Compatibilization and characterization of blends of styrene–maleic anhydride copolymer with modified polyethylenes

Potentially reactive blends of styrene–maleic anhydride (SMAH) with ethylene/methyl acrylate/glycidyl methacrylate (E‐MA‐GMA) and nonreactive blends of SMAH with ethylene/methyl acrylate (E‐MA) were produced in a Brabender batch mixer and in a corotating twin‐screw extruder. The products were characterized in terms of rheology, morphology, and mechanical properties to understand the reaction characteristics between anhydride/epoxy functional groups. Storage modulus, G′, loss modulus, G″ and complex viscosity, η* of the reactive blends were higher than those of nonreactive ones. At 25% E‐MA‐GMA content, maximum in η* was obtained for the reactive blends. The reactive blends showed finer morphology than the nonreactive ones at all concentrations studied. Mechanical characterization showed that reactive SMAH/E‐MA‐GMA blends had higher tensile strength, % strain at break, and tensile modulus than the nonreactive blends for all corresponding modified polyethylene contents. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 790–797, 2001     

Grafting of maleic anhydride onto styrene–butadiene–styrene triblock copolymer using supercritical CO2 as a swelling agent

Grafting of maleic anhydride (MA) onto styrene–butadiene–styrene triblock copolymer (SBS) was carried out by free radical polymerization using supercritical carbon dioxide (SC CO₂) as a solvent of MA and swelling agent of SBS. The effect of various factors such as monomer concentration, initiator concentration, SC CO₂ pressure, and reaction time on grafting ratio was studied. SBS and the product (SBS‐g‐MA) were characterized by Fourier transform infrared spectroscopy (FTIR), gel permeation chromatography (GPC), differential scanning calorimetry (DSC), and scanning electron microscopy (SEM). GPC data showed that the molecular weight of SBS‐g‐MA is bigger than that of SBS. DSC testing indicated that the glass transition temperature (T_g) of SBS‐g‐MA is higher than that of SBS. By SEM photo, we can observe that some particles which contain more oxygen atom grew out from the surface of SBS‐g‐MA when grafting ratio reached at 5.6%, and the amount and diameter of particles increased with increasing of grafting ratio. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 4425–4429, 2006     

Hole structure and its formation in thin films of hydrolyzed poly(styrene maleic anhydride) alternating copolymers

Maleic anhydride moieties on the backbone chains of poly(styrene maleic anhydride) alternating copolymer (SMA) hydrolyzed in a THF solution containing water and hydrochloric acid. Well‐arrayed holes were obtained in spin‐cast thin hydrolyzed SMA films on a single crystal silicon wafer, and the hole diameter and its distribution were measured with AFM data. Results showed that the hole size was almost uniform, and was influenced by water content when spin speed was kept unchanged. The THF solution with a SMA concentration of about 1 g/mL and weight ratio H₂O/SMA of 1/3 produced holes having an average diameter of 0.60 μm and depth of 206.12 nm, when cast at a spin speed of 1400 rpm. It was noted that the formation of the holes in thin hydrolyzed SMA film was different from the dewetting process in thin homopolymer films, but was associated with the intrinsic properties of the copolymer forming the films. The surfactant effect of hydrolyzed SMA was suggested to interpret the formation of the holes. The holes were described to be the traces of water droplets that were emulsified by the hydrolyzed SMA during casting. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 267–274, 2000     

Wood-fiber reinforcement of styrene–maleic anhydride copolymers

Styrene–maleic anhydride (SMA) copolymers containing either 7 or 14% maleic anhydride were filled with either pine flour or dry-process aspen fiber from a medium density fiberboard (MDF) plant. Material properties of the filled and unfilled SMA plastics were compared with those of aspen-fiber-filled and unfilled polystyrene (PS). The fiber-filled SMA composites were equivalent or superior to unfilled SMA in strength, stiffness, and notched Izod impact strength. Filled PS composites outperformed or matched the performance of filled SMA composites in the parameters tested. Unnotched Izod impact strength of filled polymers was generally inferior to that of the unfilled polymers. Water absorption from a 90% relative humidity exposure, a 24-h soak, and a 2-h boil showed mixed results when compared to the unfilled polymers. Dynamic mechanical analysis showed no change in glass transition temperature (T_g) after the addition of filler for either SMA or PS composites. The presence of the anhydride functionality on the polymer backbone did not appear to improve the strength of the composite. No evidence was found for chemical bond formation between the SMA and wood fiber. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 68: 1567–1573, 1998     

