聚氯乙烯环保型增塑剂的研究进展

概述了聚氯乙烯环保型增塑剂柠檬酸三酯类和环氧类的研究进展,指出了其发展趋势及在中国的发展前景。     

环保型增塑剂的研究开发进展

概述了环保型增塑剂主要品种柠檬酸三酯类和环氧类的研究进展,指出了其发展趋势及在我国的发展前景。     

聚氯乙烯环保型增塑剂的合成及应用

聚氯乙烯中常用的环保型增塑剂主要有柠檬酸酯类增塑剂、对苯二甲酸酯类增塑剂、聚酯类增塑剂、偏苯三酸酯增塑剂、环己烷二羧酸酯类增塑剂、植物油基增塑剂等,通过了解和分析这些增塑剂的特征和合成,推进环保型增塑剂在塑料生产中的应用.     

聚氯乙烯增塑剂研究进展

概述了传统聚氯乙烯增塑剂的种类以及聚氯乙烯增塑剂的增塑机制,重点介绍了几种环保聚氯乙烯增塑剂,分析了我国聚氯乙烯行业的现状以及聚氯乙烯增塑剂的发展前景。     

环氧棉子油在聚氯乙烯加工中的稳定作用和增塑剂行为

本文研究了环氧棉子油特性、作用和应用效果。表明环氧棉子油是优良的增塑剂兼稳定剂,适用于各种聚氯乙烯(PvC)加工配方。单用或与酯类增塑剂合用可减少迁移性,提高物料熔融流变和稳定性;与热稳定剂并用时,有显著协同效应,赋予制品较好的透明度、力学性能租和老化性。价廉无毒,可直接替代环氧大豆油,具有较高的实用价值和效益。     

无毒环保型增塑剂对聚氯乙烯性能的影响

选用了邻苯增塑剂(DOP)、柠檬酸酯类增塑剂（ATBC、ATOC）、对苯增塑剂（DOTP）、偏苯增塑剂（TOTM）及新型植物基增塑剂ID-37制备了增塑PVC材料,对所制备的PVC材料的拉伸强度、断裂伸长率、硬度、180℃热稳定性进行表征,测试结果表明,180℃静态热稳定性DOTP与TOTM最优,DOP与ID37次之,ATBC与ATOC相当。增塑剂对力学性能影响较小,对硬度差异影响较大,其中DOTP与TOTM所增塑PVC材料硬度比其余四种高约5度（邵氏A）。DSC测试结果表明,TOTM及ATBC增塑PVC的Tg相对较高,约为-22℃,其余四种较为接近,约为-25℃。     

聚氯乙烯用增塑剂

为改善塑料加工性能及其制品使用性能而在塑料加工时添加的各种组分,通常称之为塑料加工助剂。目前世界塑料加工助剂的年消费量已超过110万t,其中增塑剂消费量仅次于填充剂而居第2位,约占加工助剂总消费量的30％,其消费领域主要是聚氯乙烯,如美国用于PVC的增塑剂约占加工助剂总量的80％,西欧和我国高达90％。     

聚氯乙烯用新型增塑剂

本文叙述了一些新增塑剂的性质及用此增塑剂增塑后聚氯乙烯制品的性能。并根据国外一些国家增塑剂发展情况,指出我国今后增塑剂发展方向。     

聚氯乙烯的高分子增塑剂

本文论述了高分子增塑剂对塑料增塑的基本原理,着重介绍了国外用于PVC增塑的几类高分子增塑剂的结构和性能特点,图表中的性能数据表明,用EVA—CO三元共聚物和某些聚酯类高聚物增塑的PVC,各种性能都很优良,特别在耐久性和耐低温性方面尤为突出。     

Effects of epoxidized sunflower oil on the mechanical and dynamical analysis of the plasticized poly(vinyl chloride)

