CN111690364A - 一种单组份高温固化胶粘剂 - Google Patents
一种单组份高温固化胶粘剂 Download PDFInfo
- Publication number
- CN111690364A CN111690364A CN202010711599.5A CN202010711599A CN111690364A CN 111690364 A CN111690364 A CN 111690364A CN 202010711599 A CN202010711599 A CN 202010711599A CN 111690364 A CN111690364 A CN 111690364A
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- Prior art keywords
- diisocyanate
- polyol
- catalyst
- temperature curing
- component high
- Prior art date
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- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 6
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- NSPSPMKCKIPQBH-UHFFFAOYSA-K bismuth;7,7-dimethyloctanoate Chemical compound [Bi+3].CC(C)(C)CCCCCC([O-])=O.CC(C)(C)CCCCCC([O-])=O.CC(C)(C)CCCCCC([O-])=O NSPSPMKCKIPQBH-UHFFFAOYSA-K 0.000 claims description 4
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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 4
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- OEOIWYCWCDBOPA-UHFFFAOYSA-N 6-methyl-heptanoic acid Chemical compound CC(C)CCCCC(O)=O OEOIWYCWCDBOPA-UHFFFAOYSA-N 0.000 claims description 2
- UQOQXWZPXFPRBR-UHFFFAOYSA-K bismuth dodecanoate Chemical compound [Bi+3].CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O UQOQXWZPXFPRBR-UHFFFAOYSA-K 0.000 claims description 2
- NVJMGQMXNBBZIU-UHFFFAOYSA-N dibutyltin;1-dodecylsulfanyldodecane Chemical compound CCCC[Sn]CCCC.CCCCCCCCCCCCSCCCCCCCCCCCC NVJMGQMXNBBZIU-UHFFFAOYSA-N 0.000 claims description 2
