丙烯酸酯压敏胶粘剂的紫外光交联技术研究

通过将交联单体甲基丙烯酸环氧丙酯共聚引入到丙烯酸酯主链结构中,用二芳基碘Ｗｅｎｇ六氟锑酸盐在紫外光激发下引发环氧基交联,从而制得一种综合性能优良的紫外光交联型压敏胶粘剂,并且系统研究了紫外光剂量,光引发剂用量,交联单体用量等因素对压敏胶综合性能的影响。结果发现紫外光交联是提高压敏胶持粘强度和耐温性能的一种有效手段。     

胶粘剂新专利

光固化胶粘剂组成物及其在光学领域的应用 这种光固化胶粘剂组成物,基于可光固化单体和／或低聚物的总质量,该组成物包含：由5％。60％单或多丙烯酸酯单体或低聚物构成的（A）组分;由5％。50％硫代（甲基）丙烯酸酯单体或低聚物构成的（B）组分：由20％～50％芳香族二甲基丙烯酸酯单体或低聚物构成的（C）组分;并且该组成物中不能含有溴取代单官能度丙烯酸酯。     

含苯乙炔基的酰亚胺低聚物及其复合材料研究

制备了一种侧链含苯乙炔基的二胺单体2,4-二氨基[4'-(4-苯乙炔基酞酰亚胺基)]二苯醚(DPED),并合成了基于2,3',3,4'-联苯四甲酸二酐(3,4'-BPDA)和DPED的酰亚胺低聚物,通过热重分析,示差扫描量热分析,1H NMR,熔点和力学性能测试研究了DPED的结构及固化行为,低聚物和其固化物及其碳纤维增强复合材料的性能。结果表明:在主链化学结构相同的情况下,将DPED引入到分子质量约为5 000 g/mol的低聚物中,低聚物熔体粘度会有显著降低,侧链苯乙炔基含量越高,其熔体粘度越低,含侧链苯乙炔基的树脂基复合材料的压缩强度高于不含侧链苯乙炔基复合材料,其值分别为570 MPa和415 MPa。     

硅烷偶联剂改性环氧丙烯酸酯的合成与应用

针对环氧丙烯酸酯附着力和柔韧性差的缺点,通过在环氧丙烯酸酯中引入硅烷基团,合成硅烷改性的环氧丙烯酸酯。考察了各工艺参数对反应产品的影响,通过滴定和红外光谱分析跟踪反应进程和确定产物结构。合成产物通过和光固化单体、光引发剂混配成紫外光固化胶粘剂,并与改性之前的环氧丙烯酸酯作为主体树脂时的紫外光固化胶粘剂的性能进行了对比。研究发现,合成产物通过硅烷基团的引入,改善了环氧丙烯酸酯的柔韧性。同时,由于硅烷偶联剂基团在固化过程中水解露出的硅羟基增强了对无机底材的附着力,使得紫外光固化胶粘剂的综合性能得到了优化和改善。     

丙烯酸酯低聚物的制备及其改性PUA乳液

以丙烯酸丁酯(BA)、乙酸乙烯酯(VAc)、丙烯酸羟乙酯(HEA)、丙烯酸(AA)等为主要原料合成了丙烯酸酯低聚物,以该低聚物为改性剂,制备了丙烯酸酯改性水性聚氨酯乳液(PUA)。考察了低聚物中单体组成、引发剂种类及用量、合成PUA时低聚物加入方式对PUA性能的影响。通过傅里叶变换红外光谱、偏光显微镜照片和热重曲线研究了乳液微观结构和耐热性能,通过气相色谱测定了单体残留量。结果表明:当低聚物中单体组成为BA,VAc,HEA,AA,所用引发剂为偶氮二异丁腈(用量为单体总质量的1.17%),将低聚物与异氰酸酯基单体同时加入反应时,可得到综合性能好、单体残留量极低的水性PUA,其初黏性可达13号球,持黏性为45 min,且乳液稳定。     

单组分紫外光交联丙烯酸压敏胶粘剂的研究

本文通过将交联单体甲基丙烯酸环氧丙酯共聚引入到丙烯酯酯主链结构中,用二芳基碘六氟锑酯盐在紫外光激发下引发环氧基交联,从而制得一种综合性能优良的此外光交联型压敏胶粘剂,资助系统研究了该压敏胶作为单组分胶粘剂的使用期及性能与时间的关系。紫外光剂量、紫外光引发剂用量、交联单体用量等因素对压敏胶综合性能的影响。结果表明该体系是一种稳定性能好,综合性能尤其是持粘及耐温性能高的单一组分溶剂型压敏胶。     

