CN106750288A - 一种抗迁徙阻燃剂的制备方法 - Google Patents
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Abstract
本发明提供了一种抗迁徙阻燃剂的制备方法：2,4,6‑三(烯丙氧基)均三嗪聚合物颗粒中引入改性三聚氰酸螺旋磷酸酯，以及1‑(2,5‑二氯苯基)‑3‑丙烯酰胺基‑5‑吡唑酮，2‑[4‑(1,3‑苯并间二氧杂环戊烯‑5‑基甲基)哌嗪‑1‑基]嘧啶，提高了抗迁徙性能。
Description
技术领域
本发明涉及一种阻燃剂的制备方法，特别是一种抗迁徙阻燃剂的制备方法。
背景技术
近年来,塑料用阻燃剂的研究和开发朝着热稳定性高、相容性好、抗迁徙的含磷聚合物方向发展。添加型阻燃剂大多是一些有机小分子， 这些小分子易迁移，渗出，喷霜，不耐高温有溶剂抽提，使得材料阻燃性能逐渐降低乃至丧失，且污染环境。但液态有机磷酸酯(如间苯二酚双(磷酸二苯酯)(RDP)或双酚-A双(磷酸二苯酯)(BDP))常用于聚合物中，以制得HFFR调配物。然而，以含有液态磷酸酯的HFFR TPU组成物所制成之产品随着时间而经历磷酸酯阻燃剂之迁移。
CN101203558提供了一种阻燃剂和无机/有机复合阻燃剂组合物, 它包括无机氢氧化物和化学键合到该无机氢氧化物表面上的含碳二亚胺基的有机层。含碳二亚胺基的有机层的实例包括含下式任何一个为代表的含碳二亚胺基的化合物层，甚至当以高比例添加时，该阻燃剂可高度分散在树脂内，且可得到电性能、机械性能等劣化受到抑制的模塑制品。当这种阻燃剂包括在有机树脂内时，可抑制由所得组合物获得的成型制品机械强度和电性能(例如，抗迁移性)下降。
CN105542229A公开了一种多梯度功能化微胶囊磷酸钛阻燃剂及其制备方法，包括芯材和包裹所述芯材的壁材，芯材为磷酸钛，壁材为双层壁材，内壁为膨胀型阻燃剂，由炭源改性剂、酸源改性剂和气源改性剂反应而成，外壁为有机硅交联聚合物。其制备方法是先制备磷酸钛粉体：再将磷酸钛粉体分散于溶剂中，加入炭源改性剂、酸源改性剂和气源改性剂反应包覆内壁；最后将有机硅交联聚合物包覆外壁，即得。本发明以成炭量高、抗水性、不产生熔滴且耐热的有机硅交联聚合物作为外壁、以膨胀型阻燃剂作为内壁、具有催化成炭特性的磷酸钛粉体作为芯材制备得到的胶囊磷酸钛阻燃剂具有更高效的阻燃特性，适合在燃烧进程中展现出多功能梯度化阻燃效果。由于环状结构和硅分子链的存在，制备的阻燃剂表面极性较低，且吸潮性很低，并且抗迁移性较好。
TW201134925A提供一种无迁移、无卤素之阻燃性热塑性聚胺甲酸酯组成物，该组成物包括在模制产品诸如电缆与电线外皮及绝缘层中并不展现迁移之阻燃性芳族有机磷酸酯化合物。该组成物包括一树脂连续相，其包含一种热塑性聚胺甲酸酯弹性体、至少一种熔点至少50℃的芳族有机磷酸酯阻燃剂及一种无机水合物阻燃剂。
现有公开技术的以含有液态磷酸酯的HFFR TPU组成物所制成产品随着时间而磷酸酯阻燃剂仍迁移，以上阻燃剂虽然具有一定的抗迁移性，然而，仍无法满足软质聚氨酯的泡沫塑料的非迁移需求。
发明内容
针对现有技术的不足，本发明提供了一种抗迁徙阻燃剂的制备方法，通过以下步骤实现：
(1) 按重量份计，将100份季戊四醇双磷酸酯二酰氯; 1000-3000份丙酮，10-30份氰尿酸，50-100份三乙胺，温度50-80℃，反应时间5-10小时，产物经蒸馏，洗涤，生成改性三聚氰酸螺旋磷酸酯；
