CN114716961A - 一种自互补四重氢键超分子热熔胶及其合成方法 - Google Patents
一种自互补四重氢键超分子热熔胶及其合成方法 Download PDFInfo
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Abstract
本发明属于胶粘剂技术领域,具体涉及一种自互补四重氢键超分子热熔胶及其合成方法,所述超分子热熔胶是由以下摩尔当量份原料合成:1.0当量份大分子多元醇、2.0~2.8当量份芳香族二异氰酸酯、2.0~3.6当量份嘧啶酮衍生物。本发明在大分子二元醇链末端引入刚性苯环和含自互补四重氢键的脲基嘧啶酮基元(UPy),原料来源广泛、合成路线简单;UPy之间具有非常高的氢键结合能,可充当非共价交联基元,在室温下缔合得到高强度超分子树脂,在高温下解离,赋予超分子热熔胶重复粘接能力。该超分子热熔胶粘流温度为92~106℃,可在较低温度(120℃)下实现热熔粘接,对铝合金、钢板和环氧基材的粘接强度均大于3.2MPa,可重复使用,便于售后维修服务和工厂返修。
Description
技术领域
本发明属于胶粘剂技术领域,具体涉及一种自互补四重氢键超分子热熔胶及其合成方法。
背景技术
反应型聚氨酯热熔胶(简称PUR)是一类含端异氰酸根基团(-NCO)的聚氨酯胶粘剂。使用时,加热熔融后施胶,待胶层冷却物理固化后产生初步的粘接力后,胶层中的异氰酸根与空气中的湿气或被粘物表面的活泼氢化合物反应产生化学交联固化。与其他类型的热熔胶相比,具有使用方便,弹性高,耐溶剂,耐磨等优良性能。因此,湿固化聚氨酯热熔胶广泛的应用于汽车工业、制鞋工业、织物、木材工业、电子工业和书刊装订工业等。湿固化聚氨酯热熔胶最先是由美国于20世纪80年代初开发出来的,我国聚氨酯类胶粘剂研发起步较晚,所以目前聚氨酯类胶粘剂的高端品牌仍被国外所垄断。
PUR因其强粘附能力被广泛应用在电子、电气产品领域,然而完全固化的PUR不能被熔融,因此其粘接件难以被拆除,不便于产品的维修和维护。非反应型的TPU热熔胶能够被熔融,但其粘接强度不如PUR,且熔融温度较高熔体粘度大,其熔融通常高于120℃。如何获得兼顾高粘附能力和适宜熔融温度的非反应型热熔胶,具有挑战性和工业应用价值。
发明内容
本发明的目的在于克服上述现有技术的不足之处而提供一种自互补四重氢键超分子热熔胶及其合成方法。
为实现上述目的,本发明所采取的技术方案为:
一种自互补四重氢键超分子热熔胶,由以下摩尔当量份原料合成:
大分子多元醇1.0当量份;
芳香族二异氰酸酯2.0~2.8当量份;
嘧啶酮衍生物2.0~3.6当量份。
优选地,所述大分子多元醇为数均分子量400-5000g/mol的聚己内酯二元醇、聚对苯二甲酸乙二醇酯二元醇、聚碳酸酯二元醇、聚碳酸亚丙酯二元醇、聚四亚甲基醚二元醇、聚氧化丙烯二元醇中的一种或多种混合物。
优选地,所述芳香族二异氰酸酯为4,4’-二苯基甲烷二异氰酸酯、2,4’-二苯基甲烷二异氰酸酯、甲苯-2,4-二异氰酸酯、对苯二异氰酸酯中的一种或多种混合物。
优选地,所述嘧啶酮衍生物为胞嘧啶(CAS号71-30-7)、1-甲基胞嘧啶(1122-47-0)、5-甲基胞嘧啶(554-01-8)、2-氨基-4-羟基-6-甲基嘧啶(CAS号3977-29-5)、2-氨基-4-羟基嘧啶(CAS号108-53-2)、5,6-二甲基-2-氨基-4-羟基嘧啶(CAS号3977-23-9)、2-氨基-5-乙氧羰基-4-羟基嘧啶(CAS号15400-53-0)、2-氨基-(6苯甲基)-4(3H)嘧啶酮(CAS号717-88-4)、2-氨基-4-羟基-6-苯基嘧啶(CAS号56741-94-7)中的一种或多种混合物。
本发明还提供了所述自互补四重氢键超分子热熔胶的合成方法,包括如下步骤:
(1)将1.0当量份大分子多元醇投入反应釜中混合,在-0.1MPa真空度下加热至110℃除水1小时,降温至80℃,加入2.0~2.8当量份芳香族二异氰酸酯,搅拌反应1小时,加入催化剂继续搅拌反应1小时,得到聚氨酯预聚体;
