Interaction of polymerization conditions,structural variables,and mechanical properties of rubber-modified plastics produced from bulk polymerized styrene/poly(butadiene-co-styrene)

Rubber-modified polystyrenes were prepared by bulk polymerization with seven different butadiene–styrene copolymers of differing chemical microstructures. The products were structurally characterized through measurement of the swell ratio, percent insolubles, intrinsic viscosity of the soluble fraction, and transmission electron microscope photomicrographs. Increasing initiator concentration or raising polymerization temperature gives lower molecular weight, higher rubber crosslink density, and decreased grafting. Increasing rubber content generally leads to aggregation. Tensile stress–strain curves and Izod impact strengths were measured. High Izod impact strength and increased elongation to break are favored by increasing matrix molecular weight, rubber content, and extent of grafting.     

高转化率乳聚丁苯橡胶聚合过程中乳液相对分子质量分布与粒径分布考察

采用中石油吉化分公司乳聚丁苯橡胶高转化率大生产配方,考察了实验室聚合反应釜聚合反应单体转化率随反应时间的变化,采用激光粒度分析仪和凝胶渗透色谱仪测定了聚合反应不同单体转化率的胶乳的粒径分布与分子质量分布,结果表明：胶乳粒径呈正态分布,粒径主要集中分布在0.1μm附近,胶乳的平均粒径随反应时间的延长逐渐增大,但是增加的幅度越来越小;聚合反应时间在11 h前（即转化率小于72%）,胶乳的重均分子质量、Z均分子质量一直增大,而数均分子质量变化无明显规律;而分子质量分布宽度指数随反应的进行变小,表明调整的高转化率配方合成的丁苯橡胶可有效改善聚合生成的胶乳粒径分布。     

丙烯超临界聚合中原生晶特征

通过广角X射线衍射(WAXD)对由丙烯超临界聚合和传统本体淤浆法制得的等规聚丙烯原生结晶特征进行了研究,并讨论了聚合工艺、预聚温度、粒径、分子量等对原生晶特征的影响。结果表明,超临界聚合法制备的等规聚丙烯(SC-iPP)呈现出α和γ的混合晶型,而采用传统淤浆法制备的等规聚丙烯(C-iPP)只含有单一α晶型,这是因为超临界的高温高压状态,使得体系传热传质阻力较小,更有利于原生晶型的发展。此外,预聚温度、粒径、分子量等因素也对丙烯超临界聚合所制得的SC-iPP结晶特征有显著影响。     

橡胶粒子尺寸对ABS树脂性能的影响

通过乳液聚合制备了橡胶粒子尺寸为64～420 nm的丙烯腈-丁二烯-苯乙烯(ABS)共聚物.然后将其与SAN-T树脂熔融共混制备橡胶质量分数为15%的ABS树脂.研究了橡胶粒子尺寸对ABS树脂力学性能影响和材料内部形态结构.结果表明:随着橡胶粒子尺寸的增加ABS树脂的冲击韧性提高.当橡胶粒子尺寸在320 nm时,拉伸强度达到最大,ABS树脂的综合性能达到最好.粒子尺寸在64～110 nm时,橡胶粒子在基体内部发生团聚,材料发生脆性断裂.当橡胶粒子尺寸在216～420 nm时,材料主要以韧性断裂为主,发生脆韧转变.具有双峰分布ABS-110nm/ABS-275 nm共混物大、小橡胶粒子间发生明显的协同作用.     

Transition magnitudes and impact improvement in rubber-modified plastics

Impact strength at room temperature and dynamic mechanical properties over a temperature range have been studied for a number of rubber reinforced glassy state plastics. The rubber phases in every case were butadiene copolymers of known composition and particle size and selected for their good dispersion after blending into the various matrices. This dispersion was checked by electron microscopy and the in situ particle size evaluated. The matrices were based on homo- and co-polymers of styrene, methyl methacrylate and acrylonitrile. A vibrating reed apparatus was employed to measure the storage component of Young's modulus (E′) and loss factor (tan δ) at essentially constant frequency (～300 Hz) through the rubber relaxation region. The Izod impact strength was measured in accordance with the standard method ASTM D-256. A gross parallel was found between impact strength and transition magnitude as measured by the change in modulus between ?100°C and 20°C (ΔE′) or the tan δ peak area with, for example, increasing volume fraction of rubber phase. However, when the same rubber was dispersed in different matrices a more subtle effect was an inverse proportionality of tan δ area with E′ measured at the peak temperature. Conversely ΔE′ after correction for matrix modulus change was shown both theoretically and experimentally to be directly proportional to E′ of the matrix at room temperature. The impact strength actually increases with ΔE′ and not with tan δ area in these cases. However, a more important requirement for good impact is compatibility between the rubber and matrix, but neither ΔE′ nor tan δ reflect this. After correction of tan δ areas to constant matrix modulus there remains an increase of area with particle size. Impact strength also increases strongly with particle size for compatible systems. The applicability of Hashin's central equation and Mackenzie's equation in describing the systems is discussed.     

