PVC燃烧时HCl的释放规律

火灾中PVC燃烧后会产生大量HCl气体,危及人的生命安全.利用火灾烟气发生装置和红外傅立叶变换气体分析仪(FTIR)对PVC热解和燃烧时产生的烟气中的HCl气体浓度进行了实时在线的定量分析,结果表明PVC在受热升温后的热解阶段就会释放出大部分HCl气体,使得烟气毒性达到峰值.对于PVC燃烧产生的火灾,其烟气毒性最大工况发生在火焰出现之前.     

环氧脂肪酸甲酯接枝改性PVC及其增塑性能研究

通过巯基与聚氯乙烯(PVC)氯原子的亲核反应将羧基引入PVC大分子链,再利用环氧脂肪酸甲酯与羧基之间的反应,通过化学键将其连接入PVC大分子链,实现对PVC内增塑.用傅里叶红外(FTIR)、核磁共振(1H-NMR)、示差扫描量热法(DSC)对改性产物进行了表征.FTIR、1H-NMR结果表明,环氧脂肪酸甲酯成功共价连接到了PVC大分子链上,接枝率为1.2 mol%;DSC测试结果显示,所采用的环氧脂肪酸甲酯改性PVC方法能有效降低PVC的玻璃化转变温度(Tg),5.6 wt%的增塑剂可将PVC的Tg从81.4℃降至37.8℃;增塑剂耐溶剂抽出性与耐挥发性实验结果表明,环氧脂肪酸甲酯在测试时间内无损失,增塑剂迁移得到彻底抑制.     

PVC/MBS共混物的紫外光交联及光氧化反应

PVC及其共混物应用广泛，MBS作为PVC制品的透明抗冲改性剂，在提高PVC抗冲性能的同时，必然影响PVC在紫外光照下发生的光化学反应过程,我们用紫外可见光研究了MBS对PVC紫外光解脱HCl动力学，发现MBS对PVC光解脱HCl有抑制作用，本文利用FTIR光谱研究PVC／MBS共混体系中，MBS对PVC光氧化、光交联及光降解过程的影响。     

PVC/ABS共混塑料结构与性能的研究

本文利用透射电镜观察PVC/ABS共混塑料的结构,结合其流变性能,机械性能,探讨结构与性能之间的关系。结果表明,PVC/ABS共混望料的热性能,抗冲击强度介于纯PVC和ABS之间,而缺口冲击强度则优于PVC和ABS,且当ABS含量为30％时有个最大值,这是由于PVC/ABS共混塑料的微观结构造成的。PVC/ABS共混塑料随着ABS含量的减少,“橡胶”粒子变小,当ABS含量为30％时,二组分相容性最好。     

PVC/EVA/SBS共混体系研究

利用溶液成膜法制备了PVC/SBS薄膜 ,对其表观形态、力学性能进行了研究 ,并讨论了EVA对体系的增容作用。发现EVA在一定浓度范围内能增加PVC与SBS的相容性 ,提高断裂伸长率 .测量了溶液的相对粘度 ,得出了相反转浓度点。     

SAN共聚物组成对PVC/ABS共混物相容性的影响

采用乳液聚合技术通过改变共聚单体的投料比(St/AN)合成了一系列不同AN结合量的ABS接枝共聚物粉料和SAN共聚物.将其与聚氯乙烯(PVC)和邻苯二甲酸二辛酯(DOP)熔融共混分别制得了PVC/ABS、PVC/SAN、PVC/ABS/DOP和PVC/SAN/DOP共混物,利用SEM、TEM和动态力学粘弹谱仪(DMA)对共混物的相容性和相结构进行了表征.结果发现,在PVC/ABS共混体系中,尽管改变接枝SAN共聚物的AN结合量,PVC和SAN共聚物均为不相容体系;在该共混物中引入增塑剂DOP后,虽然当SAN共聚物AN结合量小于23.4 wt%时,共混物在室温以上只存在一个tanδ峰,但形态结构研究结果表明共混物仍为不相容体系,共混物的相区尺寸明显地依赖于SAN共聚物中的AN结合量,当AN结合量为23.4 wt%时相区尺寸最小.     

