兒茶酚型水下膠粘劑的研究進展

張承鈺^1,2，吳雯曉^1,2，楊智慧^1,2，史浩伯³，

田偉智³，謝雨辰^1,2，秦佳琦^1,2，盧海峰^1,2

（1.山東大學化學與化工學院，山東濟南 250100；2.山東省先進有機硅材料與技術重點實驗室，山東濟南  256401；3.北京星航機電裝備有限公司，北京  100074）

【摘  要】海洋工業、生物醫療等應用領域需要與浸沒在水中的表面進行粘接的膠粘劑，但水化層通常會阻礙膠粘劑和表面之間的相互作用。受生物啟發，兒茶酚官能化聚合物已被廣泛研究并用于水下黏附。盡管相較于干膠，其粘接強度和基材多樣性還有不少提升空間，但在粘接強度方面獲得了很大進步。本綜述梳理、概述了含有兒茶酚基團的水下膠粘劑的國內外最新研究進展。從海洋生物貽貝的吸附原理展開，探討兒茶酚基團的界面吸附，概述基于不同機理的水下膠粘劑的性能。最后對其可能的發展方向進行展望，為解決潮濕環境下的粘接難題提供新的思路與方法。

【關鍵詞】水下；膠粘劑；粘接；兒茶酚

牙齒粘接劑新進展

方  昭，侯丹丹，杜  超，周  同，王春堯，郭  敏

（中國石油化工股份有限公司醫用衛生材料研究與應用重點實驗室，北京 100013）

【摘  要】近年來，牙齒粘接劑通過引入各種新結構，有效改善粘接性能，提升修復效果，在簡便化與通用性方面已經取得了重大進展。為此，本文通過梳理匯總，旨在探討近年來牙齒粘接領域出現的通用型粘接劑及其所反映的發展趨勢：如功能單體增強粘接界面之間的微機械作用力、強化樹脂材料與各種底物之間的化學相互作用以提高粘接材料的性能，以及生物活性分子賦予抗菌等其他功能等。最后對行業的未來發展進行展望，認為在保持材料力學性能的基本前提下，牙齒粘接劑正朝著簡單、高效、持久的方向快速發展。

【關鍵詞】粘接劑；粘接；甲基丙烯酸酯；樹脂

聚氨酯微球及其增韌環氧樹脂的制備和性能研究

宋彩雨，薛雙樂，孫明明，郭宇婷，袁志剛，張  斌，王紅楊，謝天怡

(黑龍江省科學院石油化學研究院，黑龍江哈爾濱  150040)

【摘  要】以二元醇、多元醇和異氰酸酯為原料，采用沉淀聚合法，制備了系列純凈、尺寸均勻且保留部分活性基團的聚氨酯微球，并以三輥研磨混合方式制備了聚氨酯微球改性環氧樹脂。詳細考察了微球及其改性環氧樹脂的紅外光譜和微觀形態，對改性環氧樹脂的應用性能進行了探討。研究結果表明：⑴成功制備了系列保留—NCO活性基團的聚氨酯微球，二元醇PTMG分子質量的改變，能夠有效調控微球的尺寸及粒徑分布。⑵制備形成了系列聚氨酯微球增韌改性環氧樹脂，微球與環氧樹脂進行三輥研磨過程中，同時發生了物理混合和化學反應過程。聚氨酯微球均勻分散于環氧樹脂中，并保持穩定的球形形態。⑶聚氨酯微球能夠有效提升環氧樹脂粘接鋁合金試件的剪切強度和剝離強度。調控PM₁₀₀₀P微球引入量至20%，室溫剪切強度和90°剝離強度分別達到38.07 MPa和9.05 kN/m，較空白試樣分別提高了40%和125%，表明微球改性體系具有優異的粘接性能。

【關鍵詞】聚氨酯；微球；增韌改性；環氧樹脂；粘接性能

偏光片用可光擴散黏著層的制備和性能研究

喬立根^1,2，巫  柯¹，白永平²

(1.廣州鹿山新材料股份有限公司，廣東廣州  510530；2.哈爾濱工業大學化工與化學學院，黑龍江哈爾濱  150001)

【摘  要】采用β-丙烯酰氧基丙酸(β-CEA)作為官能單體、異丁烯酸甲酯(MMA)作為硬單體、丙烯酸-2-乙基己酯(2-EHA)作為軟單體，使用HDI三聚體為交聯劑、γ-甲基丙烯酰氧基丙基三甲氧基硅烷(KH-570)為偶聯劑，通過自由基溶劑聚合的方法合成了偏光片用可光擴散黏著層基體樹脂，并探究了軟硬單體比例、官能單體添加量對性能的影響。與交聯劑、偶聯劑復配得到了性能優異的黏著層，并在偏光片用黏著層基礎上通過與光擴散微粒復配得到了性能優異的光擴散黏著層。分別探究了交聯劑、偶聯劑添加量對黏著層性能和10 rad/s條件下儲能模量、耐候性的影響。研究結果表明：⑴當軟硬單體比例為83∶17，官能單體添加量為3%時，偏光片用可光擴散黏著層基體樹脂成膜后初粘力可達到6#球，剝離強度為21.7 N/in，持粘時間為9.0 h，10 rad/s條件下的儲能模量為85 395 Pa。⑵作為黏著層時，交聯劑質量分數在0.45%，偶聯劑質量分數在0.45%時為宜。⑶在制備光擴散黏著層時，選擇光擴散微粒添加量4%較為合適。⑷結合影響性能和模量、霧度等各項因素，制備了一款性能優異、滿足使用條件的偏光片用可光擴散黏著層。其初粘力可達2#球，180°剝離強度為4.1 N/in，85 ℃持粘時間為66 h，10 rad/s條件下的儲能模量為140 930 Pa，霧度為35%，60 ℃及90%RH環境下經時500 h無不良。

