Heats of Combustion and Formation of New Energetic Thermoplastic Elastomers Based on GAP,PolyNIMMO and PolyGLYN

Heats of combustion and formation of various energetic thermoplastic elastomers (ETPE), corresponding to linear copolyurethanes based on an energetic prepolymer and a diisocyanate, were measured by a calorimetric method. These ETPEs were synthesized from three different molecular weights of glycidyl azide polymer, from poly(3‐nitratomethyl‐3‐methyloxetane) and from poly glycidyl nitrate. The prepolymers were also analyzed for comparison with the corresponding ETPEs. A significant difference of the heats of formation was observed between the prepolymers and their ETPEs, while the heats of combustion were similar.     

动态硫化NBR/CPE/EVA热塑性弹性体的研制

为了获得一种耐热油，弹性好，强度高，橡胶感强，易加工的油封材料，我们采用动态硫化法制备了共混型NBR／CPE／EVA热塑性弹性体，系统讨论了橡塑并用比，硫化温度和硫化时间对热塑性弹性体的凝胶含量及力学性能的影响。结果表明：在一定温度和时间范围内，硫化温度升高和硫化时间延长，热塑性弹性体的凝胶含量增大，随着热塑性弹性体中EVA用量增大，弹性体的拉伸强度，赵氏硬度和拉伸永久变形有增大。     

热塑性聚酯弹性体在汽车防尘罩中的应用

简述了热塑性聚酯弹性体(TPEE)的发展动态及主要特征.详细介绍了汽车防尘罩的种类和特点,及TPEE在汽车防尘罩领域的应用优势和广阔前景.最后,通过实例阐述了汽车防尘罩用TPEE的制备技术及技术指标.     

Novel Segmented Thermoplastic Polyurethanes Elastomers Based on Tetrahydrofuran Ethylene Oxide Copolyethers as High Energetic Propellant Binders

Novel thermoplastic polyurethane (TPU) elastomers based on copolyether (tetrahydrofuran ethylene oxide) as soft segments, isophorone diisocyanate and 1,4‐butanediol as hard segments were synthesized for the purpose of using as propellant binders. In order to increase the miscibility of thermoplastic polyurethane elastomers with nitrate ester, polyethylene glycol (PEG) is incorporated in the co‐polyether (tetrahydrofuran ethylene oxide) as soft segment. When the molecular weight and content of polyethylene glycol are controlled to 4000 and 6% of soft segments, respectively, the properties of thermoplastic polyurethane elastomers are most perfect. If plasticizing ratio of nitrate ester to thermoplastic polyurethane elastomers exceeds 4 no crystallinities are determined at room temperature. The propellant samples were prepared by a conventional absorption‐rolling extrusion process and the mechanical and combustion properties evaluated afterwards. The maximum impulse reaches up to 265∼270 s which is a little bit higher than that of a HTPB propellant. The measured results reveal a promising TPE propellant candidate which shows good processing temperature (<393 K) and excellent mechanical properties. An attracting feature which can be pointed out is that the burning rate pressure exponent reaches as low as 0.36 without the addition of burning rate catalysts. This enables an easy control of propellant combustion.     

热塑性聚氨酯弹性体合成的研究

以聚四氢呋喃醚二醇、4,4’-二苯甲烷二异氰酸酯及1,4-丁二醇为原料,采用双螺杆反应挤出机进行了生产热塑性聚氨酯弹性体的研究,对有关影响因素进行了讨论。生产规模为500t／a。该合成方法具有工艺简单、生产率高等优点,产品的性能与国外同类产品相当。     

热塑性弹性体发展现状

热塑性弹性体（TPE）是一种极具发展潜力的聚合物材料。本文介绍了TPE的特性、应用，及其研究现状并指明了它的发展趋势。     

Review on Energetic Thermoplastic Elastomers (ETPEs) for Military Science

Energetic thermoplastic elastomers (ETPE) are futuristic binders for propellant/explosive formulations. Various aspects of ETPEs are addressed in this review. Synthesis modes of different copolymers for ETPEs are discussed. Attention is also given to formulations and thermal studies of ETPE‐based propellants and explosives. Processing methods and parameters of composition are included. As the cost and environmental concerns are prime factors of future generation propellants/explosives, the recovery and reprocessing methods are also briefly discussed.     

