CN106029730B - 由聚酯聚氨酯组成的耐水解聚氨酯模制品 - Google Patents
由聚酯聚氨酯组成的耐水解聚氨酯模制品 Download PDFInfo
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- CN106029730B CN106029730B CN201580009064.0A CN201580009064A CN106029730B CN 106029730 B CN106029730 B CN 106029730B CN 201580009064 A CN201580009064 A CN 201580009064A CN 106029730 B CN106029730 B CN 106029730B
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- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明涉及用于制备聚氨酯模制品的方法,其中将(a)有机多异氰酸酯与(b)包含聚酯醇的多元醇,(c)任选地发泡剂,(d)增链剂和/或交联剂,(e)胺催化剂,(f)通式Z‑N=C=N‑Z的碳二亚胺,其中Z为有机基团,并且碳二亚胺基团‑N=C=N‑的氮原子与叔碳原子连接或与芳族体系的碳原子连接,在所述芳族体系中在与C‑N键相邻的环位置上,所述芳族体系带有通过仲碳原子或叔碳原子与该芳族体系连接的有机基团,(g)至少一种选自(i)一元羧酸的酯和(ii)多元羧酸的酯的成员,每种酸的(一级)离解常数(pK)为0.5至5,和任选地(h)其他助剂和/或添加剂混合以形成反应混合物,将该混合物引入至模具中并使其反应以形成聚氨酯模制品,其中所述聚酯醇包含:聚酯醇(b1),其可通过具有2至10个碳原子的脂族二羧酸与至少一种具有5至20个碳原子的较高官能醇和任选地一种具有2至4个碳原子的较高官能醇的酯化获得,其中至少20重量%的较高官能醇为具有5个以上碳原子的较高官能醇,基于组分(b1)中的较高官能醇的总量计;和任选地聚酯醇(b2),其可通过具有2至10个碳原子的脂族或芳族二羧酸与至少一种具有2至4个碳原子的较高官能醇和少于20重量%的至少一种具有5个以上碳原子的较高官能醇的酯化获得,基于组分(b2)中的较高官能醇的总量计;和任选地其他聚酯醇(b3),其中酸组分包含至少一种二聚酸。本发明还涉及可通过此方法获得的聚氨酯模制品,以及这些聚氨酯模制品作为鞋底、特别是军靴的鞋底的用途。
Description
本发明涉及用于制备聚氨酯模制品的方法,其中将(a)有机多异氰酸酯与(b)包含聚酯醇的多元醇,(c)任选地发泡剂,(d)增链剂和/或交联剂,(e)胺催化剂,(f)通式Z-N=C=N-Z的碳二亚胺,其中Z为有机基团,并且碳二亚胺基团-N=C=N-的氮原子与叔碳原子连接或与芳族体系的碳原子连接,在所述芳族体系中在与C-N键相邻的环位置上,所述芳族体系带有通过仲碳原子或叔碳原子与该芳族体系连接的有机基团,(g)至少一个选自(i)一元羧酸的酯和(ii)多元羧酸的酯的成员,每种酸的(一级)离解常数(pK)为0.5至5,和任选地(h)其他助剂和/或添加剂混合以形成反应混合物,将该混合物引入至模具中并使其反应以形成聚氨酯模制品,其中所述聚酯醇包含:聚酯醇(b1),其可通过具有2至10个碳原子的脂族二羧酸与至少一种具有5至20个碳原子的较高官能醇和任选地一种具有2至4个碳原子的较高官能醇的酯化获得,其中至少20重量%的较高官能醇为具有5个以上碳原子的较高官能醇,基于组分(b1)中的较高官能醇的总量计,和任选地聚酯醇(b2),其可通过具有2至10个碳原子的脂族或芳族二羧酸与至少一种具有2至4个碳原子的较高官能醇和少于20重量%的至少一种具有5个以上碳原子的较高官能醇的酯化获得,基于组分(b2)中的较高官能醇的总量计,和任选地其他聚酯醇(b3),其中酸组分包含至少一种二聚酸。本发明还涉及可通过此方法获得的聚氨酯模制品,以及这些聚氨酯模制品作为鞋底、特别是作为在使用前经常储存若干年的军靴的鞋底的用途。
聚酯聚氨酯在例如鞋类应用中用作例如致密弹性体或发泡弹性体。此处,聚酯聚氨酯具有比聚醚聚氨酯更好的机械性能。此外,PESOL聚氨酯显示出在有机物质例如异辛烷存在下改善的耐溶胀性。这种耐溶胀性是用作安全鞋的重要条件,并且无法通过聚醚聚氨酯来实现。聚酯聚氨酯的缺点是其易受水解影响,尤其是在湿热环境下。这种水解不仅在使用期间发生,而且在储存期间发生。这在像军靴这样的样式不起主要作用且通常将靴子储存若干年的情况下尤其不利。
基于聚酯醇的聚氨酯通常使用通过C4-C6-二羧酸与多官能醇的缩聚得到的聚酯醇来制备。然而,这些聚氨酯具有如下缺点:其仅具有不令人满意的水解稳定性。为了改善基于聚酯醇的聚氨酯的水解稳定性,将这些C4-C6-二羧酸例如替换为更加疏水的二羧酸。如此,US 2005124711记载了由聚酯醇得到的微孔聚酯聚氨酯,所述聚酯醇由二聚脂肪酸制得。尽管如此,如US 2005124711所公开的方法并未产生水解稳定性的大幅度改善。
WO 2004/050735记载了使用基于邻苯二甲酸和具有8-12个碳原子的二羧酸的组合的聚酯醇,以便改善水解稳定性。
这些具有改善的水解稳定性的聚酯的缺点在于所使用的原料昂贵。此外,与基于通过C4-C6-二羧酸与多官能醇的缩聚得到的传统聚酯醇的聚氨酯相比,其机械性能较差。
US 20020120027公开了一种方法,其中一元或多元羧酸的酯以相对于所使用的胺催化剂的亚化学计量比使用,以改善水解稳定性。此处公开的方法的缺点在于,水解稳定性的改善仅持续短的时间(在70℃和95%相对湿度下约9天)。
