聚乙烯蜡的制备及其改性研究
摘要
聚乙烯蜡及改性聚乙烯蜡作为精细化工产品用途广泛,社会需求也逐年增加,因而由不同类型聚乙烯制备聚乙烯蜡和研究聚乙烯蜡的改性有着重要的经济和环保意义。
本文首先以纯净聚乙烯和废旧聚乙烯为原料,利用高压反应釜热裂解制备聚乙烯蜡,考察了反应温度、反应时间、催化剂、搅拌和氧等因素对裂解产物的影响。实验表明：采用铅负载量为2.5%的Pb-ZSM-5分子筛为催化剂,添加量为0.5%,在380℃下反应4个小时并缓慢搅拌,所得两种聚乙烯蜡产品综合性能较好,外观呈淡黄色和黄色,相对粘均分子量分别为1958、1668,滴熔点分别为106℃、103℃,针入度分别为10.8×10-1mm、12.9×10-1mm。
其次,对聚乙烯蜡进行了接枝改性,通过将马来酸酐接枝到聚乙烯蜡上以提高聚乙烯蜡的极性,增强其与极性物质的相容性。实验结果表明：当SF-A和SF-O两种引发剂以摩尔比1：1比例复配,复配用量为1g,并添加其它助剂组成氧化还原体系引发剂,总用量2.5g,接枝单体MAH用量为3g,反应温度为160℃,反应时间为3h时,得到了较好的接枝蜡产品,产品酸值为57.36mgKOH·g-1,接枝率达到9.40%。
最后,对聚乙烯蜡进行了氧化硬质改性。实验结果表明：采用非过渡型金属催化剂CAT-3,在空气用量10dmm3.min-1、反应温度170。C、反应时间8.5h,激发剂EMP-3用量l0g条件下对聚乙烯蜡进行氧化改性,制备出酸值为18.86mgKOH·g-1,针入度为6.25×10-1mm,具有较好性能的氧化聚乙烯蜡产品。经过进一步钙化改性,所得产品硬度进一步提高,针入度达到2.63×10-1mm。
As a kind of fine chemical products, PEW and modified PEW have a wide application and market prospects, so the study of producing PEW from waste polythene and PEW chemical modification has an important economic and environmental significance.
The first experiment involves producing PEW from pure polythene and waste polythene. The optimum reaction conditions are obtained by examining the effect of several parameters in the cracking process. The best experiment results are as below:catalyst 2.5%Pb-ZSM-5 amount:0.5%, reaction temperature:380℃,reaction time:4h, two kinds of PEW produced from pure polythene and waste polythene are obtained, whose appearance are light yellow and yellow, molecular weight are 1958 and 1668, drop melting point are 106℃、103℃, needle penetration are 10.8×10-1mm and 12.9×10-1mm.
The second experiment is the graft modification of PEW, from which we can improve and enhance its compatibility with polar material. By using the initiator of mixed SF-A and SF-C, when the amount of maleic anhydride is 3g, reaction temperature is 160℃, reaction time is 3h, the acid value and graft degree of the product can reach 52.73mgKOH·g-1 and 8.62%.
The last experiment is the research of oxidized polythene and its rigid transformation. We discussed the effects of catalyst, air amount, reaction time, reaction temperature, activator and obtained a kind of product of oxidized polythene, whose acid value was 18.86 mgKOH·g-1.Using this oxidized polythene as raw material, by adding different amount of Ca(OH)2, we produced modified oxidized polythene. The hardness of final products enhanced and its needle penetration reached 2.63×10-1mm.