- -1 polyoxypropylene Polymers 0.000 claims description 2
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- GMCXXHRAQIUECM-UHFFFAOYSA-N C(CCCCCCCCCCC)[S].C(CCCCCCCCCCC)[S].C(CCC)[Sn]CCCC Chemical compound C(CCCCCCCCCCC)[S].C(CCCCCCCCCCC)[S].C(CCC)[Sn]CCCC GMCXXHRAQIUECM-UHFFFAOYSA-N 0.000 description 1
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- C08G18/2805—Compounds having only one group containing active hydrogen
- C08G18/2815—Monohydroxy compounds
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- C08G18/2885—Compounds containing at least one heteroatom other than oxygen or nitrogen containing halogen atoms
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- C08G18/3206—Polyhydroxy compounds aliphatic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- Chemical & Material Sciences (AREA)
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- Adhesives Or Adhesive Processes (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
本发明公开了一种单组份高温固化胶粘剂,由聚氨酯预聚体与扩链剂复配而成,聚氨酯预聚体的合成材料包括聚醚多元醇,聚酯多元醇,二异氰酸酯,催化剂,有机溶剂,二异氰酸酯中的异氰酸酯基与聚醚多元醇、聚酯多元醇总的羟基的摩尔比为2:1~4:1,聚醚多元醇和聚酯多元醇的摩尔比为1:1~3:1,同时还公开了其制备方法。而通过本发明制备的聚氨酯胶粘剂对金属上具有优异的粘附力,初粘强度0.35‑0.55MPa,终粘强度7.1‑8.1MPa,拉伸强度10.3‑12.1MPa,断裂伸长率305‑378%,在150℃下9‑15分钟即固化,常温密闭储存时间超过100天。
Description
技术领域
本发明涉及胶粘剂领域,特别涉及一种单组份高温固化胶粘剂。
背景技术
聚氨酯胶粘剂以其高性能和能在苛刻的领域被使用而为大众所熟知。该种胶粘剂是由异氰酸酯和多元醇聚合而成的化合物。聚氨酯具有良好的耐磨、耐水、耐油、耐溶剂、耐化学药品、耐臭氧以及耐细菌等性能,因此它被广泛应用于纺织、家具、制鞋、电子工业、包装、建筑、汽车等领域。不同用途的聚氨酯胶粘剂有着不同的原材料选择,其取决于性能需求、加工过程及成本要求。根据形态的不同,聚氨酯胶粘剂可基本分为四大类:溶剂型、水性分散体、无溶剂型或高分子膜类。溶剂型胶粘剂和水性胶粘乳液可以在干燥后直接使用,或者可以通过添加一定量的异氰酸酯进行交联进而改善其热稳定性。
