CN112839917A - 用于碱性基底的可固化组合物 - Google Patents
用于碱性基底的可固化组合物 Download PDFInfo
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- CN112839917A CN112839917A CN201980067457.5A CN201980067457A CN112839917A CN 112839917 A CN112839917 A CN 112839917A CN 201980067457 A CN201980067457 A CN 201980067457A CN 112839917 A CN112839917 A CN 112839917A
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- polyether
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- -1 1, 2-propylenoxy groups Chemical group 0.000 claims description 83
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- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 26
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- 238000005809 transesterification reaction Methods 0.000 description 1
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- ASLWPAWFJZFCKF-UHFFFAOYSA-N tris(1,3-dichloropropan-2-yl) phosphate Chemical compound ClCC(CCl)OP(=O)(OC(CCl)CCl)OC(CCl)CCl ASLWPAWFJZFCKF-UHFFFAOYSA-N 0.000 description 1
- HQUQLFOMPYWACS-UHFFFAOYSA-N tris(2-chloroethyl) phosphate Chemical compound ClCCOP(=O)(OCCCl)OCCCl HQUQLFOMPYWACS-UHFFFAOYSA-N 0.000 description 1
- XKCQNWLQCXDVOP-UHFFFAOYSA-N tris(2-chloropropan-2-yl) phosphate Chemical compound CC(C)(Cl)OP(=O)(OC(C)(C)Cl)OC(C)(C)Cl XKCQNWLQCXDVOP-UHFFFAOYSA-N 0.000 description 1
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- 239000010457 zeolite Substances 0.000 description 1
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Abstract
本发明涉及包含至少一种具有封闭的羟基基团的聚醚作为塑化剂的可固化组合物在至少一种碱性基材上的用途。该可固化组合物存储稳定,易于处理,固化后具有很高的弹性并且没有显示任何分离或迁移的趋势。它能实现弹性粘合,密封或涂覆碱性基材,如特别是新鲜或生的混凝土或水泥砂浆,而不会出现由塑化剂皂化引发的难闻气味。
Description
技术领域
本发明涉及基于聚氨酯或SMP的可固化组合物,其适用于碱性基底,例如特别是新鲜的(生的)混凝土或水泥砂浆,尤其是用作粘合剂、密封剂或涂料。
现有技术
基于聚氨酯或硅烷改性的聚合物(SMP)的可固化组合物在建筑行业中通常用作粘合剂、密封剂或涂料。用于施加此类产品的典型基底(基材)源自结合水泥、石灰或硅酸盐的建筑材料,例如混凝土或水泥砂浆。当这些建筑材料仅在新近才进行过加工时,以地基、墙壁、找平料(Estrichen)、抹灰等形式存在的基底仍然很新鲜,它们具有明显的碱性反应性的表面,其pH值为10或更高,因为其中包含的氢氧化物尚未被碳酸盐化。新鲜混凝土也被称为“新的”或“生的”或“湿的”。为了保护可固化组合物不与碱性表面接触,可以在施加组合物之前使其充分老化或者进行预处理,例如通过使用硅氟酸盐(Fluats)(例如氟硅酸盐)进行中和或通过借助于底涂剂(底漆)如环氧树脂涂料进行密封。但是,实际上,为了节省时间和金钱,通常不这样做。在边界层中,在碱性条件下会发生可固化组合物的成分的皂化反应,这会导致令人讨厌的气味排放。尤其是大多数此类组合物中存在的塑化剂,通常是脂肪醇二羧酸酯,例如邻苯二甲酸二异癸酯(DIDP)、二异壬基-环己烷-1,2-二羧酸酯(DINCH)或己二酸二(2-乙基己基)酯(DOA),会敏感地发生反应。其皂化导致释放出具有高度令人不愉快的气味的脂肪醇,并且该脂肪醇迁移到基材的孔结构中并从那里蒸发或被洗出到环境中并在长时间内产生霉味。特别是在通过弹性聚氨酯或SMP粘合剂将拼接地板粘合在新鲜的水泥找平层上时,观察到这种持久的气味负担。
发明概述
因此,本发明的目的是提供一种用于碱性基底的可固化组合物,该组合物适合在建筑领域中用作粘合剂、密封剂或涂料,并且克服了现有技术的缺点。
该目的通过如权利要求1所述的可固化组合物来实现。可固化组合物包括至少一种具有封闭的羟基基团的聚醚作为塑化剂。其可以通过简单的方法从容易获得的原料制备,在组合物中具有良好的相容性,具有很高的弹性化作用,并且在碱性基底上发生可能的皂化反应的情况下会释放出作为基础的羟基官能的聚醚,其是气味中性的并且不会产生任何其他麻烦的影响。具有封闭的羟基基团的聚醚促进可固化组合物的良好储存稳定性和可加工性,并且没有迁移或分离的趋势,这意味着它不会在基材上引起任何粘性表面或斑点形成。可固化组合物存储稳定,易于处理,固化后具有很高的弹性并且没有显示任何分离或迁移的趋势。它能够弹性粘合,密封或涂覆碱性基材,例如特别是新鲜或生混凝土或水泥砂浆,而不会出现塑化剂皂化引发的难闻气味。
因此,通过使用本发明也可以可靠地并且持久地粘合或密封或涂覆具有高碱性表面的基材,在这种情况下所获得的粘合连接不会引起麻烦的气味排放并且非常耐迁移效果。
本发明的其他方面是另外的独立权利要求的主题。本发明的特别优选的实施方案是从属权利要求的主题。
发明详述
本发明提供了包含至少一种具有封闭的羟基基团的聚醚作为塑化剂的可固化化合物在至少一种碱性基材上的用途,当用水润湿时该碱性基材具有至少10的pH。
“可固化组合物”是指含有可聚合的大分子的组合物,其通过其反应性基团的交联反应而可固化或达到提高的机械强度的状态。
“聚醚”是指主要由亚烷基氧基重复单元组成的分子或一组低聚和/或聚合物分子。
“封闭的羟基基团”是指通过化学反应转化为对异氰酸酯基团不具有反应性的基团的羟基。
“塑化剂”是指在固化过程中不会化学地结合入聚合物中,并且对已固化的聚合物产生增塑作用的难挥发性物质。
“硅烷基团”是指结合至有机基团并且在硅原子上具有一至三个,尤其是两个或三个可水解烷氧基的甲硅烷基。
“硅烷”是指每个硅烷基团上带有一至三个有机取代基的有机烷氧基硅烷和四烷氧基硅烷二者。有机基团上除了硅烷基团之外还带有一个或多个羟基、异氰酸基、氨基或巯基的硅烷分别被称为“羟基硅烷”、“异氰酸基硅烷”、“氨基硅烷”或“巯基硅烷”。
以“聚/多”开始的物质名称,如多胺、多元醇或多异氰酸酯,是指形式上每分子包含两个或更多个在其名称中出现的官能团的物质。
“分子量”是指分子或分子残基的摩尔质量(单位为克/摩尔)。“平均分子量”是指低聚或聚合的分子或分子残基的多分散混合物的数均分子量(Mn)。通常通过凝胶渗透色谱(GPC)相对于聚苯乙烯标样确定平均分子量。
被称作“储存稳定的”或“可储存的”的可固化组合物为可以在室温下在合适的容器中保存较长时间,通常至少3个月至6个月和更久,而其应用性能或使用性能在储存过程中不会以与其使用相关的程度变化的组合物。
