CN113692418A - 聚氨酯和包含它的uv-潮气双固化pu反应性热熔胶 - Google Patents
聚氨酯和包含它的uv-潮气双固化pu反应性热熔胶 Download PDFInfo
- Publication number
- CN113692418A CN113692418A CN202080011469.9A CN202080011469A CN113692418A CN 113692418 A CN113692418 A CN 113692418A CN 202080011469 A CN202080011469 A CN 202080011469A CN 113692418 A CN113692418 A CN 113692418A
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- China
- Prior art keywords
- polyurethane
- polyol
- isocyanate
- weight
- diisocyanate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Abstract
本发明涉及一种具有异氰酸酯基团且在侧链上具有C‑C双键的聚氨酯,一种制备所述聚氨酯的方法以及一种包含所述聚氨酯的UV‑潮气双固化聚氨酯反应性热熔胶。
Description
技术领域
本发明涉及一种具有异氰酸酯基团且在侧链上具有C-C双键的聚氨酯,一种制备所述聚氨酯的方法,一种包含所述聚氨酯的UV-潮气双固化聚氨酯反应性热熔胶和该热熔胶作为粘合剂或在增材制造中的用途以及由该热熔胶生产的三维物体。
背景
低施用粘度的聚氨酯反应性热熔胶(PU RHM)在粘合剂领域和增材制造(3D打印)中对于快速和容易施用方法而言是需要的,但是缺点是形成足以进行其他处理步骤的强度需要时间。因此,该挑战是要开发一种具有低粘度、短凝结时间并且同时具有快速形成湿强度的性能的PU RHM体系。
CN105255435A公开了一种制备光学/湿双固化聚氨酯热熔胶的方法,包括非常复杂的三步合成。此外,使用HDI三聚体,这可能导致该热熔胶的高粘度和固化产物的低冲击强度。
US9453142B2公开了一种可以用于通过增材制造生产由聚氨酯、聚脲或其共聚物构成的三维物体的可聚合液体,所述可聚合液体包含(i)封闭或反应性封闭预聚物,(ii)封闭或反应性封闭二异氰酸酯或(iii)封闭或反应性封闭二异氰酸酯扩链剂的混合物。然而,在US9453142B2中使用非常复杂的双组分体系,其要求多步化学合成封闭二异氰酸酯或预聚物;该3D打印机的特殊复杂设计;在US9453142B2中的无效层是废料;打印物体的韧性并不是很好。
发明概述
本发明的目的是要提供一种聚氨酯,从而可以通过使用所述聚氨酯得到一种具有低粘度、短凝结时间并且同时具有快速形成湿强度的性能的UV-潮气双固化聚氨酯反应性热熔胶。
本发明的另一目的是要提供一种制备该聚氨酯的方法。
本发明的再一目的是要提供一种包含本发明聚氨酯的UV-潮气双固化聚氨酯反应性热熔胶。
本发明的又一目的是要提供一种通过使用该UV-潮气双固化聚氨酯反应性热熔胶制造三维物体的方法以及可以通过所述方法得到的具有高韧性的三维物体。
已经惊人地发现上述目的可以通过下列实施方案实现:
1.一种具有异氰酸酯基团且在侧链上具有C-C双键的聚氨酯,其中在合成该聚氨酯的异氰酸酯组分中的异氰酸酯是二异氰酸酯并且该异氰酸酯组分包含至少一种在侧链上具有C-C双键的二异氰酸酯。
2.根据第1项的聚氨酯,其中该C-C双键的量基于该聚氨酯的总重量为0.07-0.5mol/kg,优选0.09-0.45mol/kg。
3.根据第1或2项的聚氨酯,其中异氰酸酯基团的含量基于该聚氨酯的总重量在0.2-6重量%,优选0.8-5重量%范围内。
4.根据第1-3项中任一项的聚氨酯,其中该聚氨酯由该异氰酸酯组分与多元醇组分反应而得到。
5.根据第1-4项中任一项的聚氨酯,其中在侧链上具有C-C双键的二异氰酸酯中C-C双键的平均数为1-6个/分子,优选1.5-4个/分子。
6.根据第1-5项中任一项的聚氨酯,其中在侧链上具有C-C双键的二异氰酸酯的量基于该异氰酸酯组分和该多元醇组分的总重量在5-35重量%,优选8-20重量%范围内。
7.根据第1-6项中任一项的聚氨酯,其中该异氰酸酯组分包含至少一种其他异氰酸酯并且所述其他异氰酸酯是二异氰酸酯。
8.根据第4-7项中任一项的聚氨酯,其中该多元醇组分包含至少一种结晶聚酯多元醇和/或至少一种非结晶聚酯多元醇。
9.根据第8项的聚氨酯,其中该结晶聚酯多元醇具有在15-50mg KOH/g,优选20-40mg KOH/g范围内的羟值。
10.根据第8或9项的聚氨酯,其中该非结晶聚酯多元醇具有在10-80mg KOH/g,优选20-50mg KOH/g范围内的羟值。
11.根据第8-10项中任一项的聚氨酯,其中结晶聚酯多元醇的量基于该异氰酸酯组分和该多元醇组分的总重量在4-80重量%,优选10-65重量%范围内。
12.根据第8-11项中任一项的聚氨酯,其中非结晶聚酯多元醇的量基于该异氰酸酯组分和该多元醇组分的总重量在1-30重量%,优选2-15重量%范围内。
13.根据第4-12项中任一项的聚氨酯,其中该多元醇组分包含0-75重量%,优选5-60重量%至少一种结晶聚醚多元醇。
