CN111394040B - 一种高性能双组分聚氨酯胶黏剂及其制备方法 - Google Patents
一种高性能双组分聚氨酯胶黏剂及其制备方法 Download PDFInfo
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Abstract
本发明属于聚氨酯胶黏剂技术领域,具体地涉及一种高性能双组分聚氨酯胶黏剂及其制备方法。该双组分聚氨酯胶黏剂所述组分A包括的成分有:异佛尔酮‑二异氰酸酯、磺化聚醚多元醇、聚已内酯二醇、二月桂酸二丁基锡、二羟甲基丁酸、丙酮、水性阴离子型聚氨酯分散体、三乙胺和乙二胺,组分B包括的成分有:异佛尔酮‑二异氰酸酯、聚己二酸1,6己二醇酯和海藻糖。本发明的双组份聚氨酯胶黏剂具有高固含量、粘度低、粘接强度高,耐热性、耐水性好、无污染的特点。本发明制备方法,工艺简单、操作方便、溶剂易于回收处理,节约了成本。
Description
技术领域
本发明属于聚氨酯胶黏剂领域,具体涉及一种高性能双组分聚氨酯胶黏剂及其制备方法。
背景技术
双组份聚氨酯胶黏剂主要是由含羟基的水性多元醇组份(组份A)和含异氰酸酯基的多异氰酸酯组份(B组份)共用组成的。此外,体系中还含其他一些特殊用途的助剂。组份A和B组份是分开包装,使用前要将两组份均匀混合,通过调节组份A和B组份的比例,利用多元醇中的羟基基团(-OH)与多异氰酸酯中的异氰酸酯基团(-NCO)发生交联反应形成氨基甲酸酯,便可改变聚氨酯材料的强度、固化时间等各方面性。
目前,现有市面上销售的双组份聚氨酯胶黏剂,配制出来的混合组分,其黏度均较高,导致流动性较差,进而影响其流平性和增加上胶量,如果降低了黏度,其粘接强度又变低,对于低极性鞋材如SBS等材质的粘接,其剥离强度往往达不到要求,因此,寻找一种高固含量、黏度低、同时具有高粘接强度的双组份聚氨酯胶黏剂是本领域技术人员致力研究的课题。
发明内容
本发明为了克服现有技术的基础上,提供了一种高性能双组分聚氨酯胶黏剂及其制备方法。本发明制备得到的双组份聚氨酯胶黏剂具有高固含量、粘度低、粘接强度高,耐热性、耐水性好、无污染的特点;本发明聚氨酯胶黏剂的制备方法,工艺简单、操作方便、溶剂易于回收处理,节约成本。
为了实现上述目的,本发明采用以下技术方案:
一方面,提供了一种高性能双组分聚氨酯胶黏剂,包括组分A和组分B:
组分A包括如下重量份数的组分:异佛尔酮-二异氰酸酯15~30份、聚已内酯二醇5~10份、二月桂酸二丁基锡0.5~3份、二羟甲基丁酸1~3份、丙酮4~8份、水性阴离子型聚氨酯分散体U54 0.5~2份、三乙胺1~6份和乙二胺4~8份;
组分B包括如下重量份数的组分:4,4'-二环己基甲烷二异氰酸酯5~15份、磺化聚醚多元醇8~15份、聚己二酸1,6己二醇酯5~15份和海藻糖4~8份。
进一步地,包括组分A和组分B:
组分A包括如下重量份数的组分:异佛尔酮-二异氰酸酯20~25份、聚已内酯二醇5~8份、二月桂酸二丁基锡0.5~2份、二羟甲基丁酸1~3份、丙酮4~6份、水性阴离子型聚氨酯分散体U54 0.5~2份、三乙胺2~4份和乙二胺4~6份;
组分B包括如下重量份数的组分:4,4'-二环己基甲烷二异氰酸酯5~10份、磺化聚醚多元醇8~12份、聚己二酸1,6己二醇酯10~15份和海藻糖4~6份。
进一步地,双组分聚氨酯胶黏剂的A组分所含羟基与B组分所含异氰酸酯基团的当量比为1∶0.2至1∶5。
另一方面,提供了一种高性能双组分聚氨酯胶黏剂的制备方法,制备方法包括如下步骤:
(1)称取异佛尔酮-二异氰酸酯至反应瓶中,脱水处理,加入催化剂二月桂酸二丁基锡和聚已内酯二醇,在60~70℃下恒温反应1~2h,加入丙酮降低粘度,再加入二羟甲基丁酸恒温反应1~2h,冷却后用加入三乙胺中和,在高速搅拌下加入预先混合好的水性阴离子型聚氨酯分散体U54和去离子水,乳化10~20min后,然后加入乙二胺扩链50~70min,最后减压蒸出溶剂后,得组分A;
