Synthesis of EPDM-graft-methyl methacrylate and styrene and its toughening effect on MS resin

EPDM-graft-methyl methacrylate and styrene (EPDM-g-MS), a toughen agent for MS resin, was synthesized by solution graft copolymerization of methyl methacrylate (MMA) and styrene (St) onto ethylene-proplene-diene terpolymer (EPDM) in toluene/n-heptane cosolvent using benzoyl peroxide (BPO) as an initiator. The effects of reaction conditions on the graft copolymerization were discussed. EPDM-g-MS/MS resin blends, a novel high impact engineering plastic, was prepared by melt blending EPDM-g-MS and MS resin. The toughening effect of EPDM-g-MS on MS resin was investigated. The results showed that the optimized reaction conditions were EPDM/MMA-St ratio of 50/50, MMA/St ratio of 75/25, initiator dosage of 1%, reactant concentration of 20%, toluene/n-heptane ratio of 75/25, at 80 °C for 20h, and EPDM-g-MS with the higher EPDM content (56.8%) and grafting ratio (52.8%) was obtained under the optimized reaction conditions. SEM analysis showed that EPDM-g-MS had good compatibility with MS resin. EPDM-g-MS had excellent toughening effect on MS resin and could be used for toughen agent of MS resin.     

Novel multimonomer‐grafted polypropylene preparation and application in polypropylene/poly(vinyl chloride) blends

A novel grafted polymer was prepared in one step through free‐radical melt grafting in a single‐screw extruder. It was shown that the addition of styrene (St) to the melt‐grafting system as a comonomer could significantly enhance the grafting degree of methyl methacrylate (MMA) onto polypropylene (PP) and reduce the degradation of the PP matrix by means of Fourier transform infrared and melt flow rate testing, respectively. Then, the potential of using multimonomer‐grafted PP, which was designated PP‐g‐(St‐co‐MMA), as the compatibilizer in PP/poly(vinyl chloride) (PVC) blends was also examined. In comparison with PP/PVC blends, the average size of the dispersed phase was greatly reduced in grafted polypropylene (gPP)/PVC blends because of the addition of the PP‐g‐(St‐co‐MMA) graft copolymer. The tensile strength of the gPP/PVC blends increased significantly, and the impact strength was unchanged from that of the pure PP/PVC blends. The results of differential scanning calorimetry and scanning electron microscopy suggested that the compatibility of the PP/PVC blends was improved. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

EPDM/St‐An graft copolymerization reaction behavior by phase inversion emulsion and the toughness effect of EPDM‐g‐SAN on SAN resin

Styrene‐EPDM‐acrylonitrile tripolymer (EPDM‐g‐SAN) was synthesized by the graft copolymerization of styrene (St) and acrylonitrile (An) onto ethylene‐propylene‐diene terpolymer (EPDM) with “phase inversion” emulsification technique. The high impact strength engineering plastics AES was the blend of SAN resin and EPDM‐g‐SAN, which occupied good weathering and yellow discoloration resistivity. The effects of An percentage in comonomer and the weight proportion of EPDM to St‐An on graft copolymerization behavior and AES notched impact strength were studied. The results showed that monomer conversion ratio (CR) exhibited a peak when the An percentage changed, and the maximum value was 97.5%. Grafting ratio (GR) and grafting efficiency (GE) enhance as well. The notched impact strength of AES presented a peak with the maximum value of 53.0 KJ/m², when An percentage was at the range of 35–40%. The spectra of FTIR showed that St and An were graft onto the EPDM. DSC analysis illuminated that T_g of EPDM phase in the blends was lower than that of the pure EPDM. TEM and SEM micrographs indicated that the polarity of g‐SAN of EPDM‐g‐SAN was the main factor effect the particle morphology, in terms of size, distribution and isotropy. When weight ratio of St to An was 65/35, the polarity of g‐SAN chains was appropriate, and the EPDM‐g‐SAN particles dispersed well in the SAN matrix. The super impact toughness is interpreted in terms of EPDM phase cavitation and enhanced plastic shear yielding. The highest toughness occurs at an optimum EPDM‐g‐SAN phase particle size which is about 0.2 μm in SAN resin matrix. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