Compatibilizing effect of styrene–maleic anhydride copolymer on the properties of polyamide‐6/liquid crystalline copolyester composites

Liquid crystalline polymer–polyamide‐6 (LCP/PA6) composites containing 20 wt % LCP content were compatibilized by a random styrene–maleic anhydride copolymer (RSMA). The blending was performed via extrusion followed by injection molding. The LCP employed was a commercial copolyester, Vectra A950. The dynamic mechanical (DMA), rheological, thermal, and mechanical properties as well as the morphology of the composites were studied. The DMA and rheological results showed that RSMA is an effective compatibilizer for LCP/PA6 blends. The mechanical measurements showed that the stiffness, tensile strength, and toughness of the in situ composites are generally improved with increasing RSMA content. However, these mechanical properties deteriorated considerably when RSMA content was above 10 wt %. The drop‐weight dart impact test was also applied to analyze the toughening behavior of these composites. The results show that the maximum impact force (F_max) and crack‐initiation energy (E_init) tend to increase with increasing RSMA content. From these results, it appeared that RSMA prolongs the crack‐initiation time and increases the energies for crack initiation and impact fracture, thereby leading to toughening of LCP/PA6 in situ composites. Finally, the correlation between the mechanical properties and morphology of the blends is discussed. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 1964–1974, 2000     

SMA工业生产计量及分析方法

运用密度法建立了可用于苯乙烯－马来酸酐共聚物（SMA）工业生产听密度－温度－浓度关系式。应用表明，此式在工业生产计量仪表的标定中是可信和可靠的。利用工业生产获得了有关工艺参数，还建立了针对SMA生产的反应器方程式。经20d连续工业生产考察表明，用反应器方式式所预测的转化率与实际值非常吻合，该方程式具有指导SMA工业生产的意义。     

Polymer blends with modified coupling agent. II. Effects of LICA 44 grafted styrene–maleic anhydride copolymer on properties of flame retardant acrylonitrile–butadiene–styrene blends

Flame retardant acrylonitrile–butadiene–styrene (FR‐ABS) blends were prepared by blending tetrabromobisphenol A (TBBA) and antimony trioxide (Sb₂O₃) into the ABS resin. LICA 44 grafted styrene–maleic anhydride (SMA‐g‐L44) copolymers were used as high molecular weight (MW) coupling agents to modify the properties of the FR‐ABS blends, and the copolymers with different LICA 44 grafting ratios were produced via the in vivo and the in situ reactions, respectively. The LICA 44 percentage and the MW of the SMA‐g‐L44 copolymers are important factors influencing the effects of the high MW coupling agent. The impact strength and the tensile yield stress of SMA‐g‐L44 modified FR‐ABS blends increased obviously. The elongation at break and the limiting oxygen index of which also showed an increasing trend after the modification. The coupling effect of SMA‐g‐L44 became weaker at a higher grafting ratio. SEM observation showed that the interfacial boundary in the FR‐ABS became fuzzy after using the SMA‐g‐L44 copolymers. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 865–874, 1999     

阳离子改性苯乙烯-马来酸酐共聚物的制备与表征及应用

以2,3-环氧丙基三甲基氯化铵(ETA)为阳离子化试剂,对苯乙烯-马来酸酐共聚物(SMA)进行阳离子化改性,制备出一种阳离子性高分子分散剂(SMG)。通过红外光谱、含氮量、表面张力以及溶解性等的测定,研究了SMG的结构与性质;通过对颜料黄14的分散性考察,研究了SMG的分散性能。结果表明,SMA在阳离子化过程中,酸酐基团全部开环,部分形成酯键,阳离子化度达到7.5%左右;SMG的表面活性较低,但对颜料黄14的分散稳定性较好,在pH=7.0条件下,可以使颜料的Zeta电位提高至 35.4 mV。     

Solvothermal preparation and characterization of maleic anhydride grafting high density polyethylene copolymer

