BR和DCP在PS／LLDPE／SBS体系中的协同作用

ＢＲ和ＤＣＰ在ＰＳ／ＬＬＤＰＥ／ＳＢＳ体系中的协同作用方征平，许承威，项义崇（杭州大学化学系，杭州，３１００２８）关键词聚苯乙烯，聚乙烯，共混物，相分散－交联协同作用相分散（增容）－交联协同作用是提高不相容聚合物共混物性能的有效方法，我们曾将此方法成...     

聚苯乙烯/聚乙烯的反应性挤出共混

多官能团单体;聚苯乙烯/聚乙烯的反应性挤出共混     

Block copolymers as compatibilizers for blends of linear low density polyethylene and polystyrene

Compatibilization of blends of linear low-density polyethylene (LLDPE) and polystyrene (PS) with block copolymers of styrene (S) and butadiene (B) or hydrogenated butadiene (EB) has been studied. The morphology of the LLDPE/PS (50/50) composition typically with 5% copolymer was characterized primarily by scanning electron microscopy (SEM). The SEB and SEBS copolymers were effective in reducing the PS domain size, while the SB and SBS copolymers were less effective. The noncrystalline copolymers lowered the tensile modulus of the blend by as much as 50%. Modulus calculations based on a coreshell model, with the rubbery copolymer coating the PS particle, predicted that 50% of the rubbery SEBS copolymer was located at the interface compared to only 5–15% of the SB and SBS copolymers. The modulus of blends compatibilized with crystalline, nonrubbery SEB and SEBS copolymers approached Hashin's upper modulus bound. An interconnected interface model was proposed in which the blocks selectively penetrated the LLDPE and PS phases to provide good adhesion and improved stress and strain transfer between the phases. © 1995 John Wiley & Sons, Inc.     

Nanostructured carbon black filled polypropylene/polystyrene blends containing styrene-butadiene-styrene copolymer: Influence of morphology on electrical resistivity

This paper is part of a comprehensive study on using selective localization of carbon black (CB) at the interface of immiscible polymer blends in order to reduce the percolation threshold concentration and enhance the conductivity of the blends. CB was successfully localized at the interface of polypropylene/polystyrene (PP/PS) blend by introducing styrene-butadiene-styrene (SBS) tri-block copolymer to the blend. In CB-PP/PS/SBS blends, CB has higher affinity for the polybutadiene (PBD) section of the SBS copolymer, whereas in CB-PP/PS blends, CB prefers the PS phase. PP/PS interface is one of the preferred locations for the SBS copolymer in the (PP/PS) blend; at which the PBD section of the SBS copolymer forms a few nanometers thick layer able to accommodate the CB nano-particles. The influence of SBS addition on the morphology and electrical properties of various PP/PS blends filled with 1 vol% CB were studied. SBS influence on the conductivity of PP/PS blends was found to be a function of the PP/PS volume ratio and SBS loading. The most dramatic increase in conductivity was found in the (60/40) and (70/30) PP/PS blends upon the addition of 5 vol% SBS. 5 vol% SBS was found to be the optimum loading for most blends. Using 10 vol% of SBS was reported to deteriorate electrical conductivity of the conductive co-continuous PP/PS blends. For all blends studied, SBS addition was found to compatibilize the blends. Finer morphologies were obtained by increasing SBS loading.     

Morphology,structure, and properties of in situ compatibilized linear low‐density polyethylene/polystyrene and linear low‐density polyethylene/high‐impact polystyrene blends

