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。     

铝塑膜包装用反应型聚氨酯热熔胶的影响因素

以聚酯多元醇和异氰酸酯为主要原料、EVA(乙烯-醋酸乙烯酯共聚物)和增黏树脂为改性树脂、2,2-二吗啉基二乙基醚(DMDEE)和二月桂酸二丁基锡(T-12)为混合催化剂,制备了PUR-HMA(反应型聚氨酯热熔胶),并探讨了自制液态聚酯多元醇M、结晶性聚酯多元醇(如EVONIK 7360、EVONIK 7380等)、异氰酸酯和催化剂等对PUR-HMA性能的影响。研究结果表明:以MDI(4,4′-二苯基甲烷二异氰酸酯)作为硬段,当w(混合催化剂)=1%、w(自制液态聚酯多元醇M)=40%(均相对于多元醇总质量而言)、m(DMDEE)∶m(T-12)=1∶1和n(EVONIK 7360)∶n(EVONIK 7380)=1∶1时,PUR-HMA的综合性能相对最佳。     

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。     

铝塑膜包装用热塑性聚氨酯热熔胶的制备与性能研究

以聚酯多元醇、二异氰酸酯和1,4-丁二醇(BDO)为主要原料,合成了铝塑膜包装用热塑性聚氨酯(TPU)热熔胶(HMA),并考察了二异氰酸酯、R值[R=n(—NCO)/n(—OH)]、结晶性多元醇以及扩链剂(BDO)等对TPU-HMA粘接性能的影响。研究结果表明:以4,4′-二苯基甲烷二异氰酸酯(MDI)、聚酯多元醇EVONIK7360为原料,当R=0.99、w(BDO)=2%(相对于聚酯多元醇总质量而言)时,制备的TPU-HMA对铝塑膜具有相对较好的粘接效果,其最终剥离强度为30.0 N/8 mm。     

消防水带用聚氨酯胶黏剂的研制

采用具有较高结晶性的聚酯多元醇,以及合适的扩链剂和异氰酸酯为原料制备高初粘强度的消防水带用聚氨酯胶黏剂,并且分析了聚酯多元醇种类及数均相对分子质量(n)、扩链剂种类及用量、异氰酸酯指数(R)、纳米白炭黑及水解稳定剂对聚氨酯胶黏剂性能的影响。实验结果表明,采用n为3000左右的聚己二酸1,4-丁二醇酯,扩链剂采用1,4-丁二醇,R取1.02～1.03,并且加入经过表面改性的纳米白炭黑TS-720,加入0.5%～0.7%(与聚酯的质量比)的水解稳定剂,反应后得到的聚氨酯胶黏剂具有较高的初粘强度、较好的耐水解性能和耐老化性能。     

一种低VOC高性能聚氨酯汽车方向盘组合料的开发

以低挥发性有机化合物(VOC)聚醚多元醇、聚合物多元醇、拉力助剂、扩链剂、聚酯醚、反应型催化剂、低VOC硅油、开孔剂、除醛助剂为A组分,自制改性异氰酸酯为B组分,制备了汽车方向盘。研究了拉力助剂、扩链剂、除醛助剂以及聚酯醚等对制品性能的影响,并采用袋式法测量了产品的VOC含量。结果表明,拉力助剂、扩链剂、聚酯醚、除醛助剂质量份分别为3、8、6、0.5时,产品的力学性能、回弹性能最好。由该组合料生产的产品VOC含量满足国内目前最苛刻的VOC测试标准(袋式法)的要求。     

专利介绍

<正>纳米改性聚氨酯胶粘剂CN102 942 893(2013-02-27)。该胶粘剂(以质量分数计)由聚酯多元醇10%~40%、聚醚多元醇10%~60%、异氰酸酯15%~30%、二羟甲基丙酸3%~8%、N-甲基吡咯烷酮0.5%~1.5%、三乙胺2%~4%、纳米蒙脱土0.3%~1%和扩链剂0.05%~0.15%等组成。该胶粘剂储存稳定性好、固含量高、粘接强度大且力     

