水性含氟聚氨酯及应用

水性含氟聚氨酯及应用 1.1 水性聚氨酯 聚氨酯(PU)是聚合物分子链内含有相当数量的氨基甲酸酯单元(-NH-COO-) [1, 2]的高分子化合物。根据分散体系的不同分为溶剂型聚氨酯和水性聚氨酯。相对而言,溶剂型聚氨酯的研究更早,更深入,应用也更普遍,但是由于溶剂型聚氨酯在合成过程中使用大量有机溶剂，在制备、储存、运输、使用过程中，不仅存在严重的安全隐患，还由于有机挥发物的排放，污染环境。随着当今社会环保意识日益增强，人们日常生活中对各种建筑、涂料、染整、纺织、皮革等方面的环保要求也逐渐提高，因此，水性聚氨酯也广泛的渗透到社会的方方面面。聚氨酯水乳液广泛应用于涂料、纺织、印刷、印染、造纸、皮革涂饰等行业，且使用领 [3-4]域还在不断扩大。 水性聚氨酯的发展概况。水性聚氨酯是指聚氨酯溶解于水或分散于水中而形成的一种聚氨酯，有人也称水性聚氨酯为水系聚氨酯或水基聚氨酯。依其外观和粒径将水性聚氨酯分为三类:聚氨酯水溶液(粒径小于0.001微米，外观透明)、聚氨酯分散液(粒径在0.001-0.1微米，外观半透明)，聚氨酯乳液(粒径大于0.1微米，外观白浊)。但习惯上后两类有时又统称为聚氨酯乳液或聚氨酯分散液，区分并不严格。实际应用中，水性聚氨酯以聚氨酯乳液或分散液居多，水溶液少。然而，当前水性聚氨酯分散体的合成时通常采用所谓内乳化工艺，即在聚氨酯分子链中引入亲水性基团而获得具有自乳化性能的聚氨酯，它可以在弱的机械作用下分散于水中，引入分子链中的亲水基团能使其稳定分散。但是亲水基团通常是通过共价键连接在分子中，从而使得分散体干燥成膜后亲水基团会保留在分散体的膜材料 表 关于同志近三年现实表现材料材料类招标技术评分表图表与交易pdf视力表打印pdf用图表说话 pdf 面，导致对膜材料的疏水性产生不良影响。 1.2 水性含氟聚氨酯 众所周知，氟碳化合物具有极低的表面张力，所以将有机氟材料广泛用于各种材料的表面能改性亦获得类似的低表面能，同样，将有机氟功能链段引入其他高分子结构中合成含氟高分子乳液或分散体是有机氟功能材料的发展方向之一，这类高分子材料在成膜后由于氟的低表面能，氟将在材料表面富集同样达到有机 [5-6]氟功能材料的低表面能。含氟高分子乳液以水作为分散介质同时还具有安全环保的特点，其他高分子链段还可以赋予氟改性材料与基体的优良粘合，其中聚氨酷类的改性研究就有很实际的工业应用意义，如含氟聚氨酯类高分子乳液广泛 [7-8]应用于皮革，纺织，涂料，染整等工业领域;既能改善水性聚氨酯材料的表面性能，同时较低的含氟量可大幅降低材料成本。 [9-11]目前，国内外研究较为深入的是丙烯酸类的含氟乳液，而国内含氟水性聚氨酯的研究和开发在国内应用化研究少见报道。考虑到聚氨酯比丙烯酸酯聚合implementation model. Pay special attention to prevent floating style, do something superficial, cosmetic, overcome the love of work, short of a name, one of the benefits of bad ideas. To strengthen the sense of dedication. Office in the work of the Government "nerve centre", task, and burden, busy with work, hard, tough and sometimes thankless. Come into the Office the door, will not name, not for profit, unsung hero willing; to stand up to all kinds of misunderstandings, disappointments and setbacks, inclusive of ups and downs; "any hard labor, difficult, pick is hard to pick of Dan" the spirit of love and dedication, and hard work. Second, capacity-building, top-notch performance. Office of theWork lies in the people. Government offices at all levels must follow the 16 session of the plenum on strengthening the ruling ability construction of the party in order to improve the professional quality as the core, to strengthen capacity-building, picked up a pen to write, pen said, when anything can be done. To enhance the research capacity. Neither leaders nor the General staff, will continue to face the masses, face reality and society, doing the research work. Conditions permitting, are often grassroots, institutionalized, and perseverance. Investigation depth must not be superficial, also must have the breadth must not be biased. Through research, formed a quality, thoughtful, valuable research reports, improving the ability to analyze and solve practical 物具有更优异的性能，如良好的力学性能、耐溶剂等等，采用水性聚氨酯作为基质材料，结合氟碳材料的低表面能，以求得到一种新的既有聚氨酯材料的优异特性，而又有氟碳材料良好的低表面能高分子材料，使之能满足涂料、皮革涂饰、染整、纺织后处理等方面的应用，所以对含氟水性聚氨酯的合成和其膜的结构性能方面开展了一些有意义的探索研究。 