CN114015051B - 一种dopo-poss阻燃剂的制备方法及其应用 - Google Patents
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Abstract
本发明公开了一种DOPO‑POSS阻燃剂的制备方法及其应用,将OV‑POSS、DOPO和AIBN溶于甲苯中,氮气氛下在80~85℃反应12小时,再次加入AIBN,继续反应12小时,冷却至室温,除去上层清液,下层膏状物用二氯甲烷溶解,随后滴入沉淀剂中进行沉淀,过滤,得到DOPO‑POSS粗品,将粗品转移到分散剂中进行打浆分散,抽滤,干燥,制得DOPO‑POSS阻燃剂。本发明与现有技术相比,避免了高毒性的氯仿和苯作为反应溶剂和沉淀剂,产率高达82.7%,且有效降低了产品中的卤素含量,于95℃真空干燥5小时,氯含量<50ppm,更加符合环保要求。本发明获得的DOPO‑POSS还具有热稳定性好、成碳率高的特点,800℃残炭率高于45%。本发明制得DOPO‑POSS阻燃剂可以来改性各种聚合物,从而扩展聚合物的应用范围。
Description
技术领域
本发明涉及阻燃剂制备和应用技术领域,具体涉及一种DOPO-POSS阻燃剂的制备方法及其应用。
背景技术
DOPO-POSS作为聚乳酸、聚碳酸酯、环氧树脂以及ABS工程塑料等高分子材料的阻燃剂,是一种含磷笼型低聚硅倍半氧烷,分子式为C112H96O28P8Si8。
DOPO-POSS用于高分子阻燃,因其结构中含磷和硅的含量高,具有磷硅协效的阻燃效果,尤其是其具有笼状的硅氧烷高度对称结构,除了阻燃还具有优良的耐热性和和机械性能等。该阻燃剂首次由北京理工大学杨荣杰教授团队合成,杨荣杰教授团队采用了DOPO与乙烯基三乙氧基硅先加成生成A和B的混合物,随后再水解,所获得的DOPO-POSS(C),混杂含有裸露Si-OH结构的DOPO-POSS类似物D(图1所示)。该工艺条件下合成的DOPO-POSS的初始分解温度为334℃,在800℃残碳率为41.4%。
2016年,杨荣杰课题组又报道采用OV-POSS与DOPO在自由基引发剂AIBN的催化下于氯仿中发生加成反应来合成DOPO-POSS,后处理是将反应液在苯中沉淀,以获得DOPO-POSS(图2所示),但未报道产率。该工艺条件下合成的DOPO-POSS的初始分解温度为356℃,800℃残碳率为43.1%。使用上述工艺制备DOPO-POSS时发现,氯仿反应液在苯中沉淀易于得到粘稠物,提纯较为困难,获得纯度符合要求(≥95%)的DOPO-POSS的产率难以超过50%,且于95℃真空干燥5小时,其氯含量>9500ppm,远超过无卤阻燃剂的含卤标准(通常卤素含量要求<800ppm)。此外,采用氯仿和苯分别作为反应溶剂和沉淀剂毒性较高,对操作人员和环境不友好。
因而,急需改进DOPO-POSS的合成方法,用低毒溶剂替代,并改进产物纯化的方法,获得高的收率,有效降低产品成本以及减少废弃物的产生。
发明内容
本发明的目的是针对现有技术中的不足,提供一种DOPO-POSS阻燃剂的制备方法。该方法用甲苯作为反应溶剂,二氯甲烷作为良溶剂,甲基叔丁基醚或乙酸乙酯作为不良溶剂,替代了对操作人员和环境危害大的三氯甲烷和苯,且使用该方法合成的DOPO-POSS产率高达82.7%,卤素含量易于达标。此外,制得的DOPO-POSS还具有热稳定性好的特点,其初始分解温度为373℃,成碳率高,800℃残碳率高达45.49%。
本发明的另一目的在于提供上述DOPO-POSS阻燃剂在制备阻燃型聚合物材料中的应用。
本发明的目的通过以下技术方案实现:
一种DOPO-POSS阻燃剂的制备方法,包括如下步骤:
(1)将OV-POSS、DOPO和偶氮二异丁腈溶于甲苯中,氮气氛下在80~85℃搅拌反应24h,冷却至室温,除去上层清液,得到下层膏状混合物;
(2)将步骤(1)所述的下层膏状混合物用二氯甲烷溶解,得到混合溶液;
(3)将步骤(2)所述的混合溶液滴入沉淀剂中进行沉淀,过滤,得到块状八[2-(DOPO)乙基]倍半硅氧烷粗品;
(4)将块状八[2-(DOPO)乙基]倍半硅氧烷粗品转移到分散剂中进行打浆,搅拌至分散均匀,抽滤,干燥,制得DOPO-POSS阻燃剂材料。
优选地,所述步骤(1)中DOPO与OV-POSS的摩尔比为8.8-9.0:1,偶氮二异丁腈与OV-POSS的摩尔比为0.22:1。
优选地,所述步骤(1)中偶氮二异丁腈分两次加入:
第一次在反应开始时,偶氮二异丁腈加入量与OV-POSS的摩尔比为0.2:1;
第二次在反应进行12h,偶氮二异丁腈加入量与OV-POSS的摩尔比为0.02:1。
优选地,所述步骤(2)中二氯甲烷与膏状混合物的体积比为2~2.5:1。
优选地,所述步骤(3)中沉淀剂与混合溶液的体积比为10~11:1。
优选地,所述步骤(3)中沉淀剂为甲基叔丁基醚或乙酸乙酯。
优选地,所述步骤(4)中每克八[2-(DOPO)乙基]倍半硅氧烷粗品用10mL分散剂进行打浆分散。
优选地,所述步骤(4)中分散剂为甲基叔丁基醚或乙酸乙酯。
一种根据上述制备方法制得的DOPO-POSS阻燃剂在制备阻燃型聚合物材料中的应用,将所述DOPO-POSS阻燃剂通过共混添加到聚合物中。
本发明的有益效果是:
本发明将OV-POSS、DOPO和AIBN溶于甲苯中,氮气氛下在80~85℃反应12h,再次加入AIBN,并继续反应12h,冷却至室温,除去上层清液,下层膏状物用二氯甲烷溶解,随后滴入沉淀剂中进行沉淀,过滤,得到块状固体八[2-(DOPO)乙基]倍半硅氧烷(DOPO-POSS)粗品,将粗品分散到分散剂中打浆,待块状固体在分散剂中分散均匀后,抽滤,干燥,制得DOPO-POSS阻燃剂材料,产率高达82.7%,DOPO-POSS氯含量小于50ppm,符合无卤阻燃的要求。
本发明与现有技术相比,避免了高毒性的氯仿和苯分别作为反应溶剂和沉淀剂,且有效降低了产品中的卤素含量,于95℃真空干燥5h,氯含量<50ppm,更加符合环保要求。
本发明制得的DOPO-POSS还具有热稳定性好,成碳率高的特点,800℃残碳率高达45.49%,可以作为一种高效的高耐热阻燃剂来改性各种聚合物,从而扩展聚合物的应用范围。
附图说明
图1乙烯基三乙氧基硅与DOPO先自由基加成再水解制备DOPO-POSS路线图;
图2 OV-POSS与DOPO于氯仿中发生自由基加成制备DOPO-POSS的路线图;
图3本发明实施例2制备DOPO-POSS路线图;
图4本发明实施例2制得的DOPO-POSS的FT-IR图;
图5本发明实施例2制得的DOPO-POSS的H-NMR图;
图6本发明实施例2制得的DOPO-POSS的TGA图。
具体实施方式
为了进一步理解本发明,下面结合实施例对本发明优选实施方案进行描述,但是应当理解,这些描述只是为进一步说明本发明的特征和优点,而不是对本发明权利要求的限制。
本发明中,OV-POSS是八乙烯基倍半硅氧烷,购于苏州矽索新材料有限公司,纯度98%;
DOPO是9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物,购于优缔股份有限公司EUTECCHEMICAL CO.,LTD,纯度98%;
AIBN是偶氮二异丁腈,购于上海安耐吉化学有限公司,纯度99.5%;
DOPO-POSS是八[2-(DOPO)乙基]倍半硅氧烷。
本发明所用试剂或仪器未注明生产厂商者,均为可以通过市售购买获得的常规产品。
实施例1
将18.96mmol八乙烯基倍半硅氧烷(OV-POSS)、170.61mmol 9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物(DOPO)和3.79mmol偶氮二异丁腈(AIBN),溶于甲苯65mL中,氮气氛下在85℃反应12小时,再次加入0.38mmol的AIBN,并继续反应12小时。
反应结束后,冷却至室温,除去上层甲苯清液,得到下层膏状物。40mL下层膏状物用100mL二氯甲烷溶解,得到混合溶液。随后将100mL混合溶液滴入到1000mL甲基叔丁基醚中进行沉淀,过滤,得到50g白色块状固体八[2-(DOPO)乙基]倍半硅氧烷(DOPO-POSS)粗品。
将50g八[2-(DOPO)乙基]倍半硅氧烷(DOPO-POSS)粗品分散到500mL甲基叔丁基醚中打浆,搅拌,待块状固体成为粉状均匀分散在溶剂中时,抽滤,干燥,制得30.5g的DOPO-POSS,产率为68%。
此外,甲基叔丁基醚可在旋转蒸发仪上进行回收。
实施例2
将18.96mmol八乙烯基倍半硅氧烷(OV-POSS)、166.82mmol 9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物(DOPO)和3.79mmol偶氮二异丁腈(AIBN),溶于甲苯65mL中,氮气氛围下在80℃反应12小时,再次加入0.38mmol的AIBN,并继续反应12小时。
