高固含量丙烯酸酯改性聚氨酯胶粘剂的研制

以聚醚多元醇、聚酯多元醇和蓖麻油为混合多元醇,以改性MDI(4,4′-二苯基甲烷二异氰酸酯)及PAPI(多亚甲基多苯基多异氰酸酯)为混合异氰酸酯,合成了聚氨酯(PU)胶粘剂预聚体;然后以PA(羟基丙烯酸酯树脂)作为PU预聚体的改性剂,制得高固含量的PUA(聚丙烯酸酯改性聚氨酯)胶粘剂。结果表明:当m(改性MDI)∶m(PAPI)=1∶1、n(-NCO)∶n(-OH)=2.2∶1、w(PA)=8%(相对于PU质量而言)和w(丙烯酸羟乙酯)=3%(相对于PU质量而言)时,PUA胶粘剂的综合性能较好。     

蓖麻油改性无溶剂型双组分聚氨酯复膜胶

以蓖麻油、苯酐和二甘醇等为原料,经酯化、缩聚后,合成了蓖麻油改性聚酯多元醇,并以此作为复膜胶的固化剂;以MDI-50(二苯基甲烷二异氰酸酯)、PPG-2000/PPG400(聚醚二元醇)为原料,合成了端-NCO基聚氨酯(PU)预聚体,并以此作为复膜胶的主剂;将主剂和固化剂按一定比例混合后,制得无溶剂型双组分PU复膜胶。研究结果表明:当反应温度为45℃、反应时间为3 h和w(-NCO)=18%时,主剂的黏度、流动性相对最好;当双组分中n(-NCO)∶n(-OH)=1.9∶1、固化温度为50℃、固化时间为24 h和w(蓖麻油)=28.3%时,复膜胶的粘接性能相对最好,并且接近于进口同类产品。     

无溶剂型单组分聚氨酯胶粘剂的研制

以聚醚二元醇(PPG)、改性MDI(4,4′-二苯基甲烷二异氰酸酯)、PAPI(多亚甲基多苯基多异氰酸酯)、1,4-BDO(1,4-丁二醇)和环保型PU潜固化剂等为主要原料,采用预聚体法制得无溶剂型单组分聚氨酯(PU)胶粘剂。研究结果表明:该胶粘剂的玻璃化转变温度(Tg)为-26.9℃;当R=n(-NCO)/n(-OH)=6.5~9.0、w(-NCO)=3.5%、w(环保型PU潜固化剂)=3%和聚醚二元醇是相对分子质量为1 000的PPG210时,PU胶粘剂的黏度适中、固化速率较快和可操作性良好,并且其强度和韧性俱佳。     

聚丙烯酸酯接枝聚氨酯树脂制备与性能研究

以聚酯多元醇和异佛尔酮二异氰酸酯(IPDI)合成了异氰酸酯基封端的聚氨酯预聚体,并与自制含羟基的聚丙烯酸酯进行接枝,再加胺类扩链剂和分子质量调节剂,合成了固含量为30%的酯醇溶PUA树脂。讨论了异氰酸酯指数R值[即n(-NCO):n(-OH)]、聚氨酯(PU)与聚丙烯酸树脂(PA)的反应温度、PA羟基含量和PU/PA质量比对树脂及油墨性能的影响,结果表明:当R=2.0、PU与PA反应温度为60℃、PA羟基质量分数为1.13%和PU/PA质量比为2/1时,PUA树脂的综合性能较好。     

聚氨酯丙烯酸酯预聚体的合成及其光固化压敏胶的结构和性能

以不同摩尔质量的聚醚二元醇(PPG)及其混合物、甲苯-2,4-二异氰酸酯(TDI)和β-丙烯酸羟乙酯 (HEA)为原料,合成了聚氨酯丙烯酸酯(PUA)预聚体,研究了所合成预聚体及其光固化压敏胶的结构和性能。结果表明:预聚体是多种不同摩尔质量的聚合体的混合物;预聚体中的NH基团形成氢键。单一PPG制得的预聚体中,目标产物(三聚体)含量较高;两种PPG混合物制得的预聚体目标产物较少。由合成PUA制得的光固化压敏胶,固化和粘接性能优良;混合聚醚合成PUA所制得的光固化压敏胶粘接剥离强度比两种单一聚醚所制得的压敏胶均低。     

