CN112424249A - 用于制备聚氨酯泡沫的不含硅酮的泡沫稳定剂 - Google Patents
用于制备聚氨酯泡沫的不含硅酮的泡沫稳定剂 Download PDFInfo
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- CN112424249A CN112424249A CN201980047254.XA CN201980047254A CN112424249A CN 112424249 A CN112424249 A CN 112424249A CN 201980047254 A CN201980047254 A CN 201980047254A CN 112424249 A CN112424249 A CN 112424249A
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- Prior art keywords
- silicone
- weight
- stabilizer
- free
- polyurethane
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
本发明涉及制备聚氨酯泡沫的方法,其中将(a)多异氰酸酯、(b)具有对异氰酸酯呈反应性的基团的聚合化合物、(c)不含硅酮的稳定剂、(d)任选地扩链剂和/或交联剂、(e)催化剂、(f)发泡剂和(g)任选地助剂和添加剂混合以形成反应混合物,并使反应混合物完全反应以形成聚氨酯,其中不含硅酮的稳定剂(c)可通过用环氧烷将1至8官能的起始物分子烷氧基化获得,其中所用环氧烷的0重量%至9重量%为环氧乙烷,所用环氧烷的0重量%至50重量%为1,2‑环氧丙烷,并且所用环氧烷的至少50重量%包括至少4个碳原子,并且不含硅酮的稳定剂(c)的数均分子量为500至20000g/mol,并且其中基于硅酮的泡沫稳定剂的浓度为少于0.3重量%,基于化合物(b)、(c)、(d)、(e)和(f)的总重量计。本发明还涉及包括不含硅酮的稳定剂(c)的多元醇组分,涉及由本发明方法可获得的聚氨酯泡沫,并涉及本发明的聚氨酯泡沫在封闭空间或在车辆内部的用途。
Description
本发明涉及制备聚氨酯泡沫的方法,该方法包括将(a)多异氰酸酯、(b)具有对异氰酸酯呈反应性的基团的聚合化合物、(c)不含硅酮(silicone)的稳定剂、(d)任选地扩链剂和/或交联剂、(e)催化剂、(f)发泡剂和(g)任选地助剂和添加剂混合以得到反应混合物,并使反应混合物反应以得到聚氨酯,其中不含硅酮的稳定剂(c)可通过用环氧烷将1至8官能的起始物分子烷氧基化获得,其中所用环氧烷的0重量%至9重量%是环氧乙烷,所用环氧烷的0重量%至50重量%是1,2-环氧丙烷,并且所用环氧烷的至少50重量%包括至少4个碳原子,且不含硅酮的稳定剂(c)的数均分子量是500至20 000g/mol,并且其中基于硅酮的泡沫稳定剂的含量少于0.3重量%,基于化合物(b)、(c)、(d)、(e)和(f)的总重量计。本发明还涉及包括不含硅酮的稳定剂(c)的多元醇组分,涉及通过本发明方法可获得的聚氨酯泡沫,并且涉及本发明聚氨酯泡沫在封闭空间中或在车辆内部的用途。
在聚氨酯泡沫的制备中,液体多异氰酸酯通常与包括对异氰酸酯呈反应性的较高分子量基团的类似的液体化合物和发泡剂混合并反应,以得到聚氨酯泡沫。可用的发泡剂包括化学发泡剂(其与异氰酸酯基团反应以形成二氧化碳)和/或物理发泡剂(其由于聚氨酯制备期间释放的热而蒸发)。因此,形成聚氨酯的反应和发泡反应大体上同时进行。为确保形成稳定的泡沫,通常用泡沫稳定剂。这些化合物确保了聚氨酯反应期间形成的气体不会从反应混合物逸出,并且确保了所得的泡沫保持稳定直至聚氨酯反应已完成至使所获得的泡沫不能再塌陷的程度。
通常用的泡沫稳定剂是聚硅氧烷-聚氧亚烷基共聚物/聚醚硅氧烷。这种基于硅氧烷(siloxane)的泡沫稳定剂记载于例如“Kunststoffhandbuch”,第7卷,“Polyurethane”,Carl Hanser Verlag,1993年第三版,第3.4.4.2章中。这些硅酮稳定剂通常相当昂贵并且在很多情况下是聚氨酯泡沫制备中最昂贵的组分。因此,人们已尝试用其他具有相同作用的物质来替换基于硅酮的泡沫稳定剂。因此,WO 2016095128记载了用于制备聚氨酯泡沫的含异氰酸酯、基于全氟代的表面活性物质。WO 95/16721也记载了在聚氨酯泡沫制备中作为泡沫稳定剂的不含硅酮的聚醚化合物。它们特别被用于硬质聚氨酯泡沫的制备中,并且由聚醚组成,该聚醚包括基于聚醚中氧亚烷基单元的重量分数计,10重量%至90重量%的氧亚乙基单元和90重量%至10重量%的具有至少4个碳原子的氧亚烷基单元,并且基本上不含氧亚丙基单元。这些泡沫稳定剂的缺点特别是其在软质聚氨酯泡沫的制备中的适用性差。
因此,本发明的目的是提供一种制备聚氨酯泡沫的方法,该方法产生细泡孔的(fine-celled)聚氨酯泡沫,特别是软质聚氨酯泡沫,而不使用惯常的基于硅酮的泡沫稳定剂。
