聚脲微胶囊的研制及其在纺织上的应用
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摘要
本论文采用界面聚合法制备聚脲微胶囊并将分散染料微胶囊用于热溶染色、转移印花、多色多点印花和双面印花等。分散染料微胶囊在制备和使用过程中无甲醛、无污染。更重要的是，染料胶囊化以后，可消除废水中的游离染料，减轻环境污染；染色废水中的微胶囊染料可以通过沉淀、过滤等技术分离出来，使染色工艺逐步实现环境友好化，获得经济效益和环境效益的双重效果。
聚脲微胶囊的制备原理是异氰酸酯与水反应生成胺，胺再与未反应的异氰酸酯基团反应生成聚脲。
芯材分别为分散深兰S-3BG、分散兰2BLN、分散红3B和分散黄E-3RL。为优化胶囊化条件，在研究的初期阶段，也使用香精等液体芯材。壁材单体分别使用了2，4-甲苯二异氰酸酯、80／20-甲苯二异氰酸酯、三苯基甲烷-4，4′，4″-三异氰酸酯和二苯甲烷-4，4′-二异氰酸酯；保护胶体是聚乙烯醇(PVA)；乳化剂是聚醚2040；催化剂使用二月桂酸二丁基锡。
主要研究了影响液态芯材和固态芯材微胶囊形态和粒径大小的因素；分散染料微胶囊的释放性能；利用模糊数学法确定用于染色和印花的分散染料适宜的胶囊化工艺及分散染料微胶囊在染色和印花中的应用。
使用这种方法及配方制备微胶囊，助剂少，成本低且简便。
研究结果表明：
1．在制备聚脲微胶囊的过程中，反应150min后加入正丁胺，并加入催化剂可使反应完全，制备的微胶囊中测不出残留异氰酸酯(ASTM D2572-87)。
2．当芯材疏水性较高，催化剂加到水相制备的微胶囊具有较光滑的表面、较小的粒径及较窄的粒径分布；TDI用量增多，制备的微胶囊的外观形态变得粗糙，粒径增大，粒径分布变宽；低温下制备的微胶囊的外观形态较好；反应3小时，反应即可进行到底；相比(油／水)增大和芯壁比减小，使微胶囊的粒径变大、粒径分布变宽及囊壁变厚；乳化剂和保护胶体用量增多、提高乳化速度、延长乳化时间使微胶囊的粒径变小、壁厚减小及粒径分布变窄。
3．相比增大、芯壁比减小，分散染料微胶囊的释放速率和渗透性常数下降；乳化剂用量增加，分散染料微胶囊的释放速率和渗透性常数提高；PVA用量为1％时，分散染料微胶囊的释放速率和渗透性常数较高；提高乳化速度、延长乳化时间，分散染料微胶囊的释放速率提高；渗透性常数无明显变化。
4．使用海藻酸钠作为防泳移剂对织物进行热溶染色，得色较深，均匀性较好；随着焙烘温度升高和焙烘时间的延长，织物的表面K／S值增大。利用乳化剂2040：2.5％，相比7：93，芯壁比1：3，保护胶体PVA：1％，乳化速度9000rpm，乳化时间10min，反应时间3h的工艺配方制备的分散染料微胶囊进行染色，织物的K／S值最大；沾色牢度为4～5级；染色牢度为3～4级；经过微胶囊染料染色的织物，水洗液静置150min后变为澄清，使废水处理变得简单而有效。
5．相比(油／水)13：87，芯壁比1：3，保护胶体PVA：1％，乳化剂2040：2％，乳化
东华大学博士论文
摘要
速度:900Orpm，乳化时间IOmin，反应时间3h制备的分散染料微胶囊，由于其
匀速释放染料的性能，用于转移印花时可实现多次转移印花新工艺。可通过转印
温度和时间来控制颜色浓度。当需要较淡的转印色时，可以转移印花8次以上。
这种新工艺不但节约转印纸，还可提高染料利用率。
6.使用胶囊化的染料与未胶囊化的染料进行热溶染色，织物的染色牢度相同，但
前者染色织物的沾色牢度好于后者。
7.使用复配胶囊印花，得到了非常好的转印效果:而且可以根据两种芯材用量的
多少来调节所复配的微胶囊分散染料的颜色深度。
Interfacial polymerization method was employed to prepare polyuea microcapsules in this paper. Disperse dye microcapsules were applied in thermosol dyeing, transfer printing, multi-color and multi-dot printing and double sided printings. There is neither formaldehyde nor other pollutions when the microcapsules were being prepared and used. What more important is that, microcapsulated dyes can eliminate free dyes in waste water and lighten the environmental pollution. Microcapsulated dyes in the dyeing waste water can be separated by precipitation or filtration making the dyeing process environmental friendly and then obtain both economical and environmental benefits.
The principle of polymerization is that isocyanate reacts with water and forms amine, and then the amine reacts quickly with unreacted isocyanate and forms polyurea.