14.根据第4-13项中任一项的聚氨酯,其中该多元醇组分包含0-10重量%至少一种非结晶聚醚多元醇。
15.根据第4-13项中任一项的聚氨酯,其中异氰酸酯组分包含:5-35重量%,优选8-20重量%在侧链上具有C-C双键的二异氰酸酯;0-20重量%,优选8-20重量%至少一种其他异氰酸酯并且所述其他异氰酸酯为二异氰酸酯;以及
该多元醇组分包含:
8-80重量%,优选12-65重量%至少一种结晶聚酯多元醇;
1-30重量%,优选2-15重量%至少一种非结晶聚酯多元醇;
0-60重量%,优选5-60重量%至少一种结晶聚醚多元醇;
0-10重量%至少一种非结晶聚醚多元醇;
其中重量%基于该异氰酸酯组分和该多元醇组分的总重量。
16.根据第4-13项中任一项的聚氨酯,其中异氰酸酯组分包含:5-35重量%,优选8-20重量%在侧链上具有C-C双键的二异氰酸酯;0-20重量%,优选8-20重量%至少一种其他异氰酸酯并且所述其他异氰酸酯为二异氰酸酯;以及
该多元醇组分包含:
4-80重量%,优选10-65重量%至少一种结晶聚酯多元醇;
1-30重量%,优选2-15重量%至少一种非结晶聚酯多元醇;
0-75重量%,优选5-60重量%至少一种结晶聚醚多元醇;
0-10重量%至少一种非结晶聚醚多元醇;
其中重量%基于该异氰酸酯组分和该多元醇组分的总重量。
17.根据第4-16项中任一项的聚氨酯,其中该多元醇组分中所用多元醇具有的官能度为2。
18.一种制备根据第1-17项中任一项的聚氨酯的方法,包括使异氰酸酯组分与多元醇组分反应而得到具有异氰酸酯基团且在侧链上具有C-C双键的聚氨酯,其中该异氰酸酯组分包含至少一种在侧链上具有C-C双键的二异氰酸酯。
19.一种UV-潮气双固化聚氨酯反应性热熔胶,包含至少一种根据第1-17项中任一项的聚氨酯和至少一种光引发剂。
20.根据第19项的UV-潮气双固化聚氨酯反应性热熔胶,进一步包含至少一种脲反应催化剂。
21.根据第19或20项的UV-潮气双固化聚氨酯反应性热熔胶作为粘合剂或在增材制造中的用途。
22.一种通过使用如第19或20项所定义的UV-潮气双固化聚氨酯反应性热熔胶制造三维物体的方法。
23.根据第22项的方法,包括形成如第19或20项所定义的UV-潮气双固化聚氨酯反应性热熔胶层并用UV光辐照该层以使该层凝结的步骤,重复该步骤直到形成该三维物体。
24.根据第23项的方法,其中该方法是一种增材制造(3D打印)方法。
25.一种可以通过根据第22-24项中任一项的方法得到的三维物体。
本发明的实施方案
本发明一方面涉及一种具有异氰酸酯基团且在侧链上具有C-C双键的聚氨酯,其中在合成该聚氨酯的异氰酸酯组分中的异氰酸酯是二异氰酸酯并且该异氰酸酯组分包含至少一种在侧链上具有C-C双键的二异氰酸酯。
未限定的冠词“一个”、“一种”、“该”是指一个或多个由所述冠词之后的术语指定的种类。
该C-C双键的量基于该聚氨酯的总重量为0.07-0.5mol/kg,例如0.08-0.45,0.09-0.40,0.09-0.35,0.09-0.30,0.10-0.25,0.10-0.20,0.10-0.15mol/kg,优选0.09-0.45mol/kg。
异氰酸酯基团的量基于该聚氨酯的总重量可以在0.2-6重量%,例如0.5-6,1-5,1.5-4.5,2-4,2.5-4.5,2.5-4重量%,优选0.8-5重量%范围内。
根据一个实施方案,该聚氨酯由异氰酸酯组分与多元醇组分的反应得到,并且其中该异氰酸酯组分包含至少一种在侧链上具有C-C双键的二异氰酸酯。
根据一个优选实施方案,在侧链上具有C-C双键的二异氰酸酯中C-C双键的平均数为1-6个/分子,例如1.5-6,1.6-5,1.7-4,1.8-3,1.9-2.5个/分子或约2个/分子,优选1.5-4个/分子,例如1.8-2.5个/分子。
在侧链上具有C-C双键的二异氰酸酯的量基于该异氰酸酯组分和该多元醇组分的总重量可以在5-35重量%,例如6-35,7-30,8-25,8-20,8-15重量%,优选8-20重量%范围内。
在一个优选实施方案中,该异氰酸酯组分可以包含至少一种其他异氰酸酯并且所述其他异氰酸酯是二异氰酸酯。该其他二异氰酸酯可以调节该热熔胶的UV反应性。该其他二异氰酸酯可以选自脂族、芳族和脂环族二异氰酸酯。芳族二异氰酸酯的实例是2,4-甲苯二异氰酸酯(2,4-TDI)、4,4'-二苯基甲烷二异氰酸酯(4,4'-MDI)、2,2'-二苯基甲烷二异氰酸酯(2,2'-MDI)、2,4'-二苯基甲烷二异氰酸酯(2,4'-MDI)和所谓的TDI混合物(2,4-甲苯二异氰酸酯和2,6-甲苯二异氰酸酯的混合物)。
脂族二异氰酸酯的实例是1,4-亚丁基二异氰酸酯、1,12-十二亚甲基二异氰酸酯、1,10-十亚甲基二异氰酸酯、2-丁基-2-乙基五亚甲基二异氰酸酯、2,4,4-三甲基六亚甲基二异氰酸酯或2,2,4-三甲基六亚甲基二异氰酸酯以及尤其是六亚甲基二异氰酸酯(HDI)。
脂环族二异氰酸酯的实例是异佛尔酮二异氰酸酯(IPDI)、异氰酸2-异氰酸酯基丙基环己基酯、2,4'-亚甲基二(环己基)二异氰酸酯和4-甲基环己烷-1,3-二异氰酸酯(H-TDI)。
具有不同反应性基团的异氰酸酯的其他实例是1,3-苯二异氰酸酯、1,4-苯二异氰酸酯、1,5-萘二异氰酸酯、联苯二异氰酸酯、甲苯胺二异氰酸酯和2,6-甲苯二异氰酸酯。