“室温”是指23℃的温度。
特别地,用水润湿的碱性基材的pH使用pH试纸测定。
所述碱性基材优选是基于水泥、石灰(氢氧化钙)和/或硅酸盐(水玻璃)的新鲜但尚未完全碳酸化的基材。
特别优选地,碱性基材是新鲜的混凝土,新鲜的水泥砂浆,新鲜的石灰砂浆或新鲜的石灰或硅酸盐刷涂料。
只要混凝土仍能在10或更高的pH值下进行碱性反应,就称其为“新鲜”。混凝土仍保持新鲜的时间取决于其凝固速率和环境温度。时间段通常在1至10天的范围内变化。新鲜混凝土也称为“新的”或“生的”或“湿的”。
可固化组合物包含至少一种具有封闭的羟基基团的聚醚作为塑化剂。
具有封闭的羟基基团的聚醚基本上不含未封闭的羟基基团。这里“基本上不含”是指95%,优选99%,尤其是99.9%,最优选100%存在的羟基被封闭。
具有封闭的羟基基团的聚醚包含在可固化组合物中作为塑化剂。因此,其优选不含与水分或与组合物中存在的成分进行交联反应的反应性基团。其尤其不含异氰酸酯基团和硅烷基团。
具有封闭的羟基基团的聚醚尤其在室温下为液体。
具有封闭的羟基基团的聚醚优选在20℃下具有30-5000mPa·s、更优选40-2000mPa·s、尤其优选50-1000mPas、特别是50-500mPas范围的粘度。此处粘度使用锥板粘度计测定,所述锥板粘度计具有25mm的锥直径,锥角为1°,锥尖-板距离为0.05mm,剪切速率为10s-1。这种聚醚易于处理并且使得组合物具有高弹性。
封闭的羟基基团优选选自缩醛、酯、乙酰酯、碳酸酯和氨基甲酸酯基团。这些缩醛、酯、乙酰酯、碳酸酯或氨基甲酸酯基团优选具有1至15个碳原子。
特别优选的是酯或氨基甲酸酯基团。可以特别简单的方式将羟基转化为这些基团。
非常特别优选酯基,尤其是具有1至8个碳原子的酯基。
最优选的是乙酸酯基团。具有乙酸酯基形式的封闭的羟基基团的聚醚是低粘度的,可以以非常特别简单的方式获得并且特别便宜。如果其在碱性基材上皂化,则释放出气味中性的羟基官能的聚醚和乙酸酯,后者在碱性介质中不挥发并且没有明显的气味。
还优选的是氨基甲酸酯基团,尤其是苯基氨基甲酸酯基团或对甲苯磺酰基氨基甲酸酯基团。具有这种封闭的羟基基团的聚醚具有可处理的粘度并且可以特别简单的方式制备。
优选作为缩醛基团的是1-(异丁氧基)乙氧基或四氢吡喃-2-氧基或四氢呋喃-2-氧基,尤其是1-(异丁氧基)乙氧基。
优选的乙酰酯基是乙酰乙酸酯基。
优选的碳酸酯基团是甲基碳酸酯基团。
它们具有低粘度并且可以从廉价的原料获得。
具有封闭的羟基基团的聚醚优选具有1,2-亚乙基氧、1,2-亚丙基氧、1,3-亚丙基氧、1,2-亚丁基氧或1,4-亚丁基氧,尤其是1,2-亚丙基氧作为重复单元。
优选地,70wt%至100wt%、尤其是80wt%至100wt%的重复单元由1,2-亚丙基氧基组成,和0至30wt%、尤其是0-20wt%的重复单元由1,2-亚乙基氧基组成。
特别优选地,重复单元100%由1,2-亚丙基氧基组成。
这种聚醚易于获得,具有疏水性,因此特别适合用作吸水率低且稳定性好的可固化组合物的组分。
具有封闭的羟基基团的聚醚的平均分子量Mn优选在600至10000g/mol、更优选700-5000g/mol、尤其是800-2500g/mol的范围内,其通过凝胶渗透色谱法(GPC)确定,其中以聚苯乙烯作为标准物并使用四氢呋喃作为流动相,使用折射率检测器并且从200g/mol评价。
这种具有封闭的羟基基团的聚醚具有易于处理的粘度并且在可固化组合物中不引起迁移效果、排放或气味。
具有封闭的羟基基团的聚醚优选衍生自至少一种羟基官能的聚醚,其选自
–OH值在25至90mg KOH/g、优选50至80mg KOH/g范围内的以醇起始的,尤其是以正丁醇起始的聚氧亚丙基一元醇,
–OH值在12至155mg KOH/g,优选22-125mg KOH/g,尤其是45-125mg KOH/g范围内的聚氧亚丙基二醇,
–平均OH官能度为2.2-3和OH值在22至230mg KOH/g、优选56至165mg KOH/g范围内的由三羟甲基丙烷或尤其是甘油起始的,任选环氧乙烷封端的聚氧亚丙基三醇,和
–平均OH官能度为3-6,尤其使用苏糖醇、赤藓糖醇、木糖醇、甘露醇或山梨糖醇作为起始分子的糖醇起始的聚氧亚丙基多元醇。这种具有封闭的羟基基团的聚醚可作为SPX-80(来自Sanyo Chem.Ind.)商购获得。
其中,优选的是由醇起始的、尤其是正丁醇起始的聚氧亚丙基一元醇或聚氧亚丙基二醇。
特别优选的是聚氧亚丙基二醇。这些是特别廉价的。
优选的具有封闭的羟基基团的聚醚可以简单的方法由容易获得的原料制备,具有低粘度并且能够使可固化组合物具有良好的储存稳定性,易处理性以及在固化的状态中具有高的柔性和弹性,而没有任何迁移效应、排放或气味的趋势。
具有封闭的羟基基团的聚醚尤其通过将至少一种羟基官能的聚醚与至少一种合适的羟基的封闭剂反应获得。
对于反应,以相对于羟基至少化学计量的量使用封闭剂,从而使羟基基本上被完全封闭并且因此得到的聚醚基本上是不含羟基的。对于封闭,使用常规的用于各个反应性基团的方法,任选地并用催化剂或溶剂。如果封闭反应形成了消除产物,则通过合适的方法,尤其是通过蒸馏,将它们从反应混合物中除去。
合适的封闭剂是亲核化合物,其与羟基进行加成或取代反应。
尤其合适的是乙烯基醚、羧酸、碳酰氯、羧酸酯或羧酸酐、双烯酮、2,2,5-三甲基-4H-1,3-二噁英-4-酮、乙酰乙酸烷基酯、碳酸二烷基酯、单异氰酸酯、(甲基)丙烯酰胺、丙二酸亚甲基酯或氰基丙烯酸酯。
优选的是乙烯基醚,例如特别是甲基乙烯基醚、乙基乙烯基醚、异丙基乙烯基醚、丁基乙烯基醚、异丁基乙烯基醚、异丙烯基甲基醚、异丙烯基乙基醚、2,3-二氢呋喃或3,4-二氢-2H-吡喃,特别优选异丁基乙烯基醚、2,3-二氢呋喃或3,4-二氢-2H-吡喃,其中形成乙缩醛基形式的封闭的羟基基团。该反应优选在酸,尤其是盐酸、硫酸、磷酸或磺酸作为催化剂的存在下进行,任选地以酸性离子交换树脂的形式。
优选的是羧酸、碳酰氯、羧酸酯或羧酸酐,其中以酯基的形式形成封闭的羟基基团。其中,优选羧酸酐或羧酸酯,尤其是乙酸酐。
在乙酸酐作为封闭剂的情况下,该反应中释放出乙酸,并形成乙酸酯基团形式的封闭的羟基基团。
在异丙烯基乙酸酯作为封闭剂的情况下,反应中释放出丙酮,同样形成乙酸酯基团形式的封闭的羟基基团。
还优选的是双烯酮,2,2,5-三甲基-4H-1,3-二噁英-4-酮或空间受阻的乙酰乙酸烷基酯,例如特别是乙酰乙酸叔丁酯,并形成以乙酰酯基团形式的封闭的羟基基团。
还优选的而是碳酸二烷基酯,尤其是碳酸二甲基酯,并形成以碳酸酯基团,尤其是碳酸甲基酯基团形式的封闭的羟基基团。
还优选的是单异氰酸酯,其中以氨基甲酸酯基团的形式形成封闭的羟基基团。优选的是苯基异氰酸酯或对甲苯磺酰基异氰酸酯。
合适的羟基官能的聚醚尤其是具有1-6平均OH官能度并且平均分子量为500-10000g/mol、更优选600-5000g/mol、尤其是700-2500g/mol的那些。
优选的是OH值为25-90mg KOH/g、优选50-80mg KOH/g的聚氧亚丙基一元醇,尤其是由醇起始的聚氧亚丙基一元醇,尤其是由甲醇、乙醇、丙醇、异丙醇、正丁醇、异丁醇、叔丁醇、戊醇、己醇、2-乙基己醇、月桂醇、肉豆蔻醇、棕榈醇、烯丙醇、环己醇、苯甲醇或苯酚起始的那些。其中,优选烷基醇起始的聚氧亚丙基一元醇,尤其是由甲醇、乙醇或正丁醇起始的。特别优选的是平均分子量为650-2000g/mol、尤其是700-1500g/mol的正丁醇起始的聚氧亚丙基一元醇。正丁醇起始的聚氧亚丙基一元醇可商购获得,例如作为100-20B、100-40B或100-85B(全部来自DowDuPont Inc.)。
还优选的是OH值在12至155mg KOH/g、优选22至125mg KOH/g、尤其是45至125mgKOH/g范围内的聚氧亚丙基二醇。
进一步优选平均OH官能度为2.2-3和OH值为22-230mg KOH/g、优选56-165mg KOH/g的三羟甲基丙烷或尤其是甘油起始的、任选环氧乙烷封端的聚氧亚丙基三醇。
进一步优选平均OH官能度为至少3、尤其是3-6的由糖醇起始的聚氧亚丙基多元醇,尤其使用苏糖醇、赤藓糖醇、木糖醇、甘露醇或山梨糖醇作为起始分子的。
