CN101874051B - 含有环己烷二羧酸二烷基酯作为内脱模剂的聚氨酯整皮泡沫 - Google Patents
含有环己烷二羧酸二烷基酯作为内脱模剂的聚氨酯整皮泡沫 Download PDFInfo
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- CN101874051B CN101874051B CN200880117750.XA CN200880117750A CN101874051B CN 101874051 B CN101874051 B CN 101874051B CN 200880117750 A CN200880117750 A CN 200880117750A CN 101874051 B CN101874051 B CN 101874051B
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- Prior art keywords
- polyurethane integral
- dicarboxylic acid
- integral foams
- cyclohexane dicarboxylic
- dialkyl esters
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- C—CHEMISTRY; METALLURGY
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- C08G18/2815—Monohydroxy compounds
- C08G18/284—Compounds containing ester groups, e.g. oxyalkylated monocarboxylic acids
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- C—CHEMISTRY; METALLURGY
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2110/00—Foam properties
- C08G2110/0033—Foam properties having integral skins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2125/00—Compositions for processes using internal mould release agents
Abstract
本发明涉及一种制备聚氨酯整皮泡沫的方法,其中将以下物质混合以形成一种反应混合物:a)有机多异氰酸酯;b)具有至少两个活性氢原子的相对高分子量化合物;c)推进剂;d)环己烷二羧酸二烷基酯;以及任选地,e)增链剂和/或交联剂、f)催化剂和g)其他助剂和/或添加剂;将所述混合物倒入一个塑模中并使其反应,以形成一种聚氨酯整皮泡沫。此外,本发明还涉及含有环己烷二羧酸二烷基酯的聚氨酯整皮泡沫、所述泡沫用于交通工具内部中或用作鞋底的用途、以及环己烷二羧酸二烷基酯用作内脱模剂在制备聚氨酯整皮泡沫中的用途。
Description
本发明涉及一种制备聚氨酯整皮泡沫(integral foam)的方法,其中将以下物质混合以形成一种反应混合物:a)有机多异氰酸酯;b)具有至少两个活性氢原子的相对高分子量化合物;c)发泡剂;d)环己烷二羧酸二烷基酯;以及如果合适,e)增链剂和/或交联剂、f)催化剂和g)其他助剂和/或添加剂;将所述反应混合物引入一个塑模中并使其反应,以形成一种聚氨酯整皮泡沫。本发明还涉及含有环己烷二羧酸二烷基酯的聚氨酯整皮泡沫、所述聚氨酯整皮泡沫用于道路车辆(roadvehicle)内件中或用作鞋底的用途、以及环己烷二羧酸二烷基酯用作内脱模剂在制备聚氨酯整皮泡沫中的用途。
本发明的另外实施方案述于权利要求、说明书和实施例中。毫无疑问地,本发明主题的上述特征以及还将在下文说明的特征不仅可以以各自所述的结合方式应用,而且在不偏离本发明范围的前提下,还可以以其他结合方式应用。
