CN1890282B - 制备微粒乳状液嵌段聚合物的方法 - Google Patents
制备微粒乳状液嵌段聚合物的方法 Download PDFInfo
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- CN1890282B CN1890282B CN200480036479.9A CN200480036479A CN1890282B CN 1890282 B CN1890282 B CN 1890282B CN 200480036479 A CN200480036479 A CN 200480036479A CN 1890282 B CN1890282 B CN 1890282B
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Abstract
本发明涉及一种嵌段共聚物的水分散液,所述嵌段共聚物包含加聚物或缩聚物(聚合物I)和包含可通过自由基加聚反应获得的聚合物(聚合物II)。其中本发明的水分散液的特征在于:微粒乳状液聚合物I可通过其起始组分的反应获得,所述聚合物I的起始组分之一是自由基加聚反应引发剂的形式,并且聚合物II是在所述引发剂存在下制备。
Description
本发明涉及一种嵌段共聚物的水分散液,所述嵌段共聚物一方面包含加聚物或缩聚物(简称为聚合物I),另一方面包含可通过自由基加聚反应获得的聚合物(简称为聚合物II),其中
-聚合物I可通过其起始化合物在微粒乳状液(miniemulsion)中反应获得,
-聚合物I的起始化合物之一是自由基加聚反应的引发剂,并且
-聚合物II是在所述引发剂的存在下制备。
本发明进一步涉及制备所述嵌段共聚物的方法和所述嵌段共聚物的用途。
聚氨酯通常通过它们的起始化合物(异氰酸酯和异氰酸酯活性化合物)在有机溶剂中反应制备。将所获得的聚氨酯分散于水中,生成所谓的二次分散液。
聚氨酯分散液还可以通过起始化合物在水相中反应直接获得(一次分散液)。
这可以利用WO 02/064657中描述的在微粒乳状液中聚合的方法来实现。
在该方法中,起始化合物在少量疏水性化合物存在下于水中乳化,其中所述疏水性化合物在水中的溶解度小于10-7g/l水(在21℃下)。
利用已知方法将液滴大小调整为50-500nm。由于存在疏水性物质,没有出现奥斯特瓦尔德(Ostwald)熟化效应(液滴增长,直到出现相分离)。
相反,在液滴中,起始化合物可以反应成聚氨酯,同时液滴尺寸或多或少地保持不变。以此方式获得了聚氨酯一次分散液。
相应地,还可以制备包含聚氨酯和可通过自由基加聚反应获得的聚合物的共聚物,而且在微粒乳状液中进行该聚合。依照DE-A-10241294(PF 53898),可以将传统的自由基加聚反应引发剂加入用于此目的的聚氨酯起始化合物与可自由基聚合单体的混合物中。
期望的是高分子量的特定嵌段共聚物,以便达到有效的成膜和良好的性能。尤其期望的是所获得的膜具有高透明度,并且膜的力学性能如拉伸强度和弹性尽可能接近聚氨酯本身的性能。
利用与聚氨酯连接的偶氮引发剂制备嵌段共聚物已经描述在例如EP-A-522675或DE-A-4123223中。
与之相比,本发明的目的是具有上述性能的共聚物水分散液。另一个目的是制备它们的一种简单方法。
因此,已经发现在本文开始定义的水分散液。
本说明书中的分散液是可通过嵌段共聚物的起始化合物于水相中在微粒乳状液中反应获得的一次分散液,正如DE-A-10241294中所述。
用于此目的的起始化合物利用表面活性化合物如乳化剂或保护胶体在水中乳化。
相伴使用疏水性化合物作为共稳定剂是必要的。
这些稳定剂的水溶解度在21℃、1巴下优选小于10-5、更优选小于10-6、非常优选小于10-7g/每升水。
共稳定剂的量可以是例如按每100重量份起始化合物计的0.1-10重量份,尤其1-3重量份。
