PVC塑料制品中聚酯增塑剂的配方应用

聚酯增塑剂是极性高分子聚合物,与PVC有很好的相容性,加入PVC配方内,都能使PVC塑化时间有不同程度的提前,作为一种配方原料与助剂,常和DOP、环氧大豆油复配并用,由于聚酯增塑剂具有较强极性,与DOP在配方中亲和性还和其他的液体增塑剂产品的特性有关,当聚酯增塑剂用于PVC制品中能起到了吸引和固定其他增塑剂不向PVC制品的表面迁移的作用,     

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。     

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。     

甘油支化聚酯聚氯乙烯增塑剂的制备与性能研究

通过熔融缩聚的方法,以己二酸、二元醇、甘油作为第三单体合成了含有支化结构的聚酯增塑剂,探究了不同二元醇合成的支化聚酯,并按照一定配方将聚酯加入到聚氯乙烯（PVC）中制得PVC试片,利用傅里叶红外光谱分析、热重分析、高效凝胶色谱分析对支化聚酯进行了表征,对PVC试片进行拉伸性能、热稳定性能、耐抽出性能等性能测试。结果表明,二元醇为二缩三乙二醇时,产品相对分子质量为4871,分散系数为2.26,黏度为11.20 Pa·s,支化聚酯增塑的PVC试片断裂伸长率高于400 %,吸水量低,热稳定性高,耐抽出性能良好。     

光催化合成氯代甲氧基脂肪酸甲酯增塑剂的性能研究

以油酸甲酯、甲醇及氯气为原料,利用光催化合成了氯代甲氧基脂肪酸甲酯增塑剂,并对其替代DOP应用于PVC进行了性能研究。考察了增塑剂的含氯量以及与DOP复配对增塑PVC材料的力学性能的影响;测定了增塑剂的电绝缘性、增塑PVC材料的热稳定性。研究表明:氯代甲氧基脂肪酸甲酯增塑剂与DOP复配应用于PVC中具有优良的增塑性能,且能够赋予PVC制品更优异的电绝缘性及热稳定性。     

聚氯乙烯热塑性弹性体的阻尼性能研究

研究了增塑剂、无机填料以及酚醛树脂对聚氯乙烯(PVC)热塑性弹性体(TPE)力学性能及动态力学性能的影响。结果表明:聚酯增塑PVC弹性体材料体系的tanδ峰值明显高于DOP、DOTP、TOTM三种增塑剂,且阻尼性能最优;随着聚酯用量的增加,PVC弹性体的tanδ峰值逐渐提高,tanδ峰逐渐向低温方向移动。PVC热塑性弹性体中加入适量无机填料可以提高其tanδ峰值;可以用酚醛树脂调整PVC弹性体阻尼材料tanδ峰所对应的温域,从而改善其阻尼性能。     

苯酐的市场分析和技术进展

邻苯二甲酸酐（PA）简称苯酐，是邻二甲苯（OX）主要的市场应用领域，主要用于生产PVC增塑剂、不饱和聚酯、醇酸树脂以及染料、油漆、农药和医药等，是一种重要的有机化工原料。其有三种主要用途：其一用于制备邻苯二甲酸酯增塑剂（占全球产能一半，主要是邻苯二甲酸二辛酯DOP），掺合聚氯乙烯（PVC）树脂作增塑剂；其二用于不饱和聚酯作玻璃增强的热固工程塑料（约占22％）；其三用于醇酸树脂作表面涂层。     

苯酐的技术进展和市场分析

邻苯二甲酸酐（PA）简称苯酐，是邻二甲苯（OX）主要的市场应用领域，主要用于生产PVC增塑剂、不饱和聚酯、醇酸树脂以及染料、油漆、农药和医药等，是一种重要的有机化工原料。其有三种主要用途：其一用于制备邻苯二甲酸酯增塑剂（占全球产能一半，主要是邻苯二甲酸二辛酯DOP），掺合聚氯乙烯（PVC）树脂作增塑剂；其二用于不饱和聚酯作玻璃增强的热固工程塑料（约占22％）；其三用于醇酸树脂作表面涂层。     

国内外苯酐的市场分析和技术进展

邻苯二甲酸酐(PA)简称苯酐，是邻二甲苯(OX)主要的市场应用领域，主要用于生产PVC增塑剂、不饱和聚酯、醇酸树脂以及染料、油漆、农药和医药等，是一种重要的有机化工原料。它有三种主要用途：其一用于制备邻苯二甲酸酯增塑剂(占全球产能一半，主要是邻苯二甲酸二辛酯DOP)，掺合聚氯乙烯(PVC)树脂作增塑剂；其二用于不饱和聚酯作玻璃增强的热固工程塑料(约占22％)；其三用于醇酸树脂作表面涂层。     

