CN114127207A - 多元醇酯和阳离子聚电解质在水性聚氨酯分散体中的组合用途 - Google Patents
多元醇酯和阳离子聚电解质在水性聚氨酯分散体中的组合用途 Download PDFInfo
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- CN114127207A CN114127207A CN201980098518.4A CN201980098518A CN114127207A CN 114127207 A CN114127207 A CN 114127207A CN 201980098518 A CN201980098518 A CN 201980098518A CN 114127207 A CN114127207 A CN 114127207A
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- acid
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Abstract
本发明提供了多元醇酯和阳离子聚电解质在含有助表面活性剂的水性聚合物分散体中作为添加剂用于制备多孔聚合物涂层、优选地用于制备多孔聚氨酯涂层的组合用途。
Description
技术领域
本发明属于塑料涂层和合成皮革领域。
本发明更特别地涉及通过多元醇酯和阳离子聚电解质作为添加剂的组合使用来制备多孔聚合物涂层,特别地制备多孔聚氨酯涂层。
背景技术
涂有塑料的纺织品,例如合成皮革,通常由织物载体组成,在该载体上层压了多孔聚合物层,该聚合物层依次涂有顶层或面漆。
所述多孔聚合物层在此上下文中优选地具有在微米范围的孔,且是空气可渗透的,而因此是透气的,即水蒸气可渗透的,但是防水的。所述多孔聚合物层通常包含多孔聚氨酯。目前,通常采用凝结法制备多孔聚氨酯层,其中DMF用作溶剂。然而,由于环境问题,这种制备方法正被越来越多地批评,因此它将逐渐被其他更环保的技术所取代。这些技术中的一项是基于水性聚氨酯分散体,被称为PUD。这些分散体通常由分散在水中的聚氨酯微粒组成;其固体含量通常在30-60重量%。为了多孔聚氨酯层的制备,这些PUD被机械地发泡,被涂布到载体上(层厚度通常在300-2000μm之间),然后在高温下干燥。在此干燥步骤中,存在于PUD体系的水蒸发了,这实现了所述聚氨酯颗粒的膜的形成。为了进一步提高所述膜的机械强度,另外可以在制备过程期间将亲水性(多)异氰酸酯加入到PUD体系中,而这些亲水性(多)异氰酸酯可以在所述干燥步骤与存在于聚氨酯颗粒表面的OH基团反应,从而实现了所述聚氨酯膜的额外的交联。
如此制备的PUD涂层的机械和触觉性能在很大程度上取决于所述多孔聚氨酯膜的泡孔结构。此外,所述多孔聚氨酯膜的泡孔结构影响了所述材料的空气可渗透性和透气性。在这里可以通过非常细小的、均匀分布的泡孔来达到特别好的性能。在上述制备过程期间影响所述泡孔结构的常用方法是在所述机械发泡之前或期间将泡沫稳定剂添加到PUD体系中。合适的稳定剂的第一个效果是在所述发泡操作过程期间可以将足够量的空气搅打到所述PUD系统。其次,所述泡沫稳定剂对产生的气泡的形态具有直接的影响。所述气泡的稳定性还在很大程度上受稳定剂类型的影响。这在发泡的PUD涂层的干燥过程期间是特别地重要,因为可以用这种方式来预防干燥缺陷如泡孔粗化或干燥裂纹。
在过去,多元醇酯已被确定为用于机械发泡的PUD体系特别有效的稳定剂;参见,例如,EP 3487945。然而,多元醇酯的一个缺点是,所述PUD体系中的其它的助表面活性剂、特别地阴离子助表面活性剂的存在可以损害多元醇酯的泡沫稳定效果。然而,特别地在水性聚氨酯分散体的制备中,助表面活性剂的使用非常普遍。在这个背景下,助表面活性剂是用于聚氨酯预聚物在水中的改良的分散,且通常保留在最终产品中。在所述聚氨酯分散体的机械发泡过程中,相应的助表面活性剂可以对所述体系的发泡特性产生不利影响,尤其地当将多元醇酯用作泡沫稳定时。因此,这对于只有很少的空气,如果有的话,通常可以被搅打进所述体系;所得泡沫结构是粗糙且不规则的。助表面活性剂还会对所制备的泡沫的稳定性产生不利影响,这会导致在所述发泡的PUD体系的加工过程中出现泡沫老化,进而导致所制备的泡沫涂层的瑕疵和缺陷。
因此,本发明解决的问题是提供用于基于PUD的泡沫体系和泡沫涂层的制备的添加剂,即使在含有助表面活性剂、尤其地阴离子助表面活性剂的PUD体系中,它也能够实现有效的发泡和有效的泡沫稳定。
发明内容
已出人意料地发现,多元醇酯与阳离子聚电解质的组合使用能够实现所述问题的解决方案。
本发明因此提供了多元醇酯和阳离子聚电解质作为添加剂的组合用途,优选地在水性聚合物分散体中,优选地在水性聚氨酯分散体中,特别优选地在含有助表面活性剂,特别地含有阴离子助表面活性剂的PUD体系中作为泡沫添加剂。
根据本发明的多元醇酯和阳离子聚电解质的组合用途在这里出人意料地具有多方面优点。
这里的一个优点是本发明的多元醇酯和阳离子聚电解质的联合使用能够实现聚氨酯分散体的有效发泡,即使当助表面活性剂另外地存在于分散体系中。如此制备的泡沫另外显著地是具有特别均匀的泡孔分布的异常精细的孔结构,这进而对基于这些泡沫所制备的多孔聚合物涂层的机械和触觉性能具有非常有利的影响。此外,可以以这种方式改善所述涂层的空气渗透性或透气性。
进一步的优点是本发明的多元醇酯和阳离子聚电解质的联合使用能够实现制备特别稳定的泡沫,即使当助表面活性剂另外存在于所述PUD体系中时。这首先对如此制备的泡沫的可加工性具有有利的影响。其次,所述提高的泡沫稳定性具有以下优点,在相应泡沫的干燥过程期间,可以避免干燥缺陷如泡孔粗化或干燥裂纹。此外,所述改进的泡沫稳定性能够实现所述泡沫的更快的干燥,从环境的和经济的两个角度来看,这都提供了加工优势。
在文献WO 2018/015260 A1中已经详细描述了多元醇酯在水性聚合物分散体中作为泡沫添加剂的用途。对于本发明上下文中的多元醇酯的进一步描述,引用该文献全文。