合适的共稳定剂的实例包括烃如十六烷,卤代烃,硅烷,硅氧烷,疏水性油(橄榄油)或用于聚氨酯的其它起始化合物,前提条件是它们具有必要的疏水性。
起始化合物的乳化液滴的粒径优选为50-500nm。
粒径可通过已知方法调整,例如在高压均化器内均化或应用超声波。
与起始化合物的乳液相似,所获得的分散液具有优选50-500nm、更优选100-300nm的液滴尺寸。
在分散液中于水相中的嵌段共聚物是由加聚物或缩聚物(简称为聚合物I)和可通过自由基加聚反应获得的聚合物(简称为聚合物II)组成。
所述加聚物或缩聚物可以是例如聚酯、聚氨酯、聚脲、聚酰胺、聚酰胺酸或环氧树脂。
优选是聚氨酯。
所述聚氨酯优选由下述组分合成:
a)多异氰酸酯,
b)多元醇,其中
b1)基于多元醇(b)总量计的10-100摩尔%的该多元醇具有500-5000g/摩尔的分子量,
b2)基于多元醇(b)总量计的0-90摩尔%的该多元醇具有60-500g/摩尔的分子量,
c)不同于单体(a)和(b)的单体,其具有至少一个异氰酸酯基或至少一个对异氰酸酯基有活性的基团,并且进一步携带至少一个亲水性基团或一个潜在亲水性基团,
d)如果合适的话,不同于单体(a)-(c)的其它化合物,其具有至少2个异氰酸酯基活性基团,其中的至少一个是伯或仲氨基或巯基,
e)如果合适的话,与单体(a)-(d)不同的具有活性基团的一价化合物,其中所述活性基团为醇羟基、伯或仲氨基或异氰酸酯基。
关于单体(a),应特别提及的是二异氰酸酯X(NCO)2,其中X是具有4-15个碳原子的脂族烃基,具有6-15个碳原子的脂环族或芳族烃基,或具有7-15个碳原子的芳脂族烃基。这种二异氰酸酯的实例为四亚甲基二异氰酸酯、六亚甲基二异氰酸酯、十二亚甲基二异氰酸酯、1,4-二异氰酸酯基环己烷、1-异氰酸酯基-3,5,5-三甲基-5-异氰酸酯基甲基环己烷(IPDI)、2,2-二(4-异氰酸酯基环己基)丙烷、二异氰酸三甲基己烷酯、1,4-二异氰酸酯基苯、2,4-二异氰酸酯基甲苯、2,6-二异氰酸酯基甲苯、4,4’-二异氰酸酯基二苯基甲烷、2,4’-二异氰酸酯基二苯基甲烷、对-苯二甲撑二异氰酸酯、四甲基苯二甲撑二异氰酸酯(TMXDI),二(4-异氰酸酯基环己基)甲烷(HMDI)的异构体如反/反、顺/顺和顺/反异构体,以及这些化合物的混合物。
这种类型的二异氰酸酯可从商业获得。
关于这些异氰酸酯的混合物,其中特别重要的是二异氰酸酯基甲苯和二异氰酸酯基二苯基甲烷的各自结构异构体的混合物;尤其适合的是80摩尔%2,4-二异氰酸酯基甲苯与20摩尔%2,6-二异氰酸酯基甲苯的混合物。还特别有利的是芳族异氰酸酯如2,4-二异氰酸酯基甲苯和/或2,6-二异氰酸酯基甲苯与脂族或脂环族异氰酸酯如六亚甲基二异氰酸酯或IPDI的混合物,脂族与芳族异氰酸酯的优选混合比例为4∶1-1∶4。
另外,可以使用具有超过2个异氰酸酯基的多异氰酸酯。合适的实例包括异氰酸酯和例如六亚基二异氰酸酯的缩二脲。
用于合成聚氨酯的化合物,除上述之外,还可以使用除自由异氰酸酯基之外进一步携带封端的异氰酸酯基如脲二酮基的异氰酸酯。
从有效成膜和弹性着眼,合适的多元醇(b)原则上包括分子量较高的多元醇(b1),具有的分子量为约500-5000,优选约1000-3000g/摩尔。所述分子量为数均分子量Mn。Mn通过测定端基数(OH值)获得。
多元醇(b1)可以是聚酯多元醇,其可以例如由Ullmanns Encyklopdieder technischen Chemie第4版第19卷第62-65页获知。优选使用通过二元醇与二元酸反应获得的聚酯多元醇。替代游离聚羧酸,还可以使用相应的聚羧酸酐或相应的低级醇聚羧酸酯或其混合物制备所述的聚酯多元醇。所述聚羧酸可以是脂族、脂环族、芳脂族、芳族或杂环的,并且,如果合适的话,可以被例如卤素原子取代和/或是不饱和的。其中可以提及的实例包括:辛二酸、壬二酸、邻苯二甲酸、间苯二甲酸、邻苯二甲酸酐、四氢化邻苯二甲酸酐、六氢化邻苯二甲酸酐、四氯化邻苯二甲酸酐、内亚甲基四氢邻苯二甲酸酐、戊二酸酐、马来酸、马来酸酐、富马酸酐和二聚脂肪酸。优选通式HOOC-(CH2)y-COOH的二羧酸,其中y是1-20的数,优选2-20的偶数,例如琥珀酸、己二酸、癸二酸和十二烷二酸。
