环氧官能化ABS增韧PBT及其共混物

合成了甲基丙烯酸环氧丙酯(GMA)接枝的丙烯腈-丁二烯-苯乙烯(ABS-g-GMA)核壳粒子增韧聚对苯二甲酸丁二醇酯(PBT),加入环氧树脂(Epoxy)为扩链剂进一步提高共混物的性能。红外光谱(FTIR)结果表明:GMA成功接枝到ABS粒子上;研究发现不同GMA含量的ABS-g-GMA粒子在PBT及PBT/Epoxy共混物中均匀分散;ABS-g-GMA对PBT增韧效果较好,Epoxy进一步提高了PBT/ABS-g-GMA共混物的冲击韧性及拉伸强度;ABS-g-GMA增韧PBT的机理是橡胶粒子的空洞化和PBT基体的剪切屈服。     

ABS-g-GMA增韧聚对苯二甲酸丁二醇酯的研究

用甲基丙烯酸环氧丙酯（（MA）接枝的丙烯腈／丁二烯／苯乙烯（ABs）接枝共聚物（ABS-g-GMA）改善聚对苯二甲酸丁二醇酯（PBT）的缺口冲击韧性。动态力学分析、差示扫描量热分析以及流变性能测试结果表明，GMA引入到ABS中，随GMA含量的增加，PBT与ABS的玻璃化转变温度相互靠近，PBT的熔点降低，共混体系的扭矩、温度提高，这些结果表明GMA提高了PBT与ABS之间的相容性；增容反应导致ABS在PBT基体中均匀、稳定分散，有利于共混物性能的改善；交联反应导致交联聚集网状结构的生成，使共混物性能变差。冲击强度结果表明，1％（质量含量。下同）GMA含量就可以导致PBT／ABS-g-GMA共混物冲击韧性显著改善，当ABS-g-GMA1含量为30％时，共混物冲击强度高达850J／m。     

ACR-g-GMA的制备及对PBT的增韧

要采用乳液聚合方法合成了以丙烯酸丁酯(BA)为橡胶相内核,甲基丙烯酸甲酯(MMA)为壳层,并在壳层接枝甲基丙烯酸环氧丙酯(GMA)的核壳结构聚合物(AcR-g-GMA)。用其增韧聚对苯二甲酸丁二醇酯(PBT),制备PBT/ACR-g-GMA合金。用傅立叶变换红外光谱考察接枝聚合物的环氧基团;用电子显微镜观察共混物中粒子分布的微观形态;测试了共混物的力学性能。结果表明:采用乳液聚舍方法能够将GMA接枝到ACR上,GMA可以增强两相间的界面结合力,ACR-g-GMA粒子能有效地增韧PBT。当ACR-g-GMA粒子中GMA的质量分数为3%,m(PBT)/m(ACR-g-GMA)为80/20时,共混物的缺口冲击强度可高达389 J/m。     

乙烯-丙烯酸甲酯-甲基丙烯酸缩水甘油酯三元共聚物增韧PBT的研究

采用自制的不同接枝率的乙烯丙烯酸甲酯甲基丙烯酸缩水甘油酯三元共聚物(E MA GMA)增韧剂以及国外商业化增韧剂对聚对苯二甲酸丁二醇酯(PBT)进行增韧研究,将不同增韧剂与纯PBT树脂进行共混改性,研究了增韧改性PBT的缺口冲击强度、拉伸断裂伸长率和熔体流动速率等性能。结果表明,当自制增韧剂的接枝率为1.96 %,用量为15 %时增韧效果最好,材料的缺口冲击强度增加65 %,断裂伸长率增加30.6 %。     

耐油ABS/PET/PBT电瓶壳专用料的研制

设计了一种耐油性丙烯腈-丁二烯-苯乙烯三元共聚物(ABS)/聚对苯二甲酸乙二醇酯(PET)/聚对苯二甲酸丁二醇酯(PBT)电瓶壳专用料,通过提高改性增容PET/PBT树脂与ABS树脂的相容性,改善ABS树脂的耐油性,制备高抗冲的ABS树脂。结果表明,ABS/PET/PBT电瓶壳专用料的冲击强度可提高到17kJ/m2以上;耐油性能测试证实,当在ABS/PET/PBT中添加30%(质量分数,下同)的PET/PBT增容树脂后,就可以消除刹车油对ABS/PET/PBT的侵蚀。     

