CN107922569A - 用于制备开环聚合产物的方法 - Google Patents

用于制备开环聚合产物的方法 Download PDF

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CN107922569A
CN107922569A CN201680047087.5A CN201680047087A CN107922569A CN 107922569 A CN107922569 A CN 107922569A CN 201680047087 A CN201680047087 A CN 201680047087A CN 107922569 A CN107922569 A CN 107922569A
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polyisocyanates
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opening polymerization
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S·普茨恩
M·科勒
W·黑莫
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Sika Technology AG
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Abstract

本发明涉及一种用于通过使至少一种多异氰酸酯和2‑氧代‑1,3‑二氧戊环‑4‑甲酸反应并使反应产物在催化量的至少一种非亲核性碱存在下经受约40℃至约150℃的温度而制备开环聚合产物的方法。所得聚合产物可以作为泡沫存在，并且适合作为粘合剂、绝缘材料、密封剂或涂料且适合用于床垫或伤垫的生产。

Description

用于制备开环聚合产物的方法
本发明涉及一种用于制备开环聚合产物的方法、可通过本发明方法获得的开环聚合产物以及所述产物的用途。
环碳酸酯衍生物近来作为可固化粘合剂而受到关注。WO 2013/092011公开了可用于制备聚(羟基氨基甲酸酯)、聚(羟基碳酸酯)和聚(羟基硫基甲酸酯)(poly(hydroxylsufanylformate))的2-氧代-1,3-二氧戊环-4-甲酰胺。
WO 2014/118268公开了其中酰胺氮携带具有一个或多个异氰酸酯基团的取代基的2-氧代-1,3-二氧戊环-4-甲酰胺。该化合物通过使2-氧代-1,3-二氧戊环-4-甲酸与多异氰酸酯反应而获得，并且可以用于例如制备粘合剂。
WO 2013/028292公开了可用于制备聚(羟基氨基甲酸酯)泡沫材料的环状碳酸酯单体。
WO 2014/145732公开了由至少一种植物基多元醇和至少一种不含异氰酸酯的单体的反应产物形成的制品，其包含泡沫结构。不含异氰酸酯的单体可以是环状碳酸酯。
环状碳酸酯及其开环聚合也是许多科学出版物的主题：
未活化的5和6员环状碳酸酯如5-(2-氧代-1,3-二氧戊环-4-基)甲基-5-丙基-1,3-二烷-2-酮与DBU的阴离子开环反应由Endo等(Macromolecules 2005，38，8177-8182)报道。没有观察到发泡反应，而是形成了聚碳酸酯。
Heitz等研究了碳酸亚乙酯与不同催化剂的聚合(L.Vogdanis，B.Martens，H.Uchtmann，F.Hensel，W.Heitz，Macromol.Chem.1990，191，465-472)。提及CO2形成，但没有获得泡沫。
Lee等检测了碳酸亚乙酯与KOH的开环反应(J.-C.Lee，M.H.Litt，Macromolecules2000，33，1618-1627)。CO2蒸发导致线性混合碳酸亚乙酯/氧化乙烯聚合物。没有观察到交联和发泡。
甲基-4,6-O-亚苄基-2,3-O-羰基(cyrbonyl)-α-D-吡喃葡萄糖苷与DBU的阴离子开环聚合也由Endo等报道(O.Haba，H.Tomizuka，T.Endo，Macromolecules 2005，38，3562-3563)。没有观察到CO2形成。
Zsuga等报道了在不同碱和双酚A存在下聚合碳酸亚乙酯和碳酸亚丙酯(L.Soós，G.Deák，S.Kéki，M.Zsuga，J.Polym.Sci：Part A：Polym.Chem.1999，37，545-550)。
WO 2013/092011中公开的羧酰胺化合物是通过吸电子酰胺基团活化的环状碳酸酯。它们在制备固化产品中的使用有两个主要的缺点：a)聚(羟基氨基甲酸酯)的制备需要使用胺硬化剂如三亚乙基四胺、二亚乙基三胺等作为交联组分。由于其毒性，越来越认为使用胺是有问题的；和b)必须使用必须分开运输并且需要精确剂量和混合的两种组分。