可反应性纳米二氧化硅填充聚氯乙烯树脂在空气中的热分解行为

利用热重分析和差热重量分析(TG/DTG)技术研究了可反应性纳米二氧化硅填充聚氯乙烯(PVC/n-SiO2)树脂在空气气氛中的热分解行为,利用Ozawa-Flynn-Wall (OFW)方程和Friedman方程对其热分解进行了动力学分析.结果表明,可反应性纳米SiO2对PVC树脂热分解的第一阶段影响比较明显,当纳米S...     

溶胶-凝胶富勒烯固相微萃取-气相色谱法测定塑料水浸泡液中多种邻苯二甲酸二酯

利用新型溶胶-凝胶富勒烯涂层,结合顶空固相微萃取-气相色谱法-FID检测,对PVC塑料制品在水溶液浸泡液中的12种邻苯二甲酸二酯进行了分析和测定,其检出限为0.097～3.646 μg/L;回收率为87.9%～107%;RSD<8%.对12种邻苯二甲酸二酯类增塑剂的固相微萃取条件和色谱条件进行了优化,并与商用固相微萃取聚二甲基硅氧烷(PDMS)探头的性能进行了比较.本方法应用于PVC玩具及PVC餐垫样品的分析,结果令人满意.     

聚ε-己内酯/聚氯乙烯球晶表面的XPS研究

聚合物薄膜在微电子领域中的应用日益增加.聚ε-己内酯/聚氯乙烯（PCL/PVC）是研究得最广泛的聚合物共混薄膜之一.PCL与PVC以一定比例混合时,可以形成环带球晶；同时,体系分为结晶PCL相及PCL/PVC非晶混溶相.用XPS和成象XPS分析技术,对PCL/PVC膜的表面化学组成和元素分布情况进行了研究.观察到PCL在薄膜表面富集.此外,成象XPS表明,PVC在球晶边界处富集,且球晶边界宽度约15 μm.     

由一种新型非均相聚合方法制备的聚氯乙烯的分子结构

聚氯乙烯(PVC)树脂通常采用自由基本体聚合、悬浮聚合和乳液聚合方法制备.无链转移剂时,头-尾加成和PVC大分子自由基向单体链转移反应分别是链增长和链终止的主要方式,聚合温度成为影响PVC平均分子量及分子量分布的主要因素.     

聚氯乙烯表面共价键合肝素及抗凝血性的研究

采用Ar等离子体引发聚乙二醇(PEG)在聚氯乙烯(PVC)表面固定化,进一步对固定PEG后的PVC进行肝素化处理,以改善PVC材料的抗凝血性能。探讨了PEG浓度对Ar等离子体固定化反应效果的影响。通过X射线光电子能谱(XPS)、衰减全反射红外光谱(ATR-FTIR)、扫描电镜(SEM)和接触角测定研究了固定PEG前后PVC的表面性能和表面形貌的变化。XPS分析证实肝素已成功地共价键合于PVC表面。采用体外凝血时间测定和血小板粘附实验对材料的抗凝血性能进行评价,结果表明,被修饰PVC材料的抗凝血性能显著提高。     

Formation of nanoporous poly(aryl amide ether) (PAAE) films by selective removal of poly(ethylene glycol) (PEG) from PEG/PAAE composite films

Poly(aryl amide ether) (PAAE) thin films with nanometer-sized pores have been prepared in two steps: (1) solution casting of partially miscible poly(ethylene glycol) (PEG)/PAAE blends from one of their common solvents, dimethyl sulfoxide (DMSO), results in formation of PEG/PAAE nanocomposite films; (2) selective removal of PEG component by water washing yields nanosized, porous PAAE films. The pores have been found to have a small size variation and cover the whole surface homogeneously. With an increase in PEG contents, the sizes of the pores increase but the size distributions do not have much changes. This has been ascribed to formation of small PEG domains in PEG/PAAE composite films, which is facilitated by the strong interactions, mostly hydrogen bonds, between PEG and PAAE macromolecular chains.     