聚氨酯整皮泡沫是具有致密表面和多孔中心的聚氨酯模制品。聚氨酯整皮泡沫及其制备方法已久为所知,并述于例如ModernShoemaking No.61:Solings,November 2001,Stephen Abbott和MikeGeorge,Satra Technology Centre 2001中。聚氨酯整皮泡沫用于多个领域。一个常见的用途是作为鞋底用于例如便鞋(street shoe)、运动鞋、凉鞋和靴中,以及作为例如方向盘、头枕或传输旋钮用于机动车内件领域。其他合适的用途是作为座椅的扶手或作为摩托车车座。
用于制备聚氨酯整皮泡沫的反应混合物通常包含内脱模剂,以使所制备的模制品可更容易地从塑模中脱除。这也避免了聚氨酯整皮泡沫因粘附至塑模上而产生的缺陷。已知的内脱模剂为二甲基硅氧烷,饱和或不饱和的长链脂肪酸酯,例如硬脂酸酯或油酸酯,以及邻苯二甲酸二烷基酯。
向制备聚氨酯整皮泡沫的反应混合物中添加聚二甲基硅氧烷或脂 肪酸酯会妨碍泡沫的形成。这些内脱模剂的使用会产生不利的大泡孔,并损害致密外皮的形成,而所述致密外皮的形成对于聚氨酯整皮泡沫而言是重要的。此外,整皮泡沫的机械性能——例如硬度、拉伸强度和断裂伸长率——和水解性能也会受到不利影响。
邻苯二甲酸二烷基酯是高度有效的脱模剂,其对聚氨酯整皮泡沫的泡孔结构和结皮不会表现出上述的不利影响。然而,其用途由于环境卫生原因而受到部分地限制。
因此,本发明的一个目的是提供一种制备聚氨酯整皮泡沫的方法,其中待制备的聚氨酯整皮泡沫的泡孔结构和外皮的形成不会受到不利影响。
本发明的又一个目的是提供具有如下性能的聚氨酯整皮泡沫:其即使在水解条件下老化之后也具有优良的机械性能,例如硬度、拉伸强度和最大断裂伸长率。
出乎意料地,本发明的目的已通过一种如下的方法实现,其中将以下物质混合以形成一种反应混合物:a)有机多异氰酸酯;b)具有至少两个活性氢原子的相对高分子量化合物;c)发泡剂;d)环己烷二羧酸二烷基酯;以及如果合适,e)增链剂和/或交联剂、f)催化剂和g)其他助剂和/或添加剂;将所述反应混合物引入一个塑模中并使其反应,以形成一种聚氨酯整皮泡沫。
此外,本发明的一个目的还通过可由本发明方法获得的聚氨酯整皮泡沫实现。
基于本发明的目的,聚氨酯整皮泡沫是根据DIN 7726的如下的聚氨酯泡沫,其由于成型过程而具有密度高于中心的表面区域。中心和表面区域平均的泡沫总密度优选大于0.08g/cm3,特别优选为0.15至0.80g/cm3,特别是0.25至0.70g/cm3。
用于制备本发明聚氨酯整皮泡沫的有机和/或改性多异氰酸酯(a)包括现有技术中已知的脂族、脂环族和芳香族的二价或多价异氰酸酯(成分a-1)及其任意混合物。实例有二苯基甲烷-4,4′-二异氰酸酯、二苯基甲烷-2,4’-二异氰酸酯、单体二苯基甲烷二异氰酸酯和具有多于两个环的二苯基甲烷二异氰酸酯的同系物(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)、甲苯基-2,4-二异氰酸酯或2,6-二异氰酸酯(TDI),或所述异氰酸酯的混合物。
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(最多约10重量%)的经脲基甲酸酯或脲酮亚胺改性的多异氰酸酯。还可使用少量的聚亚苯基聚亚甲基多异氰酸酯(聚合的MDI)。这些高官能度多异氰酸酯的总量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多异氰酸酯(a-1)与多元醇(a-2)在例如30至100℃、优选约80℃的温度下反应以形成预聚物而获得。
多元醇(a-2)为本领域技术人员所已知,并记载于例如“Kunststoffhandbuch,第7卷,Polyurethane”,Carl Hanser Verlag,1993年第3版,第3.1章中。对于多元醇(a-2)而言,优选使用b)中所述的具有可与异氰酸酯反应的氢原子的高分子量化合物。
如果合适,在制备异氰酸酯预聚物的过程中,可向上述多元醇中添加常规的增链剂或交联剂。所述物质描述于下述e)中。
具有至少两个可与异氰酸酯基团反应的氢原子的相对高分子量化合物b)可为例如聚醚醇或聚酯醇。
