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。     

Reactivity of acrylonitrile-butadiene-styrene terpolymer grafted with long-chain unsaturated carboxylic acids

Reactivity of acrylonitrile-butadiene-styrene terpolymer (ABS) grafted with long-chain carboxylic acids, such as undecylenic acid and oleic acid, was investigated and compared with that of ABS grafted with short-chain carboxylic acids by reacting with dodecylamine, glycidyl methacrylate (GMA), and 2-ethyl-2-oxazoline in solution, and with polyamide (PA) in melt. The overall activation energy of ABS-g-acrylic acid, ABS-g-crotonic acid, ABS-g-undecylenic acid and ABS-g-oleic acid reacting with dodecylamine was 31.2, 16.2, 18.2 and 21.6 kJ/mol, respectively. The overall activation energy of ABS-g-acrylic acid, ABS-g-crotonic acid, ABS-g-undecylenic acid and ABS-g-oleic acid reacting with GMA was 29.0, 31.9, 61.4 and 61.8 kJ/mol, respectively. The stronger the acidity of grafted acid, the higher the percentage of the grafted acid reacted. The overall activation energy of ABS-g-acrylic acid, ABS-g-crotonic acid, ABS-g-undecylenic acid and ABS-g-oleic acid reacting with 2-ethyl-2-oxazoline was 19.5, 20.9, 23.4 and 24.5 kJ/mol, respectively. The lower the steric hindrance and the higher the chain mobility of grafted acid, the higher the percentage of the grafted acid reacted. The reactivity of dodecylamine, GMA and 2-ethyl-2-oxazoline reacting with grafted ABS is: GMA<2-ethyl-2-oxazoline<dodecylamine. The reactivity of grafted polymer is: ABS-g-acrylic acid<ABS-g-crotonic acid<ABS-g-oleic acid<ABS-g-undecylenic acid, when they react with PA in melt.     

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。     

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     

Compatibilization of polyethylene terephthalate/polypropylene blends with styrene–ethylene/butylene–styrene (SEBS) block copolymers

Blends of polyethylene terephthalate (PET) and polypropylene (PP) at compositions 20/80 and 80/20 were modified with three different styrene–ethylene/butyl–ene-styrene (SEBS) triblock copolymers with the aim of improving the compatibility and in particular the toughness of the blends. The compatibilizers involved an unfunctionalized SEBS and two functionalized grades containing either maleic anhydride (SEBS-g-MAH) or glycidyl methacrylate (SEBS-g-GMA) grafted to the midblock. The effects of the compatibilizers were evaluated by studies on morphology and mechanical, thermal and rheological properties of the blends. The additon of 5 wt % of a SEBS copolymer was found to stabilize the blend morphology and to improve the impact strength. The effect was, however, far more pronounced with the functionalized copolymers. Particularly high toughness combined with rather high stiffness was achieved with SEBS-g-GMA for the PET-rich composition. Addition of the functionalized SEBS copolymers resulted in a finer dispersion of the minor phase and clearly improved interfacial adhesion. Shifts in the glass transition temperature of the PET phase and increase in the melt viscosity of the compatibilized blends indicated enhanced interactions between the discrete PET and PP phases induced by the functionalized compatibilizer, in particular SEBS-g-GMA. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 65:241–249, 1997     

Grafting of glycidyl methacrylate onto ethylene-propylene copolymer: Preparation and characterization

Ethylene-propylene copolymer (EP) was functionalized with glycidyl methacrylate (GMA) by means of a radical-initiated melt grafting reaction. FTIR and ESCA were used to characterize the formation of EP-g-GMA copolymers. The content of GMA in EP-g-GMA was determined by using hydrochloric acid/xylene titration. Effects of concentrations of GMA and dicumyl peroxide on grafting rate were studied. It was found that contact angles of the water on surfaces of EP-g-GMA samples increased with increasing content of GMA in EP-g-GMA. The influence of the content of GMA on the crystallization structure of EP-g-GMA was investigated by DSC and WAXD. Compared with the plain EP, the crystallization temperature of propylene blocks of EP-g-GMA increased over 10 K, and the melting temperature and crystallinity decreased somewhat. Functionalization of EP led to the change of the crystal form of propylene blocks from the mixed form of α and β into the α form. © 1996 John Wiley & Sons, Inc.     