【關鍵詞】偏光片；可光擴散黏著層；聚丙烯酸酯

電子顯示屏防爆膜用丙烯酸酯壓敏膠的研制

李銘杰，李健雄

（皇冠新材料科技股份有限公司，廣東中山  528478）

【摘  要】以丙烯酸丁酯（BA）、丙烯酸異冰片酯（IBOA）為軟單體，甲基丙烯酸甲酯（MMA）、丙烯酸甲酯（MA）為硬單體，丙烯酸（AA）、丙烯酸羥乙酯（HEA）為功能單體，過氧化二苯甲酰（BPO）、偶氮二異丁腈（AIBN）為引發劑，乙酸乙酯為溶劑，添加硅烷偶聯劑，制備了電子顯示屏防爆膜用溶劑型丙烯酸酯壓敏膠。采用單因素試驗法探討了軟硬單體配比、功能單體用量、引發劑用量、硅烷偶聯劑用量、丙烯酸異冰片酯用量對壓敏膠黏度、180°剝離力、透光率、抗反彈性能的影響。研究結果表明：對于電子顯示屏防爆膜用溶劑型丙烯酸酯壓敏膠，軟硬單體配比、功能單體的用量對壓敏膠的180°剝離力和抗反彈性能影響較大；適量的硅烷偶聯劑可以提升壓敏膠對玻璃基板的粘接性能；適量的丙烯酸異冰片酯單體可以明顯改善防爆膜膠帶產品的透光率。目前所研發的壓敏膠膠水及防爆膜膠帶產品已開始批量化生產。

【關鍵詞】防爆膜；丙烯酸酯；壓敏膠；剝離力；抗反彈；透光率

濕固化聚氨酯熱熔膠中試研究

劉  晨^1,2，楊淑怡¹，張夢婷¹，李  翔¹，

曾  赟¹，蘭支利²，曾聲紅¹，鄭和根¹

（1.江西永豐工業園區管理委員會，江西吉安  331500；

2.湖南師范大學化學化工學院，湖南長沙 410081）

【摘  要】在前期250 mL燒瓶試驗基礎上，本研究采用20 L反應釜進行中試試驗。從聚酯多元醇原料、催化劑、溫濕度以及擴鏈劑等方面，研究其對濕固化聚氨酯熱熔膠性能的影響，并通過黏度、粘接強度和表干時間等方法對合成材料進行表征。研究結果表明：⑴中試試驗不同于小試加料可以是固體或液體，中試在加料方式上盡量采用液體，讓合成產物分子量均勻，另外中試需要考慮降溫和出料問題。⑵結晶性高的原料會使初始剝離強度增大，但最終剝離強度卻先升高后降低，當結晶度太高時，最終剝離強度反而要下降。表干時間隨著結晶度提高而縮短。⑶催化劑能提高濕固化聚氨酯熱熔膠的粘接力，三乙烯二胺的催化效果最佳，但是催化劑用量對熱熔膠的黏度有影響，催化劑用量過多會導致熱熔膠凝膠。試驗結果表明，三乙烯二胺質量分數選擇0.5%時，性能相對最佳。⑷溫度、濕度對濕固化聚氨酯熱熔膠的粘接力有影響，濕度越高，水汽滲透到膠層越容易，加速—NCO反應，生成極性強的氨基甲酸酯鍵和脲鍵等化學鍵。⑸擴鏈劑可以使得聚合物分子量增大、黏度增大，基材上受力點密度增大，從而提高粘接力；但用量過多或官能度高時，分子鏈之間交聯程度越高，膠粘劑容易凝膠。中試試驗選擇1,4-丁二醇（BDO），擴鏈消耗10%的—NCO的方案最佳。⑹中試研究認為，真空度≤-0.09 MPa，減壓真空脫水2 h，聚氨酯預聚體合成溫度在(80±5) ℃，反應時間2 h，擴鏈反應30 min～1 h，異氰酸酯液體投料，催化劑（三乙烯二胺）用量為0.5%，擴鏈劑（1,4-丁二醇）添加量消耗剩余—NCO（物質的量分數）為10%時，制備的聚氨酯熱熔膠性能相對最佳。

【關鍵詞】聚氨酯熱熔膠；聚酯多元醇；異氰酸酯；擴鏈劑；粘接強度

UV固化揚聲器中心膠的制備及性能研究

曾柳惠，汪堯雙，陸信航，王世偉，謝守華

(國光電器股份有限公司，廣東省電聲電子技術研發與應用企業重點實驗室，廣東廣州  510800)

