CN114163604A - 制备含氨基甲酸酯基团的烯属不饱和化合物的方法 - Google Patents
制备含氨基甲酸酯基团的烯属不饱和化合物的方法 Download PDFInfo
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Abstract
本发明涉及由以下物质制备含氨基甲酸酯基团的烯属不饱和化合物的方法：i)二异氰酸酯，ii)至少一种具有至少一个羟基和至少一个烯属不饱和可聚合基团的化合物，和iii)任选至少一种含羟基化合物，在该方法中，1.在反应前即刻测定二异氰酸酯的过氧化物含量，2.a)如果测定过氧化物含量大于或等于20mmol/kg，将二异氰酸酯蒸馏纯化直到测定过氧化物含量小于20mmol/kg，或b)如果测定过氧化物含量小于20mmol/kg，不进行蒸馏纯化，和3.然后将i)a)的经蒸馏二异氰酸酯和/或b)的未处理二异氰酸酯与ii)至少一种具有至少一个羟基和至少一个烯属不饱和可聚合基团的化合物和任选与iii)至少一种含羟基基团化合物进行反应获得含氨基甲酸酯基团的烯属不饱和化合物。
Description
技术领域
本发明涉及由二异氰酸酯和至少一种具有烯属不饱和的可聚合基团的含羟基基团的化合物制备至少一种含氨基甲酸酯基团的烯属不饱和化合物的方法。
背景技术
具有烯属不饱和基团的含氨基甲酸酯基团的化合物在辐射固化性涂料组合物中起重要作用。
例如，US 4,260,703A公开了酯二醇-氨基甲酸酯-丙烯酸酯，其可单独地或者与其它成分一起在涂料组合物中使用，所述其它成分例如溶剂、反应性低聚物和单体、交联剂、填料或其它添加剂。
WO2017/151387A1公开了制备可固化树脂组合物的方法，在该方法中使异氰酸酯、多元醇混合物和封端剂(其可以是丙烯酸羟烷基酯或甲基丙烯酸羟烷基酯)进行反应。所得的树脂组合物可用于制备复合材料、涂层、粘合剂、印刷油墨、封装件和铸件。
迄今为止，所制备的含氨基甲酸酯基团的烯属不饱和化合物或其前体具有倾向于发生不希望的过早聚合(凝胶化)的缺点。因此存在避免这种过早聚合的关注点。
令人惊奇地，已经发现特别是在含氨基甲酸酯基团的烯属不饱和化合物的相对旧的批料中存在过氧化物杂质，这些过氧化物杂质导致所提及的凝胶化。已经进一步发现，当在所使用的二异氰酸酯批料中存在的过氧化物含量小于20mmol/kg时，不会发生不希望的过早聚合/凝胶化。
发明内容
本发明因此提供由以下物质制备至少一种含氨基甲酸酯基团的烯属不饱和化合物的方法：i)二异氰酸酯，ii)至少一种具有至少一个羟基基团和至少一个烯属不饱和的可聚合基团的化合物，和iii)任选的至少一种含羟基基团的化合物，在该方法中，
1.在反应前即刻(unmittelbar)测定二异氰酸酯的过氧化物含量，
2.a)如果所测定的过氧化物含量大于或等于20mmol/kg，则将所述二异氰酸酯进行蒸馏纯化，直到所测定的过氧化物含量小于20mmol/kg，
或者
b)如果所测定的过氧化物含量小于20mmol/kg，则不进行蒸馏纯化，和
3.然后，将i)a)的经蒸馏的二异氰酸酯和/或b)的未处理的二异氰酸酯与ii)至少一种具有至少一个羟基基团和至少一个烯属不饱和的可聚合基团的化合物和任选地与iii)至少一种含羟基基团的化合物进行反应，以获得含氨基甲酸酯基团的烯属不饱和化合物。
本发明提供由二异氰酸酯和至少一种具有至少一个羟基基团和至少一个烯属不饱和的可聚合基团的化合物制备至少一种含氨基甲酸酯基团的烯属不饱和化合物的方法。所述反应物“二异氰酸酯”可以是一种单独的二异氰酸酯或者是二异氰酸酯的混合物。所述反应物优选是精确地一种二异氰酸酯。