本发明的目的是提供基于聚酯醇并具有改善的水解稳定性和优异的机械性能的聚氨酯。本发明另外的目的是提供聚氨酯模制品,其通过了采用SATRA TM344的水解测试(在70℃和95%的相对湿度下储存),且其拉伸强度保留大于初始值的80%达至少28天。此外本发明的目的是提供适于作为军靴的鞋底材料的聚氨酯模制品。
本发明的目的已能够通过一种聚氨酯模制品来实现,所述聚氨酯模制品可以通过如下方法制备,其中将(a)有机多异氰酸酯与(b)包含聚酯醇的多元醇,(c)任选地发泡剂,(d)增链剂和/或交联剂,(e)胺催化剂,(f)通式Z-N=C=N-Z的碳二亚胺,其中Z为有机基团,并且碳二亚胺基团-N=C=N-的氮原子与叔碳原子连接或与芳族体系的碳原子连接,在所述芳族体系中在与C-N键相邻的环位置上,所述芳族体系带有通过仲碳原子或叔碳原子与该芳族体系连接的有机基团,(g)至少一种选自(i)一元羧酸的酯和(ii)多元羧酸的酯的成员,每种酸的(一级)离解常数(pK)为0.5至5,和任选地(h)其他助剂和/或添加剂混合以形成反应混合物,将该混合物引入至模具中并使其反应以形成聚氨酯模制品,其中所述聚酯醇包含:聚酯醇(b1),其可通过具有2至10个碳原子的脂族二羧酸与至少一种具有5至20个碳原子的较高官能醇和任选地一种具有2至4个碳原子的较高官能醇的酯化获得,其中至少20重量%的较高官能醇为具有5个以上碳原子的较高官能醇,基于组分(b1)中的较高官能醇的总量计,和任选地聚酯醇(b2),其可通过具有2至10个碳原子的脂族或芳族二羧酸与至少一种具有2至4个碳原子的较高官能醇和少于20重量%的至少一种具有5个以上碳原子的较高官能醇的酯化获得,基于组分(b2)中的较高官能醇的总量计,和任选地其他聚酯醇(b3),其中酸组分包含至少一种二聚酸。
特别地,本发明的聚氨酯模制品为弹性体。其包括致密聚氨酯弹性体(也被称作铸塑树脂)和弹性体聚氨酯泡沫,优选整体聚氨酯泡沫(integral polyurethane foam)。出于本发明的目的,术语弹性体聚氨酯泡沫是指根据DIN 7726的聚氨酯泡沫,该聚氨酯泡沫在根据DIN 53577短暂变形厚度的50%之后,10分钟后的残余变形不大于其初始厚度的2%。出于本发明的目的,整体聚氨酯泡沫为根据DIN 7726的具有外部区域的聚氨酯泡沫,所述外部区域因成型工艺而具有高于核心的密度。在核心和外部区域上取平均值的总泡沫密度优选为>150g/l至850g/l,优选180g/l至750g/l,更优选200g/l至650g/l。致密聚氨酯弹性体的密度为>850g/l至1400g/l,优选900g/l至1300g/l,并且特别地为950g/l至1200g/l。
用于制备本发明的聚氨酯模制品的有机和/或改性多异氰酸酯(a)包括由现有技术已知的脂族、脂环族和芳族的双官能或多官能的异氰酸酯(成分a-1)及其任意混合物。实例为:单体二苯甲烷二异氰酸酯(MDI)例如二苯甲烷4,4′-二异氰酸酯、二苯甲烷2,4′-二异氰酸酯;单体二苯甲烷二异氰酸酯与具有多于两个环的二苯甲烷二异氰酸酯同系物(聚合MDI)的混合物;四亚甲基二异氰酸酯;六亚甲基二异氰酸酯(HDI);异佛尔酮二异氰酸酯(IPDI);甲苯2,4-二异氰酸酯或甲苯2,6-二异氰酸酯(TDI);或者所提及的异氰酸酯的混合物。
优选使用4,4′-MDI。优选使用的4,4′-MDI可包含0至20重量%的2,4′-MDI和少量的、最高达约10重量%的脲基甲酸酯或脲酮亚胺改性的多异氰酸酯。也可以使用少量的聚亚苯基聚亚甲基多异氰酸酯(聚合MDI)。这些高官能度多异氰酸酯的总量优选不应超过所用异氰酸酯的5重量%。
多异氰酸酯组分(a)优选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使上述种类的多异氰酸酯(a-1)例如在30至100℃的温度下,优选在约80℃下与多元醇(a-2)反应形成预聚物而获得。
多元醇(a-2)对于本领域技术人员而言是已知的,并且记载于例如“Kunststoffhandbuch”,第7卷,Polyurethane,Carl Hanser Verlag,第3版,1993,第3.1章中。优选使用b)中描述的聚酯醇作为多元醇(a-2)。
在异氰酸酯预聚物的制备中,任选地将常规的增链剂或交联剂添加至上述聚酯醇。这些物质记载于(d)中。
多元醇(b)包含聚酯醇。使用具有至少两个对异氰酸酯基团呈反应性的氢原子的聚酯醇作为聚酯醇。聚酯醇的数均分子量优选大于450g/mol,特别优选为>500至<6000g/mol,并且特别地为600至3500g/mol。优选地,组分(b)仅含有聚酯多元醇。
用于制备基于聚酯的聚氨酯的聚酯多元醇通常可以由有机二羧酸——例如具有2至12个碳原子的有机酸,优选具有2至10个碳原子并特别优选4至6个碳原子的脂族二羧酸——与具有2至12个碳原子、优选2至6个碳原子的多元醇(优选二醇)来制备。
为制备聚酯多元醇,在不存在催化剂或优选在酯化催化剂的存在下,有利地在惰性气体例如氮气、一氧化碳、氦气、氩气等的气氛中,在150至250℃、优选180至220℃温度下的熔体中,任选地在减压下,可使有机(例如芳族并优选脂族)多元羧酸和/或衍生物与多元醇缩聚至所期望的酸值,所述酸值优选小于10,特别优选小于2,并且甚至更优选小于1。在优选的实施方案中,在上述温度下,在大气压力下并且随后在小于500毫巴、优选50至150毫巴的压力下,将酯化混合物缩聚至酸值为80至30,优选40至30。可用的酯化催化剂为,例如,金属、金属氧化物或金属盐形式的铁、镉、钴、铅、锌、锑、镁、钛和锡催化剂。然而,缩聚也可以在液相中在稀释剂和/或夹带剂例如苯、甲苯、二甲苯或氯苯的存在下进行以共沸蒸馏掉缩合的水。为制备聚酯多元醇,有机多元羧酸和/或衍生物与多元醇有利地以1:1-1.8、优选1:1.05-1.2的摩尔比进行缩聚。
