Interpenetrating polymer network approach to tough and microcracking resistant high temperature polymers. Part II. LaRC-RP41

Recently, we reported on the interpenetrating polyimide network (IPN) approach to develop tough and microcracking resistant high temperature matrix resins for use in aircraft/aerospace structural components. One such polymer developed is designated LaRC-RP40. This new simultaneous semi-IPN was prepared from easy-to-process but brittle crosslinking PMR-15 and tough but difficult-to-process linear NR-150B2. Significantly improved toughness, microcracking resistance, and glass transition temperature over PMR-15 were realized from the combination. These property improvements were achieved without compromising ease of processing, high temperature mechanical performance, and cost effectiveness compared to PMR-15. These results encouraged us to further explore this approach for the development of a wider range of polymers of basic technological and economic interest. In the present work, we combine crosslinking PMR-15 and linear LaRC-TPI to provide a new sequential semi-2-IPN called LaRC-RP41. The physical and mechanical properties of the neat resin and composite reinforced with graphite fibers are presented. The phase morphology and phase stability of the neat resin and composite studied by various techniques are also discussed.     

Miscibility,crystallization, and morphology studies of thermosetting polyimide PMR-15/PEK-C blends

Miscibility, crystallization, and mechanical properties of blends of thermosetting polyimide PMR-15 and phenolphthalein poly(ether ketone) (PEK-C) were examined. With the exception of the 90/10 blend, which has two glass transition peaks, all the blends with PMR-15 less than 90 wt % are miscible in the amorphous state according to DMA results. Addition of PEK-C hindered significantly the crystallization of PMR-15, indicating that there must exist some kind of interaction between molecular chains of PMR-15 and those of PEK-C. The semi-IPN system of PMR-15/PEK-C blends exhibits good toughness. Two distinct microphases, interweaving at the phase boundaries, were found in the PMR-15/PEK-C 60/40 blend. The toughness effect of the blends is discussed in terms of the interface adhesion between the two distinct phases and the domain sizes of the phases. The relation between miscibility and toughness of the blends was investigated. © 1996 John Wiley & Sons, Inc.     

Kinetics of imidization of poly(amic acid) in miscible and immiscible polymer blends

Blends of commercial poly(amic acid), LARC-PAA polymer were prepared with thermoplastic polyimide P84. The blends were shown to be miscible over a certain composition range. Chemical imidization of LARC-PAA in the blends leads to phase separation. Thermal imidization of LARC PAA in the blends was carried out in the solid state. Miscible compositions of the blend remained miscible after imidization and showed a single glass transition for each blend. Immiscible compositions after imidization remained immiscible and showed two glass transition temperatures in the DSC scans. The kinetics of thermal imidization of PAA to polyimide (PI) in the solid state were studied using FTIR. In the immiscible blend the kinetics remained unaffected while in the miscible state the rate of imidization became faster than that of the pure PAA.     

Semi-IPNs formed from poly(ethylene glycol monomethyl ether acrylate) and an epoxy thermoset

Poly(ethylene glycol monomethyl ether acrylate) (PEGMEA) was synthesized from the reaction of poly(ethylene glycol monomethyl ether) (PEGME) with acryloyl chloride. Semi-IPNs based on various weight ratios of diglycidyl ether of bisphenol A (DGEBA)/PEGMEA were prepared, using isophronediamine (IPDA) and 2,2′-azo-bis(isobutyronitrile) (AIBN) as curing agents. The glass transition temperature and exothermic peak shifts were studied with differential scanning calorimetry (DSC). Viscosity changes during semi-IPN formation were measured with a Brookfield viscometer. Dynamic mechanical properties were investigated by rheometric dynamic spectroscopy (RDS). Stress–strain curves were obtained with an Instron tensile tester, while impact resistance was measured with a computer aided falling dart impact tester. Experimental results revealed retarded curing rates for all semi-IPNs, as evidenced from the shifts of curing exothermic peaks to higher temperatures, together with retarded viscosity increases during semi-IPN formation. These phenomena were interpreted in terms of chain entanglement between epoxy and PEGMEA. Nevertheless, the semi-IPNs indicated good compatibility as inferred from a single T_g in DSC and a single damping peak in RDS for each semi-IPN. Improved tensile stress and strain along with toughness improvements were noticed for this semi-IPN system. Shear band yielding was proposed to interpret this result. © 1999 Society of Chemical Industry     

Effect of thermal history during drying and curing process on the chain orientation of rod-shaped polyimide