优选地，所使用的二异氰酸酯中的至少一种是(环)脂族二异氰酸酯，即具有至少一个直接键合于脂族环上的异氰酸酯基团和任选具有一个另外的脂族键合(即经由亚烷基基团与所述脂族环连接)的异氰酸酯基团的二异氰酸酯。更优选地，仅使用一种(环)脂族二异氰酸酯。非常特别优选地，所使用的二异氰酸酯中的至少一种是异佛尔酮二异氰酸酯(IPDI)或4,4'-二异氰酸酯二环己基甲烷(H12MDI)。又更优选地，将异佛尔酮二异氰酸酯作为唯一的二异氰酸酯使用。如果使用异佛尔酮二异氰酸酯，则是否它是经由脲方法获得的还是经由光气方法获得的并不重要。
所述具有至少一个羟基基团和至少一个烯属不饱和的可聚合基团的化合物原则上可以是任何可能的具有至少一个羟基基团和至少一个烯属不饱和的可聚合基团的化合物。它优选具有精确地一个羟基基团和精确地一个烯属不饱和基团。
优选的具有至少一个羟基基团和至少一个烯属不饱和的可聚合基团的化合物可选自丙烯酸羟烷基酯、甲基丙烯酸羟烷基酯和羟烷基乙烯基醚。这些优选是其中其羟烷基基团具有C2-C10亚烷基基团，优选直链C2-C10亚烷基基团的化合物。非常特别优选丙烯酸羟乙酯、甲基丙烯酸羟乙酯、丙烯酸羟丙酯和甲基丙烯酸羟丙酯。
在二异氰酸酯与所述至少一种具有至少一个羟基基团和至少一个烯属不饱和的可聚合基团的化合物的部分或完全反应之前，测定待要使用的二异氰酸酯中的过氧化物含量。所述过氧化物含量是根据DIN EN ISO 27107测定的，并且是以mmol/kg为单位测定的。
在此，所述在反应“之前”优选被理解为是指在将二异氰酸酯和至少一种反应物混合之前14天至5分钟的时间范围。其非常特别优选被理解为是指在所述反应之前2天(48小时)的时间点。
如果仅使用一种二异氰酸酯，则待要使用的二异氰酸酯的过氧化物含量为基于待要使用的二异氰酸酯的以千克为单位的总质量计的以mmol为单位的过氧化物含量。如果使用多于一种的二异氰酸酯，则待要使用的二异氰酸酯的过氧化物含量为基于待要使用的所有二异氰酸酯的以千克为单位的总质量计的以mmol为单位的过氧化物总含量。
如果如上文限定那样所测定的过氧化物含量小于20mmol/kg，则不进行另外的操作，因为将预料到不会发生由于存在这样浓度的过氧化物而导致可察觉到的缺点。因此可以使所述反应物直接反应。
然而，如果如上文限定那样所测定的过氧化物含量大于或等于20mmol/kg，则将所述反应物二异氰酸酯进行蒸馏纯化。如果仅使用一种二异氰酸酯，则将具有大于或等于20mmol/kg的过氧化物含量的二异氰酸酯的每个批料(Charge)都通过蒸馏进行纯化，直到每个批料的过氧化物含量都小于20mmol/kg。如果要使用两种或更多种二异氰酸酯，则将具有大于或等于20mmol/kg的过氧化物含量的每种二异氰酸酯的每个批料都通过蒸馏进行纯化，直到每种二异氰酸酯的每个批料的过氧化物含量都小于20mmol/kg。
所述蒸馏纯化优选在合适的蒸馏塔或蒸馏单元(例如短程或薄膜蒸馏装置)中，在取决于所述二异氰酸酯的沸点温度的合适的压力和温度下进行。在这种情况下，最低蒸馏温度应优选不低于100℃。
在所述至少一种烯属不饱和化合物的制备中，除了二异氰酸酯i)和至少一种具有至少一个羟基基团和至少一个烯属不饱和的可聚合基团的化合物ii)之外，任选还可以使用iii)至少一种含羟基基团的化合物。如果情况如此，则可以制备具有有利性能的含氨基甲酸酯基团的烯属不饱和化合物。化合物iii)不具有任何烯属不饱和基团。
优选的含羟基基团的化合物iii)可选自二醇和多元醇。多元醇在此被理解为是具有(平均)多于两个羟基基团的含羟基基团的化合物。所述二醇或多元醇可以是单体、低聚的或聚合的。优选的低聚和聚合的二醇和多元醇具有5至500mg KOH/g的OH值(根据DIN ENISO 4692-2测定)。优选的二醇和多元醇是脂族的二醇和多元醇，聚酯二醇和聚酯多元醇，以及聚醚二醇和聚醚多元醇。
所使用的含羟基基团的化合物iii)优选是二醇。
i)二异氰酸酯、ii)具有至少一个羟基基团和至少一个烯属不饱和的可聚合基团的化合物和任选的iii)含羟基基团的化合物的反应优选是在至少一种催化剂的存在下，在0-160℃的温度下进行的。在这种情况下，不特别调节压力，并且压力对应于环境压力，其接近于1巴。优选的反应温度为40-140℃，并且又更优选为60-90℃。
