Ionomer/ionomer thermoplastic IPNs based on poly(n-butyl acrylate) and polystyrene

Thermoplastic interpenetrating polymer networks (IPNs) were prepared by combining poly(n-butyl acrylate) with polystyrene, both polymers crosslinked independently with acrylic acid anhydride (AAA). Decrosslinking of both polymers was carried out by hydrolysis of the anhydride bonds. Neutralization of the carboxylic acid groups to form the ionomer was carried out in a Brabender Plasticorder. Two subclasses of thermoplastic IPNs were studied: (1) Chemically blended thermoplastic IPNs (CBT IPNs) were prepared by synthesizing polymer II in polymer I in a sequential synthesis; (2) mechanically blended thermoplastic IPNs (MBT IPNs) were prepared by melt blending separately synthesized polymers. Rheovibron characterization revealed that of the two combinations, the CBT IPNs were better mixed than the MBT IPNs. Investigations of phase continuity via melt viscosity and modulus suggest that the CBT IPNs have some degree of dual phase continuity. Transmission electron microscopy suggests dual phase continuity and relatively small phase domains, 2000–5000 Å for the CBT IPNs. The mechanical properties from tensile and Izod impact tests showed that the CBT IPNs were stronger than the MBT IPNs.     

The effects of functional azo initiator on PMMA and polyurethane IPN systems. I. Synthesis,characterization, and thermal effects

The use of functional azo initiators and the thermal history of the materials have been shown to exert significant effects on the properties of interpenetrating polymer networks (IPNs). The IPNs prepared with a reactive azo initiator from MDI and 1,2-PBD (1,2-polybutadiene diol) with PMMA have been found to exhibit greater ductility, lower rigidity, and lower moduli than IPNs prepared with AIBN. This probably resulted from the attached PMMA blocks modifying the properties of the PU matrix phases. Increasing thermal treatment of IPNs prepared from either the reactive or the normal azo initiators exhibited increased T_g values in both DSC and DMTA scans. These results have been explained by increased association from chemical reactions between the hard segments of the polyurethane and poly(methyl methacrylate) ester groups.     

Thermoplastic interpenetrating polymer networks of a triblock copolymer elastomer and an ionomeric plastic. I. Rheology and morphology

The thermoplastic interpenetrating polymer networks (IPNs) are combinations of two physically crosslinked polymers. Thermoplastic IPNs were prepared by combining polymer I, an SEBS triblock elastomer with polymer II, an ionomer prepared from a random copolymer of styrene, methacrylic acid, and isoprene (90/10/1 by volume). Neutralization of the acid groups to form the ionomer was carried out on a Brabender Plasticorder. Two subclasses of the thermoplastic IPNs were identified. Chemically blended systems, prepared by a sequential polymerization method, were compared with compositionally equivalent mechanically blended systems prepared by melt blending the separately synthesized polymers. The chemically blended thermoplastic IPNs (CBT IPNs) exhibited lower melt viscosities than compositionally equivalent mechanically blended thermoplastic IPNs (MBT IPNs). Moreover, the melt viscosities of many of the CBT IPNs were even lower than that of either homopolymer component, leading to an explanation in terms of an unusually low value of the rubbery modulus front factor. Although both types of thermoplastic IPNs underwent a phase inversion during neutralization of polymer II, the phase inversions were often incomplete. Morphological studies revealed that more equal dual phase continuity existed in the MBT IPNs than in the CBT IPNs after ionomer formation.     

Polybutadiene modified by epoxidation: 2. The effect of epoxy groups on the crosslinking process with dicumyl peroxide

The process of crosslinking sodium and n-butyllithium polybutadienes as well as the products of their modification obtained by epoxidation has been studied. It has been found that the crosslinking efficiency of epoxy-1,2-polybutadiene is half that of the starting polybutadiene. However, the crosslinking efficiency of epoxy-1,4-polybutadiene was found to be similar to that of the starting 1,4-polybutadiene. The shift in glass transition temperature for epoxy-polybutadienes brought about by the change in the chemical composition (ΔT_g)_M was found to be 67 K for 1,4-polybutadiene, and 51 K for 1,2-polybutadiene. The effect of the epoxy groups and crosslinks on the glass transition temperatures of modified crosslinked polymers is also discussed.     