该其他二异氰酸酯的量基于该异氰酸酯组分和该多元醇组分的总重量可以在0-20重量%,例如5-20或10-20或8-15重量%,优选8-20重量%范围内。
根据一个优选实施方案,该多元醇组分包含至少一种结晶聚酯多元醇和/或至少一种非结晶聚酯多元醇。
该非结晶聚酯多元醇不具有熔点并且具有至少-50℃的玻璃化转变温度(Tg)。该结晶聚酯多元醇具有熔点,其中该熔点优选为至少5℃,更优选至少10℃。
玻璃化转变温度和熔点可以根据DIN 53765测量。
结晶聚酯多元醇可以由一种或多种具有至少2个碳原子,优选至少6个碳原子,特别优选6-14个碳原子的线性脂族二羧酸,如己二酸、壬二酸、癸二酸或十二烷二酸,与一种或多种具有至少2个碳原子,优选至少4个碳原子,更优选4-6个碳原子的线性二醇,如1,4-丁二醇和1,6-己二醇反应而制备。聚己内酯也合适。
该结晶聚酯多元醇的分子量可以在500-8000g/mol,优选1500-5000g/mol范围内。
根据一个实施方案,该结晶聚酯多元醇具有在15-50mg KOH/g,优选20-40mg KOH/g范围内的羟值。
结晶聚酯多元醇的量基于该异氰酸酯组分和该多元醇组分的总重量可以在4-80重量%,例如4-70,4-60,4-50,8-70,8-60,10-70,10-60,12-50,12-40,12-30,12-20重量%,优选10-65重量%范围内。
非结晶聚酯多元醇可以由一种或多种选自己二酸、间苯二甲酸和对苯二甲酸的羧酸组分与一种或多种选自乙二醇、二甘醇、丙二醇和新戊二醇的醇组分反应而制备。
该非结晶聚酯多元醇的分子量可以在500-8000g/mol,优选1500-5000g/mol范围内。
根据一个实施方案,该非结晶聚酯多元醇具有在10-80mg KOH/g,优选20-50mgKOH/g范围内的羟值。
非结晶聚酯多元醇的量基于该异氰酸酯组分和该多元醇组分的总重量可以在1-30重量%,例如2-25,4-20,6-15重量%,优选2-15重量%范围内。
在一个实施方案中,该多元醇组分包含至少一种结晶聚醚多元醇。该结晶聚醚多元醇具有熔点,该熔点优选为至少5℃,更优选至少10℃。
该结晶聚醚多元醇例如包括聚氧丙烯多元醇和聚四氢呋喃。
该结晶聚醚多元醇的分子量可以在500-5000g/mol,优选1000-3000g/mol范围内。
根据一个实施方案,该结晶聚醚多元醇具有在30-200mg KOH/g,优选50-120mgKOH/g范围内的羟值。
结晶聚醚多元醇的量基于该异氰酸酯组分和该多元醇组分的总重量可以在0-75重量%,例如5-70,10-70,20-65,30-60,40-60重量%,优选5-60重量%范围内。
在一个实施方案中,该多元醇组分包含至少一种非结晶聚醚多元醇。该非结晶聚醚多元醇没有熔点并且具有至少-50℃的玻璃化转变温度。
优选的非结晶聚醚二醇包含一种或多种线性二醇,其中羟基由重复四亚甲基和2-甲基四亚甲基醚基分开。
该类二醇的实例是具有下列结构的四氢呋喃(THF)和3-甲基-THF的液体(在室温下)共聚物:
m+n=10-30的整数;Mw约3,500;OHav约2.0;Tg-48℃。
该非结晶聚醚多元醇的分子量可以在500-5000g/mol,优选1000-3000g/mol范围内。
根据一个实施方案,该非结晶聚醚多元醇具有在30-300mg KOH/g,优选50-120mgKOH/g范围内的羟值。
非结晶聚醚多元醇的量基于该异氰酸酯组分和该多元醇组分的总重量可以在0-10重量%,例如1-8重量%范围内。
在优选实施方案中,本发明聚氨酯由异氰酸酯组分与多元醇组分的反应得到,其中异氰酸酯组分包含:
5-35重量%,优选8-20重量%在侧链上具有C-C双键的二异氰酸酯;
0-20重量%,优选8-20重量%至少一种其他异氰酸酯并且所述其他异氰酸酯为二异氰酸酯;以及
该多元醇组分包含:
8-80重量%,优选12-65重量%至少一种结晶聚酯多元醇;
1-30重量%,优选2-15重量%至少一种非结晶聚酯多元醇;
0-60重量%,优选5-60重量%至少一种结晶聚醚多元醇;
0-10重量%至少一种非结晶聚醚多元醇;
其中重量%基于该异氰酸酯组分和该多元醇组分的总重量。
在另一优选实施方案中,本发明聚氨酯由异氰酸酯组分与多元醇组分的反应得到,其中异氰酸酯组分包含:
5-35重量%,优选8-20重量%在侧链上具有C-C双键的二异氰酸酯;
0-20重量%,优选8-20重量%至少一种其他异氰酸酯并且所述其他异氰酸酯为二异氰酸酯;以及
该多元醇组分包含:
4-80重量%,优选10-65重量%至少一种结晶聚酯多元醇;
1-30重量%,优选2-15重量%至少一种非结晶聚酯多元醇;
0-75重量%,优选5-60重量%至少一种结晶聚醚多元醇;
0-10重量%至少一种非结晶聚醚多元醇;
其中重量%基于该异氰酸酯组分和该多元醇组分的总重量。
该多元醇组分中所用多元醇,例如结晶聚酯多元醇、非结晶聚酯多元醇、结晶聚醚多元醇和非结晶聚醚多元醇具有的官能度为2。
本发明另一方面涉及一种制备本发明聚氨酯的方法,包括使该异氰酸酯组分与该多元醇组分反应而得到具有异氰酸酯基团且在侧链上具有C-C双键的聚氨酯,其中该异氰酸酯组分包含至少一种在侧链上具有C-C双键的二异氰酸酯。