优选的反应时间为3分钟至3小时。
合适的催化剂是在聚氨酯化学中常用的催化剂。优选的催化剂可选自胺类催化剂(优选二氮杂双环辛烷)和基于过渡金属的催化剂。特别优选的基于过渡金属的催化剂是月桂酸二丁基锡、新癸酸铋、辛酸锌和乙酰丙酮锆。
所述催化剂的用量优选为基于所用组分的质量计的0.001重量％-1.5重量％，更优选为0.01重量％-0.8重量％，又更优选为0.05重量％-0.1重量％。
尽管原则上也可以使用溶剂(尤其是丙酮、乙酸乙酯、乙酸丁酯和乙酸甲氧基丙酯)，但优选在没有溶剂的情况下进行操作。
根据本发明的方法既可以间歇地又可以连续地进行。其优选以间歇方法进行。
如果在根据本发明的方法中使用至少一种二异氰酸酯i)、至少一种具有至少一个羟基基团和至少一个烯属不饱和的可聚合基团的化合物ii)和至少一种含羟基基团的化合物iii)，则所有反应物i)、ii)和iii)原则上可以同时与彼此反应。然而，非常特别有利的是首先使二异氰酸酯i)与至少一种具有至少一个羟基基团和至少一个烯属不饱和的可聚合基团的化合物ii)进行反应，和仅在这之后才添加至少一种含羟基基团的化合物iii)。
然而，出于其它原因，还可能有利的是：首先使二异氰酸酯i)与至少一种含羟基基团的化合物iii)进行反应，和仅在这之后才添加至少一种具有至少一个羟基基团和至少一个烯属不饱和的可聚合基团的化合物ii)(预聚物操作模式)。
当即使所测定的过氧化物含量大于或等于10mmol/kg，也将所述二异氰酸酯蒸馏纯化直到所测定的过氧化物含量小于10mmol/kg时，额外导致了特别好的含氨基甲酸酯基团的烯属不饱和化合物。更优选地，即使所测定的过氧化物含量大于或等于1mmol/kg，也将所述二异氰酸酯蒸馏纯化，直到所测定的过氧化物含量小于1mmol/kg。
另外有利的是，所述一种或多种二异氰酸酯具有至少0.1mmol/kg的过氧化物，即每个批料都具有至少0.1mmol/kg的过氧化物。
更优选地，另外如下进行根据本发明的方法，使得在步骤2中，
a)如果所测定的过氧化物含量大于10mmol/kg，则将所述二异氰酸酯进行蒸馏纯化直到所测定的过氧化物含量小于或等于10mmol/kg但大于或等于0.1mmol/kg，
或者，如果所测定的过氧化物含量小于0.1mmol/kg，则添加过氧化物直到所述过氧化物含量大于或等于0.1mmol/kg但小于或等于10mmol/kg，或者
b)如果所测定的过氧化物含量小于或等于10mmol/kg但大于或等于0.1mmol/kg，则不进行另外的操作。
具体实施方式
实施例：
本发明实施例
将139g丙烯酸羟乙酯(1.2mol，Aldrich)在30分钟内滴加到由222g具有<10mmol/kg的过氧化物含量的异佛尔酮二异氰酸酯(IPDI，1mol，Evonik Industries)和0.7g二月桂酸二丁基锡形成的混合物中，并然后将该混合物加热到70℃保持另外1小时以使反应完全。然后在该温度下在30分钟内滴加390g Poly THF 1000(DuPont，聚醚二醇，OH值为115)，并然后将该混合物再次在70℃下保持1小时。之后，NCO值为<0.1％。反应产物(氨基甲酸酯丙烯酸酯)是液体，并且是无色的。
对比例
将139g丙烯酸羟乙酯(1.2mol，Aldrich)在30分钟内滴加到由222g具有110mmol/kg的过氧化物含量的异佛尔酮二异氰酸酯(IPDI，1mol，Evonik Industries，已经在80℃下向其中吹入干燥空气三天)和0.7g二月桂酸二丁基锡形成的混合物中，并然后将该混合物加热到70℃保持另外1小时以使反应完全。然后在该温度下在30分钟内滴加390g Poly THF1000(DuPont，聚醚二醇，OH值为115)，并然后将该混合物再次在70℃下保持1小时。之后，NCO值为<0.1％。反应产物(氨基甲酸酯丙烯酸酯)是液体，并且是无色的。