EPDM-g-MS对MS树脂的增韧作用

用溶液聚合法合成三元乙丙橡胶（EPDM）与甲基丙烯酸甲酯（MMA）及苯乙烯（St）接枝共聚物（EPDM-g-Ms），用其与MMA／St共聚物（Ms树脂）共混制备高抗冲塑料（MES），研究了EPDM-g-MS对MS树脂的增韧作用，用扫描电子显微镜（SEM）和透射电子显微镜（TEM）对MES的微观相结构进行了分析。结果表明：EPDM-g-MS的接枝率、接枝链的极性及EPDM在MES中的含量是影响其对MS树脂增韧效果的主要因素。增加EPDM-g-MS的接枝率、增强其接枝链的极性及增加其用量均可提高MES的缺口冲击强度。MES相结构的TEM分析和冲击断面形态的SEM分析表明，随着EPDM在MES中的含量的增加，EPDM-g-MS分散相的粒径增大，粒面距离缩短，导致IVIES的增韧机理由空穴化向轻度剪切屈服转变，IVIES的缺口冲击强度随之而提高。     

The study of polystyrene blends: The relationship of phases and structure in blends of polystyrene with ethylene–propylene diene monomer rubber and its grafted copolymer

Pressed films of blends of polystyrene (PS) with ethylene–propylene diene monomer rubber (EPDM) or grafted copolymer of styrene (St) onto EPDM (EPDM-g-St) rubber were examined by small-angle X-ray scattering (SAXS), and scanning electron microscope (SEM). Small-angle X-ray scattering from the relation of phase was analyzed using Porod's Law and led to value of interface layer on blends. The thickness of interface layer (σ_b) had a maximum value at 50/50 (PS–EPDM-g-St) on blends. The radius of gyration of dispersed phase (domain) and correlation distances a_c in blends of PS–EPDM-g-St were calculated using the data of SAXS. The morphology and structure of blends were investigated by SEM. © 1998 John Wiley & Sons, Inc. J. Appl. Polym. Sci. 70: 805–810, 1998     

EPDM-g-MS/MS共混物的热性能及流变性能

用溶液聚合法合成的EPDM（乙烯／丙烯／二烯共聚物）与MMA（甲基丙烯酸甲酯）及St（苯乙烯）接枝共聚物（EP—DM—g—MS）与MS（苯乙烯-甲基丙烯酸甲酯共聚物）树脂共混制备MES（EPDM—g—MS增韧MS），通过热重分析研究了MES的热稳定性，通过测试MES的表观粘度、非牛顿指数和粘流活化能等流变参数，分析其流变性能。结果表明，MES具有较好的耐热性能，且随EPDM-g—MS含量及MMA／St配比的增加而提高。MES的非牛顿指数小于1，符合假塑性流体流动规律。其表观粘度随剪切速率和温度升高而降低，随EPDM-g—MS含量增加而提高。MES的粘流活化能小于MS树脂的。     

Graft copolymerization of styrene and acrylonitrile onto EPDM

Acrylonitrile–EPDM–styrene (AES) graft copolymers were synthesized by solution graft polymerization of styrene (St) and acrylonitrile (AN) onto EPDM in an n‐hexane/benzene solvent with benzoyl peroxide (BPO) as an initiator. The structure changes were studied by an FTIR spectrophotometer. The grafting parameters were calculated gravimetrically. The influence of the polymerization conditions, such as the reaction time, concentration of the initiator, EPDM content, and weight ratio of St/AN, on the structure of the products was investigated. It was found that a proper initiator concentration and EPDM content will give a high grafting ratio of the AES resin. The thermal property of the copolymer was studied using programmed thermogravimetric analysis (TGA). The results showed that the copolymer has a better heat‐resistant property than that of ABS, especially for the initial decomposition temperature (T_in) and the maximum weight loss rate temperature (T_max). Also, the mechanism of the graft reaction was discussed. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 428–432, 2002     

