CN101460544A - 有机硅共聚物 - Google Patents

有机硅共聚物 Download PDF

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CN101460544A
CN101460544A CNA2007800201935A CN200780020193A CN101460544A CN 101460544 A CN101460544 A CN 101460544A CN A2007800201935 A CNA2007800201935 A CN A2007800201935A CN 200780020193 A CN200780020193 A CN 200780020193A CN 101460544 A CN101460544 A CN 101460544A
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organosiliconcopolymere
acid
ethylenically unsaturated
vinyl
unsaturated monomers
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CN101460544B (zh
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O·明格
P·巴尔
A·克奈索尔
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Wacker Polymer Systems GmbH and Co KG
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Abstract

本发明涉及一种有机硅共聚物(O)，其通过在水性介质中自由基聚合以下组分得到：A1)选自以下的烯键式不饱和单体：N－羟甲基丙烯酰胺(NMA)、N－羟甲基甲基丙烯酰胺、N－羟甲基烯丙基氨基甲酸酯、以及N－羟甲基丙烯酰胺、N－羟甲基甲基丙烯酰胺、N－羟甲基烯丙基氨基甲酸酯的烷基醚或酯，与A2)选自乙烯酯、(甲基)丙烯酸酯、乙烯基芳族化合物、烯烃、1，3－二烯、乙烯醚和乙烯卤化物的烯键式不饱和单体，和A3)任意地辅助单体，和B)单或多烯键式不饱和聚有机硅氧烷。

Description

有机硅共聚物
本发明涉及烯键式不饱和单体和烯键式不饱和聚硅氧烷的有机硅共聚物，以及它们的制备和用途。
已知在造纸和织物整理领域中使用聚合物是必要的，以便诸如拉伸强度、断裂伸长率、弹性或干或湿耐磨性的机械性能可被赋予基体或改进。所用的聚合物不仅包括天然聚合物，特别是淀粉，而且包括由于环境条件和法规而理想地以水形态应用的合成聚合物。并且，在将聚合物或粘合剂应用到纤维上之后，与基底的粘着理想地应是好的。因此在本领域最典型应用的水加聚物分散体是被交联单体官能化的那些，交联单体在高温下干燥中能够在加聚物链之间以及加聚物和纤维之间提供共价键。这使得形成交联结构成为可能，这种结构对外部试剂的作用是有抵抗力的。
对于这种用途，最有效的官能单体是(甲基)丙烯酰胺的羟甲基衍生物，例如N-羟甲基(甲基)丙烯酰胺(N(M)MA)。这些单体的特征在于容许它们进行自由基聚合的烯键双键，以及通过在通常100℃以上的高温下并常常在酸催化作用下与其它官能团缩合反应的方式来确保交联的NHCH2OH基团。这导致在链之间或在加聚物与基体之间形成共价键。
例如，EP 1482081 A1描述了以醋酸乙烯酯和乙烯为基础的用于处理纤维非织造网的水共聚物分散体，它包括N-羟甲基丙烯酰胺型的后交联基团。所公开的粘合剂赋予该纤维以高的干和湿拉伸强度。
