稀土PVC稳定剂的作用机制研究

稀土化合物可以作为聚氯乙烯稳定剂，硬脂酸稀土是稀土复合稳定剂的重要成分。本文通过研究PVC与硬脂酸镧及其它硬脂酸盐作用前后的红外光谱，探讨了硬脂酸盐对PVC的热稳定作用机制，发现了稀土化合物对PVC的特殊稳定机制，即改变PVC的构象和抑制脱氯化氢的作用，并对稀土稳定剂独特的协同作用做出了解释。     

含二苯甲酮结构的稀土配合物对PVC光稳定性能的影响

兼具热和光稳定性的稀土稳定剂,对降低聚氯乙烯(PVC)加工成本,提高PVC的生产效率和打开稀土稳定剂的应用领域具有重要的意义,因此,通过人工加速紫外老化实验和户外自然光老化实验,研究了2,4-二羟基二苯甲酮镧(LBP)、 2-苯甲酰苯甲酸镧(LBA)及三元复合稳定剂对PVC光稳定性能的影响。结果表明：添加含LBP和含LBA的两种三元复合稳定剂(LBP∶ZnSt₂∶PE=2∶1∶2, LBA∶ZnSt₂∶PE=1∶1∶3)的PVC片材,人工紫外老化10 d后,失重率分别为2.7%和6.2%,自然光老化35 d后,拉伸强度保留率分别为87.6%和81.8%,复合稳定剂提高PVC的光稳定性能最佳。稀土稳定剂可以吸收PVC降解产生的氯化氢,降低氯化氢的浓度,从而减弱氯化氢对PVC降解的催化作用,抑制PVC脱去HCl形成双键,防止双键在氧作用下,形成过氧化物生成羰基化合物。     

纳米粒子的控制生长和自组装研究进展

由于在纳米器件上潜在应用,通过化学方法控制的纳米粒子生长,以及纳米粒子自组装的一维、二维和三维点阵受到人们的广泛关注。本文介绍来近年来纳米粒子的控制生长和组装研究的现状。主要探讨了有机稳定剂对纳米粒子形状和尺寸控制的影响。含配位基团和长链烷烃的有机化合物不但可以用控制纳米粒子生长的稳定剂,而且可以用作纳米粒子自组装的模板剂。     

热稳定剂对PVC紫外光老化过程中微观结构及宏观性能演变的影响

通过UV-Vis、FTIR、DSC、以及色差、力学性能的测试表征,实时追踪分析了在紫外光老化过程中,含Pb、Sn以及Ca-Zn热稳定剂的PVC体系微观结构和宏观性能的演变过程.结果表明,在相同光老化条件下,PVC/Pb、PVC/Sn和PVC/Ca-Zn体系的微观结构变化规律基本一致,过程中主要的化学反应是,大分子吸收光能后,发生脱HCl生成共轭双键的反应、生成羰基的氧化反应、交联反应和降解反应;不同热稳定剂的作用,主要表现在对于微观结构变化的幅度和动力学过程的影响不同.相应地,3种体系的外观色差和力学性能的变化规律也相似,但色差的变化程度和速度以及老化后力学性能的保持率因所含热稳定剂的不同而不同,其中含Sn体系的颜色稳定性最好,含Pb体系的力学性能保持率最高。     

热稳定剂及与PVC混合物的热解反应研究

采用热分析方法对PVC加工成型中热稳定型的热解反应进行了研究，根据它们的热重曲线，分别求得热稳定剂及掺入热稳定剂后PVC混合物的热分解反应的各种特性参数，运用计算动力学参数的经验公式，求得热解活化能，定量地评价了热稳定剂及掺入热稳定剂后PVC混合物的热性能，并采用静态法测定了PVC混合物的热稳定时间。     

