碳酸根基水铝钙石的制备及其在PVC中的应用研究

利用氢氧化钙[Ca(OH)2]和氢氧化铝[Al(OH)3]以及无水碳酸钠（Na2CO3）为原料,以去离子水作溶剂,制备了碳酸根基水铝钙石（Ca4Al2(OH)12CO3·5H2O）,通过傅里叶红外光谱、X射线衍射和扫描电子显微镜表征其结构。并将其作为热稳定剂应用于聚氯乙烯（PVC）中,通过热老化、刚果红、电导率和热失重分析等方法检测其热稳定性能。结果表明,Ca4Al2(OH)12CO3·5H2O具有长期型热稳定剂的特性,当其添加量为3份时,热稳定时间可达70 min,静态热稳定时间可达52 min;当Ca4Al2(OH)12CO3?5H2O/ZnSt2/DMAU复配体系的添加量为3份,并且Ca4Al2(OH)12CO3?5H2O:ZnSt2:DMAU在3：0.5：1.5~3：0：2之间时,复配体系的初期白度可达60 min左右,即使到110 min左右也未观察到“锌烧”现象发生。     

Effects of epoxidized sunflower oil on the mechanical and dynamical analysis of the plasticized poly(vinyl chloride)

Epoxidized soybean oil (ESBO), is one of the most commonly used epoxides because of its typical combined roles as a plasticizer and heat stabilizer. In this study, a novel plasticizer of poly(vinyl chloride) (PVC) resins, epoxidized sunflower oil (ESO), was synthesized, and its performance was evaluated. ESO was designed to act as a coplasticizer and a heat stabilizer like ESBO. ESO is used as organic coplasticizer for plasticized PVC containing Ca and Zn stearates as primary stabilizers and stearic acid as lubricant. Di‐(2‐ethylhexyl) phthalate (DEHP), a conventional plasticizer for PVC, was partially replaced by ESO. Mechanical properties (tensile and shore D hardness) were investigated. The performance of ESO to ESB0 (20 g) for comparison, indicated that ESO could be used as secondary plasticizer for PVC in combination with DEHP. All mechanical and dynamical properties of plasticized PVC sheets varied with the oxirane oxygen of the ESO. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Influence of nano‐CeO2 as Co‐stabilizer on the thermal stabilization efficiency of novel calcium/Zinc soap stabilizers for poly(vinyl chloride)

The novel organic calcium (Ca)/zinc (Zn) stabilizer of poly(vinyl chloride) (PVC) was synthesized from poly (zinc methylacrylate) and Ca adipate. The influences of Zn/Ca soap weight ratios and nano‐CeO₂ as co‐stabilizer on the thermal stability of PVC were investigated. Congo red testing, thermogravimetric analysis, dynamic rheology, and dynamic mechanical analysis of the mixtures were performed. The results show that the novel stabilizer has good stabilization efficiency on PVC. When 5 phr (parts by weight per hundred parts of resin) of novel stabilizer (weight ratio of Zn/Ca soap is 6/4) in 100 phr of PVC is used as stabilizer, the Congo red time can reach 192 min, which is 131 min longer than 5 phr of the mixture of 3 phr of Zn stearate and 2 phr of Ca stearate as stabilizer. If 3 phr of mixture of Zn methylacrylate with Ca adipate (weight ratio of Zn/Ca soap is 4/6) and 2 phr of nano‐CeO₂ are used as co‐stabilizers, the Congo red time is 205 min. The combination of nano‐CeO₂ with Ca/Zn soap stabilizer shows an obvious improvement for the thermal stability of the PVC. J. VINYL ADDIT. TECHNOL., 20:243–249, 2014. © 2014 Society of Plastics Engineers     

α-酮戊二酸镧的制备、复配及对PVC热稳定性能

以α-酮戊二酸、硝酸镧、氢氧化钠为原料，水为溶剂，经两步法制备了α-酮戊二酸镧。采用元素分析、ICP-OES和FTIR对产物结构进行了表征。通过刚果红试纸法测试产品对PVC的静态热稳定性，转矩流变仪法测试产品对PVC的动态热稳定性，TGA研究产品对PVC热降解动力学的影响，并将产品与β-二酮、PDOP、PER、ESO等辅助热稳定剂复配，考察其协同性能，采用SEM观察热降解不同时间的PVC的微观表面形貌。结果表明，α-酮戊二酸镧对PVC具有较好的热稳定作用，添加3 wt%时，静态热稳定时间可达13min，动态热稳定时间可达1820s，可将PVC热降解过程的平均活化能提高15.78 KJ/mol，其与PER之间协同作用最佳，复合热稳定剂对PVC的静态热稳定时间达37min，动态热稳定时间达3480s。SEM观察发现复合热稳定剂能较好的抑制PVC团聚。     