纳米SiO_2改性水性聚氨酯胶粘剂的制备及性能

以PBA(聚酯二元醇)、IPDI(异佛尔酮二异氰酸酯)、DMPA(2,2-二羟甲基丙酸)和BDO(1,4-丁二醇)为原料,DBTDL(二月桂酸二丁基锡)为催化剂,TEA(三乙胺)为中和剂,乙二胺为扩链剂,水为介质,采用共混法和原位聚合法合成了纳米SiO_2(纳米二氧化硅)改性WPU(水性聚氨酯)胶粘剂。研究结果表明:纳米SiO_2能有效提高WPU胶膜的热稳定性,并且采用原位聚合法制得的纳米SiO_2改性WPU胶粘剂之性能优于共混法;当w(纳米SiO_2)=2.0%、w(DMPA)=4.7%(均相对于预聚体质量而言)和R=n(—NCO)/n(—OH)=3.0时,采用原位聚合法制得的纳米SiO_2改性WPU胶粘剂的综合性能相对最佳。     

纳米SiO_2改性PU的合成与性能研究

以异佛尔酮二异氰酸酯(IPDI)、聚酯二元醇(PCD、PCL)、环氧树脂(EP)和1,4-丁二醇等为主要原料,纳米SiO2为改性剂,二月桂酸二丁基锡(DBTDL)为催化剂,成功合成了纳米SiO2改性聚氨酯(PU)。结果表明:纳米SiO2的加入,提高了PU的热稳定性、致密性、耐水性、硬度及耐黄变等性能;当w(纳米SiO2)=1.5%(相对于单体总质量而言)时,改性PU的综合性能较好。     

聚氨酯对第二代丙烯酸酯胶粘剂的增韧改性研究

以PU(聚氨酯)作为SGA(第二代丙烯酸酯胶粘剂)的增韧改性剂,采用单因素试验法探讨了合成PU的多元醇类型、封端剂类型、PU的Mr(相对分子质量)和PU含量等对SGA性能的影响,并优选出制备PU的最佳工艺条件。研究结果表明:以PTMEG-1000(聚四氢呋喃醚二醇)为多元醇、PETA(季戊四醇三丙烯酸酯)为封端剂和R=n(-NCO)/n(-OH)=1.7时,制成的PU-2对SGA的增韧效果相对最好;当w(PU-2)=20%(相对于SGA质量而言)时,PU-2改性SGA的拉伸剪切强度(镁铝合金-镁铝合金)相对最大(11.55 MPa)。     

Thermal and dynamic mechanical characterization of polyurethane–urea–imide coatings

A series of NCO terminated polyurethane (PU)–imide copolymers were synthesized by a systematic three‐step process and were chain extended with different diol/diamine chain extenders. In the first step, isocyanate terminated PU prepolymers were prepared by reacting soft segments such as polyester (PE) polyols and polyether polyols such as polypropylene glycol (PPG‐1000) with hard segments like 2,4‐tolylene‐diisocyanate (TDI) or isophorone‐diisocyanate (IPDI) with NCO/OH ratio 2:1. In the second step, thermally stable heterocyclic imide ring was incorporated using isocyanate terminated PU prepolymers by reacting with pyromellitic dianhydride (PMDA) in a excess‐NCO:anhydride ratio of 1:0.5. The surplus NCO content after imidization was both moisture cured or partially reacted with chain extender and moisture cured. The films were characterized by thermogravimetric (TG), differential scanning calorimetry (DSC) and dynamic mechanical thermal analysis (DMTA) instruments. The adhesion strength of these coatings on mild steel (MS), copper (Cu), and aluminum (Al) is dependent on the nature of the substrate. The TGA analysis show good thermal stability. The DMTA results show the microphase separation between the different hard and soft segments. Finally, a structure to property correlation was drawn based on the structure of the soft, hard, and chain extender and the observed properties are useful for understanding and design of intelligent coatings. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 3158–3167, 2006     