EP 143175 B2公开了以乙烯基酯-丙烯酸酯共聚物为基础的N-羟甲基丙烯酰胺-改性的聚合物分散体。
US 6913628公开了另一种方法。丙烯酸酯系粘合剂是为获得后交联能力而改性的硅烷，其确实带来提高的拉伸强度，但该纤维附件不耐用，因为形成的Si-O-C键易发生水解且是pH敏感的。
所有这些引用的方法都具有两个共同的基本缺点：
首先，当在降低的活性水平下应用时，甚至需要更大的干和湿强度，或需要更精确的确保与现有技术强度相当的聚合物。
其次，已知的聚合物通常在织物或纤维的触觉特性(手)上具有非常不适宜的效果，例如柔软度。
其他聚合物可被应用以改善纤维或织物的触觉。通常使用硅氧烷和含硅氧烷结构以正面影响例如柔软度。此外，对于活性，与基体的粘合是期望的。其实例为氨基官能化的硅油(“胺油(amine oil)”)，其如已知的特别地正向影响织物的柔软度以及其疏水性。由于其Lewis碱性氨基基团，其也具有“接近”Lewis酸性纤维的性质。此硅氧烷胺油以及其用途在例如WO2005010076中被描述，其为现有技术。然而，由胺油接近(going on)产生的耐性已知是短暂和不足的，涂层不仅能机械地而且能化学地被轻易地去除。氨基硅氧烷的另外的缺点是有期望柔软度但不期望疏水性的特定应用，因为例如纤维的吸水能力被负面影响。
本发明提供有机硅共聚物(O)，其可以通过在水性介质中自由基聚合以下组分而得到：
A1)选自以下的烯键式不饱和单体：N-羟甲基丙烯酰胺(NMA)，N-羟甲基甲基丙烯酰胺，N-羟甲基烯丙基氨基甲酸酯，以及N-羟甲基丙烯酰胺、N-羟甲基甲基丙烯酰胺、N-羟甲基烯丙基氨基甲酸酯的烷基醚或酯，与
A2))选自以下的烯键式不饱和单体：乙烯酯、(甲基)丙烯酸酯、乙烯基芳族化合物、烯烃、1，3-二烯、乙烯醚和乙烯卤化物的烯键式不饱和单体，和
A3)任选辅助单体，和
B)单或多烯键式不饱和聚有机硅氧烷。
相比于现有技术，得到的有机硅共聚物(O)赋予诸如纤维、纸张和织物的已处理基体以优越的干和湿拉伸强度，给定的适当的硅氧烷含量，也向聚合物输送了硅氧烷特征，而不会负面影响纤维的疏水性。基体的疏水性能轻易地精细可调。
优选的，自由基聚合在乳液或微乳液中发生。得到的有机硅共聚物(O)的水分散体能被直接用于处理基体。水分散体也能通过干燥被加工以形成可再分散聚合粉末。特别优选聚合在微乳液中发生。
优选的丙烯酰胺甘醇酸(AGA)和甲基丙烯酰胺甘醇酸的酯(A1)为C1-C10烷基酯。优选的N-羟甲基丙烯酰胺、N-羟甲基甲基丙烯酰胺和N-羟甲基烯丙基氨基甲酸酯的酯(A1)为C1-C10烷基羧酸的酯。优选的N-羟甲基丙烯酰胺、N-羟甲基甲基丙烯酰胺和N-羟甲基烯丙基氨基甲酸酯的醚(A1)为C1-C10烷基醚。
特别优选的烯键式不饱和单体A1)为N-羟甲基丙烯酰胺(NMA)、N-羟甲基甲基丙烯酰胺和N-羟甲基烯丙基氨基甲酸酯，其各自具有可后交联的羟甲基基团。
优选的烯键式不饱和单体A2)为具有1-15个碳原子的羧酸的乙烯酯。特别优选为醋酸乙烯酯、丙酸乙烯酯、丁酸乙烯酯、2-乙基己酸乙烯酯、月桂酸乙烯酯、醋酸1-甲基乙烯酯、新戊酸乙烯酯和具有9-11个碳原子的α-支链一元羧酸的乙烯酯，如VeoVa9R或VeoVa10R(Resolution的商标名)。特别优选醋酸乙烯酯。由丙烯酸酯或甲基丙烯酸酯中优选的单体A2)为具有1-15个碳原子的支链或非支链醇的酯。优选的甲基丙烯酸酯或丙烯酸酯为丙烯酸甲酯、甲基丙烯酸甲酯、丙烯酸乙酯、甲基丙烯酸乙酯、丙烯酸丙酯、甲基丙烯酸丙酯、丙烯酸正丁酯、甲基丙烯酸正丁酯、丙烯酸异丁酯、甲基丙烯酸异丁酯、丙烯酸叔丁酯、甲基丙烯酸叔丁酯、丙烯酸2-乙基己酯和降冰片基丙烯酸酯。特别优选丙烯酸甲酯、甲基丙烯酸甲酯、丙烯酸正丁酯、甲基丙烯酸正丁酯、丙烯酸异丁酯、丙烯酸叔丁酯、丙烯酸2-乙基己酯和降冰片基丙烯酸酯。