因此，单组分固化反应是非常需要的。因此，本发明所基于的问题在于提供可以由环状碳酸酯组分获得而不使用胺硬化剂作为第二组分的聚合/交联反应和/或产物。
令人惊讶地发现，活化的环状碳酸酯可以在催化量的非亲核性强碱如1,8-二氮杂双环[5.4.0]十一碳-7-烯(DBU)存在下固化，而无需作为第二组分的胺硬化剂。当固化反应在升高的温度(>60℃)下进行时，在1小时内获得稳定的软质泡沫。
因此，本发明的第一个实施方案是一种用于制备开环聚合产物的方法，该方法包括以下步骤：
a)提供至少一种多异氰酸酯和2-氧代-1,3-二氧戊环-4-甲酸的反应产物；和
b)在催化量的至少一种非亲核性碱存在下使所述反应产物经受40-150℃的温度。
步骤(a)的原料和反应产物
用于制备反应产物的多异氰酸酯包括所有已知用于制备聚氨酯的脂族、芳族或环脂族异氰酸酯，或它们的组合，即混合的脂族/芳族/环脂族异氰酸酯，其中-NCO官能度(分子中的NCO基团数)≥2，优选2-6，更优选2-3。
小部分可选的市售多异氰酸酯包括四甲基-1,4-二异氰酸酯、五亚甲基-1,5-二异氰酸酯、2-甲基五亚甲基-1,5-二异氰酸酯、六亚甲基-1,6-二异氰酸酯(HDI)、2,2,4-和2,4,4-三甲基六亚甲基-1,6-二异氰酸酯(TMDI)、十二亚甲基-1,12-二异氰酸酯、赖氨酸二异氰酸酯和赖氨酸酯二异氰酸酯、1-异氰酸酯基-3,3,5-三甲基-5-异氰酸酯基甲基环己烷(异佛尔酮二异氰酸酯-IPDI)、1,4-二异氰酸酯基-2,2,6-三甲基环己烷(TMCDI)、2,2'-、2,4'-和4,4'-二环己基甲烷二异氰酸酯(H12MDI)、环己烷-1,3-二异氰酸酯和环己烷-1,4-二异氰酸酯(CHDI)、1,3-和1,4-双(异氰酸酯基甲基)环己烷、4,4'-二异氰酸酯基二环己基-2,2-丙烷、间-和对苯二异氰酸酯、2,3,5,6-四甲基-1,4-二异氰酸酯基苯、3,3'-二甲基-4,4'-二异氰酸酯基二苯基(TODI)、2,4-和2,6-甲苯二异氰酸酯、2,2'-、2,4'-和4,4'-二苯基甲烷二异氰酸酯(MDI)、萘-1,2-二异氰酸酯和萘-1,5-二异氰酸酯(NDI)、间-和对苯二亚甲基二异氰酸酯(XDI)、四甲代苯二亚甲基二异氰酸酯(TMXDI)、HDI三聚体、聚合MDI及其混合物。优选的多异氰酸酯是异佛尔酮二异氰酸酯和/或2,4-甲苯二异氰酸酯(TDI)和/或2,6-甲苯二异氰酸酯。
多异氰酸酯也可以以多异氰酸酯预聚物的形式使用。所述多异氰酸酯预聚物可通过使摩尔过量的如上所定义的多异氰酸酯在例如20-100℃，优选约80℃的温度下与多元醇反应而获得。
如本文所定义的术语“摩尔过量”是指多异氰酸酯的NCO基团与多元醇的OH基团(或如下文所用的酸的COOH基团)的摩尔比大于1.1，优选大于1.2。该反应如本领域已知的进行。例如，可以使用惰性溶剂如四氢呋喃。此外，可以使用通常用于聚氨酯制备的催化剂如胺化合物和有机金属化合物如二丁基二月桂酸锡。多异氰酸酯预聚物的NCO含量优选为2-32重量％的NCO，更优选2-15重量％的NCO。此外，多异氰酸酯预聚物优选具有约500-10000，优选1000-8000的数均分子量(Mn)。
用于制备多异氰酸酯预聚物的合适多元醇在本领域是已知的，且例如在“Plastics Handbook，第7卷，“Polyurethane”，Carl Hanser Verlag，1993年第3版，第3.1章”中描述。作为多元醇，可以使用聚醚多元醇、聚碳酸酯多元醇或聚酯多元醇，优选聚醚多元醇。
通常，多元醇可以具有2-8，更优选2-6，特别是2或3的平均OH官能度。
此外，多元醇可以具有至少350克/摩尔，优选至少400克/摩尔，特别是至少500克/摩尔的数均分子量(Mn)。通常，数均分子量不高于15000克/摩尔。数均分子量优选为400-10000克/摩尔，特别是500-4000克/摩尔。
数均分子量通过使用根据DIN 53240的OH值并应用公式Mn＝Fn·1000·56.1/OH数来确定。所应用的函数是标称函数(nominal functionality)。这些化合物的OH值通常为20-850mg KOH/g，优选30-400mg KOH/g。
聚醚多元醇可以通过已知方法，例如通过氧化烯与至少一种含有2-8，优选2-6个反应性氢原子的引发剂分子在催化剂存在下的阴离子或阳离子聚合获得。作为氧化烯，在每种情况下可以单独或以混合物形式使用一种或多种在亚烷基中具有2-4个碳原子的化合物，例如氧化乙烯、四氢呋喃、1,2-氧化丙烯、1,3-氧化丙烯、1,2-或2,3-氧化丁烯，优选使用氧化乙烯或1,2-氧化丙烯。聚醚多元醇优选为数均分子量(Mn)为400-10000的聚C2-4-氧化烯。
