新型聚甲基丙酮肟基硅氧烷交联剂对硅橡胶性能的影响

以聚甲基丙酮肟基硅氧烷(PMKS)作为交联荆,将端羟基聚二甲基硅氧烷(PDMS)在室温下交联固化生成硅橡胶,并研究了PMKS对硅橡胶固化性能与力学性能的影响.计算表明,交联反应的表观活化能为104kJ/mol,IR测试表征了体系固化前后官能团的变化.硅橡胶的交联密度随PMKS含量的提高而增大.与传统交联剂相比,PMKS...     

温度和共交联剂用量对四丙氟橡胶硫化的影响

用无转子硫化仪、万能材料试验机和溶胀实验研究了硫化温度及共交联剂三烯丙基异氰脲酸酯(TAIC)用量对四丙氟橡胶(TFE-P)的硫化特性、拉伸性能和溶胀性能的影响。结果表明,TAIC对TFE-P有增塑作用,可以延长混炼胶的流动时间;交联速率随一段硫化温度和TAIC用量的增加而提高,在TAIC-P为5份之后变化很小;TFE-P硫化过程存在断链反应并导致交联密度减小;交联密度随一段硫化温度升高而降低;增加TAIC可提高交联密度,在TAIC-P为7.5份之后变化很小。一段硫化温度和TAIC用量对最终的交联密度具有调控作用,并影响最终硫化胶的拉伸性能和溶胀性能。     

用介电方法研究COPU/PMMA交联共聚物的转变与松弛

用TRS-10C型介电损耗仪,在不同频率,-180℃～170℃范围内测得COPU/PMMA交联共聚物的介电损耗谱。计算了各松弛过程的活化能,考察了组成和交联密度对分子运动、相容性及形态结构的影响。结果表明,COPU/PMMA交联共聚物是个半相容体系,其相容性随PMMA含量的增加和交联密度的减小而变坏。介电损耗谱上的次级松弛是COPU链段运动的贡献。界面极化区松弛谱的各点温度和频率的关系符合Arrhenius方程,各点温度和其高温侧松弛曲线线性部分斜率的大小可以反映相容性的好坏。     

丁基橡胶/聚异丁烯交联体系的黏弹行为

选用聚异丁烯-异戊二烯共聚物橡胶（IIR）和聚异丁烯（PIB）为原材料，研究了PIB含量与相对分子质量、IIR中异戊二烯含量和交联剂含量对IIR/PIB交联体系黏弹行为的影响。研究结果显示，完全交联的IIR体系几乎不发生应力松弛；添加不可交联的PIB显著降低了IIR交联后的模量，PIB相对分子质量越高，对模量的影响越小；IIR中异戊二烯含量和交联剂含量增加会使交联速率和交联密度提高，其中异戊二烯含量越高，交联剂含量变化对交联IIR/PIB黏弹性的影响越大。PIB质量分数为50%时，IIR/PIB体系损耗模量（G′′）在交联过程中的变化与交联密度、PIB性质密切相关：交联反应初期，G′′随弹性模量（G′）的提高而下降，交联反应后期则随着交联密度的上升而增加，且低分子量PIB和高分子量PIB体系的G′′值分别在G′=120～150 kPa和220～270 kPa时出现最低值；G′′～G′曲线在高交联密度下逐渐实现归一化，揭示了非交联分子链在交联IIR网络中的松弛行为。同时，PIB在交联IIR网络中松弛导致聚合物体系模量降低，但其归一化G(t)～t曲线几乎完全重合。     

3,3-二(叠氮甲基)氧丁环与四氢呋喃共聚醚弹性体硬段结构组成对其力学性能影响

为探索3,3-二叠氮甲基氧丁环-四氢呋喃共聚醚[Poly(BAMO-THF)]弹性体中硬段结构组成对力学性能的影响,以甲苯二异氰酸酯(TDI)为固化剂,调节扩链剂1,4-丁二醇(BDO)与交联剂三羟甲基丙烷(TMP)添加比制备了一系列固化参数与硬段含量不变、硬段组成不同的Poly(BAMO-THF)弹性体S1～S5。力学性能测试表明,随BDO含量增加、TMP含量下降,弹性体拉伸模量由S1的(0.83±0.05) MPa单调降至S5的(0.51±0.02) MPa,断裂延伸率由S1的526%±50%单调增至S5的950%±60%,拉伸强度维持恒定((2.52±0.39) MPa～(2.75±0.31) MPa)。溶胀测试表明,弹性体S1～S5平衡溶胀率随TMP含量下降呈单调上升,化学交联程度下降。低场核磁研究表明,弹性体S1～S5表观硬段含量随TMP含量下降呈单调上升。红外分析表明,随TMP含量下降弹性体中羰基与氨基氢键缔合程度增加,弹性体的物理交联程度提高。     

