环氧树脂改性水性聚氨酯的制备及性能研究

采用E-20型环氧树脂(EP)在70℃下对聚氨酯(PU)预聚体进行改性得到改性预聚体,然后将该改性预聚体进行乳化制备了EP改性PU乳液。研究了预聚体的改性反应过程、改性PU乳液的粒径及分布、乳液浇铸膜的性能及经热固化后的膜的性能。结果表明,在预聚体改性过程中,部分异氰酸酯基团主要与EP结构中的羟基发生了反应,形成了以EP封端的PU链;改性PU乳液的粒径随EP用量的增加而增大,且分布变宽;随EP用量的增加,改性乳液浇铸膜的抗水性增加、力学性能提高;将膜进行后固化,在温度达到130℃时,改性树脂中的大部分环氧基团与预聚体链上的羧基发生交联反应,使改性树脂的耐水性能和力学性能得以明显提高。     

扩链剂对PTMG／MDI体系聚氨酯弹性体力学性能的影响

将聚四氢呋喃均聚醚（PTMG）和4,4’－二苯基甲烷二异氰酸酯（MDI）合成预聚体,分别与BDO、KC、MOCA及HQEE等扩链剂制备了聚氨酯（PU）弹性体。讨论了预聚体NCO基含量、扩链剂种类及三元醇含量对聚氨酯弹性体力学性能的影响。实验结果表明：当预聚体NCO基含量基本相同时,BDO－PU比KC—PU的硬度高1～2度,撕裂强度高了7％～18％;提高预聚体NCO基含量可使聚氨酯弹性体的硬度、撕裂强度和300％模量急剧增加;扩链剂中的三元醇含量超过30％,弹性体的拉伸强度显著下降;预聚体NCO基含量在6．0～6．8下,MOCA－PU的硬度和300％模量很高;HQEE／KC—PU比HQEE—PU的硬度降低了2-4个单位,而拉伸强度却提高了60％～90％。     

导电油墨的制备与性能研究

以2,4-甲苯二异氰酸酯与聚乙二醇反应合成了端异氰酸酯聚氨酯预聚体,并将其用于环氧树脂的改性,通过傅立叶变换红外光谱(FTIP)对聚氨酯预聚体、改性环氧树脂的结构进行了表征.以改性环氧树脂作为连结料,导电炭黑、导电石墨作为导电填料,加上适量的固化剂、溶剂和分散剂,制备了改性环氧树脂基导电油墨.结果表明,聚氨酯预聚体与环氧树脂发生了接枝反应,对环氧树脂E-51成功进行了改性.用改性后的环氧树脂制成的导电油墨与PET薄膜之间有着良好的附着力,印制的导电线路抗弯折性达到了10 000次,可满足柔性印刷电路的要求.     

阳离子有机硅聚氨酯自交联乳液的制备和应用

制备一种可以改善手感和防水性的有机硅改性聚氨酯自交联乳液.制备分为3个步骤聚醚与2,4-甲苯二异氰酸酯发生预聚,得到以-NCO为端基的预聚体,用小分子扩链剂扩链,再加入羟基硅油进行改性,最后加阳离子型扩链剂反应制得含有叔胺基的预聚体,加有机酸成盐,乳化得蓝光乳白微透明乳液.这种自乳化阳离子有机硅聚氨酯乳液可明显提高涂膜的光亮性、柔软性、抗水性和手感等.     

聚氨酯对环氧树脂增韧性能研究

利用甲苯二异氰酸酯(TDI)和聚丙二醇(PPG)合成不同结构的端—NCO聚氨酯(PU)预聚体,然后由聚氨酯预聚体与环氧树脂进行接枝反应,制备聚氨酯改性环氧树脂。研究了聚氨酯预聚体结构和用量对改性环氧树脂力学性能的影响规律。结果表明,当聚醚多元醇选用PPG1000,且TDI∶PPG=2∶1时,制得的聚氨酯预聚体对环氧树脂的增韧效果最好,当ω(PU预聚体)=10%时,改性环氧树脂的应变和拉伸强度分别达到84. 7%和27. 1 MPa,是改性前的30. 47倍和3. 04倍。通过扫描电镜对聚氨酯的增韧机理进行了研究,发现改性前环氧树脂为脆性断裂,聚氨酯改性后的环氧树脂断裂时银纹明显增多,为韧性断裂。     