【摘  要】采用液化改性4,4'-二苯基甲烷二異氰酸酯（MDI）、聚丙二醇（PPG-2000）和丙烯酸羥乙酯（HEA）等原料制備聚氨酯丙烯酸酯預聚體（P）。再以4-丙烯酰嗎啉（ACMO）和三甲基環己基丙烯酸酯（TMCHA）為主要稀釋劑單體，搭配光引發劑和助劑，得到UV固化膠粘劑。分別對ACMO和TMCHA的添加量和復配比例進行探討，使復配所得的單體不但能夠增加膠粘劑的硬度，也能使膠粘劑具備較好的粘接力。研究結果表明：⑴紅外光譜表明，已經成功制備了預期產物聚氨酯丙烯酸酯。⑵通過研究單體的添加量及復配比例對膠粘劑的硬度和各種基材粘接性能的影響，得出ACMO添加量為15%，TMCHA添加量為30%時為最優配方（UV5）。此時PI/PC的剝離強度為1.95 N/mm，硬度為40D。⑶將最優配方UV5與市售AB膠(5705GB)進行基礎粘接性能以及各種音膜材料粘接性能的對比，得出在PC/PET、PC/特多龍、玻片/特多龍的粘接上，UV5更為優異。而且在基礎粘接性能的對比上，UV5的PC/PC、PC/Zn以及PC/Al的剪切強度要比市售AB膠(5705GB)的好。⑷通過承重膠水耐溫試驗的分析，在80~130 ℃的范圍下進行粘接樣條的掛重，發現UV5和市售5705GB耐溫性均比較好，耐溫均能夠達到130 ℃。⑸根據聲學性能曲線，發現配方UV5粘接的喇叭樣品符合各項聲學性能要求，且比市售5705GB產品性能更好。

【關鍵詞】UV膠粘劑；稀釋劑單體；中心膠；音膜

室溫固化耐熱型金屬修補劑的研制

王冠璋，王德鵬，田學深，夏令明，姜  哲，楊  猛

（哥倆好新材料股份有限公司，遼寧撫順  113004）

【摘  要】以特種環氧樹脂作為基料，改性脂環胺為固化劑，配以增韌劑、填料，制備出剪切強度高、耐熱性好、儲存穩定的耐熱型金屬修補劑。重點考察了特種環氧樹脂、固化劑、增韌劑、填料以及固化條件對金屬修補劑性能的影響。研究結果表明：選用E-51與AG-80作為主體樹脂時，膠體的交聯程度得到了提高，在140℃下仍有較高的剪切強度；選用改性脂環胺SF-2351作為固化劑，其脂環和長鏈的結構，不僅保證了膠體力學性能，還提高了熱變形溫度；當增韌劑QS-330C添加量為樹脂質量的10%時，不僅保證了膠體的熱變形溫度，還提高了膠體的力學性能；選用鐵粉和硅微粉配合作為填料，當添加量為50%時，膠體黏度適中，無沉降情況，且提升了力學性能；通過不同固化條件下剪切強度的對比，發現膠體在室溫固化條件下就可以達到較為完整的固化程度。

【關鍵詞】室溫固化；耐熱；金屬修補劑；剪切強度

單組分聚氨酯熱固化膠粘劑用于內嵌式推拉窗的可行性研究

詹  鋒，黃加俊，李桂妃，謝志明

（廣東普賽達材料科技股份有限公司，廣東東莞  523600）

【摘  要】將單組分聚氨酯熱固化膠和濕氣固化聚氨酯密封膠用于汽車內嵌式推拉窗制造過程中的鋁型材粘接。對比了兩種膠的固化性能、剪切性能，著重探討了熱固化膠用于內嵌式推拉窗的可行性。研究結果表明：⑴熱固化膠用于陽極氧化鋁基材與黑邊玻璃的粘接組裝時，必須配合活化劑和底涂同時使用。⑵不同溫度對兩種密封膠固化速度表現明顯差異。隨著溫度的升高，濕固化膠結皮速度加快，固化厚度呈現先增加后降低的情況，但變化幅度較小。熱固化膠粘劑低溫表干時間較慢，隨著溫度增加，固化厚度快速增加。⑶濕固化膠養護時間為8 h，23、70和90 ℃條件下，剪切力分別為203、243和187 N，均小于裝箱要求的600 N，無法滿足8 h內快速裝箱技術要求。⑷熱固化膠在70 ℃、養護4 h時，固化厚度可達3.56 mm，剪切力達到1 466 N，可以實現清膠快速裝箱；提高養護溫度到90 ℃，清膠裝箱的間隔時間可以縮短到20 min，此時固化厚度可達5.24 mm，剪切力達到2 126 N。熱固化膠的這兩種工藝條件均能有效適用于內嵌式推拉窗短周期裝配。

