27 resultados para PPS

em Chinese Academy of Sciences Institutional Repositories Grid Portal


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通过大量实验,研究了应变率效应对短纤维增强热塑性树脂PPS(聚苯硫醚)力学性能的影响。应变率变化从10~-4/s-10~2/s。并对断口形貌及破坏形式进行了观察。结果表明,应变率较高时对材料的强度和模量有明显影响,断口形貌呈脆性破坏。

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本工作旨在通过共聚、共混技术制备酚酞型聚芳醚砜共聚物(PP/BiS-T) PES和共混物(PPS/PES-C)、PPO/PES-C,以便改善酚酞型聚芳醚砜(PES-C)的加工性能(特别是注射加工性能)和耐溶剂性能。通过研究共聚物和共混物的微观结构,聚集态结构与性能的关系,探索改善酚酞型聚芳醚硕性能的有效途径第一部分:(PP/BiS-T) PES共聚物的合成、结构与性能(PP/BiS-T) PES共聚物是以4,4'二氯二苯砜(DCDPS)、酚酞(PP)和4,4'-二羟基二苯硫醚(BiS-T)为单体,采用固体无水K_2CO_3/NMP/TMSO_2 混合溶剂反应体系合成的。共聚反应规律研究表明:在NMP/TMSO_2混合溶剂中,共聚反应可以顺利进行,避免了交联反应的发生,并成功地合成了高分子量的(PP/BiS-T) PES共聚物。DSC分析结果表明(PP/BiS-T) PES系列属于无定形的均相共聚物体系,每一组成比例对应的共聚物只具有一个玻璃化转变温度。且随组成比例的改变呈线性变化,TBA分析结果与DSC基本一致,并证实了(PP/BiS-T) PES属于均相共聚物体系,而不是均聚物的共混物。TG分析表明:共聚物具有良好的耐热氧化稳定性BiS-T链节在分子链中起到了提高自身抗氧性的作用。1R光谱对共聚物的结构进行表征。~(13)C-NMR分析确认共聚物多属于无规共聚物。动态力学试验表明共聚物(PP/BiS-T) PES以及PES-C,在-100 ℃附近和0-100 ℃,存在着次级松驰与转变,并发现水分子的存在对这种转变(次级松驰)有一定的影响。共聚物的熔融流动性试验和溶解性试验表明共聚物(PP/BiS-T) PES具有稍好于PES-C的熔融流动性;溶解性与PES-C类似。力学试验说明共聚物属于强而硬类型的聚合物。第二部分:PPS/PES-C共混物的制备、聚集态结构与性能PPS/PES-C共混物是以联苯/二苯硕混合物为溶剂,采用溶液沉析方法制备的,DSC、WAXD,SEM和1R分析手段对共混物的聚集态结构和微观结构进行了表征。DSC分析认为共混物属于多相体系,PPS的结晶性随着PES-C含量增加而降低。DSC和SEM观察结果表明:相转变发生在PPS占40%左右。PPS占25%时,DSC曲线呈现出界面相玻璃化转变温度。共混物具有良好的耐热氧化稳定性和耐热分解稳定性。微晶大小计算结果:PES-C存在导致了PPS微晶大小降低。WAXD曲线表明PPS占50%,共混物中的PPS具有较好的结晶性。SEM观察发现:随着PES-C含量增加,PES-C由分散相(PES-C50%)变为连续相(PES-C70%)。PPS占50%或低于50%时,共混物体系不仅发生了微观相分离,而且发生了宏观相分离。M.I.指数表明共混物中PPS为连续相时,共混物具有良好的熔融流动性。溶解性试验结果:共混物具有较好的耐溶剂性。第三部分:PPO/PES-C共混物的合成、结构与性能 PPO/PES-C共混物系用溶液-涂膜法,以氯彷为溶剂制备的。讨论了由同一共混物溶液浓度下制备的共混物的互溶性随组成的改变而变化。DSC分析结果:PPO/PES-C属于部分相溶性体系。利用Fox方程推导式计算结果表明PPO在富PES-C相中具有良好的分散性;而PES-C在富PPO相中的分散性较差。共混物(PPO/PES-C)试样经丙酮浸泡后,PPO(>50%)发生了溶剂诱导结晶现象,同时丙酮促使共混物发生完全相分离。结晶溶化热显示共混物中少量的PES-C存在有利于PPO的溶剂诱导结晶。TG分析表明共混物具有良好的耐热分解稳定性和耐热氧化分解稳定性。偏光显微镜下观察到PPO球晶的存在。SEM和FT-1R分别对共混物的形态结构和微观结构进行了表征。WAXD试验证实了丙酮处理的(PPO/PES-C)(70/30),(90/10)共混物中PPO的结晶性。溶解性试验表明:PPO掺入有助于 PES-C的耐溶剂性提高。