可以使用作为起始剂分子的化合物如乙二醇、二甘醇、甘油、三羟甲基丙烷、季戊四醇、糖衍生物如蔗糖、己糖(hexite)衍生物如山梨糖醇、甲胺、乙胺、异丙胺、丁胺、苄基胺、苯胺、甲苯胺、甲苯二胺(尤其是1,2-甲苯二胺)、萘胺、乙二胺、二亚乙基三胺、4,4'-亚甲基二苯胺、1,3-丙二胺、1,6-己二胺、乙醇胺、二乙醇胺、三乙醇胺和其他二羟基醇或多羟基醇或者单羟基胺或多羟基胺。
所用聚酯多元醇通常通过具有2-12个碳原子的多官能醇(例如乙二醇、二甘醇、丁二醇、三羟甲基丙烷、甘油或季戊四醇)与具有2-12个碳原子的多官能羧酸(例如琥珀酸、戊二酸、己二酸、壬二酸、癸二酸、癸烷二甲酸、马来酸、富马酸、邻苯二甲酸、间苯二甲酸、对苯二甲酸、萘二甲酸的异构体或上述酸的酸酐缩合而制备。所用聚酯多元醇例如具有1.5-5，优选1.8-3.5的OH官能度。
如WO 2013/127647和WO 2013/110512中所述的聚醚多元醇/聚酯多元醇混杂物也可以作为多元醇使用。
为了制备反应产物(a)，可以使用两种方法：
(1)可以使多异氰酸酯与等摩尔量的2-氧代-1,3-二氧戊烷-4-甲酸反应。本文所用的术语“等摩尔”是指多异氰酸酯的NCO基团与2-氧代-1,3-二氧戊环-4-甲酸的COOH基团的摩尔比“基本上”等于1(即0.95-1.05)。所得反应产物具有式(I)：
其中R为通过形式上移除NCO基团而衍生自所述多异氰酸酯的x价基团，且x为2-6，优选2或3的整数。
对本发明而言，术语“x价基团”通常是指R是由x个取代基取代的基团。换言之，R是具有“x”的化合价的基团。优选地，x是2-3的整数。反应产物(a)基本上不含游离异氰酸酯基团。本文所用术语“基本上”是指NCO值小于3重量％，优选小于1重量％，特别是0重量％。
(2)作为替换，可以在第一步中使摩尔过量的多异氰酸酯与2-氧代-1,3-二氧戊环-4-甲酸反应以获得中间体，并且在第二步中使中间体与如上文所定义的多元醇反应。术语“摩尔过量”和与多元醇反应的反应条件如上文所定义。步骤(a)的反应产物也基本上不含游离异氰酸酯基团，通常也落入式(I)的范围内。“中间体”是如WO 2014/118268 A1的权利要求1中所定义的化合物。
步骤(b)中的开环聚合产物的制备
通过使步骤(a)的反应产物在催化量的非亲核性碱存在下经受约40℃至约150℃，优选60-150℃的温度而通过开环聚合得到产物而使步骤(a)的反应产物反应。
非亲核性碱可以选自1,8-二氮杂双环[5.4.0]十一碳-7-烯、1,5-二氮杂双环[4.3.0]壬-5-烯、1,4-二氮杂双环[2.2.2]辛烷、2,6-二叔丁基吡啶、二异丙基乙胺、三氮杂双环癸烯、四甲基胍、咪唑、二甲基氨基吡啶、二异丙基氨基锂、四甲基哌啶锂、叔丁醇钠、叔丁醇钾、氢化钠、氢化钾等或其混合物。优选二氮杂双环化合物，特别是1,8-二氮杂双环[5.4.0]十一碳-7-烯和四甲基胍。
此外，基于步骤(a)的反应产物的重量，非亲核性碱可以以0.1-5重量％，优选0.5-4重量％的量使用。
本发明的第二个实施方案涉及可通过如上所定义的本发明方法获得的开环聚合产物。
开环聚合产物可以呈泡沫，特别是开孔泡沫形式。
当引发开环聚合并且分解出二氧化碳时，获得开环聚合产物。在一个优选的实施方案中，聚合在约60℃至约150℃的温度下进行，得到高度交联的空间网络，由于二氧化碳的形成，所述空间网络是稳定的泡沫。开环聚合产物，特别是泡沫由下式(IIa)和(IIb)的重复单元构成：
其中R如上文对式(I)所定义。
本发明的第三个实施方案涉及包含步骤(a)的反应产物和如上文所定义的非亲核性碱的组合物。
该组合物可以是成套试剂(a kit of parts)的形式，其中一部分包含步骤(a)的反应产物，且另一部分包含非亲核性碱。
此外，本发明涉及可由本发明泡沫或组合物获得的制品。
本发明的再一实施方案涉及开环聚合产物，特别是泡沫或如上文所定义的组合物作为粘合剂、绝缘材料、密封剂或涂料或在生产建筑材料，特别是粘合剂、绝缘材料、密封剂或涂料中的用途。
本发明的再一实施方案涉及本发明的开环聚合产物或组合物在制备床垫或伤垫(wound pad)中的用途。
最后，本发明的另一个实施方案涉及2-氧代-1,3-二氧戊环-4-甲酸和/或式(I)的步骤(a)的反应产物在泡沫制备中的用途。
以下实施例说明了本发明，而不限制本发明。
图1显示了本发明产物的热重扫描。
实施例
在实施例中使用以下缩写和产品：
CYCA：2-氧代-1,3-二氧戊环-4-甲酸
IPDI：异佛尔酮二异氰酸酯
DBTL：二月桂酸二丁基锡
DMAP：4-二甲氨基吡啶
THF：四氢呋喃
RT：室温
2032：BASF SE的商品；OH值为55mg KOH/g且Mn＝3060克/摩尔的三官能聚醚多元醇
2095：BASF SE的商品；OH值为35mg KOH/g且Mn＝4800克/摩尔的三官能聚醚多元醇
DBU：1,8-二氮杂双环[5.4.0]十一碳-7-烯
TGA：热重分析
TDI：甲苯-2,4-二异氰酸酯
HDI：六亚甲基-1,6-二异氰酸酯