交联对透明聚氨酯弹性体结构与性能的影响

采用一步法以异佛尔酮二异氰酸酯（IPDI）、聚氧四亚甲基二醇（PTMG）、1，4－丁二醇（BD）和聚氧化丙烯三醇（N3010）为原料合成了透明聚氨酯弹性体，通过DSC、FT－IR、TG等方法研究了物理交联和化学交联对聚氨酯弹性体的力学性能、光学透明性和热稳定性的影响。结果表明，尽管聚醚二元醇的分子量增大，但由于硬段间的氢键作用增加，使微相分离程度提高，聚氨酯弹性体的力学强度增加。加入交联剂三元醇N3010，聚氨酯弹性体在硬段间形成化学交联、透度、热稳定性和力学性能与未加交联剂的聚氨酯弹性体相比有明显提高。     

聚四氢呋喃醚二醇/聚氧化丙烯二醇共混聚醚聚氨酯弹性体的氢键作用

分别以聚四氢呋喃醚二醇(PTMG)、聚氧化丙烯二醇(PPG)及两者共混物PTMG/PPG作为软段,以2,4-甲苯二异氰酸酯(TDI-100)和扩链剂3,3'-二氯-4,4'-二氨基二苯甲烷(MOCA)作为硬段,采用预聚体法,制备了5种PTMG/PPG不同配比的浇注型聚氨酯弹性体。通过红外分析、差示扫描量热分析、动态力学热分析着重研究了PTMG/PPG不同配比对聚氨酯弹性体氢键的影响。结果表明,随着PPG型预聚体在混合预聚体中的含量增加,聚氨酯中羰基区总氢键度及脲羰基氢键度变化不大,氨酯羰基氢键度呈现先增加后减小的趋势;氨酯羰基氢键解离活化能变大,氢键趋于完善;硬段相长程有序结构熔融焓减小,脲羰基氢键完善程度下降。     

过氧化物硫化三元乙丙橡胶的高温硫化过程模拟

通过橡胶加工分析仪探讨了采用2种一级唯象动力学方程模拟过氧化物高温硫化三元乙丙橡胶(EPDM)的可行性。结果表明,该模型与实测曲线之间具有良好的相关性,随着硫化温度的升高,过氧化物硫化EPDM橡胶的交联反应程度和断链反应程度均增大,反应速率加快。当温度低于195℃时,交联反应的活化能与断链反应的活化能基本相等;当高于195℃时,交联反应的活化能降低,而断链反应活化能的大小依赖于温度变化。并且发现高温硫化EPDM硫化胶拉伸储能模量(E’)的频率依赖性明显增强,硫化时间长短也会影响分子链的松弛行为。     

基于多重氢键的自修复超分子聚氨酯弹性体

多重氢键是一类具有较高结合强度及动态可逆性质的超分子作用,在线型聚合物中可形成物理交联网络,提高材料机械强度的同时赋予材料良好的自修复能力。以聚四氢呋喃、六亚甲基二异氰酸酯、2,4-二氨基-6-羟基嘧啶为原料,合成了具有多重氢键物理交联结构的聚氨酯。当聚四氢呋喃与扩链剂2,4-二氨基-6-羟基嘧啶的物质的量的比为7∶3及5∶5时,可得到兼具力学强度与自愈能力的超分子聚氨酯弹性体。利用核磁共振氢谱、红外光谱、凝胶渗透色谱、差示扫描量热分析、流变测试表征了弹性体的结构和基本性质。通过对2组弹性体力学性能及自愈性能的比较发现,不同的组成比例改变了多重氢键形成的物理交联强度及分子链的运动能力,聚四氢呋喃与扩链剂物质的量的比为7∶3时,材料具有较高的断裂伸长率(1280%);物质的量的比为5∶5时,材料在循环拉伸中具有更好的形变回复能力,应力松弛更慢;两组弹性体在60℃环境下均表现出一定的自修复能力。     

聚丙撑碳酸酯/三元乙丙橡胶共混改性弹性体的研究

将聚丙撑碳酸酯（ＰＰＣ）与三元乙丙橡胶（ＥＰＴ）共混制成弹性体,研究了ＰＰＣ的添加量,硫化时间,硫化温度和添加炭黑对共混弹性体的物理力学性能,交联度的影响,研究发现,ＰＰＣ能与ＥＰＴ形成化学交联,加入一定量的ＰＰＣ能使ＥＰＴ弹性体的拉伸强度,断裂伸长率提高。     

Preparation and properties of adjacency crosslinked polyurethane---urea elastomers