【關鍵詞】單組分；聚氨酯；熱固化膠；推拉窗

側羥基氟碳低聚物的合成及固化性能研究

安靖怡¹，張天福²，張孝阿¹，王成忠¹，江盛玲¹，張軍營¹

（1.北京化工大學，碳纖維及功能高分子教育部重點實驗室，材料科學與工程學院，北京 100029；2.航天化學動力技術國防科技重點實驗室，湖北航天化學技術研究所，湖北襄陽  441003）

【摘  要】以低分子量偏氟乙烯（VDF）-六氟丙烯（HFP）共聚物和氨基醇為主要原料，通過邁克爾加成反應，設計合成了三種側羥基氟碳低聚物，并進一步與固化劑HDI三聚體、擴鏈劑1,4-丁二醇反應，得到固化產物。然后采用傅里葉變換紅外光譜儀（FT-IR）和核磁共振波譜儀（¹H-NMR），研究了氨基醇種類及用量、氧化鎂用量、反應溫度、反應時間對側羥基氟碳低聚物合成的影響，進一步研究了固化物的力學性能、熱性能和耐溶劑性能。研究結果表明：⑴成功合成了側羥基氟碳低聚物，且采用4-氨基-1-丁醇作為親核試劑時，制備的側羥基氟碳低聚物具有較高的接枝率。當投料比為20∶10，接枝率為17.39%，反應時間在6.5~9.0 h時為相對最佳制備條件。⑵側羥基氟碳低聚物固化產物拉伸強度在3.41~9.21 MPa之間。隨著氟碳低聚物接枝率的提高，交聯反應位點增多，形成了穩定的三維網狀結構，使拉伸強度提升。⑶固化后形成交聯結構，阻止了聚合物鏈段的移動，提高了熱穩定性。⑷所制備的固化產物具有良好的耐強酸、強堿以及極性溶劑特性。

【關鍵詞】側羥基氟碳低聚物；氨基醇；邁克爾加成；活性基團

空氣凈化器塑料面板螺柱滑牙問題改善研究

沈凌峰¹，沈科挺¹，袁世權¹，郭國良²，鄭軍妹²，魏  俊²

（1.寧波方太廚具有限公司，浙江寧波  315336；2.健康智慧廚房浙江省工程研究中心，浙江寧波  315336）

【摘  要】為解決空氣凈化器中外觀塑料面板頻繁出現的ABS塑料螺柱滑牙問題，本研究通過不同種類單組分膠水（如瞬間膠、EVA熱熔膠、厭氧膠、溶劑膠等）之間的測試對比，以確定相對最優的螺柱螺紋修復工藝方案。研究結果表明：⑴由于瞬間膠固化后具有相對更高的硬度和粘接強度，這證明其具備更大的內聚力，這使其相比其他單組分膠水在塑料螺柱螺紋修復的工藝過程中具備明顯更突出的性能優勢。⑵測試對比發現，3種瞬間膠均能滿足塑料螺柱螺紋修復的要求，其中瞬間膠-A鑒于其更突出的材料成本優勢，被優先考慮用于最終的螺紋修復工藝。⑶通過對比試驗，確認了瞬間膠-A在不同溫濕度條件下的完全固化時間t₀以及膠水對塑料面板材料韌性的影響。在相同水汽壓下，瞬間膠-A的完全固化時間隨著溫度的升高而減少，即瞬間膠-A的固化速度與空氣溫度呈現正相關關系。⑷瞬間膠-A會導致塑料螺柱韌性略有下降，但下降幅度不影響后續螺釘的二次固定。⑸本研究一整套塑料螺柱螺紋修復工藝的探究和應用，能夠最終實現塑料面板的零報廢和降低零件成本，并且能夠對行業內頻繁出現的塑料螺柱滑牙問題的解決起到很大的經驗總結和啟示意義。

【關鍵詞】ABS塑料；螺柱滑牙；螺紋修復；瞬間膠

Research progress of catechol-based underwater adhesive

Zhang Chengyu^1,2,Wu Wenxiao^1,2,Yang Zhihui^1,2,Shi Haobo³,

Tian Weizhi³,Xie Yuchen^1,2,Qin Jiaqi^1,2,Lu Haifeng^1,2

(1.School of Chemistry and Chemical Engineering,Shandong University, Ji'nan250100, Shandong, China; 2.Shandong Key Laboratory of Advanced Organo Silicon Materials and Technologies, Ji'nan 256401, Shandong, China; 3.Beijing Xinghang Mechanical-Electric Equipment Co., Ltd., Beijing  100074, China)

【Abstract】The application fields such as marine industry and biomedicine require adhesive capable of bonding to surfaces submerged in water, however, the hydration layer often hinders the interaction between the adhesive and the surface. Inspired by biology, catechol-functionalized polymers have been extensively studied and used for underwater adhesion. Significant progress has been made in enhancing its bonding strength, although there is still room for improvement in terms of bonding strength and substrate diversity compared to dry adhesive. The latest research progress, both domestically and internationally, on underwater adhesive containing catechol groups was systematically summarized in this review. Starting from the adsorption principle of marine mussels, the interfacial adsorption of catechol groups was explored and the performance of underwater adhesive based on different mechanisms was summarized. Finally, the potential development directions were discussed, offering new ideas and methods to solve the bonding problems in humid environments.

