CN107735419A - 用于聚氨酯泡沫的醛清除剂 - Google Patents
用于聚氨酯泡沫的醛清除剂 Download PDFInfo
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- CN107735419A CN107735419A CN201580080944.7A CN201580080944A CN107735419A CN 107735419 A CN107735419 A CN 107735419A CN 201580080944 A CN201580080944 A CN 201580080944A CN 107735419 A CN107735419 A CN 107735419A
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- composition
- foam
- aldehyde
- polyurethane foam
- aldehyde scavenger
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- 239000002516 radical scavenger Substances 0.000 title claims abstract description 58
- 229920005830 Polyurethane Foam Polymers 0.000 title claims abstract description 46
- 239000011496 polyurethane foam Substances 0.000 title claims abstract description 45
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 title claims abstract 13
- 239000000203 mixture Substances 0.000 claims abstract description 102
- -1 dicarbonyl compound Chemical class 0.000 claims abstract description 59
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000000463 material Substances 0.000 claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 36
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- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 8
- 150000003863 ammonium salts Chemical class 0.000 claims abstract description 7
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- 239000006260 foam Substances 0.000 claims description 60
- 150000005846 sugar alcohols Polymers 0.000 claims description 40
- 229910052757 nitrogen Inorganic materials 0.000 claims description 34
- 150000001412 amines Chemical class 0.000 claims description 29
- 239000003054 catalyst Substances 0.000 claims description 28
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Abstract
本发明公开了包含醛清除剂的聚氨酯组合物,聚氨酯产物,和制备聚氨酯泡沫的方法。所述清除剂化合物可减少,如果没有消除,醛从聚氨酯泡沫中的释放。所述清除剂化合物包含选自以下物质组中的至少一个成员:苯酚或取代苯酚,1,3‑二羰基化合物,带有1,3‑丙烷二氨基官能的多元胺,三聚氰胺,1,2‑二氨基环烷烃,铵盐;含有亚硫酸氢根阴离子的化合物,二氧化钛和氨基硅氧烷。
Description
技术领域
本发明涉及用于减少醛的组合物,用于制备聚氨酯泡沫的方法,和具有降低的醛量的泡沫。
背景技术
通常通过使异氰酸酯和由异氰酸酯反应性组分如多元醇构成的预混物反应制备聚氨酯泡沫组合物。该预混物任选还含有其它组分,如水、阻燃剂、发泡剂、稳定泡沫的表面活性剂、交联剂和催化剂以促进异氰酸酯与多元醇反应以制备氨酯,与水反应以制备CO2和脲,并与过量异氰酸酯反应以制备异氰脲酸酯(三聚物)。该预混物中的发泡剂通常是沸点足够低以通过聚合反应过程中释放的热汽化的液体或气体。可用于制备绝缘聚氨酯泡沫的发泡剂的实例包括但不限于氢氟烃、氢氯烃、氢氟烯烃、氯氟烯烃、氢氯烯烃、氢氟氯烯烃、氢氯氟烃、甲酸酯和烃。该预混物中的组分和异氰酸酯的适当选择和组合可用于制备喷涂、现场浇注和用于如冰箱、冷冻机、热水加热器、隔热板、车库门、入户门和需要绝缘的其它各种用途之类用途的聚氨酯泡沫。
在聚氨酯模制品的制备中,使多异氰酸酯与含活性氢的化合物(例如多元醇、伯或仲胺、水)反应以使异氰酸酯当量数大致等于该混合物中的活性氢的总当量。
对关于来自聚氨酯泡沫的低量醛释放的越来越多的担忧导致汽车制造商推出释放标准。美国和欧洲聚氨酯制造商贸易集团已采用“Certipur”程序提升聚氨酯泡沫的安全、健康和环境性能。当使用ASTM方法D5116-97(采用室调理16小时的小室法)测量时,甲醛释放限值为0.1mg/m。
NIOSH和OSHA已指定醛暴露限值,包括尤其针对甲醛和乙醛的限值。这些暴露限值对汽车和块料工业意义重大,这些工业整体上在努力提高汽车座舱和垫底材料的空气品质。汽车和垫底材料的最终用户可能暴露于可能从该泡沫释放的VOC(挥发性有机化合物),包括醛。
日本汽车制造商协会(JAMA)已经确认几种VOC(包括甲醛和乙醛)是造成泡沫释放的因素。可能要求汽车泡沫通过测量这些醛的加热室试验。要求块料泡沫通过测量甲醛释放的CertiPUR/LGA/-EUROPUR/IKEA试验。因此在这一领域中需要将释放低得多的醛量的聚氨酯泡沫和用于制备此类泡沫的材料。