Preparation of PBT/POE-g-GMA/PP ternary blends with good rigidity–toughness balance by core–shell particles

Compared with poly(butylene terephthalate)/glycidyl methacrylate grafted poly(ethylene–octene) (PBT/POE-g-GMA) binary blends, supertough PBT-based ternary blends with little rigidity loss were successfully obtained by adding rigid polypropylene (PP) into PBT/POE-g-GMA blends to construct core–shell particles during melt blending. The effects of PP content and type on the phase morphology and mechanical properties of the blends were systematically investigated. Theoretical predictions and scanning electron microscopy observation showed that a core–shell structure was formed in PBT matrix with PP as the core and POE-g-GMA as the shell. The mechanical property tests showed that POE-g-GMA and PP had significant synergistic toughening effect. When PP with high melt flow index (H-PP) was used, PBT/POE-g-GMA/H-PP (70/15/15) blends possessed the highest Izod notched impact strength, which was 1.9-fold compared with PBT/POE-g-GMA (70/30) binary blends, while the tensile performance loss was little. The essential work of fracture tests was performed to evaluate the fracture resistance of different samples. The results demonstrated that PBT/POE-g-GMA/PP ternary blends possessed much better resistance to crack propagation than PBT/POE-g-GMA binary blends. The decrease of interparticle distance and the fibrillation of core–shell particles activated intense matrix shear yielding, which was the reason for the high crack resistance of ternary blends. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48872.     

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     

Recycling of polycarbonate by blending with maleic anhydride grafted ABS

Recycling of used polycarbonate (PC) was conducted via melt blending with maleic anhydride grafted ABS (ABS-g-MA) using a twin-screw extruder. The toughness of waste PC was greatly improved through the modification of ABS-g-MA. The toughening mechanism was explored based on the morphology of the blends. The grafting of MA onto ABS was considered a key factor, which resulted in a special morphology of ABS domains dispersed in PC matrix. At a certain PC/ABS-g-MA weight ratio, the ABS domains connected together forming a network and gave rise to a maximum of the notched impact strength.     

Stiffer and super-tough poly(butylene terephthalate) based blends by modification with phenoxy and maleated poly(ethylene-octene) copolymers

New super-tough poly(butylene terephthalate) (PBT) materials were obtained by melt blending PBT with both 20 wt% phenoxy (Ph) and 0-30 wt% maleic anhydride grafted poly(ethylene-octene) (mPEO) copolymers with different grafting levels. Ph was completely miscible in the PBT matrix. The presence of mPEO did not influence either the nature of the PBT-Ph matrix or the crystallization of PBT. The overall decrease in particle size and in interfacial tension upon grafting indicated that compatibilization had taken place. Super-tough (impact strength 23-fold that of the PBT) and stiffer PBT based blends were obtained at mPEO contents equal to or higher than 15%. The dependence of the critical inter-particle distance (τ_c), on both adhesion measured by means of the interfacial tension, and on the relation between the modulus of the matrix and that of the rubbery dispersed phase (E_m/E_d), is proposed.     

