Vulcanization of chlorobutyl rubber. I. The identification of crosslink precursors in compounds containing ZnO/ZnCl2

Chlorinated poly(isoprene‐coisobutylene) (CIIR or chloro‐butyl) was characterized by Nuclear Magnetic Resonance. Compounds with ZnO, ZnCl₂, and ZnO/ZnCl₂ were vulcanized in a DSC at a programmed heating rate and isothermally at 150°C in a press. Crosslink densities were determined by swelling and extracted ZnCl₂ analyzed by atomic absorption. ZnCl₂ formation precedes crosslinking, and at equilibrium only 50% of the chlorine in the rubber is extractable as ZnCl₂. ZnCl₂ promotes crosslinking, and its addition to formulations decreases but does not eliminate the induction period prior to crosslinking. Dehydrohalogenation, which is catalyzed by ZnCl₂ in an autocatalytic process, is accompanied by the formation of conjugated diene butyl on the polymer chain. It is demonstrated that both species, not only ZnCl₂, are necessary precursors to crosslink formation. Moist ZnCl₂ catalyzes dehydrohalogenation but not crosslinking, while ZnO does not promote either reaction. CIIR can be crosslinked to polybutadiene and to polyisoprene, no induction period applying when ZnCl₂ is present in the formulation, and high crosslink densities develop in blends precipitated from solution. Severe reversion occurs in formulations where there is insufficient ZnO to trap all of the HCl evolved. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 2290–2301, 2000     

Vulcanization of polychloroprene rubber. I. A revised cationic mechanism for ZnO crosslinking

Data relating to the vulcanization of mercaptan‐grade polychloroprene (CR) by ZnO and MgO (alone or in combination) are examined. Compounds were vulcanized through the isothermal heating of samples at 140°C in a laboratory press and at programmed rates in a differential scanning calorimeter. The reaction was stopped at various points during the heating process. The crosslink densities were determined via swelling. Extractable ZnCl₂ and MgCl₂ were analyzed by atomic absorption spectrometry. Three different crosslinking processes were identified. The first crosslinking process involved the activation of the highly reactive tertiary allylic 1,2‐units along the polymer chain, whereas the second and third crosslinking processes were attributed to the activation toward crosslinking of 3,4‐ and 1,4‐units, respectively. The crosslinking reactions of the 1,2‐units comprised three distinct steps: isomerization (promoted by ZnO), dechlorination, and crosslinking. ZnCl₂ (which formed during compounding and upon crosslinking) promoted crosslinking, and its addition to formulations decreased but did not eliminate the induction period before crosslinking. MgO retarded the crosslinking process by limiting the formation of ZnCl₂ during mixing. The results of the CR/ZnO system are discussed, and a modified cationic mechanism for crosslinking is proposed. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Vulcanization of chlorobutyl rubber. III. Reaction mechanisms in compounds containing combinations of zinc dimethyldithiocarbamate,tetramethylthiuram disulfide,sulfur, and ZnO

Poly(isoprene‐co‐isobutylene) (IIR or butyl) and chlorinated poly(isoprene‐co‐isobutylene) (CIIR or chlorobutyl) compounds containing combinations of zinc dimethyldithiocarbamate [Zn₂(dmtc)₄], tetramethylthiuram disulfide (TMTD), sulfur, and ZnO were vulcanized at 150°C, the reaction was stopped at various points, crosslink densities were determined by swelling, and the concentrations of residual curatives and extractable reaction intermediates and products were determined by high‐performance liquid chromatography and atomic absorption (ZnCl₂). In compounds that did not contain zinc, CIIR crosslinked more slowly than IIR and crosslinking could be explained by the same mechanism as applies to the vulcanization to highly unsaturated rubbers like polyisoprene. In zinc containing compounds, CIIR crosslinked faster because of dehydrohalogenation reactions that led to carbon–carbon crosslinks. As found with ZnO/ZnCl₂ formulations, both ZnCl₂ and conjugated diene butyl are essential precursors to crosslink formation. Zn₂(dmtc)₄ can trap HCl, thus preventing reversion and may also initiate dehydrohalogenation. When the equilibrium crosslink density is reached, 50% of the chlorine originally present in the rubber is extractable as ZnCl₂ and the remainder as dimethylthiocarbamic acid chloride. A mechanism to account for dehydrochlorination and crosslinking in the presence of Zn₂(dmtc)₄ is presented. In compounds with sulfur, crosslinking occurs via accelerated sulfur vulcanization and chlorine abstraction, leading to higher crosslink densities than is achieved with either curative system on its own. Carbon–carbon crosslinks predominate, the slower, accelerated sulfur reaction, making a lesser contribution to the overall reaction. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 1309–1316, 2001     