在本发明的整个范围内,所述术语“多元醇酯”,还包括它的烷氧基化的加合物,其可以通过多元醇酯与环氧烷,例如环氧乙烷、环氧丙烷和/或环氧丁烷的反应得到。
在本发明的整个范围内,所述术语“多元醇酯”,还包括它的离子衍生物,优选地磷酸化的和硫酸化的衍生物,特别地磷酸化的多元醇酯。所述多元醇酯的这些衍生物,特别地磷酸化的多元醇酯,是根据本发明优选适用的多元醇酯。下文进一步详细描述了所述多元醇酯的这些和其他的衍生物,并且是优选适用于本发明中。
在本发明的整个范围内,所述术语“助表面活性剂”,包括其它的表面活性剂,其可以与根据本发明的多元醇酯一起存在于所述聚合物分散体中。这些特别地包括在所述聚合物分散体的制备过程期间所使用的表面活性剂。例如,聚氨酯分散体通常是通过PU预聚物的合成而制备的,该预聚物在第二步中被分散在水中,然后与扩链剂反应。为了所述预聚物在水中的改进的分散,在这里可以使用助表面活性剂。在本发明中,所述助表面活性剂优选地是阴离子助表面活性剂。
在本发明的整个范围内,所述术语“阳离子聚电解质”包括带有通过接受质子变为阳离子的阳离子基团或碱性基团的水溶性聚合物。在本文中,“水溶性”是指所述聚合物在25℃的温度下具有至少1重量%,优选地至少5重量%,更优选地至少10重量%的水溶解度。此处应做出永久性聚电解质和弱聚电解质的区分,前者不论水溶液中的pH都带有阳离子电荷,后者的电荷状态取决于水溶液的pH。这里的聚电解质可以是均聚物,即仅具有一种重复单元的聚合物,或共聚物,即由至少两种不同的重复单元形成的聚合物。如果聚电解质是共聚物,那么它们可具有统计的或有序的结构(作为嵌段共聚物)或梯度分布。
本发明在下文中通过实施例的方式进一步被描述,但无意将本发明限制于这些说明性实施方案。在下文中指定化合物的范围、通式或类别的情况下,这些是意在不仅包括被明确地提及的化合物的相应范围或组,还包括通过去除个别的值(范围)或化合物可得到的化合物的所有子范围和子组。当在本说明书的上下文中引用文献时,它们的内容,特别地与构成了引用该文献的上下文的主题相关的内容,从它们的整体上被认为构成了本发明的公开内容的一部分。除非另有说明,百分比是重量百分比的数字。当在下面报告通过测量确定的参数时,测量是在25℃的温度下和101 325Pa的压力下进行的,除非另有说明。在本发明中使用化学(经验)式的情况下,所指定的指数不仅可以是绝对数,还可以是平均值。与聚合物相关的指数优选地是平均值。在本发明中呈现的结构和经验式是代表性的通过所述重复单元的不同排列的所有可行的异构体。
在本发明的上下文中,优选的多元醇酯是通过多元醇与至少一种羧酸的酯化可得到的那些多元醇酯。这对应于本发明的优选实施方案。
根据本发明用于所述多元醇酯的制备的优选的多元醇选自C3-C8多元醇和它们的低聚物和/或共聚低聚物。共聚低聚物由不同的多元醇的反应产生,例如由丙二醇与阿拉伯醇的反应。此处特别优选的多元醇是丙烷-1,3-二醇、丙二醇、甘油、三羟甲基乙烷、三羟甲基丙烷、脱水山梨糖醇、山梨糖醇、异山梨醇、赤藓糖醇、苏糖醇、季戊四醇、阿拉伯糖醇、木糖醇、核糖醇、岩藻糖醇、甘露糖醇、半乳糖醇、艾杜糖醇、肌醇、庚七醇和葡萄糖。非常特别的优选是甘油。优选的多元醇低聚物是具有1-20个、优选地2-10个和更优选地2.5-8个重复单元的C3-C8多元醇的低聚物。这里特别地优选的是二聚甘油、三聚甘油、四聚甘油、五聚甘油、二聚赤藓糖醇、三聚赤藓糖醇、四聚赤藓糖醇、二(三羟甲基丙烷)、三(三羟甲基丙烷)和二糖和寡糖。非常特别优选脱水山梨糖醇和低聚甘油和/或多聚甘油。特别地,可以使用不同多元醇的混合物。此外,还可以使用C3-C8多元醇、它们的低聚物和/或它们的共聚低聚物的烷氧基化的加合物用于根据本发明的多元醇酯的制备,该加合物可以通过C3-C8多元醇、它们的低聚物和/或共聚低聚物与环氧烷,例如环氧乙烷、环氧丙烷和/或环氧丁烷的反应得到。
为了制备根据本发明的多元醇酯,可以使用单羧酸和/或多官能的二-和/或三羧酸。为了制备根据本发明的多元醇酯,所使用的优选的羧酸符合通式RC(O)OH,其中R是具有3至39个碳原子、优选地具有7至21个碳原子、更优选地具有9到17个碳原子的一价脂肪族饱和的或不饱和的烃基。此处特别优选的羧酸选自以下羧酸:酪酸(丁酸)、羊油酸(己酸)、羊脂酸(辛酸)、羊蜡酸(癸酸)、月桂酸(十二烷酸)、肉豆蔻酸(十四烷酸)、棕榈酸(十六烷酸)、硬脂酸(十八烷酸)、花生酸(二十烷酸)、山萮酸(二十二烷酸)、木蜡酸(二十四烷酸)、棕榈烯酸((Z)-9-十六碳烯酸)、油酸((Z)-9-十六碳烯酸)、反油酸((E)-9-十八碳烯酸)、顺式异油酸((Z)-11-十八碳烯酸)、亚油酸((9Z,12Z)-9,12-十八碳二烯酸)、α-亚麻酸((9Z,12Z,15Z)-9,12,15-十八碳三烯酸)、γ-亚麻酸((6Z,9Z,12Z)-6,9,12-十八碳三烯酸)、二高-γ-亚麻酸((8Z,11Z,14Z)-8,11,14-二十碳三烯酸)、花生四烯酸((5Z,8Z,11Z,14Z)-5,8,11,14-二十碳四烯酸)、芥酸((Z)-13-二十二碳烯酸)、神经酸((Z)-15-二十四碳烯酸)、蓖麻油酸、羟基硬脂酸和十一碳烯酸,以及它们的混合物,例如菜籽油酸、大豆脂肪酸、向日葵脂肪酸、花生脂肪酸和/或松浆油脂肪酸。非常特别优选棕榈酸和硬脂酸,并且特别是这些物质的混合物。
合适的脂肪酸或脂肪酸酯、特别合适的甘油酯的来源可以是植物的或动物的脂肪、油和蜡。例如,可以使用:猪油、牛脂、鹅脂、鸭脂、鸡脂、马脂、鲸油、鱼油、棕榈油、橄榄油、鳄梨油、谷仁油、椰子油、棕榈核油、可可脂、棉子油、南瓜籽油、玉米粒油、向日葵油、麦胚油、葡萄籽油、芝麻油、亚麻籽油、大豆油、花生油、羽扇豆油、菜籽油、芥子油、蓖麻油、麻疯树油、核桃油、霍霍巴油、卵磷脂,例如基于大豆、菜籽或向日葵的卵磷脂,骨油、牛蹄油、琉璃苣油、羊毛脂、鸸鹋油、鹿脂、土拨鼠油、貂油、红花油、大麻油、南瓜油、月见草油、妥尔油,而且和巴西棕榈蜡、蜂蜡、小烛树蜡、小冠椰子蜡、甘蔗蜡、蔓藤(retamo)蜡、棕榈蜡、酒椰蜡、西班牙草蜡、苜蓿蜡、竹蜡、大麻蜡、花旗松蜡、软木蜡、剑麻蜡、亚麻蜡、棉蜡、达玛蜡、茶蜡、咖啡蜡、米蜡、欧夹竹桃蜡或羊毛蜡。