1.3 水性含氟聚氨酯的研究进展 用非共聚型核壳乳液聚合法制备水性含氟聚氨酯一般首先采用传统的方法合成水性聚氨酯，聚氨酯水分散体的亲水性离子基团分布在微胶粒表面从而形成一种稳定的胶体体系，然后加入含氟的丙烯酸酯类化合物，由于亲水-憎水效应，含氟丙烯酸酯进入聚氨酯胶粒内部引发聚合，形成具有核-壳结构的水性含氟聚氨酯分散乳液。 据文献报道采用非共聚型核壳乳液聚合法制备的水性含氟聚氨酯复合乳液与将含氟聚丙烯酸酯和聚氨酯直接物理共混得到的水性含氟聚氨酯分散乳液相比，具有明显的优点，采用核壳乳液聚合法得到水性含氟聚氨酯的相容性比后者好，得到的膜更透明，对水的接触角随时间的增加而降低的速度明显小于物理共混得到的水性含氟聚氨酯，其拉伸强度也明显高于采用物理共混得到的水性含氟聚氨酯。但是，采用非共聚型核壳乳液聚合法得到的水性含氟聚氨酯仍存在不足。如大部分仍以单纯的聚氨酯和含氟聚丙烯酸酯的形式存在，使得这种复混状态的树脂在成膜后，由于其结构形态所限，不能充分发挥聚氨酯和含氟聚丙烯酸酯各自的优点。 为了弥补上述非共聚型核壳乳液聚合法的不足，有研究者采用共聚型核壳乳液聚合法制备水性含氟聚氨酯。该方法是将聚氨酯和含氟丙烯酸酯单体通过化学键连接，与非共聚型核壳乳液聚合法得到的复合材料相比，共聚复合能得到在分子级别的多组分复合以及均一的多组分复合结构，因此，得到的复合材料更能充 [12][13-14]分体现各组分的优点。Jiang等就采用这种方法制备了水性含氟聚氨酯。他们先采用异佛尔酮二异氰酸酯( IPDI)、 聚乙二醇(PEG) 、二羟甲基丙酸(DMPA)进行缩聚，再用甲基丙烯酸羟乙酯分子单体，然后将该大分子单体作为表面活性剂和反应单体与丙烯酸六氟丁酯(HFBN)进行乳液聚合，首次利用乳液共聚的方法制备了具有核壳结构的新型水性含氟聚氨酯丙烯酸酯共聚乳液。 核壳乳液聚合法制备水性含氟聚氨酯乳液主要采用氟化丙烯酸酯类单体引 [15]入含氟基团，其合成原料的种类较多而且合成具有较大的灵活性等优点，但是其最大的一个缺点就是随着含氟丙烯酸酯单体用量的增大，乳液逐渐变得不稳定。 [16]汪武采用聚四氢呋喃醚二元醇(PTMG2000)和自制的含氟二元醇(DAF)implementation model. Pay special attention to prevent floating style, do something superficial, cosmetic, overcome the love of work, short of a name, one of the benefits of bad ideas. To strengthen the sense of dedication. Office in the work of the Government "nerve centre", task, and burden, busy with work, hard, tough and sometimes thankless. Come into the Office the door, will not name, not for profit, unsung hero willing; to stand up to all kinds of misunderstandings, disappointments and setbacks, inclusive of ups and downs; "any hard labor, difficult, pick is hard to pick of Dan" the spirit of love and dedication, and hard work. Second, capacity-building, top-notch performance. Office of theWork lies in the people. Government offices at all levels must follow the 16 session of the plenum on strengthening the ruling ability construction of the party in order to improve the professional quality as the core, to strengthen capacity-building, picked up a pen to write, pen said, when anything can be done. To enhance the research capacity. Neither leaders nor the General staff, will continue to face the masses, face reality and society, doing the research work. Conditions permitting, are often grassroots, institutionalized, and perseverance. Investigation depth must not be superficial, also must have the breadth must not be biased. Through research, formed a quality, thoughtful, valuable research reports, improving the ability to analyze and solve practical 为软段 ，以异佛尔酮二异氰酸酯( IPDI) 为硬段 ,DMPA引入亲水基团，1 ，4-丁二醇为扩链剂制备了水性含氟聚氨酯乳液(FPU)，并对其性能进行了研究。实验结果表明，随着含氟量的增加，水性聚氨酯膜对水的接触角逐渐增大，当含氟量增加到一定值时，由于氟在表面富集达到饱和，接触角增加的趋势趋于平缓。通过对膜表面性能的测试结果表明，氟改性的水性聚氨酯的拒水拒油性能比没有含氟的水性聚氨酯的性能有所提高。 1.4 水性含氟聚氨酯的结构、制备及性能 1,4.1 水性含氟聚氨酯的结构 图1.1 水性含氟聚氨酯基本结构图 1.4.2 水性含氟聚氨酯的制备 水性含氟聚氨酯的合成方法是将聚氨酯和含氟丙烯酸酯单体通过化学键连接，与非共聚型核壳乳液聚合法得到的复合材料相比，共聚复合能得到在分子级别的多组分复合以及均一的多组分复合结构 ,因此 ,得到的复合材料更能充分 [17]体现各组分的优点。其合成过程一般是首先合成出带双键的水性聚氨酯水分散乳液，然后加入溶有油溶性引发剂的含氟乙烯类和丙烯酸酯类单体进行自由基共聚反应，最后形成具有核壳结构的含氟聚氨酯水分散体。