作为胶粘剂的主体原料,聚氨酯的结构与性能对粘接性能有举足轻重的影响。聚氨酯可以看作是一种含软链段和硬链段的嵌端共聚物。软段由低聚物多元醇组成,硬段由多异氰酸酯和小分子扩链剂组成。软段一般分为聚酯型多元醇和聚醚型多元醇,前者有较大的极性和内聚能,因此其粘结力要比聚醚型的大,拥有更好的耐油性和耐热性,但酯键易水解的特性使得其耐水解性较差。硬段与软段的比例会大幅影响聚氨酯的力学性能,由于硬段分布在软段中,呈现微相分离的海岛结构,硬段比例的增大会导致极性增大、分子间作用力增大,拉伸强度提高;而另一方面,软段含量减少使得材料的弹性回复能力下降,因而断裂伸长率下降、永久变形能力增大。因此,硬段含量存在一个最适值。
不同种类的聚氨酯胶粘剂各自存在不同的问题,例如溶剂型聚氨酯在使用时会产生较多的挥发性有机化合物(VOC)从而导致不够环保;水性聚氨酯则存在固化速度慢,初粘性、耐热性均低于溶剂型聚氨酯的问题。双组份异氰酸酯和多元醇要在胶粘剂使用之前快速混合,单组分聚氨酯胶粘剂也带来存在一些问题,附着力差、固化速度慢、粘接强度低等问题,虽说可通过加入一些有机金属和氨类催化剂加以改进,但又使储存稳定性大大下降,这使单组分聚氨酯胶粘剂的应用受到一些影响。
因此,亟需开发一种附着力强、可以在短时间内固化、固化效果良好、力学性能、储存性能优异的单组分聚氨酯粘合剂。
发明内容
本发明要解决的技术问题是提供一种单组份高温固化胶粘剂,该胶粘剂在金属上具有优异的粘附力,150℃下固化10-15分钟即可,固化后胶粘剂与金属间具有很高的剥离强度,可以作为金属的耐高温胶粘剂使用。
为了解决上述技术问题,本发明的技术方案为一种单组份高温固化胶粘剂,其由聚氨酯预聚体与扩链剂复配而成,聚氨酯预聚体的合成材料包括聚醚多元醇、聚酯多元醇、二异氰酸酯、催化剂、有机溶剂以及封端剂,其中,二异氰酸酯中的异氰酸酯基与聚醚多元醇、聚酯多元醇总的羟基的摩尔比为2:1~4:1,聚醚多元醇和聚酯多元醇的摩尔比为1:1~3:1;
进一步优选,聚醚多元醇包括聚氧化丙烯多元醇、聚四氢呋喃多元醇、四氢呋喃-氧化丙烯共聚多元醇、聚乙二醇中的至少一种,聚醚多元醇的分子量范围在400~4000;
进一步优选,聚酯多元醇包括己二酸系聚酯多元醇、聚己内酯聚酯多元醇中的至少一种,聚酯多元醇的分子量范围在1000~2000;
进一步优选,二异氰酸酯包括甲苯二异氰酸酯、异佛尔酮二异氰酸酯、二苯基甲烷二异氰酸酯、二环己基甲烷二异氰酸酯、六亚甲基二异氰酸酯中的至少一种;
进一步优选,所述催化剂的用量为聚醚多元醇,聚酯多元醇,二异氰酸酯总质量的0.2~0.4%;再进一步优选,所述的催化剂为单独的有机锡催化剂或为有机锡催化剂和有机铋催化剂的混合物;更进一步优选,所述催化剂同时包含有机锡催化剂和有机铋催化剂;再更进一步优选,所述有机锡催化剂包括二月桂酸二丁基锡、辛酸亚锡、二(十二烷基硫)二丁基锡、二醋酸二丁基锡中的至少一种,所述有机锡催化剂选自新癸酸铋、月桂酸铋、异辛酸铋、环烷酸铋中的至少一种;所述的有机锡催化剂和有机铋催化剂在添加到反应体系之前按质量比1:1-2进行混合;
进一步优选,有机溶剂包括甲苯、二甲苯、丙酮、乙酸乙酯中的至少一种;
