LLDPE专用料的交联行为研究
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摘要
本文采用过氧化物交联方法对线性低密度聚乙烯/乙烯-α-辛烯共聚物进行了共混改性研究。
在双螺杆挤出机中对LLDPE和POE进行低温加工时,由于较强的加工剪切作用,温度升高现象比较明显,温度不易控制。应用双螺杆挤出机进行低温加工时,主机加热的稳定时间、机头温度、投料转速和螺杆转速均对熔体温度有较大的影响。不同双螺杆挤出机螺杆的长径比也是影响加工的主要因素,通常选择螺杆长径比较小的螺杆进行加工。过氧化物交联结果表明,在过氧化物交联反应中LLDPE和POE的凝胶含量随引发剂用量、交联时间的增加而增加,在达到一定量和一定时间后即可满足交联反应要求。
通过LLDPE和POE不同共混比例组成的共混物的力学性能的变化情况可以看出,LLDPE/POE随着POE在总组分中百分比的增加而冲击强度依次降低。LLDPE/POE/1.5%DCP的冲击强度与LLDPE/1.5DCP.POE冲击强度相比较有一定的升高。但升高的幅度并不十分明显。
在双辊开炼机中对LLDPE/POE共混物进行共混改性。研究了工艺、配方对LLDPE/POE共混物凝胶含量的影响,以及凝胶含量与材料力学性能的关系。结果表明,LLDPE/POE共混物的凝胶含量随引发剂的用量、交联温度和交联时间的增加而增加,达到一定程度后不再增加。在170℃,30min的条件下DCP能充分分解引发交联反应,DCP用量为1.5%时,共混物的凝胶含量可以达到80%以上,再增加时凝胶含量不再增加。DCP的加入顺序对共混物的凝胶含量影响不大。共混物的凝胶含量对其动态力学行为有影响。共混物的凝胶含量对拉伸性能和硬度影响不大。
In this paper the crosslinking behavior of linear low density poly ethylene (LLDPE)/ Poly (octylene ethylene) copolymer (POE) blends were studied by peroxide crosslinking.
While LLDPE and POE were processed in twin screw extruder in low temperature, the rising of temperature was obviously and not easy to control due to the strong effect of shearing process.when we process in twin screw extruder at low temperature. It was more effect in melt temperature by the stabilizationg of mainframe heating、machine head temperature、feed speed and screw speed. One of the main factors during process was the different length-diameter ratio of twin screw extruder.we selected low length-diameter ratio screw stem to process generally. Peroxide crosslinking results showed that the gel fraction of crosslinked LLDPE and POE increased with the content of initiator and the vulcanization time. And the gel fraction of crosslinked LLDPE was enough at certain value and certain time.
Through the change of mechanical property that blends of different blend proportion. We could see that the impact-strength of LLDPE/POE decreased with the percent of POE increasing in total constituents. Compared with the impact strength of LLDPE/1.5DCP.POE. The blend of LLDPE/POE/1.5DCP was better but the degree of rising was not obviously.
The LLDPE/POE blends were studied in Shuangkun open mill. The effect of peroxide proportion and processing technology on gel fraction of crosslinked LLDPE/POE blends and the relationship between gel fraction and the mechanical properties of compound were investigated. The results showed that the gel fraction of LLDPE/POE blends increased with the content of dicumyl peroxide (DCP)、vulcanization time and the incremental of crosslinking time and reached maximum at a certain value. The gel fraction of blends showed no difference with different feeding sequence of DCP. Dynamic mechanical thermal analysis (DMTA) behavior of blends was influenced by the gel fraction of blends. The gel fraction of blends showed no obvious effect on tensile behavior of blends.
