一剂多效油脂源钙锌热稳定剂的性能及其在PVC中的应用

采用不饱和天然油脂为原料制备了多聚脂肪酸酯的钙锌盐,并与抗氧剂、β二酮复配制得了新型一剂多效的油脂源钙锌复合热稳定剂（OMFCTS）。采用傅里叶变换红外光谱仪和电感耦合等离子体发射光谱对其进行结构表征。考察了OMFCTS对聚氯乙烯（PVC）制品的热稳定性和力学性能的影响。 结果表明,PVC/邻苯二甲酸二辛酯(DOP)/OMFCTS=100/30/3体系力学性能和热稳定性均可与PVC/DOP/市售钙锌复合热稳定剂=100/40/3体系相媲美。OMFCTS在赋予PVC制品更好的热稳定性的同时具有良好的增塑性能,可减少PVC加工过程中DOP等增塑剂用量。     

环保增塑剂及热稳定剂在PVC中的协同作用

以农林剩余物资源腰果酚为原料合成腰果酚基乙酸酯增塑剂(CA),并用不饱和天然油脂为原料制备多效的油脂源钙锌复合热稳定剂(OMFCTS),将其与聚氯乙烯(PVC)进行共混,通过动态力学性能,热重分析,拉伸性能测试以及静态热稳定性分析,研究其增塑效果及协同作用,并与增塑剂邻苯二甲酸二辛酯(DOP)及热稳定剂硬脂酸钙锌盐进行对比。结果表明,含有20份CA增塑剂及OMFCTS热稳定剂的PVC增塑体系的玻璃化转变温度及储能模量低于PVC/DOP增塑体系;热失重10%及50%的温度明显升高,第一最大失重速率温度和第二最大失重速率温度基本保持不变;断裂伸长率提高到了248.66%,拉伸强度降至5.84 MPa;静态热稳定时间可延长到50 min以上。综上可知,CA增塑剂及OMFCTS热稳定剂联用,可有效改善PVC共混体系的相容性、力学性能及热稳定性,提高制品的综合应用性能及环保性。     

哌嗪基单丁酰胺酸钙/锌的合成及对PVC热稳定性研究

以丁二酸酐、哌嗪、氯化钙、氯化锌为原料，通过两步反应制备了哌嗪基单丁酰胺酸钙/锌（PSACa/Zn）热稳定剂。采用元素分析、电感耦合等离子体原子发射光谱仪（ICP?OES）和傅里叶变换红外光谱仪（FTIR）对产品结构进行表征，通过刚果红试纸法、转矩流变仪法、热失重法考察了PSACa/Zn对PVC的热稳定性能，并筛选了PSACa和PSAZn的最佳配比。结果表明，PSACa和PSAZn对PVC的静态热稳定时间分别可达74.5、41.5 min，优于硬脂酸钙（CaSt₂）、硬脂酸锌（ZnSt₂）热稳定剂；PSACa和PSAZn复配使用时，以m_PSACa∶m_PSAZn=1∶1时性能最佳，对PVC静态热稳定时间可达92 min，动态热稳定时间可达905 s；发现PSACa/Zn对PVC的长期热稳定性良好。     

添加剂对PVC/ABS共混物热稳定性及力学性能的影响

通过熔融共混的方法制备了热稳定剂不同含量和增塑剂不同含量的聚氯乙烯/丙烯腈-丁二烯-苯乙烯(PVC/ABS)共混物,采用热失重法和刚果红试纸法对共混物的热稳定性进行了研究,并对其力学性能进行了测试.结果表明:随着热稳定剂用量的增加,PVC/ABS共混物的热稳定性提高,但力学性能却下降,热稳定剂的用量不应超过5份;热稳定剂的加人影响ABS的热稳定性,但具体的作用机理还不清楚;随着增塑剂邻苯二甲酸二辛酯(DOP)用量的增加,PVC/ABS共混物的热稳定性提高,但力学性能下降,DOP的用量不应超过15份;熔体流动速率测定和透射电镜分析表明,DOP能够改善PVC/ABS共混物的加工流动性,提高热稳定剂的分散性,从而提高共混物的热稳定性。     