Epoxidized soybean oil (ESBO), is one of the most commonly used epoxides because of its typical combined roles as a plasticizer and heat stabilizer. In this study, a novel plasticizer of poly(vinyl chloride) (PVC) resins, epoxidized sunflower oil (ESO), was synthesized, and its performance was evaluated. ESO was designed to act as a coplasticizer and a heat stabilizer like ESBO. ESO is used as organic coplasticizer for plasticized PVC containing Ca and Zn stearates as primary stabilizers and stearic acid as lubricant. Di‐(2‐ethylhexyl) phthalate (DEHP), a conventional plasticizer for PVC, was partially replaced by ESO. Mechanical properties (tensile and shore D hardness) were investigated. The performance of ESO to ESB0 (20 g) for comparison, indicated that ESO could be used as secondary plasticizer for PVC in combination with DEHP. All mechanical and dynamical properties of plasticized PVC sheets varied with the oxirane oxygen of the ESO. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Preparation and application of triglyceride plasticizers for poly(vinyl chloride)

A series of triglyceride plasticizers were prepared from glycerol, acetic acid, and benzoic acid through a two‐step reaction to develop potential uses of glycerol. The optimum reaction conditions were determined by the esterification of glycerol and acetic acid to produce glyceryl triacetate. When the molar ratio of glycerol to benzoic acid to acetic acid was 1:1:3.5, a novel plasticizer triglyceride mixture (GTM) was successfully synthesized; it had a good plasticizing effect on poly(vinyl chloride) (PVC). The elongation at break of PVC composites containing 80 phr GTM increased around 350%; the corresponding hardness (Shore D) and tensile strength decreased to around 35 D and 20 MPa, respectively. Moreover, the glass‐transition temperature (T_g) of PVC composites containing 40 phr GTM decreased to around 50°C. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Synthesis and study of properties of new oligoesters based on soybean oil as potential poly(vinyl chloride) plasticizers

New compounds as potential poly(vinyl chloride) plasticizers based on soybean oil and oligoesters of adipic acid and different glycols by one-pot transesterification are synthesized. In the first step of the plasticizer synthesis oligoesters of adipic acid and diethylene glycol, triethylene glycol, or dipropylene glycol are synthesized, and then in situ in the second step, a defined amount of soybean oil is introduced. By degradation of soybean oil with oligoesters, and transesterification reaction, different compounds are obtained. Their physicochemical properties are determined by NMR, SEC, DSC, TGA, and volatility analyses. The properties of synthesized plasticizers are compared with commercial products: monomeric (DEHP) and aliphatic oligoster of adipic acid and 1,3-butanediol (H-1).     

Compatibility of poly(vinyl chloride) with epoxidized copolymers of butadiene-styrene

The compatibility of poly(vinyl chloride) (PVC) with epoxidized styrene-butadiene copolymers is examined at different levels of epoxidation. The copolymers modified were a random (SBR) containing 45 wt% styrene and a triblock (SBS) with 30 wt% bound styrene. Blends were examined in the complete composition range and the approximate levels of epoxidation to ensure blend miscibility were determined. Epoxidized SBS (ESBS) was more effective in miscibility compared with ESBR requiring a lesser degree of epoxidation (43 versus 46 mol%). Tensile properties of the ESBS/PVC blends showed the efficiency of ESBS as a polymeric plasticizer even at levels of epoxidation (ca. 35 mol%) where immiscibility sets in.     

Influence of polluted atmospheres on the natural aging of poly(vinyl chloride) stabilized with epoxidized sunflower oil

Semirigid and plasticized poly(vinyl chloride) (PVC) samples, stabilized with epoxidized sunflower oil (ESO), Zn, and Ca stearates, were exposed in Algiers (hot, Mediterranean climate) for 12 months in three sites where the concentrations of atmospheric pollutants (NO_x, O₃, hydrocarbons) are known. The evolution of the mechanical properties (tensile test and shore D hardness) was followed according to the aging time. The modification structure of polymer was investigated by Fourier transform infrared spectroscopy. The results have shown that all the considered properties were affected. Furthermore, it seems that the O₃ exerted the most deleterious effect, followed by hydrocarbons and then by NO_x. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Benzyl ester of dehydrated castor oil fatty acid as plasticizer for poly(vinyl chloride)

