聚苯胺微乳液合成及其电致变色性

用 (NH4) 2 S2 O8为氧化剂 ,在功能质子酸 水 正丁醇三元体系中 ,用微乳液法合成了聚苯胺。以聚苯胺的电导率和电致变色性能为标准 ,讨论了引发剂、DBSA、反应温度和反应时间对聚苯胺性能的影响 ,并对影响聚苯胺 /聚乙烯醇复合膜的性能因素作了初步探讨。结果表明 :与用常规乳液法合成的聚苯胺相比 ,用微乳液法合成的聚苯胺与聚乙烯醇所成的膜 ,其电导率提高了 2个数量级 ,电致变色性能也更好。     

高含量聚苯胺水性微乳液的制备

利用分批滴加单体式微乳液聚合法制备了高含量聚苯胺水性纳米微乳液及纳米粒子。所得微乳液中聚苯胺含量达1．0％(质量分数),是其他微乳液聚合的1．25～27．8倍。研究了合成工艺条件对聚苯胺纳米粒子的粒径、产率、相对分子质量、电导率等的影响。发现前后两次滴加的单体比例、酸浓度以及酸种类是主要影响因素。当滴加的单体比例为80：20、盐酸浓度为0．1moL／L时,在20℃下反应24h,可获得稳定的聚苯胺微乳液,放置至少半年不分层。该纳米聚苯胺的粒径为10～40nm,电导率为0．12s／cm。     

H_2O_2-Cu~(2+)化学氧化法合成聚苯胺纳米纤维

以硫酸铜(CuSO4)为催化剂,H2O2为氧化剂,通过"无模板"化学氧化聚合制备出聚苯胺纳米纤维。研究了温度、H2O2的浓度、催化剂的浓度对聚苯胺的产率、电导率、反应速度的影响,确定出最佳聚合反应条件为:苯胺0.1 mol/L,盐酸1 mol/L,H2O2 0.15 mol/L,CuSO40.05 mol/L,反应时间为24小时。在此条件下合成聚苯胺的产率为58.2%,电导率为1.98 S/cm。红外光谱和紫外-可见光谱确定了合成聚苯胺的结构,扫描电镜图中发现制备导电聚苯胺呈纤维状,直径大约为60~80 nm,长度大约为400 nm。     

不同方法制备聚苯胺/MoS_2复合材料及其电容性能

结合Li插层法制备的单层MoS2,分别采用溶液法和乳液法原位聚合制备了聚苯胺/MoS2复合材料。由FT-IR光谱对其结构进行表征,由电化学工作站测试其做电容器电极材料的电化学性能。结果表明,相同MoS2用量下,乳液法制备的聚苯胺/MoS2复合材料在0.8 A/g电流密度下的比电容为245 F/g,是溶液法聚苯胺/MoS2复合材料的3倍;充放电1000圈后的比电容保持率为82%,比溶液法聚苯胺/MoS2复合材料高11%,显示出更好的电容性能。     

不同质子酸掺杂对聚苯胺合成与性能的影响

由化学氧化法制得的聚苯胺(PANI)被不同质子酸掺杂。研究盐酸(HCl)、硫酸(H2SO4)、樟脑磺酸(CSA)和十二烷基苯磺酸(DBSA)掺杂对PANI产率、溶解性以及电导率的影响。研究发现,HCl掺杂的PANI电导率为0.263 4 S/cm、产率可达到78.83%。还讨论不同HCl浓度和不同过硫酸铵/苯胺(APS/An)的物质的量比对HCl掺杂PANI产率和电导率的影响,当HCl的浓度达到1.2 mol/L、APS/An物质的量比为0.6时,PANI的电导率和产率均为最大值。     

叔-醋-丙乳液粘度影响因素的研究

采用种子乳液聚合法制备叔-醋-丙(VeoVa/VAc/BA)共聚乳液,考察了保护胶体种类和用量、乳化剂用量、聚合温度和搅拌速率对该共聚乳液粘度的影响。研究结果表明,保护胶体的醇解度和乳化剂用量对乳液粘度的影响最为明显;使用低醇解度的聚乙烯醇(PVA1788),当w(PVA1788)=10%时,乳液粘度最大;当w(乳化剂)>3%时,乳液粘度下降不明显。     