所获得的聚酯多元醇优选具有的官能度为2至4,特别是2至3,且数均分子量为480至8000g/mol,优选700至5000g/mol,并且特别是1000至3000g/mol。
其他合适的聚酯醇为聚合物改性的聚酯醇,优选接枝聚酯醇。这种聚酯醇为聚合物聚酯醇,其通常具有的优选地热塑性聚合物的含量为5至60重量%,优选10至55重量%,特别优选15至50重量%,并且特别是20至40重量%。这些聚合物聚酯醇记载于例如WO 05/098763和EP-A-250 351中,并通常由合适的烯属单体(例如苯乙烯、丙烯腈、(甲基)丙烯酸酯、(甲基)丙烯酸和/或丙烯酰胺)在用作接枝基底的聚酯醇中的自由基聚合来制备。侧链通常通过自由基由生长的聚合物链向聚酯醇或聚醚醇的转移来形成。除接枝共聚物外,聚合物聚酯醇主要包含分散于未改变的聚酯醇中的烯烃的均聚物。
在优选的实施方案中,使用丙烯腈、苯乙烯,优选丙烯腈和苯乙烯作为单体。所述单体任选地在其他单体、大分子单体(即不饱和的可自由基聚合的多元醇)、调节剂(moderator)的存在下以及在使用自由基引发剂(通常为偶氮化合物或过氧化合物)的情况下、在作为连续相的聚酯醇或聚醚醇中聚合。此方法记载于例如DE 111 394、US 3 304273、US 3 383 351、US 3 523 093、DE 1 152 536和DE 1 152 537中。
在自由基聚合过程中,大分子单体被同时并入共聚物链中。这形成了具有聚酯嵌段和聚(丙烯腈-苯乙烯)嵌段的嵌段共聚物,该嵌段共聚物在连续相和分散相的界面处充当相增容剂,并且抑制聚合物聚酯醇颗粒的附聚。大分子单体的比例通常为1至20重量%,基于用于制备聚合物多元醇的单体的总重量计。
如果包含聚合物多元醇,则其优选与其他聚酯醇共同存在。聚合物多元醇的比例特别优选大于5重量%,基于组分(b)的总重量计。聚合物聚酯醇的含量可以例如为7至90重量%或11至80重量%,基于组分(b)的总重量计。
多元醇(b)包含至少一种聚酯醇(b1),其可通过具有2至10个碳原子的脂族二羧酸与至少一种具有5至20个碳原子的较高官能醇和任选地一种具有2至4个碳原子的较高官能醇的酯化获得,其中至少20重量%、优选至少30重量%、更优选至少40重量%并且特别是多于50重量%的较高官能醇为具有5个以上碳原子的较高官能醇。除聚酯醇(b1)外,在优选的实施方案中,多元醇(b)包含聚酯醇(b2),其可通过具有2至10个碳原子的脂族或芳族二羧酸与至少一种具有2至4个碳原子的较高官能醇和少于20重量%、优选少于10重量%并且更优选少于5重量%的至少一种具有5个以上碳原子的较高官能醇的酯化获得,基于组分(b2)中的较高官能醇的总量计。优选地,碳原子数仅针对具有最大量的相互连接碳原子的结构来计算,即直链或支链烷基链中的碳原子数。这表示在该优选实施方案中,结构中有关的碳原子数仅通过考虑直链或支链烷基链中彼此连接的碳原子来确定。在该结构被杂原子中断的情况下,例如在醚结构中,例如在二乙二醇中,认为其中碳原子彼此连接的最大碳结构——其在此情况下为亚乙基结构——仅具有两个碳原子。
可能的二羧酸为,例如:琥珀酸、戊二酸、己二酸、辛二酸、壬二酸、癸二酸、癸烷二羧酸、马来酸、富马酸、邻苯二甲酸、间苯二甲酸和对苯二甲酸。所述二羧酸可以单独或彼此混合使用。也可以使用相应的二羧酸衍生物,例如具有1至4个碳原子的醇的二羧酸酯或二羧酸酐,来代替游离的二羧酸。优选使用琥珀酸、戊二酸和己二酸以例如20-35:35-50:20-32的重量比的二羧酸混合物,并且特别是己二酸。还可以使用衍生自内酯例如ε-己内酯或羟基羧酸例如ω-羟基己酸的聚酯多元醇。对于上述计算,将这些聚酯多元醇视为酸。
二元醇和多元醇、特别是二醇的实例为:乙二醇、二乙二醇、1,2-丙二醇或1,3-丙二醇、二丙二醇、1,4-丁二醇、1,5-戊二醇、1,6-己二醇、1,10-癸二醇、丙三醇和三羟甲基丙烷。优选使用乙二醇、二乙二醇、1,4-丁二醇、1,5-戊二醇、1,6-己二醇和新戊二醇,其中1,5-戊二醇、1,6-己二醇和新戊二醇被视为具有5个以上碳原子的二醇。
在优选的实施方案中,多元醇(b)还包含基于二聚酸的聚酯多元醇(b3)。在聚酯多元醇(b3)中,酸组分包含二聚酸。聚酯醇(b3)可通过使二聚酸、任选地具有2至15个碳原子的芳族或脂族二羧酸与至少一种具有2至20个碳原子的较高官能醇反应而获得。优选地,可以使用以上定义的化合物作为二羧酸和二元醇或多元醇。
术语二聚脂肪酸为本领域所公知,并且是指单不饱和脂肪酸或多不饱和脂肪酸和/或其酯的二聚产物。优选的二聚脂肪酸为C10至C30、更优选C12至C24、特别是C14至C22并且尤其是C18烷基链的二聚体。合适的二聚脂肪酸包括油酸、亚油酸、亚麻酸、棕榈油酸和反油酸的二聚产物。也可以使用在天然脂肪和油例如葵花油、豆油、橄榄油、菜油、棉籽油和妥尔油的水解中获得的不饱和脂肪酸混合物的二聚产物。还可以使用例如通过镍催化剂氢化的二聚脂肪酸。
