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.     

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     

低分子量聚四氢呋喃二苯甲酸酯的增塑性能分析

以传统的邻苯二甲酸二辛酯（DOP）和聚醚型二甘醇二苯甲酸酯（DEDB）增塑剂作对比,对聚四氢呋喃二苯甲酸酯（PTMGDB₅₀₀）增塑剂增塑的聚氯乙烯（PVC）材料进行研究。本文对增塑剂增塑的PVC材料进行了FTIR和TG表征,并考察了其力学性能、耐乙醇抽出性及耐迁移性。结果表明,增塑剂PTMGDB₅₀₀增塑的PVC材料在力学性能上介于DOP和DEDB两者之间,而PTMGDB₅₀₀与PVC间的相互作用更强,在耐迁移、耐乙醇抽出、耐热及耐压等性能方面均优于DOP及DEDB,因此PTMGDB₅₀₀可作为部分替代DOP和DEDB的增塑剂。     

Blends of vinylic copolymer with plasticized lignin: Thermal and mechanical properties

The article presents an investigation into the use of plasticizers for reducing the degree of association existing within lignin molecules, in order to overcome adverse effects on the mechanical properties of its blends with a vinyl chloride–vinyl acetate (VC–VAc) copolymer. Infrared spectroscopy and differential scanning calorimetry were performed to examine the effect of the plasticizer type and concentration in plasticizing Alcell, an organosolv lignin. The results show that the compatibility and efficiency of a plasticizer are strongly influenced by the solubility parameter, which should be close to that of the lignin. Polyblends prepared with several plasticizers, Alcell lignin, and the VC–VAc copolymer were also investigated by thermal analysis and mechanical testing. Variations in the mechanical properties of these blends were found to correlate with the lignin dispersion quality and with the plasticizer efficiency in Alcell lignin. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 861–874, 2001     

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     

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℃。     

The strong interaction between poly(vinyl chloride) and a new eco-friendly plasticizer: A combined experiment and calculation study

Hydrogenation has been proved to be an efficient way to remove the toxicity of phthalate plasticizer. However, other influences of this hydrogenation are still unknown. Here we chose di-2-ethylhexyl phthalate (DOP) and di(2-ethylhexyl) cyclohexane-1,2-dicarboxylate (DEHHP) to study the influence on interaction with poly(vinyl chloride) (PVC). By combining experiment and calculation, we found the interaction was stronger in PVC/DEHHP than in PVC/DOP. Low-Field ¹H NMR results showed that PVC chains could restrict much more DEHHP molecules than DOP. FTIR results showed that the interaction exists in form of hydrogen bonding complex, and it was stronger in PVC/DEHHP than in PVC/DOP system. Combined with FTIR results, theoretical calculation results revealed the three-center hydrogen bonded structure of the complex. Both the proportion and the binding energy of pre-complex in DEHHP are much larger than in DOP. Here, the hydrogenation-induced change of interaction was elucidated systematically and could be generalized to other phthalate plasticizers.     

Castor Epoxy Fatty Acid Alkyl Ester Estolides as Bioplasticizers for Poly(Vinyl Chloride)

Epoxy fatty acid alkyl ester estolides were synthesized from castor oil to be used as biobased plasticizers for poly(vinyl chloride) (PVC) as a safer replacement for phthalate plasticizers. Initially, castor oil was transesterified with methanol or n-butanol to quantitatively yield castor fatty acid alkyl esters. Acetylation of hydroxyl function with acetic anhydride led to the formation of estolide. The unsaturation was epoxidized, resulting in a bifunctional epoxy fatty acid alkyl ester estolide. The bioplasticizers were compounded with PVC and were evaluated for their functionality and compared with commercial phthalate plasticizer diisononyl phthalate (DINP) and nonphthalate 1,2-cyclohexanoic acid diisononyl ester (DINCH). The bioplasticizers showed excellent gelation, efficiency, and compatibility, as well as plastisol viscosity and thermal properties, comparable to or better than the plastisols prepared with commercial controls DINP and DINCH. The volatility of the methyl ester was inferior to the butyl ester. Both compounds showed low water resistance properties. Further evaluation of the butyl ester under tropical conditions of high temperature and humidity confirmed limited compatibility. This indicates that the castor epoxy fatty acid ester estolides would be better suited for applications that do not come in contact with water for prolonged periods, such as flooring, artificial leather, wiring, or wall coverings.     