（2）按重量份计，将100份2,4,6-三(烯丙氧基)均三嗪，20-50份改性三聚氰酸螺旋磷酸酯，0.1-1份1-(2,5-二氯苯基)-3-丙烯酰胺基-5-吡唑酮、0.1-1份2-[4-(1,3-苯并间二氧杂环戊烯-5-基甲基)哌嗪-1-基]嘧啶，1000-3000份甲苯，2-5份偶氮二异庚腈进行聚合，反应结束得到产品。
所述步骤2反应温度50-80℃。
所述步骤2进行15-25小时的聚合反应。
所述的2,4,6-三(烯丙氧基)均三嗪，季戊四醇双磷酸酯二酰氯为市售产品。所述的1-(2,5-二氯苯基)-3-丙烯酰胺基-5-吡唑酮为市售产品，如上海孚一生物科技有限公司生产的产品。2-[4-(1,3-苯并间二氧杂环戊烯-5-基甲基)哌嗪-1-基]嘧啶，如湖北巨胜科技有限公司生产产品。
本发明的有益效果：
2,4,6-三(烯丙氧基)均三嗪聚合物中引入三聚氰酸螺旋磷酸酯，以及含强极性基团酰胺基，二氧杂环的1-(2,5-二氯苯基)-3-丙烯酰胺基-5-吡唑酮，2-[4-(1,3-苯并间二氧杂环戊烯-5-基甲基)哌嗪-1-基]嘧啶，增强了阻燃剂与塑料如软质聚氨酯的泡沫塑料的界面作用，同时提高了阻燃剂的分子量，提高了阻燃剂和树脂间迁移阻力，从而降低了阻燃剂的迁徙性。
具体实施方式
以下实施例仅仅是进一步说明本发明，并不是限制本发明保护的范围。
实施例1
(1) 在3000L反应釜中，按重量份计，将100份季戊四醇双磷酸酯二酰氯; 1800份丙酮，19份氰尿酸，77份三乙胺，温度60℃，反应时间8小时，产物经业内公知的提纯技术，蒸馏，洗涤，干燥，生成改性三聚氰酸螺旋磷酸酯；
（2）在3000L反应釜中，按重量份计，将100份2,4,6-三(烯丙氧基)均三嗪，43份改性三聚氰酸螺旋磷酸酯，0.3份1-(2,5-二氯苯基)-3-丙烯酰胺基-5-吡唑酮、0.5份2-[4-(1,3-苯并间二氧杂环戊烯-5-基甲基)哌嗪-1-基]嘧啶，1800份甲苯，3份偶氮二异庚腈，升温至60℃进行19小时的聚合反应，使聚合物分离、干燥，得到产品。编号为M-1
实施例2
(1) 在3000L反应釜中，按重量份计，将100份季戊四醇双磷酸酯二酰氯; 1000份丙酮，10份氰尿酸，50份三乙胺，温度50℃，反应时间10小时，产物经业内公知的提纯技术，蒸馏，洗涤，干燥，生成改性三聚氰酸螺旋磷酸酯；
（2）在3000L反应釜中，按重量份计，将100份2,4,6-三(烯丙氧基)均三嗪，20份改性三聚氰酸螺旋磷酸酯，0.1份1-(2,5-二氯苯基)-3-丙烯酰胺基-5-吡唑酮、0.1份2-[4-(1,3-苯并间二氧杂环戊烯-5-基甲基)哌嗪-1-基]嘧啶，1000份甲苯，2份偶氮二异庚腈，升温至50℃进行25小时的聚合反应，使聚合物分离、干燥，得到产品。编号为M-2。
实施例3
(1) 在5000反应釜中，按重量份计，将100份季戊四醇双磷酸酯二酰氯; 3000份丙酮，30份氰尿酸， 100份三乙胺，温度80℃，反应时间5小时，产物经业内公知的提纯技术，蒸馏，洗涤，干燥，生成改性三聚氰酸螺旋磷酸酯；
（2）在5000反应釜中，按重量份计，将100份2,4,6-三(烯丙氧基)均三嗪， 50份改性三聚氰酸螺旋磷酸酯，1份1-(2,5-二氯苯基)-3-丙烯酰胺基-5-吡唑酮、1份2-[4-(1,3-苯并间二氧杂环戊烯-5-基甲基)哌嗪-1-基]嘧啶， 3000份甲苯，2-5份偶氮二异庚腈，升温至80℃进行15小时的聚合反应，使聚合物分离、干燥，得到产品。编号为M-3。
比较例1
不加入改性三聚氰酸螺旋磷酸酯，其它同实施例1。所得产品编号为M-4。
比较例2
不加入1-(2,5-二氯苯基)-3-丙烯酰胺基-5-吡唑酮，其它同实施例1。所得产品编号为M-5。
