CN105778027A - 一种阳离子型水性聚硫氨酯的制备方法 - Google Patents

一种阳离子型水性聚硫氨酯的制备方法 Download PDF

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CN105778027A
CN105778027A CN201610152453.5A CN201610152453A CN105778027A CN 105778027 A CN105778027 A CN 105778027A CN 201610152453 A CN201610152453 A CN 201610152453A CN 105778027 A CN105778027 A CN 105778027A
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polythiourethane
cation
thinned
modified polyurethane
diisocyanate
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CN105778027B (zh
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许戈文
陶灿
黄毅萍
鲍俊杰
熊潜生
程芹
王继印
韩飞龙
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Anhui University
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Anhui University
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Abstract

本发明公开了一种阳离子型水性聚硫氨酯的制备方法，包括如下步骤：将液体聚硫橡胶与异氰酸酯混合，反应合成端异氰酸酯基聚硫改性聚氨酯预聚体；将端异氰酸酯基聚硫改性聚氨酯预聚体与小分子扩链剂、阳离子亲水性扩链剂、交联剂进行扩链反应得到异氰酸酯基聚硫改性聚氨酯；将异氰酸酯基聚硫改性聚氨酯进行乳化得到阳离子型水性聚硫氨酯分散体。本发明所得阳离子型水性聚硫氨酯树脂可与酸性、中性树脂混配使用，强度大，耐磨性、附着力，柔韧性能优异，密实性，耐高低温性、耐老化性、耐臭氧、耐油性好，湿、气透过性低，尤其是与带负电荷的基材附着，并可以和阴离子体系形成“三明治”型结构，在织物涂层、胶黏剂、防腐涂料等领域应用前景广阔。

Description

一种阳离子型水性聚硫氨酯的制备方法
技术领域
本发明涉及水性聚氨酯技术领域，尤其涉及一种阳离子型水性聚硫氨酯的制备方法。
背景技术
水性聚氨酯是一类能溶于水或能均匀分散在水中的高分子材料，因其以水为分散介质，零VOC排放，得到环境的认可；因其优良的性能已被广泛应用于印刷、纺织品整理、皮革涂饰等行业。
聚硫分子主链上含有硫原子，硫化产品收缩性很小，制成的密封胶对各种被粘物有良好的粘接性，耐臭氧、耐候性、耐油性好，湿、气透过性低，尤其是具有长期耐水性，是防水密封胶的理想材料。自Thiokol公司开发出带有端巯基低相对分子质量的液体聚硫橡胶后，聚硫引起了科研工作者的兴趣。近年来，为了满足某些特殊的要求，人们研究了主链的各种可变换结构和利用其他官能团与巯基反应进行改性。前人对聚硫氨酯/脲做了一些研究和应用。ProductsResearch公司开发了一种主链为聚氨酯、端基为巯基的预聚物，并以它为原料制成弹性密封胶。空军工程大学以自主研发的聚硫氨酯液体橡胶为原胶，制备出了兼具聚氨酯、聚硫橡胶结构特征的聚硫氨酯密封胶。