本文首先以纯净聚乙烯和废旧聚乙烯为原料,利用高压反应釜热裂解制备聚乙烯蜡,考察了反应温度、反应时间、催化剂、搅拌和氧等因素对裂解产物的影响。实验表明：采用铅负载量为2.5%的Pb-ZSM-5分子筛为催化剂,添加量为0.5%,在380℃下反应4个小时并缓慢搅拌,所得两种聚乙烯蜡产品综合性能较好,外观呈淡黄色和黄色,相对粘均分子量分别为1958、1668,滴熔点分别为106℃、103℃,针入度分别为10.8×10-1mm、12.9×10-1mm。
其次,对聚乙烯蜡进行了接枝改性,通过将马来酸酐接枝到聚乙烯蜡上以提高聚乙烯蜡的极性,增强其与极性物质的相容性。实验结果表明：当SF-A和SF-O两种引发剂以摩尔比1：1比例复配,复配用量为1g,并添加其它助剂组成氧化还原体系引发剂,总用量2.5g,接枝单体MAH用量为3g,反应温度为160℃,反应时间为3h时,得到了较好的接枝蜡产品,产品酸值为57.36mgKOH·g-1,接枝率达到9.40%。
最后,对聚乙烯蜡进行了氧化硬质改性。实验结果表明：采用非过渡型金属催化剂CAT-3,在空气用量10dmm3.min-1、反应温度170。C、反应时间8.5h,激发剂EMP-3用量l0g条件下对聚乙烯蜡进行氧化改性,制备出酸值为18.86mgKOH·g-1,针入度为6.25×10-1mm,具有较好性能的氧化聚乙烯蜡产品。经过进一步钙化改性,所得产品硬度进一步提高,针入度达到2.63×10-1mm。
As a kind of fine chemical products, PEW and modified PEW have a wide application and market prospects, so the study of producing PEW from waste polythene and PEW chemical modification has an important economic and environmental significance.
The first experiment involves producing PEW from pure polythene and waste polythene. The optimum reaction conditions are obtained by examining the effect of several parameters in the cracking process. The best experiment results are as below:catalyst 2.5%Pb-ZSM-5 amount:0.5%, reaction temperature:380℃,reaction time:4h, two kinds of PEW produced from pure polythene and waste polythene are obtained, whose appearance are light yellow and yellow, molecular weight are 1958 and 1668, drop melting point are 106℃、103℃, needle penetration are 10.8×10-1mm and 12.9×10-1mm.
The second experiment is the graft modification of PEW, from which we can improve and enhance its compatibility with polar material. By using the initiator of mixed SF-A and SF-C, when the amount of maleic anhydride is 3g, reaction temperature is 160℃, reaction time is 3h, the acid value and graft degree of the product can reach 52.73mgKOH·g-1 and 8.62%.
The last experiment is the research of oxidized polythene and its rigid transformation. We discussed the effects of catalyst, air amount, reaction time, reaction temperature, activator and obtained a kind of product of oxidized polythene, whose acid value was 18.86 mgKOH·g-1.Using this oxidized polythene as raw material, by adding different amount of Ca(OH)2, we produced modified oxidized polythene. The hardness of final products enhanced and its needle penetration reached 2.63×10-1mm.
引文
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[2]Vasile C, Seymour B. Handbook of Polyolefines[M].Marcel Dekker.1993
[3]吴今坤.聚烯烃的表面改性[J].化工新型材料.1996,7：1-8
[4]周锟,孙可伟.废旧聚乙烯的再生处理技术[J].再生资源研究.2005,6(2)：12-17
[5]约翰.沙伊斯.聚合物回收[M].化学工业出版社.2002
[6]Audet C, Langlet B.Plastic Waste Management[M]. Disposal Recycling and Reuse (Mustafa N ed.).New York:Marcel Dekker.1993,141
[7]李国辉.废塑料裂解制液体燃料和化学品技术开发进展[J].化学进展.1996,8(2)：162-172
[8]肖进新,赵振国.表面活性剂应用原理[M].化学工业出版社.2003
[9]盛兴.聚乙烯蜡、聚氧化聚乙烯蜡生产应用及其粘均分子量的测定[J].湖北化工.1998,25(6)：34-35
[10]赵秀英,冯磊,胡伟康等.低相对分子量聚乙烯的热稳定性探讨[J].中国塑料.2000,14(7)：86-89
[11]张庆余,韩孝族,纪奎江.低聚物[M].科学出版社.1994：39-40
[12]S-Rev J M. Functional Modification of Polypropylene [J]. Macromol Chem Phys.2005, (34):555-606
[13]姚树君.催化裂解工艺的研究与发展[M]油气田地面工程.2004,23(2)：54
[14]瓦塞尔.聚烯烃手册[M].中国石化出版社.2005
[15]周茜.聚乙烯催化裂解产物控制与机理研究[J].燃料化学学报.2003,3
[16]齐萍.废旧聚乙烯非高温催化催化裂解研究[D].南昌大学.2007
[17]Kazuo Koizumi, Yusaku Sakata eds. Thermal and Catalytic Degradation of High and Low Density Polyethylene into Fuel Oil [C].The 5th World Congress of Chemical and Engineering. California,1996
[18]陈作义,潘朝群,江涛.聚乙烯蜡的研究进展与工业生产方法探讨[J].辽宁化工.2004,33(8)：474-476.
