PET膜用UV固化涂料的研制

以复配低聚物(聚氨酯丙烯酸酯、环氧丙烯酸酯和聚酯丙烯酸酯)、活性稀释剂和复配光引发剂(Irgacure 184、BP)为主要原料,PET(聚对苯二甲酸乙二醇酯)薄膜为基材,制备了高透光率、高耐候性和高性能的UV(紫外光)固化涂料。研究结果表明:当w(环氧丙烯酸酯)=40%、w(聚氨酯丙烯酸酯)=20%、w(活性稀释剂)30%、w[复合光引发剂(Irgacure 184+BP)]=6%、m(Irgacure 184)∶m(BP)=2∶1、w(其他助剂)=4%(相对于涂料质量而言)和UV固化时间为55 s时,固化涂层具有相对最好的综合性能,其邵D硬度为65、附着力为95%,并且PET膜可见光透光率为98%,而且固化涂层具有良好的柔韧性、耐化学药品性和耐黄变性(经150℃处理6 h后颜色无变化)。     

N,N′-4,4′-二苯甲烷双马来酰亚胺/1,6-己二醇二丙烯酸酯的紫外光固化研究

制备了N,N'-4,4'-二苯甲烷双马来酰亚胺(BDM)/1,6-己二醇二丙烯酸酯(HDDA)体系,探讨了BDM/HDDA体系实现UV固化的条件,研究了引发剂种类及其含量对BDM/HDDA体系光固化的反应性及热稳定性的影响.研究表明,2,4,6.三甲基苯甲酰基.二苯基氧化磷(TPO)的综合引发效果要好于同类引发剂安息香乙醚和提氢型光引发剂二苯甲酮-三乙醇胺体系.     

基于响应面法优化混杂UV固化胶粘剂配方

以环氧丙烯酸酯树脂、环氧树脂(EP)、自由基光引发剂和阳离子光引发剂为主要原料,制备混杂UV(紫外光)固化胶粘剂,并且采用响应面法对混杂UV固化胶粘剂的配方进行优化;以预聚体配比、光引发剂配比作为自变量,以混杂UV固化胶粘剂在玻璃上的附着力作为因变量,采用Design Expert软件对2个自变量进行多次拟合,建立相应的数学模型和3维曲面,得到最优的混杂UV固化胶粘剂配方并进行验证。研究结果表明:二项式是描述因变量和自变量之间关系的最佳模型,当环氧丙烯酸酯树脂/EP质量比为1.19、自由基光引发剂/阳离子光引发剂质量比为1.00时,制成的混杂UV固化胶粘剂在玻璃基材上的附着力(9级)相对最强。     

黄色UV固化涂料的透明性研究

为了提高黄色UV固化涂料的透明性,研究了不同种类单体、低聚物、引发剂及低聚物用量和色浆质量分数对UV固化涂料透明性的影响。结果表明,三官能团单体三羟甲基丙烷三丙烯酸酯(TMTPA)的透光率最低,单官能团单体异冰片丙烯酸(IBOA)的透光率最高。聚氨酯类低聚物比环氧类低聚物的透明性好,芳香族聚醚型聚氨酯二丙烯酸酯(6201)的透光率最高。9种引发剂中,异丙基硫杂蒽酮(ITX)的透光率最低,2-甲基-2-(4-吗啉基)-1-[4-(甲硫基)苯基]-1-丙酮(907)的透光率最高。随着低聚物和色浆用量的增加,UV固化涂料的透光性明显下降。     

POP-290阻燃剂对丙烯酸酯光固化涂料的影响

制备了双酚A环氧丙烯酸酯(EA)/阻燃剂(POP-290,聚合物聚醚多元醇)/活性单体阻燃UV涂料,主要考察了不同用量的阻燃剂对丙烯酸酯UV涂料的阻燃性能和光固化的影响.研究结果表明,阻燃剂的使用提高了UV涂料体系的固化速度、凝胶含量及玻璃化转变温度(Tg).当m(EA)∶m(活性单体)=4∶1,POP-290含量为7%(质量分数)时,水平燃烧等级达到FH-1,LOI从原来的21提高到26.     