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。     

对甲基苯甲酸铈对PVC热稳定性能的影响

用复分解法制备了对甲基苯甲酸铈,确定产物的分子式为Ce（C₈H₇O₂）₃·2H₂O。研究了对甲基苯甲酸铈对聚氯乙烯（PVC）的热稳定性能的影响。结果表明,对甲基苯甲酸铈单独作为PVC热稳定剂时,其热稳定性和抗变色性都不强。将对甲基苯甲酸铈与其他热稳定剂联合进行二元、三元及四元复配,产物的协同作用良好,热稳定性有所提升;当复合稳定剂按对甲基苯甲酸铈∶钙锌复合体系∶季戊四醇=2∶1∶2的比例添加到PVC中,PVC样品的热稳定时间和抗变色性能最好,热稳定时间为42 min;对甲基苯甲酸铈的塑化能力良好,对甲基苯甲酸铈作为热稳定剂加入PVC后,PVC混料的塑化时间缩短,动态热稳定时间增加,塑化扭矩和平衡扭矩下降;对甲基苯甲酸铈与PVC降解过程中产生的HCl反应而生成CeCl₃,降低了HCl对PVC降解的催化作用,从而达到增强PVC热稳定性能的目的。     

软质PVC环保增塑体系的性能

将自制的橡胶籽油基环氧脂肪酸甲酯(ERSO)环保型增塑剂应用于软质PVC体系,评价高增塑剂浓度ERSO的增塑效果,并与传统石油基增塑剂进行对比.力学性能及热性能测试结果表明:与石油基增塑剂相比,ERSO可使体系的拉伸强度降低24.46％,有效改进PVC增塑体系的柔韧性;ERSO可使体系的热稳定时间达到45.15 min,平衡转矩降低,利于制品稳定性的改善及加工性能的提高.     

2⁃苯甲酰苯甲酸镧对PVC热稳定作用的影响

合成了一种新型稀土热稳定剂2?苯甲酰苯甲酸镧（LBA）,通过红外光谱分析、热分析、元素分析等方法对其进行了表征,并采用刚果红实验、高温热老化实验和拉伸性能实验,研究了配合物对聚氯乙烯（PVC）热稳定性能和力学性能的影响;同时将其与几种传统热稳定剂进行复配,研究了复合热稳定剂对PVC热稳定性能和力学性能的影响。结果表明,2?苯甲酰苯甲酸镧的分子式为La（C₁₄H₉O₃）₃·2H₂O;当配合物单独作PVC热稳定剂使用时,热稳定时间为16 min,初期抗变色效果一般,但力学性能优异;当配合物与硬脂酸锌和季戊四醇复配比为1∶1∶3（质量比,下同）时,热稳定时间长达58 min,抗变色效果和力学性能最好,三者具有优异的协同效果;2?苯甲酰苯甲酸镧能吸收PVC分解产生的HCl气体,生成LaCl₃,减缓了PVC的降解。     

环氧脂肪酸甲酯增塑剂替代DOP用于PVC的研究

将自制的橡胶籽油基环氧脂肪酸甲酯(ERSO)与邻苯二甲酸二辛酯(DOP)混合,得到不同配比的混合型增塑剂,考察其对聚氯乙烯(PVC)的增塑效果,评价ERSO对DOP的有效替代性。测试结果表明,混合型增塑剂可显著改善PVC的柔韧性、耐化学药品性、耐热性及加工流变性,但耐水性、挥发性及表面硬度略差。经综合比较,优选的混合型增塑剂配方是ED–20,与单独使用DOP相比,其PVC的断裂伸长率提高了29.83%,热老化整体变色时间提高了近3倍,玻璃化转变温度降至–1.06℃,动态热稳定时间延长了32.59%。ERSO对传统石油基邻苯类增塑剂的有效替代率可达50%,大大拓展了环保增塑剂的应用范围。     

环氧大豆油-癸二酸低分子量聚酯对PVC增塑性能的研究

将环氧大豆油(ESO)与癸二酸(SA)进行开环固化反应，通过控制反应时间得到3种不同分子量的环氧大豆油-癸二酸低分子聚酯(ESO-SA₅、ESO-SA₉和ESO-SA₁₃)，并对其化学结构进行了表征；再以ESO-SA_n为增塑剂，研究其分子量和添加量对聚氯乙烯(PVC)增塑效果、热性能及力学性能的影响；此外，对比了不同成型方式(溶剂流延膜和熔融压制膜)对PVC增塑膜性能的影响；最后，分析了热稳定剂的加入对熔融压制膜性能的影响。研究表明，不同成型方式制备的PVC增塑膜中，均为添加30份ES0-SA₉的增塑膜具有最好的性能，包括增塑效果、力学性能(断裂伸长率269.6%，拉伸强度28.7 MPa)及热性能(初始热分解温度284.3℃)等；熔融压制使PVC与增塑剂分子之间能到达更好的混合效果，可实现分子水平的混合；由于钙锌稳定剂与基体的相容性较差且同时破坏了ESO-SA_n在PVC中形成的增塑网络结构，热稳定剂的加入反而导致增塑膜的力学性能及热性能等出现一定程度的降...     

