Synthesis of a novel polyester plasticizer based on glyceryl monooleate and its application in poly(vinyl chloride)

The use of bio‐based polymeric plasticizers could expand the application range of plasticized poly(vinyl chloride) (PVC) materials. In this study, a novel bio‐based polyester plasticizer, poly(glutaric acid‐glyceryl monooleate) (PGAGMO), was synthesized from glutaric acid and glyceryl monooleate via a direct esterification and polycondensation route. The polyester plasticizer was characterized by gel permeation chromatography, ¹H‐nuclear magnetic resonance, and Fourier‐transform infrared spectroscopy. The plasticizing effect of PGAGMO on PVC was investigated. The melting behavior, thermal properties, and mechanical properties of PVC blends were studied. The results showed that the PGAGMO could improve the thermal stability and reduce the glass transition temperature of PVC blends; when phthalates were substituted by PGAGMO in PVC blends, the thermal degradation temperature of PVC blends increased from 251.1°C to 262.7°C, the glass transaction temperature decreased from 49.1°C to 40.2°C, the plasticized PVC blends demonstrated good compatibility, and the decrement of the torque and the melt viscosity of PVC blends were conducive to processing. All results demonstrated that the PGAGMO could partially substitute for phthalates as a potential plasticizer of PVC. J. VINYL ADDIT. TECHNOL., 22:514–519, 2016. © 2015 Society of Plastics Engineers     

Poly(hexane succinate) plasticizer designed for poly(vinyl chloride) with a high efficiency,nontoxicity, and improved migration resistance

Poly(hexane succinate) (PHS) was designed as an alternative type of polyester plasticizer for the modification of poly(vinyl chloride) (PVC). The plasticizing effect of PHS was studied and compared with the traditional dioctyl phthalate (DOP) plasticizer. The results show that the PVC plasticized by PHS had the lowest tensile strength of 15.3 MPa and the highest elongation at break of 105.1% when 35 phr PHS was added. It also exhibited a lower glass‐transition temperature than PVC plasticized by DOP (PVC–DOP); this could be explained by the improvement of free volume for the amorphous part of PVC enhanced by high‐molecular‐weight PHS. The migration‐resistant properties of PVC–PHS was greatly superior to those of PVC–DOP. All of these results illustrate that PHS had a higher plasticizing efficiency than DOP for PVC. PHS could be used as an alternative plasticizer to remove the potential health risks of phthalates migrating out during applications. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46388.     

Synthesis,characterization, and properties of degradable poly(l‐lactic acid)/poly(butylene terephthalate) copolyesters containing 1,4‐cyclohexanedimethanol

High‐molecular‐weight copolyesters based on poly(butylene terephthalate) as rigid aromatic segments and poly(l‐lactic acid) (PLLA) as degradable aliphatic segments were synthesized via the polycondensation of terephthalic acid, 1,4‐butanediol (BDO), 1,4‐cyclohexanedimethanol (CHDM), and PLLA oligomer. By tailoring the molar ratio of diols (BDO and CHDM), we investigated in detail the effects of the CHDM rigid hexacyclic ring on the synthesis, mechanical properties, thermal stabilities, and degradation behaviors of the copolyesters. With increasing CHDM content, the initial decomposition temperature increased from 282.5 to 322.2°C, and the tensile strength improved by nearly four times, from 5.4 to 19 MPa. When the molar ratio of BDO/CHDM was 95/5, the weight‐average molecular weight of the copolyester was 89,400 g/mol with a polydispersity of 1.96. In addition, hydrolytic degradation results in phosphate buffer solution indicate that the degradation rate of the copolyesters displayed a strong dependency on the temperature and CHDM composition. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Recycling of Waste PET: Usage as Secondary Plasticizer for PVC

Postconsumer water bottle poly(ethylene terephthalate) (PET) flakes were depolymerized with ethylene glycol (EG) by the glycolysis reaction in the presence of zinc acetate as the catalyst. In the depolymerization reactions, different weight ratios of PET/EG were used. In order to obtain polyesters used as PVC plasticizers, these glycolysis products containing hydroxyl end groups were reacted with an adipic acid (AA)–containing diacid group at equivalent amounts. In order to obtain PVC plastisols, PVC was dispersed into a plasticizers' mixture composed of di-isooctyl phthalate (DOP) and polyester products by using a high-speed mixer (PVC/plasticizers, 65/35 w/w). For the preparation of plasticizer mixture polyester products were used at a weight ratio of 20%, 40%, 60% of DOP. Plasticized PVC sheets were prepared from plastisols and their glass transition temperatures (T_g), migration, and mechanical properties were determined. The results show that the polyester products obtained from glycolysis products of waste PET can be used as secondary plasticizers, with DOP for PVC.     