该目的通过制备聚氨酯泡沫的方法来实现,该方法包括将(a)多异氰酸酯、(b)具有对异氰酸酯呈反应性的基团的聚合化合物、(c)不含硅酮的稳定剂、(d)任选地扩链剂和/或交联剂、(e)催化剂、(f)发泡剂和(g)任选地助剂和添加剂混合以得到反应混合物,并使反应混合物反应以得到聚氨酯,其中不含硅酮的稳定剂(c)可通过用环氧烷将1至8官能的起始物分子烷氧基化获得,其中所用环氧烷的0重量%至9重量%是环氧乙烷,所用环氧烷的0重量%至50重量%是1,2-环氧丙烷,并且所用环氧烷的至少50重量%包括至少4个碳原子,并且不含硅酮的稳定剂(c)的数均分子量是500至20 000g/mol,并且其中基于硅酮的泡沫稳定剂的含量少于0.3重量%,基于化合物(b)、(c)、(d)、(e)和(f)的总重量计。
在本发明的上下文中,术语聚氨酯泡沫包括所有已知的发泡的多异氰酸酯加聚产物。这些包括衍生自异氰酸酯和醇的加成产物,并且还涵盖改性的聚氨酯(其可包括异氰脲酸酯结构、脲基甲酸酯结构、脲结构、碳二亚胺结构、脲酮亚胺结构、缩二脲结构)和其他异氰酸酯加成产物。本发明的这些聚氨酯泡沫尤其包括基于聚氨酯的软质泡沫、半硬质泡沫、硬质泡沫或整体泡沫。术语聚氨酯泡沫在本发明的上下文中被理解为还包括发泡的聚合物共混物,该聚合物共混物包括聚氨酯和其他聚合物。本发明聚氨酯泡沫优选为除下文所述的聚氨酯单元(a)至(g)及其反应产物之外不包括其他聚合物的聚氨酯泡沫。
在本发明的上下文中,“聚氨酯泡沫”应理解为意指按照DIN 7726的泡沫。本发明的软质聚氨酯泡沫在10%压缩/压缩强度下按照DIN 53 421/DIN EN ISO 604的压缩应力为15kPa或更少,优选1至14kPa,并且特别是4至14kPa,且密度优选为10至100g/L。本发明的半硬质聚氨酯泡沫在10%压缩下按照DIN 53 421/DIN EN ISO 604的压缩应力为大于15kPa至小于80kPa。按照DIN ISO 4590,本发明的半硬质聚氨酯泡沫和软质聚氨酯泡沫的开孔含量优选为大于85%,特别优选大于90%。关于本发明软质聚氨酯泡沫和半硬质聚氨酯泡沫的其他详细内容可见于“Kunststoffhandbuch”,第7卷,“Polyurethane”,CarlHanser Verlag,1993年第3版,第5章。
本发明的硬质聚氨酯泡沫展现了在10%压缩下不小于80kPa,优选不小于120kPa,特别优选不小于150kPa的压缩应力。此外,按照DIN ISO 4590,硬质聚氨酯泡沫具有大于80%,优选大于90%的闭孔含量。关于本发明硬质聚氨酯泡沫的其他详细内容可见于“Kunststoffhandbuch”,第7卷,“Polyurethane”,Carl Hanser Verlag,1993年第3版,第6章。
在本发明的上下文中,“弹性聚氨酯泡沫”应理解为意指按照DIN 7726的聚氨酯泡沫,在按照DIN 53 577其厚度短暂形变50%后,10分钟后,没有显示多于其初始厚度2%的持久形变。可能涉及硬质聚氨酯泡沫、半硬质聚氨酯泡沫或软质聚氨酯泡沫。
“整体聚氨酯泡沫(integral polyurethane foam)”应理解为意指按照DIN 7726的聚氨酯泡沫,其由于模制工艺而具有密度比芯部更高密度的边缘区域。基于芯部和边缘部分的平均的整体表观密度优选为大于100g/L。在本发明的上下文中,整体聚氨酯泡沫也可为硬质聚氨酯泡沫、半硬质聚氨酯泡沫或软质聚氨酯泡沫。关于本发明整体聚氨酯泡沫的其他详细内容可见于“Kunststoffhandbuch”,第7卷,“Polyurethane”,Carl HanserVerlag,1993年第3版,第7章。
本发明聚氨酯是通过以下方式获得的:将多异氰酸酯(a)与具有对异氰酸酯呈反应性的基团的聚合化合物(b)、不含硅酮的稳定剂(c)、任选地扩链剂和/或交联剂(d)、催化剂(e)、发泡剂(f)和任选地助剂和添加剂(g)混合以得到反应混合物,并使反应混合物反应以得到聚氨酯。
在优选的实施方案中,本发明的聚氨酯泡沫是平均密度为10至850g/L的聚氨酯泡沫,优选为半硬质聚氨酯泡沫或软质聚氨酯泡沫或硬质聚氨酯泡沫,特别优选弹性软质聚氨酯泡沫、半硬质聚氨酯泡沫或弹性整体聚氨酯泡沫。弹性整体聚氨酯泡沫优选具有150g/L至500g/L的基于芯部和边缘区域的平均密度。软质聚氨酯泡沫优选具有10g/L至100g/L的平均密度,半硬质聚氨酯泡沫优选具有70g/L至150g/L的平均密度,且硬质聚氨酯泡沫优选具有30g/L至120g/L的平均密度。
本发明的聚氨酯优选用于内部,例如建筑物内部或交通工具内部,特别优选交通工具(例如船、飞机、卡车、客车或公共汽车(passenger cars or buses),更优选客车或公共汽车,并且尤其是客车(passenger cars))内部。客车和公共汽车的内部在下文被称为汽车内部部件。软质聚氨酯泡沫可被用于家具制造,例如作为座垫、作为床垫或作为地毯泡沫背衬,半硬质聚氨酯泡沫作为门饰板元件或仪表板的泡沫背衬,整体聚氨酯泡沫作为方向盘、换档手柄或头垫,以及硬质聚氨酯泡沫作为顶盖内衬。
用于制备本发明的聚氨酯的多异氰酸酯组分(a)包括用于聚氨酯制备所有已知的多异氰酸酯。这些包括现有技术已知的脂族、脂环族和芳族的二价或多价异氰酸酯及其任意所需混合物。实例是二苯基甲烷2,2’-、2,4’-和4,4’-二异氰酸酯、单体二苯基甲烷二异氰酸酯与二苯基甲烷二异氰酸酯的高级同系物(聚合MDI)的混合物、异佛尔酮二异氰酸酯(IPDI)及其低聚物、甲苯2,4-或2,6-二异氰酸酯(TDI)及这些的混合物、四亚甲基二异氰酸酯及其低聚物、六亚甲基二异氰酸酯(HDI)及其低聚物、亚萘基二异氰酸酯(NDI)及其混合物。
