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Design of silane crosslinkable high density polyethylene compounds for automotive fuel tank application

机译:用于汽车油箱的硅烷可交联高密度聚乙烯化合物的设计

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摘要

A formulation was designed to produce silane crosslinkable HDPE compound extrusion blow suitable for extrusion blow molding by melt blending technique on Magicmolding machine. The formulations consist of HDPE as the base polymer, a carrier chemical pack containing an organic unsaturated silane and a free radical generating agent and condensation catalyst. In designing and formulating silane crosslinkable blow molded HDPE compounds with satisfactory properties, ASTM D 2647 was used as the reference. Grafting and crosslinking reaction was proposed for the formulated system. The product was characterized for the chemical, thermal, physical and mechanical properties. The chemical reactions during grafting and crosslinking involved a three step mechanisms. Extrusion blow molded bottle were stored in water for curing at various temperature and time. DSC, FTIR and TGA were used to determine the chemical groups involved in the reactions and gel contents were determined in parallel. The results from curing showed that a further formation of Si-O-Si crosslink’s took place after the point at which maximum gel contents has been reached. Mechanical measurements indicated that further crosslink’s were formed within the existing gel. Suitable range concentration relating to 100 parts of base polymer was found for vinyltrimethoxysilane (VTMO) to be between 1.6 to 2.0 phr. The concentration of dicumyl peroxide (DCP) initiator was between 0.1to 0.5 phr. The concentration of dibutyltin dilaurate (DBTL condensation catalyst) was being 0.005 to 0.02. When the DBTL amount was less than 0.005 phr, the crosslinking reaction did not proceed sufficiently. As the DBTL amount was larger than 0.02 phr, local crosslinking proceeds in the extruder at the time of extrusion, results in great deterioration of the products. The selected components used in the formulation are HDPE grade HB6200, vinyltrimethoxysilane (VTMO) as the crosslinking agent, dicumyl peroxide (DCP) as the initiator, dibutyltin dilaurate (DBTL) as the condensation catalyst and Irganox 1010 as the antioxidant. The blow molded bottle properties and processability of the compound depends on the formulation and process parameter. udPermeation rate of the fuel decreased proportionally with the addition of EVOH in PE structures. By taking the minimum rate of 1.14 gram petrol/day, it has clearly stated that the wall layer complies the EPA emissions regulations saying that a vehicle must emit no more than a total of 2.0 gram of hydrocarbon; measured during the diurnal ( 24 hours ) cycle. Also when using diesel as fuel, implementing EVOH content of 1% and 0.5mm off thickness, the permeation rate required by the standard of 0.35 gram/day is already achieved.ud ud udud
机译:设计配方以通过Magicmolding机器上的熔融共混技术生产适合于挤出吹塑的硅烷可交联HDPE化合物挤出吹塑。该制剂由作为基础聚合物的HDPE,包含有机不饱和硅烷和自由基产生剂的缩合剂和缩合催化剂组成。在设计和配制具有令人满意性能的硅烷可交联吹塑HDPE化合物时,使用ASTM D 2647作为参考。提出了该体系的接枝和交联反应。该产品具有化学,热,物理和机械性能。接枝和交联过程中的化学反应涉及三个步骤。将挤出吹塑成型的瓶储存在水中以在不同的温度和时间固化。用DSC,FTIR和TGA确定反应中涉及的化学基团,并平行测定凝胶含量。固化的结果表明,在达到最大凝胶含量之后,Si-O-Si交联剂进一步形成。机械测量表明,现有凝胶中形成了进一步的交联。对于乙烯基三甲氧基硅烷(VTMO),发现与100份基础聚合物有关的合适范围浓度为1.6至2.0phr。过氧化二枯基(DCP)引发剂的浓度为0.1至0.5 phr。二月桂酸二丁基锡(DBTL缩合催化剂)的浓度为0.005〜0.02。当DBTL量小于0.005phr时,交联反应不能充分进行。当DBTL的量大于0.02phr时,在挤出时在挤出机中进行局部交联,导致产物的严重劣化。配方中使用的选定组分为HDPE级HB6200,乙烯基三甲氧基硅烷(VTMO)作为交联剂,过氧化二枯基(DCP)作为引发剂,二月桂酸二丁基锡(DBTL)作为缩合催化剂和Irganox 1010作为抗氧化剂。混合物的吹塑瓶性能和可加工性取决于配方和工艺参数。燃料的渗透率与PE结构中EVOH的添加成比例地降低。通过采用每天1.14克汽油的最低排放量,它清楚地表明,该壁层符合EPA排放法规的要求,即车辆排放的碳氢化合物总量不得超过2.0克。在每日(24小时)周期内测量。同样,当使用柴油作为燃料时,如果EVOH含量为1%,厚度为0.5mm,则已经达到了标准标准0.35克/天的渗透率。

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