Study on the relaxation of polystyrene,ethylene–propylene diene monomer,and the blends of polystyrene with ethylene–propylene diene monomer by thermally stimulated current

A thermally stimulated current (TSC) was used to study the relaxation of polystyrene (PS), the ethylene–propylene diene monomer (EPDM), and the grafted copolymer of EPDM with styrene (EPDM-g-St). The effect of the measuring conditions on the relaxation of PS is discussed. Some relaxation parameters of PS, EPDM, and EPDM-g-St were calculated in two different ways. In addition, the TSC spectra of PS/EPDM and PS/EPDM-g-St showed that PS/EPDM was an immiscible system, but there existed a special interaction between the plastic phase and the rubber one in PS/EPDM-g-St blends. The compatibility of PS blends was evaluated in terms of their compositions. The results of inverse gas chromatography (IGC) agreed well with those of the TSC measurements. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 67:1199–1204, 1998     

Synthesis of high rubber styrene–EPDM–acrylonitrile graft copolymer and its toughening effect on SAN

High rubber styrene–EPDM–acrylonitrile (AES) was prepared by the graft copolymerization of styrene (St) and acrylonitrile (AN) onto ethylene–propylene–diene terpolymer (EPDM) in n‐heptane/toluene cosolvent using benzoyl peroxide as an initiator. The effects of reaction conditions, such as reaction temperature, initiator concentration, EPDM content, the solvent component, and reaction time, on the graft copolymerization are discussed. In addition, according to the research on mechanical properties of the SAN/AES blend, a remarkable toughening effect of AES on SAN resin was found. By means of scanning electron microscopy, the toughening mechanism is proposed to be crazing initiation from rubber particles and shear deformation of SAN matrix. Uniform dispersion of rubber particles, as shown by transmission electron microscopy, is attributed to the good compatibility of SAN and AES. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 416–423, 2004     

Study of multi‐monomer melt‐grafting onto polypropylene in an extruder

Free‐radical melt‐grafting of the dual‐monomer systems glycidyl methacrylate–styrene (GMA‐St) and hydroxyethyl methacrylate–styrene (HEMA‐St) onto polypropylene (PP) has been studied using a single‐screw extruder. For single monomer grafting systems, degradation of PP was unavoidable and deterioration of the mechanical properties of the grafted PP subsequently occurred because of β‐scission of PP chains during the free‐radical melt‐grafting process. However, for the dual‐monomer systems, it is shown that the addition of styrene as a comonomer can significantly enhance the GMA or HEMA grafting levels on PP and reduce the extent of β‐scission of PP backbone. It has been found that the grafting degree of dual‐monomer melt‐grafted PP, such as PP‐g‐(GMA‐co‐St) or PP‐g‐(HEMA‐co‐St), is about quadruple that of single‐monomer grafted PP for the same monomer and dicumyl peroxide concentrations. Moreover, the melt flow rate of the dual‐monomer grafted PP is smaller than that of the unmodified PP. Hence, PP not only was endowed with higher polarity, but also kept its good mechanical properties. © 2000 Society of Chemical Industry     

Blends of poly(vinyl chloride) (PVC)/natural rubber‐g‐(styrene‐co‐methyl methacrylate) for improved impact resistance of PVC

To improve the mechanical properties of poly(vinyl chloride) (PVC), the possibility of combining PVC with elastomers was considered. Modification of natural rubber (NR) by graft copolymerization with methyl methacrylate (MMA) and styrene (St) was carried out by emulsion polymerization by using redox initiator to provide an impact modifier for PVC. The impact resistance, dynamic mechanical analysis (DMA), and scanning electron microscopy (SEM) of St and MMA grafted NR [NR‐g‐(St‐co‐MMA)]/PVC (graft copolymer product contents of 5, 10, and 15%) blends were investigated as a function of the amount of graft copolymer product. It was found that the impact strength of blends was increased with an increase of the graft copolymer product content. DMA studies showed that NR‐g‐(St‐co‐MMA) has partial compatibility with PVC. SEM confirmed a shift from brittle failure to ductility with an increase graft copolymer content in the blends. The mechanical properties showed that NR‐g‐(St‐co‐MMA) interacts well with PVC and can also be used as an impact modifier for PVC. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 1666–1672, 2004     