发明专利CN1599763A“制备透明聚硫氨酯基材和尤其光学基材的方法”，该发明涉及了一种制备光学制品的聚硫氨酯透明浇铸基材的快速固化方法。该方法将具有异氰酸酯或异硫酸酯端基和聚硫氨酯预聚物的第一组份与含有硫醇端基的聚硫氨酯预聚物的第二组份和混合后填充浇铸模具装置的模腔，得到透明的聚硫氨酯固体基材。
发明专利CN1602322A“高折射指数和高抗冲聚硫氨酯/脲材料、其制造方法及在光学领域中的用途”，该发明以(α,ω)-二异(硫)氰酸酯酯环族或芳族预聚物和伯二胺为反应原料获得折射指数nD25大于1.53，高抗冲聚硫氨酯/脲材料。
发明专利CN101155848A“聚硫氨酯类聚合性组合物及使用该组合物的光学用树脂的制备方法”和CN101228202A“聚硫氨酯类聚合性组合物及由该组合物形成的光学用树脂”分别提供了一种染色性及树脂强度优异的树脂组合物，该组合物可以制备出具有充分强度的树脂。
发明专利CN1950417A“聚硫氨酯”涉及了一种含聚硫代碳酸酯聚硫醇作为聚硫醇成分的聚硫氨酯，该聚硫氨酯具有高折射率而显示低分散的优秀光学特性，拉伸和伸缩性能，可作为光学用塑料原料。
发明专利CN101277989A“聚硫氨酯组分及其制备和使用方法”提供了聚硫氨酯聚合物组分，涉及了该聚硫氨酯聚合物组分的制备方法和使用方法。该组分包括硫羟酸酯组分和异氰酸酯组分。
发明专利CN101842403A“聚脲/聚硫脲涂料”公开了以含有异氰酸酯的第一组分和含有胺的第二组分反应得到聚脲/聚硫脲涂料。
发明专利CN101702038A“一种抗冲击性高的树脂镜片”以含有异氰酸酯封端的聚硫氨酯类预聚物的溶液、含有多异氰酸酯化合物的溶液、多巯基化合物、紫外线吸收剂和催化剂为原料制得了高折射率，高抗击性能的镜片用树脂。
发明专利CN101712742A和CN101712742A分别公开了一种含巯基封端和一种含异氰酸基封端的聚硫氨酯类预聚物的溶液及其制备方法。该溶液可用于塑料透镜的生产。
发明专利CN101384636A“聚硫氨酯类光学材料用聚合性组合物”涉及了一种聚硫氨酯合成催化剂，该催化剂是有机Al、有机Fe、有机Cu、有机Zn、有机Zr或有机Bi，该催化剂具有有机锡相同或更高的催化活性。
发明专利CN101511895A“聚硫氨酯类光学材料用聚合催化剂、含有该催化剂的聚合性组合物、由该组合物得到的聚硫氨酯树脂及其制造方法”，CN101627069A“聚硫氨酯类光学材料用聚合催化剂、含有该聚合催化剂的聚合性组合物、由该组合物得到的光学材料及其制造方法”，CN102066450A“聚硫氨酯类光学材料用聚合性组合物、由该聚合性组合物得到的聚硫氨酯类光学材料及聚硫氨酯类光学材料用聚合催化剂”，CN102906143A“聚硫氨酯用聚合催化剂,可聚合液体组合物以及制备具有高折射率的有机聚硫氨酯玻璃的方法”，CN102977309A“光学材料用聚合性组合物、由该组合物得到的光学材料及光学材料用聚合催化剂”等发明专利分别公开了用于合成聚硫氨酯的不同催化剂。
通过对现有公开的相关专利分析研究，涉及论文和专利仅限于聚硫氨酯密封胶的研制，和用于聚硫氨酯树脂镜片的化合物组分及合成方法，以及其合成用催化剂的研究制备方法，没有阳离子水性聚硫氨酯制备的报道。
发明内容
基于背景技术存在的技术问题，本发明提出了一种阳离子型水性聚硫氨酯的制备方法，本发明将液体聚硫橡胶引入聚氨酯结构中以结合二者的优点而提高聚合物的性能，将聚硫氨酯水性化，以提高水性聚氨酯的环保性能，并拓展其使用领域。本发明所得阳离子型水性聚硫氨酯树脂可与酸性、中性树脂混配使用，强度大，耐磨性、附着力，柔韧性能优异，密实性，耐高低温性、耐老化性、耐臭氧、耐油性好，湿、气透过性低，尤其是与带负电荷的基材附着，并可以和阴离子体系形成“三明治”型结构，其中脂肪族和脂环族产品还具备优异的耐老化性能，是综合性能好的环保型高分子材料，在织物涂层、皮革涂饰、胶黏剂、防腐涂料等领域应用前景广阔。
