CN103333417B - 一种膨胀型无卤阻燃高等规聚丁烯-1材料及其制备方法 - Google Patents

一种膨胀型无卤阻燃高等规聚丁烯-1材料及其制备方法 Download PDF

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CN103333417B
CN103333417B CN201310254358.2A CN201310254358A CN103333417B CN 103333417 B CN103333417 B CN 103333417B CN 201310254358 A CN201310254358 A CN 201310254358A CN 103333417 B CN103333417 B CN 103333417B
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halogen
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polybutene
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CN103333417A (zh
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乔辉
杨金兴
史翎
徐慧
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Beijing University of Chemical Technology
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29BPREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
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    • B29B9/06Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/022Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the choice of material
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/04Particle-shaped
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25Component parts, details or accessories; Auxiliary operations
    • B29C48/36Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
    • B29C48/395Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
    • B29C48/40Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25Component parts, details or accessories; Auxiliary operations
    • B29C48/88Thermal treatment of the stream of extruded material, e.g. cooling
    • B29C48/911Cooling
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25Component parts, details or accessories; Auxiliary operations
    • B29C48/92Measuring, controlling or regulating
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00Indexing scheme relating to extrusion moulding
    • B29C2948/92Measuring, controlling or regulating
    • B29C2948/92504Controlled parameter
    • B29C2948/9258Velocity
    • B29C2948/9259Angular velocity
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00Indexing scheme relating to extrusion moulding
    • B29C2948/92Measuring, controlling or regulating
    • B29C2948/92504Controlled parameter
    • B29C2948/92704Temperature
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29KINDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/0005Condition, form or state of moulded material or of the material to be shaped containing compounding ingredients
    • B29K2105/0026Flame proofing or flame retarding agents

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Abstract

本发明属于改性塑料领域,提供了一种膨胀型无卤阻燃高等规聚丁烯-1材料及其制备方法。本发明材料以重量百分数计,由以下原料组成:高等规聚丁烯-1为65%~90%,抗氧剂为0.2%,膨胀型无卤阻燃剂为10%~30%,耐高温润滑剂为0~5%,矿物填充物0~10%,原料的总量为100%。该改性塑料通过双螺杆挤出机混炼造粒制得。本发明的材料在达到较高的氧指数和阻燃级别后,还具有良好的力学性能。采用无卤阻燃剂对环境友好,火灾时不会产生有害气体,影响人们的生命安全;制得的膨胀型无卤阻燃聚丁烯-1材料具有较好的阻燃效果和良好的力学性能,拓宽了应用范围。<!--1-->