The core materials used in this experiment included disperse blue S-3BG, disperse blue 2BLN, disperse red 3B and disperse yellow E-3RL. Also, the liquid core materials were used in order to optimizing the microencapsulation conditions at the primary stage, e.g. the perfumes. The wall forming materials were TDI (2,4-toluene diisocyanate) or 80/20TDI, triphenyl methane triisocyanate and biphenyl methane-4, 4-diisocyanate (liquid MDI), Poly vinyl alcohol (PVA) was used as protective colloid and GPE2040 was used as the emulsifier. The Dibutyltin dilaurate was used as the catalyst.
The effects of different elements on the morphology and particle size and the release property of disperse dye microcapsules were studied. Suitable microencapsulation techniques of disperse dyes for dyeing and printing were determined respectively.
It is economic and convenient to prepare microcapsules to use this method and formulation. Fewer auxiliaries were used.
The results indicated:
1. During preparing microcapsules, n-butylamine and catalyst were added after the reaction was running 150min to complete the reaction. The residual isocyanate groups were not be detected(ASTM D2572-87)
2. Smoother morphological structure and smaller particle size and narrower particle size distribution of microcapsules were obtained with the higher hydrophobicity of the core materials and catalyst in the aqueous phase. The morphological structures became coarser, particle sizes bigger and particle size distribution wider with increase in the amount of TDI. The morphological structures of microcapsules prepared at lower temperature were smoother. Three hours were enough to finish the shell forming polymerization. The particle sizes were bigger, particle size
distributions were wider and the wall thicknesses were thicker with the increase in phase ratios (o/w) and decrease in core/wall ratios. And the particle sizes were smaller, particle size distributions were narrower and the wall thickness became thinner with increase in the amount of emulsifier, protective colloid, emulsifying speed and emulsifying time in the range of the experiments.
3. Release rates and permeability constants decreased with increase in phase ratios and decrease in core/wall ratios. Release rates and permeability constants increased with the increase in the amount of emulsifier. Release rates increased and permeability constants hardly change with the increase in emulsifying speed and emulsifying time.
4. The deeper color and better levelness were obtained when the disperse dye microcapsules were applied to thermosol dyeing with sodium alginate as anti-migrating agent. K/S value was the highest and color fastness was 3-4 and color staining was 4-5 with the disperse dyes microcapsules prepared as follow: emulsifier2040: 2.5%, phase ratio7:93, core/wall ratiol:3, protective colloid (PVA) 1%, emulsifying speed 9000rpm,emulsifying time lOmin and react time 3h. The effluent became clear after 150min stood, which made the waste water treatment very easy and more effective.
5. Owing to its performance of releasing dyes with constant rate at elevated temperature with the microcapsules, prepared with the followin
聚脲微胶囊的制备原理是异氰酸酯与水反应生成胺，胺再与未反应的异氰酸酯基团反应生成聚脲。
芯材分别为分散深兰S-3BG、分散兰2BLN、分散红3B和分散黄E-3RL。为优化胶囊化条件，在研究的初期阶段，也使用香精等液体芯材。壁材单体分别使用了2，4-甲苯二异氰酸酯、80／20-甲苯二异氰酸酯、三苯基甲烷-4，4′，4″-三异氰酸酯和二苯甲烷-4，4′-二异氰酸酯；保护胶体是聚乙烯醇(PVA)；乳化剂是聚醚2040；催化剂使用二月桂酸二丁基锡。
主要研究了影响液态芯材和固态芯材微胶囊形态和粒径大小的因素；分散染料微胶囊的释放性能；利用模糊数学法确定用于染色和印花的分散染料适宜的胶囊化工艺及分散染料微胶囊在染色和印花中的应用。
使用这种方法及配方制备微胶囊，助剂少，成本低且简便。
研究结果表明：
1．在制备聚脲微胶囊的过程中，反应150min后加入正丁胺，并加入催化剂可使反应完全，制备的微胶囊中测不出残留异氰酸酯(ASTM D2572-87)。
2．当芯材疏水性较高，催化剂加到水相制备的微胶囊具有较光滑的表面、较小的粒径及较窄的粒径分布；TDI用量增多，制备的微胶囊的外观形态变得粗糙，粒径增大，粒径分布变宽；低温下制备的微胶囊的外观形态较好；反应3小时，反应即可进行到底；相比(油／水)增大和芯壁比减小，使微胶囊的粒径变大、粒径分布变宽及囊壁变厚；乳化剂和保护胶体用量增多、提高乳化速度、延长乳化时间使微胶囊的粒径变小、壁厚减小及粒径分布变窄。
3．相比增大、芯壁比减小，分散染料微胶囊的释放速率和渗透性常数下降；乳化剂用量增加，分散染料微胶囊的释放速率和渗透性常数提高；PVA用量为1％时，分散染料微胶囊的释放速率和渗透性常数较高；提高乳化速度、延长乳化时间，分散染料微胶囊的释放速率提高；渗透性常数无明显变化。
4．使用海藻酸钠作为防泳移剂对织物进行热溶染色，得色较深，均匀性较好；随着焙烘温度升高和焙烘时间的延长，织物的表面K／S值增大。利用乳化剂2040：2.5％，相比7：93，芯壁比1：3，保护胶体PVA：1％，乳化速度9000rpm，乳化时间10min，反应时间3h的工艺配方制备的分散染料微胶囊进行染色，织物的K／S值最大；沾色牢度为4～5级；染色牢度为3～4级；经过微胶囊染料染色的织物，水洗液静置150min后变为澄清，使废水处理变得简单而有效。
5．相比(油／水)13：87，芯壁比1：3，保护胶体PVA：1％，乳化剂2040：2％，乳化
东华大学博士论文
摘要
速度:900Orpm，乳化时间IOmin，反应时间3h制备的分散染料微胶囊，由于其