聚醚醇通过已知方法制备,例如由一种或多种在亚烷基基团中具有2至4个碳原子的环氧烷通过使用碱金属氢氧化物或碱土金属醇盐作为催化剂在添加至少一种含有2或3个结合形式的活性氢原子的引子分子(Startermollekül)的情况下进行阴离子聚合而制备,或通过使用路易斯酸——例如五氯化锑或氟化硼醚合物——进行阳离子聚合而制备。合适的环氧烷有,例如四氢呋喃、1,3-环氧丙烷、1,2-环氧丁烷或2,3-环氧丁烷,以及优选地环氧乙烷和1,2-环氧丙烷。还可使用多金属氰化物作为催化剂,即为所称的DMC催化剂。所述环氧烷可单独使用,或者相继交替使用或以混合物形式使用。优选1,2-环氧丙烷和环氧乙烷的混合物,且环氧乙烷以10至50%的量、环氧乙烷末端嵌段(“EP”封端)的形式使用,以使所形成的多元醇具有大于70%的伯羟基端基。
合适的引子分子为水,以及二元醇和三元醇,例如乙二醇、1,2-丙二醇和1,3-丙二醇、二甘醇、双丙甘醇、1,4-丁二醇、甘油或三羟甲基丙烷。
优选地,聚醚多元醇——优选聚氧丙烯-聚氧乙烯多元醇——的官能度为2至3,且分子量为1000至8000g/mol、优选2000至6000g/mol。
聚酯多元醇可由例如具有2至12个碳原子的有机二羧酸(优选具有4至6个碳原子的脂族二羧酸)和具有2至12个碳原子、优选2至6个碳原子的多元醇(优选二元醇)制备。合适二羧酸的实例有:丁二酸、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。所述二羧酸可单独使用,或彼此混合使用。作为所述游离二羧酸的替代物,也可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。优选使用重量比例如为20-35∶35-50∶20-32的丁二酸、戊二酸和己二酸的二羧酸混合物,特别是己二酸。二元醇和多元醇——特别是二元醇——的实例有:乙二醇、二甘醇、1,2-丙二醇或1,3-丙二醇、双丙甘醇、1,4-丁二醇、1,5-戊二醇、1,6-己二醇、1,10-癸二醇、甘油和三羟甲基丙烷。优选使用乙二醇、二甘醇、1,4-丁二醇、1,5-戊二醇和1,6-己二醇。还可使用由内酯(例如ε-己内酯)或羟基羧酸(例如ω-羟基己酸)衍生的聚酯多元醇。
为制备聚酯多元醇,可使有机的——例如芳香族和优选地脂族的——多元羧酸和/或衍生物与多元醇在不存在催化剂的情况下或优选在酯化催化剂的存在下、于150至250℃、优选180至220℃的温度以熔融状态缩聚至所需酸值,所述缩聚有利地在惰性气体——例如氮气、一氧化碳、氦气、氩气等——的气氛下进行,且如果合适,在减压下进行;其中所述酸值优选小于10、特别优选小于2。在一个优选的实施方案中,所述酯化混合物在大气压下、且随后在小于500mbar、优选50至150mbar的压力下于上述温度缩聚至80至30、优选40至30的酸值。合适的酯化催化剂有,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,所述缩聚也可在稀释剂和/或夹带剂——例如苯、甲苯、二甲苯或氯 苯——的存在下于液相中进行以共沸蒸除缩合的水。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的摩尔比缩聚。
优选地,所得聚酯多元醇的官能度为2至4、特别是2至3,且分子量为480至3000g/mol、优选1000至3000g/mol。
其他合适的具有至少两个对异氰酸酯具有活性的氢原子的相对高分子量化合物b)为经聚合物改性的多元醇,优选经聚合物改性的聚酯醇或聚醚醇,特别优选接枝聚醚醇或接枝聚酯醇,特别是接枝聚醚醇。通常,这些聚合物多元醇优选具有5至60重量%的热塑性聚合物,优选10至55重量%,特别优选30至55重量%,特别是40至50重量%。这些聚合物聚酯醇记载于例如WO 05/098763和EP-A-250351中,并通常通过使合适的烯烃单体——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——在用作接枝基础的聚酯醇中发生自由基聚合而制备。侧链通常通过自由基由生长中的聚合物链至聚酯醇或聚醚醇的转移而形成。所述聚合物多元醇不仅包括接枝共聚物,而且还主要包括分散于未改变的聚酯醇或聚醚醇中的烯烃的均聚物。