[19]区锦波,周卓荣.一种热降解制取聚乙烯蜡的装置[P].中国.2680664Y.2005
[20]卓寿镛,陈湘君.高效快开裂解釜[P].中国.200720187255.2007
[21]刘家琏.国内外石蜡和专用石蜡市场分析与预测[J].石油化工动态.1995,(10)：11-14
[22]Hagemeyer H J.Addition products of thermally degraded polyethylene[P].US,2811514. 1957
[23]Aguado, J. Sotelo, J.L. Se'ano,.Catalytic Conversion of Polyolefius into Liquid Fuels over MCM-41:Comparison with ZSM-5 and Amorphous SiO2-A1203 [J].Energy & Fuels.1997,11(6):1225-1231
[24]Ohkita H, Nishiyama R, Tochihara Y, et al.Acid Properties of sisica-alumina catalysts andcatalytic degradation of polyethylene[J].Ind.Eng.Chem.Res.1993,32:3112-3116
[25]A.Garforth, S.Fiddy, Y-H.Lin, A.Ghanbari·Siakhali, P.N.Sharratt and J.Dwyen Catalytic degradation of high density polyethylene:An evaluation of mesoporous and micropomus catalysts using thermal analysis[J].Thermoehimiea Aeta.1997,294(1): 65-69
[26]Zaki S.Seddegi, Uwais Budrthumal, Abdulrahman A.AI-Arfaj, Adnan M.AI-Amer and Sami A.L Barri.Catalytic cracking of polyethylene over all-silica MCM-41 molecular sieve [J].Applied Catalysis A:General.2002,225(1-2):167-176
[27]D.P.Serrano, J.Aguedo, J.M.Escola and E.Garagorri.Performance ofa continuous Screw kiln reactor for the thermal and catalytic conversion of polyethylene-lubricating oil base mixtures [J]. Applied Catalysis B:Environmental.2003,44(2):95-105
[28]常春,章武阳,张丽华等.微波辐射下稀土交换ZSM-5分子筛制各及裂解反应研究[J].高等学校化学学报.1996,12：1914-1917
[29]杨震,江勇,王世明等.废聚苯乙烯热降解回收苯乙烯单体的研究[J].环境科学.1997,18(2)：43-45
[30]许金生,张春华,谭雄文等.固体超强酸催化降解废旧聚乙烯制燃料油的研究[J].化学工程师.2009,9：9-12
[31]谢芳菲,刘福胜,解从霞.中孔分子筛Al-MCM-41的制备及催化聚乙烯裂解反应[J].青岛科技大学学报(自然科学版).2007
[32]孙载坚,周普,刘启澄.接枝共聚合[M].化学工业出版社.1989
[33]曹同玉,刘庆普,胡金生等.聚合物乳液合成原理性能及应用(第二版)[M].化学工业出版社.2007
[34]Moad G. The synthesis of polyolefin graft copolymers by reactive extrusion.ProPolym Sci.1999,24(1):81-142
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