聚醋酸乙烯酯乳液合成工艺的研究

介绍了聚醋酸乙烯酯乳液的合成工艺 ,主要考察了单体、乳化剂、引发剂、反应温度及聚乙烯醇对乳液粘度、固含量的影响。当反应温度为 75℃ ,乳化剂、引发剂用量分别为单体总量的 0 .15%和 0 .6 %条件下 ,得到粘度为 5 .8Pa·s、固含量为 4 2 %、pH值为 6～ 8,带蓝光的乳白色聚醋酸乙烯酯乳液。     

复合氧化剂法制备聚苯胺乳液及其应用性能的研究

采用正相微乳液法,以苯胺为单体、十二烷基苯磺酸为掺杂剂、抗坏血酸和过硫酸铵为复合氧化剂制备聚苯胺乳液及性能良好的聚苯胺粉体,考察了复合氧化剂组成和用量对聚苯胺性能的影响,并探讨了聚苯胺乳液直接应用于带锈涂料中防腐性能的变化规律,结果表明:以抗坏血酸与过硫酸铵复合作为氧化剂,过硫酸铵与抗坏血酸质量比为13∶1,十二烷基苯磺酸与苯胺物质的量比为1.25∶1.00,合成的聚苯胺性能优良;添加0.5%的聚苯胺乳液于带锈涂料中,可以有效地提高带锈涂料的防腐性能。     

聚苯胺的合成工艺优化及其性能表征

采用化学氧化聚合法在苯胺/过硫酸铵/HCl的水溶液体系中合成聚苯胺,并对其聚合条件([S2O2-8]/[An]比、HCl浓度变化等)进行了优化,以提高PAn的电导率和产率。通过四探针、傅立叶红外吸收光谱(FTIR)、XRD、CV等测试方法对聚苯胺电导率及掺杂前后结构的变化进行了分析。结果表明,当[S2O2-8]/[An]=1∶1、[HCl]=0.8 mol/L时电导率达到最大值2.13 S/cm,产率为94.37%。聚合物具有一定的结晶性,通过CV曲线可以分析出PAn具有掺杂/脱掺杂的电化学活性。     

高粘度苯丙乳液的制备与性能研究

采用一步乳液聚合法制备出一种具有高粘度的苯丙乳液,通过傅里叶红外光谱(FTIR)研究高粘度苯丙乳液的微观结构,探讨了聚乙烯醇(PVA)含量对聚合物乳液粘度、固含量、吸水率、力学性能等物理性能的影响。结果表明,实验成功合成了固含量稳定的高粘度苯丙乳液;当PVA含量为2.2%时,乳液粘度达到3 346.5 m Pa·s,增幅为288.32%;断裂伸长率高达2 478%,增幅为251.21%。与纯苯丙乳液相比,所制备的高粘度苯丙乳液综合性能得到明显提高。     

原位乳液聚合制备导电性聚苯胺/氯磺化聚乙烯复合材料及其性能

以十二烷基苯磺酸为乳化剂及掺杂剂,由二甲苯及水组成乳液,在氯磺化聚乙烯存在下,采用一步原位乳液聚合法制备了聚苯胺／氯磺化聚乙烯(PAn／CSPE)导电复合材料。研究了用熔融法(MP)或溶液法(SP)加工复合物材料的导电性及力学性能,并进行了表征。结果表明,MP法制得的复合材料在导电性及力学性能方面优于SP法制得的复合材料;当PAn质量分数为12％～18％时,MP法复合材料呈现热塑性弹性体行为,拉伸强度为6～8MPa,扯断伸长率大于400％,永久变形小于30％。当PAn质量分数小于18％时,SP法复合材料用闻甲酚二次渗杂后的导电率比原复合材料高出6个数量级,且其导电渗滤阈值由PAn质量分数22％降至3％。     

Preparation of conductive polyaniline/chlorosulfonated polyethylene composites via in situ emulsion polymerization and study of their properties