反应结束后,冷却至室温,除去上层甲苯清液,得到下层膏状物。40mL下层膏状物用80mL二氯甲烷溶解,得到混合溶液。随后将100mL混合溶液随后滴入1100mL乙酸乙酯中进行沉淀,过滤,得到40g白色固体八[2-(DOPO)乙基]倍半硅氧烷(DOPO-POSS)粗品。
将40g白色沉淀八[2-(DOPO)乙基]倍半硅氧烷(DOPO-POSS)粗品分散到400mL乙酸乙酯中打浆,搅拌,待块状固体成为粉状均匀分散在溶剂中时,抽滤,干燥,制得37g的DOPO-POSS,产率为82.7%。
此外,乙酸乙酯可在旋转蒸发仪上进行回收。
对本发明实施例2制得的DOPO-POSS,进行FT-IR、1H-NMR和TGA测试分析。
如图4所示,DOPO-POSS的FT-IR谱图上,1582.1-1594.6cm-1的峰归属为联苯的骨架吸收;908.5,1203.7,and 1476.8cm-1的峰分别为P-O-Ph,P=O和P-Ph键的伸缩振动吸收峰。此外,1111.8cm-1是Si-O-Si键的吸收峰,3068和2900cm-1的两个弱吸收峰为联苯和CH2-CH2的C-H振动吸收峰。与原料OV-POSS相比,未观测到其-CH=CH2的特征吸收峰(1601,1407,1274cm-1);同时,也未观测到DOPO原料分子中P-H键的吸收峰(2437cm-1),说明DOPO与POSS发生了充分的加成反应。
如图5所示,1H-NMR谱中,6.80-8.10ppm(8H,m)为DOPO-POSS分子中芳环上的氢信号,0.77(2H,m)和1.91(2H,m)ppm的峰分别为Si-CH2和P-CH2的氢信号。其中在8.17ppm有微量P-H键残留(与DOPO-POSS的摩尔比为0.01:1)和-CH=CH2的残留(与DOPO-POSS的摩尔比为0.09:1)。
如图6所示,N2气氛下测的TGA数据表明,DOPO-POSS的T5%和Tmax分别为373.4℃和493.0℃,比文献合成方法所得到的DOPO-POSS热性能更优(见表1),其残炭率在800℃时为45.49%。
表1在N2气氛下DOPO-POSS的TGA数据
根据上述说明书的揭示,本发明所属领域的技术人员还可以对上述实施方式进行适当的变更和修改。因此,本发明并不局限于上面揭示和描述的具体实施方式,对本发明的一些修改和变更也应当落入本发明的权利要求的保护范围内。此外,尽管本说明书中使用了一些特定的术语,但这些术语只是为了方便说明,并不对本发明构成任何限制。
Claims (7)
1.一种DOPO-POSS阻燃剂的制备方法,其特征在于:包括如下步骤:
(1)将OV-POSS、DOPO和偶氮二异丁腈溶于甲苯中,氮气氛下在80-85℃搅拌反应24h,冷却至室温,除去上层清液,得到下层膏状混合物;
(2)将步骤(1)所述的下层膏状混合物用二氯甲烷溶解,得到混合溶液;
(3)将步骤(2)所述的混合溶液滴入乙酸乙酯中进行沉淀,过滤,得到块状八[2-(DOPO)乙基]倍半硅氧烷粗品;
(4)将块状八[2-(DOPO)乙基]倍半硅氧烷粗品转移到乙酸乙酯中进行打浆,搅拌至分散均匀,抽滤,干燥,制得DOPO-POSS阻燃剂材料。
2.根据权利要求1所述的DOPO-POSS阻燃剂的制备方法,其特征在于:所述步骤(1)中DOPO与OV-POSS的摩尔比为8.8~9.0:1,偶氮二异丁腈与OV-POSS的摩尔比为0.22:1。
3.根据权利要求2所述的DOPO-POSS阻燃剂的制备方法,其特征在于:所述步骤(1)中偶氮二异丁腈分两次加入:
第一次在反应开始时,偶氮二异丁腈加入量与OV-POSS的摩尔比为0.2:1;
第二次在反应进行12h,偶氮二异丁腈加入量与OV-POSS的摩尔比为0.02:1。
4.根据权利要求1所述的DOPO-POSS阻燃剂的制备方法,其特征在于:所述步骤(2)中二氯甲烷与膏状混合物的体积比为2~2.5:1。
5.根据权利要求1所述的DOPO-POSS阻燃剂的制备方法,其特征在于:所述步骤(3)中沉淀剂与混合溶液的体积比为10~11:1。
6.根据权利要求1所述的DOPO-POSS阻燃剂的制备方法,其特征在于:所述步骤(4)中每克八[2-(DOPO)乙基]倍半硅氧烷粗品用10mL乙酸乙酯进行打浆分散。
7.一种根据权利要求1所述制备方法制得的DOPO-POSS阻燃剂在制备阻燃型聚合物材料中的应用,其特征在于,将所述DOPO-POSS阻燃剂通过共混添加到聚合物中。
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