CN113307941A - 一种丙烯酸酯齐聚物及其制备方法与应用方法 - Google Patents
一种丙烯酸酯齐聚物及其制备方法与应用方法 Download PDFInfo
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- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims abstract description 9
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- 150000003077 polyols Chemical class 0.000 claims description 30
- 239000012948 isocyanate Substances 0.000 claims description 20
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- 238000006243 chemical reaction Methods 0.000 claims description 15
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- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 229920000570 polyether Polymers 0.000 claims description 8
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 7
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- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 6
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- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 claims description 4
- PISLZQACAJMAIO-UHFFFAOYSA-N 2,4-diethyl-6-methylbenzene-1,3-diamine Chemical compound CCC1=CC(C)=C(N)C(CC)=C1N PISLZQACAJMAIO-UHFFFAOYSA-N 0.000 claims description 4
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 4
- 239000005062 Polybutadiene Substances 0.000 claims description 4
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 claims description 4
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- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 4
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- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 4
- 229910052753 mercury Inorganic materials 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- BJZYYSAMLOBSDY-QMMMGPOBSA-N (2s)-2-butoxybutan-1-ol Chemical compound CCCCO[C@@H](CC)CO BJZYYSAMLOBSDY-QMMMGPOBSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
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- 125000003277 amino group Chemical group 0.000 description 2
- 238000010494 dissociation reaction Methods 0.000 description 2