本发明提出的一种阳离子型水性聚硫氨酯的制备方法，包括如下步骤：
S1、将液体聚硫橡胶与异氰酸酯混合，反应合成端异氰酸酯基聚硫改性聚氨酯预聚体；
S2、将端异氰酸酯基聚硫改性聚氨酯预聚体与小分子扩链剂、阳离子亲水性扩链剂、交联剂进行扩链反应得到异氰酸酯基聚硫改性聚氨酯；
S3、将异氰酸酯基聚硫改性聚氨酯进行乳化得到阳离子型水性聚硫氨酯分散体。
优选地，包括如下步骤：
S1、按重量份将30～60份异氰酸酯加入到10～65份液体聚硫橡胶、0～47份大分子多元醇中，充入干燥氮气进行保护，升温至90～100℃，保温160～180min得到端异氰酸酯基聚硫改性聚氨酯预聚体；
S2、将端异氰酸酯基聚硫改性聚氨酯预聚体降温至38～42℃，再加入6～18份小分子扩链剂、0.5～2.6份交联剂、0.15～0.30份催化剂和溶剂，升温至78～82℃，保温120～200min，降温至34～36℃，再加入3.5～8份阳离子亲水性扩链剂，维持温度至30～50℃，保温30～180min得到异氰酸酯基聚硫改性聚氨酯；
S3、将异氰酸酯基聚硫改性聚氨酯降温至34～36℃，进行高速剪切，在高速剪切过程中加入成盐剂，然后加入210～320份水乳化得到阳离子型水性聚硫氨酯分散体，成盐剂与水的体积比为1～5：105～160。
S2中溶剂仅作为载体，提高反应速率，但不参与进行反应，故无需对溶剂使用量进行限定，往往采用丙酮作为溶剂。
S2的“保温120～200min”过程中需要适当的加入溶剂来降低反应体系粘度，促进反应进行，往往选择保温60～90min时加入溶剂以降低反应体系粘度。
优选地，阳离子型水性聚硫氨酯分散体为一种半透明、呈淡黄色、非电解质高分子水分散体，固含量为20～40％，黏度为10～800mPa·s，粒径为10～500nm。
优选地，液体聚硫橡胶含有两个或两个以上巯基官能团，其数均分子量为1000～5000，巯基含量为1.0～7.7wt％。
优选地，大分子多元醇为聚氧化丙烯二醇、聚四氢呋喃醚二醇、聚己内酯二元醇、聚碳酸酯二醇、聚己二酸-1,6-己二醇酯二醇、聚己二酸乙二醇酯二醇中的一种或两种以上组合物。
优选地，大分子多元醇的数均分子量为1000～4000。
优选地，异氰酸酯为芳香族二异氰酸酯、脂肪族二异氰酸酯和脂环族二异氰酸酯中的一种或两种以上组合物。
优选地，芳香族二异氰酸酯为甲苯二异氰酸酯、二苯基甲烷二异氰酸酯、萘二异氰酸酯、对苯二异氰酸酯、苯二亚甲基二异氰酸酯、四甲基间苯二亚甲基二异氰酸酯、二甲基联苯二异氰酸酯中的一种或两种以上组合物。
优选地，脂环族二异氰酸酯为异佛尔酮二异氰酸酯、二环己基甲烷二异氰酸酯、环己烷二亚甲基二异氰酸酯、甲基环己基二异氰酸酯中的一种或两种以上组合物，优选为异佛尔酮二异氰酸酯。
优选地，脂肪族二异氰酸酯为1，6-六亚甲基二异氰酸酯和/或三甲基-1,6-六亚甲基二异氰酸酯。
优选地，小分子扩链剂为一缩二乙二醇、乙二醇、一缩二丙二醇、新戊二醇、丁二醇、己二醇、三甲基戊二醇、三甲基戊二醇、辛二醇中的一种或两种以上组合物。
优选地，交联剂为三羟甲基丙烷、甘油、三羟甲基乙烷、季戊四醇、三乙醇胺、聚氧化丙烯三醇中的一种或两种以上组合物。
优选地，催化剂为辛酸亚锡、二月桂酸二丁锡、有机锌盐、有机铋盐中的一种或两种以上组合物。
优选地，阳离子亲水性扩链剂为N-甲基二乙醇胺、N-乙基二乙醇胺、叔丁基二乙醇胺中的一种或两种以上组合物。