在一个优选实施方案中,可以将该多元醇组分加热以熔融所有多元醇。然后加入异氰酸酯组分以进行该反应。反应温度可以在60-130℃,优选90-110℃范围内。
本发明另一方面涉及一种UV-潮气双固化聚氨酯反应性热熔胶,包含至少一种本发明的聚氨酯。
根据一个优选实施方案,该UV-潮气双固化聚氨酯反应性热熔胶进一步包含至少一种光引发剂。
合适的光引发剂例如包括在该UV-潮气双固化聚氨酯反应性热熔胶的应用温度下不降解的那些。该光引发剂的实例包括酰基氧化膦化合物,二苯甲酮化合物,苯乙酮化合物,肟酯化合物,安息香化合物,尤其是安息香醚化合物,噻吨酮等。根据优选实施方案,该光引发剂是2,4,6-三甲基苯甲酰基二苯基氧化膦。
光引发剂的量基于该PU反应性热熔胶的总重量可以在0.1-3重量%,优选0.5-1.5重量%范围内。
根据优选实施方案,本发明的UV-潮气双固化聚氨酯反应性热熔胶在110℃下测量可以具有小于7Pas,例如小于6Pas或小于5Pas的布氏粘度。
根据另一优选实施方案,本发明的UV-潮气双固化聚氨酯反应性热熔胶在90℃下测量可以具有小于15Pas,例如小于14Pas或小于12Pas或小于10Pas的布氏粘度。
在一个实施方案中,本发明的UV-潮气双固化聚氨酯反应性热熔胶可以包含至少一种脲反应催化剂以促进异氰酸酯基团与潮气反应。
有用的催化剂例如包括常用于聚氨酯化学中的所有催化剂。
聚氨酯化学中常用的催化剂优选为有机胺,尤其是脂族、脂环族或芳族叔胺。
作为常规有机胺,例如可以提到三乙胺、1,4-二氮杂双环[2,2,2]辛烷、三丁胺、二甲基苄基胺、N,N,N',N'-四甲基乙二胺、N,N,N',N'-四甲基-1,4-丁二胺、N,N,N',N'-四甲基-1,6-己二胺、二甲基环己基胺、二甲基十二烷基胺、五甲基二亚丙基三胺、五甲基二亚乙基三胺、3-甲基-6-二甲氨基-3-氮杂戊醇、二甲氨基丙基胺、1,3-二-二甲氨基丁烷、二(2-二甲氨基乙基)醚、N-乙基吗啉、N-甲基吗啉、N-环己基吗啉、2-二甲氨基乙氧基乙醇、二甲基乙醇胺、四甲基六亚甲基二胺、二甲氨基-N-甲基乙醇胺、N-甲基咪唑、N-甲酰基-N,N'-二甲基丁二胺、N-二甲氨基乙基吗啉、3,3'-二-二甲氨基二正丙基胺和/或2,2'-二哌嗪二异丙基醚、二甲基哌嗪、三(N,N-二甲氨基丙基)-s-六氢三嗪,咪唑类如1,2-二甲基咪唑、4-氯-2,5-二甲基-1-(N-甲基氨基乙基)咪唑、2-氨基丙基-4,5-二甲氧基-1-甲基咪唑、1-氨基丙基-2,4,5-三丁基咪唑、1-氨基乙基-4-己基咪唑、1-氨基丁基-2,5-二甲基咪唑、1-(3-氨基丙基)-2-乙基-4-甲基咪唑、1-(3-氨基丙基)咪唑、1-(3-氨基丙基)-2-甲基咪唑和/或2,2'-二吗啉代二乙基醚。
应理解的是也可以将上述化合物中两种或更多种的混合物用作脲反应催化剂。
脲反应催化剂的量基于该热熔胶的总重量可以在0-0.05重量%或0.01-0.04重量%范围内。
本发明的热熔胶优选包含至少一种选自增粘剂、稳定剂、填料、流动控制剂、增稠剂、润湿剂、消泡剂、交联剂、增塑剂、老化抑制剂、杀真菌剂、颜料、染料、消光剂和中和剂的其他添加剂。该热熔胶优选基于该热熔胶的总量包含20-90重量%一种或多种本文所述的本发明聚氨酯和至少10重量%的一种或多种增粘剂。
增粘剂对熟练技术人员而言本身是已知的。它们是用于改善这些体系的自粘附(粘性、固有粘性、自粘)的粘合剂或弹性体的添加剂。它们通常具有相对低分子量(Mn约200-2000g/mol),玻璃化转变温度在弹性体的玻璃化转变温度之上。增粘剂的量按重量计每100重量份该聚氨酯优选为5-100重量份,更优选10-50重量份。合适的增粘剂例如是基于天然树脂,如松香类的那些。基于天然树脂的增粘剂包括天然树脂本身以及还有例如通过歧化或异构化、聚合、二聚或氢化形成的其衍生物。它们可以以其盐形式(具有例如单价或多价抗衡离子(阳离子))或者优选以其酯化形式。用于酯化的醇可以是一元或多元的。实例是甲醇、乙二醇、二甘醇、三甘醇、1,2,3-丙三醇和季戊四醇。此外,还用作增粘剂的是酚醛树脂,烃树脂,例如香豆酮-茚树脂,聚萜烯树脂,萜烯齐聚物,基于不饱和CH化合物,如丁二烯、戊烯、甲基丁烯、异戊二烯、戊间二烯、二乙烯基甲烷、戊二烯、环戊烯、环戊二烯、环己二烯、苯乙烯、α-甲基苯乙烯、乙烯基甲苯的烃树脂。也越来越多地被用作增粘剂的是具有低分子量的聚丙烯酸酯。这些聚丙烯酸酯优选具有低于30 000的重均分子量(Mw)。聚丙烯酸酯优选由至少60重量%,更具体至少80重量%的(甲基)丙烯酸C1-C8烷基酯构成。优选的增粘剂是天然或化学改性松香类。松香类主要由枞酸或其衍生物构成。
为了改善表面润湿,该热熔胶尤其可以包含润湿助剂,实例是脂肪醇乙氧基化物、烷基酚乙氧基化物、磺基琥珀酸酯、壬基酚乙氧基化物、聚氧乙烯/丙烯或十二烷基磺酸钠。该量通常为0.05-5重量份,更具体0.1-3重量份/100重量份聚合物(固体)。
合适的稳定剂例如选自润湿剂、纤维素、聚乙烯醇、聚乙烯基吡咯烷酮及其混合物。
本发明另一方面涉及一种制备本发明的UV-潮气双固化聚氨酯反应性热熔胶的方法,包括将本发明聚氨酯与至少一种光引发剂混合。
上述至少一种添加剂也可以在加入该光引发剂之前、之中或之后加入。
使所得热熔胶远离光和水。
本发明的另一方面涉及一种胶结基材的方法,其中
a)提供如本文所述的本发明热熔胶,
b)将该热熔胶施加于至少第一基材上,以及