在一个优选的实施方案中,使用丙烯腈、苯乙烯、丙烯腈和苯乙烯作为单体,特别优选仅使用苯乙烯。如果合适,单体可在其他单体、大分子单体、调节剂、自由基引发剂——通常地偶氮化合物或过氧化物——的存在下于聚酯醇或聚醚醇中以连续相的形式聚合。所述方法记载于例如DE 111 394、US 3 304 273、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,大分子单体引入共聚物链中。这样形成具有聚酯或聚醚嵌段和聚丙烯腈-苯乙烯嵌段——其作为连续相和分散相界面处的相增容剂并抑制聚合物聚酯醇颗粒附聚——的嵌段共聚物。基于用于制备聚合物多元醇的单体的总重量,大分子单体的比例通常为1至20重量%。
如果相对高分子量化合物b)包括聚合物多元醇,则所述聚合物多元醇优选与其他多元醇一起存在,所述其他多元醇例如聚醚醇、聚酯醇或聚醚醇与聚酯醇的混合物。基于组分(b)的总重量,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,聚合物多元醇的含有量可例如为7至90重量%或11至80重量%。所述聚合物多元醇特别优选聚合物聚酯醇或聚合物聚醚醇。
此外,在制备聚氨酯整皮泡沫的过程中,存在发泡剂(c)。所述发泡剂c)可包括水。除水之外,还可使用公知的化学和/或物理作用的化合物作为发泡剂(c)。基于本发明的目的,化学发泡剂为能与异氰酸酯反应以形成气态产物的化合物,例如水或甲酸。物理发泡剂为能溶解或乳化于用于制备聚氨酯的起始物中、并在形成聚氨酯的条件下蒸发的化合物。此类发泡剂为,例如烃、卤代烃以及其他化合物,例如全氟烷烃如全氟己烷、含氯氟烃,及醚、酯、酮、缩醛,或其混合物,例如具有4至8个碳原子的(环状)脂族烃或含氯氟烃如购自SolvayFluorides LLC的 365mfc。在一个优选的实施方案中,使用含有至少一种所述发泡剂和水的混合物作为发泡剂。特别是,仅使用水作为发泡剂。如果不使用水作为发泡剂,则优选仅使用物理发泡剂。
在一个优选的实施方案中,基于所述组分(a)至(g)的总重量,含水量为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%、特别是0.4至1重量%。
在另一个优选的实施方案中,添加含有物理发泡剂的中空微球体作为组分(a)至(e)——和如果合适(f)和(g)——反应中的附加发泡剂。所述中空微球体还可以以与上述发泡剂的混合物的形式使用。
所述中空微球体通常包含热塑性聚合物的壳体,并且中心填充有基于烷烃的液态低沸点物质。所述中空微球体的制备方法记载于例如US 3 615 972中。中空微球体的直径通常为5至50μm。合适的中空微球体的实例可由Akzo Nobel以商标名 获得。
基于组分(b)、(c)和(d)的总重量,中空微球体的加入量通常为0.5至5重量%。
作为环己烷二羧酸二烷基酯d),优选使用1,2-环己烷二羧酸二烷基酯。环己烷二羧酸二烷基酯d)中的烷基优选为各自具有3至30个碳原子的饱和或不饱和、直链或支链的脂族或脂环族烃。如果合适,环己烷二羧酸二烷基酯中的烷基还可通过共价键结合。所述烷基特别 优选各自具有5至20个、更优选7至15个碳原子的饱和直链脂族烃。特别是,所述两个烷基具有相同的长度。例如,可使用1,2-环己烷二羧酸二壬基酯作为环己烷二羧酸二烷基酯。
基于组分a)至g)的总重量,环己烷二羧酸二烷基酯d)的用量优选为1至20重量%、特别优选2至15重量%、特别是3至10重量%。
所使用的增链剂和/或交联剂(e)为分子量优选小于500g/mol、特别优选为60至400g/mol的物质,其中增链剂具有两个对异氰酸酯具有活性的氢原子,且交联剂具有3个对异氰酸酯具有活性的氢原子。它们可单独使用,或优选以混合物的形式使用。优选使用分子量小于400、特别优选为60至300、特别是60至150的二元醇和/或三元醇。合适的增链剂/交联剂有,例如具有2至14、优选2至10个碳原子的脂族、脂环族和/或芳代脂肪族的二元醇,例如乙二醇、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、二甘醇、双丙甘醇,以及优选地1,4-丁二醇、1,6-己二醇和二(2-羟乙基)氢醌;三元醇,例如1,2,4-三羟基环己烷、1,3,5-三羟基环己烷、甘油和三羟甲基丙烷;以及基于环氧乙烷和/或1,2-环氧丙烷的低分子量的含羟基聚环氧烷和上述作为引子分子的二元醇和/或三元醇。特别优选使用的增链剂(c)为单乙二醇、1,4-丁二醇、甘油,或其混合物。
