Migration of additives from food grade polyvinyl chloride (PVC) films: Effect of plasticization by polymeric modifiers instead of conventional plasticizers

Based on the static and dynamic mechanical properties of the corresponding blends, the compatibility of six thermoplastic elastomers with polyvinyl chloride (PVC) was investigated. A terpolymer of ethylene, vinyl acetate and carbon monoxide (EVACO) was shown to give the optimal properties for the processing of transparent, soft, PVC‐based films. FTIR spectroscopic analysis of EVACO plasticized blends clearly shows that the interactions involve the carbonyl groups of the VA and not of the CO monomer units. The migration phenomenon was studied on PVC based samples plasticized with di‐2‐ethylhexyladipate (DEHA) and EVACO in varying amounts. The overall migration (OM) was monitored by the weight loss percentage of the samples immersed into isooctane at 40°C. The specific migrations of DEHA (SM_D) and epoxidized soybean oil (SM_E) were shown to be responsible for the overall migration (OM = SM_D + SM_E). The weight percentages of DEHA and epoxidized soybean oil (ESO) were correlated to the excess of immersion temperature (40°C) over the varying glass transition temperature of the samples. The results are explained with respect to the plasticizing effect of the additives and to the permanency of the EVACO‐plasticization.. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 1291–1299, 2003     

On the Heat Stabilization Efficiency of Polyester Plasticizers for Poly(vinyl chloride) (PVC)

Four different polyester plasticizers for poly‐(vinyl chloride) (PVC), having moderate acid numbers (11.5–20.5 mg KOH/g resin), were synthesized. These polyesters were modified by converting the terminal COOH group to Ba(II) and Cd(II) carboxylate salts in order to introduce the capability of heat stabilization for PVC. The modified polyesters were applied as dual function polyesters, i.e., as plasticizers and stabilizers at the same time. The thermal stabilization efficiency of the formed plasticized PVC films was tested photometrically and the data obtained were compared with that afforded by “Irgastab BZ 556”. The efficiencies of these modified polyesters as heat stabilizers for PVC were found to be comparable with that afforded by “Irgastab BZ 556”.     

Recent developments in plasticized flame retardant polyvinyl chloride (PVC)

Triaryl and alkylaryl phosphates are plasticizers/flame retardants for polyvinyl chloride. The former are more effective flame retardants and the latter are better plasticizers. The latter also gives less smoke. A new phosphate ester blend with good plasticizer properties and low smoke is reported. A brominated triaryl phosphate ester is shown to be a highly effective flame retardant giving plasticized polyvinyl chloride compositions with oxygen index values up to 36. These compositions are suitable for high temperature wire and cable products.     

聚氯乙烯(PVC)离心母液废水治理利用探讨

采用催化氧化工艺技术处理PVC离心母液生产废水中的高链状(或环状)有机化合物(其分子量高达2000～40000)所表征的CODCr和电石乙炔废水中的S2-有非常高的去除效果,使处理过的水质能达到业主的要求,且处理的全过程中不产生二次污染。     

Secondary Plasticizers for Polyvinyl Chloride (PVC) Epoxidized Esters

Abstract

The synthesis of epoxy esters of 3-pentadecenyl phenol a low cost indigeneous raw material is described. These epoxy esters have further been evaluated as secondary plasticizers for PVC. Epoxidized 3-pentadecenyl-phenyl linoleate seems to be an attractive candidate as a secondary plasticizer amongst the epoxy esters evaluated.     

Deformation behavior of a polyvinyl chloride (PVC) tube by mandrel drawing

Biaxial mechanical properties of products produced by drawing over an expanding mandrel are found to be closely associated with the imposed axial and hoop draw ratio. The paper assists the understanding of the deformation behavior and related mechanical improvements in a processed polyvinyl chloride (PVC) tube and shows that behavior is controlled by the polymer network structure. The effect of post-mandrel bath cooling on product straightness, spring-back, and thickness distribution was investigated, and it was shown that bath cooling greatly improves the quality and integrity of the product.     