The poly(vinyl chloride) (PVC) industry plays an important role in today's total plastics industry. The major volume of PVC is used as soft and plasticized PVC. PVC applications consume approximately 80% of the total production of plasticizers. Most of the common plasticizers are aromatic esters of phthalic acid. In the majority of countries, phthalate plasticizers are banned due to their carcinogenic properties. The concern raised about toxicity led to a large demand for bio‐based non‐toxic plasticizers. Hence, there is an increasing interest in replacing the phthalate plasticizers with those produced from simple bio‐based materials. Dehydrated castor oil fatty acid (DCOFA) is a renewable resource which can be esterified and used as an environment friendly plasticizer for PVC. Benzyl ester (BE) was prepared by reacting DCOFA with benzyl alcohol in the presence of catalyst at 170–180 °C. Esterification was further confirmed by acid value, hydroxyl number, ¹H NMR and Fourier transform IR spectroscopy. The modified plasticizer was used in various proportions as a co‐plasticizer in PVC for partial replacement of dioctyl phthalate (DOP). With an increase in the proportion of BE in PVC samples, a good plasticizing performance was observed. The incorporation of BE also resulted in a reduction in viscosity and viscosity pick‐up and improved mechanical, exudation, thermal degradation and chemical resistance properties. The presence of BE showed a reduction in the whiteness index due to presence of conjugated double bonds in the structure. The results of DSC, XRD and Shore hardness studies showed no significant variation in properties compared with those of DOP‐plasticized sheets and thus we can conclude that BE can be used as a co‐plasticizer in PVC. © 2013 Society of Chemical Industry     

Migration of Epoxidized Sunflower Oil and Dioctyl Phthalate from Rigid and Plasticized Poly(vinyl chloride)

The aim of this paper is the determination of the specific migration of epoxidized sunflower oil (ESO) from rigid and plasticized poly(vinyl chloride) (PVC) into food simulants. ESO was obtained by epoxidation of commercial sunflower oil and used as a thermal organic co-stabilizer for PVC. For that purpose, rigid and plasticized (0, 15, 30, and 45 wt% of dioctyl phthalate or DOP) PVC films stabilized with ESO in the presence of Zn and Ca stearates were used to perform migration testing in olive oil. The test conditions were 12 d at 20 and 40°C and 2 h at 70°C with and without agitation.

The determination of ESO migration was carried out by gas chromatography-mass spectrometry (GC-MS). ESO was quantified by an external standard addition method, using linoleic acid (C_18:2) as the external standard. The influence of various parameters, such as the agitation and time of contact, the temperature, the presence or the absence of the plasticizer, and the plasticizer concentration, was considered.     

Design and synthesis of HFCA-based plasticizers with asymmetrical alkyl chains for poly(vinyl chloride)

A series of bio-based diester plasticizers with various alkyl chain asymmetry and the same molecular weight were designed and synthesized, using renewable 5-hydroxymethyl-2-furancarboxylic acid (HFCA) as the raw material. The chemical structures of the HFCA-based plasticizers were characterized by Fourier transform infrared and nuclear magnetic resonance (¹H NMR and ¹³C NMR). Besides, the influence of alkyl chain asymmetry on plasticization properties of the HFCA-based plasticizers in poly(vinyl chloride) (PVC) blends was also investigated. It was found that increasing the alkyl chain asymmetry of the diester plasticizer and keeping the molecular weight unchanged simultaneously could further improve its plasticizing efficiency, without sacrificing its volatility resistance and exudation resistance. The results showed that this study provided a new approach for further optimizing the overall properties of the asymmetric diester plasticizers.     

Compatibility of plasticizers with poly(vinyl chloride)

The tendency of a plasticizer to resist exudation from poly(vinyl chloride) (PVC) under compressive stress, known technologically as “compatibility,” is treated in terms of a network model, the plasticized composition being thought of as a rubber crosslinked by crystallites. Compatibility is increased by increased solvency (Flory-Huggins χ) and decreased by increasing plasticizer molar volume. A large crosslink density and/or insufficient melting of crosslinks during processing (thermal history) also decreases compatibility. All commercial primary plasticizers are believed to be infinitely miscible with amorphous PVC. Phase separation which occurs is syneresis and not related to any phase diagram. Swelling tests for compatibility and swelling measurements on dilute PVC gels are described. Some general principles relating to gel formation and association in polymer solutions are also discussed.