紫外光/湿气双重固化改性聚氨酯丙烯酸酯胶粘剂

黄成尚¹，肖思浩¹，梅   唯¹，徐祖顺¹，易昌凤^1,2

(1.湖北大学材料科学与工程学院，湖北 武汉    430062；2.功能材料绿色制备与应用教育部重点实验室，湖北省高分子材料重点实验室，湖北  武汉    430062）

车灯密封用反应型聚氨酯热熔胶的制备及性能研究

高  丽，从赫雷，杨  影

(上海康达新材料科技有限公司，上海  201419)

动力电池用双组分聚氨酯灌封胶的制备与性能研究

陈  权，王超智，王小伟，潘守伟

（广州集泰化工股份有限公司，广东 广州  510665）

GNPs/SBR复合改性沥青的制备及性能研究

肖  凤^1,2，邓星鹤^1,2

（1.广东交科技术研发有限公司，广东广州 510550；2.广东华路交通科技有限公司，广东广州，510420）

中温固化导热抗冲击环氧灌封胶性能研究

冯朝波，黎灿光，王祥伟，娄星原，陈建军

（广州白云科技股份有限公司，广东 广州  510540）

【摘  要】以环氧树脂、增韧剂、导热填料、阻燃剂、酸酐固化剂及助剂为主要原料，制备了环氧灌封胶，并对其性能进行表征。研究结果表明：⑴综合考虑冲击强度及耐热性，复配增韧剂添加量8%~12%较合适。⑵综合考虑黏度及施工性能等，优选m(球形氮化铝)∶m(片状氮化硼)=3∶1的复配导热粉，且复配导热粉添加25%~30%较合适。⑶随着环氧灌封胶在沸水中浸泡时间的增加，起初吸水率快速增加，之后吸水率缓慢增加直至饱和。沸水浸泡1 h吸水率小于0.3%，满足SJ/T 11125—1997电子元器件用环氧系灌封材料行业标准要求。⑷采用优选的梯度固化工艺（70 ℃，1 h；95 ℃，1 h），灌封胶上、下层密度和导热性能差异小，固化物内应力均一，高低温循环后无裂纹。⑸该环氧导热灌封胶混合黏度低，可操作时间长，具有良好的灌封浸渍性能，可适应全自动化点胶设备的要求。

【关键词】环氧灌封胶；冲击强度；导热系数；热变形温度；吸水率

超高透明硅酮密封胶的研究

谢丽莎，徐文远，石正金，胡亚飞，林坤华

（广州集泰化工股份有限公司，广东广州  510665)

【摘  要】以羟基封端甲基苯基硅氧烷为原料，采用脱酸型交联剂，制备了一种超高透明硅酮密封胶，并通过透光率和雾度表征其在不同环境下的透明度。研究结果表明：⑴采用羟基封端甲基苯基硅氧烷为基础聚合物，改性后的二羟基聚二甲基硅氧烷能明显提升密封胶的透明度，其透明度优于杂化体系透明胶和中性硅酮透明胶；⑵在羟基封端聚二甲基硅氧烷分子链中引入甲苯基，可以明显改善密封胶的透明度；⑶脱酸型交联剂制备的透明胶的透明度优于脱酮肟型密封胶；⑷基础聚合物的黏度对密封胶的力学性能影响很大，当采用不同黏度树脂m(20 000)∶m(80 000)=1∶2进行复配时，密封胶的综合性能最优；⑸酸性交联剂XL27制备的密封胶综合性能最好，表干时间适中，拉伸强度高，模量低，断裂伸长率好；⑹本文制备的超高透明硅酮密封胶，在经历90 ℃、-30 ℃、浸水和水-紫外处理后，透明度基本没有变化。