SBS和SBS环氧化与顺酐化研究

SBS是(苯乙烯-丁二烯-苯乙烯)三嵌段共聚物，是含有聚苯乙烯玻璃化微区及聚丁二烯连续相的多相聚合物，具有热塑性橡胶的性质。它具有良好的拉伸性能、耐湿性、透气性、溶解性及抗滑性，而被大量用于橡胶制品、粘舍剂及沥青和树脂的改性剂等。其缺点是耐油性差，与极性物质不相容，不粘接等。用环氧化及顺酐化改性可改进这方面的缺点。SBS的环氧化改性多半使用过甲酸或过乙酸在溶液中进行。产物可作为压敏胶、热熔胶、密封胶等，用于粘接极性材料，也可作为耐油热塑性橡胶。SBS的顺酐化改性可在熔融态进行，也可在溶液中进行。产物可用作极性聚合物与非极性聚合物的共混增容剂、胶粘剂及进一步合成离聚体。     

Selective crosslinking in polymer blends. II. Its effect on impact strength and other mechanical properties of polypropylene/unsaturated elastomer blends

The effect of selective crosslinking of the unsaturated elastomer particles in polypropylene (PP) matrix was investigated. The crosslink system comprised N,N′-m-phenylene-bismaleimide and 6-ethoxy-2,2,4-trimethyl-1,2-dihydroqinoline or polymerized-(2,2,4-trimethyl-1,2-dihydroquinoline). The system, which produces only carbon radicals, crosslinks the elastomer particles selectively without causing excessive degradation of the PP matrix. The reaction was carried out under a dynamic crosslinking process using a twin extruder on PP/EPDM, PP/SBS, and PP/SIS blends, all of which comprised 80 wt % of PP and 20 wt % of the elastomer. After the crosslinking, the impact strength of the blends increased. Especially remarkable increase is obtained at 23°C where PP is above its T_g. The increase of interfacial adhesion caused by production of PP/elastomer graft copolymer at the interface is considered to be the most important factor in the improvement. It permits the interactions of the stress concentrate zone developed at the elastomer particles and causes shear yielding of the PP matrix. Impact fracture energy absorption can be thus changed by adjusting the degree of the interfacial adhesion even at essentially the same morphology. The crosslinked elastomer particles also play the role of a nucleation agent. The selective cross-linking of the elastomer particles in PP/elastomer blends is demonstrated to be an excellent technique to produce a high-impact, high-modulus PP. © 1994 John Wiley & Sons, Inc.     

Singlet oxygen generation and adhesive loss in stimuli‐responsive,fullerene‐polymer blends,containing polystyrene‐block‐polybutadiene‐block‐polystyrene and polystyrene‐block‐polyisoprene‐block‐polystyrene rubber‐based adhesives

The adhesive properties, as measured by bulk tack and peel strength analysis, were found to decrease in polystyrene‐block‐polybutadiene‐block‐polystyrene (SBS) and polystyrene‐block‐polyisoprene‐block‐polystyrene (SIS) PSA films containing common singlet oxygen generators, acridine, rose bengal, and C₆₀ fullerene, when irradiated with a tungsten halogen light in air. The addition of the singlet oxygen quencher, β‐carotene, to the C₆₀ fullerene samples was found to significantly deter the rate of adhesive loss in the fullerene‐SBS and ‐SIS PSA nanocomposites. The presence of oxygen was essential to the mechanism of adhesive loss and, in combination with the effects of singlet oxygen generators and a singlet oxygen scavenger, strongly supports a singlet‐oxygen mediated process. FTIR investigations of fullerene‐SBS and ‐SIS systems suggest the initial formation of peroxides which, upon further irradiation, lead to the generation of carbonyl‐containing compounds of a ketonic type after crosslinking. Rates of SBS and SIS C‐H abstraction were comparable and found to decrease when the high‐pressure, mercury xenon irradiation source was filtered to allow only light of λ > 390 nm. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis and characterization of maleated ionomers via ring‐opening reaction of epoxidized styrene‐butadiene rubber with potassium hydrogen maleate and study of their behavior as compatibilizer

