CN110128474A - 氮磷硫三元协效阻燃剂双dopo噻唑化合物的制备方法及其应用 - Google Patents
氮磷硫三元协效阻燃剂双dopo噻唑化合物的制备方法及其应用 Download PDFInfo
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- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
- C07F9/657163—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom
- C07F9/657172—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom the ring phosphorus atom and one oxygen atom being part of a (thio)phosphinic acid ester: (X = O, S)
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Abstract
本发明属于聚合物阻燃领域,具体涉及氮磷硫三元协效阻燃剂双DOPO噻唑化合物的制备方法及其应用。DOPO与2,4‑二氨基噻唑、4‑甲基‑2,5‑二氨基噻唑发生Atherton‑Todd反应生成含DOPO、噻唑结构单元的磷氮硫协同阻燃剂(BisDOPOAD、BisDOPOBF)。应用于聚氨酯及ABS等高分子树脂体系,具有与聚合物具有相容性好,储存稳定性优异,同时含磷、氮、硫三种元素,在燃烧过程中具有协同阻燃的效果,残炭率高,在树脂体系中磷含量为0.89 wt.%时,垂直燃烧等级即达UL‑94V‑0级。其原料价格合理,添加量少,且制备工艺环保简便,易于工业化生产。
Description
技术领域
本发明属于聚合物阻燃领域,具体涉及氮磷硫三元协效阻燃剂双DOPO噻唑化合物的制备方法,并将其应用于高分子树脂的阻燃改性。
背景技术
高聚物材料被广泛的应用于工业、农业、军事等国民经济的各个部门,但大多数高聚物属于石油基可燃材料,极性氧指数低于21,燃烧时热释放速率高,热值大,火焰传播速度快,不易熄灭,一般还会产生浓烟和有毒气体,对人们的生命财产安全造成的巨大威胁。传统的含卤阻燃材料燃烧时存在多烟、有毒或腐蚀性气体放出等二次危害,对人身安全构成了严重威胁。随着阻燃技术的发展,以及人们对环境保护和人身安全的重视,无卤、低烟、低毒、高耐热性的环保阻燃剂已成为研究热点。中国专利CN 101278001A采用亚磷酸和亚膦酸的含磷的含氧酸的酯衍生物作为聚氨酯树脂的阻燃剂,添加量达到10wt.%左右时,聚氨酯树脂的垂直燃烧等级可达UL-94V-0级,阻燃性能与DOPO相当。然而,其分子结构中无刚性环,导致其热稳定性与化学稳定性下降,且合成工艺复杂,工业化生产困难。针对ABS阻燃体系,中国专利CN 104277410 A报道了一种溴化物与三氧化二锑的混合阻燃体系,虽然ABS垂直燃烧等级达到UL-94V-0级,但阻燃剂用量达到12wt.%以上,且卤素与重金属组成,导致严重的环境污染。
含DOPO的衍生物作为一种新型阻燃材料,由于其热稳定性和化学稳定性高,阻燃性能显著,且无卤、无烟、环保、不易迁移、残炭率高等特点,是近年高分子树脂无卤阻燃的研究热点。现阶段,围绕DOPO分子结构中活泼的磷-氢键,主要通过亲核取代方式制备含DOPO结构单元的阻燃剂。另一方面,含硫类阻燃剂,具有阻燃性能优异,添加量少等优势。因此,通过将DOPO、噻唑的核心结构片断进行合理组装和修饰,合成出含DOPO、噻唑结构单元的氮磷硫三元协效阻燃剂,解决现有阻燃剂阻燃性能差、合成工艺复杂的技术难题。
发明内容
本发明要解决的技术问题是提供氮磷硫三元协效阻燃剂双DOPO噻唑化合物的制备方法;该类阻燃剂具有与高分子树脂相容性好,化学和热稳定性高,在有效磷含量为0.89wt.%时,垂直燃烧等级可达UL-94V-0级。
为了解决上述问题,本发明的技术方案是:
DOPO与2,4-二氨基噻唑或4-甲基-2,5-二氨基噻唑发生Atherton-Todd反应生成含DOPO、噻唑结构单元的磷氮硫协同阻燃剂(BisDOPOAD、BisDOPOBF),具体化学结构式为:
氮磷硫三元协效阻燃剂双DOPO噻唑化合物的制备方法,包括以下步骤:
在装有搅拌装置的容器中依次加入DOPO(9,10-二氢-9-氧杂-10-膦杂菲-10-氧化物)、2,4-二氨基噻唑或4-甲基-2,5-二氨基噻唑、四氯化碳和溶剂,搅拌使体系混合均匀,在冰浴的条件下,向反应体系中加入有机碱,室温反应,TLC跟踪反应进程,反应完成后,过滤得到滤液。滤液经萃洗、浓缩后,加入石油醚-丙酮(V石油醚∶V丙酮=1∶3)使之沉淀,真空干燥得含磷氮硫元素的阻燃剂(BisDOPOAD、BisDOPOBF)。
所述2,4-二氨基噻唑或4-甲基-2,5-二氨基噻唑、DOPO(9,10-二氢-9氧杂-10-膦杂菲-10-氧化物)、四氯化碳、有机碱的摩尔比为1.0∶(2.2~3.0)∶(2.2~3.0)∶(2.2~3.0)。
所述溶剂为二氯甲烷、乙酸乙酯、乙腈、四氢呋喃、氯仿中的一种或多种。
所述溶剂用量为DOPO质量的3~8倍。
所述有机碱选自三甲胺、三乙胺、甲醇钠、乙醇钠中的一种或多种
所述无机碱选自碳酸钠、碳酸钾、碳酸铯、氢氧化钠、氢氧化钾中的一种或多种。
本发明所述含氮磷硫三元协效阻燃剂双DOPO噻唑化合物的极限氧指数含量为21.7~39.1,残炭率为23.8~35.4%。
本发明制备的氮磷硫三元协效阻燃剂双DOPO噻唑化合物,具有热稳定性和化学稳定性高、无卤、抑烟、与高分子树脂相容性好、有效含磷量低至0.89wt.%时,垂直燃烧等级可达UL-94V-0级等。可以广泛应用于聚氨酯、ABS胶等各种聚合物防火阻燃改性。
与现有技术相比,本发明的有益效果是:
(1)将DOPO结构单元引入到噻唑分子中,分子结构内同时含有S、N、P三种元素协效阻燃,磷和硫元素能促进形成炭层,氮能燃烧后生成氨气有气相阻燃效果,协同作用克服了单一阻燃元素的不足,提高了耐热性和高温成炭率,有效含磷量低至0.89wt.%时,高分子树脂垂直燃烧等级可达UL-94V-0级等。
(2)本阻燃剂制备简单,条件温和,原料易得,易于工业化生产。
(3)本发明合成的产品热稳定好,具有较高的热稳定性和耐水解性。
具体实施方式
以下结合实施例对本发明作进一步说明,但本发明要求保护的范围并不局限于实施例表述的范围。
实施例1:
在N2保护下,向装有机械搅拌器的反应瓶中加入2,4-二氨基噻唑11.5g(0.1mol)、DOPO47.6g(0.22mol)、33.9g(0.22mol)四氯化碳和150mL二氯甲烷加入到反应瓶中,搅拌30min。在冰浴条件下,将20ml二氯甲烷和22.3g(0.22mol)三乙胺的混合溶液缓慢滴加上述反应烧瓶中,滴加完成后,室温反应,TLC跟踪反应进程,反应完成后,过滤得到滤液。滤液经萃洗、浓缩后,加入石油醚-丙酮(V石油醚∶V丙酮=1∶3)使之沉淀,真空干燥得产品。BisDOPOAD,浅黄色固体粉末,产率81.2%。
其它条件不变,2,4-二氨基噻唑换成4-甲基-2,5-二氨基噻唑,BisDOPOBF,浅黄色固体粉末,产率72.5%。
本发明制得的磷硫协同阻燃剂双DOPO噻唑化合物BisDOPOAD、BisDOPOBF,起始分解温度约分别为286℃、252℃,800℃阻燃剂的残炭率分别达到18%、23%,BisDOPOAD、BisDOPOBF阻燃剂具有较好的热稳定性,残炭率高,因此合成的阻燃剂具有较好的阻燃效果。
本发明制得的BisDOPOAD的分析结果如下:
化合物红外光谱分析结果:FT-IR(KBr),v/cm-1:3296(N-H),3035(Ar-H),1431(P-Ph),1228(P=O),1142(P-O-Ar)。
核磁共振氢谱分析结果:1H NMR(DMSO-d6,400MHz):8.09-8.01(m,3H,ArH),7.76-7.61(m,3H,ArH),7.56-7.43(m,6H,ArH),7.36-7.22(m,4H,ArH),6.62(s,1H,噻唑环-H),5.8(s,1H,N-H),12.1(s,1H,N-H).
本发明制得的BisDOPOBF的分析结果如下:
化合物红外光谱分析结果:FT-IR(KBr),v/cm-1:3432(N-H),3041(Ar-H),1439(P-Ph),1226(P=O),1142(P-O-Ar)。
核磁共振氢谱分析结果:1H NMR(DMSO-d6,400MHz):2.1(s,3H,CH3),8.07-8.02(m,4H,ArH),7.71-7.67(m,3H,ArH),7.61-7.56(m,5H,ArH),7.45-7.31(m,4H,ArH),5.3(s,1H,N-H),11.3(s,1H,N-H).