【关键词】超高透明；硅酮密封胶；透明度

可食性壳聚糖-大豆分离蛋白抗菌膜的制备与性能分析

陈 华，马永胜，李泽阳，唐雅兰

（广州科技职业技术大学，广东 广州  510550）

【摘  要】为了改善传统聚乙烯包装材料给人体带来的不可逆转的危害问题，本研究提出将壳聚糖与大豆分离蛋白（SPI）作为基础材料，组合制备得到了一种安全环保、可再生降解新型复合抗菌膜包装材料。制备过程中分别探究了不同干燥温度、不同大豆蛋白浓度以及不同甘油浓度下复合膜的性能，最终得到有效的组成成分。研究结果表明：壳聚糖与大豆蛋白相互结合所制备膜性能良好的配方确定为0.66%SPI、0.51%甘油、干燥温度为55 ℃。在此配方下，当添加ε-多聚赖氨酸抑菌剂浓度为0.30%以及Nisin抑菌剂浓度为0.20%时，抑菌膜的效果十分显著。本研究提出的可再生降解新型包装材料制备过程较为简易，性能较优，能够为未来环保新型包装材料的制备提供新的思路。

【关键词】抗菌膜；壳聚糖；大豆分离蛋白；制备；性能

高导热底填胶对星载端机BGA器件可靠性影响评估

张  晟，张晨晖，许培伦，刘志丹，金 星

（中国电子科技集团公司第二十研究所，陕西 西安  710068）

【摘 要】针对星载产品对高导热绝缘底填胶可靠性应用需求，开展双组分高导热绝缘胶对BGA焊点可靠性及环境适应性影响评估。采用导热绝缘胶填充工艺，设计制作星载端机典型BGA菊花链网络结构试验件及端机模拟件，并开展菊花链试验件一系列鉴定级环境与可靠性试验。研究结果表明：采用BGA菊花链器件和印制板设计制作的菊花链网络结构试验件，通过高导热绝缘底填胶填充，实现导热底填胶对BGA焊点可靠性的影响评价，设计方案合理；全过程菊花链电路电阻均无增大、中断现象，无焊点失效、断裂现象，导热绝缘胶填充过程中对菊花链试验件没有引进的缺陷，高导热底填胶对BGA焊点没有影响；模拟件经过星载产品验收级环境与可靠性试验，试验前后电性能指标及监测过程无明显差异，符合指标设计要求；导热绝缘胶填充过程中对模拟件没有引进的缺陷，表明模拟件具有经受环境应力和工作应力的能力；高导热绝缘底填胶对模拟件电性能指标没有异常影响，满足星载产品散热及抗高载荷的需求，实现可靠性应用。

【关键词】高导热底填胶；BGA器件；菊花链；模拟件；焊点；环境试验；可靠性

模塑型环氧底填料的研究与应用进展

戴晟伟¹，张有生²，杨昶旭¹，王晓蕾¹，齐悦新¹，韩淑军¹，职欣心¹，刘金刚¹

（1.地质碳储与资源低碳利用教育部工程研究中心，中国地质大学（北京）材料科学与工程学院，北京 100083；2.浙江嘉民新材料有限公司，浙江嘉兴  314011）

【摘  要】底填料是倒装芯片（FC）型先进电子封装的关键材料之一，而模塑型底填料（MUF）是近年来发展起来的一类重要的底填料品种。本文综述了国内外近年来在MUF材料基础与应用领域中的研究与应用进展情况，从先进FC封装技术的发展对MUF材料的性能需求、MUF材料组成结构设计以及当前FC封装应用中的主流MUF材料的研究与应用现状等几个方面进行了阐述。最后对先进FC封装技术用MUF材料的未来发展趋势进行了展望。

【关键词】集成电路封装；倒装芯片；模塑型底填料；环氧树脂；熔体流动性

反应型聚氨酯热熔胶的研究进展概述

黄    磊，汪    雷

[旭川化学(苏州)有限公司，江苏  苏州    215434]

【摘 要】反应型聚氨酯热熔胶因其性能优异、适用范围广等特点正逐渐替代传统的胶粘剂。鉴于人们对可持续发展理论的认识深化，从非石油基的生物质衍生物出发制备可循环使用的聚氨酯热熔胶已成为科学家们现阶段亟待解决的目标。本文综述了近几年国内外在新型多元醇材料（生物基、二氧化碳基）开发以及反应型聚氨酯热熔胶再加工方面（如利用动态共价键再加工、利用氨基甲酸酯交换再加工）的进展，并对反应型聚氨酯热熔胶未来的发展方向进行了展望。

