CN116120382B - 一种糖基环状磷酰胺衍生物、制备方法及阻燃剂 - Google Patents
一种糖基环状磷酰胺衍生物、制备方法及阻燃剂 Download PDFInfo
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Abstract
本发明公开了一种糖基环状磷酰胺衍生物、制备方法及阻燃剂，属于化合物合成领域。所述的糖基环状磷酰胺衍生物是以D‑木糖为原料，经过三步反应得到目标产品。该制备方法产率高，工艺简单，原料成本较低，环境污染小，且制备出的糖基环状磷酰胺衍生物阻燃性能优异，易于实现工业化。
Description
技术领域
本发明涉及化合物领域，具体涉及一种糖基环状磷酰胺衍生物及其制备方法，以及含有该组分的阻燃剂。
背景技术
20世纪以来，多用途多功能的高分子材料已经成为现代生活的必需品。然而，大多数高分子材料因其固有的易燃性，潜在威胁着人类的生命财产安全[Velencoso M M,Battig A,Markwart J C,Angew Chem Int Ed Engl,2018,57(33):10450-10467.]。为了降低火灾风险、满足消防安全要求，开发无卤、低毒、高效的阻燃剂一直是学界的研究重点。其中，生物基磷系阻燃剂因其具有良好的可持续性、优异的环境效益和阻燃效率等优点，已经成为新一代阻燃剂最有前途的方向之一。已被证明具备优异的成炭性能和阻燃效率的生物基材料包括：木质素[Yu Y,Fu S,Song P A.Polymer Degradation and Stability,2012,97(4):541-546.]、蛋白质[Alongi J,Carletto R A,Bosco F.Polymer Degradation&Stability,2014,99:111-117.]、淀粉[Wang J,Ren Q,Zheng W.Industrial&EngineeringChemistry Research,2014,53(4):1422-1430.]、壳聚糖[Hu S,Song L,Pan H.Journal ofAnalytical&Applied Pyrolysis,2012,97:109-115.]等。
磷系阻燃剂主要分为添加型和反应型两大类。其中，添加型磷系阻燃剂因其直接和高分子材料混合而成的引入方式，在保存和使用过程中往往存在阻燃剂迁移、水解等问题，可能会影响材料的阻燃和机械性能，并存在潜在的健康风险[Morgan A B.PolymerReviews,2018,59(1):25-54.]。而反应型阻燃剂与高分子基体材料间通过化学键键合，在赋予材料良好阻燃性能的基础上，克服了添加型阻燃剂不稳定、机械性能差等缺点[Ménard,Negrell-Guirao,Claire；Ferry,Laurent.European Polymer Journal,2014,57:109-120.]。目前大量的对反应型磷系阻燃剂的研究表明，环状的磷酸酯阻燃剂以及含苯环的磷酸酯阻燃剂具有更优越的成炭性和热稳定性，因而阻燃性能更好[Guo,Q Q,Cao J,HanY Y.Green Chemistry,2017,19(14):3418-3427.]。
发明内容
本发明的目的在于提供一种基于D-木糖结构的新型糖基环状磷酰胺衍生物的制备方法及其在阻燃剂领域的应用。该制备方法工艺简单，原料成本较低，环境污染小，且制备出的糖基环状磷酰胺衍生物阻燃性能突出，易于实现工业化。
本发明的目的可以通过以下技术方案实现：
一种新型糖基环状磷酰胺衍生物，糖基环状磷酰胺衍生物的结构特征如下：
一种新型糖基环状磷酰胺衍生物的制备方法，该方法包括以下步骤：
第一步：
方法一：将D-木糖溶于有机溶剂中，加入2,2-二甲氧基丙烷和酸，0～90℃反应1～2h，监测反应完成后，向反应体系加入无机碱淬灭反应，旋干有机相，乙酸乙酯萃取，得到化合物2粗品；
方法二：将D-木糖溶于有机溶剂中，加入丙酮和酸，0～90℃反应1～2h，监测反应完成后，向反应体系加入无机碱淬灭反应，旋干有机相，乙酸乙酯萃取，得到化合物2粗品；
