聚碳酸酯型聚氨酯互穿网络聚合物的研究概况

简述了聚磷酸酯型聚氨酯（PCU）互穿网络聚合物（IPN）的发展及最新研究动态。介绍了其制备、表征、结构与性能的关系。预示了聚碳酸酯型聚氨酯互穿网络聚合物材料的开发前景。     

端羟基聚丁二烯型聚氨酯/聚苯乙烯(或聚甲基丙烯酸甲酯)互穿网络的形态和玻璃化转变

互穿聚合物网络(IPN'S)已经成为高聚物共混改性,高聚物间相容性的一个重要研究领域,IPN材料的宏观性能与其微观形态有着密切的关系,如能通过改变结构、组成、交联密度及合成条件等因素来控制IPN的形态,则就可以入为地制备各种性能优良的材料。本文用透射电镜和差示扫描量热仪对同步法合成的端羟基聚丁二烯型聚氨     

聚环氧氯丙烷聚氨酯／聚甲基丙烯酸甲酯互穿网络聚合物的相容性与力学性能

用同步法合成了聚环氧氯丙烷聚氨酯／聚甲基丙烯酸甲酯互穿网络聚合物［ＰＵ（ＰＥＣＨ）／ＰＭＭＡＩＰＮ］，调节ＩＰＮ中两组分组成比制备出由完全弹性体、增强弹性体、增韧塑料到脆性塑料多种高聚物合金材料．用ＤＳＣ、动态力学谱、ＴＥＭ对ＩＰＮ的研究结果表明，ＰＵ（ＰＥＣＨ）／ＰＭＭＡＩＰＮ的两组分是完全相容的；同时对各种组成比的ＩＰＮ材料进行力学性能测试，用相容性ＩＰＮ中互穿、缠结结构解释其力学行为，并用ＳＥＭ对断面形貌进行了观察解释．     

聚氨酯型互穿网络聚合物的研究

以甲苯二异氰酸酯和蓖麻油反应，合成了一系列室温固化的蓖麻油型聚氨酯。分别研究了蓖麻油聚氨酯（ＣＯＰＵ）／聚苯乙烯（ＰＳｔ）ＩＰＮｓ、ＣＯＰＵ／聚丙烯腈（ＰＡＮ）ＩＰＮｓ的结构和性能。结果表明：ＣＯＰＵ／ＰＡＮ的力学性能较ＣＯＰＵ／ＰＳｔ的力学性能为好。为进一步改善聚合物之间的相容性，在聚苯乙烯网络中引入极性较大的丙烯腈制备了ＣＯＰＵ／Ｐ（Ｓｔ－ＣＯ－ＡＮ）ＩＰＮｓ，并对它的力学性能、热分析、动态力学性能、热稳定性等作了系统的研究。结果表明：当聚氨酯浓度为６０％时，改变Ｓｔ、ＡＮ的比例，随ＡＮ含量的增加，体系的微相分离程度降低。改变ＣＯＰＵ／Ｐ（Ｓｔ－ＣＯ－ＡＮ）的比例，ｔａｎδ－Ｔ曲线上均呈现一个较宽的玻璃化转变温度；热重分析表明，其初始分解温度可达２４４℃。     

聚氨酯／聚（苯乙烯—甲基丙烯酸甲酯—甲基丙烯酸互穿聚合物网络的研究

研究了聚氨酯／聚互穿合笺网络，动态力学性能及透射电镜结果均表明该体系相分离较严重。ＩＮＰ具有两个玻璃化转变温度，它们有不同程度的内移，形成一定程度分子水平的混合。而ＩＰＮ（５０／５０）其分子混合水平较大，互穿缠结程度较高。     