Nano-SiO_2/PU胶黏剂的制备及性能研究

文章采用硅烷偶联剂(KH550、KH560和KH570)改性纳米SiO2,并利用超声设备将其分散在聚醚二醇中,再加入TDI进行预聚反应,得到-NCO封端的预聚体。利用二乙烯三胺扩链得到A组分,加入固化剂B组分,制得醇溶型纳米SiO2/PU胶黏剂。并对改性后的胶黏剂进行了微观结构分析和性能测试。测试结果表明:经偶联剂改性后的纳米SiO2能够与聚氨酯达到很好的纳米尺度的复合,且掺杂SiO2后的聚氨酯胶黏剂剪切强度和耐水性进一步提高。     

PTMG／MDI体系聚氨酯弹性体的力学性能研究

以4,4′-二苯基甲烷二异氰酸酯（MDI）和聚四氢呋喃均聚醚（PTMG）为原料合成聚氨酯（PU）预聚体,再分别与BDO、MOCA、HQEE扩链剂及混合扩链剂制备Pu弹性体。讨论了预聚体NCO基含量、聚醚软段相对分子质量、三羟甲基丙烷（TMP）小分子醇含量及扩链剂类型对PU弹性体力学性能的影响。结果表明,提高预聚体NCO基含量可使PU弹性体的硬度、撕裂强度和300％模量明显提高;当预聚体NCO基含量基本相同时,软段Mn=2000比Mn=1000的PU冲击弹性高;混合扩链剂中的TMP质量分数超过30％时,弹性体的力学性能明显下降;BDO—PU的拉伸强度比HQEE-PU的强度高出70％以上,撕裂强度比HQEE—PU低了40％以上,硬度比MOCA-PU小。     

聚氨酯对环氧树脂增韧性能研究

利用甲苯二异氰酸酯(TDI)和聚丙二醇(PPG)合成不同结构的端—NCO聚氨酯(PU)预聚体,然后由聚氨酯预聚体与环氧树脂进行接枝反应,制备聚氨酯改性环氧树脂。研究了聚氨酯预聚体结构和用量对改性环氧树脂力学性能的影响规律。结果表明,当聚醚多元醇选用PPG1000,且TDI∶PPG=2∶1时,制得的聚氨酯预聚体对环氧树脂的增韧效果最好,当ω(PU预聚体)=10%时,改性环氧树脂的应变和拉伸强度分别达到84. 7%和27. 1 MPa,是改性前的30. 47倍和3. 04倍。通过扫描电镜对聚氨酯的增韧机理进行了研究,发现改性前环氧树脂为脆性断裂,聚氨酯改性后的环氧树脂断裂时银纹明显增多,为韧性断裂。     

环氧树脂用KH550开环改性水性聚氨酯涂料的合成及性能研究

由于环氧树脂中环氧基团的存在,在合成环氧树脂改性水性聚氨酯预聚体和后扩链过程中,会消耗部分—NCO、胺类扩链剂,对整个合成的配方设计造成影响,重现性也差。通过KH550中的伯胺先打开环氧基团,然后改性的水性聚氨酯作为大分子扩链剂接到水性聚氨酯预聚体中,成功制备了稳定的水性聚氨酯乳液。通过傅里叶变换红外光谱和接触角测量仪对树脂的结构进行了表征。研究结果表明:KH550成功打开了环氧基团,并且树脂接上了有机硅类功能性材料,使得合成的树脂接触角大大提高。     

PU改性TDE-85/ MeTHPA环氧体系的显微形貌特征研究

本实验选用聚醚二元醇、甲苯二异氰酸酯（TDI）作为原料，合成了聚醚型聚氨酯预聚体。采用该预聚体扩链剂1，4-丁二醇（1，4-BDO）、交联剂三羟甲基丙烷（TMP）对TDE-85／甲基四氢苯酐（MeTHPA）环氧树脂体系行改性。利用扫描电镜分析，探讨了聚氨酯（PU）改性TDE-85／甲基四氢苯酐（MeTHPA）环氧树脂体系结构特征。结果表明，当合成PＵ预聚体的PPG相对分子质量不同时，改性环氧树脂体系的表面形貌随聚氨酯预聚体加入量的变趋势是相同的。当聚氨酯含量较小时，呈明显的“海岛”结构。随着聚氨酯加入量增多到一定量时，两网络互穿程度高，相分离程度不明显，具有互穿网络聚合物结构特征。随着聚氨酯含量的继续增多，相区尺寸明显增大，两相相容变差，相界面变得较清晰。     

