聚氨酯阻尼材料的结构设计及其性能研究

发布时间：2018-05-14 05:20

本文选题：PU阻尼材料 + 结构设计　；参考：《河北工业大学》2015年博士论文

【摘要】：结构是决定材料性能的根本因素,研究分子结构对聚氨酯(PU)阻尼材料的影响是提高其性能的有效途径。本文根据基团贡献分析法和聚合物阻尼性能定量化理论对聚醚型、聚酯型以及聚醚酯型PU阻尼材料进行分子结构设计,调节软硬段种类及含量制备了一系列PU阻尼材料,并对其性能进行了系统研究。通过四氢呋喃聚醚(PTMG)、聚丙二醇聚醚(PPG)与甲苯二异氰酸酯(TDI100)、二苯基甲烷二异氰酸酯(MDI50)反应合成PU预聚体,用含有不同侧基结构的二醇和二胺扩链剂扩链,制备了聚醚型PU阻尼材料。PPG型PU的损耗角正切(tanδmax)明显高于PTMG型PU,力学性能次之。PPG2000型PU的tanδmax略高于PPG1000型PU,且tanδ0.3的阻尼温域向低温方向移动。二醇扩链剂中醚键和侧甲基的引入,有助于tanδmax值增大,tanδ0.3的阻尼温域拓宽;二胺扩链剂中苯环的引入,使tanδ0.3的阻尼温域变窄且移向高温。TDI100/MOCA硬段体系的PU比MDI50/BDO的DMA谱图的峰形扁而宽,tanδ0.3的阻尼温域靠近高温,力学性能较好。通过聚丁二酸新戊二醇酯(PNS)、聚己二酸新戊二醇酯(PNA)与TDI100、异佛尔酮二异氰酸酯(IPDI)反应合成PU预聚体,用不同结构二胺扩链剂扩链,制备了聚酯型PU阻尼材料。PNA型PU比PNS型PU的tanδmax稍高,Tg偏小,tanδ0.3的阻尼温域靠近低温。随PNS分子量增加,tanδmax由0.73增加到1.10,tanδ0.3的阻尼温域略向低温移动,力学性能有所降低。TDI100型PU比IPDI型PU的tanδmax和Tg都高,但tanδ0.3的阻尼温域较窄,力学性能偏低。二胺扩链的PU阻尼性能的大小依次为:MOCAL-MOCAM-CDEA。扩链系数降低,tanδmax明显增大,力学性能有所下降。通过丙氧基新戊二醇(PNP)与丁二酸(SA)、己二酸(AA)反应合成了聚丁二酸丙氧基新戊二醇酯(PNPS)和聚己二酸丙氧基新戊二醇酯(PNPA),与TDI100反应合成PU预聚体,用MOCA扩链,制备了聚醚酯型PU阻尼材料。PNPS型PU的阻尼性能优于PNPA型PU阻尼材料。随着PNPS分子量增大,阻尼性能提高并移向低温,力学性能有所下降。采用FTIR和1H-NMR对其原料、聚酯及聚醚酯结构进行表征,GPC测试的聚醚酯二醇实际分子量和理论分子量相近。AFM显示了PU阻尼材料明暗相间的微相分离结构,颜色较亮的为硬段均匀分散于颜色较暗的软段中,随软段分子量增大,相分离明显。SEM进一步验证了聚酯型PU阻尼材料明显的微相分离结构。TGA和DSC结果表明:PU阻尼材料具有较好的耐热性能,聚醚型PU阻尼材料具有两个明显的软、硬段Tg,而聚酯型PU阻尼材料只有软段的Tg转变峰。随着软段分子量的增加,耐热性能变差。XRD结果表明:聚酯型PU阻尼材料具有极少量的的微晶存在。对PNS型PU阻尼结构进行测试,激励幅值和加载频率对等效水平刚度、等效阻尼比、屈服后刚度以及屈服力都有重要影响,需要综合考虑各参数之间的关系,应用于实际阻尼结构设计中。
[Abstract]:The structure is the fundamental factor to determine the properties of the materials. It is an effective way to improve the properties of the damping materials by studying the influence of molecular structure on the properties of polyurethane (pu) damping materials. In this paper, the molecular structure of polyether type, polyester type and polyether ester type pu damping materials were designed according to the group contribution analysis method and the quantitative theory of polymer damping properties. A series of pu damping materials were prepared by adjusting the types and contents of soft and hard segments. And its performance is studied systematically. Pu prepolymer was synthesized by the reaction of tetrahydrofuran polyether (PTMGN), poly (propylene glycol) polyether (PPG) and toluene diisocyanate (TDI100) and diphenyl methane diisocyanate (MDI50). The loss angle tangent tan 未 max. of polyether pu damping material, PPG type pu, is obviously higher than that of PTMG type pu, and the tan 未 max of PPG type pu is slightly higher than that of PPG1000 type pu, and the damping temperature range of tan 未 0.3 moves to low temperature. The introduction of ether bond and side methyl in diol chain extender can increase the damping temperature range of tan 未 max value to increase the damping temperature range of tan 未 0.3, and the introduction of benzene ring in diamine chain extender. The damping temperature range of tan 未 0.3 is narrowed and moved to high temperature. TDI 100 / MOCA hard segment system has better mechanical properties than the