CN112552195A - 一种低聚的天冬树脂的制备方法 - Google Patents
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Abstract
本发明公开了一种低聚的天冬树脂的制备方法，包括如下步骤：由马来酸酐与二元醇或多元醇形成以羟基封端的低聚的聚酯，聚合度在2‑10；然后位阻型的伯胺再对上述聚酯进行Michael加成反应合成低聚的多官天冬树脂。本发明通过合成多官能度的天冬树脂，即提升聚天门冬氨酸酯中仲胺的官能度可以增加聚天门冬氨酸酯聚脲的交联密度，从而达到改善天冬聚脲在极端环境情况下的性能。
Description
技术领域
本发明涉及树脂制备技术领域，尤其涉及一种低聚的天冬树脂的制备方法。
背景技术
天冬聚脲是聚天门冬氨酸酯聚脲的简称，是第三代聚脲。而聚天门冬氨酸酯(Polyaspartic Ester，PAE)是一类特殊的位阻型仲胺，由于酯基的空间位阻和诱导效应，特别是胺基邻位取代基的位阻效应与低粘度异氰酸酯固化剂的凝胶时间可在几分钟到几小时之间进行调节。
目前的天冬聚脲体系都以双官能度的仲胺与双官或三官的异氰酸酯固化剂聚合而成。常规环境情况下，这种天冬聚脲树脂的应用是非常优秀的，它有卓越的耐紫外光性和耐候性(不黄变并具有极高的保光性)，耐化学性和耐溶剂性
以及出色的外观。但在一些极端环境情况下：如常年处于较高温度，较大湿度，较严重盐雾的情况下。上述天冬聚脲的性能就会打折扣。这些都有可能是交联密度不够，聚合物分子量不够而引起的。
发明内容
本发明提出了一种低聚的天冬树脂的制备方法，以解决上述背景技术中提出的问题。
本发明提出了一种低聚的天冬树脂的制备方法，包括如下步骤：
由马来酸酐与二元醇或多元醇形成以羟基封端的低聚的聚酯，聚合度在2-10；然合位阻型的伯胺再对上述聚酯进行Michael加成反应合成低聚的多官天冬树脂；其合成由以下式(1)和式(2)表示，其中：R为各种醚基，烷基，芳香基，R’为各种链状或环状位阻胺如叔丁胺，环已胺，2-甲基环己胺，2-乙基环己胺，2，6-二甲基环己胺，n＝0-8，其结构式如下：
本发明提出的一种低聚的天冬树脂的制备方法，有益效果在于：本发明通过合成多官能度的天冬树脂，即提升聚天门冬氨酸酯中仲胺的官能度可以增加聚天门冬氨酸酯聚脲的交联密度，从而达到改善天冬聚脲在极端环境情况下的性能。
具体实施方式
下面结合具体实施例来对本发明做进一步说明。
实施例1
本发明提出了一种低聚的天冬树脂的制备方法，包括如下步骤：
马来酸酐98g与己二醇142g在150摄氏度温度下，在氮气保护的情况下进行酯化反应，通过酸值测定监控反应终点，当酸值为11时停止反应。
上述反应得到的低聚的不饱和聚酯在氮气氛围下滴加入装有2-甲基环己胺226g(2equiv.)的烧瓶中。升温至60摄氏度，通过测定胺值监控反应终点。减压蒸除多余的2-甲基环己胺得到相应的低聚的天冬树脂。
实施例2
本发明提出了一种低聚的天冬树脂的制备方法，包括如下步骤：
马来酸酐98g与19.8g新戊二醇，3.04g丙二醇，32.28g乙二醇，4.24g二甘醇和34.88g一缩二丙二醇，在150摄氏度温度下，在氮气保护的情况下进行酯化反应，通过酸值测定监控反应终点，当酸值为10时停止反应。
上述反应得到的低聚的不饱和聚酯在氮气氛围下滴加入装有环己胺200g(2equiv.)的烧瓶中。升温至60摄氏度，通过测定胺值监控反应终点。减压蒸除多余的环己胺得到相应的低聚的天冬树脂。
实施例3
本发明提出了一种低聚的天冬树脂的制备方法，包括如下步骤：
马来酸酐98g与31.66g乙二醇，72.45g一缩二丙二醇，在150摄氏度温度下，在氮气保护的情况下进行酯化反应，通过酸值测定监控反应终点，当酸值为12时停止反应。
上述反应得到的低聚的不饱和聚酯在氮气氛围下滴加入装有2-乙基环己胺254g(2equiv.)的烧瓶中。升温至80摄氏度，通过测定胺值监控反应终点。减压蒸除多余的2-乙基环己胺得到相应的低聚的天冬树脂。
实施例4
本发明提出了一种低聚的天冬树脂的制备方法，包括如下步骤：
马来酸酐98g与19.79g乙二醇，16.14g乙二醇，19.8g新戊二醇，80.5g一缩二丙二醇，在150摄氏度温度下，在氮气保护的情况下进行酯化反应，通过酸值测定监控反应终点，当酸值为12时停止反应。
上述反应得到的低聚的不饱和聚酯在氮气氛围下滴加入装有2,6-二甲基环己胺254g(2equiv.)的烧瓶中。升温至80摄氏度，通过测定胺值监控反应终点。减压蒸除多余的2,6-二甲基环己胺得到相应的低聚的天冬树脂。
实施例5
本发明提出了一种低聚的天冬树脂的制备方法，包括如下步骤：
马来酸酐98g与400g PEG400，在150摄氏度温度下，在氮气保护的情况下进行酯化反应，通过酸值测定监控反应终点，当酸值为12时停止反应。
上述反应得到的低聚的不饱和聚酯在氮气氛围下滴加入装有2,6-二甲基环己胺254g(2equiv.)的烧瓶中。升温至80摄氏度，通过测定胺值监控反应终点。减压蒸除多余的2-乙基环己胺得到相应的低聚的天冬树脂。
实施例6
本发明提出了一种低聚的天冬树脂的制备方法，包括如下步骤：