将这两种反应产物在避光条件下在60℃下贮存。由根据本发明的方法制备的氨基甲酸酯丙烯酸酯在60℃下两周后仍一直是液体，而粘度没有任何显著变化。基于具有高过氧化物含量的IPDI的氨基甲酸酯丙烯酸酯在60℃下5小时后是固体，并且因此不是贮存稳定的。
Claims (12)
1.由以下物质制备至少一种含氨基甲酸酯基团的烯属不饱和化合物的方法：
i)二异氰酸酯，
ii)至少一种具有至少一个羟基基团和至少一个烯属不饱和的可聚合基团的化合物，和
iii)任选的至少一种含羟基基团的化合物，
在该方法中
1.在反应前即刻测定二异氰酸酯的过氧化物含量，
2.a)如果所测定的过氧化物含量大于或等于20mmol/kg，则将所述二异氰酸酯进行蒸馏纯化，直到所测定的过氧化物含量小于20mmol/kg，
或者
b)如果所测定的过氧化物含量小于20mmol/kg，则不进行蒸馏纯化，和
3.然后，将i)a)的经蒸馏的二异氰酸酯和/或b)的未处理的二异氰酸酯与ii)至少一种具有至少一个羟基基团和至少一个烯属不饱和的可聚合基团的化合物和任选地与iii)至少一种含羟基基团的化合物进行反应，以获得含氨基甲酸酯基团的烯属不饱和化合物。
2.根据权利要求1的方法，其特征在于所述方法使用二异氰酸酯。
3.根据权利要求1或2的方法，其特征在于所使用的二异氰酸酯中的至少一种是(环)脂族二异氰酸酯。
4.根据前述权利要求中任一项的方法，其特征在于所使用的二异氰酸酯中的至少一种是异佛尔酮二异氰酸酯或4,4'-二异氰酸酯二环己基甲烷。
5.根据前述权利要求中任一项的方法，其特征在于所述具有至少一个羟基基团和至少一个烯属不饱和基团的化合物选自丙烯酸羟烷基酯、甲基丙烯酸羟烷基酯和羟烷基乙烯基醚。
6.根据权利要求5的方法，其特征在于所述丙烯酸羟烷基酯、甲基丙烯酸羟烷基酯或羟烷基乙烯基醚的亚烷基基团是C2-C10亚烷基基团。
7.根据前述权利要求中任一项的方法，其特征在于在所述方法中使用至少一种含羟基基团的化合物iii)。
8.根据权利要求7的方法，其特征在于所述至少一种含羟基基团的化合物iii)选自脂族二醇，脂族多元醇，聚酯二醇和聚酯多元醇，以及聚醚二醇和聚醚多元醇。
9.根据前述权利要求中任一项的方法，其特征在于所述反应是在至少一种催化剂的存在下在0-160℃的温度下进行的。
10.根据权利要求9的方法，其特征在于所述催化剂选自二氮杂双环辛烷、月桂酸二丁基锡、新癸酸铋、辛酸锌和乙酰丙酮锆。
11.根据权利要求7-10中任一项的方法，其特征在于如下进行所述方法：首先使二异氰酸酯i)与至少一种具有至少一个羟基基团和至少一个烯属不饱和的可聚合基团的化合物ii)进行反应，和仅在这之后才添加至少一种含羟基基团的化合物iii)。
12.根据前述权利要求中任一项的方法，其特征在于在步骤2中，
a)如果所测定的过氧化物含量大于10mmol/kg，则将所述二异氰酸酯进行蒸馏纯化，直到所测定的过氧化物含量小于或等于10mmol/kg但大于或等于0.1mmol/kg，
或者
如果所测定的过氧化物含量小于0.1mmol/kg，则添加过氧化物直到所述过氧化物含量大于或等于0.1mmol/kg但小于或等于10mmol/kg，或者
b)如果所测定的过氧化物含量小于或等于10mmol/kg但大于或等于0.1mmol/kg，则不进行另外的操作。
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| US4260703A (en) | 1979-10-26 | 1981-04-07 | Union Carbide Corporation | Novel urethane-acrylate and radiation curable compositions |
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