Effects of poly(1,2‐propylene glycol adipate) and nano‐CaCO3 on DOP migration and mechanical properties of flexible PVC

Nano‐CaCO₃ was used as nano‐scale filler and poly(1,2‐propylene glycol adipate) (PPA) was used as polymeric plasticizer in flexible poly(vinyl chloride) (PVC) sheets for the partial replacement of di(2‐ethyl hexyl) phthalate (DOP) in this paper. The effect of PPA and nano‐CaCO₃ on restraining DOP migration was evaluated via extraction tests. The results showed that the introduction of nano‐CaCO₃ can decrease the extraction rate of DOP in the PVC matrix. The tensile strength and elongation at break of CaCO₃‐1/PPA‐20/DOP‐30/PVC were similar to those of DOP‐50/PVC, and CaCO₃‐1/PPA‐20/DOP‐30/PVC exhibited the superior suppression of DOP migration compared with DOP‐50/PVC. Thermogravimetry analysis (TGA) indicated that the addition of nano‐CaCO₃ effectively improved the thermal stability of the nanocomposites. Therefore, the combination of PPA and nano‐CaCO₃ is an effective approach to suppress the migration of DOP. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

增塑剂对PVC电缆料电性能的影响

介绍了DBP、TPP、DOP、TOTM、TCP、DIDP及M－50等增塑剂在不同用量时对PVC电缆科电性能的影响：随着增剂用量的增加,PVC电缆料的电性能一般呈下降趋势。实验发现TOTM和TCP两种增剂的电性能较优,其最佳用量为35－40份。     

PVC包装膜中己二酸酯类增塑剂在水中的迁移行为研究

采用顶空固相微萃取方式和气相色谱-质谱单离子监测技术,以己二酸二(1-丁基戊基)酯为内标,对PVC包装膜在水介质中己二酸二乙酯、己二酸二异丁酯、己二酸二丁酯、己二酸二(2-丁氧基乙基)酯、己二酸二(乙基己基)酯5种己二酸酯类增塑剂的迁移行为进行了研究,对其固相微萃取条件和色谱条件进行了优化,并对PVC包装膜在水介质中的浸泡条件进行了研究。该方法的检测限量为0.022~0.912μg/L,回收率为86.16%~104.33%,相对标准偏差为7.75%~8.44%。     

PVC塑料中邻苯二甲酸酯类增塑剂在体液中的迁移行为研究

利用新型溶胶-凝胶富勒烯涂层,采用顶空固相微萃取-气相色谱法对PVC塑料制品中的邻苯二甲酸酯类增塑剂在模拟体液(模拟人体汗液、模拟人体唾液)中的迁移行为进行了研究,对其固相微萃取条件和色谱分析条件进行了优化,并对PVC塑料制品在模拟体液中的浸泡条件进行了研究。该方法的最低检出限分别为0.082~0.730μg/L(模拟人体汗液)和0.079 1~1.370 0μg/L(模拟人体唾液),回收率为82%~107%,RSD<8%。     

聚氯乙烯薄膜及其胶带中增塑剂迁移的研究

用全反射红外技术对聚氯乙烯薄膜及其胶带进行了增塑剂迁移性能研究。增塑剂迁移经一定时间后达到平衡,测出聚氯乙烯薄膜中增塑剂迁移的扩散系数约为０１ｎｍ２／ｍｉｎ。实验证明：影响其增塑剂迁移性能的因素是催化剂的类型、用量及胶粘剂的种类。     

软质PVC中增塑剂在不同溶媒中的迁移行为

研究软质PVC交联前后,增塑剂对苯二甲酸二辛酯在蒸馏水、3%乙酸、10%乙醇和橄榄油浸泡溶媒中的迁移行为。结果表明:增塑剂在蒸馏水和乙醇浸泡溶媒中,前24 h缓慢上升后趋于平缓;在乙酸浸泡环境中,交联改性延迟了增塑剂迁移出来的时间;在橄榄油浸泡溶媒中,前24 h迅速上升后也逐渐趋于平缓,交联改性对增塑剂迁移有一定的抑制作用,凝胶含量越大,迁移率越小。无论PVC交联与否,增塑剂在不同溶媒中的迁移率大小顺序均为:橄榄油>10%乙醇>蒸馏水>3%乙酸。     

PVC包装膜中多种己二酸酯类增塑剂的同时测定

利用傅立叶变换红外光谱法———ATR技术测定样品的红外光谱,采用偏最小二乘法对所测的红外光谱进行分析,建立了一种无损快速分析方法,定量地测定聚氯乙烯塑料中多种己二酸酯类增塑剂的含量。该方法测量精密度的变异系数小于6%,测量准确度的变异系数小于2%;并且不受基体的干扰,简单快速,适合于生产流水线的质量控制。     