【关键词】反应性聚氨酯热熔胶；生物基多元醇；二氧化碳基多元醇

UV/moisture dual curing modified polyurethane acrylate adhesive

Huang Chengshang¹, Xiao Sihao¹, Mei Wei¹, Xu Zushun¹, Yi Changfeng^1,2

(1.School of Materials Science and Engineering, Hubei University, Wuhan 430062, Hubei, China; 2. Key Laboratory of Green Preparation and Application for Functional Materials, Ministry of Education, Hubei Key Laboratory of Polymer Materials, Wuhan    430062, Hubei, China)

【Abstract】Siloxane-modified polyurethane acrylate (PUA) UV/moisture dual curing resin was synthesized by using isophorone diisocyanate (IPDI), polytetramethylene ether glycol (PTMEG), 2-hydroxyethyl methacrylate (HEMA) and 3-aminopropyltriethoxysilane (KH-550) as raw materials. The dual curing resin was mixed with the photoinitiator diphenyl-(2,4,6-trimethylbenzoyl) phosphine oxide (TPO) and active diluent 1,6-hexanediol diacrylate (HDDA), the UV/moisture dual curing adhesive was prepared by solvent-free method,  and its structure and properties were characterized. The research results showed that PUA prepolymer containing siloxane was successfully synthesized. The conversion rate of double bonds of adhesive after a period of moisture curing was 99%. When the content of active diluent HDDA was 50% of the total mass of adhesive and KH-550 was 0.6% of the total mass of PUA prepolymer, the surface drying time of dual curing adhesive was only a few seconds, its curing rate was rapid, and the tensile shear strength could reach 2.88 MPa. The mechanical properties and thermal stability of the prepared dual curing adhesive were relatively good.

【Keywords】adhesive; UV curing; moisture curing; siloxane; polyurethane acrylate

Preparation and properties of reactive polyurethane hot melt adhesive for vehicle lamp sealing

Gao Li, Cong Helei, Yang Ying

（Shanghai Kangda New Material Technology Co., Ltd., Shanghai  201419, China）

【Abstract】Reactive polyurethane prepolymer was synthesized by using crystalline polyester polyols, liquid polyether polyols and polyisocyanates as the main raw materials. At the same time, reactive polyurethane hot melt adhesive for lamp bonding and sealing was prepared by compounding with acrylic resin powder, curing agent, thixotropic agent and other additives. The main influencing factors of reactive polyurethane hot melt adhesive such as viscosity, viscosity thermal stability, shear strength and so on were explored, and the molecular structure, thermal properties and mechanical properties of the prepared reactive polyurethane hot melt adhesive were characterized. The research results showed that when two crystalline polyesters, namely polyester polyols n（HJ-3500）∶n（7380）=1∶1, the isocyanate index R=1.5-1.9, m(polyester polyol)∶m(polyether polyol)=1∶2, and acrylic resin powder, curing agent, thixotropic agent and other additives were used for compounding, the prepared reactive polyurethane hot melt adhesive had good resistance to high and low temperatures. The reactive polyurethane hot melt adhesive for vehicle lamp sealing could solve the problem of poor bonding performance to low polarity plastic materials, the open time was short and the positioning speed was fast, which could meet the production line operation requirements of timely movement and assembly of vehicle lamp samples in the vehicle lamp industry after gluing construction. In addition, the shear performance indicators of the self-developed product basically met the standards of imported products and were superior to some domestic products, which could replace certain imported products.