传统泡沫制备材料的一个实例公开在US 6,540,936 B1中,其要求保护使用吸附到二氧化硅上的多亚乙基多胺作为从树脂纤维,如聚酯、尼龙、聚氨酯和其它天然和合成材料中吸收醛的载体。由于这些是固体醛清除剂,它们不能用于制备聚氨酯泡沫,因为在制备聚氨酯产品的工业方法中通常只能泵送和混合液体材料。EP 1,428,847 B1描述了使用含伯和仲胺基团的聚合物质减少来自聚氨酯泡沫的甲醛的方法。在US 2006/0141236 A1中,使用含肼的化合物减少来自聚氨酯泡沫的甲醛和乙醛释放。肼是有毒和爆炸性的,从而限制它们的使用。在EP 1,874,853 B2中要求保护酚类和磷酸酯抗氧化剂的混合物作为防止聚氨酯泡沫和前体中的醛形成的化合物。尽管这些酚类抗氧化剂防止通过聚氨酯前体的氧化形成醛,但这些抗氧化剂不除去用于制备聚氨酯泡沫的“预混物”溶液中已存在的醛。在US 2009/0326089 A1中,在相同分子中含酰氨基和氰基的化合物被描述为聚氨酯组合物中的甲醛清除剂。醛的减少需要大量该要求保护的分子。在US 2011/0009512 A1中描述了伯胺化合物与叔胺催化剂的组合以减少来自聚氨酯泡沫的甲醛释放,但这种方案无法减少其它醛,如乙醛。工业上需要降低甲醛、乙醛和丙烯醛释放。Goh等人在US 7,879,928 B2中描述了通过将酚类抗氧化剂、胺类抗氧化剂、苯并呋喃-2-酮和亚磷酸酯或亚膦酸酯结合入用于聚氨酯生产的配制剂中而防止聚氨酯和前体中的醛类污染物形成的方法。Haas等人在US2012/0184639 A1中要求保护使用含有氨基脲的化合物减少聚氨酯泡沫中的甲醛。工业上需要降低甲醛、乙醛和丙烯醛释放。WO 2013/156237 A2描述了使用含胍的添加剂用于从聚氨酯体系中清除甲醛。在US 2009/0227758中也公开了醛清除剂,但其具有在多元醇和异氰酸酯中都需要添加剂的限制。WO 2015/050876 A1预处理和再加工胺催化剂以降低醛释放。上述发明并不符合工业标准。
上文提出的专利和专利申请经此引用并入本文。
发明内容
本发明可以通过提供醛清除剂解决与传统组合物和方法相关的问题。本发明公开内容涉及醛清除剂组合物,其可用于制备低或无醛释放的软质聚氨酯泡沫以及硬质绝缘聚氨酯泡沫,其用含有聚醚、聚酯、曼尼希多元醇以及有机含卤素阻燃剂和发泡剂的体系制成。可通过将一种或多种醛清除剂结合入用于生成泡沫的“预混的”配制剂中实现这种降低的醛释放。“低或无释放”是指当根据下文描述的GM试验方法GMW15635-2012测试泡沫样品时,使用本发明的清除剂制成的泡沫没有来自该泡沫的甲醛或乙醛释放或甲醛释放低于大约2μg/g泡沫;低于大约0.1μg/g泡沫、低于大约1.0μg/g泡沫、低于大约1.5μg/g泡沫;在一些情况下低于大约0.25μg/g泡沫且乙醛释放低于大约0.35μg/g泡沫;低于大约0.05μg/g泡沫;低于大约1.0μg/g泡沫;在一些情况下低于大约2.0μg/g泡沫;低于大约。此外,“低或无释放”也是指当根据下文描述的10L袋法(Q/BYD-1901.771-2012(BYD)或(NES 0402方法#2))测试泡沫样品时,使用本发明的清除剂制成的泡沫没有来自该泡沫的甲醛或乙醛释放,或甲醛释放低于大约165μg/m3;低于大约1.0μg/m3、低于大约50μg/m3、低于大约75μg/m3泡沫,在一些情况下低于大约25μg/g泡沫且乙醛释放低于大约82μg/m3、低于大约2μg/m3、低于大约50μg/m3,在一些情况下低于大约40μg/m3。在本公开内容中“μg/m3”和“ug/m3”可互换使用并且是指每立方米(m3)气体计醛的微克数。不希望受制于任何理论或解释,但相信本发明的醛清除剂可与醛相互作用或反应,由此将醛转化成另一材料或将醛截留在该泡沫内。
本发明的一个方面涉及一种醛清除剂,其包含选自以下物质组中的至少一个成员:
a)苯酚或取代苯酚
b)1,3-二羰基化合物
c)带有1,3-丙烷二氨基官能的多元胺
d)三聚氰胺
e)1,2-二氨基环烷烃
f)铵盐;和
g)含有亚硫酸氢根阴离子的化合物
h)二氧化钛
i)氨基硅氧烷
本发明的另一个方面涉及一种组合物,其包含与至少一种用于制备聚氨酯的其它化合物组合的至少一种醛清除剂。例如,本发明的醛清除剂可与至少一种包含多元醇和异氰酸酯化合物的预混物组合。优选地,所述醛清除剂与用于制备聚氨酯的非醛化合物是没有反应性的。
本发明的一个方面涉及一种组合物,其包含至少一种醛清除剂、至少一种催化剂和任选的至少一种稀释剂。
本发明的一个方面涉及通过使用包含如下组分的聚氨酯配制剂制备聚氨酯泡沫:
1.至少一种醛清除剂,其可以是如下化合物中的一种或化合物的组合:
a.苯酚或取代苯酚
b.1,3-二羰基化合物
c.带有1,3-丙烷二氨基官能的多元胺
d.三聚氰胺
e.1,2-二氨基环烷烃
f.铵盐;和
g.含有亚硫酸氢根阴离子的化合物
h.二氧化钛
i.氨基硅氧烷
2.至少一种多元醇
3.含有异氰酸酯反应性氢原子的化合物
4.水和其它发泡剂
5.催化剂
6.表面活性剂
7.添加剂、颜料或阻燃剂
8.二异氰酸酯或多异氰酸酯化合物。
所述醛清除剂在环境条件下通常是液体。所述醛清除剂可占预混物组合物的约0.05pphp至约2.0pphp,约1pphp至约2pphp和约1.5pphp至约2.0pphp。
本发明的一个方面涉及一种组合物,其包含至少一种醛清除剂、至少一种多元醇、水和至少一种胺催化剂。
本发明的另一个方面涉及其中所述醛清除剂包含选自以下物质组中的至少一个成员的上述方面:苯酚或取代苯酚化合物,1,3-二羰基化合物,带有1,3-丙烷二氨基官能的多元胺,三聚氰胺,1,2-二氨基环烷烃,铵盐;含有亚硫酸氢根阴离子的化合物,二氧化钛和氨基硅氧烷。
本发明的另一个方面涉及其中所述醛清除剂包含选自以下物质组中的至少一个成员的任一上述方面:苯酚,腰果酚,2-甲基苯酚,4-甲基苯酚,4-叔丁基苯酚,2-甲氧基苯酚,4-甲氧基苯酚,水杨酰胺和4-壬基苯酚。
本发明的另一个方面涉及其中所述醛清除剂包含选自以下物质组中的至少一个成员的任一上述方面:乙酰乙酸乙酯,丙二酸二乙酯,丙二酸二甲酯,2,4-戊二酮,1,3-环己二酮丙二酰胺,乙酰乙酰胺和N,N,N'N'-四甲基丙二酰胺。
本发明的另一个方面涉及其中所述醛清除剂包含选自以下物质组中的至少一个成员的任一上述方面:N,N'-二甲基丙二胺,N'N'-二苯基丙二胺,1-苄基-1,3-丙二胺,异十三烷氧基丙基-1,3-二氨基丙烷,十二烷氧基丙基-1,3-二氨基丙烷和己氧基丙基-1,3-二氨基丙烷。
本发明的另一个方面涉及其中所述醛清除剂包含三聚氰胺的任一前述方面。