Macroscopic analysis of polyvinyl chloride (PVC) fracture modes under impact loads

In this paper, the PVC impact fracture modes and processes were analyzed via the technique of successively increasing impact energies. Force-displacement and microscopic analyses were employed at macroscopic level to study PVC fracture modes. The fracture modes were classified as: ductile, brittle, and mixed. The mixed mode was separated into: semi-ductile and semi-brittle. In the semi-ductile mode, radial cracks were initiated and propagated, but were ultimatley arrested. For the semi-brittle mode, the fracture was characterized by connected radial and circumferential cracks. It was verified that the primary elements which governed the fracture modes and impact resistance of PVC were the crack initiation and propagation processes.     

Mechanical and barrier properties of polyvinyl chloride plasticized with dioctyl phthalate,epoxidized soybean oil,and epoxidized cardanol

Plasticized polyvinyl chloride (PVC) films were prepared by melt compounding and compression molding using epoxidized cardanol (EC), a biobased plasticizer and its plasticization effect was compared with epoxidized soybean oil (ESBO) and dioctyl phthalate (DOP). The mechanical, migration, thermal, and barrier properties of the plasticized films were compared. The effect of replacing DOP with EC on the properties of PVC films was also investigated. The tensile strength, elongation at break, tensile modulus and impact strength values of PVC/EC films were higher in comparison to PVC/DOP and PVC/ESBO films at a fixed plasticizer loading of 40 wt.%. Also, the films prepared with a mixture of DOP + EC showed higher tensile strength and elongation at break compared to that of films prepared with only DOP. The PVC/EC films showed good thermal stability and reduced oxygen transmission rate (OTR) compared to PVC/DOP films. The addition of graphene and nanoclay in the PVC/plasticizer system exhibited an increase in oxygen transmission. However, the oxygen barrier property of nano filler incorporated PVC/EC films was better than PVC/DOP films. All the films showed negligible water vapor transmission rate (WVTR).     

异氰酸酯交联聚氯乙烯泡沫塑料的制备研究

以PVC树脂为基体材料,以不饱和酸酐为接枝剂,以异氰酸酯为交联剂制备了交联型硬质聚氯乙烯泡沫塑料。推测了交联型硬质聚氯乙烯泡沫塑料在制备过程中所发生的化学反应;通过对增塑糊、模压块及泡沫塑料进行FTIR和DSC测试,证明了我们对制备过程中所发生的化学反应推测的正确性;讨论了马来酸酐对交联型硬质聚氯乙烯泡沫塑料凝胶含量的影响,实验表明,随着马来酸酐用量的增加,其交联反应程度提高,凝胶含量随之增大。     

An introduction to the new degradation of polyvinyl chloride (PVC) shower hose

Recently, polyvinyl chloride (PVC) shower hoses have hardened throughout the eastern Shizuoka Prefecture, Japan. According to the elemental analysis results, the carbon and oxygen concentrations were much lower in the damaged hoses. These findings reveal that oxygen-containing, carbon-based plasticisers may leach from the damaged hose. As a result, the hoses lost flexibility after one year of use. The highest number of heterotrophic bacteria was detected by PCR-denaturing gradient gel electrophoresis in the shower water, and the bacterial DNA concentration was higher when hot water contacted the hose surface. I conclude that the plasticiser was leached from the stiffened hose through a bioaccumulation process.     

Acetal derivatives of methyl 9(10)-formylstearate: Plasticizers for PVC

Several acetals and an enol ether were prepared from methyl 9(10)-formylstearate and characterized with respect to their thermal, spectroscopic and chromatographic properties. These low-melting (below −80 C) compounds were generally compatible as secondary poly(vinyl chloride) plasticizers and imparted low-temperature properties that were intermediate between those obtained with dioctyl phthalate and dioctyl sebacate. Presented at AOCS Meeting, Atlantic City, October 1971. N. Market. Nutr. Res. Div., ARS, USDA.     

导电（抗静电）聚氯乙烯

阐述了影响炭黑填充聚氯乙烯（PVC）导电笥的诸多因素,分析后可知：炭黑在PVC树脂内的分散性是影响其导电性和加工性的关键因素之一;而表面积和结构度可影响炭黑的分散性。当炭黑粒径小于2nm时,其具有很强的吸附能力,需要更多的能量浸润,故分散较困难。同时,由于炭黑吸附在PVC分子链上,降低了PVC的流动性,即降低了加工性能,但提高了其玻璃化温度和力学强度。     

HCl formation via pyrolytic degradation of polyvinyl chloride (PVC): An empirical approach to kinetic modelling

The pyrolysis of polyvinyl chloride (PVC) has been described in terms of a relatively simple kinetic model, based on a large number of laboratory tests. The model predictions are in a good agreement with experimental data, regarding hydrochloric acid and non-condensable combustible gases. Therefore, the proposed model can be used to predict with good approximation the distributions of the above classes of compounds, in the whole range of applied experimental conditions.     