研磨改性废轮胎热解炭黑及其应用研究

本文主要研究采用研磨的方法改性CBp,并将其应用到丁苯橡胶中,对比考察了不同研磨时间的CBp、未改性CBp、N774的粒径分布差异及在丁苯橡胶中的性能差异。研究结果表明：研磨的方法可有效减小CBp的粒径,有助于其在橡胶中更好的分散,且研磨时间越长,炭黑粒子粒径越小,门尼粘度越大,扭矩差越大。研磨后的CBp补强的丁苯橡胶的拉伸强度、撕裂强度、300%定伸强度、硬度得到有效提高,综合改性效果良好。     

Rubber-modified epoxies: III. Influence of the rubber molecular weight on the phase separation process

The effect of varying the rubber molecular weight on the reaction induced phase separation taking place in rubber-modified epoxies is reported. Three butadiene–acrylonitrile copolymers with number-average molecular weights of 2030, 3600 and 6050 g mol^?1 were used. The thermosetting polymer was an epoxy based on diglycidylether of bisphenol-A cured with a cycloaliphatic diamine. Increasing the rubber molecular weight showed the following effects: (i) a decrease in the conversion at the cloud point; (ii) a corresponding decrease in the viscosity at the cloud point; (iii) a primary morphology of a low concentration of particles with a large size; (iv) a more complete segregation of the rubber from the matrix leading to a smaller decrease of the glass transition temperature of the system; (v) a decrease in the toughening. The Flory–Huggins lattice model may be used as a simple approximation to describe the phase separation process when varying the rubber molecular weight.     

Rubber particle agglomeration phenomena in acrylonitrile-butadiene-styrene (ABS) polymers. I. Structure-property relationships study on rubber particle agglomeration and molded surface appearance

The effects of molecular structures of ABS fabricated under a severe molding condition on rubber particle agglomeration and molded specular gloss were studied. An agglomeration index (N_P) obtained by measuring particle size was used to determine the degree of rubber particle agglomeration. It was found that as graft level decreased, agglomeration increased. The rubber particle agglomeration also increased when graft molecular weight was increased. Lowering the particle size also led to a higher degree of agglomeration. Furthermore, increasing the compositional acrylonitrile mismatch between the grafted and matrix styrene-acrylonitrile copolymers increased the rubber particle agglomeration. Molecular structures that increased rubber particle agglomeration decreased the molded gloss. © 1996 John Wiley & Sons, Inc.     

Polyisoprene modified polystyrene

Polyisoprenes have been used to prepare modified polystyrenes in an attempt to improve impact strength. It has been determined that polyisoprene reinforces polystyrene by the formation of complex rubber phase particles, similar to those in commercial polybutadiene reinforced polystyrenes. These particles, however, are subject to breakdown by melt shearing, resulting in a significant drop in impact strength and an increase in tensile strength. This particle destruction is due to the fact that polyisoprene does not crosslink during the polymerization process. It is significant that before shearing these uncrosslinked rubber particles satisfactorily toughen polystyrene.     

Synthesis of functionalized copolymers and their compatibilization effects on acrylonitrile butadiene styrene/poly(butylene terephthalate) blends

