CN109485907A - 一种橡塑发泡绝热保温材料 - Google Patents

一种橡塑发泡绝热保温材料 Download PDF

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CN109485907A
CN109485907A CN201811164064.XA CN201811164064A CN109485907A CN 109485907 A CN109485907 A CN 109485907A CN 201811164064 A CN201811164064 A CN 201811164064A CN 109485907 A CN109485907 A CN 109485907A
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chlorosilane
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袁勇
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Nanjing Vanward New Materials Co Ltd
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Abstract

本发明提供的一种橡塑发泡绝热保温材料，自上而下包括反射层和隔热层。本发明还提供了上述橡塑发泡绝热保温材料的制备方法。该橡塑发泡绝热保温材料包括反射层和隔热层双层结构，反射层能够将热量反射，隔热层进一步提高了隔热效果，该保温材料保温隔热效果好。

Description

一种橡塑发泡绝热保温材料
技术领域
本发明属于材料领域，特别涉及一种橡塑发泡绝热保温材料。
背景技术
随着能源消耗的日益增加，有效利用能源和节约能源已经成为全人类关注的最重要问题之一。自20世纪90年代以来，我国出台《节能法》并制定了一系列节能法规，对节能提出了具体的标准和要求。传统的建筑保温材料，以泡沫材料为主要、再加上粘合剂之类，其不足之处在于，强度较低，不抗压，抗冲压能力小、易老化，不耐用，综合成本高。
保温材料一般是指导热系数小于或等于0.2的材料，保温材料发展很快，在工业和建筑中采用良好的保温技术与材料往往可以起到事半功倍的效果。保温材料具有密度小、柔韧性高、防水等特性，可收集多余热量，随意性好，无空腔，可避免负风压撕裂和脱落。保温材料一般分为无机类和有机类两种。有机类保温材料主要有聚氨酯泡沫、聚苯板、酚醛泡沫等。无机保温材料主要集中在气凝胶毡、玻璃棉、岩棉、膨胀珍珠岩、微纳隔热板等具有一定保温效果的材料，能够达到A级防火。
橡塑(NBR/PVC)保温材料以耐磨、耐热及阻燃性能优异的丁腈橡胶、聚氯乙烯等为主要原料，加入发泡剂经过密炼、发泡而成，系含有大量微小独立气泡的柔性泡沫绝热材料。可广泛用于中央空调、建筑、化工、医药、轻纺、冶金、船舶、电气等领域各类冷热介质管道、容器保温，能达到降低冷、热损耗的优良效果，亦可加工制作健身器材、医疗器械及日用品的把套、护套等。然而，目前橡塑发泡保温材料绝热效果仍需进一步提升。
发明内容
技术问题：为了解决现有技术的缺陷，本发明提供了一种橡塑发泡绝热保温材料。
