CN109280137A - 一种松香基tdi型水性聚氨酯微球的制备方法 - Google Patents
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Abstract
本发明公开了一种松香基TDI型水性聚氨酯微球的制备方法。以松香等为原料经改性得到松香基TDI型水性聚氨酯，然后在聚乙烯吡咯烷酮以及引发剂作用下与苯乙烯共聚得到松香基TDI型水性聚氨酯微球。本发明最显著的特点是以松香等为原料制备得到粒径较小、单分散性和球形均较好的离子型水性聚氨酯微球。这不仅赋予了松香和聚氨酯更为广泛的应用，而且合成的水性聚氨酯微球可以应用在药物负载与释放、金属离子吸附、污水处理等领域。
Description
技术领域
本发明涉及一种松香基TDI型水性聚氨酯微球的制备方法。
背景技术
随着全球不可再生化石能源的日益枯竭以及人们环保意识的不断提高，以天然可再生资源部分或全部代替化石能源来缓解能源危机的研究已经成为化学工作者的主要任务之一。松香是自然界中一种极其丰富的天然可再生资源，虽然产量丰富，但存在酸值较高和易氧化的缺陷，限制了它在许多工业生产中的应用。利用松香结构中的双键和羧基对其进行改性，可以达到扩大其应用范围的目的。松香在高分子合成中的应用主要是通过羧基和双键将其引入到高分子链中。以松香为原料合成的功能性聚合物，对人体无毒无害，可安全地用于医药和食品领域。
聚氨酯微球是一种新型的聚氨酯产品，它含有氨基甲酸酯等极性基团和微相分离结构，由于微球的表面和内部有较多的褶皱和孔道，以及自身粒径较小，具有较大的比表面积，分散在溶液中具有较好的稳定性，使其具有良好的吸附、离子交换、螯合、生物相容性及高弹性和高强度等特点，在分离提纯、生化诊断、药物载体、涂料、胶粘剂和油墨等方面显示出广阔的应用前景。聚氨酯微球的制备方法主要有自乳化法、悬浮聚合法、分散聚合法等。通过对聚氨酯树脂设计、合成及改性，可得到粒径可控、形貌、力学性能、耐水性和稳定性较好的聚氨酯微球。
本发明以松香为原料，通过改性得到松香基TDI型水性聚氨酯，然后与苯乙烯进行共聚得到松香基TDI型水性聚氨酯微球。本发明为合理开发利用松香资源提供了新的应用途径，制备的聚氨酯微球可应用于色谱分析、吸附分离技术以及废水处理等领域。
发明内容
本发明的目的是提供一种松香基TDI型水性聚氨酯微球的制备方法。
本发明的具体步骤为：
将3.20～1.60质量份松香基TDI型水性聚氨酯、0.80～2.40质量份化学纯苯乙烯、0.08～0.32质量份化学纯聚乙烯吡咯烷酮以及0.02～0.08质量份分析纯偶氮二异丁腈置于烧杯中，加入40～60质量份蒸馏水，超声分散10分钟混合均匀，然后将混合液加入反应釜中，在N2保护作用下加热至80～100℃，设置转速为200r·min-1，反应持续4～10小时，最后在10000r·min-1转速下离心分离15分钟，用蒸馏水洗涤3～5次、离心分离，自然晾干得到平均粒径为85～200nm松香基TDI型水性聚氨酯微球。
所述松香基TDI型水性聚氨酯的制备方法步骤为：
(1)将100.0质量份松香加入到装有搅拌棒、回流冷凝管、温度计、氮气保护装置的反应釜中，加热熔化后在400r·min-1下进行搅拌，加热至230℃后，开始缓慢滴加28.60质量份化学纯丙烯酸，持续1小时，滴加完毕后使其在230℃下继续反应2小时，待温度降至200℃出料，得到丙烯酸松香加成物。
(2)在反应釜中将108.51质量份步骤(1)所得丙烯酸松香加成物溶解于191.86质量份分析纯甲苯中，加入82.40质量份纯度97％甲基丙烯酸缩水甘油酯、0.54质量份分析纯三乙胺和0.41质量份分析纯1,4-对苯二酚，升温至120℃，反应4小时，测酸值为2.40mgKOH/g，旋转蒸发除去甲苯，即得到松香基多元醇。
