SMAH型低温流动改进剂的研究

选用马来酸酐,苯乙烯,十六醇为原料,采用"先聚合,后酯化"的方法,合成了低温流动性改进剂:马来酸酐-苯乙烯-十六醇酯共聚物(SMAH)。正交实验确定了最佳的制备条件,聚合:n(马来酸酐)/n(苯乙烯)=1:0.5、w(引发剂)=1.5%、聚合时间t=4 h、聚合温度T=85℃、w(溶剂)=156%。酯化:n(马来酸酐-苯乙烯聚合物)/n(十六醇)=1:1.5、w(催化剂)=1.5%、酯化时间t=3 h。IR结果表明:所制备产物的官能团结构与设计的目标产物吻合。将合成的产物按0.42%的剂量加入到俄罗斯原油提炼的0#柴油中,冷滤点可降低10℃。通过XRD和偏光显微镜观察结果表明:蜡晶的形态及结构均发生了变化。     

水性苯乙烯-丙烯酸-马来酸酐共聚物的合成及表征

以过氧化苯甲酰为引发剂、二丙二醇二甲醚为溶剂,采用自由基聚合方法,合成苯乙烯-丙烯酸-马来酸酐三元共聚物。考察单体配比、引发剂用量、反应温度对聚合物性能的影响,并用红外光谱、凝胶色谱、差示扫描量热法等对共聚物进行表征。结果表明,最佳工艺条件是:n(ST):n(AA):n(MA)=6:3:1,反应温度为85℃,引发剂为单体质量的12%;得到数均分子量为4678、分子量多分散指数为1.45的三元共聚物。     

溶液聚合法合成苯乙烯-马来酸酐交替共聚物

在过氧化苯甲酰(BPO)引发下,以丁酮为溶剂,采用溶液聚合法合成了苯乙烯-马来酸酐共聚物,并详细研究了温度、引发剂用量、苯乙烯与马来酸酐配比、单体(苯乙烯与马来酸酐)质量分数及聚合时间对聚合反应的影响。研究表明,在温度80℃,x(BPO)=0.6%(相对于苯乙烯与马来酸酐),n(苯乙烯)∶n(马来酸酐)=1∶1,w(单体)=15%(相对于混合溶液),反应时间4 h的条件下,聚合物收率可达99%。采用13CNMR、IR、GPC、元素分析对共聚物结构进行了表征。利用TG测定了其热稳定性。结合共聚物的元素分析与13CNMR的分析结果,表明合成的苯乙烯-马来酸酐共聚物是一种交替共聚物。     

本体聚合法制备低分子量水基钻井液降粘剂

采用本体聚合的方法,以苯乙烯(St)和马来酸酐(MA)为原料制备苯乙烯-马来酸酐聚合物(SMA),采用氯磺酸进一步磺化后得到低分子量的水基钻井液降粘剂磺化苯乙烯-马来酸酐(SSMA)。研究了单体配比、聚合温度、引发剂用量以及链转移剂用量对产物降粘性能的影响。结果表明,SMA的最佳合成条件为:在St与MA的摩尔比为1∶1的条件下,聚合温度为65℃,引发剂的用量为单体总质量的1.5%,链转移剂的用量为单体总质量的4%,经磺化改性制得的SSMA降粘剂能显著降低钻井液的粘度。利用红外光谱仪、凝胶色谱仪和差热分析仪对聚合物进行表征,可知所合成的聚合物结构与设计结构基本一致,重均分子量在3 000⁵ 000之间,分子量较低;通过热重分析曲线可知,在289℃左右失重保持在90%以上,聚合物热稳定性能良好。     

MA-St型低温流动改进剂的制备及性能评价

采用"先酯化,后聚合"的方法,以马来酸酐、苯乙烯、十六醇、二十二醇为原料,合成了低温流动性改进剂马来酸酐混合酯-苯乙烯共聚物,最佳制备条件为:①酯化:n(马来酸酐)∶n(混合醇)=0.5∶1,w(催化剂)=1.8%、w(溶剂)=90%,酯化时间2.5 h;②聚合:n(苯乙烯)∶n(马来酸酐混合酯)=1∶1,w(引发剂)=1.25%,聚合温度为75℃,聚合时间4 h,溶剂用量为55%。将合成的产物按1.0‰的剂量加入到俄罗斯原油提炼的俄柴油中,冷滤点可降低12℃。     