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- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
- 238000010146 3D printing Methods 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 1
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- 230000007613 environmental effect Effects 0.000 description 1
- OYQYHJRSHHYEIG-UHFFFAOYSA-N ethyl carbamate;urea Chemical compound NC(N)=O.CCOC(N)=O OYQYHJRSHHYEIG-UHFFFAOYSA-N 0.000 description 1
- WBJINCZRORDGAQ-UHFFFAOYSA-N ethyl formate Chemical group CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 description 1
- 150000004675 formic acid derivatives Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
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- 238000007639 printing Methods 0.000 description 1
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Abstract
本发明公开了一种丙烯酸酯齐聚物，所述丙烯酸酯齐聚物由异氰酸酯基封端的齐聚物与甲基丙烯酸乙二醇甲酸酯反应得到。本发明提供的丙烯酸酯齐聚物在光固化之后，其分子结构、交联密度等网络结构特征可以经过特定的后处理进行改变，从而其热、力学性能也能通过后处理进行调整。由于热处理后生成的甲酸酯组分不具有吸水性且玻璃化温度较低，所以热处理后最终得到的材料具有较低的吸水率和玻璃化转变温度。本发明同时还提供了一种丙烯酸酯齐聚物的制备方法及应用方法。
Description
技术领域
本发明属于光固化低聚物领域，特别涉及一种丙烯酸酯齐聚物及其制备方法与应用方法。
背景技术
光固化是以光为能源，引发具有光反应活性的液态物质快速转变为固态的过程。光固化技术具有高效、适应性广、经济、节能、环保的特点。光固化技术还应用于涂料、油墨、胶黏剂、光刻胶、3D打印等等领域。
光固化体系主要由齐聚物、活性稀释剂和光引发剂组成，其中齐聚物性能决定固化后的性能，如硬度、韧性等。通常，光固化形成的是一个非常稳定的不融化不溶解的三维聚合物网络结构，也被称为热固性聚合物。为保证较高的固化速度，光固化形成的聚合物通常具有较高的交联密度，导致其力学性能差，具体表现为质脆、韧性差。
公开号为201910790012.1的中国专利公开了一种聚氨酯丙烯酸酯齐聚物，分子结构中含有可解离的大位阻氨酯键，该聚氨酯丙烯酸酯齐聚物在光固化之后，大位阻氨酯键会发生解离，暴露出的异氰酸酯基团与水汽反应，导致材料的分子结构、交联密度等网络结构特征发生改变，最终是材料力学性能发生变化。公开号为202110198554.7的中国专利公开了一种聚脲丙烯酸酯齐聚物，也是含有可解离的大位阻胺酯键，该聚脲丙烯酸酯齐聚物在光固化之后，大位阻胺酯键发生解离，体系中产生的异氰酸酯基会和体系中存在的脲键反应(不需要水汽作用)，使分子结构和力学性能发生改变。上述两个专利都是在分子结构中引入大位阻氨酯键，利用其在一定温度下的解离，引起网络结构和性能改变。大位阻氨酯键在解离之后会产生氨基会使体系具有吸湿性，另外网络结构重排后体系中的含氨基的组分具有较高的玻璃化转变温度(大于45℃)，使整个体系的玻璃化温度也不能降低，材料的低温弹性会较差。
因此，如果能引入另一种区别于大位阻氨酯键的可解离的基团和结构，将解决上述问题。
发明内容
本发明的目的在于提供一种丙烯酸酯齐聚物，光固化之后，其分子结构、交联密度等网络结构特征可以经过特定的后处理进行改变，从而其热、力学性能也能通过后处理进行调整。本发明还提供了一种丙烯酸酯齐聚物的制备方法和在制备光固化聚合物上的应用方法。
本发明目的通过如下技术路线实现：
一种丙烯酸酯齐聚物，所述丙烯酸酯齐聚物由异氰酸酯基封端的齐聚物与甲基丙烯酸乙二醇甲酸酯反应得到：
其中，R为氢或甲基。