优选的乙烯芳族化合物A2)为苯乙烯、α-甲基苯乙烯、乙烯基甲苯和乙烯基二甲苯和二乙烯基苯的同分异构体。特别优选苯乙烯。
优选的乙烯卤素化合物为氯乙烯、1，1-二氯乙烯、四氟乙烯、二氟乙烯、己基全氟乙烯、3，3，3-三氟丙烯、全氟丙基乙烯基醚、六氟丙烯、一氯三氟乙烯和氟乙烯。特别优选氯乙烯。
优选的乙烯醚A2)为例如甲基乙烯基醚。优选的烯烃A2)为乙烯、丙烯、1-烷基乙烯和多不饱和烯烃，优选的二烯为1，3-丁二烯和异戊二烯。特别优选乙烯和1，3-丁二烯。
特别优选作为单体A2)的为一种或多种单体，选自醋酸乙烯酯、具有9-11个碳原子的α-支链一元羧酸的乙烯酯、氯乙烯、乙烯、丙烯酸甲酯、甲基丙烯酸甲酯、丙烯酸乙酯、甲基丙烯酸乙酯、丙烯酸丙酯、甲基丙烯酸丙酯、丙烯酸正丁酯、甲基丙烯酸正丁酯、丙烯酸2-乙基己酯、苯乙烯、1，3-丁二烯。也特别优选作为单体A2)的是丙烯酸正丁酯和丙烯酸2-乙基己酯和/或甲基丙烯酸甲酯的混合物；苯乙烯和一种或多种选自丙烯酸甲酯、丙烯酸乙酯、丙烯酸丙酯、丙烯酸正丁酯、丙烯酸2-乙基己酯的单体的混合物；醋酸乙烯酯和一种或多种选自丙烯酸甲酯、丙烯酸乙酯、丙烯酸丙酯、丙烯酸正丁酯、丙烯酸2-乙基己酯和任意地乙烯的混合物；1，3-丁二烯和苯乙烯和/或甲基丙烯酸甲酯的混合物。
任选地，基于单体A1)+A2)的总重量的0.1wt％-5wt％的辅助单体A3)能被共聚。优选使用05wt％-2.5wt％的辅助单体。辅助单体A3)的实例为烯键式不饱和单和二羧酸，优选丙烯酸、甲基丙烯酸、富马酸和马来酸；烯键式不饱和羧酸酰胺和腈，优选丙烯酰胺和丙烯腈；富马酸和马来酸的单和二酯，如二乙酯和二异丙酯，以及马来酸酐、烯键式不饱和磺酸及其盐，优选乙烯基磺酸、2-丙烯酰胺-2-甲基丙磺酸。同样适合的为环氧官能化的烯键式不饱和共聚单体，如甲基丙烯酸缩水甘油酯和丙烯酸缩水甘油酯。也可以论及具有羟基或CO基团的烯键式不饱和单体，例如甲基丙烯酸羟基烷基酯和丙烯酸羟基烷基酯，诸如丙烯酸羟乙酯、丙烯酸羟丙酯、丙烯酸羟丁酯、甲基丙烯酸羟乙酯、甲基丙烯酸羟丙酯、甲基丙烯酸羟丁酯，以及诸如二丙酮丙烯酰胺和乙酰乙酸乙基丙烯酸酯或甲基丙烯酸酯。其他可被提及的为可共聚烯键式不饱和硅烷，例如乙烯基硅烷，如乙烯基三甲氧基硅烷或乙烯基三乙氧基硅烷或(甲基)丙烯酰硅烷，例如市场销售的产自Wacker-Chemie AG，慕尼黑，德国的硅烷，商标名为GENIOSILGF-31(甲基丙烯酰氧丙基三甲氧基硅烷)、XL-33(甲基丙烯酰氧甲基三甲氧基硅烷)、XL-32(甲基丙烯酰氧甲基二甲基甲氧基硅烷)、XL-34(甲基丙烯酰氧甲基甲基二甲氧基硅烷)和XL-36(甲基丙烯酰氧丙基三乙氧基硅烷)。
优选的单或多烯键式不饱和聚有机硅氧烷B)具有通式[1]：
(SiO4/2)k(R1SiO3/2)m(R1 2SiO2/2)p(R1 3SiO1/2)q
[O1/2SiR3 2-L-X]s[O1/2H]t            [1]
其中
L表示二价的任意取代的芳基、杂芳基环或脂族基(CR4 2)b，R1、R3、R4表示氢原子或单价C1-C20烃基或C1-C20烃氧基，其任意地被-CN、-NCO、-NR2 2、-COOH、-COOR2、-PO(OR2)2、卤素、丙烯酰、环氧、-SH、-OH或-CONR2 2取代，并且在每个中的一种或多种相互非相邻的亚甲基单元可以被基团-O-、-CO-、-COO-、-OCO-、或-OCOO-、-S-、或-NR2-替代，以及在每个中的一种或多种相互不相邻的次甲基单元可以被基团-N＝、-N＝N-、或-P＝替代，
X表示烯键式不饱和基，
R2表示氢或单价的任选取代的烃基，
b代表至少为1的整数值，
s代表至少为1的整数值，
t代表0或整数值，
k+m+p+q代表至少为2的整数值.
