CN111995926A - 一种石墨烯改性自愈合微胶囊涂层及其制备方法 - Google Patents
一种石墨烯改性自愈合微胶囊涂层及其制备方法 Download PDFInfo
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Abstract
一种石墨烯改性自愈合微胶囊涂层及其制备方法,属于环氧树脂复合涂层技术领域。包括微胶囊的制备、金属盐化合物与咪唑类化合物络合产物‑潜伏固化剂的制备、氧化石墨烯的分散、石墨烯改性自愈合微胶囊涂层的制备等四个步骤。本发明通过石墨烯的二维层状结构负载微胶囊和潜伏固化剂,使涂层具有高的拉伸强度和高修复效率。通过该方法制备的石墨烯改性自愈合微胶囊涂层各组分分散均匀,且涂层粘合力大,不易脱落。该微胶囊涂层具有良好的力学性能、较高的修复后力学性能恢复率,从而实现环氧树脂复合涂层在提高力学强度等方面的应用。
Description
技术领域
本发明属于环氧树脂复合涂层技术领域,具体涉及一种石墨烯改性自愈合微胶囊涂层及其制备方法,该微胶囊涂层具有良好的力学性能、较高的修复后力学性能恢复率,从而实现环氧树脂复合涂层在提高力学强度等方面的应用。
背景技术
涂层在使用过程中易受到划痕、创口等伤害而造成涂层的力学性能降低,从而降低涂层使用寿命。自修复材料作为一种新型的智能材料的出现,很大程度上延长了涂层的使用寿命。涂层的自修复一般分为三类:一是涂层本身不借助外界条件,利用涂层内分子之间的作用力,如氢键、范德瓦尔斯力等进行修复;二是在涂层中铺构微血管网路,当发生损伤时,微血管中的修复剂溢出来达到修复的目的;三是在涂层中分布微胶囊,当微胶囊受到外力的作用而破碎时,微胶囊包覆的修复剂流出达到修复的效果。
微胶囊自愈合环氧树脂涂层是一类以环氧树脂为基体,掺入功能化微胶囊来达到改性目的的一种涂层,而且具有优异的断裂韧性和修复效率。目前,微胶囊自愈合环氧树脂涂层已经在金属表面防腐、混凝土表面防护等领域展现了良好的应用。蔡杰(CN111269607A)以金属-有机骨架材料吸附碘/异氰酸酯衍生物为芯材,以脲醛树脂为囊壁制备自愈合微胶囊。胥维昌等人(CN107312140B)发明了以羟基或多氨基化合物与异氰酸酯的反应物为芯材,双层壁材的内壁为聚氨酯,双层壁材的外壁为三聚氰胺甲醛树脂,纳米粒子和金属缓蚀剂为缓蚀材料的自愈合微胶囊。尽管微胶囊自愈合环氧树脂涂层方面已经取得了一定的进展,然而由于微胶囊的加入破坏了环氧树脂基体的连续性,使其力学强度降低,因而制备一类具有更高的力学强度的微胶囊自愈合环氧树脂涂层显得尤为重要。
新一代微胶囊自修复环氧树脂涂层是一类具有高断裂韧性和拉伸强度的新型复合材料。目前,还少有利用石墨烯构架基体以提高力学强度的报道。
发明内容
本发明的目的是针对现有体系的缺陷,提供一种石墨烯改性自愈合微胶囊涂层。通过石墨烯的二维层状结构负载微胶囊和潜伏固化剂,使涂层具有高的拉伸强度和高修复效率。通过该方法制备的石墨烯改性自愈合微胶囊涂层各组分分散均匀,且涂层粘合力大,不易脱落。
该方法适用于在各类基底表面进行涂覆,通过该涂层对基底进行保护,并利用涂层的自修复性能延长涂层的使用寿命,使制备的涂层在金属表面防腐、建筑表面防护的方面发挥良好的作用。
本发明所述的石墨烯改性自愈合微胶囊涂层的制备方法,其步骤如下:
(1)微胶囊的制备:将1.00~6.30g三聚氰胺、1.8~9.00g尿素、2.70~13.48g甲醛溶液混合,用三乙醇胺调节反应体系pH为8~9,在60~80℃下搅拌0.5~2h,得到三聚氰胺-尿素-甲醛混合溶液;将1.00~3.00g吐温-80、1.00~4.00g三聚氰酸三缩水甘油环氧树脂、0.20~0.50mL正丁醇混合,在70~80℃下搅拌1.5~2.5h,待其冷却到室温后加入三聚氰胺-尿素-甲醛混合溶液和2.00~3.00g间苯二酚,用0.1mol/L稀盐酸调节pH为3~4,在70~80℃下均匀搅拌2~3h,反应结束后冷却到室温,将产物分别用丙酮、无水乙醇、去离子水抽滤2~3次,得到微胶囊;