(2)称取4,4'-二环己基甲烷二异氰酸酯、磺化聚醚多元醇、聚己二酸1,6己二醇酯至反应瓶中,脱水处理,再加入海藻糖,在70~80℃下恒温反应4~6h,得组分B;
(3)将步骤(1)制得的组分A和步骤(2)制得的组分B进行混合,得双组分聚氨酯胶黏剂。
进一步地,步骤(1)中高速搅拌的搅拌速度为17000~18000r/min
进一步地,制备方法中,步骤(1)在减压蒸馏脱除溶剂后,还包括向反应液中加入消泡剂和增稠剂。
进一步地,消泡剂为水性消泡剂Afcona 2501、Afcona 2502或Afcona 2524中的任意一种;增稠剂为SHEUR或LHEUR中的任意一种。
本发明的积极效果如下:
1.本发明选用磺化聚醚多元醇和聚己二酸1,6己二醇酯作为主要的固体物质来源,磺化聚醚多元醇和聚己二酸1,6己二醇酯的可以提高聚氨酯粒径,从而提高固含量,同时固含量的提高有利于粘接强度剂剥离强度的提高。
2.本发明选用海藻糖作为内交联剂,不但能增加聚氨酯粒径,而且使聚氨酯粒径分布变宽且分布均匀。由于海藻糖具有交联和扩链效果,使生成的聚氨酯分子量增长,分子链相互缠结,导致粒径增大,另一方面,海藻糖分子的刚性较大,参与反应后,在聚氨酯中形成了更多的疏水的硬段结构,导致乳液的平均粒径增大,从而使得胶膜的粘结强度、耐水性以及机械强度得到大幅度提高。
3.本发明选用磺酸型扩链剂二羟甲基丁酸作为亲水扩链剂,由于含有羧基和羟基等亲水基团,能减薄水合层,增强乳液流动性,一定程度上降低了聚氨酯的黏度。
4.本发明制备方法,工艺简单、操作方便、溶剂易于回收处理,获得的产品应用于制鞋业上,由于固含量高、黏度低、粘接强度高,耐水性好,在胶粘鞋生产过程中,极大方便了施工,也可降低鞋材的上胶量,不仅能保证质量,而且节约了成本。
具体实施方式
下面结合实施例对本发明做进一步的描述,有必要在此指出的是以下实施例只是用于对本发明进行进一步的说明,不能理解为对本发明保护范围的限制,该领域的技术熟练人员根据上述发明内容所做出的一些非本质的改进和调整,仍属于本发明的保护范围。
实施例1
一种高性能双组分聚氨酯胶黏剂的制备方法:
(1)称取25g异佛尔酮-二异氰酸酯至反应瓶中,脱水处理,再加入1g催化剂二月桂酸二丁基锡和6g聚已内酯二醇,在65℃下恒温反应1.5h;加入5g丙酮降低粘度,加入2g二羟甲基丁酸恒温反应1.5h,冷却后加入4g三乙胺中和,转移至搅拌机中,以17000r/min的转速条件下高速搅拌加入预先混合好的1g水性阴离子型聚氨酯分散体U54和8g去离子水,乳化15min后,然后加入5g乙二胺扩链60min,最后减压蒸出溶剂后,得组分A;
(2)称取8g 4,4'-二环己基甲烷二异氰酸酯、10g磺化聚醚多元醇与12g聚己二酸1,6己二醇酯至反应瓶中,再加入交联剂5g海藻糖,在75℃下恒温反应5h,得组分B。然后采用丙酮-二正丁胺滴定法对合成的固化剂中的异氰酸酯基含量进行测定分析。
(3)将步骤(1)制得的组分A和步骤(2)制得的B进行混合,含量使得双组分聚氨酯胶黏剂的A组分所含羟基与B组分所含异氰酸酯基团的当量比为1∶2。
实施例2
一种高性能双组分聚氨酯胶黏剂的制备方法:
(1)称取15g异佛尔酮-二异氰酸酯至反应瓶中,脱水处理,再加入0.5g催化剂二月桂酸二丁基锡和10g聚已内酯二醇,在60℃下恒温反应1h;加入4g丙酮降低粘度,加入1g二羟甲基丁酸恒温反应1h,冷却后加入4g三乙胺中和,转移至搅拌机中,以17000r/min的转速条件下高速搅拌加入预先混合好的1g水性阴离子型聚氨酯分散体U54和8g去离子水,乳化15min后,然后加入5g乙二胺扩链60min,最后减压蒸出溶剂后,得组分A;
(2)称取5g 4,4'-二环己基甲烷二异氰酸酯、10g磺化聚醚多元醇与8g聚己二酸1,6己二醇酯至反应瓶中,再加入交联剂4g海藻糖,在75℃下恒温反应5h,得组分B。然后采用丙酮-二正丁胺滴定法对合成的固化剂中的异氰酸酯基含量进行测定分析。