优选的聚有机硅氧烷B)为R1、R3、R4可以是脂肪族饱的或不饱和的、芳族的、直链的或支链的C1-C20烃基或C1-C20烃氧基。R1、R3、R4优选具有1-12个原子，特别是1-6个原子，优选仅为碳原子，或一个烷氧基氧原子和其他仅为碳原子。
优选R1、R3、R4为直链或支链C1-C6烷基或苯基。特别优选的基团为甲基、乙基、丙基、苯基和乙烯基。
优选R3为甲基和R4为氢。
X优选为一个乙烯型(-C2H3)、丙烯酰型(-OCOC2H3)或甲基丙烯酰型(-OCOC2H2CH3)的烯键式不饱和基。
优选b的值不超过50，特别是不超过10。在特别优选实施方案中b等于2或3。
通式[1]的聚有机硅氧烷B)可以是线形、环状、直链型或交联的。k、m、p、q、s和t的总和优选为3-20000，特别是8-1000。
通式[1]的聚有机硅氧烷B)的其他优选变体为有机硅树脂。此树脂可由两个或多个通式[1]中所述的单元构成，在此情况下存在的单元的摩尔百分比用指数k、m、p、q表示。k+m必须>0。在此优选使用k+m>50％的聚硅氧烷树脂B)，基于k、m、p、q的总和。特别优选k+m>90％的树脂。
通式[1]的聚有机硅氧烷B)的其他优选变体为只由或几乎只由SiO4/2单元构成的有机硅树脂；在此规定k大于m+p+q。作为k、m、p、q的总和的百分比的k的比例至少为51％，更优选>95％或在55-65％的范围内。
通式[1]的聚有机硅氧烷B)的其他优选变体为只包括或几乎只包括SiO2/2单元的线形聚有机硅氧烷；在此规定硅氧烷只包括双管能化单元p。作为k、m、p、q的总和的百分比的p的比例优选至少为95％并更优选>95％。
单体的选择，或者更精确的为共聚单体A1)、A2)、任选A3)和B)的重量分数的选择，通常使玻璃转化温度Tg≤60℃，优选为-50℃至+60℃间。有机硅共聚物(O)的玻璃转化温度Tg可以用已知的方式通过差示扫描量热法(DSC)测定。Tg也可以通过Fox方程近似估计。依据Fox T.G.，Bull.Am.Physics Soc.1，3，page 123(1956)，下列方程为：1/Tg＝x1/Tg1+x2/Tg2+...+xn/Tgn，在此xn表示单体n的质量分数(wt％/100)，而Tgn是单体n的均聚物的开氏温度的玻璃转化温度。聚合物的Tg值在PolymerHandbook 2nd Edition，J.Wiley & Sons，New York(1975)中报道。
使用的烯键式不饱和单体A1)的量优选至少为2，特别是至少为8重量份并优选不超过100重量份，特别是不超过30重量份，基于100重量份的烯键式不饱和单体A2)。
使用的烯键式不饱和单体B)的量优选至少为3，特别是至少为10重量份并优选不超过150重量份，特别是不超过500重量份，基于100重量份的烯键式不饱和单体A2)。
有机硅共聚物(O)用多相方法制备，优选通过已知的技术，即悬浮、乳液或微乳液聚合(参看例如PeterA.Lovell，MS.El-Aasser，“EmulsionPolymerization and Emulsion Polymers”1997，John Wiley and Sons，Chichester)。在一个特别优选的形式中，反应通过微乳液聚合的方法实施。
微乳液聚合与其他多相聚合区别的一些基本点使其特别适于不溶于水的共聚用单体或大单体的共聚(参看例如K.Landfester，“Polyreactions inMiniemulsions”，Macromol.Rapid.Commun.2001，22，896-936和M.S.El-Aasser，E.D.Sudol，“Miniemulsions：Overview of Research andApplications”2004，JCT Research，1，20-31)。