Chain orientation in polyimide (PI) film is influenced by the thermal history during drying and curing process. The amount of residual solvent and the degree of imidization, among other factors, play a major role in determining the chain orientation during the process. In the present study, poly(amic acid), the precursor of PI, coated on the glass substrate was imidized to PI through different drying and curing protocols. On the way of complete imidization, the residual solvent concentration and the degree of imidization were characterized using confocal Raman spectroscopy. The poly(amic acid) began to imidize quickly while retaining more solvent in the film as the initial drying temperature increased. The degree of in-plane chain orientation in fully imidized PI film made by different process protocols was compared using polarized Raman spectroscopy. The fully imidized PI showed the lowest degree of in-plane chain orientation when it was processed by the protocol with the highest drying temperature. The difference in the degree of in-plane chain orientation among different PI films significantly influenced the in-plane thermal expansion coefficient, while no significant change in crystallinity or glass transition temperature was observed.     

Simulation of dry‐spinning process of polyimide fibers

As one type of high‐performance fibers, the polyimide fibers can be prepared from the precursor polyamic acid via dry‐spinning technology. Unlike the dry‐spinning process of cellulose acetate fiber or polyurethane fiber, thermal cyclization reaction of the precursor in spinline with high temperature results in the relative complex in the dry‐spinning process. However, the spinning process is considered as a steady state due to a slight degree of the imidization reaction from polyamic acid to polyimide, and therefore a one‐dimensional model based on White‐Metzer viscoelastic constitutive equation is adopted to simulate the formation of the fibers. The changes of solvent mass fraction, temperature, axial velocity, tensile stress, imidization degree, and glass transition temperature of the filament along the spinline were predicted. The effects of spinning parameters on glass transition temperature and imidization degree were thus discussed. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

高性能/高温聚合物(Ⅴ)反应性端基聚酰亚胺齐聚物及固化技术

综述了高性能/高温聚合物中的反应性端基齐聚物与热固性聚酰亚胺及其固化技术,其包括PMR-15、PMR-Ⅱ,端乙炔基聚酰亚胺、苯乙炔封端聚酰亚胺、Thermcon聚酰亚胺、其它热固性聚酰亚胺、苯并环丁烯端基聚酰亚胺,对其化学结构与性能的关系也进行了讨论。     

高性能/高温聚合物(Ⅴ)反应性端基聚酰亚胺齐聚物及固化技术

综述了高性能/高温聚合物中的反应性端基齐聚物与热固性聚酰亚胺及其固化技术,其包括PMR-15、PMR-Ⅱ,端乙炔基聚酰亚胺、苯乙炔封端聚酰亚胺、Thermcon聚酰亚胺、其它热固性聚酰亚胺、苯并环丁烯端基聚酰亚胺,对其化学结构与性能的关系也进行了讨论。     

电位滴定法测定聚酰胺酸固相热环化动力学

针对二步法合成聚酰亚胺的固相热环化过程,采用改进的自动电位滴定法和GPC测定了反应的剩余聚酰胺酸含量及相对分子质量随反应时间及反应温度的变化。结果表明:聚合物平均相对分子质量随热处理时间和温度的增加而逐步增大,相对分子质量分布指数则呈现先增后降的变化趋势。聚合物剩余聚酰胺酸的质量分数随热处理时间增加而逐渐降低,并出现初期的快速和后期的慢速2个阶段。提高热处理温度,则环化速率明显增大,环化程度亦增大。采用两步一级动力学模型关联并得到了2个阶段的热环化动力学参数,快速和慢速阶段的活化能较为接近,而指前因子和过渡熵相差较大。     

聚酰胺酸薄膜热环化过程热分析

用差热扫描量热仪(DSC)和傅立叶红外光谱仪(FTIR),考察了梯度升温过程中聚酰胺酸PAA[由4,4-二胺基二苯醚(ODA)和3,3,4,4-二苯醚四酸二酐(ODPA)制备]薄膜环化度和玻璃化温度(Tg)随反应温度的变化。结果表明,随着温度的升高,聚合物薄膜的亚胺化程度和Tg不断增大,且各恒温点的薄膜Tg均高于反应温度。另外,由亚胺化程度与Tg的关系曲线可见,在环化程度低时,薄膜Tg增长缓慢;随着亚胺化程度继续增高,薄膜的Tg迅速增大。用热环化过程中分子活动性的变化解释了酰亚胺化反应过程中环化速率的变化。     

Dynamic mechanical properties of N-phenylnadimide modified PMR polyimide composites

Temperature-frequency dependence of α, β, and γ transitions was determined using a Rheometrics dynamic spectrometer on a series of unidirectional Celion 6000/N-phenylnadimide (PN) modified PMR polyimide composites. The objective was to see if any correlations exist between crosslinked network structure and dynamic mechanical properties. Variation in crosslinked network structures was achieved by altering the polyimide formulation through addition of various quantities of PN into the standard PMR-15 composition. As a control, PMR-15 composite system exhibited well-defined α, β, and γ transitions in the regions of 360, 100, and −120°C, respectively. Their activation energies were estimated to be 232, 60, and 14 kcal/mole, respectively. Increasing the amount of PN concentration caused (a) lowering of the activation energies of the three relaxations, (b) a decrease of the glass transition temperature, and (c) increasing intensities of the three damping peaks, compared to the control PMR-15 counterpart. These dynamic mechanical responses were in agreement with formation of a more flexible co-polymer from PN and PMR-15 prepolymer.     

