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%.     

超支化聚氨酯丙烯酸酯的合成及其紫外光固化膜性能研究

以季戊四醇为核、2,2-二羟甲基丙酸为臂,采用一步熔融法合成了含16个端羟基的超支化聚酯(HBPE).利用异佛尔酮二异氰酸酯和丙烯酸-2-羟乙酯的半加成产物改性HBPE,制备了一系列末端含有不同数量C＝C的超支化聚氨酯丙烯酸酯(HBPUA),并对HBPUA涂料固化过程和固化膜性能进行研究.结果表明,HBPUA改性度越大...     

可UV固化的超支化聚酯改性聚氨酯丙烯酸酯的合成

采用两步法合成了可UV固化的超支化聚酯改性聚氨酯丙烯酸酯(HBUA),优化了合成条件,采用FT-IR对HBUA进行表征,并测试了其UV固化漆膜的综合性能。结果表明,合成HBUA的最佳反应条件是以质量分数0.5%的二月桂酸二丁基锡为催化剂,将相同摩尔数的异氟尔酮二异氰酸酯和甲基丙烯酸羟乙酯在35℃反应2.5 h,然后加入适量的超支化聚酯H20在70℃条件下反应3.0 h,UV固化HBUA漆膜与PUA漆膜相比具有更高的硬度和更好的耐磨性。     

UV固化超支化聚酯丙烯酸酯的合成及其固化性能

以季戊四醇、2,2-二羟甲基丙酸、丁二酸酐和甲基丙烯酸羟乙酯为原料,合成一种新型UV固化超支化聚酯丙烯酸酯(HPA)。通过红外光谱、核磁共振谱表征了其结构;测试了相对分子质量及其分布和黏度;并考察了其紫外光固化性能。结果表明:在反应时间6 h、反应温度90 ℃、n[HP-(COOH)₈]∶n(HEMA)=1∶8时合成的HPA,当用4.5%的光引发剂1173引发固化时,UV辐照能量最小,为600 J/m ²,且固化速度比市售低聚物RJ544组成的相似体系快5倍,其双键的转化率可达89.8%。在制备的HPA经UV固化后,涂膜的铅笔硬度为2H,附着力为1级,柔韧性为0.5 mm。     

UV固化超支化聚氨酯丙烯酸酯的最新研究进展

介绍了UV(紫外光)固化HPUA(超支化聚氨酯丙烯酸酯)的合成方法,指出了各种合成方法所存在的问题;说明了固化动力学和流变行为对产品的重要影响,突出了固化机制研究的必要性,阐述了UV固化HPUA的应用研究现状及发展趋势。最后指出了UV固化HPUA目前所存在的不足之处以及解决办法,并对其未来的发展方向进行了展望。     

可UV固化超支化聚氨酯丙烯酸酯的制备及性能研究

以异佛尔酮二异氰酸酯和丙烯酸羟乙酯等为原料,采用不同扩链剂对自制的超支化聚氨酯进行改性,制备出一系列可紫外光固化的超支化聚氨酯丙烯酸酯(HBPUA-X)。利用红外光谱(FT-IR)、核磁共振(NMR)、热重分析(TG)、示差扫描量热仪(DSC)和乌氏黏度计对HBPUA-X的结构和性能进行了研究。FT-IR与NMR测试结果证实了合成产物为HBPUA-X;黏度计的测试结果表明:产品的特性黏度随扩链剂长度的增加而升高;将HBPUA添加到光固化环氧丙烯酸中成膜,TG与DSC的测试表明:涂膜的热分解温度有不同程度的降低,随着扩链剂长度的增加,涂膜的残余量逐渐减少,涂膜的玻璃化温度逐渐下降;性能测试表明:当添加10%质量分数的HBPUA-X时,涂膜的附着力由3级提高到1级以上,柔韧性由8 mm提高到2 mm以上;同时摆杆硬度与抗冲击强度也有明显提高。     