技术方案：本发明提供的一种橡塑发泡绝热保温材料，自上而下包括反射层和隔热层；所述反射层至少由以下重量份的组份制成：NBR15-20份、SBR5-15份、EVA10-15份、PVC6-8份、无卤阻燃剂20-30份、纳米氧化铝4-6份、氧化硅2-5份、氢氧化铝1-3份、聚乙二醇1-2份、三氧化二锑1-2份、防护蜡1-2份、氧化石蜡5-8份、二辛脂1-2份、Ca/Zn热稳定剂1-2份、发泡剂4-6份、膨胀型隔热阻燃材料5-15份；所述隔热层至少由以下重量份的组份制成：NBR15-20份、EVA 10-15份、PVC 6-8份、无卤阻燃剂20-30份、玻璃纤维5-15份、膨胀珍珠岩6-8份、膨润土2-4份、空心微球5-15份、聚乙二醇1-2份、三氧化二锑1-2份、防护蜡1-2份、氧化石蜡5-8份、二辛脂1-2份、Ca/Zn热稳定剂1-2份、发泡剂4-6份、滑石粉2-4份、膨胀型隔热阻燃材料5-15份；所述膨胀型隔热阻燃材料的结构如式(I)所示：
式中，n为460-990之间的整数；R为烷基。
作为改进，自上而下包括反射层和隔热层；所述反射层至少由以下重量份的组份制成：NBR 18份、SBR 10份、EVA 12份、PVC 7份、无卤阻燃剂25份、纳米氧化铝5份、氧化硅4份、氢氧化铝2份、聚乙二醇1.5份、三氧化二锑1.5份、防护蜡1.5份、氧化石蜡7份、二辛脂1.5份、Ca/Zn热稳定剂1.5份、发泡剂5份、膨胀型隔热阻燃材料10份；所述隔热层至少由以下重量份的组份制成：NBR 18份、EVA 12份、PVC 7份、无卤阻燃剂25份、玻璃纤维10份、膨胀珍珠岩7份、膨润土3份、空心微球10份、聚乙二醇1.5份、三氧化二锑1.5份、防护蜡1.5份、氧化石蜡6份、二辛脂1.5份、Ca/Zn热稳定剂1.5份、发泡剂5份、滑石粉3份、膨胀型隔热阻燃材料10份。
所述空心微球为包括以下重量份数组分：SiO2 50-90份，Al2O3：10-50份，K2O：5-10份，CaO 1-10份，B2O3 1-12份。
本发明还提供了上述橡塑发泡绝热保温材料的制备方法，包括以下步骤：
(1)膨胀型隔热阻燃材料的制备：在惰性气体的保护、室温条件下，将氯硅烷和膦酸二甲酯反应，制得烷基硅基膦酸二甲酯；在惰性气体的保护、350～400℃下，将步骤(1)所得物烷基硅基膦酸二甲酯与三聚氰胺在催化剂作用下反应，冷却后真空干燥即得；步骤(1)所得物烷基硅基膦酸二甲酯与三聚氰胺的摩尔比为1∶(1～1.2)；
(2)反射层的制备：将NBR、SBR、EVA、PVC、Ca/Zn热稳定剂投入密炼机进行高温密炼，温度为150～160℃，时间为8～12min；降温至90-110℃，恒温条件下，再加入无卤阻燃剂、纳米氧化铝、氧化硅、氢氧化铝、聚乙二醇、三氧化二锑、防护蜡、氧化石蜡、二辛脂、膨胀型隔热阻燃材料，混炼10-20min，出料至发泡炉内，加入发泡剂，130-150℃下发泡15-45min；冷却，即得反射层；
(3)隔热层的制备：将NBR、EVA、PVC、Ca/Zn热稳定剂投入密炼机进行高温密炼，温度为150～160℃，时间为8～12min；降温至90-110℃，恒温条件下，再加入无卤阻燃剂、玻璃纤维、空心微球、聚乙二醇、三氧化二锑、防护蜡、氧化石蜡、二辛脂、滑石粉、膨胀型隔热阻燃材料，混炼10-20min，出料至发泡炉内，加入发泡剂、膨胀珍珠岩、膨润土，130-150℃下发泡15-45min，得隔热层原料；将隔热层原料涂覆于反射层上，即得。
步骤(1)中，所述氯硅烷选自三甲基氯硅烷、三乙基氯硅烷、三丙基氯硅烷、二甲基乙基氯硅烷、二甲基丙基氯硅烷和二乙基甲基氯硅烷。
步骤(1)中，所述氯硅烷与膦酸二甲酯的摩尔比为1∶(3～4)。
步骤(1)中，膦酸二甲酯与氯硅烷反应的溶剂选自二氯甲烷、氯仿和丙酮。
步骤(1)中，催化剂选自无水氯化镁、磷酸三苯酯、三乙胺中的一种或几种。