Blends of linear low‐density polyethylene (LLDPE) with polystyrene (PS) and blends of LLDPE with high‐impact polystyrene (HIPS) were prepared through a reactive extrusion method. For increased compatibility of the two blending components, a Lewis acid catalyst, aluminum chloride (AlCl₃), was adopted to initiate the Friedel–Crafts alkylation reaction between the blending components. Spectra data from Raman spectra of the LLDPE/PS/AlCl₃ blends extracted with tetrahydrofuran verified that LLDPE segments were grafted to the para position of the benzene rings of PS, and this confirmed the graft structure of the Friedel–Crafts reaction between the polyolefin and PS. Because the in situ generated LLDPE‐g‐PS and LLDPE‐g‐HIPS copolymers acted as compatibilizers in the relative blending systems, the mechanical properties of the LLDPE/PS and LLDPE/HIPS blending systems were greatly improved. For example, after compatibilization, the Izod impact strength of an LLDPE/PS blend (80/20 w/w) was increased from 88.5 to 401.6 J/m, and its elongation at break increased from 370 to 790%. For an LLDPE/HIPS (60/40 w/w) blend, its Charpy impact strength was increased from 284.2 to 495.8 kJ/m². Scanning electron microscopy micrographs showed that the size of the domains decreased from 4–5 to less than 1 μm, depending on the content of added AlCl₃. The crystallization behavior of the LLDPE/PS blend was investigated with differential scanning calorimetry. Fractionated crystallization phenomena were noticed because of the reduction in the size of the LLDPE droplets. The melt‐flow rate of the blending system depended on the competition of the grafting reaction of LLDPE with PS and the degradation of the blending components. The degradation of PS only happened during the alkylation reaction between LLDPE and PS. Gel permeation chromatography showed that the alkylation reaction increased the molecular weight of the blend polymer. The low molecular weight part disappeared with reactive blending. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 1837–1849, 2003     

Thermomechanical and shape memory properties of SCF/SBS/LLDPE composites

A thermally triggered shape memory polymer composite was prepared by blending short carbon fiber (SCF) into a blend of poly(styrene-b-butadiene-b-styrene) triblock copolymer (SBS)/linear low density polyethylene (LLDPE) prior to curing. These composites have excellent processability compared with other thermosets. The dynamic mechanical analysis (DMA) and differential scanning calorimetry (DSC) were investigated to assess the thermomechanical properties of the SCF/SBS/LLDPE composite. Scanning electron microscope (SEM) imaging of the samples was performed to show the distribution of the SCF in the composite. The study specifically focused on the effect of SCF on the shape memory behavior of the SCF/SBS/LLDPE composite. The results indicated that the large amount of SCF significantly improved the mechanical property of the polymer composites while not damaging the shape memory performance. The SCF/SBS/LLDPE composites exhibited excellent shape memory behavior when the SCF content was less than 15.0 wt%. Moreover, the shape fixity ratio and shape recovery time of the SCF/SBS/LLDPE composites increased with the SCF content.     

Studies on thermal, thermal ageing and morphological characteristics of EPDM-g-VTES/LLDPE

A novel graft copolymer of vinyltriethoxysilane onto ethylene propylene diene terpolymer has been developed by grafting varying contents of VTES using dicumyl peroxide as an initiator in a twin-screw extruder. Grafting of VTES and EPDM has been ascertained using FTIR. The EPDM-g-VTES developed has been blended with different weight percentage of linear low density polyethylene [LLDPE] by melt mixing. Thermal, thermal ageing and morphological behaviour of the blends are studied with respect to the effect of blend composition, static vulcanization and dynamic vulcanization with varying quantities of VTES and LLDPE. The incorporation of silane moiety onto EPDM raises the inception and final decomposition temperature. The stability EPDM-g-VTES/LLDPE blend increases with increase in concentration of EPDM-g-VTES due to thermally stable Si-O-Si linkage. It was ascertain from SEM micrograph that EPDM-g-VTES/LLDPE blends lead to formation of interpenetrating crosslinked network during hot water treatment and by treatment with DCP, respectively. The linear, statically vulcanized, dynamically vulcanized and filled blends of EPDM-g-VTES/LLDPE have been characterized to assess the suitability of the blends for high performance applications. In addition, it is also observed that the incorporation of fillers improves thermal stability of the blends.     