软质聚氯乙烯材料的改性研究

研究了己二酸二辛酯(DOA)、聚酯增塑剂与粉末丁腈橡胶(P83)高分子改性剂对软质聚氯乙烯(PVC)材料的低温脆化温度、分子迁移率和空气热失重等性能的影响。结果表明，DOA可改善软质PVC材料的耐低温性能，但却降低了材料的耐久性能；聚酯增塑剂则正好相反；P83则可以同时显著提高材料的耐低温性和耐久性。     

Evaluating effects of biobased 2,5‐furandicarboxylate esters as plasticizers on the thermal and mechanical properties of poly (vinyl chloride)

We synthesized 2,5‐furandicarboxylate esters [i.e., dibutylfuran‐2,5‐dicarboxylate, diisoamylfuran‐2,5‐dicarboxylate, and di(2‐ethylhexyl)furan‐2,5‐dicarboxylate] and investigated their potential application as plasticizers of commercial poly(vinyl chloride) (PVC) products. Fourier transform infrared analysis, mechanical tests, scanning electron microscopy investigation, differential scanning calorimetry analysis, dynamic mechanical thermal analysis, thermogravimetric analysis (TGA), melt flow rate (MFR) measurement, and plasticizer migration measurements were used to the evaluate the comprehensive properties of the blended products. The results of the tensile tests demonstrate that the blends exhibited antiplasticization and flexible plastic characteristics at 10 and 50 phr in PVC, respectively. Moreover, flexural and impact test data indicate that the three types of blends exhibited a similar tendency: the hardness decreased continuously as the amount of plasticizer increased. Their morphology indicated that all of the plasticizers had good compatibility with PVC. The resulting glass‐transition temperature of the investigated plasticizers was lower than that of pure PVC, and reduction was largest for the plasticizer with the highest molecular weight. TGA revealed that the thermal degradation of blended polymers occurred in three stages and that all of the blends were stable up to 180°C. Finally, the MFRs of all of the specimens indicated that the addition of a higher concentration of lower molecular weight biobased esters resulted in improved fluidity, but these compounds migrated more easily from the blends. Hence, 2,5‐furandicarboxylic acid derived from biomass has potential as a plasticizer. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40938.     

耐热耐迁移绿色环保聚酯增塑剂的合成及其对PVC增塑性能的研究

以1,4环己烷二甲醇、戊二酸和2丙基庚醇为原料,采用酯化缩聚法,以钛酸四正丁酯为催化剂、环己烷为带水剂,合成了新型的聚戊二酸1,4环己烷二甲醇酯增塑剂。目标分子结构中含有六元脂环、线性碳链及酯基的多官能团组成,通过傅里叶变换红外光谱仪、核磁共振谱仪和高效液相色谱仪等对聚酯的结构、相对分子质量进行表征。结果表明,制备的聚酯作为增塑剂混合到聚氯乙烯（PVC）中,PVC/聚酯复合材料的断裂伸长率为677.15 %,而PVC/邻苯二甲酸二辛酯（DOP）复合材料的断裂伸长率在相同测试条件下为693.82 %,聚酯与DOP在加入到PVC中的拉伸性能相差不大,但是,PVC/聚酯复合材料耐热性相对于PVC/DOP复合材料来说提高了158 ℃,并且在活性炭中的迁移性降低了16 %;PVC/聚酯复合材料相对于PVC/DOP具有较好的耐热性和耐迁移性。     