Polyol 1374：Bayer的商品；OH值为25-29mg KOH/g且Meq＝2078克/摩尔的三官能聚醚多元醇
N3600：Bayer的商品；多官能脂族多异氰酸酯，即HDI三聚体；NCO含量为23.5±0.5％
实施例1：4-甲氧基羰基-2-氧代-1,3-二氧戊环的制备(参照)
将80g碳酸钠溶于1000ml三颈烧瓶中的200ml蒸馏水中。将溶液冷却至10℃。然后加入58.5g丙烯酸甲酯，且在约10分钟后，同样在10℃下，搅拌加入400ml的7％浓度的次氯酸钠水溶液。然后，立即使该体系用CO2强力冲洗。使温度升高至室温。将烧瓶在约25-30℃下再用CO2强力冲洗1小时，在此期间通过用冰浴偶尔冷却使温度保持在所述范围内。所得白色固体通过吸滤器滤出。将滤液用4×90ml二氯甲烷萃取。将合并的有机相用硫酸钠干燥并滤出。滤液在旋转蒸发器上移除。环氧丙酸甲酯以50-60％的收率获得，纯度为97％。
将20g环氧丙酸甲酯与20g叔丁基甲基醚和1g四丁基溴化铵混合。将均匀的混合物转移至100ml加压反应器中，并在40℃和20巴的CO2压力下羧化4天。羧化后，获得两相体系；上层相由叔丁基甲基醚组成，而下层相由4-甲氧基羰基-2-氧代-1,3-二氧戊环(纯度94％(GC)，收率94％)组成。
实施例2：碳酸甘油酯的有氧氧化(参照)
将11.81g(0.1摩尔)碳酸甘油酯(4-(羟基甲基)-2-氧代-1,3-二氧戊环)、0.50g(0.002摩尔)四水合硝酸锰(II)(Mn(NO3)2·4H2O)、0.58g(0.002摩尔)六水合硝酸钴(II)(Co(NO3)2·6H2O)和1.88g(0.012摩尔)TEMPO(2,2,6,6-四甲基哌啶-1-氧基)溶解在100毫升乙酸中。将淡红色溶液在室温下在氧气气氛下搅拌72小时，蒸发至干燥，通过重结晶将粗产物纯化。这得到了呈白色至淡黄色晶体针状物形式的2-氧代-1,3-二氧戊环-4-甲酸。收率为约75％，且分析数据与已知数据一致。
在WO 2014/118268中给出了用于制备实施例1和2的化合物的其他实施例。
实施例3：CYCA-I 2032，基于CYCA、IPDI和Lupranol 2032的粘合剂体系可在3重量％DBU存在下固化，以在100℃下在1小时内得到淡黄色泡沫。
3.1预聚物CYCA-I 2032的制备
在N2气氛下，将91.80g Lupranol 2032(0.03摩尔)、20.01g IPDI(0.09摩尔)和0.022g DBTL在250mL干燥THF中加热至60℃并搅拌1.25小时，直至达到所需的3.0％的NCO值。使反应混合物冷却至室温，并加入10.70gCYCA(根据3.0％的最终NCO值)和0.10g DMAP，将反应混合物搅拌12小时，直至没有再发现残留的NCO(IR对照)。真空除去溶剂，且以定量收率获得高度粘稠的淡黄色油状粘合剂。
3.2 CYCA-I2032的1K固化
将12.0g CYCA-12032和0.36g(3重量％)DBU在塑料烧杯中剧烈混合并在干燥器中加热至100℃并保持1小时。得到淡黄色软质泡沫。泡沫不溶于最常见的有机溶剂，如THF、二甲亚砜、丙酮、甲苯和水。在某些情况下观察到溶胀。
IR(ν，cm-1)：3312(bm)，2969(m)，2928(m)，2866(m)，1714(w)，1648(m)，1603(w)，1532(w)，1453(m)，1372(m)，1343(w)，1324(w)，1303(w)，1241(w)，1094(s)，1014(w)，925(m)，868(w)，766(w)。
在N2下通过TGA检测泡沫的稳定性(图1)。分解开始于约150℃，并在350℃强烈增加。
实施例4：CYCA-T2095，基于CYCA、TDI和Lupranol 2095的粘合剂体系可以在稍微升高的温度下在1重量％的DBU存在下固化而在1小时内得到淡黄色弹性泡沫。
4.1预聚物CYCA-T 2095的制备
在N2气氛下，将584.76g Lupranol 2095(0.36摩尔OH)、100.0gTDI-CYCA中间体(15.35％NCO，0.36摩尔NCO；类似于WO 2014/118268的实施例11或12获得)和0.09g DBTL在烧瓶中混合，加热至60℃并搅拌，直至没有发现残留NCO(约6小时，IR对照)。将反应混合物冷却至室温，且以定量收率获得呈粘稠淡黄色油状物的粘合剂。
4.2 CYCA-T 2095的固化
将12.0g CYCA-T 2095和0.12g(1重量％)DBU在塑料烧杯中混合，并在80℃下固化1小时。得到淡黄色稳定的弹性泡沫。
实施例5：CYCA-T 1374，基于CYCA、TDI和Arcol Polyol 1374的粘合剂体系可以在稍微升高的温度下在3重量％的DBU存在下固化而得到淡黄色的弹性膜。
5.1 CYCA-T 1374的制备