合适的多元醇包括例如乙二醇、1,2-丙二醇、1,3-丙二醇、1,3-丁二醇、1,4-丁烯二醇、1,4-丁炔二醇、1,5-戊二醇、新戊二醇,二(羟甲基)环己烷如1,4-二(羟甲基)环己烷,2-甲基-1,3-丙二醇,甲基戊二醇、以及二甘醇、三甘醇、四甘醇、聚乙二醇、双丙甘醇、聚丙二醇、二丁二醇和聚丁二醇。优选的是通式HO-(CH2)x-OH的醇,其中x是1-20的数,优选2-20的偶数。其中实例为乙二醇、1,4-丁二醇、1,6-己二醇、1,8-辛二醇和1,12-十二烷二醇。另外优选的是新戊二醇。
如果合适的话,还合适的是聚碳酸酯二醇,例如,通过例如光气与过量的规定作为聚酯多元醇合成组分的低分子量醇反应获得的那些。
如果合适的话,还可以使用基于内酯的聚酯多元醇,它们是内酯的均聚物或共聚物,优选内酯与合适的双官能起始分子的加合物,所述加合物包含端羟基。合适的内酯优选包括由通式HO-(CH2)z-COOH的化合物衍生的那些,其中z是1-20的数并且其中亚甲基单元中的一个氢原子可以被C1-C4烷基取代。实例为ε-己内酯、β-丙内酯、γ-丁内酯和/或甲基-ε-己内酯以及它们的混合物。合适的起始组分是例如上述规定的作为聚酯多元醇合成组分的低分子量二元醇。ε-己内酯的相应聚合物是特别优选的。低级聚酯二醇或聚醚二醇也可以用作制备内酯聚合物的起始剂。替代内酯聚合物,还可以使用相应的、化学等同的、与内酯对应的羟基羧酸的缩聚物。
聚醚多元醇可特别通过下述方式获得:氧化乙烯、氧化丙烯、氧化丁烯、四氢呋喃、氧化苯乙烯或表氯醇在例如BF3存在下与自身聚合,或使这些化合物,如果合适的话,作为混合物或连续地与包含活性氢原子的组分如醇或胺加成,例如水、乙二醇、1,2-丙二醇、1,3-丙二醇、2,2-二(4-羟苯基)丙烷或苯胺。特别优选的是分子量为240-5000、尤其500-4500的聚氧化丙烯、聚四氢呋喃。
b1)仅包含这样的聚醚多元醇:其中低于20重量%的该聚醚多元醇是由氧化乙烯组成。具有至少20重量%氧化乙烯的聚醚二醇是亲水性聚醚二醇,其包括在单体c)中。
如果合适的话,还可以使用多羟基烯烃,优选具有2个端羟基的那些,例如α,ω-二羟基聚丁二烯、α,ω-二羟基聚甲基丙烯酸酯或α,ω-二羟基聚丙烯酸酯作为单体(c1)。这样的化合物可由例如EP-A 0622378获知。其它合适的多元醇为聚缩醛、聚硅氧烷和醇酸树脂。
除二醇(b1)之外,使用分子量为约60-500、优选62-200g/摩尔的二醇(b2)作为二醇(b)可以提高聚氨酯的硬度和弹性模量。
作为单体(b2),首先使用上述为制备聚酯多元醇规定的短链链烷二醇的合成组分,特别优选具有2-12个碳原子且碳原子数为偶数的无支链二醇,以及1,5-戊二醇和新戊二醇。
合适的多元醇b2)包括例如乙二醇、1,2-丙二醇、1,3-丙二醇、1,3-丁二醇、1,4-丁烯二醇、1,4-丁炔二醇、1,5-戊二醇、新戊二醇,二(羟甲基)环己烷如1,4-二(羟甲基)环己烷,2-甲基-1,3-丙二醇、甲基戊二醇、以及二甘醇、三甘醇、四甘醇、聚乙二醇、双丙甘醇、聚丙二醇、二丁二醇和聚丁二醇。优选的是通式HO-(CH2)x-OH的醇,其中x是1-20的数,优选2-20的偶数。其中实例为乙二醇、1,4-丁二醇、1,6-己二醇、1,8-辛二醇和1,12-十二烷二醇。另外优选的是新戊二醇。