进一步优选,聚氨酯预聚体中的异氰酸酯基与扩链剂含有的羟基的摩尔比为2:1~1:1;再进一步优选,所述扩链剂包括1,3-丁二醇、1,4-丁二醇、丙二醇、丙三醇、三羟甲基丙烷中的至少一种;
进一步优选,封端剂与异氰酸酯基的摩尔比为1:2~3:2,封端剂包括丙酮肟、甲乙酮肟、苯酚、邻氯苯酚、己内酰胺中的至少一种;
进一步优选,一种单组份高温固化聚氨酯胶粘剂的制备方法如下:
S1.在反应器里添加上述的聚醚多元醇,聚酯多元醇,二异氰酸酯,预热至75~85℃;
S2.滴加上述催化剂,反应时间为30分钟至2小时;
S3.滴加封端剂,反应温度为45~75℃,反应时间为30分钟至1小时;
S4.在所述的步骤S3的基础上通过有机溶剂调节反应体系的黏度,用量为整个反应体系体积的1~10%,若添加过少,体系黏度过大会影响后续步骤的实施,若添加过多则固化时可能会发生固化不完全和气泡较多的问题;
S5.加入所述扩链剂,反应温度为55~75℃,反应时间为15分钟至1小时。
采用上述技术方案,通过聚醚多元醇,聚酯多元醇,二异氰酸酯的混配,并通过控制其混合的比例,得到的胶粘剂对金属上具有优异的粘附力,初粘强度为0.35-0.55MPa,终粘强度为7.1-8.1MPa,拉伸强度10.3-12.1MPa,断裂伸长率为305-378%,该胶粘剂作为单组分聚氨酯,比起双组份聚氨酯无需考虑配比以及使用前的混合,其力学性能接近普通双组分聚氨酯,同时该胶粘剂采用对聚氨酯预聚体进行封端的方法,即使是单组份聚氨酯亦能拥有优异的储存性能,常温密闭储存时间超过100天,同时本发明胶粘剂固化时间短。而基于上述的优点,本发明可以应用于瓶盖印刷领域,相较于传统的需直接对铁片进行涂布胶粘剂,本发明可以直接作用于印刷凸头上,再印制于铁片上,实现具体位置的点涂,从而节省胶粘剂的用量。
具体实施方式
下面对本发明的具体实施方式作进一步说明。在此需要说明的是,对于这些实施方式的说明用于帮助理解本发明,但并不构成对本发明的限定。此外,下面所描述的本发明各个实施方式中所涉及的技术特征只要彼此之间未构成冲突就可以相互组合。
实施例1
具体的反应条件为:
S1.在反应器里添加聚氧化丙烯二醇,己二酸聚酯二醇,甲苯二异氰酸酯,其中异氰酸酯基和羟基的摩尔比为2:1,聚氧化丙烯二醇和己二酸聚酯二醇的摩尔比为1:1,预热至75~85℃;
S2.在S1的温度条件下,滴加二月桂酸二丁基锡催化剂,其用量为S1步骤中反应体系总质量的0.4%,反应时间为30分钟至2小时;
S3.滴加封端剂丙酮肟,封端剂与甲苯二异氰酸酯的异氰酸酯基的摩尔比为1:2,反应温度为45~75℃,反应时间为30分钟至1小时;
S4.在步骤S3的基础上通过甲苯调节反应体系的黏度,用量为整个反应体系体积的7%;
S5.加入扩链剂1,3-丁二醇,反应温度为55~75℃,反应时间为15分钟至1小时,其中异氰酸酯基和扩链剂中含有的羟基的摩尔比为2:1,反应完成后即得到单组份高温固化聚氨酯胶粘剂。
对聚氨酯胶粘剂的固化性能,力学性能以及储存性能按国家标准进行测试,其中,拉伸强度参照GB/T 528-2009检测;分别测试15分钟以及7天固化后的情况,对应作为初粘强度和终粘强度的检测。
测试结果表明,将聚氨酯胶粘剂置于金属板上,在150℃下加热12分钟即固化;
而对聚氨酯胶粘剂的力学性能进行测试,初粘强度为0.46MPa,终粘强度为7.5Mpa,拉伸强度10.3Mpa,断裂伸长率为330%;
本实施例的聚氨酯胶粘剂无需冷藏,常温密闭储存时间超过100天。
实施例2