(3)将30.00质量份步骤(2)所得松香基多元醇、0.21质量份化学纯二丁基二月桂酸锡和100.00质量份分析纯丙酮加入反应釜中，在N2保护下加热至30℃，加入11.89质量份实验试剂甲苯-2,4-二异氰酸酯(TDI)，设置转速为400r·min-1，待-NCO含量降至理论值，加入4.61质量份分析纯2,2-二羟甲基丙酸并升温至55℃，反应至-NCO含量降为0，降温至18℃，加入3.48质量份分析纯三乙胺中和10分钟，在1300r·min-1机械搅拌下加入200mL去离子水乳化分散30分钟，减压蒸馏除去丙酮，得到松香基TDI型水性聚氨酯，测固体质量百分比为18.20％。
本发明与其它相关技术相比，最显著的特点是以天然可再生林产资源松香等为原料，经改性得到松香基TDI型水性聚氨酯，然后在引发剂作用下与苯乙烯共聚合成了松香基TDI型水性聚氨酯微球。不仅得到了单分散性和球形均较好的亚微米级聚氨酯微球，而且还赋予了松香更为广泛的应用。
具体实施方式
实施例1：
将2.80质量份松香基TDI型水性聚氨酯、1.20质量份化学纯苯乙烯、0.24质量份化学纯聚乙烯吡咯烷酮以及0.04质量份分析纯偶氮二异丁腈置于烧杯中，加入46质量份蒸馏水，超声分散10分钟混合均匀，然后将混合液加入反应釜中，在N2保护作用下加热至85℃，设置转速为200r·min-1，反应持续8小时，最后在10000r·min-1转速下离心分离15分钟，用蒸馏水洗涤4次，离心分离，自然晾干得到平均粒径为187.10nm松香基TDI型水性聚氨酯微球。
所述松香基TDI型水性聚氨酯的制备方法步骤为：
(1)将100.0质量份松香加入到装有搅拌棒、回流冷凝管、温度计、氮气保护装置的反应釜中，加热熔化后在400r·min-1下进行搅拌，加热至230℃后，开始缓慢滴加28.60质量份化学纯丙烯酸，持续1小时，滴加完毕后使其在230℃下继续反应2小时，待温度降至200℃出料，得到丙烯酸松香加成物。
(2)在反应釜中将108.51质量份步骤(1)所得丙烯酸松香加成物溶解于191.86质量份分析纯甲苯中，加入82.40质量份纯度97％甲基丙烯酸缩水甘油酯、0.54质量份分析纯三乙胺和0.41质量份分析纯1,4-对苯二酚，升温至120℃，反应4小时，测酸值为2.40mgKOH/g，旋转蒸发除去甲苯，即得到松香基多元醇。
(3)将30.00质量份步骤(2)所得松香基多元醇、0.21质量份化学纯二丁基二月桂酸锡和100.00质量份分析纯丙酮加入反应釜中，在N2保护下加热至30℃，加入11.89质量份实验试剂甲苯-2,4-二异氰酸酯(TDI)，设置转速为400r·min-1，待-NCO含量降至理论值，加入4.61质量份分析纯2,2-二羟甲基丙酸并升温至55℃，反应至-NCO含量降为0，降温至18℃，加入3.48质量份分析纯三乙胺中和10分钟，在1300r·min-1机械搅拌下加入200mL去离子水乳化分散30分钟，减压蒸馏除去丙酮，得到松香基TDI型水性聚氨酯，测固体质量百分比为18.20％。
实施例2：
将2.40质量份松香基TDI型水性聚氨酯、1.60质量份化学纯苯乙烯、0.24质量份化学纯聚乙烯吡咯烷酮以及0.04质量份分析纯偶氮二异丁腈置于烧杯中，加入46质量份蒸馏水，超声分散10分钟混合均匀，然后将混合液加入反应釜中，在N2保护作用下加热至85℃，设置转速为200r·min-1，反应持续8小时，最后在10000r·min-1转速下离心分离15分钟，用蒸馏水洗涤4次，离心分离，自然晾干得到平均粒径为160.80nm松香基TDI型水性聚氨酯微球。
所述松香基TDI型水性聚氨酯的制备方法步骤为：
(1)将100.0质量份松香加入到装有搅拌棒、回流冷凝管、温度计、氮气保护装置的反应釜中，加热熔化后在400r·min-1下进行搅拌，加热至230℃后，开始缓慢滴加28.60质量份化学纯丙烯酸，持续1小时，滴加完毕后使其在230℃下继续反应2小时，待温度降至200℃出料，得到丙烯酸松香加成物。
(2)在反应釜中将108.51质量份步骤(1)所得丙烯酸松香加成物溶解于191.86质量份分析纯甲苯中，加入82.40质量份纯度97％甲基丙烯酸缩水甘油酯、0.54质量份分析纯三乙胺和0.41质量份分析纯1,4-对苯二酚，升温至120℃，反应4小时，测酸值为2.40mgKOH/g，旋转蒸发除去甲苯，即得到松香基多元醇。