c)使涂敷了该热熔胶的基材与涂敷或未涂敷第二基材接触,并且在这两种基材相互接触之前或之后通过UV光和潮气固化所施加的热熔胶。基材例如可以选自聚合物薄膜,纸张,金属箔,薄木板,由天然合成纤维制成的纤维非织造布,成型固体制品—实例是由金属、涂漆金属、木材、木质材料、纤维材料或塑料制成的成型部件。特别优选的第一基材是聚合物薄膜。聚合物薄膜更具体是厚度为0.05-5毫米的柔性片状塑料,其可以卷绕。这类聚合物薄膜通常通过涂敷、浇注、压延或挤出生产并且通常可以以卷材市购或者在现场生产。它们可以具有单层或多层构造。聚合物薄膜的塑料优选是热塑性塑料,例如聚酯,如聚对苯二甲酸乙二醇酯(PET),热塑性聚烯烃(TPO)如聚乙烯、聚丙烯、聚氯乙烯,尤其是增塑的PVC,聚乙酸酯,乙烯/乙酸乙烯酯共聚物(EVA),ASA(丙烯腈/苯乙烯/丙烯酸酯),PU(聚氨酯),PA(聚酰胺),聚(甲基)丙烯酸酯,聚碳酸酯或其塑料合金,包括尤其是发泡PVC薄膜和发泡的热塑性聚烯烃薄膜(TPO)。特别优选PVC和热塑性聚烯烃(TPO)。成型部件也可以是由合成或天然纤维或碎屑构成的模制品,它们由粘合剂结合在一起形成模制品;尤其合适的还有由塑料,例如ABS制成的模制品。模制品可以具有任何所需形状。
基材或模制品可以通过常规施用技术,例如喷涂、铺展、刮涂、模头施用、辊施或流延施用方法用该热熔胶涂敷。
热熔胶的施用量优选为0.5-100g/m2,更优选2-80g/m2,非常优选10-70g/m2。
本发明另一方面涉及一种通过使用本发明的UV-潮气双固化聚氨酯反应性热熔胶制造三维物体的方法。
根据优选实施方案,该制造三维物体的方法包括形成本发明的UV-潮气双固化聚氨酯反应性热熔胶层并用UV光辐照该层以使该层凝结的步骤,重复该步骤直到形成该三维物体。
根据一个优选实施方案,该方法是一种增材制造方法。
本发明另一方面涉及可以由本发明方法得到的三维物体。
本发明的UV-潮气双固化聚氨酯反应性热熔胶具有下列优点:对于快速和容易施用而言粘度低;短凝结时间和良好湿强度;以及固化产物,尤其是通过该增材制造方法由该热熔胶生产的三维物体具有高韧性(高冲击强度)。
实施例
A)所用物质
·结晶聚酯多元醇:由己二酸和己二醇合成,分子量3500,羟值30mgKOH/g,官能度2;
·在侧链上具有碳-碳双键的二异氰酸酯:低粘度异氰酸酯官能不饱和脂族丙烯酸酯(CAS(78567-28-9));C-C双键的平均数为约2个/分子;异氰酸酯基团的数目为2个/分子且分子量为约800g/mol;
·结晶聚醚多元醇:聚THF 2000,分子量2000g/mol,羟值约55mg KOH/g,官能度2;
·二异氰酸酯:4,4'-MDI;
·光引发剂:Irgacure TPO(2,4,6-三甲基苯甲酰基二苯基氧化膦);
B)测试方法
B1)湿强度
DIN EN 1465
1.在烘箱中将该样品(密封于牙膏管中)在100℃下预热0.5小时。
2.在透明PMMA基材(第一基材)上标记用于样品施用的12.5mm*25mm区域(结合区域)并且不标记附着表面。
3.将该样品施用于第一基材的结合区域上;该样品的厚度为0.2mm。
4.在小于20秒内将第二基材放在该样品上并且对所有样品保持该时间相同。
5.用0.5kg铁棒压制这两块基材以挤出过量热熔胶,其中t=0秒是当将该棒放在样品上时的时间;然后对于来自实施例1、实施例2和对比例2的样品立即用UV光(Technigraf UN50049-0002)辐照结合的基材10s(对于来自对比例1的样品,不应用UV辐照,因为该样品不包含C-C双键)。
6.在给定时间之后通过通用机器(来自Zwick)测量拉伸强度(取决于该配方的开放时间)并将该值记录为湿强度。湿强度时间为从t=0到开始测量时的时间。在样品制备和测试过程中,相对湿度为50%。
B2)凝结时间和开放时间
1.在加热烘箱中将该PU RHM样品(密封于牙膏管中)在100℃下预热0.5小时。
2.在加热台上将该特氟隆纸基材和刮刀在100℃下预热。
3.在该特氟隆纸基材上用该刮刀制造一片500μm厚PU RHM薄膜并同时开始计时为t=0秒;将带有PU RHM的该特氟隆纸放在该UV灯(Technigraf UN50049-0002)的传送带上并在传送过程中辐照该PU RHM(对于来自对比例1的样品,不应用UV辐照,因为该样品不包含C-C双键)。
4.在UV辐照之后立即将该PU RHM薄膜转移到在室温下的通风橱台板上,并使用纸张测试方法来用小片纸以一定时间间隔轻拍薄膜表面,以检查它是否发粘;将该PU RHM薄膜保持在50%R.H.下的湿度实验室中。
5.将直到该RHM形状固定的持续时间记录为凝结时间。
6.将直到该表面不发粘的持续时间记录为开放时间。
B3)粘度
粘度计(布氏粘度计)。
1.样品准备:在预热的烘箱中将样品(密封于牙膏管中)在100℃下加热30分钟。
2.打开布氏粘度计的的总开关和温控器(位于该机器后部)以预热机器。
3.取出锭子的保护器,校准该粘度计并在屏幕指引下设定参数。
4.同时将铝样品管放入加热室中并将其预热至70℃。
5.将样品填充到预热的铝管中直到2/3充满。
6.将样品管放入加热室中。升起粘度计马达,安装相应马达。降下马达并让马达进入样品管中。调节该加热室的位置以避免马达接触管壁。用盖子覆盖加热室。