DMA spectrum of MDI50/BDO. Pu prepolymer was synthesized by the reaction of poly (neopentanediol succinate) PNSN, poly (neopentylenediol adipate) PNAwith TDI100, isophorone diisocyanate (IP DIA), and chain extension with different structures of diamine chain extender. The damping temperature range of polyester pu damping material. PNA pu is slightly higher than that of tan 未 max of PNS pu. The damping temperature range is close to low temperature. With the increase of the molecular weight of PNS, the damping temperature range from 0.73 to 1.10 tan 未 0.3 shifts slightly to low temperature, and the mechanical properties of pu of type TDI100 are lower than those of tan 未 max and TG of IPDI type pu, but the damping temperature range of tan 未 0.3 is narrower, and the mechanical properties of tan 未 0.3 is lower than that of IPDI type pu. The order of pu damping property of diamine chain extension is: MOCAL-MOCAM-CDEA. The chain extension coefficient decreases and the max increases obviously, and the mechanical properties decrease. Pu prepolymer was synthesized by the reaction of propyl neopentanediol (PNPN) with succinic acid (PNPS) and poly (propylneopentanediol adipate) (PNPs) and poly (propanediol adipate) (PNPs). Pu prepolymer was synthesized by reaction with TDI100, and the chain was extended by MOCA. The damping property of polyether ester type pu damping material and PNPS pu damping material was better than that of PNPA pu damping material. With the increase of molecular weight of PNPS, the damping property increases and moves to low temperature, and the mechanical properties decrease. FTIR and 1H-NMR were used to characterize the structure of the raw material, polyester and polyether ester. The actual molecular weight and theoretical molecular weight of polyether diol were similar. AFM showed the microphase separation structure between light and dark phase of pu damping material. The brightly colored hard segments were evenly dispersed in the darker soft segments, and the molecular weight of the soft segments increased with the increase of the molecular weight of the soft segments. The results of phase separation, SEM and DSC showed that the w pu damping material had better heat resistance, and polyether pu damping material had two obvious soft properties. The hard segment Tg, while the polyester pu damping material has only the soft segment TG transition peak. With the increase of molecular weight of soft segment, the heat resistance becomes worse. XRD results show that the polyester pu damping material has a very small amount of microcrystals. The PNS type pu damping structure is tested. The excitation amplitude and loading frequency have important effects on the equivalent horizontal stiffness, equivalent damping ratio, yield stiffness and yield force. It is applied to the actual damping structure design.
【学位授予单位】：河北工业大学
【学位级别】：博士
【学位授予年份】：2015
【分类号】：TQ317;TB535

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