优选甲苯2,4-和/或2,6-二异氰酸酯(TDI)或其混合物、单体二苯基甲烷二异氰酸酯和/或二苯基甲烷二异氰酸酯的高级同系物(聚合MDI)及其混合物。其他可能的异氰酸酯记载于例如“Kunststoffhandbuch”,第7卷,“Polyurethane”,Carl Hanser Verlag,1993年第3版,第3.2和3.3.2章。
多异氰酸酯组分(a)可以多异氰酸酯预聚物的形式使用。这些多异氰酸酯预聚物可通过以下方式获得:使过量的上述多异氰酸酯(成分(a-1))与具有对异氰酸酯呈反应性的基团的聚合化合物(b)(成分(a-2))和/或扩链剂(d)(成分(a-3))例如在20℃至100℃,优选在约80℃的温度下反应,以得到异氰酸酯预聚物。
具有对异氰酸酯呈反应性的基团的聚合化合物(a-2)和扩链剂(a3)是本领域技术人员已知的,并且被记载于例如“Kunststoffhandbuch[Plastics Handbook],第7卷,Polyurethane[Polyurethanes]”,Carl Hanser Verlag,1993年第3版,第3.1章。因此,下文中所述的具有对异氰酸酯呈反应性的基团的聚合化合物(b)也可用作具有对异氰酸酯呈反应性的基团的聚合化合物(a-2)。
可用的具有对异氰酸酯呈反应性的基团的聚合化合物(b)包括所有已知的具有至少两个对异氰酸酯呈反应性的氢原子的化合物,例如官能度为2至8且数均分子量为400至20000g/mol的那些。因此,可使用例如选自聚醚多元醇、聚酯多元醇及其混合物的化合物。
聚醚醇是使用催化剂,例如由环氧化物(如,环氧丙烷和/或环氧乙烷),或由四氢呋喃与氢活性起始化合物(如,脂族醇、酚、胺、羧酸、水和基于天然物质的化合物(如,蔗糖、山梨糖醇或甘露糖醇))来制备的。这些可包括碱性催化剂或双金属氰化物催化剂,如在例如PCT/EP2005/010124、EP 90444或WO 05/090440中记载的。聚醚醇的数均分子量M由下式确定
F,其中F表示起始物分子的官能度,在起始物分子混合物的情况下,表示起始物分子的数均官能度,且OHN表示由滴定法确定的羟值。
聚酯醇是例如由脂族或芳族二羧酸与多元醇、聚硫醚多元醇、聚酯酰胺、羟基化聚缩醛和/或羟基化脂族聚碳酸酯,优选在酯化催化剂的存在下制备的。其他可能的多元醇被记载于例如“Kunststoffhandbuch”,第7卷,“Polyurethane”,Carl Hanser Verlag,1993年第3版,第3.1章。
除所述的聚醚醇和聚酯醇之外,也可使用含填充剂的聚醚醇和聚酯醇,又名聚合物聚醚醇或聚合物聚酯醇。这样的化合物优选包括热塑性塑料的分散颗粒,例如由烯属单体(如,丙烯腈、苯乙烯、甲基丙烯酸酯、甲基丙烯酸和/或丙烯酰胺)构成的热塑性塑料分散颗粒。这样的含填充剂的多元醇是已知的并且是市售可得的。其制备被记载于例如DE 111394、US 3 304 273、US 3 383 351、US 3 523 093、DE 1 152 536、DE 1 152 537、WO 2008/055952和WO2009/128279。
在特别优选的实施方案中,所用的具有对异氰酸酯呈反应性的基团的聚合化合物(b)是聚醚醇(b1),该聚醚醇(b1)可通过将环氧乙烷、1,2-环氧丙烷或其混合物加成至起始物分子而获得。特别优选地,这些聚醚醇的平均官能度为1.8至3且OH值为20至120KOH/g,特别优选25至100KOH/g,并且特别是30至80KOH/g。基于用于制备聚醚醇(b1)的环氧烷的总重量计,环氧丙烷和环氧乙烷的比例优选是至少80重量%,特别优选至少90重量%,更优选特别是95重量%,且特别是100重量%。
不含硅酮的稳定剂(c)可通过用环氧烷将1至8-官能的起始物分子烷氧基化获得,其中所用环氧烷的0重量%至9重量%是环氧乙烷,所用环氧烷的0重量%至50重量%是1,2-环氧丙烷,且所用环氧烷的至少50重量%包括至少4个碳原子,且不含硅酮的稳定剂(c)的数均分子量是500至20 000g/mol,优选1000至15 000g/mol,特别优选1500至8000g/mol,更优选1800至7000g/mol,且特别是2000至5000g/mol,并且甚至更优选2500至4500g/mol。
可用于制备不含硅酮的泡沫稳定剂(c)的起始物分子包括所有已知的官能度为1至8的起始物分子。这些包括上述用于制备聚醚醇的起始物分子。这样的起始物分子是例如,甲醇、乙醇、丙醇、丁醇、戊醇、己醇、庚醇、辛醇、壬醇、癸醇、水、乙二醇、二乙二醇、丙二醇、二丙二醇、甘油、三羟甲基丙烷、季戊四醇、糖衍生物(如,蔗糖)、己糖醇衍生物(如,山梨糖醇)、甲胺、乙胺、异丙胺、丁胺、苄胺、苯胺、甲苯胺、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、三乙醇胺和其他单、二或多羟基醇,或单或多价胺,或其混合物。聚醚多元醇(例如聚环氧烷,如聚环氧乙烷或聚环氧丙烷)也可用作起始物分子。当聚环氧烷被用作起始物分子时,这些聚环氧烷优选官能度为2至6且数均分子量为200至5000g/mol,特别优选300至3000g/mol,更优选500至2000g/mol,且特别是500至1000g/mol。包括促进聚氨酯反应的基团的化合物也可作为起始物分子。这样的起始物分子的实例是3-(二甲基氨基)-1-丙基胺和3-(吡咯烷-1-基)丙-1-胺。优选的是用于制备不含硅酮的稳定剂(c)的起始物分子的平均官能度(优选平均羟基官能度)是1至6,更优选1至4,更优选1至3,特别优选1.5至2.5,且特别是2。优选的起始物分子是甲醇、乙醇、丙醇、丁醇、水、乙二醇、二乙二醇、丙二醇、二丙二醇,且特别优选水或二丙二醇。