第二步：将化合物2粗品溶于水中，加入酸，0～40℃反应5～6小时。监测反应完成后，向反应体系加入无机碱淬灭反应，旋干反应液，二氯甲烷萃取，得到化合物3粗品；
第三步：将化合物3粗品溶于有机溶剂中，加入缚酸剂，在0～60℃条件下缓慢加入三氯氧磷，40～80℃条件下反应，监测反应完成后，加入乙二胺，40～80℃条件下反应，监测反应完成后，旋干溶剂，二氯甲烷萃取，旋干有机层，得到化合物4粗品。
上述方法中：所述的有机溶剂为乙酸乙酯、二氯甲烷、二氯乙烷、氯仿、四氯化碳、乙腈、N,N-二甲基甲酰胺、二甲亚砜、四氢呋喃、二氧六环或乙醚；所述的无机碱为NaHCO3、Na2CO3、KHCO3、K2CO3、LiOH、NaOH或KOH。
上述方法中：所述的缚酸剂为乙二胺、三乙胺、二异丙基乙胺、N-甲基咪唑、吡啶类、钠氢、甲醇钠、乙醇钾或叔丁醇钾；所述的酸为盐酸、硫酸、对甲苯磺酸、甲酸、乙酸、三氟乙酸、无水硫酸铜、樟脑磺酸或酸型阳离子交换树脂。
本发明技术方案中：所述的糖基环状磷酰胺衍生物的阻燃性能及其在阻燃剂领域的应用。
本发明的有益效果：该制备方法产率高，工艺简单，原料成本较低，环境污染小，且制备出的糖基环状磷酰胺衍生物阻燃性能突出，易于实现工业化。
附图说明
图1是化合物4的热重(TG)曲线和热重微分(DTG)曲线(N2氛围)；
图2是化合物4的红外图谱。
具体实施方式
下面结合具体实例对本发明作进一步阐述，但本发明不局限于这些实施例。
合成路线如下：
实施例1
将D-木糖(500g，3.33mol)溶于DMF中，加入樟脑磺酸(0.1eq)和2,2-二甲氧基丙烷(4eq)，90℃反应1～2h，监测反应完成后，旋干有机相，乙酸乙酯萃取，旋干有机相，得到化合物2粗品，产率为97％。1H NMR(300MHz,Chloroform-d)δ6.02(d,J＝3.9Hz,1H),4.54(d,J＝3.6Hz,1H),4.30(d,J＝2.7Hz,1H),4.02–4.10(m,3H),1.47(s,3H),1.45(s,3H),1.33(s,3H)；1.30(s,3H)；13C NMR(75MHz,Chloroform-d)δ111.8,105.3,97.4,84.4,73.1,71.5,60.0,28.8,26.6,26.0,18.5.。
实施例2
将化合物2(500g，2mol)溶于水中，加入浓盐酸，调整溶液PH值为1～2,室温下反应3～5h。监测反应完成后，向反应体系加入碳酸氢钠淬灭反应，乙酸乙酯萃取，旋干有机相，得到化合物3粗品，产率为95％。1H NMR(300MHz,Chloroform-d)δ5.95(d,J＝3.7Hz,1H),4.50(d,J＝3.7Hz,1H),4.27(d,J＝2.7Hz,1H),4.16(m,1H),4.04–3.89(m,2H),1.47(s,3H),1.30(s,3H)；13C NMR(75MHz,Chloroform-d)δ111.8,104.8,85.5,79.3,76.1,60.6,26.7,26.1.。
实施例3
将化合物3(50g，262.9mmol)溶于1,4-二氧六环中，加入三乙胺(3.6eq,131.6mL，946.4mmol)，在冰浴条件下缓慢加入三氯氧磷(1.1eq,26.9mL，289.2mmol)，移入油浴40℃反应2h。监测原料反应完全，加入乙二胺(3eq,47.4mL，788.7mmol)，反应2h，监测反应完全，抽滤，旋干有机相，二氯甲烷萃取，旋干有机相，分离得到化合物4，产率93％。
熔点(mp),105-110℃；1H NMR(300MHz,Chloroform-d)δ6.01–5.96(m,1H),4.93(d,J＝2.3Hz,1H),4.88–4.72(m,1H),4.69(d,J＝2.3Hz,1H),4.64(d,J＝3.7Hz,1H),4.48(m,1H),4.16–4.09(m,1H),3.12–2.82(m,2H),2.75(s,1H),1.46(s,3H),1.31(s,3H)；13CNMR(75MHz,Chloroform-d)δ112.4,104.9,84.3,80.4,72.0,65.2,42.6,26.6,26.1；MS(ESI)m/z,296.3357[M+H]+。
