光固化低黏度环氧丙烯酸酯的合成与性能研究

合成了可紫外光固化的低黏度环氧丙烯酸酯树脂,通过红外光谱、核磁共振氢谱、碳谱对树脂结构进行了表征;采用综合热分析仪(DSC-TG)对树脂固化膜的耐热性能进行了分析。结果表明,在树脂中添加活性单体时,随单体官能度的增加,固化膜的耐热性能增加,但双官能团单体的用量对固化膜的耐热性能没有明显影响。固化膜具有较好的耐热性,初始分解温度为330.7℃,玻璃化转变温度为76.9℃。所得树脂黏度仅为3~4Pa.s(60℃),为市售产品的1/3,附着力1级,硬度4 H,耐水性能优异,无需添加单体使用。     

水性聚氨酯/丙烯酸酯复合乳液的制备及性能研究

以聚四氢呋喃二醇（PTMG）、甲苯二异氰酸酯（TDI）、2,2–双（羟甲基）丙酸（DMPA）和1,4–丁二醇（BDO）为主要原料,经逐步聚合制得水性聚氨酯,并利用红外光谱对其结构进行表征。以水性聚氨酯自乳化包覆丙烯酸酯单体,制备系列水性聚氨酯/丙烯酸酯核壳复合乳液（WPUA）,并探究丙烯酸酯单体含量、种类及壳层水性聚氨酯结构对复合乳液和固化膜性能的影响。结果表明,随着对丙烯酸酯单体的乳化包覆比从0增加到1.2,乳液粒径从24.65 nm增加到543.61 nm,黏度从31.4mPa·s增加到2 571.2 mPa·s,而固化膜的拉伸强度从12.16 MPa先降到6.73 MPa,再升到16.38 MPa,断裂伸长率从1771.4%降到63.8%,材料的耐水性和耐热性得到提高;探究不同丙烯酸酯种类对固化膜性能的影响,结果表明,随着单体官能度的增大,固化膜的拉伸强度明显升高,但断裂伸长率降低;通过改变壳层水性聚氨酯结构表明,线型水性聚氨酯制得的WPUA固化膜拉伸强度较低,为7.25 MPa,但断裂伸长率有325%,而多支链型水性聚氨酯制得的WPUA固化膜拉伸强度较高,达13.94 MPa,...     

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。     

含羧基超支化聚酯丙烯酸酯的合成及其性能研究

以季戊四醇为"核",二羟甲基丙酸为AB2单体,利用逐步聚合方法合成了不同代数超支化聚酯。将得到的不同代数超支化聚酯用丁二酸酐和六亚甲基二异氰酸酯与丙烯酸羟乙酯的半加成产物按不同比例进行改性,得到了含羧基超支化聚酯丙烯酸酯。对得到的含羧基超支化聚酯丙烯酸酯的结构用傅里叶红外光谱、核磁共振波谱等手段进行了表征。紫外光谱表明,所有超支化低聚物在210 nm处有强紫外吸收;差示扫描结果表明,所有超支化聚酯丙烯酸酯都具有低的玻璃化转变温度;热重分析测试结果显示,随着超支化聚酯代数增加,超支化聚酯丙烯酸酯固化膜耐热性能提高。     

UV固化丙烯酸酯压敏胶的制备及性能研究

以线性丙烯酸酯共聚物及聚合单体丙烯酸酯为原料,采用光聚合技术,制备了UV固化丙烯酸酯压敏胶。通过红外光谱(FT-IR)分析了产物的结构;对压敏胶的粘接性能进行了研究。结果表明:光引发剂含量为0.4~0.8phr,官能单体含量为1~3phr,软/硬单体配比为8:2时,压敏胶的综合性能最佳。     

迈克尔加成高效制备丙烯酸酯化光敏性聚酰亚胺

为克服传统光敏聚酰亚胺加工温度过高、成本高、介电性不佳、感光效率低、溶解性差等问题,利用多官能酸酐转化为多官能酰亚胺及酰亚胺对多官能丙烯酸酯的迈克尔加成反应,设计制备了10个光敏型丙烯酸酯化聚酰亚胺树脂（PI）,并通过加入光引发剂进行自由基紫外光固化成膜。以核磁共振谱（NMR）、傅立叶变换红外光谱仪（FT-IR）对所得树脂PI结构进行了表征,通过FT-IR跟踪表征了PI光固化行为,并考察了活性稀释剂、光固化条件等对树脂固化行为的影响。再通过差示扫描量热仪（DSC）、热重分析仪（TG）以及介电谱和应力-应变测试等表征了聚酰亚胺丙烯酸酯固化膜的基本性能。结果表明：树脂光固化过程双键转化程度可达90%,树脂结构与固化膜性能之间存在一定关联,未添加稀释剂PI固化膜相对介电常数基本低于3.0,显著低于常规光固化丙烯酸酯单体,添加特种N-乙烯基环酰胺活性稀释剂可使PI介电性略有升高。     

