采用熔融密炼接枝工艺,以三元乙丙橡胶(EPDM)为基体,低分子量液体丁苯橡胶(LSBR)为接枝物,制备了接枝聚合物EPDM-g-LSBR,研究了制备条件对接枝聚合物红外光谱和热失重行为的影响;将EPDM-g-LSBR作为相容剂用于EPDM/SBR的增容性共混,并与常用的商业化嵌段聚合物乙烯-乙酸乙烯酯(EVM)和苯乙烯-乙烯-丙烯-苯乙烯嵌段共聚物(SEPS)的增容效果进行了对比,研究了其用量对并用胶硫化特性和硫化胶力学性能的影响。结果表明,LSBR接枝到EPDM分子主链上,接枝量的变化未对产物的热降解温度造成显著影响;接枝物EPDM-g-LSBR增容后EPDM/SBR并用胶力学性能有明显改善,添加8份时,材料的拉伸强度和断裂伸长率比未添加相容剂的体系提高了24.3%和15%,邵A硬度由未添加的75.4降低到72.6。通过对混炼胶的断面进行扫描电镜分析发现EPDM-g-LSBR的加入使EPDM在SBR中的海岛分散结构消失,增加了两相的相容性。
The graft polymer EPDM-g-LSBR was prepared by melt blending grafting process with ethylene-propylene-diene monomer (EPDM) as matrix and low molecular weight liquid styrene butadiene rubber (LSBR) as graft.The effects of preparation conditions on the infrared spectrum and thermogravimetric behavior of the grafted polymers were studied.EPDM-g-LSBR was used as a compatibilizer for the compatibilization of EPDM/SBR blends,and the compatibilization effects of EPDM-g-LSBR were compared with those of the commonly used commercial block polymers,ethylene-vinyl acetate copolymer rubber (EVM) and styrene-ethylene-propylene-styrene block copolymer (SEPS).The effects of its dosage on the vulcanization characteristics of the blends and the mechanical properties of the vulcanizate were investigated.Infrared spectrum showed that LSBR was successfully grafted onto the main chain of EPDM,and the change of grafting amount of LSBR had no significant effect on the thermal degradation temperature of the products.The mechanical properties of EPDM/SBR blends were significantly improved after adding EPDM-g-LSBR.When the content of EPDM-g-LSBR reached 8 phr,the tensile strength and elongation at break of EPDM/SBR vulcanizate were 24.3% and 15% higher than those of the system without compatibilizer,respectively,and the Shore A hardness decreased from 75.4 to 72.6.By scanning electron microscopy analysis of the fracture surface of the compound,it was found that the addition of EPDM-g-LSBR eliminated the island dispersion structure of EPDM in SBR and increased the compatibility of the two phases.
[1] 殷俊,陈朝霞,艾书伦,等.三元乙丙橡胶共混改性的研究进展[J].合成橡胶工业,2015,38(3):244-248.
[2] 肖建斌,唐梓铭,王晗,等.EVM/EPDM无卤阻燃橡胶材料的制备及性能[J].弹性体,2021,31(3):27-31.
[3] 毛泽誉,胡瀚中,刘岩,等.PBT/EPDM/EPDM-g-GM共混物的形态与性能研究[J].塑料工业,2020,48(5):145-149.
[4] 王明超,王敏,周俊,等.笼型八乙烯基POSS改性EPDM的热稳定性[J].弹性体,2019,29(3):23-26.
[5] 程超,宋唯,史明学,等.三元乙丙橡胶共混改性研究进展[J].世界橡胶工业,2015,42(10):33-38.
[6] 文华银,张文焕,刘涛,等.白炭黑粒子对三元乙丙橡胶硫化性能、黏弹性及泡孔结构的影响[J].材料工程,2021,49(3):100-106.
[7] Bak K M,Kumar G R,Ramasamy N,et al.Experimental and numerical studies on the mechanical characterization of EPDM/S-Sbr nano clay composites[J].IOP Conference Series:Materials Science and Engineering,2020,912(5):52016-52027.
