环保型阻燃ABS母料的开发
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摘要
ABS树脂是在聚苯乙烯改性的基础上发展起来的三元共聚物,它体现了三种组分丙烯腈-丁二烯-苯乙烯的协同性能。由于它具有价格较低,综合性能优良的特点,被广泛应用于汽车、电子电器和建筑等行业。所以它是目前世界上产量最大,应用极广的一种通用工程塑料之一。随着科学技术的不断发展,近年来国内外对汽车、电子电器及建筑方面使用的材料相继作了有关阻燃规定,ABS树脂阻燃改性可用三种方法实现:(1)在合成ABS过程中添加反应型阻燃剂;(2)ABS与含卤阻燃剂等共混(3)ABS树脂与高阻燃性聚合物共混。
本课题研究开发了马来酸酐(MAH)、苯乙烯(St)、接枝ABS的相容化剂。文中探索了其接枝机理,探讨了MAH、St的用量对ABS树脂的接枝率的影响。文中以此相容化剂作为载体与阻燃剂和加工助剂混炼而成阻燃母料。把阻燃母料和纯ABS树脂以一定的比例复配就可以与阻燃ABS树脂一样直接注塑产品。但加工母料与加工阻燃ABS相比而言,可以减少约2/3的能源。
根据欧盟的RoHS指令的要求,本研究所采用的阻燃剂和其它加工助剂均不含RoHS指令所禁止的有害物质。本研究的环保意义在于所开发的母料符合欧盟的RoHS指令。因此,本课题所开发的母料与纯ABS树脂复配注塑成塑料产品可以出口到欧盟地区。
本研究分为两步:第一步,先开发阻燃ABS,这样可以确定母料的基本配方。第二步,再添加加工助剂确定阻燃ABS母料的配方。文中探讨了阻燃剂的用量对阻燃ABS树脂的力学性能的影响和阻燃性能的影响。文中还讨论了润滑剂对阻燃ABS木料的流动性影响。
本研究的母料分为两种:(1)A#母料的开发。此母料采用含卤阻燃剂及加工助剂与与自制的相容剂共混而成,其特点是;加工温度比较高,可以在240℃以上加工。但是成本比较高。此母料与其它母料的优势在于采用了高接枝率的相容剂作为载体,改善了阻燃剂与ABS树脂的相容性,提高了力学强度。(2)B#母料的开发。此母料主要采用高阻燃性聚合物PVC及加工助剂共混成而成,此母料与A#相比稳定性不好,加工温度最高只能是180℃,温度过高会分解,变色。但此母料的成本比A#母料低。
The development of ABS resin copolymer based on PS modification. It shows synergy properties of acrylonitrile-butadiene-styrene. ABS resin is applied Automotive、Electronic & Electric production construction etc. Because of cheap and excellent properties. At Present, the ABS resin is one of the greatest yields and applied widely of generally engineering plastics. Last years ,with development of science & technique, there have been great demand for flame retarded material abroad and domestics which are applied in Automotive、Electronic & Electric production construction etc. Flame retardant ABS can be modified by three way: (1) adding reactive flame retardant to ABS in the process of ABS synthesis;(2) blending ABS resin and halogen flame retardant together; (3) blending ABS resin and high-flame retardant polymer.
The characteristics of the research includes the compatibilizer (ABS-g-(MAH-St)) is produced by ourselves which is used for vector resin, the flame retardant and the other additives & vector are blended together , and the flame retardant masterbatch is prepared. The masterbatch & ABS resin can be mixed at suitable proportion, and the mixture can be injected directly as the flame retardant ABS. Compared with the flame retardant ABS, the masterbatch can save about 2/3 energy.
Based on the instructions of RoHS of EU, the flame retardant and the other additives do not contain material which is forbidden by RoHS. So products of plastics which are injected by the masterbatch and ABS resin mixing can export EU.
The research is divided two steps: firstly, the flame retardant ABS development. As to it, formulation of masterbatch can be determined probably. Secondly, additives add to then the formulation of masterbatch of flame retardant ABS.