光固化超支化聚氨酯丙烯酸酯的合成及其固化膜性能

以新戊二醇为核,二羟甲基丙酸为支化单体合成得到每个分子中含有16个端羟基的超支化脂肪族聚酯,将其与自制甲苯-2,4-二异氰酸酯.丙烯酸羟丙醅单体的NCO端基团反应,获得新型可紫外光固化的超支化聚氨酯丙烯酸醑.应用红外光谱分别对超支化聚酯、超支化聚氨酯丙烯酸酯及其紫外光固化胶膜的化学结构进行分析,同时应用力学性能测试、差示扫描量热分析、热重分析等手段对单体官能度及用量对固化膜物理性能和热性能的影响进行研究.结果表明:随着活性单体用量的增加,固化膜的抗冲击强度增加,硬度减小,活性单体官能度的增加有利于提高其硬度;热重分析结果表明固化膜具有两个热分解温度,初始分解温度大于200℃,另一分解温度约为375℃;差示扫描量热分析结果显示,固化膜具有两个玻璃化转变温度(Tg.s,Tg.h),随着活性单体官能度的增加,Tg.s降低,Tg.h升高,有利于相分离,而其用量的增加却不利于相分离;利用红外和凝胶法分析对比研究超支化聚氨酯丙烯酸酯的光固化行为,结果表明其不饱和双键的最终转化率高达90%.     

硅烷/聚硅氧烷改性含氟丙烯酸酯共聚物的研究

制备了低毒性溶剂型硅烷偶联剂改性含氟甲基丙烯酸酯、甲基丙烯酸异丁酯和甲基丙烯酸异冰片酯共聚物,通过测量水接触角、吸水率、铅笔硬度、IR光谱、DSC和TGA等测试,探讨了含硅丙烯酸酯、含氟甲基丙烯酸酯单体种类和用量及其共聚工艺及羟基硅油共混改性对共聚物表面憎水性能、强度和耐热性能的影响.结果表明采用延时后滴加含氟丙烯酸酯单体工艺和使用催化交联剂可使的共聚物膜表面的憎水性能和强度大大提高.     

紫外光固化低黏度环氧丙烯酸酯的合成

引入新的催化剂和新的阻聚剂构成催化-阻聚复合助剂体系,合成了可紫外光固化的低黏度环氧丙烯酸酯树脂,利用傅里叶变换红外光谱、核磁共振氢谱、碳谱对树脂结构进行了表征;研究了复合助剂及常用的催化剂、阻聚剂对反应过程及树脂性能的影响,发现复合助剂体系具有更好的催化和阻聚效果,反应活化能仅为37.69 kJ·mol-1·K-1,所得树脂黏度仅为3 000～4 000 mPa·s(60℃),为市售产品的1/3;最后利用综合热分析仪对树脂固化膜的耐热性能进行了分析.     

异氰酸酯改性环氧丙烯酸酯的合成与性能

合成了可紫外光(UV)固化的异氰酸酯改性的环氧丙烯酸酯树脂,利用元素分析、傅里叶变换红外光谱、核磁共振氢谱对树脂结构进行了表征;研究了异氰酸酯种类及用量对反应过程及产物性能的影响,表明TDI/80体系所得产物具有较好的综合性能,固化膜具有较好的柔韧性,其用量以n(-NCO)∶n(-OH)比值在0.25为宜.对树脂及其涂膜性能测试表明,所得改性树脂60 ℃时黏度为4 500 mPa·s,柔韧性大幅度提高,为3 mm,并保持了较好的耐热性、附着力(1级)和硬度(3H).     