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聚苯硫醚(PPS)是特种工程塑料中应用最广、价格最低的品种。但由于其耐冲击性差,限制了其做为结构材料的应用。本论文通过多种研究方法,研究了PPS抗冲击性差的根本原因和改善途径,从改变其聚集态结构入手,使韧性得到了很大改善,为高抗冲PPS的研制提供和积累了丰富了可靠的数据,其创新性成果体现在:提出了含刚性非晶相、可动(类液)非晶相和晶相的PPS三相模型并计算了各相的相对含量、测定了各相的密度;发现了PPS的冲击强度与其结晶度呈近似线性的关系。是十分有意义的基础性工作。用核壳乳液聚合物做为PC的增韧剂,有效地控制了共混物的形态结构、计算出了界面层厚度与界面张力,为制备具有综合性能的改性PC材料奠定了理论和实践基础。

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Blends of poly(ether-sulfone) (PES) and poly(phenylene sulfide) (PPS) with various compositions were prepared using an internal mixer at 290degreesC and 50 rpm for 10 min. The thermal and dynamic mechanical properties of PES/PPS blends have been investigated by means of DSC and DMA. The blends showed two glass transition temperatures corresponding to PPS-rich and PES-rich phases. Both of them decreased obviously for the blends with PES matrix. On the other hand, T-g of PPS and PES phase decreased a little when PPS is the continuous phase. In the blends quenched from molten state the cold crystallization temperature of PPS was detected in the blends of PES/PPS with mass ratio 50/50 and 60/40. The melting point, crystallization temperature and the crystallinity of blended PPS were nearly unaffected when the mass ratio of PES was less than 60%, however, when the amount of PES is over 60% in the blends, the crystallization of PPS chains was hindered. The thermal and the dynamic mechanical properties of the PPS/PES blends were mainly controlled by the continued phase.

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结晶-非晶高聚物共混体系的相容性和结晶行为的研究已有许多报道。本工作研究了含酞侧基聚芳醚酮(PEK-C)与聚苯硫醚(PPS)共混物的相容性和结晶行为。 PEK-C为徐州工程塑料厂产品,未作封端处理,η?p/c=0.70;PPS为日本东丽产品。两者用双螺杆挤出机在320~350℃制成共混物。仪器为Perkin-Elmer DSC-7型差示扫描量热仪,升温速率10℃/min;DDV-Ⅱ-EA型全自动动态粘弹谱仪和理学D/max-ⅡBX-射线衍射仪。

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研究了聚芳醚砜(PES-C)/聚苯硫醚(PPS)共混物的聚集态结构与熔融流动性以及两者之间的内在关系。结果表明,PES-C/PPS共混体系属于多相体系,PES-C占50%时,PPS成为连续相,共混物在该组成比例下具有良好的熔融流动性。

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利用霍普金森分离杆(SHPB)方法,对三种连续玻璃纤维和碳纤维增强聚苯硫醚(PPS)复合材 料层压板进行冲击试验,集中讨论材料的破坏特征,试图为建立更为合理的高应变率下复合材料横向冲击动态响应模型提供依据。结果显示,采用不同的铺层设计以及不同的纤维增强所得材料的损伤形貌有很大区别,纤维/树脂的界面粘结对微观开裂机理的影响显著。