Toughening of nylon 6 with grafted rubber impact modifiers

Recent work has shown that nylon 6/acrylonitrile–butadiene–styrene (ABS) blends can be made tough by the addition of some polymer additives that are chemically reactive with nylon 6 and physically compatible with the styrene-acrylonitrile copolymer (SAN) phase of ABS. Imidized acrylic polymers (IA) represent a successful example of such additives that improve the dispersion of ABS in the nylon 6 matrix and render the blends tough. This article examines the possibility of toughening nylon 6 with ethylene/propylene/diene elastomer grafted with SAN copolymer (EPDM-g-SAN). This EPDM-g-SAN consists of 50% rubber and 50% SAN by weight. However, it was found that the same IA that works well to disperse ABS materials of similar rubber content is not as effective for EPDM-g-SAN, primarily because the EPDM forms the continuous phase, not SAN, and, thus, interfaces with nylon 6 during melt blending. Maleated elastomers like maleic anhydride grafted ethylene–propylene copolymer (EPR-g-MA) and styrene–(ethylene-co-butylene)–styrene triblock copolymer (SEBS-g-MA) were more effective for dispersing EPDM-g-SAN in the nylon 6 matrix than IA. Various mechanisms that improve the dispersion are discussed. © 1995 John Wiley & Sons, Inc.     

Mechanical and aging resistance performance of acrylic sheets containing EPDM-graft-poly(styrene-co-methyl methacrylate)

The addition of ethylene-propylene-diene rubber (EPDM) into acrylic sheets was expected to enhance their thermal and UV aging resistance for outdoor applications. According to the dissimilar polarity of EPDM and styrene (ST)/methyl methacrylate (MMA) monomer mixture (20/80% (w/w)) used for preparation of acrylic sheets, this research aimed to modify EPDM via graft copolymerization with ST and MMA to increase its compatibility. The graft copolymerization of ST and MMA at a ST/MMA ratio of 25/75% (w/w) onto EPDM was carried out in the solution polymerization initiated by benzoyl peroxide at 90 °C for 16 h, resulting in 88.1% grafting efficiency. The addition of 1.0–3.0% (w/w) of graft EPDM (GEPDM) into the acrylic sheets increased their impact strength (~ 17–22%), but decreased their flexural strength (~ 12–36%). However, their mechanical properties were improved after thermal and UV aging. Scanning electron microscopy (SEM) based analysis of the modified acrylic sheets revealed that the fracture surface shifted from brittle to ductile failure characteristics after modification. The thermogravimetric analysis results also exhibited that the addition of GEPDM improved the thermal and UV resistance of the modified acrylic sheets by increasing their initial decomposition temperature and activation energy of thermal decomposition.     

EPDM／St-AN相反转乳液接枝共聚合及AES的结构与性能

以过氧化二苯甲酰为引发剂,正庚烷为溶剂,用"相反转"乳液共聚合法合成了三元乙丙橡胶和苯乙烯-丙烯腈(St-AN)的接枝共聚物(EPDM-g-SAN),并与苯乙烯-丙烯腈共聚物(SAN)熔融共混(共混物简称 AES)。研究了丙烯腈 AN 在共单体中的含量和 EPDM/St-AN 的质量比对单体转化率、接枝率和接枝效率的影响。冲击实验表明,AN 含量为35%～40%时,接枝率约为35%,所制备的 EPDM-g-SAN 对 SAN 树脂有显著的增韧作用,增韧后所制得的工程塑料 AES 的悬臂梁缺口冲击强度最高可达50.7 kJ/m~2;差示扫描量热分析表明 AES 存在界面相;动态热力学分析表明 EPDM-g-SAN 与 SAN 树脂之间的相界面结合紧密;透射电镜和扫描电镜分析表明,AN 在共单体中的含量为35%时,EPDM-g-SAN 在 SAN 树脂基体中有良好的分散性,相界面模糊,因而两相结合紧密,其增韧机理以空穴化为主兼有剪切屈服。     

