二硫代水杨酸衍生物对光固化材料性能的影响

设计、合成了一种二硫代水杨酸衍生物(MAPBS),详细研究了MAPBS对丙烯酸酯类单体光聚合动力学及其聚合物膜体积收缩、耐热性能及硬度的影响。研究结果表明,在365 nm LED光源照射下,MAPBS能够引发甲基丙烯酸酯类单体聚合和降低聚合物膜体积收缩。随着MAPBS含量的增加,光聚合体系的双键转化率和聚合速率随之增加,分别达到64.9%和1.19%/s,而体积收缩呈现先降低再增加的趋势,聚合物膜热稳定性略微降低,硬度略有增加。MAPBS兼具引发和降低体积收缩的双重功能,在LED光聚合体系表现出一定的应用潜力。     

UV固化聚氨酯丙烯酸酯涂料的研制及其应用

以丙烯酸羟丙酯(HPA)、1,6-己二异氰酸酯(HDI)三聚体为主要原料合成低相对分子质量三官能度聚氨酯丙烯酸酯(PUA)低聚物,以该低聚物为主体树脂,添加活性稀释剂、丙烯酸共聚体系、光引发剂及其他涂料助剂制成紫外光(UV)固化聚氨酯丙烯酸酯涂料。同时对UV固化膜性能进行研究,分别讨论了主体树脂含量、活性稀释剂含量、丙烯酸体系含量及光引发剂含量对UV固化涂膜性能的影响,进而对涂料不同组分的种类及配比进行优化,确定了紫外光(UV)固化聚氨酯丙烯酸酯涂料的工艺配方,研究结果表明:该涂料的玻璃化温度(Tg)为60.9℃,涂膜具有较好的综合性能。     

有机硅改性丙烯酸酯的UV固化

在80℃下以OP-10和DBS作为混合乳化剂,以有机硅预聚体和丙烯酸酯单体采用自由基共聚制得了有机硅改性丙烯酸酯乳液,降温后再加入3%光聚合单体(HDDA和EO-TMPT)和光引发剂安息香甲醚,得到可紫外固化硅丙树脂乳液。其成膜经过紫外光照后,固化效率大大提高。经性能测试的结果为:断裂伸长率达到367%,抗张强度达到19.3 MPa,吸水率为32.2%,玻璃化温度(Tg)为-45.7℃。     

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℃。     

不同官能度水性聚氨酯丙烯酸酯的合成及性能

以丙烯酸羟乙酯与季戊四醇三丙烯酸酯作为封端剂,分别合成了二官能度水性聚氨酯丙烯酸酯(WPUA2)和六官能度的水性聚氨酯丙烯酸酯(WPUA6),并用红外光谱、粒径仪、热重分析对合成产物结构和性能进行表征。研究表明,相比于使用低官能度WPUA2紫外光固化所得聚氨酯丙烯酸酯(PUA)涂膜,加入单体或使用多官能度WPUA6,都可使PUA固化膜凝胶率提高20%以上,吸水率降低30%;质量损失10%,分解温度增大82℃。提高预聚物官能度可有效提高涂膜交联密度和耐热性能,并具有与加入活性单体相似的应用效果。     

聚氨酯丙烯酸酯齐聚物制备紫外光固化胶粘剂

按正交实验的方法,采用自制的聚氨酯改性丙烯酸酯齐聚物(PUA)与改性剂,研制出了紫外光(UV)快速固化胶粘剂,并对其影响因素进行了简要分析。结果表明,由PUA改性的UV固化胶粘剂具有较好的粘接性能。在所考察的影响因素中,对胶粘剂强度的影响程度大小顺序为:自制改性剂>1,6-己二醇二丙烯酸酯(HDDA)/三羟甲基丙烷三丙烯酸酯(TPGDA)>聚酯丙烯酸酯(EB-524)/PUA齐聚物≈多官能度单体>单官能度单体=KH570>光引发剂。     

聚氨酯丙烯酸酯的涂膜制备及性能研究

以甲苯-2,4-二异氰酸酯、丙烯酸羟乙酯及聚四氢呋喃二醇为原料,采用本体法合成了聚氨酯丙烯酸酯(PUA)预聚物。选用Irgacure 2959为光引发剂,二官能度的PEG200DA作为活性稀释剂,将PUA预聚物与Irgacure 2959、PEG200DA及乙醇的混合物溶液涂覆于热塑性聚氨酯表面进行紫外光固化,考察了不同含量的Irgacure 2959和PEG200DA对固化膜附着力、凝胶率、力学性能以及耐化学腐蚀性的影响,并确定了Irgacure 2959和PEG200DA的质量分数分别为固体分的5%和20%时,所制备的固化膜的性能最优,固化效率最高,附着力为0级,具有优异的耐水和耐化学腐蚀性;且固化膜的玻璃化转变温度为-58℃,分解温度为260℃。     