上述齐聚物中通过异氰酸酯和甲酸酯的反应，生成了氨酯酯键。该化学键是一个不稳定化学键，在加热条件会解离重新生成异氰酸酯和甲酸酯。生成的异氰酸酯可以通过水汽固化形成聚脲或者和体系中脲键反应生成脲氨酯，从而改变网络结构和材料性能。由于热处理后生成的甲酸酯组分不具有吸水性且玻璃化温度较低，所以热处理后最终得到的材料具有较低的吸水率和玻璃化转变温度(甲酸酯组分的Tg约为20℃)。
或者
本发明提出的丙烯酸酯齐聚物是由异氰酸酯基封端的齐聚物与甲基丙烯酸乙二醇甲酸酯反应得到。所述异氰酸酯基封端的齐聚物由含异氰酸酯化合物与含活泼氢化合物反应得到，异氰酸酯与活泼氢的摩尔比大于1。
含活泼氢化合物可以选自多元醇或多元胺的一种或几种。
作为优选，所述多元醇选自聚酯多元醇、聚醚多元醇、聚碳酸酯多元醇、聚丁二烯多元醇、聚烯烃多元醇或聚丙烯酸酯多元醇中的一种或几种；
作为优选，所述多元胺选自聚醚胺、二氯二氨基二苯甲烷、二乙基甲苯二胺的一种或几种。
所述含异氰酸酯化合物选自甲苯二异氰酸酯、二苯基甲烷二异氰酸酯六亚甲基二异氰酸酯、异氟尔酮二异氰酸酯、苯二亚甲基二异氰酸酯、二环己基甲烷二异氰酸酯的一种或几种。
本发明还提出一种上述的丙烯酸酯齐聚物的方法，包括如下步骤：
1)将多元醇或多元胺或多元醇和多元胺的组合物于40-60℃下滴加进入含异氰酸酯化合物，用二正丁胺滴定反应终点，得到异氰酸酯基封端的齐聚物；
2)将甲酸甲基丙烯酸乙二醇酯中滴加进入异氰酸酯基封端的齐聚物，60℃反应，用二正丁胺滴定体系中异氰酸酯含量为0，得到所述丙烯酸酯齐聚物。
在步骤1)中，所述多元醇选自聚酯多元醇、聚醚多元醇、聚碳酸酯多元醇、聚丁二烯多元醇、聚烯烃多元醇或聚丙烯酸酯多元醇中的一种或至少两种的组合。所述多元胺选自聚醚胺、二氯二氨基二苯甲烷、二乙基甲苯二胺的一种或几种。
在步骤1)中，所述含异氰酸酯化合物选自甲苯二异氰酸酯、二苯基甲烷二异氰酸酯六亚甲基二异氰酸酯、异氟尔酮二异氰酸酯、苯二亚甲基二异氰酸酯、二环己基甲烷二异氰酸酯的一种或几种。
本发明还提出了一种所述丙烯酸酯齐聚物在制备光固化聚丙烯酸酯上的应用方法，所述应用方法包括以下步骤：
1)将丙烯酸酯齐聚物与活性稀释剂混合，加入引发剂，得到混合物；
2)使用跟引发剂相匹配的光源将步骤1)中的混合物固化，得到光固化样品；
3)若丙烯酸酯齐聚物中不含有脲键，则将步骤2)得到的光固化样品置在温度为60-100℃，湿度为60-90％的条件下处理1-48小时；若丙烯酸酯齐聚物中含有脲键，则将步骤2)得到的光固化样品置在温度为60-100℃的条件下处理1-48小时。
同现有技术相比，本发明的有益效果体现在：光固化后的聚合物经过后处理后交联密度降低，同时生成聚脲结构，这两点都有利于提高聚合物的韧性。另外，本发明中发生解离的甲酸酯结构不吸水，玻璃化转变温度低，有利于制备吸水率低且兼顾低温性能的弹性体。
具体实施方式
下面结合具体实施例对本发明内容进一步地说明，以下的实施例并非对本发明实质精神的简单限定，任何基于本发明实质精神所作出的简单变化或同等替换均应属于本发明所要求保护的范围之内。
实施例1
1)在装有机械搅拌桨、温度计、冷凝管、恒压漏斗的反应釜中，加入2mol六亚甲基二异氰酸酯(HDI，Mw＝168)，温度为40℃，通过漏斗滴入1mol聚四氢呋喃醚二醇(PTMG，Mw＝1000)，控制温度低于60℃，通过正丁胺法确认反应结束，得到异氰酸酯基团封端的齐聚物。
2)将2mol甲基丙烯酸乙二醇甲酸酯滴加到上述中间产物中，滴加完成后加入7g的二月桂酸二丁基锡(DBTDL)，升温至50℃继续反应3h，通过正丁胺法确认NCO值为0时反应结束，得到丙烯酸酯齐聚物。
取上述丙烯酸酯齐聚物5g，加入0.15g光引发剂819，光源为高压汞灯，在透明模具中浇铸出符合ASTM D412标准的样条，测试单向拉伸性能，将上述样条在温度110℃，湿度75％的恒温恒湿箱中后处理16小时，测试单向拉伸性能。处理前断裂伸长率为42％，断裂强度为5MPa；处理后断裂伸长率为200％，断裂强度为10MPa。
实施例2
1)在装有机械搅拌桨、温度计、冷凝管、恒压漏斗的反应釜中，加入2mol六亚甲基二异氰酸酯(HDI，Mw＝168)，通过漏斗滴入1mol聚醚胺(D2000，Mw＝2000)，控制温度低于40℃，通过正丁胺法确认反应结束，得到异氰酸酯基团封端的聚脲齐聚物。
2)将2mol甲基丙烯酸乙二醇甲酸酯滴加到上述中间产物中，滴加完成后加入7g的二月桂酸二丁基锡(DBTDL)，常温继续反应3h，通过正丁胺法确认NCO值为0时反应结束，得到丙烯酸酯齐聚物。
取上述丙烯酸酯齐聚物5g，加入0.15g光引发剂819，光源为高压汞灯，在透明模具中浇铸出符合ASTM D412标准的样条，测试单向拉伸性能，将上述样条在温度110℃烘箱中后处理10小时，测试单向拉伸性能。处理前断裂伸长率为50％，断裂强度为2.3MPa；处理后断裂伸长率为350％，断裂强度为4.5MPa。