Dechlorination behaviour of flexible poly(vinyl chloride) in NaOH/EG solution

Flexible poly(vinyl chloride) (PVC) was found to be dechlorinated in NaOH/ethylene glycol (EG) solution at moderate temperature and at atmospheric pressure. The degree of dechlorination increased over time with all particle sizes and with decreasing particle size. Decreased particle size resulted in an increased effective surface area, increasing the contact between the material and OH⁻ in the NaOH/EG solution, which contributed to the high degree of dechlorination. The dechlorination of flexible PVC in NaOH/EG solution was expressed as a first-order reaction and proceeded under chemical reaction control. Diisononyl-phthalate (DINP) in the flexible PVC powder decomposed readily into phthalic acid and isononyl alcohol in a short time. For the dechlorination of the flexible PVC, the substitution (S_N2) of chloride by the hydroxyl group was considered to be preferential to the elimination (E2) of hydrogen chloride.     

Dechlorination of poly(vinyl chloride) by 1-butyl-3-methylimidazoliumhydroxide

Highly efficient dechlorination of PVC has been realized at 180 °C and at atmospheric pressure, using 1-butyl-3-methylimidazoliumhydroxide ([Bmim]OH) as an environment-friendly reaction medium: in the absence of an external base or solvent the dechlorination efficiency is as high as 91.2%, while it is only 38.1% for PVC without ionic liquids. The dechlorination process follows first-order kinetics with apparent activation energy of 44 kJ mol⁻¹. Mechanistic analysis provides evidence for the equilibrium presence of carbene species, together with the hydroxide ions in [Bmim]OH, thus enhancing the dechlorination of PVC via a combined elimination and substitution mechanism.     

Preparation of interpenetrating polymer network composed of poly(ethylene glycol) and poly(acrylamide) hydrogels as a support of enzyme immobilization

Poly(ethylene glycol)(PEG)‐based interpenetrating polymeric network (IPN) hydrogels were prepared for the application of enzyme immobilization. Poly(acrylamide)(PAAm) was chosen as the other network of IPN hydrogel and different concentration of PAAm networks were incorporated inside the PEG hydrogel to improve the mechanical strength and provide functional groups that covalently bind the enzyme. Formation of IPN hydrogels was confirmed by observing the weight per cent gain of hydrogel after incorporation of PAAm network and by attenuated total reflectance/Fourier transform infrared (ATR/FTIR) analysis. Synthesis of IPN hydrogels with higher PAAm content produced more crosslinked hydrogels with lower water content (WC), smaller M_c and mesh size, which resulted in enhanced mechanical properties compared to the PEG hydrogel. The IPN hydrogels exhibited tensile strength between 0.2 and 1.2 MPa while retaining high levels of hydration (70–81% water). For enzyme immobilization, glucose oxidase (GOX) was immobilized to PEG and IPN hydrogel beads. Enzyme activity studies revealed that although all the hydrogels initially had similar enzymatic activity, enzyme‐immobilizing PEG hydrogels lost most of the enzymatic activity within 2 days due to enzyme leaching while IPN hydrogels maintained a maximum 80% of the initial enzymatic activity over a week due to the covalent linkage between the enzyme and amine groups of PAAm. Copyright © 2008 John Wiley & Sons, Ltd.     

Poly(ethylene glycol)-lipase complexes catalytically active in fluorous solvents

Lipase-catalyzed alcoholysis between vinyl cinnamate and benzyl alcohol in fluorous solvents was investigated. This is the first report of a lipase-catalyzed reaction in a fluorous solvent. Forming the poly(ethylene glycol)(PEG)-lipase PL complex enhanced lipase activity over 16-fold over that of native lipase powder. The PEG-lipase PL complex exhibited markedly higher alcoholysis activities in fluorous solvents than in conventional organic solvents such as isooctane and n-hexane. The optimum reaction temperature for FC-77 (perfluorooctane) was 55 [degree]C and the optimum pH for the preparation of the PEG-lipase complex was 9.0; similar to the conditions for lipase PL-catalyzed reaction in aqueous solution. The alcoholysis reaction in fluorous solvent requires the addition of a FC77-miscible organic solvent (isooctane) in order to dissolve non-fluorinated substrates. Lipase activity in the fluorous solvent was significantly influenced by the volume ratio of isooctane in the reaction medium. Vinyl cinnamate inhibition of the lipase-catalyzed reaction occurred at a much lower concentration in the fluorous solvent than in isooctane. These results can be explained by the localization of substrates around lipase molecules, induced by adsorption of the substrates to the PEG layer of the PEG-lipase complex.     