本发明的另一个方面涉及其中所述醛清除剂包含1,2-二氨基环己烷的任一前述方面。
本发明的另一个方面涉及其中所述醛清除剂包含选自以下物质组中的至少一个成员的任一上述方面:碳酸铵,硫酸铵,氯化铵和硝酸铵。
本发明的另一个方面涉及其中所述醛清除剂包含选自以下物质组中的至少一个成员的任一上述方面:亚硫酸氢钠,亚硫酸氢钾,亚硫酸氢锂和四烷基亚硫酸氢铵。
本发明的另一个方面涉及任一前述方面,并进一步包含至少一种稀释剂。
本发明的一个方面涉及一种组合物,其包含任一前述的醛清除剂组合物、至少一种胺催化剂和至少一种稀释剂。
本发明的一个方面涉及制备聚氨酯泡沫的方法,所述方法包括在如下物质的存在下使至少一种多元醇和至少一种二异氰酸酯接触和反应:1)至少一种发泡剂,2)至少一种胺催化剂,和3)任何前述组合物。
本发明的另一方面涉及制备聚氨酯泡沫的方法,所述方法包括反应合并1)至少一种多元醇,2)至少一种发泡剂,3)至少一种胺催化剂,和4)任何前述组合物,和与至少一种多异氰酸酯接触,从而使所述多元醇和多异氰酸酯反应以制备所述聚氨酯泡沫。
本发明的另一个方面涉及通过任何前述方法制备的聚氨酯泡沫。
本发明的另一个方面涉及其中所述泡沫包含低释放泡沫的任何前述聚氨酯泡沫。
本发明的另一个方面涉及其中所述泡沫包含无释放泡沫的任何前述聚氨酯泡沫。
本发明的另一个方面涉及任何前述组合物用于制备聚氨酯泡沫的用途。
本发明的各个方面和实施方案可单独使用或与彼此组合使用。
发明详述
本发明提供本发明的方法、聚氨酯组合物、聚氨酯产品和制备聚氨酯泡沫的方法。本公开内容的实施方案可通过将醛清除剂结合入用于制备如上所述的泡沫的配制剂中而减少来自聚氨酯泡沫的醛释放。这些化合物经证实显著减少(如果不是消除)来自这些泡沫的醛释放并在一些情况下已经符合或优于工业释放标准。
本发明的清除剂可用于制备多种多样的泡沫,包括硬质绝缘泡沫,并特别可用于喷涂泡沫、电器绝缘、隔热建筑板和含有闭孔硬质聚氨酯泡沫的各种其它绝缘产品。本发明包括具有大约20和大约500、大约50至大约270和通常大约70至大约150的异氰酸酯指数的泡沫。本发明包括具有大约5至大约600、大约100至大约600和在一些情况下大约50至大约100的OH值的多元醇。
本发明中描述的清除剂可以与任何合适的含卤素发泡剂组合使用。可用于制备绝缘聚氨酯泡沫的发泡剂的实例包括但不限于氢氟烃、氢氯烃、氢氟烯烃、氢氯烯烃、氢氟氯烯烃、氯氟烯烃、氢氯氟烃、甲酸酯和烃。氢卤烯烃发泡剂的实例是HFO-1234ze(反式-1,3,3,3-四氟丙-1-烯)、HFO-1234yf(2,3,3,3-四氟丙烯)和HFCO-1233zd(1-丙烯,1-氯-3,3,3-三氟),以及其他HFO。发泡剂的量可以为大约0.5pphp至大约5pphp、大约5pphp至大约20pphp和在一些情况下大约20pphp至大约50pphp。
本发明的一个方面可用于制备具有低或无醛释放的软质聚氨酯泡沫,该聚氨酯泡沫用于汽车用途,如汽车座椅、扶手、头枕、方向盘和具有开孔软质泡沫的各种其它产品。本发明包括具有大约60至大约200、大约70至大约180和通常大约70至大约150的异氰酸酯指数的泡沫。本发明包括具有大约5至大约600的OH值的多元醇。软质泡沫通常使用包含水或基本由水组成的发泡剂制备。
在一个实施方案中,包含苯酚或取代苯酚(得自如上名单)的醛清除剂1a由如下结构表示:
R=在所述苯酚上的取代基。这可以是H,1-20个碳原子的烷基,带有诸如N、S、O的杂原子的烷基。所述取代基可处在相对于所述OH基团的邻位、间位或对位位置。在这一实施方案中不要求保护具有与所述羟基基团相邻的位阻丁基烷基的酚类抗氧化剂,例如丁基化的羟基甲苯和丁基化的羟基苯甲醚。
这种类型的化合物的实例包括选自以下物质组中的至少一个成员:苯酚,腰果酚,2-甲基苯酚,4-甲基苯酚,4-叔丁基苯酚,2-甲氧基苯酚,4-甲氧基苯酚,和4-壬基苯酚。优选的化合物是腰果酚、4-叔丁基苯酚和4-壬基苯酚。最优选的是腰果酚、水杨酰胺和4-壬基苯酚。
另一个实施方案中,所述醛清除剂包含1,3-二羰基。1b的这样的化合物可由如下所示的化学结构表示:
X,Y=烷基,芳基,烷氧基,NR2(R=H,烷基,芳基)。所述1,3-二羰基基团还可以被包含在五元或六元环中。这样的化合物的实例包括选自以下物质组中的至少一个成员:乙酰乙酸乙酯,丙二酸二乙酯,丙二酸二甲酯,2,4-戊二酮,1,3-环己二酮丙二酰胺,(乙酰乙酰胺),N,N,N'N'-四甲基丙二酰胺。优选的1,3-二羰基化合物是乙酰乙酸乙酯,2,4-戊二酮和乙酰乙酰胺和1,3-环己二酮。最优选的是乙酰乙酰胺和1,3-环己二酮。
在另一个实施方案中,所述醛清除剂包含至少一种1c的多元胺,其带有1,3-丙烷二氨基官能。这可由如下结构表示:
R、R1可以是H、烷基或芳基烷基。R2和R3可以是烷基或芳基。
在相同的分子中可存在多个1,3-丙烷胺基团,例如如下结构:
这样的1c的多元胺的实例包括选自以下物质组中的至少一个成员:N,N'-二甲基丙二胺,N'N'-二苯基丙二胺,1-苄基-1,3-丙二胺,异十三烷氧基丙基-1,3-二氨基丙烷,十二烷氧基丙基-1,3-二氨基丙烷,和己氧基丙基-1,3-二氨基丙烷。优选的1,3-丙烷二氨基化合物是1-苄基-1,3-丙二胺,异十三烷氧基丙基-1,3-二氨基丙烷,十二烷氧基丙基-1,3-二氨基丙基,和己氧基丙基-1,3-二氨基丙烷。最优选的1,3-丙烷二氨基化合物是异十三烷氧基丙基-1,3-二氨基丙烷。
在另一个实施方案中,所述清除剂包含三聚氰胺(1d)。
在另一个实施方案中,所述清除剂包含1,2-二氨基环己烷(1e)。
所述醛清除剂可以是铵盐(1f)。这些的实例包括碳酸铵,硫酸铵,氯化铵,硝酸铵。最优选的铵盐是碳酸铵。
在一个实施方案中,所述醛清除剂包含至少一种亚硫酸氢盐,其可以是亚硫酸氢钠,亚硫酸氢钾,亚硫酸氢锂和四烷基亚硫酸铵,(1g)。优选的亚硫酸氢盐是亚硫酸氢钠和四烷基亚硫酸氢铵。最优选的是亚硫酸氢钠。
在另一个实施方案中,所述醛清除剂包含二氧化钛(h)。
在另一个实施方案中,所述醛清除剂包含至少一种氨基硅氧烷以及烷醇氨基硅氧烷。现有技术中在如下文献中描述了氨基硅氧烷和烷醇氨基硅氧烷:US2013/0017359A1,US5707435,GB1363069,US3565936和US 2014/0054228A1;它们通过引用并入本文中。氨基硅氧烷的实例包括选自如下物质组的至少一个成员:N-(2-氨基乙基)-3-氨基丙基三甲氧基硅烷,N-(氨基乙基氨基甲基)苯基三甲氧基硅烷,N-(2-氨基乙基)-3-氨基丙基三(2-乙基己氧基)-硅烷,3-氨基丙基三甲氧基(methyxy)硅烷,三甲氧基甲硅烷基-丙基二亚乙基三胺,双(2-羟基乙基)-3-氨基丙基三甲氧基硅烷等。