低温合成苯乙烯-马来酸酐交替共聚物

苯乙烯(St)和马来酸酐(MA)自由基引发共聚反应,生成共聚物SMA,是典型的交替共聚。在过氧化苯甲酰(BPO)引发下,以丙酮为溶剂,采用溶液聚合法合成苯乙烯-马来酸酐共聚物,并用收率作为评价标准,对反应条件进行研究。结果表明,在温度为60℃,BPO的质量分数x(BPO)=0.3%,n(苯乙烯)∶n(马来酸酐)=1∶1,w(单体)=30%,反应2 h的条件下,聚合物的收率可达到98.5%。利用化学滴定法测得聚合物中马来酸酐摩尔分数为49.91%,结合理论,证明了合成的苯乙烯-马来酸酐共聚物是一种交替共聚物。一种低温合成苯乙烯-马来酸酐交替共聚物的工艺得到开发。     

本体聚合法制备低分子量水基钻井液降粘剂

采用本体聚合的方法,以苯乙烯(St)和马来酸酐(MA)为原料制备苯乙烯-马来酸酐聚合物(SMA),采用氯磺酸进一步磺化后得到低分子量的水基钻井液降粘剂磺化苯乙烯-马来酸酐(SSMA)。研究了单体配比、聚合温度、引发剂用量以及链转移剂用量对产物降粘性能的影响。结果表明,SMA的最佳合成条件为:在St与MA的摩尔比为1∶1的条件下,聚合温度为65℃,引发剂的用量为单体总质量的1.5%,链转移剂的用量为单体总质量的4%,经磺化改性制得的SSMA降粘剂能显著降低钻井液的粘度。利用红外光谱仪、凝胶色谱仪和差热分析仪对聚合物进行表征,可知所合成的聚合物结构与设计结构基本一致,重均分子量在3 000~5 000之间,分子量较低;通过热重分析曲线可知,在289℃左右失重保持在90%以上,聚合物热稳定性能良好。     

马来酸酐/丙烯酸/丙烯酸甲酯共聚阻垢剂的合成及应用性能研究

以马来酸酐、丙烯酸、丙烯酸甲酯为原料合成了新型三元共聚物阻垢分散剂,探讨了单体配比、引发剂用量、聚合温度、聚合时间等对共聚物阻垢性能的影响,得出了最佳合成条件:引发剂用量4%;n(马来酸酐):n(丙烯酸):n(丙烯酸甲酯)=2∶2∶1;反应温度70℃;反应时间3 h;得到的产品阻垢率为88.37%。并研究了水质条件及共聚物用量与阻垢性能之间的关系。     

可生物降解苯乙烯-马来酸酐共聚物的合成工艺研究

以苯乙烯与马来酸酐为聚合单体,在适宜的条件下合成得到可降解的苯乙烯-马来酸酐共聚物。考察了引发剂用量、反应温度、反应时间、物料比等因素对SMA共聚物中马来酸酐含量及特性粘数的影响。结果表明,BPO量为0.3%、n(St)/n(MA)=1.2∶1、聚合反应温度125℃、聚合反应时间3 h,可以得到相对分子质量Mn=27 303、分子量分布Mw/Mn=1.873 736的SMA共聚物。利用红外谱(IR)、凝胶渗透色谱(GPC)对产物进行了表征确认。     

可生物降解苯乙烯-马来酸酐共聚物的合成工艺研究

以苯乙烯与马来酸酐为聚合单体,在适宜的条件下合成得到可降解的苯乙烯-马来酸酐共聚物。考察了引发剂用量、反应温度、反应时间、物料比等因素对SMA共聚物中马来酸酐含量及特性粘数的影响。结果表明,BPO量为0.3%、n(St)/n(MA)=1.2∶1、聚合反应温度125℃、聚合反应时间3 h,可以得到相对分子质量Mn=27 303、分子量分布Mw/Mn=1.873 736的SMA共聚物。利用红外谱(IR)、凝胶渗透色谱(GPC)对产物进行了表征确认。     