水滑石在钙锌复合体系中的热稳定性研究

以普通的碱性物质为参比，用刚果红、转矩流变仪等方法测试了水滑石在钙锌体系协同作用下对PVC树脂静态和动态热稳定时间的影响。试验结果表明。水滑石改善PVC树脂的热稳定性效果明显优于在Ca／Zn体系中用的辅助组分弱碱A，在PVC中的适宜用量为2份左右。并简单探讨了水滑石的热稳定机理。     

油酸⁃苯甲酸钙/锌液体复合热稳定剂的制备与表征

以油酸、苯甲酸、氢氧化钙和氧化锌为主要原料,氧化植物油为溶剂,一锅化反应制备了油酸?苯甲酸钙/锌液体复合热稳定剂。采用刚果红试纸法和热老化法考察了其对聚氯乙烯（PVC）的静态热稳定性能及与辅助热稳定剂β?二酮、亚磷酸苯二异辛酯、季戊四醇间的协同作用。通过转矩流变仪、紫外光谱仪、场发射扫描电子显微镜测试了最优样品对PVC热稳定性能。结果表明,油酸?苯甲酸钙/锌液体复合热稳定剂对PVC的静态热稳定时间可达50 min,与亚磷酸苯二异辛酯具有最好的协同作用,最优样品对PVC的静态热稳定时间可达71 min,动态热稳定时间可达970 s,平衡扭矩37.3 N·m;紫外分析表明其具有较强地抑制共轭数3以上的共轭多烯生成的能力;其与PVC间的相容性较好,能均匀的分散在PVC颗粒表面,60 min前具有较好地抑制PVC降解的能力。     

亚磷酸酯和季戊四醇对聚氯乙烯热稳定作用的研究

通过热老化法、白度测试、电导法及热重分析法,研究并对比了亚磷酸-苯二异辛酯(PDOP)和季戊四醇(PER)作为辅助稳定剂对PVC的热稳定作用。结果表明:PDOP能有效抑制锌烧,当PDOP/Zn比例为4:2时抑制效果最好;硬脂酸钙与硬脂酸锌存在协同效应,最佳Ca/Zn配比是2:1;三元热稳定剂的热稳定效果明显好于二元热稳定剂,且PDOP与Ca/Zn较PER与Ca/Zn有更优良的协同效应,PER/Ca/Zn体系在加热25min时出现泛黄现象P,DOP/Ca/Zn体系在加热45min时仍保持较高白度;证明PER有吸收氯化氢的作用。     

自制环保稳定剂在增塑PVC制品中应用性能的评价

通过刚果红热稳定性实验、热老化实验、流变、力学性能以及黄色指数测定等实验,对比研究了自制钙/锌稳定剂与国外知名钙/锌稳定剂对增塑PVC热稳定性能、加工性能、热老化性能和力学性能的影响。研究发现:自制钙/锌稳定剂在增塑PVC制品方面各种性能几乎与该国外知名钙/锌稳定剂没有差别,在热老化性能和力学性能方面还优于该国外知名钙/锌稳定剂。     

多元醇对聚氯乙烯热稳定作用的影响

采用静态热老化法、动态热老化法、刚果红变色法、红外光谱分析(FT-IR)、热失重分析(TGA)等现代仪器分析方法,评价了多元醇单独使用以及与硬脂酸锌(ZnSt2)复配使用时,对聚氯乙烯(PVC)的热稳定作用,并研究其协同作用机理。结果表明,多元醇单独使用时,能吸收聚氯乙烯受热分解产生的氯化氢(HCl),改善PVC的初期着色性,随着多元醇含量的增加,PVC热稳定时间延长。当硬脂酸锌与山梨糖醇复配含量为(0.7/0.4)份时,PVC的静态热稳定时间从15 min增加到21 min,热失重第一阶段试样残留量由44.97%增加到49.78%,表明山梨糖醇与ZnSt2复配能与降解产生的ZnCl2络合,缓解"锌烧"现象,改善了PVC的长期热稳定性。     

Phosphate ester groups‐containing ricinoleic acid‐based Ca/Zn: Preparation and application as novel thermal stabilizer for PVC