A novel method for synthesizing maleate ionomer of (styrene‐co‐butadiene) rubber (SBR) from epoxidized SBR was developed. The epoxidized SBR was prepared via epoxidation of SBR with performic acid formed in situ by H₂O₂ and formic acid in cyclohexane. The maleated ionomer was obtained by ring‐opening reaction of the epoxidized SBR solution with an aqueous solution of potassium hydrogen maleate. The optimum conditions were studied. It was found that it is necessary to use phase transfer catalyst and ring‐opening catalyst for enhancing the epoxy group conversion. To obtain 100% conversion addition of dipotassium maleate is important. The product was characterized by FTIR spectrophotometry and transmission electron microcroscopy (TEM). The results showed that the product was really an ionomer with domains of maleate ionic groups. Some properties of the ionomer, such as water absorbency, oil absorbency and dilute solution behavior were studied. With increasing ionic groups, the water absorbency of the ionomer increases, whereas the oil absorbency decreases. The dilute solution viscosity of the ionomer increases abruptly with increasing ionic group content. The ionomer can be used as a compatibilizer for the blends of SBS and chlorosulfonated polyethylene (CSPE). Addition of a small amount of the ionomer to the blend can enhance the mechanical properties of the blends. 3 wt % ionomer based on the blend can increase the tensile strength and ultimate elongation of the blend nearly twice. The compatibility of the blends enhanced by adding the ionomer was shown by scanning electron microscopy. The blend of equal parts of SBS and CSPE compatibilized by the ionomer behaves as an oil resistant thermoplastic elastomer. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 792–798, 2006     

Macrolattice structure of a block copolymer in a selective solvent

Macrolattice structure in the ordered phase of a poly(styrene-b-butadiene-b-styrene) (SBS, with the bulk morphology of spherical polystyrene microdomains in the polybutadiene matrix) dissolved in a selective solvent (dodecyl methacrylate, C₁₂MA, or a 75/25 w/w mixture of C₁₂MA and butylene diacrylate, BDA) which mixes preferentially with the polybutadiene matrix was examined by means of transmission electron microscopy. The use of C₁₂MA/BDA mixture as the selective solvent provided the opportunity of freezing the macrolattice structure upon UV-initiated polymerization of the acrylic monomers when the SBS content is above ca. 60 wt%. Results indicated clearly a body-centered cubic structure, in contrast to the simple cubic packing previously proposed.     

Blending of styrene‐block‐butadiene‐block‐styrene copolymer with sulfonated vinyl aromatic polymers

Different polymers containing sulfonic groups attached to the phenyl rings were prepared by sulfonation of polystyrene (PS) and styrene‐block‐(ethylene‐co‐1‐butene)‐block‐styrene (SEBS). The sulfonation degree (SD) was varied between 1 and 20 mol% of the styrene units. Polyphase materials containing sulfonated units were prepared by blending styrene‐block‐butadiene‐block‐styrene (SBS), with both sulfonated PS and sulfonated SEBS in a Brabender mixer. Such a procedure was performed as an alternative route to direct sulfonation of SBS which is actually not selective towards benzene rings because of the great reactivity of the double bonds in polybutadiene (PB) blocks to sulfonation agents. Thermal and dynamic‐mechanic analysis, together with morphology characterization of the blends, is consistent with obtaining partially compatible blends characterized by higher T_g of the polystyrene domains and improved thermal stability. © 2001 Society of Chemical Industry     

Decrease in the etch rate of polymers in the oxygen afterglow with increasing gas flow rate

In this paper we report the variation of the etch rate of polymers in the afterglow of a radio frequency discharge in oxygen as a function of total flow rate in the range 2–10 cm³ (STP)/min. The measurements were made at ambient temperature with the O(³P) concentration held essentially constant. We report results on three polymers: cis-polybutadiene, a polybutadiene with 33% 1,2 double bonds, and a polybutadiene with 40% 1,2 double bonds. We have observed that the etch rate of these polymers decreases significantly with increasing flow rate, strongly suggesting that the vapor-phase products of polymer degradation contribute to the degradation process.     

Facile preparation of Cu(I) impregnated MIL‐101(Cr) and its use in a mixed matrix membrane for olefin/paraffin separation

Cu(I) impregnated MIL‐100(Cr) [denoted Cu@MIL‐101(Cr)] is fabricated by a facile method and utilized in mixed matrix membranes (MMMs) for propylene/propane separation. Cu(I) is prepared from a CuCl₂ solution via mild reduction process using sodium sulfite as the reducing agent. The filler is incorporated into a polystyrene‐b‐polybutadiene‐b‐polystyrene (SBS) block copolymer matrix to form MMMs. As a result, both the permeability and selectivity of propylene/propane are improved after Cu(I) impregnation. The best performance is obtained for SBS/Cu@MIL‐101(Cr) MMM, and these values represent 17% and 54% improvements compared to those of SBS/MIL‐101(Cr) MMM, respectively. This result is attributed to the π‐complexation of the loaded Cu(I) by propylene gas, indicating that Cu@MIL‐101(Cr) with internal Cu(I) and a high pore volume acted as an effective filler to aid propylene/propane separation. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46545.     