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     

Effect of ketal group in castor oil acid-based plasticizer on the properties of poly(vinyl chloride)

Two castor oil acid esters containing a ketal or ketone group (KCL or CL), as alternative plasticizers for poly(vinyl chloride) (PVC), were prepared. The structures were confirmed by ¹H NMR and FTIR spectroscopies. The effects of the presence of a ketal or ketone group in these compounds on PVC plasticization were examined. The DMA and SEM results showed that both plasticizers were miscible with PVC and exhibited excellent plasticizing properties, compared to those of dioctyl phthalate (DOP). The PVC plasticized by KCL displayed a lower T_g value of 20.6 ° C, which was lower than that of PVC plasticized with DOP (22.3 ° C) and PVC plasticized with CL (40.5 ° C). Tensile tests indicated that PVC plasticized using KCL showed a 37% higher of elongation at break than PVC plasticized by CL and 30% higher than PVC plasticized by DOP. The plasticizing mechanism was also investigated. Moreover, exudation, volatility, and extraction tests, along with TGA indicated that the presence of ketal groups effectively improved the migration resistance of plasticizer and the thermal stability of PVC blends. Taken together, introducing ketal groups into plasticizer might be an effective strategy for improving its plasticizing efficiency.     

An efficient plasticizer based on waste cooking oil: Structure and application

Recently, phthalates have been continuously banned in numerous fields by many countries. Therefore, the development of sustainable and efficient plasticizers has become particularly urgent. The waste cooking oil was used as the main raw materials in this study to synthesize an efficient plasticizer (acetylated-fatty acid methyl ester-trimellitic acid ester, AC-FAME-TAE). The structure of AC-FAME-TAE was characterized by FT-IR and ¹H NMR. The performance of the poly(vinyl chloride) (PVC) plasticized by AC-FAME-TAE was tested and compared with those of the PVC plasticized with di-2-ethylhexyl phthalate (DOP) and EFAME (epoxy fatty acid methyl ester), respectively. DSC results indicated that AC-FAME-TAE had excellent plasticizing efficiency for PVC. The mechanical properties of PVC plasticized by AC-FAME-TAE were as comparable as PVC plasticized by DOP from the results of tensile test. In addition, the PVC plasticized by AC-FAME-TAE had excellent thermal stability and solvent resistance by the results of leaching test and TGA.     

Effect of plasticizers on mechanical,electrical, permanence,and thermal properties of poly(vinyl chloride)

Effects of three different plasticizers and their blends with dioctyl phthalate (DOP) on thermal stability, flammability, mechanical, electrical, and permanence properties of poly(vinyl chloride) (PVC) compound were studied. Various plasticizers used were DOP, butyl benzyl phthalate (BBP), isodecyl diphenyl phosphate (IDDP), and polybutylene adipate (PBA) at concentrations of up to 40 phr level. Studies showed that processability and softness were improved by addition of BBP. An increase in the content of IDDP increased the electrical and flammability properties, whereas compositions with PBA exhibited the best permanence properties. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 3278–3284, 2003     

The UV resistance of adipate based polymeric plasticizers in PVC

DOA, (di-2-ethylhexyl) adipate, is a monomeric ester plasticizer frequently used in PVC compositions to enhance flexibility at low temperatures. DOA has several drawbacks; it lacks permanence in the PVC matrix and it has poorer compatibility than its phthalate homologue (DOP). By reacting adipic acid with polyols, polymer chains of increased molecular weights can be formed. These polyester plasticizers offer increased permanence over DOA. The focus of this paper is to demonstrate how adipate plasticizers, starting with DOA and increasing in molecular weight, affect the performance of flexible vinyl, especially in regard to UV resistance and permanence. The following series of evaluations will show that as the molecular weight of plasticizers increases, the permanence properties (volatility and extraction by various media) increase. The ability to withstand degradation from ultraviolet light also increases with higher molecular weight.     