In this study, the copolymers of methyl methacrylate-co-glycidyl methacrylate (MGD) with different epoxy contents and molecular weights, the styrene-co-glycidyl methacrylate (SGD) and methyl methacrylate-co-maleic anhydride (MAD) were synthesized. The synthesized copolymers, styrene-co-maleic anhydride (SMA) and styrene-acrylonitrile-co-glycidyl methacrylate (SAG) were used as compatibilizers to enhance the impact strength of the acrylonitrile butadiene styrene/poly(butylene terephthalate) (ABS/PBT). The effects of differences in the structure, reactive group type, and molecular weight of the compatibilizers on the mechanical properties, phase morphology, melt viscosity, thermal stability, and melting temperature of the blend were studied. The results showed that functionalized copolymers were successfully synthesized with high monomer conversions. Addition of the functionalized copolymers increased melt viscosity but did not considerably affect thermal stability, tensile strength, flexural strength and melting temperature of the ABS/PBT blends. The compatibilizers improved the dispersion of the PBT phase and prevented brittle fracture, thereby increasing the impact strength of the blend. Among the studied compositions, the ABS/PBT/MGD-5 blend exhibited the highest impact strength of 25.8 kJ/m² and an appropriate melt flow index of 19.1 g/10 minutes. The compatibilizer should have an appropriate molecular weight to improve the interface bonding force. Regarding the melting viscosity, the reactive group content and compatibilizer dosage should be adjusted to ensure high impact strength.     

Polypropylene–rubber blends: 1. The effect of the matrix properties on the impact behaviour

The effect of matrix properties, i.e. crystallinity and molecular weight, on the impact behaviour of polypropylene–EPDM blends was studied. The blends were made on a twin-screw extruder. The impact strength was determined as a function of temperature, using a notched Izod impact test. The matrix crystallinity was varied by varying the matrix isotacticity, and ranged from 33 to 50 wt%.

With increasing temperature the polymers show a sharp brittle–ductile transition. This brittle–ductile transition temperature (T_bd) shifts to higher temperatures with increasing crystallinity of the polypropylene. However, the balance of properties and the modulus–T_bd relationship were better with blends made with higher crystalline PP.

The matrix molecular weight was decreased by treating a high molecular weight PP–EPDM (85/15 vol%) master blend with peroxide. In this way blends were obtained with a high MFI and a small rubber particle size. The matrix MFI of the blends thus obtained ranged from 2 to 30 dg min⁻¹. With decreasing matrix molecular weight the T_bd increased. The peroxide treated blends exhibited a considerably lower T_bd than comparable blends made in the standard way with a similarly small particle size. Peroxide treatment of a master blend is an effective method of preparing blends with a high MFI, small particle size and good ductility.     

Compatibilization effects of styrenic/rubber block copolymers in polypropylene/polystyrene blends

Compatibilizing effects of styrene/rubber block copolymers poly(styrene‐b‐butadiene‐b‐styrene) (SBS), poly(styrene‐b‐ethylene‐co‐propylene) (SEP), and two types of poly(styrene‐b‐ethylene‐co‐butylene‐b‐styrene) (SEBS), which differ in their molecular weights on morphology and selected mechanical properties of immiscible polypropylene/polystyrene (PP/PS) 70/30 blend were investigated. Three different concentrations of styrene/rubber block copolymers were used (2.5, 5, and 10 wt %). Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) were used to examine the phase morphology of blends. The SEM analysis revealed that the size of the dispersed particles decreases as the content of the compatibilizer increases. Reduction of the dispersed particles sizes of blends compatibilized with SEP, SBS, and low‐molecular weight SEBS agrees well with the theoretical predictions based on interaction energy densities determined by the binary interaction model of Paul and Barlow. The SEM analysis confirmed improved interfacial adhesion between matrix and dispersed phase. The TEM micrographs showed that SBS, SEP, and low‐molecular weight SEBS enveloped and joined pure PS particles into complex dispersed aggregates. Bimodal particle size distribution was observed in the case of SEP and low‐molecular weight SEBS addition. Notched impact strength (a_k), elongation at yield (ε_y), and Young's modulus (E) were measured as a function of weight percent of different types of styrene/rubber block copolymers. The a_k and ε_y were improved whereas E gradually decreased with increasing amount of the compatibilizer. The a_k was improved significantly by the addition of SEP. It was found that the compatibilizing efficiency of block copolymer used is strongly dependent on the chemical structure of rubber block, molecular weight of block copolymer molecule, and its concentration. The SEP diblock copolymer proved to be a superior compatibilizer over SBS and SEBS triblock copolymers. Low‐molecular weight SEBS appeared to be a more efficient compatibilizer in PP/PS blend than high‐molecular weight SEBS. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 291–307, 1999     

Compatibilization efficacy of poly(isoprene–butyl acrylate) block copolymers in natural/acrylic rubber blends