在双螺杆挤出机中对LLDPE和POE进行低温加工时,由于较强的加工剪切作用,温度升高现象比较明显,温度不易控制。应用双螺杆挤出机进行低温加工时,主机加热的稳定时间、机头温度、投料转速和螺杆转速均对熔体温度有较大的影响。不同双螺杆挤出机螺杆的长径比也是影响加工的主要因素,通常选择螺杆长径比较小的螺杆进行加工。过氧化物交联结果表明,在过氧化物交联反应中LLDPE和POE的凝胶含量随引发剂用量、交联时间的增加而增加,在达到一定量和一定时间后即可满足交联反应要求。
通过LLDPE和POE不同共混比例组成的共混物的力学性能的变化情况可以看出,LLDPE/POE随着POE在总组分中百分比的增加而冲击强度依次降低。LLDPE/POE/1.5%DCP的冲击强度与LLDPE/1.5DCP.POE冲击强度相比较有一定的升高。但升高的幅度并不十分明显。
在双辊开炼机中对LLDPE/POE共混物进行共混改性。研究了工艺、配方对LLDPE/POE共混物凝胶含量的影响,以及凝胶含量与材料力学性能的关系。结果表明,LLDPE/POE共混物的凝胶含量随引发剂的用量、交联温度和交联时间的增加而增加,达到一定程度后不再增加。在170℃,30min的条件下DCP能充分分解引发交联反应,DCP用量为1.5%时,共混物的凝胶含量可以达到80%以上,再增加时凝胶含量不再增加。DCP的加入顺序对共混物的凝胶含量影响不大。共混物的凝胶含量对其动态力学行为有影响。共混物的凝胶含量对拉伸性能和硬度影响不大。
In this paper the crosslinking behavior of linear low density poly ethylene (LLDPE)/ Poly (octylene ethylene) copolymer (POE) blends were studied by peroxide crosslinking.
While LLDPE and POE were processed in twin screw extruder in low temperature, the rising of temperature was obviously and not easy to control due to the strong effect of shearing process.when we process in twin screw extruder at low temperature. It was more effect in melt temperature by the stabilizationg of mainframe heating、machine head temperature、feed speed and screw speed. One of the main factors during process was the different length-diameter ratio of twin screw extruder.we selected low length-diameter ratio screw stem to process generally. Peroxide crosslinking results showed that the gel fraction of crosslinked LLDPE and POE increased with the content of initiator and the vulcanization time. And the gel fraction of crosslinked LLDPE was enough at certain value and certain time.
Through the change of mechanical property that blends of different blend proportion. We could see that the impact-strength of LLDPE/POE decreased with the percent of POE increasing in total constituents. Compared with the impact strength of LLDPE/1.5DCP.POE. The blend of LLDPE/POE/1.5DCP was better but the degree of rising was not obviously.
The LLDPE/POE blends were studied in Shuangkun open mill. The effect of peroxide proportion and processing technology on gel fraction of crosslinked LLDPE/POE blends and the relationship between gel fraction and the mechanical properties of compound were investigated. The results showed that the gel fraction of LLDPE/POE blends increased with the content of dicumyl peroxide (DCP)、vulcanization time and the incremental of crosslinking time and reached maximum at a certain value. The gel fraction of blends showed no difference with different feeding sequence of DCP. Dynamic mechanical thermal analysis (DMTA) behavior of blends was influenced by the gel fraction of blends. The gel fraction of blends showed no obvious effect on tensile behavior of blends.
引文
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[2]Scott H QCrosslinking Method for Polyolefin with a Silane,[J].U. S. Patent,3646 155,1972.
[3]仇武林,方鲲,麦堪成,曾汉民.聚烯烃的硅烷交联技术,[J].高分子材料与工程,14(4)：136～139,1998.
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[5]潘祖仁.高分子化学,[M].化学工业出版社.
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[7]陈海文,陈兴茂等.辐射交联聚乙烯发泡卷材生产工艺技术关键,[J].辐射研究与辐射工艺学报,23(2)：111,2005.
[8]王全国,王秀芬.聚合物改性,[M].中国轻工业出版社.
[9]吴崇周.塑料加工原理及应用,[M].化学工业出版社.