如果使用增链剂、交联剂或其混合物,则基于组分(b)和(e)的重量,它们的用量有利地为1至60重量%、优选1.5至50重量%、特别是2至40重量%。
作为用于制备聚氨酯泡沫的催化剂(f),优选使用能极大地促进组分(b)和如果合适(e)的含羟基化合物与任选改性的有机多异氰酸酯(a)的反应的化合物。可提及例如,脒,如2,3-二甲基-3,4,5,6-四氢嘧啶;叔胺,如三乙胺、三丁胺、二甲基苄基胺、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,以及优选地1,4-二氮杂双环-[2.2.2]辛烷;和链 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、及二甲基乙醇胺。也可使用有机金属化合物,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),以及有机羧酸的二烷基锡(Ⅳ)盐,如双乙酸二丁基锡、二月桂酸二丁基锡、马来酸二丁基锡和双乙酸二辛基锡;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。所述有机金属化合物可单独使用,或优选与强碱性胺结合使用。如果组分(b)为酯,则优选仅使用胺催化剂。
基于组分(b)的重量,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。
如果合适,也可向制备聚氨酯泡沫的反应混合物中加入助剂和/或添加剂(g)。可提及的有,例如表面活性物质、稳泡剂、泡孔调节剂、其他脱模剂、填充剂、染料、颜料、水解抑制剂、气味吸收物质以及抑制霉菌和/或抑制细菌的物质。
合适的表面活性物质例如为用于有助于起始物均化、并也可适用于调节泡孔结构的化合物。可提及例如,乳化剂,例如蓖麻油硫酸盐或脂肪酸的钠盐,以及胺的脂肪酸盐如油酸二乙胺、硬脂酸二乙醇胺、蓖麻醇酸二乙醇胺盐,磺酸的盐如十二烷基苯磺酸或二萘基甲烷二磺酸和蓖麻油酸的碱金属盐或铵盐;稳泡剂例如硅氧烷-氧杂亚烷基共聚物和其他有机聚硅氧烷、乙氧基化烷基酚、乙氧基化脂肪醇、石蜡油、蓖麻油或蓖麻油酯、土耳其红油和花生油;泡孔调节剂例如石蜡、脂肪醇和二甲基聚硅氧烷。具有聚亚氧烷基和氟代烷基作为侧基的低聚丙烯酸酯也适用于改善乳化作用、泡孔结构和/或稳定泡沫。表面活性物质的用量通常为0.01至5重量份/100重量份组分(b)。
合适的其他脱模剂有,例如:脂肪酸酯与多异氰酸酯的反应产物、含有氨基的聚硅氧烷的盐和脂肪酸的盐、具有至少8个碳原子的饱和或不饱和的(环状)脂族羧酸及叔胺的盐,以及特别是内脱模剂,例如通过使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与至少二官能度的分子量为60至400g/mol的烷醇胺、多元醇和/或多胺进行酯化或酰胺化而制得的羧酸酯和/或碳酰胺(carboxamide)(如例如EP 153 639中所公开的),有机胺、硬脂 酸和有机单羧酸和/或二羧酸或其酸酐的金属盐的混合物(如例如DE-A-3 607 447中所公开的),或亚氨化合物、羧酸的金属盐——和如果合适羧酸——的混合物(如例如US 4 764 537中所公开的)。本发明的反应混合物优选不包括任何其他脱模剂。
基于本发明的目的,填充剂——特别是增强填充剂——为本身已知的常规的有机和无机填充剂、增强材料、增重剂、涂层剂等。可提及的具体实例有:无机填充剂,例如,硅质矿物,例如页硅酸盐(sheetsilicate),如叶蛇纹石、膨润土、蛇纹石、角闪石、闪石、纤蛇纹石和滑石;金属氧化物,例如高岭土、铝氧化物、钛氧化物、锌氧化物和铁氧化物;金属盐,例如白垩和重晶石;以及无机颜料,例如硫化镉、硫化锌;以及玻璃等。优选使用高岭土(瓷土)、硅酸铝和硫酸钡与硅酸铝的共沉淀物,以及天然和合成的纤维状矿物例如硅灰石、金属丝和特别是各种长度的玻璃纤维,如果合适,其可被胶料涂覆。合适的有机填充剂有,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、基于芳香族和/或脂族二羧酸酯的聚酯纤维,以及特别是碳纤维。