UV-光固化光纤涂料的研制

本文采用环氧丙烯酸酯与聚氨酯丙烯酸酯共混聚合的方法制备出新型的UV．光固化光纤涂料,其主要性能较好．研究了基体组成、引发剂、稀释剂以及固化工艺对UV-固化光纤涂料的光固化速度的影响．通过实验发现,环氧丙烯酸酯与聚氨酯丙烯酸酯的配比为4：6～6：4、稀释剂的含量不大于20％时固化速度较快、性能较好,同时固化时灯距与固化膜厚度对固化速度的影响较大．     

PP薄膜UV光固化涂层制备

以聚氨酯丙烯酸酯(PUA)和环氧丙烯酸酯(EA)为预聚体,单体丙烯酸异冰片酯(EM70)为活性稀释剂,1-羟基环己基苯酮(184)和二苯甲酮(BP)为光引发剂,添加多种功能性助剂,制备了用于PP薄膜的UV光固化涂层材料。研究了预聚物、活性稀释剂、光引发剂等成分对涂料的固化速率、附着力和耐候性的影响,并讨论了涂膜厚度对PP薄膜性能的影响。结果表明,当m(PUA)∶m(EA)∶m(EM70)∶m(184)∶m(BP)∶m(助剂)=45.0∶28.1∶20.1∶1.62∶1.62∶3.56,涂层厚度为25μm时,涂层材料的附着力为0级,硬度为3H,耐酸碱性大于72 h,透光率达到91.5%,雾度为0.9%。     

适用于纸制餐具柔性印刷的环保UV光油的研制

利用正交实验设计方法,研制出一种新型的环保UV光油。将预聚物种类和比例、活性单体种类和比例、光引发剂种类以及比例和固化时间作为考察因素,以UV光油在纸制餐具基材上的附着力和耐摩擦性能作为因变量,得到最优的UV光油配方。选择聚氨酯丙烯酸酯(PUA)与环氧丙烯酸酯(EPA)作为预聚物,其比例为1∶1;选择活性单体TMPTA和NPGDA作为活性稀释剂,其比例为1∶2;选择自由基光引发剂和阳离子光引发剂作为混杂引发剂,其比例为1∶1。该配方为混杂光固化体系,兼具自由基光固化和阳离子光固化特点,固化程度高,活性单体和光引发剂残余少,有优良的附着力和耐摩擦性。     

聚氨酯丙烯酸酯UV固化涂料的制备及性能研究

以甲苯二异氰酸酯(TDI)、聚氧化丙烯三醇和甲基丙烯酸羟乙酯(HEMA)为主要单体,1,6-己二醇二丙烯酸酯(HDDA)为活性稀释剂,二月桂酸二丁基锡(DBTDL)为催化剂,合成了UV固化涂料制备用聚氨酯丙烯酸酯(PUA)低聚物。研究结果表明:当n(TDI)∶n(聚氧化丙烯三醇)∶n(HEMA)=3.08∶1∶3时,PUA低聚物的Mr(相对分子质量)比较理想;当固化时间为4 min、w(PUA低聚物)=87%、w(光引发剂Irgacure184)=5%、w(HDDA)=4%和w(其他助剂)=3%(均相对于总物料质量而言)时,UV固化涂料的综合性能相对最好,其胶膜硬度为2H、附着力为1级、耐酸碱性大于72 h和Tg(玻璃化转变温度)为38.9℃。     

紫外光辐射固化粘合剂主成分的分离和鉴定

本文介绍了ＴＢ－３０５１型紫外光辐射固化粘合剂主成分的分离和鉴定。实验结果表明该粘合剂的主成分是预聚体双酚Ａ环氧双丙烯酸醋树脂，活性稀释剂甲基丙烯酸Ｂ－羟乙酯和双酚Ａ环氧双丙烯酸酯；光引发剂安息香乙醚。     

A novel UV‐curable epoxy acrylate resin containing arylene ether sulfone linkages: Preparation,characterization, and properties

UV‐curing processes are used in industrial applications because of their advantages such as high‐speed applications and solvent‐free formulations at ambient temperature. UV‐curable epoxy acrylate resins containing arylene ether sulfone linkages (EAAES) were synthesized through the condensation of bis(4‐chlorophenyl)sulphone and bisphenol‐A, followed by end‐caping of epichlorohydrin and subsequently acrylic acid. UV‐cured coatings were formulated with epoxy acrylates, reactive diluents such as pentaerythritol tri‐acrylate and pentaerythritol dia‐crylate and photoinitiator. Fourier transfer infrared, ¹H NMR, and thermal gravimetrical analysis were employed to investigate the structures and thermal properties of the EAs films. The introduction of EAAES into epoxy acrylate substantially improves its thermal properties and thermo‐oxidative stability at high temperatures. In addition, the acrylate containing arylene ether sulfone linkages can also improve pencil hardness and chemical and solvent resistance of the epoxy acrylate. The obtained UV‐curable epoxy acrylate containing arylene ether sulfone linkages is promising as oligomer for UV‐curable coatings, inks, and adhesives in some high‐tech regions. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41067.     