Adjacency crosslinked polyurethane--urea (PUU) elastomers with different crosslinking density were prepared by using hydroxyl-terminated liquid butadiene-nitrile (HTBN), toluene diisocyanate (TDI) and chain extender 3,5-dimethyl thio-toluene diamine (DMTDA) as raw materials, dicumyl peroxide (DCP) as initiator, and N,N'-m-phenylene dimaleimide (HVA-2) as the crosslinking agent. The influences of the crosslinking density and temperature on the structure and properties of such elastomers were investigated. The crosslinking density of PUU elastomer was tested by the NMR method. It is found that when the content of HVA-2 is 1.5%, the mechanical properties of polyurethane elastomer achieve optimal performance. By testing thermal performance of PUU, compared with linear PUU, the thermal stability of the elastomers has a marked improvement. With the addition of HVA-2, the loss factor tanδ decreases. FT-IR spectral studies of PUU elastomer at various temperatures were performed. From this study, heat-resistance polyurethane could be prepared, and the properties of PUU at high temperature could be improved obviously.     

Investigation of novel polyurethane elastomeric networks based on polybutadiene-ol/polypropyleneoxide mixture and their structure–properties relationship

Polyurethane elastomer networks were designed and synthesized based on hydroxyl terminated polybutadiene/polypropyleneoxide (HTPB/PPO) mixtures, 2,4-toluene diisocyanate and 1,4-butanediol. Various networks with different molar ratio of HTPB to PPO (0/100, 25/75, 50/50, 75/25 and 100/0) had been prepared. Depending on the length of soft segment, average functionality of polyol mixtures, mechanical and thermal properties of samples were varied. Our observations confirmed that final properties of the networks can be attributed to two synergistic factors: (a) formation of chemical network (crosslinking) and (b) soft segment length. An optimum composition was found. This optimum composition shows that both physical (hard domains) and chemical network (crosslinking) have synergistic effects. Moreover, Flory–Hugins interaction parameters of soft and hard segments were calculated. Synthesized polyurethane elastomer networks have a structure similar to semi interpenetrating polymer networks, which is named pseudo-semi-IPN. These novel polyurethane elastomer networks show higher tensile strength and economic benefit than polyurethanes which are based on other non-polar polyols.     

Effect of supramolecular hydrogen bonded network on the properties of maleated ethylene propylene diene rubber/maleated high density polyethylene blend based thermoplastic elastomer

A thermoplastic elastomer having supramolecular hydrogen bonded network was prepared by the melt mixing of maleated ethylene propylene diene rubber and maleated high density polyethylene in presence of 3-amino-1,2,4-triazole (ATA), which acts as a coupling agent. The hydrogen bonded network formation in the blend system enhanced the physical properties of the blend. The storage modulus and glass transition temperature of the elastomer–plastic blend containing ATA was found to be increased as compared to the blend without ATA. It was observed that polyblends containing ATA exhibit a rubbery plateau above the melting temperature of the maleated high density polyethylene. Reprocessability study confirmed the thermoplastic elastomeric nature of the polyblend system.     

TiO_2填充聚氨酯弹性体复合材料的性能

以聚己二酸乙二醇酯二醇(PEA)、甲苯二异氰酸酯(TDI)、3,3-二氯-4-4-二苯基甲烷二胺(MOCA)为原料,采用预聚法合成聚氨酯弹性体,并选用微米级的TiO2对聚氨酯弹性体进一步增强,考察了TiO2加入量及交联剂MOCA用量对聚氨酯弹性体复合材料力学性能的影响。结果表明,微米级的TiO2对聚氨酯弹性体的力学性能有一定的提高,并且在TiO2加入量为4%(相对于PEA而言),MOCA用量为理论用量的82%~87%时,复合材料综合力学性能最好。SEM对其表面和断口形貌分析表明,TiO2在复合材料中分布较均匀,其断裂为韧性断裂。     

聚氨酯/13X分子筛复合材料的制备及表征

本文采用预聚法制备了聚酯类聚氨酯/13X分子筛复合材料,考察了分子筛含量和交联系数对聚氨酯弹性体力学性能、耐溶剂性能的影响。结果表明,13X分子筛的加入量为7%,交联系数为0.90时,聚氨酯弹性体的耐撕裂强度从73.1 kN/m提高到94.2 kN/m,拉伸强度从44.5 M Pa提高到49.9 M Pa,断裂伸长率从580%提高到640%,溶胀度从103.78%降低到72.58%。由DSC和DM A分析可知PU/13X复合材料具有更好的微相分离及动态力学性能。     

