CN110218159B - 一种n-异冰片基丙烯酰胺单体、阻燃单体、阻燃性材料及阻燃性材料的制备方法 - Google Patents
一种n-异冰片基丙烯酰胺单体、阻燃单体、阻燃性材料及阻燃性材料的制备方法 Download PDFInfo
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Abstract
本发明公开了一种N‑异冰片基丙烯酰胺单体、阻燃单体、阻燃性材料及阻燃性材料的制备方法。N‑异冰片基丙烯酰胺单体，其结构式为：
阻燃单体的结构式为：
本发明N‑异冰片基丙烯酰胺单体，为松节油衍生物，可用于制备阻燃单体等，原料为可再生的生物质材料，无毒无害，环境友好；由阻燃单体N‑三甲氧基硅丙基‑N‑异冰片基丙烯酰胺制备的阻燃材料为与高分子材料相容性好、阻燃性能好、环境友好的含氮有机硅阻燃材料。
Description
技术领域
本发明涉及一种N-异冰片基丙烯酰胺单体、阻燃单体、阻燃性材料及阻燃性材料的制备方法，属于无卤阻燃剂领域。
背景技术
近年来，阻燃材料已经成为工业和研究领域中的主要问题之一。传统上，多采用有机卤化物制备阻燃材料，然而卤化物中的氯、溴元素会在燃烧过程中生成有毒和腐蚀性的烟雾。因此，需要寻找环保的无卤阻燃剂来保护人类健康和生态系统。常见的无卤阻燃剂主要包括硼原子、含磷化合物和有机硅衍生物等，其中有机硅被认为是“环保”添加剂，因为与现有材料相比，它的使用可以减少对环境的有害影响。
中国专利文献CN108359174A公开了一种低气味低溴阻燃聚丙烯复合物及其制备方法，采用聚丙烯(PP)62％-90.6％、复合阻燃剂3％-15％、增韧剂5％-15％、除味剂1％-5％、抗氧剂0.1％-1.5％、其他加工助剂0.3％-1.5％，阻燃性得到提高，但是由于使用卤元素，仍然含有毒性，对人体有害。
现有的阻燃材料仍然存在阻燃性能和环保要求不能很好地兼顾的问题，且所用原料多限于石化产品。
发明内容
为了解决现有技术中存在的燃性能和环保要求不能很好地兼顾等缺陷，本发明提供一种N-异冰片基丙烯酰胺单体、阻燃单体、阻燃性材料及阻燃性材料的制备方法。
为解决上述技术问题，本发明所采用的技术方案如下：
一种N-异冰片基丙烯酰胺单体，其结构式为：
上述N-异冰片基丙烯酰胺为松节油衍生物，其合成路线为：
上述N-异冰片基丙烯酰胺可用于制备阻燃单体。
作为一种优选方案，由上述N-异冰片基丙烯酰胺单体制备的阻燃单体的结构式为：
上述阻燃单体，由N-异冰片基丙烯酰胺和γ-氯丙基三甲氧基硅烷制成。
γ-氯丙基三甲氧基硅烷为萨恩化学技术有限公司提供。
为了提高产品得率，上述阻燃单体的合成路线为：
由上述阻燃单体所制备的阻燃材料的结构式为：
上述松节油改性的阻燃性材料由N-三甲氧基硅丙基-N-异冰片基丙烯酰胺和N-异丙基丙烯酰胺在引发剂的作用下反应生成。
N-异丙基丙烯酰胺为萨恩化学技术有限公司提供，纯度为98％。
上述用N-三甲氧基硅丙基-N-异冰片基丙烯酰胺(NPSBAM)作为阻燃单体，与N-异丙基丙烯酰胺(NIPAM)无规共聚制备阻燃型材料。阻燃单体来源于松节油，是一种天然的可再生的生物质材料，无毒无害，申请人经研究发现，松节油衍生物的氮元素，可以与有机硅协同阻燃，具有良好的应用前景。
为了分提高反应效率，引发剂为偶氮二异丁腈(AIBN)，反应路线为：
为了兼顾产品的质量和效率，进一步优选，阻燃性材料的制备方法，包括如下步骤：
(1)将N-三甲氧基硅丙基-N-异冰片基丙烯酰胺和N-异丙基丙烯酰胺溶于40±5℃的叔丁醇(TBA)中；
(2)在氮气保护下，升温至70±5℃后，加入引发剂，70±5℃下继续反应5±0.5小时，即得松节油改性的阻燃性材料。
为了进一步提高产品的阻燃性和相容性，步骤(1)中，N-三甲氧基硅丙基-N-异冰片基丙烯酰胺和N-异丙基丙烯酰胺的质量比为(0.5～4)：(96～99.5)；叔丁醇与N-三甲氧基硅丙基-N-异冰片基丙烯酰胺和N-异丙基丙烯酰胺的质量和之比为(80～90)：15。
为了保证产品质量，步骤(2)中，在25～35min，升温至70±5℃；引发剂的质量用量为步骤(1)中物料质量和的0.7～0.8％；反应结束后，反应液倒入聚四氟乙烯铺膜板中，在45±5℃下干燥45～50h，制得松节油改性的阻燃性材料。
本发明未提及的技术均参照现有技术。
本发明N-异冰片基丙烯酰胺单体，为松节油衍生物，可用于制备阻燃单体等，原料为可再生的生物质材料，无毒无害，环境友好；由阻燃单体N-三甲氧基硅丙基-N-异冰片基丙烯酰胺制备的阻燃材料为与高分子材料相容性好、阻燃性能好、环境友好的含氮有机硅阻燃材料。
附图说明