此外,可有利的是使用多官能的二元羧酸和三元羧酸或它们的环状酸酐来制备根据本发明的多元醇酯,通过这种方法多元醇多酯是可得到的。四官能的羧酸和更高官能的羧酸或它们的酸酐在本发明的上下文中同样是优选适用的。优选的羧酸是具有2至18个碳原子的链长的脂肪族线性的或枝化的二元羧酸和/或三元羧酸,和/或通过具有12至22个碳原子的不饱和脂肪酸的催化二聚所得到的二聚体脂肪酸。相应的多官能的酸的实例是草酸、丙二酸、琥珀酸、戊二酸、己二酸、庚二酸、辛二酸、壬二酸、癸二酸、巴西基酸、十六碳二酸、丙醇二酸、酒石酸、苹果酸或柠檬酸。特别优选地,如上所述,多官能的二元羧酸和三元羧酸与单官能的羧酸组合使用,通过这种方式部分交联的多元醇酯是可得到的。
在本发明的一个特别优选的实施方案中,所述多元醇酯选自脱水山梨糖醇酯和/或聚甘油酯。非常特别优选聚甘油酯,特别是聚甘油棕榈酸酯和聚甘油硬脂酸酯以及这些物质的混合物。
这里特别优选的是符合通式1的聚甘油酯:
MaDbTc 式1
其中
M=[C3H5(OR1)2O1/2]
D=[C3H5(OR1)1O2/2]
T=[C3H5O3/2]
a=1至10,优选地2至3,特别优选地2,
b=0至10,优选地大于0至5,特别优选地1至4,
c=0至3,优选地为0,
其中R1基团独立地是相同或不同的R2-C(O)-形式的基团或H,
其中R2是具有3至39个碳原子、优选地具有7至21个碳原子、更优选地具有9至17个碳原子的一价脂肪族饱和的或不饱和的烃基,
其中至少一个R1基团对应于所述R2-C(O)-形式的基团。
结构单元M、D和T在每种情况下在此通过氧桥连接。两个O1/2基团总是在这里连接以形成氧桥(-O-),其中任何O1/2基团只可连接到另外一个O1/2基团。
甚至更优选的是对应于通式2的聚甘油酯:
MxDyTz 式2
其中
x=1至10,优选地2至3,特别优选地2,
y=0至10,优选地大于0至5,特别优选地1至4,
z=0至3,优选地大于0至2,特别优选地0,
条件是至少一个R1基团不是氢,R1仍然如式1中所定义。
进一步优选的是通式3的聚甘油酯:
其中
k=1至10,优选地2至3,特别优选地2,
m=0至10,优选地大于0至5,特别优选地1至3,
条件是所述R1基团中至少一个不是氢,R1仍然如式1中所定义,并且k+m的总和大于零,并且具有所述下标k和m的片段是统计分布的。
在本发明的上下文中,所述术语“聚甘油”特别地是被理解为还可以含有甘油的聚甘油。因此,为了计算数量、质量和其类似的目的,还应考虑任何甘油的分数。在本发明的上下文中,聚甘油因此也是包含至少一种甘油低聚物和甘油的混合物。甘油低聚物在每种情况下都应理解为是指所有相关的结构,即例如,线性的、枝化的和环状的化合物。
统计分布是由具有任何理想的数目的嵌段和任何理想的顺序或随机分布的嵌段组成;它们也可以具有交替的结构,或者沿着所述链形成梯度;特别地,它们还可以构成任何的混合形式,其中不同分布的组可以任选地相互跟随。特定的实施方案可导致对所述统计分布的限制以作为所述实施方案的结果。在对于所有区域的统计分布内没有变化,不受所述限制影响。
优选地,根据本发明所述适用的聚甘油酯具有不超过5个、更优选地不超过4个和甚至进一步优选地不超过3个所述R2-C(O)-形式的R1基团。特别地,所述R1基团选自如上所述的羧酸。
在本发明的一个同样优选的实施方案中,在水性聚合物分散体中用作添加剂的聚甘油酯是通过用至少一种如上所述的聚甘油与至少一种如上所述的羧酸的反应可得到的那些聚甘油酯。该反应的合适的反应条件是优选地在200和260℃之间的温度和优选地在20-800mbar之间、优选地在50和500mbar之间的降低的压力,这能够实现水的更容易的去除。
在结构方面,多元醇酯可以通过湿化学指数来表征,例如它们的羟值、它们的酸值和它们的水解值。测定羟值的合适方法特别地是根据DGF C-V 17a(53)、Ph.Eur.2.5.3方法A和DIN 53240的那些方法。测定酸值的合适方法特别地是根据DGF C-V 2,DIN EN ISO2114、Ph.Eur.2.5.1、ISO 3682和ASTM D 974的那些方法。测定水解值的合适方法特别地是根据DGF C-V 3、DIN EN ISO 3681和Ph.Eur.2.5.6的那些方法。
根据本发明优选的且对应于本发明的一个特别优选的实施方案的是,为了所述聚甘油酯的制备,使用具有平均缩合度1-20、优选地2-10和更优选地2.5-8的聚甘油。在此可基于所述聚甘油的OH值(OHN,以mg KOH/g为单位)来测定平均缩合度N,而其中根据以下公式关联:
所述聚甘油的OH值在此可以如上所述来测定。因此,为了根据本发明的聚甘油酯的制备,优选的聚甘油特别地是具有1829至824、更优选地1352-888和特别优选地1244-920mg KOH/g的OH值的那些。
此处可以通过不同的常规方法来提供所使用的聚甘油,例如缩水甘油的聚合(例如碱催化)、表氯醇的聚合(例如在碱例如NaOH的存在下)或甘油的缩聚。根据本发明,优选是通过甘油的缩合而提供聚甘油,特别地在催化量的碱,特别地NaOH或KOH的存在下。合适的反应条件是200和260℃之间的温度和20和800mbar之间、特别地50和500mbar之间的降低的压力,这能够实现水的更容易的去除。此外,可从例如Solvay、Innovyn、Daicel和SpigaNord S.p.A.得到各种商业聚甘油。
聚甘油和羧酸,特别是脂肪酸和/或脂肪酸酯(如甘油三酯)的反应,和聚甘油的提供,都可以通过本领域技术人员熟悉的广泛使用的方法来实现。相应的方法在例如Chemie Lexikon[的化学词典](Thieme-Verlag,1996)中有所描述。
本发明中优选的脱水山梨糖醇酯是那些通过山梨糖醇或山梨糖醇水溶液与上述的至少一种羧酸在200-260℃的温度下、任选地在合适的催化剂的存在下,反应可得到的那些脱水山梨糖醇酯,主要得到1,4和1,5脱水山梨糖醇酯的混合物。相应的方法在例如Chemie Lexikon(Thieme-Verlag,1996)中有所描述。