中国专利介绍

共聚胶乳　ＣＮ　１２０７４３０Ａ（１９９９．２．１０），住友道株式会社（日本）。脂肪共轭二烯系单体在环状不饱和烃存在下乳液聚合，用作胶粘剂，地毯挂里用胶，石棉纤维用胶等。建造结构用胶粘剂　ＣＮ１２０７７５７Ａ（１９９９．２．１０），旭化成工业株式会社（日本）。主成分为环氧丙烯酸酯树脂和活性单体及促进剂叔胺；固化剂为有机过氧化物。可交联粉状织物胶粘剂　ＣＮ１２０８０６２Ａ（１９９９．２．１７），瓦克化学有限公司（德国）。乙烯基酯、（甲基）丙烯酸酯，氯乙烯等共聚粉末，Ｔｇ或熔点大于４０℃，含环氧或异…     

丙烯酸酯液体橡胶改性环氧树脂胶粘剂的研究

以侧链含环氧基团的丙烯酸酯液体橡胶为改性剂 ,二乙撑三胺基甘油正丁基醚为固化剂制备了一种室温固化环氧树脂胶粘剂。重点研究了其粘接工艺性、力学性能和丙烯酸酯液体橡胶的改性作用。研究结果表明 :该胶粘剂具有较好的粘接工艺性能和拉剪强度 ,加入丙烯酸酯液体橡胶后拉伸剪切强度有显著的提高 ;液体橡胶环氧基含量和橡胶添加量对胶粘剂拉剪强度有重要的影响 ,每百份环氧树脂加 10份环氧基含量为 1.2mmol·g-1的丙烯酸酯液体橡胶 ,铝合金胶接试片拉剪强度提高了 133% ,复合材料胶接试片拉剪强度提高了 12 4 % ,4 5 # 钢胶接试片拉剪强度提高了 84 %。     

水基丙烯酸酯胶的自交联反应研究

在丙烯酸酯乳液聚合中引入环氧基和酰胺基可实现自交联,当混合单体为１００份、两种交联单体的加入量为７：６时,胶粘剂有最好的粘接性和耐焊性。本文用交联前后的红外光谱图为说明自交联反应历程,并与外加交联剂的反应型水基丙烯酸酯进行了综合性能比较。     

UV固化聚氨酯改性环氧丙烯酸酯的制备

通过聚氨酯丙烯酸酯(PUA)预聚物中的端-NCO与双酚F型环氧丙烯酸酯(BPF-EA)低聚物中的侧-OH反应,制备了一种光活性聚氨酯改性环氧丙烯酸酯(PMEA)低聚物。将两种低聚物与活性稀释剂以及光引发剂均匀混合并进行了UV固化。研究了EA和PMEA低聚物及固化膜的性能。结果表明,制备的BPF-EA低聚物与自制的双酚A型环氧丙烯酸酯低聚物相比黏度大幅下降。EA和PMEA固化膜具有高的交联密度、良好的附着力以及优异的耐化学品性能。由于PUA预聚物的引入,聚合物链中具有一定量的柔性基团,PMEA固化膜的铅笔硬度、热稳定性和拉伸强度略有下降,断裂伸长率明显增加。固化膜的柔韧性变好。其中,以20%(质量分数)TPGDA为稀释剂配制的UV固化涂料,固化膜的综合性能最好。     

紫外光（UV）固化胶黏剂收缩率与强度的研究

UV胶黏剂的固化收缩率与固化后的残留应力乃至粘接强度有着密切关系。对比UV胶黏剂中不同丙烯酸单体、几种低聚物和阳离子单体的收缩率和相应的粘接强度。讨论了单体和树脂类型对收缩率和粘接强度的影响。介绍了以低收缩丙烯酸酯树脂和阳离子树脂为主体树脂,以低收缩单体为稀释剂、配合填料和适当增强剂制备出混合型UV胶黏剂。该胶黏剂粘接强度和耐久性好,其固化收缩率为3．5％,远低于普通自由基型UV胶黏剂。经湿热老化试验后,粘接强度保持率仍保持在80％。     