Description

一种膨胀型无卤阻燃高等规聚丁烯-1材料及其制备方法
技术领域
本发明属于改性塑料领域,涉及一种无卤阻燃材料,具体涉及一种膨胀型无卤阻燃高等规聚丁烯-1材料及其制备方法。
背景技术
聚丁烯-1具有良好的物理力学性能,突出的抗蠕变性,耐低温性,耐环境应力开裂性和高填料填充性。它不仅有良好的介电性和耐化学药品性,而且有很好的机械强度和高韧性。它的屈服值、拉伸强度、冲击强度分别是LDPE的2倍、6-10倍、3-4倍。与其它聚烯烃相比,聚丁烯-1的耐应力开裂性最好。耐蠕变性比聚乙烯、聚丙烯高,在不超过屈服点的应力作用下突出的耐蠕变性一直到80℃仍保持不变。
阻燃剂分为卤素阻燃剂和无卤阻燃剂。目前卤素阻燃剂仍然占据着主导地位,因为它阻燃效果好,可以满足很多塑料制品的阻燃要求。但它在燃烧过程中,产生较多的烟雾和有毒的腐蚀性气体(如溴化氢)。这种气体在火灾中非常危险,因为它扩散速度极快,在火灾中严重妨碍了消防人员的扑救工作,给人民的生命财产造成了极大的危害。鉴于卤素阻燃剂的严重弊端,寻找卤素阻燃剂的替代品-无卤阻燃剂就提上日程。膨胀型阻燃剂体系的阻燃机理主要与膨胀炭层的绝热效应有关,属于凝聚相阻燃机理,受热时成炭剂在酸源作用下形成脱水成炭,并在发泡剂分解的气体作用下形成蓬松有孔封闭结构的炭层,其绝热效应就在于束缚在膨胀炭层的气体导热比固体差一个数量级以及热辐射的反射作用。炭层还可以限制氧气扩散到聚合物表面,防止可然气体的放出,从而终止聚合物的燃烧。
发明内容
针对现有技术中存在的不足,本发明的目的在于,提供一种膨胀型无卤阻燃高等规聚丁烯-1材料及其制备方法,在保持力学性能的前提下,提供一种阻燃性能良好且对环境无污染的高等规聚丁烯-1阻燃材料。
为了实现上述任务,本发明采用如下技术方案予以实现:
一种膨胀型无卤阻燃高等规聚丁烯-1材料,以重量百分数计,由以下原料组成:高等规聚丁烯-1为65%~90%,抗氧剂225为0.2%,膨胀型无卤阻燃剂为10%~30%,耐高温润滑剂为0~5%,硫酸钡为0~10%,原料的总量为100%,其中:
所述的抗氧剂225为抗氧剂1010和抗氧剂168按质量比1:1组成的复合抗氧剂;
所述的膨胀型无卤阻燃剂主要成分为聚磷酸铵,聚合度大于1000;
所述的耐高温润滑剂为硅油。
本发明还具有如下技术特征:
所述的膨胀型无卤阻燃剂为山东旭锐新材有限公司的50A阻燃剂或日本TDK公司的FP-2100J阻燃剂。
一种制备如上所述的膨胀型无卤阻燃高等规聚丁烯-1材料的方法,该方法按照以下步骤进行:
步骤一,将膨胀型无卤阻燃剂干燥;
步骤二,将原料按照配方比例进行预混,使得各原料初步混合均匀,得到预混料,其中:
所述的配方比例以重量百分数计,由以下原料组成:高等规聚丁烯-1为65%~90%,抗氧剂225为0.2%,膨胀型无卤阻燃剂为10%~30%,耐高温润滑剂为0~5%,硫酸钡为0~10%,原料的总量为100%;
步骤三,将步骤二得到的预混料加入双螺杆挤出机中进行混炼,其中:
所述的双螺杆挤出机的螺杆为同向双螺杆,长径比为1:32~1:48。
所述的双螺杆挤出机的转速为140~150r/min;
所述的双螺杆挤出机加工温度为170℃~185℃;
步骤四,将从双螺杆挤出机中出来的物料进行风冷,造粒,得到膨胀型无卤阻燃高等规聚丁烯-1材料。
本发明与现有技术相比,有益的技术效果是:
本发明的膨胀型无卤阻燃聚丁烯-1材料在达到较高的氧指数和阻燃级别后,还具有良好的力学性能。采用无卤阻燃剂对环境友好,火灾时不会产生有害气体,影响人们的生命安全;采用以聚磷酸铵为主的膨胀型阻燃剂,具有添加量较少,对制品的力学性能影响较小的优点;值得的膨胀型无卤阻燃聚丁烯-1材料具有较好的阻燃效果和良好的力学性能,拓宽了应用范围。
具体实施方式
遵从上述技术方案,下述实施例给出一种膨胀型无卤阻燃高等规聚丁烯-1材料,以重量百分数计,由以下原料组成:高等规聚丁烯-1为65%~90%,抗氧剂225为0.2%,膨胀型无卤阻燃剂为10%~30%,耐高温润滑剂为0~5%,硫酸钡为0~10%,原料的总量为100%,其中:
所述的抗氧剂225为抗氧剂1010和抗氧剂168按质量比1:1组成的复合抗氧剂;
所述的膨胀型无卤阻燃剂主要成分为聚磷酸铵,聚合度大于1000;
所述的耐高温润滑剂为硅油。
所述的膨胀型无卤阻燃剂为旭锐新材的50A阻燃剂或日本TDK公司的FP-2100J阻燃剂。
一种制备如上所述的膨胀型无卤阻燃高等规聚丁烯-1材料的方法,该方法按照以下步骤进行:
步骤一,将膨胀型无卤阻燃剂干燥;
步骤二,将原料按照配方比例进行预混,使得各原料初步混合均匀,得到预混料,其中:
所述的配方比例以重量百分数计,由以下原料组成:高等规聚丁烯-1为65%~90%,抗氧剂225为0.2%,膨胀型无卤阻燃剂为10%~30%,耐高温润滑剂为0~5%,硫酸钡为0~10%,原料的总量为100%;
步骤三,将步骤二得到的预混料加入双螺杆挤出机中进行混炼,其中:
所述的双螺杆挤出机的螺杆为同向双螺杆,长径比为1:32~1:48;
所述的双螺杆挤出机的转速为140~150r/min;
所述的双螺杆挤出机加工温度为170℃~185℃;
步骤四,将从双螺杆挤出机中出来的物料进行风冷,造粒,得到膨胀型无卤阻燃高等规聚丁烯-1材料。
本实验所用仪器为:
缺口型制样机:QYJ1251,美特斯工业系统(中国)有限公司;