【Keywords】underwater; adhesive; bonding; catechol

New progress in dental adhesives

Fang Zhao, Hou Dandan, Du Chao, Zhou Tong, Wang Chunyao, Guo Min

(Sinopec Key Laboratory of Research and Application of Medical and Hygienic Materials, Beijing 100013, China)

【Abstract】In recent years, dental adhesives have made significant progress in simplification and universality by introducing various new structures to effectively improve bonding performance and enhance repair effectiveness. Therefore, the universal adhesives that have emerged in the field of dental bonding in recent years and the development trends they reflect, such as functional monomers enhancing the micro mechanical forces between bonding interfaces, strengthening the chemical interactions between resin materials and various substrates to improve the performance of bonding materials, and biologically active molecules endowing antibacterial and other functions were explored in this article. Finally, the future development of the industry was discussed, believing that while maintaining the basic mechanical properties of materials, dental adhesives were rapidly advancing towards simplicity, efficiency, and durability.

【Keywords】adhesive; bonding; methacrylate; resin

Preparation and properties of polyurethane microspheres and their toughened epoxy resins

Song Caiyu, Xue Shuangle, Sun Mingming, Guo Yuting,

Yuan Zhigang, Zhang Bin, Wang Hongyang, Xie Tianyi

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

【Abstract】A series of pure polyurethane microspheres with uniform size and partially retained active groups were prepared by precipitation polymerization method using diols, polyols and isocyanates as raw materials, and then polyurethane microspheres modified epoxy resins were prepared by three-roll grinding mixing. The infrared spectra and microscopic morphology of the microspheres and their modified epoxy resins were investigated in details, and the application properties of modified epoxy resins were discussed. The research results showed that, ⑴ A series of polyurethane microspheres retaining —NCO active groups were successfully prepared. The particle size and distribution of the microspheres could be effectively regulated by the change of molecular weight of diol PTMG. ⑵A series of polyurethane microspheres toughening modified epoxy resins were prepared. During the three-roll grinding process of the microspheres and epoxy resins, physical mixing and chemical reaction occurred at the same time. The polyurethane microspheres were uniformly dispersed in the epoxy resins and maintained the stable spherical shape. ⑶ Polyurethane microspheres could effectively improve the shear strength and peel strength of epoxy resin bonded aluminum alloy specimens. When the amount of PM₁₀₀₀P microspheres was adjusted to 20%, the shear strength at room temperature and 90° peel strength reached 38.07 MPa and 9.05 kN/m, respectively, which increased by 40% and 125% compared with the blank sample, indicating that the microsphere modified system had excellent bonding properties.

【Keywords】polyurethane; microsphere; toughening modification; epoxy resin; bonding property

Preparation and performance of photo-diffusible adhesive layer for polarizer

Qiao Ligen^1,2, Wu Ke¹,Bai Yongping²

(1.Guangzhou Lushan New Materials Co., Ltd., Guangzhou 510530, Guangdong, China;2.School of Chemistry and Chemical Engineering, Harbin Institute of Technology, Harbin  150001, Heilongjiang, China)

【Abstract】Using β-acryloyloxypropionic acid (β-CEA) as the functional monomer, methyl methacrylate (MMA) as the hard monomer, 2-ethylhexyl acrylate (2-EHA) as the soft monomer, HDI trimer as the crosslinking agent, and γ-methacryloyloxypropyltrimethoxysilane (KH-570) as the coupling agent, the photo-diffusible adhesive matrix resin for polarizer was synthesized by free-radical solvent polymerization. The effects of the ratio of soft and hard monomers and the amount of functional monomer added on the performance were investigated.The high-performance adhesive layer was obtained by compounding with crosslinking agents and coupling agents, and the high-performance photo-diffusible adhesive layer was obtained by compounding with photo-diffusible particles on the basis of the adhesive layer for polarizer.The effects of crosslinking agent and coupling agent addition on the performance of adhesive layer, as well as the storage modulus under 10 rad/s condition and weather resistance were investigated, respectively. The research results showed that, ⑴ When the ratio of soft and hard monomers was 83:17 and the amount of functional monomer added was 3%, after the photo-diffusible adhesive layer substrate resin was formed into film, the initial tack could reach 6# ball, the peel strength was 21.7 N/in, the holding time was 9.0 h, and the storage modulus under 10 rad/s condition was 85 395 Pa.⑵ When used as the adhesive layer, it was advisable to have the crosslinking agent mass fraction of 0.45% and the coupling agent mass fraction of 0.45%. ⑶ When preparing the photo-diffusible adhesive layer, it was advisable to choose the photo-diffusible particle addition amount of 4%. ⑷ A photo-diffusible adhesive layer for polarizer with excellent performance and meeting usage conditions was prepared by combining various factors that affected performance, modulus, and haze. Its initial tack could reach 2# ball, 180° peel strength was 4.1 N/in, the holding time at 85 ℃ was 66 h, the storage modulus under 10 rad/s condition was 140 930 Pa, the haze was 35%, and there were no defects after 500 h in 60 ℃&90% RH environment.