实施例3
1)在装有机械搅拌桨、温度计、冷凝管、恒压漏斗的反应釜中，加入2mol异氟尔酮二异氰酸酯(IPDI，Mw＝222)，温度为40℃，通过漏斗滴入1mol聚四氢呋喃醚二醇(PTMG，Mw＝1000)，控制温度低于60℃，通过正丁胺法确认反应结束，得到异氰酸酯基团封端的齐聚物。
2)2)将2mol甲基丙烯酸乙二醇甲酸酯滴加到上述中间产物中，滴加完成后加入7g的二月桂酸二丁基锡(DBTDL)，升温至50℃继续反应3h，通过正丁胺法确认NCO值为0时反应结束，得到丙烯酸酯齐聚物。
取上述丙烯酸酯齐聚物5g，加入0.15g光引发剂819，光源为高压汞灯，在透明模具中浇铸出符合ASTM D412标准的样条，测试单向拉伸性能，将上述样条在温度90℃，湿度75％的恒温恒湿箱中后处理10小时，测试单向拉伸性能。处理前断裂伸长率为38％，断裂强度为3.2MPa；处理后断裂伸长率为400％，断裂强度为3.8MPa。
实施例4
1)在装有机械搅拌桨、温度计、冷凝管、恒压漏斗的反应釜中，加入2mol六亚甲基二异氰酸酯(HDI，Mw＝168)，温度为40℃，通过漏斗滴入0.8mol聚四氢呋喃醚二醇(PTMG，Mw＝1000)和0.2mol聚醚胺(D230，Mw＝230)，控制温度低于60℃，通过正丁胺法确认NCO值为6.28时反应结束，得到异氰酸酯基团封端的齐聚物。
2)2)将2mol甲基丙烯酸乙二醇甲酸酯滴加到上述中间产物中，滴加完成后加入7g的二月桂酸二丁基锡(DBTDL)，升温至50℃继续反应3h，通过正丁胺法确认NCO值为0时反应结束，得到丙烯酸酯齐聚物。
取上述丙烯酸酯齐聚物5g，加入0.15g光引发剂819，光源为高压汞灯，在透明模具中浇铸出符合ASTM D412标准的样条，测试单向拉伸性能，将上述样条在温度90℃烘箱中后处理10小时，测试单向拉伸性能。处理前断裂伸长率为56％，断裂强度为4.3MPa；处理后断裂伸长率为250％，断裂强度为6MPa。
Claims (9)
1.一种丙烯酸酯齐聚物，其特征在于，所述丙烯酸酯齐聚物由异氰酸酯基封端的齐聚物与甲基丙烯酸乙二醇甲酸酯反应得到：
其中，R为氢或甲基。
2.根据权利要求1所述的丙烯酸酯齐聚物，其特征在于，所述异氰酸酯基封端的齐聚物由含异氰酸酯化合物与含活泼氢化合物反应得到，异氰酸酯与活泼氢的摩尔比大于1。
3.根据权利要求2所述的丙烯酸酯齐聚物，其特征在于，所述含活泼氢化合物选自多元醇或多元胺的一种或几种。
4.根据权利要求2或3所述的丙烯酸酯齐聚物，其特征在于，所述多元醇选自聚酯多元醇、聚醚多元醇、聚碳酸酯多元醇、聚丁二烯多元醇、聚烯烃多元醇或聚丙烯酸酯多元醇中的一种或几种；所述多元胺选自聚醚胺、二氯二氨基二苯甲烷、二乙基甲苯二胺的一种或几种。
5.根据权利要求2所述的丙烯酸酯齐聚物，其特征在于，所述含异氰酸酯化合物选自甲苯二异氰酸酯、二苯基甲烷二异氰酸酯六亚甲基二异氰酸酯、异氟尔酮二异氰酸酯、苯二亚甲基二异氰酸酯、二环己基甲烷二异氰酸酯的一种或几种。
6.一种制备权利要求1-5任一所述的丙烯酸酯齐聚物的方法，其特征在于，所述制备方法包括如下步骤：
1)将多元醇或多元胺或多元醇和多元胺的组合物于40-60℃下滴加进入含异氰酸酯化合物，用二正丁胺滴定反应终点，得到异氰酸酯基封端的齐聚物；
2)将甲基丙烯酸乙二醇甲酸酯中滴加进入异氰酸酯基封端的齐聚物，60℃反应，用二正丁胺滴定体系中异氰酸酯含量为0，得到所述丙烯酸酯齐聚物。
7.根据权利要求6所述的丙烯酸酯齐聚物的制备方法，其特征在于，在步骤1)中，所述多元醇选自聚酯多元醇、聚醚多元醇、聚碳酸酯多元醇、聚丁二烯多元醇、聚烯烃多元醇或聚丙烯酸酯多元醇中的一种或至少两种的组合。所述多元胺选自聚醚胺、二氯二氨基二苯甲烷、二乙基甲苯二胺的一种或几种。
8.根据权利要求6所述的丙烯酸酯齐聚物的制备方法，其特征在于，在步骤1)中，所述含异氰酸酯化合物选自甲苯二异氰酸酯、二苯基甲烷二异氰酸酯六亚甲基二异氰酸酯、异氟尔酮二异氰酸酯、苯二亚甲基二异氰酸酯、二环己基甲烷二异氰酸酯的一种或几种。
9.一种根据权利要求1-5任一所述的丙烯酸酯齐聚物在制备光固化聚丙烯酸酯上的应用方法，所述应用方法包括以下步骤：
1)将丙烯酸酯齐聚物与活性稀释剂混合，加入引发剂，得到混合物；
2)使用跟引发剂相匹配的光源将步骤1)中的混合物固化，得到光固化样品；
3)若丙烯酸酯齐聚物中不含有脲键，则将步骤2)得到的光固化样品置在温度为60-100℃，湿度为60-90％的条件下处理1-48小时；若丙烯酸酯齐聚物中含有脲键，则将步骤2)得到的光固化样品置在温度为60-100℃的条件下处理1-48小时。
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