多元醇(b1)的优选比例是基于二醇(b)总量计的10-100摩尔%,单体(b2)的比例是基于二醇(b)总量计的0-90摩尔%。特别优选的是,二醇(b1)与单体(b2)之比为0.1∶1-5∶1,更优选0.2∶1-2∶1。
为了改善聚氨酯在水中的分散性,聚氨酯可以包含单体(c)作为合成组分,单体(c)不同于组分(a)、(b)和(d),其携带至少一个异氰酸酯基或至少一个对异氰酸酯基活泼的基团,并且另外携带至少一个亲水基或一个能转化为亲水基的基团。
虽然可以使用这种类型的亲水性单体,然而对于稳定的微粒乳状液而言不是必须的。离子性基团的量优选低于100mmol/1000g聚氨酯,并且特别优选不包含单体c)的聚氨酯。
单体(d),不同于单体(a)-(c),并且如果合适的话也是聚氨酯的成分,一般起交联或扩链的作用。
可用于设定支化或交联程度的、官能度大于2的醇是例如三羟甲基丙烷、甘油或糖,
另外合适的是除羟基之外携带额外异氰酸酯基活性基团的一元醇,例如具有一个或多个伯和/或仲氨基的一元醇,例如单乙醇胺。
当扩链和/或交联在水存在下发生时,首先使用具有2个或更多个伯和/或仲氨基的多胺,这是因为胺与异氰酸酯的反应通常快于醇或水。当期望获得交联聚氨酯或具有高摩尔重量的聚氨酯的水分散液时,这常常是必要的。
适用于该目的的胺一般为摩尔重量在32-500g/摩尔、优选60-300g/摩尔范围内的多官能胺,其包含至少两个选自伯氨基和仲氨基的氨基。其中的实例为二胺,例如二氨基乙烷、二氨基丙烷、二氨基丁烷、二氨基己烷、哌嗪、2,5-二甲基哌嗪、氨基-3-氨基甲基-3,5,5-三甲基环己烷(异佛尔酮二胺,IPDA)、4,4’-二氨基二环己基甲烷、1,4-二氨基环己烷、氨基乙基乙醇胺、肼、水合肼或三胺,例如二乙烯三胺或1,8-二氨基-4-氨基甲基辛烷。
所述胺可以封端形式使用,例如以相应的酮亚胺形式(参见例如CA-A 1 129 128)、酮连氮(例如US-A 4 269 748)或胺盐(参见US-A 4 292 226)。对于预聚物的扩链,唑烷类,正如在例如US-A 4 192 937中所用,也是可用于制备本发明聚氨酯的封端多胺。
如果合适的话,还使用的单体(e)为一异氰酸酯、一元醇、一元伯胺和一元仲胺。一般而言,它们的比例不超过基于单体总摩尔量计的10摩尔%。这些单官能化合物通常携带其它官能团,如烯属基团或羰基,并用于向聚氨酯引入允许聚氨酯分散和/或交联或进行其它类似聚合物反应的官能团。适于该目的单体包括例如异丙烯基-α,α-二甲基苄基异氰酸酯(TMI)和丙烯酸或甲基丙烯酸的酯,例如丙烯酸羟乙酯或甲基丙烯酸羟乙酯。
当实质上只有脂族二异氰酸酯、脂环族二异氰酸酯或芳脂族二异氰酸酯用作单体(a)时,首先获得具有特别良好性能分布的涂料。
通常,选择组分(a)-(e)以及它们各自的摩尔量以使A∶B之比为0.5∶1-2∶1,优选0.8∶1-1.5,更优选0.9∶1-1.2∶1;其中
A是异氰酸酯基的摩尔量,并且
B是羟基摩尔量和能与异氰酸酯按加成反应进行反应的官能团的摩尔量的总和。
非常特别优选A∶B之比尽可能接近1∶1。
单体(a)-(e)通常携带平均1.5-3、优选1.9-2.1、更优选2.0个异氰酸酯基和分别地能够与异氰酸酯按加成反应进行反应的官能团。
依照本发明,聚合物I的起始化合物之一是自由基加聚反应的引发剂。因此,该引发剂由于起始化合物的反应而连接在聚合物I上。
所述引发剂因此包含至少一个、优选一个或两个、更优选两个能够使其连接在聚合物I上的活性基团。在聚氨酯作为聚合物I的情况下,所讨论的活性基团可以是异氰酸酯基或异氰酸酯活性基团,例如羟基、氨基或羧酸酯基。所讨论的基团优选是异氰酸酯基或羟基。
所述引发剂包括至少一个能够引发自由基加聚反应的基团,例如偶氮或过氧基团。
所述引发剂优选包含引发基团,尤其是偶氮基。合适的引发剂可由例如EP-A-522675和DE-A-4123223获知。