Preparation and mechanical properties of clay/polystyrene‐block‐polybutadiene‐block‐polystyrene triblock copolymer (SBS) intercalated nanocomposites using organoclay containing stearic acid

Organoclays containing various amounts of stearic acid (SA) were synthesized, and clay/polystyrene‐block‐polybutadiene‐block‐polystyrene triblock copolymer (SBS) intercalated nanocomposites were prepared using organoclays containing SA by melt‐blending. Montmorillonite was the clay used, and both stearylamine and SA were used as surface modifiers. The amount of SA added was 0, 20, 50 and 100% of the cation‐exchange capacity (CEC). In this study, the effects of SA on the microstructure and mechanical properties of the clay/SBS nanocomposites were investigated. In clay/SBS with 100% CEC of SA, although no exfoliation of the clay occurred, the stacked clay layers were uniformly dispersed at the nanometer level (100–800 nm) without agglomeration. Clay/SBSs containing SA exhibited superior mechanical properties compared to clay/SBS without SA. It was found that SA effectively improved the clay dispersion in the SBS matrix and the mechanical properties of the clay/SBSs. Copyright © 2006 Society of Chemical Industry     

通过环氧化苯乙烯-丁二烯-苯乙烯嵌段共聚物与亚硫酸氢钠的开环反应制备磺化离聚体

用环氧化苯乙烯-丁二烯-苯乙烯嵌段共聚物（ESBS）在相转移催化剂、开环催化剂存在下与亚硫酸氢钠的水溶液进行开环反应制备了SBS磺化离聚体,用傅里叶变换红外光谱法对产物进行了表征。研究表明,当环氧基转化率达90％时,反应条件为ESBS的质量浓度0．12g／mL。NaHSO3／环氧基（摩尔比）1．8,促进剂／NaHSO3（质量比）0．36。四乙基澳化铵／ESBS（质量比）0．05,二甲基苯胺／ESBS（质量比）0．05,60℃,7h。     

Nanoscale Cellular Foams from a Poly(propylene)‐Rubber Blend

Plastic foams with nano/micro‐scale cellular structures were prepared from poly(propylene)/thermoplastic polystyrene elastomer (PP/TPS) systems, specifically the copolymer blends PP/hydrogenated polystyrene‐block‐polybutadiene‐block‐polystyrene rubber and PP/hydrogenated polystyrene‐block‐polyisoprene‐block‐polystyrene. These PP/TPS systems have the unique characteristic that the elastomer domain can be highly dispersed and oriented in the machine direction by changing the draw‐down ratio in the extrusion process. A temperature‐quench batch physical foaming method was used to foam these two systems with CO₂. The cell size and location were highly controlled in the dispersed elastomer domains by exploiting the differences in CO₂ solubility, diffusivity, and viscoelasticity between the elastomer domains and the PP matrix. The average cell diameter of the PP/TPS blend foams was controlled to be 200–400 nm on the finest level by manipulating the PP/rubber ratio, the draw‐down ratio of extrusion and the foaming temperature. Furthermore, the cellular structure could be highly oriented in one direction by using the highly‐oriented elastomer domains in the polymer blend morphology as a template for foaming.

     

Investigation of morphology formation in SBS block copolymer/homopolystyrene blends

Polymer blends comprising a polystyrene‐block‐polybutadiene‐block‐polystyrene (SBS) block copolymer and atactic homopolystyrene (hPS) were investigated using injection molded and solution cast samples. The morphology of the materials was studied by means of transmission electron microscopy (TEM) and scanning force microscopy (SFM). Dynamic mechanical analysis (DMA) was used to characterize the phase behavior and the morphology formation of the block copolymer as well as of the SBS/hPS blends. The glass transition temperatures seem to strongly depend on the homogeneity of the corresponding phases. A distinct difference was found between the morphologies of the blends prepared by different methods. While the SBS block copolymer always shows a lamellar morphology in injection molded or as‐cast samples, the injection molded blends show a disturbance in the morphology consisting of alternating layers. In contrast, in the case of as‐cast samples, added hPS forms polystyrene domains dispersed in a matrix of the pure block copolymer. Regarding the change in the glass transition temperature, in the effective volume and in the interfacial volume obtained from DMA curves, the morphology formation of the injection molded samples (pure SBS block copolymer and the corresponding blends) was investigated. Two different structural models for the blends are proposed. Polym. Eng. Sci. 44:1534–1542, 2004. © 2004 Society of Plastics Engineers.     