【Keywords】polarizer; photo-diffusible adhesive layer; polyacrylate

Development of acrylate pressure sensitive adhesive for explosion-proof film of electronic display screen

Li Mingjie, Li Jianxiong

（Crown New Materials Technology Co., Ltd., Zhongshan  528478, Guangdong, China）

【Abstract】Solvent-based acrylate pressure sensitive adhesive for explosion-proof film of electronic display screen was prepared by using butyl acrylate (BA) and isobornyl acrylate (IBOA) as soft monomers, methyl methacrylate (MMA) and methyl acrylate (MA) as hard monomers, acrylic acid (AA) and hydroxyethyl acrylate (HEA) as functional monomers, benzoyl peroxide (BPO) and azobisisobutyronitrile (AIBN) as initiators, ethyl acetate as solvent, and adding silane coupling agent. The single factor experimental method was used to investigate the effects of soft and hard monomer ratio, functional monomer dosage, initiator dosage, silane coupling agent dosage, and isobornyl acrylate dosage on the viscosity, 180° peeling force, transmittance, and rebound resistance of pressure sensitive adhesive. The research results showed that, for solvent-based acrylate pressure sensitive adhesive used in explosion-proof film for electronic display screen, the ratio of soft and hard monomers and the amount of functional monomers had the significant impact on the 180° peeling force and rebound resistance of pressure sensitive adhesive. An appropriate amount of silane coupling agent could enhance the bonding performance of pressure sensitive adhesive to glass substrates. An appropriate amount of isobornyl acrylate monomer could significantly improve the light transmittance of explosion-proof film tape products. At present, the developed pressure sensitive adhesive and explosion-proof film tape products had entered mass production.

【Keywords】explosion-proof film; acrylate; pressure sensitive adhesive; peeling force; rebound resistance; light transmittance

Pilot study on moisture-cured polyurethane hot melt adhesive

Liu Chen^1,2, Yang Shuyi¹, Zhang Mengting¹, Li Xiang¹,

Zeng Yun¹, Lan Zhili², Zeng Shenghong¹, Zheng Hegen¹

(1.Jiangxi Yongfeng Industrial Zone Management Committee, Ji'an 331500, Jiangxi, China;2.College of Chemistry and Chemical Engineering, Hunan Normal University, Changsha, 410081, Hunan, China)

【Abstract】On the basis of the preliminary 250 mL flask experiment, the pilot-scale experiment was conducted by using a 20 L reactor in this study. The effects of polyester polyol raw materials, catalysts, temperature, humidity, and chain extenders on the properties of moisture-cured polyurethane hot melt adhesive were investigated, and the synthesized materials were characterized by using methods such as viscosity, bonding strength, and surface drying time. The research results showed that, ⑴ The pilot experiment was different from the small-scale experiment in that the feeding of the small-scale experiment could be solid or liquid. In the pilot experiment, liquid was used as much as possible in the feeding method to make the molecular weight of synthesized product uniform. In addition, in the pilot experiment, cooling and discharge issues needed to be considered. ⑵ Raw materials with high crystallinity could increase the initial peel strength, but the final peel strength first increased and then decreased. When the crystallinity was too high, the final peel strength actually decreased. The surface drying time decreased with increasing crystallinity. ⑶ The catalyst could improve the adhesion of moisture-cured polyurethane hot melt adhesive, and the catalytic effect of triethylenediamine was the best, but the amount of catalyst had an impact on the viscosity of hot melt adhesive, and excessive amount of catalyst could cause hot melt adhesive to gel. The test results indicated that the performance was relatively optimal when the mass fraction of triethylenediamine was selected as 0.5%. ⑷ Temperature and humidity had an impact on the bonding strength of moisture-cured polyurethane hot melt adhesive. The higher the humidity, the easier it was for water vapor to penetrate into the adhesive layer, accelerating the —NCO reaction and generating highly polar chemical bonds such as urethane and urea bonds. ⑸ Chain extender could increase the molecular weight and viscosity of polymer, increase the density of stress points on the substrate, and thus improve the bonding strength. However, when the dosage was excessive or the functionality was high, the higher the degree of crosslinking between the molecular chains, the easier the adhesive was to gel. In the pilot experiment, 1,4-butanediol (BDO) was selected and the optimal solution was to expand the chain by consuming 10% —NCO. ⑹In the pilot study, it concluded that the performance of polyurethane hot melt adhesive prepared was optimal when vacuum degree ≤ -0.09 MPa, vacuum dehydration under reduced pressure was for 2 hours, synthesis temperature of polyurethane prepolymer was at (80±5) ℃, reaction time was 2 hours, chain extension reaction was for 30 minutes to 1 hour, liquid isocyanate was added, catalyst (triethylenediamine) dosage was 0.5%, and the addition of chain extender (1,4-butanediol) was 10% of residual —NCO (mass fraction) consumption.