马来酸酐98g与100g PEG200，31g乙二醇在150摄氏度温度下，在氮气保护的情况下进行酯化反应，通过酸值测定监控反应终点，当酸值为10时停止反应。
上述反应得到的低聚的不饱和聚酯在氮气氛围下滴加入装有2-甲基环己胺226g(2equiv.)的烧瓶中。升温至80摄氏度，通过测定胺值监控反应终点。减压蒸除多余的2-甲基环己胺得到相应的低聚的天冬树脂。
实施例7
本发明提出了一种低聚的天冬树脂的制备方法，包括如下步骤：
马来酸酐98g与106g双酚A(12H)，30g己二醇，15g乙二醇在150摄氏度温度下，在氮气保护的情况下进行酯化反应，通过酸值测定监控反应终点，当酸值为10时停止反应。
上述反应得到的低聚的不饱和聚酯在氮气氛围下滴加入装有叔丁胺146g(2equiv.)的烧瓶中。升温至80摄氏度，通过测定胺值监控反应终点。减压蒸除多余的叔丁胺得到相应的低聚的天冬树脂。
实施例8
本发明提出了一种低聚的天冬树脂的制备方法，包括如下步骤：马来酸酐98g与53g双酚A(12H)，100g PEG400，30g乙二醇在150摄氏度温度下，在氮气保护的情况下进行酯化反应，通过酸值测定监控反应终点，当酸值为10时停止反应。
上述反应得到的低聚的不饱和聚酯在氮气氛围下滴加入装有环已胺200g(2equiv.)的烧瓶中。升温至80摄氏度，通过测定胺值监控反应终点。减压蒸除多余的叔丁胺得到相应的低聚的天冬树脂。
对比例1：
所用天冬树脂如下：
性能测试
将实施例制得的低聚的天冬树脂用于制备聚脲涂料；所述聚脲涂料的制备原料，包括A组分和B组分；所述A组分，按重量份计，包括以下组分：实施例制得的聚脲树脂与对比例分别为100份，流平剂(鸿昶化学的MT-310)0.5份，消泡剂(LY-A)0.3份，附着力促进剂(KH550)3份；所述B组份为固化剂；所述固化剂为HDI；实施例1-8对应固化剂的用量，按重量份计，分别为71、57.5、44、41、25、54、55.6、44份，对比例1为36份。
1、伸长率、拉伸强度的测试方法为：GB/T 16777-2008《建筑防水涂料试验方法》。2、附着力的测试方法为：GB/T 5210-2006《色漆和清漆拉开法附着力试验》；基材为磁砖。3、耐冲击的测试方法为GB/T1732-1993《漆膜耐冲击测定法》测试漆膜耐冲击性能。4、耐盐雾测试方法：GB/T 1771-2007《色漆和清漆耐中性盐雾性能的测定》，模拟海上的盐雾环境，从而考察涂料板的耐中性盐雾性能。5、耐水性的测试方法为：GB/T 1733-1993《漆膜耐水性测定法》。测试环境湿度为80％，测试结果见表1。
表1.实施例对应聚脲涂料的性能测试结果
从以上性能测试的结果我们可以看出：这种低聚的天冬树脂与常规的非聚合型天冬聚脲树脂(对比例)在使用性能上没有太大差异，成膜后的力学性能基本相当。而在极端条件下(盐雾，湿气)这种聚合型的天冬树脂聚脲的成膜性能表现更为优异，耐盐雾达1500小时。耐水性也比常规的天冬聚脲树脂优秀，泡水240小时涂层无明显变化。
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 (1)
1.一种低聚的天冬树脂的制备方法，其特征在于，包括以下步骤：
由马来酸酐与二元醇或多元醇形成以羟基封端的低聚的聚酯，聚合度在2-10；
然合位阻型的伯胺再对上述聚酯进行Michael加成反应合成低聚的多官天冬树脂；
其合成由以下式(1)和式(2)表示，其中：R为各种醚基，烷基，芳香基，R’为各种链状或环状位阻胺如叔丁胺，环已胺，2-甲基环己胺，2-乙基环己胺，2，6-二甲基环己胺，n＝0-8，
其结构式如下：
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113354792A (zh) * | 2021-04-30 | 2021-09-07 | 浙江艾特普科技有限公司 | 一种低粘度高渗透聚天门冬氨酸酯 |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3345338A (en) * | 1962-08-11 | 1967-10-03 | Bayer Ag | Polyurethanes prepared from amino polyesters |
| GB1447674A (en) * | 1972-11-29 | 1976-08-25 | Dainippon Ink & Chemicals | Method of preparing curable polyester resins containing the bisphenol a radical |
| US4874837A (en) * | 1988-01-11 | 1989-10-17 | Owens-Corning Fiberglas Corporation | Aminated hydroxylated polyester polyol resin and molding compositions comprised thereof |