聚氯乙烯胶带增塑剂迁移的研究

用全反射红外技术对聚氯乙烯薄膜及其胶带进行了增塑剂迁移性能的研究。增塑剂的迁移经一定时间后达到平衡。对聚氯乙烯薄膜来说,增塑剂迁移的扩散系数约为1×10~(-7)mm~2/min.而对不同配方的聚氯乙烯胶带,影响增塑剂迁移性能的因素是催化剂的类型及用量,及胶粘剂的类型。     

Formulation and mechanical characterization of PVC plastisols based on low‐toxicity additives

New formulations of plastisols based on low‐toxicity plasticizers were proposed and characterized. Traditional phthalate plasticizers were replaced in the plastisols studied in this research by polymeric plasticizers (i.e., saturated polyesters), produced by the reaction of a diol and a carboxylic acid. The main drawback for the use of these plasticizers in formulations of PVC plastisols is a significant increase of the paste viscosity, which decreases their processability; thus, the use of additional additives to reduce viscosity is recommended. This study also includes the optimization of the processing conditions (cure temperature and time) of the proposed plastisols: complete cure was obtained at 140°C and 10 min. It is reported that the final properties of plastisols are very sensitive with respect to the processing conditions; in fact, insufficient plasticization or degradation can affect the material when processed out of the optimum conditions. The influence of the plasticizer concentration on mechanical and optical properties, such as tensile strength, hardness, brightness, and the like, is also reported. In summary, the proposed plastisols, with low‐toxicity plasticizers, offer a valid alternative to traditional PVC plastisols based on phthalate plasticizers. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 1881–1890, 2001     

采用凝胶渗透色谱法分析医用PVC中增塑剂的种类及含量

在不对样品进行萃取分离等前处理的条件下,利用凝胶渗透色谱(GPC)示差(RI)-紫外(UV)双检测器连用测定医用PVC粒料中增塑剂的种类及含量.通过RI检测器可以确定粒料中PVC树脂、增塑剂环己烷1,2-二甲酸二异壬酯(DINCH)和环氧大豆油(ESO)的质量分数约分别为70.1%,22.6%和7.3%;通过UV检测器...     

PVC增塑机理及PVC-增塑剂的相互作用

介绍了PVC增塑剂的增塑机理,即润滑性理论、凝胶理论、自由体积理论和动力学理论,探讨了PVC-增塑剂的相互作用及其强度的预测方法。     

Fracture behavior of PVC/Blendex/nano‐CaCO3 composites

PVC/Blendex/Nano‐CaCO₃ composites were prepared by melt‐blending method. The Blendex (BLENDEX® 338) (GE Specialty Chemicals Co., Ltd., Shanghai, China) was an acrylonitrile‐butadiene‐styrene copolymer with high butadiene content. The fracture behavior of PVC/Blendex/nano‐CaCO₃ composites was studied using a modified essential work of fracture model, U/A = u₀ + u_dl, where u₀ is the limiting specific fracture energy and u_d is the dissipative energy density. The u₀ of PVC/Blendex blend could be greatly increased by the addition of nano‐CaCO₃, while the u_d was decreased. Nano‐CaCO₃ with particle size of 38 nm increased the u₀ of PVC/Blendex blend more effectively than that with particle size of 64 nm, when nano‐CaCO₃ content was below 10 phr. Both the u₀ and u_d of PVC/Blendex/nano‐CaCO₃ composites were not much affected by increasing specimen thickness from 3 mm to 5 mm, while the two fracture parameters were increased with increasing loading rate from 2 mm/min to 10 mm/min, and u_d was found to be more sensitive to the loading rate than u₀. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 95: 953–961, 2005     

邻苯二甲酸二(乙二醇醚)酯绿色合成及增塑PVC性能

以邻苯二甲酸酐和低毒型乙二醇醚（乙二醇甲/乙/丁醚、二乙二醇甲/乙/丁醚）为原料,固体酸\mathrm{S}{\mathrm{O}}_{\mathrm{4}}^{\mathrm{2}-}/TiO₂为催化剂,采用直接酯化法催化合成邻苯二甲酸二(乙二醇醚)酯（酯化率?97.0%）,并利用傅里叶红外光谱（FTIR）、¹H核磁共振（¹H NMR）确定产物结构。对合成产物邻苯二甲酸二(乙二醇醚)酯的基本物性（酯含量、酸度、黏度、加热减量等）及其增塑后聚氯乙烯（PVC）制品的力学性能、热稳定性以及抗迁移性能进行测试。结果表明,邻苯二甲酸二(乙二醇醚)酯的增塑性能与其结构中乙氧基数目成正比,而与其末端烷基碳链长度呈现先增加后下降趋势。与邻苯二甲酸二辛酯（DOP）增塑后PVC制品（PVC/DOP）相比,邻苯二甲酸二(二乙二醇乙醚)酯增塑后PVC制品（PVC/DEEEP）的断裂伸长率和拉伸强度分别提高87.4%和3.4MPa,初始热分解温度（T_5%）提高21.5℃。     