Design and synthesis of bio-based UV curable PU acrylate resin from itaconic acid for coating applications

UV curable PUA resin was successfully synthesized from polyol based on sustainable resource originated from itaconic acid (IA), isophorone diisocyanate (IPDI) and 2-hydroxyethyl methacrylate (HEMA). A polyol was synthesized by condensation reaction of IA with 16-hexanediol in the presence of p-Toluenesulfonic acid (pTSA). The synthesized PUA resin was characterized for its structural elucidation by using Fourier Transform Infrared Spectrophotometer (FTIR), ¹H and ¹³C NMR spectroscopy. The synthesized UV curable PUA resin was incorporated in varying concentrations in conventional PUA coating system. The effects of varying concentration of synthesized UV curable PUA resin on rheology, crystallinity, thermal and coating properties were evaluated. The rheological behavior of the resins were evaluated at variable stress and result showed decrease in viscosity of resin as concentration of synthesized UV curable PUA resin increases in conventional PUA resin. The cured coatings have been evaluated for glass transition temperature (T_g) and thermal behavior by differential scanning calorimeter and thermogravimetric analysis respectively. The degree of crystallinity of the coatings was determined from X-ray diffraction patterns using the PFM program. It was found that increase in the mass proportion of IA based PUA in coatings, the coating becomes more rigid and crystalline. The synthesized UV curable PUA coatings showed interesting mechanical, chemical, solvent and thermal properties as compared to the conventional PUA. Further, cured coatings were also evaluated for gel content and water absorption.     

聚氨酯丙烯酸酯浸渍固化对淀粉-纤维素复合膜性能的影响

利用聚氨酯丙烯酸酯树脂（PUA）对淀粉-纤维素膜进行改性,以改善材料性能。先以玉米淀粉和纤维素为主要原料,在无机盐氯化锌水溶液中溶解,用流延法制备淀粉-纤维素混合膜（RSC）;再以PUA为浸渍树脂,采用浸渍固化法制备淀粉-纤维素-聚氨酯丙烯酸酯复合膜（RSC-PUA）,考察树脂浓度、光固化时间等因素对复合膜力学性能、吸水性能的影响,并通过扫描电镜、X射线衍射仪、热重分析等手段表征复合膜形貌和结构。实验结果表明：最适宜树脂质量分数为30%,光固化时间为120s;RSC-PUA复合膜比RSC膜拉伸强度提高2.4倍,断裂伸长率提高6倍,吸水率降低了53.6%,热裂解温度增高113℃。以上结果表明,经PUA树脂改性后的复合膜的力学性能、耐湿性、热稳定性提高。     

Preparation and properties of UV‐curable waterborne polyurethane–acrylate emulsion

Polyurethane–acrylate oligomer terminated with multiple unsaturated bonds was prepared using isophorone diisocyanate, (IPDI), methylene diphenyl diisocyanate, and polyols as monomers, using 2,2‐dimethylol propionic acid as hydrophilic chain extender, together with pentaerythritol triacrylate (PETA) as end‐capper. The UV‐curable waterborne polyurethane–acrylate (UV‐WPUA) composite emulsion was obtained by mixing the PUA oligomer with certain content of reactive diluents and then dispersing the mixture in water. The molecular structure of the polyurethane prepolymer, PUA oligomer, and UV‐cured polymer was investigated by Fourier transform infrared spectroscopy. The influence of the composition and content of the diluents and end‐capper on UV‐WPUA properties, including the emulsion stability, thermal property, water resistance, adhesion, hardness, glossiness of polymer film were studied. The results show that the WPUA emulsion has excellent stability, and the UV‐cured film features good hardness and remarkable water resistance when PETA is used as end‐capper and the end‐capping ratio of the polyurethane prepolymer is 70% and dipentaerythritol hexaacylate/dipropylene glycol diacrylate (mass ratio 1:1) is used as diluent. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45208.     

丙烯酸酯改性水性聚氨酯乳液性能的研究

用乳液聚合的方法制备出丙烯酸酯改性的水性聚氨酯共聚乳液（ＰＵＡ乳液）,并对ＰＵＡ乳液的耐溶剂性,热性能和机械性能进行的初步的研究。结果表明,具有核壳结构的ＰＵＡ乳液耐溶剂性,热稳定性和机械性能比水性ＰＵ有明显的提高。     

Study on polyurethane-acrylate/cerium dioxide modified by 3-(Methylacryloxyl)propyltrimethoxy silane and its UV absorption property