The conductive composites of polyaniline (PAn) and chlorosulfonated polyethylene (CSPE) were prepared by polymerization of aniline in the presence of CSPE, using a direct, one‐step in situ emulsion polymerization method. The polymerization of aniline was performed in an emulsion comprising water and xylene containing CSPE in the presence of dodecylbenzene sulfonic acid, which acts both as a surfactant and a dopant for PAn. The composites can be processed by either melt method (MP) or solution method (SP). Conductivity of the composites obtained by different processing methods shows different percolation thresholds: 14 wt % for MP samples and 22 wt % for SP samples. At the same content of PAn, the conductivity of MP composites is higher than that of SP composites. The relationships between mechanical properties and PAn content obtained by the two different processing methods were also investigated. When PAn content of MP samples is between 12 and 18 wt %, the composites behave like a thermoplastic elastomer with tensile strength at 6–8 MPa, ultimate elongation > 400% and permanent set < 30%. The conductivity of composites obtained by SP method after secondary doping with m‐cresol is about 6 orders of magnitude higher than the original at below 18 wt % PAn content and the percolation threshold for conductivity is lowered to 3 wt % PAn content. The composite shows no electrochromic activity in acidic solution of LiClO₄ in propylene carbonate, but after secondary doping exhibits electrochromic activity even in neutral electrolyte. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 845–850, 2000     

苯胺在聚醋酸乙烯酯中的聚合研究

以过硫酸铵为氧化剂,十二烷基苯磺酸为掺杂剂,将苯胺在聚醋酸乙烯酯(PVAc)基质中进行原位氧化聚合,制备导电聚苯胺PAn/PVAc复合材料,采用溶液浇铸法制成可溶性导电复合膜,电导率达10-2s/cm。考察了反应条件对复合膜电导率的影响,并进行了环境稳定性测试,用红外光谱进行了复合膜的结构表征,用扫描电镜对复合膜的表面形态进行了观察。     

乳液聚合法制备聚苯胺及其导电性能

以十二烷基苯磺酸(DBSA)为乳化剂,十六醇(CA)为助乳化剂,盐酸和十二烷基苯磺酸（DBSA）为掺杂剂, 过硫酸铵为引发剂,采用乳液聚合法合成了导电聚苯胺（PAn）.研究了反应温度、反应时间及苯胺、十二烷基磺酸、十六醇、盐酸和过硫酸铵配比对聚苯胺电导率的影响.研究结果表明,较佳的工艺条件为：反应温度为7 ℃,反应时间为6 h,较佳的原料物质的量的比为苯胺∶十二烷基苯磺酸∶十六醇∶盐酸∶ 过硫酸铵=0.05∶0.028∶0.04∶0.01∶0.05;以十六醇为助乳化剂,采用十二烷基苯磺酸和盐酸为掺杂剂,提高了聚苯胺的导电性.同时对聚苯胺导电机理进行了分析.     

DBSA掺杂聚苯胺的制备、表征及其导电性

采用过硫酸铵(APS)为氧化剂在十二烷基苯磺酸(DBSA)微胶束中化学氧化制备纳米棒状聚苯胺;DBSA既起乳化剂也起掺杂剂的作用。制备的掺杂聚苯胺用红外光谱(FTIR)、紫外光谱(UV-vis)、X-射线衍射(XRD)和扫描电镜(SEM)进行了表征;透射电镜(TEM)下首次观察到了聚苯胺的有序排列结构,晶面间距为5.99 Å。考察了掺杂剂/苯胺、氧化剂/苯胺的摩尔比和反应温度、时间等对聚苯胺电导率影响,最高电导率达到了0.72 S/cm。透射电镜怎能看到5.99     

Change of conductivity of polyaniline/(styrene–butadiene–styrene) triblock copolymer composites during mechanical deformation