The thermal gravimetric studies for polymer samples of polyvinyl chloride (PVC) and polyvinyl alcohol (PVA) obtained by treatment with ionic liquid [bmim]Br

The development related to the effective degradation or recycling of polymeric material are of high priority in research because of solid waste removal problems in the environment and to establish sustainable conditions. Ionic liquids having low vapour pressure and other useful properties are finding increasing applications in the field of polymer science. In the present report, we describe the studies related to the plasticizing effect of simple 1-butyl-3-methyl-imidazolium bromide (an ionic liquid) on polyvinyl chloride. The admixtures of PVC and IL were subjected to heating (353–453 K) as a function of time (1–7 h). The resulting product stability was studied by TGA. Similar studies were carried out with PVA via glycolysis, i.e. in presence of ethylene glycol and products obtained were studied by TGA. Our results indicate that the addition of ionic liquid stabilizes the polyvinyl chloride and prevents liberation of HCl, while the polyvinyl alcohol gets degraded rapidly. These findings support the hypothesis of solubilization and degradation depending upon structural characteristics of polymeric molecules. The implications of these findings are discussed in terms of electrostatic, ion dipole and H-bonding interactions within polymer molecules influenced by thermal energy effects.     

Odor and PVC: Identification and quantification of volatiles in clear polyvinyl chloride processing

Trapping experiments will be described in which standard workplace monitoring devices were used to collect samples over the dynamic mill, Brabender, and single screw laboratory extruder. Additionally, the results of static (unsheared) heating on clear PVC compound and finished goods with collection of emitted organic vapors are compared to the dynamic case. Identification and quantification of the possible contributors to process odor will be discussed.     

Acetoxyglycerol acetal derivatives of mono- and polyformyloctadecanoate esters: Plasticizers for poly(vinyl chloride)

Methyl and butyl(acetoxyglycerol acetal) esters were prepared from 9(10)-formyloctadecanoate or its dimethyl acetal. Mixtures of acetoxy mono- and diglycerol acetals, plus acetoxy mono-, di-, and triglycerol acetals, were prepared respectively from hydroformylated safflower and linseed methyl esters. The glycerol acetals were characterized with respect to physical, thermal, chromatographic, and spectroscopic properties. Acetoxy-mixed glycerol acetals from safflower and linseed methyl esters were good primary plasticizers for poly(vinyl chloride) (PVC), whereas acetoxyglycerol acetals of hydroformylated methyl and butyl oleate were good secondary PVC plasticizers. As primary plasticizers, the poly(acetoxyglycerol acetal) esters showed less migration, better heat stability, and higher tensile strength than the generally used PVC plasticizer di(2-ethylhexyl) phthalate.     

用国产分散剂PVA生产聚氯乙烯树脂

以国产分散剂ＰＶＡ（２０８０、ＷＨ－６）代替进口分散剂ＰＶＡ（ＫＨ－１０、Ｌ－９或ＡＬＣＯＴＥＸ７２．５）,在引进的７０．５ｍ＾３聚合釜中生产聚氯乙烯树脂。分散体系始终正常、稳定,生产的树脂质量同使用进口ＰＶＡ相比无任何差异,在粘釜问题上未见异常,经济效益较为显著。     

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.     

9,9 (10,10)-Bis(acetoxymethyl)octadecanoate Esters as Plasticizers for Poly(vinyl chloride)

Four alkyl 9,9(10,10)-bis(acetoxymethyl)octadecanoates were evaluated as plasticizers for poly(vinyl chloride). They were all compatible and imparted properties generally equal or superior to those obtained with a dioctyl phthalate (DOP) control. Permanence properties were also generally equal or superior to those reported for analogous acetoxy and acetoxymethyl plasticizers. Volatility was half that for DOP. On heating, the experimental samples remained flexible to failure, whereas the control samples with DOP became stiff and rigid. Acetone acetals of alkyl 9,9(10,10)-bis(hydroxymethyl)octadecanoates were incompatible with poly(vinyl chloride).