匀速释放染料的性能，用于转移印花时可实现多次转移印花新工艺。可通过转印
温度和时间来控制颜色浓度。当需要较淡的转印色时，可以转移印花8次以上。
这种新工艺不但节约转印纸，还可提高染料利用率。
6.使用胶囊化的染料与未胶囊化的染料进行热溶染色，织物的染色牢度相同，但
前者染色织物的沾色牢度好于后者。
7.使用复配胶囊印花，得到了非常好的转印效果:而且可以根据两种芯材用量的
多少来调节所复配的微胶囊分散染料的颜色深度。
Interfacial polymerization method was employed to prepare polyuea microcapsules in this paper. Disperse dye microcapsules were applied in thermosol dyeing, transfer printing, multi-color and multi-dot printing and double sided printings. There is neither formaldehyde nor other pollutions when the microcapsules were being prepared and used. What more important is that, microcapsulated dyes can eliminate free dyes in waste water and lighten the environmental pollution. Microcapsulated dyes in the dyeing waste water can be separated by precipitation or filtration making the dyeing process environmental friendly and then obtain both economical and environmental benefits.
The principle of polymerization is that isocyanate reacts with water and forms amine, and then the amine reacts quickly with unreacted isocyanate and forms polyurea.
The core materials used in this experiment included disperse blue S-3BG, disperse blue 2BLN, disperse red 3B and disperse yellow E-3RL. Also, the liquid core materials were used in order to optimizing the microencapsulation conditions at the primary stage, e.g. the perfumes. The wall forming materials were TDI (2,4-toluene diisocyanate) or 80/20TDI, triphenyl methane triisocyanate and biphenyl methane-4, 4-diisocyanate (liquid MDI), Poly vinyl alcohol (PVA) was used as protective colloid and GPE2040 was used as the emulsifier. The Dibutyltin dilaurate was used as the catalyst.
The effects of different elements on the morphology and particle size and the release property of disperse dye microcapsules were studied. Suitable microencapsulation techniques of disperse dyes for dyeing and printing were determined respectively.
It is economic and convenient to prepare microcapsules to use this method and formulation. Fewer auxiliaries were used.
The results indicated:
1. During preparing microcapsules, n-butylamine and catalyst were added after the reaction was running 150min to complete the reaction. The residual isocyanate groups were not be detected(ASTM D2572-87)
2. Smoother morphological structure and smaller particle size and narrower particle size distribution of microcapsules were obtained with the higher hydrophobicity of the core materials and catalyst in the aqueous phase. The morphological structures became coarser, particle sizes bigger and particle size distribution wider with increase in the amount of TDI. The morphological structures of microcapsules prepared at lower temperature were smoother. Three hours were enough to finish the shell forming polymerization. The particle sizes were bigger, particle size
distributions were wider and the wall thicknesses were thicker with the increase in phase ratios (o/w) and decrease in core/wall ratios. And the particle sizes were smaller, particle size distributions were narrower and the wall thickness became thinner with increase in the amount of emulsifier, protective colloid, emulsifying speed and emulsifying time in the range of the experiments.
3. Release rates and permeability constants decreased with increase in phase ratios and decrease in core/wall ratios. Release rates and permeability constants increased with the increase in the amount of emulsifier. Release rates increased and permeability constants hardly change with the increase in emulsifying speed and emulsifying time.
4. The deeper color and better levelness were obtained when the disperse dye microcapsules were applied to thermosol dyeing with sodium alginate as anti-migrating agent. K/S value was the highest and color fastness was 3-4 and color staining was 4-5 with the disperse dyes microcapsules prepared as follow: emulsifier2040: 2.5%, phase ratio7:93, core/wall ratiol:3, protective colloid (PVA) 1%, emulsifying speed 9000rpm,emulsifying time lOmin and react time 3h. The effluent became clear after 150min stood, which made the waste water treatment very easy and more effective.
5. Owing to its performance of releasing dyes with constant rate at elevated temperature with the microcapsules, prepared with the followin
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