Reactive compatibilization of polyamide-12/poly(butylene terephthalate) blends with hyperbranched PEI-g-PA12: Morphology and thermal properties

Thermal and morphology properties of polyamide-12 (PA12)/poly(butylene terephthalate) (PBT) blends with hyperbranched poly(ethyleneimine)-g-polyamide-12 (PEI-g-PA12) as reactive compatibilizer were studied by a combination of Optical Microscopy, DSC and ¹³C NMR. This compatibilizer was synthesized by simple amidation reactions. The addition of PEI-g-PA12 greatly modified the morphology of PA12/PBT blends, which were originally an incompatible polymer pair. At the beginning of the addition of compatibilizers, the sizes of PA12 and PBT rich phases decreased and the blends dispersed better. Then the phase structures became more diffused with time. At last, bi-phase morphology disappeared totally and one homogeneous structure was obtained at 260 °C. The higher the PEI-g-PA12 compatibilizer content was, the faster the morphology changed. Our DSC measurements provided a consistent picture of the crystallization behavior of PA12 and PBT components. The comparison of ¹³C NMR spectrums between PA12/PBT and PA12/PBT/PEI-g-PA12 undergoing the same thermal treatment indicated that compatibilization was originated from the formation of hyperbranched PBT-co-PEI-co-PA12 copolymers.     

环氧官能化ABS增韧PBT树脂的性能研究

采用乳液聚合方法合成了甲基丙烯酸环氧丙酯(GMA)共聚的丙烯腈/丁二烯/苯乙烯核壳粒子ABS-g-GMA,用于不同分子量聚对苯二甲酸丁二醇酯(PBT)的增韧。红外光谱证明GMA接枝共聚到了ABS粒子上。DMA测试发现PBT与ABS、ABS-g-GMA之间有一定的相容性。SEM表明ABS-g-GMA均匀分散在不同分子量的PBT树脂中。ABS-g-GMA可以实现对PBT树脂的有效增韧,PBT树脂的分子量越大,增韧效率越高,共混物的断裂伸长率越大。     

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     

Reactive mixing of PET and PET/PP blends with glycidyl methacrylate–modified styrene‐b‐(ethylene‐co‐olefin) block copolymers

Styrene‐b‐(ethylene‐co‐butylene)‐b‐styrene (SEBS) and styrene‐b‐(ethylene‐co‐propylene) (SEP, SEPSEP) block copolymers with different styrene contents and different numbers of blocks in the copolymer chain were functionalized by melt radical grafting with glycidyl methacrylate (GMA) and employed as compatibilizers for PET‐based blends. Binary blends of PET with both functionalized (SEBS‐g‐GMA, SEP‐g‐GMA, SEPSEP‐g‐GMA) and neat (SEBS, SEP, SEPSEP) copolymers (75 : 25 w/w) and ternary blends of PET and PP (75 : 25 w/w) with various amounts (2.5–10 phr) of both modified and unmodified copolymers were prepared in an internal mixer, and their properties were evaluated by SEM, DSC, melt viscosimetry, and tensile and impact tests. The roles of the chemical structure, grafting degree, and concentration of the various copolymers on blend compatibilization was investigated. The blends with the grafted copolymers showed a neat improvement of phase dispersion and interfacial adhesion compared to the blends with nonfunctionalized copolymers. The addition of grafted copolymers resulted in a marked increase in melt viscosity, which was accounted for by the occurrence of chemical reactions between the epoxide groups of GMA and the carboxyl/hydroxyl end groups of PET during melt mixing. Blends with SEPSEP‐g‐GMA and SEBS‐g‐GMA, at concentrations of 5–10 phr, showed a higher compatibilizing effect with enhanced elongation at break and impact resistance. The effectiveness of GMA‐functionalized SEBS was then compared to that of maleic anhydride–grafted SEBS. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 2201–2211, 2005     

Morphological,thermal, and mechanical properties of polypropylene/polycarbonate blend

This work deals with the effect of compatibilizer on the morphological, thermal, rheological, and mechanical properties of polypropylene/polycarbonate (PP/ PC) blends. The blends, containing between 0 to 30 vol % of polycarbonate and a compatibilizer, were prepared by means of a twin-screw extruder. The compatibilizer was produced by grafting glycidyl methacrylate (GMA) onto polypropylene in the molten state. Blend morphologies were controlled by adding PP-g-GMA as compatibilizer during melt processing, thus changing dispersion and interfacial adhesion of the polycarbonate phase. With PP-g-GMA, volume fractions increased from 2.5 to 20, and much finer dispersions of discrete polycarbonate phase with average domain sizes decreased from 35 to 3 μm were obtained. The WAXD spectra showed that the crystal structure of neat PP was different from that in blends. The DSC results suggested that the degree of crystallization of PP in blends decreased as PC content and compatibilizer increased. The mechanical properties significantly changed after addition of PP-g-GMA. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 63: 1857–1863, 1997     