(3)将30.00质量份步骤(2)所得松香基多元醇、0.21质量份化学纯二丁基二月桂酸锡和100.00质量份分析纯丙酮加入反应釜中，在N2保护下加热至30℃，加入11.89质量份实验试剂甲苯-2,4-二异氰酸酯(TDI)，设置转速为400r·min-1，待-NCO含量降至理论值，加入4.61质量份分析纯2,2-二羟甲基丙酸并升温至55℃，反应至-NCO含量降为0，降温至18℃，加入3.48质量份分析纯三乙胺中和10分钟，在1300r·min-1机械搅拌下加入200mL去离子水乳化分散30分钟，减压蒸馏除去丙酮，得到松香基TDI型水性聚氨酯，测固体质量百分比为18.20％。
实施例3：
将2.40质量份松香基TDI型水性聚氨酯、1.60质量份化学纯苯乙烯、0.32质量份化学纯聚乙烯吡咯烷酮以及0.04质量份分析纯偶氮二异丁腈置于烧杯中，加入46质量份蒸馏水，超声分散10分钟混合均匀，然后将混合液加入反应釜中，在N2保护作用下加热至80℃，设置转速为200r·min-1，反应持续8小时，最后在10000r·min-1转速下离心分离15分钟，用蒸馏水洗涤5次，离心分离，自然晾干得到平均粒径为120.00nm松香基TDI型水性聚氨酯微球。
所述松香基TDI型水性聚氨酯的制备方法步骤为：
(1)将100.0质量份松香加入到装有搅拌棒、回流冷凝管、温度计、氮气保护装置的反应釜中，加热熔化后在400r·min-1下进行搅拌，加热至230℃后，开始缓慢滴加28.60质量份化学纯丙烯酸，持续1小时，滴加完毕后使其在230℃下继续反应2小时，待温度降至200℃出料，得到丙烯酸松香加成物。
(2)在反应釜中将108.51质量份步骤(1)所得丙烯酸松香加成物溶解于191.86质量份分析纯甲苯中，加入82.40质量份纯度97％甲基丙烯酸缩水甘油酯、0.54质量份分析纯三乙胺和0.41质量份分析纯1,4-对苯二酚，升温至120℃，反应4小时，测酸值为2.40mgKOH/g，旋转蒸发除去甲苯，即得到松香基多元醇。
(3)将30.00质量份步骤(2)所得松香基多元醇、0.21质量份化学纯二丁基二月桂酸锡和100.00质量份分析纯丙酮加入反应釜中，在N2保护下加热至30℃，加入11.89质量份实验试剂甲苯-2,4-二异氰酸酯(TDI)，设置转速为400r·min-1，待-NCO含量降至理论值，加入4.61质量份分析纯2,2-二羟甲基丙酸并升温至55℃，反应至-NCO含量降为0，降温至18℃，加入3.48质量份分析纯三乙胺中和10分钟，在1300r·min-1机械搅拌下加入200mL去离子水乳化分散30分钟，减压蒸馏除去丙酮，得到松香基TDI型水性聚氨酯，测固体质量百分比为18.20％。
Claims (1)
1.一种松香基TDI型水性聚氨酯微球的制备方法，其特征在于具体步骤为：
将3.20～1.60质量份松香基TDI型水性聚氨酯、0.80～2.40质量份化学纯苯乙烯、0.08～0.32质量份化学纯聚乙烯吡咯烷酮以及0.02～0.08质量份分析纯偶氮二异丁腈置于烧杯中，加入40～60质量份蒸馏水，超声分散10分钟混合均匀，然后将混合液加入反应釜中，在N2保护作用下加热至80～100℃，设置转速为200 r·min-1，反应持续4～10小时，最后在10000 r·min-1转速下离心分离15分钟，用蒸馏水洗涤3～5次、离心分离，自然晾干得到平均粒径为85～200 nm松香基TDI型水性聚氨酯微球；
所述松香基TDI型水性聚氨酯的制备方法步骤为：
（1）将100.0质量份松香加入到装有搅拌棒、回流冷凝管、温度计、氮气保护装置的反应釜中，加热熔化后在400 r·min-1下进行搅拌，加热至230℃后，开始缓慢滴加28.60质量份化学纯丙烯酸，持续1小时，滴加完毕后使其在230℃下继续反应2小时，待温度降至200℃出料，得到丙烯酸松香加成物；
（2）在反应釜中将108.51质量份步骤（1）所得丙烯酸松香加成物溶解于191.86质量份分析纯甲苯中，加入82.40质量份纯度97%甲基丙烯酸缩水甘油酯、0.54质量份分析纯三乙胺和0.41质量份分析纯1,4-对苯二酚，升温至120℃，反应4小时，测酸值为2.40 mgKOH/g，旋转蒸发除去甲苯，即得到松香基多元醇；
