Adhesion properties of eco-friendly PVAc emulsion adhesive using nonphthalate plasticizer

An eco-friendly poly (vinyl acetate) emulsion adhesive was synthesized without phthalate. Four types of eco-friendly plasticizers for use in these adhesives were selected to confirm their primary properties by injecting the eco-friendly plasticizer without any prior change to its processing or cost. The four types of eco-friendly plasticizers used were dibutyl phthalate DBP-based product, dialkyl ester, acetyl tributyl citrate, and pentandiol-di-isobutyrate. Their properties were determined by comparison with the existing (DBP)-based product. As a result, an emulsion adhesive was produced without addition of phthalate or need for additional additives, resulting in a significant decrease in cost. However, the low temperature characteristics of the eco-friendly plasticizers were slightly inferior to those of DBP. These adhesives containing eco-friendly plasticizer were studied and their characteristics for adhesion strength, water resistance, ability for low temperature film formation, excellent storage stability, and lack of volatile organic compounds productions (including phthalate) were confirmed.     

Renewable (waste) material based polyesters as plasticizers for adhesives

The aim of the presented work was to replace phthalate based plasticizers with environmentally friendly materials to provide similar properties for poly(vinyl acetate) (PVAc) adhesives.Polyesters synthesized from the liquefied wood (PE-LW) and depolymerized polyethylene terephthalate (PE-PET) were used as renewable raw materials and evaluated as plasticizers used in PVAc dispersion adhesives for flooring applications. As a reference plasticizer, 1,2,3-triacetoxypropane was used.PVAc adhesives were evaluated with respect to solids content, viscosity, glass transition temperature (T_g), tensile shear strength and binding strength.TGA analysis showed significant differences between the thermal stability of added polyesters and the commercial plasticizer. Samples prepared with PE-PET exhibit the best thermal stability even with an increase of 25% PE-PET. The addition of coalescing agents or plasticizers leads to a temporary softening of the PVAc polymer and a decrease in the glass transition temperature.The type and content of plasticizer have great influence on wood–wood binding strength, tensile strength and elongation.The requirements for the mechanical properties of adhesives were fulfilled by the compositions containing 8.8% (w/w) of PE-PET and 20% (w/w) of PE-LW.     

Highly filled blends of a vinylic copolymer with plasticized lignin: Thermal and mechanical properties

The objective of this study was the development of new vinyl flooring formulations with increased resistance to attack by fungi and microorganisms, formulated with plasticizers having chemical compositions different from that of common dioctyl phthalate (DOP). Alkyl phthalate plasticizers are considered to be toxicological and ecotoxicological hazards, although this is still under debate. It is suspected that during the service life of poly(vinyl chloride) (PVC) flooring, the attack of fungi and microorganisms leads to the degradation of DOP and the release of some volatile organic compounds. For this reason, in the new flooring formulations, the vinyl chloride/vinyl acetate copolymer (VC–VAc) was partially replaced with lignin, a natural polymer and a major component of wood and vascular plants. Besides its other functions in wood, lignin imparts resistance to microorganisms. An organosolv lignin from Alcell Technologies, Inc. (AL), was used as a partial replacement of PVC. The influence of the new plasticizers, as well as the influence of the partial replacement of VC–VAc with lignin, on the morphology and thermal and mechanical properties of the composites was investigated with scanning electron microscopy, differential scanning calorimetry, and tensile testing. Butyl benzyl phthalate and diethylene glycol dibenzoate were used as plasticizers; both were compatible with PVC and AL. The results indicated that diethylene glycol dibenzoate was the best plasticizer for these blend composites. In these formulations, AL could replace up to 20 parts of the copolymer. At this level of replacement, the key mechanical properties of the new composites compared very favorably with those of the DOP control formulations. The obtained formulation will be tested further for resistance to fungi and microorganisms. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2000–2010, 2003     

Correlation of the glass transition temperature of plasticized PVC using a lattice fluid model

A model has been developed to estimate the glass transition temperature of polymer+plasticizer mixtures (up to 30 wt% plasticizer). The model is based on the Sanchez-Lacombe equation of state and the Gibbs-DiMarzio criterion, which states that the entropy of a mixture is zero at the glass transition. The polymers studied included polystyrene and poly(vinyl chloride). The plasticizers studied included a wide range of chemicals from methyl acetate to di-undecyl phthalate. The model qualitatively accounted for the effect of different plasticizers on the mixture glass transition temperature.     