已经清楚的是,在本发明的整个范围内,所述术语“多元醇酯”还包括它们的离子衍生物,优选地它们的磷酸化和硫酸化的衍生物,特别地磷酸化的多元醇酯。磷酸化的多元醇酯可通过所述多元醇酯与磷酸化试剂的反应和任选的、优选地强制的随后的中和得到(特别参阅Industrial Applications of Surfactants.II.Preparation and IndustrialApplications of Phosphate Esters.Edited by D.R.Karsa,Royal Society ofChemistry,Cambridge,1990)。本发明上下文中优选的磷酸化试剂是三氯氧化磷、五氧化二磷(P4O10),更优选地多磷酸。在本发明整个范围内内,所述术语“磷酸化的多元醇酯”也涵盖部分地磷酸化的多元醇酯,和在本发明整个范围内,所述术语“硫酸化的多元醇酯”同样也涵盖部分地硫酸化的多元醇酯。
此外,在本发明的整个范围内,所述多元醇酯的离子衍生物也可以是通过所述多元醇酯与二元或三元羧酸或相应的环状酸酐、更优选地与琥珀酸酐反应和任选存在的、优选地强制的中和得到。在本发明的背景下,这些多元醇酯是特别优选适用的。
此外,在本发明的整个范围内,所述多元醇酯的离子衍生物也可以是通过所述多元醇酯与不饱和的二元或三元羧酸或相应的环状酸酐的反应和随后的磺化和任选存在的、优选地强制的中和得到。在本发明的背景下,这些多元醇酯也是特别优选适用的。
在本发明的整个范围内,所述术语“中和”也涵盖部分的中和。对于中和,包括部分的中和,可以使用常规碱。这些包括水溶性金属氢氧化物,例如氢氧化钡、氢氧化锶、氢氧化钙、氢氧化铊(I)和优选地碱金属氢氧化物,该碱金属氢氧化物在水溶液中离解成游离的金属离子和氢氧根离子,特别地NaOH和KOH。这些还包括与水反应形成氢氧根离子的脱水碱,例如氧化钡、氧化锶、氧化钙、氧化锂、氧化银和氨。除了上述这些碱之外,可用作碱的固体物质还有同样在没有HO-(在所述固体化合物中)的情况下,在溶解于水中时发生碱性反应的那些;这些的实例包括胺,例如单、二和三烷基胺,其也可以是官能化的烷基,例如在酰胺胺的情况下,单、二和三烷醇胺,单、二和三氨基烷基胺,和例如弱酸的盐类,如氰化钾、碳酸钾、碳酸钠、磷酸三钠等。
关于根据本发明的多元醇酯的离子衍生物,特别优选磷酸化的脱水山梨醇酯和/或磷酸化的聚甘油酯,特别是磷酸化的聚甘油酯。更特别地,在本发明的范围内,磷酸化的和中和的聚甘油硬脂酸酯和聚甘油棕榈酸酯以及这两种物质的混合物是优选的多元醇酯的离子衍生物。
本发明的一个特别优选的实施方案设想了如上文所述,式1、2和/或3的多元醇酯的根据本发明的用途,其额外的附带条件是它们已经(至少部分地)被磷酸化,使得所述式1、2和/或3的这些多元醇酯,特别地带有至少一个(R3O)2P(O)-基团作为所述R1基团。其中所述R3基团独立地是阳离子,优选地是Na+、K+或NH4+,或单-、二-和三烷基胺的铵离子,其中的烷基也可以是官能化的烷基,例如在酰胺胺的情况下,单-、二-和三烷醇胺的铵离子,单-、二-和三氨基烷基胺的铵离子,或H或R4-O-,
其中R4是具有3至39个碳原子,优选地7至22个和更优选地具有9至18个碳原子的一价脂肪族饱和或不饱和的烃基或多元醇基团。
在硫酸化的多元醇酯的情况下,特别优选可通过多元醇酯与三氧化硫或氨基磺酸反应获得的那些。在此优选硫酸化的脱水山梨糖醇酯和/或硫酸化的聚甘油酯,特别是硫酸化的聚甘油硬脂酸酯和硫酸化的聚甘油棕榈酸酯以及这两种物质的混合物。
在本发明的上下文中,也优选的是与多元醇酯组合使用的阳离子聚电解质是聚乙烯亚胺和它的缩合产物;含有精氨酸和/或组氨酸的肽和聚酰胺;胺-和胍-官能的硅氧烷;和以下物质的(共)聚合物:烯丙胺、二烯丙胺、它们的烷基衍生物和季铵化产物,特别是二烯丙基二甲基氯化铵,乙烯基胺、二乙烯基胺、乙烯基吡啶和它们的季铵化产物,乙烯基咪唑、它们的烷基衍生物和季铵化产物,烯键式不饱和羧酸与氨基醇的酯,烯键式不饱和羧酸与N,N-二烷基氨基烷基胺的酰胺和这些物质的混合物。此处非常特别的优选是基于乙烯基胺的(共)聚合物。
在本发明的上下文中,还特别优选的是所述阳离子聚电解质是具有至少一个如下式4的重复单元A和任选地具有至少一个如下式5的重复单元B的聚合物:
其中R5和R6基团独立地是相同或不同的具有1至10个碳原子,优选地1至10个,更优选地具有1至5个碳原子的一价脂肪族或芳香族、饱和或不饱和的烃基、或H,更优选是H。
根据本发明,此处优选的是所述重复单元A是以至少50摩尔%、优选地至少60摩尔%、更优选地至少70摩尔%、甚至更优选地至少80摩尔%、甚至更优选地至少90摩尔%、最优选达到100摩尔%的程度存在于聚合物中。
根据本发明,优选的所述重复单元A和B的聚合物可以通过N-乙烯基羧酰胺的自由基聚合和随后的所述酰胺官能团到胺官能团的完全或部分的水解来制备。此处所述水解可在酸性或碱性条件下实现。此处优选的N-乙烯基羧酰胺是N-乙烯基甲酰胺、N-乙烯基-N-甲基甲酰胺、N-乙烯基-N-乙基甲酰胺、N-乙烯基-N-丙基甲酰胺、N-乙烯基-N-异丙基甲酰胺、N-乙烯基-N-丁基甲酰胺、N-乙烯基-N-异丁基甲酰胺、N-乙烯基乙酰胺、N-乙烯基-N-甲基乙酰胺、N-乙烯基-N-乙基乙酰胺、N-乙烯基-N-丙基乙酰胺、N-乙烯基-N-异丙基乙酰胺、N-乙烯基-N-丁基乙酰胺、N-乙烯基-N-异丁基乙酰胺、N-乙烯基丙酰胺、N-乙烯基甲基丙酰胺、N-乙烯基-N-乙基丙酰胺、N-乙烯基-N-丙基丙酰胺和这些物质的混合物,特别的优选是N-乙烯基甲酰胺。
其它的单烯键式不饱和共聚单体或共聚单体的混合物可以和所述重复单元A和B一起被任选地加入到根据本发明优选的聚合物中,从而得到进一步改性的聚合物。这些可以是非离子、阳离子或阴离子单体。此处优选的非离子共聚单体是:不饱和醇,例如乙烯醇或烯丙醇和它们的烷氧基化物;不饱和腈;脂肪族或芳香族烯烃;N-乙烯基内酰胺,例如N-乙烯基吡咯烷酮或N-乙烯基己内酰胺;有机羧酸的乙烯基酯;单烯键式不饱和羧酸的酯;和单烯键式不饱和羧酸的酰胺。优选的阳离子共聚单体是乙烯基咪唑和含有乙烯基咪唑单元的单体、它们的烷基衍生物和季铵化产物;乙烯基吡啶和它们的季铵化产物;烯键式不饱和羧酸与氨基醇的碱性酯;和烯键式不饱和羧酸与N,N-二烷基氨基烷基胺的碱性酰胺。优选的阴离子共聚单体是α,β-不饱和单羧酸、不饱和二羧酸和不饱和二羧酸的偏酯。