NB R / Zn (MAA) 2合金的硫化与交联

用硫化仪研究了NBR／Zn(MAA)2合金的硫化特性,结果表明,随着Zn(MAA)2用量的增大,合金的硫化速度提高,焦烧时间缩短,表现活化能下降,平衡溶胀及平衡应力一应变实验表明,NBR／Zn(MAA)2合金的交联密度随Zn(MAA)2用量的增大而增大。差示扫描量热分析表明合金内部发生了复杂的化学交联,同时Zn(MAA)2均聚物与NBR交联网络互相贯穿缠结,起到了强迫相容的作用。     

纳米CuO/ZnO去除H2S反应条件及机理研究

以纳米CuO/ZnO作为去除H2S的活性组分,考察了反应温度、空速、氧分压等反应条件和掺铜量对纳米CuO/ZnO脱硫性能的影响,并分析了CuO对脱硫剂脱硫机理的影响。结果表明:脱硫剂TZ2(Cu:Zn物质的量比为1:18.40)有较高的脱硫性能;空速越低脱硫性能越高;反应温度由25℃升高到120℃,脱硫性能先下降后升高,120℃的脱硫性能略高于25℃;氧分压为10%时,有最佳的脱硫性能;CuO的加入增大了脱硫产物向多硫化物及单质硫的转化。     

ZnCl2/C气固催化氯化吡啶制备2,3,5,6-四氯吡啶

以氯化锌为活性组分,活性炭为载体,通过气固催化氯化吡啶合成2,3,5,6-四氯吡啶。催化剂在低温下具有较高的收率,但易发生平行副反应而导致催化剂失活,高温下ZnCl2/C具有较好的稳定性,催化剂高温失活原因主要是活性组分的流失。在氯气与吡啶摩尔配比为7、空速为1400h^-1、温度为420℃下,催化剂连续运行实验表明,2,3,5,6-四氯吡啶的收率大于54％,多氯吡啶的总收率稳定在91％以上。     

Photoluminescence mechanism of annealed ZnO/Zn/Al2O3 sandwich structures deposited on glass substrates

ZnO/Zn/Al₂O₃ sandwich structures are grown on glass substrates by magnetron sputtering. The effect of Al₂O₃ layers on optical properties of ZnO/Zn/Al₂O₃ sandwich structures is investigated. Results indicated that as the deposition time of Al₂O₃ increases, violet peak centered at 402 nm gradually shifted to 412 nm and the intensity firstly decreases and then increases. We discuss the intensity change and shift of violet peak relating to V_Zn defects and the band alignment of ZnO/Zn/Al₂O₃ sandwich structures, respectively. We proposed that ZnO/Zn/Al₂O₃ sandwich structures can be approximately regarded as a quasiquantum-well-like structure. So the electron tunneling from Zn to Al₂O₃ layer is suppressed and the photogenerated carriers can be confined in the Zn Fermi level. In order to further understand the effect of posttreatment on optical properties of samples, samples are annealed in vacuum at 350 °C for 1 h. PL emissions are weakened with the increase of Al₂O₃ deposition time. Interestingly, at a same deposition condition, PL emissions are still improved after posttreatment. Combined Al₂O₃ layer modulation with annealing treatment, steady PL properties can be effectively improved.     