Plasticizer migration from cross‐linked flexible PVC: Effects on tribology and hardness

Uses of flexible poly(vinyl chloride) (PVC) are restricted by plasticizer migration affecting material properties. Moreover, the use of phthalate‐based plasticizers is being questioned worldwide because of their potential toxicity to humans and environment. Chemical modification of PVC structure is one of the most effective tools for reduction of plasticizer diffusion. In this work, a flexible dry blend based on cross‐linked PVC was obtained using a difunctional amine, namely isophoron diamine (IPDA) as the cross‐linking agent. The gel fraction was evaluated from insoluble portions obtained by means of solvent extraction; the efficiency of cross‐linking in reducing the plasticizer leaching was evaluated by migration tests. Effects of addition of IPDA on PVC thermal stability were determined by thermogravimetric analysis (TGA). The cross‐linking reaction turned out to be responsible for accelerating thermal degradation. Tribological properties of flexible uncross‐linked, cross‐linked and rigid PVC were determined. Flexible formulations were held in contact for 32 days with rigid PVC sheets. Plasticizer migration towards the interface caused an increase of dynamic friction compared to that of the reference rigid PVC.Vickers microhardness h_Vickers values of rigid PVC sheets decreased due to plasticizer surface absorption. POLYM. ENG. SCI., 2012. © 2011 Society of Plastics Engineers     

Epoxidized vegetable oil and bio‐based materials as PVC plasticizer

Phthalate esters received a considerable attention owing to its various applications and the harmful health effects resulting from phthalate exposure; thus, finding an alternative to phthalate derivatives became a necessity. Phthalate esters are commonly used as plasticizer in polymer formulation; in particular for poly(vinyl chloride) (PVC) formulation. According to the researches in the last 18 years, epoxidized vegetable oils are one of the alternatives that are strongly encouraged to substitute phthalate esters since they were proven to be valid in various applications, eco‐friendly and sustainable resource. However, most of the production practices for epoxidized vegetable oil are via conventional epoxidation that concentrates on a catalyst that is homogeneous and non‐reusable. This type of catalyst, however, causes several problems later in the process. Therefore, the selective epoxidation of vegetable oils process requires new catalytic systems that are more aligned with the green chemistry principles. This article reviews the harmful health effects associated with the exposure to phthalate esters products, explains the usage of oleochemicals resources as a substitute to phthalate esters and describes different approaches for the epoxidation of vegetable oils. Finally, it draws attention to the usage of epoxy and bio‐based compounds as plasticizers in PVC manufacturing. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46270.     

Copolyesters as non‐toxic plasticizers

Plasticized polymer materials have taken an enormous role in our everyday life. Most of the common plasticizers are aromatics, esters of phthalic acid. Since they are not chemically bonded to the polymer matrix, they can be released from material while being used. The concerns raised about toxicity led to a large demand for producing biodegradable and non‐toxic plasticizers. We investigated aliphatic copolyesters synthesized via ring opening polymerization of lactones as plasticizers for poly(vinyl chloride). The material properties of the formulations, such as glass transition temperature and mechanical performance, were studied. Copyright © 2011 Society of Chemical Industry     

PVC螺旋增强软管的生产技术

介绍了ＰＶＣ螺旋增强软管的生产工艺、配方、容易出现的问题及性能指标。     

聚氯乙烯环保型增塑剂的研究进展

综述了聚氯乙烯环保型增塑剂的研究及应用状况,介绍了目前研究较多、应用广泛而且价格较低廉的环氧植物油、柠檬酸三丁酯和乙酰柠檬酸三丁酯.对比传统催化剂,阐述了其合成方法的进展,突出了新型高效催化剂的应用.指出环保型增塑剂是聚氯乙烯增塑剂的发展方向,符合可持续发展道路.     

PVC基热塑性弹性体的制备

采用机械共混法制备PVC基弹性体，研究了聚合物的质量配比、增塑剂的用量及增塑剂的配合使用对体系性能的影响，并考察了填料对体系性能的影响。结果表明，通过不同的聚合物质量配比、增塑剂的选择以及不同填料的选用，可制得不同性能的热塑性弹性体。     

甘油酯型聚氯乙烯增塑剂的研究

以甘油、苯甲酸和乙酸为原料合成了苯甲酸乙酸甘油酯,采用FTIR和力学性能测试研究了合成产物的结构及其对聚氯乙烯的增塑性能.结果表明,合成的苯甲酸乙酸甘油酯对PVC具有优良的增塑性能.