对甲基苯甲酸镧作为PVC热稳定剂的研究
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摘要
以氯化镧、对甲基苯甲酸、氢氧化钠为原料合成了对甲基苯甲酸镧。通过元素分析、红外光谱分析、热分析等方法对合成产物进行了表征;通过刚果红试纸法和高温老化箱实验研究了对甲基苯甲酸镧对聚氯乙烯热稳定性能的影响;同时,将对甲基苯甲酸镧与硬脂酸锌、硬脂酸钙、硬脂酸镧和季戊四醇等进行比较,并将对甲基苯甲酸镧与上述一种或者一种以上稳定剂进行复配。结果表明,当对甲基苯甲酸镧单独作为聚氯乙烯(PVC)稳定剂时,稳定性效果不理想,长期稳定性一般,抗变色能力也不好;当对甲基苯甲酸镧/钙锌复合体系/季戊四醇=2∶1∶2时,PVC的稳定时间达到48 min;对甲基苯甲酸镧可以吸收PVC分解释放的HCl生成LaCl_3,减少了HCl对PVC降解的催化作用,从而抑制PVC的降解。
Lanthanum p-methyl benzoate(LPB) was synthesized by using lanthanum chloride, p-Toluic acid and sodium hydroxide as raw materials, and the resultant product was characterized by means of elemental analysis and FTIR. The effect of LPB on the thermal stability and discoloration of polyvinyl chloride(PVC) were investigated by Congo red experiment and high-temperature hot aging tests. Moreover, a comparative study was carried out for LPB with other stabilizers such as zinc stearate, calcium stearete, lanthanum stearate and pentaerythrotol, and LPB was also mixed with other stabilizers to form a complex stabilizer. The results indicated that the thermal stabilizing effect on PVC is not good enough when LPB was used alone, which also resulted in poor long-term stability and anti-discoloration performance. When the mass ratio of LPB/calcium zinc composite/pentaerythrotol mixture was set to 2/1/2 and its total dosage was determined as 4 wt % of PVC, the stability time of PVC reached 48 min. The stable mechanism of LPB could be ascribed to the absorption of the HCl released by the decomposition of PVC. Such absorption could result in the production of LaCl_3 and therefore reduced the catalytic effect of HCl on the degradation of PVC and inhibited the degradation of PVC accordingly.
Lanthanum p-methyl benzoate(LPB) was synthesized by using lanthanum chloride, p-Toluic acid and sodium hydroxide as raw materials, and the resultant product was characterized by means of elemental analysis and FTIR. The effect of LPB on the thermal stability and discoloration of polyvinyl chloride(PVC) were investigated by Congo red experiment and high-temperature hot aging tests. Moreover, a comparative study was carried out for LPB with other stabilizers such as zinc stearate, calcium stearete, lanthanum stearate and pentaerythrotol, and LPB was also mixed with other stabilizers to form a complex stabilizer. The results indicated that the thermal stabilizing effect on PVC is not good enough when LPB was used alone, which also resulted in poor long-term stability and anti-discoloration performance. When the mass ratio of LPB/calcium zinc composite/pentaerythrotol mixture was set to 2/1/2 and its total dosage was determined as 4 wt % of PVC, the stability time of PVC reached 48 min. The stable mechanism of LPB could be ascribed to the absorption of the HCl released by the decomposition of PVC. Such absorption could result in the production of LaCl_3 and therefore reduced the catalytic effect of HCl on the degradation of PVC and inhibited the degradation of PVC accordingly.
引文
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[19] ZHANG J,LI D,FU M,et al.Synergistic Effect of Adipic Acid Pentaerythritol Ester with Calcium and Zinc Stearates on Poly(Vinyl chloride) Thermal Stability[J].Journal of Vinyl & Additive Technology,2016,22(3):293-299.
[20] 李梅,姜在勇,柳召刚,等.氰尿酸镧的合成及其对PVC热稳定作用的研究[J].塑料科技,2012,40(4):114-118.LI M,JIANG Z Y,LIU Z G,et al.Synthesis of Lanthanum Cyanurate and Its Effect on Thermal Stability of PVC [J].Plastics Science and Technology,2012,40 (4):114-118.
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[22] 方继彪,宋姣,郭永强,等.稀土热稳定剂的合成与表征[J].辽宁化工,2017,46(9):873-875.FANG J B,SONG J,GUO Y Q,et al.Synthesis and Characterization of Rare Earth Thermal Stabilizers[J].Liaoning Chemical Industry,2017,46 (9) :873-875.
[2] STEENWIJK J,LANGEROCK R,ES D S V,et al.Long-term Heat Stabilisation by (natural) Polyols in Heavy Metal-and Zinc-free Poly(Vinyl Chloride)[J].Polymer Degradation & Stability,2006,91(1):52-59.
[3] 段少陪,李子恒,陈挡,等.绿色环保PVC的结构机理及热稳定剂的研究[J].建材与装饰,2018(15).DUAN S P,LI Z H,CHEN D,et al.Study on the Structure Mechanism and Thermal Stabilizer of Green Environmental Protection PVC[J].Building Materials and Decoration,2018(15).
[4] DONG W,RUAN X,NI Z,et al.Influence of Soy Protein Isolate on the Thermal Stability of Poly(Vinyl Chloride) in the Presence or Absence of Calcium And Zinc Stearates[J].Polymer Degradation & Stability,2013,98(1):96-101.