Hybridization of aqueous PU/epoxy resin via a dual self‐curing process

Amino‐terminated and carboxyl‐containing polyurethane (PU) is prepared by an isocyanate‐terminated PU prepolymer process. Carboxyl‐containing epoxy resin is obtained from a half‐esterification of epoxy resin with maleic anhydride. These two aqueous resins are obtained after neutralization with triethylamine and dispersion into water phase, respectively. A latent curing agent (TMPTA‐AZ) is prepared by a Michael addition of aziridine with trimethylolpropane triacrylate (TMPTA). A self‐curing system of PU/epoxy hybrid is obtained from a blending of these two aqueous resins with latent curing agent. PU/epoxy hybrid is derived from two self‐curing reactions on drying. The first curing for hybridization between PU amino groups with oxirane groups of epoxy resin is via a ring‐opening reaction and the secondary curing takes place on carboxyl groups of PU/epoxy hybrid with aziridine of TMPTA‐AZ. The final properties of these dual self‐cured PU/epoxy hybrids are reported. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Modification and compatibility of epoxy resin with hydroxyl-terminated or amine-terminated polyurethanes

Phenolic hydroxyl-terminated (HTPU) and aromatic amine-terminated (ATPU) PU modifiers were prepared by reacting two different macroglycols (PTMG, polytetramethylene glycol, M_n = 2000, and PBA, Polybutylene adpate, M_n = 2000) with 4,4′-diphenylmethane diisocyanate (MDI), then further coupling with two different coupling agents, bisphenol A or 4,4′-diaminodiphenyl sulfone (DDS). These four types of PU prepolymers were used to modify the epoxy resin with 4,4′-diamino-diphenyl sulfone as a curing agent. From the experimental results, it was shown that the values of fracture energy, G_IC, for PU-modified epoxy were dependent on the macroglycols and the coupling agents. Scanning electron microscopy (SEM) revealed that the ether type (PTMG) of PU-modified epoxy showed the presence of an aggregated separated phase, which varied between 0.5 μm and 4 μm in the ATPU (PTMG) and between 1 μm and 1.5 μm in HTPU (PTMG) modified system. On the contrary, the ester type (PBA) PU-modified epoxy resin showed a homogeneous morphology and consequently a much smaller effect on toughening for its good compatibility with the epoxy network. In addition, it was found that the hydroxyl-terminated bisphenol A as a coupling agent improved fracture toughness more than the amine-terminated DDS because of effective molecular weight buildup by a chain extension reaction. The glass transition temperature (T_g) of modified epoxy resin as measured by dynamic mechanical analysis (DMA) was lower in PTMG-based PU than in a PBA-based PU series with the same weight of modifier.     

聚氨酯增韧环氧灌封材料的制备与表征

以异氰酸酯封端的聚氨酯预聚体（PU）与环氧树脂（EP）发生反应,制备了聚氨酯接枝改性环氧灌封材料。FTIR表明异氰酸酯封端的聚氨酯预聚体与环氧树脂中的仲羟基完全反应,同时考察了活性稀释剂用量对树脂黏度的影响及固化过程中温度的变化。聚氨酯预聚体的加入,使材料的冲击强度和弯曲强度都有所升高,当聚氨酯质量分数为5％时,材料的弯曲强度提高了30%,而冲击强度提高了近200%,玻璃化转变温度没有降低,SEM分析了其增韧机理。     

New type of phenolic resin: Curing reaction of phenol‐novolac based benzoxazine with bisoxazoline or epoxy resin using latent curing agent and the properties of the cured resin

In this study, we aimed to reduce the cure time, and to lower the cure temperature of the benzoxazine compound. Therefore, curing reaction of benzoxazine with bisoxazoline or epoxy resin using the latent curing agent and the properties of the cured resins were investigated. The cure behavior of benzoxazine with bisoxazoline or epoxy resin using the latent curing agent was monitored by differential scanning calorimetry and measurements for storage modulus (G′). The properties of the cured resin were estimated by mechanical properties, electrical insulation, water resistance, heat resistance, and flame resistance. As a result, it was confirmed that by using the latent curing agent, cure time of benzoxazine and bisoxazoline or epoxy resin was reduced, and cure temperature was lowered. And it was found that the curing reaction using phenol‐novolac based benzoxazine (Na) as the benzoxazine compound could proceed more rapidly than that using bisphenol‐A based benzoxazine (Ba) as the benzoxazine compound. However, the cured resins from Ba and bisoxazoline or epoxy resin using the latent curing agent showed good heat resistance, flame resistance, and mechanical properties compared with those from Na and bisoxazoline or epoxy resin using the latent curing agent. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

聚氨酯改性环氧树脂性能研究

采用2,4-甲苯二异氰酸酯、聚乙二醇为主要原料合成端异氰酸酯基聚氨酯预聚体,将预聚体和环氧树脂、活性稀释剂混合。用D-230进行固化,得到PU／EP增韧固化物。研究了聚氨酯不同含量对环氧树脂力学性能的影响,并用FT—IR进行了表征。用DMA研究了PU／EP固化物的阻尼性能。结果表明,加入聚氨酯预聚体明显改善了EP的阻尼性能;随着DMA测试频率的增大,tan δ-T谱向高温移动。     