可固化组合物优选包含具有聚醚结构单元,尤其主要是聚氧亚丙基结构单元部分的至少一种可固化的聚合物。具有封闭的羟基基团的聚醚在这种可固化组合物中是特别相容的,并且几乎没有显示任何分离或迁移的趋势。
可固化组合物优选包含至少一种含异氰酸酯和/或硅烷基团的聚合物。
含有异氰酸酯和/或硅烷基团的聚合物优选具有1000-30000g/mol,尤其是2000-20000g/mol的平均分子量。
其优选在室温下为液体。
在一个优选的实施方案中,组合物含有至少一种含异氰酸酯基团的聚合物。这种组合物也被称为“聚氨酯组合物”。
含有异氰酸酯基团的合适的聚合物尤其是由至少一种多元醇与超化学计量的至少一种二异氰酸酯的反应获得的。该反应优选在排除水分的条件下在20至160℃、尤其是40至140℃的温度下进行,任选地在合适的催化剂存在下进行。
NCO/OH比优选在1.3/1至10/1的范围内。可以除去OH基团反应后残留在反应混合物中的单体二异氰酸酯,尤其是通过蒸馏的方法。
如果通过蒸馏除去过量的单体二异氰酸酯,则反应中的NCO/OH比优选在4/1至7/1的范围内,并且在蒸馏后所得的包含异氰酸酯基的聚合物优选包含不大于0.5wt%,更优选不大于0.3wt%的单体二异氰酸酯。单体二异氰酸酯尤其是通过在减压下的短程蒸馏除去的。
如果不从聚合物中除去过量的单体二异氰酸酯,则反应中的NCO/OH比优选在1.3/1至2.5/1范围内。
所得聚合物中异氰酸酯基的含量优选为0.5-10wt%,尤其是1-5wt%,更优选为1-3wt%,并且平均分子量为1500至20000g/mol、尤其是2000至15000g/mol。
任选地通过并用塑化剂或溶剂来制备聚合物,在这种情况下,所用的塑化剂或溶剂不包含任何对异氰酸酯具有反应性的基团。
优选的是脂肪族、环脂族或芳香族二异氰酸酯,尤其是1,6-六亚甲基二异氰酸酯(HDI)、1-异氰酸基-3,3,5-三甲基-5-异氰酸基甲基环己烷(异佛尔酮二异氰酸酯或IPDI)、全氢2,4'-和/或4,4'-二苯基甲烷二异氰酸酯(H12MDI)、4,4'-二苯基甲烷二异氰酸酯(其任选具有2,4'-和/或2,2'-二苯基甲烷二异氰酸酯部分(MDI)),或2,4-甲苯二异氰酸酯或其与2,6-甲苯二异氰酸酯的混合物(TDI)。
特别优选的是HDI,IPDI,MDI或TDI,或其混合物。
合适的多元醇为市售多元醇或其混合物,尤其是
–聚醚多元醇,尤其是聚氧化亚烷基二元醇和/或聚氧化亚烷基三元醇,尤其是环氧乙烷或1,2-环氧丙烷或1,2-或2,3-环氧丁烷或氧杂环丁烷或四氢呋喃或其混合物的聚合产物,其中它们可以借助于具有两个或更多个活性氢原子的起始剂分子聚合,所述起始剂分子尤其是例如水,氨或具有多个OH-基团或NH-基团的化合物,例如1,2-乙二醇、1,2-或1,3-丙二醇、新戊二醇、二乙二醇、三乙二醇、异构的二丙二醇或三丙二醇、异构的丁二醇、戊二醇、己二醇、庚二醇、辛二醇、壬二醇、癸二醇、十一烷二醇、1,3-或1,4-环己烷二甲醇、双酚A、氢化双酚A、1,1,1-三羟甲基乙烷、1,1,1-三羟甲基丙烷、甘油或苯胺,或上述化合物的混合物。同样合适的是具有分散在其中的聚合物颗粒的聚醚多元醇,尤其是具有苯乙烯-丙烯腈-颗粒(SAN)或聚脲颗粒或聚亚肼基二甲酰胺颗粒(PHD)的那些。
优选的聚醚多元醇为聚氧亚丙基二元醇或聚氧亚丙基三元醇,或所谓的环氧乙烷封端的(EO-封端的或EO-封闭的)聚氧亚丙基二元醇或三元醇。后者为聚氧亚乙基-聚氧亚丙基-混合多元醇,所述聚氧亚乙基-聚氧亚丙基-混合多元醇尤其这样获得:在聚丙氧基化反应结束之后用环氧乙烷进一步烷氧基化聚氧亚丙基二元醇或三元醇,并且使其因此具有伯羟基。
优选的聚醚多元醇具有小于0.02mEq/g,尤其是小于0.01mEq/g的不饱和度。
–聚酯多元醇(也被称为低聚酯醇),其根据已知方法(尤其是羟基羧酸或内酯的缩聚或脂族和/或芳族多羧酸与二元或多元醇的缩聚)制得。优选的是得自二元醇(例如特别是1,2-乙二醇、二乙二醇、1,2-丙二醇、二丙二醇、1,4-丁二醇、1,5-戊二醇、1,6-己二醇、新戊二醇、甘油、1,1,1-三羟甲基丙烷或上述醇的混合物)与有机二羧酸或其酸酐或酯(例如特别是丁二酸、戊二酸、己二酸、辛二酸、癸二酸、十二烷二羧酸、马来酸、富马酸、邻苯二甲酸、间苯二甲酸、对苯二甲酸、1,2-环己烷二羧酸、1,3-环己烷二羧酸或1,4-环己烷二羧酸或上述酸的混合物)的反应的聚酯二元醇,或由内酯(例如特别是ε-己内酯)形成的聚酯多元醇。特别优选的是得自己二酸或癸二酸或十二烷二羧酸和己二醇或新戊二醇的聚酯多元醇。
–聚碳酸酯多元醇,例如可通过例如上述(为了构建聚酯多元醇所使用的)醇与碳酸二烷基酯、碳酸二芳基酯或光气的反应获得的那些。
–带有至少两个羟基的嵌段共聚物,所述嵌段共聚物具有至少两个不同的具有上述类型的聚醚、聚酯和/或聚碳酸酯结构的嵌段,尤其是聚醚聚酯多元醇。
–聚丙烯酸酯多元醇和聚甲基丙烯酸酯多元醇。
–多羟基官能的脂肪或油,例如天然脂肪和油,尤其是蓖麻油;或通过天然脂肪和油的化学改性获得的——所谓油脂化学的——多元醇,例如通过不饱和油的环氧化和之后的用羧酸或醇开环获得的环氧聚酯或环氧聚醚,或通过不饱和油的加氢甲酰化和氢化获得的多元醇;或由天然脂肪和油通过分解过程(例如醇解或臭氧分解)和之后所获得的分解产物或其衍生物的化学键接(例如通过酯交换或二聚)获得的多元醇。天然脂肪和油的合适的分解产物特别是脂肪酸和脂肪醇以及脂肪酸酯,特别是甲基酯(FAME),其可以例如通过加氢甲酰化和氢化而衍生成羟基脂肪酸酯。
–聚烃多元醇,也被称为低聚烃醇,例如特别是多羟基官能的聚烯烃、聚异丁烯、聚异戊二烯;多羟基官能的乙烯-丙烯-共聚物、乙烯-丁烯-共聚物或乙烯-丙烯-二烯-共聚物,例如由Kraton Polymers公司制备的那些;多羟基官能的二烯(特别是1,3-丁二烯)聚合物,所述聚合物特别也可以通过阴离子聚合制备;多羟基官能的二烯(例如1,3-丁二烯)或二烯混合物和乙烯基单体(例如苯乙烯、丙烯腈、氯乙烯、乙酸乙烯酯、乙烯醇、异丁烯或异戊二烯)的共聚物,尤其是多羟基官能的丙烯腈/丁二烯-共聚物,例如特别可通过环氧化物或氨基醇和羧基封端的丙烯腈/丁二烯-共聚物(例如以名称CTBN或CTBNX或ETBN从Emerald Performance Materials市售获得)制备的那些;或氢化的多羟基官能的二烯聚合物或共聚物。
尤其合适的还有多元醇的混合物。
优选的是聚醚多元醇、聚酯多元醇、聚碳酸酯多元醇、聚(甲基)丙烯酸酯多元醇或聚丁二烯多元醇。
特别优选的是聚醚多元醇、聚酯多元醇,尤其是脂肪族聚酯多元醇,或聚碳酸酯多元醇,尤其是脂肪族聚碳酸酯多元醇。
尤其优选的是聚醚多元醇,尤其是聚氧亚烷基多元醇。
最优选的是聚氧亚丙基二元醇或三元醇或环氧乙烷封端的聚氧亚丙基二元醇或三元醇。
优选的是平均分子量在400至20000g/mol、优选1000至15000g/mol范围内的多元醇。
优选的是平均OH-官能度在1.6至3范围内的多元醇。
优选的是在室温下为液体的多元醇。
在制备含异氰酸酯基团的聚合物时还可以并用一定量的双官能或多官能醇,尤其是1,2-乙二醇、1,2-丙二醇、1,3-丙二醇、2-甲基-1,3-丙二醇、1,2-丁二醇、1,3-丁二醇、1,4-丁二醇、1,3-戊二醇、1,5-戊二醇、3-甲基-1,5-戊二醇、新戊二醇、二溴新戊二醇、1,2-己二醇、1,6-己二醇、1,7-庚二醇、1,2-辛二醇、1,8-辛二醇、2-乙基-1,3-己二醇、二乙二醇、三乙二醇、二丙二醇、三丙二醇、1,3-或1,4-环己烷二甲醇、乙氧基化双酚-A、丙氧基化双酚-A、环己二醇、氢化双酚-A、二聚脂肪酸醇、1,1,1-三羟甲基乙烷、1,1,1-三羟甲基丙烷、甘油、季戊四醇、糖醇例如尤其是木糖醇、山梨醇或甘露醇,或糖例如特别是蔗糖,或上述醇或上述醇混合物的烷氧基化衍生物。
含异氰酸酯基团的聚合物优选具有1500至20000g/mol,尤其是2000至15000g/mol范围内的平均分子量。
除了含异氰酸酯基团的聚合物之外,组合物可以包含至少一种低聚异氰酸酯或在室温下为液体的MDI的形式。