本实验就采用这种方法制备了水性含氟聚氨酯。他们先采用异佛尔酮二异氰酸酯(IPDI)、聚环氧丙烷二元醇(PE2000)、二羟甲基丙酸(DMPA)进行缩聚 ,再用甲基丙烯酸羟乙酯(HEMA)和甲醇进行封端 ,用三乙胺中和 ,从而得到末端带双键的水性聚氨酯丙烯酸酯大分子单体，然后以甲基丙烯酸六氟丁酯、丙烯酸丁酯(BA)为原料，过硫酸钾作引发剂，十二烷基硫酸钠作链转移剂加入到丙烯酸羟乙酯封端的阴离子水性聚氨implementation model. Pay special attention to prevent floating style, do something superficial, cosmetic, overcome the love of work, short of a name, one of the benefits of bad ideas. To strengthen the sense of dedication. Office in the work of the Government "nerve centre", task, and burden, busy with work, hard, tough and sometimes thankless. Come into the Office the door, will not name, not for profit, unsung hero willing; to stand up to all kinds of misunderstandings, disappointments and setbacks, inclusive of ups and downs; "any hard labor, difficult, pick is hard to pick of Dan" the spirit of love and dedication, and hard work. Second, capacity-building, top-notch performance. Office of theWork lies in the people. Government offices at all levels must follow the 16 session of the plenum on strengthening the ruling ability construction of the party in order to improve the professional quality as the core, to strengthen capacity-building, picked up a pen to write, pen said, when anything can be done. To enhance the research capacity. Neither leaders nor the General staff, will continue to face the masses, face reality and society, doing the research work. Conditions permitting, are often grassroots, institutionalized, and perseverance. Investigation depth must not be superficial, also must have the breadth must not be biased. Through research, formed a quality, thoughtful, valuable research reports, improving the ability to analyze and solve practical 酯中，合成了具有核壳结构的含氟丙烯酸酯改性水性聚氨酯。其合成过程如图1.2所示: 图1.2 水性含氟聚氨酯合成的工艺 流程 快递问题件怎么处理流程河南自建厂房流程下载关于规范招聘需求审批流程制作流程表下载邮件下载流程设计 1.4.3 水性含氟聚氨酯的性能 水性含氟聚氨酯以水为主要介质，不含或仅含有少量有机溶剂，根据配方及助剂的不可调制成涂料、胶粘剂及其它用途的处理剂。与溶剂型聚氨酯相比，具有以下特点: (1)大多数水性含氟聚氨酯无溶剂、无臭味、无污染，具有不燃、成本低等优点。 (2)大多数单组分水性聚氨酯产品中不含有-NCO基团，主要是靠分子内极性基团产生内聚力和粘附力，水分挥发后固化。水性含氟聚氨酯中含有羧基、羟基等基团，也可引入其它反应性基团，适宜条件下可参与反应，使树脂产生交联。加交联剂则组成双组分体系。 (3)影响水性含氟聚氨酯粘度的主要因素有乳液粒径、离子电荷性质及数量等。聚合物分子上的离子及反离子(指溶液中的与聚氨酯主链、侧链中含有的离子基团相反的自由离子)越多，粘度越大;而固含量(树脂质量分数)、聚氨酯树脂的分子量等影响溶剂型聚氨酯树脂粘度的因素对水性聚氨酯粘度的影响并不明显。固体含量相同时，水性含氟聚氨酯的粘度较溶剂型聚氨酯小。 (4)由于水的挥发性比有机溶剂差，故水性含氟聚氨酯胶粘剂干燥较慢，并且由于水的表面张力大，对表面疏水性的基材的润湿能力差。由于大多数水性含氟聚氨酯是由含亲水性的聚氨酯为主要的固体成分，且有时还含水溶性助剂(如增稠剂等)，胶膜干燥后一般须形成一定程度的交联，否则耐水性不佳。 implementation model. Pay special attention to prevent floating style, do something superficial, cosmetic, overcome the love of work, short of a name, one of the benefits of bad ideas. To strengthen the sense of dedication. Office in the work of the Government "nerve centre", task, and burden, busy with work, hard, tough and sometimes thankless. Come into the Office the door, will not name, not for profit, unsung hero willing; to stand up to all kinds of misunderstandings, disappointments and