环氧官能化ABS核壳比对增韧PBT性能的影响

采用种子乳液聚合的方法,合成了不同核壳比的甲基丙烯酸缩水甘油酯接枝丙烯腈-丁二烯-苯乙烯塑料耐冲击改性剂(ABS-g-GMA).将合成的耐冲击改性剂用于增韧聚对苯二甲酸丁二酯(PBT),考察耐冲击改性剂核壳比对增韧PBT拉伸性能、缺口冲击强度以及相容性的影响.结果表明,耐冲击改性剂的核壳比对增韧PBT有重要的影响.耐冲...     

ABS接枝物的制备及其对r-PET/ABS的增容作用

通过反应挤出法制备马来酸酐(MAH)接枝丙烯腈-丁二烯-苯乙烯三元共聚物(ABS)(ABS-g-MAH)和甲基丙烯酸缩水甘油酯(GMA)接枝ABS(ABS-g-GMA),将其用于增容回收聚对苯二甲酸乙二酯(PET)瓶片(r-PET)/ABS共混物,发现能显著提高共混物的冲击强度。ABS-g-MAH的增容效果优于ABS-g-GMA;ABS-g-MAH的接枝率为1.35%,w(ABS-g-MAH)为5%时对r-PET/ABS的增容作用最佳,此时r-PET/ABS/ABS-g-MAH的简支梁缺口冲击强度和无缺口冲击强度比r-PET/ABS分别提高了42%和23%。扫描电子显微镜观察表明,加入ABS接枝物能使ABS在r-PET连续相中的分散更均匀,粒径尺寸更均一。     

PPC/ABS-g-GMA/MMT复合材料的制备及其形态结构和动态力学性能研究

将甲基丙烯酸缩水甘油酯接枝丙烯腈-丁二烯-苯乙烯(ABS-g-GMA)、聚碳酸亚丙酯(PPC)及蒙脱土(MMT)——无机蒙脱土(IMMT)或有机蒙脱土(OMMT)熔融共混制备了PPC/ABS-g-GMA/IMMT和PPC/ABS-g-GMA/OMMT复合材料。采用傅里叶红外光谱(FTIR)对自制的ABS-g-GMA进行了表征,并通过X射线衍射分析(XRD)、透射电子显微镜(TEM)及动态机械分析(DMA)研究了PPC/ABS-g-GMA/MMT复合材料的形态结构及动态力学性能。结果表明:甲基丙烯酸缩水甘油酯(GMA)成功地接枝到了丙烯腈-丁二烯-苯乙烯(ABS)分子链上;IMMT主要以团聚体的形式聚集在ABS-g-GMA相,有少部分ABS-g-GMA插入到了IMMT的片层结构中,而OMMT主要以剥离态的形式存在于复合材料中;IMMT及OMMT的加入使复合材料的储能模量有了很大程度的提高。     

弹性体/无机纳米粒子复合体系增强增韧回收ABS树脂

分别研究了弹性体和无机纳米粒子对回收丙烯腈-丁二烯-苯乙烯共聚物(ABS)的增韧。结果表明:弹性体能使回收ABS树脂的韧性得到恢复,但导致刚性下降;无机纳米粒子对ABS树脂的增韧能力有限,但能增加ABS的刚性。最后采用弹性体/无机纳米粒子复合体系改性回收ABS树脂,添加质量分数5%~8%的高胶粉和质量分数2%~3%无机纳米粒子时,实现了对回收ABS树脂的增强增韧。     