(2)金属盐化合物与咪唑类化合物络合产物-潜伏固化剂的制备:将0.67~4.38g金属盐化合物和0.68~8.20g咪唑类化合物分别溶解到10~50mL甲醇中,超声分散;然后将二者混合在一起,25℃下搅拌12~24h,将得到的溶液洗涤离心,在50~70℃下干燥12~24h,得到潜伏固化剂;
(3)氧化石墨烯的分散:将100~300mg氧化石墨烯超声分散在四氢呋喃中,得到1~5mg/mL的氧化石墨烯分散溶液,在70~90℃下加热20~40min;
(4)石墨烯改性自愈合微胶囊涂层的制备:将步骤(3)得到的氧化石墨烯分散溶液中分别加入5.00~8.00g三聚氰酸三缩水甘油环氧树脂、0.20~0.40g步骤(2)制备的潜伏固化剂、1.00~3.00g步骤(1)制备的微胶囊,缓慢搅拌均匀,再加入1.20~2.00g固化剂,在25~40℃下固化1.5~3.0h,80~100℃下固化1~2h,从而得到本发明所述已固化的石墨烯改性自愈合微胶囊涂层。
上述金属盐化合物为氧化铜、硝酸铜、氢氧化铜、醋酸铜、氢氧化镍、氧化镍、无水碳酸镍、乙酸镍、乙酸钴、碳酸钴、六水硝酸钴中的一种;上述咪唑类化合物为1-乙烯基咪唑、4-硝基咪唑、1-丙基咪唑、2-丙基咪唑、1-乙酰基咪唑、4-乙酰基咪唑、4-甲基咪唑中的一种;上述固化剂为间苯二胺、二氨基二苯基甲烷、二氨基二苯基胺、间苯二甲胺中的一种。
进一步,所述的金属盐化合物为氧化铜,所述的咪唑类化合物为2-丙基咪唑,所用固化剂为间苯二胺。
与现有技术相比,本发明具有如下有益效果
1.本发明所制备的微胶囊的粒径小,可以在基体中分散更为均匀,当出现创伤时,可以使更多数量的微胶囊破碎,修复效果更佳;
2.本发明采用的潜伏固化剂的潜伏周期可达半年以上,适用期长,可以保证涂层长时间使用。
3.本发明所制备的涂层的力学性能较原始基体只降低了10.79%,很大程度上体改了复合基体的力学强度。
4.本发明的工艺简单,成本低廉。
附图说明
图1:为本发明例1微胶囊原料的SEM图片;
图2:为本发明例1潜伏固化剂的红外图谱;
图3:为本发明例1氧化石墨烯的XRD图像;
图4:为本发明例1的液氮粹断的截面SEM图片;
图5:为本发明例1的修复前后拉伸曲线对比图;
如图1所示:微胶囊分布均匀,粒径大小一致,均为4~8μm。
如图2所示:潜伏固化剂上已经负载了咪唑基团。
如图3所示:氧化石墨烯的物相均匀,纯度高。
如图4所示:石墨烯改性自愈合微胶囊涂层中石墨烯的层状结构清晰可见,已成功在基体中构架。
如图5所示:采用氧化铜和2-丙基咪唑络合的潜伏固化剂和间苯二胺固化的氧化石墨烯改性自愈合微胶囊涂层划痕修复后,拉伸强度恢复到89.21%。
具体实施方式
下面通过实施例对本发明做进一步的描述,但本发明的实施方式不限于此,不能理解为对本发明的保护范围的限制。
实施例1
称量1.26g三聚氰胺、1.80g尿素、2.70g甲醛溶液,混合均匀,用三乙醇胺调节pH为8.6,在70℃下搅拌1h;将1.00g吐温-80、1.00g三聚氰酸三缩水甘油环氧树脂、0.2mL正丁醇混合,在70℃下搅拌1h,待其冷却到25℃后加入三聚氰胺-尿素-甲醛混合溶液和2.00g间苯二酚,用0.1mol/L稀盐酸调节pH为3.6,在70℃下均匀搅拌2h,反应结束后冷却到室温,将产物分别用丙酮、无水乙醇、去离子水抽滤3次,得到已经包覆成功的微胶囊。
