CN115028792B - 一种超支化磷-溴协效聚氨酯阻燃剂及其制备方法 - Google Patents
一种超支化磷-溴协效聚氨酯阻燃剂及其制备方法 Download PDFInfo
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Abstract
本发明涉及一种超支化磷‑溴协效聚氨酯阻燃剂及其制备方法，该阻燃剂由以下质量份数的原料制备得到：含磷阻燃单体8.25～10份，二异氰酸酯22～35份，亲水扩链剂0.9～1.5份，含溴阻燃单体1.21～2.8份，中和剂0.6～1.13份，催化剂0.015～0.053份，胺类扩链剂0.8～1.5份，溶剂10～16份，去离子水87.5～107.1份。与现有技术相比，本发明超支化磷‑溴协效聚氨酯，不仅赋予了材料良好的阻燃性、热稳定性和耐候性，同时超支化结构也具有较高的稳定性，有助于提高水性聚氨酯的综合性能，具有极大的应用价值。
Description
技术领域
本发明涉及阻燃技术领域，具体涉及一种超支化磷-溴协效聚氨酯阻燃剂及其制备方法。
背景技术
当下，聚氨酯材料已广泛应用于生活中的各个领域，成为生活中不可或缺的存在。但是聚氨酯材料是可燃物，未经过阻燃处理的聚氨酯的氧指数非常低，遇火会燃烧并不断分解产生大量NO、NO2、HCN等有毒烟雾，极大地危害了群众生命健康和财产安全。同时，各国政府陆续颁布相关法令和法规，明确规定某些场合下，使用的聚氨酯材料要达到一定的阻燃标准。由此看来，聚氨酯在阻燃方面的研究就显得越来越重要。
相比较添加型阻燃剂而言，反应型阻燃水性聚氨酯具有涂层透明、阻燃剂添加量小、耐水洗等优点。超支化聚合物是一类具有高度支化结构的大分子，活性位点多、易于改性，将其应用在阻燃水性聚氨酯中，便于引入多种阻燃单体，不仅阻燃性能更好，而且还能释放更少的有毒或腐蚀气体。同时，超支化聚氨酯还能够改善乳液流动性和力学性能，对水性超支化聚氨酯阻燃改性及各项性能研究都具有极大的现实意义。
目前，超支化水性聚氨酯阻燃剂虽已有众多的研究，但仍然存在许多不足，阻燃性能差、材料力学性能和稳定性欠缺等仍是亟待解决的问题。
发明内容
本发明的目的是提供一种超支化磷-溴协效聚氨酯阻燃剂及其制备方法，提高阻燃性。
本发明的目的可以通过以下技术方案来实现：一种超支化磷-溴协效聚氨酯阻燃剂，由以下质量份的原料制得：含磷阻燃单体8.25～10份，二异氰酸酯22～35份，亲水扩链剂0.9～1.5份，含溴阻燃单体1.21～2.8份，中和剂0.6～1.13份，催化剂0.015～0.053份，胺类扩链剂0.8～1.5份，溶剂10～16份，去离子水87.5～107.1份。
优选地，所述的含磷阻燃单体的核分子为三羟甲基氧化磷(THPO)。
优选地，所述的二异氰酸酯为六亚甲基二异氰酸酯(HDI)、异佛尔酮二异氰酸酯(IPDI)、甲苯二异氰酸酯(TDI)、4,4'-二苯基甲烷二异氰酸酯(MDI)中的一种或几种混合。
进一步优选地，所述的二异氰酸酯为六亚甲基二异氰酸酯(HDI)、异佛尔酮二异氰酸酯(IPDI)。
优选地，所述的亲水扩链剂为二羟甲基丙酸(DMPA)。
优选地，所述的含溴阻燃单体为二溴新戊二醇。
优选地，所述的中和剂选自三乙胺、氢氧化钠、氢氧化钾中的一种或一种以上的混合物。
优选地，所述的催化剂为二月桂酸二丁基锡(DBTDL)。
优选地，所述的胺类扩链剂为己二胺(EDA)、二乙烯三胺(DETA)、异佛尔酮二胺(IPDA)中的一种或一种以上的混合物。
一种上述超支化磷-溴协效聚氨酯阻燃剂的制备方法，包括以下步骤：
(1)将已除水的含磷阻燃单体、二异氰酸酯和催化剂，在保护气体保护的条件下催化反应；
(2)加入亲水扩链剂，反应过程中加入溶剂；
(3)引入含溴阻燃单体，进行反应；
(4)加入中和剂进行中和；
(5)加入去离子水分散乳化；
(6)乳化后加入胺类扩链剂，扩链结束后除去溶剂，得到超支化磷-溴协效聚氨酯阻燃剂。
进一步优选地，所述的制备方法具体包括以下步骤：