除二聚脂肪酸外,二聚作用通常导致存在不同量的低聚脂肪酸(所谓的“三聚体”)和单体脂肪酸的残余物(所谓的“单体”)或者它们的酯。可以例如通过蒸馏来减少单体的量。合适的二聚脂肪酸具有的二羧酸(或二聚体)含量为大于60重量%,优选大于75重量%,更优选在80至96重量%的范围内,特别是85至92重量%,并且尤其是87至89重量%。三聚体的含量适当地小于40重量%,优选在2至25重量%的范围内,更优选5至15重量%,特别是7至13重量%,并且尤其是9至11重量%。单体的含量优选小于10重量%,更优选在0.2至5重量%的范围内,特别是0.5至3重量%,并且尤其是1至2重量%。以上重量%值全部基于所存在的三聚体、二聚体和单体的总重量计。
在优选的实施方案中,聚酯醇(b3)中的二聚酸的含量为至少20重量%,更优选在30至90重量%的范围内,并且特别地为40至80重量%,基于多元醇(b3)中二酸的总量计。基于二聚酸的聚酯醇(b3)是市售可得的,例如从Corda International Plc以商品名购得。
聚酯醇(b3)的分子量优选在450至6000g/mol的范围内,更优选为1000至3000g/mol,并且最优选为1500至2500g/mol。更优选地,聚酯醇(b3)的羟值在10至100、更优选30至80、特别是40至70并且尤其是50至60mg KOH/g的范围内。此外,聚酯醇(b3)的酸值优选小于2,更优选小于1.7,特别是小于1.3,并且尤其是小于1.0。
除聚酯醇外,也可以使用其他数均分子量大于500g/mol的多元醇、例如聚醚醇作为多元醇(b),然而在优选的实施方案中,仅使用聚酯醇作为多元醇(b)。在更优选的实施方案中,基本上仅使用聚酯醇(b1)和(b2)以及任选地(b3)作为组分(b)。如果接枝聚酯多元醇是多元醇(b)的一部分,则仅考虑载体聚合物来判断是否将该接枝多元醇视为多元醇(b1)、(b2)或(b3)中的一种。
优选地,聚酯醇(b1)的含量为15至60重量%,更优选20至50重量%,聚酯醇(b2)的含量为20至80重量%,更优选35至70重量%,以及聚酯醇(b3)的含量为5至20重量%,更优选10至15重量%,各自基于聚酯醇(b1)、(b2)和(b3)的总重量计。
此外,在聚氨酯泡沫模制品的制备中存在发泡剂c)。这些发泡剂c)可以包含水。除水以外,可以另外使用通常已知的化学和/或物理作用的化合物作为发泡剂c)。出于本发明的目的,化学发泡剂为与异氰酸酯反应形成气体产物的化合物,例如水或甲酸。物理发泡剂为在用于制备聚氨酯的起始物料中溶解或乳化并在聚氨酯形成条件下汽化的化合物。这些发泡剂为,例如,烃、卤代烃和其他化合物,例如全氟化烷烃(如全氟己烷)、含氯氟烃以及醚、酯、酮、缩醛或其混合物,例如具有4至8个碳原子的(环)脂族烃或氟化烃(如购自SolvayFluorides LLC的365mfc)。在优选的实施方案中,使用包含这些发泡剂中的至少一种和水的混合物作为发泡剂,并且特别地使用水作为唯一的发泡剂。如果不使用水作为发泡剂,则优选仅使用物理发泡剂。
在优选的实施方案中,水的含量为0.1至2重量%,优选0.2至1.5重量%,特别优选0.3至1.2重量%,基于组分a)至h)的总重量计。
在另一优选实施方案中,将包含物理发泡剂的中空微球作为额外发泡剂添加至组分a)至h)的反应中。中空微球也可以与上述发泡剂混合使用。
中空微球通常包括热塑性聚合物的壳,并用基于烷烃的液态、低沸点物质填充于核中。这种中空微球的制备记载于例如US 3 615 972中。中空微球的直径通常为5至50μm。合适的中空微球的实例可以从Akzo Nobel以商品名获得。
中空微球的加入量通常为0.5至5重量%,基于组分b)、c)和d)的总重量计。
作为增链剂和/或交联剂d),使用分子量优选小于450g/mol、特别优选为60至400g/mol的物质,其中增链剂具有2个对异氰酸酯呈反应性的氢原子且交联剂具有3个对异氰酸酯呈反应性的氢原子。这些物质可优选地单独使用或以混合物的形式使用。优选使用分子量为400以下、特别优选为60至300并且特别是60至150的二醇和/或三醇。可能的为例如具有2至14个、优选2至10个碳原子的脂族、脂环族和/或芳脂族二醇,如乙二醇、1,3-丙二醇、1,10-癸二醇、1,2-二羟基环己烷、1,3-二羟基环己烷、1,4-二羟基环己烷、二乙二醇、二丙二醇和1,4-丁二醇、1,6-己二醇以及双(2-羟基乙基)氢醌;三醇,如1,2,4-三羟基环己烷、1,3,5-三羟基环己烷、丙三醇和三羟甲基丙烷;以及基于环氧乙烷和/或1,2-环氧丙烷以及上述二醇和/或三醇作为起始分子的低分子量的含羟基的聚环氧烷。特别优选使用单乙二醇、1,4-丁二醇、二乙二醇、丙三醇或其混合物作为增链剂(d)。
如果使用增链剂、交联剂或其混合物,则其用量有利地为1至60重量%,优选1.5至50重量%,并且特别是2至40重量%,基于组分b)和d)的重量计。
作为用于制备聚氨酯泡沫的催化剂,优选使用极大地促进多元醇(b)和任选地增链剂和交联剂(d)与有机、任选改性的多异氰酸酯(a)相互反应的化合物。这些化合物包括胺催化剂。可提及的为例如:脒,例如2,3-二甲基-3,4,5,6-四氢嘧啶;叔胺,例如三乙胺、三丁胺、二甲基苄胺、N-甲基吗啉、N-乙基吗啉、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、双(二甲基氨基乙基)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]辛烷和优选地1,4-二氮杂双环[2.2.2]辛烷;以及烷醇胺化合物,例如三乙醇胺、三异丙醇胺、N-甲基二乙醇胺、N-乙基二乙醇胺和二甲基乙醇胺。优选使用三乙胺、三丁胺、二甲基苄胺、N-甲基吗啉、N-乙基吗啉、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、双(二甲基氨基乙基)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、1,4-二氮杂双环[2.2.2]辛烷、1,8-二氮杂双环[5.4.0]十一碳-7-烯(DBU)及其混合物作为胺催化剂。特别地,使用1,4-二氮杂双环[2.2.2]辛烷作为胺催化剂。