(2)投入稀释剂调节粘度,将2.0~3.6当量份的嘧啶酮衍生物分2~4次投入反应体系,通过傅里叶变换红外监控NCO特征峰消失后停止反应,除去稀释剂,得到超分子热熔胶。
优选地,所述催化剂为有机锡类化合物,更优选地,所述催化剂为二月桂酸二丁基锡、双(乙酰丙酮酸)二丁基锡中的一种或两种混合物,催化剂用量为大分子多元醇、芳香族二异氰酸酯和嘧啶酮衍生物总质量的0.05%。
优选地,所述稀释剂为N,N-二甲基甲酰胺、二甲基亚砜、,N-甲基吡咯烷酮、N,N-二甲基乙酰胺中的一种或多种混合物,稀释剂用量为大分子多元醇、芳香族二异氰酸酯和嘧啶酮衍生物总质量的2倍。
优选地,所述自互补四重氢键超分子热熔胶的粘流温度为92~106℃。
优选地,所述自互补四重氢键超分子热熔胶根据HG/T 3660A法测试120℃下的熔融粘度为8900~13500mPa·s。
优选地,按照GB/T 7214-2008测定,所述自互补四重氢键超分子热熔胶对铝合金、钢板、环氧无机非金属基材的搭接剪切强度均大于3.2MPa,可用于金属与金属的粘结,也可用于金属与无机非金属基材的粘接。
相对于现有技术,本发明的有益效果如下:
(1)本发明含单官能度氨基的嘧啶酮衍生物与聚氨酯预聚体主链末端的异氰酸根反应生成脲基嘧啶酮结构(UPy),原料来源广泛、合成路线简单。
(2)UPy之间具有非常高的氢键结合能,可充当非共价交联基元,在室温下缔合得到高强度超分子树脂,在高温下解离,赋予超分子热熔胶重复粘接能力。
(3)本发明的超分子热熔胶粘流温度低,可在较低温度(120℃)下实现热熔粘接,相比于反应型热熔胶PUR,可重复使用,经80℃左右烘烤10~30分钟易于揭开粘接基材,降至室温亦能恢复高强度粘接,便于售后维修服务和工厂返修。
附图说明
图1,实施例8样品对铝板、钢板、环氧基材搭接样品的剪切强度-位移曲线。
图2,实施例8样品的温度扫描流变结果。
具体实施实例
为更好的说明本发明的目的、技术方案和优点,下面将结合具体实施例对本发明作进一步说明。
本发明实施例及对比例中实验所用的原料如下,但是不限于以下原料,本发明只是以以下原料为具体例子来进一步具体说明本发明中所述自互补四重氢键超分子热熔胶及其合成方法的效果。
聚己内酯二元醇:PCL 2102,数均分子量1000g/mol,深圳志道。
聚对苯二甲酸乙二醇酯二元醇:Dynacoll 7360,数均分子量3500g/mol,德国赢创。
聚碳酸酯二元醇:PCDL 1011,数均分子量1000g/mol,广州昊毅。
芳香族二异氰酸酯:MDI-50,烟台万华。
脂肪族二异氰酸酯:六亚甲基二异氰酸酯(HDI),山东豪顺化工。
嘧啶酮衍生物:胞嘧啶,河南君柘化工。
氨基吡啶:2-氨基吡啶,南通润丰石油化工。
本发明设置实施例1~8及对比例1~4,其配方如表1所示:
表1
实施例1~8按下述工艺制备:
(1)将总计1.0当量份大分子多元醇投入反应釜中混合,在-0.1MPa真空度下加热至110℃除水1小时,降温至80℃,加入2.0~2.8当量份芳香族二异氰酸酯,搅拌反应1小时,加入催化剂继续搅拌反应1小时,得到聚氨酯预聚体;
(2)投入稀释剂调节粘度,将2.0~3.6当量份的胞嘧啶分2~4次投入反应体系,通过傅里叶变换红外监控NCO特征峰消失后停止反应,除去稀释剂,得到超分子热熔胶。
对比例1~4按下述工艺制备:
(1)将总计1.0当量份大分子多元醇投入反应釜中混合,在-0.1MPa真空度下加热至110℃除水1小时,降温至80℃,加入2.0~3.0当量份芳香族二异氰酸酯或脂肪族二异氰酸酯,搅拌反应1小时,加入催化剂继续搅拌反应1小时,得到聚氨酯预聚体;
(2)投入稀释剂调节粘度,将2.0~4.0当量份的胞嘧啶或2-氨基吡啶分2~4次投入反应体系,通过傅里叶变换红外监控NCO特征峰消失后停止反应,除去稀释剂,得到超分子热熔胶。