PVC硬脂酸轻稀土热稳定剂的复配与应用研究

为了进一步研发性价比高且"无铅化"的稀土复合热稳定剂,研究了系列硬脂酸轻稀土盐(镧/铈/镨/钕/钐/铕/混合)与其他常用PVC热稳定(助)剂的复配效果。通过刚果红试纸法、红外光谱分析(FT-IR)、转矩流变仪等探究了复合热稳定剂对PVC性能的影响。结果表明:复合热稳定剂配方为硬脂酸轻稀土盐0.7~1.0份、硬脂酸锌0.8~0.9份、β-二酮0.3~0.6份和季戊四醇0.8~0.9份。将3份复合热稳定剂添加到100份PVC树脂中,静态及动态热稳定时间延长至100和35 min左右;动态热稳定性能和力学性能优于市售钙锌热稳定剂,与市售铅盐较接近。红外光谱分析表明复合热稳定剂可在加热初期减缓PVC氧化降解,较好地抑制初期着色,对PVC性能影响顺序为:镧组钕组混合组铈组镨组钐组铕组。     

甲基丙烯酸甲酯、苯乙烯与顺丁烯二酸二丁基锡三元共聚物的合成与表征

以过氧化苯甲酰(BPO)为引发剂,将顺丁烯二酸二丁基锡(DBTM)与苯乙烯(St)、甲基丙烯酸甲酯(MMA)进行本体三元共聚反应,探讨了共聚反应条件.用液相色谱、红外光谱、核磁共振氢谱和热重分析对共聚物的结构和性能进行了表征.动态热流变性实验结果表明,在含锡量相同的情况下,共聚物对PVC的热稳定效果优于DBTM,可以作为多功能化的PVC热稳定剂.     

新型有机高分子型PVC热稳定剂的合成

以经部分硝化和还原的低分子量聚苯乙烯为母链,利用其胺基和丙烯酰基异硫氰酸酯加成,合成了一种新型有机高分子型PVC热稳定剂——丙烯酰基硫脲接枝聚苯乙烯,其结构经IR和元素分析表征。     

顺丁烯二酸二丁基锡-苯乙烯-丙烯酸丁酯三元共聚物的结构与性能表征

采用本体聚合的方法，在氧化苯甲酰（BPO）存在下，合成了顺丁烯二酸二丁基锡－苯乙烯－丙烯酸丁酯（DBTM－St-BA)三元共聚物，用GPC，FTIR，1H NMR，TG和刚果红法及布拉本热流变仪对共聚产物的结构和性能进行了有征，结果表明，在所选定的聚合条件下，共聚产物为DBTM－St-BA的三元共聚物，在含锡量相同的情况下，共聚物对PVC的热稳定效果和加工性能的影响优于DBTM，可以作为多功能化的PVC热稳定剂。     

PVC热稳定剂——羧酸疏基乙酯锑的合成及性质

以Sb2O3和HSCH2CH2OH为原料合成Sb(SCH2CH2OH)3;再将Sb(SCH2CH2OH)3与RCOOH反应,以钛酸丁酯作催化剂,二甲苯为溶剂,加热回流反应,得到酯锑。产品的热稳定性能测试表明：当逆酯锑的添 加量为2％时,PVC树脂的热稳定时间为8－40min(200℃）。还对该类热稳定剂对PVC的热稳定机理进行了初步探讨。     

Vanillin–Schiff’s bases as organic thermal stabilizers and co-stabilizers for rigid poly(vinyl chloride)

Vanillin–Schiff’s bases (VSB) were examined as thermal stabilizers and co-stabilizers for rigid poly(vinyl chloride) (PVC) in air at 180 °C. Their high stabilizing efficiency were shown by their high thermal stability value (Ts), which is the time elapsed for the detection of HCl gas, if compared with dibasic lead carbonate and cadmium–zinc soap reference stabilizers used industrially, with better extent of discoloration. Blending these derivatives with reference stabilizers in different ratios greatly lengthens the thermal stability and the extent of discoloration of the PVC.Condensation products of Vanillin with amines are very active biologically, besides having good complexation ability with metal ions. The Ni²⁺ and Co²⁺ complexes of VSB derivatives gave better thermal stability and less discoloration than the parent organic stabilizer. Also, blending these complexes with either of the used reference stabilizers in different ratios gave better thermal stability and lower extent of discoloration. Thermogravimetric analysis confirmed the improved stability of PVC in the presence of the VSB derivatives, compared to blank PVC, PVC stabilized with reference stabilizers and PVC stabilized with binary mixture of VSB derivatives with reference stabilizer.The stabilizing efficiency of Vanillin–Schiff’s base (VSB) derivatives is attributed to the replacement of the labile chlorine atoms on the PVC chains by a relatively more stable moiety of the organic stabilizer.     