合适的低聚异氰酸酯尤其为HDI缩二脲例如N 100或N 3200(来自Covestro AG),HDB或HDB-LV(来自Vencorex Holding SAS)或24A-100(来自Asahi Kasei Corp.);HDI异氰尿酸酯,例如N 3300,N 3600或N3790 BA(所有均来自Covestro AG),HDT,HDT-LV或HDT-LV2(来自VencorexHolding SAS),TPA-100或THA-100(来自Asahi Kasei Corp.)或HX(来自Tosoh Corp.);HDI脲二酮例如N 3400(来自Covestro AG);HDI亚氨基噁二嗪二酮例如XP 2410(来自Covestro AG);HDI脲基甲酸酯例如VP LS 2102(来自Covestro AG);IPDI异氰脲酸酯,例如在溶液中的Z 4470(来自Covestro AG)或以固体的形式的T1890/100(来自Evonik Industries AG);TDI低聚物例如IL(来自Covestro AG);或基于TDI/HDI的混合的异氰尿酸酯,例如HL(来自Covestro AG)。
在室温下呈液态的MDI形式是通过部分化学改性(尤其是碳二亚胺化或形成脲酮亚胺或与多元醇形成加合物)而被液化的4,4'-MDI,或者是通过共混有目的产生的或由生产工艺产生的4,4'-MDI与其他MDI异构体(2,4'-MDI和/或2,2'-MDI)和/或与MDI低聚物和/或MDI同系物(聚合物MDI或PMDI)的混合物。
在本发明的一个优选实施方案中,可固化组合物除包含含有异氰酸酯基的至少一种聚合物外,还包含至少一种潜在固化剂。这种聚氨酯组合物在固化过程中特别极少起泡。
优选的潜在固化剂是酮亚胺、醛亚胺或噁唑烷,尤其是噁唑烷或醛亚胺,最优选醛亚胺。
A优选为任选地具有环状组分的亚烷基或具有5至15个碳原子的二价或三价聚氧化亚烷基,尤其是1,6-亚己基、(1,5,5-三甲基环己-1-基)甲烷-1,3或平均分子量在170至300g/mol的α,ω-聚氧亚丙基或平均分子量在330至500g/mol的三羟甲基丙烷起始的三(ω-聚氧亚丙基)。
B优选为具有7至22个碳原子的有机基团,尤其是2,2-二甲基-3-乙酰氧基亚丙基、2,2-二甲基-3-月桂酰氧基亚丙基、2,2-二甲基-3-(N-吗啉代)亚丙基、亚苄基或烷基取代的亚苄基,尤其是4-癸基亚苄基、4-十一烷基亚苄基、4-十二烷基亚苄基、4-十三烷基亚苄基或4-十四烷基亚苄基,其中4-烷基基团主要是分支的。
特别优选地,B是具有至少15个碳原子的基团,尤其是2,2-二甲基-3-月桂酰氧基亚丙基或烷基取代的亚苄基。这种醛亚胺是无味的。
优选的胺A-(NH2)y是脂肪族或脂环族的伯二胺或三胺,尤其是1,6-六亚甲基二胺、异佛尔酮二胺、α,ω-聚氧亚丙基二胺,其平均分子量为200至350g/mol,尤其是D-230(来自Huntsman Corp.),或三羟甲基丙烷起始的三(ω-聚氧亚丙基胺),尤其是T-403(来自Huntsman Corp.)。
作为醛O=B优选的是羧酸的羟醛酯,尤其是2,2-二甲基-3-乙酰氧基丙醛、2,2-二甲基-3-月桂酰氧基氧丙醛、2,2-二甲基-3-(N-吗啉代)丙醛、苯甲醛或烷基取代的苯甲醛,尤其是4-癸基苯甲醛、4-十一烷基苯甲醛、4-十二烷基苯甲醛、4-十三烷基苯甲醛或4-十四烷基苯甲醛,其中4-烷基主要为支链的,以及这些被烷基取代的苯甲醛的混合物。
与水分接触时,会从潜在固化剂会释放出氨基和可能的羟基,其与异氰酸酯反应并充当交联剂。这过程中会释放出醛或酮。
在其中B是长链基团、尤其是具有15个或更多个碳原子的基团的优选的式O=B的醛的情况下,这不会引起任何气味问题并且在固化后保留在组合物中,在组合物中其具有良好的相容性并且可作为进一步的塑化剂。
与水和异氰酸酯的直接反应相比,通过潜在固化剂进行交联具有不释放CO2的优点,这大大降低了固化过程中形成气泡的趋势。
在另一个优选的实施方案中,所述可固化组合物含有至少一种含硅烷基团的有机聚合物。这种聚合物也被称为“硅烷改性的聚合物”(SMP),并且这种组合物因此也被称为SMP组合物。
含硅烷基团的有机聚合物优选具有式
其中
Ra为具有1至5个碳原子的直链或支化的一价烃基,尤其是甲基或乙基,
Rb为具有1至8个碳原子的直链或支化的一价烃基,尤其是甲基,并且
x具有0或1或2,优选0或1,特别是0的值。
在此,甲氧基硅烷基团的优点在于其特别具有反应性。乙氧基硅烷基团的优点在于其在毒理学上是有利的并且特别是储存稳定的。
特别优选的是三甲氧基硅烷基团、二甲氧基甲基硅烷基团或三乙氧基硅烷基团。
最优选的是三甲氧基硅烷基团或三乙氧基硅烷基团。
优选的含硅烷基团的有机聚合物是聚烯烃或聚酯或聚酰胺或聚(甲基)丙烯酸酯或聚醚或这些聚合物的混合形式。硅烷基团可以位于链的侧面或端部并且通过碳原子连接至有机聚合物。
更优选地,含硅烷基团的有机聚合物是含硅烷基团的聚醚。
“含硅烷基团的聚醚”是指含有至少一个硅烷基团的有机聚合物,其聚合物链主要具有聚醚单元,尤其是1,2-氧化亚丙基单元。除了聚醚单元之外,还尤其可以包含氨基甲酸酯基团、脲基团、硫代氨基甲酸酯基团、酯基团或酰胺基团。
含硅烷基团的聚醚优选含有至少50重量%,尤其是至少70重量%,更优选优选至少80重量%的1,2-氧化亚丙基单元。
用于制备合适的含硅烷基团的聚醚的方法是本领域技术人员已知的。
在一个优选的方法中,含硅烷基团的聚醚可由含烯丙基的聚醚与含氢硅烷的反应获得,任选使用例如二异氰酸酯进行链延长。
在另一优选的方法中,含硅烷基团的聚醚可由环氧烷和环氧硅烷的共聚获得,任选使用例如二异氰酸酯进行链延长。
在另一优选的方法中,含硅烷基团的聚醚可由聚醚多元醇与异氰酸基硅烷的反应获得,任选使用二异氰酸酯进行链延长。
在另一优选的方法中,含硅烷基团的聚醚可由含异氰酸酯基团的聚醚与氨基硅烷、羟基硅烷或巯基硅烷的反应获得。得自所述方法的含硅烷基团的聚醚是特别优选的。所述方法允许使用大量市售容易获得的廉价的起始材料,因此可以获得不同的聚合物性能,尤其是高可拉伸性、高强度、低弹性模量、低玻璃化转变点或高耐候性。
特别优选地,含硅烷基团的聚醚可由含异氰酸酯基团的聚醚与氨基硅烷和/或羟基硅烷和/或巯基硅烷的反应获得。
合适的含异氰酸酯基团的聚醚尤其可由聚醚多元醇(尤其是聚氧化亚烷基二元醇或聚氧化亚烷基三元醇,优选聚氧化亚丙基二元醇或聚氧化亚丙基三元醇)与超化学计量的二异氰酸酯的反应获得。
优选地,二异氰酸酯和聚醚多元醇之间的反应在排除水分的情况下在50℃至160℃的温度下任选在合适催化剂的存在下进行,其中计量加入二异氰酸酯,使得其异氰酸酯基团相比于多元醇的羟基以化学计量过量存在。特别地,选择过量的二异氰酸酯,使得在所有羟基反应之后获得0.1至5重量%,优选0.2至4重量%,更优选0.3至3重量%的游离异氰酸酯基团含量,以整个聚合物计。
优选的二异氰酸酯为已经以上提及的那些。特别优选的是IPDI或TDI。最优选的是IPDI。因此获得具有特别良好的耐光性的含硅烷基团的聚醚。
尤其适合作为聚醚多元醇的是不饱和度低于0.02mEq/g,尤其是低于0.01mEq/g并且平均分子量为400至25000g/mol,尤其是1000至20000g/mol范围内的聚氧化亚丙基二元醇。
除了聚醚多元醇之外,还可以按比例使用其它多元醇,尤其是聚丙烯酸酯多元醇,以及低分子量二元醇或三元醇。
用于与含异氰酸酯基团的聚醚反应的合适的氨基硅烷是伯氨基硅烷和尤其是仲氨基硅烷。优选的是3-氨基丙基三甲氧基硅烷、3-氨基丙基二甲氧基甲基硅烷、4-氨基丁基三甲氧基硅烷、4-氨基-3-甲基丁基三甲氧基硅烷、4-氨基-3,3-二甲基丁基三甲氧基硅烷、N-丁基-3-氨基丙基三甲氧基硅烷、N-苯基-3-氨基丙基三甲氧基硅烷、伯氨基硅烷(例如3-氨基丙基三甲氧基硅烷、3-氨基丙基二甲氧基甲基硅烷或N-(2-氨基乙基)-3-氨基丙基三甲氧基硅烷)和迈克尔受体(例如丙烯腈、(甲基)丙烯酸酯、(甲基)丙烯酰胺、马来酸二酯或富马酸二酯、柠康酸二酯或衣康酸二酯,尤其是N-(3-三甲氧基甲硅烷基丙基)氨基琥珀酸二甲基酯或二乙基酯)的加合物。同样合适的是上述氨基硅烷的在硅上具有乙氧基代替甲氧基的相似物。
用于与含异氰酸酯基团的聚醚反应的合适的羟基硅烷尤其可获自氨基硅烷在内酯或环状碳酸酯或交酯上的加成反应。