有益效果：本发明提供的橡塑发泡绝热保温材料包括反射层和隔热层双层结构，反射层能够将热量反射，隔热层进一步提高了隔热效果，该保温材料保温隔热效果好。
具体实施方式
下面对本发明作出进一步说明。
实施例1
膨胀型阻燃材料的制备方法，包括如下步骤：
(1)在惰性气体的保护、室温条件下，反应的溶剂为二氯甲烷，将氯硅烷和膦酸二甲酯反应，制得烷基硅基膦酸二甲酯；所述氯硅烷为三甲基氯硅烷；所述氯硅烷与膦酸二甲酯的摩尔比为1∶3.5；
(2)在惰性气体的保护、370℃下，将步骤(1)所得物烷基硅基膦酸二甲酯与三聚氰胺在无水氯化镁作用下反应，冷却后真空干燥即得；步骤(1)所得物烷基硅基膦酸二甲酯与三聚氰胺的摩尔比为1∶1.1。
水洗、烘干和粉碎，即得所述阻燃材料，聚合度750，1％的热失重分解温度为247.6℃。
实施例2
膨胀型阻燃材料的制备方法，包括如下步骤：
(1)在惰性气体的保护、室温条件下，反应的溶剂为二氯甲烷，将氯硅烷和膦酸二甲酯反应，制得烷基硅基膦酸二甲酯；所述氯硅烷为三乙基氯硅烷；所述氯硅烷与膦酸二甲酯的摩尔比为1∶3；
(2)在惰性气体的保护、350℃下，将步骤(1)所得物烷基硅基膦酸二甲酯与三聚氰胺在无水氯化镁作用下反应，冷却后真空干燥即得；步骤(1)所得物烷基硅基膦酸二甲酯与三聚氰胺的摩尔比为1∶1.1.。
水洗、烘干和粉碎，即得所述阻燃材料，聚合度990，1％的热失重分解温度为235.7℃。
实施例3
膨胀型阻燃材料的制备方法，包括如下步骤：
(1)在惰性气体的保护、室温条件下，反应的溶剂为氯仿，将氯硅烷和膦酸二甲酯反应，制得烷基硅基膦酸二甲酯；所述氯硅烷为三丙基氯硅烷；所述氯硅烷与膦酸二甲酯的摩尔比为1∶4；
(2)在惰性气体的保护、350℃下，将步骤(1)所得物烷基硅基膦酸二甲酯与三聚氰胺在磷酸三苯酯作用下反应，冷却后真空干燥即得；步骤(1)所得物烷基硅基膦酸二甲酯与三聚氰胺的摩尔比为1∶1.1.。
水洗、烘干和粉碎，即得所述阻燃材料，聚合度800，1％的热失重分解温度为237.6℃。
实施例4
膨胀型阻燃材料的制备方法，包括如下步骤：
(1)在惰性气体的保护、室温条件下，反应的溶剂为丙酮，将氯硅烷和膦酸二甲酯反应，制得烷基硅基膦酸二甲酯；所述氯硅烷为二甲基乙基氯硅烷；所述氯硅烷与膦酸二甲酯的摩尔比为1∶3.2；
(2)在惰性气体的保护、360℃下，将步骤(1)所得物烷基硅基膦酸二甲酯与三聚氰胺在磷酸三苯酯作用下反应，冷却后真空干燥即得；步骤(1)所得物烷基硅基膦酸二甲酯与三聚氰胺的摩尔比为1∶1。
水洗、烘干和粉碎，即得所述阻燃材料，聚合度460，1％的热失重分解温度为219.1℃。
实施例5
膨胀型阻燃材料的制备方法，包括如下步骤：
(1)在惰性气体的保护、室温条件下，反应的溶剂为丙酮，将氯硅烷和膦酸二甲酯反应，制得烷基硅基膦酸二甲酯；所述氯硅烷为二乙基甲基氯硅烷；所述氯硅烷与膦酸二甲酯的摩尔比为1∶3.8；
(2)在惰性气体的保护、390℃下，将步骤(1)所得物烷基硅基膦酸二甲酯与三聚氰胺在三乙胺作用下反应，冷却后真空干燥即得；步骤(1)所得物烷基硅基膦酸二甲酯与三聚氰胺的摩尔比为1∶1.2。
水洗、烘干和粉碎，即得所述阻燃材料，聚合度680，1％的热失重分解温度为231.2℃。
实施例6
膨胀型阻燃材料的制备方法，包括如下步骤：
(1)在惰性气体的保护、室温条件下，反应的溶剂为丙酮，将氯硅烷和膦酸二甲酯反应，制得烷基硅基膦酸二甲酯；所述氯硅烷为二甲基丙基氯硅烷；所述氯硅烷与膦酸二甲酯的摩尔比为1∶3.5；