在一个实施方案中,本发明涉及一种预混物,其包含至少一种醛清除剂,多元醇组分,至少一种表面活性剂组分,至少一种发泡剂组分和至少一种交联性组分。所述多元醇组分包含一种或多种标准多元醇,一种或多种天然油多元醇,一种或多种聚酯多元醇,一种或多种曼尼希多元醇,或它们的组合。通过如下物质的缩合反应获得曼尼希碱:1)羰基化合物,2)伯胺或仲胺和3)具有可烯醇化酸性氢的有机化合物,例如酚类,酮类,但最通常是苯酚和取代苯酚。所述曼尼希碱可用作与环氧乙烷和环氧丙烷进行的烷氧基化反应的引发剂,该反应得到被称为曼尼希多元醇的含胺聚醚多元醇。多元醇的量的范围可以为约80pphp至约100pphp,约80pphp至约50pphp和在一些情况下约50pphp至约10pphp。表面活性剂的量的范围可以为约0.10pphp至约10pphp,约0.20pphp至约8.0pphp和在一些情况下约0.5pphp至约3.0pphp。发泡剂组分的量的范围可以为约1pphp至约30pphp,约5pphp至约20pphp和在一些情况下约8pphp至约15pphp。交联性组分的范围可以为约0.20pphp至约10pphp,约0.5pphp至约5pphp和在一些情况下约0.5pphp至约3.0pphp。所述预混物可通过使用任何合适的条件形成,所述条件例如在配备有机械搅拌器的反应容器中混合所有组分,或在转鼓中简单混合所有预混物组分,和在密封前在所述转鼓内部机械混合所述组分。
在一个实施方案中,所述标准多元醇包括聚醚多元醇。在一个实施方案中,所述标准多元醇的用量范围为约0pphp至约100pphp,约0pphp至约80pphp和在一些情况下约20pphp至约60pphp。在一个实施方案中,所述天然油多元醇的量为大于约0至约40pphp,大于约0至约20pphp和在一些情况下大于约0pphp至约10pphp。在一个实施方案中,单独使用所述标准多元醇,并且其是聚酯多元醇。在一个实施方案中,所述聚酯多元醇的用量为约0pphp至约100pphp,约10pphp至约80pphp和在一些情况下约20pphp至约60pphp。在一个实施方案中,所述曼尼希多元醇与其它多元醇组合使用,并且其用量范围为0pphp至80pphp,约0pphp至约50pphp和在一些情况下约0pphp至约20pphp。
在一个实施方案中,所述预混物进一步包含以下物质中至少一种:水,泡孔稳定剂,扩链剂,颜料,填料,阻燃剂,辅助氨酯凝胶催化剂,辅助氨酯发泡催化剂,过渡金属催化剂,或它们的组合。上述物质的量的范围可以为约0.1pphp至约10pphp,约10pphp至约30pphp和在一些情况下约30pphp至约50pphp。如下文中所述的,在一些实施方案中,所述预混物包括通过任何合适的设备和过程(包括之前描述的那些)和/或在所述方法的任何合适部分合并的另外组分。
本发明的预混物可包含任何合适的泡孔稳定剂,其包括但不限于有机硅表面活性剂,阴离子型表面活性剂,或它们的组合。在一个实施方案中,所述泡孔稳定剂是有机硅表面活性剂,例如聚烷基硅氧烷,聚氧基亚烷基多元醇改性的二甲基聚硅氧烷,亚烷基二醇改性的二甲基聚硅氧烷,或它们的组合。在一个实施方案中,所述泡孔稳定剂是阴离子型表面活性剂,例如脂肪酸的盐、硫酸酯的盐,磷酸酯的盐,磺酸的盐,或它们的组合。
在一个实施方案中,所述预混物包括合适预定量的所述泡孔稳定剂。合适的阳离子型表面活性剂包括但不限于季铵盐(pH依赖性的或永久带电的),例如鲸蜡基三甲基氯化铵,鲸蜡基氯化吡啶,聚乙氧基化的牛脂胺,苯扎氯铵,苄索氯铵等。合适的两性离子的或两性的表面活性剂包括但不限于磺基甜菜碱(sultaine),氨基酸,亚氨基酸,甜菜碱和磷酸酯(盐)。合适的非离子表面活性剂包括但不限于脂肪醇,聚氧亚乙基二醇烷基醚,聚氧亚丙基二醇烷基醚,葡糖苷(例如癸基、月桂基和辛基葡糖苷),聚氧亚乙基二醇烷基酚醚,二醇烷基酯等。合适的预定量包括但不限于约0.1pphp至约20pphp,0.1pphp至约10pphp,0.1pphp至约5pphp,或它们的任何合适的组合或亚组合。
本发明的预混物可包含至少一种交联剂。合适的交联剂(形成交联的部分或全部)包括但不限于含有至少两个异氰酸酯反应性结构部分的低分子量化合物,所述异氰酸酯反应性结构部分例如羟基,伯氨基,仲氨基,其它与异氰酸酯基团为反应性的含活性氢的基团,或它们的组合。在一个实施方案中,所述交联剂是多元醇(例如三元醇,例如甘油或三羟甲基丙烷),多元胺,或它们的组合。在其中所述交联剂是多元胺的一个实施方案中,所述交联剂是二乙基甲苯二胺,氯代二氨基苯,二乙醇胺,二异丙醇胺,三乙醇胺,三丙醇胺,1,6-己二胺,或它们的组合。在其中所述交联剂是二胺的一个实施方案中,所述交联剂包括12个或更少个碳原子,7个碳原子或小于7个碳原子。交联剂的量的范围可以为约0.20pphp至约10pphp,约0.5pphp至约5pphp和在一些情况下约0.5pphp至约3.0pphp。
本发明的预混物可包含至少一种扩链剂。合适的扩链剂包括但不限于具有羟基或氨基官能团的化合物,例如二醇(glycol),胺,二元醇(diol),水,或它们的组合。在一个实施方案中,所述扩链剂是乙二醇,二乙二醇,丙二醇,二丙二醇,1,4-丁二醇,1,3-丁二醇,1,5-戊二醇,新戊二醇,1,6-己二醇,1,10-癸二醇,1,12-十二烷二醇,乙氧基化的氢醌,1,4-环己烷二醇,N-甲基乙醇胺,N-甲基异丙醇胺,4-氨基环己醇,1,2-二氨基乙烷(1,2-diaminothane),2,4-甲苯二胺,或它们的组合。扩链剂的量的范围可以为约0.20pphp至约10pphp,约0.5pphp至约5pphp和在一些情况下约0.5pphp至约3.0pphp。
本发明的预混物可包含至少一种颜料。合适的颜料包括但不限于有机颜料,无机颜料,或它们的组合。所述颜料允许着色(例如,为了匹配颜色等级),遮盖(例如为了遮盖发黄),或它们的组合。在其中所述颜料是有机颜料的一个实施方案中,所述颜料是偶氮/重氮染料,酞菁,二嗪,炭黑,或它们的组合。在其中所述颜料是无机颜料的一个实施方案中,所述颜料是二氧化钛,氧化铁,氧化铬,或它们的组合。颜料的量的范围可以为约0pphp至约10pphp,约0pphp至约5pphp和在一些情况下约0.1pphp至约3.0pphp。
本发明的预混物可包含至少一种填料。合适的填料增加了聚氨酯泡沫的密度和承载性能。在一个实施方案中,所述填料是硫酸钡,碳酸钙,或它们的组合。填料的量的范围可以为约0pphp至约20pphp,约0pphp至约10pphp和在一些情况下约1.0pphp至约5.0pphp。