本实施例中:
聚醚多元醇选择聚四氢呋喃三元醇;
聚酯多元醇选择聚己内酯聚酯二醇;
二异氰酸酯选择异佛尔酮二异氰酸酯;
催化剂选择辛酸亚锡;
有机溶剂选择甲苯;
扩链剂选择1,4-丁二醇;
封端剂选择甲乙酮肟;
其中,异氰酸酯基(异佛尔酮二异氰酸酯)和羟基(聚四氢呋喃三元醇、聚己内酯聚酯二醇加总)的摩尔比为3:1,聚四氢呋喃三元醇和聚己内酯聚酯二醇的摩尔比为2:1,辛酸亚锡添加量为反应体系总质量的0.3%,异氰酸酯基和扩链剂中含有的羟基的摩尔比为1:1,封端剂与异氰酸酯基的摩尔比为2:2,采用有机溶剂二甲苯调节反应体系的黏度,用量为反应体系体积的3%。
本实施例除上述不同外,其他反应条件及步骤均与实施例1相同。
测试结果:
将聚氨酯胶粘剂置于金属板上,在150℃下加热13分钟即固化;
而对聚氨酯胶粘剂的力学性能进行测试,初粘强度为0.40MPa,终粘强度为7.1Mpa,拉伸强度11.5Mpa,断裂伸长率为305%;
本实施例的聚氨酯胶粘剂无需冷藏,常温密闭储存时间超过100天。
实施例3
本实施例中:
聚醚多元醇选择四氢呋喃-氧化丙烯共聚二醇;
聚酯多元醇选择聚己内酯聚酯三醇;
二异氰酸酯选择二苯基甲烷二异氰酸酯;
催化剂选择二(十二烷基硫)二丁基锡;
有机溶剂选择丙酮;
扩链剂选择丙二醇;
封端剂选择苯酚;
其中,异氰酸酯基(二苯基甲烷二异氰酸酯)和羟基(四氢呋喃-氧化丙烯共聚二醇、聚己内酯聚酯三醇加总)的摩尔比为4:1,四氢呋喃-氧化丙烯共聚二醇和聚己内酯聚酯三醇的摩尔比为3:1,辛酸亚锡添加量为反应体系总质量的0.2%,异氰酸酯基和扩链剂中含有的羟基的摩尔比为1:1,封端剂与异氰酸酯基的摩尔比为3:2,采用有机溶剂丙酮调节反应体系的黏度,用量为反应体系体积的10%。
本实施例除上述不同外,其他反应条件及步骤均与实施例1相同。
测试结果:
将聚氨酯胶粘剂置于金属板上,在150℃下加热12分钟即固化;
而对聚氨酯胶粘剂的力学性能进行测试,初粘强度为0.35MPa,终粘强度为7.7Mpa,拉伸强度12.1Mpa,断裂伸长率为373%;
本实施例的聚氨酯胶粘剂无需冷藏,常温密闭储存时间超过100天。
实施例4
本实施例中:
聚醚多元醇选择聚氧化丙烯二醇;
聚酯多元醇选择己二酸聚酯二醇;
二异氰酸酯选择二环己基甲烷二异氰酸酯;
催化剂选择二醋酸二丁基锡;
有机溶剂选择丙酮;
扩链剂选择丙三醇;
封端剂选择邻氯苯酚;
其中,异氰酸酯基(二环己基甲烷二异氰酸酯)和羟基(聚氧化丙烯二醇、己二酸聚酯二醇加总)的摩尔比为2:1,聚氧化丙烯二醇和己二酸聚酯二醇的摩尔比为1:1,辛酸亚锡添加量为反应体系总质量的0.3%,异氰酸酯基和扩链剂中含有的羟基的摩尔比为1:1,封端剂与异氰酸酯基的摩尔比为2:2,采用有机溶剂丙酮调节反应体系的黏度,用量为反应体系体积的1%。
本实施例除上述不同外,其他反应条件及步骤均与实施例1相同。
测试结果:
将聚氨酯胶粘剂置于金属板上,在150℃下加热13分钟即固化;
而对聚氨酯胶粘剂的力学性能进行测试,初粘强度为0.5MPa,终粘强度为7.9Mpa,拉伸强度10.9Mpa,断裂伸长率为320%;
本实施例的聚氨酯胶粘剂无需冷藏,常温密闭储存时间超过100天。
实施例5
本实施例中:
聚醚多元醇选择聚乙二醇;
聚酯多元醇选择己二酸聚酯二醇;
二异氰酸酯选择六亚甲基二异氰酸酯;
催化剂选择二月桂酸二丁基锡;
有机溶剂选择乙酸乙酯;
扩链剂选择三羟甲基丙烷;
封端剂选择己内酰胺;