聚氨酯／聚甲基丙烯酸甲酯互穿聚合物网络的研究

本文对(蓖麻油-聚乙二醇)聚氨酯/聚甲基丙烯酸甲酯(PU/PMMA)互穿聚合物网络(IPN)体系进行了研究.实验结果表明:IPN的力学性能受网络化学构型控制.在PU/PMMA为25/75时,应力-应变曲线出现屈服点,产生类似皮革行为,并在此点抗张强度最高,表现明显的协同效应.动态力学性能及电镜均证明该体系相分离十分严重,通过加入扩链剂及网间交联剂能显著改善两组分相容性,其中网间交联剂效果最好。     

聚氨酯/聚苯乙烯互穿聚合物网络的研究

互穿聚合物网络形态和力学性能的研究已有报道^[1～3],但有关合成过程中分子量变化形态和性能的影响研究甚少。本文在动力学研究的基础上^[4],用GPC、DSC和Instron万能机研究了聚氨酯/聚苯乙烯互穿聚合物网络(PU/PSt-IPN)的分子量,玻璃化转变温度和力能,考察了分子量与相分离点之间的关系。     

聚氨酯/聚甲基丙烯酸甲酯离子聚合体型互穿聚合物网络生成动力学研究

本文采用在聚氨酯中引入丁基二乙醇胺,形成带有叔氮原子的聚氨酯(NPU)和聚甲基丙烯酸甲酯中引入甲基丙烯酸的方法,合成了带有离子键的离子聚合体型互穿聚合物网络(IPN),动力学研究表明,离子聚合体型IPN形成速率明显低于非离子聚合体型IPN,两网络的聚合速率相互抑制,并随离子键浓度增加而显著,两网络的聚合机理互不干扰。     

聚氨酯／聚（苯乙烯－甲基丙烯酸甲酯－甲基丙烯酸）互穿聚合物网络的研究

研究了（蓖麻油－聚乙二醇）聚氨酯／聚（苯乙烯－甲基丙烯酸甲酯－甲基丙烯酸）（ＰＵ／Ｐ（Ｓｔ－ＭＭＡ－ＭＡＡ））互穿聚合物网络（ＩＰＮ）．动态力学性能及透射电镜结果均表明该体系相分离较严重；ＩＰＮ具有两个玻璃化转变温度，它们有不同程度的内移，形成一定程度分子水平的混合，而ＩＰＮ（５０／５０）其分子混合水平较大，互穿缠结程度较高。形成ＩＰＮ后，其力学性能得以改善。透射电镜结果表明，聚氨酯网的交联密度直接影响ＩＰＮ的相区尺寸。形成ＩＰＮ后热稳定性提高，易于降解断链的Ｓｔ－ＭＭＡ－ＭＡＡ单体起到了自由基消除剂的作用。     

聚甲基丙烯酸甲酯/星形聚乙二醇半互穿聚合物网络的形状记忆性能和分子机理

采用非共价复合方法,设计并合成了具有星形结构的聚甲基丙烯酸甲酯/星形聚乙二醇半互穿聚合物网络(PMMA/SPEG)和聚甲基丙烯酸甲酯/线性聚乙二醇半互穿聚合物网络(PMMA/LPEG).研究了PEG分子量对PMMA/SPEG和PMMA/LPEG的热性能、机械性能、动态机械性能和形状记忆性能的影响.结果表明,与PMMA/LPEG相比,星形结构的嵌入显著提高了PMMA/SPEG复合物的机械性能、形状回复率和回复速度.采用Edwards管道模型理论对其形状记忆效应的分子机理进行了阐释,利用材料的应力松弛特性对机理分析进行了验证.     