(2)在惰性气体的保护、380℃下，将步骤(1)所得物烷基硅基膦酸二甲酯与三聚氰胺在三乙胺作用下反应，冷却后真空干燥即得；步骤(1)所得物烷基硅基膦酸二甲酯与三聚氰胺的摩尔比为1∶1.1。
水洗、烘干和粉碎，即得所述阻燃材料，聚合度590，1％的热失重分解温度为229.0℃。
实施例7
橡塑发泡绝热保温材料，自上而下包括反射层和隔热层；所述反射层至少由以下重量份的组份制成：NBR 15份、SBR15份、EVA 10份、PVC 8份、无卤阻燃剂20份、纳米氧化铝4份、氧化硅5份、氢氧化铝1份、聚乙二醇2份、三氧化二锑1份、防护蜡2份、氧化石蜡5份、二辛脂2份、Ca/Zn热稳定剂1份、发泡剂6份、膨胀型隔热阻燃材料5份；所述隔热层至少由以下重量份的组份制成：NBR 15份、EVA 15份、PVC 8份、无卤阻燃剂20份、玻璃纤维15份、膨胀珍珠岩8份、膨润土2份、空心微球15份、聚乙二醇1份、三氧化二锑1份、防护蜡2份、氧化石蜡5份、二辛脂2份、Ca/Zn热稳定剂1份、发泡剂4份、滑石粉4份、实施例1的膨胀型隔热阻燃材料5份。
所述空心微球为包括以下重量份数组分：SiO2 90份，Al2O3：10份，K2O：5份，CaO10份，B2O3 1份。
上述橡塑发泡绝热保温材料的制备方法，包括以下步骤：
(1)反射层的制备：将NBR、SBR、EVA、PVC、Ca/Zn热稳定剂投入密炼机进行高温密炼，温度为150℃，时间为12min；降温至90℃，恒温条件下，再加入无卤阻燃剂、纳米氧化铝、氧化硅、氢氧化铝、聚乙二醇、三氧化二锑、防护蜡、氧化石蜡、二辛脂、膨胀型隔热阻燃材料，混炼10min，出料至发泡炉内，加入发泡剂，150℃下发泡15min；冷却，即得反射层；
(2)隔热层的制备：将NBR、EVA、PVC、Ca/Zn热稳定剂投入密炼机进行高温密炼，温度为150℃，时间为12min；降温至90℃，恒温条件下，再加入无卤阻燃剂、玻璃纤维、空心微球、聚乙二醇、三氧化二锑、防护蜡、氧化石蜡、二辛脂、滑石粉、膨胀型隔热阻燃材料，混炼10min，出料至发泡炉内，加入发泡剂、膨胀珍珠岩、膨润土，150℃下发泡15min，得隔热层原料；将隔热层原料涂覆于反射层上，即得。
实施例8
橡塑发泡绝热保温材料，自上而下包括反射层和隔热层；所述反射层至少由以下重量份的组份制成：NBR20份、SBR5份、EVA15份、PVC 6份、无卤阻燃剂30份、纳米氧化铝6份、氧化硅2份、氢氧化铝3份、聚乙二醇1份、三氧化二锑2份、防护蜡1份、氧化石蜡8份、二辛脂1份、Ca/Zn热稳定剂2份、发泡剂4份、膨胀型隔热阻燃材料15份；所述隔热层至少由以下重量份的组份制成：NBR 20份、EVA15份、PVC 6份、无卤阻燃剂30份、玻璃纤维5份、膨胀珍珠岩6份、膨润土4份、空心微球5份、聚乙二醇2份、三氧化二锑2份、防护蜡1份、氧化石蜡8份、二辛脂1份、Ca/Zn热稳定剂2份、发泡剂6份、滑石粉2份、实施例2的膨胀型隔热阻燃材料15份。
所述空心微球为包括以下重量份数组分：SiO2 50份，Al2O3：50份，K2O：10份，CaO 1份，B2O3 12份。
上述橡塑发泡绝热保温材料的制备方法，包括以下步骤：
(1)反射层的制备：将NBR、SBR、EVA、PVC、Ca/Zn热稳定剂投入密炼机进行高温密炼，温度为160℃，时间为8min；降温至110℃，恒温条件下，再加入无卤阻燃剂、纳米氧化铝、氧化硅、氢氧化铝、聚乙二醇、三氧化二锑、防护蜡、氧化石蜡、二辛脂、膨胀型隔热阻燃材料，混炼20min，出料至发泡炉内，加入发泡剂，130℃下发泡45min；冷却，即得反射层；