Effect of carboxylic acids on 2‐bisbenzothiazole‐2,2′‐disulfide‐ and tetramethylthiuram disulfide‐accelerated sulfur vulcanization. II. Vulcanization of polyisoprene in the absence of ZnO

Polyisoprene was vulcanized by 2‐bisbenzothiazole‐2,2′‐disulfide (MBTS)/sulfur and tetramethylthiuram disulfide (TMTD)/sulfur in the absence and presence of benzoic and stearic acids. It was found that the crosslink density of MBTS vulcanizates is halved by the addition of carboxylic acids and this can be explained in terms of the attack of the acids on the accelerator polysulfides. TMTD polysulfides are more reactive toward polyisoprene than are MBTS polysulfides, and their addition to the polymer chain occurs before significant attack by the carboxylic acids can reduce the polysulfide concentration. Consequently, the acids have little effect on the crosslink density of TMTD vulcanizates. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 1007–1012, 1999     

A comparison of tetraethylthiuram and tetramethylthiuram disulfide vulcanization. II. Reactions in rubber

The reactions of tetraethylthiuram disulfide (TETD) with polyisoprene were investigated under vulcanization conditions. Samples of polyisoprene compounded with various combinations of TETD, sulfur, and ZnO were heated in a differential scanning calorimeter to various degrees of vulcanization. The crosslink density of the compounds was determined by swelling, and the extractable residual curatives and reaction products were analyzed with high‐performance liquid chromatography. TETD caused crosslinking to occur in the absence of added sulfur, as did tetramethylthiuram disulfide (TMTD), both sulfur donors. In the presence of sulfur, the formation of TETD polysulfides occurred immediately before the crosslinking reaction started. The TETD polysulfides were the initial crosslinking agents. The ready reaction between TETD and zinc oxide to form zinc diethyldithiocarbamic acid resulted in considerably higher crosslink densities. This greater reactivity between TETD and zinc oxide, compared with that between TMTD and zinc oxide, did not lead to any noticeable differences in the vulcanizate. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 1119–1127, 2002     

Dimethylammonium dimethyldithiocarbamate‐accelerated sulfur vulcanization. II. Vulcanization of rubbers and model compound 2,3‐dimethyl‐2‐butene

Rubber and model compound 2,3‐dimethyl‐2‐butene were vulcanized for various times with dimethylammonium dimethyldithiocarbamate [(dma)dmtc]‐accelerated sulfur formulations in the absence of ZnO. Model compound systems were analyzed by HPLC, and no reaction intermediates containing pendent groups were found. Crosslinked sulfides, characterized by ¹H‐NMR, were found to be essentially bis(alkenyl). Residual curatives were extracted from rubber compounds vulcanized for various times and analyzed by HPLC. Compounds, cured to various crosslink densities, were found to crystallize readily in a density column at subambient temperatures. This supports evidence from model compound systems that pendent groups are largely absent from vulcanizates. It is suggested that a reaction mechanism, similar to that applicable to zinc dimethyldithiocarbamate‐accelerated sulfur vulcanization, may be applicable with (dma)dmtc accelerated formulations. Very limited crosslinking occurred on heating compounds under vacuum, and this can be attributed largely to the rapid loss of (dma)dmtc from rubber at elevated temperatures. However, the slower rate of crystallization on cooling of the gels, compared to the rate in press‐cured vulcanizates of similar crosslink density, was interpreted as evidence that some pendent groups did form during heating with (dma)dmtc/sulfur. Crosslinking of such pendent groups may be inhibited by the loss of (dma)dmtc, that, like zinc dimethyldithiocarbamate, may catalyze their crosslinking, and/or to the loss under vacuum of dimethyldithiocarbamic acid that would form thiol pendent groups that would rapidly crosslink with thiuram pendent groups. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 3074–3083, 2001     

TiO2/ZnO水溶胶稳定性因素探讨

以钛酸丁酯和乙酸锌为前驱物,采用溶胶-凝胶技术制备TiO2/ZnO复合水溶胶。分析了TiO2与ZnO的掺杂比例,乙醇与钛酸丁酯比例,冰乙酸用量对溶胶稳定性的影响。结果表明:TiO2/ZnO复合水溶胶的稳定性随着ZnO所占比例的增大,冰乙酸量的增多都逐渐增强;TiO2/ZnO复合水溶胶的稳定性随乙醇和钛酸丁酯的比例的增大而不稳定。     

N,N′‐Pentamethylenethiuram disulfide and N,N′‐pentamethylenethiuram hexasulfide accelerated sulfur vulcanization. III. Vulcanization of polyisoprene and 2,3‐dimethyl‐2‐butene in the absence of ZnO