【Keywords】polyurethane; hot melt adhesive; vehicle lamp; bonding; sealing

Preparation and properties of two-component polyurethane potting adhesive for power battery

Chen Quan, Wang Chaozhi, Wang Xiaowei, Pan Shouwei

（Guangzhou Jointas Chemical Co., Ltd., Guangzhou  510665, Guangdong , China）

【Abstract】Polyurethane prepolymers were prepared by using castor oil polyols, polyether triols, polyether diols, polymethylene polyphenyl polyisocyanates (PAPI) and diphenylmethane diisocyanate (MDI) as raw materials. Component A was prepared by using castor oil polyol, polyether triol N303, polyether diol N220, etc. Component B was prepared with polyurethane prepolymer, MDI-50, diluent, etc. Then, components A and B were mixed in the mass ratio of 5∶1 to prepare polyurethane potting adhesive. The effects of different ratios of polyols, prepolymers synthesized from different polyols, different ratios of isocyanates, aluminum hydroxide particle size and filling amount on the performance of two-component polyurethane potting adhesive were explored. The research results showed that the potting adhesive had excellent mechanical properties when the ratio of castor oil (CO), polyether N303 and polyether N220 was m(CO)∶m(N303)∶m(N220)=2∶1∶2 in component A. The potting adhesive prepared by polyurethane prepolymer synthesized with castor oil in component B had better toughness and mechanical properties, with the tensile strength reaching 6.7 MPa, the elongation at break reaching 66%, and the shear strength reaching 6.2 MPa. When isocyanates (CO-PU) and MDI-50 were mixed in the mass ratio of 1∶1 in component B, the good balance could be achieved between the mechanical properties, operation time, and hardness of the potting adhesive. In the compounding ratio of m(5 μm aluminum hydroxide)∶m(20 μm aluminum hydroxide)=1∶4, and the total mass fraction of the filling was 60%, the viscosity and tensile strength of the polyurethane potting adhesive were excellent, with the flame retardant grade of UL94 V0 and the thermal conductivity of 0.80 W/(m • K).

【Keywords】two-component polyurethane; potting adhesive; flame retardant; thermal conductivity

Preparation and properties of GNPs/SBR composite modified asphalt

Xiao Feng^1,2, Deng Xinghe^1,2

(1.Guangdong Transportation Science and Technology R&D Co., Ltd., Guangzhou 510550, Guangdong, China; 2.Guangdong Hualu Traffic Technology Co., Ltd., Guangzhou 510420, Guangdong, China)

【Abstract】GNPs/SBR composite modified asphalt was prepared by compounding butadiene styrene rubber (SBR) with graphene (GNPs) using the high-speed shearing machine. The physical and rheological properties of GNPs/SBR composite modified asphalt were evaluated by three major indicators, dynamic shear rheometer (DSR), multi stress creep recovery test (MSCR), Fourier transform infrared spectrometer (FT-IR), fluorescence microscope, and thermal analysis technology. The research results showed that the addition of GNPs could improve the high-temperature performance of modified asphalt and reduce temperature sensitivity. Compared with the single SBR, GNPs/SBR modified asphalt improved high-temperature stability and deformation resistance. However, due to the large specific surface area of graphene, aggregation was prone to occur in asphalt, and the deformation recovery ability in low-temperature environments was reduced. The FT-IR spectra of GNPs/SBR modified asphalt showed no new absorption peaks, indicating that GNPs and SBR belonged to physical blending in asphalt. Thermal performance analysis showed that SBR and GNPs had the positive effect on improving the high-temperature stability of modified asphalt, making the performance of modified asphalt more stable.

【Keywords】graphene nanosheet; styrene-butadiene rubber; composite modified asphalt; rheological property

Study on properties of thermal conduction and impact resistance epoxy potting adhesive

curing at medium temperature

Feng Chaobo, Li Canguang, Wang Xiangwei, Lou Xingyuan, Chen Jianjun

(Guangzhou Baiyun Technology Co., Ltd., Guangzhou 510540, Guangdong, China)

