy adhesive systems showed that J-3-2 adhesive had superior performance compared to other formulations, making it a more reasonable formulation with broad application prospects.

【Keywords】bismaleimide; epoxy resin; epoxy adhesive; adhesive preparation; adhesive property

Preparation of high molecular weight polyurethane acrylate and its performance modification in UV adhesive for PET substrate

Zheng Kexin^1,2,Ling Lixia¹, Wu Jianbing², Wang Baojun¹

(1.College of Chemical Engineering and Technology, Taiyuan University of Technology, Taiyuan 030024, Shanxi, China; 2.Shanxi Research Institute of Applied Chemistry, Taiyuan 030024, Shanxi, China)

【Abstract】In response to the low surface tension of polyethylene terephthalate (PET) substrate and the low bonding strength of UV adhesive,using poly(neopentyl glycol adipate) (PNA), toluene diisocyanate (TDI), small molecule diols, and hydroxyethyl methacrylate (HEMA) as raw materials,a series of low viscosity, high molecular weight polyurethane acrylate oligomers (PUA) were synthesized by molecular structure design and molecular weight control. The structure and molecular weight of PUA were characterized by Fourier transform infrared spectroscopy and gel permeation chromatography. Then, the UV adhesive for PET substrate was prepared by using oligomers, monomers, photoinitiators, and phosphate ester as raw materials. The effects of initial n(NCO)/n(OH) value (Rvalue), type and proportion of chain extenders, and types of soft and hard monomers on the viscosity, mechanical properties, volume shrinkage, and high and low temperature resistance of UV adhesive were investigated. The research results showed that when the initial Rvalue was 1.6, the chain extender was propylene glycol, and the molar ratio of propylene glycol to PNA was 5:10, the molecular weight and viscosity of PUA were balanced, and the bonding strength of UV adhesive was the highest, reaching 4.09 MPa.When using isobornyl acrylate (IBOA) as the hard monomer and tetrahydrofuran acrylate (THFA) as the soft monomer in a certain proportion to prepare UV adhesive, the obtained UV adhesive had the best performance, with the tensile strength of 8.38 MPa, the elongation at break of 948.94%, and the curing volume shrinkage of 4.38%, the resistance to high and low temperature was relatively the best.

【Keywords】polyurethane acrylate; ultraviolet curing; PET substrate; soft and hard segment; adhesive

Study on the curing process of E-7 high temperature structural adhesive

Zhao Xueting^1,2, Liu Xiangyu^1,2, Zhang Chengxiang^1,2, Zou Junjun^1,2, Zhang Yuefeng^1,2

(1.Shanghai Composite Material Science & Technology Co., Ltd., Shanghai   201112, China; 2.Shanghai Engineering Technology & Research Center of Aerospace Resin Based Composites, Shanghai    201112, China)

【Abstract】In order to study the characteristics of E-7 high temperature structural adhesive (E-7 adhesive) for engineering application, non isothermal differential scanning calorimetry (DSC) was used to study the reaction exothermic behavior and curing degree (α) curves at different heating rates (β), to obtain the reaction characteristic temperature (T). The theoretical curing temperature was obtained through T-β extrapolation method, and the activation energy (E_a) at different α values was calculated by using the Ozawa-Flynn-Wall method.The curing end time of adhesive solution was obtained at 60, 70 and 80 ℃ by isothermal DSC test.The research results showed that the E_a of E-7 adhesive increased with the increase of α, and the average activation energy of the reaction was 69 kJ/mol. The exothermic reaction of adhesive solution was completed at 140 min, 70 min and 46 min, respectively under isothermal DSC test at 60 ℃, 70 ℃ and 80 ℃, and the theoretical gelation point was 67 ℃.In addition, in combination with the gelation time test, viscosity-temperature characteristics and viscosity-time characteristics of adhesive solution, it was concluded that the parts to be bonded could be preheated to 60 ℃ during the actual adhesive brushing. At this temperature, the gelation time was 40 min, and the viscosity was low, which was convenient for the actual adhesive brushing operation. The research results of ultrasonic non-destructive testing equipment indicated that the bonding gap should be controlled within (0.10 ± 0.02) mm.

【Keywords】curing temperature; gelation time; viscosity; activation energy; bonding gap

Preparation of chlorinated polyether resin/nano-SiO₂ modified acrylate compositeemulsion and its application in water-based ink

Zhang Tianxiang, Pei Kemei

(School of Chemistry and Chemical Engineering, Zhejiang Sci-Tech University, Hangzhou   310018,  Zhejiang,  China)

【Abstract】The chlorinated polyether resin/nano-SiO₂ modified acrylate composite emulsion was prepared by semi-batch seed emulsion polymerization with chlorinated polyether resin and vinyl nano-SiO₂ as comonomers. The research results showed that: ⑴ The composite emulsion was successfully prepared. ⑵The dispersion of SiO₂ particles in the emulsion film was relatively uniform, and the performance of chlorinated polyether resin/nano-SiO₂modified acrylate composite emulsion was stable. Compared with the similar product E0503 acrylate emulsion, the solid content of composite emulsion was higher, the viscosity was smaller, and the cured film was more flexible, which had certain extent of advantages in application. ⑶ When the composite emulsion and color paste were mixed at the ratio of 10∶4 to prepare the water-based ink, the ink layer performance could reach the average level in the industry. Compared with the water-based ink prepared with the similar product E0503 acrylate emulsion, the water-based ink layer with composite emulsion had obvious advantages in  adhesion fastness and light aging resistance.