除胺催化剂外,也可以使用其他催化活性化合物作为催化剂,例如有机金属化合物,优选有机锡化合物,例如有机羧酸的锡(II)盐如乙酸锡(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)盐如二乙酸二丁基锡、二月桂酸二丁基锡、马来酸二丁基锡和二乙酸二辛基锡;以及铋的羧酸盐,例如新癸酸铋(III)、2-乙基己酸铋和辛酸铋,或者它们的混合物。优选仅使用胺催化剂。
优选使用0.001至5重量%、特别是0.05至2重量%的催化剂或催化剂结合物,基于组分b)的重量计。
作为碳二亚胺(g),使用通式Z-N=C=N-Z的化合物,其中Z为有机基团,并且碳二亚胺基团-N=C=N-的氮原子与叔碳原子连接或与芳族体系的碳原子连接,在所述芳族体系的与C-N键相邻的环位置上,所述芳族体系带有通过仲碳原子或叔碳原子与该芳族体系连接的基团。合适的基团Z的实例为叔丁基、异丙基和被大体积基团(bulky group)取代的芳基。
已发现,使用2位和6位被取代基取代的苯基作为大体积基团是有利的,其中所述取代基为大体积基团例如叔丁基或优选异丙基。
在优选的实施方案中,使用通式(1)的化合物作为空间位阻碳二亚胺(b),
其中R1为异丙基或异丁基或其混合物,且R2至R3各自为氢原子或有机基团。
在式1中,R2优选为氢原子。
在式1中,R3优选为氢原子或1-甲基-1-苯基乙基基团、苯氧基基团或叔丁基基团。
在式1中,R1特别优选为异丙基基团。
在优选的实施方案中,使用通式(2)的化合物作为空间位阻碳二亚胺(b),
其中基团R1相同或不同,并且各自为有机基团,优选为氢原子,
基团R2相同或不同,并且各自为烷基基团,优选为甲基,并且
基团R3相同或不同,并且各自为氢原子、烷基基团,或者选自-NCO、-NHCONHR4、-NHCONR4R5和-NHCOOR6基团,其中R4和R5相同或不同,并且各自为烷基基团、环烷基基团或芳烷基基团,并且R6为R4或烷氧基聚氧亚烷基(alkoxypolyoxalkylene)基团,并且
n为0至10的整数。
这种碳二亚胺被用于例如改善水解性能。这种碳二亚胺是已知的,并且可以商品名Elastostab H01或Stabaxol I购得。
使用一元羧酸或多元羧酸的酯作为组分(g)。一元羧酸的酯(i)和/或多元羧酸的酯(ii)包含至少一种一元羧酸的酯(i)和/或多元羧酸的酯(ii)。这些羧酸的(一级)离解常数的pK值(在25℃的水溶液中测定)通常在0.5至5的范围内,优选为0.5至4,并且更优选为1至3。合适的酸组分的实例包括:烷基一元羧酸,例如甲酸;烷基多元羧酸,例如草酸、丙二酸、马来酸、富马酸和柠檬酸;芳基一元羧酸,例如[α]-萘甲酸;和芳基多元羧酸,例如邻苯二甲酸、偏苯三酸和苯均四酸的同分异构体和烷基取代衍生物以及萘二羧酸的同分异构体;和[α]-羟基羧酸例如扁桃酸或乳酸的环状双酯。优选使用饱和的C2-C4烷基多元羧酸;特别优选为草酸。合适的醇组分的实例包括脂族一元醇和多元醇,例如甲醇、乙醇、丙醇、异丙醇、乙二醇、1,2-丙二醇和1,3-丙二醇、丁醇的同分异构体、2-丁烯-1,4-二醇、2-丁炔-1,4-二醇、新戊二醇、丙三醇、三羟甲基丙烷和季戊四醇。合适的芳基醇的实例包括酚及其取代衍生物、萘酚及其烷基取代衍生物、氢醌、间苯二酚、三羟基苯,以及(d)增链剂和/或交联剂下列举的全部聚醚和聚醚酯多元醇。优选为脂族一元醇,特别是甲醇、乙醇、正丙醇或异丙醇、或正丁醇、异丁醇或叔丁醇。最优选为草酸酯如草酸二乙酯。
在优选的实施方案中,化合物(g)包含:如上文所公开的(g1)至少一种一元羧酸的酯(i)和/或多元羧酸的酯(ii),所述酸的(一级)离解常数(pK)为0.5至4,优选1至3;和(g2)一种环酯。优选地,环酯在环结构中具有5至8个、更优选5或6个原子,并且可带有例如脂族基团的取代基或可为未取代的。这种环酯的实例为4-羟基丁酸(γ-丁内酯)、5-羟基戊酸和6-羟基己酸的环酯化产物。此外,可以将环状碳酸酯例如碳酸亚乙酯、碳酸1,2-亚丙酯或碳酸1,3-亚丙酯用作环酯(g2)。最优选作为环酯(g2)的为γ-丁内酯或碳酸1,2-亚丙酯。优选地,化合物(g1)与化合物(g2)之间的重量比为1:15至15:1,更优选为1:10至10:1。优选地,化合物(g)的用量为0.01至10重量%,更优选0.05至5重量%,基于化合物(a)至(h)的总重量计。
还可以任选地将助剂和/或添加剂(h)添加至用于制备聚氨酯泡沫的反应混合物。可提及的实例有:脱模剂、填料、染料、颜料、水解抑制剂、气味吸收物质以及抑制真菌和/或抑制细菌物质。
作为合适的脱模剂,可提及的实例有:脂肪酸酯与多异氰酸酯的反应产物、包含氨基的聚硅氧烷和脂肪酸的盐、具有至少8个碳原子的饱和或不饱和(环)脂族羧酸和叔胺的盐,以及特别是内脱模剂,例如羧酸酯和/或羧酰胺,其由褐煤酸和至少一种具有至少10个碳原子的脂族羧酸的混合物借助于以下物质的酯化或酰胺化反应制备:如公开于例如EP153 639中的分子量为60至400g/mol的至少双官能的烷醇胺、多元醇和/或多胺;如公开于例如DE-A-3 607 447中的有机胺、硬脂酸的金属盐和有机一元羧酸和/或二元羧酸或其酸酐的混合物;或如公开于例如US 4 764 537中的亚氨化合物、羧酸金属盐和任选的羧酸的混合物。本发明的反应混合物优选不包含任何其他脱模剂。