【Abstract】Epoxy potting adhesive was prepared by using epoxy resin, toughening agent, thermal conductive filler, flame retardant, anhydride curing agent and additives as main raw materials, and its properties were characterized. The research results showed that, ⑴ Considering the impact strength and heat resistance comprehensively, it was more appropriate to add 8% to 12% of the compound toughening agent. ⑵ Considering the viscosity and construction performance comprehensively, the compound thermal conductive powders with the ratio of m(spherical aluminum nitride) to m(flake boron nitride)=3:1 were selected, it was more suitable to add 25% to 30% of the compound thermal conductive powders. ⑶ As the soaking time of epoxy potting adhesive in boiling water increased, the initial water absorption rate increased rapidly, and then the water absorption rate slowly increased until saturation. The water absorption rate after soaking in boiling water for 1 hour was less than 0.3%, which met the industry standard requirements of SJ/T 11125-1997 encapsulation materials of epoxy series for use in electronic components. ⑷ Using the optimal gradient curing process (70 ℃, 1 hour; 95 ℃, 1 hour), the upper and lower density and thermal conductivity of potting adhesive had little difference, the internal stress of the cured material was uniform, and there were no cracks after high and low temperature cycling. ⑸ This thermal conductive epoxy potting adhesive had low mixing viscosity, long operating time, and good potting and impregnation performance, which could meet the requirements of fully automated dispensing equipment.

【Keywords】epoxy potting adhesive; impact strength; thermal conductivity; thermal deformation temperature; water absorption rate

Research on ultra high transparent silicone sealant

Xie Lisha, Xu Wenyuan, Shi Zhengjin, Hu Yafei, Lin Kunhua

(Guangzhou Jointas Chemical Co., Ltd., Guangzhou 510665, Guangdong, China)

【Abstract】An ultra high transparent silicone sealant was prepared by using hydroxyl terminated methylphenyl siloxane as raw material and deacidification crosslinking agent. Its transparency in different environments was characterized by transmittance and haze. The research results showed that ⑴ Using hydroxyl terminated methylphenyl siloxane as the base polymer, the modified dihydroxy polydimethylsiloxane could significantly improve the transparency of the sealant. Its transparency was superior to hybrid system transparent adhesive and neutral silicone transparent adhesive. ⑵ Introducing a toluene group into the hydroxyl terminated polydimethylsiloxane molecular chain could significantly improve the transparency of the sealant. ⑶ The transparency of transparent adhesive prepared by deacidifying crosslinking agent was better than that of ketone oxime type sealant. ⑷ The viscosity of the basic polymer had a significant impact on the mechanical properties of the sealant. When the resin viscosity was m(20 000)∶m(80 000)=1∶2for compounding, the comprehensive performance of the sealant was optimal. ⑸ The viscosity of base polymer had a significant impact on the mechanical properties of the sealant. When different viscosity resins m(20 000):m(80 000)=1:2 were used for compounding, the comprehensive performance of the sealant was optimal.⑹ The ultra high transparency silicone sealant prepared in this paper showed little change in transparency after subjected to 90 ℃, -30 ℃, water immersion and water-UV treatment.

【Keywords】ultra high transparency; silicone sealant; transparency

Preparation and performance analysis of edible chitosan-soy protein isolate antibacterial film

Chen Hua, Ma Yongsheng, Li Zeyang, Tang Yalan

(Guangzhou Vocational University of Science and Technology, Guangzhou 510550, Guangdong, China)

【Abstract】In order to improve the irreversible harm caused by traditional polyethylene packaging materials to the human body, a new safe, environmentally friendly, renewable and degradable composite antibacterial film packaging material was prepared by combining chitosan and soybean protein isolate (SPI) as the basic materials. During the preparation process, the performance of composite film was investigated under different drying temperatures, soybean protein concentrations, and glycerol concentrations, and the effective components were ultimately obtained. The research results showed that the formula with good film performance prepared by the combination of chitosan and soy protein was determined as 0.66% SPI, 0.51% glycerol, and the drying temperature of 55 ℃. Under this formula, when adding the concentration of ε-polylysine antibacterial agent was 0.30% and the concentration of Nisin antibacterial agent was 0.20%, the effect of the antibacterial film was very significant. The preparation process of the new renewable and degradable packaging material proposed in this study was relatively simple and had excellent performance, which could provide new ideas for the preparation of new environmentally friendly packaging materials in the future.