In the article, there are two masterbatches are developed. (1)A# masterbatch development. The masterbatch is prepared by halogen flame retardant & additives & vector resin blending. The features of the masterbatch : processing temperature of it can be more 240℃. However, the cost is high. (2)B# masterbatch development, the masterbatch is prepared by high-flame retardant polymer & additives & vector resin blending. The masterbatch is easily decomposition when the processing of temperature more 180℃. As a result, the color of the products will become yellow even red. But the cost is low than the A#. So the processing of masterbatch have to be below 180℃.
本课题研究开发了马来酸酐(MAH)、苯乙烯(St)、接枝ABS的相容化剂。文中探索了其接枝机理,探讨了MAH、St的用量对ABS树脂的接枝率的影响。文中以此相容化剂作为载体与阻燃剂和加工助剂混炼而成阻燃母料。把阻燃母料和纯ABS树脂以一定的比例复配就可以与阻燃ABS树脂一样直接注塑产品。但加工母料与加工阻燃ABS相比而言,可以减少约2/3的能源。
根据欧盟的RoHS指令的要求,本研究所采用的阻燃剂和其它加工助剂均不含RoHS指令所禁止的有害物质。本研究的环保意义在于所开发的母料符合欧盟的RoHS指令。因此,本课题所开发的母料与纯ABS树脂复配注塑成塑料产品可以出口到欧盟地区。
本研究分为两步:第一步,先开发阻燃ABS,这样可以确定母料的基本配方。第二步,再添加加工助剂确定阻燃ABS母料的配方。文中探讨了阻燃剂的用量对阻燃ABS树脂的力学性能的影响和阻燃性能的影响。文中还讨论了润滑剂对阻燃ABS木料的流动性影响。
本研究的母料分为两种:(1)A#母料的开发。此母料采用含卤阻燃剂及加工助剂与与自制的相容剂共混而成,其特点是;加工温度比较高,可以在240℃以上加工。但是成本比较高。此母料与其它母料的优势在于采用了高接枝率的相容剂作为载体,改善了阻燃剂与ABS树脂的相容性,提高了力学强度。(2)B#母料的开发。此母料主要采用高阻燃性聚合物PVC及加工助剂共混成而成,此母料与A#相比稳定性不好,加工温度最高只能是180℃,温度过高会分解,变色。但此母料的成本比A#母料低。
The development of ABS resin copolymer based on PS modification. It shows synergy properties of acrylonitrile-butadiene-styrene. ABS resin is applied Automotive、Electronic & Electric production construction etc. Because of cheap and excellent properties. At Present, the ABS resin is one of the greatest yields and applied widely of generally engineering plastics. Last years ,with development of science & technique, there have been great demand for flame retarded material abroad and domestics which are applied in Automotive、Electronic & Electric production construction etc. Flame retardant ABS can be modified by three way: (1) adding reactive flame retardant to ABS in the process of ABS synthesis;(2) blending ABS resin and halogen flame retardant together; (3) blending ABS resin and high-flame retardant polymer.
The characteristics of the research includes the compatibilizer (ABS-g-(MAH-St)) is produced by ourselves which is used for vector resin, the flame retardant and the other additives & vector are blended together , and the flame retardant masterbatch is prepared. The masterbatch & ABS resin can be mixed at suitable proportion, and the mixture can be injected directly as the flame retardant ABS. Compared with the flame retardant ABS, the masterbatch can save about 2/3 energy.
Based on the instructions of RoHS of EU, the flame retardant and the other additives do not contain material which is forbidden by RoHS. So products of plastics which are injected by the masterbatch and ABS resin mixing can export EU.
The research is divided two steps: firstly, the flame retardant ABS development. As to it, formulation of masterbatch can be determined probably. Secondly, additives add to then the formulation of masterbatch of flame retardant ABS.
In the article, there are two masterbatches are developed. (1)A# masterbatch development. The masterbatch is prepared by halogen flame retardant & additives & vector resin blending. The features of the masterbatch : processing temperature of it can be more 240℃. However, the cost is high. (2)B# masterbatch development, the masterbatch is prepared by high-flame retardant polymer & additives & vector resin blending. The masterbatch is easily decomposition when the processing of temperature more 180℃. As a result, the color of the products will become yellow even red. But the cost is low than the A#. So the processing of masterbatch have to be below 180℃.