Phosphate ester groups containing ricinoleic acid‐based Ca/Zn (LPPRA‐Ca and LPPRA‐Zn) stabilizer was successfully synthesized from ricinoleic acid (RA) and used as thermal stabilizers for poly(vinyl chloride) (PVC). These thermal stabilizers were characterized by Fourier transform infrared spectrometry, ¹H nuclear magnetic resonance, and inductively‐coupled plasma atomic emission spectroscopy. The effects of LPPRA‐Ca/LPPRA‐Zn, CaSt₂/ZnSt₂, and other stabilizers on the thermal stability of PVC were studied through Congo Red test, discoloration tests, thermogravimetric analysis (TGA), TGA–infrared, and TGA–mass spectrometry. The thermal stability tests show that LPPRA‐Ca/LPPRA‐Zn displays the best initial color stability and long‐term thermal stability for PVC. The superior performance is attributed to the synergistic effect of LPPRA‐Ca and LPPRA‐Zn. Moreover, a lower Zinc content of LPPRA‐Zn in PVC helps to decrease the “zipper dehydrochlorination” of the product, which contributes to a better initial thermal stability. Except for the better stabilization performance, LPPRA‐Ca/LPPRA‐Zn also displays better plasticization performance for PVC compared with other stabilizers. A possible stabilizing mechanism of PVC/LPPRA‐Ca/LPPRA‐Zn system was presented. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45940.     

氰尿酸钙/锌的制备及其在PVC制品中的应用

以氰尿酸、氢氧化钙和氧化锌为原料,去离子水为溶剂,分别合成了聚氯乙烯(PVC)用热稳定剂氰尿酸钙、氰尿酸锌。采用元素分析仪(EA)、傅里叶变换红外光谱仪(FTIR)、热失重分析仪(TG)以及扫描电镜(FESEM)对氰尿酸钙/锌进行了表征分析。通过烘箱热老化和刚果红测试考察了氰尿酸钙/锌对PVC制品热稳定性能的影响,并对热稳定机理进行了探究。结果表明,单独加入PVC质量1%的氰尿酸钙或氰尿酸锌,PVC制品的热稳定性要优于加入等量的硬脂酸钙或硬脂酸锌;氰尿酸钙/锌复配后表现出良好的协调作用,氰尿酸钙/锌最佳质量比为3∶1,热稳定时间达28 min,PVC试片在70 min完全锌烧;并且,环氧大豆油(ESBO)是一种非常适合氰尿酸钙/锌体系的辅助稳定剂,能够进一步提高PVC体系的热稳定性能。     

Synthesis and evaluation of poly(dioctyltin maleate‐styrene‐methyl acrylate) as a stabilizer for poly(vinyl chloride)

A novel thermal stabilizer poly(dioctyltin maleate‐styrene‐methyl acrylate) [P(DOTM‐St‐MA)] was synthesized by radical solution polymerization with benzene as the solvent and 2,2‐azobisisobutyronitrile as the initiator. The structure of terpolymer was characterized by FTIR and ¹H‐NMR spectra, and thermal stability of the stabilizer was measured by thermogravimetric analysis (TGA). Evaluation of [P(DOTM‐St‐MA)] as thermal stabilizer for poly(vinyl chloride) (PVC) was measured by acidimeter, and the extent of changing color of PVC was measured by thermal aging method. Compatibilities of four stabilizers with PVC were characterized by scanning electron microscope (SEM). The results showed that, with the same tin content in PVC mixtures, [P(DOTM‐St‐MA)] exhibited better performance as a PVC stabilizer compared with other stabilizers,such as poly(dibutylin maleate‐styrene‐methyl acrylate), DOTM, and dibutylin maleate (DBTM). Furthermore, [P(DOTM‐St‐MA)] had better compatibility with PVC in PVC processing. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

钙/锌复合稳定剂对PVC热稳定性能与耐候性能影响的研究

研究了钙/锌复合稳定剂对PVC热稳定与耐候性能的影响。结果表明,流变仪热分解时间试验能反映PVC加工过程中的长期热稳定性能;钙/锌复合稳定剂添加量达到一定数值时,对PVC热稳定性能与耐候性能的影响较小。此研究对稳定剂添加量的确定有指导意义。     

钙／锌复合热稳定剂在硬质PVC中的应用研究

自制了高效、无毒的钙锌复合热稳定剂,利用静态热老化法、刚果红法及脱氯化氢法等研究方法,研究了自制钙锌稳定剂、进口钙锌稳定剂及复合铅盐稳定剂在硬质聚氯乙烯（PVC）中的热稳定性能。结果表明：自制钙锌的初期着色性与复合铅盐稳定剂及进口钙锌稳定剂相当,长期热稳定性优于进口钙锌。自制钙锌稳定剂的降解活化能介于进口钙锌稳定剂与复合铅盐稳定剂之间,降解活化能的差值为1～2kJ／mol,其热稳定性达到了复合铅盐的水平,PVC硬制品加工的要求。     