无机填充剂和有机填充剂可单独使用,或以混合物形式使用,并可有利地基于组分(a)至(c)的重量以0.5至50重量%、优选1至40重量%的量加入反应混合物中,但天然和合成纤维的席纹布(matt)、无纺布和机织物的含量可最高达80重量%。
为了制备本发明的聚氨酯整皮泡沫,组分(a)至(g)以使多异氰酸酯(a)的NCO基团与组分(b)、(c)和(d)的活性氢原子的总和的当量比为1∶0.8至1∶1.25、优选1∶0.9至1∶1.15的量彼此混合。
本发明的聚氨酯整皮泡沫优选使用低压或高压技术通过一步法在封闭的、有利地加热的塑模中制备。所述塑模通常含有金属,例如铝或钢。这些方法记载于例如Piechota和 的“lntegralschaumstoff”,Carl-Hanser-Verlag,Munich,Vienna,1975或“Kunststoff-handbuch”,第7卷,Polyurethane,第3版,1993,第7章中。
为此,将起始组分(a)至(g)优选在15至90℃、特别优选25至55 ℃的温度下混合,并将反应混合物——如果合适在超级大气压下——引入封闭的塑模中。混合可使用搅拌器或搅拌螺杆(stirring screw)或在高压下以逆流注液法机械进行。塑模温度有利地为20至160℃,优选30至120℃,特别优选30至60℃。基于本发明的目的,以异氰酸酯基团计反应转化率小于90%的组分(a)至(g)的混合物被称为反应混合物。
计算引入塑模中的反应混合物的量,以使所得整皮泡沫模制品的密度优选为0.08至0.90g/cm3、特别优选0.15至0.80g/cm3、特别是0.25至0.70g/cm3。用于制备本发明聚氨酯整皮泡沫的密实度在1.1至8.5范围内,优选2.1至7.0。
本发明还提供一种可通过本发明方法获得的聚氨酯整皮泡沫。本发明的这种聚氨酯整皮泡沫优选用作鞋底,例如作为便鞋、运动鞋、凉鞋和靴的鞋底,以及作为例如车内的方向盘、头枕或传输旋钮或作为座椅臂靠用于道路车辆内件中。其他合适的用途是作为座椅的扶手或作为摩托车车座。本发明的聚氨酯整皮泡沫特别优选用作鞋底或用于机动车内件中。
本发明还提供f)中所述的环己烷二羧酸二烷基酯用作内脱模剂在制备聚氨酯整皮泡沫中的用途。
本发明在下文中通过实施例进行示例说明。
组分A和组分B如表1所示制备,然后以100的异氰酸酯指数彼此混合,并引入封闭的模塑中,从而得到平均密度为550g/l的模制品。
表1
C1 | C2 | C3 | C4 | 实施例1 | |
A组分 | |||||
多元醇1 | 79.47 | 86.47 | 88.47 | 82.47 | 86.47 |
单乙二醇 | 6.5 | 6.5 | 6.5 | 6.5 | 6.5 |
催化剂 | 1.7 | 1.7 | 1.7 | 1.7 | 1.7 |
抗静电剂 | 2 | 2 | 2 | 2 | 2 |
水 | 0.33 | 0.33 | 0.33 | 0.33 | 0.33 |
IMR 1 | 10 | 0 | 0 | 0 | 0 |
IMR 2 | 0 | 3 | 0 | 0 | 0 |
IMR 3 | 0 | 0 | 1 | 0 | 0 |
IMR 4 | 0 | 0 | 0 | 3 | 0 |
IMR 5 | 0 | 0 | 0 | 0 | 7 |
总A组分 | 100 | 100 | 100 | 100 | 100 |
B组分 (NCO含量=16%) | |||||
4,4-MDI | 49 | 49 | 49 | 49 | 49 |
经脲酮亚胺改性的 MDI | 4 | 4 | 4 | 4 | 4 |
多元醇2 | 29 | 29 | 29 | 29 | 29 |
多元醇3 | 10 | 10 | 10 | 10 | 10 |
γ-丁内酯 | 7 | 7 | 7 | 7 | 7 |
草酸二乙酯 | 1 | 1 | 1 | 1 | 1 |
总B组分 | 100 | 100 | 100 | 100 | 100 |
多元醇1:基于己二酸、单乙二醇和二甘醇的聚酯醇;重均分子量=2000g/mol