高强度自修复聚氨酯弹性体的制备及性能

针对自修复材料力学性能和自修复性难以兼顾的问题,采用传统预聚体法,引入含双硫结构的交联剂,制备得到既具有一定力学强度、又具有良好自修复性的聚氨酯弹性体。采用红外光谱进行化学结构表征;采用邵氏硬度计进行硬度测定;采用万能力学试验机考察了不同条件下的自修复效率;通过三维视频显微镜和拍照记录弹性体自修复过程;采用热重分析仪对样品进行热性能表征。结果表明,双硫键被成功引入弹性体中,弹性体邵氏硬度大多可达50 HA以上。升高温度和延长时间都能提高弹性体的自修复效率:24 h时,自修复效率从25 ℃的31.3%升高到80 ℃的99.5%;在80 ℃下,自修复效率从2 h的48.4 %提高到24 h的99.5%。双硫交联剂质量分数的增加也有利于自修复,弹性体的自修复效率从PUSS 3的54.5%提高到PUSS 6的99.5%。热重分析显示,弹性体的热稳定性随双硫质量分数的增加而略有下降,但所有弹性体的5%热失重温度都高于265.0 ℃。     

Development of a Morphing Skin Based on the Honeycomb Reinforced Elastomer

The morphing skin has been a main obstacle in the real-world implementation of morphing aircrafts. This paper presents a morphing skin made of the elastomer reinforced by the honeycomb structure. A matrix made from elastomer provides possibilities to configure the morphing skin and the honeycomb structure with smaller in-plane modulus and larger out-of-plane modulus is thought to be suitable to reinforce the elastomer. The polyurethane elastomer is selected and synthesized by the casting method with the prepolymer approach, after which a tensile test is conducted to get its stress-strain relationship. To decrease the skin depth and diminish the local deformation in the honeycomb cell, the elastomer is filled into the honeycomb core rather than just working as the flexible face sheets, which leads to the so-called honeycomb reinforced elastomer. To present its mechanical properties finite element method is applied to analyze the morphing skin with a plug-in of commercial software Abaqus developed to model the skin in details. Different geometry and material parameters are taken into consideration with three kinds of results calculated namely, the equivalent tensile modulus, the non-dimensionalized equivalent three-point bending stiffness and the linear strain capacity. After the simulation analysis, samples of the morphing skins are fabricated by the compression molds method and the tensile tests have verified both the concept and the simulation results. At last, an optimization performed has shown a significant decline of the tensile modulus and out-of-plane displacement of the morphing skin.     

Giant electrostrictive response in poly(vinylidene fluoride-hexafluoropropylene) copolymers

Electrostrictive strains were measured in three different polymeric materials: a low modulus polyurethane elastomer, previously studied by Scheinbeim et al. (1994), and two higher modulus random copolymers of poly(vinylidene fluoride-hexafluoropropylene) [P(VDF-HFP)] with 5% and 15% HFP content. Measurements at increasing voltage (electric fields ranging from 0 to 60 MV/m) were taken using an air gap capacitance system and then converted to sample thickness. Copolymer samples with different thermal histories were compared, ice water quenched, air quenched, and slow cooled, for both compositions. The ice water-quenched 5% P(VDF-HFP) copolymer exhibited the highest strain response (>4%) with a dielectric constant of 13.9. The previously studied polyurethane elastomer exhibited the second highest strain response, >3%, with the lowest dielectric constant, 8.5. The ice water-quenched 15% HFP copolymer exhibited the lowest strain response among the three polymeric materials tested, /spl ap/3%, with a dielectric constant of 12.2. The strain energy density of the 5% HFP ice water-quenched copolymer, /sup 1///sub 2/ YS/sub m//sup 2/ (/sup 1///sub 2/ Young's modulus, Y, times the maximum electrostrictive strain, S/sub max/ squared), is the largest known for any semi-crystalline polymer: 0.88J/cm/sup 3/.     

Synthesis and characterization of a biodegradable elastomer featuring a dual crosslinking mechanism

The need for advanced materials in emerging technologies such as tissue engineering has prompted increased research to produce novel biodegradable polymers elastic in nature and mechanically compliant with the host tissue. We have developed a soft biodegradable elastomeric platform biomaterial created from citric acid, maleic anhydride, and 1,8-octanediol, poly(octamethylene maleate (anhydride) citrate) (POMaC), which is able to closely mimic the mechanical properties of a wide range of soft biological tissues. POMaC features a dual crosslinking mechanism, which allows for the option of the crosslinking POMaC using UV irradiation and/or polycondensation to fit the needs of the intended application. The material properties, degradation profiles, and functionalities of POMaC thermoset networks can all be tuned through the monomer ratios and the dual crosslinking mechanism. POMaC polymers displayed an initial modulus between 0.03 and 1.54 MPa, and elongation at break between 48% and 534% strain. In vitro and in vivo evaluation using cell culture and subcutaneous implantation, respectively, confirmed cell and tissue biocompatibility. POMaC biodegradable polymers can also be combined with MEMS technology to fabricate soft and elastic 3D microchanneled scaffolds for tissue engineering applications. The introduction of POMaC will expand the choices of available biodegradable polymeric elastomers. The dual crosslinking mechanism for biodegradable elastomer design should contribute to biomaterials science.