Poly(isoprene–butyl acrylate) block copolymers with a variety of molecular weights and compositions were prepared via a controlled free‐radical polymerization with an iniferter. Subsequently, the block copolymers were used as compatibilizers in natural/acrylic rubber blends. Scanning electron micrographs revealed a cocontinuous morphology in the case of the normal blends with a low natural rubber content (20 wt %), whereas the blends that contained more natural rubber showed a dispersed‐particle morphology. When the rubbers were blended with 5 wt % block copolymer, the particle size decreased, and the tensile strength of the resulted blends increased, regardless of the block copolymer characteristics. For the blend that exhibited a cocontinuous morphology, the most effective compatibilizer was the block copolymer with an average molecular weight of 22,000 g/mol, containing mainly (87%) polyisoprene block. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 921–927, 2003     

橡胶相结构特征对ABS树脂力学性能的影响

采用乳液聚合法合成了具有橡胶结构特征的丙烯腈丁二烯苯乙烯共聚物（ABS）,将其与苯乙烯丙烯腈共聚物（SAN）共混,制备了ABS/SAN共混物,并系统地研究了橡胶相结构特征的影响因素及其对共混物力学性能及其形变机理的影响。结果表明,随着聚丁二烯（PB）橡胶粒子粒径的增大,共混物的冲击强度提高,拉伸强度降低;随着橡胶粒子粒径的增大,共混物形变机理从单一的银纹向橡胶粒子空洞化诱发基体剪切屈服转变。     

Bio‐based diblock copolymers prepared from poly(lactic acid) and natural rubber

New bio‐based diblock copolymers were synthesized from poly(lactic acid) (PLA) and natural rubber (NR). NR polymer chains were modified to obtain hydroxyl telechelic natural rubber oligomers (HTNR). Condensation polymerization between PLA and HTNR was performed at 110°C during 24 or 48 h. The molecular weight of PLA and HTNR and the molar ratio PLA : HTNR were varied. The new ester linkage in the diblock copolymers was determined by ¹H‐NMR. The molecular weight of the diblock copolymers determined from SEC agreed with that expected from calculation. The thermal behavior and degradation temperature were determined by DSC and TGA, respectively. The diblock copolymers were used as a toughening agent of PLA and as a compatibilizer of the PLA/NR blend. PLA blended with the diblock copolymer showed higher impact strength, which was comparable to the one of a PLA/NR blend. The former blend showed smaller dispersed particles as showed by SEM images, indicating the increase in miscibility in the blend due to the PLA block. The compatibilization was effective in the blends containing ～10 wt % of rubber. At a higher rubber content (>10 wt %), coalescence of the NR and diblock copolymer was responsible of the larger rubber diameter in the blends, which causes a decrease of the impact strength. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41426.     

Eigenschaftskennfunktionen thermisch hergestellter polystyrole unterschiedlichen molekulargewichts und unterschiedlicher molekulargewichtsverteilung

Mechanical properties and melt flow behaviour have been measured on thermal polystyrenes in order to study the effect of different molecular weight and different molecular weight distribution. The mechanical properties (impact strength, tensile strength and flexural strength) were found to depend upon a critical molecular weight M_w = 1.5 × 10⁵, where the polystyrenes reached ultimate strength. An influence of molecular weight distribution only can be observed when the average molecular weight is near the critical molecular weight limit. The broader the distribution, the poorer are mechanical properties. Injection molded specimens with different molecular weight distribution but equal average molecular weight showed different molecular orientation and different anisotropic mechanical properties. On the basis of equal orientation the narrow distributed specimens showed higher mechanical strength in direction of orientation. The broader the distribution, the higher the elastic properties of melt. An optimum of physical properties and ease of fabrication will be obtained with narrow molecular weight distributed polystyrenes with an average molecular weight slightly above the critical molecular weight limit.     

Toughness enhancement of poly(lactic acid) by melt blending with natural rubber

Rubber toughened poly(lactic acid) (PLA) was prepared by blending with natural rubber (NR)‐based polymers. The blends contained 10 wt % of rubber and melt blended with a twin screw extruder. Enhancement of impact strength of PLA was primarily concernced. This study was focused on the effect of rubber polarity, rubber viscosity and molecular weight on mechanical properties of the blends. Three types of rubbers were used: NR, epoxidized natural rubber (ENR25 and ENR50), and natural rubber grafted with poly(methyl methacrylate) (NR‐g‐PMMA). Effect of viscosity and molecular weight of NR, rubber mastication with a two‐roll mill was investigated. It was found that all blends showed higher impact strength than PLA and NR became the best toughening agent. Viscosity and molecular weight of NR decreased with increasing number of mastication. Impact strength of PLA/NR blends increased after applying NR mastication due to appropriate particle size. DMTA and DSC characterization were determined as well. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