多元醇2:基于己二酸、单乙二醇和1,4-丁二醇的聚酯醇;重均分子量=2000g/mol
多元醇3:基于己二酸、单乙二醇和三羟甲基丙烷的聚酯醇;重均分子量=2500g/mol
催化剂:33重量%的于单乙二醇中的四亚乙基二胺(tetraethylenediamine)
抗静电剂:单乙二醇中的铵盐
IMR1:购自Oleon的内脱模剂 7171,油酸和季戊四醇的酯,推荐添加:A组分的8至12重量%
IMR2:内脱模剂,油酸和脂族胺的酰胺,推荐添加:A组分的2至4重量%
IMR4:环氧化豆油,推荐添加:A组分的2至4重量%
将以此方式获得的聚氨酯整皮泡沫在70℃和95%的相对湿度条 件下水解老化7天,并在此之前和之后均根据DIN 53505测定整皮泡沫的硬度并根据DIN 53504测定其拉伸强度和断裂伸长率。所得数据和泡沫中心的泡孔结构以及在不进一步添加外脱模剂的情况下脱模的最大数记于表2中。为进行所述测定,将内脱模剂一次性引入一个清洁的塑模中。然后在不进一步添加外脱模剂的情况下制备测试板,并测定在没有粘性的条件下可能制备的测试板的数目。
表2
C1 | C2 | C3 | C4 | 实施例1 | |
硬度(Shore A) | 43 | 43 | 不可测 | 42 | 45 |
水解后的硬度 | 41 | 35 | 不可测 | 40 | 44 |
不可测 | |||||
拉伸强度[N/mm2] | 5 | 5.2 | 不可测 | 4.8 | 5.4 |
水解后的拉伸强度 [N/mm2] | 5.5 | 3.5 | 不可测 | 4.5 | 6.4 |
不可测 | |||||
断裂伸长率[%] | 470 | 480 | 不可测 | 370 | 490 |
水解后的断裂伸长率 [%] | 520 | 370 | 不可测 | 420 | 532 |
泡孔结构 | 粗糙 | 精细 | 极粗糙,差的结 皮 | 精 细 | 精细,极 均一 |
脱模最大值 | 4 | 2 | 2 | 1 | 4 |
当使用硅氧烷作为脱模剂时,泡沫的机械性能由于差的泡沫结构而无法确定。使用环氧化豆油作为脱模剂制备的泡沫确实显示出所需的精细泡孔结构,但在使用该内脱模剂而不使用其他外部脱模剂的情况下脱模数仅为1,并且所得的模制品是脆的。这特别是可通过较差的拉伸强度和断裂伸长率的值而明显地看出。油酸和季戊四醇的酯在水解老化之前和之后均显示出可接受的机械值,但具有不想要的粗糙泡孔结构。使用由油酸和脂族胺衍生得到的酰胺作为内脱模剂导致模制品在水解老化后具有极差的机械性能。当使用环己烷二羧酸二异壬基酯作为内脱模剂时,获得水解老化前后泡孔结构都极精细均一且机械性能优良的模制品。此外,环己烷二羧酸二异壬基酯表现出极好的脱模性。
Claims (5)
1.一种制备聚氨酯整皮泡沫的方法,其中
将以下物质混合以形成一种反应混合物:
a)有机多异氰酸酯;
b)具有至少两个活性氢原子的相对高分子量化合物,选自聚醚醇、聚酯醇、经聚合物改性的聚醚醇或经聚合物改性的聚酯醇;
c)发泡剂;
d)1,2-环己烷二羧酸二烷基酯,其中所述环己烷二羧酸二烷基酯中的烷基各自包括3至30个碳原子;以及如果合适,
e)增链剂和/或交联剂,
f)催化剂,以及
g)其他助剂和/或添加剂;
将所述反应混合物引入一个塑模中并使其反应,以形成一种聚氨酯整皮泡沫。
2.一种通过权利要求1的方法获得的聚氨酯整皮泡沫。
3.权利要求2的聚氨酯整皮泡沫用于道路车辆内件中的用途。
4.权利要求2的聚氨酯整皮泡沫用作鞋底的用途。
5.1,2-环己烷二羧酸二烷基酯用作脱模剂在聚氨酯整皮泡沫中的用途,其中所述环己烷二羧酸二烷基酯中的烷基各自包括3至30个碳原子。
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JP2005320407A (ja) * | 2004-05-07 | 2005-11-17 | Dainippon Ink & Chem Inc | (メタ)アクリル系樹脂ペースト及び成形物 |
DE102004029732A1 (de) * | 2004-06-21 | 2006-01-19 | Basf Ag | Hilfsmittel enthaltend Cyclohexanpolycarbonsäurederivate |