在N2气氛下，将211.38g Arcol Polyol 1374(0.10摩尔OH)溶解在750ml干燥THF中。加入27.98g TDI-CYCA中间体(15.27％NCO，0.10摩尔NCO；类似于WO 2014/118268的实施例11或12获得)和0.06g DBTL。将反应混合物加热至60℃，直至没有发现残留的NCO(约6小时，IR对照)。将反应混合物冷却至室温，并真空除去溶剂。以定量收率获得呈高度粘稠淡黄色油状物的纯粘合剂。
5.2 CYCA-T 1374的固化
将12.0g CYCA-T 1374和0.36g(3重量％)DBU在塑料烧杯中混合，并在40℃下固化1小时。获得淡黄色的稳定弹性膜。
IR(ν，cm-1)：3267(vw)，2968(m)，2866(m)，1703(w)，1648(w)，1615(w)，1534(w)，1453(m)，1373(m)，1344(w)，1296(w)，1241(w)，1093(s)，926(m)，870(w)，832(w)，769(w)。
实施例6：CYCA-H 9046(TRICYCA)，基于CYCA和Desmodur N3600(HDI-异氰脲酸酯)的粘合剂体系可以在1重量％DBU存在下固化
6.1 CYCA-H 9046(TRICYCA)的制备
在N2气氛下，用400mL无水THF稀释78.21g Desmodur N 3600(0.43摩尔NCO)、57.28g环状碳酸酯羧酸(CYCA)(0.43摩尔)和0.52g 4-DMAP，并将反应混合物在室温下搅拌，直至没有发现残留的NCO(约6小时，IR对照)。真空除去溶剂，且以定量收率获得呈淡黄色粘稠液体的纯粘合剂。
6.2 CYCA-H 9046(TRICYCA)的固化
将12.0g CYCA-H 9046和0.12g(1重量％)DBU在塑料烧杯中混合，并使其在80℃下固化1h。获得淡褐色的硬而脆的多孔材料。
实施例7：N3600-GC，基于碳酸甘油酯和Desmodur N3600(HDI-异氰脲酸酯)的粘合剂体系(实施例6的对比例)
7.1 N3600-GC的制备
在N2气氛下，用600mL干燥THF稀释320.39g Desmodur N 3600(1.72摩尔NCO)、202.78g碳酸甘油酯(1.72摩尔)和0.1g DBTL，并将反应混合物加热至60℃，直至没有发现残留NCO(约6小时，IR对照)。将反应混合物冷却至室温，并真空除去溶剂。以定量收率获得呈澄清粘稠液体的纯粘合剂。
7.2 N3600-GC的固化
将12.0g N3600-GC和0.12g(1重量％)DBU在塑料烧杯中混合，并在80℃下反应1小时。没有观察到固化和发泡，获得澄清粘稠液体。
与本发明的实施例相反，该粘合剂的环状碳酸酯不能由吸电子基团活化。在这种情况下，没有观察到固化和发泡反应。
实施例8：T-2095-GC，基于碳酸甘油酯、TDI和Lupranol 2095的粘合剂体系(实施例4的对比例)
8.1 T-2095-GC的制备
在N2气氛下，将211.2g Lupranol 2095(Meq＝1600克/摩尔，0.13摩尔OH)用350mL干燥THF稀释，加入23.00g TDI(48.2％NCO，0.13摩尔)并将反应混合物加热至50℃并保持20分钟。测定NCO含量并加入相应量的碳酸甘油酯(16.92g，0.14摩尔)以及0.04g(0.02重量％)的DBTL。将反应混合物在室温下搅拌8小时，且在除去溶剂后，以定量收率获得呈粘稠澄清油状物的粘合剂。
8.2 T-2095-GC的固化
将12.0g T-2095-GC和0.12g(1重量％)DBU在塑料烧杯中混合，并在80℃下反应3天。没有观察到固化和发泡，并且获得混浊的淡褐色液体。

Claims (17)

1.一种用于制备开环聚合产物的方法，其包括以下步骤：
a)提供至少一种多异氰酸酯和2-氧代-1,3-二氧戊环-4-甲酸的反应产物；和
b)使所述反应产物在催化量的至少一种非亲核性碱存在下经受40-150℃的温度。
2.权利要求1的方法，其中所述多异氰酸酯选自脂族异氰酸酯、芳族异氰酸酯、环脂族异氰酸酯或其组合，所述多异氰酸酯具有≥2的-NCO官能度。
3.权利要求1的方法，其中所述多异氰酸酯选自甲苯二异氰酸酯、异佛尔酮二异氰酸酯、二苯基甲烷二异氰酸酯、4,4'-二异氰酸酯基二环己基甲烷、四亚甲基二异氰酸酯、五亚甲基二异氰酸酯、六亚甲基二异氰酸酯、其异构体、二聚体、三聚体、低聚物和混合物。
4.权利要求1的方法，其中所述多异氰酸酯为多异氰酸酯预聚物，所述多异氰酸酯预聚物可通过使如权利要求2或3所定义的摩尔过量的多异氰酸酯与多元醇反应而获得。
5.权利要求4的方法，其中所述多元醇具有2-8，优选2-6，特别是2或3的平均OH官能度。
6.权利要求5的方法，其中所述多元醇为数均分子量Mn为400-10000的聚氧化C2-4烯烃。
7.前述权利要求中任一项的方法，其中步骤(a)的反应产物可通过以下获得：