电子万能拉力机:CMT4204,美特斯工业系统(中国)有限公司;
简支梁冲击试验机:XJJ-5,承德市金建检测仪器有限公司;
双螺杆挤出机:MHS-20,昆山美弧螺杆机械公司;
氧指数测定仪:JF-3,南京市江宁区分析仪器厂;
水平垂直燃烧仪:CZF-3,南京市江宁区分析仪器厂;
以下给出本发明的具体实施例,需要说明的是本发明并不局限于以下具体实施例,凡在本申请技术方案基础上做的等同变换均落入本发明的保护范围。
实施例1:
本实施例给出一种膨胀型无卤阻燃高等规聚丁烯-1材料,以重量百分数计,由以下原料组成:等规度为93%的聚丁烯-1为89.8%,抗氧剂225为0.2%,阻燃剂FP-2100J为10%。所用双螺杆挤出机为直径25cm,长径比为1:32,加工温度为170℃~185℃。
遵从上述制备方法制备本实施例的膨胀型无卤阻燃高等规聚丁烯-1材料并且模压成型进行性能测试,其测试结果如表1所示。
实施例2:
本实施例给出一种膨胀型无卤阻燃高等规聚丁烯-1材料,以重量百分数计,由以下原料组成:等规度为93%的聚丁烯-1为79.8%,抗氧剂225为0.2%,阻燃剂FP-2100J为20%。所用双螺杆挤出机为直径25cm,长径比为1:32,加工温度为170℃~185℃。
遵从上述制备方法制备本实施例的膨胀型无卤阻燃高等规聚丁烯-1材料并且模压成型进行性能测试,其测试结果如表1所示。
实施例3:
本实施例给出一种膨胀型无卤阻燃高等规聚丁烯-1材料,以重量百分数计,由以下原料组成:等规度为93%的聚丁烯-1为74.8%,抗氧剂225为0.2%,阻燃剂FP-2100J为25%。所用双螺杆挤出机为直径25cm,长径比为1:32,加工温度为170℃~185℃。
遵从上述制备方法制备本实施例的膨胀型无卤阻燃高等规聚丁烯-1材料并且模压成型进行性能测试,其测试结果如表1所示。
实施例4:
本实施例给出一种膨胀型无卤阻燃高等规聚丁烯-1材料,以重量百分数计,由以下原料组成:等规度为93%的聚丁烯-1为89.8%,抗氧剂225为0.2%,阻燃剂50A为10%。所用双螺杆挤出机为直径25cm,长径比为1:32,加工温度为170℃~185℃。
遵从上述制备方法制备本实施例的膨胀型无卤阻燃高等规聚丁烯-1材料并且模压成型进行性能测试,其测试结果如表1所示。
实施例5:
本实施例给出一种膨胀型无卤阻燃高等规聚丁烯-1材料,以重量百分数计,由以下原料组成:等规度为93%的聚丁烯-1为79.8%,抗氧剂225为0.2%,阻燃剂50A为20%。所用双螺杆挤出机为直径25cm,长径比为1:32,加工温度为170℃~185℃。
遵从上述制备方法制备本实施例的膨胀型无卤阻燃高等规聚丁烯-1材料并且模压成型进行性能测试,其测试结果如表1所示。
实施例6:
本实施例给出一种膨胀型无卤阻燃高等规聚丁烯-1材料,以重量百分数计,由以下原料组成:等规度为93%的聚丁烯-1为74.8%,抗氧剂225为0.2%,阻燃剂50A为25%。所用双螺杆挤出机为直径25cm,长径比为1:32,加工温度为170℃~185℃。
遵从上述制备方法制备本实施例的膨胀型无卤阻燃高等规聚丁烯-1材料并且模压成型进行性能测试,其测试结果如表1所示。
实施例7:
本实施例给出一种膨胀型无卤阻燃高等规聚丁烯-1材料,以重量百分数计,由以下原料组成:等规度为93%的聚丁烯-1为69.8%,抗氧剂225为0.2%,阻燃剂50A为30%。所用双螺杆挤出机为直径25cm,长径比为1:32,加工温度为170℃~185℃。
遵从上述制备方法制备本实施例的膨胀型无卤阻燃高等规聚丁烯-1材料并且模压成型进行性能测试,其测试结果如表1所示。
实施例8:
本实施例给出一种膨胀型无卤阻燃高等规聚丁烯-1材料,以重量百分数计,由以下原料组成:等规度为93%的聚丁烯-1为77.8%,抗氧剂225为0.2%,阻燃剂50A为20%,硫酸钡为2%。所用双螺杆挤出机为直径25cm,长径比为1:32,加工温度为170℃~185℃。
遵从上述制备方法制备本实施例的膨胀型无卤阻燃高等规聚丁烯-1材料并且模压成型进行性能测试,其测试结果如表1所示。
实施例9:
本实施例给出一种膨胀型无卤阻燃高等规聚丁烯-1材料,以重量百分数计,由以下原料组成:等规度为93%的聚丁烯-1为79.2%,抗氧剂225为0.2%,阻燃剂50A为20%,硅油为0.6%。所用双螺杆挤出机为直径25cm,长径比为1:32,加工温度为170℃~185℃。
遵从上述制备方法制备本实施例的膨胀型无卤阻燃高等规聚丁烯-1材料并且模压成型进行性能测试,其测试结果如表1所示。
实施例10:
本实施例给出一种膨胀型无卤阻燃高等规聚丁烯-1材料,以重量百分数计,由以下原料组成:等规度为93%的聚丁烯-1为83.3%,抗氧剂225为0.2%,阻燃剂50A为15%,硅油为1.5%。所用双螺杆挤出机为直径25cm,长径比为1:32,加工温度为170℃~185℃。
遵从上述制备方法制备本实施例的膨胀型无卤阻燃高等规聚丁烯-1材料并且模压成型进行性能测试,其测试结果如表1所示。
表1实施例的膨胀型无卤阻燃高等规聚丁烯-1材料的性能数据
从表1中可知,由表中数据可以看出在加入相同含量的阻燃剂后,FP-2100J的阻燃效果较50A的好,但加入协效阻燃剂后,添加阻燃剂50A的材料也能达到阻燃和力学性能俱佳的效果。