(2)隔热层的制备：将NBR、EVA、PVC、Ca/Zn热稳定剂投入密炼机进行高温密炼，温度为160℃，时间为8min；降温至110℃，恒温条件下，再加入无卤阻燃剂、玻璃纤维、空心微球、聚乙二醇、三氧化二锑、防护蜡、氧化石蜡、二辛脂、滑石粉、膨胀型隔热阻燃材料，混炼20min，出料至发泡炉内，加入发泡剂、膨胀珍珠岩、膨润土，130℃下发泡15min，得隔热层原料；将隔热层原料涂覆于反射层上，即得。
实施例9
橡塑发泡绝热保温材料，自上而下包括反射层和隔热层；所述反射层至少由以下重量份的组份制成：NBR 18份、SBR10份、EVA12份、PVC 7份、无卤阻燃剂25份、纳米氧化铝5份、氧化硅4份、氢氧化铝2份、聚乙二醇1.5份、三氧化二锑1.5份、防护蜡1.5份、氧化石蜡7份、二辛脂1.5份、Ca/Zn热稳定剂1.5份、发泡剂5份、膨胀型隔热阻燃材料10份；所述隔热层至少由以下重量份的组份制成：NBR 18份、EVA12份、PVC 7份、无卤阻燃剂25份、玻璃纤维10份、膨胀珍珠岩7份、膨润土3份、空心微球10份、聚乙二醇1.5份、三氧化二锑1.5份、防护蜡1.5份、氧化石蜡6份、二辛脂1.5份、Ca/Zn热稳定剂1.5份、发泡剂5份、滑石粉3份、实施例3的膨胀型隔热阻燃材料10份。
所述空心微球为包括以下重量份数组分：SiO2 70份，Al2O3：30份，K2O：8份，CaO5份，B2O3 6份。
上述橡塑发泡绝热保温材料的制备方法，包括以下步骤：
(1)反射层的制备：将NBR、SBR、EVA、PVC、Ca/Zn热稳定剂投入密炼机进行高温密炼，温度为155℃，时间为10min；降温至100℃，恒温条件下，再加入无卤阻燃剂、纳米氧化铝、氧化硅、氢氧化铝、聚乙二醇、三氧化二锑、防护蜡、氧化石蜡、二辛脂、膨胀型隔热阻燃材料，混炼15min，出料至发泡炉内，加入发泡剂，140℃下发泡30min；冷却，即得反射层；
(2)隔热层的制备：将NBR、EVA、PVC、Ca/Zn热稳定剂投入密炼机进行高温密炼，温度为155℃，时间为10min；降温至100℃，恒温条件下，再加入无卤阻燃剂、玻璃纤维、空心微球、聚乙二醇、三氧化二锑、防护蜡、氧化石蜡、二辛脂、滑石粉、膨胀型隔热阻燃材料，混炼15min，出料至发泡炉内，加入发泡剂、膨胀珍珠岩、膨润土，140℃下发泡30min，得隔热层原料；将隔热层原料涂覆于反射层上，即得。
测试实施例7-9的橡塑发泡绝热保温材料的性能，见表1。
将实施例7-9的橡塑发泡绝热保温材料制成保温板拼成边长0.5m的立方体，将立方体置于105℃烘箱内20min；对比例为将橡塑发泡绝热保温材料替换为市售橡塑保温材料。测试立方体内部温度，本发明的保温板制得的立方体的表面温度相较于对比例低20℃以上。

Claims (8)

1.一种橡塑发泡绝热保温材料，其特征在于：自上而下包括反射层和隔热层；所述反射层至少由以下重量份的组份制成：NBR 15-20份、SBR 5-15份、EVA10-15份、PVC 6-8份、无卤阻燃剂20-30份、纳米氧化铝4-6份、氧化硅2-5份、氢氧化铝1-3份、聚乙二醇1-2份、三氧化二锑1-2份、防护蜡1-2份、氧化石蜡5-8份、二辛脂1-2份、Ca/Zn热稳定剂1-2份、发泡剂4-6份、膨胀型隔热阻燃材料5-15份；所述隔热层至少由以下重量份的组份制成：NBR15-20份、EVA 10-15份、PVC 6-8份、无卤阻燃剂20-30份、玻璃纤维5-15份、膨胀珍珠岩6-8份、膨润土2-4份、空心微球5-15份、聚乙二醇1-2份、三氧化二锑1-2份、防护蜡1-2份、氧化石蜡5-8份、二辛脂1-2份、Ca/Zn热稳定剂1-2份、发泡剂4-6份、滑石粉2-4份、膨胀型隔热阻燃材料5-15份；所述膨胀型隔热阻燃材料的结构如式(I)所示：
