CN109988285B - 一种多元羧酸及其阻燃环氧树脂的制备方法 - Google Patents
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Abstract
本发明公开了一种多元羧酸及其阻燃环氧树脂的制备方法,其制备步骤包括:(1)多元羧酸的制备:分为酯化、加成、提纯三步。(2)阻燃环氧树脂的制备。本发明的多元羧酸以三(2‑羟乙基)异氰脲酸酯、顺丁烯二酸酐、9,10‑二氢‑9‑氧杂‑10‑磷杂菲‑10‑氧化物为原料合成而来,其制备方法简单环保,生产成本低廉。该多元羧酸同时具有阻燃性和反应性,不仅能够显著提高普通环氧树脂的阻燃性能,还能保持环氧树脂良好的工艺性能和优异的物理机械性能。解决了目前环氧树脂添加型阻燃剂工艺性与稳定性差,反应型卤系阻燃剂不环保等技术难题。所制得的阻燃环氧树脂可广泛应用于电子电器、化工环保、房屋建筑、交通运输、航空航天等领域。
Description
技术领域
本发明涉及一种含有磷氮元素的多元羧酸及其阻燃环氧树脂的制备方法,属于材料领域。
背景技术
环氧树脂因为具有较好的粘接性能、电气绝缘性能、耐化学腐蚀以及高强度等特点,能应用于金属与非金属的粘结、电子电气的绝缘材料、纤维复合材料等的制造,广泛应用于航空航天、船舶运输、电子电气、机械制造等领域。但普通环氧树脂容易燃烧,限制了其在一些高阻燃要求领域的应用,因此提高环氧树脂的阻燃性能意义重大。
环氧树脂的阻燃方法一般是通过添加卤素、磷、氮、硅、硼等元素提高树脂阻燃性能。传统阻燃剂中比较常见的是含卤阻燃剂,虽然其阻燃效率高,但因在燃烧过程中会产生有毒的卤化氢气体造成环境污染而被限制使用。目前广泛采用含磷氮元素的阻燃剂,能达到磷氮协同效果从而大幅提高环氧树脂阻燃性能。常见的有六氯环三磷腈的衍生物,聚磷酸铵,聚磷酸三聚氰胺以及以季戊四醇为基的双环笼状磷酸脂及其衍生物与三聚氰胺复配等阻燃剂或阻燃体系。
中国专利CN 101993456 B报道了一种磷杂菲磷腈无卤阻燃剂的制备方法,是将六-(4-醛基-苯氧基)-环三磷腈与9,10-二氢-9-氧氢-10-磷杂菲-10-氧化物(DOPO)进行熔融加成反应获得了一种含磷氮阻燃剂。但此类添加型阻燃剂大多是高熔点且难以溶解的固体,只能以物理状态分散于树脂体系中,这极大地恶化了环氧树脂的工艺性能和力学性能。此外,添加型阻燃剂会随着时间的延长而发生迁移渐渐地从树脂基体中析出,从而导致阻燃效率下降和环境污染。而具有反应活性的阻燃剂能参与固化反应并固定到树脂基体的交联网络之中,在提高阻燃性能的同时,较好保持树脂基体原有的工艺性能与物理机械性能。
鉴于此,本发明通过分子结构与配方设计,制备出一种同时含有多个磷氮元素和羧基的反应型阻燃剂并应用于普通环氧树脂的阻燃改性。
本发明的多元羧酸阻燃剂是以三(2-羟乙基)异氰脲酸酯(THEIC),顺丁烯二酸酐(MAH)和DOPO为原料,通过简单的酯化和加成反应合成得来。其合成成本低廉,且合成过程中无毒性气体生成,符合环保要求,此类同时含有磷氮元素和多元羧酸的合成及应用尚未见报道。
发明内容
本发明所要解决的技术问题是:提供一种含有磷氮元素的多元羧酸及其阻燃环氧树脂的制备方法,以便在保持环氧树脂原本优良的工艺性能和力学性能的前提下,提高环氧树脂的阻燃性能。
本发明解决其技术问题采用以下技术方案:
本发明提供的多元羧酸及其阻燃环氧树脂,是一种含有磷氮元素的多元羧酸及其阻燃环氧树脂,所述多元羧酸同时含有多个磷、氮元素和羧基,其结构为:
本发明提供的多元羧酸及其阻燃环氧树脂的制备方法,是以三(2-羟乙基)异氰脲酸酯(THEIC),顺丁烯二酸酐(MAH)和9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物(DOPO)为原料,通过酯化和加成反应合成得到的是一种含有磷氮元素的多元羧酸,可用于制备一种反应型无卤阻燃环氧树脂,所述多元羧酸同时含有多个磷、氮元素和羧基,其结构如下:
上述制备方法中,多元羧酸的制备按以下步骤进行:
(1)酯化:在装有搅拌器、冷凝管、温度计的圆底烧瓶中按一定比例加入THEIC和MAH以及适量溶剂a,升温至80~95℃,持续搅拌2~4h;
(2)加成:将一定量DOPO和适量溶剂a依次加入到步骤(1)中反应液,升温至回流状态,持续搅拌8~10h;
(3)提纯:将步骤(2)中所得溶液倒入溶剂b中并搅拌,过滤得到白色粘稠液体。再用大量溶剂b洗涤。最后将产物放入真空烘箱中干燥24h,取出研磨,得到淡黄色粉末,封袋备用。
上述多元羧酸的制备方法中,所用原料的摩尔比为THEIC:MAH:DOPO=1:(3~3.15):(3~3.15)。
上述多元羧酸的制备方法中,所用溶剂a为二氧六环,提纯所用溶剂b为去离子水或乙酸乙酯。
本发明阻燃环氧树脂的制备按以下步骤进行:
将合成的多元羧酸阻燃剂、环氧树脂以及酸酐类固化剂按一定比例在120~140℃下进行混合均匀,待温度降至60~80℃后再加入0.2~1wt%的促进剂,搅拌均匀后脱泡5min,再倒入预热模具中,按一定的固化制度进行固化,固化制度为100℃/(3~4h)+130℃/(2~3h)+180℃/(1~2h)+200℃/(1~2h)。
所述的环氧树脂是E-53、E-51或E-44双酚A型缩水甘油醚类环氧树脂,或其它种类的环氧树脂。
所述的酸酐类固化剂是甲基四氢邻苯二甲酸酐、甲基六氢邻苯二甲酸酐、甲基纳迪克酸酐液体酸酐中的一种或多种。
所述的促进剂是三乙胺、N,N-二甲基苄胺、2,4,6-三(二甲胺基甲基)苯酚等叔胺、咪唑或季铵盐。
本发明方法制备的多元羧酸及其阻燃环氧树脂,其用于包括电子电器、化工环保、房屋建筑、交通运输、航空航天领域。
本发明的技术方案与现有技术相比具有以下优点:
(1)本发明的多元羧酸为反应型含磷氮元素的无卤阻燃剂,解决了传统卤系反应型阻燃剂污染环境的问题,同时克服了添加型阻燃剂与基体相容性差且容易析出,造成机械性能恶化以及阻燃效率下降等缺点。该阻燃剂中的羧酸基团可以参与环氧树脂的固化反应,如图3所示,环氧树脂的固化放热峰从140.7℃变化到161.9℃,证明了该阻燃剂的反应性。
(2)本发明的阻燃环氧树脂具有良好的工艺性能和优异的物理机械性能,特别是力学性能,相对普通环氧树脂还略有提高。如表1所示,阻燃环氧树脂的弯曲模量能从3.40GPa提高到3.71GPa,弯曲强度从112MPa提高到117MPa,能满足绝大多数阻燃领域的应用要求。
(3)本发明的工艺条件具有可控性,可通过添加不同用量的多元羧酸阻燃剂制得具有不同工艺性能和阻燃级别的环氧树脂。如表1所示,在E-51环氧树脂中添加13.0~19.5%的阻燃剂时,LOI值达到28.3~30.7%,UL-94达到V-1等级;当阻燃剂的添加量为26.0%时,LOI值高达32.8%,UL-94达到V-0等级。
(4)本发明所述的多元羧酸阻燃剂的合成过程简单易行,反应条件温和,生产成本较低,另外原材料无毒且生产过程中也无有害物质生成,具有良好的工业化生产价值。
附图说明
图1为DOPO和多元羧酸的31P NMR图谱。
图2为多元羧酸的红外光谱图。
图3为添加不同含量阻燃剂的环氧树脂的DSC曲线。
具体实施方式