优选地，成盐剂为乙酸和/或丁酸。
本发明的有益效果如下：
1.本发明制备工艺简单、稳定，采用聚硫橡胶中的-SH与多异氰酸酯中的-NCO进行逐步共聚反应技术，将液体聚硫橡胶作为软段引入聚氨酯结构中，充分发挥聚氨酯与聚硫材料各自的性能优势，并利用阳离子水性化工艺，在聚合物分子链中引入亲水基团，将合成的聚合物分散于水中，摒弃了VOC对环境的污染，环保性好；
2.本发明所得阳离子型水性聚硫氨酯是一种阳离子型高分子分散体，是通过亲水基团与水分子间的缔合作用以及阳离子同种电荷的排斥力形成平衡，使得聚合物分子稳定分散在水相中，环保性能优异；
3.本发明所得阳离子型水性聚硫氨酯既具有聚硫橡胶优异的耐臭氧、耐水、耐油性，湿、气低透过性，亦具有聚氨酯优良的粘接性能和良好的机械性能、耐摩擦、耐老化性能；
4.本发明所得阳离子型水性聚硫氨酯的胶膜软硬度、机械强度可调，可应用于皮革涂饰、织物涂层、胶黏剂、防腐涂料等行业。
本发明所得阳离子型水性聚硫氨酯的性能指标如下所示：
测试项目 测试结果
pH值 4～5
抗张强度(MPa) 5.8～8.9
断裂伸长率(％) 320～550
100％模量(MPa) 3.1～6.1
硬度(邵A) 60～82
耐盐性(5％NaCl，96h)重量增加(％) 6.8～11.6
耐水性(96h)重量增加(％) 8.2～12.6
耐水压(kPa，1min) 2.5～4.4
具体实施方式
下面，通过具体实施例对本发明的技术方案进行详细说明。
实施例1
本发明提出的一种阳离子型水性聚硫氨酯的制备方法，包括如下步骤：
S1、将58.1g异佛尔酮二异氰酸酯加入到经110℃真空脱水1h的14.3g液体聚硫橡胶LP3和36.5g数均分子量为1000的聚氧化丙烯二醇混合溶液中，充入干燥氮气进行保护，升温至95℃，保温180min得到端异氰酸酯基聚硫改性聚氨酯预聚体；
S2、将端异氰酸酯基聚硫改性聚氨酯预聚体降温至40℃，再加入15.5g一缩二乙二醇、0.95g三羟甲基丙烷、0.1g辛酸亚锡、0.12g二月桂酸二丁锡和20mL丙酮，升温至80℃，保温150min，降温至35℃，再缓慢滴加6.8gN-甲基二乙醇胺和15mL丙酮的混合溶液，维持温度至50℃，保温90min，接着加入30mL丙酮以降低粘度得到异氰酸酯基聚硫改性聚氨酯；
S3、将异氰酸酯基聚硫改性聚氨酯降温至35℃，进行高速剪切，在高速剪切过程中加入4.5mL乙酸，然后加入245g水乳化得到阳离子型水性聚硫氨酯分散体。
实施例2
本发明提出的一种阳离子型水性聚硫氨酯的制备方法，包括如下步骤：
S1、将58.1g异佛尔酮二异氰酸酯加入到经110℃真空脱水1h的50g液体聚硫橡胶LP3中，充入干燥氮气进行保护，升温至95℃，保温180min得到端异氰酸酯基聚硫改性聚氨酯预聚体；
S2、将端异氰酸酯基聚硫改性聚氨酯预聚体降温至40℃，再加入14.6g一缩二丙二醇、0.9g甘油、0.11g辛酸亚锡、0.12g二月桂酸二丁锡和25mL丙酮，升温至80℃，保温150min，降温至35℃，再缓慢滴加6.9gN-甲基二乙醇胺和15mL丙酮的混合溶液，维持温度至50℃，保温90min，接着加入40mL丙酮以降低粘度得到异氰酸酯基聚硫改性聚氨酯；
S3、将异氰酸酯基聚硫改性聚氨酯降温至35℃，进行高速剪切，在高速剪切过程中加入9.4mL丁酸，然后加入245g水乳化得到阳离子型水性聚硫氨酯分散体。
实施例3
本发明提出的一种阳离子型水性聚硫氨酯的制备方法，包括如下步骤：