Correlation between artificial and natural weathering tests on polystyrene‐block‐polybutadiene‐block‐polystyrene block copolymer

The effects of artificial and natural weathering tests on the structure and mechanical properties of polystyrene‐block‐polybutadiene‐block‐polystyrene (SBS) block copolymer were studied by spectrophotometry, Fourier Transform Infrared (FTIR) Spectroscopy, hardness measurements, and tensile testing. The correlation between artificial and natural weathering tests was also investigated. The results showed that the surface of SBS became yellow with increasing aging time. FTIR spectra confirmed the formation of carbonyl group in the aging process. The elongation at break, the tensile strength, and the tear strength decreased rapidly in the initial stage of the aging process and then leveled off, while the hardness increased with aging time. The correlation between artificial and natural weathering tests in Wanning and Hailaer, in China, could be expressed in terms of t₁ = 2.50t₀^1.99 and t₂ = 1.92t₀^2.56, respectively. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008.     

Photodegradation and stabilization of styrene–butadiene–styrene rubber

Photooxidative degradation and stabilization of a polystyrene–block–polybutadiene–block–polystyrene thermoplastic elastomer using a polychromatic UV light in air at 60°C has been studied by monitoring the appearance of the hydroxyl and carbonyl groups in Fourier transform infrared spectroscopy. The extent of photooxidative degradation in different samples has been compared. The rate of photooxidation was also estimated in the presence of different concentrations of 2,6‐di‐tert‐butyl‐4‐methylphenol [BHT], 2‐(2′‐hydroxy‐5′‐methylphenyl)benzotriazole [Tinuvin P] and tris(nonylphenyl) phosphite [Irgafos TNPP], and 1,2,2,6,6‐pentamethyl piperidinyl‐4‐acrylate was grafted onto the surface of the SBS film. The kinetic evolution of the oxidative reaction was determined. The morphological changes upon irradiation in the solution cast SBS films were studied by scanning electron microscopy. Based on the experimental data a suitable photooxidative degradation mechanism also has been proposed. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 1097–1102, 2000     

Interfacial Modification of Polystyrene‐block‐polybutadiene‐block‐polystyrene/Magnesium Hydroxide Composites, 1

Composites based on polystyrene‐block‐polybutadiene‐block‐polystyrene (SBS triblock thermoplastic elastomer) and magnesium hydroxide (Mg(OH)₂) (5–60 wt.‐%) have been prepared by twin screw extrusion. Interfacial modifiers included dispersants, i.e., isostearic acid, oleic acid, stearic acid; and coupling agents, i.e., maleanised polybutadiene and vinyltriethoxysilane. In each case, approximately one monolayer of treatment was used. A dual bore motor driven extrusion rheometer was used for assessment shear and elongation flow behavior (Cogswell's method) over a shear rate range of 100 s^?1 to 5 000 s^?1. Untreated filler and filler treated with coupling agents gave composites that become increasingly pseudoplastic as filler level increased. Fatty acid structure was shown to have some influence over the level of melt viscosity reduction normally associated with such treatments; stearic acid gave the most pronounced reduction in melt viscosity possibly due to the tightly packed monolayer. Elongational flow properties, determined using Cogswell's method, indicated significant chain extension/branching of the bulk matrix when high levels of untreated filler were present and long range filler‐matrix interaction in composites modified with maleanised polybutadiene.

Elongational viscosity versus extensional stress (obtained by Cogswell's method) for SBS blended with filler surface treatments (□) unfilled matrix, and unfilled matrix plus (?) Hⁱst and (?) MPBD.     

Efficiencies of various metallocene/reducing agent catalyst systems in the hydrogenation of polystyrene‐b‐polybutadiene‐b‐polystyrene block copolymers

Various metallocenes, including bis(η⁵‐cyclopentadienyl)cobalt, bis(η⁵‐cyclopentadienyl)nickel, and bis(η⁵‐cyclopentadienyl)titanium dichloride, combined with various reducing agents, including n‐butyllithium, phenyllithium, and triethylaluminum, have been evaluated for their catalytic efficiencies in the hydrogenation of polystyrene‐b‐polybutadiene‐b‐polystyrene (SBS) block copolymer. The efficiencies were determined by monitoring the extent of saturation of double bonds on the polybutadiene segment of the copolymer using FTIR and ¹H‐NMR spectroscopy. The cobaltocene/n‐butyllithium catalyst system was found the most active. The effects of H₂ pressure and the ratio of n‐butyllithium to cobaltocene ratio on the hydrogenation efficiency were also investigated. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 1807–1815, 1999