[5] SHNAWA H A,JAHANI Y,KHALAF M N .Rheological Properties of PVC Stabilized with Tannin Based Epoxy Resin as Non Metallic Thermal Stabilizer[J].Polymer Bulletin,2017,74(4):1 077-1 090.
[6] XIE L,LI D,ZHANG J.The Effect of Pentaerythritol-Aluminum on the Thermal Stability of Rigid Poly(vinyl chloride)[J].Journal of Applied Polymer Science,2014,130(5):3 704-3 709.
[7] LI S,YAO Y.Effect of Thermal Stabilizers Composed of Zinc Barbiturate and Calcium Stearate for Rigid Poly(vinyl chloride)[J].Polymer Degradation & Stability,2011,96(4):637-641.
[8] DU Y,GAO J,LIU X,et al.Influence of Nano-CeO2 as Co-stabilizer on the Thermal Stabilization Efficiency of Novel Calcium/Zinc Soap Stabilizers for Poly(vinyl chloride)[J].Journal of Vinyl & Additive Technology,2015,20(4):243-249.
[9] 北京化工研究所,北京稀土办公室.PVC稀土RE-120热稳定剂试制[J].有色金属与稀土应用,1988(4):3-9.Beijing Institute of Chemical Technology,Beijing Rare Earth Office.Preparation of PVC Rare Earth RE-120 Thermal Stabilizer[J].Non-ferrous metals and rare earth applications,1988,(4):3-9.
[10] 于静,李敏贤,李德玲.羧酸对复合羧酸镧热稳定剂性能的影响[J].中国稀土学报,2015,33(1):60-65.YU J,LI M X,LI D L.Effects of Carboxylic Acid on the Properties of Complex Lanthanum Carboxylate Thermal Stabilizer[J].Chinese Journal of Rare Earths,2015,33(1):60-65.
[11] 李先铭,张宁.PVC硬脂酸轻稀土热稳定剂的复配与应用研究[J].中国稀土学报,2015,33(3):349-354.LI X M,ZHANG N.Preparation and Application of PVC Stearic Acid Light Rare Earth Heat Stabilizer [J].Chinese Journal of Rare Earths,2015,33(3):349-354.
[12] 于静.PVC用稀土热稳定剂研究进展[J].中国塑料,2013,27(10):12-17.YU J.Progress in Research on Rare Earth Thermal Stabilizers for PVC [J].China Plastics,2013,27(10):12-17.
[13] 李梅,王晓川,吴锦绣,等.碱式柠檬酸镧作为PVC热稳定剂的研究[J].稀土,2017,(3):60-67.LI M,WANG X C,WU J X,et al.Study of Basic Lanthanum Citrate as a Thermal Stabilizer for PVC [J].Rare Earth,2017,(3):60-67.
[14] 罗曼,关平,刘文江.利用红外光谱鉴别饱和脂肪酸及其盐[J].光谱与光谱分析,2007,27(2):250-253.LUO M,GUAN P,LIU W J.Identification of Saturated Fatty Acids and Their Salts by Infrared Spectroscopy [J].Spectrum and Spectral Analysis,2007,27 (2):250-253.
[15] ZHANG W,DONG D D,WEI Z,et al.Synthesis of Lanthanum Ricinoleate and Its Effect on Thermal Stability and Mechanical Properties in PVC[J].Journal of Rare Earths,2014,32(11):1 089-1 094.
[16] 杜永刚,王昕,文卓奇,等.己二酸锌钙皂-纳米氧化铈/氧化镧对PVC/ASA的热稳定作用[J].中国塑料,2016,30(1):104-108.DU Y G,WANG X,WEN Z Q,et al.Thermal Stability of Calcium Zinc Adipate Soap-Nano Cerium Oxide/Lanthanum Oxide on PVC/ASA [J].China Plastics,2016,30 (1):104-108.
[17] LIU Y B,LIU W Q,HOU M H.Metal Dicarboxylates as Thermal Stabilizers for PVC[J].Polymer Degradation & Stability,2007,92(8):1 565-1 571.
[18] 许家友,谢琼,龙金风,等.多元醇对PVC热稳定和色泽的影响[J].塑料,2011,40(4):75-77.XU J Y,XIE Q,LONG J F,et al.Effect of Polyols on Thermal Stability and Color of PVC [J].Plastics,2011,40 (4):75-77.
[19] ZHANG J,LI D,FU M,et al.Synergistic Effect of Adipic Acid Pentaerythritol Ester with Calcium and Zinc Stearates on Poly(Vinyl chloride) Thermal Stability[J].Journal of Vinyl & Additive Technology,2016,22(3):293-299.
[20] 李梅,姜在勇,柳召刚,等.氰尿酸镧的合成及其对PVC热稳定作用的研究[J].塑料科技,2012,40(4):114-118.LI M,JIANG Z Y,LIU Z G,et al.Synthesis of Lanthanum Cyanurate and Its Effect on Thermal Stability of PVC [J].Plastics Science and Technology,2012,40 (4):114-118.
[21] RONY F K,RAY S K,HOQUE A,et al.Zinc Stearate From Galvanizing Waste Materials and Its Use as Thermal Stabilizer in PVC Industries[J].Bangladesh Journal of Scientific & Industrial Research,2016,51(4):261-270.
[22] 方继彪,宋姣,郭永强,等.稀土热稳定剂的合成与表征[J].辽宁化工,2017,46(9):873-875.FANG J B,SONG J,GUO Y Q,et al.Synthesis and Characterization of Rare Earth Thermal Stabilizers[J].Liaoning Chemical Industry,2017,46 (9) :873-875.