Optimizing performance of benzoate and phthalate blends for vinyl applications

To achieve required performance, blends of plasticizers are commonly used in flexible vinyl applications. Typically, when fast fusion is required, high solvating phthalates have been utilized in plasticizer blends. Benzoate esters are high solvators and can also be used in these blends. However, even though benzoate plasticizers offer additional performance benefits that can complement general‐purpose phthalate performance, most of the literature does not include the use of benzoate plasticizers in blends with phthalates. The purpose of this article is to demonstrate the performance benefits of blending benzoate and phthalate plasticizers. The approach selected to accomplish this task was to develop performance data by utilizing a mixture design approach with DOE (design of experiments) software. A resilient flooring plastisol formulation was selected as the model. The following properties were obtained: degassing, low and high shear viscosity, viscosity stability of the plastisol, gel and fusion characteristics, tensile strength vs. temperature, vinyl heat stability, stain resistance, volatility, and UV stability. The data indicate how to utilize the advantage of benzoates as “process aids” to speed production rates and improve product quality. J. VINYL. ADDIT. TECHNOL. 11:150–154, 2005. © 2005 Society of Plastics Engineers     

Polymer blends containing liquid crystals: A Review

This paper reviews the literature of polymer blends containing low and high molar mass liquid crystals. Low molar mass liquid crystals have been used as plasticizers for thermoplastic polymers and in applications such as electrooptics, optical recording media, and membranes. High molar mass liquid crystalline polymers have been primarily used in polymer blends as processing aids and as an incipient reinforcing phase for “self-reinforced” materials. This review discusses the phase behavior, rheology, and mechanical properties of these blends.     

Energy and material cost savings with polyester/monomeric plasticized PVC compounds

Many plasticized PVC articles are exposed to harsh environments that cause loss of plasticizer through extraction, volatility, or migration. In order to survive in these applications, the PVC must contain plasticizers that have a reasonable degree of permanence. Two approaches are the use of low molecular weight polyester plasticizers, or higher molecular weight polyester/monomeric plasticizer blends. The blend approach can give better cost-performance and, due to faster fusion, reduced energy/manufacturing costs. The blends maintain their advantages even upon further dilution with monomeric plasticizers and in permanence tests of long duration. Although better than monomeric plasticizers, neither the low molecular weight polyester nor the blend system is recommended for applications requiring the ultimate in migration resistance.     

New benzoate plasticizers for polyvinyl chloride: Introduction and performance example

Two new unique benzoate ester plasticizers that will offer the vinyl formulator improved performance have been developed. One is an excellent solvator that will yield lower plastisol viscosities than existing plasticizers. The other will provide an excellent alternate with low volatility. The new products provide expanded performance utility over existing benzoates and phthalates on a global basis. Basic plastisol performance data and an example of use in a specific application, vinyl leathercloth, are presented. The data demonstrates that these blends are compatible, effective high solvating plasticizers and are performance alternates for plastisols and other polyvinyl chloride applications.     

The interactions and partitioning of low molecular weight polyethylene glycols and diethyl phthalate in ethylcellulose/hydroxypropyl methylcellulose blends

The interactions and partitioning of diethyl phthalate and low molecular weight polyethylene-glycols in blends of ethylcellulose/hydroxypropyl methylcellulose have been studied. Both plasticizers were shown to diffuse in both phases according to the overall volume composition. The plasticizers interacted preferentially with one polymer component of the blend as predicted from studies of the individual polymers. Diethyl phthalate, a preferential plasticizer for ethylcellulose, demonstrated increased partitioning in the ethylcellulose-rich phase only at 80/20 w/w ethylcellulose/hydroxypropyl methylcellulose compositions. Polyethylene glycols, PEG200 and PEG400, preferential plasticizers for hydroxypropyl methylcellulose, showed increased partitioning in the hydroxypropyl-methycellulose-rich phase also in blends containing 80% w/w ethylcellulose. The general effect of the mechanism and kinetics of the phase separation of the blend on the plasticizer partitioning has also been discussed.     

New dibenzoate plasticizer blends for PVC applications

Dibenzoates plasticizers are well‐established and are used in PVC applications. Chemically, these plasticizers are non‐phthalates and function well as high‐solvating. In the past, new benzoates, dibenzoate blends, and grades were developed to keep pace with formulators' needs. More recently, a new generation of dibenzoate triblend platform has been developed to offer formulators an improved high solvator to complement general purpose plasticizer performance. A basic plastisol evaluation protocol was utilized to help determine how to formulate with these new blends. In addition to the basic data that were developed, examples of performance in starting plastisol formulations are shown. J. VINYL ADDIT. TECHNOL., 20:137–142, 2014. © 2014 Society of Plastics Engineers     

高聚合度PVC／PP／相容剂共混改性体系研究

采用ＣＰＥ、ＡＢＳ和ＰＰ溶体接枝物等作相容剂恶性状聚合物ＰＶＣ／ＰＰ共混物的相容性，并考察共混比、相容剂用量、增塑剂用量、ＥＰＤＭ用量、相容剂种类对高聚合度ＰＶＣ／ＰＰ共混物力学性能和微观形态的影响。     

淀粉/PVA生物降解材料的热塑性研究

将聚乙烯醇(PVA)、淀粉、增塑剂在Hakke流变仪中共混制备了热塑性淀粉/PvA材料,研究了2种PVA-PVA1799、PVA1788,2种淀粉-玉米淀粉、木薯淀粉的热塑性情况;比较了甘油、乙二醇、乙酰胺3种增塑剂的增塑效果.结果表明:采用合适的增塑剂与适当的PVA、淀粉组合可以使PVA/淀粉共混体系在高温下热塑成型...     