在含有共聚单体的聚合物的情况下,此处优选的是所述共聚单体基于所述聚合物的整体组合物以0.1-50摩尔%,优选地0.5-25摩尔%,更优选地1-15摩尔%的浓度被使用。
在本发明的上下文中,特别优选的阳离子聚电解质是具有平均摩尔质量为1000-500 000g/mol、优选地5000-250 000g/mol、更优选地10 000-100000g/mol的那些。此处所述聚电解质的摩尔质量可以通过本领域技术人员已知的方法确定,例如特别地通过凝胶渗透色谱法(GPC)。
在具有依赖于pH的离解度的阳离子聚电解质的情况下,本发明的另外的优选的实施方案是通过添加酸,例如盐酸、乳酸、柠檬酸或硫酸来调节这些化合物的离解度和从而调节它们的阳离子特性。
如已经描述的,本发明设想了如上所述的多元醇酯和阳离子聚电解质在水性聚合物分散体中、优选地水性聚氨酯分散体中作为添加剂的组合用途。此处所述聚合物分散体优选地选自水性聚苯乙烯分散体、聚丁二烯分散体、聚(甲基)丙烯酸酯分散体、聚乙烯基酯分散体和聚氨酯分散体。这些分散体的固体含量优选地是20-70重量%,更优选地25-65重量%。根据本发明,特别的优选是多元醇酯和阳离子聚电解质在水性聚氨酯分散体中,特别地在含有助表面活性剂的水性聚氨酯分散体中作为添加剂的用途。此处特别优选的是基于聚酯多元醇、聚酯酰胺多元醇、聚碳酸酯多元醇、聚缩醛多元醇和聚醚多元醇的聚氨酯分散体。
在本发明的上下文中,优选的是多元醇酯和阳离子聚电解质的总量,基于水性聚合物分散体的总重量,是0.2-20重量%,更优选地0.4-15重量%,特别优选地0.5-10重量%。
进一步优选的是阳离子聚电解质基于多元醇酯和阳离子聚电解质的整个混合物,以2.5-80重量%,优选地5-75重量%,更优选地7.5-50重量%的量被使用.
优选地,本发明的多元醇酯和阳离子聚电解质的组合为了分散体的发泡作为发泡助剂或泡沫稳定剂用于水性聚合物分散体中。此外然而,它们还可用作干燥助剂、流平添加剂、润湿剂和流变添加剂。
除了本发明的多元醇酯和阳离子聚电解质的组合外,所述水性聚合物分散体还可以包含进一步的添加剂,如彩色颜料、填料、消光剂、稳定剂如水解或UV稳定剂、抗氧化剂、吸收剂、交联剂、流平添加剂、增稠剂和其他助表面活性剂。
可以将多元醇酯和阳离子聚电解质以纯的或在适当溶剂中的混合的形式加入到所述水性分散体中。在这种情况下,可以预先将所述两种组分在一种溶剂中或分别在两种不同的溶剂中混合。也可以预先只将两种组分中的一种混合在合适的溶剂中,而将另一种组分以纯的形式加入到水性分散体中。在这方面优选的溶剂选自水、丙二醇、二丙二醇、聚丙二醇、丁基二甘醇、丁基三甘醇、乙二醇、二甘醇、聚乙二醇、基于EO、PO、BO和/或SO的聚亚烷基二醇,和这些物质的混合物,非常特别优选水性稀释液或共混物。多元醇酯和/或阳离子聚电解质的共混物或稀释液优选地含有添加剂浓度为10-80重量%,更优选地15-70重量%,甚至更优选地20-60重量%。
在多元醇酯和/或阳离子聚电解质的水性稀释液或共混物的情况下,当将水溶助长化合物加入到所述共混物中以改善其配制物性能(粘度、均匀性等)可以是有利的。此处水溶助长化合物是由亲水部分和疏水部分组成的水溶性有机化合物,但分子量太低而不能具有表面活性剂性能。它们实现有机、特别地疏水性有机物质在水性配制物中的溶解度或溶解度性能的改进。所述术语“水溶助长化合物”是本领域技术人员已知的。本发明上下文中,优选的水溶助长化合物是甲苯磺酸碱金属和甲苯磺酸铵、二甲苯磺酸碱金属和二甲苯磺酸铵、萘磺酸碱金属和萘磺酸铵、异丙苯磺酸碱金属和异丙苯磺酸铵、和苯酚烷氧基化物,特别地苯酚乙氧基化物,具有至多6个烷氧基化单元。为了改善配制物性能,多元醇酯和/或阳离子聚电解质的共混物也可同样含有另外的助表面活性剂。根据本发明优选的助表面活性剂,在本发明上下文中是例如脂肪酸酰胺、环氧乙烷-环氧丙烷嵌段共聚物、甜菜碱类,例如酰胺丙基甜菜碱、胺氧化物、季铵盐表面活性剂、两性乙酸铵和/或脂肪酸的碱金属盐、烷基硫酸盐、烷基醚硫酸盐、烷基磺酸盐、烷基苯磺酸盐、烷基磷酸盐、烷基磺基琥珀酸盐、烷基磺基琥珀酰胺盐和烷基肌氨酸盐。此外,所述助表面活性剂可以包含基于有机硅的表面活性剂,例如三硅氧烷表面活性剂或聚醚硅氧烷。在脂肪酸的铵盐和/或脂肪酸的碱金属盐的情况下,优选的是它们含有小于25重量%的硬脂酸盐,和特别地是不含硬脂酸盐。
由于如上所述,多元醇酯和阳离子聚电解质的组合使用实现了由水性聚合物分散体制备的多孔聚合物涂层的明显改进,特别地在含有助表面活性剂的聚合物分散体的情况下,本发明同样提供包含至少一种根据本发明的多元醇酯和至少一种根据本发明的阳离子聚电解质的水性聚合物分散体,如上文详细描述。
本发明还提供由水性聚合物分散体、优选地含有助表面活性剂的水性聚合物分散体制备的多孔聚合物层,其通过本发明的多元醇酯和阳离子聚电解质的组合使用得到,如上文详细描述。
优选地,根据本发明的多孔聚合物涂层可以通过包括以下步骤的方法来制备:
a)提供包含至少一种水性聚合物分散体、至少一种根据本发明的多元醇酯、至少一种根据本发明的阳离子聚电解质和任选存在的另外的添加剂的混合物,
b)使所述混合物发泡以得到均匀的细孔泡沫,
c)任选地添加至少一种增稠剂以调节湿泡沫的粘度,
d)将所述发泡的聚合物分散体的涂层施加到适当的载体上,
e)干燥/固化所述涂层。
考虑到优选的配置,特别地考虑到在所述方法中优选可适用的多元醇酯、阳离子聚电解质和聚合物分散体,参考了前面的描述和也参考了前面提到的优选的实施方案,特别地如在权利要求中详细说明的。
清楚的是,根据本发明的方法的方法步骤如上所述在时间上是不受任何固定顺序的影响。例如,方法步骤c)可以在早期阶段执行,与方法步骤a)同时。