UV固化丙烯酸酯胶粘剂的合成及性能研究

以甲基丙烯酸甲酯(MMA)、丙烯酸丁酯(BA)、甲基丙烯酸缩水甘油酯(GMA)和丙烯酸羟乙酯(HEA)为共聚单体,并以二缩三丙二醇二丙烯酸酯(TPGDA)为交联剂、十二烷基硫醇(NDM)为链转移剂和乙酸乙酯为极性溶剂,采用核/壳溶液聚合法合成了侧链含C=C的丙烯酸酯预聚体;然后以此为基体树脂、丙烯酸异冰片酯(IBOA)和三羟甲基丙烷二丙烯酸酯(TMPTA)为活性稀释剂、651为自由基光引发剂和碘鎓盐为阳离子光引发剂,制备了UV固化胶粘剂。研究结果表明:合成丙烯酸酯预聚体的最佳工艺条件是m(BA)∶m(MMA)∶m(GMA)∶m(TPGDA)∶m(HEA)=20∶60∶10∶4∶6、n(TPGDA)∶n(NDM)=2∶2、w(热引发剂)=3%和w(乙酸乙酯)≥70%(均相对于共聚单体总质量而言);自由基/阳离子混杂双重UV固化胶粘剂比单一自由基UV固化胶粘剂具有更大的附着力和耐酸碱性,此时前者的最佳配方中w(预聚体)=55%、w(651或碘鎓盐)=5%、w(IBOA)=15%、w(TMPTA)=12%和w(GMA)=8%(均相对于胶粘剂总物料质量而言)。     

新型醇溶性双组分PUA复膜胶的制备与性能

以烯丙基缩水甘油醚(AGE)、丙烯酸羟丙酯(HPA)、丙烯酸乙酯(EA)和醋酸乙烯酯(VAc)作为共聚单体,合成了复膜胶的主剂——环氧基聚丙烯酸酯;以TDI(甲苯二异氰酸酯)、PPG2000(聚醚二元醇)为主要原料,二乙烯三胺为封端剂,合成了复膜胶的固化剂——端氨基PU(聚氨酯);将主剂和固化剂按一定比例共混后,制得新型双组分醇溶性复膜胶。研究结果表明:当反应温度为75℃、反应时间为8 h、w(引发剂)=1.8%和m(EA)∶m(VAc)∶m(AGE)∶m(HPA)=41∶14∶35∶10时,主剂的醇溶性相对最好;当反应温度为70℃、反应时间为2 h和R=n(-NCO)/n(-OH)=1.25时,固化剂的性能相对最好;当n(氨基)∶n(环氧基)=20∶3、固化温度为50℃和固化时间为24 h时,复膜胶的性能接近于进口同类产品。     

A novel ferrocenium salt as visible light photoinitiator for cationic and radical photopolymerization

A novel hybrid photoinitiator for visible light photopolymerization, (η⁶-3-benzoyl-4-chlorodiphenylamine) (η⁵-cyclopentadienyl) iron hexafluorophosphate (Fc-NBP), was synthesized and studied. Its absorption in the UV and visible light regions showed much stronger activity than those of either the commercialized cationic photoinitiator I-261 or the conventional free radical photoinitiator benzophenone, especially above wavelengths of 350 nm. When exposed to visible light, the photoinitiator under study initiates both cationic polymerization and radical polymerization. The photoinitiator's abilities in the photopolymerization of acrylates and epoxides were evaluated by near infrared (NIR) spectroscopy. The results from NIR clearly indicate that Fc-NBP exhibited high efficiency in photopolymerizing acrylate monomers. In the same lamp, however, benzophenone showed no photoinitiating ability. The photopolymerization rate of the diglycidyl ether of the bisphenol-A epoxy (DGEBA) oligomer was found to be slower than that of acrylates when using Fc-NBP as the photoinitiator. This study shows that the polymerization of epoxide DGEBA can be speeded up by adding a photosensitizer benzoyl peroxide (BPO), but BPO and tertiary amines do not affect the free radical photopolymerization of tripropylene glycol diacrylate (TPGDA). We conclude by providing a possible photoinitiation mechanism.     

引发剂对UV油墨固化速度影响的研究

为提高UV油墨的固化速度,研究了羟烷基苯酮类1173、胺烷基苯酮类907、酰基磷氧化物类819、二苯甲酮类BP、硫杂蒽酮类ITX 5种引发剂及复配对UV油墨固化速度的影响。结果表明,引发剂浓度为2%,颜料浓度为4%,单体浓度为30%时,引发剂1173、BP的固化时间分别为20.88 s和70.56 s,引发剂907的光固化时间为7.14 s,引发剂819和ITX的光固化时间均可达到1.5 s。引发剂1173与BP进行1∶3复配时,固化速度是BP的4.9倍;引发剂907与BP进行1∶3复配时,固化速度是BP的4.3倍;引发剂ITX与907进行1∶1复配时,固化速度是907的2.3倍。     