The effect of the architecture and concentration of styrene–butadiene compatibilizers on the morphology of polystyrene/low‐density polyethylene blends

The effect of styrene–butadiene block copolymers (SB) with varying number of blocks and length of styrene blocks on the morphology, rheology, and impact strength of 4/1 polystyrene/low‐density polyethylene (PS/LDPE) blends was studied. The scanning and transmission electron microscopy and X‐ray scattering were used for determination of the size of LDPE particles and the localization and structure of SB copolymers in blends. It is shown that the dependence of the LDPE particle size on the amount of added SB and localization of SB copolymers in blends is predominantly controlled by the length of their styrene blocks. It follows from thermodynamic considerations that the reason is the difference in composition asymmetry between SB with short and long styrene blocks. Coalescence of particles of SB having short styrene blocks at the surface of LDPE droplets and movement of SB with long styrene blocks to the PS–LDPE interface were observed during annealing of PS/LDPE/SB blends. Pronounced migration of SB copolymer during annealing shows that their localizations in blends in steady state on long steady mixing and at thermodynamic equilibrium are different. The values of tensile impact strength of PS/LDPE/SB blends correlate well with the size of LDPE particles and the amount of SB at the interface. Viscosity of PS/LDPE/SB depends on molecular structure of SB copolymers by a manner different from that of tensile impact strength. The results of this study and literature data lead to the conclusion that the compatibilization efficiency of SB copolymers for a certain polystyrene‐polyolefin pair is a function of not only molecular parameters of SB but also of the polystyrene/polyolefin ratio, the amount of SB in a blend, and mixing and processing conditions. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2803–2816, 2006     

Evaluation of the interfacial state in high impact polystyrene through dynamic mechanical analysis as a function of the synthesis conditions

High impact polystyrene was synthesized using two series of styrene/butadiene (SB) tapered block copolymers with a polystyrene (PS)/polybutadiene (PB) composition of 30/70 and 10/90 wt%. During the synthesis, concentration of initiator, SB and transfer agent were varied. From dynamic mechanical analysis, the corresponding α relaxation of the rubber phase was detected at low temperature (near ?100°C) and that of the glassy PS phase at high temperature (near 100°C). Also, another relaxation at temperature near 40°C was identified, which was associated to the β relaxation of the glassy PS phase. The variations found in the α relaxation of the rubber phase, were attributed to changes in the morphological structure as a consequence of variation in initiator, SB or transfer agent concentrations and in SB composition. β relaxation showed a strong dependency with the interfacial state between the rubber and the glassy phase, where an increase in the amount of graft PS at the interface, which promotes the interfacial adhesion between phases, causes an increase in the magnitude of β relaxation of the PS phase. The results were attributed to variations in the interfacial area as a result of the change in the particle size and to the contribution of molecular chains of each phase in participating in the relaxation process. POLYM. ENG. SCI., 47:1827–1838, 2007. © 2007 Society of Plastics Engineers     

Properties of a new synthetic rubber: High‐trans 1,4‐poly(butadiene‐co‐isoprene) rubber

A high‐trans 1,4‐butadiene/isoprene copolymer (TBIP) was synthesized in a 5‐L autoclave with hydrogen as an effective molecular weight modifier. The effects of hydrogen on the catalyst efficiency and molecular weight of the copolymers were investigated. The processability and physicomechanical properties of TBIP and their relationship to the composition, composition distribution, and molecular weight of TBIP were examined in detail. Increasing the H₂ pressure effectively reduced the molecular weight of TBIP. The optimum Mooney viscosity of TBIP and the 1,4‐butadiene molar content in the feed were 30–50 and 5–25%, respectively. No cis–trans isomerization was observed during the roll processing procedure for TBIP. The vulcanization characteristics of TBIP were similar to those of general rubbers, and no reverse vulcanization was observed for TBIP. A high green strength was the typical characteristic of TBIP. Vulcanized TBIP (TBIR) with an optimum composition and molecular weight presented outstanding antifatigue properties and low heat buildup in comparison with general rubbers. Compared with general sidewall stock [natural rubber (NR)/butadiene rubber (BR) = 50/50], TBIR exhibited a greater than 15‐fold increase in its crack‐initiation resistance. The other mechanical properties of TBIR were similar to those of 50/50 NR/BR. The heat‐aging mechanism of TBIR was crosslinking aging. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2941‐2948, 2004