[10]山西省化工研究所,塑料橡胶加工助剂,北京：[M].化学工业出版社,1997.
[11]叶蕊.实用塑料加工技术,[M].金盾出版社.
[12]杨明山,塑料改性工艺,配方与应用,[M].化学工业出版社.
[13]左瑞霖,张广成,何宏伟等.聚乙烯的硅烷交联技术进展,[J].塑料,29(6),2000.
[14]黄德骏.交联聚乙烯管的应用及评价方法,[J].现代塑料加工应用,(2)：45～48,1993.
[15]段景宽,罗炎,王亚珍.硅烷接枝交联聚乙烯技术,[J].桂林电子工业学院学报,(3)：45～48,2005.
[16]谢侃,张建耀等.硅烷交联聚乙烯电力电缆绝缘料基础树脂的性能,[J].高分子材料与工程,22(1),2006.
[17]Gerald Oster,Gisela K,Oster,Harold Moroson,Ultraviolet induced crosslinking and grafting of solid high polymers,[J] Journal of Polymer Science,34 (127): 671-6.
[18]刘春林,承民联,宋平生,何银坤.过氧化物交联聚乙烯的研究,[J].现代塑料加工应用,10(2)：14～17,1997.
[19]钱仲裕,夏荣秀.过氧化物交联的LDPE和LDPE/EVA, [J].塑料科技.1988.
[20]郭林敏,李珍馥.过氧化物交联聚乙烯管及其专用料性能研究,[J].塑料,31(4)：69～73,2002.
[21]R.根赫特,H.米勒.塑料添加剂手册,北京：[M].化学工业出版社,2000.
[22]辛忠.合成材料添加剂化学,[M].化学工业出版社.
[23]刘新民,杨金平,葛涛,[M].塑料,2003年03期.
[24]汉斯·茨魏费尔.塑料添加剂手册,[M].化学工业出版社.
[25]罗河胜.塑料工艺与实用配方,[M].广东科技出版社.
[26]龙文保,吴大鸣,刘颖.反应挤出硅烷交联聚乙烯热收缩管坯的研制,[J].塑料科技,(3)：3-6,1996.
[27]伊智生,杜建强.硅烷交联LDPE电缆料的研究,[J].中国工程塑料应用第一届年会论文集,(5)：98-104,1998.
[28]刘颖,龙文保,吴大鸣.硅烷交联聚乙烯管材生产过程中的化学反应及其主要影响因素,[J].塑料,(4)：29～32,2001.
[29]邓长胜,蒋佩南.[J].电线电缆报,(4)：15,1991.
[30]蒋佩南,邓长胜.交联电缆的发展动向与需求预测,[J].供用电,(1),1995.
[31]李晓东,甘理.硅烷交联聚乙烯铝塑复合管材的发展概况,[J].塑料,(5)：14～16,1999.
[32]Jay B. Class.过氧化物交联基础,[J].橡胶参考资料.2000,(30),2：24-29.
[33]曹正平,印哲夫.线性低密度电缆护套料的研制,[J].塑料科技.1998,(4)：37-38.
[34]陆小义,徐振明,李建峰.高性能LLDPE电缆护套的研制,[J].工程塑料应用.2005,(33),8：38-42.
[35]Banby B, Babek J F. ESR Spectorscopy in Polymer Research. [J].Berlin:Spring Verlag,1977.88.
[36]王雁冰,黄志维,张联盟.DMA在高分子材料研究中的应用,[J].国外建材科技.2004,(25),2：25-27.
[37]Pradip.Sonawane,S.Radhakrishnan,J.A.Bhangale,A.L.Gadhavi,AnaghaKhare.Dev elopment of Nanofibro us Morphology in LDPE/LLDPE/PP Blends and Its Effect on Mechanical Properties of Blend Films. [J]. Journal of Applied Polymer Science, Vol.107,4005-4012(2008).
[38]刘新民,许春霞,葛涛等.过氧化物交联聚乙烯的力学性能研究.[J].现代塑料加工应用.2003,(15),6：14-16.