超支化聚氨酯丙烯酸酯的性能与UV固化动力学研究

采用2-羟基-2-甲基-1-苯基-1-丙酮（Darocur 1173）作为超支化聚氨酯丙烯酸酯（HBUA）的紫外光（UV）固化引发剂,研究了Darocur 1173用量、活性单体种类及用量对HBUA固化膜机械性能的影响,并用光差扫描量热法（Photo—DSC）对HBUA的光固化动力学进行了表征。结果表明,随着Darocur 1173用量的增加,光固化膜的摆杆硬度及冲击强度增大,最大光固化反应速率Rp^max提高,到达Rp^max的时间缩短。己二醇二丙烯酸酯（HDDA）作活性单体更有利于提高光固化膜的机械性能,并有利于促进光固化反应的进行。Darocur 1173和HDDA的适宜用量分别为4％（wt）和20％（wt）。     

超支化聚氨酯水分散体的合成及其涂膜性能

将聚氨酯预聚体接枝到以双季戊四醇为核、二羟甲基丙酸为单体的超支化聚酯上,得到了超支化聚氨酯水分散体。采用IR、SEM和化学滴定等方法对产物进行了表征和分析。结果表明,超支化聚氨酯水分散体的粒径约100nm,并在水中有良好的分散性和稳定性;其树脂具有良好的成膜性、耐水性和物理机械性能。     

超支化聚氨酯丙烯酸酯涂料的UV固化动力学研究

用FTIR和光差扫描量热法Photo-DSC对超支化聚氨酯丙烯酸酯(HBUA)的光固化动力学进行了表征。结果表明,不同固化气氛对HBUA体系的固化速率影响很大,在空气中,HBUA的最大反应速率(Rpmax)和最终碳碳双键转化率(Pf)均比在N2中的相应值低;当光引发剂Darocur1173浓度为4%,HDDA浓度为20%时,HBUA体系具有较快的反应速率及最高的最终碳碳双键转化率,分别为7.25 J/(g.s)和84.5%。     

超支化水性聚氨酯乳液的制备及性能研究

以顺丁烯二酸酐改性的超支化聚酯Boltorn H20、聚四氢呋喃2000和异佛尔酮二异氰酸酯为主要原料合成了超支化水性聚氨酯乳液,研究了改性超支化聚酯Boltorn H20的合成,以及改性超支化聚酯中羧基含量、初聚—NCO/—OH物质的量比、催化剂用量等对制备水性聚氨酯的影响,并探讨了亲水基团含量、乳化温度、中和度等因素对乳液及涂膜性能的影响,进一步使用傅里叶红外和热重分析分别对超支化聚氨酯涂膜的结构和热稳定性能进行了表征及测试。结果表明,在不加催化剂,初聚—NCO/—OH物质的量比为2∶1,亲水基团含量为2.05%的条件下,合成得到的含固量为30%的超支化水性聚氨酯乳液稳定性好。由此得到的超支化聚氨酯薄膜的耐水性和热稳定性较好。     

Synthesis and photopolymerization of hyperbranched polyurethane acrylates applied to UV curable flame retardant coatings

A series of hyperbranched polyurethane acrylates containing phosphorus were prepared by reaction of a phosphorus‐containing triol with toluene‐2,4‐diisocyanate and hydroxylethyl acrylate at given ratios. The resins obtained were found to polymerize rapidly in the presence of a photofragmenting initiator under UV irradiation, and the maximum polymerization rate increased with temperature up to 125 °C, then decreased quickly. The UV cured films have flame retardancy with a limiting oxygen index of 27.0. © 2002 Society of Chemical Industry     

三官能度含磷聚氨酯丙烯酸酯的合成及性能研究

采用异佛尔酮二异氰酸酯、羟基封端的聚丙二醇或聚己二酸丁二醇酯、丙烯酸羟乙酯合成含异氰酸基的聚氨酯丙烯酸酯与三氯氧磷和乙二醇合成的磷酸三乙二醇酯反应,制备了三官能度的含磷聚氨酯丙烯酸酯聚合物,并用红外光谱对其进行了表征。以该类聚合物和三缩丙二醇双丙烯酸酯为基料配制光固化涂料,并对其固化膜性能进行了研究。结果表明:不同聚合物所配制的涂料性能有一定差异,但都具有较好的光固化性能,固化涂膜各种物理性能优良,热稳定性能好,480℃下残重7.8%以上。     