苯乙烯-马来酸酐共聚物的酯化改性及其对炭黑的分散性能

采用异丁醇对苯乙烯-马来酸酐共聚物(SMA)进行酯化改性,研究了反应温度、时间、催化剂用量、异丁醇用量等因素对共聚物酸值的影响。红外光谱测试表明,SMA中酸酐与异丁醇发生了酯化反应。在以丁酮为反应溶剂,SMA质量占反应体系总质量的5%,异丁醇质量占反应体系总质量的12%,对甲苯磺酸质量占SMA质量的1%,反应温度80℃,反应时间4 h的条件下,SMA部分酯化物(SME)的酸值降低到了271.6 mg KOH/g。炭黑分散研究结果表明,SME对炭黑分散效率优于SMA,当SME酸值低于355.1 mg KOH/g,其用量为炭黑质量的20%,pH=9时,制备炭黑分散体平均粒径为154 nm,制备的炭黑分散体表现出良好的离心稳定性。     

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。     

苯乙烯-马来酸酐共聚物的酯化改性及其对碳黑的分散性能

采用脂肪醇对苯乙烯-马来酸酐共聚物（SMA）进行酯化改性,研究了反应温度、时间、催化剂用量、脂肪醇结构和用量等反应条件对SMA酯化程度的影响。红外光谱测试结果表明SMA酯化改性成功,其较佳的改性工艺条件为异丁醇对SMA的摩尔用量12%,对甲苯磺酸对SMA的质量分数为1%,在80℃条件下反应4h,此时SMA部分酯化物（SME）的酯化度达到了35%。碳黑分散研究结果表明SME对碳黑分散效率明显优于SMA,当SME酯化度超过15%,用量对碳黑质量为20%,pH为9时,制备碳黑分散体粒径为160nm,得到的分散体表现出良好的耐热和离心稳定性。     

Styrene maleic anhydride and styrene glycidyl methacrylate copolymers as in situ reactive compatibilizers of polystyrene/nylon 6,6 blends

The reactive type copolymers styrene maleic, anhydride (SMA) and styrene glycidyl methacrylate (SG) are used as in situ compatibilizers in polyblends of polystyrene (PS) and nylon 6, 6 (N66). Both copolymers can react with N66 to form copolymers as effective compatibilizers to reduce interfacial tension and increase phase adhesion. However, the toughness of the compatibilized blends is significantly lower than of the corresponding noncompatibilized blends. Only a small fraction of SMA is actually reacted in a typical melt blending, and SG copolymer seems to be more reactive than SMA. The unreacted copolymers are expected to be distributed mostly in the PS phase because of their structural similarity. The reacted copolymers are not exclusively distributed along the interface; some may distribute in both matrices. SMA is known as a very brittle polymer, and the way it is distributed can greatly influence the toughness of the resulting blends. PS is also very brittle relative to N66, and moreover a high amount of SMA in the N66 phase is detrimental since N66 is responsible for the toughness of PS/N66 blends. The better compatibilized blends have the tendency to bring more SMA and reacted SMA into the N66 phase. The relative detrimental effect on the inherent toughness of N66 is much more severe than in case of PS, if they contain the same amount of SMA. This study demonstrates that polyblends with good compatibilizers do not guarantee toughness improvement. The way the compatibilizers affect the inherent properties of the matrix needs also to be taken into consideration.     

Study of the Interfacial Reaction of Styrene/Maleic Anhydride Copolymerand (Amine)-Terminated Butadiene-Acrylonitrile Copolymer Using FTIR Imaging Techniques

The interfacial reaction between styrene/maleic anhydride copolymer (SMA) and amine-terminated butadiene-acrylonitrile copolymer (ATBA) was observed using Fourier transform infrared (FTIR) imaging spectroscopy. The anhydride and amine reacted to form an imide. Each component was detected using a characteristic wavenumber, which was 1601 cm -1 for SMA, 2237 cm -1 for ATBA, and 1701 cm -1 for the imide. FTIR images were taken as the reaction proceeded at 150, 160, 170, and 180°C. At low temperatures (150 and 160°C), diffusion-controlled kinetics were observed since interdiffusion between the reactants did not appear in the images. On the other hand, both the diffusion front and the reaction front are observed in the images at high reaction temperatures (170 and 180°C), which indicates that the kinetics became reaction-controlled rather than diffusion-controlled. Absorbance profiles were extracted from the images and used for the calculation of the extent of reaction. The data were analyzed using the Frederickson and Milner theory based on the assumption of diffusion-controlled kinetics, and this theory fit the low reaction temperature data.     