Hydroxylbenzylthioethers as novel organic thermal stabilizers for rigid PVC

An investigation was carried out on the performances of hydroxylbenzylthioethers employed as organic thermal stabilizers for rigid poly(vinyl chloride). The efficiency of these compounds as thermal stabilizers was evaluated by using Haake polydrive mixer and TGA. The stabilizing efficiency was compared with Ca-Zn soap and methyltin stabilizer. Hydroxylbenzylthioethers exhibit greater efficiency than both of these stabilizers. This is attributed to the ability of these compounds to prevent the formation of polyene sequences. The hydroxylbenzylthioethers-stabilized PVC showed a slightly lower glass transition temperature (T_g) in comparison with the original PVC. Hydroxylbenzylthioethers and epoxidized soybean oil (ESBO) exhibit synergistic effect on the stabilizing effect, when the mass ratios of ESBO to hydroxylbenzylthioethers are less than 0.5.     

稀土PVC热稳定剂作用模式及协同效应研究

稀土化合物对ＰＶＣ良好的稳定作用，并存在广泛的协同效应。探索了一种计算机辅助研究稀土ＰＶＣ热稳定剂作用模式及效应的方法，可以预测稳定剂的稳定效能。结果表明，在稀土硬脂酸盐及同类稳定剂中，曲线回归方程参数有效地反映了热稳定剂类型的差别；引入协同效应函数，不仅提高了回归方程的可信度，而且能反映协同效应的形成规律。     

Improvement of Structural and Thermal Stabilities of PVC and Wood/PVC Composite by Zn and Pb Stearates,and Zeolite

Three different chemical stabilizers were introduced into neat PVC and a wood/PVC composite (containing 50 phr wood flour) to improve their thermal and structural stabilities. The changes in CIE yellowness index, polyene index, %wt loss, and decomposition temperature (T_d) were monitored. The effects of type and content of thermal stabilizers, thermal ageing time, and the presence of wood flour were our main interests. The experimental results suggested that the additions of Zn and Pb stearates into PVC and wood/PVC composite could improve the thermal stability of the PVC. At the test temperature of 177°C, the additions of Zn and Pb stearates could improve the thermal stabilities of PVC by retarding the upzipped reaction and by reducing the conjugated double bonds in PVC, Pb stearate being the most suitable for thermally stabilizing the PVC. Around the T_d range (～264°C), the addition of Zn stearate reduced the T_d value of PVC whereas that of Pb stearate had no effect on the change in T_d value. Zeolite loading could shift the T_d value of the PVC from 264 to 280°C. The addition of wood particles increased the polyene content and decreased the decomposition temperature of the PVC. The effect of wood flour on the thermal and structural changes of PVC overruled that of thermal stabilizer loading.     

Novel antimicrobial and antitumor organic thermal stabilizers for rigid Poly (vinyl chloride)