含苯并噁唑结构共聚酰亚胺的合成及其性能

联苯四羧酸二酐(BPDA)与4,4′-二氨基二苯醚(ODA)及自制的2,6-二(对氨基苯)苯并[1,2-d;5,4-d']二噁唑(DAPBBO)在二甲基乙酰胺中共聚,然后进行铺膜和热酰亚胺化,得到了含有双苯并噁唑的共聚酰亚胺薄膜,对其结构、热性能、力学性能及光学性能进行了表征。结果表明:杂环单体的引入提高了聚酰亚胺的力学性能,增加了聚酰亚胺的玻璃化转变温度,并且使聚酰亚胺薄膜具有良好的紫外吸收能力。     

Synthesis and properties of novel benzocyclobutene‐functionalized siloxane thermosets

Two kinds of novel benzocyclobutene (BCB) functionalized monomers were synthesized through imidization of siloxane‐containing dianhydride with 4‐aminobenzocyclobutene. The BCB monomers obtained exhibited good solubility in various organic solvents. They were converted into crosslinked polymer via ring opening and the following Diels–Alder reaction at proper temperature. The curing kinetics were studied by non‐isothermal differential scanning calorimetry. The BCB polymers showed good thermal stability, excellent dielectric properties, low water absorption and good planarization. Moreover, the thermal and mechanical properties of the BCB resins could be adjusted by the length of the siloxane unit. The BCB resins with a shorter siloxane chain exhibited higher glass transition temperature, higher modulus and lower coefficient of thermal expansion than BCB resins with longer chains. © 2013 Society of Chemical Industry     

Dynamic mechanical study of filled semi-interpenetrating polymer networks: Influence of γ-Fe2O3 on microphase structure

The preparation of filled two-component semi-interpenetrating polymer networks (semi-IPNs) is described and the results of an investigation of their morphology by means of dynamic mechanical spectroscopy are considered. The influence of an active dispersed filler (γ-Fe₂O₃) on the semi-IPNs phase structure is studied. A comparison is made between filled and unfilled semi-IPNs consisting of compatible or incompatible polymers. In the case of a semi-IPN of compatible polymers, the introduction of γ-Fe₂O₃ was observed to cause phase separation. With a two-phase semi-IPN the introduction of the filler enhanced the phase separation. The presence of two distinct peaks (the dynamic glass transition temperatures) corresponding to those of the two initial homopolymers shows the semi-IPN to have a two-phase structure.     

Fourier transform infrared spectroscopic characterization of aromatic bismaleimide resin cure states

Interesting polyimide materials, possessing good mechanical and thermal properties, are obtained by homopolymerization or reaction of 4,′4-bis(maleimidodiphenylmethane) with a diamine. Fourier transform infrared spectroscopy has been used to characterize the crosslinking of such materials using maleimide and amine absorption bands. Amine group reaction on double bonds is readily achieved and appears to be insensitive to the temperature of curing. On the other hand, the decrease of maleimide double bonds is strongly dependent on the reaction temperature. The residual amount of double bonds present in the cured material is a function of the temperature: a linear relationship holds between residual double bond concentration vs. curing temperature. The general behavior during crosslinking of this kind of polyimide was related to glass transition temperature changes.     

新型含吡啶环芳香二胺及其可溶性聚酰亚胺的合成与表征

以苯甲醛和3-(4-硝基苯氧基)苯乙酮(NPAP)为原料,通过改进的Chichibabin反应制备了硝基化合物4-苯基-2,6-双[3-(4-硝基苯氧基)苯基]吡啶(PNPP),再用Pd/C和水合肼将PNPP进行还原,成功制备了一种新型含吡啶环的芳香二胺4-苯基-2,6-双[3-(4-胺基苯氧基)苯基]吡啶(PAPP)。以PAPP作为二胺,3,3′,4,4′-二苯醚四羧酸二酐(ODPA)作为二酐,N,N-二甲基甲酰胺(DMF)为溶剂,通过常规的两步法,经热或者化学亚胺化形成聚酰亚胺,制得了一种新型的含吡啶环聚酰亚胺。所得聚酰胺酸和聚酰亚胺的粘度分别为0.59 dL/g和0.56 dL/g。化学亚胺化所得的聚酰亚胺速溶于常见有机溶剂如DMF、N,N-二甲基乙酰胺(DMAc)、N-甲基-2-吡咯烷酮(NMP)、四氢呋喃(THF)等。制得了柔韧的聚酰亚胺膜,膜有很好的热稳定性,玻璃化转变温度(T_g)为230.8℃,氮气氛中10%失重温度为552.0℃,同时,膜还有较好的力学性能,拉伸强度为88.6 MPa,拉伸模量为1.04 GPa,断裂伸长率为8.7%,膜的吸水率为0.89%。     