通过这种方式获得的优选的羟基硅烷为N-(3-三乙氧基甲硅烷基丙基)-2-羟基丙酰胺、N-(3-三甲氧基甲硅烷基丙基)-2-羟基丙酰胺、N-(3-三乙氧基甲硅烷基丙基)-4-羟基戊酰胺、N-(3-三乙氧基甲硅烷基丙基)-4-羟基辛酰胺、N-(3-三乙氧基甲硅烷基丙基)-5-羟基癸酰胺或N-(3-三乙氧基甲硅烷基丙基)-2-羟基丙基氨基甲酸酯。
其它合适的羟基硅烷可获自氨基硅烷在环氧化物上的加成反应或胺在环氧硅烷上的加成反应。
通过这种方式获得的优选的羟基硅烷为2-吗啉代-4(5)-(2-三甲氧基甲硅烷基乙基)环己烷-1-醇、2-吗啉代-4(5)-(2-三乙氧基甲硅烷基乙基)环己烷-1-醇或1-吗啉代-3-(3-(三乙氧基甲硅烷基)丙氧基)丙烷-2-醇。
用于与含异氰酸酯基团的聚醚反应的合适的巯基硅烷特别是3-巯基丙基三甲氧基硅烷或3-巯基丙基三乙氧基硅烷。
适合作为含有硅烷基团的聚醚的还有可商购获得的产品,尤其是如下:MSPolymerTM(得自Kaneka Corp.;尤其是S203H,S303H,S227,S810,MA903和S943产品);MSPolymerTM或SilylTM(得自Kaneka Corp.;尤其是SAT010,SAT030,SAT200,SAX350,SAX400,SAX725,MAX450,MAX951型的产品);(得自Asahi Glass Co.Ltd.;尤其是S2410,S2420,S3430,S3630产品);SPUR+*(得自Momentive Performance Materials Inc.;尤其是1010LM,1015LM,1050MM型的产品);VorasilTM(得自DowDuPont Inc.;尤其是602和604型产品);(得自Covestro AG;尤其是S XP 2458,S XP 2636,S XP 2749,SXP 2774和S XP 2821型产品),(得自Evonik Industries AG;尤其是Seal 100,Bond 150,Bond 250型产品),聚合物ST(得自Hanse Chemie AG/Evonik Industries AG,尤其是47,48,61,61LV,77,80,81型产品);STP(得自Wacker Chemie AG;尤其是E10,E15,E30,E35型产品)。
特别优选地,含硅烷基团的聚醚由至少一种含异氰酸酯基团的聚醚与至少一种氨基硅烷和/或羟基硅烷和/或巯基硅烷的反应获得。
优选地,在此氨基硅烷和/或羟基硅烷和/或巯基硅烷选自N-(3-三甲氧基甲硅烷基丙基)氨基琥珀酸二甲酯、N-(3-三甲氧基甲硅烷基丙基)氨基琥珀酸二乙酯、N-(3-三乙氧基甲硅烷基丙基)氨基琥珀酸二甲酯、N-(3-三乙氧基甲硅烷基丙基)氨基琥珀酸二乙酯、N-(3-三甲氧基甲硅烷基丙基)-2-羟基丙酰胺、N-(3-三乙氧基甲硅烷基丙基)-2-羟基丙酰胺、3-巯基丙基三甲氧基硅烷和3-巯基丙基三乙氧基硅烷。
含硅烷基团的有机聚合物的优选实施方式能够使得组合物具有良好的储存稳定性、迅速的固化和特别良好的机械性能,特别是高弹性和可拉伸性以及良好的强度和高耐热性。
优选地,可固化组合物额外地包含尤其选自填料、增粘剂、干燥剂、增稠剂和催化剂的一种或多种其它成分。
合适的填料尤其是任选涂布有脂肪酸、特别是硬脂酸酯的研磨或沉淀的碳酸钙,重晶石(Schwerspate),石英粉,石英砂,白云石,硅灰石,煅烧高岭土,层状硅酸盐例如云母或滑石,沸石,氢氧化铝,氢氧化镁,二氧化硅(包括来自热解过程的高分散性二氧化硅),水泥,石膏,粉煤灰,工业制得的炭黑,石墨,金属粉末例如铝、铜、铁、银或钢,PVC-粉末或空心球。
优选的是任选涂布有脂肪酸、尤其是硬脂酸酯的碳酸钙,煅烧高岭土或工业制得的炭黑。
在一个优选的实施方案中,组合物包含基于碳酸钙的至少一种填料。尤其在具有以酯基团的形式,例如特别是乙酸酯基团形式的封闭的羟基基团的聚醚的情况下,这是特别有利的,因为从中通过水解可能释放出的任何酸,特别是例如乙酸会被碳酸钙结合,并且因此不会引起任何气味排放。
所述组合物优选含有5wt%至50wt%,尤其是10wt%至40wt%的基于碳酸钙的填料。
合适的增粘剂尤其是氨基硅烷,例如特别是3-氨基丙基三甲氧基硅烷、3-氨基丙基二甲氧基甲基硅烷、N-(2-氨基乙基)-3-氨基丙基三甲氧基硅烷、N-(2-氨基乙基)-3-氨基丙基二甲氧基甲基硅烷、N-(2-氨基乙基)-N'-[3-(三甲氧基甲硅烷基)丙基]乙二胺或其具有乙氧基代替甲氧基的相似物,此外还有N-苯基-、N-环己基-或N-烷基氨基硅烷、巯基硅烷、环氧硅烷、(甲基)丙烯酰基硅烷、酸酐基硅烷、氨基甲酸酯基硅烷、烷基硅烷或亚氨基硅烷,这些硅烷的低聚形式,伯氨基硅烷与环氧硅烷或(甲基)丙烯酰基硅烷或酸酐基硅烷的加合物,氨基官能的烷基倍半硅氧烷,尤其是氨基官能的甲基倍半硅氧烷或氨基官能的丙基倍半硅氧烷,或钛酸酯。
对于含异氰酸酯基团的组合物,尤其适合作为增粘剂的是环氧硅烷,例如特别是3-缩水甘油氧基丙基三甲氧基硅烷或3-缩水甘油氧基丙基三乙氧基硅烷,(甲基)丙烯酰基硅烷,酸酐硅烷,氨基甲酸酯基硅烷,烷基硅烷或亚氨基硅烷或这些硅烷的低聚形式。
用于包含含硅烷基团的聚合物的组合物的合适的干燥剂尤其是四乙氧基硅烷,乙烯基三甲氧基硅烷,乙烯基三乙氧基硅烷或在硅烷基团的α-位具有官能团的有机烷氧基硅烷,尤其是N-(甲基二甲氧基甲硅烷基甲基)-O-甲基氨基甲酸酯,(甲基丙烯酰氧基甲基)硅烷,甲氧基甲基硅烷,原甲酸酯,氧化钙或分子筛粉。
用于含异氰酸酯基团的组合物的合适的干燥剂尤其是分子筛粉、氧化钙、高反应性异氰酸酯例如对甲苯磺酰异氰酸酯,单体二异氰酸酯或原甲酸酯。
合适的增稠剂尤其是脲,片状硅酸盐如膨润土,蓖麻油的衍生物,氢化蓖麻油,聚酰胺,聚氨酯或热解法二氧化硅。
优选的增稠剂是可在室温下铺展的糊状物,其含有10wt%至25wt%的脲化合物和75wt%至90wt%的上述具有封闭的羟基基团的聚醚。这种糊剂尤其是通过使二异氰酸酯,尤其是4,4'-二苯基甲烷二异氰酸酯,和一元胺、尤其是正丁胺,在具有封闭的羟基基团的聚醚中反应而制得的。
合适的催化剂是用于硅烷基团的交联的催化剂,尤其是金属催化剂,例如特别是锡、钛、锆、铝或锌的化合物,和/或含氮化合物。优选的是二有机锡(IV)化合物,例如特别是二乙酸二丁基锡(IV)、二月桂酸二丁基锡(IV)、二新癸酸二丁基锡(IV)、二(乙酰丙酮酸)二丁基锡(IV)或二月桂酸二辛基锡(IV),还有特别具有烷氧基配体、羧酸酯配体、1,3-二酮酸配体、1,3-酮酸酯配体或1,3-酮酰胺化物配体的钛(IV)-络合物或锆(IV)-络合物或铝(III)-络合物或锌(II)-络合物,尤其是有机钛酸酯,以及还有胺,脒例如特别是1,8-二氮杂双环[5.4.0]十一碳-7-烯(DBU)、1,5-二氮杂双环[4.3.0]壬-5-烯(DBN)、6-二丁基氨基-1,8-二氮杂双环[5.4.0]十一碳-7-烯、6-二丁基氨基-1,8-二氮杂双环[5.4.0]十一碳-7-烯、N,N'-二正己基乙脒(DHA)、2-甲基-1,4,5,6-四氢嘧啶、1,2-二甲基-1,4,5,6-四氢嘧啶、2,5,5-三甲基-1,4,5,6-四氢嘧啶、N-(3-三甲氧基甲硅烷基丙基)-4,5-二氢咪唑、N-(3-三乙氧基甲硅烷基丙基)-4,5-二氢咪唑,1-(3-二甲基氨基丙基)-2-甲基-1,4,5,6-四氢嘧啶,1-(3-氨基丙基)-2-甲基-1,4,5,6-四氢嘧啶或其反应产物,或胍例如特别是1-丁基胍、1,1-二甲基胍、1,3-二甲基胍、1,1,3,3-四甲基胍(TMG)、2-(3-(三甲氧基甲硅烷基)丙基)-1,1,3,3-四甲基胍、2-(3-(甲基二甲氧基甲硅烷基)丙基)-1,1,3,3-四甲基胍、2-(3-(三乙氧基甲硅烷基)丙基)-1,1,3,3-四甲基胍、1,5,7-三氮杂双环[4.4.0]癸-5-烯(TBD)、7-甲基-1,5,7-三氮杂双环[4.4.0]癸-5-烯、7-环己基-1,5,7-三氮杂双环[4.4.0]癸-5-烯、1-苯基胍、1-(邻甲苯基)胍(OTG)、1,3-二苯基胍、1,3-二(邻甲苯基)胍、2-胍基苯并咪唑或来自单胺、多胺或氨基硅烷与碳二亚胺,尤其是二环己基碳二亚胺或二异丙基碳二亚胺反应的胍,以及双胍类或咪唑类。