引文
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[2]邢德琪,秦凯.共混阻燃—ABS树脂性能的探讨.炼油与化工, 2006.15～19
[3]黄立本,张立基.ABS树脂及其应用.北京:化学工业出版社,2001.1～12
[4] Homsby PR. The non-hanlogen fire retardant.Fire and Material, 2007.269～276
[5] Arthur H L. Handbook of plastics Flammability and Combustion toxico logy, new york:Noyespubication, 1983.23
[6]邓兰,储林.阻燃剂的应用及发展.西南石油学院学报,1996,18(2):105～110
[7]史翎,段雪.我国阻燃剂的研究与发展[J].中国科技成果,2003,(8):43～47
[8]王震. ABS阻燃技术进展及市场需求.塑料工业(增刊),2006,(5):81
[9] HaiyunMa.A novel intumescent flame retardant:synthesis and application in ABS copolymer, Polymer Dergradation and Stability,2007(3).1～7
[10] Wang gui-xiang, Li Ning. Process of direct copper plating on ABS plastics,applied surface science,253 2006:480～484
[11]马伯文.发展民族的ABS工业争夺迅速扩大的国内市场.石化技术及应用,2003,21(1):29～36
[12]王国全,王秀芬.聚合物改性.中国轻工业出版社,2006.23
[13]张殿奎. ABS国内外生产技术及发展.吉化科技,1995,3(4):11～23
[14] ShaoFeng Wang, Yuan Hu.Preparation and characterization of flame retardant ABS/montmorillonite nanocomposite.Applied Clay Science. 25 (2004) 49～55
[15]山西化工研究所编.《塑料橡胶加工助剂》.北京:化学工业出版, 1983.238～313
[16]王建祺.无卤阻燃聚合物基础与应用.北京:科学出版,2005. 48
[17]欧育湘.阻燃高分子材料.北京:国防工业出版社,2001. 1～10
[18]王克智.塑料助剂开发及应用-热稳定剂.塑料科技,1995,(5):39
[19]欧育湘.新型无卤阻燃剂的研究与应用.应用化工,2006, 2(4):4
[20]李志娟,李青山.走向21世纪的新型阻燃剂.化学工程师,2007,(4):34～36
[21]王晓栋.环保型阻燃剂的研究进展.化学工程师, 2006,(4):5
[22]张军,夏延致.聚合物燃烧和阻燃技术.北京:化学工业出版社,2005.43
[23] P.Roma,M.P.Luda.Synergisticaction of fluorine-containing additives in bromine/antimony fire retardant ABS.Polymer Degradation and Stability 641999.297-500
[24] S.R.Owen, J.F.Harper. Mechanical,microscopical and fire retardant studies of ABS polymers.Poly Degradation and Stability 64 (1999). 449～455
[25]鹿海军,马小燕.磷系阻燃剂研究新进展.化工新型材料,2001,29(12):7～10
[26]薛恩钰,曾敏修.阻燃科学与研究进展.北京国防出版社,2005
[27]欧育湘.阻燃剂-制造、性能及应用[M].北京:兵器工业出版社. 1999.148～149
[28]欧育湘.有机阻燃剂最新进展.现代化工, 1997, 4:9～12
[29]金霖.磷系阻燃剂的研究与应用.应用化工,2002,(10):30
[30]李晓丽,李斌.阻燃ABS树脂及其合金的研究进展.高分子材料科学工程,2005,(1):49
[31]夏英.聚磷酸铵/季戊四醇复合膨胀型阻燃剂阻燃ABS的研究.中国塑料,2005,19(5):42
[32]陈兴娟,王金阳等.无机阻燃剂的表面处理技术.化学工程师,2001,(4):22～23
[33]黄雪晟,李峰.纳米双羟基复合金属氧化物的阻燃性能.应用化学,2002,1:70～75
[34]程志凌,陈文捷.塑料阻燃剂技术的进展[J].齐鲁石油化工,2002,30(1): 56～58
[35] Bonsignore P V, Hsieh H P. in: Proceedings of the Fire Retardant Chemincals Association JiontMeetingwith the Society of plastics Engineers.Houston,Tx,1978.101～127
[36] E.Gutman, A.Bobovitch, Rubinchchik.Thermaldegradation of flame-retardant components in filled and unfilled ABS plastics.Polymer Degradation and Stabitity,49(1995).399～402
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