SBS型热塑性弹性体的加工技术和性能研究

报道了SBS热塑性弹性体混合料的性能研究。探讨了软化油、聚苯乙烯,填料含量以及填料品种对材料性能影响,研究过氧化物交联对材料性能影响,比较了SBS星形结构和线形结构及其并用对材料性能的影响。结果表明,化学交联对材料性能影响甚微;星形结构具有较高的撕裂强度,线形结构的拉伸强度和硬度较高;软化油含量对材料性能影响较大;轻质碳酸钙使材料具有最高的性能价格比,白炭黑真充料的综合性能最佳。     

活化胶粉/POE-g-MAH/POE热塑性弹性体的制备和性能

采用熔融法制备了马来酸酐接枝乙烯-1-辛烯共聚物（POE-g-MAH）, 利用红外光谱对POE-g-MAH进行了表征。考察了MAH和过氧化二异丙苯（DCP）的用量对接枝率的影响。并对胶粉进行了活化处理,探讨了活化效果的影响因素,研究了活化胶粉/POE-g-MAH/POE共混物的物理性能,讨论了共混物的断裂机理。实验结果表明,随着MAH和DCP用量的增加, POE-g-MAH的接枝率逐渐增大后趋于平缓并减小;在胶粉活化过程中,硬脂酸的加入有利于胶粉的细化;不含POE的共混物（活化胶粉/POE-g-MAH）的综合性能最佳。对活化胶粉/POE-g-MAH的流变性能和再加工性能的分析表明,该混合料具有良好的切敏性和再加工性。     

Metallized SWCNT–Promising Way to Low Sensitive High Energetic Nanocomposites

The single‐walled carbon nanotube (SWCNT) is proposed as the best protective coating for energetic metal nanoparticles. An advanced laser‐based technology has been applied to synthesize SWCNT filled or covered by metal. This laser synthesis of metallized SWCNT operates under the normal conditions that could be a basis for a high‐productive technology of continuous synthesis of metalllized SWCNT.     

热塑性聚氨酯对膨胀型阻燃聚丙烯的增容作用

热塑性聚氨酯（TPU）含有氨基甲酸酯链段,该结构有利于受热成炭,提高阻燃性能,又可以通过超分子间力与膨胀型阻燃剂（IFR）作用,而TPU的软段与聚丙烯（PP）结构相似,因此可作为PP/IFR体系的增容剂.力学性能和阻燃性能测试表明,3%TPU的加入,使材料的拉伸和冲击性能分别提高了9.8%和16.6%,离火自熄时间由45s降低到25 s;在TPU添加量为4%时,材料的冲击性能提高显著,已经达到纯PP的水平.流变性能测试结果表明,在测试温度下,由于TPU软化点较低,而IFR中季戊四醇（PT）又处于熔化状态,加入TPU和IFR使粘度降低,但加入量增加到5%时,体系粘度增大,说明TPU对体系起到了增容作用.SEM微观形态分析表明,随TPU含量增大,IFR与PP界面作用力增强,断裂由发生在IFR与PP的界面,变为发生在底材内部,说明TPU对体系起到了增容的作用.事实证明TPU是PP/IFR共混体系有效的增容剂.     

玻纤增强PP热塑性片材的制备及力学性能研究

采用熔融浸渍法制备了玻璃纤维毡增强聚丙烯（PP）热塑性复合片材;通过在PP中加入复合改性PP改善了基体与增强纤维间的相容性;考察了相容剂、PP种类及玻纤毡种类对复合片材的影响。结果表明,相容剂的加入可使复合片材的拉伸强度提高29％、拉伸模量提高23％、弯曲强度提高42％、弯曲模量提高25％;高熔体质量流动速率PP可使片材的弯曲与冲击性能进一步改善。连续玻纤毡和长玻纤毡增强PP复合片材,前者综合力学性能良好,而后者则冲击强度较弱、弯曲性能加强。     

硼酸铝晶须及其在增强热塑性聚合物中的应用

对硼酸铝晶须的结构、性能、制备方法和表面处理以及硼酸铝晶须在热塑性聚合物中的应用进行了综述,同时简单概述了晶须的生长机制和增强机理     

GAP基含能热塑性弹性体的合成与表征

以聚叠氮缩水甘油醚(GAP)为软段,1,4-丁二醇(BDO)和4,4′-二苯基甲烷二异氰酸酯(MDI)为硬段,采用熔融预聚体法合成了GAP基含能热塑性弹性体(ETPE)。研究了扩链剂加料方式、催化剂用量、异氰酸酯指数、硬段含量等因素对弹性体力学性能的影响。采用傅里叶变换红外光谱(FT-IR)、凝胶渗透色谱(GPC)、热台显微镜、差示扫描量热(DSC)、热重分析(TG)表征了ETPE的性能。结果表明,采用恒速滴加扩链剂方法合成的ETPE具有良好的热稳定性和力学性能。当催化剂质量分数为0.6‰,异氰酸酯指数(R)为0.98,硬段质量分数(Y)为35%时,热塑性弹性体的数均相对分子质量为52 312,软化点为96℃,拉伸强度为14.52MPa,断裂伸长率为518.78%。     