优选的是有机钛酸酯,尤其是双(乙基乙酰乙酸基)二异丁氧基钛(IV)(可商购获得的,例如IBAY,来自Dorf Ketal)、双(乙基乙酰乙酸基)二异丙氧基钛(IV)(可商购获得的,例如DC,来自Dorf Ketal)、双(乙酰丙酮基)二异丙氧基钛(IV)、双(乙酰丙酮基)二异丁氧基钛(IV)、三(氧乙基)胺异丙氧基钛(IV)、双[三(氧乙基)胺]二异丙氧基钛(IV)、双(2-乙基己烷-1,3-二氧基)钛(IV)、三[2-((2-氨基乙基)氨基)乙氧基]乙氧基钛(IV)、双(新戊基(二烯丙基)氧基)二乙氧基钛(IV)、四(异丙氧基)钛酸酯、四(正丁氧基)钛酸酯、四(2-乙基己氧基)钛酸酯或聚丁基钛酸酯,尤其是双(乙基乙酰乙酸基)二异丁氧基钛(IV)或双(乙基乙酰乙酸基)二异丙氧基钛(IV)。
进一步优选的是脒或胍,尤其是DBU、1-(3-二甲基氨基丙基)-2-甲基-1,4,5,6-四氢嘧啶、1-(3-氨基丙基)-2-甲基-1,4,5,6-四氢嘧啶或其反应产物,或来自单胺、多胺或氨基硅烷与二环己基碳二亚胺或二异丙基碳二亚胺的反应的胍。
进一步优选的是这些催化剂的组合,尤其是至少一种有机碳酸酯和至少一种脒或胍的组合。
合适的催化剂还有促进异氰酸酯基团的反应的催化剂,尤其是有机锡(IV)化合物例如尤其是二乙酸二丁基锡、二月桂酸二丁基锡、二氯化二丁基锡、二乙酰丙酮二丁基锡、二月桂酸二甲基锡、二乙酸二辛基锡、二月桂酸二辛基锡或二乙酰丙酮二辛基锡,铋(III)或锆(IV)的配合物,尤其是具有选自醇盐、羧酸酯、1,3-二酮化物、羟基喹啉盐、1,3-酮酸酯和1,3-酮酰胺化物的配体的铋(III)或锆(IV)的配合物,或含有叔氨基基团的化合物如尤其是2,2'-二吗啉代二乙基醚(DMDEE)。
合适的催化剂还有用于潜在固化剂,尤其是羧酸如2-乙基己酸,月桂酸,硬脂酸,新癸酸,苯甲酸,水杨酸或2-硝基苯甲酸,有机羧酸酐,羧酸的甲硅烷基酯,有机磺酸,磺酸酯,其它有机或无机酸,或上述酸或酯的混合物的水解的催化剂。优选的是芳族羧酸,例如苯甲酸,2-硝基苯甲酸或尤其是水杨酸。
可固化组合物可以包含其它成分,尤其是:
–无机或有机颜料,尤其是二氧化钛,氧化铬或氧化铁;
–额外的塑化剂;
–纤维,尤其是玻璃纤维、碳纤维、金属纤维、陶瓷纤维、塑料纤维如聚酰胺纤维或聚乙烯纤维,或天然纤维如羊毛、纤维素、大麻或剑麻;
–纳米填料如石墨烯或碳纳米管;
–染料;
–促进异氰酸酯基和/或硅烷基团反应的其他催化剂,尤其是锡(II)、铁、铝、钼、二氧代钼或钾的盐、皂或络合物,尤其是乳酸铝、油酸铝或乙酸钾;含有叔氨基的化合物,尤其是N-乙基二异丙基胺、N,N,N',N'-四甲基亚烷基二胺、五甲基亚烷基三胺及其更高级同系物,双(N,N-二乙基氨基乙基)己二酸酯、三(3-二甲基氨基丙基)胺、1,4-二氮杂双环[2.2.2]辛烷(DABCO)、N-烷基吗啉、N,N'-二甲基哌嗪;含氮芳族化合物如4-二甲基氨基吡啶、N-甲基咪唑、N-乙烯基咪唑或1,2-二甲基咪唑;有机铵化合物,如苄基三甲基氢氧化铵或烷氧基化叔胺;以及所谓的“延迟作用”催化剂,其是已知的金属或胺催化剂的变体;
–溶剂,尤其是丙酮、乙酸甲酯、乙酸叔丁酯、1-甲氧基-2-丙基乙酸酯、乙基-3-乙氧基丙酸酯、二异丙醚、二乙二醇二乙醚、乙二醇二乙醚、乙二醇单丁醚、乙二醇单-2-乙基己基醚、缩醛例如丙缩醛、丁缩醛、2-乙基己缩醛、二氧戊环、甘油缩甲醛或2,5,7,10-四氧杂十一烷(TOU)、甲苯、二甲苯、庚烷、辛烷、石脑油、石油溶剂油、石油醚或汽油,尤其是SolvessoTM类型(来自ExxonMobil Chemical Co.),以及碳酸亚丙酯、碳酸二甲酯、丁内酯、N-甲基吡咯烷酮、N-乙基吡咯烷酮、对氯三氟甲苯或三氟甲苯;
–天然树脂、脂肪或油例如松香、虫胶、亚麻籽油、蓖麻油或大豆油;
–非反应性聚合物,尤其是不饱和单体的均聚物或共聚物,所述不饱和单体尤其选自乙烯、丙烯、丁烯、异丁烯、异戊二烯、乙酸乙烯酯或(甲基)丙烯酸烷基酯,尤其是聚乙烯(PE)、聚丙烯(PP)、聚异丁烯、乙烯乙酸乙烯酯-共聚物(EVA)或无规立构聚-α-烯烃(APAO);
–阻燃物质,尤其是上文所述的填料氢氧化铝或氢氧化镁,以及特别是有机磷酸酯,例如特别是三乙基磷酸酯、三甲苯基磷酸酯、三苯基磷酸酯、二苯基甲苯基磷酸酯、异癸基二苯基磷酸酯、三(1,3-二氯-2-丙基)磷酸酯、三(2-氯乙基)磷酸酯、三(2-乙基己基)磷酸酯、三(氯异丙基)磷酸酯、三(氯丙基)磷酸酯、异丙基化三苯基磷酸酯、不同异丙基化程度的单-、双-和三(异丙基苯基)磷酸酯、间苯二酚-双(二苯基磷酸酯)、双酚-A-双(二苯基磷酸酯)或多磷酸铵;
–添加剂,尤其是湿润剂、流平剂、消泡剂、脱气剂,抗氧化、热、光或紫外辐射的稳定剂或杀生物剂;
或其它通常在可固化组合物中使用的物质。
可能合意的是某些成分在被混入组合物之前进行化学或物理干燥。
可固化组合物优选基本上不含含脂肪醇酯的塑化剂。它尤其不含邻苯二甲酸酯。其优选含有小于2wt%,更优选小于1wt%,尤其是小于0.5wt%的邻苯二甲酸酯。
可固化组合物优选含有10-40wt%的具有封闭的羟基基团的聚醚。
一种优选的可固化组合物,其包含
–10wt%至50wt%的含有异氰酸酯和/或硅烷基团的聚合物,
–20wt%至60wt%的填料和
–10wt%至40wt%的具有封闭的羟基基团的聚醚。
可固化组合物尤其在排除水分的情况下制备和在环境温度下在隔绝水分的容器中储存。合适的隔绝水分的容器尤其由任选涂覆的金属和/或塑料组成,并且尤其为桶、运输箱、提桶、筒、罐、盒、袋、管状袋、料盒或管。
可固化组合物可以以单组分组合物的形式或者以多组分(尤其是双组分)组合物的形式存在。
称为“单组分”组合物的组合物是其中组合物的所有成分都在同一容器中,其本身是储存稳定的并且可用水分固化。
称为“双组分”组合物的组合物是这样一种组合物,其中组合物的成分处于两个不同的组分中,它们被存储在彼此分开的容器中并且直到在施用所述组合物之前或期间才彼此混合。
可固化组合物优选是单组分和湿固化的。如果提供合适的包装和存储,其通常可以在几个月内存储稳定,最长可达一年或更长时间。
在本发明的用途中,可固化组合物被施加到至少一种碱性基材上。可以在施加之前对基材进行预处理,尤其是通过清洁方法或施加活化剂或底漆进行预处理,在这种情况下任选施加的活化剂或底漆通常不会完全密封基材的表面,使得其如现有技术一样会产生碱性反应,至少在某些部分上。
在施加组合物时,开始固化过程。由此形成固化的组合物。
在单组分湿固化组合物的情况下,将其原样施加,并且然后在湿气或水的影响下开始固化。为了促进固化,可以在施用时将含有或释放水和/或催化剂的促进剂组分混合到组合物中,或者可以在施用后使该组合物与这种促进剂组分接触。
在双组分组合物的情况下,在两种组分混合后将其施加并通过内部反应开始固化,其中任选通过外部水分的作用完成固化。可以用动态混合器或静态混合器连续或间歇地混合这两种组分。
在固化过程中,存在的异氰酸酯基在水分的影响下彼此和/或与任选在组合物中存在的其他反应性基团,尤其是羟基或氨基基团反应。另外,存在的异氰酸酯基团与任选存在的潜在固化剂的水解反应性基团反应。存在的硅烷基在固化过程中在水分的影响下彼此反应。它们可以在与水分接触时水解得到硅烷醇基团(Si-OH基团)。存在的硅烷基团可以与存在的硅烷醇基团缩合而得到硅氧烷基团(Si-O-Si基团)。
湿固化性组合物的固化所需的水分优选通过从空气扩散(空气湿气)而进入组合物中。在该过程中,在与空气接触的组合物表面上形成固化组合物的固体层(皮肤)。固化沿着从外向内的扩散方向继续进行,该过程中皮肤变得越来越厚并最终覆盖了所施加的整个组合物。水分也可以额外地或完全地从一个或多个已经施用了组合物的基材进入组合物中,和/或可以来自促进剂组分,该促进剂组分在施用时混合到组合物中或在施用后与其接触,例如通过刷涂或喷涂。
可固化组合物优选在环境温度下施加,尤其是在约-10至50℃的范围内、优选在-5至45℃的范围内、尤其是0至40℃。
组合物优选同样在环境温度下固化。