其中,异氰酸酯基(六亚甲基二异氰酸酯)和羟基(聚乙二醇、己二酸聚酯二醇加总)的摩尔比为2:1,聚乙二醇和己二酸聚酯二醇的摩尔比为1:1,辛酸亚锡添加量为反应体系总质量的0.3%,异氰酸酯基和扩链剂中含有的羟基的摩尔比为1:1,封端剂与异氰酸酯基的摩尔比为2:2,采用有机溶剂乙酸乙酯调节反应体系的黏度,用量为反应体系体积的5%。
本实施例除上述不同外,其他反应条件及步骤均与实施例1相同。
测试结果:
将聚氨酯胶粘剂置于金属板上,在150℃下加热15分钟即固化;
而对聚氨酯胶粘剂的力学性能进行测试,初粘强度为0.55MPa,终粘强度为8.1Mpa,拉伸强度10.8Mpa,断裂伸长率为362%;
本实施例的聚氨酯胶粘剂无需冷藏,常温密闭储存时间超过100天。
实施例6
本实施例中:
聚醚多元醇选择聚乙二醇;
聚酯多元醇选择己二酸聚酯二醇;
二异氰酸酯选择六亚甲基二异氰酸酯;
催化剂选择二月桂酸二丁基锡和新癸酸铋,两者按质量比1:2进行混合;
有机溶剂选择乙酸乙酯;
扩链剂选择三羟甲基丙烷;
封端剂选择己内酰胺;
其中,异氰酸酯基(六亚甲基二异氰酸酯)和羟基(聚乙二醇、己二酸聚酯二醇加总)的摩尔比为2:1,聚乙二醇和己二酸聚酯二醇的摩尔比为1:1,催化剂添加量为反应体系总质量的0.3%,异氰酸酯基和扩链剂中含有的羟基的摩尔比为1:1,封端剂与异氰酸酯基的摩尔比为2:2,采用有机溶剂乙酸乙酯调节反应体系的黏度,用量为反应体系体积的5%。
本实施例除上述不同外,其他反应条件及步骤均与实施例1相同。
测试结果:
将聚氨酯胶粘剂置于金属板上,在150℃下加热10分钟即固化;
而对聚氨酯胶粘剂的力学性能进行测试,初粘强度为0.53MPa,终粘强度为7.9Mpa,拉伸强度10.5Mpa,断裂伸长率为358%;
本实施例的聚氨酯胶粘剂无需冷藏,常温密闭储存时间超过100天。
实施例7
本实施例中:
聚醚多元醇选择聚乙二醇;
聚酯多元醇选择己二酸聚酯二醇;
二异氰酸酯选择六亚甲基二异氰酸酯;
催化剂选择辛酸亚锡和环烷酸铋,两者按质量比1:1进行混合;
有机溶剂选择乙酸乙酯;
扩链剂选择三羟甲基丙烷;
封端剂选择己内酰胺;
其中,异氰酸酯基(六亚甲基二异氰酸酯)和羟基(聚乙二醇、己二酸聚酯二醇加总)的摩尔比为2:1,聚乙二醇和己二酸聚酯二醇的摩尔比为1:1,催化剂添加量为反应体系总质量的0.3%,异氰酸酯基和扩链剂中含有的羟基的摩尔比为1:1,封端剂与异氰酸酯基的摩尔比为2:2,采用有机溶剂乙酸乙酯调节反应体系的黏度,用量为反应体系体积的5%。
本实施例除上述不同外,其他反应条件及步骤均与实施例1相同。
测试结果:
将聚氨酯胶粘剂置于金属板上,在150℃下加热9分钟即固化;
而对聚氨酯胶粘剂的力学性能进行测试,初粘强度为0.5MPa,终粘强度为8.4Mpa,拉伸强度10.3Mpa,断裂伸长率为378%;
本实施例的聚氨酯胶粘剂无需冷藏,常温密闭储存时间超过100天。
实施例8
本实施例中:
聚醚多元醇选择聚乙二醇;
聚酯多元醇选择己二酸聚酯二醇;
二异氰酸酯选择六亚甲基二异氰酸酯;
催化剂选择辛酸亚锡和环烷酸铋,两者按质量比1:1进行混合;
有机溶剂选择乙酸乙酯;
扩链剂选择三羟甲基丙烷;
封端剂选择己内酰胺;
其中,异氰酸酯基(六亚甲基二异氰酸酯)和羟基(聚乙二醇、己二酸聚酯二醇加总)的摩尔比为2:1,聚乙二醇和己二酸聚酯二醇的摩尔比为1:1,催化剂添加量为反应体系总质量的0.3%,异氰酸酯基和扩链剂中含有的羟基的摩尔比为1:1,封端剂与异氰酸酯基的摩尔比为2:2,采用有机溶剂乙酸乙酯调节反应体系的黏度,用量为反应体系体积的5%。