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。     

Emissivity values for poly(vinyl chloride) with varying plasticizer compositions

The emissivity of plasticized poly(vinly chloride) (PVC) containing varying compositions and amounts of plasticizer was investigated. The four plasticizers examined were dibutyl phthalate (DBP), dioctyl phthalate (DOP), diisodecyl phthalate (DIDP) (Phthalic acid type), and dioctyl adipate (DOA) (adipic acid type). The emmissivity of plasticized PVC film increased almost equally with the difference in the compositions between DOP and DOA. It was also clear that the emissivity of the plasticized PVC film decreased gradually with the molecular sequence length of DBP, DOP, and DIDP.     

塑料中增塑剂渗出的分析研究

针对邻苯二甲酸酯类增塑剂如邻苯二甲酸二甲酯（DMP）和邻苯二甲酸二辛酯（DOP）以及环保类增塑剂如二丙二醇二苯甲酸酯（DPGDB）和乙酰基柠檬酸三正丁酯（ATBC）在潮湿条件下渗出进行了定量分析。分析表明,增塑剂的渗出除了与塑料相容性有关,还与试验温度、试验时间有相关性。80％、一周时间试验塑料中增塑剂DPGDB的渗出124．7mg,约为相同试验周期60℃时的30倍。该方法简便、准确,适用于塑料增塑剂渗出的测定。     

Characterization of 1,5‐pentanediol dibenzoate as a potential “green” plasticizer for poly(vinyl chloride)

1,5‐Pentanediol dibenzoate (PDDB) was evaluated as a potential “green” plasticizer for poly(vinyl chloride) (PVC) at concentrations ranging between 20 and 80 parts by weight per hundred parts of resin. The results of glass transition temperature (T_g) and tensile tests of PDDB blends with PVC were compared with those for blends of the commercial plasticizers di(2‐ethylhexyl) phthalate (DEHP), di(ethylene glycol) dibenzoate (DEGDB), and di(propylene glycol) dibenzoate (DPGDB) in PVC. The depression in T_g and the tensile properties were comparable for a PDDB/PVC blend at a fixed composition to those of blends with DEHP, DEGDB, and DPGDB. The PDDB was subjected to biodegradation using co‐metabolism by the common soil bacterium Rhodococcus rhodochrous (ATCC 13808). After 16 days of growth, nearly all of the PDDB was degraded, and only small amounts of transient, unidentified metabolites were observed in the growth medium during the experiment. J. VINYL ADDIT. TECHNOL., 2009. © 2009 Society of Plastics Engineers     

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.     

Synthesis of random and block copolymers of vinyl chloride and vinyl acetate by RAFT miniemulsion polymerizations mediated by a fluorinated xanthate

Reversible addition–fragmentation chain transfer miniemulsion (co)polymerizations of vinyl acetate (VAc) and vinyl chloride (VC) are conducted in the presence of a fluorinated xthanate (X1). VAc miniemulsion polymerization can be well controlled by X1, and PVAc with small polydispersity index (PDI, <1.20) are obtained. X1 also shows well mediative effect to VC‐VAc miniemulsion copolymerization, while the PDI of VC‐VAc copolymer is greater than that of PVAc since a chain transfer rate to VC is greater than that to VAc. PVAc‐b‐PVC copolymers are synthesized by VC miniemulsion polymerizations mediated by X1‐terminated PVAc. PDIs of PVAc‐b‐PVC copolymers are greater than that of PVAc and VC‐VAc random copolymers with close monomer compositions, and increase with the increase of VC conversion. This is caused by the increased chain transfer to monomer and the formation of monomer‐rich and polymer‐rich phases during the VC polymerization stage. As‐prepared PVAc‐b‐PVC copolymers exhibit a micro‐phase separated morphology. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45074.     

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).