可固化组合物可以以使其具有高的流动极限的糊状稠度的方式配制,尤其是用作粘合剂或密封剂。这样的组合物可以通过刮刀或在压力下借助于合适的装置来施加,例如借助于料盒枪或滚筒泵或涂装机器人,其中所述组合物尤其以具有基本上圆形或三角形横截面的胶条的形式排出。所施加的组合物的层厚度尤其在0.5至50mm的范围内,优选在1至30mm的范围内。
还可以如此配制可固化组合物,使得其是流体的和所谓“自流平”的或仅具有轻微触变性的,尤其是用作密封剂或涂料。这样的组合物可以通过倾倒或用刮刀来施加。然后可以以涂层的形式将其平面分布直至所需的层厚度,例如借助于辊、刮刀、带齿铲刀或橡胶刮板。在一种操作中,通常施加0.5至5mm、尤其是1至3mm范围内的层厚度。
可固化组合物是存储稳定的,易于处理,固化后具有很高的弹性,并且没有显示任何分离或迁移的趋势。其可以实现弹性粘合、密封或涂覆碱性基材,例如特别是新鲜或生的混凝土或水泥砂浆,而不会在此期间出现由塑化剂皂化引起的难闻气味。
本发明进一步提供了粘合或密封或涂覆的方法,其包含以下步骤:
(i)提供如上所述的可固化组合物,
(ii)提供如上所述的至少一种碱性基材,
(iii)使可固化组合物与碱性基材接触,
(iv)固化该组合物。
在两组分组合物或多组分组合物的情况下,在步骤(iii)之前混合各组分。
步骤(iii)可以通过将可固化组合物施加到碱性基材上来进行。
另外,步骤(iii)可以通过将可固化组合物施加到任何基材上,然后使所施加的组合物与碱性基材接触来进行。
所述组合物可以施加在两个或更多个基材之间,或者可以在施加到第一基材上之后使其与另外的基材接触。在这种情况下,至少一种施加了组合物的基材与如上所述的碱性基材接触。
可以与组合物接触的其它基材尤其是:
–玻璃、玻璃陶瓷、混凝土、砂浆、水泥找平料、纤维水泥尤其是纤维水泥板、砖、瓦、石膏(尤其是石膏板或无水石膏找平料),或天然石材例如花岗石或大理石;
–基于PCC(聚合物改性的水泥砂浆)或ECC(环氧树脂改性的水泥砂浆)的修复或匀平材料;
–金属或合金,例如铝、铜、铁、钢、有色金属,包括经表面处理的金属或合金,例如镀锌或镀铬的金属;
–柏油或沥青;
–皮革、织物、纸、木材、与树脂(例如酚醛树脂、三聚氰胺树脂或环氧树脂)结合的木质材料、树脂-织物-复合材料或其它所谓的聚合物复合材料;
–塑料,例如硬质和软质PVC、聚碳酸酯、聚苯乙烯、聚酯、聚酰胺、PMMA、ABS、SAN、环氧树脂、酚醛树脂、PUR、POM、TPO、PE、PP、EPM或EPDM,各自是未处理的或例如借助于等离子体、电晕或火焰进行表面处理的;
–纤维增强的塑料,例如碳纤维增强的塑料(CFK)、玻璃纤维增强的塑料(GFK)和片状模塑复合物(SMC);
–绝缘泡沫,尤其是由EPS、XPS、PUR、PIR、石棉、玻璃棉或发泡玻璃(泡沫玻璃)制成的绝缘泡沫;
–经涂布或经涂漆的基材,尤其是经涂漆的瓷砖、经涂覆的混凝土、经粉末涂布的金属或合金或经涂漆的金属板。
如果需要,可以在施加之前预处理基材,尤其是通过物理和/或化学清洗方法或者通过施加活化剂或底漆。
可以粘合和/或密封相同或不同的基材。
尤其是在用于连接的密封剂的情况下,通常施加在多个基材之间,而对于粘合剂而言通常的是施加在第一基材上和随后与第二基材接触。在此,这种粘合剂也可以具有密封功能。
涂层通常仅施加到一个基材上,尽管也可能存在涂料与其他基材接触(例如在边缘区域)的情况。
根据其用途,可固化组合物优选为粘合剂或密封剂或涂料。
固化的粘合剂或密封剂或固化的涂料优选是弹性的。
作为粘合剂,该组合物尤其适用于建筑工业中在碱性基材上的粘合和密封应用,尤其适用于新鲜水泥找平层上的拼接地板粘合或适用于新鲜混凝土上的构建粘合。
作为密封剂,该组合物尤其适用于密封建筑中的碱性基材的接头、接缝或空腔,尤其适用于密封部件之间的膨胀接头或连接接头。
作为涂料,该组合物尤其适合于保护碱性基材,尤其是地板或墙壁,尤其是用作阳台、露台、广场、桥梁、停车场的涂料,或用于密封屋顶,尤其是平坦的屋顶或稍微倾斜的屋顶区域或屋顶花园,或在建筑物内部进行水封,例如在卫生间或厨房中的瓷砖或陶瓷板下面,或在厨房、工业建筑物或生产空间中用作地板覆盖物,或在集水箱中、通道、竖井、筒仓、水箱或废水处理厂中作为密封料。
由粘合或密封或涂覆的方法得到一种制品。
因此,本发明进一步提供了用所述组合物粘合、密封或涂覆的制品。
该制品尤其是在地上或地下的建筑结构或其一部分,尤其是桥梁、屋顶、楼梯、地板或立面或其安装组件。
特别优选地,该制品是粘合到混凝土或水泥砂浆找平层上的拼接地板,其被粘合到仍然新鲜的并因此碱性的找平层上。在此,使用在碱性介质中不会释放强烈气味的裂解产物的粘合剂特别重要,因为该粘合剂是在相对大面积上在室内施用的,由此可能产生的任何气味排放都特别强烈、持久而令人厌烦。
由粘合或密封或涂覆的方法得到一种粘合连接体。
因此,本发明还提供了一种粘合连接体,其包含如上所述的固化的组合物和粘附至该组合物的至少一种基材,如上所述,其表面在与组合物接触的时刻为碱性。
该固化的组合物优选包含
–10wt%-50wt%的固化的聚合物,
–20wt%-60wt%的填料,和
–10wt%-40wt%的具有封闭的羟基基团的聚醚。
本发明的粘合连接体中的固化组合物的层厚度优选为0.5至50mm,优选1至30mm。
粘合连接体是用该组合物粘合、密封或涂覆的制品的一部分。
根据本发明的用途能够使碱性基材,例如特别是新鲜的或生的混凝土或水泥砂浆进行弹性粘合、密封或涂覆,而不会出现由塑化剂皂化引起的令人厌烦的气味,而这种情况通常会在常规塑化剂例如DIDP或DINCH的情况中出现。
实施例
在下文中给出了工作实施例,其旨在阐明所描述的发明。当然,本发明不限于这些所描述的工作实施例。
“标准气候条件”(“NK”)是指温度为23±1℃,相对空气湿度为50±5%。
除非另有说明,否则所使用的化学品均来自Sigma-Aldrich Chemie GmbH。
具有封闭的羟基基团的聚醚的制备:
用恒温锥板式粘度计Rheotec RC30(锥直径25mm,锥角1°,锥尖至板的距离0.05mm,剪切速度10s-1)测量粘度。
红外光谱(FT-IR)在Thermo Scientific的配备有具有金刚石晶体的水平ATR-测量单元的FT-IR设备Nicolet iS5上以未稀释膜的形式进行测量。吸收带用波数(cm–1)表示。
1H NMR光谱是在Bruker Ascend 400型光谱仪上在400.14MHz下测量的。化学位移δ相对于四甲基硅烷(TMS)以ppm表示。不区分真实耦合和伪耦合模式。
聚醚-1:由正丁醇起始的乙酰化PPG一元醇,平均分子量约为800g/mol
首先在氮气气氛下将120.00g由正丁醇起始的聚氧亚丙基一元醇(100-20B,平均分子量约为750g/mol;来自DowDuPont Inc.)和18.74g乙酸酐装入带有蒸馏附件的圆底烧瓶中。然后将反应混合物在温和的氮气流下于130℃下搅拌,其中收集乙酸作为馏出物。随后,在80℃和10mbar的减压下从反应混合物中除去挥发性成分。得到澄清的无色液体,其在20℃下的粘度为75mPa·s。
FT-IR:2970,2931,2867,1738,1454,1372,1345,1296,1241,1098,1014,959,925,866,827。
1H NMR(CDCl3):5.02(hept.,1H,CH2(CH3)CH-OAc),3.75–3.34(2xm,约39H,OCH2CH(CH3)O),3.33–3.28(m,2H,CH3CH2CH2CH2O),2.04(s,3H,O(CO)CH3),1.55(quint.,2H,CH3CH2CH2CH2O),1.36(sext.,2H,CH3CH2CH2CH2O),1.22(d,3H,CH2(CH3)CH-OAc),1.17–1.10(m,约36H,OCH2CH(CH3)O),0.91(t,3H,CH3CH2CH2CH2O)。
聚醚-2:二乙酰化的PPG二醇,平均分子量约1100g/mol
如对聚醚-1所述那样,将80.00g的聚氧亚丙基二醇(P 1010,OH值为110mg KOH/g;来自DowDuPont Inc.)和18.74g的乙酸酐反应。得到澄清的无色液体,其在20℃下的粘度为145mPa·s。
聚醚-3:二乙酰化的PPG二醇,平均分子量约2100g/mol