Firstly, cerium dioxide(CeO₂) was modified by 3-(Methylacryloxyl)propyltrimethoxy silane (KH-570), and modified CeO₂ (mCeO₂) was prepared. Then poly (urethane-acrylate) was modified by mCeO₂, and poly (urethane-acrylate)/modified CeO₂ (PUA/mCeO₂) composites with ultraviolet absorption property were prepared. The morphology, thermal hydrophobicity, mechanical properties, optical properties, and UV-absorption properties of PUA/mCeO₂ composites were studied. XRD and SEM analysis showed that the modified CeO₂ had better dispersion in the matrix than that of pure CeO₂. Ultraviolet–visible spectrum and thermogravimetric analysis were used to characterize the optical properties and thermal stability of PUA/mCeO₂ composites. The results showed that with the increasing of the mCeO₂ content, the UV-absorption property of PUA/mCeO₂ composites was improved gradually. When the content of mCeO₂ is 3%, the absorption of ultraviolet of PUA/mCeO2 composites is about 5 times of pure PUA film, and the absorption band is mainly in the UVA section. The thermal stability of PUA/mCeO₂ composites was improved with the adding of mCeO₂. With the increasing of mCeO₂ content, the contact angle of PUA/mCeO₂ composites increased significantly. And the UV-absorption mechanism of PUA/mCeO₂ Composites was studied. UV-curable PUA/mCeO₂ composites have good UV absorption property and water resistance. They will be used in the sun screen and protect people's skin.     

新型聚氨酯-聚丙烯酸酯水性体系的热固化与UV固化研究

利用多官能度的三羟甲基丙烷三丙烯酸酯(TMPTA)制备了一种新型的聚氨酯-丙烯酸酯(PUA)复合乳液,分别对所得乳液及相应涂膜进行热固化和UV同化.利用FT-IR光谱对PUA的结构进行了表征,考察了PUA复合乳液的乳液性能;对两种固化体系的双键转化率进行了研究;同时对两种固化方式所得到的涂膜性能进行了研究和比较.实验结果发现,固化后涂膜的力学性能、耐水性、耐溶剂性和耐化学品性均得到显著提高.通过比较发现,UV固化体系涂膜的综合性能优于热固化体系.     

水性聚氨酯与丙烯酸酯共聚乳液的研究

用乳液聚合的方法 ,制备出了具有核壳结构的水性聚氨酯与丙烯酸酯共聚乳液 (PUA乳液 ) ,对PUA的性能进行了初步的研究。结果表明 ,丙烯酸酯的用量对吸水率、热性能和机械性能产生重要的影响     

丙烯酸酯改性非离子型水性聚氨酯的合成及性能

以异佛尔酮二异氰酸酯(IPDI)、聚氧化丙烯二醇(N-210)、聚氧化乙烯二醇(PEG)等为基本原料,丙烯酸羟乙酯(HEA)为封端剂,合成了非离子型双键封端水性聚氨酯(HPU)自乳化乳液,然后与甲基丙烯酸甲酯(MMA)及丙烯酸丁酯(BA)进行自由基聚合,得到丙烯酸酯改性非离子型水性聚氨酯(PUA)乳液.对这种材料进行了耐水性、粒径及热力学等方面的测试,结果表明:PUA乳液粒子有明显核壳结构,乳液的平均粒径增大;胶膜耐水性随着HPU添加量的提高而降低,胶膜的耐热性有明显提高.     

低亲水基丙烯酸酯-聚氨酯复合乳液涂膜的热分析研究

以异佛尔酮二异氰酸酯(IPD I)、聚已二酸-1,4丁-二醇酯(PBA)、二羟甲基丙酸(DMPA)、丙烯酸酯(PA)为主要原料,采用自乳化工艺制备了固体质量分数均为40%,亲水基团(DMPA的羧基)占固体质量百分数为1%的一系列稳定的聚氨酯-丙烯酸酯复合乳液(PUA);用热重分析(TG)、示差扫描量热分析(DSC)、动态机械热分析(DMA)方法研究PBA的相对分子质量、聚氨酯与丙烯酸酯的质量分数比(PU/PA)对PUA膜热性能的影响。热分析研究表明,增加PBA相对分子质量和加入适量的丙烯酸酯能提高PUA分子的有序程度,有利于PUA成膜物耐热性能的改善;随着PBA相对分子质量的增加,PU软段的非晶部分和PA的硬段相容性增强,微观相分离减小,乳液的混合能达到分子水平。     

丙烯酸酯改性水性聚氨酯乳液的制备及性能研究

采用物理共混和核-壳聚合法制备了丙烯酸酯改性水性聚氨酯(PU/PA,PUA)乳液,并对不同改性方法制得的乳液进行了研究。通过红外(FTIR)、透射电镜(TEM)、差示扫描量热(DSC)、热重分析(TGA)、耐水性和力学性能测试等研究了丙烯酸酯改性聚氨酯乳液及涂膜的结构与性能。结果表明具有核-壳结构的PUA乳液涂膜耐水性、耐热性和固含量较水性聚氨酯(PU)有明显的提高,力学性能稍有下降;PUA综合性能优于PU/PA。