实施例2:
DOPO的量增大至51.84g(0.24mol),其它同实例一,BisDOPOAD收率87.1%,BisDOPOBF收率74.3%。
DOPO的量增大至56.2g(0.26mol),其它同实例一,BisDOPOAD收率91.2%,BisDOPOBF收率80.1%。
DOPO的量增大至60.5g(0.28mol),其它同实例一,BisDOPOAD收率90.8%,BisDOPOBF收率80.8%。
DOPO的量增大至64.9g(0.30mol),其它同实例一,BisDOPOAD收率88.4%,BisDOPOBF收率79.5%。
实施例3:
四氯化碳的量增大至36.9g(0.24mol),其它同实例一,BisDOPOAD收率88.3%,BisDOPOBF收率75.2%。
四氯化碳的量增大至40.0g(0.26mol),其它同实例一,BisDOPOAD收率90.5%,BisDOPOBF收率80.2%。
四氯化碳的量增大至43.1g(0.28mol),其它同实例一,BisDOPOAD收率90.6%,BisDOPOBF收率76.1%。
四氯化碳的量增大至46.1g(0.30mol),其它同实例一,BisDOPOAD收率88.3%,BisDOPOBF收率75.1%。
实施例4:
三乙胺的量增大至24.3g(0.24mol),其它同实例一,BisDOPOAD收率87.5%,BisDOPOBF收率74.3%。
三乙胺的量增大至26.3g(0.26mol),其它同实例一,BisDOPOAD收率89.6%,BisDOPOBF收率75.1%。
三乙胺的量增大至28.3g(0.28mol),其它同实例一,BisDOPOAD收率88.3%,BisDOPOBF收率73.5%。
实施例5:
碱换成甲醇钠,其它同实例一,BisDOPOAD收率59.2%,BisDOPOBF收率51.3%。
碱换成乙醇钠,其它同实例一,BisDOPOAD收率60.3%,BisDOPOBF收率50.2%。
本发明提供的氮磷硫协同阻燃剂双DOPO噻唑化合物BisDOPOAD、BisDOPOBF作为聚氨酯、ABS的阻燃添加剂的应用如下:
按照绝缘层压板燃烧性能测试标准制成样条,分别用JF-3型氧指数测定仪进行限氧指数(LOI)测试,FZ-5401型垂直燃烧仪进行UL94垂直燃烧性能测试,测定结果如下表1-4。含氮磷硫三元协效阻燃剂双DOPO噻唑化合物的含磷量为0.89wt.%~1.14wt.%。含氮磷硫三元协效阻燃剂双DOPO噻唑化合物的极限氧指数含量为21.7~39.1,残炭率为23.8~35.4%。所述阻燃型高分子树脂中含磷量分别为0.89wt.%时,垂直燃烧等级可达UL-94V-0级。
表1 本发明实施例1合成的BisDOPOAD作为聚氨酯阻燃添加剂的阻燃效果
表2 本发明实施例1合成的BisDOPOBF作为聚氨酯阻燃添加剂的阻燃效果
表3 本发明实施例1合成的BisDOPOAD作为ABS阻燃添加剂的阻燃效果
表4 本发明实施例1合成的BisDOPOBF作为ABS阻燃添加剂的阻燃效果
Claims (8)
1.氮磷硫三元协效阻燃剂双DOPO噻唑化合物,其特征在于,化学结构式如下:
2.根据权利要求1所述氮磷硫三元协效阻燃剂双DOPO噻唑化合物的制备方法,其特征在于,具体步骤如下:在装有搅拌装置的容器中依次加入9,10-二氢-9-氧杂-10-膦杂菲-10-氧化物、2,4-二氨基噻唑或4-甲基-2,5-二氨基噻唑、四氯化碳和溶剂,搅拌使体系混合均匀,在冰浴的条件下,向反应体系中加入有机碱,室温反应,TLC跟踪反应进程,反应完成后,过滤得到滤液,滤液经萃洗、浓缩后,加入石油醚-丙酮V石油醚∶V丙酮=1∶3使之沉淀,真空干燥得含磷氮硫元素的阻燃剂,即BisDOPOAD、或BisDOPOBF。
3.根据权利要求2所述的氮磷硫三元协效阻燃剂双DOPO噻唑化合物的制备方法,其特征在于:所述2,4-二氨基噻唑或4-甲基-2,5-二氨基噻唑、9,10-二氢-9氧杂-10-膦杂菲-10-氧化物、四氯化碳、有机碱的摩尔比为1.0∶(2.2~3.0)∶(2.2~3.0)∶(2.2~3.0)。
4.根据权利要求2所述的氮磷硫三元协效阻燃剂双DOPO噻唑化合物的制备方法,其特征在于:所述溶剂为二氯甲烷、乙酸乙酯、乙腈、四氢呋喃、氯仿中的一种或多种。
5.根据权利要求2所述的氮磷硫三元协效阻燃剂双DOPO噻唑化合物的制备方法,其特征在于:所述溶剂用量为9,10-二氢-9氧杂-10-膦杂菲-10-氧化物质量的3~8倍。
6.根据权利要求1所述的氮磷硫三元协效阻燃剂双DOPO噻唑化合物的制备方法,其特征在于:所述有机碱选自三甲胺、三乙胺、甲醇钠、乙醇钠中的一种或多种。
7.根据权利要求1所述的氮磷硫三元协效阻燃剂双DOPO噻唑化合物的制备方法,其特征在于:所述无机碱选自碳酸钠、碳酸钾、碳酸铯、氢氧化钠、氢氧化钾中的一种或多种。
8.根据权利要求1所述的氮磷硫三元协效阻燃剂双DOPO噻唑化合物在聚氨酯及ABS树脂上的应用,其特征在于,含氮磷硫三元协同阻燃剂双DOPO噻唑化合物的含磷量为0.89wt.%~1.14wt.%。
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