两种不同橡胶粒径的ABS树脂协同作用研究

采用两种不同橡胶粒径的丙烯腈-丁二烯-苯乙烯共聚物(ABS)掺混制备橡胶粒子尺寸双峰分布的ABS树脂。恒定ABS树脂的橡胶含量,通过调节不同粒径橡胶的质量比,考察其对ABS树脂力学性能的影响,并利用扫描电子显微镜和透射电子显微镜观察了ABS树脂的微观结构,分析了协同作用的增韧机理。结果表明,ABS树脂的冲击强度和屈服强度都随着大粒径橡胶粒子比例的减少而增大;当L-PB/S-PB为1/9时,ABS树脂的冲击强度和屈服强度最高,两种橡胶粒子发生了明显的协同作用。     

Phase morphology development during processing of compatibilized and uncompatibilized PBT/ABS blends

The development of the multiphase morphology of uncompatibilized blends of poly(butylene terephthalate) (PBT) and acrylonitrile–butadiene–styrene terpolymer (ABS) and PBT/ABS blends compatibilized with methyl‐methacrylate glycidyl‐methacrylate (MMA‐GMA) reactive copolymers during compounding in a twin‐screw extruder and subsequent injection molding was investigated. Uncompatibilized PBT/ABS 60/40 (wt %) and compatibilized PBT/ABS/MMA‐GMA with 2 and 5 wt % of MMA‐GMA showed refined cocontinuous morphologies at the front end of the extruder, which coarsened towards the extruder outlet. Coarsening in uncompatibilized PBT/ABS blends is much more pronounced than in the compatibilized PBT/ABS/MMA‐GMA equivalents and decreases with increasing amounts of the MMA‐GMA. For both systems, significant refinement on the phase morphology was found to occur after the blends pass through the extruder die. This phenomenon was correlated to the capacity of the die in promoting particles break‐up due to the extra elongational stresses developed at the matrix entrance. Injection molding induces coarsening of the ABS domains in the case of uncompatibilized PBT/ABS blends, while the reactive blend kept its refined phase morphology. Therefore, the compatibilization process of PBT/ABS/MMA‐GMA blends take place progressively leading to a further refinement of the phase morphology in the latter steps, owing to the slow reaction rate relative to epoxide functions and the carboxyl/hydroxyl groups. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 102–110, 2007     

Toughening of poly(butylene terephthalate) with epoxy-functionalized acrylonitrile-butadiene-styrene

Glycidyl methacrylate (GMA) functionalized acrylonitrile-butadiene-styrene (ABS) copolymers have been prepared via an emulsion polymerization process. These functionalized ABS copolymers (ABS-g-GMA) were blended with poly(butylene terephthalate) (PBT). DMA result showed PBT was partially miscible with ABS and ABS-g-GMA, and DSC test further identified the introduction of GMA improved miscibility between PBT and ABS. Scanning electron microscopy (SEM) displayed a very good dispersion of ABS-g-GMA particles in the PBT matrix compared with the PBT/ABS blend when the content of GMA in PBT/ABS-g-GMA blends was relatively low (<8 wt% in ABS-g-GMA). The improvement of the disperse phase morphology was due to interfacial reactions between PBT chains end and epoxy groups of GMA, resulting in the formation of PBT-co-ABS copolymer. However, a coarse, non-spherical phase morphology was obtained when the disperse phase contained a high GMA content (≥8 wt%) because of cross-linking reaction between the functional groups of PBT and GMA. Rheological measurements further identified the reactions between PBT and GMA. Mechanical tests showed the presence of only a small amount of GMA (1 wt%) within the disperse phase was sufficient to induce a pronounced improvement of the impact and tensile properties of PBT blends. SEM results showed shear yielding of PBT matrix and cavitation of rubber particles were the major toughening mechanisms.     