In this article, the grafting copolymerization of maleic anhydride (MAH) onto high density polyethylene (HDPE) was carried out through solvothermal process. Infrared spectra (IR) revealed that MAH had been successfully grafted onto the HDPE backbone. The influences of the reaction parameters on the grafting copolymerization, e.g., the concentration of the initiator, MAH and HDPE content, reaction time, reaction temperature, comonomer, and different solvents were also studied. Further studies found that MAH could be grafted onto HDPE in both good solvents and poor solvents, which was much different from the traditional solution grafting method. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Peroxide‐initiated comonomer grafting of styrene and maleic anhydride onto polyethylene: Effect of polyethylene microstructure

Maleic anhydride has been grafted onto various polyethylenes (PEs) using 2,5‐dimethyl‐2,5‐(di‐t‐butylperoxy)hexane as a free radical initiator in the presence of styrene as a comonomer. Three polyethylenes, differing systematically in their levels of terminal unsaturation and branching, were selected to investigate the effect of these microstructural characteristics on the course of both grafting and crosslinking. It was observed that when polyethylenes containing high levels of terminal unsaturation were reacted in the presence of peroxide or peroxide–maleic anhydride, crosslinking events were enhanced. When styrene was added as comonomer to the reaction medium to eliminate these undesirable side reactions, crosslinking was still observed with those polyethylenes that contained a high concentration of terminal unsaturation. This is attributed to a low reactivity between styrene and the allylic radical generated on the polyethylene backbone, which is believed to be responsible for the increased crosslinking. However, in the presence of high concentrations of styrene, crosslinking was eliminated for PEs containing high degrees of branching. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 96–107, 2001     

酯化淀粉接枝马来酸酐共聚物微球制备及对Mn2+的吸附

首先以淀粉为原料、多聚磷酸钠为酯化剂制得磷酸酯淀粉,然后采用反相乳液聚合法制备磷酸酯淀粉微球,并用马来酸酐对微球进行改性。通过单因素试验法探讨了m(淀粉)∶m(多聚磷酸钠)配比、乳化剂含量、交联剂含量和温度等因素对微球的形成和产率等影响,并对微球的结构、溶胀性和吸附性等进行了分析。结果表明:当m(淀粉+多聚磷酸钠)=10 g、m(淀粉)∶m(多聚磷酸钠)=60∶40、环氧氯丙烷(ECH)交联剂为5 g、乳化剂为0.10 g和反应时间为5.0 h时,微球产率相对最高;当Mn2+浓度为0.03 g/L时,磷酸酯淀粉微球、马来酸酐改性淀粉微球对Mn2+的常温吸附量分别为0.616、0.793 mg/g。     

马来酸酐-丙烯酸酯类共聚物作油煤浆燃料稳定剂研究

以马来酸酐与丙烯酸酯的共聚物为稳定剂,当共聚物中,n(马来酸酐):n(丙烯酸丁酯)=1:5,用吡啶中和,稳定剂的添加量为0.4%时,油煤浆(COM)燃料在3个星期后的棒惯时间仍然小于2 s,碳粉的最高质量含量可达59.4%.该稳定剂用量少、原料易得,有较好的应用前景.     

Acrylonitrile–maleic anhydride copolymer membranes with different molecular weights

The structure and performance of acrylonitrile–maleic anhydride copolymer membranes with different molecular weights were investigated. The results showed that the water flux of the membrane decreased gradually with increasing molecular weight of the copolymer; the rejection increased only when there was an obvious increase of molecular weight. The addition of an additive (polyvinylpyrrolidone) largely decreased the water flux and rejection of the membrane when the concentration of the copolymer remained unchanged. The higher the molecular weight, the thicker were the transition layer and the wall of the support pore and the better was the anticompactness of the membrane. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 2521–2527, 2002     

氯化聚丙烯及其马来酸酐接枝物的氯含量研究

通过氧瓶燃烧法测定的氯化聚丙烯及其马来酸酐接枝物的氯含量,可以对接枝反应机理和马来酸酐在接枝物中的存在状态进行估计。根据实验所测得的氯含量和接枝率(马来酸酐含量),可以求得接枝物的结构单元。根据结构单元可以计算接枝物结构单元的相对分子质量,这种方法要比用仪器法测定分子质量简单明确。     

Synthesis and characterization of solid‐phase graft copolymer of polypropylene with styrene and maleic anhydride