本发明公开了一种多元羧酸及其阻燃环氧树脂的制备方法,其制备步骤包括:(1)多元羧酸的制备:分为酯化、加成、提纯三步。(2)阻燃环氧树脂的制备。本发明的多元羧酸以三(2-羟乙基)异氰脲酸酯(THEIC)、顺丁烯二酸酐(MAH)、9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物(DOPO)为原料合成而来,其制备方法简单环保,生产成本低廉。该多元羧酸同时具有阻燃性和反应性,不仅能够显著提高普通环氧树脂的阻燃性能,还能保持环氧树脂良好的工艺性能和优异的物理机械性能。解决了目前环氧树脂添加型阻燃剂工艺性与稳定性差,反应型卤系阻燃剂不环保等技术难题。所制得的阻燃环氧树脂可广泛应用于电子电器、化工环保、房屋建筑、交通运输、航空航天等领域。
下面结合具体实施例对本发明进行详细说明,但本发明并不局限于以下实施例。
实施例1
在装有搅拌器、冷凝管、温度计的500mL圆底烧瓶中加入78.3g THEIC,88.2g MAH和80mL二氧六环,升温至95℃,持续搅拌2h。再将194.4g DOPO和130mL二氧六环在半小时内分5批加入到反应液中,升温至回流状态(大约110℃),持续搅拌8h。反应原料摩尔比为THEIC:MAH:DOPO=1:3:3。反应完成后利用二氧六环,去离子水和产物间的极性差别进行提纯。将所得溶液倒入去离子水中并搅拌,过滤得到白色粘稠液体。再用大量去离子水洗涤。最后将产物放入真空烘箱中60℃干燥24h至恒重,取出研磨,得到325.2g淡黄色粉末,封袋备用。取少量粉末进行核磁共振磷谱和红外光谱测试,其结果如图1和图2所示。磷谱中磷原子化学位移发生变化,红外中-COOH,C=O,C-N,P=O特征吸收峰分别出现在3430,1740和1690,1360,1200cm-1处。以上结果证明了含有磷氮元素多元羧酸的成功合成。
实施例2
称取100g环氧树脂(E-51)和84.7g甲基四氢邻苯二甲酸酐于250mL圆底烧瓶中在室温下搅拌10min,再加入0.2wt%的2,4,6-三(二甲胺基甲基)苯酚搅拌10min后脱气5min,再倒入预热模具中,按100℃/4h+130℃/2h+180℃/2h+200℃/2h固化制度进行固化。树脂固化后按标准制样,所得试样记为EP,其为参比试样,未添加阻燃剂。
实施例3
在装有搅拌器和温度计的250mL圆底烧瓶中加入12.5g阻燃剂和100g环氧树脂(E-51)在130℃下搅拌均匀(大约1h),再加入79.5g甲基四氢邻苯二甲酸酐,停止加热,待温度降至75℃时再加入0.2wt%的2,4,6-三(二甲胺基甲基)苯酚,搅拌10min后脱气5min,再倒入预热模具中,按100℃/4h+130℃/2h+180℃/2h+200℃/2h固化制度进行固化。树脂固化后按标准制样,所得试样记为EP-1,阻燃剂含量为6.5%。
实施例4
在装有搅拌器和温度计的250mL圆底烧瓶中加入12.5g阻燃剂和100g环氧树脂(E-51)在130℃下搅拌均匀(大约1h),再加入73.9g甲基四氢邻苯二甲酸酐,停止加热,待温度降至75℃时再加入0.2wt%的2,4,6-三(二甲胺基甲基)苯酚,搅拌均匀后脱气5min,再倒入预热模具中,按100℃/4h+130℃/2h+180℃/2h+200℃/2h固化制度进行固化。树脂固化后按标准制样,所得试样记为EP-2,阻燃剂含量为13.0%。
实施例5
在装有搅拌器和温度计的250mL圆底烧瓶中加入12.5g阻燃剂和100g环氧树脂(E-51)在130℃下搅拌均匀(大约1h),再加入67.8g甲基四氢邻苯二甲酸酐,停止加热,待温度降至75℃时再加入0.2wt%的2,4,6-三(二甲胺基甲基)苯酚,搅拌均匀后脱气5min,再倒入预热模具中,按100℃/4h+130℃/2h+180℃/2h+200℃/2h固化制度进行固化。树脂固化后按标准制样,所得试样记为EP-3,阻燃剂含量为19.5%。