【Keywords】polyurethane hot melt adhesive; polyester polyol; isocyanate; chain extender; bonding strength

Preparation and performance study of UV curing speaker center adhesive

Zeng Liuhui, Wang Yaoshuang, Lu Xinhang, Wang Shiwei, Xie Shouhua

（GuoGuang Electric Company Limited, Guangdong Provincial Key Laboratory of Electroacoustic Electronic Technology R&D and Application, Guangzhou  510800, Guangdong, China）

【Abstract】Polyurethane acrylate prepolymer (P) was prepared by using liquefied modified 4,4'- diphenylmethane diisocyanate (MDI), polypropylene glycol (PPG-2000), and hydroxyethyl acrylate (HEA) as raw materials. UV curing adhesive was then obtained by using 4-acryloylmethiolane (ACMO) and trimethylcyclohexyl acrylate (TMCHA) as the main diluent monomers, combined with photoinitiators and additives. The addition amount and compounding ratio of ACMO and TMCHA were explored respectively, so that the monomers obtained from compounding could not only increase the hardness of adhesive, but also made the adhesive have good adhesion. The research results showed that, ⑴ The infrared spectrum indicated that the expected product polyurethane acrylate was successfully prepared. ⑵ By studying the effects of monomer addition amount and compounding ratio on the hardness of adhesive and the bonding performance of various substrates, it was found that the optimal formula (UV5) was obtained when the ACMO addition amount was 15% and the TMCHA addition amount was 30%. At this time, the peel strength of PI/PC was 1.95 N/mm and the hardness was 40D. ⑶ Comparing the basic bonding performance of the optimal formula UV5 with commercially available AB adhesive (5705GB) and the bonding performance of various acoustic membrane materials, it was found that UV5 was superior in the bonding of PC/PET, PC/Tedroson, and glass slide/Tedroson. Moreover, in terms of basic adhesive performance comparison, the shear strength of UV5 on PC/PC, PC/Zn, and PC/Al was better than that of commercially available AB adhesive (5705GB). ⑷ Through the analysis of the temperature resistance test of the load-bearing adhesive, the hanging weight of the adhesive strip was carried out in the range of 80-130 ℃. It was found that UV5 and the commercially available 5705GB had good temperature resistance, both of which could reach 130 ℃. ⑸ According to the acoustic performance curve, it was found that the speaker sample bonded with formula UV5 met various acoustic performance requirements and performed better than the commercially available 5705GB product.

【Keywords】UV adhesive; diluent monomer; center adhesive; acoustic membrane

Development of room-temperature curing heat-resistant metal repair agent

Wang Guanzhang, Wang Depeng, Tian Xueshen, Xia Lingming, Jiang Zhe, Yang Meng

(Gleihow New Materials Co., Ltd., Fushun 113004, Liaoning, China)

【Abstract】A heat-resistant metal repair agent with high shear strength, excellent heat resistance, and stable storage was prepared by using special epoxy resins as the base materials, modified alicyclic amine as the curing agent, and incorporating toughening agent and filler. The effects of special epoxy resins, curing agents, toughening agents, fillers, and curing conditions on the properties of metal repair agent were investigated emphatically. The research results showed thatwhen E-51 and AG-80 were selected as the main resins, the crosslinking degree of adhesive was improved, and there was still a high shear strength at 140 ℃. Using modified alicyclic amine SF-2351 as the curing agent, its alicyclic and long-chain structure not only ensured the mechanical properties of adhesive, but also increased the thermal deformation temperature. When the amount of toughening agent QS-330C added was 10% of the resin mass, it not only ensured the thermal deformation temperature of adhesive, but also improved the mechanical properties of adhesive. Using iron powder and silicon micro powder as fillers, when the addition amount was 50%, the adhesive viscosity was moderate, there was no sedimentation, and the mechanical properties were improved. By comparing the shear strength under different curing conditions, it was found that adhesive could achieve a relatively complete curing degree under room-temperature curing conditions.

【Keywords】room-temperature curing; heat-resistant; metal repair agent; shear strength

Feasibility study of one-component polyurethane thermosetting adhesive for embedded sliding window

Zhan Feng, Huang Jiajun, Li Guifei, Xie Zhiming

(Guangdong Pustar Material Technology Co., Ltd., Dongguan 523600, Guangdong, China)

【Abstract】The one-component polyurethane thermosetting adhesive and moisture-curing polyurethane sealant were applied to the bonding of aluminum profiles in the manufacturing process of automotive embedded sliding window. The curing properties and shear performance of two types of adhesive were compared, and the feasibility of using the thermosetting adhesive for embedded sliding window was analyzed. The research results indicated that, ⑴When thermosetting adhesive was used for bonding and assembling anodized aluminum substrate with black edge glass, it must be used together with activator and primer. ⑵There was a significant difference in the curing speed of two sealants at different temperatures. With the increase of temperature, the skinning speed of moisture-curing adhesive accelerated, and the curing thickness showed a trend of first increasing and then decreasing, but the change range was relatively small. The surface drying time of thermosetting adhesive was slow at low temperature, and as the temperature increased, the curing thickness increased rapidly. ⑶The curing time of the moisture-curing adhesive was 8 hours. Under the conditions of 23, 70, and 90 ℃, the shear forces were 203, 243, and 187 N, respectively, all of which were less than the required 600 N for packaging, and could not meet the technical requirements for rapid packaging within 8 hours. ⑷When the thermosetting adhesive was cured at 70 ℃ for 4 hours, the curing thickness could reach 3.56 mm, and the shear force could reach 1 466 N, which could achieve rapid cleaning adhesive and packaging. By increasing the curing temperature to 90 ℃, the interval time between cleaning adhesive and packaging could be shortened to 20 minutes. At this time, the curing thickness could reach 5.24 mm and the shear force could reach 2 126 N. Both of these process conditions for thermosetting adhesive could be effectively applied to the short cycle assembly of embedded sliding window.