Influence of core–shell particles structure on the morphology and brittle‐ductile transition of PBT/ABS‐g‐GMA blends

The performance of glycidyl methacrylate (GMA) functionalized acrylonitrile‐butadiene‐styrene core–shell impact modifiers (R‐ABS) with varied GMA content, crosslinking degree of rubber phase, core–shell ratio, and initiator type in toughening of poly(butylene terephthalate) (PBT) was investigated. Results show that 1 wt% GMA is sufficient to induce a pronounced improvement of the impact strength of PBT and too much GMA induces the crosslinking of R‐ABS. Divinylbenzene improves the crosslinking degree of polybutadiene and decreases its cavitation ability. The brittle‐ductile transition shifts to higher R‐ABS content. When the core–shell ratio of R‐ABS is beyond 70/30, compatibilization reaction is not sufficient to retard the agglomeration of core–shell particles. R‐ABS particles with the core–shell ratio between 50/50 and 60/40 are suitable. Initiator type can influence the internal structure of R‐ABS. For R‐ABS prepared with azobisisobutyronitrile (AIBN) as initiator, big subinclusion structure decreases its toughening ability. R‐ABS prepared with redox initiator shows better toughening behavior. POLYM. COMPOS., 2013. © 2012 Society of Plastics Engineers     

Influence of the degree of grafting on the morphology and mechanical properties of blends of poly(butylene terephthalate) and glycidyl methacrylate grafted poly(ethylene‐co‐propylene) (EPR)

Poly(ethylene‐co‐propylene) (EPR) was functionalized to varying degrees with glycidyl methacrylate (GMA) by melt grafting processes. The EPR‐graft‐GMA elastomers were used to toughen poly(butylene terephthalate) (PBT). Results showed that the grafting degree strongly influenced the morphology and mechanical properties of PBT/EPR‐graft‐GMA blends. Compatibilization reactions between the carboxyl and/or hydroxyl of PBT and epoxy groups of EPR‐graft‐GMA induced smaller dispersed phase sizes and uniform dispersed phase distributions. However, higher degrees of grafting (>1.3) and dispersed phase contents (>10 wt%) led to higher viscosities and severe crosslinking reactions in PBT/EPR‐graft‐GMA blends, resulting in larger dispersed domains of PBT blends. Consistent with the change in morphology, the impact strength of the PBT blends increased with the increase in EPR‐graft‐GMA degrees of grafting for the same dispersion phase content when the degree of grafting was below 1.8. However, PBT/EPR‐graft‐GMA1.8 displayed much lower impact strength in the ductile region than a comparable PBT/EPR‐graft‐GMA1.3 blend (1.3 indicates degree of grafting). Morphology and mechanical results showed that EPR‐graft‐GMA 1.3 was more suitable in improving the toughness of PBT. SEM results showed that the shear yielding properties of the PBT matrix and cavitation of rubber particles were major toughening mechanisms. Copyright © 2006 Society of Chemical Industry     

Effect of reactive group types on the properties of core-shell modifiers toughened PA6

Summary  Reactive monomers such as acrylic acid (AA), maleic anhydride (MA) and glycidyl methacrylate (GMA) were grafted onto acrylonitrile-butadiene-styrene core-shell copolymer (ABS) by emulsion polymerization method. These functionalized ABS were used to toughen PA6. FTIR and Molau tests showed that these monomers were introduced onto ABS copolymers and compatibilization reactions took place between PA6 and the AA, MA and GMA grafted ABS. TEM result showed that the modified ABS copolymer dispersed in PA6 matrix uniformly and no obvious difference could be found between the different PA6 blends. However, mechanical test showed that GMA and MA modified ABS achieved much better toughening effect than the AA grafted ABS copolymer due to the stronger interfacial reactions. Fracture characterization indicated that PA6 toughened with GMA and MA modified ABS showed higher G_ivalues according to the Vu-Khanh approach and much obvious shear yielding in the deformed zone could be found.     

Polylactide toughening with epoxy‐functionalized grafted acrylonitrile–butadiene–styrene particles