用于制备不含硅酮的泡沫稳定剂的环氧烷是至少50重量%的具有至少4个碳原子,例如具有4至20个,优选4至12个,且特别是4至10个碳原子的环氧烷,如环氧丁烷、环氧戊烷、环氧己烷、环氧庚烷、环氧辛烷、环氧壬烷或环氧癸烷。更优选使用这些化合物的1,2-环氧化物。特别优选地,具有至少4个碳原子的环氧烷包括1,2-环氧丁烷和/或1,2-环氧戊烷,特别是1,2-环氧丁烷。在特别优选的实施方案中,具有至少4个碳原子的环氧烷由1,2-环氧丁烷、1,2-环氧戊烷或其混合物组成,特别是由1,2-环氧丁烷组成。优选组分(c)制备期间,具有至少4个碳原子的环氧烷的比例是至少70重量%,特别优选至少90重量%,更优选至少95重量%,且特别是100重量%,在每种情况下基于用于制备不含硅酮的泡沫稳定剂(c)的环氧烷的总重量计。
用于制备不含硅酮的泡沫稳定剂(c)的环氧烷还包括少于9重量%,优选少于5重量%,更优选少于2重量%的环氧乙烷,且特别是不包括环氧乙烷。当存在环氧丙烷,优选1,2-环氧丙烷时,环氧丙烷的比例是少于50重量%,优选5重量%至40重量%,且特别优选10重量%至30重量%,在每种情况下基于用于制备不含硅酮的泡沫稳定剂(c)的环氧烷的总重量计。在其他同样优选的实施方案,不使用环氧丙烷来制备化合物(c)。环氧烷可以沿着链以无规或嵌段方式排列,并且例如可以在开始时将环氧丁烷嵌段并随后将环氧丙烷加成至起始分子,或者开始时将环氧丙烷并随后将环氧丁烷或环氧丙烷与环氧丁烷的混合物加成至起始分子。用于聚烷氧基化的惯常催化剂可被用作催化剂。这些可包括碱性催化剂或双金属氰化物催化剂,如例如在PCT/EP2005/010124、EP 90444或WO 05/090440所记载的。
不含硅酮的稳定剂(c)的其余OH基团的全部或一些可在烷氧基化后被“封端”。这被理解为是指多元醇羟基基团的反应:例如a)与例如异氰酸酯反应得到氨基甲酸酯,b)与例如酸酐、酰基氯等反应得到酯,c)与例如烷基化试剂或磺酸衍生物反应得到醚,或d)与例如硅烷或甲硅烷基卤反应得到甲硅烷基醚。这降低了对异氰酸酯的官能度,并且在全部OH基团完全转化的情况下也可产生对异氰酸酯无反应性的稳定剂(c)。优选地,不含硅酮的泡沫稳定剂(c)包括1至8个,特别优选1.5至4个,并且特别是1.8至2.5个对异氰酸酯呈反应性的基团,特别是羟基基团。当组分(c)包括对异氰酸酯呈反应性的基团时,其为具有对异氰酸酯呈反应性的基团的化合物(b)的一部分。当化合物(c)包括对异氰酸酯呈反应性的基团时,优选使用除具有对异氰酸酯呈反应性的基团的不含硅酮的泡沫稳定剂(c)之外的其他具有对异氰酸酯呈反应性的基团的化合物,特别优选聚醚醇,且特别是聚醚醇(b1)。
不含硅酮的泡沫稳定剂(c)的比例为优选0.01重量%至10重量%,更优选0.05重量%至5重量%,更优选0.05重量%至3重量%,特别优选0.1重量%至2重量%,再更优选0.1重量%至1.5重量%,再更优选0.1重量%至1重量%,且特别是0.1重量%至0.5重量%,基于化合物(b)、(c)、(d)、(e)和(f)的总重量计,并且也可使用不同的不含硅酮的泡沫稳定剂的混合物。
可使用的扩链剂和交联剂(d)包括具有至少两个对异氰酸酯呈反应性的基团且分子量小于400g/mol的化合物,其中具有两个对异氰酸酯呈反应性的氢原子的分子被称为扩链剂,而具有多于两个异氰酸酯反应性氢的分子被称为交联剂。然而,本文中可省略扩链剂或交联剂。然而,加入扩链剂、交联剂或任选地其混合物,可证明对于改变机械性能(例如,硬度)是有利的。
当使用扩链剂和/或交联剂(d)时,可使用聚氨酯的制备中常见的扩链剂和/或交联剂。这些优选是具有对异氰酸酯呈反应性的基团的低分子量化合物,例如甘油、三羟甲基丙烷、二醇和二胺。其他可能的低分子量扩链剂和/或交联剂被记载于例如“Kunststoffhandbuch”,第7卷,“Polyurethane”,Carl Hanser Verlag,1993年第3版,第3.2和3.3.2章。