悬浮接枝共聚合成POE-g-MAS及其对SAN树脂的增韧作用

合成了乙烯-辛烯共聚物(POE)和甲基丙烯酸甲醋(MMA)-丙烯腈(SAN)-苯乙烯(St)的接枝共聚物(POE-g-MAS)。研究了单体比率、POE/单体比率和引发剂浓度等因素对接枝共聚合反应的影响。聚合产物用丙酮抽提得到接枝共聚物POE-g-MAS,傅里叶变换红外光谱分析证明MMA-AN-St已经接枝在POE分子链上。用POE-g-MAS与Stet树脂共混制备了具有高抗冲性能的POE-g-SAN/SAN共混物,并用扫描电镜观察共混物的冲击断面,探讨了其增韧机理。     

Preparation of microwave radiation induced graft copolymers and their applications as reinforcing material in phenolic composites

Flax fiber was modified through grafting of binary vinyl monomers mixtures such as methyl methacrylate (MMA)/vinyl acetate (VA), MMA/acrylamide (AAm), and MMA/styrene (Sty) under the influence of microwave radiations. 24.64% grafting was found at 210 W microwave power under optimum reaction conditions. Graft copolymers obtained were characterized with FTIR spectroscopy, scanning electron microscopy, and TGA/DTA techniques. Graft copolymers were found to be moisture retardant with better tensile strength. Phenolic composites using graft copolymers vis‐à‐vis flax as reinforcing material were subjected for the evaluation of different mechanical properties such as wear resistance, tensile strength, compressive strength, modulus of rupture (MOR), modulus of elasticity (MOE), and stress at the limit of proportionality (SP). Composites reinforced with graft copolymers showed better mechanical properties in comparison to composites reinforced with flax. Phenolic composites reinforced with Flax‐g‐poly(MMA/Sty) showed maximum wear resistance followed by reinforcement with flax, Flax‐g‐poly (MMA/AAm), and Flax‐g‐poly(MMA/VA). Composites reinforced with Flax‐g‐poly(MMA/Sty) and flax fibers have been found to show 150 N tensile strength with extension of 3.94 and 2.17 mm, respectively. It has also been found that composites reinforced with Flax‐g‐poly(MMA/Sty) showed maximum compressive strength (1,000 N) with compression of 3.71 mm in comparison to other graft copolymers and flax fibers reinforcement. Reinforcement of phenolic resin with Flax‐g‐poly(MMA/Sty) and flax fibers could improve the MOR and MOE. POLYM. COMPOS., 2008. © 2008 Society of Plastics Engineers     

复合引发剂引发GMA熔融接枝聚1-丁烯

采用复合引发剂用Haake流变仪研究了甲基丙烯酸缩水甘油酯(GMA)-苯乙烯(St)多组分单体熔融接枝高全同聚1-丁烯(iPB)。用傅里叶变换红外光谱对接枝物进行了分析,并分别考察了复合引发剂比例、GMA用量、引发剂总用量和St用量对接枝的影响。结果表明:在复合引发剂引发下,GMA和iPB可熔融接枝,接枝率最高可达1.74%;St作为共单体可明显提高GMA的接枝率和接枝效率,当n(St)/n(GMA)为1.5时,接枝率为单独使用GMA时的2.3倍。     

Melt grafting of maleic anhydride onto polypropylene with 1‐decene as a second monomer

