CN110156958B - 一种生物基磷杂菲固化剂阻燃环氧树脂材料及其制备方法 - Google Patents
一种生物基磷杂菲固化剂阻燃环氧树脂材料及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种生物基磷杂菲固化剂阻燃环氧树脂材料及其制备方法,该材料是通过将生物基磷杂菲固化剂添加到环氧树脂中,搅拌至完全反应后,在鼓风烘箱中固化成型,得到无卤阻燃环氧树脂材料。本方法使用的生物基磷杂菲固化剂,不仅原料来自生物质材料而且同时具备阻燃和固化的功效。在较少的添加量下,明显地提高了环氧树脂的极限氧指数(可达35.7%),垂直燃烧(UL94)级别可达V‑0级,显著提高了环氧树脂的冲击强度,具有良好的应用前景。
Description
技术领域
本发明涉及一种由生物基磷杂菲固化剂阻燃环氧树脂材料,属于在普通环氧树脂中添加特定助剂成分获得阻燃环氧树脂材料的技术领域。
背景技术
近年来,环氧树脂作为电子电器行业领域重要的基础材料获得了显著的发展。然而环氧树脂的阻燃性较差,易于自燃,难以自熄,且大多数应用在环氧树脂中的阻燃剂在燃烧过程中都会释放有毒物质,不仅污染环境,而且会影响树脂的物理机械性能。因此,研发一种能够高效阻燃环氧树脂的阻燃剂并不影响其力学性能是十分必要的。
中国发明专利CN101376665公开了一种含均三嗪结构氧杂膦菲阻燃性化合物,该化合物含磷、氮阻燃元素,理论磷含量为8.53wt.%,可作为阻燃剂用于环氧树脂中,添加量为15wt.%可使环氧固化物通过UL94V-0阻燃等级,LOI为34.2%。但该化合物结构上的羟基位阻大,反应活性低,无固化作用,不能用于制备本征阻燃环氧固化物,仅作为添加型阻燃剂使用。
中国发明专利CN108192078A发明公开了一种全生物基阻燃环氧树脂,它是利用没食子酸上的活性基团,引入9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物(DOPO)和环氧基团,得到生物基环氧单体,替代一般工业上使用的双酚A环氧树脂DGEBA,并且合成了一种活性较高的生物基固化剂——二糠胺,与制得的环氧单体在一定条件下混合固化,制得带有阻燃性能的全生物基环氧树脂制品。该全生物基环氧树脂制品的极限氧指数最高可达到34%,垂直燃烧等级最高可达到V-0级,然而该生物基固化剂没有改善环氧树脂的力学性能。
相比于上述阻燃固化剂,本方法使用的生物基磷杂菲固化剂,不仅原料来自生物质材料,而且同时具备阻燃和固化的功效,在较少的添加量下,明显地提高了环氧树脂的极限氧指数(可高达35.7%),垂直燃烧(UL94)级别可达V-0级,且显著提高了环氧树脂的冲击强度。
目前,生物基磷杂菲固化剂用于阻燃环氧树脂的研究还尚未报道,在国内外尚属首次提出,为发展环境友好的具有优异综合性能的生物基磷杂菲固化剂阻燃环氧树脂材料提供了新的思路。
发明内容
生物基磷杂菲固化剂(简称FPD)作为环氧树脂材料的反应型改性添加剂,是一种新型的来自于生物基材料的阻燃固化剂,生物基磷杂菲固化剂FPD的化学结构式如下:
其制备方法包括如下步骤:
(1)通过生物基原料糠醛和对苯二胺之间的溶液体系进行缩合反应,制得席夫碱中间体F-Schiff base;
(2)通过席夫碱中间体F-Schiff base和9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物(DOPO)之间的溶液体系加成反应,制得生物基磷杂菲阻燃固化剂FPD。