聚癸二酸甘油单月桂酸酯的合成及对聚氯乙烯增塑性能的研究

以甘油单月桂酸酯和癸二酸为原料,以钛酸正丁酯为催化剂,在180℃下合成了高分子量聚酯产品：聚癸二酸甘油单月桂酸酯。采用红外光谱、核磁共振仪和凝胶渗透色谱仪对豆油聚酯的结构和分子量进行了表征;并将该聚酯作为增塑剂与聚氯乙烯热塑共混成型后,采用热重分析仪、差示扫描量热仪和万能拉力试验机对共混物的热性能和力学性能进行了表征。结果显示：通过甘油单月桂酸和癸二酸的直接缩聚反应得到了高分子量聚癸二酸甘油单月桂酸酯,该聚酯产品能够提高聚氯乙烯的热稳定性,降低聚氯乙烯的玻璃化转变温度,可以与邻苯类增塑剂复配,得到热性能与力学性能兼顾的聚氯乙烯产品。     

PVC增塑剂偏苯三酸基聚酯的研究

采用“二步法”将偏苯三酸酐（TMA）和甘油（Gl）经酯化、缩聚反应得到环保、可生物降解的偏苯三酸聚酯（P-Gl-TMAI）。将合成的P-GI-TMAI与邻苯二甲酸（2-乙基己基）酯（DOP）分别添加到聚氯乙烯（PVC）树脂中进行塑炼实验,研究2种增塑剂与PVC树脂的相容性能、塑炼试片的力学性能以及耐迁移性能。结果表明,与DOP相比,P-Gl-TMAI与PVC的相容性较好;且前者塑炼试片的拉伸强度达18.99 MPa,断裂伸长率为454.89 %;在挥发性和抽出性试验中,P-Gl-TMAI制备的试片分别仅有3.02 %和15.31 %的质量损失率,其韧性与耐迁移性均高于DOP。     

Evaluation effects of biobased plasticizer on the thermal,mechanical, dynamical mechanical properties,and permanence of plasticized PVC

Sunflower oil (SO) is a renewable resource that can be epoxidized, and the epoxidized SO has potential uses as an environmentally friendly in polymeric formulations, especially for poly (vinyl chloride) (PVC). Epoxidized sunflower oil (ESO) was prepared by treating the oil with peracetic acid generated in situ by reacting glacial acetic acid with hydrogen peroxide. Epoxidation was confirmed using spectroscopic and titration methods. ESO was used as a coplasticizer in PVC for the partial replacement of di‐(2‐ethyl hexyl) phthalate (DEHP). The effect of ESO on the thermal stability of plasticized PVC was evaluated by using synmero scale for the sheets. In presence of ESO plasticized PVC samples showed a reduction in discoloration and the number of conjugated double bonds. By using thermogravimetry, the incorporation of 15/45 of ESO/DEHP in PVC presents the lowest weight loss. The results of the shore hardness and mechanical properties showed that a proportion of DEHP could be substituted by ESO. By use of DMA, the formulation which contains 25 % wt of ESO in plasticizer system shifts the glass transition temperature (T_g) to ambient temperature. The migration phenomenon was studied on PVC based samples plasticized with DEHP and ESO in varying amounts. The migration was monitored by the weight loss percentage of the samples immersed into n‐hexane or heated in an oven. The amount of extracted or volatilized DEHP is proportional to the added ratio of ESO in plasticizer system. All of this favored the partial replacement of DEHP by ESO as biobased plasticizer for flexible PVC. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Influences of diallyl phthalate as chain extender on the properties of high molecular weight poly(vinyl chloride) resin

A higher porosity with better thermostability is desirable for poly(vinyl chloride) (PVC) resin. In this study, high molecular weight PVC resins are prepared by vinyl chloride monomer (VCM)‐diallyl phthalate (DAP) suspension copolymerization in a 20‐L reactor at 50 °C using DAP as chain extender. SEM, BET, and analyses of plasticizer absorption results show the high molecular weight poly(vinyl chloride) (HPVC) by DAP‐VCM copolymerization is loose and porous. With increasing DAP content when the mass ratio of DAP/VCM (ω) is below the gel point, the porosity and the degree of polymerization increase. Nevertheless, the bulk density and particle size decrease. When more than the gel point, these relationships are reversed. Thermogravimetric analysis revealed that the HPVC had better thermostability than that of commercial PVC, and its thermostability increases with increasing ω before it reaches the gel point. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45093.     