A measuring method for a conductivity change through a current change during extension deformation or compression deformation of conductive elastomeric composites composed of a polyaniline (PAn)/styrene–butadiene–styrene (SBS) triblock copolymer was established. The composites were prepared by in situ emulsion polymerization of aniline in the presence of SBS using dodecylbenzene sulfonic acid (DBSA) as an emulsifier and a dopant. The product was melt‐processed (MP), solution‐processed (SP), or secondary doped with m‐cresol (SSP). The results for measurement of the conductivity change of the composites processed by the three different methods showed that for the MP and SP samples conductivity increases with extension, whereas for the SSP sample when the PAn content is lower than the percolation threshold, conductivity diminishes with increasing extension, but when the PAn content exceeds the percolation threshold value, conductivity followed an empirical equation with a maximum value. During compression, the conductivities of most of the MP, SP, and SSP samples exhibited a maximum value with change of the compression force, except the MP sample with a higher PAn content, the conductivity of which increased with the compression force. All the differences are related to their different morphological structures. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 2156–2164, 2000     

Preparation of conductive polyaniline‐sulfonated EPDM ionomer composites from in situ emulsion polymerization and study of their properties

The composites of polyaniline (PAn) and zinc sulfonated ethylene–propylene–diene rubber (EPDM) ionomer were made by polymerization of aniline in the presence of the ionomer by using a direct, one‐step in situ emulsion polymerization technique. The ionomers were prepared by sulfonation of EPDM rubber with acetyl sulfate in petroleum ether, followed by neutralization with zinc acetate solution. The ionomers with sulfonate contents of 10, 24, and 42 mmol SO₃H/100 g were used for preparation of PAn/ionomer composites. The in situ polymerization of aniline was carried out in an emulsion comprising water and xylene containing the ionomer in the presence of dodecyl benzene sulfonic acid, acting as both a surfactant and a dopant for PAn. The composite was characterized by IR and WAXD. The composite obtained can be processed by melt method. The conductivity of the composite with lower sulfonate content was higher than that with higher sulfonate content. Conductivity of the composites exhibits a percolation threshold at about 13 wt % PAn. When the sulfonated content is 10 or 24 mmol SO₃H/100 g and PAn content is 4–10 wt %, the composites behave as a thermoplastic elastomers with high ultimate elongation and low permanent set. The conductivity of the composite after secondary doping with m‐cresol is higher than the composite before secondary doping by about one order. Addition of zinc stearate as an ionic plasticizer lowers both the conductivity and the mechanical strength of the composites. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 2211–2217, 2004     

导电聚苯胺复合膜的研制

以聚甲基丙烯酸甲酯(PMMA)为基质，过硫酸铵为氧化剂，十二烷基苯磺酸为掺杂剂，进行苯胺的原位氧化聚合，制备聚苯胺(PAn)／PMMA复合材料，采用溶液浇铸法制成了性能优良的可溶性导电复合膜，电导率达10^-2S／cm；考察了反应条件对复合膜电导率的影响，并进行了环境稳定性测试，用红外光谱进行了复合膜的结构表征，用元素分析法测定了复合膜的组成，结果表明复合的聚苯胺存在—饱和值，超过饱和值，对电导率影响不大。     

Conductive polyaniline/polyacrylonitrile composite fibers: Effect of synthesis parameters on polyaniline content and electrical surface resistivity

Conductive polyaniline/polyacrylonitrile (PAn/PAN) composite fibers were prepared by keeping PAN fibers in various solutions containing aniline and then by polymerization of aniline sorbed by fibers with potassium dichromate as an oxidant. In examined polymerization media, aqueous HCl gave composite fibers with the highest PAn amount and these fibers also had the lowest electrical surface resistivity. It was found that, as PAn content of PAn/PAN composite fibers increased, its density also increased and mechanical properties such as tensile strength and breaking elongation decreased. From optical cross‐section images of composite fibers, it was observed that PAn coating was limited only with the PAN fiber surface. POLYM. COMPOS., 2009. © 2008 Society of Plastics Engineers     

十二烷基苯磺酸乳化液膜法净化湿法磷酸除镁

采用乳化液膜技术对湿法磷酸进行净化处理,针对磷酸-镁体系,选用带磺酸基团(-S03H)的十二烷基苯磺酸作为萃取剂,在其不同浓度下对pH=0.27的磷酸体系中的镁离子进行净化实验,得到了乳化时表面活性剂十二烷基苯磺酸的临界浓度。最佳实验条件:十二烷基苯磺酸在有机相中的临界浓度为摩尔分率10%,最佳油水体积比为1/3,最佳乳化转速为5400 r/min,最佳乳化时间45 s。