催化剂e)极大地促进了多元醇(b)和任选地扩链剂和交联剂(d)和化学发泡剂(f)与有机的、任选改性的多异氰酸酯(a)的反应。催化剂(e)优选包括可结合(incorporable)的胺催化剂——例如在有机化合物的排放要尽可能低时。所述催化剂具有至少1个,优选1至8个,且特别优选1至2个对异氰酸酯呈反应性的基团,如伯胺基、仲胺基、羟基、酰胺或脲基,优选伯胺基、仲胺基、羟基。可结合的胺催化剂通常被用于(尤其是用于汽车内部的)低排放聚氨酯的制备。这样的催化剂是已知的,并被记载于EP1888664中。它们包括:除一个或多个对异氰酸酯呈反应性的基团之外还优选包括一个或多个叔氨基的化合物。优选地,可结合的催化剂的叔氨基中至少一个带有至少两个脂族烃基团——优选每个基团具有1至10个碳原子,特别优选每个基团具有1至6个碳原子。特别优选地,叔氨基带有两个独立选自甲基和乙基的基团以及一个其他的有机基团(例如吡咯烷基)。可用的可结合的催化剂的实例是例如双(二甲基氨基丙基)脲、双(N,N-二甲基氨基乙氧基乙基)氨基甲酸酯、二甲基氨基丙基脲、N,N,N-三甲基-N-羟乙基双(氨基丙基醚)、N,N,N-三甲基-N-羟乙基双(氨基乙基醚)、二乙基乙醇胺、双(N,N-二甲基-3-氨基丙基)胺、二甲基氨基丙基胺、3-(吡咯烷-1-基)丙-1-胺、3-二甲基氨基丙基-N,N-二甲基丙-1,3-二胺、二甲基-2-(2-氨基乙氧基乙醇)和(1,3-双(二甲基氨基)丙-2-醇)、N,N-双(3-二甲基氨基丙基)-N-异丙醇胺、双(二甲基氨基丙基)-2-羟乙胺、N,N,N-三甲基-N-(3-氨基丙基)-双(氨基乙基醚)、3-二甲基氨基异丙基二异丙醇胺或其混合物。
除可结合的胺催化剂之外,可使用其他用于制备聚氨酯的惯常催化剂。实例包括脒(如,2,3-二甲基-3,4,5,6-四羟基嘧啶)、叔胺(如,三乙胺、三丁胺、二甲基苄胺、N-甲基吗啉、N-乙基吗啉和N-环己基吗啉、N,N,N',N'-四甲基乙二胺、N,N,N',N'-四甲基丁二胺、N,N,N',N'-四甲基己二胺、五甲基二亚乙基三胺、四甲基二氨基乙基醚、双(二甲基氨基丙基)脲、二甲基哌嗪、1,2-二甲基咪唑、1-氮杂双环[3.3.0]辛烷,且优选1,4-二氮杂双环[2.2.2]辛烷)和烷醇胺化合物(如,三乙醇胺、三异丙醇胺、N-甲基二乙醇胺和N-乙基二乙醇胺,和二甲基乙醇胺)。同样合适的为有机金属化合物,优选有机锡化合物,如有机羧酸的锡(II)盐,例如醋酸锡(II)、辛酸锡(II)、乙基己酸锡(II)和月桂酸锡(II),和有机羧酸的二烷基锡(IV)盐,例如二醋酸二丁基锡、二月桂酸二丁基锡、马来酸二丁基锡和二醋酸二辛基锡,以及羧酸铋,如新癸酸铋(III)、2-乙基己酸铋和辛酸铋,或其混合物。有机金属化合物可单独使用,或优选与强碱性胺组合使用。如果组分(b)是酯,优选仅使用胺催化剂。在特别优选的实施方案中,仅将可结合的催化剂用作催化剂(e)。
当使用催化剂(e)时,这些可例如以基于组分(b)的重量计0.001重量%至5重量%,特别是0.05重量%至2重量%的浓度作为催化剂/催化剂组合来使用。
所有已知用于制备聚氨酯的发泡剂可被用作发泡剂(f)。这些可包括化学和/或物理发泡剂。这样的发泡剂被记载于例如“Kunststoffhandbuch”,第7卷,“Polyurethane”,Carl Hanser Verlag,1993年第3版,第3.4.5章中。“化学发泡剂”被理解为意指通过与异氰酸酯反应形成气态产物的化合物。这样的发泡剂的实例是水或羧酸。“物理发泡剂”被理解为意指溶解或乳化于聚氨酯制备原料并在形成聚氨酯的条件下蒸发的化合物。其实例包括烃、卤代烃和其他化合物,例如全氟代烷烃,如全氟己烷、氟氯烃,以及醚、酯、酮、缩醛和/或液体二氧化碳。可以任何期望的量使用发泡剂。发泡剂优选的用量应使所得聚氨酯泡沫密度为10至850g/L,特别优选为20至800g/L,且特别为25至500g/L。特别优选使用包括水的发泡剂,尤其是水作为唯一的发泡剂。
也可使用助剂和/或添加剂(g)。本文可使用已知用于制备聚氨酯的所有助剂和添加剂物质。实例包括表面活性物质、泡孔调节剂、脱模剂、填充剂、染料、颜料、阻燃剂、水解稳定剂以及抑真菌和抑细菌物质。这些物质是已知的,并且被记载于例如“Kunststoffhandbuch,Band 7,Polyurethane”[Plastics Handbook,第7卷,Polyurethanes],Carl Hanser Verlag,1993年第3版,第3.4.4章和第3.4.6至3.4.11章。也可用已知的基于硅酮的泡沫稳定剂。所使用的基于硅酮的泡沫稳定剂是基于硅酮的化合物,该基于硅酮的化合物降低多元醇(b)的表面张力,并且在该基于硅酮的化合物中至少两个硅原子各自通过氧原子连接。这些化合物优选为具有两亲结构(即,包括具有不同极性的两个分子部分)的化合物。基于硅酮的泡孔稳定剂优选具有包括有机硅单元(如二甲基硅氧烷或甲基苯基硅氧烷)的分子部分和具有类似多元醇(b)的化学结构的分子部分。这些优选为聚氧亚烷基单元。特别优选用作基于硅酮的泡沫稳定剂的是基于聚氧亚烷基单元总比例计,氧亚乙基比例为少于75重量%的聚硅氧烷-聚氧亚烷基嵌段共聚物。这些优选具有聚环氧乙烷和/或聚环氧丙烷单元。聚氧亚烷基侧链的分子量优选为至少1000g/mol的侧链。这些化合物是已知的,并被记载于例如“Kunststoffhandbuch”,第7卷,“Polyurethane”,CarlHanser Verlag,1993年第3版,第3.4.4.2章,并可例如通过硅氧烷(例如聚二甲基硅氧烷)与聚氧化烯(特别是聚环氧乙烷、聚环氧丙烷或聚环氧乙烷和聚环氧丙烷的共聚物)的反应来制备。这可获得具有氧亚烷基链作为端基或作为一个或多个侧链的聚硅氧烷-聚氧亚烷基嵌段共聚物。基于硅酮的泡沫稳定剂可包括OH基团,但优选为不含OH基团。这可通过如下实现:用于制备聚氧化烯的起始物为单羟基醇,如丁醇。