生物基甘油酯类增塑剂的合成及增塑性能

以甘油和不同结构脂肪酸（辛酸、2-乙基己酸、戊酸和2-甲基丁酸）为原料，采用直接酯化法制备得到4种不同结构的甘油衍生脂肪酸酯，作为增塑剂用于聚氯乙烯（PVC）。利用FTIR和1HNMR分析增塑剂的结构与纯度，将4种增塑剂塑化的PVC试片与邻苯二甲酸二（2-乙基己）酯（DEHP）塑化的PVC试片进行对比研究。结果表明，与DEHP塑化的PVC试片比，甘油三戊酸酯PVC试片的断裂伸长率提高了151%；甘油三辛酸酯PVC试片的初始降解温度提高了12.3 ℃；甘油三（2-甲基丁酸）酯PVC试片的耐挥发性更好，均具有替代DEHP的潜力。另外，分析增塑剂的构效关系，发现分子结构中支链多的增塑剂与PVC之间的相容性和耐抽出性更好，但热稳定性和耐挥发性降低。     

低挥发环保增塑剂对苯二甲酸二（2⁃丙基庚）酯的应用研究

以对苯二甲酸和2?丙基庚醇为原料,在钛酸异丙酯为催化剂的条件下制备对苯二甲酸二（2?丙基庚）酯（DPHTP）,并将DPHTP作为增塑剂用于制备聚氯乙烯（PVC）柔性薄膜,与市售DOP和DOTP进行应用性能的比较。通过傅里叶变换红外光谱和核磁共振氢谱对产物进行结构分析;通过热失重分析、拉伸测试、耐迁移测试和耐挥发性测试等比较DPHTP、DOP以及DOTP增塑的PVC薄膜在力学性能等方面的差异。结果表明,相比DOP和DOTP,DPHTP具有更低的挥发性,其增塑的薄膜有着更优异的热稳定性以及更高的体积电阻率;其中,DPHTP的加热减量为0.031 90 %,DPHTP增塑的薄膜的热失重5 %的温度为272 ℃,体积电阻率为6.5×10⁹ Ω·m;DPHTP具有更低的挥发性且可以赋予PVC材料优异的电绝缘性能,在包装材料和电线电缆行业具有广阔的开发前景。     

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).     

Synthesis and application of an environmental epoxy plasticizer with phthalate-like structure based on tung oil and cardanol for poly(vinyl chloride)

An epoxidized cardanol tungoleate (ECT) based on tung oil and cardanol was synthesized through esterification and epoxidation. The chemical structure of the compound was verified by Fourier transform infrared spectroscopy (FTIR) and proton nuclear magnetic resonance (¹H-NMR). The plasticizing effects of ECT as the main plasticizer in poly(vinyl chloride) (PVC) was studied and compared with the commercial plasticizer dioctyl phthalate (DOP). The thermal migration stabilities, the thermal degradation process and the mechanical properties of PVC samples and the plasticization mechanism of ECT for PVC were investigated through the use of volatility, extraction, discoloration, and tensile tests as well as thermal gravity analysis (TGA), TGA–FTIR analysis, electronic universal testing machine and dynamic mechanical analysis (DMA). Compared with DOP, the ECT plasticized PVC can exhibits better thermal stability, more excellent tensile strength (17.28 MPa) and higher stretchability (629.41%), which is 1161% higher than DOP (1.37 MPa) plasticized PVC film. In addition, the migration resistance and volatility stability of ECT are much better than DOP. Therefore, this fully bio-based plasticizer based on tung oil and cardanol is a promising alternative plasticizer for PVC and may be an excellent phthalate substitute from the perspective of human health and sustainable development.     

Sustainable synthesis of bio‐based hyperbranched ester and its application for preparing soft polyvinyl chloride materials

In this study, bio‐based hyperbranched ester was synthesized from castor oil. The chemical structure of the bio‐based hyperbranched ester obtained was characterized with Fourier transform infrared and ¹H NMR spectra. Soft polyvinyl chloride (PVC) materials were prepared via thermoplastic blending at 160 °C using bio‐based hyperbranched ester as plasticizer. The performances including the thermal stability, glass transition temperature (T_g), crystallinity, tensile properties, solvent extraction resistance and volatility resistance of soft PVC materials incorporating bio‐based hyperbranched ester were investigated and compared with the traditional plasticizer dioctyl phthalate (DOP). The results showed that bio‐based hyperbranched ester enhanced the thermal stability of the PVC materials. The T_g of PVC incorporating bio‐based hyperbranched ester was 23 °C, lower than that of PVC/DOP materials at 28 °C. Bio‐based hyperbranched ester showed a better plasticizing effect, solvent extraction resistance and volatility resistance than DOP. The plasticizing mechanism is also discussed. © 2018 Society of Chemical Industry     