(3)将步骤(1)制得的组分A和步骤(2)制得的B进行混合,含量使得双组分聚氨酯胶黏剂的A组分所含羟基与B组分所含异氰酸酯基团的当量比为1∶0.2。
实施例3
一种高性能双组分聚氨酯胶黏剂的制备方法:
(3)称取30g异佛尔酮-二异氰酸酯至反应瓶中,脱水处理,再加入3g催化剂二月桂酸二丁基锡和10g聚已内酯二醇,在70℃下恒温反应2h;加入8g丙酮降低粘度,加入3g二羟甲基丁酸恒温反应2h,冷却后加入6g三乙胺中和,转移至搅拌机中,以17000r/min的转速条件下加入预先混合好的1g水性阴离子型聚氨酯分散体U54和10g去离子水,乳化15min后,然后加入8g乙二胺扩链60min,最后减压蒸出溶剂后,得组分A;
(4)称取15g 4,4'-二环己基甲烷二异氰酸酯、15g磺化聚醚多元醇与15g聚己二酸1,6己二醇酯至反应瓶中,再加入交联剂8g海藻糖,在80℃下恒温反应5h,得组分B。然后采用丙酮-二正丁胺滴定法对合成的固化剂中的异氰酸酯基含量进行测定分析。
(3)将步骤(1)制得的组分A和步骤(2)制得的B进行混合,含量使得双组分聚氨酯胶黏剂的A组分所含羟基与B组分所含异氰酸酯基团的当量比为1∶1。
实施例4
一种高性能双组分聚氨酯胶黏剂的制备方法:
(1)称取25g异佛尔酮-二异氰酸酯至反应瓶中,脱水处理,再加入1g催化剂二月桂酸二丁基锡和10g聚已内酯二醇,在65℃下恒温反应1.5h;加入5g丙酮降低粘度,加入2g二羟甲基丁酸恒温反应1.5h,冷却后加入4g三乙胺中和,转移至搅拌机中,以17000r/min的转速条件下加入预先混合好的1g水性阴离子型聚氨酯分散体U54和10g去离子水,乳化15min后,然后加入5g乙二胺扩链60min,最后减压蒸出溶剂后,得组分A;
(2)称取5g 4,4'-二环己基甲烷二异氰酸酯、10g磺化聚醚多元醇与12g聚己二酸1,6己二醇酯至反应瓶中,再加入交联剂5g海藻糖,在75℃下恒温反应5h,得组分B。然后采用丙酮-二正丁胺滴定法对合成的固化剂中的异氰酸酯基含量进行测定分析。
(3)将步骤(1)制得的组分A和步骤(2)制得的B进行混合,含量使得双组分聚氨酯胶黏剂的A组分所含羟基与B组分所含异氰酸酯基团的当量比为1∶4。
实施例5
一种高性能双组分聚氨酯胶黏剂的制备方法:
(1)称取25g异佛尔酮-二异氰酸酯至反应瓶中,脱水处理,再加入1g催化剂二月桂酸二丁基锡和6g聚已内酯二醇,在65℃下恒温反应1.5h;加入5g丙酮降低粘度,加入2g二羟甲基丁酸恒温反应1.5h,冷却后加入4g三乙胺中和,转移至搅拌机中,以17000r/min的转速条件下加入预先混合好的1g水性阴离子型聚氨酯分散体U54和10g去离子水,乳化15min后,然后加入5g乙二胺扩链60min,最后减压蒸出溶剂后,得组分A;
(2)称取12g 4,4'-二环己基甲烷二异氰酸酯、10g磺化聚醚多元醇与6g聚己二酸1,6己二醇酯至反应瓶中,再加入交联剂5g海藻糖,在75℃下恒温反应5h,得组分B。然后采用丙酮-二正丁胺滴定法对合成的固化剂中的异氰酸酯基含量进行测定分析。
(3)将步骤(1)制得的组分A和步骤(2)制得的B进行混合,含量使得双组分聚氨酯胶黏剂的A组分所含羟基与B组分所含异氰酸酯基团的当量比为1∶5。
对比例1
与实施例1比,组分A中不含有二羟甲基丁酸,余同;
对比例2
与实施例1比,组分B中三羟甲基丙烷代替海藻糖,余同;
对比例3
与实施例1比,组分B中不含有海藻糖,余同;
性能测试:
将实施例1-5与对比例1-3的试样进行以下指标的检测,结果如下表1。
(1)固含量:称取试样1.0-1.5g于已称重的称量瓶中,干燥至恒重,求固含量;
(2)黏度:按GB/T 4851-84测定;
(3)初粘力:按GB/T2791-1995测定;将乳液涂抹于PVC/PVC薄膜复合膜之间经烘干后,测试T-剥离强度;