(1)将已除水的含磷阻燃单体、二异氰酸酯，在温度为70～90℃、干燥保护气体保护的条件下催化反应至反应物的NCO残余量接近理论值9.53％时，停止反应；
(2)然后降温至65～75℃，再加入亲水扩链剂，反应至NCO残余量接近理论值6.28％时，停止反应；一般在加料后的一小时内体系粘度变化较大，当体系粘度超过7×104mPa·s时，预聚体在搅拌过程中呈波纹状，此时需要加入溶剂；
(3)保持温度在65～75℃，再引入含溴阻燃单体，采用二正丁胺-HCl滴定NCO残余量接近理论值2.82％时，停止反应；
(4)降温至40℃，加入中和剂进行中和；
(5)降温至20～30℃，在1500～2000r/min转速下加入去离子水分散乳化；
(6)乳化后加入胺类扩链剂，扩链结束后旋蒸除去溶剂，得到超支化磷-溴协效聚氨酯阻燃剂。
优选地，步骤(1)所述的保护气体为干燥氮气(N2)。
优选地，步骤(1)所述的反应温度为80℃，反应时间4.5h时，实测NCO％为9.72％，接近理论值9.53％，可视为达到反应终点。
优选地，步骤(2)所述的反应温度为70℃，反应时间2.5h时，实测NCO％为6.65％，接近理论值6.28％，可视为达到反应终点。
优选地，步骤(2)所述的溶剂为丙酮、丁酮、甲苯中的一种或一种以上的混合物。
进一步优选地，步骤(2)所述的溶剂为丙酮，适合用量为预聚体质量份的20％。
优选地，步骤(3)所述的反应温度为70℃，反应时间2h时，实测NCO％为3.07％，接近理论值2.82％，可视为达到反应终点。
优选地，步骤(4)所述的中和剂为三乙胺(TEA)，中和时间为20min。
优选地，步骤(5)所述的乳化温度为25℃。
优选地，步骤(6)所述的胺类扩链剂为异佛尔酮二胺。
应注意，随着合成配方的改变，反应各步骤达到反应终点的时间不尽相同，NCO残余量也不尽相同，一般认为实际滴定NCO％略高于理论值0.5％左右即可认为达到反应终点。
本发明以含磷阻燃单体的三羟甲基氧化磷为核分子，在催化剂作用下依次与二异氰酸酯、二羟甲基丙酸反应，合成一种端异氰酸酯基的超支化聚合物，再与二溴新戊二醇反应引入含溴阻燃单体，最后经中和、乳化分散及后扩链制得一种同时具备磷-溴阻燃单体的超支化聚氨酯阻燃剂。三羟甲基氧化磷含磷量可达22％，二溴新戊二醇含溴量可达30％，通过超支化同时引入两者阻燃单体，不仅达到了本质阻燃，而且材料具有极好的阻燃性、力学性及稳定性。
与现有技术相比，本发明具有以下优点：
1.本发明可提高现有水性聚氨酯阻燃剂的阻燃性，降低粘度，提高固含量，改善力学性能；
2.本发明制备的超支化磷-溴协效聚氨酯，不仅赋予了材料良好的阻燃性、热稳定性和耐候性，同时超支化结构也具有较高的稳定性，有助于提高水性聚氨酯的综合性能，具有极大的应用价值；
3.本发明通过超支化同时引入三羟甲基氧化磷和二溴新戊二醇，提高了材料的含磷量和含溴量，使得材料具有极好的阻燃性、力学性及稳定性；
4.本发明以二羟甲基丙酸为亲水扩链剂，以胺类扩链剂进行后扩链，同时引入含溴及含磷的两种阻燃单体，通过调控不同组分的含量，不仅得到具有较好乳液稳定性和材料力学性能的超支化聚氨酯，而且更优化了两种阻燃单体的各自用量，极大增强了阻燃性能和与材料的相容性。
具体实施方式
下面对本发明的实施例作详细说明，以下实施例在以本发明技术方案为前提下进行实施，给出了详细的实施方式和具体的操作过程，但本发明的保护范围不限于下述的实施例。
实施例1
在装有搅拌器，回流冷凝管，温度计的500mL四口烧瓶中加入8.25份THPO，28.8份IPDI及0.02份催化剂，于80℃在N2保护下反应4h，反应至NCO含量接近理论值后，降温至70℃，分别加入1.25份DMPA和1.21份二溴新戊二醇，依次反应约2.5h，反应过程中加入10份丙酮调节体系粘度；然后降温至40℃，加入0.93份三乙胺中和反应20min；加入去离子水，在25℃，2000r/min下分散20min，乳化完毕后，加入1份异佛尔酮二胺后扩链1h，降温出料，旋蒸除去溶剂，得到含磷-溴阻燃单体的超支化聚氨酯乳液。