式中，n为460-990之间的整数；R为烷基。
2.根据权利要求1所述的一种橡塑发泡绝热保温材料，其特征在于：自上而下包括反射层和隔热层；所述反射层至少由以下重量份的组份制成：NBR 18份、SBR 10份、EVA 12份、PVC 7份、无卤阻燃剂25份、纳米氧化铝5份、氧化硅4份、氢氧化铝2份、聚乙二醇1.5份、三氧化二锑1.5份、防护蜡1.5份、氧化石蜡7份、二辛脂1.5份、Ca/Zn热稳定剂1.5份、发泡剂5份、膨胀型隔热阻燃材料10份；所述隔热层至少由以下重量份的组份制成：NBR 18份、EVA 12份、PVC 7份、无卤阻燃剂25份、玻璃纤维10份、膨胀珍珠岩7份、膨润土3份、空心微球10份、聚乙二醇1.5份、三氧化二锑1.5份、防护蜡1.5份、氧化石蜡6份、二辛脂1.5份、Ca/Zn热稳定剂1.5份、发泡剂5份、滑石粉3份、膨胀型隔热阻燃材料10份。
3.根据权利要求1所述的一种橡塑发泡绝热保温材料，其特征在于：所述空心微球为包括以下重量份数组分：SiO2 50-90份，Al2O3：10-50份，K2O：5-10份，CaO 1-10份，B2O3 1-12份。
4.权利要求1所述的一种橡塑发泡绝热保温材料的制备方法，其特征在于：包括以下步骤：
(1)膨胀型隔热阻燃材料的制备：在惰性气体的保护、室温条件下，将氯硅烷和膦酸二甲酯反应，制得烷基硅基膦酸二甲酯；在惰性气体的保护、350～400℃下，将步骤(1)所得物烷基硅基膦酸二甲酯与三聚氰胺在催化剂作用下反应，冷却后真空干燥即得；步骤(1)所得物烷基硅基膦酸二甲酯与三聚氰胺的摩尔比为1∶(1～1.2)；
(2)反射层的制备：将NBR、SBR、EVA、PVC、Ca/Zn热稳定剂投入密炼机进行高温密炼，温度为150～160℃，时间为8～12min；降温至90-110℃，恒温条件下，再加入无卤阻燃剂、纳米氧化铝、氧化硅、氢氧化铝、聚乙二醇、三氧化二锑、防护蜡、氧化石蜡、二辛脂、膨胀型隔热阻燃材料，混炼10-20min，出料至发泡炉内，加入发泡剂，130-150℃下发泡15-45min；冷却，即得反射层；
(3)隔热层的制备：将NBR、EVA、PVC、Ca/Zn热稳定剂投入密炼机进行高温密炼，温度为150～160℃，时间为8～12min；降温至90-110℃，恒温条件下，再加入无卤阻燃剂、玻璃纤维、空心微球、聚乙二醇、三氧化二锑、防护蜡、氧化石蜡、二辛脂、滑石粉、膨胀型隔热阻燃材料，混炼10-20min，出料至发泡炉内，加入发泡剂、膨胀珍珠岩、膨润土，130-150℃下发泡15-45min，得隔热层原料；将隔热层原料涂覆于反射层上，即得。
5.根据权利要求4所述的一种橡塑发泡绝热保温材料的制备方法，其特征在于：步骤(1)中，所述氯硅烷选自三甲基氯硅烷、三乙基氯硅烷、三丙基氯硅烷、二甲基乙基氯硅烷、二甲基丙基氯硅烷和二乙基甲基氯硅烷。
6.根据权利要求4所述的一种橡塑发泡绝热保温材料的制备方法，其特征在于：步骤(1)中，所述氯硅烷与膦酸二甲酯的摩尔比为1∶(3～4)。
7.根据权利要求4所述的一种橡塑发泡绝热保温材料的制备方法，其特征在于：步骤(1)中，膦酸二甲酯与氯硅烷反应的溶剂选自二氯甲烷、氯仿和丙酮。
8.根据权利要求4所述的一种橡塑发泡绝热保温材料的制备方法，其特征在于：步骤(1)中，催化剂选自无水氯化镁、磷酸三苯酯、三乙胺中的一种或几种。
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