（3）将30.00质量份步骤（2）所得松香基多元醇、0.21质量份化学纯二丁基二月桂酸锡和100.00质量份分析纯丙酮加入反应釜中，在N2保护下加热至30℃，加入11.89质量份实验试剂甲苯-2,4-二异氰酸酯，设置转速为400 r·min-1，待-NCO含量降至理论值，加入4.61质量份分析纯2,2-二羟甲基丙酸并升温至55℃，反应至-NCO含量降为0，降温至18℃，加入3.48质量份分析纯三乙胺中和10分钟，在1300 r·min-1机械搅拌下加入200 mL去离子水乳化分散30分钟，减压蒸馏除去丙酮，得到松香基TDI型水性聚氨酯，测固体质量百分比为18.20 %。
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110467719A (zh) * | 2019-08-01 | 2019-11-19 | 桂林理工大学 | 一种松香基tdi型抑菌聚氨酯的制备方法 |
| CN110483733A (zh) * | 2019-08-01 | 2019-11-22 | 桂林理工大学 | 一种松香基ipdi型抑菌聚氨酯的制备方法 |
| CN114605084A (zh) * | 2022-03-29 | 2022-06-10 | 武昌理工学院 | 绿色节能建筑玻璃及其制备方法 |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101766981A (zh) * | 2010-01-13 | 2010-07-07 | 桂林理工大学 | 利用松香丙烯酸羟基酯制备聚合物微球的方法 |
| CN105778028A (zh) * | 2016-03-13 | 2016-07-20 | 桂林理工大学 | 一种松香基tdi型聚氨酯预聚体的制备方法 |
-
2018
- 2018-08-14 CN CN201810925532.4A patent/CN109280137B/zh active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101766981A (zh) * | 2010-01-13 | 2010-07-07 | 桂林理工大学 | 利用松香丙烯酸羟基酯制备聚合物微球的方法 |
| CN105778028A (zh) * | 2016-03-13 | 2016-07-20 | 桂林理工大学 | 一种松香基tdi型聚氨酯预聚体的制备方法 |
Non-Patent Citations (4)
| Title |
|---|
| 任鹏等: "悬浮聚合法制备含松香GMA 酯的聚合物微球", 《中国化学会第十届全国天然有机化学学术会议论文集》 * |
| 张天鹭: "具有核壳结构的水性聚氨酯/导电聚合物复合纳米弹性微球的制备与表征", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
| 张鹏等: "分散聚合法制备Fe3O4 /P( St－PU) 磁性微球", 《广州化工》 * |
| 王志强: "药物缓释材料丙烯酸酯改性水性聚氨酯的研究及应用", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110467719A (zh) * | 2019-08-01 | 2019-11-19 | 桂林理工大学 | 一种松香基tdi型抑菌聚氨酯的制备方法 |
| CN110483733A (zh) * | 2019-08-01 | 2019-11-22 | 桂林理工大学 | 一种松香基ipdi型抑菌聚氨酯的制备方法 |
| CN114605084A (zh) * | 2022-03-29 | 2022-06-10 | 武昌理工学院 | 绿色节能建筑玻璃及其制备方法 |
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