COMPATIBILIZERS FOR LOW DENSITY POLYETHYLENE/POLYPROPYLENE BLENDS

The role of polyolefin elastomers as compatibilizers in Low Density Polyethylene/Polypropylene (LDPE/PP) blends, in the presence of di-cumyl peroxide (DCP) has been studied. Mixtures of 90/10 LDPE/PP ratio, were prepared in a Brabender plasticorder and tested for their mechanical properties and calorimetric response. Then the elastomers ethylene-propylene-diene copolymer (EPDM) and polybutadiene (BR) were added, alone or together with 0.2% DCP at concentrations up to 2%. The mixing torque and gel content of the above products were recorded as a function of the blend consistency. Also, the mechanical properties of specimens were measured as an additional evidence to explore the capabilities of these additives to promote compatibility of the blend components. It was found that EPDM and BR can be easily incorporated into polyolefin blends and appear suitable as potential compatibilizers for those materials, probably acting within the PP phase. Both elastomers result in an increase of strength and modulus, the BR having more enhanced effect. The latter gives low elongation, which allows its use in applications where high tensile properties are desired and flexural behavior is not critical.     

聚乙烯-g-聚苯乙烯对线性低密度聚乙烯/聚苯乙烯共混物机械性能和发泡行为的影响

以通过开环易位聚合、加氢反应和原子转移自由基聚合技术结合制备的聚乙烯-g-聚苯乙烯(PE-g-PS)作为增容剂,研究了加入不同PS支链长度的PE-g-PS对于线性低密度聚乙烯/聚苯乙烯(LLDPE/PS)共混物的机械性能和发泡行为的影响。 以典型组成m(LLDPE):m(PS)=70:30共混物为例,考察了PE-g-PS对共混物拉伸性能的影响。 相对于二元共混物,增容剂的加入使得断裂伸长率、拉伸强度和屈服强度皆提高,且含长PS支链的增容体系提高更明显。 采用超临界CO₂釜式发泡工艺,考察了PE-g-PS中PS支链长度对共混物发泡行为的影响。 结果表明,相对于短PS支链体系,加入PE-g-PS_1.59k(PS相对分子质量为1590)后的泡孔结构更加均一,完全没有“缝隙”形貌的出现。 当发泡温度降至80 ℃时,即使存在LLDPE发泡空间限制作用(LLDPE无法发泡),加入支链长度更长的PE-g-PS_1.59k后泡孔分布也更加均一。     

Studies on dynamic mechanical and mechanical properties of vinyloxyaminosilane grafted ethylene propylene diene terpolymer/linear low density polyethylene (EPDM-g-VOS/LLDPE) blends

The dynamic mechanical properties of vinyloxyaminosilane grafted ethylene propylene diene terpolymer/linear low density polyethylene (EPDM-g-VOS/LLDPE) blends have been evaluated with special reference to the effect of blend ratio. It has been found that increasing the proportion of LLDPE in the blends decreases the T_g values and increases the storage modulus (E^′) and loss modulus (E^′′) due to increase in crystallinity. A gradual increase in the values of tanδ_max is observed for the blends with increase in EPDM-g-VOS concentration, which indicates that no phase inversion occurs. But however the higher increase in tanδ_max after 50 wt.% of EPDM-g-VOS composition is due to small change in crystallinity and is ascertained by SEM micrographs. Mechanical properties such as tensile strength, Young’s modulus and hardness increase with increases in LLDPE concentration in the blends and with dicumyl peroxide (DCP) concentration whereas the values of elongation at break are decreased with increase in LLDPE and DCP concentration.     

Thermal Stability Evaluation of PA6/LLDPE/SEBS-g-DEM Blends

Summary: The thermal stability of a polyamide-6/low linear density polyethylene blend (PA6/LLDPE) was studied using thermal analysis techniques. The thermogravimetric studies carried out showed that when a diethyl maleate grafted styrene- ethylene/butadiene-styrene terpolymer (SEBS-g-DEM) is added to the PA6/LLDPE blend there is an actual enhancement of the thermal stability due to the increase in the interfacial area within the blend. The Invariant Kinetic Parameter method (IKP) proved to be a qualitative technique unfolding the type of degradation mechanisms taking place in the material vicinity. Nucleation and phase boundary reactions are the kinetic models of thermal decomposition with the most significant probability of occurring.     

