以助交联剂为第二单体的聚丙烯熔融接枝反应
|
摘要
以助交联剂三烯丙基异氰尿酸酯(TAIC)或三聚氰酸三烯丙酯(TAC)作为聚丙烯(PP)熔融接枝马来酸酐(MAH)过程中的第二单体制备PP-g-MAH,与苯乙烯、丙烯酸、甲基丙烯酸甲酯等常用的第二单体进行了对比,对其反应机理进行了探讨;以TAIC为例,研究了其用量对PP-g-MAH接枝率、熔体流动速率(MFR)等性能的影响。结果表明,与苯乙烯等第二单体相比,以助交联剂TAIC或TAC为第二单体,制备的PP-g-MAH接枝率更高,MFR更低,且未产生刺激性气味;在MAH用量不变的条件下,当TAIC用量(占PP-g-MAH中PP质量的百分数)由0%增加至0.5%时,接枝率由0.36%增至0.85%,MFR由95.7 g/10 min降至38.2 g/10 min。将制备的PP-g-MAH应用于PP/玻璃纤维(GF)复合材料和PP/尼龙(PA)6合金中,结果表明,随TAIC用量增加,两种材料的力学性能整体提高,TAIC用量以0.5%为宜。在PP/GF/PP-g-MAH质量比为70/30/0.7或PP/PA6/PP-g-MAH质量比为20/70/10时,与未加TAIC的相比,PP/GF复合材料的冲击强度、弯曲强度和弯曲弹性模量分别提升了10.9%,20.8%和17.7%,PP/PA6合金的断裂伸长率、冲击强度、弯曲强度和弯曲弹性模量分别提升了42.9%,8%,12.9%和8.8%。
During the melt grafting of maleic anhydride(MAH) onto polypropylene(PP),the co-crosslinking agent triallyl isocyanurate(TAIC) or trimethylene cyanurate(TAC) were added as the second monomer for preparing PP-g-MAH,which were compared with the common second monomers such as styrene,acrylic acid and methyl methacrylate,and the reaction mechanism was discussed. Taking TAIC as an example,the effects of TAIC content on the grafting rate,melt flow rate(MFR) and other properties of PP-g-MAH were studied. The results show that,compared with the second monomer such as styrene,the grafting rate of PPg-MAH is higher,the MFR is lower,and no irritation odor is produced by using TAIC or TAC as the second monomer. The grafting rate increases from 0.36% to 0.85% when the TAIC content(the percentage of PP mass in PP-g-MAH) increases from 0% to 0.5% with constant content of MAH,the MFR decreases from 95.7 g/10 min to 38.2 g/10 min. The prepared PP-g-MAH was used in PP/glass fiber(GF) composite and PP/nylon(PA) 6 alloys. The results show that with the increase of TAIC content, the mechanical properties of both materials are improved as a whole,the TAIC content of 0.5% is appropriate. Compared with non-TAIC,when the mass ratio of PP/GF/PP-g-MAH is 70/30/0.7,the impact strength,flexural strength and flexural modulus of PP/GF composites increase 10.9%,20.8% and 17.7% respectively,when the mass ratio of PP/PA6/PP-g-MAH is 20/70/10,the elongation at break,impact strength,flexural strength and flexural modulus of the alloy increase 42.9%,8%,12.9% and 8.8% respectively.
During the melt grafting of maleic anhydride(MAH) onto polypropylene(PP),the co-crosslinking agent triallyl isocyanurate(TAIC) or trimethylene cyanurate(TAC) were added as the second monomer for preparing PP-g-MAH,which were compared with the common second monomers such as styrene,acrylic acid and methyl methacrylate,and the reaction mechanism was discussed. Taking TAIC as an example,the effects of TAIC content on the grafting rate,melt flow rate(MFR) and other properties of PP-g-MAH were studied. The results show that,compared with the second monomer such as styrene,the grafting rate of PPg-MAH is higher,the MFR is lower,and no irritation odor is produced by using TAIC or TAC as the second monomer. The grafting rate increases from 0.36% to 0.85% when the TAIC content(the percentage of PP mass in PP-g-MAH) increases from 0% to 0.5% with constant content of MAH,the MFR decreases from 95.7 g/10 min to 38.2 g/10 min. The prepared PP-g-MAH was used in PP/glass fiber(GF) composite and PP/nylon(PA) 6 alloys. The results show that with the increase of TAIC content, the mechanical properties of both materials are improved as a whole,the TAIC content of 0.5% is appropriate. Compared with non-TAIC,when the mass ratio of PP/GF/PP-g-MAH is 70/30/0.7,the impact strength,flexural strength and flexural modulus of PP/GF composites increase 10.9%,20.8% and 17.7% respectively,when the mass ratio of PP/PA6/PP-g-MAH is 20/70/10,the elongation at break,impact strength,flexural strength and flexural modulus of the alloy increase 42.9%,8%,12.9% and 8.8% respectively.
引文
[1]王雅珍.聚丙烯接枝马来酸酐相容剂:CN1456430A[P].2003-11-09.Wang Yazhen.Compatilizer for graft copolymerization of polypropylene with maleic anhydride:CN1456430A[P].2003-11-09.
[2]徐冬,徐永,马旭辉.一种熔融挤出低气味PP接枝马来酸酐及其制备方法:CN101942061A[P].2011-01-12.Xu Dong,Xu Yong,Ma Xuhui.A melting extruded lowsmell maleic anhydride grafted PP and preparation method thereof:CN101942061A[P].2011-01-12.
[3]刘轶群,郭敏.一种马来酸酐接枝的聚丙烯树脂接枝物的制备方法:CN101724128A[P].2010-06-09.Liu Yiqun,Gou Min.A preparation method of maleic anhydride grafted polypropylene resin grafting polymer:CN101724128A[P].2010-06-09.