可用的基于硅酮的泡孔稳定剂包括例如已知的基于硅酮的泡沫稳定剂,例如来自Momentive的Niax Silicone L1501、L 1505、L1540、L 1593、L 1602或L 1609;来自Air Products的DC 193、DC3041、DC 3042、DC3043、DC 5000、DC 5169、DC 2525、DC 2584、SI 1101、SI 1103或DC 5160;来自Goldschmidt的BF 2270、BF 2370、BF 2470、B 8110、B 8225、B 8255、B 8317、B 8325、B 8905、B8946PF、B 8948、B 8950、B 8952、B8960、B 8715LF2、B 8734LF2、B 8736LF2、B 8761LF2、B 8724LF2、B 8738LF2、B 8742LF2、B 8747LF2、B 8745LF2、B 8749LF2或B8486。在本发明的上下文中,使用了基于化合物(b)、(c)、(d)、(e)和(f)的总重量计少于0.3重量%的基于硅酮的稳定剂。在本发明优选的实施方案中,使用了基于化合物(b)、(c)、(d)、(e)和(f)的总重量计少于0.2重量%,特别优选少于0.1重量%,更优选少于0.01重量%的基于硅酮的泡沫稳定剂,且特别是不使用基于硅酮的泡沫稳定剂。
制备本发明的聚氨酯通常包括使化合物(a)至(g)以这样的量反应,使得多异氰酸酯(a)的NCO基团与组分(b)、(c)、(e)和(f)以及任选地(d)和(g)的反应性氢原子之和的当量比为0.60至1.5:1,优选0.70至1.25:1,且特别优选0.80至1.10:1。如果多孔塑料至少部分地包括异氰脲酸酯基团,则通常使用多异氰酸酯(a)的NCO基团与组分(b)、(c)、(e)、(f)以及任选地(d)和(g)的反应性氢原子之和的比值为1.5至20:1,优选1.5至8:1,且特别优选1.50至5:1。本文中比值为1:1相当于异氰酸酯指数为100。
当待制备的本发明聚氨酯是软质泡沫、半硬质泡沫、硬质泡沫或整体泡沫时,用于制备本发明聚氨酯的具体起始物质(a)至(g)在各种情况下仅在定量和定性方面稍有不同。此外,例如通过具有至少两个反应性氢原子、分子量较高的化合物的官能度和链长,可改变本发明的聚氨酯的弹性和硬度。这样的改性是本领域技术人员已知的。
用于制备软质泡沫的反应物被记载于例如PCT/EP2005/010124和EP 1529792中,用于制备半硬质泡沫的反应物记载于“Kunststoffhandbuch”,第7卷,“Polyurethane”,Carl Hanser Verlag,1993年第3版,第5.4章,用于制备硬质泡沫的反应物记载于PCT/EP2005/010955中,而用于制备整体泡沫的反应物记载于EP 364854、US 5506275或EP897402中。不含硅酮的泡沫稳定剂(c)在各种情况下被加入这些文献所记载的反应物中。特别优选本发明的聚氨酯泡沫是软质聚氨酯泡沫。
所谓“双组分方法”经常被用于制备本发明的聚氨酯泡沫。这包括将对异氰酸酯呈反应性的组分以及(例如选自助剂和添加剂物质(g)的)非反应性组分混合,以得到多元醇组分,该多元醇组分随后在聚氨酯泡沫制备期间与异氰酸酯组分的异氰酸酯混合。异氰酸酯组分可不仅包括异氰酸酯(a),还包括其他化合物。因此,本发明还提供多元醇组分,该多元醇组分包括:(b)具有对异氰酸酯呈反应性的基团的聚合化合物,(c)不含硅酮的稳定剂,(d)任选地扩链剂和/或交联剂,(e)催化剂,(f)发泡剂和(g)任选地助剂和添加剂,其中不含硅酮的稳定剂(c)可通过用环氧烷将1至8官能的起始物分子烷氧基化获得,其中所用环氧烷的0重量%至9重量%为环氧乙烷,所用环氧烷的0重量%至50重量%为1,2-环氧丙烷,且所用环氧烷的至少50重量%包括至少4个碳原子,且不含硅酮的稳定剂(c)的数均分子量为500至20 000g/mol,并且其中基于硅酮的泡沫稳定剂的含量为基于化合物(b)、(c)、(d)、(e)和(f)的总重量计少于0.3重量%。不含硅酮的稳定剂(c)也可被加入异氰酸酯组分,特别是在不含硅酮的稳定剂(c)不包括对异氰酸酯呈反应性的基团时。
本发明不仅提供本发明的方法,还提供通过本发明的方法可获得的聚氨酯泡沫。本发明的聚氨酯出人意料地仅显示出较低的有机物质排放,并且因此优选用于封闭空间,例如住宅建筑的绝热材料,如用于管道和冰箱的绝热材料、家具结构中的绝热材料,例如作为座垫、作为床垫,以及汽车内部的绝热材料,例如作为方向盘、仪表盘、门饰板、地毯泡沫背衬、吸音泡沫,如汽车内顶(headliner),以及头垫或换档杆。最后,本发明还提供的是本发明的不含硅酮的稳定剂(c)(特别是不含硅酮的稳定剂(c)),其可用1,2-环氧丁烷和/或1,2-环氧戊烷将1至8官能起始物分子烷氧基化获得,其中用于制备稳定剂(c)的环氧烷的至少50重量%为1,2-环氧丁烷和/或1,2-环氧戊烷,且不含硅酮的稳定剂(c)的数均分子量为500至20000g/mol。
本发明在下文中藉由实施例来阐明。
使用以下原料:
多元醇A:基于环氧乙烷和环氧丙烷的甘油起始的聚醚多元醇,其平均OH值为28mgKOH/g并且环氧丙烷含量为基于聚醚总重量计84重量%。
多元醇B:基于环氧乙烷和环氧丙烷的甘油起始的聚醚多元醇,其平均OH值为42mgKOH/g并且环氧乙烷含量为基于聚醚总重量计74重量%。