实施例2
在装有搅拌器，回流冷凝管，温度计的500mL四口烧瓶中加入8.25份THPO，30份IPDI及0.02份催化剂，于80℃在N2保护下反应4h，反应至NCO含量接近理论值后，降温至70℃，分别加入1.25份DMPA和2.8份二溴新戊二醇，依次反应约2.5h，反应过程中加入13份丙酮调节体系粘度；然后降温至40℃，加入0.93份三乙胺中和反应20min；加入去离子水，在25℃，2000r/min下分散20min，乳化完毕后，加入1份异佛尔酮二胺后扩链1h，降温出料，旋蒸除去溶剂，得到含磷-溴阻燃单体的超支化聚氨酯乳液。
实施例3
在装有搅拌器，回流冷凝管，温度计的500mL四口烧瓶中加入8.25份THPO，30份IPDI及0.02份催化剂，于80℃在N2保护下反应4h，反应至NCO含量接近理论值后，降温至70℃，分别加入1.25份DMPA和4.08份二溴新戊二醇，依次反应约2.5h，反应过程中加入15份丙酮调节体系粘度；然后降温至40℃，加入0.93份三乙胺中和反应20min；加入去离子水，在25℃，2000r/min下分散20min，乳化完毕后，加入1份异佛尔酮二胺后扩链1h，降温出料，旋蒸除去溶剂，得到含磷-溴阻燃单体的超支化聚氨酯乳液。
实施例4
在装有搅拌器，回流冷凝管，温度计的500mL四口烧瓶中加入8.25份THPO，30份IPDI及0.02份催化剂，于80℃在N2保护下反应4h，反应至NCO含量接近理论值后，降温至70℃，分别加入1.25份DMPA和5.78份二溴新戊二醇，依次反应约2.5h，反应过程中加入16份丙酮调节体系粘度；然后降温至40℃，加入0.93份三乙胺中和反应20min；加入去离子水，在25℃，2000r/min下分散20min，乳化完毕后，加入1份异佛尔酮二胺后扩链1h，降温出料，旋蒸除去溶剂，得到含磷-溴阻燃单体的超支化聚氨酯乳液。
实施例5
在装有搅拌器，回流冷凝管，温度计的500mL四口烧瓶中加入8.25份THPO，4.4份HDI和23.98份IPDI及0.025份催化剂，于80℃在N2保护下反应4h，反应至NCO含量接近理论值后，降温至70℃，分别加入1.25份DMPA和1.21份二溴新戊二醇，依次反应约2.5h，反应过程中加入14份丙酮调节体系粘度；然后降温至40℃，加入0.93份三乙胺中和反应20min；加入去离子水，在25℃，2000r/min下分散20min，乳化完毕后，加入1份异佛尔酮二胺后扩链1h，降温出料，旋蒸除去溶剂，得到含磷-溴阻燃单体的超支化聚氨酯乳液。
实施例6
在装有搅拌器，回流冷凝管，温度计的500mL四口烧瓶中加入8.25份THPO，22.3份TDI，于60℃在N2保护下反应3h，反应至NCO含量接近理论值后，升温至70℃，分别加入1.25份DMPA和1.21份二溴新戊二醇，依次反应约2.5h，反应过程中加入14份丙酮调节体系粘度；然后降温至40℃，加入0.93份三乙胺中和反应20min；加入去离子水，在25℃，2000r/min下分散20min，乳化完毕后，加入1份异佛尔酮二胺后扩链1h，降温出料，旋蒸除去溶剂，得到含磷-溴阻燃单体的超支化聚氨酯乳液。
对比例1
在装有搅拌器，回流冷凝管，温度计的500mL四口烧瓶中加入8.25份THPO，27.59份IPDI及0.022份催化剂，于80℃在N2保护下反应4h，反应至NCO含量接近理论值后，降温至70℃，加入1.25份DMPA，反应约2.5h，反应过程中加入10份丙酮调节体系粘度；然后降温至40℃，加入0.93份三乙胺中和反应20min；加入去离子水，在25℃，2000r/min下分散20min，乳化完毕后，加入1份异佛尔酮二胺后扩链1h，降温出料，旋蒸除去溶剂，得到含磷阻燃单体的超支化聚氨酯乳液。
对比例2