[4]黄金勇,倪青林,范家起.一种马来酸酐接枝聚丙烯材料及其制备方法:CN101357968A[P].2009-02-04.Huang Jinyong,Ni Qinglin,Fan Jiaqi.A maleic anhydride grafted polypropylene material and preparation method thereof:CN101357968A[P].2009-02-04.
[5]Cartie H,Hu Guohua.Styrene-assisted free radical grafting of glycidyl methaacrylate onto polyethylene in the melt[J].Journal of Polymer Science:Part A:Polymer Chemistry,1998,36:2 763–2 774.
[6]刘晶如,许淑义,俞强.马来酸酐/苯乙烯熔融接枝无规共聚聚丙烯的流变及结晶行为[J].高校化学工程学报,2017,31(2):428–433.Liu Jingru,Xu Shuyi,Yu Qiang.Rheology and crystallization of maleic anhydride/styrene melt grafted random copolypropylene[J].Journal of Chemical Engineering of Chinese Universities,2017,31(2):428–433.
[7]Li Ying,Xie Xuming,Guo Baohua.Study on styrene-assisted melt free-radical grafting of maleic anhydride onto polypropylene[J].Polymer,2001,42:3 419–3 425.
[8]Gaylord N G,Mehta M.Role of homopolymerization in the peroxide catalyzed reaction of anhydride and polyethylene in the absence of solvent[J].J Polym Sci,1982,20(9):481–486.
[9]Liu N C,Baker W E,Rusell K E.Functionalization of polyethylenes and their use in reactive blending[J].J Appl Polym Sci,1990,41(9–10):2 285–2 300.
[10]Anita S,Joan M,Rusell K E.Kinetic studies of grafting of maleic anhydride to hydrocarbon substtates[J].J Polym Sci Part A:Polym Chem,1989,27(10):3 353–3 362.
[11]Gaylord N G,Mishra M K.Nondegradative reaction of maleic anhydride and molten polypropylene in the presence of peroxide[J].J Polym Sci:Polym Lett Ed,1983,21(11):23–30.
[12]Roover B D,Sdavons M,Carher V,et al.Molecular characterization of maleic anhydride functionalized polypro-pylene[J].J Polym Sci Part A:Polym Chem,1995,33(5):829–842.
[13]Heinen W,Roseraoller C H,Wenze1 C B,et al.13C–NMR study of the grafting of maleic anhydride onto polyethene,polypropene and ethene-propene copolymer[J].Macromolecules,1996,29(4):1 151–1 157.
[2]徐冬,徐永,马旭辉.一种熔融挤出低气味PP接枝马来酸酐及其制备方法:CN101942061A[P].2011-01-12.Xu Dong,Xu Yong,Ma Xuhui.A melting extruded lowsmell maleic anhydride grafted PP and preparation method thereof:CN101942061A[P].2011-01-12.
[3]刘轶群,郭敏.一种马来酸酐接枝的聚丙烯树脂接枝物的制备方法:CN101724128A[P].2010-06-09.Liu Yiqun,Gou Min.A preparation method of maleic anhydride grafted polypropylene resin grafting polymer:CN101724128A[P].2010-06-09.
[4]黄金勇,倪青林,范家起.一种马来酸酐接枝聚丙烯材料及其制备方法:CN101357968A[P].2009-02-04.Huang Jinyong,Ni Qinglin,Fan Jiaqi.A maleic anhydride grafted polypropylene material and preparation method thereof:CN101357968A[P].2009-02-04.
[5]Cartie H,Hu Guohua.Styrene-assisted free radical grafting of glycidyl methaacrylate onto polyethylene in the melt[J].Journal of Polymer Science:Part A:Polymer Chemistry,1998,36:2 763–2 774.
[6]刘晶如,许淑义,俞强.马来酸酐/苯乙烯熔融接枝无规共聚聚丙烯的流变及结晶行为[J].高校化学工程学报,2017,31(2):428–433.Liu Jingru,Xu Shuyi,Yu Qiang.Rheology and crystallization of maleic anhydride/styrene melt grafted random copolypropylene[J].Journal of Chemical Engineering of Chinese Universities,2017,31(2):428–433.
[7]Li Ying,Xie Xuming,Guo Baohua.Study on styrene-assisted melt free-radical grafting of maleic anhydride onto polypropylene[J].Polymer,2001,42:3 419–3 425.
[8]Gaylord N G,Mehta M.Role of homopolymerization in the peroxide catalyzed reaction of anhydride and polyethylene in the absence of solvent[J].J Polym Sci,1982,20(9):481–486.
[9]Liu N C,Baker W E,Rusell K E.Functionalization of polyethylenes and their use in reactive blending[J].J Appl Polym Sci,1990,41(9–10):2 285–2 300.
[10]Anita S,Joan M,Rusell K E.Kinetic studies of grafting of maleic anhydride to hydrocarbon substtates[J].J Polym Sci Part A:Polym Chem,1989,27(10):3 353–3 362.
[11]Gaylord N G,Mishra M K.Nondegradative reaction of maleic anhydride and molten polypropylene in the presence of peroxide[J].J Polym Sci:Polym Lett Ed,1983,21(11):23–30.
[12]Roover B D,Sdavons M,Carher V,et al.Molecular characterization of maleic anhydride functionalized polypro-pylene[J].J Polym Sci Part A:Polym Chem,1995,33(5):829–842.
[13]Heinen W,Roseraoller C H,Wenze1 C B,et al.13C–NMR study of the grafting of maleic anhydride onto polyethene,polypropene and ethene-propene copolymer[J].Macromolecules,1996,29(4):1 151–1 157.