摘要
本文围绕不同环化单体的开环聚合制备了两种共聚物,探求了结构与性能的关系。
其一研究了在较高温度进行的不同结构助催化剂引发的己内酰胺阴离子开环聚合反应,并以端羟基聚硅氧烷对助催化剂进行改性,成功制备了相容性较好的聚酰胺-聚硅氧烷的嵌段共聚物。研究表明,聚硅氧烷中的醚链段可改善体系的相容性,疏水的柔性聚硅氧烷链段的引入可提高产物的耐水性、表面润滑性和冲击韧性等性能。对聚酰胺-聚硅氧烷共聚物反应挤出制备进行了初步探索,获知由于助催化剂反应活性受聚硅氧烷分子的影响,致使反应的诱导期过长,直接进行反应挤出制备聚酰胺-聚硅氧烷的嵌段共聚物的条件苛刻。
其二研究了开环聚合反应挤出制备聚己内酯型聚氨酯。首先用不同的聚醚二元醇对四异丙氧基钛进行改性,制得改性烷氧基钛混合物,以其作为ε-己内酯(CL)开环聚合的引发剂,首次探讨了由这种双端具有反应活性的较大分子量的引发剂引发的CL的开环聚合反应,分别采用DSC和1H-NMR表征方法跟踪非等温和等温聚合反应动力学。研究获得,改性烷氧基钛混合物可有效地引发CL遵循配位-插入机理进行聚合,其中聚醚的自由羟基与隐含羟基具有相同的引发活性。等温开环聚合反应的表观活化能Ea为108-109 KJ/mol,拟合得到的等温聚合反应动力参数可较好地用于预测实验过程。由Flynn-Wall、Kissiger和Ozawa等三种经验方程拟合非等温聚合反应动力学数据,得到的表观聚合反应活化能Ea基本一致,Ti(OPEG400)4和PEG-400混合物引发聚合的Ea为55-61 KJ/mol, Ti(OPEG1000)4和PEG-1000混合物引发的为69-73 KJ/mol。聚合反应的反应级数在0.98与1.30之间,近似为1级反应。
在上述配位-插入开环聚合动力学研究的基础上,以CL单体和4,4’-二苯基甲烷二异氰酸酯(MDI)为原料,改性烷氧基钛混合物为引发剂和催化剂,通过反应挤出原位制备了一系列以PCL和PTMG或PEG多嵌段共聚物为软段的聚氨酯(PCLU)。与已报导的PCLU的分步制备方法相比,反应挤出法制备不仅是实现PCLU快速制备的方法,而且还是一种简单、可控、易实现PCLU连续化大规模生产的技术。保持反应挤出体系中MDI和烷氧基钛摩尔比恒定,通过调整体系中CL单体的相对含量,即可制得不同PCL嵌段平均聚合度(DPn)的PTMG-PCLU和PEG-PCLU。1H-NMR、GPC和DSC测试结果显示,所有投料的CL单体都已完成聚合,制备所得PCLU数均分子量约8×104 g／mol和多分散系数约为2.4。随着PCL嵌段DPn增大,PCLU的拉伸性能逐渐增大,然后稍有降低,而结晶熔融温度则逐渐升高。当PTMG-PCLU, PCL嵌段DPn从25增大至40时,拉伸强度由16.5 MPa提高至22.7 MPa,而结晶熔融温度由46.1℃增大至49.5℃。在制备过程中,反应体系中有机钛含量的降低对PCLU的力学性能造成较大影响,随着有机钛含量的降低拉伸性能逐渐减小。
为了研究结晶性的PCL嵌段DPn和聚醚嵌段类型对反应挤出制备的PCLU结晶行为和结晶动力学及其对材料的性能的影响,采用DSC研究了不同类型的PCLU的非等温结晶结晶行为和动力学,并使用Jeziomy改进的Avrami模型、Ozawa模型和莫志深混合模型等对非等温结晶过程的数据进行了分析。结果给出,PCLU中PCL嵌段和聚醚嵌段的结晶相互受限,PCL嵌段具有较强的结晶能力,总体结晶速率随PCL嵌段的DPn增大而增大。Jeziomy改进的Avrami模型和莫志深混合模型都能对PCLU非等温结晶过程进行较好的描述,而Ozawa模型则只能对部分PCLU样品非等温结晶过程进行较好的描述。动力学特征表明,PCLU非等温结晶的成核和结晶生长机理均较为复杂,但主要以热成核和球晶生长为主,PCL嵌段DPn和聚醚嵌段类型对此影响不大；非等温结晶的表观活化能数值随PCLU的PCL嵌段的DPn增大而减小。
进一步地,联合使用DSC、DMA和POM等多种方法,考察了形变幅度、形变’温度和形变速率等因素对反应挤出所得PCLU的形状记忆性能的影响。DSC测试表明,PCLU的结晶熔融温度和结晶度均随PCL嵌段DPn的增大而单调升高。PCLU的回复力随着回复温度升高而增大,并在45-55℃达到最大值,最大回复力为6-7 MPa,与聚乳酸型聚氨酯的最大回复力相近。首次提出了具有两个回复阶段的改进的形状记忆原理模型,并用POM分析进行证实,该模型可以较好地对PCLU形变的回复力发展和回复过程进行解释。PCLU拉伸形变回复过程可以回复的拐点温度为界分成两个阶段,拐点温度为43-48℃；压缩形变回复过程亦然,拐点温度为64-66℃。PCLU的临时形状固定率为60-70%,并可以通过选用合适的形变温度提高至100%。由于PCLU中聚醚嵌段的吸水性,PCLU的拉伸形变回复率在80-98%之间；而压缩形变回复率几乎均可达100%。另外,形变回复的最低回复温度受形变温度、形变速率、PCL嵌段DPn和聚醚嵌段分子量等因素的影响,可以在24-47℃之间进行调整。根据不同的回复要求,PCLU形变记忆性能可进行设计和调整。
In the first part of this paper, the anionic polymerizationε-caprolactam initiated by activators with different structure at relatively high temperature was investigated. And the polyamide-polysiloxane copolymer was synthesized by the anionic polymerization ofε-caprolactam initiated by the activator modified by polysiloxane. Results show that the ether block of the polysiloxane can improve the compatibility between the polyamide block and polysiloxane block. The introducing of hydrophobic flexible polysiloxane block can improve the water resistance, surface properties and impact toughness of the polyamide-polysiloxane copolymer. However, the experiments on the Haake extruder indicate that it is difficult to realize the preparation of polyamide-polysiloxane copolymer via reactive extrusion for the increased reaction induce time resulted from the effect of polysiloxane chain on the reactivity of the activator.