Claims (4)

1.一种膨胀型无卤阻燃高等规聚丁烯-1材料,其特征在于:以重量百分数计,由以下原料组成:高等规聚丁烯-1为65%~90%,抗氧剂225为0.2%,膨胀型无卤阻燃剂为10%~30%,耐高温润滑剂为0~5%,硫酸钡为0~10%,原料的总量为100%,其中:
所述的抗氧剂225为抗氧剂1010和抗氧剂168按质量比1:1组成的复合抗氧剂;
所述的耐高温润滑剂为硅油。
2.如权利要求1所述的一种膨胀型无卤阻燃高等规聚丁烯-1材料,其特征在于:所述的膨胀型无卤阻燃剂为50A或FP-2100J。
3.如权利要求1所述的一种膨胀型无卤阻燃高等规聚丁烯-1材料,其特征在于:所述的高等规聚丁烯-1为等规度大于80%的聚丁烯-1。
4.制备如权利要求1所述的一种膨胀型无卤阻燃高等规聚丁烯-1材料的方法,其特征在于,该方法按照以下步骤进行:
步骤一,将膨胀型无卤阻燃剂干燥;
步骤二,将原料按照配方比例进行预混,使得各原料初步混合均匀,得到预混料,其中:
所述的配方比例以重量百分数计,由以下原料组成:高等规聚丁烯-1为65%~90%,抗氧剂225为0.2%,膨胀型无卤阻燃剂为10%~30%,耐高温润滑剂为0%~5%,硫酸钡为0~10%,原料的总量为100%;
步骤三,将步骤二得到的预混料加入双螺杆挤出机中进行混炼,其中:
所述的双螺杆挤出机的螺杆为同向双螺杆,长径比为1:32~1:48;
所述的双螺杆挤出机的转速为140~150r/min;
所述的双螺杆挤出机加工温度为170℃~185℃;
步骤四,将从双螺杆挤出机中出来的物料进行风冷,造粒,得到膨胀型无卤阻燃高等规聚丁烯-1材料。
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