(1)使多异氰酸酯与等摩尔量的2-氧代-1,3-二氧戊环-4-甲酸反应；或
(2)在第一步中使摩尔过量的多异氰酸酯与2-氧代-1,3-二氧戊环-4-甲酸反应以获得中间体，并在第二步中使中间体与如上文所定义的多元醇反应。
8.前述权利要求中任一项的方法，其中步骤(a)的反应产物具有式(I)
其中R为通过形式上移除NCO基团而衍生自所述多异氰酸酯的x价基团，且x为2-6，优选2或3的整数。
9.前述权利要求中任一项的方法，其中步骤(b)在40-150℃，优选60-150℃的温度下进行。
10.前述权利要求中任一项的方法，其中所述非亲核性碱选自1,8-二氮杂双环[5.4.0]十一碳-7-烯、1,5-二氮双环[4.3.1]壬-5-烯、1,4-二氮杂双环[2.2.2]辛烷、2,6-二叔丁基吡啶、二异丙基乙基胺、四甲基胍或其混合物。
11.一种可通过前述权利要求中任一项的方法获得的开环聚合产物。
12.权利要求11的产物，其呈泡沫，特别是开孔泡沫形式。
13.一种包含步骤(a)的反应产物和非亲核性碱的组合物。
14.权利要求13的组合物，其呈成套试剂的形式，其中一部分包含步骤(a)的反应产物，且另一部分包含非亲核性碱。
15.权利要求11-12的开环聚合产物或权利要求13或14的组合物作为建筑材料，特别是粘合剂、绝缘材料、密封剂或涂料或在制备建筑材料，特别是粘合剂、绝缘材料、密封剂或涂料中的用途。
16.权利要求11-12的开环聚合产物或权利要求13-14的组合物在生产床垫或伤垫中的用途。
17.2-氧代-1,3-二氧戊环-4-甲酸和/或式(I)的步骤(a)的反应产物在泡沫生产中的用途。
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Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3464405A1 (de) * 2016-06-03 2019-04-10 Basf Se Verwendung von verbindungen mit n 2-oxo-1,3-dioxolan-4-carbonsäureamid-einheiten in zweikomponentenklebstoffen
JP6876740B2 (ja) * 2018-04-02 2021-05-26 株式会社エフコンサルタント 被覆材
WO2021108289A1 (en) * 2019-11-27 2021-06-03 Presidium Usa, Inc. Foamed polyurethane compositions

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5112879A (en) * 1989-09-19 1992-05-12 Imperial Chemical Industries Plc Chemical blowing agent
US20110054064A1 (en) * 2009-08-28 2011-03-03 International Business Machines Corporation Hydrogel Compositions and Methods of Preparation Thereof
CN102574997A (zh) * 2009-08-27 2012-07-11 道达尔石油化学产品研究弗吕公司 使用有机催化剂体系的环状碳酸酯的开环聚合
WO2014118268A1 (en) * 2013-01-31 2014-08-07 Construction Research & Technology Gmbh 2-oxo-1,3-dioxolane-4-carboxamide building blocks, their preparation and use
US20140235875A1 (en) * 2011-05-14 2014-08-21 Rajni Hatti-Kaul Method for producing cyclic carbonates
CN104011040A (zh) * 2011-12-22 2014-08-27 建筑研究和技术有限公司 2-氧代-1,3-二氧戊环-4-甲酰胺、其制备方法和用途
WO2014185856A1 (en) * 2013-05-16 2014-11-20 Cyclicor Ab Urethanes, polymers thereof, coating compositions and their production from cyclic carbonates