本发明的预混物可包含至少一种阻燃剂。合适的阻燃剂降低了聚氨酯泡沫的可燃性。在一个实施方案中,所述阻燃剂是氯化的磷酸酯,氯化的石蜡,三聚氰胺粉末,或它们的组合。在一个实施方案中,所述预混物包括任何合适量的所述阻燃剂。合适的量包括但不限于约0pphp至约30pphp,约0pphp至约20pphp,约0pphp至约10pphp,约1pphp至约20pphp,约1pphp至约10pphp,约1pphp至约5pphp,或它们的任何合适的组合或亚组合。
在一个实施方案中,所制备的组合物是聚氨酯组合物。在这个实施方案中,所述方法包括使包括本发明的胺组合物的所述预混物与所述异氰酸酯反应以形成所述聚氨酯组合物。所述聚氨酯组合物的形成包括使用传统设备和方法(例如描述在Ron Herrington和Kathy Hock的DOW POLYURETHANES Flexible Foams,Dow Plastics 1997中的那些)将异氰酸酯组分与所述预混物合并。将所述组分在预定的叶片旋转速度下(例如约6,000转/分钟)合并预定的持续时间(例如约6秒),或它们的组合。另选地,所述聚氨酯组合物的形成包括利用喷涂泡沫设备将异氰酸酯组分与所述预混物合并,其由在高压下在喷涂机的混合头中接触所有组分组成。
在一个实施方案中,将所述异氰酸酯组分与所述预混物组合物以化学计量比例或大致化学计量比例进行合并。在一个实施方案中,所述化学计量比例基于NCO指数。所述NCO指数是所述异氰酸酯的当量数,除以活性氢的当量的总数,乘以100(例如,基于NCO指数是[NCO/(OH+NH)]*100)。所述聚氨酯组合物包括在预定范围内的NCO指数。在一个实施方案中,所述预定范围在约20和约500之间。在一个实施方案中,如果所述聚氨酯组合物用于制备喷涂泡沫应用,则所述范围在约20和约500之间。对于其它应用,所述NCO指数的范围可以为约50至约300,约80至约250和约90至约110。在一个实施方案中,所述聚氨酯组合物与三聚催化剂一起用于制备聚异氰脲酸酯泡沫,其用于泡沫层压材料中,并包括适合于所述用途的范围。
所述异氰酸酯组分包括任何合适的有机异氰酸酯化合物。合适的有机异氰酸酯化合物包括但不限于以下物质中至少一种:六亚甲基二异氰酸酯(HDI),亚苯基二异氰酸酯(PDI),甲苯二异氰酸酯(TDI),4,4'-二苯基甲烷二异氰酸酯(MDI),异佛尔酮二异氰酸酯(IPDI),或它们的组合。在一个实施方案中,所述异氰酸酯组分包括2,4-TDI,2,6-TDI,或它们的组合。在一个实施方案中,所述异氰酸酯组分包括按重量计约80%的2,4-TDI,和约20%或余量的2,6-TDI。在一个实施方案中,所述异氰酸酯组分包括粗MDI,例如约60%的4,4'-MDI和/或化学计量量连同其它异构体的和类似的更高级多异氰酸酯的混合物。在美国专利4,394,491中示出和描述了其它合适的异氰酸酯,该文献以其全文通过引用并入本文中。
在一个实施方案中,所述预混物包括,按重量计,至少约20%的多元醇,约0.5%-约10%的表面活性剂,约1%-约30%的是所述发泡剂组分,约0.5%-约4%的是交联性组分,约0.25%-约15%的是所述催化剂组合物,其中基于所述NCO指数的所述异氰酸酯组分的量在约20和约500之间。在另一个实施方案中,所述多元醇组分包括聚醚多元醇,天然油多元醇和/或聚酯多元醇。在一个实施方案中,所述聚醚多元醇具有在约500和约20,000之间的平均分子量和/或在约400和约10之间的羟基值,和更优选在2000和5000之间的平均分子量和/或在约50和约20之间的羟基值。
在一个实施方案中,所述预混物包括约100pphp的所述多元醇组分(例如约70pphp是聚酯多元醇和/或约30pphp是曼尼希多元醇),约2.0pphp是所述表面活性剂组分,约1.5pphp是水,和所述异氰酸酯组分具有约180的NCO指数。所述预混物还包括本发明的催化剂组合物。在另一个实施方案中,所述预混物包括约30pphp的所述阻燃剂(例如磷酸三(2-氯丙基)酯),20pphp的发泡剂,1.0pphp金属催化剂和0.10pphp至10pphp的三聚催化剂。
在所述预混物中的基础多元醇与所述异氰酸酯反应以制备所述聚氨酯泡沫组合物。在一个实施方案中,所述基础多元醇是聚醚多元醇。合适的聚醚多元醇示于并描述在如下文献中:WO 03/016373 A1、WO 01/58976 A1、WO 04/060956 A1、WO 03/016372 A1和WO03/055930 A1,它们中的每一篇都通过引用以其全文并入本文中。在一个实施方案中,所述聚醚多元醇是聚(环氧烷烃)聚合物,例如聚(环氧乙烷),聚(环氧丙烷)和/或具有衍生自多羟基化合物(例如二醇和三醇)的末端羟基基团的共聚物。在一个实施方案中,所用的二醇和三醇是乙二醇,丙二醇,1,3-丁二醇,1,4-丁二醇,1,6-己二醇,新戊二醇,二乙二醇,二丙二醇,季戊四醇,甘油,双甘油,三羟甲基丙烷,其它合适的低分子量多元醇,或它们的组合。在一个实施方案中,所述聚醚多元醇是或包括多羟基封端的缩醛树脂,羟基封端的胺,羟基封端的多元胺,或它们的组合。在一个实施方案中,所述基础多元醇是或包括基于聚碳酸亚烷基酯的多元醇,基于磷酸酯的多元醇,或它们的组合。
在一个实施方案中,所述基础多元醇包括单一的高分子量聚醚多元醇。在另一个实施方案中,所述基础多元醇包含多种高分子量聚醚多元醇的混合物,所述多种高分子量聚醚多元醇各自具有不同的分子量或不同的化学组成。在这个实施方案中,所述基础多元醇包含二官能和三官能材料,例如但不限于聚乙二醇、聚丙二醇、基于甘油的聚醚三元醇,基于三羟甲基丙烷的聚醚三元醇,其它类似的化合物或混合物,或它们的组合。
在一个实施方案中,所述聚脲改性的多元醇是由在所述起始多元醇的存在下二胺和二异氰酸酯的反应形成的。在这个实施方案中,所述聚脲改性的多元醇包括聚脲分散体。在一个实施方案中,所述聚脲改性的多元醇是或包括多异氰酸酯聚加成(PIPA)多元醇,例如由在所述起始多元醇中的所述异氰酸酯和烷醇胺的反应原位形成的那些。