| US5118783A (en) * | 1990-09-12 | 1992-06-02 | Reichhold Chemicals, Inc. | Chain-stopped unsaturated polyester resins |
| US5925711A (en) * | 1996-07-10 | 1999-07-20 | Bayer Aktiengesellschaft | Polyamines and their use in aqueous coating compositions |
| JP2006096911A (ja) * | 2004-09-30 | 2006-04-13 | Showa Highpolymer Co Ltd | 靭性を有する不飽和ポリエステル樹脂、その製造方法及びその利用 |
| CN110396053A (zh) * | 2019-07-30 | 2019-11-01 | 深圳市前海博扬研究院有限公司 | 天冬聚脲预聚体及制备方法以及一种涂料 |
| CN111620789A (zh) * | 2020-06-12 | 2020-09-04 | 深圳市前海博扬研究院有限公司 | 一种天门冬氨酸酯树脂的制备方法 |
| CN112920393A (zh) * | 2021-01-28 | 2021-06-08 | 深圳飞扬兴业科技有限公司 | 一种不饱和聚酯改性天冬树脂的合成方法和应用 |
| CN113548974A (zh) * | 2021-06-22 | 2021-10-26 | 浙江艾特普科技有限公司 | 一种聚天门冬氨酸酯及其制备方法和应用 |
-
2020
- 2020-12-11 CN CN202011460194.5A patent/CN112552195A/zh active Pending
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3345338A (en) * | 1962-08-11 | 1967-10-03 | Bayer Ag | Polyurethanes prepared from amino polyesters |
| GB1447674A (en) * | 1972-11-29 | 1976-08-25 | Dainippon Ink & Chemicals | Method of preparing curable polyester resins containing the bisphenol a radical |
| US4874837A (en) * | 1988-01-11 | 1989-10-17 | Owens-Corning Fiberglas Corporation | Aminated hydroxylated polyester polyol resin and molding compositions comprised thereof |
| US5118783A (en) * | 1990-09-12 | 1992-06-02 | Reichhold Chemicals, Inc. | Chain-stopped unsaturated polyester resins |
| US5925711A (en) * | 1996-07-10 | 1999-07-20 | Bayer Aktiengesellschaft | Polyamines and their use in aqueous coating compositions |
| JP2006096911A (ja) * | 2004-09-30 | 2006-04-13 | Showa Highpolymer Co Ltd | 靭性を有する不飽和ポリエステル樹脂、その製造方法及びその利用 |
| CN110396053A (zh) * | 2019-07-30 | 2019-11-01 | 深圳市前海博扬研究院有限公司 | 天冬聚脲预聚体及制备方法以及一种涂料 |
| CN111620789A (zh) * | 2020-06-12 | 2020-09-04 | 深圳市前海博扬研究院有限公司 | 一种天门冬氨酸酯树脂的制备方法 |
| CN112920393A (zh) * | 2021-01-28 | 2021-06-08 | 深圳飞扬兴业科技有限公司 | 一种不饱和聚酯改性天冬树脂的合成方法和应用 |
| CN113548974A (zh) * | 2021-06-22 | 2021-10-26 | 浙江艾特普科技有限公司 | 一种聚天门冬氨酸酯及其制备方法和应用 |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113354792A (zh) * | 2021-04-30 | 2021-09-07 | 浙江艾特普科技有限公司 | 一种低粘度高渗透聚天门冬氨酸酯 |
| CN113354792B (zh) * | 2021-04-30 | 2022-04-01 | 浙江艾特普科技有限公司 | 一种低粘度高渗透聚天门冬氨酸酯 |
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