阴离子改性PUA紫外光固化胶粘剂的制备及性能

以异佛尔酮二异氰酸酯(IPDI)、二羟甲基丁酸(DMBA)和聚四氢呋喃醚二醇(PTMG)等为主要原料,制得聚氨酯(PU)预聚体;然后将其与丙烯酸羟乙酯(HEA)反应,制得HEA封端的聚氨酯丙烯酸酯(PUA)预聚体;最后在PUA预聚体中加入中和剂等助剂,制备出阴离子改性PUA紫外光(UV)固化胶粘剂。研究结果表明:当w(DMBA中-COOH)=1.2%(相对于PU预聚体质量而言)、中和度=n(中和剂)∶n(DMBA)=80%、以PTMG为多元醇且偶联剂采用预处理法加入时,相应的阴离子改性PUA型UV固化胶粘剂的耐水性、粘接强度和耐久性俱佳。     

水性光敏聚氨酯丙烯酸酯的合成与性能研究

用IPDI、DMPA、PTMG和HEMA合成了紫外光固化聚氨酯丙烯酸酯(PUA)水乳液。采用FTIR、国标GB12009.4-89等方法对该PUA预聚体合成过程和组分进行了测试和表征,考察了n(-NCO)/n(-OH)、羧基含量、pH值等对此乳液及涂膜性能的影响。结果表明:当n(-NCO)/n(-OH)=1.3左右,-COOH含量为1.4%～3.4%(质量分数),中和度为85%～100%时,合成的乳液制成的涂膜具有更加优良的机械性能、耐化学性、耐水性等。     

PP或PE用双组分PU胶粘剂的制备与性能研究

以聚酯多元醇、混合异氰酸酯(MDI/TDI)、扩链剂(1,2-丙二醇)、异氰酸酯固化剂(TMP-TDI)和溶剂(乙酸乙酯)等为主要原料,制备了PP(聚丙烯)、PE(聚乙烯)粘接用双组分PU(聚氨酯)胶粘剂。研究结果表明:当m(结晶性聚酯多元醇)∶m(非结晶性聚酯多元醇)=80∶20~60∶40、R=n(-NCO)/n(-OH)=0.95~0.97、m(MDI)∶m(TDI)=90∶10~60∶40和w(功能性聚酯多元醇XCP-2325)=2%时,PU预聚体的相对分子质量为(9~11)×104,其常温固化12 h后的邵A硬度(76)有利于PU预聚体的破碎;当PU预聚体/乙酸乙酯溶液的固含量为12%时,双组分PU胶粘剂的操作性能(黏度为22 mPa.s)、180°剥离强度(初始2.3 N/25 mm、最终41.0 N/25 mm)俱佳。     

双组分聚氨酯嵌缝密封剂的制备与性能研究

以TDI(甲苯二异氰酸酯)、N-220(聚醚二元醇)和N-330(聚醚三元醇)等为主要原料合成PU(聚氨酯)预聚体,并以此作为PU密封剂的甲组分;以MOCA(3,3′-二氯-4,4′-二氨基二苯甲烷)、EP330N(聚醚三元醇)、增塑剂邻苯二甲酸二辛酯(DOP)、轻质碳酸钙和辛酸亚锡等作为PU密封剂的乙组分。研究结果表明:以D3(PU类)为底涂剂,当R=n(-NCO)/n(-OH)=1.05～1.10、混合固化剂中n(MOCA中-OH)∶n(EP330N中-OH)=2∶1和w(DOP)=40%时,室温固化双组分PU密封剂具有良好的拉伸性能和定伸粘接性能,并且满足大变形、高位移量水泥伸缩缝的嵌缝工艺要求。     

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。     

Preparation and properties of maleimide capped polyurethane/allyl novolac resin AB crosslinked polymers

To improve the miscibility and tensile strength of the ABCPs material, we conducted a study in which maleimide end-capped polyurethane was prepared from the PU prepolymer and maleimide by reacting 4,4′-diphenylmethane diisocyanate (MDI) with poly(tetramethylene oxide) (PTMO), whose molecular weights were M_n=600∼700 (PA650), M_n=900∼1050 (PA1000) and M_n=1900∼2100 (PA2000). AB crosslinked polymers (ABCPs), synthesized from the PU prepolymer and the novolac resin, were studied. The study confirmed the occurrence of phase mixing. Further investigation through dynamic mechanical analysis (DMA), differential scanning calorimetry (DSC) and transmission electron microscopy (TEM) revealed that the tensile strength and phase mixing were,improved.     