在装有搅拌器，回流冷凝管，温度计的500mL四口烧瓶中加入12份聚四氢呋喃醚二醇(PTMG-1000)和5份聚己内酯二醇(PCL-2000)以及0.95份DMPA，于80℃在N2保护下加入7.59份IPDI及0.025份催化剂，反应4h，反应至NCO含量接近理论值后，反应过程中加入10份丙酮调节体系粘度；然后降温至40℃，加入0.73份三乙胺中和反应20min；加入去离子水，在25℃，2000r/min下分散20min，乳化完毕后，加入1份异佛尔酮二胺后扩链1h，降温出料，旋蒸除去溶剂，得到不含阻燃单体的聚氨酯乳液。
支化度是表征超支化聚合物的重要参数，通过对以上实施例进行13CNRM谱图分析计算其支化度，结果如表1所示：
表1支化度测试
支化度是指完全支化单元和末端单元所占的摩尔数。完全支化具有规整结构的树枝状大分子，只存在末端单元和支化单元，因此树枝状大分子的支化度为1。而超支化聚合物因为具有线性单元，其支化度都小于1。由表1中可以看出，以上实施例1～6的支化度都小于1，因此所制备的聚氨酯均符合超支化结构。
将实施例1至实施例6及对比例乳液制备成膜，进行性能测试：
表2氧指数测试
| 项目 | 阻燃单体比例(Br/P) | 氧指数％ |
| 实施例1 | 1：19 | 25 |
| 实施例2 | 1:9 | 28.3 |
| 实施例3 | 1:5.6 | 29.9 |
| 实施例4 | 1:4 | 32.2 |
| 实施例5 | 1：19 | 25.9 |
| 实施例6 | 1：19 | 25.4 |
| 对比例1 | 0:1 | 21 |
| 对比例2 | 0 | 17 |
表3力学性能测试
| 项目 | 拉伸强度/MPa | 断裂伸长率/％ |
| 实施例1 | 3.75 | 670 |
| 实施例2 | 5.72 | 575 |
| 实施例3 | 3.79 | 655 |
| 实施例4 | 4.96 | 543 |
| 实施例5 | 3.39 | 665 |
| 实施例6 | 5.87 | 590 |
| 对比例1 | 3.92 | 680 |
| 对比例2 | 4.62 | 550 |
从表2数据可以看出，超支化聚氨酯中引入含磷、溴阻燃单体后，其极限氧指数明显提高，且随着阻燃单体含量的增加，阻燃效果也相应提高。表3数据中，断裂伸长率随着阻燃单体加入量的增加而先增大再减小，说明阻燃单体对其具有一定的增塑性。以上均说明该超支化聚氨酯阻燃剂在阻燃和力学方面的优异性能，且其制备工艺简单，因此具有极大的应用价值。
上述的对实施例的描述是为便于该技术领域的普通技术人员能理解和使用发明。熟悉本领域技术的人员显然可以容易地对这些实施例做出各种修改，并把在此说明的一般原理应用到其他实施例中而不必经过创造性的劳动。因此，本发明不限于上述实施例，本领域技术人员根据本发明的揭示，不脱离本发明范畴所做出的改进和修改都应该在本发明的保护范围之内。
Claims (7)
1.一种超支化磷-溴协效聚氨酯阻燃剂，其特征在于，由包括以下质量份的原料制备得到：含磷阻燃单体8.25~10份，二异氰酸酯22~35份，亲水扩链剂0.9~1.5份，含溴阻燃单体1.21~2.8份，中和剂0.6~1.13份，催化剂0.015~0.053份，胺类扩链剂0.8~1.5份，溶剂10~16份，去离子水87.5~107.1份；
所述的含磷阻燃单体的核分子为三羟甲基氧化磷；
所述的亲水扩链剂为二羟甲基丙酸；
所述的含溴阻燃单体为二溴新戊二醇；
所述的超支化磷-溴协效聚氨酯阻燃剂的制备方法，包括以下步骤：
（1）将已除水的含磷阻燃单体、二异氰酸酯和催化剂，在保护气体保护的条件下催化反应；
（2）加入亲水扩链剂，反应过程中加入溶剂；
（3）引入含溴阻燃单体，进行反应；
（4）加入中和剂进行中和；
（5）加入去离子水分散乳化；
（6）乳化后加入胺类扩链剂，扩链结束后除去溶剂，得到超支化磷-溴协效聚氨酯阻燃剂。
2.根据权利要求1所述的超支化磷-溴协效聚氨酯阻燃剂，其特征在于，所述的二异氰酸酯为六亚甲基二异氰酸酯、异佛尔酮二异氰酸酯、甲苯二异氰酸酯、4,4'-二苯基甲烷二异氰酸酯中的一种或几种混合。