出于本发明的目的,填料、特别是增强填料为本身已知的常规有机和无机填料、增强材料、增重剂、涂布剂等。具体实例为:无机填料,例如含硅矿物,例如片状硅酸盐如叶蛇纹石、膨润土、蛇纹石、角闪石、闪石、温石棉和滑石;金属氧化物,例如高岭土、氧化铝、氧化钛、氧化锌和氧化铁;金属盐,例如白垩和重晶石;和无机颜料,例如硫化镉、硫化锌以及玻璃等。优选使用高岭土(瓷土)、硅酸铝以及硫酸钡和硅酸铝的共沉淀物。可能的有机填料为,例如:炭黑、三聚氰胺、松香、环戊二烯基树脂和接枝聚合物,以及纤维素纤维、聚酰胺纤维、聚丙烯腈纤维、聚氨酯纤维和基于芳族和/或脂族二羧酸酯的聚酯纤维,并且特别是碳纤维。
无机填料和有机填料可以单独或作为混合物使用,并且添加至反应混合物的量有利地为0.5至50重量%,优选1至40重量%,基于组分a)至(h)的重量计。
作为水解抑制剂,可以使用常规的水解抑制剂,例如环氧化物和噁唑烷。
在本发明的方法中,将起始组分(a)至(h)以一定量彼此混合,使得多异氰酸酯(a)的NCO基团与组分(b)、(c)和(d)的反应性氢原子总和的当量比为1:0.8至1:1.25,优选1:0.9至1:1.15。此处,1:1的比例对应于异氰酸酯指数100。出于本发明的目的,异氰酸酯指数为异氰酸酯基团与对异氰酸酯呈反应性的基团的化学计量比乘以100。
为了制备本发明的铸塑聚氨酯树脂,将该铸塑聚氨酯树脂体系的组分优选在30至90℃、特别优选40至80℃、更优选45至70℃并且特别是在50至60℃的温度下进行混合。然后,将混合物优选在模具中固化以产生铸塑聚氨酯树脂。模具温度通常为0至130℃,优选60至120℃,并且特别优选80至110℃。组分的混合通常在低压机中进行。为了进一步改善机械性能,可以将自模具中移出后的成品铸塑聚氨酯树脂在升高的温度例如50至120℃、优选60至110℃并且特别是80至100℃下进行进一步热处理,时间通常为10至24小时。此处,用于制备铸塑聚氨酯树脂的反应混合物基本不包含发泡剂(c)。“基本无发泡剂”表示不添加额外的发泡剂。然而,由于其制备方法,多元醇可以包含例如少量的水。为避免水在组分中积聚并因此使聚氨酯发泡,具有对异氰酸酯呈反应性的基团的化合物优选包含干燥剂,例如沸石。
本发明的铸塑聚氨酯树脂优选用作工业或农业应用中的工程部件例如滚筒或辊,或用作采矿业中的工程部件例如筛。
本发明的聚氨酯泡沫模制品优选通过一步法利用低压或高压技术在密闭、有利地加热的模具中制备。模具通常由金属例如铝或钢构成。这些加工技术例如由Piechota和记载于“Integralschaumstoff”,Carl-Hanser-Verlag,Munich,Vienna,1975中,或记载于“Kunststoff-handbuch”,第7卷,Polyurethane,第3版,1993,第7章中。
为此,将起始组分(a)至(h)优选在15至90℃、特别优选25至55℃的温度下混合,并任选地在超大气压下将反应混合物引入至模具中。可借助搅拌器或搅拌螺杆或在高压下以逆流喷射法实施机械混合。模具温度有利地为20至160℃,优选30至120℃,特别优选30至60℃。出于本发明的目的,将基于异氰酸酯基团计的反应转化率小于90%的组分a)至h)的混合物称作反应混合物。在优选的实施方案中,将化合物以包含异氰酸酯(a)的异氰酸酯组分和包含多元醇(b)、如果存在发泡剂(c)、增链剂和/或交联剂(d)、催化剂(e)以及碳二亚胺(f)的多元醇组分的形式进行预混合。化合物(g)和化合物(h)可以添加至异氰酸酯组分或添加至多元醇组分。在优选的实施方案中,异氰酸酯组分包含化合物(g)而多元醇组分包含化合物(h)。为了制备本发明的聚酯聚氨酯,将多元醇化合物和异氰酸酯化合物如上所述地混合和处理。
选择引入模具中的反应混合物的量,使得所获得的模制品、特别是整体泡沫的密度优选为150g/l至850g/l,更优选180g/l至750g/l,特别优选200g/l至700g/l,并且特别是200至650g/l。用于制备本发明的整体聚氨酯泡沫的压实度在1.1至8.5、优选1.6至7.0的范围内。
本发明的聚氨酯泡沫模制品优选用作鞋底并且特别优选用作中底(midsole),例如便鞋(street shoes)、运动鞋、凉鞋和靴子的中底。此外,本发明的聚氨酯泡沫可以用于车辆内饰,例如在汽车中作为方向盘、头枕或变速杆把手或者作为座椅扶手。其他可能的用途为作为椅子扶手或摩托车车座。铸塑聚氨酯树脂可以例如用作鞋外底或用作密封垫(seal)。特别地,本发明的聚氨酯模制品用作鞋底,尤其是安全鞋或军靴的鞋底。这些鞋底可以是致密底或发泡底,特别是整体聚氨酯泡沫。出乎意料地,本发明的聚氨酯模制品、尤其是本发明的聚氨酯泡沫通过了采用SATRA TM344的水解测试(在70℃和95%相对湿度下储存),且其根据DIN 53504测量的拉伸强度保留大于初始值的80%达至少28天,并且保持了低的磨耗。这相当于在低湿度和20℃的正常气候下的贮存期限为至少约8年,以及在高湿度和30℃的热带气候下的贮存期限为约4年。
以下借助实施例来说明本发明:
所用的起始物料:
多元醇1:基于己二酸、单乙二醇(MEG)和1,4-丁二醇(BD)(重量比MEG:BD=2:1)的聚酯多元醇,其OH值为56mg KOH/g
