釜内合金型和共混型热塑性聚烯烃热稳定性的流变学研究
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摘要
利用丙烯基弹性体(PBE)和乙烯基弹性体(POE)分别对NAX-9釜内合金型热塑性聚烯烃(TPO)进行共混改性,当PBE或POE质量分数为50%时,通过动态热机械分析(DMA)得到的储能模量与巴塞尔釜内合金工艺制备的TPO CA10A相近。采用流变学方法,通过动态时间扫描研究CA10A、NAX-9/PBE和NAX-9/POE共混型TPO的热稳定性。结果表明,CA10A和NAX-9/PBE共混型TPO发生热氧老化时,容易形成β-断链反应,导致其黏度随扫描时间的延长而逐步降低;而NAX-9/POE共混型TPO发生热氧老化时,容易形成交联反应,导致其黏度随扫描时间的延长而逐步增大。在不添加抗氧剂的NAX-9/PBE共混型TPO中,PBE含量越高,黏度随时间下降的趋势越明显。CA10A和NAX-9/PBE共混型TPO中的橡胶相和均聚聚丙烯相的相容性比较好,使得抗氧剂在基体中的分散均匀性要高,因此CA10A和NAX-9/PBE共混型TPO的热氧稳定性要好,其中CA10A的热稳定性能最佳。
Two kinds of physical blending thermoplastic polyolefin( TPO) were obtained by mixing NAX-9 with propylene based elastomer( PBE) and ethylene based elastomer( POE),respectively. When the weight fraction of PBE or POE was 50%,the storage modulus of the blends observed from DMA was close to in-reactor TPO CA10 A from catalloy process of Basel. The thermal stability of the CA10 A and NAX-9/PBE and NAX-9/POE were studied by dynamic time scanning with the method of rheology. The results show when CA10 and NAX-9/PBE mixed TPO occur thermal-oxidization aging,the β-chain scission reaction could be formed to decrease the viscosity with the increase of scanning time. When NAX-9/PBE mixed TPO occur thermal-oxidization aging,the cross-linking reaction could be formed to increase the viscosity with the increase of scanning time. In the NAX-9/PBE mixed TPO without antioxidant compound,the viscosity could decrease obviously with the increase of PBE contents. The rubber phase in CA10 A and NAX-9/PBE mixed TPO has good compatibility with the homo-polypropylene phase, which shows the dispersion uniformity of the antioxidant in the matrix is higher. Therefore,both CA10 A and NAX-9/PBE mixed TPO blends show better thermal stability,and CA10 A is the best.
Two kinds of physical blending thermoplastic polyolefin( TPO) were obtained by mixing NAX-9 with propylene based elastomer( PBE) and ethylene based elastomer( POE),respectively. When the weight fraction of PBE or POE was 50%,the storage modulus of the blends observed from DMA was close to in-reactor TPO CA10 A from catalloy process of Basel. The thermal stability of the CA10 A and NAX-9/PBE and NAX-9/POE were studied by dynamic time scanning with the method of rheology. The results show when CA10 and NAX-9/PBE mixed TPO occur thermal-oxidization aging,the β-chain scission reaction could be formed to decrease the viscosity with the increase of scanning time. When NAX-9/PBE mixed TPO occur thermal-oxidization aging,the cross-linking reaction could be formed to increase the viscosity with the increase of scanning time. In the NAX-9/PBE mixed TPO without antioxidant compound,the viscosity could decrease obviously with the increase of PBE contents. The rubber phase in CA10 A and NAX-9/PBE mixed TPO has good compatibility with the homo-polypropylene phase, which shows the dispersion uniformity of the antioxidant in the matrix is higher. Therefore,both CA10 A and NAX-9/PBE mixed TPO blends show better thermal stability,and CA10 A is the best.
引文
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[3]明明.TPO防水卷材的原材料与配方设计[J].中国建筑防水,2010,22:29-33.
[4]刘述梅,赵建青,叶华.聚烯烃塑料改性的研究进展[J].石油化工,2007,36(7):645-652.
[5]方园园,于鲁强,李如贤.聚烯烃嵌段共聚物技术的研究进展[J].石油化工,2014,43(8):861-869.
[6]曹艳霞,樊卫华,王经武,等.辐照对PP、EPDM及其共混物动态流变行为的影响[J].塑料工业,2007,35(9):41-43.
[7]彭志宏,唐昌伟,张旭文.丙烯基弹性体对聚丙烯增韧改性的研究[J].合成材料老化与应用,2015,44(5):11-14.
[8]AL-MALAIKA S.Oxidative degradation and stabilistation of polymers[J].Int Mater Rev,2003,48(3):165-185.
[9]APOSTOLOV A A,DJOUMALIISKY S.Some practical aspects of the oxidative stability of polypropylene pipes[J].Mater Sci Appl,2014,5:579-591.
[10]PETERSON J D,VYAZOVKIN S,WIGHT C A.Kinetics of the thermal and thermo-oxidative degradation of polystyrene,polyethylene and poly(propylene)[J].Macromol Chem Phys,2001,202:775-784.
[11]GEORGE G A,CELINA M,VASSALLO A M,et al.Real-time analysis of the thermal oxidation of polyolefins by FT-IR emission[J].Polym Degrad Stab,1995,48(2):199-210.
[12]CORRALES T A,CATALINA F A,PEINADO C A,et al.Photooxidative and thermal degradation of polyethylenes:Interrelationship by chemiluminescence,thermal gravimetric analysis and FTIR data[J].J Photochem Photobiol A:Chem,2002,147:213-224.
[13]王帅,王克俭,马伊,等.动态流变法表征聚丙烯复合材料中粒子的分散效果[J].塑料工业,2017,45(7):85-88.
[14]谭宁,段文锋,毛炳权,等.聚丙烯/聚烯烃弹性体三元共混物的动态流变行为及其相容性[J].石油化工,2017,46(7):896-901.
[15]常杰云,张帆.Nano-CaCO3/HDPE复合材料流变性能的研究[J].塑料工业,2012,40(4):99-101.
[16]YANG K,YU W,ZHOU C X.Thermal oxidation of metallocene-catalyzed poly(ethylene ctane)by a rheological method[J].J Appl Polym Sci,2007,105:846-852.
[17]曹艳霞,郑强,杜淼.EPDM受热氧化与动态流变行为[J].高分子学报,2005(3):408-412.
[18]FERRARA G,BERTOLDO M,SCOPONI M,et al.Diffusion coefficient and activation energy of Irganox 1010 in poly(propylene-co-ethylene)copolymers[J].Polym Degrad Stab,2001,73:411-416.