3.根据权利要求1所述的超支化磷-溴协效聚氨酯阻燃剂，其特征在于，所述的中和剂选自三乙胺、氢氧化钠、氢氧化钾中的一种或一种以上的混合物。
4.根据权利要求1所述的超支化磷-溴协效聚氨酯阻燃剂，其特征在于，所述的催化剂为二月桂酸二丁基锡。
5.根据权利要求1所述的超支化磷-溴协效聚氨酯阻燃剂，其特征在于，所述的胺类扩链剂为己二胺、二乙烯三胺、异佛尔酮二胺中的一种或一种以上的混合物。
6.一种如权利要求1~5任一项所述的超支化磷-溴协效聚氨酯阻燃剂的制备方法，其特征在于，包括以下步骤：
（1）将已除水的含磷阻燃单体、二异氰酸酯和催化剂，在保护气体保护的条件下催化反应；
（2）加入亲水扩链剂，反应过程中加入溶剂；
（3）引入含溴阻燃单体，进行反应；
（4）加入中和剂进行中和；
（5）加入去离子水分散乳化；
（6）乳化后加入胺类扩链剂，扩链结束后除去溶剂，得到超支化磷-溴协效聚氨酯阻燃剂。
7.根据权利要求6所述的超支化磷-溴协效聚氨酯阻燃剂的制备方法，其特征在于，所述的保护气体为干燥氮气；溶剂为丙酮、丁酮、甲苯中的一种或一种以上的混合物。
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1382739A (zh) * | 2001-04-23 | 2002-12-04 | 中国科学技术大学 | 辐射可固化含磷超支化聚氨酯丙烯酸酯阻燃剂及制备方法 |
| CN106977681A (zh) * | 2017-04-07 | 2017-07-25 | 北京理工大学 | 一种超支化共混硬段改性后扩链阻燃水性聚氨酯 |
| CN108059913A (zh) * | 2017-12-21 | 2018-05-22 | 四川东材科技集团股份有限公司 | 一种水性磷-硅阻燃聚氨酯涂层材料的制备方法 |
| CN112480166A (zh) * | 2020-11-30 | 2021-03-12 | 上海应用技术大学 | 一种氮磷型阻燃剂的制备方法 |
| CN114230752A (zh) * | 2021-11-30 | 2022-03-25 | 山东一诺威新材料有限公司 | 本征阻燃自修复聚氨酯及其制备方法 |
-
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- 2022-07-04 CN CN202210786789.2A patent/CN115028792B/zh active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1382739A (zh) * | 2001-04-23 | 2002-12-04 | 中国科学技术大学 | 辐射可固化含磷超支化聚氨酯丙烯酸酯阻燃剂及制备方法 |
| CN106977681A (zh) * | 2017-04-07 | 2017-07-25 | 北京理工大学 | 一种超支化共混硬段改性后扩链阻燃水性聚氨酯 |
| CN108059913A (zh) * | 2017-12-21 | 2018-05-22 | 四川东材科技集团股份有限公司 | 一种水性磷-硅阻燃聚氨酯涂层材料的制备方法 |
| CN112480166A (zh) * | 2020-11-30 | 2021-03-12 | 上海应用技术大学 | 一种氮磷型阻燃剂的制备方法 |
| CN114230752A (zh) * | 2021-11-30 | 2022-03-25 | 山东一诺威新材料有限公司 | 本征阻燃自修复聚氨酯及其制备方法 |
Non-Patent Citations (1)
| Title |
|---|
| "超支化聚氨酯的应用研究进展";张子文等;《胶体与聚合物》;第38卷(第1期);42-45 * |
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