Synthesis and evaluation of some fatty esters as plasticizers and fungicides for poly(vinyl acetate) emulsion

n-Fatty alcohols (average molecular weight 187), prepared from n-paraffins, were treated with a series of dibasic acids such as malonic, succinic, glutaric, adipic and phthalic anhydride to give the corresponding fatty esters. The prepared fatty esters were formulated with poly(vinyl acetate) emulsion and used as films or textile coatings. Tests such as rate of drying, mechanical properties and resistance to micro-organisms were carried out. Samples of poly(vinyl acetate) plasticized with dibutyl phthalate were also prepared and evaluated for the purpose of comparison. The antifungal activity of these compounds was studied. The results obtained indicate that the prepared fatty esters can be used not only as plasticizers but also as fungicides and in some respects they are better than the conventional dibutyl phthalate plasticizer.     

增塑剂在吸收片中迁移的研究

定量分析了邻苯二甲酸酯类增塑剂如邻苯二甲酸二正辛酯(DNOP)、邻苯二甲酸二辛酯(DOP)、邻苯二甲酸二甲酯(DMP)以及环保型增塑剂二丙二醇二苯甲酸酯(DPGDB)在吸收片中的迁移。结果表明,不同的吸收片,增塑剂的迁移量不同,在乙烯-乙酸乙烯酯共聚物(EVA)中发生的迁移最大,高密度聚乙烯(HDPE)最小。在压力为49N,温度70℃,试验时间为24h时,增塑剂DOP在吸收片EVA中的质量损失高达141.7mg,而在HDPE中仅有15mg。     

The effects of plasticizers on the properties of poly(vinyl chloride) foams

The effects of plasticizers on poly(vinyl chloride) (PVC) plastisol mixtures were investigated. The investigations were carried out by determining the density of the PVC foam obtained by gelling the plastisol, as well as its elasticity and degree of expansion. Two series of experiments using different types of PVC were performed, using eight plasticizers, individually or as mixtures. Two-component plasticizer mixtures showed better properties than single-component plasticizers, and mixtures of di-iso-heptyl phthalate (DiHP) and butyl benzyl phthalate (BBP) proved to be the most appropriate. The effect of plasticizer amount also was investigated, and of the three parameters studied, the foam density, which steadily increased with plasticizer amount, was the critical one. It was also shown that in order to obtain consistent results, the foam expansion had to be precisely timed and the temperature carefully chosen.     

Studies in Estolides,Part III : Plasticizer for Polyvinyl Chloride

Acetoxy butyl esters prepared from estolides (derived from castor oil fatty acids) were evaluated as plasticizers for poly (vinyl chloride) (PVC) resin. They showed limited compatibility. They were useful as secondary plasticizers for PVC along with dioctyl phthalate plasticizer. The properties of the plasticized stocks were generally comparable to the ones obtained by incorporating 12-acetoxy butyl oleate, the commercial secondary plasticizer. Among the estolides derivatives tried, the acetoxy butyl ester obtained from estolides of acid value 83 showed better performance. 1For parts I and II in the series ,see Refference 3 and 4     

Plasticizer structure/performance relationships

Plasticizers for poly(vinyl chloride) may be organized into eight chemical families and by seven key performance criteria. Cost-effective general-purpose phthalates provide a base line for comparing all other plasticizers. The wide range of performance characteristics associated with various phthalate isomers substantiates the large proportion of phthalate esters that are utilized as plasticizers. This article summarizes plasticizer structural/performance relationships using quantitative comparisons of cost, plasticizing efficiency, plastisol solvation characteristics, dryblending, volatility, and low temperature performance properties in PVC. Some generalizations are also made concerning structural effects of the alcohol isomers used in the syntheses of the various types of plasticizer esters.     