Polyisoprene and model compound, 2,3‐dimethyl‐2‐butene, were vulcanized with N,N′‐dipentamethylenethiuram disulfide (CPTD), CPTD/sulfur and N,N′‐dipentamethylenethiuram hexasulfide (CPTP6) in the absence of ZnO and residual extractable curatives and reaction intermediates analyzed by HPLC at various stages of the reaction. Accelerator polysulfides, required for the formation of accelerator‐terminated polysulfidic pendent groups, form rapidly, or are present from the outset in the case of CPTP6. Model compounds confirm the formation of thiuram‐terminated polysulfidic pendent groups as intermediates in the vulcanization process. Removal of pentamethylenedithiocarbamic acid (Hpmtc) from the system during heating delays the onset of vulcanization and leads to very low crosslink densities. Rubbers heated under vacuum can subsequently be crosslinked by the addition of zinc stearate, pointing to the presence in the compound of thiuram‐terminated pendent groups. However, such pendent groups do not readily crosslink on their own, and hydrogen‐terminated polysulfidic pendent groups, formed by the reaction of sulfurated Hpmtc with the polymer, are suggested to be involved in the crosslink formation. N,N′‐Pentamethylenethiurea forms in the vulcanizate, but is not as product of crosslinking reactions, rather of CPTD degradation. The data are discussed with respect to mechanisms proposed in the literature for crosslinking, and it is concluded that the data support recently formulated mechanisms in which crosslinking involves reaction between thiuram and thiol‐terminated pendent groups, with Hmptc playing and essential role in the overall process. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 1100–1111, 2000     

The role of thiol intermediates in 2‐mercaptobenzothiazole accelerated sulfur vulcanization of rubber model compounds

The model compound, 2,3‐dimethyl‐2‐butene (TME), was vulcanized using 2‐mercaptobenzothiazole (MBT) and sulfur. MBT was not consumed during the vulcanization reaction. The resultant crosslink products were bis(alkenyl) in nature. 2,3‐Dimethyl‐2‐buten‐1‐thiol (TME‐SH) was identified as being present in the vulcanization mixture by a postcolumn derivatization technique. The appearance of thiol was coincident with crosslinking. Polysulfanes (H₂S_n) were formed on crosslinking. Studies of the reaction of TME‐SH and sulfur indicated a rapid reaction to form crosslink products and polysulfanes. No monosulfidic crosslink species were formed in these reactions. Closer investigation revealed the presence of small quantities of what appeared to be highly reactive polysulfidic thiols. This is the first time that such species have been identified in vulcanization systems. Consequently, MBT‐accelerated vulcanization of TME is proposed to occur via the reaction of MBT and S₈ to form polysulfidic MBT, which then reacts with TME to form polysulfidic thiols. These thiols then rapidly react via a metathesis reaction pathway to provide crosslink products and polysulfanes. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 47–54, 2003     

TiO2、ZnO和TiO2/ZnO三种氧化物粉体材料的抗菌性能对比

氧化物具有化学性质稳定、原材料丰富易得的优点,其作为抗菌材料日益受到关注。对氧化物的抗菌性能及影响因素开展深入研究,能够为新型抗菌材料的开发提供科学依据。通过溶胶-凝胶法制备出了TiO₂/ZnO复合粉体,并将其与TiO₂、ZnO进行对比,分别对它们的晶相结构、微观形貌和粒径进行了表征。利用大肠杆菌ATCC25922作为受试菌株,通过抑菌环试验和菌液接触试验对3种氧化物粉体材料的抗菌性能进行测试。考察了钛锌比、光照等条件对抗菌效果的影响。结果表明,所使用的TiO₂主要由锐钛矿相和金红石相组成,ZnO主要为六方纤锌矿相,制备出的TiO₂/ZnO则主要是锐钛矿型TiO₂在六方纤锌矿型ZnO的孔隙间沉积而成,这3种粉体材料的粒径由大到小分别为TiO₂/ZnO、TiO₂和ZnO。从抑菌环和菌液接触试验的结果可以看出,ZnO粉体材料的抗菌效果明显优于TiO₂粉体材料,ZnO和TiO₂/ZnO在黑暗条件下仍有良好的抗菌性能,但在可见光照射条件下抗菌效果更佳。ZnO含量是TiO₂/ZnO复合材料抗菌性能的关键因素。制备TiO₂/ZnO粉体材料时的煅烧温度对其抗菌性能没有明显影响。     