UV固化涂料用长臂多官能度大分子光引发剂的合成及性能

利用乙氧基化季戊四醇/双季戊四醇与由聚乙二醇(PEG400)、异佛尔酮二异氰酸酯(IPDI)、2-羟基-2-甲基-1-[4-(2-羟基乙氧基)苯基]-1-丙酮(Irgacure 2959)反应形成的端异氰酸酯预聚体合成了2种可用于紫外光固化的长臂多官能度大分子光引发剂(MPIs)。利用红外光谱、核磁共振谱表征其结构。利用紫外-可见光谱研究了MPIs的光分解过程,用实时红外光谱研究了MPIs引发1,6-己二醇二丙烯酸酯(HDDA)的聚合动力学。结果表明:MPIs的引发效率稍高于Irgacure 2959;光引发速度随引发剂用量增加而提高;与Irgacure 2959相比,MPIs在光固化单体及树脂中的溶解性有所提高,光固化膜中残留光引发剂的迁移率降低。MPIs引发光固化聚合后的固化膜性能优异,表明MPIs是一类性能优异的大分子光引发剂。     

UV固化聚氨酯丙烯酸酯的非催化合成及性能

在不使用任何催化剂的条件下,合成了UV固化的聚氨酯丙烯酸酯树脂。采用傅里叶变换红外光谱、核磁共振氢谱、碳谱对合成树脂进行了表征,并采用综合热分析仪对固化膜的耐热性进行分析。试验结果表明:随着活性单体官能度的增大,固化膜的耐热性提高;随着双官能团单体三缩丙二醇二丙烯酸酯(TPGDA)用量的增加,固化膜的耐热性略有提高,但变化不明显;其他性能测试表明:固化膜具有优异的综合性能。     

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。     

Photopolymerization and thermal behavior of phosphate diacrylate and triacrylate used as reactive‐type flame‐retardant monomers in ultraviolet‐curable resins

Tri(acryloyloxyethyl)phosphate (TAEP) and di(acryloyloxyethyl)ethyl phosphate (DAEEP) were used as reactive‐type flame‐retardant monomers along with commercial epoxy acrylate and polyurethane acrylate oligomers in ultraviolet (UV)‐curable resins. The concentrations of the monomers were varied from 17 to 50 wt %. The addition of the monomers greatly reduced the viscosity of the oligomers and increased the photopolymerization rates of the resins. The flame retardancy and thermal degradation behavior of the UV‐cured films were investigated with the limiting oxygen index (LOI) and thermogravimetric analysis. The results showed that the thermal stability at high temperatures greater than 400°C and the LOI values of the UV‐cured resins, especially those containing epoxy acrylate, were largely improved by the addition of the monomers. The dynamic mechanical thermal properties of the UV‐cured films were also measured. The results showed that the crosslink density increased along with the concentrations of the monomers. However, the glass‐transition temperature decreased with an increasing concentration of DAEEP because of the reduction in the rigidity of the cured films, whereas the glass‐transition temperature increased with the concentration of TAEP because of the higher crosslink density of the cured films. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 185–194, 2005     

Synthesis and properties of novel polyurethane acrylate containing 3-(2-hydroxyethyl) isocyanurate segment

Novel UV curable multi-functional polyurethane acrylate (PUA) containing 3-(2-hydroxyethyl) isocyanurate (THEIC) segment was synthesized through three step reactions, the ring-opened reaction of ?-caprolactone with THEIC under the catalysis of tetrabutyl titanate (TBT), the polyaddition reaction between formed hydroxyl compounds and isophorone diisocyanate (IPDI) and condensation reaction between the product of the second step and pentaerythritol triacrylate (PETA). The chemical structure of PUA oligomer and some influence factors in synthesis process were characterized with GPC, ¹H NMR and FTIR. And its photopolymerization process and properties of cured films were also investigated.     

Ultraviolet curing of liquid polysulfide thiourethane acrylate

A series of liquid polysulfide thiourethane acrylate prepolymers were synthesized by the reaction of liquid polysulfide with isocyanate and hydroxyethyl acrylate. With and without a combination of acrylic monomers, the prepolymers were cured with ultraviolet radiation. The films exhibited a higher soft‐segment glass‐transition temperature than metal oxide cured polysulfide. With the addition of a diluent, the tensile strength and modulus increased, whereas the ultimate elongation decreased. The polysulfide backbone, combined with the crosslink generated from the photopolymerization of acrylic, produced films with superior oil resistance. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 2358–2363, 2004     