Family Cites Families (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0001088A1 (de) 1977-09-05 1979-03-21 BASF Aktiengesellschaft Carbonatgruppen enthaltende Polymerisate
JP3586881B2 (ja) 1994-04-19 2004-11-10 三菱化学株式会社 ジオキソラン含有溶剤
WO2004003001A1 (en) 2002-06-28 2004-01-08 Altus Biologics Inc. Process for the enzymatic resolution of 1,3-dioxolane-4-carboxylates
JP2006003433A (ja) 2004-06-15 2006-01-05 Sekisui Chem Co Ltd 液晶表示素子用シール剤、上下導通材料及び液晶表示素子
EP1932840B1 (en) 2005-10-03 2014-04-09 Ono Pharmaceutical Co., Ltd. Nitrogen-containing heterocyclic compound and pharmaceutical application thereof
EP1941946A1 (en) 2007-01-04 2008-07-09 Max-Planck-Gesellschaft zur Förderung der Wissenschaften e.V. Carbonitrides as catalysts
EP2403886A2 (en) * 2009-03-06 2012-01-11 Biopolymer Technologies, Ltd. Protein-containing foams, manufacture and use thereof
US8044194B2 (en) 2009-06-12 2011-10-25 International Business Machines Corporation Cyclic carbonyl monomers functionalized with carbohydrates, polymers derived therefrom, and methods of preparation thereof
JP5668354B2 (ja) * 2010-03-08 2015-02-12 株式会社リコー ポリマーの製造方法
US8742137B2 (en) 2010-06-17 2014-06-03 Construction Research & Technology Gmbh 2-oxo-1, 3-dioxolane-4-carboxylic acid and derivatives thereof, their preparation and use
EP2397474A1 (de) 2010-06-17 2011-12-21 Construction Research & Technology GmbH 2-Oxo-1,3-dioxolan-4-carbonsäureester, ihre Herstellung und Verwendung
EP2640714B1 (en) 2010-11-16 2014-09-10 Basf Se Process for the preparation of 2-oxo-[1,3]dioxolane-4-carboxylic acid esters
JP2014524468A (ja) 2011-08-22 2014-09-22 ダウ グローバル テクノロジーズ エルエルシー 環状炭酸塩モノマーおよびそれより調製されるポリマー
EP2617748A1 (de) 2012-01-23 2013-07-24 Basf Se Polyetherester-Polyole und Verfahren zu deren Herstellung
BR112014019688A8 (pt) 2012-03-01 2017-07-11 Basf Se Polieteréster poliol, processo para produzir espumas rígidas de poliuretano, espuma rígida de poliuretano, mistura de poliol, e, uso de polieteréster polióis
EP2890690B1 (de) * 2012-08-28 2016-04-27 Covestro Deutschland AG Bindemittel mit cyclischen carbonatstrukturen
US9228058B2 (en) 2013-03-15 2016-01-05 EcoSurg Comfort apparatus and method of manufacture