S1、将45.1g二环己基甲烷二异氰酸酯加入到经110℃真空脱水1.5h的10g液体聚硫橡胶LP3、12.3g数均分子量为2000的聚四氢呋喃醚二醇和16.21g数均分子量为2000的聚己二酸乙二醇酯二醇混合溶液中，充入干燥氮气进行保护，升温至95℃，保温120min得到端异氰酸酯基聚硫改性聚氨酯预聚体；
S2、将端异氰酸酯基聚硫改性聚氨酯预聚体降温至40℃，再加入10.2g乙二醇、0.65g三乙醇胺、0.07g辛酸亚锡、0.08g二月桂酸二丁锡和25mL丙酮，升温至80℃，保温120min，降温至35℃，再缓慢滴加3.8g叔丁基二乙醇胺和15mL丙酮的混合溶液，维持温度至50℃，保温120min，接着加入20mL丙酮以降低粘度得到异氰酸酯基聚硫改性聚氨酯；
S3、将异氰酸酯基聚硫改性聚氨酯降温至35℃，进行高速剪切，在高速剪切过程中加入2.3mL乙酸，然后加入212g水乳化得到阳离子型水性聚硫氨酯分散体。
实施例4
本发明提出的一种阳离子型水性聚硫氨酯的制备方法，包括如下步骤：
S1、将40.3g1,6-六亚甲基二异氰酸酯加入到经110℃真空脱水1.5h的15g液体聚硫橡胶LP33、15g数均分子量为1000的聚四氢呋喃醚二醇和30g数均分子量为2000的聚己二酸-1,6-己二醇酯二醇混合溶液中，充入干燥氮气进行保护，升温至95℃，保温180min得到端异氰酸酯基聚硫改性聚氨酯预聚体；
S2、将端异氰酸酯基聚硫改性聚氨酯预聚体降温至40℃，再加入6.3g三甲基戊二醇、0.55g季戊四醇、0.06g辛酸亚锡、0.1g有机铋盐和15mL丙酮，升温至80℃，保温150min，降温至35℃，再缓慢滴加4.8gN-甲基二乙醇胺和15mL丙酮的混合溶液，维持温度至50℃，保温150min，接着加入20mL丙酮以降低粘度得到异氰酸酯基聚硫改性聚氨酯；
S3、将异氰酸酯基聚硫改性聚氨酯降温至35℃，进行高速剪切，在高速剪切过程中加入2.9mL乙酸，然后加入220g水乳化得到阳离子型水性聚硫氨酯分散体。
实施例5
本发明提出的一种阳离子型水性聚硫氨酯的制备方法，包括如下步骤：
S1、将18.3g三甲基-1,6-六亚甲基二异氰酸酯和23.27g异佛尔酮二异氰酸酯混合后，加入到经110℃真空脱水1h的32g液体聚硫橡胶LP2、29g液体聚硫橡胶LP32和40.1g数均分子量为2000的聚碳酸酯二醇混合溶液中，充入干燥氮气进行保护，升温至95℃，保温160min得到端异氰酸酯基聚硫改性聚氨酯预聚体；
S2、将端异氰酸酯基聚硫改性聚氨酯预聚体降温至40℃，再加入6.2g辛二醇、6.7g三甲基戊二醇、0.91g三羟甲基丙烷、0.12g有机锌盐、0.15g有机铋盐和25mL丙酮，升温至80℃，保温150min，降温至35℃，再缓慢滴加5gN-甲基二乙醇胺、3gN-乙基二乙醇胺和20mL丙酮的混合溶液，维持温度至50℃，保温150min，接着加入30mL丙酮以降低粘度得到异氰酸酯基聚硫改性聚氨酯；
S3、将异氰酸酯基聚硫改性聚氨酯降温至35℃，进行高速剪切，在高速剪切过程中加入4.8mL乙酸，然后加入300g水乳化得到阳离子型水性聚硫氨酯分散体。
实施例6
本发明提出的一种阳离子型水性聚硫氨酯的制备方法，包括如下步骤：
S1、将10.3g环己烷二亚甲基二异氰酸酯和40.2g甲基环己基二异氰酸酯混合后，加入到经110℃真空脱水1.5h的30g液体聚硫橡胶LP2、10g数均分子量为1000的聚氧化丙烯二醇和20g数均分子量为2000的聚己内酯混合溶液中，充入干燥氮气进行保护，升温至90℃，保温120min得到端异氰酸酯基聚硫改性聚氨酯预聚体；