7.在温控器上设定所要求的温度,点击“设定”键进入设定模式,点击上下键设定温度,再次点击“设定”以确认该设置,点击“运行”键以确定在设定温度下运行该测试。
8.在加热室的温度稳定在设定温度下之后逐渐提高显示器上的转速。点击“运行”键以运行该粘度计并观察扭矩读数。若扭矩没有达到70%或超过90%,则停止粘度测量并重新设置转速。在完成粘度测量之后,按上下翻页键记录数据。
B4)冲击强度
ISO 179
1.将样品施加于特氟隆冲击样品模具上。使用载玻片刮擦并确保该模具完全填充该样品。
2.将具有样品的模具用UV光辐照10s(582mJ/cm2)(对于来自对比例1的样品,不应用UV辐照,因为该样品不包含C-C双键)。
3.然后将具有样品的模具在25℃下于50%R.H.的湿度实验室中保持24小时以实现完全潮气固化。
4.将模塑样品从模具中取出并测试模塑样品的冲击强度。
实施例1
将107g结晶聚酯多元醇、53g非结晶聚酯多元醇和374g结晶聚醚多元醇加入1L反应器中。然后密封该反应器;将多元醇加热至80℃以熔融所有多元醇。
在机械搅拌下将多元醇在动力真空下干燥,直到没有可见气泡。
在机械搅拌下将66g在侧链上具有碳-碳双键的二异氰酸酯和99g 4,4'-MDI加入该反应器中。
将反应物加热至100℃并在机械搅拌下维持该温度1.5小时,以生产该聚氨酯。
将7g光引发剂加入该聚氨酯中并将该混合物再搅拌0.5小时以确保该光引发剂均匀分布于该聚氨酯中。最后得到该UV-潮气双固化PU反应性热熔胶(RHM)。
将该UV-潮气双固化PU RHM包装到铝袋中并在真空下密封。将铝袋储存于暗处。
根据上述方法测试该UV-潮气双固化PU RHM的湿强度、凝结时间和开放时间,测试结果和NCO含量示于表1中。该UV-潮气双固化PU RHM的凝结时间和开放时间在不应用UV辐照下分别为2小时和4小时。根据上述方法测试该UV-潮气双固化PU RHM的粘度,结果示于表2中。冲击强度示于表3中。
实施例2
将441g结晶聚酯多元醇和26g非结晶聚酯多元醇加入1L反应器中。然后密封该反应器;将多元醇加热至80℃以熔融所有多元醇。
在机械搅拌下将多元醇在动力真空下干燥,直到没有可见气泡。
在机械搅拌下将226g在侧链上具有碳-碳双键的二异氰酸酯加入该反应器中。
将反应物加热至100℃并在机械搅拌下维持该温度1.5小时,以生产该聚氨酯。
将7g光引发剂加入该聚氨酯中并将该混合物再搅拌0.5小时以确保该光引发剂均匀分布于该聚氨酯中。最后得到该UV-潮气双固化PU RHM。
将该UV-潮气双固化PU RHM包装到铝袋中并在真空下密封。将铝袋储存于暗处。
根据上述方法测试该UV-潮气双固化PU RHM的湿强度、凝结时间和开放时间,测试结果和NCO含量示于表1中。该UV-潮气双固化PU RHM的凝结时间和开放时间在没有应用UV辐照下均为60s。根据上述方法测试该UV-潮气双固化PU RHM的粘度,结果示于表2中。
实施例3
将438g结晶聚酯多元醇加入1L反应器中。然后密封该反应器。将该多元醇加热至80℃以熔融所有多元醇。
在机械搅拌下将多元醇在动力真空下干燥,直到没有可见气泡。
在机械搅拌下将242g在侧链上具有碳-碳双键的二异氰酸酯加入该反应器中。
将反应物加热至100℃并在机械搅拌下维持该温度1.5小时,以生产该聚氨酯。
将21g光引发剂加入该聚氨酯中并将该混合物再搅拌0.5小时以确保该光引发剂均匀分布于该聚氨酯中。最后得到该UV-潮气双固化PU RHM。
将该UV-潮气双固化PU RHM包装到铝袋中并在真空下密封。将铝袋储存于暗处。
该UV-潮气双固化PU RHM的NCO含量为3.3重量%。根据上述方法测试该UV-潮气双固化PU RHM的凝结时间和开放时间。当UV辐照时间为10s时(UV辐照剂量582mJ/cm2),凝结时间为5s且开放时间为25s。当将UV辐照时间减至0.75s时(UV辐照剂量96mJ/cm2),凝结时间和开放时间维持不变。根据上述方法测试该UV-潮气双固化PU反应性热熔胶的粘度,结果示于表2中。
实施例4
将35g结晶聚酯多元醇和510g结晶聚醚多元醇加入1L反应器中。然后密封该反应器;将多元醇加热至80℃以熔融所有多元醇。
在机械搅拌下将多元醇在动力真空下干燥,直到没有可见气泡。
在机械搅拌下将35g在侧链上具有碳-碳双键的二异氰酸酯和122g4,4'-MDI加入该反应器中。
将反应物加热至100℃并在机械搅拌下维持该温度1.5小时,以生产该聚氨酯。
将7g光引发剂加入该聚氨酯中并将该混合物再搅拌0.5小时以确保该光引发剂均匀分布于该聚氨酯中。最后得到该UV-潮气双固化PU RHM。
将该UV-潮气双固化PU RHM包装到铝袋中并在真空下密封。将铝袋储存于暗处。
该UV-潮气双固化PU RHM的NCO含量为3.3重量%。根据上述方法测试该UV-潮气双固化PU RHM的凝结时间和开放时间。当UV辐照时间为10s时(UV辐照剂量582mJ/cm2),凝结时间为20s且开放时间为2.5h。根据上述方法测试该UV-潮气双固化PU反应性热熔胶的粘度,结果示于表2中。
对比例1
将107g结晶聚酯多元醇、53g非结晶聚酯多元醇和374g结晶聚醚多元醇加入1L反应器中;然后密封该反应器;将多元醇加热至80℃以熔融所有多元醇。
在机械搅拌下将多元醇在动力真空下干燥,直到没有可见气泡。
在机械搅拌下将125g 4,4'-MDI加入该反应器中。