Plasticization effect of lignin in some highly filled vinyl formulations

The present study evaluates the impact of partially replacing (vinyl chloride)‐(vinyl acetate) (VC‐VAc) copolymer with lignin (L) in a vinyl flooring formulation. Lignin is a natural polymer resulting in huge quantities from wood delignification in the pulp and paper industry. An organsolv lignin, Alcell lignin (AL), was utilized. Also examined is the impact of replacing the common diethylhexyl phthalate (DOP) with plasticizers having chemical compositions different from those of DOP, i.e., diethylene glycol dibenzoate (2–45), tricresyl phosphate (Lindol®), and phenol alkylsulphonic ester (Mesamoll®). The reason for using other plasticizers is the suspicion that during the service life of vinyl flooring, the attack of fungi and microorganisms leads to the degradation of DOP and to the release of some volatile organic compounds (VOC). For the same reason, in the new flooring formulations, the VC‐VAc copolymer was partially replaced with L. Besides its other functions in wood, L imparts resistance to the attack of most microorganisms. The efficiency in plasticizing AL was also taken into consideration in choosing the above‐mentioned plasticizers. The influence of the new plasticizers, their concentration, and the influence of the partial replacement of VC‐VAc copolymer with AL on the mechanical and thermal properties of the new formulations are discussed. Laboratory data indicated that at a level of 20 parts VC‐VAc copolymer reduction and 5 parts plasticizer reduction, some of the obtained VC‐VAc‐AL blends compare very favorably with VC‐VAc copolymer control plasticized with 35 phr of DOP, the formulation of choice in vinyl flooring materials. J. VINYL ADDIT. TECHNOL., 13:14–21, 2007. © 2007 Society of Plastics Engineers.     

水溶性粘合剂的配制及其性能研究

先通过聚乙酸乙烯酯(PVAc)的醇解制备出聚乙烯醇(PVA),再用聚乙烯醇在酸性条件下与甲醛缩合,得到聚乙烯醇缩甲醛(PVF),再以聚乙烯醇和聚乙烯醇缩甲醛为基料,以邻苯二甲酸二丁酯(DBP)为增塑剂,聚乙二醇-400(PEG-400)为增韧剂,水为溶剂,以鱼油为分散剂,配制了不同工艺配方的水基粘合剂,考察了增塑剂、增韧剂的加入量对粘合剂的透明度、稳定性、溶解度、粘弹性等的影响。实验结果表明,当质量比PVA∶PVA∶水=9.6∶9.6∶80.8,鱼油、聚乙二醇-400、DBP的添加量分别为4%、1.6%、2.0%时,所配制的粘合剂有相对较好的综合性能。     

Thermal analysis of compounded poly(vinyl chloride)

Differential thermal analysis of mixtures of poly(vinyl chloride) and dioctyl phthalate shows a compound endothermic peak due to decomposition of both polymer and plasticizer. The thermal behavior of other plasticizers is similarly affected in the presence of poly(vinyl chloride). The addition of zinc oxide or ferric oxide decreases the thermal stability of the mixture and, under isothermal conditions, a resultant induction period allows the estimation of an activation energy for the dehydrochlorination of poly-(vinyl chloride) and of the relative effectiveness of thermal stabilizer systems.     