[39]D.Abraham, K.E. George, D.J.Francis. Study on LDPE/LLDPE blends. [J]. Die Angewandte Makromolekulare Chemie 200(1992)15-25(Nr.3468).
[40]Daniel Abraham, K.E.George, D.Joseph Francis.Structure-Property-Processing Relationships in Chemically Modified LDPE and LDPE/LLDPE Blend. [J]. Journal of Applied Polymer Science, Vol.67,789-797(1998).
[41]Junwei Gu, Qiuyu Zhang,Jing Dang.Thermal Conductivity and Mechanical Properties of Aluminum Nitride Filled Linear Low-Density Polyethylene Composites. [J].Polymer Engineering And Science-2009.1031-1034.
[42]G.Guerrica-Echecarria, J.I.Eguiazabal,J.Nazabal. Structure and Mechanical Properties of Compatibilized Poly (ethylene terephthalate)/Poly (ethylene octane) Blends. [J].Polymer Engineering and Science-2006.172-180.
[43]Ibenelwaleed A.Hussein,Tayyab Hameed.Influence of Branching Characteristics on Thermal and Mechanical Properties of Ziegler-Natta and Metallocene Hexene LinearLow-Density Polyethylene Blends with Low-Density Polyethylene. [J] Journal of Applied Polymer Science, Vol.97,2488-2498(2005).
[2]Scott H QCrosslinking Method for Polyolefin with a Silane,[J].U. S. Patent,3646 155,1972.
[3]仇武林,方鲲,麦堪成,曾汉民.聚烯烃的硅烷交联技术,[J].高分子材料与工程,14(4)：136～139,1998.
[4]Wong W K, Varrall D C,Role of molecular structure on the silane crosslinking of polyethylene:the importance of resin molecular structure change during silane grafting,[J].Polymer,35 (25):5447-5452,1994.
[5]潘祖仁.高分子化学,[M].化学工业出版社.
[6]王睿,李树忠.聚合物辐射交联热收缩材料研究进展,[J].辐射研究与辐射工艺学报,21(3)：161～168,2003.
[7]陈海文,陈兴茂等.辐射交联聚乙烯发泡卷材生产工艺技术关键,[J].辐射研究与辐射工艺学报,23(2)：111,2005.
[8]王全国,王秀芬.聚合物改性,[M].中国轻工业出版社.
[9]吴崇周.塑料加工原理及应用,[M].化学工业出版社.
[10]山西省化工研究所,塑料橡胶加工助剂,北京：[M].化学工业出版社,1997.
[11]叶蕊.实用塑料加工技术,[M].金盾出版社.
[12]杨明山,塑料改性工艺,配方与应用,[M].化学工业出版社.
[13]左瑞霖,张广成,何宏伟等.聚乙烯的硅烷交联技术进展,[J].塑料,29(6),2000.
[14]黄德骏.交联聚乙烯管的应用及评价方法,[J].现代塑料加工应用,(2)：45～48,1993.
[15]段景宽,罗炎,王亚珍.硅烷接枝交联聚乙烯技术,[J].桂林电子工业学院学报,(3)：45～48,2005.
[16]谢侃,张建耀等.硅烷交联聚乙烯电力电缆绝缘料基础树脂的性能,[J].高分子材料与工程,22(1),2006.
[17]Gerald Oster,Gisela K,Oster,Harold Moroson,Ultraviolet induced crosslinking and grafting of solid high polymers,[J] Journal of Polymer Science,34 (127): 671-6.
[18]刘春林,承民联,宋平生,何银坤.过氧化物交联聚乙烯的研究,[J].现代塑料加工应用,10(2)：14～17,1997.
[19]钱仲裕,夏荣秀.过氧化物交联的LDPE和LDPE/EVA, [J].塑料科技.1988.
[20]郭林敏,李珍馥.过氧化物交联聚乙烯管及其专用料性能研究,[J].塑料,31(4)：69～73,2002.