将反应物加热至100℃并在机械搅拌下维持该温度2小时,以生产标准聚氨酯,即标准PU RHM。
将该标准PU RHM包装到铝袋中并在真空下密封。将铝袋储存于暗处。
根据上述方法测试该标准PU RHM的湿强度、凝结时间和开放时间,测试结果和NCO含量示于表1中。根据上述方法测试该标准PU RHM的粘度,测试结果示于表2中。冲击强度示于表3中。
对比例2
预聚物的生产:使815g HDI三聚体(Basonat HI)与184g甲基丙烯酸羟乙基酯在65℃下反应2小时,所得预聚物具有13.5%的NCO含量。
将104g结晶聚酯多元醇、52g非结晶聚酯多元醇和364g结晶聚醚多元醇加入1L反应器中。然后密封该反应器;将多元醇加热至80℃以熔融所有多元醇。
在机械搅拌下将多元醇在动力真空下干燥,直到没有可见气泡。
在机械搅拌下将71g上面制备的预聚物和97g 4,4'-MDI加入该反应器中。将反应物加热至100℃并在机械搅拌下维持该温度1.5小时,以生产该聚氨酯。
将7g光引发剂加入该聚氨酯中并将该混合物再搅拌0.5小时以确保该光引发剂均匀分布于该聚氨酯中。最后得到该UV-潮气双固化PU RHM。
将该UV-潮气双固化PU RHM包装到铝袋中并在真空下密封。将铝袋储存于暗处。
根据上述方法测试该UV-潮气双固化PU RHM的湿强度、凝结时间和开放时间,测试结果和NCO含量示于表1中。该UV-潮气双固化PU RHM的凝结时间和开放时间在不应用UV辐照下分别为40分钟和4小时。根据上述方法测试该UV-潮气双固化PU RHM的粘度,测试结果示于表2中。冲击强度示于表3中。
表1
*在实施例2中,当将UV辐照时间减至3s时(UV辐照剂量133mJ/cm2),凝结时间、开放时间和湿强度维持不变。
表2
实施例 | 在90℃下的粘度(Pas) |
对比例1(标准) | 5.7 |
实施例1 | 8.1 |
实施例2 | 13.5 |
对比例2 | 20.2 |
实施例3 | 9.6 |
实施例4 | 4.6 |
表3
实施例 | 冲击强度(卡毕,缺口)[KJ/m<sup>2</sup>] |
对比例1(标准) | 15.7 |
实施例1 | 16.4 |
对比例2 | 9.88 |
来自实施例1的UV-潮气双固化PU RHM的粘度与来自对比例1的标准PU RHM的类似;然而,来自对比例2的UV-潮气双固化PU RHM比标准PU RHM和来自实施例1-4的UV-潮气双固化PU RHM的那些要高得多。高粘度对于该热熔胶的应用而言是不利的。
来自实施例1的UV-潮气双固化PU RHM的凝结时间在没有UV辐照下为2小时,但在应用10s UV辐照时可以将它设定在10s以内,该性能对热熔胶是有利的。在实施例2和3中,甚至进一步缩短UV辐照时间,凝结时间、开放时间或湿强度与10s UV辐照时间相比维持不变,这意味着来自实施例2和3的UV-潮气双固化PU RHM具有更高反应性。
来自实施例1的UV-潮气双固化PU RHM可以保持粘性高达4小时(开放时间)。
来自实施例1和2的双固化PU RHM,尤其是来自实施例1的双固化PU RHM具有优异的湿强度。
来自实施例1的双固化PU反应性热熔胶的冲击强度比来自对比例1的标准PU反应性热熔胶的要高并且比来自对比例2的UV-潮气双固化PU反应性热熔胶的高得多。
Claims (25)
1.一种具有异氰酸酯基团且在侧链上具有C-C双键的聚氨酯,其中在合成所述聚氨酯的异氰酸酯组分中的异氰酸酯是二异氰酸酯并且所述异氰酸酯组分包含至少一种在侧链上具有C-C双键的二异氰酸酯。
2.根据权利要求1的聚氨酯,其中所述C-C双键的量基于所述聚氨酯的总重量为0.07-0.5mol/kg,优选0.09-0.45mol/kg。
3.根据权利要求1或2的聚氨酯,其中异氰酸酯基团的含量基于所述聚氨酯的总重量在0.2-6重量%,优选0.8-5重量%范围内。
4.根据权利要求1-3中任一项的聚氨酯,其中所述聚氨酯由所述异氰酸酯组分与多元醇组分的反应得到。
5.根据权利要求1-4中任一项的聚氨酯,其中在侧链上具有C-C双键的二异氰酸酯中C-C双键的平均数为1-6个/分子,优选1.5-4个/分子。
6.根据权利要求1-5中任一项的聚氨酯,其中在侧链上具有C-C双键的二异氰酸酯的量基于所述异氰酸酯组分和所述多元醇组分的总重量在5-35重量%,优选8-20重量%范围内。
7.根据权利要求1-6中任一项的聚氨酯,其中所述异氰酸酯组分包含至少一种其他异氰酸酯并且所述其他异氰酸酯为二异氰酸酯。
8.根据权利要求4-7中任一项的聚氨酯,其中所述多元醇组分包含至少一种结晶聚酯多元醇和/或至少一种非结晶聚酯多元醇。
9.根据权利要求8的聚氨酯,其中所述结晶聚酯多元醇具有在15-50mg KOH/g,优选20-40mg KOH/g范围内的羟值。
10.根据权利要求8或9的聚氨酯,其中所述非结晶聚酯多元醇具有在10-80mg KOH/g,优选20-50mg KOH/g范围内的羟值。
11.根据权利要求8-10中任一项的聚氨酯,其中结晶聚酯多元醇的量基于所述异氰酸酯组分和所述多元醇组分的总重量在4-80重量%,优选10-65重量%范围内。
12.根据权利要求8-11中任一项的聚氨酯,其中非结晶聚酯多元醇的量基于所述异氰酸酯组分和所述多元醇组分的总重量在1-30重量%,优选2-15重量%范围内。
13.根据权利要求4-12中任一项的聚氨酯,其中所述多元醇组分包含0-75重量%,优选5-60重量%至少一种结晶聚醚多元醇。