基于PTMG-TDI的低游离TDI浇注型PU弹性体的制备与性能研究

以四氢呋喃均聚醚和甲苯二异氰酸酯为原料,采用分子蒸馏法合成PU预聚体,以3,3′-二氯-4,4′-二氨基二苯甲烷为扩链剂制备低游离甲苯二异氰酸酯浇注型PU弹性体,并对其性能进行研究。结果表明,与常规PU预聚体与扩链剂的混合体相比,低游离PU预聚体与扩链剂的混合体具有良好的流动性和较快的固化速度;低游离PU弹性体与常规PU弹性体拉伸强度和撕裂强度相差不大,但前者回弹值较大、压缩永久变形较小、动态性能较好。     

High performance poly(urethane-imide) prepared by introducing imide blocks into the polyurethane backbone

A series of novel linear poly(urethane-imide)s were synthesized by the reaction between isocyanate-terminated polyurethane (PU) prepolymer and amine- or anhydride-terminated oligoimide. PU prepolymer was synthesized by reacting polyethylene adipatediol of molecular weight 1000 with tolylene-2,4-diisocyanate at the molar ratio of 2:3 or 1:2. Oligoimide was synthesized from the reaction of 4,4′-(hexafluoroisopropylidene)diphthalic acid with 4,4′-oxydianiline at various molar ratios. Equimolar amounts of PU prepolymer and oligoimide were reacted in N-methyl-2-pyrrolidone, followed by casting on glass plates and heat treatment at 100 and 150 °C for 1 h each to give linear poly(urethane-imide)s as transparent yellowish brown films. Poly(urethane-imide) films with less of 30% of imide component became elastomer, and films with more than 36% imide component became plastic. The effects of end-groups of oligoimide, molecular weight of oligoimide, and molecular weight of PU prepolymer on the solvent resistance, the tensile properties, viscoelastic properties, and thermogravimetric properties of poly(urethane-imide) films were systematically examined. Solvent resistance and tensile modulus of poly(urethane-imide) films from amine-terminated oligoimides were better than those from anhydride-terminated oligoimides. On the other hand, thermal stability and elongation at break for the poly(urethane-imide) films from anhydride-terminated oligoimides were higher than those from amine-terminated oligoimides.     

多交联体系PU/分子筛复合材料的制备及表征

以聚酯多元醇(PEA)、2,4-甲苯二异氰酸酯(TDI-100)和13X分子筛为原料,采用预聚法制备PU/13X分子筛预聚体,再将预聚体分成两部分,分别与不同比例的扩链剂(MOCA)混合反应,然后将两种体系混合后浇铸成型,制备出多交联体系PU/13X分子筛复合材料.对其力学性能、耐溶剂性能进行了测试并与聚氨酯材料的性能进行了比较.结果表明,多交联体系PU/13X复合材料的耐撕裂性能明显提高,拉伸性能稍有下降;通过DMA、DSC测定,表明多交联体系PU/13X复合材料的玻璃化转变温度降低,微相分离更好,阻尼性能下降;分子筛可以改善多交联体系PU/13X复合材料的耐溶剂性能.     