Poly(ε-caprolactone)-based additives: Plasticization efficacy and migration resistance

A family of poly(caprolactone) (PCL)-based oligomeric additives was evaluated as plasticizers for poly(vinyl chloride) (PVC). We found that the entire family of additives, which consist of a PCL core, diester linker, and alkyl chain cap, were effective plasticizers that improve migration resistance. The elongation at break and tensile strength of the blends made with the PCL-based additives were comparable to blends prepared with diisononyl phthalate (DINP), a plasticizer typically used industrially, and diheptyl succinate (DHPS), an alternative biodegradable plasticizer. Increasing concentration was found to decrease glass transition temperature (T_g) and increase elongation at break, confirming their role as functional plasticizers. We found that all of the PCL-based plasticizers exhibited significantly reduced leaching into hexanes compared to DINP and DHPS. The PCL-based plasticizers with shorter carbon chain lengths reduced leaching more than those with longer carbon chain lengths.     

Poly(vinyl chloride)/plasticizer-mixture interactions. Part I. Phthalate ester mixtures

Flory-Huggins interaction parameters, χ, have been determined as a function of plasticizer composition for poly(vinyl chloride) in various binary mixtures of phthalate ester plasticizers using a method involving the micro-determination of the temperature at which PVC particles in excess plasticizer appear to melt. An optimum composition at which χ goes through a minimum was found to exist for some of the systems. A good correlation between the apparent melting temperature t_m and χ for the neat plasticizers with PVC was also established.     

Plastification of poly(vinyl chloride) by polymer blending

Blends of poly(vinyl chloride) (PVC) with different copolymers have been studied to obtain a plasticized PVC with improved properties and the absence of plasticizer migration. The copolymers used as plasticizers in the blends were acrylonitrile butadiene rubber, ethylene vinyl acetate (EVA), and ethylene-acrylic copolymer (E-Acry). Blends were studied with regard to their processing, miscibility, and mechanical properties, as a function of blend and copolymer composition. The results obtained were compared with those of equivalent compositions in the PVC/dioctyl phthalate (DOP) system. Better results than PVC/DOP were obtained for PVC/acrylonitrile butadiene rubber blends. The plasticizing effect on PVC of EVA and E-Acry copolymers was similar to that of DOP. It is shown that crosslinking PVC/E-Acry blends or increasing the vinyl acetate content in PVC/EVA blends, are alternatives that can increase the compatibility and mechanical properties of these blends. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 1303–1312, 2000     

Rheometric study of the gelation and fusion processes of poly(vinyl chloride‐co‐vinyl acetate) plastisols with different commercial plasticizers

Evolution of the complex viscosity of pastes of PVC‐VA (vinyl chloride‐vinyl acetate copolymer) plasticized with different commercial plasticizers has been studied. Knowledge of the rheological behavior of the formulations allows for better understanding of the gelation and fusion processes. Twenty commercial plasticizers of different types and with different functional groups have been studied and are grouped into five families: phthalate esters with linear chains, phthalate esters with branched chains, adipates (normal and polymeric), citrates, and rest of the plasticizers (carboxylates, alkylsulfonates, and pentaerythritol ester derivatives). Interesting relationships among the observed rheologies and the nature and molecular weight of the plasticizer have been observed. The evolution of the complex viscosity with temperature—at the temperatures where the blowing agents normally used in PVC plastisol foaming processes generate the main amount of gas—has been newly discussed with regard to the chemical structure and molecular weight of all of the plasticizers used. It was found that several different dynamic processes must be synchronized in order to understand the relationships among the chemical structure, plasticization, plasticizer compatibility, rheological properties, and foaming process of such materials. J. VINYL ADDIT. TECHNOL., 2012. © 2012 Society of Plastics Engineers     

Application of new oligomeric plasticizers based on waste poly(ethylene terephthalate) for poly(vinyl chloride) compositions