超支化聚氨酯的合成与表征

以异佛尔酮二异氰酸酯(IPDI)、二乙醇胺(DEA)为反应单体,采用阶段升温的方法合成了具有超支化结构的聚氨酯(HBPU)。合成产物经分离提纯后采用红外光谱(FT-IR)和差示扫描量热(DSC)技术进行表征。研究结果表明:反应体系发生了超支化反应,生成了目标产物HBPU;该HBPU的玻璃化转变温度(Tg)达到-59.75℃,可溶于二甲基亚砜(DMSO)、二甲基甲酰胺(DMF)等极性溶剂中;羟值滴定各代生成的HBPU的羟值,第一代HBPU羟值的理论值为4.17,测量值为4.64,说明该HBPU羟值的实测值与理论值比较接近。     

Mechanical and thermal properties of UV cured mixtures of linear and hyperbranched urethane acrylates

The properties of urethane acrylate resin mixtures based on the linear and hyperbranched aliphatic polyesters were examined. Linear polyester was synthesized from neopentil glycol and adipic acid. Hyperbranched polyester of the third generation was synthesized from 2,2-bis(hydroxymethyl)propionic acid and di-trimethylol propane. The modification of 60% of hyperbranched aliphatic polyester OH end groups was carried out with isononanoic acid or with soybean fatty acids. Two hyperbranched urethane acrylates, with the same degree of acrylation, and one linear urethane acrylate were obtained by reaction of appropriate polyester and isophorone diisocyanate and 2-hydroxyethyl acrylate. The influence of added amount of HUA and nature of non-acrylic end groups on the rheological, mechanical and thermal properties of the uncured and UV cured mixtures diluted with 20 wt.% hexanediol diacrylate was examined. The nature of non-acrylic end groups have great effect on the interaction between linear and hyperbranched urethane acrylates, which further has a crucial influence on the examined properties of uncured and UV cured mixture samples.     

UV固化超支化聚酯的合成及性能研究

以马来海松酸(MPA),环氧氯丙烷(ECH)合成了超支化聚酯(HBPE),通过丙烯酸羟乙酯(HEA)对HBPE改性合成了涂料可用UV固化超支化聚酯。采用GPC,FT-IR,DSC等对产物结构进行了表征,研究了原料配比、加料方式和反应温度等对产物的影响,并考察了其光固化行为,测试了固化膜的性能。结果表明,HBPE合成最佳条件:n(MPA)∶n(ECH)=1∶1,反应温度90℃,HBPE与HEA最佳物质的量比为1∶2。该UV固化超支化聚酯固化膜附着力1级,抗冲击力40 kg/cm,铅笔硬度4H,耐甲乙酮100,可作为UV固化涂料中的主体树脂。     

Highly branched polyurethane acrylates and their waterborne UV curing coating

A series of UV curable highly branched waterborne polyurethane acrylates (BWPUAs) were synthesized using an “oligomeric A₂ + B₃” approach. The thiol-endcapped difunctional oligomeric A₂ was synthesized first by the addition reaction of isophorone diisocyanate, α,α-dimethylol propionic acid and 2-hydroxyethyl acrylate, then further underwent thiol-Michael reaction with 1,6-hexamethylene bis(thioglycolic acetate). Trimethylolpropane triacrylate was used as a B₃ monomer. The molecular structures were characterized with FT-IR and ¹H NMR spectroscopy. 1,6-Hexanediol diacrylate (HDDA) was incorporated into the polymeric chain for preparing the HDDA-modified BWPUAs (BWPUA-Hs). For the comparison, the linear waterborne polyurethane acrylate (LWPUA) was synthesized. The UV curing kinetics study results by using the photo-DSC approach showed that the BWPUAs possessed higher photopolymerization rate and final unsaturation conversion in the UV cured films compared with the LWPUA, which increased with the increase of unsaturation concentration in BWPUA. Moreover, the photopolymerization performance, and water and solvent resistance properties were greatly enhanced by the incorporation of HDDA segment into the BWPUA chain. The dynamic mechanical thermal analysis results showed that the elastic modulus in the rubbery plateau, and the glass transition temperature of UV cured film increased with increasing unsaturation concentration in BWPUA, whereas decreased with the introduction of HDDA flexible segment. The thermogravimetric analysis confirmed the high thermal stability of UV cured BWPUA films. All UV cured BWPUA and BWPUA-H films showed better flexibility and middle refractive indices due to the thioether linkage in the polymer network.     