Dynamic mechanical and thermal properties of plasticized poly(lactic acid)

The blends of low molecular weight triacetin (TAC) and oligomeric poly(1,3‐butylene glycol adipate) (PBGA) were used as multiple plasticizers to lubricate poly(lactic acid) (PLA) in this study. The thermal and mechanical properties of plasticized polymers were investigated by means of dynamic mechanical analysis and differential scanning calorimetry. Atomic force microscopy (AFM) was used to analyze the morphologies of the blends. Multiple plasticizers were effective in lowering the glass transition temperature (T_g) and the melting temperature (T_m) of PLA. Moreover, crystallinity of PLA increased with increasing the content of multiple plasticizers. Tensile strength of the blends decreased following the increasing of the plasticizers, but increased in elongation at break. AFM topographic images showed that the multiple plasticizers dispersed between interfibrillar regions. Moreover, the fibrillar crystallite formed the quasicrosslinkings, which is another cause for the increase in elongation at break. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 1583–1590, 2006     

Effect of two different plasticizers on the properties of poly(3‐hydroxybutyrate) binary and ternary blends

Plasticized poly(3‐hydroxybutyrate) (PHB) films were obtained by solvent casting. The effects of two different additives on several properties of PHB have been examined, utilizing tributyrin and poly[di(ethyleneglycol) adipate] (A). Based on changes in the glass transition temperature (T_g) and cold crystallization temperature of host PHB, the two components are miscible with PHB and they can act as plasticizers. Binary and ternary blends were obtained by adding both plasticizers separately or together, respectively. The effect of plasticizer addition on the optical transparency, water vapor permeability, and tensile properties of the films was studied. It was found that the blends remain transparent and water vapor permeability was maintained constant until a 20 wt % of plasticizer content. Plasticizing effect was corroborated and it depended on the plasticizer percentage. Binary blends had an increased plasticity, in concordance with T_g diminution of PHB. Although ternary blends presented T_g diminution, mechanical properties were not improved probaby due to strong interactions between plasticizers. Finally, binary and ternary blends presented enhanced properties, causing an increment on processability. A correct knowledge between the formulation of the film and the role played by each component could allow getting custom films. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46016.     

A contribution to the investigation of PVC-plasticizer interactions

Temperature dependent characteristics of blends of suspension poly(vinyl chloride) with low and high molecular weight plasticizers in the region of processing temperatures have been investigated. The interaction process has been studied under dynamic conditions using the differential thermal analysis (DTA) method under non-iso-thermal conditions. As a result of the DTA curves evaluation as well as of the discussion of results it has been shown that the energy transformation occurring during the PVC-plasticizer system processing is manifested by changes of thermal behavior. The values of heat released, corresponding to the maximum heat transfer rate have been identified as primary data which can be used in correlations describing the quality of plasticizers present in the system. The correlational relations covering the region of processing temperatures provide a “homogeneity” criterion of the system, corresponding to the plasticizing capability of the plasticizer involved.     

Simulation studies of the interfaces of incompatible glycidyl azide polymer/hydroxyl-terminated polybutadiene blends by dissipative particle dynamics. I. The effect of block copolymers and plasticizers

Dissipative particle dynamics (DPD) simulations were used to investigate the interfaces of incompatible glycidyl azide polymer (GAP)/hydroxyl-terminated polybutadiene (HTPB) blends in the presence of block copolymers and plasticizers. They were GAP-b-HTPB copolymers and commonly used nitrate ester or inert plasticizers in the formulations of propellants. The results show that there were two abilities that determined the effects of the block copolymers and plasticizers on reducing the interfacial tension (γ). These were the penetrability into each homopolymer phase and the ability for assembling at the interface. The plasticizers mainly depended on the first ability, and the block copolymers depended on the other ability. In addition, block copolymers with the different chain lengths had the different influences on γ of the GAP/HTPB blends. Moreover, this phenomenon could also be explained by the above two abilities. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

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.     