图1为本发明实施例中所得产物的FT-IR图(a为N-三甲氧基硅丙基-N-异冰片基丙烯酰胺，b为松节油改性的阻燃性材料)；
图2为本发明实施例中所得产物的1HNMR图(c为γ-氯丙基三甲氧基硅烷，d为N-异冰片基丙烯酰胺，e为松节油改性的阻燃性材料)；
图3为本发明实施例2所得N-三甲氧基硅丙基-N-异冰片基丙烯酰胺的质谱图；
图4为本发明实施例所得松节油改性的阻燃性材料氧指数图；
图5为本发明实施例所得松节油改性的阻燃性材料拉伸性能图。
具体实施方式
为了更好地理解本发明，下面结合实施例进一步阐明本发明的内容，但本发明的内容不仅仅局限于下面的实施例。
实施例1
N-异冰片基丙烯酰胺单体的制备：将7.05g莰烯和0.82g水加入装有9ml丙烯腈的耐压瓶中，然后再加入2g磷钨酸和2g吩噻嗪，在100℃下反应，采用GC跟踪监测，反应完全后，停止反应。将反应液减压蒸馏回收丙烯腈后，溶于乙酸乙酯中，用饱和食盐水洗涤3次，再经减压蒸馏除去溶剂即得N-异冰片基丙烯酰胺产品。为了获得高纯度产品，将产物溶于一定量的乙醇中重结晶，然后将析出的固体用乙醇洗涤4次，所得产物纯度达98％。所得N-异冰片基丙烯酰胺单体的1HNMR见图2中曲线d。
实施例2
N-三甲氧基硅丙基-N-异冰片基丙烯酰胺的制备：称取1mol的N-异冰片基丙烯酰胺和1.2mol NaH溶于10mol N，N-二甲基甲酰胺(DMF)中，在60℃下反应3h，然后加入1molγ-氯丙基三甲氧基硅烷，在80℃下反应10h。反应结束后，将反应液溶于乙酸乙酯中，先用去离子水洗涤三次，再用饱和食盐水洗涤7次，减压蒸馏除去乙酸乙酯即得N-三甲氧基硅丙基-N-异冰片基丙烯酰胺，所得N-三甲氧基硅丙基-N-异冰片基丙烯酰胺的红外谱图见图1中曲线a，质谱图见图3。
实施例3
阻燃性材料的制备方法，包括如下步骤：
(1)将N-三甲氧基硅丙基-N-异冰片基丙烯酰胺和N-异丙基丙烯酰胺溶于40℃的叔丁醇中；
(2)在氮气保护下，在25～35min，升温至70℃后，加入引发剂偶氮二异丁腈(AIBN)，70℃下继续反应5小时，将反应液倒入聚四氟乙烯铺膜板中，在45℃下干燥48h，即得松节油改性的阻燃性材料。
表1 P(NIPAM-co-NIBAM)共聚物的各组分配比
表中，NPSBAM为N-三甲氧基硅丙基-N-异冰片基丙烯酰胺，NIPAM为N-异丙基丙烯酰胺，AIBN为偶氮二异丁腈，TBA为叔丁醇；NPSBAM(wt％)+NIPAM(wt％)+TBA(wt％)＝100％，AIBN(wt％)为相对NPSBAM(wt％)+NIPAM(wt％)+TBA(wt％)的百分比，各例所得松节油改性的阻燃性材料氧指数见图4，防火等级UL94都达到HB；NPSBAM-4.0所得松节油改性的阻燃性材料的红外谱图见图1中曲线b，1HNMR见图2中曲线e；各例所得松节油改性的阻燃性材料拉伸性能见图5。
Claims (8)
1.一种由N-异冰片基丙烯酰胺单体制备的阻燃单体，其特征在于：其结构式为：
2.一种权利要求1所述的由N-异冰片基丙烯酰胺单体制备的阻燃单体的制备方法，其特征在于：由N-异冰片基丙烯酰胺和γ-氯丙基三甲氧基硅烷制成。
3.如权利要求2所述的制备方法，其特征在于：其合成路线为：
4.由权利要求1所述的阻燃单体所制备的阻燃材料，其特征在于：其结构式为：
其中，n为7-10，m为7-10。
5.权利要求4所述的阻燃性材料的制备方法，其特征在于：由N-三甲氧基硅丙基-N-异冰片基丙烯酰胺和N-异丙基丙烯酰胺在引发剂的作用下反应生成。
6.如权利要求5所述的制备方法，其特征在于：引发剂为偶氮二异丁腈，反应路线为：
7.如权利要求5或6所述的制备方法，其特征在于：包括如下步骤：
(1)将N-三甲氧基硅丙基-N-异冰片基丙烯酰胺和N-异丙基丙烯酰胺溶于40±5℃的叔丁醇中；
(2)在氮气保护下，升温至70±5℃后，加入引发剂，70±5℃下继续反应5±0.5小时，即得松节油改性的阻燃性材料。
8.如权利要求7所述的制备方法，其特征在于：步骤(1)中，N-三甲氧基硅丙基-N-异冰片基丙烯酰胺和N-异丙基丙烯酰胺的质量比为(0.5～2.5)：(97.5～99.5)；叔丁醇与N-三甲氧基硅丙基-N-异冰片基丙烯酰胺和N-异丙基丙烯酰胺的质量和之比为(80～90)：15；
步骤(2)中，在25～35min，升温至70±5℃；引发剂的质量用量为步骤(1)中物料质量和的0.7～0.8％；反应结束后，反应液倒入聚四氟乙烯铺膜板中，在45±5℃下干燥45～50h，制得松节油改性的阻燃性材料。
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