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。     

Formulation and properties' evaluation of PVC/(dioctyl phthalate)/(epoxidized rubber seed oil) plastigels

Epoxidized rubber seed oil (4.5% oxirane content, ERSO) was prepared by treating the oil with peracetic acid generated in situ by reacting glacial acetic acid with hydrogen peroxide. The thermal behavior of the ERSO was determined by differential scanning calorimetry. The effect of the epoxidized oil on the thermal stability of poly (vinyl chloride) (PVC) plastigels, formulated to contain dioctyl phthalate (DOP) plasticizer and various amounts of the epoxidized oil, was evaluated by using discoloration indices of the polymer samples degraded at 160°C for 30 min and thermogravimetry at a constant heating rate of 10°C/min up to 600°C. The thermal behavior of the ERSO was characterized by endothermic peaks at about 150°C, which were attributed to the formation of network structures via epoxide groups, and at temperatures above 300°C, which were due to the decomposition of the material. Up to 50% of the DOP plasticizer in the PVC plastisol formulation could be substituted by ERSO without a marked deleterious effect on the consistency of the plastigel formed. In the presence of the epoxidized oil, PVC plastigel samples showed a marked reduction in discoloration and the number of conjugated double bonds, as well as high temperatures for the attainment of specific extents of degradation. These results showed that the ERSO retarded/inhibited thermal dehydrochlorination and the formation of long (n > 6) polyene sequences in PVC plastigels. The plasticizer efficiency/permanence of ERSO in PVC/DOP plastigels was evaluated from mechanical properties' measurements, leaching/migration tests, and water vapor permeability studies. The results showed that a large proportion of DOP could be substituted by ERSO in a PVC plastisol formulation without deleterious effects on the properties of the plastigels. J. VINYL ADDIT. TECHNOL., 2008. © 2008 Society of Plastics Engineers.     

Synthesis and application of a novel thermostable epoxy plasticizer based on levulinic acid for poly(vinyl chloride)

Epoxy bisphenol acid isooctyl ester (EBAIE) was synthesized and characterized by FTIR and H-NMR. EBAIE was used as poly(vinyl chloride) (PVC) plasticizer for the first time, and its addition amount was 30 wt% of PVC. The mechanical properties, thermal stability, compatibility, and decomposition activation energy of PVC blends were systematically studied. Compared to the commercial plasticizer-dioctyl phthalate (DOP), the tensile strength had been significantly increased from 30.64 to 45.07 MPa, while the elongation at break had little difference. The thermal stability analysis showed that the static stability time at 180°C had been extended from 40 to 300 min. The decomposition activation energy indicated that the EBAIE plasticized PVC was with a higher thermal stability. The extraction and volatility resistance of the novel plasticizer were superior to those of DOP.     

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.     

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。     

The effect of an epoxidized plasticizer on the thermo-oxidative ageing of poly(vinyl chloride)/epoxidized natural rubber thermoplastic elastomers

The effects of an epoxidized plasticizer on the mechanical properties and thermo-oxidative ageing behaviour of poly(vinyl chloride)/epoxidized natural rubber thermoplastic elastomers (TPEs) were investigated. Aged and unaged blends were characterized by FTIR, tensile properties, tear strength, hardness and dynamic mechanical analysis (DMA). The properties of the epoxidized soya oil (ESO) plasticized TPEs were compared with those of the di-2-ethylhexylphthalate (DOP) plasticized counterparts. The presence of epoxide groups in ESO has been shown to produce two conflicting effects. On the one hand, the presence of excessive epoxide groups has resulted in poor ageing behaviour. On the other hand, it has resulted in a good interaction and compatibility with PVC/ENR. It was found that the tensile strength of the ESO plasticized blends were comparable with the DOP plasticized ones, but the elongation at break (EB) of the ESO blends fell short of that of the DOP blends. Also the retention of both tensile properties for the ESO blends was poorer than for DOP blends. Hardening and embrittlement also occurred in the ESO blends. Despite these weaknesses, ESO could be an ideal plasticizer for the PVC/ENR system as indicated by plasticizer permanence and the greater efficiency of plasticization. © 1998 SCI.