本实施例除上述不同外,其他反应条件及步骤均与实施例1相同。
测试结果:
将聚氨酯胶粘剂置于金属板上,在150℃下加热9分钟即固化;
而对聚氨酯胶粘剂的力学性能进行测试,初粘强度为0.58MPa,终粘强度为8.6Mpa,拉伸强度10.7Mpa,断裂伸长率为361%;
本实施例的聚氨酯胶粘剂无需冷藏,常温密闭储存时间超过100天。
对比例1
具体的反应条件为:
S1.在反应器里添加聚氧化丙烯二醇,甲苯二异氰酸酯,其中异氰酸酯基和羟基的摩尔比为2:1,预热至75~85℃;
S2.在S1的温度条件下,滴加二月桂酸二丁基锡催化剂,其用量为S1步骤中反应体系总质量的0.4%,反应时间为30分钟至2小时;
S3.滴加封端剂丙酮肟,封端剂与甲苯二异氰酸酯的异氰酸酯基的摩尔比为1:2,反应温度为45~75℃,反应时间为30分钟至1小时;
S4.在步骤S3的基础上通过甲苯调节反应体系的黏度,用量为整个反应体系体积的7%;
S5.加入扩链剂1,3-丁二醇,反应温度为55~75℃,反应时间为15分钟至1小时,其中异氰酸酯基和扩链剂中含有的羟基的摩尔比为2:1,反应完成后即得到单组份高温固化聚氨酯胶粘剂。
测试结果:
将聚氨酯胶粘剂置于金属板上,在150℃下加热18分钟即固化;
而对聚氨酯胶粘剂的力学性能进行测试,初粘强度为0.15MPa,终粘强度为4.2Mpa,拉伸强度5.8Mpa,断裂伸长率为180%;
本实施例的聚氨酯胶粘剂无需冷藏,常温密闭储存时间超过100天。
对比例2
具体的反应条件为:
S1.在反应器里添加己二酸聚酯二醇,甲苯二异氰酸酯,其中异氰酸酯基和羟基的摩尔比为2:1,预热至75~85℃;
S2.在S1的温度条件下,滴加二月桂酸二丁基锡催化剂,其用量为S1步骤中反应体系总质量的0.4%,反应时间为30分钟至2小时;
S3.滴加封端剂丙酮肟,封端剂与甲苯二异氰酸酯的异氰酸酯基的摩尔比为1:2,反应温度为45~75℃,反应时间为30分钟至1小时;
S4.在步骤S3的基础上通过甲苯调节反应体系的黏度,用量为整个反应体系体积的7%;
S5.加入扩链剂1,3-丁二醇,反应温度为55~75℃,反应时间为15分钟至1小时,其中异氰酸酯基和扩链剂中含有的羟基的摩尔比为2:1,反应完成后即得到单组份高温固化聚氨酯胶粘剂。
测试结果:
将聚氨酯胶粘剂置于金属板上,在150℃下加热20分钟即固化;
而对聚氨酯胶粘剂的力学性能进行测试,初粘强度为0.32MPa,终粘强度为6.1Mpa,拉伸强度7.1Mpa,断裂伸长率为242%;
本实施例的聚氨酯胶粘剂无需冷藏,常温密闭储存时间小于60天。
以上实施例中,聚醚多元醇的分子量范围在400~4000;聚酯多元醇的分子量范围在1000~2000;并且上述实施例中的聚醚多元醇、聚酯多元醇为二元醇或三元醇,但本发明对聚醚多元醇、聚酯多元醇中羟基的数量没有限制,在这里仅仅作为示例,并不是对其进行限制,只要其满足分子量以及反应基团之间的比例即可。
本发明所获得的聚氨酯胶粘剂,其不仅具体快速固化的效果,在150℃下最快仅需9分钟,同时固化后其力学性能也能得到保证,同时通过对聚氨酯预聚体进行封端,也保证了储存性能,在常温密闭储存时间超过100天。而通过实施例5-8可以发现,在实施例6-8中减少有机锡催化剂,并换成有机铋催化剂,本领域技术人员清楚,有机铋催化剂相对于有机锡催化剂来说,其催化效率要低得多,但其固化时间却并不比实施例5慢,而且反而更快,证明有机锡催化剂与有机铋催化剂一起可以加快催化效率,起到协同增效的作用。