S2、将端异氰酸酯基聚硫改性聚氨酯预聚体降温至40℃，再加入6.4g己二醇、8g新戊二醇、2.6g数均分子量为300的聚氧化丙烯三醇、0.09g辛酸亚锡、0.15g二月桂酸二丁锡和30mL丙酮，升温至80℃，保温150min，降温至35℃，再缓慢滴加7.8gN-乙基二乙醇胺和20mL丙酮的混合溶液，维持温度至50℃，保温120min，接着加入30mL丙酮以降低粘度得到异氰酸酯基聚硫改性聚氨酯；
S3、将异氰酸酯基聚硫改性聚氨酯降温至35℃，进行高速剪切，在高速剪切过程中加入4.7mL乙酸，然后加入310g水乳化得到阳离子型水性聚硫氨酯分散体。
实施例7
本发明提出的一种阳离子型水性聚硫氨酯的制备方法，包括如下步骤：
S1、将48.7g甲苯二异氰酸酯加入到经110℃真空脱水1h的15g液体聚硫橡胶LP3、35g数均分子量为1000的聚氧化丙烯二醇混合溶液中，充入干燥氮气进行保护，升温至90℃，保温150min得到端异氰酸酯基聚硫改性聚氨酯预聚体；
S2、将端异氰酸酯基聚硫改性聚氨酯预聚体降温至40℃，再加入14.5g一缩二乙二醇、0.91g三羟甲基丙烷、0.1g辛酸亚锡、0.12g二月桂酸二丁锡和20mL丙酮，升温至80℃，保温120min，降温至35℃，再缓慢滴加6.8gN-甲基二乙醇胺和15mL丙酮的混合溶液，维持温度至40℃，保温45min，接着加入30mL丙酮以降低粘度得到异氰酸酯基聚硫改性聚氨酯；
S3、将异氰酸酯基聚硫改性聚氨酯降温至35℃，进行高速剪切，在高速剪切过程中加入4.5mL乙酸，然后加入245g水乳化得到阳离子型水性聚硫氨酯分散体。
实施例8
本发明提出的一种阳离子型水性聚硫氨酯的制备方法，包括如下步骤：
S1、将20.2g二苯基甲烷二异氰酸酯和30g萘二异氰酸酯混合后，加入到经110℃真空脱水1h的50g液体聚硫橡胶LP3中，充入干燥氮气进行保护，升温至90℃，保温180min得到端异氰酸酯基聚硫改性聚氨酯预聚体；
S2、将端异氰酸酯基聚硫改性聚氨酯预聚体降温至40℃，再加入14.6g一缩二丙二醇、0.9g甘油、0.11g有机铋盐、0.12g二月桂酸二丁锡和25mL丙酮，升温至80℃，保温120min，降温至35℃，再缓慢滴加6.83gN-甲基二乙醇胺和15mL丙酮的混合溶液，维持温度至40℃，保温50min，接着加入40mL丙酮以降低粘度得到异氰酸酯基聚硫改性聚氨酯；
S3、将异氰酸酯基聚硫改性聚氨酯降温至35℃，进行高速剪切，在高速剪切过程中加入4.5mL乙酸，然后加入245g水乳化得到阳离子型水性聚硫氨酯分散体。
实施例9
本发明提出的一种阳离子型水性聚硫氨酯的制备方法，包括如下步骤：
S1、将35.4g对苯二异氰酸酯加入到经110℃真空脱水1.5h的10g液体聚硫橡胶LP3、15g数均分子量为2000的聚四氢呋喃醚二醇和15g数均分子量为2000的聚己二酸乙二醇酯二醇混合溶液中，充入干燥氮气进行保护，升温至90℃，保温120min得到端异氰酸酯基聚硫改性聚氨酯预聚体；
S2、将端异氰酸酯基聚硫改性聚氨酯预聚体降温至40℃，再加入10g三甲基戊二醇、0.55g三羟甲基乙烷、0.07g辛酸亚锡、0.08g有机锌盐和15mL丙酮，升温至80℃，保温120min，降温至35℃，再缓慢滴加3.8g叔丁基二乙醇胺和15mL丙酮的混合溶液，维持温度至40℃，保温50min，接着加入20mL丙酮以降低粘度得到异氰酸酯基聚硫改性聚氨酯；
S3、将异氰酸酯基聚硫改性聚氨酯降温至35℃，进行高速剪切，在高速剪切过程中加入2.3mL乙酸，然后加入210g水乳化得到阳离子型水性聚硫氨酯分散体。
实施例10
本发明提出的一种阳离子型水性聚硫氨酯的制备方法，包括如下步骤：
S1、将40.1g苯二亚甲基二异氰酸酯加入到经110℃真空脱水1.5h的15g液体聚硫橡胶LP33、15g数均分子量为1000的聚四氢呋喃醚二醇和30g数均分子量为2000的聚己二酸-1,6-己二醇酯二醇混合溶液中，充入干燥氮气进行保护，升温至90℃，保温120min得到端异氰酸酯基聚硫改性聚氨酯预聚体；