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1.热可交联聚酰亚胺/高性能热塑性树脂共混体系的研究聚苯硫醚[Poly(phenylene sulfide),PPS]是由刚性结构的苯环和柔性的硫醚连接起来,交替排列构成的线性高分子化合物,具有高的热稳定性、良好的耐化学药品性、优良的电绝缘性、耐老化性和阻燃性等综合性能优异的高性能树脂。聚醚矾〔Poly(ether sulfone),PES]是一种非结晶性的热塑性工程塑料一,具有优异的热稳定性、耐高温蠕变性及优异的物理机械性能。其高的玻璃化转变温度(Tg=225℃),使其可以在较高温度下作为结构材料使用。本论文研究了PPS/PES二元共混物的热性能和动态力学性能,并以热可控交联的低分子量多官能单体PMR-POI(聚醚酰亚胺)为界面增强剂,分别研究了POI与PPS、PES之间的接枝和/或交联反应,POI对PPS结晶行为的影响,POI对PES分子运动的影响和POI对PPS/PES共混体系的界面增强。主要结果如下:1.PPS/PES共混物相容性的特征在于选择性的部分相容,少量的非晶PPS分子可以扩散进入PES相区,相反的扩散过程则不会发生。2.PPS/PES共混物的热学性质和动态力学性能主要受连续相的控制。3.PPS相的性能主要受其结晶度的影响,因此能够改变其结晶度的因素均会改变PPS相的性质。4.光谱学和流变的证据表明,POI同PES,PPs共混过程中有接枝反应发生,分子链增长,分子量加大。这种接枝和/或交联反应的程度是热可控的。5.POI是PPS的增塑剂,成核剂和扩链剂,与POI共混使得PPS结晶速率增加,平衡熔点上升,表面折叠自由能降低。6;在PES/POI体系中Pol对PEs起到了增塑的作用,Tg降低,经高温热处理后Tg上升。因此,POI对PES性能的影响也是热可控的。7.PMR-POI能够在PPS/PES共混体系中有效地扩散并起到了降低分散相粒子的尺寸、增强界面的作用。它是该共混体系的有效界面增强剂。8."高温退火既能够提高扩散速率也能够提高反应速率;二者相互竞争。2.马来酸配封端溉碳酸丙撑酯的研究二氧化碳与环氧丙烷交替共聚物(polypropylene careonate,PPC)是由二氧化碳活化并与环氧丙烷共聚而成的一类可完全生物降解的新型高分子材料,具有巨大的潜在应用价值。本论文讨论了马来酸配封端的聚碳酸丙撑酯(MA-PPC)和未封端的PPC的粘弹性、流变行为以及热降解和热分解行为,并得出如下结论:1.马来酸配封端抑制了PPC解拉链式的热分解和无规链断裂热降解,PPC的热稳定性和力学性能得到提高。2.PPC和MA-PPC在玻璃化转变温度有相似的自由体积分数,PPC的Tg比MA-PPC稍低。虽然PPC和MA-PPC玻璃化转变表观活化能E。和平均松弛时间T随温度升高单调降低,但PPC的分子运动对温度更敏感,而MA-PPC较稳定。马来酸配封端改变了PPC分子运动的特征及松弛行为,许多实验证据证明,这是由于封端后的PPC大分子链间的相互作用增强及分子链缠结密度增加。3.MA-PPC在70℃左右会发生脱水,实现大分子偶联反应并得到变温红外光谱、分子量成倍增加及线膨胀数据的有力支持。4.用零剪切粘度几。的方法测得PPC及MA-PPC加工过程中的热降解温度,它们分别为150℃和175℃,在此温度以上,η0降低速率的增加归因于大分子的主链断裂以及解拉链反应。5.测得了PPC的临界缠结分子量,它几乎是MA-PPC相应值(6613)的3倍。这表明马来酸配封端不仅改善了PPC的熔体弹性,而且也大大增强了PPC的缠结密度以及分子链间的相互作用。6.在本实验条件下在氮气和空气的气氛中,MA-PPC同PPC的热降解和热分解行为几乎一致,即在PPc的加土过程可以忽略氧气对其的影响。7.虽然MA-PPC的玻璃化温度在40℃左右,但在40℃-120℃的温度区间内,MA-PPC达不到粘流状态。8.没有剪切力时在120℃-150℃,30分钟内,MA-PPC几乎没有降解,在静态条件下,低于170℃时,MA-PPC的解拉链式降解是十分轻微的,当温度超过170℃,PPC降解相当严重。9.在热机械力存在的情况下,发生无规断链的机会增加,无规断链又会加速解拉链降解,因此实际加工中的加工窗口比静态下窄,MIA-PPC的加工窗口应为130℃-160℃。10.MA-PPC的热分解过程是一步完成的,热分解温度随升温速率的加快而提高,并计算出热分解的表观活化能为623.3KJ/mol。