聚环氧氯丙烷聚氨酯／聚（甲基丙烯酸甲酯－苯乙烯）IPN的研究

改变聚（甲基丙烯酸甲酯－苯乙烯）（Ｐ（ＭＭＡ－ｃｏ－Ｓｔ）中甲基丙烯酸甲酯的含量（Ｗ_（ＭＭＡ）），通过一步法合成出聚环氧氯丙烷聚氨酯（ＰＵ（ＰＥＣＨ）／Ｐ（ＭＭＡ－ｃｏ－Ｓｔ）ＩＰＮ．ＤＳＣ、ＴＥＭ和动态粘弹谱研究结果表明：当Ｐ（ＭＭＡ－ｃｏ－Ｓｔ）中Ｗ_（ＭＭＡ）大于０．６时，ＩＰＮ仅有一个Ｔｇ；当Ｗ_（ＭＭＡ）小于０．４时，ＩＰＮ有２个Ｔ_ｇ，ＴＥＭ上出现相区，Ｐ（ＭＭＡ－ｃｏ－Ｓｔ）溶度参数（δ）及δ的氢键作用分量（δｈ）与相态、力学性能有密切关系。     

Studies on Poly(Methyl Methacrylate) (PMMA) and Thermoplastic Polyurethane (TPU) Blends

Blends of poly(methyl methacrylate) (PMMA) and thermoplastic polyurethane (TPU) in different compositions viz., 95/5, 90/10, 85/15 and 80/20 (by wt/wt, % of PMMA/TPU) were blended by melt mixing using a twin‐screw extruder. All the PMMA/TPU blends have been characterized for physico‐mechanical properties such as density, melt flow index, tensile behavior and izod impact strength. The impact strength of the PMMA/TPU blends were found to increase significantly with an increase in the percentage of TPU up to 20%, by retaining the tensile strength of PMMA. The effect of chemical aging on the performance of blends has been studied.     

聚环氧氯丙烷聚氨酯／聚甲基丙烯酸甲酯IPN力学性能

利用改变组成比、聚氨酯ＰＵ软段的分子量、Ｒ值、异氰酸酯和两网络各自交联剂含量合成出５个系列的聚环氧丙烷聚氨酯／聚甲基丙烯酸甲酯互穿聚合物网络，利用ＩＰＮ中交联、互穿、缠结程度的不同，并结合ＤＣＳ、ＴＥＭ、动态粘弹谱讨论了ＩＰＮ力学性能。     

Polyepichlorohydrin polyurethane/poly(methyl methacrylate) interpenetrating polymer networks

Polyurethane (PU) based on polyepichlorohydrin/poly(methyl methacrylate) (PECH/PMMA) interpenetrating polymer networks (IPNs) was synthesized by a simultaneous method. The effects of composition, hydroxyl group number of PECH, NCO/OH ratio and crosslinking agent content in IPNs were investigated in detail. Some other glycols, such as poly(ethylene glycol), poly(propylene glycol) and hydroxyl-terminated polybutadiene, were also used to obtain PU/PMMA IPNs. The interpenetrating and fracture behaviors of the IPNs are explained briefly.     

Effect of Specific Interactions on Structure-Property Relationships of Thermoplastic IPNs Based on Polyurethane and Styrene-co-Acrylic Acid Ionomers

Summary: The structure-property relationships of thermoplastic polymer blends based on poly(ether-urethane) ionomer (PEUI) and K⁺-Ion containing styrene-acrylic acid random copolymer (S-co-AA(K)) have been investigated by different methods. Convergence of the glass transition temperature values of the PEUI and the S-co-AA(K) components in the blends studied and improvement of end-use properties have been found.     

聚碳酸亚丙酯-聚醚聚氨酯的合成与性能

本文报道用CO2与环氧丙烷共聚产物聚碳酸亚丙酯和环氧丙烷均聚物来制备聚氨酯（PPCPOPU）弹性体。探讨了这类弹性体的最佳合成方法，考察了异氰酸酯基与羟基的比值；扩链交联剂用量等因素对弹性体的力学性能的影响。研究了弹性体的形态结构及其性能对配比的依赖关系。发现聚碳酸亚丙酯的耐热性因聚氨酯的形成而得到较大的改善，并发现该类弹性体具有优异的耐水性能。     

