梳型UV固化水性聚氨酯树脂的制备与表征

通过引入含双键基团的中间体制备了分子链侧基、端基均含可UV固化基团的梳型水性聚氨酯树脂。采1用红外光谱仪FTIR、核磁共振仪H NMR、热重分析仪TGA等分析手段对样品的结构与性能进行了表征。分析表明,所得产品符合预期分子结构的设计,为半透明泛蓝光乳液,粒径细微均匀;固化层呈现2个快速失重温度区间。中间体的加入增强了固化层的耐溶剂性和硬度,附着力、拉伸强度和交联密度也得到提高。()()()     

Water resistance of the membranes for UV curable waterborne polyurethane dispersions

The water absorption of the membranes made from UV curable waterborne polyurethane dispersions (UV-PUDs) was investigated systematically and correlated with the nature of the polymer and its gel content after curing. It was found that the water absorption of the membranes was reduced significantly by using polyester polyols, reducing the COOH content and increasing the gel content through a higher CC level. In particular, the membranes made from polyurethanes having hydroxyl-terminated polybutadiene (HTPB) or modified with dihydroxybutyl-terminated polydimethylsiloxane (PDMS) presented a superior water resistance. The results showed a linear relationship between the water absorption and the surface tension of the membrane.     

光/湿双固化聚氨酯热熔胶的制备与性能研究

以多元醇、异氰酸酯、含羟基丙烯酸酯和光引发剂等为原料,制备了PET(聚酯)基材粘接用光/湿双固化PU(聚氨酯)-PUA(聚氨酯丙烯酸酯)型反应性HMA(热熔胶)。研究结果表明:该HMA中同时含有可光固化基团(C=C)和可湿固化基团(-NCO);当n(C=C)∶n(-NCO)=20∶80、w(复合光引发剂)=1.5%~2.0%和引入甲基丙烯酸羟乙酯(HEMA)时,相应HMA具有较高的初始强度和最终强度;光/湿双固化HMA的透明度高于湿固化HMA,说明UV固化是增加光/湿双固化HMA透明度的主要原因。     

一种高性能紫外光固化胶粘剂的制备

以异佛尔酮二异氰酸酯IPDI、改性聚醚多元醇、甲基丙烯酸羟乙酯(HEMA)为主要原料,制备了聚氨酯丙烯酸酯PU1。考查了水解剥离型紫外光固化胶粘剂的基本配方中各主要组分对粘接强度和水解剥离性能的影响。研究结果表明,PU1作为基础树脂玻璃粘接强度高同时剥离时间短分别为12.2 MPa和30 min;亲水性单体聚乙二醇二丙烯酸酯比单官能甲氧基聚乙二醇丙烯酸酯在粘接强度和水解剥离速度上优异。其中FA-260A均衡性最佳,玻璃粘接强度12.5 MPa,水解剥离时间20 min;高折射率、疏水性环状单体对基本配方的折射率的调节有帮助,可以实现胶粘剂折射率1.50的要求,其中低官能度邻苯基苯氧乙基丙烯酸酯性能最佳;溶剂选用环保型低级醇对水解剥离性能有帮助。()()     

紫外光固化水性聚氨酯技术

紫外光固化水性聚氨酯(UV-WPU)属高效、节能、环保的高新固化体系,是目前PU化学中最活跃分支之一。本文简述UV-WPU特性、发展过程、组成及其制备方法。     

聚氨酯丙烯酸酯软段结构对UV胶性能的影响

以几种不同结构的多元醇、异佛尔酮二异氰酸酯(IPDI)和丙烯酸羟乙酯为原料,合成了多种聚氨酯丙烯酸酯预聚物(PUA).按照同样比例的单体、引发剂及其他助剂配制成光固化胶粘剂(UV胶),考察了聚氨酯中多元醇结构对UV胶固化速度、黏结强度、胶膜性能等的影响.结果表明,聚氨酯结构中软段结构对UV胶粘剂性能影响比较大,合理地选...     

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     

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.     