Local compositional fluctuations in PPO/HIPSand PPO/SBS blends

Solid-state NMR relaxation has been used to explore the distribution of components in poly(phenylene oxide) (PPO) high impact polystyrene (HIPS) and PPO/poly(styrene-b-butadiene-b-styrene) (SBS) blends. The nuclear relaxation of PPO in the former system is single exponential for all compositions, but the relaxation of PS in the blend is simple exponential only when the PPO content is low but is otherwise nonexponential. The nuclear magnetization decay curves were analyzed in terms of statistical compositional fluctuation at the scale of spin diffusion distances of several nm. Distribution functions for nuclear relaxation and for blend composition have been derived. Extraction of low molecular weight occluded PS from HIPS resulted in blends having reduced homogeneity. Addition of low molecular weight PS enhanced homogeneity in both the PPO/HIPS and PPO/SBS blends. © 1994 John Wiley & Sons, Inc.     

MODIFICATION OF POLYETHYLENE BY in situ FORMED SODIUM ACRYLATE

To improve the water tree resistance of PE, linear low-density polyethylene （LLDPE） was compounded with sodium acrylate （NaAA） for in situ polymerization, in which NaAA was fbrmed through the neutralization of acrylic acid （AA） with sodium hydroxide （NaOH） before adding dicumyl peroxide （DCP） to initiate the in situ graft polymerization and homo polymerization. A series of LLDPE/NaAA compounds were investigated for their water absorption ratio （WAR） measurement, water treeing, mechanical and dielectric properties. The results strongly suggest that NaAA can improve the water tree resistance of LLDPE. In addition, the LLDPE/NaAA compounds possess satisfactory mechanical properties and dielectric properties. Characterization of LLDPE/NaAA compounds by using Fourier transform infrared spectrometry （FTIR） suggests that the neutralization and polymerization reaction could be achieved effectively. Using adequate DCP content is the key factor for controlling the polymerization of NaAA with precise conversion ratio.     

Nonisothermal crystallisation, melting behavior and wide angle X-ray scattering investigations on linear low density polyethylene (LLDPE)/ethylene vinyl acetate (EVA) blends: effects of compatibilisation and dynamic crosslinking

Crystallisation studies on LLDPE/EVA blends and the individual components were performed with wide angle X-ray scattering (WAXS) technique and differential scanning calorimetry (DSC) DSC was used to characterise the quiescent crystallisation behavior. The heat of fusion and crystallinity of the blends were reduced by the addition of EVA. The experimental and theoretical values of crystallinity of the blends were found to be mutually agreeing. Crystallisation of LLDPE remains impeded to some extent due to the presence of amorphous EVA. Compatibilisation does not affect crystallinity whereas crosslinking decreases crystallinity. Crosslinking and compatibilisation make no significant change in the melting temperature of the blends. X-ray diffraction studies were carried out on un-crosslinked and crosslinked LLDPE/EVA blends with a view to study the effect of blend composition and crosslinking on crystallinity and lattice distance. Studies revealed that LLDPE and EVA have orthorhombic unit cell. Blending with EVA did not affect the crystalline structure of LLDPE, but the crystallinity decreases with EVA content. At low concentrations of EVA the lattice parameters remain unchanged. Above 30% EVA content however, a linear increase has been observed. Dicumyl peroxide (DCP) crosslinked samples show considerable shift of (1 1 0), (2 0 0) and (0 2 0) crystalline peaks towards lower 2θ values indicating an increase of unit cell parameters of the orthorhombic unit cell of polyethylene. At lower EVA-concentrations (<50%) the crystalline structure remains unchanged. For EVA-contents of more than 70% however, increasing DCP-content reduces the crystallinity of the blends and increases the lattice distance. This indicates that DCP-crosslinking is more effective in EVA phase than in the LLDPE phase.     