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耐热树脂或称特种工程塑料主要包括聚芳飒类、聚醚酮类、聚芳酷、液晶类、聚酞亚胺和聚苯硫醚等。长春应化所已获得有关聚芳醚酮(PEK-C),聚芳醚砜(PES-C)和聚酞亚胺(PEI)等特种工程塑料的专利12项。在特种工程塑料中,PEK-C,PES-C和PEI有着最高的机械强度(室温下的拉伸强度在100MPa以上)。PES-C和PEI的耐热等级最高(热变形温度分别为225℃和220-260℃)。PE工有极好的阻燃性(氧指数为47)和耐磨性。而PEK-C的加工性好、韧性高、耐磨损和抗电击穿等性质突出,其综合物性与英国ICI公司的聚醚醚酮(PEEK)相近,是良好的高性能复合材料基体树脂。具有优异综合物性的PEK-C、PES-C、PEI及其改性系列材料在机械、电子电气、军工、医疗及食品等许多领域有着广泛的应用前景。近年来,长春应化所在酞侧基聚芳醚酮和聚芳醚矾的结构一加工一物性关系及开发应用等方面作了大量的研究工作,主要涉及此两种聚合物的粘弹性、屈服行为、断裂行为、转变与松弛以及复合与共混等方面内容。这些研究工作表明,酞侧基聚芳醚酮和聚芳醚矾经过共混和复合改性能够具有更优异的使用性能,而且这些研究中的一些方法同样可以应用于其它耐热树脂的改性。高分子材料科学的发展趋势就是在更深层次上把握材料的结构特点及其与宏观物性间的相互关耽达到高分子分子设计和材料设计的目标,实现高性能化和高功能化使现有的高分子材料找到更广泛而合理的应用。工程塑料的高性能化是高分子材料科学近年来发展的一个主要方向。为满足航天航空、电子信息、汽车工业家用电器以及机械等多方面技术领域的需要,要求材料的机械性能、耐热性、耐腐蚀性和长期使用性等性能进一步提高。在现有工程塑料品种的基础上通过共混增韧、复合增强等改性方法使其成为高性能的结构材料,是高分子材料私}学的前沿课题及重要任务。本文采用熔融加工的方法制备了PEK-C和PES-C耐热树脂的共混与复合材料,利用热分析、力学性能检测、微观形貌观察、加工性能检测等手段研究了共混物及复合材料的结构与性能。通过对PEK-C和PES-C的冲击断裂过程的研究,我们发现,两种材料在裂纹起始扩展时所能承受的最大应力值相同,但PES-C的裂纹引发(ti)和扩展(tp)所需时间仅是PEK-C的一半,此即PES-C的冲击强度(I)和断裂韧性(KIC)较低的原因。因此,如能延长裂纹引发和扩展的时间,也就是说如能扩大断裂过程区,抑制裂纹的早期形成就能达到增韧的目的。在PES-C的增韧研究方面,我们可以借鉴通用塑料的增韧方法,即在高聚物基体中,以适当的手段掺加第二相粒子,通过粒子的变形和引发基体在粒子周围产生剪切屈服或银纹化等作用机理,实现增韧目的。所不同的是,对PES-C类耐热树脂来说,实现增韧的同时应保持材料原有的高强度和高耐热性等优良险质。另一方面,由于耐热树脂的加工温度极高,适合于通用塑料的偶联剂等界面改性技术已不再适用于特种工程塑料。针对PES-C的增韧方法和机理的研究工作可归纳为以下三个方面:①刚性有机粒子(PPS,LCP等)增韧;②柔性有机粒子(UHMWPE)增韧;③刚性无机粒子(硅灰石)增韧。物理老化或结构松弛效应使得高聚物材料的结构和宏观物性随时间而发生变化。随时间的增长,PES-C和PES-C/PPS共混物的拉伸强度增加、冲击韧性减小,而且这种变化趋势表现出物理老化过程的自衰减特性。研究结果表明,PES-C/pps共棍物的结构松弛速率比PES-C慢。具有良好界面相互作用的PES一C/PPS共混物材料的强度和韧性始终高于PES-C纯组份聚合物。因此说,pES-C/PPS共混物不仅具有良好的短期性能,而且在高温下长期使用过程中,其力学性能将始终优于纯组份聚合物。我们研究了热固性聚酞亚胺预聚物(P01)增容聚芳醚酮/聚苯硫醚共混物的热学性能、力学性能、形态结构及加工性,对POI在聚芳醚酮/聚苯硫醚共混物中所起的增容作用机理进行了初步探讨。实验发现,PEK-C/PPS共混物在保持PEK一C原有的高强度和高模量的同时,加工流动性和韧性得到一定程度的改善。PEK-C/ppS/Pm三元共混物中,少量的POI能够控制PPS分散相的相区尺寸,防止分散相粒子的自凝聚,起到了增容剂的作用。热固性高聚物预聚体可用于增容热塑性高聚物共混体系,这种增容方法有其特殊性和新颖性,增容后的聚芳醚酮/聚苯硫醚共棍物的力学性能得以改善。利用纤维可以作为结晶性高聚物的异相成核剂的特性,将合适的结晶性高聚物与非晶高聚物共混,可以在在一定程度上改善非晶高聚物与纤维间的界面粘结,提高纤维增强效率。这种方法对PEK-C类耐热树脂尤为重要。通过与即S共混,玻纤增强PEK-C复合材料中纤维与基体间的界面粘结以及纤维的长径比明显增加,因而复合材料的强度和模量显著提高,而且加工流动性也得到一定程度的改善。从考虑综合物性的角度出发,利用结晶性高聚物改善纤维与非晶树脂基体间的界面粘结时,结晶性高聚物的用量存在一个最佳值。与PEEK/GF复合材料相比,PEK-C/PPS/GF复合材料在加工能耗、价格等方面存在很大优势,可以预期这一高性能复合材料可应用于制造高强度、高耐热、耐腐蚀、耐磨损、耐疲劳的往复运动部件、振动或转动等机械零部件。