JP6060803B2 (ja) * 2013-04-30 2017-01-18 株式会社リコー ポリマー生成物、フイルム、成型品、シート、粒子、繊維、及びポリマーの製造方法
EP2818465A1 (en) 2013-06-26 2014-12-31 Construction Research & Technology GmbH 2-Oxo-1,3-dioxolane-4-acyl halides, their preparation and use
EP2915808A1 (en) 2014-03-07 2015-09-09 Construction Research & Technology GmbH 2-Hydroxyethyl 2-oxo-1,3-dioxolane-4-carboxylates, their preparation and use
EP2998331A1 (en) 2014-09-17 2016-03-23 Construction Research & Technology GmbH A curable organic polymer comprising at least one acylurea unit, its preparation and use
CN107148415B (zh) 2014-10-23 2020-11-13 建筑研究和技术有限公司 制备甘油酸碳酸酯的方法
BR112017009437B1 (pt) 2014-11-07 2021-11-16 Basf Se Método para preparar uma mistura em tanque, formulação pesticida, método de controle de fungos fitopatogênicos e uso do adjuvante de mistura em tanque

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5112879A (en) * 1989-09-19 1992-05-12 Imperial Chemical Industries Plc Chemical blowing agent
CN102574997A (zh) * 2009-08-27 2012-07-11 道达尔石油化学产品研究弗吕公司 使用有机催化剂体系的环状碳酸酯的开环聚合
US20110054064A1 (en) * 2009-08-28 2011-03-03 International Business Machines Corporation Hydrogel Compositions and Methods of Preparation Thereof
US20140235875A1 (en) * 2011-05-14 2014-08-21 Rajni Hatti-Kaul Method for producing cyclic carbonates
CN104011040A (zh) * 2011-12-22 2014-08-27 建筑研究和技术有限公司 2-氧代-1,3-二氧戊环-4-甲酰胺、其制备方法和用途
WO2014118268A1 (en) * 2013-01-31 2014-08-07 Construction Research & Technology Gmbh 2-oxo-1,3-dioxolane-4-carboxamide building blocks, their preparation and use
WO2014185856A1 (en) * 2013-05-16 2014-11-20 Cyclicor Ab Urethanes, polymers thereof, coating compositions and their production from cyclic carbonates

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
OSAMU HABA等: "Anionic Ring-Opening Polymerization of Methyl 4,6-O-Benzylidene-2,3-O- carbonyl-α-d-glucopyranoside: A First Example of Anionic Ring-Opening Polymerization of Five-Membered Cyclic Carbonate without Elimination of CO2", 《MACROMOLECULES》 *

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