邻甲硼酚醛树脂固化双酚-A环氧树脂及其复合材料的性能

用邻甲硼酚醛树脂(BoPFR)固化双酚-A环氧树脂(BPAER),制备了含硼酚醛的高性能玻璃钢复合材料.分析了固化过程,研究了固化树脂以及玻璃纤维层压板的力学性能、热性能和电性能.当m(BoPFR)/m(BPAER)为1.0∶0.5时,复合材料的玻璃化转变温度从198.4 ℃下降到134.5℃,材料韧性提高.固化物有良好的耐热性能,当m(BoPFR)/m(BPAER)为1.0∶0.2时,材料在900℃时的残留率为25.83％,热降解动力学符合一级反应动力学;玻璃纤维层压板拉伸强度提高了一倍,而电性能变化不大.     

Simulation of polyimide fibers with trilobal cross section produced by dry‐spinning technology

As one type of high performance fibers, polyimide fibers can be prepared from polyamic acid (PAA) solution by dry‐spinning technology. The transformation from the precursor of polyamic acid to polyimides via thermal cyclization reaction in the dry‐spinning process is a main distinguishing feature, which is very different from other fibers produced by dry‐spinning such as cellulose acetate fiber and polyurethane fiber. In this report, the dry‐spinning formation of polyimide fibers with trilobal cross section from PAA solution in N,N‐dimethylacetamide is simulated via a one‐dimensional model based on a viscoelastic constitutive equation, combined with profile degree equation of cross section and imidization kinetics equation. The glass transition temperature, imidization degree and profile degree of the filament along the spinline are predicted by the model, as well as relative parameters such as solvent mass fraction and temperature. As a simulated result, solidification of polyimide fibers take place about 150 cm from the spinneret which is farther than for cellulose acetate fiber (70 cm). Moreover, the final profile degree of fiber is affected by many spinning parameters, such as spinning temperature, surface tension, spinning solution concentration, major, and minor axis length of the spinneret hole. POLYM. ENG. SCI., 55:2148–2155, 2015. © 2015 Society of Plastics Engineers     

PMR-15 processing,properties and problems—a review

The frontrunner in the race to develop a high temperature resin for use in advanced composites intended for high temperature applications is the NASA developed polyimide PMR-15. One of the key factors in the success of the material is the relatively easy processing which is due mainly to the use of the PMR approach (Polymerisation of Monomeric Reactants). Prepreg and high quality composite laminates (glass or carbon) can be prepared with ease. Laminate properties compare well with conventional epoxy based systems but thermal stability is much greater. Continuous use temperatures are in the range 280-300°C, some 150-170°C higher than epoxy systems. Applications of PMR-15 composites include aero-engines, missiles, spacecraft and military aircraft. Despite being the leading system available today PMR-15, like all materials, has a number of limitations affecting its widespread use. Included in these are reliable methods of quality control, prepreg batch to batch variability, microcracking from thermal cycling, health and safety hazards and high temperature processing. This paper reviews the present status of PMR-15 development and outlines work designed to identify and where possible overcome these limitations.     

Cure kinetics and physical properties of dicyanate/polyetherimide semi‐IPNs

The curing behavior and physical properties of dicyanate/polyetherimide (PEI) semi‐interpenetrating polymer network (IPN) systems were investigated. Differential scanning calorimetry (DSC) was used to study the curing behavior of the dicyanate/PEI semi‐IPN systems. The curing rate of the semi‐IPN system decreased as the PEI content increased. An autocatalytic reaction mechanism can describe well the curing kinetics of the semi‐IPN systems. The reaction kinetic parameters were determined by fitting DSC conversion data to the kinetic equation. The glass transition temperature of the semi‐IPNs decreased with increasing PEI content. Two glass transitions due to phase‐separated morphology were observed for the semi‐IPN containing over 15 phr (parts per hundred parts of dicyanate resin) PEI. The thermal stability and dynamic mechanical properties of the semi‐IPNs were measured by thermal analysis.