Toughening of epoxy resin by functional‐terminated polyurethanes and/or semicrystalline polymer powders

Hydroxyl‐, amine‐, and anhydride‐terminated polyurethane (PU) prepolymers, which were synthesized from polyether [poly(tetramethylene glycol)] diol, 4,4′‐diphenylmethane diisocyanate, and a coupling agent, bisphenol‐A (Bis‐A), 4,4′‐diaminodiphenyl sulphone (DDS), or benzophenonetetracarboxylic dianhydride, were used to modify the toughness of Bis‐A diglycidyl ether epoxy resin cured with DDS. Besides the crystalline polymers, poly(butylene terephthalate) (PBT) and poly(hexamethylene adipamide) (nylon 6,6), with particle sizes under 40 μm were employed to further enhance the toughness of PU‐modified epoxy at a low particle content. As shown by the experimental results, the modified resin displayed a significant improvement in fracture energy and also its interfacial shear strength with polyaramid fiber. The hydroxyl‐terminated PU was the most effective among the three prepolymers. The toughening mechanism is discussed based on the morphological and the dynamic mechanical behavior of the modified epoxy resin. Fractography of the specimen observed by the scanning electron microscopy revealed that the modified resin had a two‐phase structure. The fracture properties of PBT‐particle‐filled epoxy were better than those of nylon 6,6‐particle‐filled epoxy. Nevertheless, the toughening effect of these crystalline polymer particles was much less efficient than that of PU modification. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 2903–2912, 2001     

环氧树脂室温固化用柔性固化剂的制备与性能研究

首先将聚醚多元醇和甲基丙烯酸甲酯(MMA)进行酯交换反应,然后利用多元胺与烯双键的加成反应原理,将多乙烯多胺与甲基丙烯酸酯进行反应,合成了含甲基丙烯酸聚醚多元醇酯柔性基团的新型环氧树脂室温固化剂。通过FT-IR等方法对产物结构进行表征,探讨并优化了各种反应条件,最后考察了该柔性固化剂对环氧树脂性能的影响。研究结果表明,柔性固化剂合成反应的优化条件是n(聚醚多元醇)∶n(MMA)为1∶5,n(催化剂)∶n(聚醚多元醇+MMA)为2∶100,n(聚醚多元醇酯)∶n(多乙烯多胺)为1∶2.0,反应时间为8h;在此条件下所得固化剂的产率和收率分别为96.3%和96.38%;改性固化剂/环氧树脂体系的凝胶时间仅为29min,拉伸剪切强度达到30MPa。     

聚醚对环氧-聚氨酯互穿网络制备的影响

研究了聚丙二醇醚（PPG）、聚四氢呋喃醚及二者的共聚醚分别形成的聚氨酯预聚体与低分子羟基化合物和环氧树脂的反应性,应用聚氨酯对环氧进行了IPN改性,测试了其红外光谱和冲击强度.结果说明：聚四氢呋喃醚型聚氨酯的反应活性太大,不适宜用于环氧树脂的IPN改性 聚丙二醇醚及其与聚四氢呋喃的共聚醚型的聚氨酯反应活性适中,适合作为环氧IPN改性的聚氨酯组分.采用PPG型聚氨酯对环氧进行了IPN改性,改性后的环氧体系冲击强度大大提高.     

环氧树脂低温快速固化剂的合成及性能研究

以苯酚、多聚甲醛、二乙烯三胺、硫脲为单体,以DMP-30为促进剂,合成了环氧树脂低温快速固化剂.分析了反应温度、反应时间以及各材料用量对环氧树脂固化剂性能的影响,并进一步考察了固化剂与环氧树脂最佳用量比.在( 110±2)℃下反应2.5 h,苯酚、多聚甲醛、二乙烯三胺、硫脲之比为1∶1.25∶1.3∶1.1,且DMP-...     

含二氮杂萘酮环氧树脂体系的固化反应动力学研究

以 4- (4-羟基苯基 ) - 2 ,3 -二氮杂萘 - 1-酮 (DHPZ)为固化剂 ,用示差扫描量热法 (DSC)对环氧E44 /DHPZ体系的固化反应过程作了系统的研究 ,计算出固化反应的表观活化能为 10 4 0 4kJ/mol,固化反应近似为一级反应。通过固化剂份数对化学反应程度影响的研究 ,得知当DHPZ份数为 4 5～ 5 5时固化反应完全