【Keywords】chlorinated polyether resin; nano-SiO₂; acrylate emulsion; water-based ink

Research progress on binder removal and recovery from spent lithium battery

Ma Yi, Cao Shiwei, Xing Yan, Cao Tengliang, Lin Liqun, Wang Jiajun, Wang Hong, Lu Feng, Jiang Lizhong

(Cangzhou Risun Chemicals Co., Ltd., Cangzhou061113, Hebei, China)

【Abstract】Under the background of “Dual Carbon”, the tide of large-scale power battery retirement is approaching, and the green recycling of lithium-ion batteries (LIBs) has become an inevitable trend. Among them, the extraction of precious metals from cathode materials is the main purpose of recycling, and effectively stripping current collector aluminum foil, binder and acetylene black from cathode materials is the key to truly realizing the whole process of green recycling of cathode materials. However, the strong bonding force of the organic binder polyvinylidene fluoride (PVDF) hinders the effective separation of the cathode material and the current collector, which in turn affects the recovery and purification of the metal. Moreover, the HF gas generated by industrial direct crushing and roasting causes serious pollution to the environment. Therefore, the removal and recovery of lithium battery binder PVDF is imminent. In this paper, the physical and chemical properties, functions, and binding mechanisms of PVDF were reviewed, with a focus on the removal and recovery technologies of PVDF, providing theoretical basis and technical support for the green recovery of PVDF and cathode materials in the future.

【Keywords】cathode material; current collector; PVDF; separation; recovery

Research progress of polyurethane hot melt adhesive

Xu Jianing, Qian Bo, Wang Yuepeng, You Zhengwei

（College of Materials Science and Engineering, Donghua University, Shanghai  201620, China）

【Abstract】With the enhancement of global environmental awareness, solvent-free, green and environmentally friendly adhesives have attracted widespread attention. As one of the environmentally friendly adhesives, polyurethane hot melt adhesive has a large volume and rapid development, its structure has highly designability, and its performance can be adjusted in a wide range, which has been widely studied and applied. In this paper, the classification, molecular structure, bonding mechanism and performance characteristics of polyurethane hot melt adhesive were elaborated, its research progress in recent years was summarized, and finally its future development direction was prospected.

【Keywords】green and environmentally friendly; polyurethane; hot melt adhesive

Research on the standard of epoxy adhesive for prefabricated concrete segmental assembly

Wang Xianqian¹, Zeng Bing^2,3, Yao Shufang^2,3,An Shaodu^2,3

(1.Shenzhen Municipal Design & Research Institute Co., Ltd., Shenzhen 518029, Guangdong, China; 2.China Academy of Building Research, Beijing  100013, China; 3. CABR Testing Center Co., Ltd., Beijing  100013, China)

【Abstract】Epoxy adhesive is the key material in the joint of prefabricated segmental assembly structure, which affects the safety and durability of the structure. In this paper, the main testing items, technical indexes, testing methods and application scope of the relevant standards of splicing adhesive products at home and abroad were reviewed, the differences between these standards were compared. Based on the development of a new national standard for epoxy adhesive products used for prefabricated concrete segmental assembly, the ideas and key issues to be addressed in the standard formulation were proposed.

【Keywords】segment; epoxy adhesive; standard

Research progress of solventless polyurethane laminating adhesive

Liu Pengcheng, Hu Yang, Li Xing, Fu Xiaofang

(China Adhesives and Tape Industry Association, Beijing 100027, China)

【Abstract】Solventless polyurethane laminating adhesive has undergone several generations of product changes due to its safety, environmental protection and other performance advantages. Its performance is more optimized, and the product is more mature, continuously increasing its proportion in the laminating adhesive market. In this paper, the construction characteristics of solventless laminating adhesive, including the latest research progress of universal solventless single-component and two-component polyurethane laminating adhesive, water resistant and steam resistant two-component polyurethane laminating adhesive, and bio-based two-component polyurethane laminating adhesive were summarized. The current problems and status of solventless polyurethane laminating adhesive for flexible packaging were analyzed, and the future development direction was also prospected.

【Keywords】flexible packaging; polyurethane; solventless; laminating adhesive; two-component; water resistant and steam resistant