异氰酸酯1:以下物质的混合物:41.5重量%的4,4’-MDI、25.3重量%的2,4’-MDI和33.2重量%的二苯基甲烷二异氰酸酯与二苯基甲烷二异氰酸酯的高级同系物的混合物(来自BASF SE的M20S)。
催化剂2:Niax A-1,来自Momentive的胺催化剂。
稳定剂2:1,2-丙二醇起始的聚醚多元醇,其平均OH值为74mg KOH/g并包括在各种情况下基于聚醚多元醇的总重量计,53.7重量%的环氧丁烷和42.2重量%的环氧乙烷,其中环氧乙烷被用作末端嵌段。
稳定剂3:1,2-丙二醇起始的聚醚多元醇,其平均OH值为34mg KOH/g并包括在各种情况下基于聚醚多元醇的总重量计,79重量%的环氧丁烷和19.3重量%的环氧乙烷,其中环氧乙烷被用作末端嵌段。
稳定剂4:1,2-丙二醇起始的聚醚多元醇,其平均OH值为26mg KOH/g并包括在各种情况下基于聚醚多元醇的总重量计,60.6重量%的环氧丁烷和38.3重量%的环氧乙烷,其中环氧乙烷被用作末端嵌段。
稳定剂5:二丙二醇起始的聚醚多元醇,包括仅1,2-环氧丁烷作为环氧烷并且平均OH值为44mg KOH/g。
稳定剂6:二丙二醇起始的聚醚多元醇,包括仅1,2-环氧丁烷作为环氧烷并且平均OH值为33mg KOH/g。
稳定剂7:二丙二醇起始的聚醚多元醇,包括仅1,2-环氧丁烷作为环氧烷并且平均OH值为26mg KOH/g。
稳定剂8:二丙二醇起始的聚醚多元醇,包括仅1,2-环氧丁烷作为环氧烷并且平均OH值为21mg KOH/g。
稳定剂9:二丙二醇起始的聚醚多元醇,包括仅1,2-环氧戊烷作为环氧烷并且平均OH值为47mg KOH/g。
不含硅酮的泡沫稳定剂的合成
泡沫稳定剂的制备:稳定剂1至8在钢反应器中以两步法进行。这包括在KOH催化下将丙二醇/二丙二醇丁氧基化的第一步,以制备前体产物,该前体产物随后在第二步中同样在KOH催化下被丁氧基化和任选地乙氧基化。所获得的多元醇的羟值在纯化和干燥后通过滴定法来确定。稳定剂9的制备是通过类似的步骤,但使用CsOH而非KOH来进行的。
为了制备实施例和对比例,将94重量份的多元醇A、6重量份的多元醇B、0.6重量份的催化剂1、0.1重量份的催化剂2、3.3重量份的水和表1中记录的相应量的各稳定剂在室温下用实验室混合器混合2分钟,并静置30分钟。然后,加入异氰酸酯1,并且在异氰酸酯指数90下将混合物用实验室混合器以1800rpm混合5秒并在烧杯中反应得到聚氨酯泡沫。自由发泡密度为约45g/L。对泡沫的质量、泡孔结构和外观进行评估。通过在混合后将反应混合物置于体积为8升(40cm x 40cm x 5cm)且温度被控制在50℃的模具中,以类似的方式获得模制泡沫。选择用量,以使模制泡沫的平均密度为53g/L。4分钟后,脱模、转鼓并在室温下静置24小时。用于机械测量和排放测量的测试样品取自模制泡沫。当其尺寸稳定且不收缩,并具有开放的细孔的泡孔结构和表面均匀而无缺陷时,将自由发泡泡沫和模制泡沫的质量评估为“好”。当泡沫具有粗糙孔结构,泡沫芯部和表面中有孔时,这些被评估为“差”。
表1
机械测量
表2中的机械测量测定如下:
密度:DIN EN ISO 845
压缩强度和迟滞现象:DIN EN ISO 3386
拉伸强度和断裂伸长率:DIN EN ISO 1798,
压缩形变:DIN EN ISO 1856
透气性:DIN EN ISO 7231
回弹性:DIN EN ISO 8307
表2所选的实施例泡沫的机械性能
表1和2中的结果证明:使用本发明的不含硅酮的泡沫稳定剂导致通常仅使用基于硅酮的泡沫稳定剂才能获得的泡沫。
此外,本发明的泡沫稳定剂显示出显著更低的有机物质排放值。这示于表4中。
排放
以类似于上述实施例和对比例的方式制备泡沫样品,以确定排放值。使用了表3所示的原料。异氰酸酯1被用作异氰酸酯组分。使用了90的异氰酸酯指数。所获得的泡沫的密度为约50kg/m3。如下文详细说明那样确定排放量。
表3:
对比例I | 实施例I | 实施例II | |
多元醇A | 90.6 | 90.6 | 90.6 |
多元醇B | 3 | 3 | 3 |
催化剂3 | 0.1 | 0.1 | 0.1 |
催化剂4 | 1 | 1 | 1 |
水 | 3.9 | 3.9 | 3.9 |
甘油 | 0.5 | 0.5 | 0.5 |
二乙醇胺 | 0.4 | 0.4 | 0.4 |
稳定剂1 | 0.5 | ||
稳定剂5 | 0.5 | ||
稳定剂6 | 0.5 |
在箱室试验中测定甲醛排放:
通过类似于ASTM D-5116-06的方法测定甲醛和乙醛。箱室尺寸为4.7升。所用聚氨酯样品为取自泡沫内部的尺寸为100mm x 100mm x25mm的块。测量期间,测量箱室中的温度为65℃,相对湿度为50%。空气交换速率为3.0升/小时。包括来自聚氨酯的挥发性醛类的排出的空气流在120分钟中通过包括涂覆有2,4-二硝基苯基肼的二氧化硅的柱。然后用乙腈和水的混合物对DNPH柱进行洗脱。洗脱液中甲醛和乙醛的浓度由HPLC来确定。在该程序中,甲醛排放的检测极限为≤11μg/m3,而乙醛排放的检测极限为≤6μg/m3。
根据VDA 278测定VOC和FOG。
表4:
Claims (15)