环保型涂料印花粘合剂的研制

选用了多种交联单体参与乳液聚合,确定丙烯酸丁酯为软单体,甲基丙烯酸甲酯和苯乙烯为硬单体,软、硬比为5:1,选用环氧丙烯酸酯为活性单体,用量为5%～6%,阴、非离子乳化剂用量比例1:2～3,乳化剂为2.5%～3%,引发剂用量0.3%,温度控制在80～85℃,合成的粘合剂在使用过程中不会释放游离甲醛,产品性能如摩擦牢度、手感、成膜性能及乳液稳定性优良,属新一代的环保型粘合剂。     

Surface modification of polyethylene by radiation-induced grafting for adhesive bonding. I. Relationship between adhesive bond strength and surface composition

A number of vinyl monomers have been surface grafted onto a polyethylene sheet by the mutual irradiation in monomer vapor and by a trapped-radical technique. The surface composition of the grafted sheets has been determined by means of ATR infrared spectrophotometry and compared with the peel strength of the joints bonded with conventional structural adhesives. In the methyl acrylate grafts followed by a saponification treatment, only the surfaces having graft compositions of more than 80 mole-% methyl acrylate give a high peel strength. A similar relationship between peel strength and surface composition is found in the surface grafts of vinyl acetate, acrylic acid, acrylamide, and methylolacrylamide. It is concluded that the formation of a surface with such a high monomer content is a necessary condition for the strong adhesive bonding of grafted polyethylenes at bonding temperatures below the softening point. Moreover, the adhesive bondability of the highly modified surfaces with epoxy adhesives is significantly enhanced by the introduction of carboxy and carbamyl radicals.     

Effect of chemical structure and shear force on the morphology and properties of jet printed black micropatterns using imide epoxy binders

Epoxy and epoxy acrylates with phthalimide groups on the main chain or pendent side chain were synthesized and used as binders for solvent‐free UV‐curable inks. Effects of chemical structures on the solubilities of binders in monomers, together with the influences of shear force and ink compositions on the morphology and nanoindentation properties of the microstripes were studied. PIK1 inks containing BAPSBD epoxy with phthalimide groups on the main chain showed shear‐thinning behaviors and pigment aggregation problems. Variations of the shear stress at different positions of the dispenser led to PIK1 microstripes with rough central regions and smoother edges. AMPDP acrylate with pendent phthalimide side chain afforded not only good solubility in monomers but also good thermal and mechanical properties after curing. Stripes prepared by the PIK2 ink containing AMPDP exhibited straight edge and smooth surface. Considering the solubility and compatibility in inks, together with properties of cured stripe, binders with pendent phthalimide groups are better candidate as UV‐curable ink compositions than those with main chain phthalimide groups. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Preparation and performance of new antifouling resins containing BIT group

New acrylate grafting epoxy antifouling resins containing benzoisothiazoline ketone (BIT) group were successfully synthesized, and their structures and performances were determined. Experimental data indicated that the new acrylate grafting epoxy antifouling resins have a strong bonding to the cured epoxy resin coating through chemical reaction and self-stratifying. And the paint prepared by using the new resin as matrix has excellent self-polishing and antifouling properties. Especially its antifouling period could be modified by changing the weight ratio of the usage of the mixed monomers and epoxy resin in the preparing process of the acrylate grafting epoxy antifouling resins.     

Preparation and properties of heat and ultraviolet‐induced bonding and debonding epoxy/epoxy acrylate adhesives

Heat and ultraviolet (UV)‐induced bonding and debonding (BDB) adhesives were designed and prepared through blending an epoxy resin, diglycidyl ether of bisphenol A (DGEBA) with an epoxy acrylate resin, bisphenol‐A epoxy acrylate resin (BEA). The variation of the chemical structure of DGEBA and BEA in the sequential heat‐ and UV‐curing processes was characterized by Fourier transform infrared spectroscopy (FTIR). The FTIR results indicate that DGEBA and BEA successfully took part in both the heat‐curing and UV‐curing processes. The effects of the mass ratio of BEA to DGEBA, amount of heat‐curing agent, type of diluents, and UV irradiation time on the BDB properties of BDB adhesive were systematically investigated. The results show that the bonding strength increases with the decrease of the mass ratio of BEA to DGEBA and with the increase of the amount of heat‐curing agent in a certain range. The debonding strength decreases with the increase of the mass ratio of BEA to DGEBA. The mass ratio of BEA to DGEBA was set at 10 to ensure the ratio of the bonding strength to debonding strength greater than 10 times. The debonding strength of BDB adhesives also depends on the UV irradiation time, decreasing with the increase of UV irradiation time in a certain range. Based on the FTIR results and the dependence of the bonding and deboning strengths on the reaction conditions, a possible BDB mechanism of BDB adhesive was proposed. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46435.     