(4)耐水性:放入50℃水中24h后进行观察;
(5)耐热性:观察80℃温度下开裂情况。
表1性能测试结果
从表1结果可知,本发明实施例1-5制备的双组份聚氨酯胶黏剂固含量为60%~63%,黏度为210mpa.s~310mpa.s,剥离强度为9.1N~10.3N,耐水性无发白脱落,耐热性54~73min不开裂,各种性能结果良好。且从实施例1-5结果可知,实施例1制备得到双组份聚氨酯胶黏剂性能最优。
对比例1考察了二羟甲基丁酸的影响。对比例1制备的双组份聚氨酯胶黏剂黏度上升到710mpa.s,黏度较实施例1骤然升高,固含量和耐热性能下降。
对比例2-3考察了海藻糖作为内交联剂时对黏度的影响。对比例2当采用三羟甲基丙烷代替海藻糖后,制备得到的双组份聚氨酯胶黏剂固含量下降到51%,黏度和耐热性也变差;当组分B中不含海藻糖内交联剂时对比例3制备的双组份聚氨酯胶黏剂固含量下降到43%,耐水性和耐热性性能最差。
因此,由以上结果可知,本发明制备得到的双组份聚氨酯胶黏剂性能优良,不但固含量高、黏度低、粘接力强、耐水性和耐热好。
Claims (5)
1.一种高性能双组分聚氨酯胶黏剂,其特征在于,包括组分A和组分B:
所述组分A包括如下重量份数的组分:异佛尔酮-二异氰酸酯15~30份、聚已内酯二醇5~10份、二月桂酸二丁基锡0.5~3份、二羟甲基丁酸1~3份、丙酮4~8份、水性阴离子型聚氨酯分散体U54 0.5~2份、三乙胺1~6份和乙二胺4~8份;
所述组分B包括如下重量份数的组分:4,4'-二环己基甲烷二异氰酸酯5~15份、磺化聚醚多元醇8~15份、聚己二酸1,6己二醇酯5~15份和海藻糖4~8份;
所述双组分聚氨酯胶黏剂的A组分所含羟基与B组分所含异氰酸酯基团的当量比为1∶0.2至1∶5;
所述双组分聚氨酯胶黏剂的制备方法包括如下步骤:
(1)称取异佛尔酮-二异氰酸酯至反应瓶中,脱水处理,加入催化剂二月桂酸二丁基锡和聚已内酯二醇,在60~70℃下恒温反应1~2h,加入丙酮降低粘度,再加入二羟甲基丁酸恒温反应1~2h,冷却后用加入三乙胺中和,在高速搅拌下加入预先混合好的水性阴离子型聚氨酯分散体U54和去离子水,乳化10~20min后,然后加入乙二胺扩链50~70min,最后减压蒸出溶剂后,得组分A;
(2)称取4,4'-二环己基甲烷二异氰酸酯、磺化聚醚多元醇、聚己二酸1,6己二醇酯至反应瓶中,脱水处理,再加入海藻糖,在70~80℃下恒温反应4~6h,得组分B;
(3)将步骤(1)制得的组分A和步骤(2)制得的组分B进行混合,得双组分聚氨酯胶黏剂。
2.根据权利要求1所述的一种高性能双组分聚氨酯胶黏剂,其特征在于,包括组分A和组分B:
所述组分A包括如下重量份数的组分:异佛尔酮-二异氰酸酯20~25份、聚已内酯二醇5~8份、二月桂酸二丁基锡0.5~2份、二羟甲基丁酸1~3份、丙酮4~6份、水性阴离子型聚氨酯分散体U54 0.5~2份、三乙胺2~4份和乙二胺4~6份;
所述组分B包括如下重量份数的组分:4,4'-二环己基甲烷二异氰酸酯5~10份、磺化聚醚多元醇8~12份、聚己二酸1,6己二醇酯10~15份和海藻糖4~6份。
3.根据权利要求1所述的一种高性能双组分聚氨酯胶黏剂,其特征在于,所述步骤(1)中高速搅拌的搅拌速度为17000~18000r/min。
4.根据权利要求1所述的一种高性能双组分聚氨酯胶黏剂,其特征在于,所述制备方法中,步骤(1)在减压蒸馏脱除溶剂后,还包括向反应液中加入消泡剂和增稠剂。
5.根据权利要求4所述的一种高性能双组分聚氨酯胶黏剂,其特征在于,所述消泡剂为水性消泡剂Afcona 2501、Afcona 2502或Afcona 2524中的任意一种;所述增稠剂为SHEUR或LHEUR中的任意一种。
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