Crystallization behavior of PBT/ABS polymer blends

Poly(butylene terephthalate) (PBT) crystallization behavior is modified by blending it with acrylonitrile‐butadiene‐styrene copolymers (ABS). The effects of ABS on melting and crystallization of PBT/ABS blends have been examined. Most ABS copolymers of different rubber content and styrene/acrylonitrile ratios studied showed little effect on the melting behavior of PBT crystalline phase. However, ABS copolymer with high acrylonitrile content had a significant effect on the crystallization behavior of the PBT/ABS blends. The nucleation rate of the PBT crystalline phase decreased due to the presence of the high acrylonitrile content ABS, whereas the spherulitic growth rate increased significantly. These phenomena are attributed to changes in nucleation and growth mechanisms of PBT crystalline phase promoted by ABS. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 423–430, 1999     

Toughening of polyamide 6 with a maleic anhydride functionalized acrylonitrile–butadiene–styrene copolymer

Maleic anhydride functionalized acrylonitrile–butadiene–styrene (ABS‐g‐MA) copolymers were prepared via an emulsion polymerization process. The ABS‐g‐MA copolymers were used to toughen polyamide 6 (PA‐6). Fourier transform infrared results show that the maleic anhydride (MA) grafted onto the polybutadiene phase of acrylonitrile–butadiene–styrene (ABS). Rheological testing identified chemical reactions between PA‐6 and ABS‐g‐MA. Transmission electron microscopy and scanning electron microscopy displayed the compatibilization reactions between MA of ABS‐g‐MA and the amine and/or amide groups of PA‐6 chain ends, which improved the disperse morphology of the ABS‐g‐MA copolymers in the PA‐6 matrix. The blends compatibilized with ABS‐g‐MA exhibited notched impact strengths of more than 900 J/m. A 1 wt % concentration of MA in ABS‐g‐MA appeared sufficient to improve the impact properties and decreased the brittle–ductile transition temperature from 50 to 10°C. Scanning electron microscopy results show that the shear yielding of the PA‐6 matrix was the major toughening mechanism. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

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.     

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     

Structure–properties relationship in toughening of poly(butylene terephthalate) with core–shell modifier

The performance of acrylonitrile–butadiene–styrene (ABS) core–shell modifier with different grafting degree, acrylonitrile (AN) content, and core–shell ratio in toughening of poly(butylene terephthalate) (PBT) matrix was investigated. Results show PBT/ABS blends fracture in ductile mode when the grafting degree is high, and with the decrease of grafting degree PBT/ABS blends fracture in a brittle way. The surface of rubber particles cannot be covered perfectly for ABS with low grafting degree and agglomeration will take place; on the other hand, the entanglement density between SAN and PBT matrix decreases because of the low grafting degree, inducing poor interfacial adhesion. The compatibility between PBT and ABS results from the strong interaction between PBT and SAN copolymer and the interaction is influenced by AN content. Results show ABS cannot disperse in PBT matrix uniformly when AN content is zero and PBT/ABS fractures in a brittle way. With the addition of AN in ABS, PBT/ABS blends fracture in ductile mode. The core–shell ratio of ABS copolymers has important effect on PBT/ABS blends. When the core–shell ratio is higher than 60/40 or lower than 50/50, agglomeration or cocontinuous structure occurs and PBT/ABS blends display lower impact strength. © 2006 Wiley Periodicals, Inc. J Appl PolymSci 102: 5363–5371, 2006