合适的引发剂具有的分子量在58和5000g/摩尔之间。
特别地,所述分子量为100-1000g/摩尔。
特别适宜的是下述式I-VI的引发剂:
这些式中的变量具有下述定义:
R1:氢原子或C1-C4烷基,优选氢原子或甲基,
R2:CN基或C1-C4烷基,
R3,R4:彼此独立地为具有最多30个碳原子、优选2-20个碳原子的二价有机基团。在式I和II中,R3还可以是单键;换句话说,R3可在这时省略。
所述引发剂可以是多异氰酸酯(a)、多元醇(b)或其它单体(c)-(e),这取决于活性基团的性质和它们的数量。
引发剂在聚合物I中的比例最终受在嵌段共聚物中聚合物II的所需量支配,因为引发剂的目的在于引发制备聚合物II。
引发剂在聚合物I中的量优选为按每100重量份聚合物II计的0.1-100重量份,更优选0.1-5重量份,非常特别优选0.3-3重量份。
聚合物II可通过烯键不饱和化合物(单体)的自由基加聚反应获得。
所述聚合物包含至少60重量%、优选至少80重量%、更优选至少90重量%的所谓主要单体。
所述主要单体选自(甲基)丙烯酸C1-C20烷基酯,包含最多20个碳原子的羧酸的乙烯基酯,包含最多20个碳原子的乙烯基芳烃,烯键不饱和腈,乙烯基卤化物,包含1-10个碳原子的醇的乙烯基醚,具有2-8个碳原子和一个或两个双键的脂族烃,或这些单体的混合物。
可以提及的是例如具有C1-C10烷基的(甲基)丙烯酸烷基酯,例如甲基丙烯酸甲酯、丙烯酸甲酯、丙烯酸正丁酯、丙烯酸乙酯和丙烯酸2-乙基己基酯。
(甲基)丙烯酸烷基酯的混合物也是特别适宜的。
具有1-20个碳原子的羧酸的乙烯基酯是例如月桂酸乙烯酯、硬脂酸乙烯酯、丙酸乙烯酯、Versatic酸乙烯酯和乙酸乙烯酯。
合适的乙烯基芳族化合物包括乙烯基甲苯,α-和p-甲基苯乙烯,α-丁基苯乙烯,4-正丁基苯乙烯,4-正癸基苯乙烯,优选是苯乙烯。腈的实例为丙烯腈和甲基丙烯腈。
所述乙烯基卤化物是氯-、氟-或溴-取代的烯键不饱和化合物,优选氯乙烯和偏二氯乙烯。
可以提及的乙烯基醚的实例包括乙烯基甲基醚和乙烯基异丁基醚。优选包含1-4个碳原子的醇的乙烯基醚。
可以提及的具有4-8个碳原子和两个烯烃双键的烃是丁二烯、异戊二烯和氯丁二烯。
优选的主要单体是丙烯酸和甲基丙烯酸的C1-C10烷基酯,尤其甲基丙烯酸的C1-C8烷基酯,和乙烯基芳烃,特别是苯乙烯,和它们的混合物。
非常特别优选的是丙烯酸甲酯、甲基丙烯酸甲酯、丙烯酸乙酯、丙烯酸正丁酯、丙烯酸正己酯、丙烯酸辛酯、丙烯酸-2-乙基己基酯、苯乙烯,和这些单体的混合物。
除主要单体之外,所述聚合物可以包含其它单体,例如含羧酸、磺酸或膦酸基的单体。羧酸基是优选的。可以提及的实例包括丙烯酸、甲基丙烯酸、衣康酸、马来酸和富马酸。
其它的单体是例如还包含羟基的单体,特别是(甲基)丙烯酸的C1-C10羟烷基酯以及(甲基)丙烯酰胺。
此外,可以提及的其它单体包括苯氧基乙基二醇单(甲基)丙烯酸酯(phenyloxyethyl glycol mono(meth)acrylate)、丙烯酸缩水甘油酯、甲基丙烯酸缩水甘油酯,(甲基)丙烯酸氨基酯,如(甲基)丙烯酸-2-氨基乙基酯。
交联单体也可以作为其它单体提及。
特别地,所述聚合物由至少60重量%、更优选至少80重量%和非常优选至少95重量%的(甲基)丙烯酸C1-C20烷基酯合成。
作为所述嵌段共聚物的一部分,聚合物I的比例优选为5-95重量%,更优选20-80重量%。相应地,聚合物II的比例为5-95重量%,更优选20-80重量%,所述比例基于所述嵌段共聚物的总量(相当于聚合物I和II重量之和)。
非常特别优选的是,聚合物I和II的比例在各种情况下为40-60重量%。
所述嵌段共聚物的分散液优选通过在微粒乳状液中聚合制备。该方法已经在本文的开始描述。