本发明的胶粘剂可广泛地应用于各个行业,特别是对于铁瓶盖制造行业来说,该胶粘剂的出现,对其制造工艺产生了极大的影响,本发明的胶粘剂对金属具有强的吸附性能,使铁瓶盖制造能够直接通过辊轮凸印将胶粘剂直接印制于铁片上,而不是传统的先进行铁片涂布胶粘剂,再通过辊轮凸印印出相应的位置,而位于铁片其他位置的胶粘剂则随铁片废料一起丢弃。
而本发明的胶粘剂,除了上述铁瓶盖行业的应用外,还可用于作为瓶盖的垫片以及作为密封圈材料。
Claims (10)
1.一种单组份高温固化胶粘剂,其特征在于:其由聚氨酯预聚体与扩链剂复配而成,聚氨酯预聚体的合成材料包括聚醚多元醇、聚酯多元醇、二异氰酸酯、催化剂、有机溶剂以及封端剂,其中,二异氰酸酯中的异氰酸酯基与聚醚多元醇、聚酯多元醇总的羟基的摩尔比为2:1~4:1,聚醚多元醇和聚酯多元醇的摩尔比为1:1~3:1。
2.根据权利要求1所述的单组份高温固化胶粘剂,其特征在于:所述聚醚多元醇包括聚氧化丙烯多元醇、聚四氢呋喃多元醇、四氢呋喃-氧化丙烯共聚多元醇、聚乙二醇中的至少一种,聚醚多元醇的分子量范围在400~4000。
3.根据权利要求1所述的单组份高温固化胶粘剂,其特征在于:所述聚酯多元醇包括己二酸系聚酯多元醇、聚己内酯聚酯多元醇中的至少一种,聚酯多元醇的分子量范围在1000~2000。
4.根据权利要求1所述的单组份高温固化胶粘剂,其特征在于:所述二异氰酸酯包括甲苯二异氰酸酯、异佛尔酮二异氰酸酯、二苯基甲烷二异氰酸酯、二环己基甲烷二异氰酸酯、六亚甲基二异氰酸酯中的至少一种。
5.根据权利要求1至4中任一项所述的单组份高温固化胶粘剂,其特征在于:所述催化剂的用量为聚醚多元醇,聚酯多元醇,二异氰酸酯总质量的0.2~0.4%。
6.根据权利要求5所述的单组份高温固化聚氨酯胶粘剂,其特征在于:所述的催化剂包括有机锡催化剂和有机铋催化剂至少一种,所述有机锡催化剂选自二月桂酸二丁基锡、辛酸亚锡、二(十二烷基硫)二丁基锡、二醋酸二丁基锡中的至少一种;所述有机锡催化剂选自新癸酸铋、月桂酸铋、异辛酸铋、环烷酸铋中的至少一种。
7.根据权利要求1所述的单组份高温固化胶粘剂,其特征在于:所述有机溶剂包括甲苯、二甲苯、丙酮、乙酸乙酯中的至少一种。
8.根据权利要求1所述的单组份高温固化胶粘剂,其特征在于:所述异氰酸酯基与扩链剂含有的羟基的摩尔比为2:1~1:1,所述扩链剂包括1,3-丁二醇、1,4-丁二醇、丙二醇、丙三醇、三羟甲基丙烷中的至少一种。
9.根据权利要求1所述的单组份高温固化胶粘剂,其特征在于:所述封端剂与异氰酸酯基的摩尔比为1:2~3:2,所述封端剂包括丙酮肟、甲乙酮肟、苯酚、邻氯苯酚、己内酰胺中的至少一种。
10.一种如权利要求1至9中任一项所述的单组份高温固化胶粘剂的制备方法,其特征在于:制备方法如下,
S1.在反应器里添加所述的聚醚多元醇,聚酯多元醇,二异氰酸酯,预热至75~85℃;
S2.滴加所述催化剂,反应时间为30分钟至2小时;
S3.滴加封端剂,反应温度为45~75℃,反应时间为30分钟至1小时;
S4.在所述的步骤S2的基础上通过有机溶剂调节反应体系的黏度,用量为整个溶液体系体积的1~10%;
S5.加入所述扩链剂,反应温度为55~75℃,反应时间为15分钟至1小时。
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