Accelerated-curing epoxy structural film adhesive for bonding lightweight honeycomb sandwich structures

Accelerating the curing of epoxy/aromatic amine adhesives and improving their toughness are challenges in heat-resistant epoxy structural adhesives. Herein, we report an epoxy/aromatic amine adhesive accelerated curing system with an oxo-centered trinuclear (chromium III) complex, which is toughened using a thermoplastic block copolymer (TPBC). The reaction characteristics, heat resistance, microstructure, and bonding properties of the accelerated epoxy adhesives were analyzed. The reaction peak temperature of the epoxy with 3% catalyst was 113.1°C, which was 113.6°C lower than that of epoxy without catalyst, and the modified epoxy resin demonstrated a potential for rapid curing at medium temperature. The glass transition temperature of the TPBC-toughened epoxy adhesive was 125°C after curing, indicating excellent thermal stability after medium temperature curing. The introduction of the TPBC increased the single-lap shear strength of the epoxy adhesive without reducing its heat resistance. The shear strength at room temperature and 120°C of the modified epoxy adhesive with 50 phr of TPBC was 25.2 and 10.9 MPa, respectively. Moreover, the epoxy film adhesive exhibited outstanding bonding properties when used in the bonding of lightweight honeycomb sandwich structures.     

聚丙烯酸酯增韧改性环氧树脂的研究

以丙烯酸正丁酯(BA)、甲基丙烯酸甲酯(MMA)及甲基丙烯酸缩水甘油酯(GMA)为单体通过悬浮聚合反应合成了共聚物P(MMA-BA-GMA)简称(PMBG),采用傅里叶红外光谱仪、核磁共振波谱仪、凝胶渗透色谱仪对PMBG的结构与组成进行了表征。采用合成的PMBG对环氧树脂(DER663)/固化剂(HTP-305)体系进行增韧改性,研究了PMBG含量对体系力学性能和热性能的影响,并通过扫描电镜(SEM)对固化物断面的微观结构进行了分析。结果表明:PMBG改性后的环氧树脂冲击强度及断裂伸长率提高,当PMBG的质量分数为5%时,冲击强度显著提高,增韧改性效果最好,并且对体系的玻璃化转变温度(Tg)影响不大;共聚物在体系固化时发生微相分离,因而提高了环氧树脂的韧性。     

碳纤维布浸胶及与钢粘接用胶的性能研究

研究了用以浸碳纤维布的环氧胶及粘接浸胶碳布与钢的胶粘剂组成及粘接性能。发现高温性能主要取决于浸碳布胶,室温性能较好的胶,高温性能则明显偏低。制成了室温～250℃剪切强度都在10MPa以上,300℃为8～9MPa的浸碳布胶和粘接用胶。该胶具有不燃性、无烟,以及优异的耐烧蚀性能。     

Facile fabrication and modification of epoxy acrylate latexes by epoxy resin and silane coupling agent

For the purpose of obtaining solvent-free epoxy acrylate latexes of good stability and excellent integrated performance, the epoxy acrylate latexes were fabricated using facile semi-continuous emulsion polymerization with varying amounts of epoxy resin and were modified by a silane coupling agent γ-methacryloxypropyltrimethoxysilane (KH-570). The effects of epoxy resin and KH-570 amounts on the performance of latexes and films were investigated from the aspects of particle size, morphology, tensile measurements, resistance properties, adhesion force, and thermal behavior. The results indicated that the acrylate monomers did graft onto the molecular chain of E-51 characterized by both epoxy value and Fourier transform infrared. Additionally, an emulsion of 80–100 nm particle size with a narrow distribution was obtained. The latex films retain resistances to satisfactory water, acid, alkali, and alcohol while maintaining good thermal stability, adhesion force, and flexibility. The importing of KH-570 could reinforce the spatial structure and cross-linking density and then improve the tensile strength of the latex films properly while keeping other performances well. This work provides a facile pathway for the optimized performance for epoxy acrylate latexes, and represents a tendency for environmental protection.