一种可能的步骤是首先使聚合物I的起始化合物反应以形成聚合物I,然后使聚合物II的起始化合物在聚合物I存在下反应。
用于制备聚氨酯的组分(a)-(e)的加聚反应优选在大气压力或在超计大气压力下、在最高180℃的温度下进行,优选在大气压力、最高100℃下进行。
为形成聚合物II的起始化合物的自由基加聚反应同样优选在大气压力或在超计大气压力下、在最高130℃的温度下进行,特别在大气压力、最高100℃下进行。
在一种优选实施方式中,微粒乳状液由聚合物I和II的所有起始化合物形成,并且所有起始化合物形成嵌段共聚物的反应在一个工艺步骤中进行。
所获得的嵌段共聚物具有高摩尔重量和均匀的嵌段结构。有利的性能特别是所获得的膜具有高透明度和良好的力学性能。
特别是,即使在低温,例如低于50℃,尤其是在室温(21℃)在大气压力下也可以由所述分散液形成膜。
所述分散液具有良好的性能,特别包括与由金属、塑料或木材制成的常规物质具有良好的粘合力。
所述分散液非常适合用作用于粘合剂、密封剂、涂料组合物、皮革修整涂料或纸张涂层的基料。
所述分散液还非常适合用作用于化妆品制剂例如发胶、造型凝胶、指甲油、粉底或洗发液的基料。
它们可特别用作有机或无机固体的分散剂或用作相间相容剂,特别是在聚合物共混物中。
实施例1:
将6.1g pTHF 1000与0.4g来自WAKO的偶氮引发剂VA085(2,2’-偶氮二(N-丁醇-2-基)-2-甲基丙酰胺)、4g苯乙烯、0.2g十六烷和1.63g IPDI混合,并且将该混合物与2.17g Steinapol NLS于27.9g去离子水中的溶液一起迅速搅拌。接着使用Branson超声波仪W 450以100%振幅和50%脉冲超声处理2分钟,同时在冰浴中冷却。之后,加入2滴DBTL并在60℃下加热该混合物5小时。然后将温度升高到72℃,持续5小时,之后升高到95℃持续5小时。其中不再有任何可辨别的苯乙烯气味。在通过40my过滤后,发现固含量为29.2%。粒径:150nm
实施例2:
将6.2g pTHF 1000与0.358g来自WAKO的偶氮引发剂VA086(2,2’-偶氮二(2-甲基-N-(2-羟乙基))丙酰胺),4.1g苯乙烯、0.2g十六烷和1.65g IPDI混合,并且将该混合物与2.19g Steinapol NLS于28.1g去离子水中的溶液一起迅速搅拌。接着使用Branson超声波仪W 450以100%振幅和50%脉冲超声处理2分钟,同时在冰浴中冷却。之后,加入2滴DBTL并在60℃下加热该混合物5小时。然后将温度升高到72℃,持续5小时,之后升高到95℃再持续5小时。其中不再有任何可辨别的苯乙烯气味。在通过40my过滤后,发现固含量为27.6%。粒径:148nm。
Claims (6)
1.一种制备嵌段共聚物的水分散液的方法,其中所述嵌段共聚物一方面包含加聚物或缩聚物作为聚合物I,另一方面包含可通过自由基加聚反应获得的聚合物作为聚合物II,其中
-聚合物I可通过其起始化合物在微粒乳状液中反应获得,
-聚合物I的起始化合物之一是自由基加聚反应的引发剂,并且
-聚合物II是在所述引发剂存在下制备,
其中由聚合物I的起始化合物和聚合物II的单体形成微粒乳状液,并且所述起始化合物与单体形成所述嵌段共聚物的反应是在微粒乳状液中且在一个工艺步骤中进行的,
其中聚合物I是聚氨酯,并且相应的起始化合物是异氰酸酯和异氰酸酯活性化合物,
其中所述引发剂是包含至少一个异氰酸酯基或一个异氰酸酯活性基团的偶氮化合物。
2.如权利要求1所述的方法,其中所述微粒乳状液具有50-500nm的单体液滴尺寸。
3.如权利要求1或2所述的方法,其中作为聚合物I的起始化合物的引发剂的量是按每100重量份聚合物II计的0.1-10重量份。
4.如权利要求1或2所述的方法,其中聚合物I的量是基于嵌段共聚物的5-95重量%。
5.如权利要求1所述的方法,其中作为所述嵌段共聚物一部分的聚氨酯由下述组分合成:
a)多异氰酸酯,
b)多元醇,其中
b1)基于多元醇(b)总量计的10-100摩尔%的该多元醇具有500-5000g/摩尔的分子量,
b2)基于多元醇(b)总量计的0-90摩尔%的该多元醇具有60-500g/摩尔的分子量,
c)不同于单体(a)和(b)的单体,其具有至少一个异氰酸酯基或至少一个对异氰酸酯基有活性的基团,并且进一步携带至少一个亲水性基团或一个潜在亲水性基团,
d)在合适时,不同于单体(a)-(c)的其它化合物,其具有至少2个异氰酸酯活性基团,其中的至少一个所述基团是伯氨基、仲氨基或巯基,
e)在合适时,与单体(a)-(d)不同的具有活性基团的一价化合物,其中所述活性基团是醇羟基、伯氨基、仲氨基或异氰酸酯基。
6.如权利要求1或2所述的方法,其中聚合物II已经由至少60重量%的主要单体合成,所述主要单体选自(甲基)丙烯酸C1-C20烷基酯,包含最多20个碳原子的羧酸的乙烯基酯,包含最多20个碳原子的乙烯基芳族化合物,烯键不饱和腈,乙烯基卤化物,包含1-10个碳原子的醇的乙烯基醚,具有2-8个碳原子和一个或两个双键的脂族烃,或这些单体的混合物。
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PCT/EP2004/013812 WO2005054323A1 (de) | 2003-12-08 | 2004-12-04 | Verfahren zur herstellung von blockcopolymerisaten in miniemulsion |
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US5612406A (en) * | 1991-07-11 | 1997-03-18 | Dainippon Ink & Chemicals Inc. | Processes for production of azo macroinitiators for the synthesis of block copolymers and of aqueous block copolymer dispersions and emulsions and the use thereof |
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DE19852784A1 (de) * | 1998-11-16 | 2000-05-18 | Max Planck Gesellschaft | Osmotische Stabilisierung von Mini- und Mikroemulsionen und deren Anwendung zur Herstellung von Nanohybridpartikeln |
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US7786207B2 (en) | 2010-08-31 |
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ATE557052T1 (de) | 2012-05-15 |
EP1701987A1 (de) | 2006-09-20 |
EP1701987B1 (de) | 2012-05-09 |
DE10357533A1 (de) | 2005-07-07 |
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CN1890282A (zh) | 2007-01-03 |
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