本发明是通过将生物基磷杂菲固化剂添加到环氧树脂中,搅拌至完全反应后,在真空条件下脱除混合体系中的空气,再加热固化,得到生物基无卤阻燃环氧树脂材料。
本发明涉及的生物基磷杂菲固化剂阻燃环氧树脂材料制备方法如下:
(1)将生物基磷杂菲固化剂FPD加入到环氧树脂中,搅拌升温至FPD完全溶解后,FPD上的氨基与环氧树脂中的环氧基之间发生开环加成反应,获得FPD与环氧树脂的预固化产物;
(2)FPD和环氧树脂反应结束后,加入与环氧树脂中剩余环氧基团等当量的固化剂,搅拌至固化剂充分溶解或分散后,先在真空条件下脱除混合体系中的空气,再加热固化,制得目标产物生物基磷杂菲固化剂阻燃环氧树脂材料。优选的,步骤(1)中所述的环氧树脂是环氧值在0.40-0.51的双酚A二缩水甘油醚型环氧树脂和酚醛环氧树脂中的一种或多种的混合。
优选的,步骤(1)中所述的FPD是环氧树脂的质量的0.3%-15%。
优选的,步骤(1)中所述的升温是指升至温度为100-180℃,反应时间为0.5-8小时。
优选的,步骤(2)中所述的固化剂为二氰二胺(DICY)、4,4’-二氨基二苯砜(DDS)、线性酚醛树脂(PN)和4,4’-二氨基二苯甲烷(DDM)中的一种或多种的组合。
优选的,步骤(2)中所述的固化温度是100-220℃,固化时间为4-15小时。
本发明使用的生物基磷杂菲固化剂不仅原料来自于生物质材料,而且同时具备阻燃和固化功效,添加到环氧树脂中达到了优异的阻燃效果且提高了环氧树脂的冲击性能。仅在添加量为3wt.%的时候使得环氧树脂的LOI达到33.6%,垂直燃烧UL94级别可达V-1级,冲击强度从10.1kJ·m-2提升至了19.1kJ·m-2,提高了89.1%;在添加量为5wt.%的时候使得环氧树脂的LOI达到35.7%,UL94级别可达V-0级,冲击强度从10.1kJ·m-2提升至了13.7kJ·m-2,提高了35.6%,改善了环氧树脂的滴落现象,提高了环氧树脂的物理机械性能。本发明涉及的生物基磷杂菲固化剂FPD在较低的添加量下有效地提高了环氧树脂材料制件的抗冲击性能和防火安全性能,使其在电子电器领域具有更好的应用前景。
附图说明
图1生物基磷杂菲衍生物FPD的核磁共振氢谱;
图2生物基磷杂菲衍生物FPD的红外谱图。
具体实施方式
本发明的生物基磷杂菲衍生物FPD是通过糠醛和对苯二胺之间的溶液体系进行缩合反应,制得席夫碱中间体F-Schiff base;再通过席夫碱中间体F-Schiff base和DOPO之间的溶液体系加成反应制得,其一种具体制备实例可如下:
称取对苯二胺16.2g(0.15mol),糠醛57.6g(0.6mol),往1000ml三口烧瓶中加入500ml二氧六环,依次加入称量好的原料,三口烧瓶中通入5min的氦气,搅拌至完全溶解,在80℃条件下反应9h后,得到席夫碱型中间体;加入129.6g(0.6mol)的DOPO,油浴条件下升温至95℃,回流反应15h,反应结束后,将溶剂脱除干燥。烘干,得到生物基磷杂菲阻燃固化剂FPD,其核磁共振氢谱、红外谱图如图1、2。
实施例1
将100g环氧值为0.46的双酚A二缩水甘油醚环氧树脂加热至120℃,加入3.88g的FPD,搅拌至FPD完全溶解后,溶液呈透明状态后,加入37.90g固化剂DDM,搅拌至DDM完全溶解后,进行3分钟的120℃真空脱气,先在100℃固化2小时,再在120℃固化4小时,制得的生物基磷杂菲阻燃固化剂阻燃环氧树脂材料的极限氧指数为32.8%,并通过UL94V-1级,冲击强度达到17.8kJ·m-2。
实施例2