多元醇2:基于己二酸、单乙二醇、二乙二醇和三羟甲基丙烷的聚酯醇,其OH值为60mg KOH/g,且官能度为2.65
多元醇3:基于己二酸、1,4-丁二醇和1,5-戊二醇(PD)(重量比BD:PD=1:1.2)的聚酯多元醇,其OH值为70mg KOH/g
多元醇4:基于己二酸、1,4-丁二醇和新戊二醇(NPG)(重量比BD:NPG=1:1.7)的聚酯多元醇,其OH值为56mg KOH/g
多元醇6:基于二聚酸的聚酯醇,其基于二聚酸、己二酸、单乙二醇和丁二醇(重量比BD:MEG:二聚酸=1:1.4:4.9),OH值为56mg KOH/g,
催化剂1:溶解于单乙二醇中的浓度为33%的三亚乙基二胺
催化剂2:由酸封端的三亚乙基二胺
交联剂:OH值为270mg KOH/g,官能度=3
KV:单乙二醇
稳定剂1:购自Air Products的泡孔稳定剂Dabco DC 193
ISO:基于4,4'-MDI、碳二亚胺改性的MDI、多元醇1和多元醇2的预聚物,其NCO含量为18重量%,含有7重量%的γ-丁内酯和1重量%的草酸二乙酯
本发明的对比实施例和实施例的制剂按照下表制备。通过低压机EMB F20,在多元醇混合物和异氰酸酯的温度为约45℃的情况下对发泡聚氨酯模制品进行处理。
通过鞋业中的现有技术渗透试验来确定多元醇和异氰酸酯组分(使用ISO作为全部实施例和对比实施例的异氰酸酯)的最佳混合比。在确定最佳混合比后,将相应的混合物引入模具中以制备试验板。
在进行机械表征前,使材料在标准温度和湿度条件下适应至少2天。此处,拉伸强度按照DIN 53504测量。为测定水解性能,将根据DIN 53504(SATRA TM344)制备的试验样品储存在70℃和95%相对大气湿度下,并在水解老化21、28和35天后(ZF 21d HL;ZF 28d HL和ZF 35d HL)测量样品的拉伸强度。磨耗按照DIN53516测量。
中底配方(recipe)
外底配方
单一密度配方
可见,本发明的聚酯聚氨酯模制品显示出优良的水解老化性。特别是当另外使用二聚酸时,耐水解性进一步提高。相比之下,如果使用二聚酸而不使用多元醇(b1),则耐水解性不能得到提高。
Claims (17)
1.一种用于制备聚氨酯模制品的方法,其中
将a)有机多异氰酸酯,与
b)包含聚酯醇的多元醇,
c)任选地发泡剂,
d)增链剂和/或交联剂,
e)胺催化剂,
f)通式Z-N=C=N-Z的碳二亚胺,其中Z为有机基团,并且碳二亚胺基团-N=C=N-的氮原子与叔碳原子连接或与芳族体系的碳原子连接,在所述芳族体系中在与C-N键相邻的环位置上,所述芳族体系带有通过仲碳原子或叔碳原子与芳族体系连接的有机基团,
g)至少一种选自(i)一元羧酸的酯和(ii)多元羧酸的酯的成员,每种酸的一级离解常数(pK)为0.5至5,和任选地
h)其他助剂和/或添加剂,
混合以形成反应混合物,将混合物引入至模具中并使其反应以形成聚氨酯模制品,
其中聚酯醇包含:
15至60重量%的聚酯醇(b1),其通过具有2至10个碳原子的脂族二羧酸与至少一种具有5至20个碳原子的较高官能醇和任选地一种具有2至4个碳原子的较高官能醇的酯化获得,其中至少20重量%的较高官能醇为具有5个以上碳原子的较高官能醇,基于组分(b1)中的较高官能醇的总量计,和
20至80重量%的聚酯醇(b2),其通过具有2至10个碳原子的脂族或芳族二羧酸与至少一种具有2至4个碳原子的较高官能醇和少于20重量%的至少一种具有5个以上碳原子的较高官能醇的酯化获得,基于组分(b2)中的较高官能醇的总量计,和
5至20重量%的其他聚酯醇(b3),其中酸组分包含至少一种二聚酸,
其中较高官能醇为二元醇或多元醇,
其中聚酯醇(b1)、(b2)和(b3)的含量各自基于聚酯醇(b1)、(b2)和(b3)的总重量计。
2.根据权利要求1所述的方法,其中较高官能醇为二醇。
5.根据权利要求4所述的方法,其中有机基团为氢原子。
6.根据权利要求4所述的方法,其中在基团R2中,烷基基团为甲基。
7.根据权利要求1至4中任一项所述的方法,其中碳二亚胺具有对异氰酸酯呈反应性的基团。
8.根据权利要求1至4中任一项所述的方法,其中碳二亚胺具有通过环氧烷烃的聚合获得的聚醚基团。
9.根据权利要求1至4中任一项所述的方法,其中碳二亚胺(f)的含量为0.1至5重量份,基于化合物(b)至(g)的总重量计。
10.根据权利要求1至4中任一项所述的方法,其中一元羧酸的酯(i)和/或多元羧酸的酯(ii)包含:(g1)至少一种一元羧酸的酯(i)和/或多元羧酸的酯(ii),所述酸的一级离解常数(pK)为0.5至4;和(g2)一种环酯。
11.根据权利要求10所述的方法,其中化合物(g1)与化合物(g2)之间的比例为1:15至15:1。
12.根据权利要求1至4中任一项所述的方法,其中化合物(g)的总含量为0.01至10重量%,基于化合物(a)至(h)的总重量计。
13.根据权利要求1至4中任一项所述的方法,其中聚酯醇包含聚酯醇(b3),并且其中聚酯醇(b3)通过使二聚酸、任选地具有2至15个碳原子的芳族或脂族二酸与至少一种具有2至20个碳原子的较高官能醇反应而获得,其中较高官能醇为二元醇或多元醇。
14.根据权利要求13所述的方法,其中二聚酸通过不饱和脂肪酸的二聚作用而获得。
15.根据权利要求13所述的方法,其中二聚酸的含量为至少10摩尔%,基于具有2至20个碳原子的聚酯醇(b3)中的二聚酸和芳族或脂族二酸的总量计。
16.聚氨酯模制品,其通过权利要求1至15中任一项所述的方法获得。
17.根据权利要求16所述的聚氨酯模制品作为鞋底的用途。