复印机清洁刮片用聚氨酯弹性体的研制

采用预聚体法和半预聚体法合成了复印机清洁刮片用聚氨酯（PU）弹性体,研究了预聚体法中三羟甲基丙烷（TMP）用量和和半预聚体法中扩链剂1,4-丁二醇（BDO）／TMP的摩尔比对PU弹性体物理机械性能的影响,同时对由预聚体法和半预聚体法合成的3种PU弹性体的动态力学性能进行了表征。研究结果表明,用预聚体法和半预聚体法合成的PU弹性体均具有优良的物理机械性能、动态力学性能和外观透明性,均可满足复印机清洁刮刮片的应用要求。     

聚氨酯接枝聚丙烯酸共聚物网络的合成与性能表征

介绍聚氨酯接枝聚丙烯共聚物网络的合成与性能表征。利用异氰酸酯封端的聚氨酯预聚物同丙烯酸／丙烯酸羟丙酯共聚物反应得到了聚氨酯接枝聚丙烯酸共聚物网络。用利叶变换红外光谱表征了网络的化学组成，用应力－应变实验测试了本聚合物网络的力学性能，用动态粘弹谱以及差示扫描量热法研究了随着ＰＵ与ＰＡ链段比例的改变，该交联体系相结合的变化。     

聚氨酯改性环氧树脂胶粘剂的制备及性能研究

由端-NCO基聚氨酯(PU)预聚物与环氧树脂反应,制备了PU接枝改性环氧树脂。着重探讨了PU预聚物的含量、活性稀释剂的含量和异氰酸酯结构等因素,对改性环氧树脂的粘度和粘接性能的影响。实验结果表明,该改性环氧树脂的粘度随着PU预聚物含量的增加而逐渐增大,随着活性稀释剂含量的增加而逐渐降低,而且在相同的条件下,用不同的二异氰酸酯改性环氧树脂的粘度大小次序为:IPDI型>MDI型>TDI型;该改性环氧树脂在PU预聚物含量为20%时,对铝片/铝片的剪切强度最大(7.82 MPa);在PU预聚物含量为10%时,对铁片/铁片的剪切强度最大(11.70 MPa),而且TDI型和IPDI型改性环氧树脂的粘接性能明显好于MDI型改性环氧树脂。     

Synthesis of anionic water‐borne polyurethane with the covalent bond of a reactive dye

We successfully synthesized an anionic water‐borne polyurethane (PU) capable of reacting with a reactive dye to form a covalent bond with the dye molecule. The anionic water‐borne PU was synthesized and grafted with the reactive dye to form a dyed PU. First, the PU prepolymer was synthesized from 4,4′‐methylene bis(isocyanatocyclohexane), poly(tetramethylene glycol), 2,2′‐bis(hydroxymethyl) propionic acid (as an anionic center), and triethyleneamide (as a neutralizer). Then, pure water was added to emulsify and disperse the prepolymer to form an anionic water‐borne PU prepolymer. Finally, the extender N‐(2‐hydroxyethyl) ethylene diamine was used to extend the anionic water‐borne prepolymer to form a PU polymer with hydroxyl groups that could further react with the reactive dye molecule. With respect to the heating properties, the dyed PU polymers exhibited higher glass‐transition temperatures of the hard segment than those without dye molecules. However, neither the glass‐transition temperature of the soft segment nor the melting temperature of the soft segment varied in the presence of dye molecules, but they were changed with various chain lengths of the soft segment. As for the mechanical properties, the modulus and strength of the dyed PU polymers decreased because of the bulkiness of their dye molecules, but the breaking elongation increased. Moreover, the inherent viscosity decreased in the presence of the dye molecules. As for the dyeing properties, the percentage of dye grafting was greater than 90%. The dye‐grafted PU exhibited a lower percentage of migration than PU extended with ethylene diamine (without hydroxy groups) and also showed a higher grade of colorfastness to light. © 2002 John Wiley & Sons, Inc. J Appl Polym Sci 84: 797–805, 2002; DOI 10.1002/app.10336     

PBA/MDI体系聚氨酯弹性体力学性能的研究

采用二步法以聚己二酸丁二醇酯(PBA)、4,4-′二苯基甲烷二异氰酸酯(MDI)和二元醇1,4-丁二醇(BDO)或混合扩链剂(二元醇和三元醇)合成了聚氨酯(PU)弹性体。研究了软段相对分子质量、预聚体-NCO质量分数和扩链剂对聚氨酯弹性体力学性能的影响。实验结果表明:PBA相对分子质量大,PU断裂伸长率和冲击弹性好;PU硬度、撕裂强度和模量随预聚体-NCO相对质量分数增加而增加;弹性体的交联密度过高,硬度和撕裂强度下降。