Polypropylene (PP) was modified by solid‐phase graft copolymerization with maleic anhydride (MAH) and styrene (St), using benzoyl peroxide as the initiator and xylene as the interfacial agent. Effects of various factors such as monomer concentration, monomer ratio, initiator concentration on grafting percentage, and acid value were investigated. The graft copolymer was characterized by Fourier transform infrared, pyrolysis gas chromatography—mass spectroscopy, and dynamic mechanical analysis, and the intrinsic viscosity of the extractive from the reaction product was investigated. The results showed that the grafting percentage and acid value of the graft copolymer of PP with two monomers (MAH and St) were considerably higher than those of the graft copolymer of PP with MAH alone. The graft segments were shown to be the copolymer of St and MAH with a substantial molecular weight. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 2482–2487, 2000     

马来酸酐熔融接枝LDPE的性能

采用熔融接枝法制备了低密度聚乙烯(LDPE)与马来酸酐(MAH)接枝物,通过调整反应物的用量及反应条件控制接枝率。随着MAH及引发剂用量的增加,接枝率呈先增大后降低的趋势。低剪切速率时,接枝物的最大初始剪切黏度达4750 Pa·s,远高于纯LDPE;高剪切速率时,接枝物的剪切黏度与纯LDPE趋于相同,约500 Pa·s。接枝物的拉伸强度在8 MPa左右,同纯LDPE接近,断裂伸长率略有下降。     

Copolymerization of styrene and maleic anhydride in supercritical carbon dioxide

The copolymerization of styrene (St) and maleic anhydride (MA) was carried out in supercritical carbon dioxide (SC CO₂). It was found that St and MA are easy to copolymerize in SC CO₂ and the conversion can reach 97%, and that very fine and dry powders are obtained. The products were characterized using Fourier transform infrared spectroscopy (FTIR), gel permeation chromatography (GPC), scanning electron microscopy (SEM), differential scanning calorimetry (DSC), and thermogravimetric analysis (TGA). GPC data showed that the molecular weight of the copolymer reach 3.62 × 10⁴ g mol^?1. Scanning electron microphotographs showed the minimum particle size of the product is about 200 nm. DSC measurements indicated that the glass transition temperature (T_g) of the copolymer increases with increasing the MA content in the copolymer. TGA curve showed that the copolymers were decomposed at about 350°C. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

二釜串联连续本体法制备SMA

用二釜串联连续本体工艺制备苯乙烯-顺丁烯二酸酐无规共聚物,分别研究并获得了首釜和第二釜的启动操作策略和稳态工艺条件。     

Modification of cellulase by synthesized copolymer with polyethylene oxide and maleic acid anhydride

Copolymer containing functional groups such as polyethylene oxide (PEO) and maleic acid anhydride (MA) was synthesized to modify cellulase. MA was attached to the PEO allyl ester, which was the product formed by the reaction between PEO allyl alcohol and lauric acid. The number of ethylene oxide (EO) units in one PEO chain was varied from 10 to 40, and MA formed the chemical bond with the amino acid groups of the cellulase for the modification reaction. When cellulase was modified with synthesized copolymer, activity of the modified cellulase decreased slightly as the degree of modification increased. The modified enzyme showed high remaining activity regardless of a high degree of modification. At the maximum modification degree of 52%, the modified cellulase activity retained more than 65% of the unmodified native cellulase. Modified cellulase retained higher reactivity than native cellulase in an organic solvent and at various pH values. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 368–373, 2000     

马来酸酐熔融接枝二元乙丙橡胶的研究

在转矩流变仪中,以过氧化二异丙苯(DCP)为引发剂,采用多单体熔融接枝技术,研究了二元乙丙橡胶(EPM)熔融接枝马来酸酐(MAH),考察了MAH含量、DCP用量、反应温度、反应时间、转子转速以及第二单体苯乙烯(St)的用量对接枝反应的影响,并用红外光谱(FTIR)对接枝产物进行了表征.研究结果表明:对于EPM-g-MAH体系,MAH和DCP最佳用量分别为3.0 phr和0.22 phr,最佳反应温度为170℃,反应时间8 min,转子转速60 r/min,此时接枝率最高达到0.46％;加入第二单体St后,当n(St) /n(MAH)为1/1时,EPM-g-(MAH-co-St)的接枝率为0.64％,接枝率明显提高.