1.一种制备聚氨酯泡沫的方法,包括将以下混合
(a)多异氰酸酯,
(b)具有对异氰酸酯呈反应性的基团的聚合化合物,
(c)不含硅酮的稳定剂,
(d)任选地扩链剂和/或交联剂,
(e)催化剂,
(f)发泡剂,
(g)任选地助剂和添加剂,
以得到反应混合物,并使所述反应混合物反应以得到聚氨酯,
其中所述不含硅酮的稳定剂(c)可通过用环氧烷将1至8官能的起始物分子烷氧基化获得,其中所用环氧烷的0重量%至9重量%为环氧乙烷,所用环氧烷的0重量%至50重量%为1,2-环氧丙烷,并且所用环氧烷的至少50重量%包括至少4个碳原子,并且所述不含硅酮的稳定剂(c)的数均分子量是500至20 000g/mol,并且其中基于硅酮的泡沫稳定剂的含量少于0.3重量%,基于化合物(b)、(c)、(d)、(e)和(f)的总重量计。
2.根据权利要求1所述的方法,其中在不含硅酮的稳定剂(c)的制备中所用环氧烷的至少90重量%包括至少4个碳原子。
3.根据权利要求1或2所述的方法,其中在不含硅酮的稳定剂(c)的制备中所用的包括至少4个碳原子的环氧烷选自1,2-环氧丁烷、1,2-环氧戊烷及其混合物。
4.根据权利要求1至3中任一项所述的方法,其中用于制备不含硅酮的稳定剂(c)的起始物分子的平均官能度为1至3。
5.根据权利要求1至4中任一项所述的方法,其中不含硅酮的稳定剂(c)的其余OH基团的一些或全部在烷氧基化后被封端。
6.根据权利要求1至5中任一项所述的方法,其中具有对异氰酸酯呈反应性的基团的聚合化合物包括聚醚醇(b1),所述聚醚醇(b1)可通过将环氧乙烷、环氧丙烷或其混合物加成至起始物分子而获得,其中用于制备聚醚醇(b1)的环氧烷的至少90mol%选自环氧乙烷、1,2-环氧丙烷及其混合物。
7.根据权利要求6所述的方法,其中不含硅酮的泡沫稳定剂(c)的比例优选为0.01重量%至10重量%,基于化合物(b)、(c)、(d)、(e)和(f)的总重量计。
8.根据权利要求1至7中任一项所述的方法,其中不使用基于硅酮的泡沫稳定剂。
9.根据权利要求1至8中任一项所述的方法,其中所述聚氨酯泡沫是按照DIN 53 421/DIN EN ISO 604在10%压缩下压缩应力为15kPa或更小且密度为10至100g/L的软质聚氨酯泡沫。
10.根据权利要求1至9中任一项所述的方法,其中所述催化剂(e)包括可结合的胺催化剂。
11.多元醇混合物,包括
(b)具有对异氰酸酯呈反应性的基团的聚合化合物,
(c)不含硅酮的稳定剂,
(d)任选地扩链剂和/或交联剂,
(e)催化剂,
(f)发泡剂,和
(g)任选地助剂和添加剂,
其中所述不含硅酮的稳定剂(c)可通过用环氧烷将1至8官能的起始物分子烷氧基化获得,其中所用环氧烷的0重量%至9重量%为环氧乙烷,所用环氧烷的0重量%至50重量%为1,2-环氧丙烷,并且所用环氧烷的至少50重量%包括至少4个碳原子,并且所述不含硅酮的稳定剂(c)的数均分子量为500至20 000g/mol,并且其中基于硅酮的泡沫稳定剂的含量少于0.3重量%,基于化合物(b)、(c)、(d)、(e)和(f)的总重量计。
12.由权利要求1至10中任一项所述的方法可获得的聚氨酯。
13.根据权利要求12所述的聚氨酯在封闭空间或在车辆内部的用途。
14.根据权利要求13所述的用途,用于生产床垫或座垫或车辆中的座垫或头垫。
15.不含硅酮的稳定剂(c),可通过用1,2-环氧丁烷和/或1,2-环氧戊烷将1至8官能的起始物分子烷氧基化获得,其中所用环氧烷的至少50重量%为1,2-环氧丁烷和/或1,2-环氧戊烷,并且所述不含硅酮的稳定剂(c)的数均分子量为500至20 000g/mol。
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Publication number | Priority date | Publication date | Assignee | Title |
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CN114163678A (zh) * | 2021-12-14 | 2022-03-11 | 南京美思德新材料有限公司 | 提高组合聚醚与戊烷发泡剂相容性能的聚氨酯泡沫稳定剂 |
CN114163678B (zh) * | 2021-12-14 | 2023-03-03 | 南京美思德新材料有限公司 | 提高组合聚醚与戊烷发泡剂相容性能的聚氨酯泡沫稳定剂 |
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JP7600097B2 (ja) | 2024-12-16 |
CN112424249B (zh) | 2023-08-25 |
US20210292468A1 (en) | 2021-09-23 |
WO2020020709A1 (de) | 2020-01-30 |
KR20210037709A (ko) | 2021-04-06 |
JP2021532236A (ja) | 2021-11-25 |
EP3827039A1 (de) | 2021-06-02 |
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