Polyhedral oligomeric silsesquioxane-reinforced polyurethane acrylate

Hybride nanocomposite films of polyhedral oligomeric silsesquioxane (POSS) and polyurethane acrylate (PUA) were prepared by introducing POSS into PUA by free-radical photopolymerization, to enhance thermo-mechanical properties of PUA. The addition of POSS to PUA resulted in increases in the following properties: elasticity, glass transition temperature, thermal stability and dimensional stability. With increasing POSS content, the elastic modulus and thermal stability of PUA films increased due to an increased crosslinking density and the reinforcing effect of POSS particles on the PUA, whereas the surface free energies of these films decreased. The water contact angle against water increased due to the enhancement of the hydrophobicity of the polymer surface, caused by the low surface energy of POSS molecular. However, at high POSS content the mechanical properties of the films were decreased, as a result of aggregation of the POSS particles.     

From rosin to high adhesive polyurethane acrylate: Synthesis and properties

A high adhesion polyurethane acrylate (HPUA) was synthesized from isophorone diisocyanate (IPDI), hydroxyethyl acrylate (HEA) and hydrogenated rosin. The chemical structure was characterized by ¹H NMR and FTIR; storage modulus and glass transition temperature (T_g) were measured with dynamic mechanical analyzer. Real time infrared spectroscopy (RTIR) was used to investigate the effect of different concentrations of photoinitiator on the double bond conversion of HPUA. Real time volume shrinkage and adhesion on glass, poly(ethylene terephthalate) (PET), polycarbonate (PC) and polyvinyl chloride (PVC) substrates were also measured by laser micrometer and universal testing machine. Results showed that this kind of HPUA has a high photopolymerization rate, low volume shrinkage and high adhesion compared with commercial polyurethane acrylate competitor.     

Design and Preparation of Tertiary Amine Modified Polyurethane Acrylate Oligomer with Co‐Initiation/Polymerization Bifunctions for Photo‐Curable Inkjet Printing of Textiles

In order to resolve the conflict issues existing in currently available polyurethane acrylate (PUA) oligomers for photo‐curable inkjet printing of textile, and to avoid the safety problems caused by the immigration of small molecule amine co‐initiator, a series of tertiary amine modified PUA oligomers are delicately designed and synthesized. The chemical structures of the synthesized PUA oligomers are confirmed by FTIR and ¹H‐NMR analyses. The optimized PUA oligomer/hydroxyethyl acrylate based polymerization system show a low viscosity, high storage stability and good compatibility with various functional segments. Furthermore, the modified PUA oligomer acts as both the photopolymerization constituent and the macromolecular co‐initiator assisting to achieve high photopolymerization rate and conversion rate, and avoiding the disadvantages caused by the migration of small amine co‐initiators. Benefitting from the semi‐IPN formed by this polymerization system with suitable crosslinking density and phase separation degree, a soft, strong and flexible cured film is obtained. The high photo‐reactivity with low viscosity of the polymerization system and the good flexibility with high strength of the resultant photo‐cured film ensures the applications of the modified PUA oligomer, and the printed fabrics achieve 4 grade of colorfastness with improved handle properties, as well as brilliant color and fine patterns.     

聚己内酯三元醇型双固化聚氨酯丙烯酸酯的合成及其固化膜性能研究

以聚己内酯三元醇、异佛尔酮二异氰酸酯和羟基丙烯酸酯为原料,合成了一种新型聚氨酯丙烯酸酯。该树脂含有C C双键和未封闭的—NCO基团,可同时进行光固化和热固化反应。研究了不同双键含量对体系成膜性能的影响。结果表明,随着双键含量的上升,体系光固化后的摆杆硬度变大,耐溶剂性、玻璃化转变温度、铅笔硬度提高,但是柔韧性下降。同时发现,后期的热固化对体系的硬度和热性能有补强的作用,但是会在一定程度上导致涂膜的柔韧性下降。     

Initiator‐free photopolymerization of common acrylate monomers with 254 nm light

Using an available light source at a wavelength of 254 nm, common acrylate monomers were polymerized without any photoinitiators, which was confirmed using Fourier transform IR (FTIR) spectroscopy, ¹H NMR, gel permeation chromatography and fast atom bombardment mass spectrometric measurements. It was found that phenyl acrylate shows higher conversion than n‐ and t‐butyl acrylates. A trifunctional acrylate was also used for UV curing. The cured films were fabricated successfully on different kinds of substrates by using a batch‐ or conveyor‐type irradiation apparatus. It is indicated from FTIR spectral measurements that ca 40%–50% of acryloyl groups are consumed by the photopolymerization. Oxygen concentration in the sample chamber influences the photopolymerization, indicating that the polymerization proceeds via a radical process. © 2018 Society of Chemical Industry