Structural study of BSA/poly(ethylene glycol) lipid conjugate complexes

In this work we report the structural characteristics of bovine serum albumin/poly(ethylene glycol) lipid conjugate (BSA/PEG(2000)-PE) complexes under physiological conditions (37 degrees C and pH 7.4) for particular fractions of BSA to PEG-lipid concentration, c(BSA)/c(PEG)(2000)-PE. Ultraviolet fluorescence spectroscopy (UV) results shown that PEG(2000)-PE is associated to BSA, leading to protein unfolding for fixed c(BSA) = 0.01 wt % and variable c(PEG)(2000)-PE = 0.0015-0.6 wt %. Tryptophan groups on the BSA surface are in contact with the PEG-lipid at c(PEG)(2000)-PE = 0.0015 wt %, while they are exposed to water at c(PEG)(2000)-PE > 0.0015 wt %. Dynamic and static light scattering (DLS and SLS) and small-angle neutron scattering (SANS) point out the existence of individual BSA/PEG-lipid complexes in the system for fixed c(BSA) = 1 wt % and variable c(PEG)(2000)-PE = 0.15-2 wt %. DLS shows that there is only one BSA molecule per protein/PEG-lipid complex, while SLS shows that the PEG-lipid associates to the BSA without promoting aggregation between adjacent protein/polymer-lipid conjugate complexes. SANS was used to show that BSA/PEG(2000)-PE complexes adopt an oblate ellipsoidal shape. Partially unfolded BSA is contained in the core of the oblate ellipsoid, which is surrounded by an external shell containing the PEG(2000)-PE.     

溶剂性能对部分解缠结聚氯乙烯有序结构形成的影响

一般的高分子非晶态是线团相互穿透的多链凝聚态,是分子固体中非常独特的一种分子凝聚态[1～4].而高分子链的缠结是高聚物凝聚态的重要特征之一.缠结是指高分子链之间形成物理交联点,构成网络结构,使分子链的运动受到周围分子的羁绊和限制[5],因此缠结对链的构象调整以及链单元     

聚对二氧环己酮/聚乙二醇两亲性聚合物共网络的合成与表征

以辛酸亚锡为催化剂,季戊四醇(PTOL)为引发剂,引发对二氧环己酮(PDO)单体开环聚合,合成了以PTOL为核的四臂聚对二氧环己酮(4s-PPDO).通过直接将4s-PPDO预聚物和聚乙二醇(PEG)于熔点以上、惰性气体保护下与偶联剂甲苯二异氰酸酯(TDI)交联共聚得到聚对二氧环己酮/聚乙二醇(PPDO-b-PEG)两亲性共网络聚合物(PPDO-PEG APCNs).研究了两亲性聚合物共网络结构、配比组成、溶剂种类等对聚合物溶胀率的影响,结果表明APCNs在不同类型的溶剂中表现出不同的溶胀行为,可以通过调节偶联剂的用量及PPDO/PEG的投料比来满足不同的实际需求.通过示差扫描量热分析(DSC)详细研究APCNs的结晶性能,证实交联反应降低APCNs的结晶度和结晶尺寸.     

Dehydrochlorination of Poly(vinyl Chloride) in Pyridine. 1. Effect of Conditions

Poly(viny1 chloride) (PVC) was dehydrochlorinated thermally in pyridine solution under N₂ atmosphere and the effect of variation of reaction time, temperature, and concentration of PVC in pyridine was studied. The extent of dehydrochlorination (or conversion, x%) increases with an increase in reaction time and temperature, and with a decrease in the concentration of PVC. Incomplete precipitation of dehydrochlorinated PVC (DHPVC) occurs by nonsolvent (methanol). During dehydrochlorination there is no HCl evolution as it forms a pyridine hydrochloride complex which is supposed to act as a catalyst for dehydrochlorination. A possible mechanism has been proposed. Chain scission and cross-linking reactions are responsible for the molecular weight changes that take place during the reaction.