14.根据权利要求4-13中任一项的聚氨酯,其中所述多元醇组分包含0-10重量%至少一种非结晶聚醚多元醇。
15.根据权利要求4-13中任一项的聚氨酯,其中异氰酸酯组分包含:5-35重量%,优选8-20重量%在侧链上具有C-C双键的二异氰酸酯;
0-20重量%,优选8-20重量%至少一种其他异氰酸酯并且所述其他异氰酸酯为二异氰酸酯;以及
所述多元醇组分包含:
8-80重量%,优选12-65重量%至少一种结晶聚酯多元醇;
1-30重量%,优选2-15重量%至少一种非结晶聚酯多元醇;
0-60重量%,优选5-60重量%至少一种结晶聚醚多元醇;
0-10重量%至少一种非结晶聚醚多元醇;
其中重量%基于所述异氰酸酯组分和所述多元醇组分的总重量。
16.根据权利要求4-13中任一项的聚氨酯聚合物,其中异氰酸酯组分包含:
5-35重量%,优选8-20重量%在侧链上具有C-C双键的二异氰酸酯;
0-20重量%,优选8-20重量%至少一种其他异氰酸酯并且所述其他异氰酸酯为二异氰酸酯;以及
所述多元醇组分包含:
4-80重量%,优选10-65重量%至少一种结晶聚酯多元醇;
1-30重量%,优选2-15重量%至少一种非结晶聚酯多元醇;
0-75重量%,优选5-60重量%至少一种结晶聚醚多元醇;
0-10重量%至少一种非结晶聚醚多元醇;
其中重量%基于所述异氰酸酯组分和所述多元醇组分的总重量。
17.根据权利要求4-16中任一项的聚氨酯,其中用于所述多元醇组分中的多元醇具有的官能度为2。
18.一种制备根据权利要求1-17中任一项的聚氨酯的方法,包括使异氰酸酯组分与多元醇组分反应而得到所述具有异氰酸酯基团且在侧链上具有C-C双键的聚氨酯,其中所述异氰酸酯组分包含至少一种在侧链上具有C-C双键的二异氰酸酯。
19.一种UV-潮气双固化聚氨酯反应性热熔胶,包含至少一种根据权利要求1-17中任一项的聚氨酯和至少一种光引发剂。
20.根据权利要求19的UV-潮气双固化聚氨酯反应性热熔胶,进一步包括至少一种脲反应催化剂。
21.根据权利要求19或20的UV-潮气双固化聚氨酯反应性热熔胶作为粘合剂或在增材制造中的用途。
22.一种通过使用如权利要求19或20所定义的UV-潮气双固化聚氨酯反应性热熔胶制造三维物体的方法。
23.根据权利要求22的方法,包括形成如权利要求19或20所定义的UV-潮气双固化聚氨酯反应性热熔胶层并用UV光辐照所述层以使所述层凝结的步骤,重复所述步骤直到形成所述三维物体。
24.根据权利要求23的方法,其中所述方法是增材制造(3D打印)方法。
25.可以通过根据权利要求22-24中任一项的方法得到的三维物体。
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CN1334833A (zh) * | 1998-12-23 | 2002-02-06 | Basf公司 | 可通过与异氰酸酯基团的加成以及与活化碳碳共价双键的辐射诱导加成而固化的涂层剂 |
US6617413B1 (en) * | 1998-12-23 | 2003-09-09 | Basf Aktiengesellschaft | Coating agents which can be hardened by the addition of isocyanate groups as well as by the radiation-induced addition of activated c-c double covalent bonds |
US20100029800A1 (en) * | 2004-12-22 | 2010-02-04 | Basf Aktiengesellschaft | Radiation-hardenable compounds |
US20080194725A1 (en) * | 2005-04-01 | 2008-08-14 | Reinhold Schwalm | Radiation-Hardenable Compounds |
CN104822727A (zh) * | 2012-12-06 | 2015-08-05 | 巴斯夫欧洲公司 | 可辐射固化的聚氨酯水分散体 |
CN107001570A (zh) * | 2014-12-17 | 2017-08-01 | 巴斯夫欧洲公司 | 基于链增长和交联的聚氨酯的可辐射固化的涂料组合物 |
CN107108850A (zh) * | 2014-12-25 | 2017-08-29 | 旭硝子株式会社 | 固化性树脂组合物 |
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WO2020156802A1 (en) | 2020-08-06 |
CN113692418B (zh) | 2024-04-05 |
EP3917984A1 (en) | 2021-12-08 |
KR20210122823A (ko) | 2021-10-12 |
JP2022518861A (ja) | 2022-03-16 |
TW202030217A (zh) | 2020-08-16 |
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