Preparation of waterborne hyperbranched polyurethane acrylate/LDH nanocomposite

A series of novel waterborne hyperbranched polyurethane acrylate (WHPUA)/layered double hydroxide (LDH) nanocomposites based on hyperbranched aliphatic polyester Boltorn H20 (H20) and MgAl-LDH were successfully synthesized by in situ polymerization approach. The MgAl-LDH was firstly modified by sodium dodecyl sulfate (SDS) through the coprecipitation method, and then grafted by isophorone diisocyanate (IPDI), forming a complex with NCO groups at the surface and interlayer of LDH (LDH-DS-NCO). The residual hydroxyl groups after modification with succinic anhydride were crosslinked by the semi-adduct of IPDI reacted with HEA, and LDH-DS-NCO, followed by a neutralization reaction with triethylamine. The resulting water dispersible hyperbranched polyurethane acrylate WHPUA/LDH hybrid oligomer was then exposed to a medium pressure mercury lamp, forming a partially exfoliated WHPUA/LDH nanocomposite in the presence of a fragmental photoinitiator. The chemical structure, crystal configuration, morphology of WHPUA/LDH nanocomposite were characterized by Fourier transform infrared spectroscopy, X-ray diffraction, thermogravimetric analysis, and high resolution transmission electron microscopy. The experimental results indicated that both the intercalated and exfoliated structures were formed in the UV cured polymer/LDH nanocomposite. The TGA results showed that the thermal stability was improved. Moreover, the pencil hardness was greatly increased, and the flexibility remained at an acceptable level for the UV cured polymer/LDH nanocomposites.     

UV固化聚氨酯丙烯酸酯预聚体的合成及其性质

聚氨酯丙烯酸酯预聚体的制备是由二步反应完成,本文对预聚体合成过程中各种影响因素进行分析比较,确定最佳合成聚氯酯丙烯酸酯预聚体的工艺条件为：第一步反应温度为60-65℃,时间为4h,n(NCO)：n(OH)=3,催化剂为物料总量的0．4％,第二步反应温度为70．75℃,时间为4h。     

水性紫外光固化超支化聚氨酯的制备

以聚环氧丙烷二醇醚(PPG1000)、季戊四醇、2,2-二羟甲基丙酸(DMPA)和异佛尔酮二异氛酸酯(IPDI)为主要聚合单体,甲基丙烯酸羚乙酯(HEMA)为封端剂,合成了超支化紫外光固化水性聚氨醋树脂.研究了各组分用量对涂膜性能的影响,确定了较佳工艺条件,并用红外光谱和核磁共振谱对该超支化聚氨醋树脂的结构进行了表征....     

Synthesis of hyperbranched polyester‐amides and their application as crosslinkers for polyurethane curing systems

A series of hyperbranched polyester‐amides (S1, S2, S3) with trimethylolpropane as a core molecule were synthesized using core‐dilution/slow monomer addition strategy. The products were characterized by FTIR, ¹³C NMR, GPC, TGA, hydroxyl value measurement, and viscosity measurement. The result showed that the hyperbranched polyester‐amides synthesized had narrow molecular weight distribution and high degree of branching (DB). The hyperbranched polyester‐amides synthesized were used as crosslinkers for polyurethane curing systems and the mechanical properties of the polyurethane curing systems were investigated. It was found that the best tensile property and tear strength were obtained when the S2 were used as crosslinkers and the molar ratio of  OH and  NCO was 1 : 1. It was also found that the polyurethane curing systems had the highest hardness and T_g when the S3 were used as crosslinkers. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011