丙烯酸酯乳胶涂料的制备及其在室内设计中的应用

基于互穿网络聚合法合成了丙烯酸酯乳胶涂料乳化剂,选用二烷基磺基琥珀酸盐、聚氧乙烯烷酚基醚、聚二甲基硅氧烷、聚氨酯类增稠剂、乙二醇、2-甲基-4-噻唑啉-3-酮、5-氯-2-甲基-4-异噻唑啉-3-酮等助剂,加入不同的颜料,完成丙烯酸酯乳胶涂料的制备,并分别对其防腐耐霉性、摩擦系数、耐磨性、抗冲击性能进行分析。结果表明:丙烯酸酯乳胶涂料不易发霉,稳定性强;聚二甲基硅氧烷与聚氨酯类增稠剂质量比为10∶3时,涂料摩擦系数较大;62℃时,涂料的各项性能最优,尤其耐磨性和抗冲击性能最好,满足室内设计需求。     

Study on esterification of acrylic phenolic resin by maleic anhydride and photocrosslinking properties of the alkali‐soluble product

An alkali‐soluble, photocrosslinkable polymer was synthesized by esterification of OH groups of acrylic phenolic resin with maleic anhydride. The OH groups were formed by the ring‐opening reaction of epoxy groups of epoxy phenolic resin with acrylic acid. The esterification conditions were studied. The results showed that it is better to use tetramethyl ammonium bromide as catalyst than N,N‐dimethylbenzylamine. The conversion of maleic anhydride in acetone can reach about 80% at 56°C for 4 h. The purified product was characterized by IR, DSC, and TGA. The product containing acrylate and maleic acid monoester groups, above a certain content, can be dissolved in 1% Na₂CO₃ solution. The photocrosslinkable properties of the product were investigated through selection of photoinitiator, accelarator, crosslinkable diluent monomer, etc. The acrylate and maleic acid monoester group‐containing phenolic resin exhibited very good photocrosslinking behavior, since it contains double bonds from both acrylate groups and maleic acid monoester groups. The activity of photoinitiator decreases in the order: isopropylthioanthraquinone > benzoin ethyl ether (BE) > anthraquinone (AQ) > benzophenone > Michel ketone (MK) > 2,2‐diethoxyacetophenone. The combination of some photoinitiators showed synergistic effects. The order of increasing activity for the accelerator is as follows: MK > ethyl p‐(dimethylamino)benzoate > N,N‐dimethylaniline > triethanolamine. The optimum diluent monomer is trimethylolpropane trimethacrylate. The gel content of the mixture of the resin and trimethylolpropane trimethacrylate could reach 85% using the combined photoinitiators of BE and AQ under UV exposure for 120 s. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 1607–1614, 2005     

UV涂料对光纤附加光衰减的影响

采用双酚A环氧丙烯酸酯(EA)和聚氨酯丙烯酸酯(PUA)共混,加入活性稀释剂、光引发剂、颜料等制备了紫外光固化光纤涂料。讨论了EA与PUA的配比,预聚物与活性稀释剂的配比以及光引发剂及颜料的含量对光纤带附加光衰减的影响。结果表明:当EA/PUA为1∶1.5(质量比),预聚物质量分数为52%,活性稀释剂质量分数为28%,光引发剂质量分数为14%,颜料质量分数为1.5%时,光纤具有最小的附加光衰减值。     

光固化光纤彩色涂料的研制

采用环氧丙烯酸酯和脂肪族聚氨酯丙烯酸酯共混的方法研制了一种新型光固化光纤彩色涂料。研究了基料树脂、活性稀释剂、光引发剂、颜料、助剂等对涂料综合性能的影响。结果表明，环氧丙烯酸树脂与脂肪族聚氨酯丙烯酸酯配比为40：20，单、双、多官能团稀释单体配比为3：20：10，复合光引发剂用量10％，有机颜料用量1．5％，所配制的光固化光纤涂料性能优良。     

Surface protection of poly(vinyl chloride) by photografting of epoxy–acrylate coatings

UV-curable epoxy–acrylate coatings were used to protect poly(vinyl chloride) against superficial degradation. With α-hydroxy–acetophenone photoinitiators, the crosslinking polymerization develops in the ms time scale; 50% degree conversion is reached after irradiation times of 2.5 ms in a nitrogen atmosphere and 17 ms in air. The adhesion of the coating on to the PVC substrate can be greatly improved by inducing a photochemical grafting process. The best results are obtained by incorporating the photoinitiator into the top layer of the PVC sheet. Highly crosslinked epoxy–acrylate coatings are very stable toward UV radiations and chemical agents like organic solvents and strong acids. By their light-screening effect they provide an excellent protection against photodegradation for light-sensitive polymeric materials.