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本论文主要包括三个部分。第一部分简单介绍了四极杆质谱仪的工作原理和所用实验技术;第二部分首先综述了质谱技术在高分子链结构和热分解机理研究中的应用,然后以直接裂解质谱(DPMS)为主要手段研究了聚对苯硫醚(PPS)、聚噻吩(PT)、聚苯胺(PAn)、聚邻甲基苯胺(POT)和聚β-羟基丁酸酯(PHB)及其共聚物的热分解行为和某些结构性质。主要讨论了电子能量、裂解温度、电离方式等对高分子裂解产物的影响,表明DPMS是研究高分子热分解机理的有效方法。几种导电聚合物的热分解均以自由基方式降解,PPS裂解形成环状和线状齐聚物,PT、PAn及POT只能形成线状齐聚物;聚β-羟基烷酸酯的热分解通过β-CH转移反应形成由羟基和烯烃结尾的齐聚物,形成的齐聚物准分子离子可进一步脱去一个分子水。第三部分用GC、GC/MS分离鉴定了山核桃油中的脂肪酸,并用FABMS测定了山核油中混合甘油三酸酯的组成。FABMS能反映不同甘油三酸酯的组成和含量,而GC、GC/MS能对各种脂肪酸进行定性和定量分析,两种方法相互补充,较全面地获得了山核桃油的组成信息。

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HIRFL is a tandem cyclotron complex for heavy ion. On the beam line between SFC and SSC, there is a stripper. Behind it, the distribution of charge states of beam is a Gauss distribution. The equilibrium charge state Q_0 is selected by 1BO2(a 50° dipole behind the stripper) and delivered to SSC. One of two new small beam line (named SLAS) after 1B02 will be builded in or der to split and deliver the unused ions of charge states (Q_0 ± n) to aspecific experimental area. Q_0 ± n ions are septumed and separated from initial(Q_0) ion beam by two septum magnets SM1, SM2. The charge state selected by SM1 will be Q_0 ± 1(6 ≤ Q_0 < 17), Q_0 ± 2(17 ≤ Q_0 < 33) and Q_0 ± 3 (Q_0 ≥ 33) forming a beam in one of the two possine new beam line with the stripping energy of (0.2 to 9.83 Mev/A), an emittance of 10π mm.mrad in the two transverse planes and an intensity ranging from 10~(11) pps for z ≤ 10 to some 10~5 pps for the heaviest element. Behind SM2, a few transport elements (three dipoles and seven qudrupoles) tra nsport Q_0 ± n beam to target positions T1, T2 (see fig. 1) and generate small beam spots (φ ≤ 4mm, φ ≤ 6mm). The optics design of the beam line has been done based on SLAC-75 (a first and second - order matrix theory). beam optics calculation has been worked out with the TRANSPORT program. The design is a very economical thinking, because without building a new accelerator we can obtain a lower energy heavy ion beam to provide for a lot of atomic and solid state physical experiments