耐老化抗冲击PC/SMA合金的研究

用动态力学热分析法(DMTA)分析丁马来酸酐(MAH)含量不同的3种苯乙烯／MAH共聚物(SMA)与聚碳酸酯(PC)共混物的相容性。结果表明,SMA与PC共混物的相容性随SMA树脂马来酸酐含量的增加而提高,MAH 质量分数为18％d SMA树脂与PC的共混物在整个组成范围内都只有一个玻璃化转变温度。以丙烯酸酯类核壳结构共聚物(ACR)作冲击改性剂制备了不同组成的PC／SMA合金,测试表明合金有良好的力学强度、冲击强度、高耐热性和优良的耐老化性。     

Grafting of Maleic Anhydride Copolymers onto Cellulose Acetate and Methyl Cellulose

A high level of control over grafting reactions onto cellulose derivatives was achieved by an acyl transfer reaction mechanism. Ethylene/maleic anhydride copolymer (EMA) and styrene/maleic anhydride copolymer (SMA) were grafted onto cellulose acetate (CA) and methyl cellulose (MC) in a simple and effective way under homogeneous reaction conditions. While pyridine, a commonly used catalyst for the reaction of an anhydride with an alcohol to form an ester, gave an inconveniently long reaction time, N-methylimidazole (NMID) and 4-(N,N-dimethylamino)pyridine (DMAP) were found to increase greatly the rate of esterification.     

Study of the Interfacial Reaction of Styrene/Maleic Anhydride Copolymerand (Amine)-Terminated Butadiene-Acrylonitrile Copolymer Using FTIR Imaging Techniques

The interfacial reaction between styrene/maleic anhydride copolymer (SMA) and amine-terminated butadiene-acrylonitrile copolymer (ATBA) was observed using Fourier transform infrared (FTIR) imaging spectroscopy. The anhydride and amine reacted to form an imide. Each component was detected using a characteristic wavenumber, which was 1601 cm ?1 for SMA, 2237 cm ?1 for ATBA, and 1701 cm ?1 for the imide. FTIR images were taken as the reaction proceeded at 150, 160, 170, and 180°C. At low temperatures (150 and 160°C), diffusion-controlled kinetics were observed since interdiffusion between the reactants did not appear in the images. On the other hand, both the diffusion front and the reaction front are observed in the images at high reaction temperatures (170 and 180°C), which indicates that the kinetics became reaction-controlled rather than diffusion-controlled. Absorbance profiles were extracted from the images and used for the calculation of the extent of reaction. The data were analyzed using the Frederickson and Milner theory based on the assumption of diffusion-controlled kinetics, and this theory fit the low reaction temperature data.     

苯乙烯-马来酸酐共聚物阳离子化改性及其在颜料分散中的应用

采用环氧丙基三甲基氯化铵(ETA),通过界面反应对苯乙烯-马来酸酐共聚物(SMA)进行改性,制备高分子分散剂(SMG)。红外光谱测试结果表明,ETA和SMA中酸酐发生反应,生成了酯键,当ETA对SMA摩尔比为1.3、对甲苯磺酸占SMA总质量的14%、反应时间6 h、反应温度78℃时,SMG阳离子化度为30.96%。应用实验表明,SMG对炭黑的分散效果明显优于SMA,当SMG阳离子度大于14%、pH=9、SMG对颜料的质量分数为7%时,制备炭黑分散体粒径为170 nm,炭黑分散体热稳定性较佳,60℃处理24 h,粒径变化率仅为3.6%。所制备分散体在pH=3时,炭黑Zeta电位为+28.61 mV,当pH>6.5后,Zeta电位变为负值,表现出两性特征。