Controlled migration of antifog additives from LLDPE compatibilized with LLDPE grafted maleic anhydride

This paper summarizes a study of controlled migration of an antifog (AF) additive; sorbitan monooleate (SMO), from linear low density polyethylene (LLDPE) films containing a compatibilizer, LLDPE grafted maleic anhydride (LLDPE‐g‐MA). LLDPE/LLDPE‐g‐MA/SMO blends were prepared by melt compounding. Bulk and surface properties of compression molded LLDPE films containing SMO and LLDPE‐g‐MA were characterized using Fourier transform infrared spectroscopy and contact angle measurements. Thermal properties were investigated using a thermal gravimetric analyzer. Diffusion coefficient (D) was calculated, and AF properties were characterized using a “hot fog” test. Compression molded films were characterized for their morphology using high‐resolution scanning electron microscopy, and rheological properties were measured using a parallel‐plate rotational rheometer. It was found that the LLDPE/LLDPE‐g‐MA/SMO systems are characterized by a slower SMO migration rate, a lower diffusion coefficient, and lower contact angle values compared with LLDPE/SMO blends. These results are well correlated with results of a hot fog test. Morphological studies revealed a very fine dispersion of SMO in the LLDPE films, when 3 phr LLDPE‐g‐MA was combined with 1 phr SMO. Thermal analysis results show that the incorporation of 3 phr LLDPE‐g‐MA and 1 phr SMO significantly increases the decomposition temperature of the blend at T > 400°C. At high shear rates, the LLDPE blends show that the AF and the compatibilizer have a lubrication effect on LLDPE. Copyright © 2014 John Wiley & Sons, Ltd.     

Morphology development in PS/LLDPE blend during and after elongational deformation

The morphology development within a PS/LLDPE blend with 5 wt % of LLDPE at various stages of uniaxial deformation and after cessation of the flow was studied. Under given deformation conditions the dispersed LLDPE particles stretch and form highly elongated fibrils in agreement with a modified capillary number model. The morphology development after deformation was investigated for two different modes—relaxation and recovery. It was found that the stress in the sample is the crucial parameter determining the morphology development. During the first part of relaxation the stress in the sample is sufficient to hold the particles in the highly elongated state and, therefore, Rayleigh breakup takes place according to the Tomotika theory. It results in considerably finer phase structure. Contrary to this, in the absence of the stress in the sample, that is, in the recovery mode, the fibrils start to shrink immediately after the deformation and after a certain time the spherical morphology is restored. During elongation and recovery no evidence of coalescence was observed. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 16–27, 2008     

SUBSTITUTION OF RETINAL BY ANALOGUES IN RETINAL PIGMENTS OF HALOBACTERIUM HALOBIUM. CONTRIBUTION OF BACTERIORHODOPSIN AND HALORHODOPSIN TO PHOTOSENSORY ACTIVITY

Abstract— In Halobacrerium hnlobium. retinal is the chromophore of the light-energy converting pigments bacteriorhodopsin (BR) and halorhodopsin (HR) and of the sensory photosystems. PS 370 and PS 565. In both photosystems as well as in BR and HR. retinal was substituted by retinal analogues. Retinal₂ ( 3,4-dehydro-retinal ) . shifts the main sensitivity maximum of PS 370 and of PS 565 by about 1.5 nm to longer wavelengths. The absorption maxima of BR and HR are both shifted in the same direction, but by 37 nm. 13-Ethylretinal and 13-propylretirnal shift the main sensitivity maximum of each sensory photosystem to shorter wavclengths; the absorption maxima of BR and HR are shifted in the same direction but to a smaller extent. Both sensory photosystems are equally active with retinal and with each of the three analogues as the chromophore. After substitution of retinal by the analogues, the action spectra of PS 565 of the BR-containing strain R₁L₃ show a secondary bensitivity peak in addition to the main peak. This secondary peak matches the absorption maximum of the corresponding BR. In the action spectra of the BR-deficient strainET–15 this secondary peak is missing. Action spectra of PS 565 of the BR-deficient strainL–33, which synthesizes increased amounts of HR. with all retinals show a secondary peak which matches the absorption maximum of the corresponding HR.
The results show that the analogues can substitute retinal in both sensory pigments as well as in BR and HR. Moreover, the data support the previous assumption that both BRand HR, although not required for photosensory activity can contribute to photosensing through PS 565.     