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。     

Synthesis of a bio-based plasticizer from vanillic acid and its effects on poly(vinyl chloride)

A new bio-based plasticizer, VA8-8, was prepared derived from vanillic acid, and its structure was verified by nuclear magnetic resonance. It was incorporated into poly(vinyl chloride) (PVC) to replace dioctyl phthalate (DOP), and its plasticizing performance was evaluated. The results indicated that VA8-8 shows good compatible with PVC resin, and has a excellent plasticizing effect for PVC. When DOP was partially or completely substituted with VA8-8, the T_g value PVC blends dropped from 34.6 to 24.3°C and the elongation at break increased from 196.4% to 301.9%, suggesting the enhanced plasticizing efficiency of plasticizer. The plasticizing mechanism was also simulated, and the interactions between VA8-8 and PVC molecules were discussed. The thermogravimetric analysis showed VA8-8 can more effectively improve the thermal stability of PVC than DOP. In addition, the migration resistance of VA8-8 was generally superior to that of DOP. Therefore, VA8-8 is a comparable to or better plasticizer than DOP, and it is a promising alternative plasticizer for PVC.     

低相对分子质量PBA在PVC中的增塑作用研究

以己二酸和1,4丁二醇为原料,通过熔融缩聚法制备一系列不同特性黏度的低相对分子质量聚己二酸1,4丁二醇酯(PBA)。将低相对分子质量PBA作为增塑剂用于聚氯乙烯(PVC)中, 通过测定其玻璃化转变温度(Tg)、拉伸强度、断裂伸长率、极限氧指数和液相迁出,研究不同特性黏度的低相对分子质量PBA的增塑效率。结果表明,当添加量为30份时,PVC/PBA的Tg低于PVC/邻苯二甲酸二辛酯(DOP),并随着特性黏度的增加而增加;特性黏度为0.115 dL/g的PBA加入PVC时具有最佳断裂伸长率,可达271.9 %,优于加入同等量的DOP体系;此外PBA液相迁出率随特性黏度的增加而降低,最低几乎为零;且PVC/PBA比PVC/DOP具有更好的热稳定性和阻燃性。     

环保型钙锌复合热稳定剂与增塑剂在 PVC中的协效作用研究

将生物基增塑剂橡胶籽油基环氧脂肪酸甲酯（ERSO）与热稳定剂油脂源多聚脂肪酸基钙锌（OMFCTS）复配,以β-二酮作辅助热稳定剂,改性聚氯乙烯（PVC）,通过热老化烘箱法、刚果红法、热重分析（TGA）、热重红外联用（TGA-FTIR）分析、热重质谱联用（TGA-MS）分析、力学性能测试及动态力学性能分析（DMA）考察了改性PVC的热稳定性及力学性能,并对8个配方改性后PVC的性能进行了对比。结果表明：与DOP/CaSt₂/ZnSt₂、DOP/OMFCTS和ERSO/CaSt₂/ZnSt₂体系相比,ERSO/OMFCTS体系的热稳定性最优,力学性能较好,改性PVC的玻璃化转变温度（38.2℃）最低,拉伸断裂伸长率达265.6%;静态热稳定时间（200℃）最长（46'21"）。ERSO和OMFCTS具有良好的协同作用,二者可有效替代传统增塑剂邻苯二甲酸二辛酯（DOP）及热稳定剂硬脂酸钙锌（CaSt₂/ZnSt₂）。     

Application of Poly(butylenes 2-methylsuccinate) as Migration Resistant Plasticizer for Poly(vinyl chloride)

The bio-based and biodegradable polyester poly(butylenes 2-methylsuccinate) (PBM) was successfully used as a polymeric plasticizer to modify poly(vinyl chloride) (PVC) in this work. The tensile properties, plasticization efficiency estimated by the lowered glass transition temperature and the enhanced elongation at break of the PVC/PBM blends and the migration stability of the PBM were investigated. It was indicated that the migration-resistant property of PVC plasticized with PBM was greatly superior to that with dioctyl phthalate (DOP). Furthermore, the tensile properties were comparable to that of PVC/DOP, indicating that the environmentally friendly PBM can be used as an alternative plasticizer to remove the potential health risks from migrating phthalates during applications.