FT-IR and XPS studies of polyurethane-urea-imide coatings

A series of polyurethane (PU)-urea-imide coatings were synthesized by a systematic three-step reaction process. Initially isocyanate terminated PU prepolymers were prepared by reacting soft segments such as polyester polyols (prepared from neopentyl glycol, adipic acid, isophathalic acid and trimethylol propane) or polyether polyols (polypropylene glycol-1000) with hard segments such as 2,4-toluene diisocyanate or isophorone diisocyanate with NCO/OH ratio of 2:1. Heterocyclic imide ring into the PU backbone was incorporated by co-polymerization with pyromellitic dianhydride (PMDA) from the excess NCO groups in the PU prepolymer with an NCO/anhydride ratio of 1:0.5 and the surplus NCO content after imidization was moisture cured. PU-urea-imide coatings were also obtained by partial chain extension of the excess NCO groups in the NCO terminated PU-imide copolymers, and the remaining excess NCO groups were completely reacted with atmospheric moisture. The obtained polymers were analyzed with Fourier transform-infrared (FT-IR) and angle resolved X-ray photoelectron spectroscopy (AR-XPS). The type and change in intermolecular H-bonding interaction in the PU-urea-imide films with structural variables was identified by deconvolution of the FT-IR spectra using Origin 6.0 software through Gaussian curve-fitting method. The FT-IR analyses of the PU-urea-imide coating films show dependence of phase separation on the nature of chain extender. Surface characterization data from AR-XPS suggests the dependence of phase segregation behaviour on the nature of the chain extender, which also supports the FT-IR observations.     

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。     

高固含量聚醚型水性聚氨酯的合成与影响因素

以异佛尔酮二异氰酸酯(IPDI)和六次甲基二异氰酸酯(HDI)为硬段、聚醚(N-220)为软段,二羟甲基丙酸(DMPA)为亲水性物质、乙二胺为后扩链剂和三羟甲基丙烷(TMP)为交联剂等,合成了高固含量的聚醚型水性聚氨酯(WPU)乳液。采用衰减全反射红外光谱(ATR)对其结构进行了表征,并探讨了溶剂(丙酮)和DMPA含量、反应过程中预聚体的黏稠度、扩链剂的加料顺序和扩链时间等因素对WPU乳液固含量的影响。实验结果表明,在保持其他条件不变的情况下,即n(-NCO)∶n(-OH)=1.2∶1、m(HDI)∶m(IPDI)=2∶1和n(TMP中-OH)∶n(聚醚中-OH)=1∶4、w(DMPA)=1.5%(相对于树脂而言)且w(丙酮)=50.4%～75.5%(相对于树脂而言)时,在预聚反应过程中,若体系较稀(即黏度较低),在乳化时先加入乙二胺,待反应4～7min后再加入水,如此易制得稳定的高固含量(40%～46%)聚醚型WPU乳液。     

不同结构的水性聚氨酯的合成及其性能研究

选用不同的软链段比例、不同的异氰酸酯比例和不同的扩链剂制备了水性聚氨酯(WPU),并讨论了n(-NCO)∶n(聚醚和聚酯中-OH)比值和R值的变化对WPU性能的影响。研究结果表明,在预聚反应中,当软链段中n(聚醚)∶n(聚酯)比值为0.5∶0.5、异氰酸酯中n(TDI)∶n(MDI)比值为0.5∶0.5、w(-COOH)为1.0%时,选用DEG为扩链剂、固定R值为1.3左右,可以得到性能优越的WPU。     

木材加工用水性聚氨酯胶粘剂的研究

为了获得稳定性较好的水性聚氨酯(WPU)胶粘剂,以丙酮为溶剂、聚醚(N210)为软段、二苯基甲烷-4,4′-二异氰酸酯(MDI)为硬段、二羟甲基丙酸(DMPA)为亲水性扩链剂、三乙胺(TEA)为成盐剂和聚乙烯醇(PVA)为增稠剂等,制备了环保型木材粘接用WPU胶粘剂。研究了MDI、N210、DMPA、TEA和PVA用量等对乳液稳定性、胶粘剂剪切强度及黏度的影响。结果表明:当n(MDI)∶n(N210)∶n(DMPA)∶n(TEA)=2.4∶1∶0.8∶0.64、w(PVA)=2.0%～3.0%时,可制得常温(20～30℃)存放90 d以上、剪切强度超过4.2 MPa的稳定WPU胶粘剂。     

以聚酯多元醇为基的聚氨酯弹性体的动态力学性能研究

合成了以聚酯多元醇为基的聚氨酯弹性体(PUE),研究了聚酯多元醇结构及相对分子质量、扩链剂类型及用量等因素对聚氨酯弹性体的动态力学性能的影响。结果表明:以相对分子质量为2000及3000的聚酯多元醇制得的PUE中存在明显的相分离;当扩链剂中带有苯环结构时,PUE的玻璃化转变温度(Tg)升高,储能模量增加,阻尼因子下降;PUE的Tg及储能模量随着扩链剂L-MOCA用量的增加线性升高,阻尼因子线性下降。