将0.67g氯化铜和1.64g 1-乙烯基咪唑分别溶解到35mL甲醇中,超声分散,将二者混合在一起,25℃下搅拌24h,将得到的溶液洗涤离心,在60℃下干燥12h,得到Cu(MI)4Cl2,得到由Cu2+络合的潜伏固化剂。
将300mg氧化石墨烯分散在四氢呋喃中,超声分散,得到5mg/mL的氧化石墨烯溶液,在80℃下加热30min,得到分散的氧化石墨烯溶液。
将6.00g三聚氰酸三缩水甘油环氧树脂、0.20g Cu(MI)4Cl2、1.00g微胶囊分别加入到石墨烯分散溶液中,用机械桨缓慢搅拌均匀,再加入1.50g间苯二胺,在25℃下固化2h,100℃下固化1h,得到由Cu2+络合的潜伏固化剂构成的已固化的氧化石墨烯改性自愈合微胶囊涂层,涂层有效使用时间6个月以上。
实施例2
称量2.52g三聚氰胺、3.60g尿素、5.41g甲醛溶液,混合均匀,用三乙醇胺调节pH为8.2,在70℃下搅拌1h;将1.50g吐温-80、2.70g三聚氰酸三缩水甘油环氧树脂、0.3mL正丁醇混合,在70℃下搅拌1h,待其冷却到25℃后加入三聚氰胺-尿素-甲醛混合溶液和2.60g间苯二酚,用0.1mol/L的稀盐酸调节pH为3.5,在70℃下均匀搅拌2h,反应结束后冷却到室温,将产物分别用丙酮、无水乙醇、去离子水抽滤3次,得到已经包覆成功的微胶囊。
将3.72g醋酸镍和4.88g 4-甲基咪唑分别溶解到25mL甲醇中,超声分散,将二者混合在一起,25℃下搅拌24h,将得到的溶液洗涤离心,在60℃下干燥12h,得到Ni(MI)4AC2,得到由Ni2+络合的潜伏固化剂。
将100mg氧化石墨烯分散在四氢呋喃中,超声分散,得到4mg/mL的氧化石墨烯溶液,在80℃下加热30min,得到分散的氧化石墨烯溶液。
将8.00g三聚氰酸三缩水甘油环氧树脂、0.26g Ni(MI)4AC2、1.20g微胶囊分别加入到石墨烯分散溶液中,用机械浆缓慢搅拌均匀,再加入1.20g间苯二甲胺,在25℃下固化2h,83℃下固化1h,得到由Ni2+络合的潜伏固化剂构成的已固化的氧化石墨烯改性自愈合微胶囊涂层,涂层有效使用时间为5个月。
实施例3
称量3.78g三聚氰胺、5.41g尿素、8.11g甲醛溶液,混合均匀,用三乙醇胺调节pH为8.3,在70℃下搅拌1h;将1.20g吐温-80、2.40g三聚氰酸三缩水甘油环氧树脂、0.5mL正丁醇混合,在70℃下搅拌1h,待其冷却到25℃后加入三聚氰胺-尿素-甲醛混合溶液和2.80g间苯二酚,用0.1mol/L的稀盐酸调节pH为3.4,在70℃下均匀搅拌2h,反应结束后冷却到室温,将产物分别用丙酮、无水乙醇、去离子水抽滤2次,得到已经包覆成功的微胶囊。
将2.92g六水硝酸钴和3.28g 4-硝基咪唑分别溶解到50mL甲醇中,超声分散,将二者混合在一起,25℃下搅拌24h,将得到的溶液洗涤离心,在60℃下干燥12h,得到Ni(MI)4NO3,得到由Co2+络合的潜伏固化剂。
将100mg氧化石墨烯分散在四氢呋喃中,超声分散,得到2mg/mL的氧化石墨烯溶液,在80℃下加热30min,得到分散的氧化石墨烯溶液。
将7.20g三聚氰酸三缩水甘油环氧树脂、0.28g Ni(MI)4NO3、1.47g微胶囊分别加入到石墨烯分散溶液中,用机械浆缓慢搅拌均匀,再加入1.60g二氨基二苯基甲烷,在25℃下固化2h,94℃下固化1h,得到由Co2+络合的潜伏固化剂构成的已固化的氧化石墨烯改性自愈合微胶囊涂层。涂层有效使用时间为3个月。
实施例4
称量5.04g三聚氰胺、7.21g尿素、10.81g甲醛溶液,混合均匀,用三乙醇胺调节pH为8.5,在70℃下搅拌1h;将2.30g吐温-80、3.50g三聚氰酸三缩水甘油环氧树脂、0.4mL正丁醇混合,在70℃下搅拌1h,待其冷却到25℃后加入三聚氰胺-尿素-甲醛混合溶液和2.50g间苯二酚,用0.1mol/L的稀盐酸调节pH为3.1,在70℃下均匀搅拌2h,反应结束后冷却到室温,将产物分别用丙酮、无水、去离子水抽滤3次,得到已经包覆成功的微胶囊。