JP2006063102A (ja) * | 2004-08-24 | 2006-03-09 | Kobayashi Kk | スラッシュ成形、回転成形またはディップ成形用のプラスチゾル組成物 |
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2008
- 2008-11-25 EP EP08855271A patent/EP2215138B1/de not_active Not-in-force
- 2008-11-25 US US12/742,267 patent/US8148437B2/en not_active Expired - Fee Related
- 2008-11-25 CN CN200880117750.XA patent/CN101874051B/zh not_active Expired - Fee Related
- 2008-11-25 KR KR1020107014207A patent/KR101554757B1/ko not_active IP Right Cessation
- 2008-11-25 JP JP2010534499A patent/JP5414686B2/ja not_active Expired - Fee Related
- 2008-11-25 ES ES08855271T patent/ES2406688T3/es active Active
- 2008-11-25 WO PCT/EP2008/066119 patent/WO2009068515A1/de active Application Filing
- 2008-11-25 PT PT88552716T patent/PT2215138E/pt unknown
- 2008-11-25 BR BRPI0820314-8A patent/BRPI0820314A2/pt not_active IP Right Cessation
Patent Citations (2)
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US4487852A (en) * | 1983-10-25 | 1984-12-11 | Texaco Inc. | Modified Mannich condensates and manufacture of rigid polyurethane foam with alkoxylation products thereof |
EP0297519A1 (en) * | 1987-07-01 | 1989-01-04 | BASF Corporation | Process for the preparation of integral skin polyurethane steering wheels |
Also Published As
Publication number | Publication date |
---|---|
US8148437B2 (en) | 2012-04-03 |
KR101554757B1 (ko) | 2015-09-21 |
WO2009068515A1 (de) | 2009-06-04 |
EP2215138A1 (de) | 2010-08-11 |
ES2406688T3 (es) | 2013-06-07 |
JP5414686B2 (ja) | 2014-02-12 |
EP2215138B1 (de) | 2013-03-13 |
US20100286297A1 (en) | 2010-11-11 |
JP2011505443A (ja) | 2011-02-24 |
BRPI0820314A2 (pt) | 2015-05-26 |
CN101874051A (zh) | 2010-10-27 |
KR20100119748A (ko) | 2010-11-10 |
PT2215138E (pt) | 2013-05-07 |
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