The influence of 1‐decene as the second monomer on the melt‐grafting behavior of maleic anhydride (MAH) onto polypropylene (PP) was studied with differential scanning calorimetry and Fourier transform infrared spectroscopy. We found that the value of the grafting degree increased from 0.68% for pure MAH‐g‐PP to 1.43% for the system with a 1‐decene/MAH molar ratio of 0.3, whereas the maximum value with styrene (St) as the second monomer was 0.98% under an St/MAH molar ratio of 1.0. Compared with the contribution of St/MAH‐g‐PP to the peeling strength between the PP and polyamide (PA) layer for a PP/PA laminated film, the introduction of 1‐decene/MAH‐g‐PP increased the peeling strength from 180 g/15 mm to 250 g/15 mm. 1‐Decene inhibited the chain scission behavior of PP. 1‐Decene reacted with MAH to form a 1‐decene/MAH copolymer or the Alder‐ene reaction product before the two monomers grafted onto PP. The grafting of the reactive product onto PP greatly improved the grafting degree of MAH. What is more, because of the similar chemical structures of 1‐decene and PP, the affinity of 1‐decene with PP was higher than that of St. Compared with St, the introduction of less 1‐decene led to a higher grafting degree and higher peeling strength. Therefore, we concluded that 1‐decene was more effective for improving the grafting degree of MAH onto PP. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Poly(styrene)‐ and Poly(styrene‐co‐methyl methacrylate)‐graft‐hydrogenated natural rubber latex: Aspect on synthesis,properties, and compatibility

The undesirable properties of natural rubber (NR) can be improved via hydrogenation and graft copolymerization. Hydrogenated NR (HNR) latex was prepared via diimide reduction and then grafted with styrene (ST) or ST/methyl methacrylate (MMA) to form poly(ST)‐graft‐HNR (poly(ST)‐g‐HNR, GHNRS) or poly(ST‐co‐MMA)‐g‐HNR (GHNRSM), respectively. For the grafting of ST monomer onto HNR particles, the %monomer conversion and %grafting efficiency (%GE) were monitored as functions of %hydrogenation, monomer and initiator concentrations, temperature, and time. Under the optimum condition (HNR with 54.3% hydrogenation; 100 phr of ST, 1 phr of initiator at 50°C for 8 h), maximum %conversion and %GE of 44.6% and 36.9%, respectively, were achieved. Thermogravimetric analysis revealed that the HNR grafted with ST or ST/MMA had higher decomposition temperature than an ungrafted one. When these graft products were blended at 10% (w/w) with acrylonitrile‐butadiene‐styrene (ABS) resin, the GHNRS/ABS and GHNRSM/ABS composites exhibited the higher flexural strength and heat aging tolerance compared to the ungrafted HNR/ABS composite. Scanning electron microscopy (SEM) also showed the higher degree of homogeneity at the fractural surface, supporting the higher compatibility between the ABS and the GHNRS or GHNRSM phases in the blends. J. VINYL ADDIT. TECHNOL., 22:100–109, 2016. © 2014 Society of Plastics Engineers     

Photografting of PVC containing N,N‐diethyldithiocarbamate groups with vinyl monomers

Poly(vinyl chloride) (PVC) with pendent N,N‐diethyldithiocarbamate groups (PVC–SR) was prepared through the reaction of PVC with sodium N,N‐diethyldithiocarbamate (NaSR) in butanone and used as a photoinitiator for the grafting polymerization of three vinyl monomers [styrene (St), methyl methacrylate (MMA), and acrylamide (Am)]. The effects of ultraviolet (UV) irradiation time, PVC–SR amount, and the monomer amount on grafting and grafting efficiency were investigated. The results showed that PVC–SR could initiate the polymerization of three vinyl monomers effectively and obtained crosslinked copolymers. The grafting and grafting efficiency of styrene and methyl methacrylate were higher than those of acrylamide. The polymerization activity of three monomers was acrylamide > methyl methacrylate > styrene. By analyzing the UV spectrum of PVC–SR with a different irradiation time, it was confirmed that PVC–SR was dissociated mainly into macromolecular the sulfur radical PVC–S · and the small molecular carbon radical · C(S)N(C₂H₅)₂; the grafting polymerization mechanism was discussed. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 2569–2574, 2000