将1.77g乙酸钴和0.68g 4-甲基咪唑分别溶解到25mL甲醇中,超声分散,将二者混合在一起,25℃下搅拌24h,将得到的溶液洗涤离心,在60℃下干燥12h,得到Co(MI)4AC2,得到由Co2+络合的潜伏固化剂。
将150mg氧化石墨烯分散在四氢呋喃中,超声分散,得到3mg/mL的氧化石墨烯溶液,在80℃下加热30min,得到分散的氧化石墨烯溶液。
将7.60g三聚氰酸三缩水甘油环氧树脂、0.34g Co(MI)4AC2、2.49g微胶囊分别加入到石墨烯分散溶液中,用机械浆缓慢搅拌均匀,再加入1.80g二氨基二苯基胺,在25℃下固化2h,80℃下固化1h,得到由Co2+络合的潜伏固化剂构成的已固化的氧化石墨烯改性自愈合微胶囊涂层,涂层有效使用时间为14天。
Claims (4)
1.一种石墨烯改性自愈合微胶囊涂层的制备方法,其步骤如下:
(1)微胶囊的制备:将1.00~6.30g三聚氰胺、1.8~9.00g尿素、2.70~13.48g甲醛溶液混合,用三乙醇胺调节反应体系pH为8~9,在60~80℃下搅拌0.5~2h,得到三聚氰胺-尿素-甲醛混合溶液;将1.00~3.00g吐温-80、1.00~4.00g三聚氰酸三缩水甘油环氧树脂、0.20~0.50mL正丁醇混合,在70~80℃下搅拌1.5~2.5h,待其冷却到室温后加入三聚氰胺-尿素-甲醛混合溶液和2.00~3.00g间苯二酚,用0.1mol/L稀盐酸调节pH为3~4,在70~80℃下均匀搅拌2~3h,反应结束后冷却到室温,将产物分别用丙酮、无水乙醇、去离子水抽滤2~3次,得到微胶囊;
(2)金属盐化合物与咪唑类化合物络合产物-潜伏固化剂的制备:将0.67~4.38g金属盐化合物和0.68~8.20g咪唑类化合物分别溶解到10~50mL甲醇中,超声分散;然后将二者混合在一起,25℃下搅拌12~24h,将得到的溶液洗涤离心,在50~70℃下干燥12~24h,得到潜伏固化剂;
(3)氧化石墨烯的分散:将100~300mg氧化石墨烯超声分散在四氢呋喃中,得到1~5mg/mL的氧化石墨烯分散溶液,在70~90℃下加热20~40min;
(4)石墨烯改性自愈合微胶囊涂层的制备:将步骤(3)得到的氧化石墨烯分散溶液中分别加入5.00~8.00g三聚氰酸三缩水甘油环氧树脂、0.20~0.40g步骤(2)制备的潜伏固化剂、1.00~3.00g步骤(1)制备的微胶囊,缓慢搅拌均匀,再加入1.20~2.00g固化剂,在25~40℃下固化1.5~3.0h,80~100℃下固化1~2h,从而得到本发明所述已固化的石墨烯改性自愈合微胶囊涂层。
2.如权利要求1所述的一种石墨烯改性自愈合微胶囊涂层的制备方法,其特征在于:金属盐化合物为氧化铜、硝酸铜、氢氧化铜、醋酸铜、氢氧化镍、氧化镍、无水碳酸镍、乙酸镍、乙酸钴、碳酸钴或六水硝酸钴中的一种;咪唑类化合物为1-乙烯基咪唑、4-硝基咪唑、1-丙基咪唑、2-丙基咪唑、1-乙酰基咪唑、4-乙酰基咪唑或4-甲基咪唑中的一种;固化剂为间苯二胺、二氨基二苯基甲烷、二氨基二苯基胺或间苯二甲胺中的一种。
3.如权利要求1所述的一种石墨烯改性自愈合微胶囊涂层的制备方法,其特征在于:金属盐化合物为氧化铜,咪唑类化合物为2-丙基咪唑,固化剂为间苯二胺。
4.一种石墨烯改性自愈合微胶囊涂层,其特征在于:是由权利要求1、2或3所述的方法制备得到。
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Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1927444A (zh) * | 2005-09-06 | 2007-03-14 | 西北工业大学 | 脲甲醛树脂双层膜包覆环氧树脂微胶囊及其制备方法 |