[8] Ayatollahi M R,Heydari-Meybodi M,Berto,et al.Mixed-mode fracture in EPDM/SBR/nanoclay rubber composites:an experimental and theoretical investigation[J].Composites,2019,176(1):107312-107324.
[9] 王飞云.EPDM橡胶的性能影响材料分析[J].橡塑技术与装备,2016,42(6):30-31.
[10] 齐兴国,王进,刘光烨,等.化学改性三元乙丙橡胶在聚合物中的应用研究概况[J].弹性体,2006,16(6):69-73.
[11] 朱宝宁,李方山,章于川.丙烯腈接枝三元乙丙橡胶共聚物增容三元乙丙橡胶/丁腈橡胶共混胶的性能[J].合成橡胶工业,2016,39(3):21-26.
[12] 李海东,程凤梅,罗靖,等.熔融法制备EPDM-g-GMA及其对PEN脆韧转变的研究[J].工程塑料应用,2004,32(12):8-10.
[13] 宋义虎,杜淼,杨红梅,等.橡胶材料的结构与黏弹性[J].高分子学报,2013(9):1115-1130.
[14] Deng F Q,Jin H,Zhang L,et al.Higher tear strength of EPDM/SBR/TPR composites foam based on double foaming system[J].Elastomer Plast,2021,53(5):373-385.
[15] 李方山,管华平,杨兆苇,等.三元乙丙橡胶/丁腈橡胶并用胶增容剂丙烯腈接枝三元乙丙橡胶共聚物的研制[J].橡胶科技,2017,15(5):15-18.
[16] 杨永清,马宇翔,王小龙.生胶结构参数对三元乙丙橡胶性能的影响[J].中国粉体技术,2021,27(2):87-95.
[17] Vishvanathperumal S,Gobiraman A.Effect of nanoclay/nanosilica on the mechanical properties,abrasion and swelling resistance of EPDM/SBR composites[J].Silicon,2020,12(8):1925-1941.
[18] 彭雪丽.次磺酰胺类促进剂对EPDM/SBR并用胶性能的影响[J].世界橡胶工业,2002,29(3):2-7.
[19] 赵义平,李树才,揣成智.反应性共混体系研究进展[J].中国塑料,2000,14(9):8-13.
[20] 唐若谷,黄兆阁,赵宗超.高分子合金相容剂的研究进展[J].高分子通报,2012,10(12):8-11.
[21] Estagy S,Movahed S O,Yazdanbakhsh S,et al.A novel chemical technique for compatibility of ethylene-propylene-diene monomer rubber and styrene-butadiene rubber in their blends[J].Elastomer Plast,2017,49(4):298-314.
[22] Park G,Kim Y H,Kim D S,et al.Morphology and vulcanizate properties of ethylene-propylene-diene rubber/styrene-butadiene rubber blends[J].Journal of Nanoscience and Nanotechnology,2010,10(5):3720-3722.
[23] 于晓飞,张勇,王晋园.相容剂对SBR/EPDM共混体系的性能影响研究[J].橡塑技术与装备,2018,44(13):9-13.
[24] 瞿雄伟,商淑瑞,刘国栋,等.丙烯腈-三元乙丙橡胶-苯乙烯接枝共聚物的合成与表征[J].高分子材料科学与工程,2002,18(5):104-107.
[25] 徐建平,刘涛涛,承民联,等.无水AlCl3作用下EPDM的交联与接枝性能[J].高分子材料科学与工程,2009,25(6):70-73.
[26] 傅志昂,王亨缇,董文勇,等.反应性杂化纳米粒子的合成及其对不相容共混物的增容研究[J].高分子学报,2017(2):334-341.
[27] Mechbal N,Bousmina M.Effect of copolymer addition on drop deformation during uniaxial elongation and during relaxation after cessation of flow[J].Macromolecules,2007,40(4):967-975.
[28] 赵雪燕,黄亚江,李光宪.共聚物增容剂对高分子共混物形态与流变行为的影响[J].高分子通报,2014(6):25-31.
[29] 焦淑瑞,徐建平.Friedel-Crafts烷基化反应就地增容PS/EPDM合金[J].常州大学学报(自然科学版),2011,23(1):5-8.