本发明实施例及对比例所制得成品在120℃下施胶制样品;粘流温度采用旋转流变仪测定,应变幅度0.1%,频率1Hz,温度范围25~180℃,通过储能模量与损耗模量的交点确定粘流温度;120℃熔融粘度根据HG/T 3660A法测定;搭接剪切强度根据GB/T 7124-2008规定的方法测定。
本发明实施例1~8及对比例1~4的性能评价结果如表2所示:
表2
从表2可以看出,超分子主链末端含自互补四重氢键基元UPy的实施例1~8,剪切强度高,粘流温度和熔融粘度适中,适于实际应用场景。而芳香族二异氰酸酯和嘧啶酮衍生物高出本发明限定配比的对比例1,尽管剪切强度优异,但熔融粘度显著增大,影响施工。采用脂肪族二异氰酸酯的对比例2,链末端刚性降低,粘流温度和熔融粘度下降,由于本体强度下降,相应的剪切强度也下降。采用2-氨基吡啶封端的对比例3~4,链末端无多重氢键基元,粘流温度和熔融粘度明显降低,剪切强度也大幅降低。由此表明,本发明在大分子多元醇链末端引入带刚性苯环和自互补四重氢键基元UPy,赋予材料适宜的粘流温度、熔融粘度和较高的剪切强度。
最后所应当说明的是,以上实施例仅用以说明本发明的技术方案而非对本发明保护范围的限制,尽管参照较佳实施例对本发明作了详细说明,本领域的普通技术人员应当理解,可以对本发明的技术方案进行修改或者等同替换,而不脱离本发明技术方案的实质和范围。
Claims (10)
1.一种自互补四重氢键超分子热熔胶,其特征在于,由以下摩尔当量份原料合成:1.0当量份大分子多元醇、2.0~2.8当量份芳香族二异氰酸酯、2.0~3.6当量份嘧啶酮衍生物。
2.如权利要求1所述的自互补四重氢键超分子热熔胶,其特征在于,所述大分子多元醇为数均分子量400-5000g/mol的聚己内酯二元醇、聚对苯二甲酸乙二醇酯二元醇、聚碳酸酯二元醇、碳酸亚丙酯二元醇、聚四亚甲基醚二元醇、聚氧化丙烯二元醇中的一种或多种混合物。
3.如权利要求1所述的自互补四重氢键超分子热熔胶,其特征在于,所述芳香族二异氰酸酯为4,4’-二苯基甲烷二异氰酸酯、2,4’-二苯基甲烷二异氰酸酯、甲苯-2,4-二异氰酸酯、对苯二异氰酸酯中的一种或多种混合物。
4.如权利要求1所述的自互补四重氢键超分子热熔胶,其特征在于,所述嘧啶酮衍生物为胞嘧啶、1-甲基胞嘧啶、5-甲基胞嘧啶、2-氨基-4-羟基-6-甲基嘧啶、2-氨基-4-羟基嘧啶、5,6-二甲基-2-氨基-4-羟基嘧啶、2-氨基-5-乙氧羰基-4-羟基嘧啶、2-氨基-(6苯甲基)-4(3H)嘧啶酮、2-氨基-4-羟基-6-苯基嘧啶中的一种或多种混合物。
5.一种如权利要求1~4任一项所述的自互补四重氢键超分子热熔胶的合成方法,其特征在于,包括如下步骤:
(1)将1.0当量份大分子多元醇投入反应釜中混合,在-0.1MPa真空度下加热至110℃除水1小时,降温至80℃,加入2.0~2.8当量份芳香族二异氰酸酯,搅拌反应1小时,加入催化剂继续搅拌反应1小时,得到聚氨酯预聚体;
(2)投入稀释剂调节粘度,将2.0~3.6当量份的嘧啶酮衍生物分2~4次投入反应体系,通过傅里叶变换红外监控NCO特征峰消失后停止反应,除去稀释剂,得到超分子热熔胶。
6.如权利要求5所述的自互补四重氢键超分子热熔胶的合成方法,其特征在于,所述催化剂为二月桂酸二丁基锡、双(乙酰丙酮酸)二丁基锡中的一种或两种混合物,催化剂用量为大分子多元醇、芳香族二异氰酸酯和嘧啶酮衍生物总质量的0.05%。
7.如权利要求5所述的自互补四重氢键超分子热熔胶的合成方法,其特征在于,所述稀释剂为N,N-二甲基甲酰胺、二甲基亚砜、N-甲基吡咯烷酮、N,N-二甲基乙酰胺中的一种或多种混合物,稀释剂用量为大分子多元醇、芳香族二异氰酸酯和嘧啶酮衍生物总质量的2倍。
8.如权利要求1~4任一项所述的自互补四重氢键超分子热熔胶,其特征在于,所述自互补四重氢键超分子热熔胶的粘流温度为92~106℃。
9.如权利要求1~4任一项所述的自互补四重氢键超分子热熔胶,其特征在于,所述自互补四重氢键超分子热熔胶根据HG/T 3660 A法测试120℃下的熔融粘度为8900~13500mPa·s。