Study on pentaerythritol–zinc as a novel thermal stabilizer for rigid poly(vinyl chloride)

Pentaerythritol–zinc (penzinc) was prepared by a solid‐phase reaction technique. The principal volatile products of the reaction between pentaerythritol and ZnO were analyzed with a coupled thermogravimetry—mass spectrometery system. The results indicated that a large amount of water was formed at the reaction temperature. Scanning electron microscopy (SEM) results showed the appearance of penzinc as flaky particles. Accordingly, the penzinc obtained through the dehydration between pentaerythritol and ZnO is likely to be a monopentaerythritol complex, such as zinc monoglycerolate. The thermal stability of poly(vinyl chloride) (PVC) with penzinc as a thermal stabilizer was investigated by a Congo Red test, Oven aging test and thermal gravimetric analysis (TGA). The Congo Red test showed the thermal stability time of PVC with penzinc was 38 min, longer than those with commercial thermal stabilizers. TGA indicated that the penzinc had little impact on the thermal degradation of PVC, but could increase the mass of residues. Oven aging test showed that the penzinc could significantly retard the discoloration during the long‐term decomposition of PVC. Meanwhile, no “zinc burning” was observed in the PVC with penzinc. These results indicate that the penzinc is an excellent thermal stabilizer for rigid PVC. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Insights into the use of zinc–mannitol alkoxide as a novel thermal stabilizer for rigid poly(vinyl chloride)

Zinc–mannitol alkoxide (Zn–Man) was synthesized through alcohol exchange reaction, and investigated by means of Fourier transform infrared spectroscopy and elemental analysis. The thermal stability of Zn–Man for rigid poly(vinyl chloride) (PVC) was evaluated by Congo red testing, conductivity measurements, thermal aging testing, thermogravimetric analysis (TGA), and ultraviolet–visible (UV–vis) spectroscopy test. The experimental results demonstrate that the addition of Zn–Man not only apparently prolonged the static thermal stability time to approximately 96.5 min but also evidently improved the initial color of PVC. More importantly, the color of the PVC sheets stabilized with Zn–Man did not change to black within 180 min; this showed that no zinc‐burning phenomenon occurred. In addition, the results of TGA reveal that Zn–Man raised the initial degradation temperature of PVC to about 273.4°C. UV–vis testing indicated that the presence of Zn–Man decreased the content and shortened the length of the conjugated double bonds of PVC. The possible thermal stability mechanism is discussed. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42038.     

PVC材料环保型热稳定剂的研究

研究将水滑石、水滑石和钙锌复合物作为热稳定剂,加入PVC中,在85℃真空条件下劣化40 d,对其力学性能和热稳定性进行了研究,并探讨了复合稳定剂的作用效果。结果表明,热稳定剂水滑石及水滑石、钙锌复合物的加入均能较好的改善PVC的力学性能和热稳定性,且复合稳定剂的作用效果比水滑石单独使用更好,虽然断裂伸长率有所降低,但断裂强度有所增强。     

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。     

新型PVC辅助热稳定剂乙酰丙酮镁的制备及热稳定性能

以氢氧化镁[Mg(OH)₂]和乙酰丙酮为原料,乙醇为溶剂,通过一步异相沉淀转化法制备配合物乙酰丙酮镁[Mg(acac)₂],用作聚氯乙烯（PVC）辅助热稳定剂。首先,采用XRD、FTIR、TG对产物进行了结构表征,然后通过静态热老化试验和刚果红试验,对乙酰丙酮镁的热稳定性能进行研究。结果表明,成功制备出产物乙酰丙酮镁,且含有2个结晶水;在PVC中,当主效热稳定剂与辅助热稳定剂的质量比为3∶5时,PVC 的热稳定时间长达57min。该生产技术克服了乙酰丙酮镁传统合成方法产率低、操作过程复杂、污染等缺点,制备的产物乙酰丙酮镁与主效热稳定剂具有良好的协同作用,可以有效提高PVC的热稳定性能。     

PVC食用菌棚膜热稳定体系的研究

采用Brabender方法和辊压色相评价方法研究了用软PVC压延食用菌棚膜的稳定体系,着重讨论了新型复合稳定剂—膏状Ba/Cr/Zn和膏状Ba/Zn用量以及不同辅助稳定剂并用体系对PVC稳定效果的影响。实验结果表明:亚磷酸酯及环氧大豆油对A及B两种不同复合稳定剂均具有增效作用,并且两种稳定体系均可满足加工要求