In this study, chemical recycling products of waste poly(ethylene terephthalate) with oligoesters were used as new plasticizers for poly(vinyl chloride) (PVC). The preparation conditions of the dry blend mixtures of the suspension PVC containing synthesised plasticizers were similar to the conditions of the preparing mixtures with commercial plasticizers. The plasticization efficiency of PVC plasticizers was then examined by analysis of the mechanical, physical and chemical properties, as well as the thermal resistance and migration of plasticizer molecules from polymer matrix. Test results proved that compositions with synthesised oligomeric plasticizers possessed similar or better properties than those containing commercial oligomeric plasticizers and much better properties than those having monomeric plasticizers. Thermal stabilities of the proposed plasticizers were higher than those of the commercial plasticizers either monomeric (bis(2-ethylhexyl)phthalate) or oligomeric, despite the fact that the synthesised oligoesters did not contain any antioxidant. The best properties, especially low volatility, very good mechanical properties, low migration were resulted of the transesterification of the waste PET with oligoesters based on adipic acid, triethylene glycol and 2-ethylhexanol which were selected as plasticizers synthesised on the technical scale. The tested plasticized PVC compositions possessed very good tear resistance, tensile strength, decrease of weight loss after 168 h at 80 °C and low migration. Processing properties of PVC compositions containing these synthesised plasticizers confirmed their effectiveness in these compositions for extrusion process.     

Polyhedral oligomeric silsesquioxane as a novel plasticizer for poly(vinyl chloride)

This study focuses on investigating the use of polyhedral oligomeric silsesquioxanes (POSS) to plasticize poly(vinyl chloride) (PVC). Conventional organic plasticizers for PVC, such as dioctyl phthalate (DOP), are somewhat volatile, leading to plasticizer loss and unwanted deterioration of the material properties over time. Previous experimental results indicate that methacryl-POSS, which is much less volatile due to its hybrid organic-inorganic structure, has the ability to plasticize PVC. Methacryl-POSS is miscible in the PVC only up to 15 wt%, thereby limiting its suitability as a plasticizer. However, through the use of ternary compositions it is possible to increase the proportion of methacryl-POSS in PVC substantially. The T_g of appropriately formulated ternary PVC/POSS/DOP compounds can be reduced to near room temperature, and these materials exhibit desirable ductile behavior. Binary (PVC/DOP) and ternary (PVC/POSS/DOP) compounds formulated to the same T_g values showed considerably different mechanical properties. Such findings reveal the possibility of using POSS to engineer the mechanical properties of plasticized PVC.     

Contributions to characterization of poly(vinyl chloride)–lignin blends

The present study evaluates the impact of blending organosolv and kraft lignins, which are natural polymer by‐products in the pulp and paper industry, with plasticized poly(vinyl chloride) (PVC) in flooring formulations. Also examined is the impact of replacing dioctyl phthalate, a PVC industry general‐purpose plasticizer, with diethylene glycol dibenzoate (Benzoflex 2‐45), tricresyl phosphate (Lindol), or alkyl sulfonic phenyl ester (Mesamoll) in these formulations. The influence of the different types of lignins and plasticizers on the processibility, thermal, and mechanical properties of the blends is discussed. These properties demonstrate that partial replacement of PVC (20 parts) with different lignins is feasible for some formulations that can be successfully used as matrices for a high level of calcium carbonate filler in flooring products. In addition, the data demonstrate that the presence of certain plasticizers, which interfere with the intramolecular interactions existing in lignins, may allow the lignin molecules to have more molecular mobility. The morphology and the properties of PVC plasticized lignin blends are strongly influenced by the degree and mode of the lignin plasticization and its dispersion within the PVC matrix. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 2732–2748, 2006     

The migration of plasticizers from poly(vinyl chloride) into edible oils

The migration of phthalate plasticizers from poly (vinyl chloride) into edible oils has been analyzed. The principal method used involved ¹⁴C-labeled dibutyl and dioctyl phthalates with detection by liquid scintillation spectrophotometry. In most cases, the migration of the main plasticizer was accompanied by the migration of the secondary plasticizer, when present, and by diffusion of the oil into the polymer. Comparison of the scintillation results with those obtained by weight loss measurements can give quantitative information on the amount of the liquid medium that diffuses during the migration process. The effect of the following factors on the migration process was examined; (a) the nature and acidity of the edible oil, (b) the composition and amount of phthalate plasticizer, (c) the amount of epoxy plasticizer, and (d) the temperature and time of contact.