将100g环氧值为0.48的双酚A二缩水甘油醚环氧树脂加热至140℃,加入6.94g的FPD,搅拌至FPD完全溶解后,溶液呈透明状态后,加入44.50g固化剂DDM,搅拌至DDM完全溶解后,进行3分钟的120℃真空脱气,先在120℃固化2小时,再在170℃固化4小时,制得的生物基磷杂菲阻燃固化剂阻燃环氧树脂材料的极限氧指数为33.6%,并通过UL94V-0级,冲击强度达到15.6kJ·m-2。
实施例3
将100g环氧值为0.49的双酚A二缩水甘油醚环氧树脂加热至160℃,加入7.98g的FPD,搅拌至FPD完全溶解后,溶液呈透明状态,加入37.31g固化剂DDM,搅拌至DDM完全溶解后,进行3分钟的120℃真空脱气,先在140℃固化2小时,再在180℃固化4小时,制得的生物基磷杂菲阻燃固化剂阻燃环氧树脂材料的极限氧指数为33.9%,并通过UL94V-0级,冲击强度达到18.9kJ·m-2。
实施例4
将100g环氧值为0.50的酚醛环氧树脂加热至130℃,加入8.00g的FPD,搅拌至FPD完全溶解后,溶液呈透明状态,加入28.97g固化剂DDM,搅拌至DDM完全溶解后,进行3分钟的120℃真空脱气,先在150℃固化2小时,再在200℃固化6小时,制得的生物基磷杂菲阻燃固化剂阻燃环氧树脂材料,极限氧指数为35.7%,通过UL94V-0级,冲击强度达到20.6kJ·m-2。
实施例5
将100g环氧值为0.51的双酚A二缩水甘油醚环氧树脂加热至180℃,加入9.84g的FPD,搅拌至FPD完全溶解后,溶液呈透明状态,加入32.34g固化剂DDS,搅拌至DDS完全溶解后,进行3分钟的120℃真空脱气,先在160℃固化2小时,再在180℃固化2小时,再在200℃固化2小时,制得的生物基磷杂菲阻燃固化剂阻燃环氧树脂材料极限氧指数为36.2%,并通过UL94V-0级,冲击强度达到21.4kJ·m-2。
Claims (6)
2.制备如权利要求1所述的一种生物基磷杂菲固化剂阻燃环氧树脂材料的方法,其特征在于,包括如下步骤:
(1)将生物基磷杂菲固化剂FPD加入到环氧树脂中,搅拌升温至FPD完全溶解后,FPD上的氨基与环氧树脂中的环氧基之间发生开环加成反应,获得预固化产物;
(2)FPD和环氧树脂反应结束后,加入与环氧树脂中剩余环氧基团等当量的固化剂,搅拌至固化剂充分溶解后,先在真空条件下脱除混合体系中的空气,再加热固化,制得生物基磷杂菲固化剂阻燃环氧树脂材料。
3.根据权利要求2所述的一种生物基磷杂菲固化剂阻燃环氧树脂材料的制备方法,其特征在于,步骤(1)中所述的环氧树脂是环氧值在0.40-0.51的双酚A二缩水甘油醚型环氧树脂和酚醛环氧树脂中的一种或多种的混合。
4.根据权利要求2所述的一种生物基磷杂菲固化剂阻燃环氧树脂材料的制备方法,其特征在于,步骤(1)中所述的FPD的质量是环氧树脂的质量的0.3%-15%。
5.根据权利要求2所述的一种生物基磷杂菲固化剂阻燃环氧树脂材料的制备方法,其特征在于,所述的升温是指升至温度为100-180℃,开环加成反应时间为0.5-8小时。
6.根据权利要求2所述的一种生物基磷杂菲固化剂阻燃环氧树脂材料的制备方法,其特征在于,步骤(2)中所述的固化剂为二氰二胺(DICY)、4,4’-二氨基二苯砜(DDS)、线性酚醛树脂(PN)和4,4’-二氨基二苯甲烷(DDM);所述的环氧树脂固化温度是100-220℃,固化时间为4-15小时。
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