本发明的优选实施方案是,在方法步骤b)中,所述水性聚合物分散体通过高剪切力的施加而发泡。此处所述发泡可以借助本领域技术人员熟悉的剪切部件进行,例如Dispermats、溶解器、Hansa混合器或Oakes混合器。
此外,优选的是在方法步骤c)结束时制得的湿泡沫具有至少5、优选地至少10、更优选地至少15和甚至更优选地至少20Pa·s但不超过500Pa·s、优选地不超过300Pa·s、更优选地不超过200Pa·s、甚至更优选地不超过100Pa·s的粘度。所述泡沫的粘度可以优选地在这里借助配备有LV-4转子的LVTD型Brookfield粘度计来测定。用于测定所述湿泡沫粘度的相应测试方法是本领域技术人员已知的。
如上所述,可以将另外的增稠剂添加到所述体系中以调节所述湿泡沫的粘度。
优选地,可有利地用于本发明上下文中的增稠剂在这里是选自缔合增稠剂类别。缔合增稠剂在这里是通过在所述聚合物分散体中存在的颗粒表面的缔合而实现增稠效果的物质。所述术语是本领域技术人员已知的。优选的缔合增稠剂选自聚氨酯增稠剂、疏水改性的聚丙烯酸酯增稠剂、疏水改性的聚醚增稠剂和疏水改性的纤维素醚。非常特别的优选是聚氨酯增稠剂。此外,在本发明的上下文中优选的是所述增稠剂的浓度基于所述分散体的整体组合物是0.01-10重量%、更优选地0.05-5重量%、最优选是0.1-3重量%。
在本发明的上下文中,额外优选的是在方法步骤d)中,制得具有10-10000μm,优选地50-5000μm,更优选地75-3000μm、甚至更优选地100-2500μm的层厚度的发泡的聚合物分散体的涂层。所述发泡的聚合物分散体的涂层可以通过本领域技术人员熟悉的方法制备,例如刮涂法。此处可以使用直接或间接涂层方法(称为转移涂层)。
在本发明的上下文中还优选的是在方法步骤e)中,在升温下进行所述发泡的和涂覆的聚合物分散体的干燥。根据本发明,此处优选是最低50℃、优选地60℃、更优选地至少70℃的干燥温度。此外,可以在不同温度下在多个阶段干燥所述发泡的和涂覆的聚合物分散体,以避免干燥缺陷的发生。相应的干燥技术在工业中是广泛的且是本领域技术人员已知的。
如已经描述的,方法步骤c)-e)可以借助在本领域技术人员已知的广泛实践的方法进行。例如,在“Coated and laminated Textiles”(Walter Fung,CR-Press,2002)中给出了这些的概述。
在本发明的上下文中,特别优选的是包含多元醇酯和阳离子聚电解质且具有小于350μm、优选地小于200μm、特别优选地小于150μm、最优选地小于100μm的平均泡孔尺寸的那些多孔聚合物涂层。所述平均泡孔尺寸可以优选地通过显微镜术、优选地通过电子显微术来测定。为此目的,通过具有足够放大倍数的显微镜来观察所述多孔聚合物涂层的横截面且确定至少25个泡孔的尺寸。为了得到这种评估方法的足够统计数据,优选地选择所述显微镜的放大倍数以便至少10x 10个泡孔存在于其观察视野中。然后将所述平均泡孔尺寸计算为所观察的泡孔或泡孔尺寸的算术平均值。借助显微镜的所述泡孔尺寸的测定是本领域技术人员熟悉的。
本发明的包含多元醇酯、阳离子聚电解质和任选存在的另外的添加剂的多孔聚合物层(或聚合物涂层)可用于例如纺织工业,例如合成皮革材料;建筑和建筑工业;电子工业,例如用于泡沫密封;运动行业,例如运动垫的制备;或汽车行业。
实施例
物质:
粘度测量:
所有粘度测量都使用配备LV-4转子的LVTD型Brookfield粘度计,以12rpm的恒定转速进行。对于所述粘度测量,将样品转移到一个100毫升的罐中,所述测量转子浸入其中。一直等待恒定粘度计测量的显示。
实施例1:多元醇酯表面活性剂的混合
将24g聚甘油-3硬脂酸酯与6.3g丙二醇和69.7g水混合并在80℃下匀化,该聚甘油-3硬脂酸酯是由103.3g聚甘油(OHN=1124mg KOH/g,Mw=240g/mol)与155.0g工业级硬脂酸(棕榈酸:硬脂酸=50:50;155.0g)的反应制备的。
实施例2:发泡实验
为了测试根据本发明的添加剂组合的功效,进行了一系列发泡实验。为此目的,使用了来自陶氏的YS 3000聚氨酯分散体。这含有1重量%至3重量%的十二烷基苯磺酸钠(CAS:25155-30-0)以作为阴离子助表面活性剂。所用的泡沫稳定剂是实施例1中描述的表面活性剂共混物。所用的阳离子聚电解质是两种物质FG 1904和4570。表1给出了各个实验的组合物的概述。在实验#1至#3中,仅使用多元醇酯表面活性剂或仅使用阳离子聚电解质作为添加剂;这些实验用作对比实验,以显示各个组分的效果。相比之下,在实验#4和#5中,使用多元醇酯表面活性剂和阳离子聚电解质的本发明的组合来证明这些添加剂组合的改进效果。
所有发泡实验均手动进行。为此目的,首先将聚氨酯分散体、表面活性剂和阳离子聚电解质置于500ml的塑料杯中,并用配备有分散盘(直径=6cm)的溶解器以1000rpm均质化3分钟。为了使所述混合物发泡,然后将剪切速率增大到2000rpm,确保所述溶解盘始终充分地浸入所述分散体中以形成适当的涡流。在此速度下,所述混合物起泡至约为350ml的体积。随后,借助注射器将PV 301增稠剂逐渐添加到所述泡沫配制物中,并将所述混合物以1000rpm再剪切15分钟。在这一步中,所述溶解盘充分深地浸入所述混合物中,使得不会将另外的空气引入体系中,但整个体积仍在运动中。
表1:泡沫配制物概述
对于仅含有多元醇酯表面活性剂的泡沫的情况(实验#1),在所述发泡操作结束时得到了相当粗的且不均匀的泡沫。当这种泡沫在密闭容器中储存30分钟后,观察到泡沫结构进一步变粗。还值得注意的是,所述泡沫的粘度非常低,因此它具有流动的稠度(所述泡沫的粘度同样在表1中注明)。在只含有阳离子聚电解质的泡沫的情况下(实验#2和#3),其混合物可以毫无问题地发泡到350ml的体积,但在起泡后几分钟观察到所述泡沫体积下降到约250ml。所述混合物的粘度在这里显著上升,以至于几乎不能搅拌它们。在样品的储存超过30分钟后,观察到粘度进一步升高。在使用本发明的多元醇酯表面活性剂和阳离子聚电解质的添加剂组合进行的实验中(实验#4和#5),在发泡操作结束时得到具有细孔的均匀泡沫,且这些泡沫在储存30分钟的过程中只略微变粗。