10.如权利要求1~4任一项所述的自互补四重氢键超分子热熔胶,其特征在于,按照GB/T 7214-2008测试,所述自互补四重氢键超分子热熔胶对铝合金、钢板和环氧基材的搭接剪切强度均大于3.2MPa。
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Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5208270A (en) * | 1992-01-03 | 1993-05-04 | The Dow Chemical Company | Catalyst systems useful for forming isocyanurate, amide and/or oxazolidinone groups and a method for their use |
US20070054131A1 (en) * | 2005-09-07 | 2007-03-08 | Stewart Kevin J | Optical elements that include curable film-forming compositions containing blocked isocyanate adhesion promoters |
CN106279619A (zh) * | 2016-08-25 | 2017-01-04 | 华南理工大学 | 一种基于氢键作用热驱动自修复弹性体的制备方法 |
CN109181555A (zh) * | 2018-07-11 | 2019-01-11 | 惠州市德佑威电子材料有限公司 | 一种高初始强度反应型聚氨酯热熔胶及其制备方法 |
CN110627993A (zh) * | 2019-10-22 | 2019-12-31 | 华南理工大学 | 一种含四重氢键的水性聚氨酯分散体及其制备方法 |
-
2022
- 2022-05-04 CN CN202210477295.6A patent/CN114716961B/zh active Active
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5208270A (en) * | 1992-01-03 | 1993-05-04 | The Dow Chemical Company | Catalyst systems useful for forming isocyanurate, amide and/or oxazolidinone groups and a method for their use |
US20070054131A1 (en) * | 2005-09-07 | 2007-03-08 | Stewart Kevin J | Optical elements that include curable film-forming compositions containing blocked isocyanate adhesion promoters |
CN106279619A (zh) * | 2016-08-25 | 2017-01-04 | 华南理工大学 | 一种基于氢键作用热驱动自修复弹性体的制备方法 |
CN109181555A (zh) * | 2018-07-11 | 2019-01-11 | 惠州市德佑威电子材料有限公司 | 一种高初始强度反应型聚氨酯热熔胶及其制备方法 |
CN110627993A (zh) * | 2019-10-22 | 2019-12-31 | 华南理工大学 | 一种含四重氢键的水性聚氨酯分散体及其制备方法 |
Non-Patent Citations (1)
Title |
---|
高菲;曹建诚;刘敬成;刘仁;袁妍;刘晓亚;: "聚碳酸酯二元醇基光固化自修复聚氨酯的制备及性能研究", 涂料工业, no. 10 * |
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