setbacks, inclusive of ups and downs; "any hard labor, difficult, pick is hard to pick of Dan" the spirit of love and dedication, and hard work. Second, capacity-building, top-notch performance. Office of theWork lies in the people. Government offices at all levels must follow the 16 session of the plenum on strengthening the ruling ability construction of the party in order to improve the professional quality as the core, to strengthen capacity-building, picked up a pen to write, pen said, when anything can be done. To enhance the research capacity. Neither leaders nor the General staff, will continue to face the masses, face reality and society, doing the research work. Conditions permitting, are often grassroots, institutionalized, and perseverance. Investigation depth must not be superficial, also must have the breadth must not be biased. Through research, formed a quality, thoughtful, valuable research reports, improving the ability to analyze and solve practical (5)水性含氟聚氨酯可与多种水性树脂混合，以改进性能或降低成本。此时应注意离子型水性胶的离子性质和酸碱性，否则可能引起凝聚。因受到聚合物间的相容性或在某些溶剂中的溶解性的影响，溶剂型聚氨酯只能与为数有限的其它树脂共混。 (6)水性含氟聚氨酯产品气味小，可用水稀释，操作方便，易于清理;而溶剂型聚氨酯在使用中有时还需耗用大量溶剂，特别是双组分涂料或胶的清理也不及水性胶方便。 水性含氟聚氨酯的应用:水性含氟聚氨酯是水性含氟聚氨酯胶粘剂、涂料和其它应用形态的基础树脂。其主要应用包括:1)柔软底物涂饰。如织物、橡胶、皮革、纸张和乙烯基塑料的表面涂层;2)工业产品涂饰，如机器外壳，塑料制品和金属底漆等;3)江木制品，如家具和地板的涂饰;4)玻璃纤维的表面涂饰，如玻璃纤维的浸润等。除此之外，水性含氟聚氨酯还可以用于各种底物的粘合剂，在我国，水性含氟聚氨酯在皮革表面涂饰方面应用很广泛。 implementation model. Pay special attention to prevent floating style, do something superficial, cosmetic, overcome the love of work, short of a name, one of the benefits of bad ideas. To strengthen the sense of dedication. Office in the work of the Government "nerve centre", task, and burden, busy with work, hard, tough and sometimes thankless. Come into the Office the door, will not name, not for profit, unsung hero willing; to stand up to all kinds of misunderstandings, disappointments and setbacks, inclusive of ups and downs; "any hard labor, difficult, pick is hard to pick of Dan" the spirit of love and dedication, and hard work. Second, capacity-building, top-notch performance. Office of theWork lies in the people. Government offices at all levels must follow the 16 session of the plenum on strengthening the ruling ability construction of the party in order to improve the professional quality as the core, to strengthen capacity-building, picked up a pen to write, pen said, when anything can be done. To enhance the research capacity. Neither leaders nor the General staff, will continue to face the masses, face reality and society, doing the research work. Conditions permitting, are often grassroots, institutionalized, and perseverance. Investigation depth must not be superficial, also must have the breadth must not be biased. Through research, formed a quality, thoughtful, valuable research reports, improving the ability to analyze and solve practical