The second part of the paper is focused on the polycaprolactone based polyurethanes. First, the modified titanium alkoxide mixture used for the ring-opening polymerization (ROP) ofε-caprolactone (CL) was synthesized through the ester-exchange reaction of titanium n-propoxide and poly ether diol. The mechanism and kinetics of the bulk polymerization of CL initiated by the modified titanium alkoxide mixture were investigated by DSC and 1H-NMR. The results demonstrate that the polymerization of CL initiated by the modified titanium alkoxide mixture proceeds through the coordination-insertion mechanism and all hydroxyl groups of the polyether share a similar activity in initiating ROP of CL, including the free and potential hydroxyl groups of the polyether. The isothermal polymerization process can be well predicted by the obtained kinetic parameters, and the activation energy is 108-109 KJ/mol. The activation energies of the non-isothermal CL ROP determined by Flynn-Wall, Kissiger and Ozawa methods agree quite well, for Ti(OPEG400)4 and PEG-400 mixture is 55-61 KJ/mol and Ti(OPEG1000)4 and PEG-100069-73 KJ/mol. The ROP of CL initiated by the modified titanium alkoxide mixture can approximately to be 1 order reaction.
On the basis of the kinetics for CL ROP, PCLU with multi-block copolymer of polycaprolactone (PCL) and poly(tetramethylene oxide) glycol (PTMG) or polyethylene glycol (PEG) as soft segment was in-situ synthesized via reactive extrusion from CL and 4,4'-diphenylmethane diisocyanate (MDI). The modified titanium alkoxide mixture was utilized as initiator and catalyst. Compared to the reported fabrication of PCLU, the in-situ reactive extrusion preparation not only explored a new rapid route for fabrication of PCLU but also offered a simplified controllable approach for the production of PCLU in a successive mass scale. A series of PTMG-PCLU and PEG-PCLU of different PCL block average degree of polymerization (DPn) were prepared by only adjusting the relative concentration of the CL in the reaction system, with the mole ratio of MDI to titanium alkoxide kept at a certain constant.1H-NMR, GPC and DSC results indicate that all the CL monomers have been converted in the polymerization and the molecular weight of the copolymers is about 8×104 g/mol with a polydispersity index of approximate 2.4. With increasing the PCL block DPn in PTMG-PCLU from 25 to 40, the tensile strength increases from 16.5 MPa to 22.7 MPa, and the melting point increases from 46.1℃to 49.5℃. It was also verified by PEG-PCLU prepared with organic Ti of lowered content in the initiator mixture that the mechanical properties can be greatly affected and dropped with the decrease of the content of organic Ti in the initiator mixture.
Since the properties of the PCLU will be affected by the crystallization behavior of the PCL block, to study the effects of the PCL block DPn and the type of polyether block on the PCLU obtained via reactive extrusion, the non-isothermal crystallization kinetics were investigated by DSC. The DSC experiment data was analyzed by a Jeziorny modified Avrami model, Ozawa model, and Mo mixed Avrami-Ozawa model, respectively. The results demonstrate that the non-isothermal crystallization can be well described by the Jeziorny modified Avami model, and Mo mixed model, but Ozawa model can only do for some of the products. The kinetic results indicate that the nucleation and crystal growth for the non-isothermal crystallization of PCLU is complicated, but mainly in a way of a thermal nucleation followed by three-dimensional spherical growth. In the non-isothermal crystallization, the PCL block DPn and the type polyether block does not affect the crystallization mechanism. The activated energy of non-isothermal crystallization decreases with increasing the PCL block DPn.
The shape memory properties were investigated in terms of the deformation amplitude, temperature and rate by DSC, DMA and POM. DSC analysis shows that the crystalline melting temperature and crystallinity of PCLU increased monotonically with increasing the PCL block DPn. The retract force increased with increasing the temperature and reached the maximum within 45-55℃. The maximum retract force of PCLU is 6-7 MPa which is as high as that of polylactic acid based polyurethanes. Furthermore, a modified model with two recovery stages was postulated to elucidate the shape memory process, which is visually presented by POM analysis. The two stages of tensile and compressive recovery are distinguished by the inflexion temperature, within 43-48℃and 64-66℃respectively. The temporary shape fixity of the products is about 60-70% and can be improved to 100% by choosing proper deformation temperature. The tensile deformation recovery ratio was 80-98% due to the water absorption, while the compressive deformation recovery ratio was almost 100%. Besides, recovery tests show that the lowest recovery temperature which ranged from 24-47℃was influenced by the deformation temperature, deformation rate, the PCL block DPn and the molecular weight of the polyether diol. Thus, the shape memory properties can be adjusted according to different purposes.
引文
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