环保型增塑剂对丙烯酸酯橡胶/乙烯丙烯酸酯橡胶共混胶性能的影响

研究了环保型增塑剂RS-107、RS-700、RS-735和TegMeR?812对丙烯酸酯橡胶(ACM)/乙烯丙烯酸酯橡胶(AEM)共混胶性能的影响,结果表明,随着增塑剂的加入,ACM/AEM共混胶的转矩明显下降,不同增塑剂对共混胶硫化影响的差别不大。加入4种增塑剂均使得共混硫化胶的硬度、拉伸强度和100%定伸应力减小而扯断伸长率增大,压缩永久变形性能和热稳定性都出现了不同程度的下降,耐低温性能得以改善,提高了耐IRM 903标准油性能,但对耐ASTM No 1标准油性能的影响不大。加入增塑剂使得共混胶的玻璃化转变温度明显向低温方向偏移、储能模量减小。其中,RS-700赋予共混硫化胶最好的综合性能。     

Oligomeric isosorbide esters as alternative renewable resource plasticizers for PVC

Oligo(isosorbide adipate) (OSA), oligo(isosorbide suberate) (OSS), and isosorbide dihexanoate (SDH) were synthesized and evaluated as renewable resource alternatives to traditional phthalate plasticizers. The structure of the synthesized oligomers was confirmed by nuclear magnetic resonance spectroscopy (¹H‐ and ¹³C‐NMR), and molecular weight was determined by size exclusion chromatograph. The plasticizers were blended with poly(vinyl chloride) (PVC), and the miscibility and properties of the blends were evaluated by differential scanning calorimetry, fourier transform infrared spectroscopy, tensile testing, and thermogravimetry. Especially the blends plasticized with SDH had almost identical properties with PVC/diisooctyl phthalate (DIOP) blends. The blends containing OSA and OSS plasticizers, based on dicarboxylic acids, had somewhat lower strain at break but higher stress at break and better thermal stability compared to the PVC/DIOP or PVC/SDH blends. All the synthesized isosorbide plasticizers showed potential as alternative PVC plasticizers. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

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     

Orientation in uniaxially stretched plasticized atactic polystyrene

Summary Fourier transform infrared spectroscopy and birefringence measurements have been used to study the changes in molecular orientation which occur on drawing of plasticized as compared to pure polystyrene (PS) at a temperature T=Tg+Cte. No influence of plasticizers on orientation can be detected whatever the interactions between small molecules and PS chains are. Comparison with previous results obtained on PS-poly(vinylmethyl ether) compatible blends confirms the importance of the macromolecular nature of the second component to enhance the friction coefficient leading to higher level of chain orientation.     

Interactions in poly(vinyl chloride)–lignin blends

In rigid poly(vinyl chloride) (PVC)-lignin (L) blends the possibility of forming intermolecular interactions between the PVC and L can take place only at low L loading (up to 10 parts). At high L loading there is an imbalance between the tendency of L molecular components to associate by H-secondary bonds, and the potential for forming intermolecular bonds with PVC. Our studies have shown that specific plasticizers could break parts of the H-secondary bonds present in L, thus creating possibilities of interactions at a molecular scale with other polar polymers by forming intermolecular bonds. The presence of specific plasticizers strongly influences the properties and the morphology of the blends, and permits higher L loading. The data regarding the properties of plasticized copolymer (vinyl chloride-vinyl acetate) (VC-VAc)-L blends show the important role of these specific plasticizers. Some results show also the possibility of L-filler interaction. The blends were studied with regard to their morphology by Differential Scanning Calorimetry (DSC), Dynamic Mechanical Analysis (DMA), Fourier Transform Infrared (FT-IR) Spectroscopy, Scanning Electron Microscopy (SEM) and with regard to their mechanical properties by tensile testing.     

Thermomechanical film properties and aging of blends of poly(lactic acid) and malonate oligomers

Malonate oligomers were synthesized as plasticizers for poly(lactic acid) (PLA). Esterification reactions were performed between diethyl bishydroxymethyl malonate (DBM) and either adipoyl dichloride or succinyl dichloride. Two molar masses were obtained within each series. Blending was carried out with PLA and the four oligomers as well as the monomeric unit from the syntheses (DBM). Dynamic mechanical analysis and differential scanning calorimetry were used to investigate the viscoelastic mechanical and thermal film properties of the blends. All the investigated plasticizers reduced the glass‐transition temperature of PLA, and the plasticization effect was better for the plasticizers of low molar mass. However, the amorphous domains of PLA became saturated with plasticizer at a certain concentration, and phase separation occurred. A higher molar mass of the plasticizer caused this saturation to occur at lower plasticizer concentrations. Subsequently, the aging of the blends at the ambient temperature for 4 months induced phase separation in the blends containing DBM, whereas those with an oligomeric plasticizer were stable and remained compatible with PLA within the aging period. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 2140–2149, 2004     

Transparency of rubber‐toughened polymer blend containing plasticizer

Transparency and its temperature dependence were studied for rubber‐toughened polymer blends composed of poly(methyl methacrylate), core–shell latex–rubber particles, and plasticizers such as tricresyl phosphate and di(2‐ethylhexyl)adipate. The transparency of the blends was found to be improved by the addition of the plasticizers. This phenomenon is attributed to the uneven distribution of the plasticizer in the blends. Furthermore, it was found that the plasticizers improve the transparency in a wide temperature range, because the plasticizer addition reduces the difference in the thermal expansion, and thus the temperature dependence of the refractive index, between poly(methyl methacrylate) and the rubber phases. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40775.