然后借助来自Mathis AG的Labcoater LTE-S实验室铺展台/干燥机将所述泡沫刮涂到织物载体上(层厚~800μm),然后在60℃下干燥5分钟和在120℃下再干燥5分钟。此处值得注意的是,仅含有多元醇酯表面活性剂的泡沫(实验#1)在干燥操作期间进一步变粗,因此所制得的织物涂层显示出相当粗的泡孔和不均匀的泡沫结构。这一结果是相应的样品具有较不吸引人的触觉特性以及视觉上较差的外观。在仅含有阳离子聚电解质的涂层的情况下(实验#2和#3),由于发泡后粘度立即明显升高,因此可能只是很难将所述泡沫刮涂到织物载体上。这导致其泡沫涂层中的缺陷位点和不规则性。以上以及只有轻微发泡的密实块是刮涂的事实,具有额外的结果是相应的样品感觉非常硬和刚性,且具有较不吸引人的触觉特性。相比之下,可以无缺陷地刮涂含有本发明的多元醇酯和阳离子聚电解质的添加剂组合的泡沫(实验#4和#5)。干燥后,没有观察到泡沫结构的明显粗化,从而得到了无缺陷和细孔的泡沫涂层,其不仅具有均匀的外观,而且具有良好的触感。这些实验因此清楚地显示了根据本发明的添加剂组合的改进效果。
Claims (16)
1.多元醇酯和阳离子聚电解质在水性聚合物散体中、优选地在水性聚氨酯分散体中、特别优选地在含有助表面活性剂、特别地含有阴离子助表面活性剂的水性聚氨酯分散体中作为添加剂、优选地作为泡沫添加剂的组合用途。
2.根据权利要求1的用途,其特征在于所述多元醇酯通过多元醇与至少一种羧酸的酯化可得到。
3.根据权利要求2的用途,其特征在于所述多元醇选自C3-C8多元醇和它们的低聚物,
优选的多元醇是丙烷-1,3-二醇、丙二醇、甘油、三羟甲基乙烷、三羟甲基丙烷、脱水山梨糖醇、山梨糖醇、异山梨醇、赤藓糖醇、苏糖醇、季戊四醇、阿拉伯糖醇、木糖醇、核糖醇、岩藻糖醇、甘露糖醇、半乳糖醇、艾杜糖醇、肌醇、庚七醇和葡萄糖,特别地是甘油,
和优选的多元醇低聚物是具有1至20个、优选地2至10个、更优选地2.5至8个重复单元的C3-C8多元醇的低聚物,这里特别优选的是二聚甘油、三聚甘油、四聚甘油、五聚甘油、二聚赤藓糖醇、三聚赤藓糖醇、四聚赤糖藓醇、二(三羟甲基丙烷)、三(三羟甲基丙烷)和二糖和寡糖,特别地是脱水山梨糖醇和低聚和/或多聚甘油。
4.根据权利要求2和3中至少一项的用途,其特征在于所述羧酸符合通式R-C(O)OH,其中R是具有3至39个碳原子、优选地具有7至21个碳原子、更优选地具有9至17个碳原子的一价脂肪族饱和的或不饱和的烃基,
和其中优选的羧酸选自酪酸(丁酸)、羊油酸(己酸)、羊脂酸(辛酸)、羊蜡酸(癸酸)、月桂酸(十二烷酸)、肉豆蔻酸(十四烷酸)、棕榈酸(十六烷酸)、硬脂酸(十八烷酸)、花生酸(二十烷酸)、山萮酸(二十二烷酸)、木蜡酸(二十四烷酸)、棕榈烯酸((Z)-9-十六碳烯酸)、油酸((Z)-9-十六碳烯酸)、反油酸((E)-9-十八碳烯酸)、顺式异油酸((Z)-11-十八碳烯酸)、亚油酸((9Z,12Z)-9,12-十八碳二烯酸)、α-亚麻酸((9Z,12Z,15Z)-9,12,15-十八碳三烯酸)、γ-亚麻酸((6Z,9Z,12Z)-6,9,12-十八碳三烯酸)、二高-γ-亚麻酸((8Z,11Z,14Z)-8,11,14-二十碳三烯酸)、花生四烯酸((5Z,8Z,11Z,14Z)-5,8,11,14-二十碳四烯酸)、芥酸((Z)-13-二十二碳烯酸)、神经酸((Z)-15-二十四碳烯酸)、蓖麻油酸、羟基硬脂酸和十一碳烯酸,以及它们的混合物,例如菜籽油酸、大豆脂肪酸、向日葵脂肪酸、花生脂肪酸和/或松浆油脂肪酸,
非常特别优选棕榈酸和硬脂酸以及这两种物质的混合物,
和/或其中使用多官能的二和/或三羧酸,优选地使用具有2至18个碳原子的链长的脂肪族线性的或枝化的二和/或三羧酸,和/或通过具有12至22个碳原子的不饱和脂肪酸的催化二聚所得到的二聚体脂肪酸,
和/或其中使用上述通式R-C(O)OH的羧酸与多官能的二和/或三羧酸的混合物。
5.根据权利要求1至4中至少一项的用途,其特征在于所使用的多元醇酯包括选自脱水山梨糖醇酯和/或聚甘油酯的那些多元醇酯、优选地聚甘油酯,优选地符合以下通式1的那些聚甘油酯:
MaDbTc 式1
其中
M=[C3H5(OR1)2O1/2]
D=[C3H5(OR1)1O2/2]
T=[C3H5O3/2]
a=1至10,优选地2至3,特别优选地2,
b=0至10,优选地大于0至5,特别优选地1至4,
c=0至3,优选地为0,
其中R1基团独立地是相同或不同的R2-C(O)-形式的基团或H,
其中R2是具有3至39个碳原子、优选地具有7至21个碳原子、更优选地具有9至17个碳原子的一价脂肪族饱和的或不饱和的烃基,
其中至少一个R1基团对应于所述R2-C(O)-形式的基团,
和/或符合以下通式2的聚甘油酯:
MxDyTz 式2
其中
x=1至10,优选地2至3,特别优选地2,
y=0至10,优选地大于0至5,特别优选地1至4,
z=0至3,优选地大于0至2,特别优选地0,
条件是至少一个R1基团不是氢,R1仍然如上所定义,
和/或符合通式3的聚甘油酯:
其中
k=1至10,优选地2至3,特别优选地2,
m=0至10,优选地大于0至5,特别优选地1至3,
条件是所述R1基团中的至少一个不是氢,R1仍然如上所定义,并且k+m的总和大于零,并且具有下标k和m的片段是统计学上分布的。
6.根据权利要求1至5中至少一项的用途,其特征在于所述式1、2和/或3的多元醇酯已被磷酸化,特别地带有至少一个(R3O)2P(O)-基团作为所述R1基团,其中所述R3基团独立地是阳离子,优选地是Na+、K+或NH4 +,或单-、二-和三烷基胺的铵离子,其中的烷基也可以是官能化的烷基,例如在酰胺胺的情况下,单-、二-和三烷醇胺的铵离子,单-、二-和三氨基烷基胺的铵离子,或H或R4-O-,
其中R4是具有3至39个碳原子、优选地7至22个和更优选地具有9至18个碳原子的一价脂肪族饱和或不饱和烃基,或多元醇基团。
7.根据权利要求1至6中至少一项的用途,其特征在于所述阳离子聚电解质是聚乙烯亚胺和它的缩合产物,含有精氨酸和/或组氨酸的肽和聚酰胺,胺-和胍-官能的硅氧烷,和以下物质的(共)聚合物:
烯丙胺、二烯丙胺、它们的烷基衍生物和季铵化产物,特别是二烯丙基二甲基氯化铵;乙烯基胺、二乙烯基胺、乙烯基吡啶和它们的季铵化产物;乙烯基咪唑、它们的烷基衍生物和季铵化产物;烯键式不饱和羧酸与氨基醇的酯;烯键式不饱和羧酸与N,N-二烷基氨基烷基胺的酰胺;和这些物质的混合物,
非常特别优选基于乙烯基胺的(共)聚合物。
9.根据权利要求7和8中至少一项的用途,其特征在于所述聚合物可以由所述重复单元A和/或B通过N-乙烯基羧酰胺的自由基聚合和随后的所述酰胺官能到胺官能的完全或部分的水解来制备,优选的N-乙烯基羧酰胺选自N-乙烯基甲酰胺、N-乙烯基-N-甲基甲酰胺、N-乙烯基-N-乙基甲酰胺、N-乙烯基-N-丙基甲酰胺、N-乙烯基-N-异丙基甲酰胺、N-乙烯基-N-丁基甲酰胺、N-乙烯基-N-异丁基甲酰胺、N-乙烯基乙酰胺、N-乙烯基-N-甲基乙酰胺、N-乙烯基-N-乙基乙酰胺、N-乙烯基-N-丙基乙酰胺、N-乙烯基-N-异丙基乙酰胺、N-乙烯基-N-丁基乙酰胺、N-乙烯基-N-异丁基乙酰胺、N-乙烯基丙酰胺、N-乙烯基甲基丙酰胺、N-乙烯基-N-乙基丙酰胺、N-乙烯基-N-丙基丙酰胺和/或这些物质的混合物,非常特别优选N-乙烯基甲酰胺。
10.根据权利要求7至9中至少一项的用途,其特征在于与所述重复单元A和B一起,已将其它的单烯键式不饱和共聚单体或共聚单体的混合物任选地并入到所述聚合物中,其中这些共聚单体是:
非离子单体,优选地是不饱和醇例如乙烯醇或烯丙醇和它们的烷氧基化物、不饱和腈、脂肪族或芳香族烯烃、N-乙烯基内酰胺例如N-乙烯基吡咯烷酮或N-乙烯基己内酰胺、有机羧酸的乙烯基酯、单烯键式不饱和羧酸的酯和单烯键式不饱和羧酸的酰胺;
阳离子单体,优选地是含有乙烯基咪唑和乙烯基咪唑啉单元、它们的烷基衍生物和季铵化产物、乙烯基吡啶和它们的季铵化产物、烯键式不饱和羧酸与氨基醇的碱性酯、和烯键式不饱和羧酸与N,N-二烷基氨基烷基胺的碱性酰胺;
和阴离子单体,优选地是α,β-不饱和的单羧酸、不饱和的二羧酸和/或不饱和的二羧酸的偏酯。
11.根据权利要求1至10中任一项的用途,其特征在于所述水性聚合物分散体选自水性聚苯乙烯分散体、聚丁二烯分散体、聚(甲基)丙烯酸酯分散体、聚乙烯酯分散体和聚氨酯分散体,特别是聚氨酯分散体,特别优选含有助表面活性剂的分散体,其中这些分散体的固体含量基于所述整个分散体优选地是20-70重量%、更优选地25-65重量%。
12.根据权利要求1至11中任一项的用途,其特征在于多元醇酯和阳离子聚电解质的总量基于所述水性聚合物分散体的总重量是0.2-20重量%、更优选地0.4-15重量%、特别优选地0.5-10重量%。
13.根据权利要求1至12中任一项的用途,其特征在于所述阳离子聚电解质基于多元醇酯和阳离子聚电解质的总重量以2.5-80重量%、优选地5-75重量%、更优选地7.5-50重量%的量被使用。
14.水性聚合物分散体、优选地水性聚氨酯分散体,其包含多元醇酯和阳离子聚电解质,优选地如权利要求1至13所述,优选的是含有助表面活性剂的水性聚合物分散体、特别地是含有助表面活性剂的水性聚氨酯分散体。
15.制备多孔聚合物涂层、优选地多孔聚氨酯涂层的方法,包括在水性聚合物分散体中组合使用多元醇酯和阳离子聚电解质作为添加剂,所述水性聚合物分散体优选地是水性聚氨酯分散体、特别地是含助表面活性剂的水性聚氨酯分散体,所述方法包括以下步骤:
a)提供混合物,所述混合物包含至少一种水性聚合物分散体、优选地水性聚氨酯分散体、特别地含有助表面活性剂的水性聚氨酯分散体,至少一种多元醇酯,至少一种阳离子聚电解质和任选存在的其它的添加剂,
b)使所述混合物发泡以得到均匀的、细孔的泡沫,
c)任选地添加至少一种增稠剂以调节所述湿泡沫的粘度,
d)将所述发泡的聚合物分散体、优选地聚氨酯分散体的涂层施加到适合的载体上,
e)干燥所述涂层。
16.多孔聚合物涂层、优选地多孔聚氨酯涂层,其通过在水性聚合物分散体中组合使用多元醇酯和阳离子聚电解质作为添加剂可得到,所述水性聚合物分散体优选地是含有助表面活性剂的聚合物分散体、进一步优选地是含有助表面活性剂的水性聚氨酯分散体,特别在此类聚合物涂层的制备中,优选地通过根据权利要求15的方法可得到,
条件是所述多孔聚合物涂层优选地具有小于150μm、优选地小于120μm、特别优选地小于100μm、最优选地小于75μm的平均泡孔尺寸。
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- 2019-07-18 BR BR112022000803A patent/BR112022000803A2/pt active Search and Examination
- 2019-07-18 KR KR1020227005030A patent/KR20220035449A/ko not_active Application Discontinuation
- 2019-07-18 CN CN201980098518.4A patent/CN114127207A/zh active Pending
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EP3999602A4 (en) | 2023-04-05 |
WO2021007838A1 (en) | 2021-01-21 |
KR20220035449A (ko) | 2022-03-22 |
JP7392103B2 (ja) | 2023-12-05 |
BR112022000803A2 (pt) | 2022-03-08 |
MX2021015925A (es) | 2022-01-31 |
US20220315797A1 (en) | 2022-10-06 |
JP2022541533A (ja) | 2022-09-26 |
EP3999602A1 (en) | 2022-05-25 |
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