CN104945992A (zh) * | 2015-07-07 | 2015-09-30 | 上海理工大学 | 含石墨烯的自修复涂料及其制备方法 |
WO2015171429A1 (en) * | 2014-05-07 | 2015-11-12 | Wichita State University | Nanocomposite microcapsules for self-healing of composite articles |
KR20170052187A (ko) * | 2015-11-04 | 2017-05-12 | 한국기술교육대학교 산학협력단 | 자기치유성 마이크로캡슐, 이의 제조방법 및 이를 포함하는 코팅제 |
CN110627413A (zh) * | 2019-10-22 | 2019-12-31 | 江苏理工学院 | 一种自修复人造石英石及其制备方法 |
CN110975773A (zh) * | 2019-12-17 | 2020-04-10 | 肇庆市海特复合材料技术研究院 | 一种具备自修复功能环氧树脂微胶囊的制备方法 |
-
2020
- 2020-08-14 CN CN202010816416.6A patent/CN111995926A/zh active Pending
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1927444A (zh) * | 2005-09-06 | 2007-03-14 | 西北工业大学 | 脲甲醛树脂双层膜包覆环氧树脂微胶囊及其制备方法 |
WO2015171429A1 (en) * | 2014-05-07 | 2015-11-12 | Wichita State University | Nanocomposite microcapsules for self-healing of composite articles |
CN104945992A (zh) * | 2015-07-07 | 2015-09-30 | 上海理工大学 | 含石墨烯的自修复涂料及其制备方法 |
KR20170052187A (ko) * | 2015-11-04 | 2017-05-12 | 한국기술교육대학교 산학협력단 | 자기치유성 마이크로캡슐, 이의 제조방법 및 이를 포함하는 코팅제 |
CN110627413A (zh) * | 2019-10-22 | 2019-12-31 | 江苏理工学院 | 一种自修复人造石英石及其制备方法 |
CN110975773A (zh) * | 2019-12-17 | 2020-04-10 | 肇庆市海特复合材料技术研究院 | 一种具备自修复功能环氧树脂微胶囊的制备方法 |
Non-Patent Citations (2)
Title |
---|
TAO YIN: ""Self-healing epoxy composites – Preparation and effect of the healant consisting of microencapsulated epoxy and latent curing agent"", 《COMPOSITES SCIENCE AND TECHNOLOGY》 * |
卢少忠: "《建筑涂料工程 性能•生产•施工》", 31 August 2007, 中国建筑工业出版社 * |
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