A facile microwave enhanced synthesis of sulfur-containing 5-membered heterocycles derived from 2-mercaptobenzothiazole over ZnCl 2/DMF and antimicrobial activity evaluation

An efficient and extremely fast procedure for the synthesis of 4-thiazolidinones 4a–j by the reaction of arylidene-[(2-benzothiazolylthio)-acetamidyl] 3a–j with thioglycolic acid in DMF in the presence of a catalytic amount of anhydrous ZnCl ₂ under microwave irradiation is described. A considerable increase in the reaction rate has been observed with better yield in microwave technique. All the compounds have been screened for their antifungal activity against Candida albicans (ATCC-64550), Candida krusei (ATCC-14243) and Candida parapsilosis (ATCC-22019) and antibacterial activity against Escherchia coli (Gram?ve) (ATCC-8739), Staphylococcus aureus (Gram+ve) (ATCC-6538) and Bacillus substilis (Gram+ve) (ATCC-6633). The structures of the synthesised compounds 4a–j have been characterized on the basis of their elemental analysis and spectral data.     

CaF_2/ZnO的制备及光催化性能研究

ZnO因其费用低、活性高、无毒等特点,在光催化领域有着广泛的应用前景。通过向ZnO中掺入其它物质制备复合材料,可以达到调控ZnO的光催化性能的目的,扩大ZnO的具体应用范畴。以ZnO为主体研究材料,向ZnO中加入不同质量比的CaF_2,通过沉淀法制备CaF_2/ZnO复合材料。利用x-射线衍射分析(XRD)、扫描电镜(SEM)等手段对此复合材料的晶相、组份及微观结构进行表征。通过紫外-可见吸收光谱研究该复合材料在可见光、紫外光下降解亚甲基蓝的效率,发现与纯ZnO相比,可见光下CaF_2/ZnO复合材料对亚甲基蓝的降解效率随着掺入CaF_2的质量比的提高,呈现先下降后升高的趋势;而紫外光下CaF_2/ZnO复合材料对亚甲基蓝的降解效率都要比纯ZnO要高。     

ZnO/Al_2O_3复合粉体对Cu~(2+)的吸附研究

采用共沉淀法制备ZnO/Al_2O_3复合粉体,探究了粉体的ZnO∶Al_2O_3不同质量比对Cu2+的吸附性能影响,进一步探讨了投加量、pH值、振荡时间、温度对吸附效果的影响。结果表明,ZnO∶Al_2O_3在质量比为4∶1,投加量为30mg,pH=6,吸附时间为15min,温度为40℃的条件下,ZnO/Al_2O_3复合粉体对Cu2+的吸附率最高,达到92.5%。     

ZnO/Al_2O_3复合粉体对Cu~(2+)的吸附研究

采用共沉淀法制备ZnO/Al_2O_3复合粉体,探究了粉体的ZnO∶Al_2O_3不同质量比对Cu2+的吸附性能影响,进一步探讨了投加量、pH值、振荡时间、温度对吸附效果的影响。结果表明,ZnO∶Al_2O_3在质量比为4∶1,投加量为30mg,pH=6,吸附时间为15min,温度为40℃的条件下,ZnO/Al_2O_3复合粉体对Cu2+的吸附率最高,达到92.5%。     

氧化锌氧化钛复合光催化剂的制备及活性研究

二氧化钛光催化氧化技术是目前比较有效的环境治理新技术,而开发高效二氧化钛光催化材料是该技术得以推广应用的前提。采用一种简单的浸渍法成功制备出氧化锌/氧化钛复合纳米光催化剂,并进行了XRD、XPS和SEM等测试表征。从测试结果发现,pH值对样品的光催化活性有重要影响。经对比样品对亚甲基蓝的降解率随着pH值的上升而增加,当pH值为12时,样品的光催化活性达到最高。根据我们对机理的深入分析,发现氧化锌和二氧化钛之间的协同作用是导致该复合催化剂具有如此高的催化活性的根本原因。