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The isothermal crystallization and melting behaviors of poly(propylene carbonate) end-capped with benzenesulfonyl/poly (vinyl alcohol) (PPC-BS/PVA) blends over rich PVA composition range were first investigated by differential scanning calorimetry (DSC). PPS-BS/PVA interaction parameter, chi(12), calculated from equilibrium melting temperature depression was -0.44, revealing miscibility of PPC-BS with PVA in the melt and favorable interactions. The temperature dependence of crystallization rate constant at initial crystallization stage was analyzed using the modified Lauritzen-Hoffman expression. The chain width, a(0), the thickness of a monomolecular layer, b(0), the fold and lateral surface-free energies, sigma(e) and sigma, and the work of chain folding, q, for neat PVA were first reckoned to be 4.50 Angstrom, 4.78 Angstrom, 76.0 erg.cm(-2), and 4.70 kcal.mol(-1), respectively. The values of sigma(e) and q for PVA in PPC-BS/PVA blends exhibited a maximum in the neighborhood of 10/90 PPC-BS/PV, respectively.

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The crystallization behavior of neat PPS and PPS in blends with PMR-POI prepared by melt mixing were investigated by differential scanning calorimetry (DSC). It was found that POI was an effective nucleation agent of the crystallization for PPS. The enthalpy of crystallization of PPS in the blends increased compared with that of neat PPS. During isothermal crystallization from melt, the dependence of relative degree of crystallinity on time was described by the Avrami equation. It has been shown that the addition of POI causes an increase in the overall crystallization rate of PPS; it also changed the mechanism of nucleation of the PHB crystals from homogeneous nucleation to heterogeneous nucleation. The equilibrium melting temperature of PPS and PPS/POI blends were determined. The analysis of kinetic data according to nucleation theories shows that the increase in crystallization rate of PPS in the composite is due to the decrease in surface energy of the extremity surface.

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The effect of polymerization of monomer reactant-polyimide (POI) as the interfacial agent on the interface characteristics, morphology features, and crystallization of poly(ether sulfone)/poly(phenylene sulfide) (PES/PPS) blends were investigated using a scanning electron microscope, FTIR, WAXD, and XPS surface analysis. It was found that the interfacial adhesion was enhanced, the particle size of the dispersed phase was reduced, and the miscibility between PES and PPS was improved by the addition of POI. It was also found that POI was an effective nucleation agent of the crystallization for PPS.

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The effects of thermally crosslinkable polymerization of monomer reactant-polyimide (POI) on the miscibility, morphology, and crystallization of partially miscible poly(ether sulfone) (PES)/poly(phenylene sulfide) (PPS) blends were investigated with differential scanning calorimetry and scanning electron microscopy. The addition of POI led to a significant reduction in the size of PPS particles, and the interfacial tension between PPS and crosslinked POI was smaller than that between PES and crosslinked POI. During melt blending, crosslinking and grafting reactions of POI with PES and PPS homopolymers were detected; however, the reaction activity of POI with PPS was much higher than that with PES. The crosslinking and grafting reactions were developed further when blends were annealed at higher temperatures. Moreover, POI was an effective nucleation agent of the crystallization of PPS, but crosslinking and grafting hindered the crystallization of PPS. The final effect of POI on the crystallinity of the PPS phase was determined by competition between the two contradictory factors. The crosslinking and grafting reactions between the two components was controlled by the dosage of POI in the blends, the premixing sequence of POI with the two components, the annealing time, and the temperature.