【Keywords】one-component; polyurethane; thermosetting adhesive; sliding window

Synthesis and curing properties of side hydroxyl fluorocarbon oligomers

An Jingyi¹,Zhang Tianfu², Zhang Xiaoa¹, Wang Chengzhong¹, Jiang Shengling¹, Zhang Junying¹

(1.Key Laboratory of Carbon Fiber and Functional Polymers of Ministry of Education, College of Materials Science and Engineering, Beijing University of Chemical Technology, Beijing 100029, China;2. Science and Technology on Aerospace Chemical Power Laboratory, Hubei Institute of Aerospace Chemotechnology, Xiangyang  441003, Hubei, China)

【Abstract】Three types of side hydroxyl fluorocarbon oligomers were designed and synthesized via Michael addition reaction by using low-molecular-weight vinylidene fluoride (VDF)-hexafluoropropylene (HFP) copolymer and amino alcohol as the main raw materials. Subsequently, they were reacted with curing agent HDI trimer and chain extender 1,4-butanediol to obtain the cured products. Then, Fourier transform infrared spectroscopy (FT-IR) and nuclear magnetic resonance spectroscopy (¹H-NMR) were used to investigate the effects of amino alcohol type and dosage, magnesium oxide dosage, reaction temperature, and reaction time on the synthesis of side hydroxyl fluorocarbon oligomers. Furthermore, the mechanical properties, thermal properties, and solvent resistance of the cured products were studied. The research results showed that, ⑴ The side hydroxyl fluorocarbon oligomers were successfully synthesized. When 4-amino-1-butanol was used as the nucleophilic reagent, the oligomers exhibited a higher grafting rate. When the feeding ratio was 20:10, the grafting rate was 17.39%, and the reaction time was between 6.5 and 9.0 hours, which were the optimal preparation conditions. ⑵The tensile strength of the cured product of side hydroxyl fluorocarbon oligomers was between 3.41 and 9.21 MPa. As the grafting rate of fluorocarbon oligomers increased, the number of crosslinking reaction sites increased, forming a stable three-dimensional network structure that enhanced tensile strength. ⑶After curing, a cross-linked structure was formed, which prevented the movement of polymer segments and improved thermal stability. ⑷ The prepared cured product had good resistance to strong acids, strong bases, and polar solvents.

【Keywords】side hydroxyl fluorocarbon oligomers; amino alcohol; Michael addition; active group

Research on the improvement of screw stripping problems in plastic panel studs of air purifiers

Shen Lingfeng¹, Shen Keting¹, Yuan Shiquan¹, Guo Guoliang², Zheng Junmei², Wei Jun²

(1.Ningbo Fotile Kitchen Ware Co., Ltd., Ningbo 315336, Zhejiang, China; 2.Healthy & Intelligent Kitchen Engineering Research Center of Zhejiang Province, Ningbo  315336, Zhejiang, China)

【Abstract】In order to solve the frequent problems of screw studs stripping in the ABS plastic panel of air purifiers, various types of single-component adhesive (such as cyanoacrylate adhesive, EVA hot melt adhesive, anaerobic adhesive, and solvent-based adhesive) were compared and tested in this study to determine the relatively optimal repair process for screw threads. The research results showed that, ⑴ Cyanoacrylate adhesive exhibited relatively higher hardness and bonding strength after curing, indicating greater cohesive strength compared to other single-component adhesive. This made it significantly more effective in the process of repairing plastic screw threads.⑵ Among the three kinds of cyanoacrylate adhesive tested, all met the requirements for repairing plastic screw threads. However, cyanoacrylate adhesive A was prioritized for its superior cost-effectiveness in the final repair process. ⑶ Through comparative tests, the complete curing time t₀ of cyanoacrylate adhesive A under different temperature and humidity conditions, as well as its impact on the toughness of the plastic panel material were confirmed. Under the same water vapor pressure, the complete curing time of cyanoacrylate adhesive A decreased with increasing temperature, indicating a positive correlation between the curing speed of cyanoacrylate adhesive A and air temperature. ⑷ Cyanoacrylate adhesive A caused a slight decrease in the toughness of the plastic screw studs, but this reduction did not affect the secondary fixation of the screw. ⑸The comprehensive exploration and application of this plastic screw thread repair process in this study could ultimately achieve zero scrap rate for plastic panels and reduced part costs, and provide valuable experience and insights for addressing the frequent problems of screw studs stripping in the industry.

【Keywords】ABS plastic; screw studs stripping; thread repair; cyanoacrylate adhesive