热重分析(TGA-DTG)采用德国NETZSCH公司STA449F3同步热分析仪对泡沫样品进行测定，氮气流速为100ml/min，升温速率10℃/min，测试温度范围30～800℃。由图1可见，其初始分解温度(分解5％时的温度)Tonset为209℃，在此温度之前TG曲线较为平稳，这说明当温度低于209℃时，化合物4具有较好的热稳定性。由图可知，温度低于240℃时，样品质量损失很少，此阶段主要是水的蒸发引起的质量损失。当温度继续升高时，样品迅速降解，且其分解速率在246℃达到最大值3.19％/min。在DTG曲线中观察到化合物4在246℃出现一个明显的热降解峰，判断化合物4的热降解主要发生在240℃-260℃，推测可能是由于P-O-C键或P-N-C键的断裂，生成含磷酸盐。化合物4在800℃时的残炭量为41.7wt％，通常来说，残炭量是评价阻燃剂阻燃性能的重要指标，残炭量越高，阻燃性能越好。由此可认为，化合物4是一种性能优异的反应型阻燃剂，适合不同阻燃材料的制备。
表1 单独添加TCPP对聚氨酯极限氧指数的影响
| TCPP阻燃剂加入量/％ | 0 | 7 | 20 | 28 | 42 |
| 极限氧指数/％ | 18 | 19 | 21 | 22 | 24 |
表2 化合物4和TCPP复配对聚氨酯极限氧指数的影响
极限氧指数测试(LOI)按GB/T 2406-1993标准采用南京市江宁区分析仪器厂JF-3氧指数测定仪测定，泡沫的尺寸要求为130mm×6.5mm×3.0mm。极限氧指数是指聚合物在氧气和氮气混合气体中恰好能支持其燃烧时氧气的体积分数浓度，是表征材料燃烧行为的指数，是评价阻燃剂阻燃性能的重要指标，材料的LOI值越高，则表示越不易燃烧，一般情况下LOI小于22％属于易燃，LOI在22～27％之间属于可燃，而LOI大于27％则属于难燃。我们将化合物4与TCPP复配使用，测试其对聚氨酯极限氧指数的影响。由表2可看出当化合物4和TCPP分别添加20％和8％时，极限氧指数可达到31％，具有良好的阻燃效果；阻燃剂化合物4和TCPP分别添加30％和12％时，极限氧指数可达到33％，已经达到难燃材料的要求。由此可认为，化合物4对聚氨酯的阻燃效果十分优异。
Claims (3)
1.一种糖基环状磷酰胺衍生物，其特征在于：糖基环状磷酰胺衍生物的结构式如下：
2.一种糖基环状磷酰胺衍生物的制备方法，其特征在于：合成路线如下
所述步骤a如下：
将D-木糖溶于N,N-二甲基甲酰胺中，加入樟脑磺酸和2,2-二甲氧基丙烷，90℃反应1～2h，监测反应完成后，旋干有机相，乙酸乙酯萃取，旋干有机相，得到化合物2；
所述步骤b如下：
将化合物2溶于水中，加入浓盐酸，调整溶液PH值为1～2,室温下反应3～5h，监测反应完成后，向反应体系加入碳酸氢钠淬灭反应，乙酸乙酯萃取，旋干有机相，得到化合物3；
所述步骤c如下：
将化合物3溶于有机溶剂1,4-二氧六环中，加入缚酸剂三乙胺，在冰浴条件下缓慢加入三氯氧磷，移入油浴40℃反应2h，监测原料反应完全，加入乙二胺，反应2h，监测反应完全，抽滤，旋干有机相，二氯甲烷萃取，旋干有机相，分离得到化合物4。
3.一种糖基环状磷酰胺衍生物的阻燃剂，其特征在于，所述阻燃剂含有权利要求1所述的糖基环状磷酰胺衍生物。
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| WO2016040479A1 (en) * | 2014-09-09 | 2016-03-17 | The Board Of Regents Of The Nevada System Of Higher Education On Behalf Of The University Of Nevada, Las Vegas | N-heterocyclic phosphines |
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