Pyrazolodithiones of expected biological activity were examined as thermal stabilizers and co-stabilizers for rigid poly(vinyl chloride) (PVC) in air at 180?°C. Their high stabilizing efficiency were shown by their high thermal stability values (T _s), which is the time needed for the liberation of HCl gas, if compared with dibasic lead carbonate (DBLC) and calcium?Czinc soap (Ca?CZn soap) reference stabilizers used industrially, with better extent of discoloration. Blending these derivatives with reference stabilizers in different ratios greatly lengthens the thermal stability value and improves the extent of discoloration of the PVC. The structure of the novel organic stabilizers was confirmed by elemental analysis, FTIR, Mass spectra, and ¹H-NMR. Thermogravimetric analyses confirmed the improved stability of PVC in the presence of the investigated organic stabilizers, compared to blank PVC and PVC stabilized with the reference stabilizers. Also, GPC measurements were done to investigate the changes occurred in the molecular masses of the degraded samples of PVC in presence of the newly synthesized stabilizers. The stabilizing efficiency of pyrazolodithiones is attributed to the replacement of the labile chlorine atoms on the PVC chains by a relatively more stable moiety of the organic stabilizer. The investigated stabilizers showed a good antimicrobial activity toward two kinds of bacteria, Escherichia coli and Staphylococcus aureus; and also toward two kinds of fungi, Aspergillus flavus and Candida albicans. They also exhibited antitumor activity against both liver and colon human cell lines.     

Organic thermal stabilizers for rigid poly(vinyl chloride). Part XIII: Eugenol (4-allyl-2-methoxy-phenol)

Eugenol (4-allyl-2-methoxy-phenol) has been examined as a thermal stabilizer and co-stabilizer for rigid PVC in air, at 180 °C. Its high stabilizing efficiency is detected by its high thermal stability value (Ts) when compared with some of the common reference stabilizers used industrially such as dibasic lead carbonate, calcium-zinc soap and octyl tin mercaptide.Blending this organic stabilizer with some of the reference stabilizers in different ratios had synergistic effect on both the induction period and the dehydrochlorination rate together with the longer extent of discolouration of PVC stabilized by eugenol as compared with the blank and the samples stabilized with reference commercial stabilizers.A probable mechanism for the stabilizing action of eugenol has been proposed. The stabilizing efficiency is attributed partially to the stabilizer's ability to intervene in the radical chain degradation process of PVC and to the replacement of the labile chlorine atoms on PVC chains by a relatively more stable moiety of the organic stabilizer.     

Organic thermal stabilizers for rigid poly(vinyl chloride). Part XI: Anthraquinone derivatives

Anthraquinone and 1-aminoanthraquinone derivatives have been examined as thermal stabilizers or co-stabilizers for rigid PVC in air, at 180 °C. Their high stabilizing efficiency is detected by their high induction period values (Ts) when compared with some of the common reference stabilizers used industrially such as dibasic lead carbonate, calcium-zinc soap and octyl tin mercaptide. Blending these organic stabilizers with some of the reference stabilizers in different ratios had synergistic effect on both the induction period and the dehydrochlorination rate.A probable mechanism for the stabilizing mode of these derivatives has been proposed. The stabilizing efficiency is attributed partially to the stabilizers' ability to intervene in the radical chain degradation process of PVC and to the replacement of the labile chlorine atoms on PVC chains by a relatively more stable moiety of the organic stabilizer.     

Effect of thermal stabilizers composed of zinc barbiturate and calcium stearate for rigid poly(vinyl chloride)

Zinc barbiturate [Zn(H₂L)₂·2H₂O, abbreviated as ZnL₂] was synthesized by a precipitation method in aqueous solution, and investigated as a co-stabilizer with calcium stearate (CaSt₂) for rigid poly(vinyl chloride) (PVC) by the discoloration test and the dehydrochlorination test at 180 °C. ZnL₂ exhibits high stabilizing effect with excellent initial colour of PVC films. In comparison with the synergistic effect of CaSt₂/ZnSt₂ stabilizers, the CaSt₂/ZnL₂ stabilizers in mass ratios ranging from 0.3/1.2 to 0.6/0.9 exhibit better synergistic effect. Moreover, PVC films stabilized by CaSt₂/ZnL₂ show better initial colour with the addition of dibenzoyl methane as an auxiliary stabilizer. The mechanism of stabilizing action of ZnL₂ is also proposed. ZnL₂ may replace the labile chlorine atoms to interrupt the formation of conjugated double bonds in PVC chains, and act as the absorber of hydrogen chloride to restrain the self-catalytic dehydrochlorination.