比较例3
不加入2-[4-(1,3-苯并间二氧杂环戊烯-5-基甲基)哌嗪-1-基]嘧啶，其它同实施例1。所得产品编号为M-6。
实施例4
软质聚氨酯的泡沫塑料阻燃剂残余量用磷钼蓝光分光光度计测定。
将实施例1-3和比较例1-2的阻燃剂加入软质聚氨酯的泡沫塑料的标准配方中，制成240mm×210mm×97mm的样板，放入烘箱烘烤，温度120℃，时间15天，取出检测软质聚氨酯的泡沫塑料阻燃剂残余含量，数值越大，阻燃剂抗迁徙性能越大，已知未烘烤前软质聚氨酯的泡沫塑料阻燃剂残余含量1.23%，并与常用的三（2-氯丙基）磷酸酯阻燃剂进行对比，见表1。
表1.检测阻燃剂抗迁徙性能：
| 产品编号 | 阻燃剂残余含量% |
| M-1 | 0.96 |
| M-2 | 0.92 |
| M-3 | 0.98 |
| M-4 | 0.52 |
| M-5 | 0.72 |
| M-6 | 0.71 |
| 三（2-氯丙基）磷酸酯阻燃剂 | 0.23 |
由表1可知，本发明的阻燃剂产品具有较强的抗迁徙性能，优于三（2-氯丙基）磷酸酯阻燃剂。
Claims (4)
1.一种抗迁徙阻燃剂的制备方法，其特征在于，通过以下步骤实现：
按重量份计，将100份2,4,6-三(烯丙氧基)均三嗪，20-50份改性三聚氰酸螺旋磷酸酯，0.1-1份1-(2,5-二氯苯基)-3-丙烯酰胺基-5-吡唑酮、0.1-1份2-[4-(1,3-苯并间二氧杂环戊烯-5-基甲基)哌嗪-1-基]嘧啶，1000-3000份甲苯，2-5份偶氮二异庚腈进行聚合，反应结束得到产品。
2.权利要求1的一种抗迁徙阻燃剂的制备方法，其特征在于，所述改性三聚氰酸螺旋磷酸酯的制备方法为：
按重量份计，将100份季戊四醇双磷酸酯二酰氯; 1000-3000份丙酮，10-30份氰尿酸，50-100份三乙胺，温度50-80℃，反应时间5-10小时，产物经业内公知的提纯技术，蒸馏，洗涤，干燥，生成三聚氰酸螺旋磷酸酯。
3.权利要求1的一种抗迁徙阻燃剂的制备方法，其特征在于，步骤2反应温度50-80℃。
4.权利要求1的一种抗迁徙阻燃剂的制备方法，其特征在于，步骤2进行15-25小时的聚合反应。
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| CN1414000A (zh) * | 2002-09-26 | 2003-04-30 | 东北林业大学 | 季戊四醇双磷酸酯二酰氯的合成方法 |
| CN101157839A (zh) * | 2006-10-02 | 2008-04-09 | 信越化学工业株式会社 | 阻燃粘合剂组合物以及使用其的粘合剂片、盖膜和柔性铜包覆叠层物 |
| CN104448555A (zh) * | 2014-11-21 | 2015-03-25 | 济南泰星精细化工有限公司 | 一种新型聚丙烯用无卤阻燃剂的制备方法 |
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| CN101157839A (zh) * | 2006-10-02 | 2008-04-09 | 信越化学工业株式会社 | 阻燃粘合剂组合物以及使用其的粘合剂片、盖膜和柔性铜包覆叠层物 |
| CN104448555A (zh) * | 2014-11-21 | 2015-03-25 | 济南泰星精细化工有限公司 | 一种新型聚丙烯用无卤阻燃剂的制备方法 |
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