【Keywords】antibacterial film; chitosan; soybean protein isolate; preparation; performance

Evaluation of the effect of high thermal conductivity underfill on the reliability of BGA device in satellite-borne terminal equipment

Zhang Sheng, Zhang Chenhui, Xu Peilun, Liu Zhidan, Jin Xing

(China Electronics Technology Group Corporation No.20th Research Institute, Xi′an 710068, Shaanxi, China)

【Abstract】In response to the reliability application requirements of high thermal conductivity insulation underfill for satellite-borne products, the impact of two-component high thermal insulation adhesive on the reliability and environmental adaptability of BGA solder spots was evaluated. By using the thermal insulation adhesive filling process, the typical BGA daisy-chain network structure test pieces and satellite-borne terminal simulation parts were designed and manufactured, and a series of certified-level environmental and reliability tests for daisy-chain test pieces were carried out. The research results showed that the daisy-chain network structure test piece designed and manufactured by using BGA daisy-chain devices and printed circuit boards, was filled with high thermal conductivity insulation underfill, the impact evaluation of thermal conductivity underfill on the reliability of BGA solder spots was achieved, which proved the design was reasonable. The resistance of the daisy-chain circuit did not increase or interrupted throughout the entire process, there was no failure and fracture phenomenon of solder spots, there was no introduced defects to the daisy-chain test pieces in the process of filling the thermal insulation adhesive, demonstrating that the high thermal conductivity underfill had no effect on BGA solder spots. The simulation parts passed the acceptance-level environmental and reliability tests of satellite-borne products, and there were no significant differences in the electrical performance indexes and monitoring process before and after the test, which met the requirements of the design indicators. There were no introduced defects in the process of filling the thermal insulation adhesive, which indicated that the simulation parts had the ability to withstand the environmental stress and working stress. The high thermal conductivity insulation underfill had no abnormal influence on the electrical performance indexes of the simulation parts, which met the requirements of heat dissipation and high load resistance of satellite-borne products and achieved reliable application.

【Keywords】high thermal conductivity underfill; BGA device; daisy-chain; simulation parts; welding spot; environmental test; reliability

Progress on the research and application of molded epoxy underfill

Dai Shengwei¹, Zhang Yousheng², Yang Changxu¹, Wang Xiaolei¹, Qi Yuexin¹, Han Shujun¹, Zhi Xinxin¹, Liu Jingang¹

(1.Engineering Research Center of Ministry of Education for Geological Carbon Storage and Low Carbon Utilization of Resources, School of Materials Science and Technology, China University of Geosciences, Beijing100083, China; 2.Zhejiang Jameen New Material Co., Ltd., Jiaxing  314011, Zhejiang, China )

【Abstract】Underfill is one of the key materials for advanced electronic packaging of flip chip (FC) type, while molded underfill (MUF) is an important type of underfill in recent years. In this paper, the progress on the research and application in the field of MUF material both domestically and internationally in recent years was reviewed. From the development of advanced FC packaging technology to the performance requirements of MUF materials, the structural design of MUF material composition, and the current research and application status of mainstream MUF materials in FC packaging application were elaborated in several aspects. At last, the future developing trends of MUF materials in advanced FC packaging technology were prospected.

【Keywords】integrated circuit packaging; flip chip; molded underfill; epoxy resin; melting flowability

Overview of research progress of reactive polyurethane hot melt adhesive

Huang Lei, Wang Lei

[Xuchuan Chemical (Suzhou) Co., Ltd., Suzhou 215434, Jiangsu, China]

【Abstract】Reactive polyurethane hot melt adhesive is gradually replacing traditional adhesive due to its excellent performance and wide applicability. Given the deepening understanding of sustainable development theory, the preparation of recyclable polyurethane hot melt adhesive from non-petroleum based biomass derivatives has become an urgent goal for scientists at this stage. In this paper, the progress in the development of new polyol materials (bio-based, carbon dioxide based) and the reprocessing of reactive polyurethane hot melt adhesive (such as using dynamic covalent bonds for reprocessing and using amino ester exchange for reprocessing) both domestically and internationally in recent years was reviewed, and the future development direction of reactive polyurethane hot melt adhesive were prospected.

【Keywords】reactive polyurethane hot melt adhesive; bio-based polyols; carbon dioxide polyols