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US5210170A (en) * | 1990-06-07 | 1993-05-11 | Bayer Aktiengesellschaft | Process for stabilizing plastics containing ester groups |
US5498747A (en) * | 1994-05-12 | 1996-03-12 | Basf Aktiengesellschaft | Carbodiimides and/or oligomeric polycarbodiimides based on 1,3-bis (1-methyl-1-isocyanatoethyl)benzene, their preparation, and their use as hydrolysis stabilizers |
EP0794974B1 (de) * | 1994-12-01 | 2000-02-02 | Basf Aktiengesellschaft | Stabilisierte polyester formmassen |
CN1953984A (zh) * | 2004-05-13 | 2007-04-25 | 巴斯福股份公司 | 含有脲基和硅烷基团的碳二亚胺 |
CN102414236A (zh) * | 2009-04-29 | 2012-04-11 | 巴斯夫欧洲公司 | 基于三羧酸的酯的软质热塑性聚氨酯 |
CN103328525A (zh) * | 2010-11-16 | 2013-09-25 | 巴斯夫欧洲公司 | 具有低密度的尺寸稳定的聚氨酯模塑体 |
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WO2012065299A1 (en) * | 2010-11-16 | 2012-05-24 | Basf Se | Dimensionally stable low-density polyurethane moldings |
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2015
- 2015-02-11 WO PCT/EP2015/052838 patent/WO2015124476A1/en active Application Filing
- 2015-02-11 EP EP15703612.0A patent/EP3107947B1/en active Active
- 2015-02-11 CN CN201580009064.0A patent/CN106029730B/zh active Active
- 2015-02-11 KR KR1020167025547A patent/KR20160122252A/ko not_active Application Discontinuation
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
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US5210170A (en) * | 1990-06-07 | 1993-05-11 | Bayer Aktiengesellschaft | Process for stabilizing plastics containing ester groups |
US5498747A (en) * | 1994-05-12 | 1996-03-12 | Basf Aktiengesellschaft | Carbodiimides and/or oligomeric polycarbodiimides based on 1,3-bis (1-methyl-1-isocyanatoethyl)benzene, their preparation, and their use as hydrolysis stabilizers |
EP0794974B1 (de) * | 1994-12-01 | 2000-02-02 | Basf Aktiengesellschaft | Stabilisierte polyester formmassen |
CN1953984A (zh) * | 2004-05-13 | 2007-04-25 | 巴斯福股份公司 | 含有脲基和硅烷基团的碳二亚胺 |
CN102414236A (zh) * | 2009-04-29 | 2012-04-11 | 巴斯夫欧洲公司 | 基于三羧酸的酯的软质热塑性聚氨酯 |
CN103328525A (zh) * | 2010-11-16 | 2013-09-25 | 巴斯夫欧洲公司 | 具有低密度的尺寸稳定的聚氨酯模塑体 |
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WO2015124476A1 (en) | 2015-08-27 |
CN106029730A (zh) | 2016-10-12 |
EP3107947B1 (en) | 2019-01-02 |
KR20160122252A (ko) | 2016-10-21 |
EP3107947A1 (en) | 2016-12-28 |
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