Synthesis of poly(butylene succinate‐co‐butylene terephthalate) (PBST) copolyesters with high molecular weights via direct esterification and polycondensation

In this article, biodegradable poly(butylene succinate‐co‐butylene terephthalate) (PBST) copolyesters with high molecular weights were synthesized by direct esterification and polycondensation route. The reaction conditions and catalytic systems were investigated in detail. Through balancing the reaction efficiency and the costs of reactants, the proper molar ratio of diol to diacid was determined. Titanium tetraisopropoxide (TTiPO) was found to be an effective catalyst both in esterification and polycondensation reaction, and its content was optimized based on the esterification ratio and amount of formed by‐products. The complex reaction was determined to be the dominant catalytic reaction mechanism. By importing the additives of metal oxides coupled with TTiPO, the weight‐average molecular weights of PBST increased sharply from 8.51 × 10⁴ to 14.38 × 10⁴, manifesting the additives promoted the polymerization reaction greatly. The enhancement of carbonyl polarization and provision of suitable reaction space arose from the metal oxides were the reasons for promoting the polymerization reaction. With respect to thermal properties, the same melting point and heat of fusion were found, while thermal stability increased with the import of additives. The result was prone to be interpreted by the higher molecular weights of PBST in the presence of additives. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Synthesis of poly(alkylene succinate) biodegradable polyesters I. Mathematical modelling of the esterification reaction

Synthesis of three biodegradable aliphatic polyesters, namely poly(ethylene succinate), poly(propylene succinate) and poly(butylene succinate) is presented using the appropriate diols and succinic acid in the presence of tetrabutoxytitanium as catalyst. A theoretical mathematical model for the esterification reaction, based on the functional group approach, is developed and applied successfully in the simulation of all experimental data. Values for the kinetic rate constants are proposed for different catalyst molar ratios and comonomer chemical structure. It was found that the presence of the metal catalyst used leads to a poor activity of self-catalyzed acid and the main kinetic rate constant of the esterification reaction correlates well with the square root of the catalyst concentration. Different glycols do not influence much the number average degree of polymerization (NADP) values of the oligomers produced, even thought they slightly affect esterification rates in the order BG>PG>EG. In contrast, these values are affected by the amount of catalyst, with larger catalyst molar ratio giving polymer with bigger average molecular weight. These results were verified from measurements of the final polyester average molecular weight obtained at different polycondensation temperatures. Finally, from theoretical simulation results it was found that although higher initial ratios of glycol to succinic acid are useful to increase the esterification rate, they lower the NADP of the oligomers formed at a fixed conversion of acid end groups.     

Viscosity aging of poly(vinyl chloride) plastisol: The effect of the resin type and plasticizer type

The viscosity of freshly prepared poly(vinyl chloride) (PVC) plastisol increases with time, and this phenomenon is called viscosity aging. The increase is rapid in the beginning and slows down to a quasistable value, but a very slow increase continues. The phenomenon may be a result of either the deagglomeration of agglomerated particles or the dissolution of low‐molecular‐weight PVC into the plasticizer. In this work, two typical commercial resins were used, one containing friable agglomerates and the other containing nonfriable agglomerates. With the friable‐agglomerate resin, about 40% of the initially present agglomerates deagglomerated, whereas the viscosity increased in a week to twice the initial value. With the nonfriable‐agglomerate resin, very fine and very low molecular weight particles, about 3% of all the particles, dissolved into the plasticizer in 2 days. The effect of the plasticizer type on the viscosity aging through deagglomeration was investigated with four plasticizers and three plasticizer blends. The emulsifiers used for polymerization, and retained through drying, affected the aging in the beginning. On the other hand, the viscosity after 1 week was free from the effect of the emulsifier and was affected only by the plasticizer type. With the exception of two blends, the 1‐week viscosity was quantitatively related to the dielectric constant divided by the molecular weight of the plasticizer. For the plasticizer blends, one of the plasticizers could have a dominant effect on the promotion of deagglomeration. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 95: 448–464, 2005     

Effects of poly(butylene succinate) and ultrafine wollastonite on the physical properties of plasticized poly(vinyl chloride)