Glycidyl methacrylate functionalized acrylonitrile–butadiene–styrene (ABS‐g‐GMA) particles were prepared and used to toughen polylactide (PLA). The characteristic absorption at 1728 cm^?1 of the Fourier transform infrared spectra indicated that glycidyl methacrylate (GMA) was grafted onto the polybutadiene phase of acrylonitrile–butadiene–styrene (ABS). Chemical reactions analysis indicated that compatibilization and crosslinking reactions took place simultaneously between the epoxy groups of ABS‐g‐GMA and the end carboxyl or hydroxyl groups of PLA and that the increase of GMA content improved the reaction degree. Scanning electron microscopy results showed that 1 wt % GMA was sufficient to satisfy the compatibilization and that ABS‐g‐GMA particles with 1 wt % GMA dispersed in PLA uniformly. A further increase of GMA content induced the agglomeration of ABS‐g‐GMA particles because of crosslinking reactions. Dynamic mechanical analysis testing showed that the miscibility between PLA and ABS improved with the introduction of GMA onto ABS particles because of compatibilization reactions. The storage modulus decreased for the PLA blends with increasing GMA content. The decrease in the storage modulus was due to the chemical reactions in the PLA/ABS‐g‐GMA blends, which improved the viscosity and decreased the crystallization of PLA. A notched impact strength of 540 J/m was achieved for the PLA/ABS‐g‐GMA blend with 1 wt % GMA, which was 27 times than the impact strength of pure PLA, and a further increase in the GMA content in the ABS‐g‐GMA particles was not beneficial to the toughness improvement. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Effect of core-shell particles dispersed morphology on the toughening behavior of PBT/PC blends

Methyl methacrylate-co-styrene-co-glycidyl methacrylate grafted polybutadiene (PB-g-MSG) and styrene-co-glycidyl methacrylate grafted polybutadiene (PB-g-SG) core-shell particles were prepared to toughen poly (butylene terephthalate) (PBT) and polycarbonate (PC) blends. The compatibilization reaction between the epoxy groups of glycidyl methacrylate and the carboxyl groups of PBT induced the PB-g-SG particles dispersed in the PBT phase. On the other hand, the good miscibility between PMMA (the shell phase of PB-g-MSG) and PC induced the PB-g-MSG particles dispersed in the PC phase. The different phase morphology led to different toughening behavior. The PBT/PC/PB-g-MSG blends with the PC encapsulated morphology showed much lower brittle-ductile transition core-shell particles content (10-15 wt% or 15-20 wt%) compared with the PBT/PC/PB-g-SG blends (20-25 wt%). The difference between the toughening efficiency of the core-shell particles was due to the change of deformation mechanisms. In PBT/PC/PB-g-MSG blends, the cavitation of PB rubber phase led to the occurrence of shear yielding of the matrix. While in the PBT/PC/PB-g-SG blends, the debonding between PBT and PC interface induced the shear yielding of the matrix. The variation of the core-shell particles dispersed phase morphology also affected the crystallization properties and DMA results of the PBT/PC blends. Modification of the phase morphology provided an useful strategy to prepare PBT/PC blends with higher toughening efficiency.     

Modification of the reactive core-shell particles properties to prepare PBT/PC blends with higher toughness and stiffness

Glycidyl methacrylate (GMA) functionalized methyl methacrylate-butadiene-styrene core-shell particles (PB-g-MSG) were prepared to toughen poly (butylene terephthalate) (PBT) and polycarbonate (PC) blends. T-dodecyl mercaptan (TDDM) was used to modify the grafting character of the core-shell particles. The addition of TDDM decreased the grafting degree, particles size and crosslinking degree of PB-g-MSG particles. At the same time, the free methyl methacrylate-co-styrene-co-glyceryl methacrylate copolymer (f-MSG) increased. The f-MSG reacted with PBT and suppressed the transesterification between PBT and PC. On the other hand, f-MSG promoted the crystallization of PBT by heterogeneous nucleation. When the TDDM content was lower than 0.76%, PB-g-MSG particles dispersed in the matrix uniformly, otherwise, agglomeration took place. The change of TDDM content in the PB-g-MSG particles influenced the toughening ability and tensile properties. When the TDDM content was 0.76%, the PBT/PC/PB-g-MSG blend showed the optimum impact toughness and yield strength, which are 908 J/m and 49.4Mpa. Fracture mechanism results indicated that cavitation induced shear yielding occurred in the PBT/PC/PB-g-MSG blend when no TDDM addition for the core-shell particles. With the addition of TDDM, the interfacial strength decreased between the PB-g-MSG core-shell particles and the matrix. So voids appeared due to debonding, which also could promote the shear yielding process.