实施例6
在装有搅拌器和温度计的250mL圆底烧瓶中加入12.5g阻燃剂和100g环氧树脂(E-51)在130℃下搅拌均匀(大约1h),再加入61.2g甲基四氢邻苯二甲酸酐,停止加热,待温度降至75℃时再加入0.2wt%的2,4,6-三(二甲胺基甲基)苯酚,搅拌均匀后脱气5min,再倒入预热模具中,按100℃/4h+130℃/2h+180℃/2h+200℃/2h固化制度进行固化。树脂固化后按标准制样,所得试样记为EP-4,阻燃剂含量为26.0%。
通过对实施例2-6所得试样参照标准进行极限氧指数(LOI)、阻燃等级(UL-94)以及弯曲性能测试,测试结果如表1所示。
上述实施例采用的技术方案,其产品的阻燃性能和弯曲性能是依据以下标准进行的:
极限氧指数LOI测定所依据的测试标准为:GB 2406-80;
阻燃等级测定所依据的测试标准为:ASTM D3801;
弯曲性能测定所依据的测试标准为:GB/T 2567-2008。
上述实施例所用到原料的分子结构如下:
利用本发明提供的技术方案成功制备出一种同时含有磷氮元素的多元羧酸,将其应用于普通环氧树脂制备的阻燃环氧树脂不仅具有显著的阻燃效果,而且保持了普通环氧树脂原本良好的工艺性能和优异的物理机械性能。解决了目前环氧树脂添加型阻燃剂工艺性与稳定性差,反应型卤系阻燃剂不环保等技术难题。所制得的阻燃环氧树脂可广泛应用于电子电器、化工环保、房屋建筑、交通运输、航空航天等领域。
表1多元羧酸阻燃环氧树脂的阻燃性能与弯曲性能
Claims (9)
3.根据权利要求2所述的制备方法,其特征在于多元羧酸的制备按以下步骤进行:
(1)酯化:在装有搅拌器、冷凝管、温度计的圆底烧瓶中按一定比例加入THEIC和顺丁烯二酸酐以及适量溶剂a,升温至80~95℃,持续搅拌2~4h;溶剂a为二氧六环;
(2)加成:将一定量DOPO和适量溶剂a依次加入到步骤(1)中反应液,升温至回流状态,持续搅拌8~10h;
(3)提纯:将步骤(2)中所得溶液倒入溶剂b中并搅拌,过滤得到白色粘稠液体;再用大量溶剂b洗涤,溶剂b为去离子水或乙酸乙酯;最后将产物放入真空烘箱中干燥24h,取出研磨,得到淡黄色粉末,封袋备用。
4.根据权利要求3所述的制备方法,其特征在于所用原料的摩尔比为THEIC:MAH:DOPO=1:(3~3.15):(3~3.15)。
5.一种阻燃环氧树脂的制备方法,其特征在于阻燃环氧树脂的制备按以下步骤进行:
将权利要求1所述的多元羧酸阻燃剂、环氧树脂以及酸酐类固化剂按一定比例在120~140℃下进行混合均匀,待温度降至60~80℃后再加入0.2~1wt%的促进剂,搅拌均匀后脱泡5min,再倒入预热模具中,按一定的固化制度进行固化,固化制度为100℃/(3~4h)+130℃/(2~3h)+180℃/(1~2h)+200℃/(1~2h)。
6.根据权利要求5所述的阻燃环氧树脂的制备方法,其特征在于所述的环氧树脂是E-53、E-51或E-44双酚A型缩水甘油醚类环氧树脂,或其它种类的环氧树脂。
7.根据权利要求5所述的阻燃环氧树脂的制备方法,其特征在于所述的酸酐类固化剂是甲基四氢邻苯二甲酸酐、甲基六氢邻苯二甲酸酐、甲基纳迪克酸酐液体酸酐中的一种或多种。
8.根据权利要求5所述的阻燃环氧树脂的制备方法,其特征在于所述的促进剂是三乙胺、N,N-二甲基苄胺、2,4,6-三(二甲胺基甲基)苯酚、咪唑或季铵盐。
9.权利要求5至8中任一所述方法制备的阻燃环氧树脂的用途,其用于包括电子电器、化工环保、房屋建筑、交通运输、航空航天领域。
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