In this study, diisononyl phthalate (DINP), a conventional plasticizer of poly(vinyl chloride) (PVC), was partially replaced by a polymeric plasticizer, poly(butylene succinate) (PBS), in order to reduce the leaching out of low‐molecular‐weight plasticizer from the plasticized PVC. Samples were prepared by melt mixing on a two‐roll mill followed by compression molding into a 3‐mm thick sheet. The DINP/PBS‐plasticized PVC provides a dose‐dependent increase in the tensile properties (tensile strength, Young's modulus, and elongation at break), tear strength, and thermal stability, as compared with the DINP‐plasticized PVC. According to the overall properties, PVC plasticized with 10/30 phr (parts by weight per hundred parts of resin) DINP/PBS was selected for preparing composites with varied loadings of an ultrafine wollastonite (particle size of 1,200 mesh). Their tensile properties, tear strength, thermal stability, and morphology were evaluated and compared with the 40 phr of DINP‐plasticized PVC composites. The results showed an increase in the Young's modulus and thermal stability but a decrease in the tensile strength, elongation at break, and tear strength of either 40 phr of DINP‐ or 10/30 phr of DINP/PBS‐plasticized PVC composites. Therefore, the products may be useful where the dimensional and thermal stability of the plasticized PVC are needed. J. VINYL ADDIT. TECHNOL. 21:220–227, 2015. © 2014 Society of Plastics Engineers     

高摩尔质量PBS的合成工艺研究

用丁二酸、丁二醇为原料,以钛酸四丁酯为催化剂,采用直接酯化缩聚的方法合成了聚丁二酸丁二醇酯(PBS)。考察了醇酸比、催化剂用量、聚合温度对PBS的黏度及酸值的影响。实验获得最佳合成条件为:醇酸物质量之比1.3,催化剂质量分数为0.03%,并在酯化后加入,缩聚温度为230℃。用凝胶渗透色谱仪对聚合物的摩尔质量进行了表征,通过工艺优化可得到重均摩尔质量约为12万g/mol的PBS。     

MPO改性PBS共聚酯的合成及其热性能研究

采用直接酯化-熔融缩聚的方法合成聚丁二酸丁二醇酯(PBS)和2-甲基-1,3-丙二醇(MPO)改性的PBS共聚酯(PBMS).通过傅里叶红外光谱仪(FTIR)、核磁共振谱仪(NMR)和凝胶渗透色谱仪(GPC)分别对其化学结构和分子量进行了表征;通过差示扫描量热仪(DSC)、同步热分析仪(STA)和熔体流动速率测定仪(M...     

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.     

Bis(nitrone) as crosslinking agent for unsaturated polyesters via 1,3‐dipolaric cycloaddition

The microwave‐assisted polycondensation of maleic anhydride and 1,6‐hexanediol was carried out using p‐toluenesulfonic acid as catalyst. The resulting unsaturated polyester was characterized using Fourier transform infrared (FTIR) and ¹H NMR spectroscopy, and the molecular weight determined using gel permeation chromatography. 4,4′‐Decanediyldioxydi(N‐methyl‐p‐phenylenenitrone) was chosen as a model compound for the crosslinking of the unsaturated polyester. The crosslinking, which is known to proceed via 1,3‐dipolaric cycloaddition, was followed using differential scanning calorimetry. Additionally, the kinetics of the cycloaddition was evaluated at 120 °C using FTIR spectroscopy. Copyright © 2012 Society of Chemical Industry     

Synthesis and application of an alternative plasticizer Di(2‐Ethylhexyl)‐1,2‐cyclohexane dicarboxylate

Cyclohexane dicarboxylic acid esters are environmentally friendly and non‐toxic plasticizers, and have similar performance with phthalates which have potential toxicity to human health. In this article, di(2‐ethylhexyl)‐1,2‐cyclohexane dicarboxylate (DEHCH) was synthesized via esterification between hexahydrophthalic anhydride (HHPA) with iso‐octanol by using concentrated sulfuric acid as a catalyst. The effects of reaction parameters on esterification were studied by investigating the temperature, reaction time, molar ratio of iso‐octanol‐to‐HHPA, and catalyst content. Conversions of HHPA to esters were determined. Functional group analysis was conducted by using FTIR and ¹H‐NMR spectroscopy. PVC compounds after addition of the synthesized plasticizer DEHCH presented similar plasticizing performance with DEHP and DINCH, as demonstrated by comparisons of the results of mechanical properties, transparency, and volatilization and migration tests obtained for plasticized PVC compounds. DEHCH can also be considered as an alternative plasticizer for DEHP. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39763.