如对聚醚-1所述那样,将160.00g的聚氧亚丙基二醇(2000L,OH值为56mg KOH/g;来自DowDuPont Inc.)和18.74g的乙酸酐反应。得到澄清的无色液体,其在20℃下的粘度为400mPa·s。
其它起始材料的制备:
聚合物P1:
将3080g的聚氧亚丙基二醇(4200,来自Covestro AG;OH值为28.5mgKOH/g)、1540g的聚氧亚丙基聚氧亚乙基三醇(MD34-02,来自Shell ChemicalsCo.;OH值为35.0mg KOH/g)和385g甲苯二异氰酸酯(T 80P,Covestro AG)在80℃下通过已知的方法反应,得到NCO封端的聚氨酯聚合物,其在室温下为液态并具有1.50wt%的游离异氰酸酯基团的含量。
醛亚胺-1:N,N'-双(2,2-二甲基-3-月桂酰氧基亚丙基)-3-氨基甲基-3,5,5-三甲基环己基胺
在氮气气氛下,首先将598g(2.1mol)的2,2-二甲基-3-月桂酰氧基丙醛加入到圆底烧瓶中。随后在良好搅拌下加入170.3g(1mol)的3-氨基甲基-3,5,5-三甲基环己基胺(IPD,来自Evonik Industries AG),并且随后在80℃和10mbar的减压下移除挥发性成分。获得了732g的无色液体,其具有2.73mmol N/g的胺含量,这相应于367g/mol的计算的酰亚胺当量。
触变剂T-1:
首先在真空混合器中装入300g聚醚-1和48g的4,4'-亚甲基二苯基二异氰酸酯(44MC L,来自Covestro AG),并且稍微加热,然后在剧烈搅拌下缓慢滴加27g的正丁胺。将得到的糊状物在冷却的同时在减压下再搅拌1小时。获得白色、细分、均匀、可涂抹的糊剂。
触变剂T-2:
如对于触变剂T-1所述那样制备,除了使用300g聚醚-2代替聚醚-1。获得白色、细分、均匀、可涂抹的糊剂。
触变剂T-3:
触变剂T-4:
砂浆棱柱体的制备:
使用1300重量份(GT)的0至1毫米石英砂,200GT的研磨石灰石(未灼烧的)和900GT的CEM I 42.5N波特兰水泥生产干混料。分别地,将400GT的水与6.3GT的(缓凝剂/塑化剂;来自Sika Schweiz AG)混合,并将该混合物与干混料在机械混合器中充分混合3分钟。将获得的砂浆倒入几个80x40x40mm的模具中,用塑料薄膜覆盖并在标准气候条件下存储。
24小时后,将塑料薄膜除去并固化,但从模具中取出仍新鲜的砂浆棱柱体,用钢刷在外侧清洁并除去灰尘。将如下所述的可固化组合物立即施加到由此制备的新鲜(生)砂浆棱柱体上。
可固化的(单组分)组合物的制备:
组合物Z1-Z5
对于每种组合物,在排除水分并以3000rpm进行一分钟的条件下,借助于离心混合器(SpeedMixerTMDAC 150,FlackTek Inc.)以指定的量(以重量份计)混合表1中指明的成分。
如下测试每种组合物:
作为开放时间的量度,确定结皮时间(HBZ)。为此,将几克组合物以约2毫米的层厚度涂在纸板上,并且在标准气候条件下确定直至在借助于LDPE移液管轻轻敲打组合物的表面时移液管上首次不再残留有残余物的时间。
根据DIN 53505,在标准气候条件下固化14天的试样上测定肖氏A硬度。
为了确定机械性能,将组合物施加到涂有PTFE的薄膜上,得到厚度为2mm的薄膜,将该薄膜在标准气候条件下存储14天,并从膜上冲出30mm棒长和4mm棒宽并具有75mm长度的几个哑铃体并且根据DIN EN 53504以200mm/分钟的拉伸速率测试它们的拉伸强度(断裂力)、断裂伸长率、5%弹性模量(伸长率为0.5%-5%下的)和25%弹性模量(伸长率为0.5%-25%下的)。
视觉上评价所制备的薄膜上的外观。“好”用于描述不粘且无气泡的膜。
与新鲜制备的薄膜相距2cm通过鼻子闻来评估气味。“无”表示没有感知到气味。
在表1中报道结果。
标记为(Ref.)的组合物不含有任何本发明的具有封闭羟基基团的聚醚。
表1:Z1至Z5的组成(以重量份计)和性能。“n.b."表示"未检测到"
4 5wt%,在二(2-乙基己基)己二酸酯中
可固化组合物在新鲜砂浆上的用途:
实施例1至5
将如上所述制备的组合物Z1至Z5中的每一个以2mm的层厚度在30×80mm的区域上施加至如上所述制备的两个新鲜的(生的)砂浆棱柱上。将以此方式涂覆的第一个棱柱在空气循环炉中于80℃的密闭铝罐中存放24小时,然后测试气味形成。将这些结果标记为“(1d80℃)”。将第二个涂覆的棱柱在标准气候条件下存储在密闭的铝罐中7天,然后同样测试气味发展。这些结果标记为“(7d NK)”。通过在标准气候条件下小心地打开铝罐并立即在铝罐和组合物的顶部空间通过鼻子闻来检测任何气味来确定气味形成。“否”表示没有感知到气味。“温和”是指轻微的气味,如在温暖状态下作为固有气味的组合物的典型特征那样。“明显”是指明显可察觉的霉味。“强烈”是指强烈的霉味。
结果报道在表2中。
标记为(Ref.)的实施例为对比实施例。
表2:在新鲜(生)砂浆上组合物Z1至Z5的性能(气味形成)。
Claims (15)
1.包含至少一种具有封闭的羟基基团的聚醚作为塑化剂的可固化组合物的用途,用在当用水润湿时具有至少10的pH值的至少一种碱性基材上。
2.如权利要求1所述的用途,其特征在于所述碱性基材为新鲜的混凝土、新鲜的水泥砂浆、新鲜的石灰砂浆或新鲜的石灰或硅酸盐刷涂料。
3.如权利要求1和2的任一所述的用途,其特征在于封闭的羟基基团选自乙缩醛基团、酯基团、乙酰酯基团、碳酸酯基团和氨基甲酸酯基团。
4.如权利要求1-3任一项所述的用途,其特征在于在聚醚中70wt%到100wt%的重复单元由1,2-亚丙基氧基组成,和0到30wt%的重复单元由1,2-亚乙基氧基组成。
5.如权利要求1-4任一项所述的用途,其特征在于,具有封闭的羟基基团的聚醚的平均分子量Mn在600至10000g/mol范围内,其通过凝胶渗透色谱法(GPC)以聚苯乙烯作为标样并使用四氢呋喃作为流动相确定,其中使用折射率检测器并且从200g/mol评价。
6.如权利要求1-5任一项所述的用途,其特征在于,具有封闭的羟基基团的聚醚衍生自选自以下的至少一种羟基官能的聚醚:
–OH值在25至90mg KOH/g范围内的以醇起始的,尤其是以正丁醇起始的聚氧亚丙基一元醇,
–OH值在12至155mg KOH/g范围内的聚氧亚丙基二醇,
–平均OH官能度为2.2-3和OH值在22至230mg KOH/g范围内的由三羟甲基丙烷或尤其是由甘油起始的、任选环氧乙烷封端的聚氧亚丙基三醇,和
–平均OH官能度为3-6的糖醇起始的聚氧亚丙基多元醇,尤其使用苏糖醇、赤藓糖醇、木糖醇、甘露醇或山梨糖醇作为起始分子的糖醇起始的聚氧亚丙基多元醇。
7.如权利要求1-6任一项所述的用途,其特征在于可固化组合物包含至少一种含有异氰酸酯和/或硅烷基团的聚合物。
8.如权利要求1-7任一项所述的用途,其特征在于可固化组合物包含至少一种含有异氰酸酯基团的聚合物和至少一种潜在固化剂。
9.如权利要求1-8任一项所述的用途,其特征在于可固化组合物包含至少一种基于碳酸钙的填料。
10.如权利要求1-9任一项所述的用途,其特征在于可固化组合物包含:
–10-50wt%的含有异氰酸酯和/或硅烷基团的聚合物,
–20-60wt%的填料,和
–10-40wt%的具有封闭的羟基基团的聚醚。
11.如权利要求1-10任一项所述的用途,其特征在于可固化组合物为单组分和湿固化性的。
12.粘合或密封或涂覆的方法,包含以下步骤:
(i)提供如权利要求1或3至11任一项中所述的可固化组合物,
(ii)提供在权利要求1或2任一项中所述的至少一种碱性基材,
(iii)使可固化组合物与碱性基材接触,
(iv)固化该组合物。
13.由如权利要求12所述的方法获得的制品。
14.如权利要求13所述的制品,其特征在于其为粘合到混凝土或水泥砂浆的找平层上的拼接地板。
15.由如权利要求1-11任一项所述的用途或如权利要求12所述的方法获得的粘合连接体,其包含固化的组合物和粘合至组合物的至少一种基材,所述基材的表面在接触组合物的时刻是碱性的并且当用水润湿时具有至少10的pH值。
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