聚环氧乙烷／脂肪族聚碳酸酯共混研究

本文用差热分析(DSC)和红外光谱仪(FTIR)研究了聚环氧乙烷(PEO)和新型聚合物——脂肪族聚碳酸脂(PPC)共混热行为和大分子间的相互作用。由熔点下降方法给出PEO/PPC混合体系在320K下相互作用参数为-0.46;FTIR谱表明PPC大分子链和PEO大分子链存在较强的相互作用;PEO/PPC共混形态随PPC含量增加发生了较大变化。     

Interpenetrating polymer networks of poly(dimethyl siloxane–urethane) and poly(methyl methacrylate)

Simultaneous IPNs of poly(dimethyl siloxane-urethane) (PDMSU)/poly(methyl methacrylate) (PMMA) and related isomers have been prepared by using new oligomers of bis(β-hydroxyethoxymethyl)poly(dimethyl siloxane)s (PDMS diols) and new crosslinkers biuret triisocyanate (BTI) and tris(β-hydroxylethoxymethyl dimethylsiloxy) phenylsilane (Si-triol). Their phase morphology have been characterized by DSC and SEM. The SEM phase domain size is decreased by increasing crosslink density of the PDMSU network. A single phase IPN of PDMSU/PMMA can be made at an M_c = 1000 and 80 wt % of PDMSU. All of the pseudo- or semi-IPNs and blends of PDMSU and PMMA were phase separated with phase domain sizes ranging from 0.2 to several micrometers. The full IPNs of PDMSU/PMMA have better thermal resistance compared to the blends of linear PDMSU and linear PMMA. © 1993 John Wiley & Sons, Inc.     

Poly(ethylene oxide)/poly(methyl methacrylate) (semi-)interpenetrating polymer networks: Synthesis and phase diagrams

Interpenetrating polymer networks (IPNs) of poly(ethylene oxide) (PEO) and poly(methyl methacrylate) (PMMA) were prepared by simultaneous network formation. The PEO network was produced by acid-catlayzed self-condensation of α,ω-bis(triethoxysilane)-terminated PEO in the presence of small amounts of water. The PMMA network was formed by free radical polymerization of MAA in the presence of divinylbenzene as crosslinker. The reaction conditions were adjusted to obtain similar crosslinking kinetics for both reactions. An attempt was made to construct a phase diagram of the IPNs by measuring the composition of the IPNs at the moment of the appearance of the phase separation, as indicated by the onset of turbidity. This composition could be determined because the siloxane crosslinks of the PEO network could be hydrolyzed in aqueous NaOH with the formation of linear, soluble PEO chains. The phase diagram was compared with phase diagrams of blends of linear polymers and of semi-IPNs (crosslinked PMMA and linear PEO), obtained under similar conditions, i.e. polymerization of MMA in the presence of varying amounts of PEO. It was observed that the form of the phase diagrams of the linear polymers is similar to that of the IPNs, but is quite different from that of the semi-IPNs. Thus, homogeneous transparent materials containing up to 60% of PEO could be prepared in the blends and the IPNs, but in the semi-IPNs, phase separation occurred with PEO contents as low as 10%.     

PU／PMMA—IPN体系的反应动力学研究

采用FT-IR法研究了聚氨酯/聚甲基丙烯酸甲酯互穿网络聚合物(PU/PMMA-IPN)的光固化和热固化动力学以及固化方式对聚合物形态和力学性能的影响。实验结果表明:当PU/PMMA-IPN的组成百分含量为75/25时,光固化试样的抗张强度(22.6MPa)和伸长率(201%)均高于热固化试样(抗张强度18.6PMa伸长率69%)。这是因为光固化时甲基丙烯酸甲酯(MMA)迅速聚合形成凝胶产生“速冻”效应,阻碍了PU予聚体迁移分相,从而提高了聚合物网络的互穿程度,此结果亦为电镜照片所证实。