S2、将端异氰酸酯基聚硫改性聚氨酯预聚体降温至40℃，再加入6.3g乙二醇、0.55g三羟甲基乙烷、0.06g辛酸亚锡、0.1g二月桂酸二丁锡和15mL丙酮，升温至80℃，保温90min，降温至35℃，再缓慢滴加4.8gN-甲基二乙醇胺和15mL丙酮的混合溶液，维持温度至40℃，保温50min，接着加入20mL丙酮以降低粘度得到异氰酸酯基聚硫改性聚氨酯；
S3、将异氰酸酯基聚硫改性聚氨酯降温至35℃，进行高速剪切，在高速剪切过程中加入2.9mL乙酸，然后加入220g水乳化得到阳离子型水性聚硫氨酯分散体。
实施例11
本发明提出的一种阳离子型水性聚硫氨酯的制备方法，包括如下步骤：
S1、将20.2g四甲基间苯二亚甲基二异氰酸酯和20g二甲基联苯二异氰酸酯混合后，加入到经110℃真空脱水1h的30g液体聚硫橡胶LP12、30g液体聚硫橡胶LP32和40.1g数均分子量为2000的聚碳酸酯二醇混合溶液中，充入干燥氮气进行保护，升温至90℃，保温180min得到端异氰酸酯基聚硫改性聚氨酯预聚体；
S2、将端异氰酸酯基聚硫改性聚氨酯预聚体降温至40℃，再加入6.4g1,4-丁二醇、6.92g新戊二醇、0.95g季戊四醇、0.09g辛酸亚锡、0.15g二月桂酸二丁锡和25mL丙酮，升温至80℃，保温150min，降温至35℃，再缓慢滴加4.9gN-甲基二乙醇胺、3gN-乙基二乙醇胺和20mL丙酮的混合溶液，维持温度至40℃，保温50min，接着加入30mL丙酮以降低粘度得到异氰酸酯基聚硫改性聚氨酯；
S3、将异氰酸酯基聚硫改性聚氨酯降温至35℃，进行高速剪切，在高速剪切过程中加入4.8mL乙酸，然后加入310g水乳化得到阳离子型水性聚硫氨酯分散体。
实施例12
本发明提出的一种阳离子型水性聚硫氨酯的制备方法，包括如下步骤：
S1、将20.1g甲苯二异氰酸酯和30.6g四甲基间苯二亚甲基二异氰酸酯混合后，加入到经110℃真空脱水1.5h的30g液体聚硫橡胶LP3、10g数均分子量为1000的聚乙二醇和20g数均分子量为2000的聚己内酯混合溶液中，充入干燥氮气进行保护，升温至90℃，保温120min得到端异氰酸酯基聚硫改性聚氨酯预聚体；
S2、将端异氰酸酯基聚硫改性聚氨酯预聚体降温至40℃，再加入6.4g己二醇、7.9g三甲基戊二醇、2.5g数均分子量为300的聚氧化丙烯三醇、0.09g辛酸亚锡、0.15g二月桂酸二丁锡和30mL丙酮，升温至80℃，保温150min，降温至35℃，再缓慢滴加7.9gN-乙基二乙醇胺和20mL丙酮的混合溶液，维持温度至40℃，保温40min，接着加入30mL丙酮以降低粘度得到异氰酸酯基聚硫改性聚氨酯；
S3、将异氰酸酯基聚硫改性聚氨酯降温至35℃，进行高速剪切，在高速剪切过程中加入9.4mL乙酸，然后加入320g水乳化得到阳离子型水性聚硫氨酯分散体。
其中上述实施例中，液体聚硫橡胶的参数如下：
对实施例1-12所得阳离子型水性聚硫氨酯分散体进行性能测试，其测试结果如下：
以上所述，仅为本发明较佳的具体实施方式，但本发明的保护范围并不局限于此，任何熟悉本技术领域的技术人员在本发明揭露的技术范围内，根据本发明的技术方案及其发明构思加以等同替换或改变，都应涵盖在本发明的保护范围之内。

Claims (10)

1.一种阳离子型水性聚硫氨酯的制备方法，其特征在于，包括如下步骤：
S1、将液体聚硫橡胶与异氰酸酯混合，反应合成端异氰酸酯基聚硫改性聚氨酯预聚体；
S2、将端异氰酸酯基聚硫改性聚氨酯预聚体与小分子扩链剂、阳离子亲水性扩链剂、交联剂进行扩链反应得到异氰酸酯基聚硫改性聚氨酯；