脂肪族聚氨酯二丙烯酸酯的合成与性能研究

以聚己内酯二醇、3-异氰酸酯基亚甲基-3,5,5-三甲基环己基异氰酸酯、丙烯酸羟乙酯为原料合成脂肪族聚氨酯二丙烯酸酯。实验结果表明,预聚物64份,四氢呋喃丙烯酸酯30份,γ-缩水甘油醚基丙基三甲氧基硅烷1份,1-羟基环己基苯基甲酮3份,纳米二氧化硅2份配制的UV胶,具有较佳的力学性能、耐热、耐湿热性能,综合性能接近loctite3106。     

脂肪族水性聚氨酯胶膜的合成和性能研究

用傅里叶变换红外光谱以及凝胶渗透色谱对异氟尔酮二异氰酸酯（IPDI）型脂肪族水性聚氨酯胶膜进行了结构表征及分子量分布测试。在此基础上，详细研究了影响胶膜拉强度，断裂伸长率，24h吸水率等性能的关键因素。结果表明：用IPDI为原料合成的脂肪族中性聚氨酯胶膜的耐光性比用甲苯二异氰酸酯为原料合成的芳香族水性聚氨酯胶膜强；异氰酯基/羟基（NCO/OH，摩尔比）对胶膜的拉伸强度和断裂伸长率有显著影响。NCO/OH增大，胶膜的拉伸强度也增大；NCO/OH越大，胶膜越硬，断裂伸长率越小，亲水基团含量越大，胶膜24h吸水率也越大，胶膜的耐水性越低。     

UV固化氨基胍盐改性蓖麻油基水性聚氨酯的制备及抗菌性能

以蓖麻油（CO）、异佛尔酮二异氰酸酯(IPDI)、阳离子扩链剂N-甲基二乙醇胺（MDEA）、封端剂甲基丙烯酸羟乙酯（HEMA）为主要原料制备一系列紫外（UV）固化型蓖麻油基水性聚氨酯（UWPU）。为进一步提升其抗菌性能，通过引入胍基的方法，成功制备出抗菌型UV固化蓖麻油基水性聚氨酯(GWPU)。通过耐水性测试、抑菌圈测试、抗菌性能测试对实验制备胶膜性能进行检测。 结果表明：GWPU胶膜相对UWPU吸水率有所上升，但均保持在10%以下；GWPU胶膜抗菌方式为接触性杀菌同时不具有溢出性；当氨基胍盐（AH）质量分数为预聚物1.2%时GWPU对金黄色葡萄球菌(S.aureus)、大肠杆菌(E.coli)的抗菌率可达99.9%，且经过抗菌持久性测试后仍能保持99.9%的抗菌性。     

Synthesis and properties of hyperbranched polyurethane acrylate used for UV curing coatings

The hyperbranched polyurethane acrylate (HPUA) was synthesized through the addition of hyperbranched polyurethane endcapped by hydroxyl groups (HPU-OH), with the semiadduct urethane monoacrylate (IPDI-HEA). The HPU-OH was prepared by the amidation reaction of diethanolamine with isophorone diisocyanate. The molecular structure of HPUA was characterized by FTIR and ¹H NMR analyses. The number average molecular weight and its polydispersity index were measured by GPC to be 7714 g mol⁻¹ and 1.24, respectively. The HPUA was blended with epoxy acrylate EB600 and difunctional monomer TPGDA in different ratios, and exposed to a UV lamp for photopolymerization in the presence of Runtecure 1104 as a photoinitiator at room temperature. The photopolymerization rate and final unsaturation conversion reached to the highest values with only 5 wt% HPUA addition, whereas decreased as further added. The tensile strength of UV-cured films was improved by adding less than 10 wt% HPUA without damaging the modulus, having the value of 62.56 MPa for EB₉₀HPUA₁₀ film. Besides, the elongation at break increased continuously with the addition of HPUA, reaching to 130% for EB₇₀HPUA₃₀ film. Moreover, the impact strength was greatly enhanced by the addition of HPUA, possessing nearly two times high for EB₇₀HPUA₃₀ film compared with pure EB600 film. However, the T_g decreased as HPUA was added from the DMTA measurements. According to the ratios of T_s/T_g the HPUA has good compatibility with EB600/TPGDA resin.     