在一个实施方案中,所述基础多元醇是或包括天然油多元醇。通常,所述天然油多元醇是较不昂贵的,并且来自可再生资源,从而提供环境益处。所述天然油多元醇包括具有在12和24之间的碳链长度的饱和和/或不饱和酸的甘油三酯。所述饱和酸是月桂酸、肉豆蔻酸、棕榈酸、硬脂酸、花生酸、木蜡酸或它们的组合。所述不饱和酸是单不饱和的(例如棕榈油酸、油酸或它们的组合)和/或多不饱和的(例如亚油酸、亚麻酸、花生四烯酸或它们的组合)。一种天然油多元醇是蓖麻油,一种蓖麻油酸的天然甘油三酯,其通常用于制备聚氨酯泡沫,即使其具有某些限制,例如低羟基含量。其它天然油需要被化学改性以引入充分的羟基含量,从而使得它们可用于制备聚氨酯聚合物。当尝试将天然油或脂肪改性成有用的多元醇时存在两个可以考虑的化学反应性位点:1)不饱和位点(双键);和2)酯官能团。在油或脂肪中存在的不饱和位点可以通过如下方式羟基化:环氧化,随后开环,或加氢甲酰化,随后氢化。另选地,酯交换也可用于在天然油和脂肪中引入OH基团。使用环氧化途径制备天然多元醇的化学方法涉及如下反应混合物,其需要环氧化的天然油,开环酸催化剂和开环剂。环氧化的天然油包括环氧化的植物基油(环氧化的植物油)和环氧化的动物脂肪。所述环氧化的天然油可被完全或部分地环氧化,并且这些油包括大豆油、玉米油、葵花油、橄榄油、芥花油、芝麻油、棕榈油、菜籽油、桐油、棉籽油、红花油、花生油、亚麻籽油和它们的组合。动物脂肪包括鱼油、牛脂和猪油。这些天然油是脂肪酸的甘油三酯,所述脂肪酸可以是饱和的或不饱和的,具有C12至C24的各种链长。这些酸可以是:1)饱和的:月桂酸,肉豆蔻酸,棕榈酸,硬脂酸,花生酸和木蜡酸;2)单不饱和的:棕榈油酸,油酸,3)多不饱和的:亚油酸,亚麻酸,花生四烯酸。当在合适的反应条件下使过氧酸反应时可制备部分或完全环氧化的天然油。在油的环氧化中使用的过氧酸的实例已经描述在WO 2006/116456 A1中;其通过引用并入本文中。可以使用环氧化的油采用醇、水和其它具有一个或多个亲核基团的化合物的开环过程。取决于所述反应条件,还可能发生所述环氧化油的低聚。开环产生天然油多元醇,其可用于制备聚氨酯产物。在所述加氢甲酰化/氢化过程中,在填充有氢/一氧化碳混合物的反应器中,在合适的催化剂(典型地钴或铑)的存在下,将所述油加氢甲酰化以形成醛,所述醛在钴或镍催化剂的存在下被氢化以形成多元醇。另选地,来自天然油和脂肪的多元醇可通过使用碱金属或碱土金属碱或盐作为酯交换催化剂,与合适的含多羟基的物质进行酯交换制备。任何天然油或另选地任何部分氢化的油可用于所述酯交换过程。油的实例包括但不限于大豆油、玉米油、棉籽油、花生油、蓖麻油、葵花油、芥花油、菜籽油、红花油、鱼油、海豹油、棕榈油、桐油、橄榄油或任何掺混物。还可以使用任何多官能羟基化合物,例如乳糖、麦芽糖、棉子糖、蔗糖、山梨糖醇、木糖醇、赤藻糖醇、甘露糖醇或任何组合。
在一个实施方案中,用作或用于所述基础多元醇的天然油多元醇是蓖麻油。所述蓖麻油是天然的具有低羟基含量的蓖麻油酸的甘油三酯。
在一个实施方案中,将天然油或脂肪改性以形成所述天然油多元醇。在这个实施方案中,使环氧化的天然油与开环酸催化剂和开环剂反应。所述环氧化天然油是植物基油,例如环氧化的植物油和/或环氧化的动物脂肪。作为植物基油的合适的环氧化天然油包括但不限于大豆油、玉米油、葵花油、橄榄油、芥花油、芝麻油、棕榈油、菜籽油、桐油、棉籽油、红花油、花生油、亚麻籽油或它们的组合。作为环氧化的动物脂肪的合适的环氧化天然油是鱼油、牛脂、猪油或它们的组合。在WO 06/116456 A1中示出和描述了其它合适的环氧化天然油,该文献通过引用以其全文并入本文中。
在一个实施方案中,所述天然油或所述脂肪通过经由在不饱和位点和/或在酯官能团处的化学反应提高羟基含量而改性。例如,在一个实施方案中,通过环氧化/开环和/或加氢甲酰化/氢化将所述不饱和位点羟基化。在一个实施方案中,所述环氧化天然油的开环是用醇、水和其它具有一个或多个亲核基团的化合物进行的。在另一个实施方案中,所述环氧化天然油也被低聚。在一个实施方案中,所述环氧化天然油的加氢甲酰化/氢化是在填充有氢/一氧化碳混合物的反应器(未示出)中,在合适催化剂(例如钴,铑或它们的组合)的存在下进行的,从而形成醛,该醛在钴催化剂或镍催化剂的存在下被氢化以形成多元醇。
在一个实施方案中,通过酯交换改性在合适的反应物中的酯官能团以引入羟基。在这个实施方案中,合适的含有多羟基的物质和酯交换催化剂(例如碱金属或碱土金属碱或盐)制备了所述天然油或脂肪的多元醇。所述酯交换包括任何合适的天然油或部分氢化的油。合适的天然油包括但不限于大豆油、玉米油、棉籽油、花生油、蓖麻油、葵花油、芥花油、菜籽油、红花油、鱼油、海豹油、棕榈油、桐油、橄榄油或它们的组合。合适的多官能羟基化合物包括但不限于乳糖、麦芽糖、棉子糖、蔗糖、山梨糖醇、木糖醇、赤藻糖醇、甘露糖醇或它们的组合。
在一个实施方案中,所述多元醇组分包括典型地用于制备硬质PIR/PUR(聚异氰脲酸酯和/或聚氨酯)泡沫的多元醇。这样的多元醇包括但不限于聚亚烷基醚和聚酯多元醇。在一个实施方案中,所述聚亚烷基醚包括聚(环氧烷烃)聚合物,例如聚(环氧乙烷)和聚(环氧丙烷)聚合物和具有末端羟基的共聚物,所述末端羟基衍生自包括二醇和三醇的多羟基化合物,例如尤其是乙二醇、丙二醇、1,3-丁二醇、1,4-丁二醇、1,6-己二醇、新戊二醇、二乙二醇、二丙二醇、季戊四醇、甘油、双甘油、三羟甲基丙烷、环己烷二醇、诸如蔗糖的糖和类似的低分子量多元醇,或它们的组合。在另一个实施方案中,所述多元醇组分包括胺聚醚多元醇,其可在胺(例如乙二胺、二亚乙基三胺、甲苯二胺、二苯基甲烷二胺、三乙醇胺或类似物)与环氧乙烷或环氧丙烷进行反应时制备。在一个涉及喷涂泡沫配制剂的实施方案中,所述多元醇组分包括聚醚多元醇,由此提高了所述聚氨酯组合物的反应性。在一个实施方案中,所述聚醚多元醇是通过酚与甲醛在含羟基的胺(例如二乙醇胺、乙醇胺等)的存在下的缩合制备的。
在一个实施方案中,所述多元醇组分包括单一的高分子量聚醚多元醇。附加地或替代地,在一个实施方案中,在所述多元醇组分中包括高分子量聚醚多元醇的混合物,例如不同的多官能材料和/或不同分子量的或不同化学组成的混合物。
在一个实施方案中,所述多元醇组分包括聚酯多元醇,其是当二羧酸与过量的二醇进行反应时制备的,例如己二酸、邻苯二甲酸、邻苯二甲酸酐与乙二醇、二乙二醇、聚乙二醇、丙二醇,二丙二醇、聚丙二醇或丁二醇进行反应时制备的,或者当内酯与过量的二醇进行反应时,例如己内酯与丙二醇进行反应时制备的。
多元醇(包括其掺混物)的总量的范围可以是所述预混物的约10重量%至约80重量%,约20重量%至约60重量%和约30重量%至约50重量%。
本发明的一个方面涉及一种组合物,其包含至少一种本发明的醛清除剂、至少一种催化剂和任选的至少一种稀释剂。合适的催化剂的实例包括选自如下物质组中的至少一个成员:叔胺催化剂组分,其是或包括单一的叔胺催化剂或多种叔胺催化剂的组合。所述叔胺催化剂组分是非挥发性(non-fugitive)叔胺催化剂。在一个实施方案中,所述叔胺催化剂组分是预定量的,例如在约0.1pphp和约20pphp之间,在约0.1pphp和约10pphp之间,在约0.1pphp和约5pphp之间,在约0.1pphp和约0.5pphp之间,大于约0.5pphp,为约0.4pphp,或任何合适的组合,亚组合,范围或其中的子范围。