S3、将异氰酸酯基聚硫改性聚氨酯进行乳化得到阳离子型水性聚硫氨酯分散体。
2.根据权利要求1所述阳离子型水性聚硫氨酯的制备方法，其特征在于，包括如下步骤：
S1、按重量份将30～60份异氰酸酯加入到10～65份液体聚硫橡胶、0～47份大分子多元醇中，充入干燥氮气进行保护，升温至90～100℃，保温160～180min得到端异氰酸酯基聚硫改性聚氨酯预聚体；
S2、将端异氰酸酯基聚硫改性聚氨酯预聚体降温至38～42℃，再加入6～18份小分子扩链剂、0.5～2.6份交联剂、0.15～0.30份催化剂和溶剂，升温至78～82℃，保温120～200min，降温至34～36℃，再加入3.5～8份阳离子亲水性扩链剂，维持温度至30～50℃，保温30～180min得到异氰酸酯基聚硫改性聚氨酯；
S3、将异氰酸酯基聚硫改性聚氨酯降温至34～36℃，进行高速剪切，在高速剪切过程中加入成盐剂，然后加入210～320份水乳化得到阳离子型水性聚硫氨酯分散体，成盐剂与水的体积比为1～5：105～160。
3.根据权利要求1或2所述阳离子型水性聚硫氨酯的制备方法，其特征在于，阳离子型水性聚硫氨酯分散体为一种半透明、呈淡黄色、非电解质高分子水分散体，固含量为20～40％，黏度为10～800mPa·s，粒径为10～500nm。
4.根据权利要求1-3任一项所述阳离子型水性聚硫氨酯的制备方法，其特征在于，液体聚硫橡胶含有两个或两个以上巯基官能团，其数均分子量为1000～5000，巯基含量为1.0～7.7wt％。
5.根据权利要求1-4任一项所述阳离子型水性聚硫氨酯的制备方法，其特征在于，大分子多元醇为聚氧化丙烯二醇、聚四氢呋喃醚二醇、聚己内酯二元醇、聚碳酸酯二醇、聚己二酸-1,6-己二醇酯二醇、聚己二酸乙二醇酯二醇中的一种或两种以上组合物；优选地，大分子多元醇的数均分子量为1000～4000。
6.根据权利要求1-5任一项所述阳离子型水性聚硫氨酯的制备方法，其特征在于，异氰酸酯为芳香族二异氰酸酯、脂肪族二异氰酸酯和脂环族二异氰酸酯中的一种或两种以上组合物；优选地，芳香族二异氰酸酯为甲苯二异氰酸酯、二苯基甲烷二异氰酸酯、萘二异氰酸酯、对苯二异氰酸酯、苯二亚甲基二异氰酸酯、四甲基间苯二亚甲基二异氰酸酯、二甲基联苯二异氰酸酯中的一种或两种以上组合物；优选地，脂环族二异氰酸酯为异佛尔酮二异氰酸酯、二环己基甲烷二异氰酸酯、环己烷二亚甲基二异氰酸酯、甲基环己基二异氰酸酯中的一种或两种以上组合物，优选为异佛尔酮二异氰酸酯；优选地，脂肪族二异氰酸酯为1，6-六亚甲基二异氰酸酯和/或三甲基-1,6-六亚甲基二异氰酸酯。
7.根据权利要求1-6任一项所述阳离子型水性聚硫氨酯的制备方法，其特征在于，小分子扩链剂为一缩二乙二醇、乙二醇、一缩二丙二醇、新戊二醇、丁二醇、己二醇、三甲基戊二醇、三甲基戊二醇、辛二醇中的一种或两种以上组合物。
8.根据权利要求1-7任一项所述阳离子型水性聚硫氨酯的制备方法，其特征在于，交联剂为三羟甲基丙烷、甘油、三羟甲基乙烷、季戊四醇、三乙醇胺、聚氧化丙烯三醇中的一种或两种以上组合物；优选地，催化剂为辛酸亚锡、二月桂酸二丁锡、有机锌盐、有机铋盐中的一种或两种以上组合物。
9.根据权利要求1-8任一项所述阳离子型水性聚硫氨酯的制备方法，其特征在于，阳离子亲水性扩链剂为N-甲基二乙醇胺、N-乙基二乙醇胺、叔丁基二乙醇胺中的一种或两种以上组合物。
10.根据权利要求1-9任一项所述阳离子型水性聚硫氨酯的制备方法，其特征在于，成盐剂为乙酸和/或丁酸。
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