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。     

电子束固化水性聚氨酯丙烯酸酯的制备及性能

研究了一种制备水性聚氨酯丙烯酸酯的新方法,通过在扩链剂分子结构中组装离子基团来改善亲水性,解决了聚氨酯丙烯酸酯与水难相溶的问题。采用这种方法制备了一种聚氨酯丙烯酸酯产物,使用FTIR和1H NMR对产物结构进行了表征。对产物与水的储存稳定性、黏度、电子束固化行为及固化后性能进行了研究。结果表明,分散乳液储存稳定性好,经电子束固化后性能(如硬度、附着力、光泽度、柔韧性、热稳定性)优良。     

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.     

紫外固化粉末涂料的合成及固化研究

用E-12、E-20环氧树脂与丙烯酸反应,合成了可紫外光固化的环氧丙烯酸酯预聚物,并对产物进行固化研究。讨论了催化剂的种类、反应温度、反应时间等对合成产物的影响,光引发剂的种类、光照时间等对固化产物的影响。结果表明:环氧树脂与丙烯酸以甲苯为溶剂、四丁基溴化铵为催化剂,在110℃下反应180 min为较适宜的反应条件;环氧丙烯酸酯以TPO为引发剂,120 w/cm的紫外灯光照15 s为较宜适的固化条件。     

脂肪族水性聚氨酯的制备及性能研究

以异佛尔酮二异氰酸酯(IPDI)和聚醚二醇(PPG)为主要原料、二羟甲基丙酸(DMPA)为亲水扩链剂和乙二胺(EDA)为小分子扩链剂,采用预聚体分散法制备出一种水性聚氨酯(WPU)乳液。考察了n(-NCO)∶n(-OH)比例、EDA扩链方式等对WPU稳定性、玻璃化转变温度、力学性能和耐水性等影响。结果表明:将EDA先溶于水中,采用乳化与扩链同时进行的工艺,并且当n(-NCO)∶n(-OH)=1.5∶1时,WPU乳液稳定性好、粒径(14 nm)较小且分布较窄,WPU胶膜的力学性能(拉伸强度为3.683 MPa、断裂伸长率为347%)和耐水性(吸水率为19.7%)俱佳。     

Study on synthesis and thickening property of hyperbranched waterborne polyurethane

A series of hyperbranched waterborne polyurethanes (HWPU-4, HWPU-6 and HWPU-12) containing hydrophobic end groups were prepared by the hyperbranched core and the polyurethane prepolymer. The core was polyol including pentaerythritol (PE-4), hyperbranched polyester with six hydroxyl end groups (HPE-6) and hyperbranched polyester with 12 hydroxyl end groups (HPE-12). The polyurethane prepolymer was synthesized by hexamethylene diisocyanate (HDI), polyethylene glycol (PEG) and hexadecanol. The structures of the hyperbranched cores and HWPUs were characterized by Fourier transform infrared spectra (FTIR), nuclear magnetic resonance spectra (¹H NMR and ¹³C NMR) and gel permeation chromatography (GPC). The influences of HWPU content and structure on its thickening property were studied by the measurement of rotary viscosity. The results showed that the thickening effect of HWPU enhanced with the increase of HWPU content in the aqueous polyurethane emulsion. The thickening effect of HWPU-6 was superior to that of HWPU-4 and HWPU-12 with the same length of hydrophilic chain. In addition, the thickening effect of HWPU with the same core was related to the length of hydrophilic chain and the relative content of hydrophobic end groups.     

聚酯型水性聚氨酯的合成和性能研究

以甲苯二异氰酸酯(TDI)、聚酯二元醇、二羟甲基丙酸等为主要原料合成了聚酯型水性聚氨酯乳液。研究了三羟甲基丙烷(TMP),二羟甲基丙酸(DMPA),异氰酸酯基与羟基物质的量比(n/n)等对水性聚氨酯耐水性能、稳定性以及力学性能等的影响。结果表明,当n/n为NCO OH NCO OH2,DMPA含量为6%,TMP加入量0.6%,水性聚氨酯性能最佳。