在一些情况下,所述叔胺催化剂组分包括异氰酸酯反应性基团。在一个实施方案中,所述叔胺催化剂组分是或包括N,N-双(3-二甲基氨基丙基)-N-异丙醇胺,N,N-二甲基氨基乙基-N'-甲基乙醇胺,N,N,N'-三甲基氨基丙基乙醇胺,N,N-二甲基乙醇胺,N,N-二乙基乙醇胺,N,N-二甲基-N',N'-2-羟基(丙基)-1,3-丙二胺,二甲基氨基丙胺,(N,N-二甲基氨基乙氧基)乙醇,N-甲基-N'-羟基乙基-哌嗪,双(N,N-二甲基-3-氨基丙基)胺,N,N-二甲基氨基丙基脲,二乙基氨基丙基脲,N,N'-双(3-二甲基氨基丙基)脲,N,N'-双(3-二乙基氨基丙基)脲;双(二甲基氨基)-2-丙醇,6-二甲基氨基-1-己醇,N-(3-氨基丙基)咪唑),N-(2-羟基丙基)咪唑,和N-(2-羟基乙基)咪唑,或它们的组合。附加地或替代地,在一个实施方案中,所述叔胺催化剂组分是或包括所述发泡催化剂组分。例如,在一个实施方案中,所述叔胺催化剂组分是或包括2-[N-(二甲基氨基乙氧基乙基)-N-甲基氨基]乙醇,N,N-二甲基氨基乙基-N'-甲基-N'-乙醇,二甲基氨基乙氧基乙醇,N,N,N'-三甲基-N'-3-氨基丙基-双(氨基乙基)醚,或它们的组合。在一个实施方案中,所述叔胺催化剂组分是高度挥发性的,并且不是异氰酸酯反应性的。例如,在一个实施方案中,所述叔胺催化剂组分是挥发性的凝胶催化剂,并且是或包括重氮二环辛烷(三亚乙基二胺),1,8-二氮杂双环十一碳-7-烯,三(二甲基氨基丙基)胺,二甲基氨基环己基胺,双(二甲基氨基丙基)-N-甲基胺,或它们的组合。附加地或替代地,在一个实施方案中,所述叔胺催化剂组分是或包括挥发性发泡催化剂,并且是或包括双-二甲基氨基乙基醚,五甲基二亚乙基三胺,六甲基三亚乙基四胺,七甲基四亚乙基五胺和相关的组合物,更高级的全甲基化多元胺,2-[N-(二甲基氨基乙氧基乙基)-N-甲基氨基]乙醇和相关的结构,烷氧基化的多元胺,咪唑-硼组合物,氨基丙基-双(氨基-乙基)醚组合物,或它们的组合。
在一个实施方案中,将所述叔胺催化剂组分与过渡金属催化剂组合使用。例如,在一个实施方案中,将所述叔胺催化剂组分与金属络合物组分(例如有机锡化合物)一起使用。在一个实施方案中,所述有机锡化合物包括二月桂酸二丁基锡,二月桂酸二甲基锡,二乙酸二甲基锡,二乙酸二丁基锡,二月桂基硫醇二甲基锡,二月桂基硫醇二丁基锡,二异辛基马来酸二甲基锡,二异辛基马来酸二丁基锡。
合适的稀释剂的实例包括选自以下物质组中的至少一个成员:水,乙二醇,丙二醇,1,3-丁二醇,1,4-丁二醇,1,6-己二醇,新戊二醇,二乙二醇,二丙二醇,季戊四醇,甘油,双甘油,三羟甲基丙烷,环己烷二醇,糖类,例如蔗糖,和类似的低分子量多元醇,或它们的组合。稀释剂的量的范围可以为约5重量%至约50重量%,约20重量%至约30重量%和在一些情况下约10重量%至约20重量%。可以将本发明的这个方面的组合物与其它组分组合以制备聚氨酯。例如,可以将本发明的这个方面的组合物与其它组分组合以制备前述预混物,该预混物反过来与至少一种异氰酸酯接触以制备聚氨酯泡沫。
提供如下实施例来举例说明本发明的某些实施方案,并且它们不限制在此所附的权利要求的范围。
具体实施方式
实施例1
可使用典型的已经向其中添加了氨酯催化剂的聚氨酯配制剂,根据本领域中已知的方法制备泡沫,所述氨酯催化剂包含一种或多种烷基叔胺。在根据本发明的聚氨酯配制剂中使用的多异氰酸酯的量不受限制,但其典型地将在本领域技术人员已知的那些范围内。示例性的范围在表中给出,其通过参照“NCO指数”(异氰酸酯指数)指示。如在本领域中已知的,所述NCO指数被定义为异氰酸酯的当量数,除以活性氢的当量的总数,乘以100。所述NCO指数由下列公式表示。
NCO指数=[NCO/(OH+NH)]×100
在本发明的一些实施方案中,所述醛清除剂组合物可以与一种或多种聚酯多元醇和任选与一种或多种发泡剂和/或在聚氨酯配制剂中通常使用的其它添加剂一起被合并成套装。这些其它任选的组分的实例之前已经列举,并且它们不影响本发明的基本性质。这样的混合物可随后,任选在本领域中已知的其它添加剂的存在下,与有机异氰酸酯合并以形成聚氨酯泡沫。除了制备硬质喷涂泡沫,本发明还可用于制备通常用于许多工业应用的其它硬质泡沫,所述工业应用例如电器、用于构造和绝缘的层压板。
使用如下所示的配制剂以常规的方式制备和测试聚氨酯泡沫。将如下配制剂用于制备泡沫并研究醛的释放。使用如下示于表1的配制剂制备泡沫样品。采用如下的混合条件制备所述聚氨酯泡沫样品。
将所述预混物组分(预混物指除了MDI以外的所有组分)在约6,000RPM下使用置顶搅拌器(Premier Mill Corporation Dispensator Series 2000Model 89)混合约10秒,所述搅拌器配备有一个2英寸(5.1cm)直径的搅拌桨,并使其冷却到约5℃,之后使用机械搅拌器(Premier Mill Corporation Dispensator Series 2000Model 89)在2升塑料容器中与相应量的异氰酸酯(表1)混合。使用GM测试方法GMW 15635-2012(GM)测试所述醛释放。该测试包括将尺寸为40mm宽度×100mm长度的泡沫样品放置在从含有50mL水的PE瓶的瓶盖上悬挂的钩子上。将所述泡沫放置在距离所述水表面40mm处。将含有所述样品的瓶在60℃下加热3小时。所释放的醛被溶解到所述水中,并通过HPLC,通过与已知标准进行比较测定各自的浓度。以ug/g泡沫样品表示结果。这种方法用于测定从不含有清除剂(对照物)和具有添加的清除剂的样品中释放的醛。
表1
多元醇GEP 828是由Sinopec Shanghai Gaoqiao Company(中石化上海高桥公司)供应的标准聚醚多元醇,其具有的平均官能度=3,和大致MW=6000。CP1421是由Dow Chemicals供应的甘油乙氧基化的-丙氧基化的聚醚多元醇,并且通常用于制备柔性的软质泡沫以及用于模塑泡沫的开孔剂。 DC2525是由Air Productsand Chemicals供应的有机硅表面活性剂稳定剂。 DEOA-LF是由Air Productsand Chemicals供应的二乙醇胺在水交联剂中的85%溶液。 NE1070是由AirProducts and Chemicals供应的胺催化剂,其由单-和双(二甲基氨基丙基)-脲的混合物组成。TMAPBAEE是N,N,N'-三甲基-N'-3-氨基丙基-双(氨基乙基)醚。3133是由Bayer供应的异氰酸酯,其由4,4'-MDI、2,4-MDI和PMDI的混合物组成,其具有约32.5重量%的平均NCO含量。
