聚1,2-丙二醇新戊二醇己二酸酯增塑性能的研究

将合成的聚1,2-丙二醇新戊二醇己二酸酯(简称PG-AA-NPG)聚酯增塑剂增塑PVC的试片制成复合材料,并进行耐迁移、DSC、力学性能、热稳定性能测试,分析PG-AA-NPG的综合性能,并且与加入DOP和市售聚酯增塑剂A的PVC试片进行对比.结果表明PG-AA-NPG的耐溶剂迁移性优于DOP;PVC/PG-AA-NP...     

偏苯三酸聚甘油酯PVC增塑剂的合成及性能研究

以偏苯三酸酐(TMA)作为酸源,以甘油(Gl)为醇源,钛酸四正丁酯为催化剂,2-乙基己醇为封端剂,经低温酯化、高温缩聚得到偏苯三酸聚甘油酯(P-Gl-TMA)。核磁表征聚酯的结构,将P-Gl-TMA和邻苯二甲酸二(2-乙基己)酯(DOP)分别加入到PVC树脂中,进行力学性能、耐迁移性能以及热稳定性能的对比测试。结果表明:P-Gl-TMA与DOP相比,可使得试片具有更高的韧性,较高的热稳定性以及优良的耐迁移性能。     

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。     

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。     

环氧化菜籽油基PVC增塑剂的制备与性能研究

先将菜籽油用苯甲醇醇解,然后再将所得的苯甲醇酯环氧化,制得环氧菜籽油脂肪酸卞酯增塑剂。研究了该增塑剂对聚氯乙烯(PVC)玻璃化转变温度、热稳定性和力学性能的影响。结果表明:每100份PVC树脂加入80份环氧菜籽油脂肪酸卞酯后,PVC树脂的玻璃化转变温度从80℃下降到-28℃,5%热失重温度由240.1℃提升到272.8℃,10%热失重温度由259.9℃提高到288.4℃;分别用环氧菜籽油脂肪酸苄酯和DOP增塑的PVC树脂在常温下显示出相似的力学性能和耐迁移性能。     

中长碳链氯化石蜡在聚氯乙烯制品中的应用及性能研究

在以邻苯二甲酸二（2⁃乙基己）酯（DEHP）为增塑剂的聚氯乙烯（PVC）制片中复配中长碳链氯化石蜡（氯化石蜡⁃52,CP⁃52）,研究复配氯化石蜡前后PVC制片的性能变化。利用热失重分析仪研究复配前后PVC制片的热稳定性变化;利用伺服控制拉力试验机研究复配前后PVC制片力学性能的变化;最后分析复配前后PVC制片中增塑体系的耐迁移情况。结果表明,在DEHP中复配CP⁃52后,可以提高PVC试片的热稳定性,起始分解温度T_i从251.6 ℃（0⁃CP⁃52/DEHP）最高提高到259.0 ℃（40⁃CP⁃52/DEHP）,提高了7.4 ℃。氯化石蜡的添加也有助于提高PVC的耐老化性。另外,断裂伸长率和拉伸强度都有很大提升,复配比例为30 %时,PVC试片的断裂伸长率和拉伸强度分别提高至原来的4.7倍和4倍。耐抽出和耐挥发性能以及在食品模拟液中的耐迁移性都有所提高。复配CP⁃52后可降低PVC制品的成本,为PVC制品提供低成本高性能的配方。     

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。     

生物基增塑剂异山梨醇二庚酯在PVC中的应用

以异山梨醇和正庚酸为原料合成了一种生物基增塑剂异山梨醇二庚酯(SDH),并与石油基增塑剂邻苯二甲酸二辛酯(DOP)和对苯二甲酸二辛酯(DOTP)对比考察了对聚氯乙烯(PVC)的增塑性能。通过红外分析表征增塑剂与PVC分子间相互作用;通过拉伸试验与动态力学测试表征PVC试样的力学性能;通过热重分析与迁移性实验表征增塑剂的稳定性。结果表明,SDH与PVC分子间的相互作用更强;PVC/40SDH试样较同比例的DOP和DOTP增塑PVC表现出更高柔韧性,其中PVC/40SDH的断裂伸长率较PVC/40DOP和PVC/40DOTP分别提高26.29%和33.89%,玻璃化转变温度则分别降低1.67℃和4.15℃;SDH的热稳定性、挥发性和耐抽提性介于DOP和DOTP之间。SDH的综合增塑性能较优,可以替代DOP和DOTP用于PVC的增塑。     

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.     

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.     

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.     

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.     

抑制PVC制品中小分子增塑剂迁移的研究

采用气-固相氯化法和氯化原位接枝法对小分子增塑剂邻苯二甲酸二辛酯(DOP)进行了改性,得到的产物分别与PVC共混,并对其失重率、沸点、力学性能进行了研究。结果表明:氯含量为30%左右的氯化DOP,从PVC制品表面迁移出来的几率最小;DOP氯化原位接枝丙烯酸丁酯(BA)后作为PVC的增塑剂,当BA含量在1～10份时材料的失重较少,而BA含量在10份时材料的强度及韧性最好。     

Hydrothermic aging of plasticized poly(vinyl chloride): Its effect on the dielectric,thermal, and mechanical properties

Accelerated hydrolytic aging (according to the NFT 5166 method) was performed on samples of poly(vinyl chloride) (PVC) plasticized with dioctylphthalate (DOP) and dinonyladipate (DNA) at different concentration ratios. The aging test consisted of immersing the samples in boiling water at 100°C. The samples were removed from water regularly, that is, every 2 h, for mechanical, thermal, and dielectric characterizations. Thermograms of PVC plasticized with DOP revealed no migration of the plasticizer independent of the concentration used. Moreover, the thermal stability of the samples was not affected by the hydrothermal aging. However, for PVC samples plasticized with DNA, a small amount of the plasticizer migrated from the polymer matrix with a considerable effect on the thermal stability. In fact, the data indicated a decrease in the decomposition temperature from 275 to 225°C, particularly for samples containing 50% (w/w) DNA immersed up to 10 h. The mechanical results showed that for a plasticizer content greater than 30% (w/w), the strain at break obtained for samples plasticized with DNA was lower than that for samples plasticized with DOP because the DNA molecules were more likely to be removed by water on account of their polarity and dimension. Finally, the dielectric measurements showed that the permittivity of all the PVC samples plasticized with DOP and immersed in boiling water was higher than that of the virgin samples. On the contrary, the permittivity of the aged unplasticized PVC was less than that of the nonimmersed samples. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 3447–3457, 2003     

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).     

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。