短切CF增强TPEE热塑性复合材料的注射成型及力学性能研究

以热塑性聚酯弹性体(TPEE)为基体材料,8 mm短切碳纤维(CF)为增强材料,制备CF/TPEE复合材料。材料通过双螺杆挤出系统混合塑化、挤出造粒后,再经过注塑成型制备成标准拉伸试样,通过力学性能测试及微观结构观察,系统研究了碳纤维含量和等离子表面处理对CF/TPEE复合材料拉伸性能的影响。结果表明,当碳纤维含量为20%时,CF/TPEE复合材料的拉伸强度最大,为39.08 MPa;相比于纯TPEE,其拉伸强度提高了217%;经过等离子表面处理后,拉伸强度进一步提高了5%。结合拉伸后断面的SEM图发现,注塑试样表层碳纤维取向度高,而近中区和中心层取向度相对较低,这是注射CF/TPEE复合材料拉伸性能提高效应不明显的主要原因。     

Energetic Material/Polymer Interaction Studied by Atomic Force Microscopy

The interactions of energetic materials and polymers have important implications in safety, long‐term storage, and performance of explosives and explosive mixtures. Atomic force microscopy was used to investigate adhesion forces at the molecular scale of nine energetic materials, organic explosives and energetic salts, on eleven common polymers (polyethylene, polyvinylalcohol, poly(vinyl chloride), polycarbonate, polystyrene, poly(methyl methacrylate), styrene‐butadiene rubber, poly(4‐vinyl phenol), poly(2,6‐dimethylphenylene oxide), poly(2,6‐diphenyl‐p‐phenylene oxide) (Tenax®), and polytetrafluoroethylene (Teflon®)). Teflon was the least adhesive polymer to all energetic materials, while no distinct trend could be elucidated among the other polymers or energetic materials.     

Characterization of P(BAMO/AMMO) ETPE Prepared Using Different Diisocyanates

Poly(3,3‐bisazidomethyl oxetane/3‐azidomethyl‐3‐methyl oxetane) energetic thermoplastic elastomers (P(BAMO/AMMO) ETPEs) is one of the most valuable ETPEs in the field of energetic binders. P(BAMO/AMMO) ETPEs were prepared using different diisocyanates (TDI, HMDI, IPDI, and HDI) to investigate the influence of the diisocyanate on the performance of P(BAMO/AMMO) ETPEs. Mechanical properties and heats of formation were investigated. FT‐IR spectroscopy results showed that TDI‐based ETPE has the highest degree of hydrogen bonding with a value of 69.00 %. Mechanical test results showed that the TDI‐based ETPE has better mechanical property with maximum stress at 5.24 MPa and breaking elongation at 390 %. The order for degree of hydrogen bonding and mechanical property of different diisocyanate‐based ETPEs was TDI>HMDI>IPDI>HDI. The heats of formation were calculated by the group additivity method and by the heat of combustion method. The values of heats of formation for TDI‐based ETPE were 3.44 kJ g⁻¹ and 3.75 kJ g⁻¹ according to the two methods. Additionally, TDI‐based ETPE has a lager heat of formation than the other ETPEs.     

Thermoplastic Elastomers 4. Poly(ether-ester-imide)s Derived from Trimellitic Anhydride, 1,6 Diaminohexane,1,4-Dihydroxybutane and Poly(ethylene oxide)

Abstract

Four thermoplastic elastomers having the structure of poly(ether-ester-imide)s, PEEIs, were prepared and characterized. The hard segments were synthesized from 1,4-dihydroxybutane and from an imide dicarboxylic acid based on 1,6-diaminohexane and trimellitic anhydride. Poly(tetramethylene oxide)-1000, poly(ethylene oxide)-1000 or mixtures of both oligoethers served as soft segments. The PEEI based on neat PEO-1000 was also modified by a solid state post-condensation which raised the n _rel value by a factor three. All PEEIs were characterized by H NMR spectroscopy, inherent viscosity and DSC measurements, and stress-strain measurements. The PEEIs based on neat PEO-1000 were also characterized by dynamic thermal mechanical analysis, by hysteresis measurements and by melt rheology.     

相容剂对硅橡胶/TPU动态硫化热塑性弹性体性能的影响

以热塑性聚氨酯弹性体(TPU)和有机硅橡胶(SIR)为基体,加入不同相容剂通过Hakke密炼机采用动态硫化的方法制备了热塑性弹性体(TPV),研究了不同相容剂对弹性体性能的影响.结果表明,KH550在TPV中相容性较好,并且当KH550乙醇溶液的质量分数为20％分散较好,力学性能优异;当基体树脂预热后加入KH550的加料顺序最优;当KH550含量为0.4 phr时拉伸强度较好且黏度最大;随着KH550含量的增加,弹性体熔体质量流动速率和压缩永久变形都逐渐降低.     

共混型热塑性弹性体的制备技术

以PP／EPDM-TPE为例,从共混、动态硫化／交联工艺和设备等方面介绍了共混型热塑性弹性体制备技术的发展状况。同时指出,反应型双螺杆挤出共混工艺是制备共混型TPE的发展方向。