[21]R.根赫特,H.米勒.塑料添加剂手册,北京：[M].化学工业出版社,2000.
[22]辛忠.合成材料添加剂化学,[M].化学工业出版社.
[23]刘新民,杨金平,葛涛,[M].塑料,2003年03期.
[24]汉斯·茨魏费尔.塑料添加剂手册,[M].化学工业出版社.
[25]罗河胜.塑料工艺与实用配方,[M].广东科技出版社.
[26]龙文保,吴大鸣,刘颖.反应挤出硅烷交联聚乙烯热收缩管坯的研制,[J].塑料科技,(3)：3-6,1996.
[27]伊智生,杜建强.硅烷交联LDPE电缆料的研究,[J].中国工程塑料应用第一届年会论文集,(5)：98-104,1998.
[28]刘颖,龙文保,吴大鸣.硅烷交联聚乙烯管材生产过程中的化学反应及其主要影响因素,[J].塑料,(4)：29～32,2001.
[29]邓长胜,蒋佩南.[J].电线电缆报,(4)：15,1991.
[30]蒋佩南,邓长胜.交联电缆的发展动向与需求预测,[J].供用电,(1),1995.
[31]李晓东,甘理.硅烷交联聚乙烯铝塑复合管材的发展概况,[J].塑料,(5)：14～16,1999.
[32]Jay B. Class.过氧化物交联基础,[J].橡胶参考资料.2000,(30),2：24-29.
[33]曹正平,印哲夫.线性低密度电缆护套料的研制,[J].塑料科技.1998,(4)：37-38.
[34]陆小义,徐振明,李建峰.高性能LLDPE电缆护套的研制,[J].工程塑料应用.2005,(33),8：38-42.
[35]Banby B, Babek J F. ESR Spectorscopy in Polymer Research. [J].Berlin:Spring Verlag,1977.88.
[36]王雁冰,黄志维,张联盟.DMA在高分子材料研究中的应用,[J].国外建材科技.2004,(25),2：25-27.
[37]Pradip.Sonawane,S.Radhakrishnan,J.A.Bhangale,A.L.Gadhavi,AnaghaKhare.Dev elopment of Nanofibro us Morphology in LDPE/LLDPE/PP Blends and Its Effect on Mechanical Properties of Blend Films. [J]. Journal of Applied Polymer Science, Vol.107,4005-4012(2008).
[38]刘新民,许春霞,葛涛等.过氧化物交联聚乙烯的力学性能研究.[J].现代塑料加工应用.2003,(15),6：14-16.
[39]D.Abraham, K.E. George, D.J.Francis. Study on LDPE/LLDPE blends. [J]. Die Angewandte Makromolekulare Chemie 200(1992)15-25(Nr.3468).
[40]Daniel Abraham, K.E.George, D.Joseph Francis.Structure-Property-Processing Relationships in Chemically Modified LDPE and LDPE/LLDPE Blend. [J]. Journal of Applied Polymer Science, Vol.67,789-797(1998).
[41]Junwei Gu, Qiuyu Zhang,Jing Dang.Thermal Conductivity and Mechanical Properties of Aluminum Nitride Filled Linear Low-Density Polyethylene Composites. [J].Polymer Engineering And Science-2009.1031-1034.
[42]G.Guerrica-Echecarria, J.I.Eguiazabal,J.Nazabal. Structure and Mechanical Properties of Compatibilized Poly (ethylene terephthalate)/Poly (ethylene octane) Blends. [J].Polymer Engineering and Science-2006.172-180.
[43]Ibenelwaleed A.Hussein,Tayyab Hameed.Influence of Branching Characteristics on Thermal and Mechanical Properties of Ziegler-Natta and Metallocene Hexene LinearLow-Density Polyethylene Blends with Low-Density Polyethylene. [J] Journal of Applied Polymer Science, Vol.97,2488-2498(2005).
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