采用对照物和清除剂的醛释放的结果示于下表2中。
表2
方法检出限=0.35ug/g
实施例2
如实施例1中那样制备的聚氨酯样品也通过标准10L袋法(Q/BYD-1901.771-2012(BYD))进行测试。如下进行这个测试方法:
将尺寸为80×100mm的泡沫样品放置到10L 袋中。将该袋放置到密封的测试室中。所述袋配备有阀和Teflon管,该管连接于醛收集筒(含有被涂覆有二硝基苯基肼(DPNH)的硅胶)和真空泵。所述Teflon阀、Teflon管、收集筒和真空泵位于所述测试室的外部。在所述收集筒被断开连接的情况下,在所述袋中空气被排空并将其填充以2L氮气。然后将所述室加热到60℃并保持2小时,之后从所述样品袋中泵出前100ml的氮气。然后将所述收集筒安装到所述泵上,并将所述醛泵送到所述收集筒中。在所述收集筒中收集的醛通过Waters HPLC,使用H2O/CH3CN作为移动相和1cc/min的流速,在ODS柱上,采用40℃的柱温和在360nm下的UV/VIS检测器进行分析。
通过这种方法的所述醛释放的结果示于表3中。
表3
ND=未检出,方法检出限50ug/m3
实施例3
如实施例1中那样制备的聚氨酯样品也通过标准2L袋法(NES0402;方法#2,NissanMotor Co)进行测试。如下进行这个测试方法:
将尺寸为80×100mm的泡沫样品放置到10L Tedlar袋中。将该袋放置到密封的测试室中。所述袋配备有Teflon阀和Teflon管,该管连接于醛收集筒(含有被涂覆有二硝基苯基肼(DPNH)的硅胶)和真空泵。所述Teflon阀、Teflon管、收集筒和真空泵位于所述测试室的外部。在所述收集筒被断开连接的情况下,在所述袋中空气被排空并将其填充以2L氮气。然后将所述室加热到65并保持2小时,之后从所述样品袋中泵出前100ml的氮气。然后将所述收集筒安装到泵上,并将所述醛泵送到所述收集筒中。在所述收集筒中收集的醛通过 HPLC,使用H2O/CH3CN作为移动相和1cc/min的流速,在Zorbax ODS柱上,采用40℃的柱温和在360nm下的UV/VIS检测器进行分析。
表4
方法检出限=10ug/m3
尽管已经参照某些方面或实施方案描述了本发明,但本领域技术人员将理解的是可以进行各种变化,并且可以将其要素用等同物替换,而不背离本发明的范围。另外,可以进行许多组合和改良以适应本发明的教导,而不背离其实质范围。因此,本发明不意图限于用于实施本发明而公开的具体实施方案,而是本发明将包括落在所附权利要求的范围内的所有实施方案。
Claims (17)
1.一种组合物,其包含至少一种醛清除剂、至少一种多元醇、水和至少一种胺催化剂。
2.权利要求1的组合物,其中所述醛清除剂包含选自以下物质组中的至少一个成员:苯酚或取代苯酚化合物,1,3-二羰基化合物,带有1,3-丙烷二氨基官能的多元胺,三聚氰胺,1,2-二氨基环烷烃,铵盐;和含有亚硫酸氢根阴离子的化合物。
3.权利要求2的组合物,其中所述醛清除剂包含选自以下物质组中的至少一个成员:苯酚,腰果酚,2-甲基苯酚,4-甲基苯酚,4-叔丁基苯酚,2-甲氧基苯酚,4-甲氧基苯酚,水杨酰胺和4-壬基苯酚。
4.权利要求2的组合物,其中所述醛清除剂包含选自以下物质组中的至少一个成员:乙酰乙酸乙酯,丙二酸二乙酯,丙二酸二甲酯,2,4-戊二酮,1,3-环己二酮丙二酰胺,乙酰乙酰胺和N,N,N'N'-四甲基丙二酰胺。
5.权利要求2的组合物,其中所述醛清除剂包含选自以下物质组中的至少一个成员:N,N'-二甲基丙二胺,N,N'-二苯基丙二胺,1-苄基-1,3-丙二胺,异十三烷氧基丙基-1,3-二氨基丙烷,十二烷氧基丙基-1,3-二氨基丙烷和己氧基丙基-1,3-二氨基丙烷。
6.权利要求2的组合物,其中所述醛清除剂包含三聚氰胺。
7.权利要求2的组合物,其中所述醛清除剂包含1,2-二氨基环己烷。
8.权利要求2的组合物,其中所述醛清除剂包含选自以下物质组中的至少一个成员:碳酸铵,硫酸铵,氯化铵和硝酸铵。
9.权利要求2的组合物,其中所述醛清除剂包含选自以下物质组中的至少一个成员:亚硫酸氢钠,亚硫酸氢钾,亚硫酸氢锂和四烷基亚硫酸铵。
10.权利要求1-9的任一项的组合物,其进一步包含至少一种稀释剂。
11.一种组合物,其包含至少一种醛清除剂、至少一种胺催化剂和至少一种稀释剂。
12.制备聚氨酯泡沫的方法,所述方法包括在如下物质的存在下使至少一种多元醇和至少一种二异氰酸酯接触和反应:1)至少一种发泡剂,2)至少一种胺催化剂,和3)权利要求1-11的任一项的组合物。
13.制备聚氨酯泡沫的方法,所述方法包括反应合并1)至少一种多元醇,2)至少一种发泡剂,3)至少一种胺催化剂,和4)权利要求1-11的任一项的组合物,并与至少一种多异氰酸酯接触,从而使所述多元醇和多异氰酸酯反应以制备所述聚氨酯泡沫。
14.通过权利要求12和13的任一项制备的聚氨酯泡沫。
15.权利要求14的聚氨酯泡沫,其中所述泡沫包含低释放泡沫。
16.权利要求14的聚氨酯泡沫,其中所述泡沫包含无释放泡沫。
17.权利要求1-11的任一种组合物用于制备聚氨酯泡沫的用途。
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KR20180018758A (ko) | 2018-02-21 |
WO2016201615A1 (en) | 2016-12-22 |
CA2989370C (en) | 2022-11-01 |
JP2018517826A (ja) | 2018-07-05 |
JP6657267B2 (ja) | 2020-03-04 |
CA2989370A1 (en) | 2016-12-22 |
PL3310824T3 (pl) | 2021-01-11 |
EP3310824A4 (en) | 2019-03-13 |
US20180171064A1 (en) | 2018-06-21 |
EP3310824B1 (en) | 2020-08-12 |
EP3310824A1 (en) | 2018-04-25 |
MX2017016191A (es) | 2018-04-24 |
ES2819454T8 (es) | 2021-04-27 |
ES2819454T3 (es) | 2021-04-16 |
US10683385B2 (en) | 2020-06-16 |
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