HIPS-g-GMA相容剂对PC/HIPS共混物相容性的影响*

将两种或两种以上聚合物进行共混是获得性能优异合金材料的简单而有效的途径[1,2 ] .但是大多数聚合物共混时 ,由于混合焓ΔＨ >0且混合熵ΔＳ非常小 ,导致混合自由能大于零 ,故大多数共混体系是不相容的 .而对于不相容的共混 ,由于两相间的界面张力大 ,两相间形成锐形界面 ,两相之间的界面粘结力低 ,导致材料性能很差 .为了改善两相间的相容性 ,需要加入相容剂[3 ,4 ] .绝大多数增容剂是嵌段或接枝共聚物 .这类增容剂分子量较大 ,在加工条件下 ,由于其粘度较大往往难于迁移到两相的界面处 ,起不到应有的增容作用 .聚合物反应加工技术是近 2…     

Selective swelling blends of block copolymers for nanoporous membranes with enhanced permeability and robustness

Block copolymers (BCPs) are important precursors to produce membranes with well‐defined porosities. However, it remains challenging to prepare robust and affordable BCP‐based membranes. In this work, cheap commodity styrene‐butadiene‐styrene (SBS) elastic triblock copolymers are mixed with polystyrene‐block‐poly (2‐vinylpyridine) (SV) block copolymers in solutions, leading to macroscopically stable blend films upon casting because of the compatibilizer effect of PS existing in both copolymers. By soaking the blend films in ethanol, the microdomains of poly(2‐vinylpyridine) are selectively swollen and cavitated upon drying, resulting in a hierarchical structure with perforated SV phases interwoven with the SBS phases. The blend membranes with 30% SBS exhibit improved water permeability and mechanical robustness due to the presence of elastic SBS compared to neat SV membranes; meanwhile, the rejections of the blend membranes remain largely unchanged. Moreover, the blend membranes exhibit a pH‐responsive function, and homoporous SV regions are obtained by pre‐aligning the SV phases. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55, 1617–1625     

Environmentally degradable LLDPE/esterified styrene-maleic anhydride (ESMA) blends

LLDPE was blended with esterified styrene-maleic anhydride (ESMA) to improve the environmental degradation characteristics of LLDPE. ESMA was synthesized by esterifying styrene maleic anhydride (SMA) with n-decanol. LLDPE was blended with ESMA (EDP blends) and SMA separately in a single screw extruder by melt mixing. Composition of ESMA was varied from 20 to 40 wt% in the blends. LLDPE grafted with glycidyl methacrylate (LLDPE-g-GMA) was used as compatibilizer to improve the compatibility. Scanning electron photomicrograph (SEM) of cryofractured impact specimens showed significant reduction in domain size and uniform distribution of ESMA in LLDPE matrix in presence of compatibilizer in 70/30 blends. Environmental degradability was assessed by subjecting the films to soil burial test and exposure to buffer solution of different pH. Environmental degradation was followed by measuring the periodic change in weight of the blend samples. Films were exposed to accelerated and natural weathering and photodegradation was assessed by noting the embrittlement time of the film. Films of compatibilized blends fragmented at a faster rate than the films of uncompatibilized blend. Carbonyl index of films subjected to natural weathering was also found to be higher than that for the virgin LLDPE films.