反应温度为0℃-100℃，优选5℃-80℃和更优选30℃-80℃。分散介质的pH为2-9，优选为4-8。在一个特别优选实施方案中为6.5-7.5。在反应开始前，pH能用盐酸或氢氧化钠水溶液设定。聚合可以分批或连续进行，通过反应混合物的全部或各个组分的起始加载、通过反应混合物的各个组分的部分起始加载和随后的计量添加、或者通过计量过程而无起始加载。所有的计量添加优选以各自成分消耗的速率。特别优选分批操作聚合。
多相中的聚合优选在一种或多种分散剂存在下进行。可用的分散剂包括任何典型使用的乳化剂和/或保护胶体。适合的保护胶体为例如部分水解的聚乙烯醇、聚乙烯吡咯烷酮、聚醋酸乙烯酯以及淀粉和纤维素和其羧甲基、甲基、羟乙基和羟丙基衍生物。适合的乳化剂不仅包括阴离子和阳离子的而且包括非离子的乳化剂，例如阴离子表面活性剂，如具有8-18个碳原子的链长的烷基硫酸盐、在疏水部分具有8-18个碳原子并达到60个环氧乙烷或环氧丙烷单元的烷基和烷基芳基醚硫酸盐、具有8-18个碳原子的烷基或烷基芳基磺酸盐、磺基琥珀酸与一元醇或烷基苯酚的酯或半酯，或非离子表面活性剂，如具有达到60个环氧乙烷或环氧丙烷单元的烷基聚乙二醇醚或烷芳基聚乙二醇醚。其他可用的乳化剂和保护胶体在“McCutchen’sDetergents and Emulsifiers”，North American Edition，1979被发现。保护胶体和/或乳化剂通常在聚合期间以基于共聚用单体A1)、A2)、任选地A3)和B)的总重量一共为1wt％-20wt％的量被添加。
聚合通过惯用的、通常至少部分水溶性的引发剂或氧化还原引发剂结合引发。引发剂的实例为过氧二硫酸的钠、钾和铵盐、过氧化氢、叔丁基过氧化物、叔丁基过氧化氢、过氧焦磷酸钾、叔丁基过氧化新戊酸、枯基氢过氧化物、异丙基苯单氢过氧化物和偶氮二异丁腈。提及的引发剂优选以基于共聚用单体A1)、A2)、任选地A3)和B)的总重量的0.01wt％-4.0wt％的量应用。所用的氧化还原引发剂结合包含上述引发剂与还原剂的结合。适合的还原剂为单价阳离子的亚硫酸盐和酸性亚硫酸盐，例如亚硫酸钠，诸如锌或碱金属甲醛合次硫酸盐的次硫酸衍生物，例如羟基甲烷合次硫酸钠以及抗坏血酸。还原剂的用量优选为基于共聚用单体A1)、A2)、任选地A3)和B)的总重量的0.15wt％-3wt％。少量的可溶于聚合介质中并且其金属成分在聚合条件下为氧化还原活性的金属化合物能被额外地引入，例如基于铁或钒的金属化合物。特别优选的引发剂为过氧二硫酸盐，特别是过氧二硫酸铵，任选地与还原剂，特别是羟基甲亚磺酸钠结合。
当反应依照微乳液聚合方法实施时，也可以使用主要油溶性的引发剂，例如枯基氢过氧化物、异丙基苯单氢过氧化物、过氧化二苯甲酰或偶氮二异丁腈。优选的微乳液聚合引发剂为过硫酸钾、过硫酸铵、偶氮二异丁腈以及过氧化苯甲酰。除了正在描述的典型引发剂外的适合的引发剂的总览在“Handbook of Free Radical Initiators”，E.T.Denisov，T.G.Denisova，T.S.Pokidova，2003，Wiley Verlag中被发现。
为了生产可水再分散聚合粉末，有机硅共聚物(O)的水分散体用传统方式干燥，优选喷雾干燥法。
依据计划的用途，有机硅共聚物(O)能与一种或多种适当的掺合料掺合。掺合料的实例为溶剂或成膜助剂；两种或多种有机溶剂的混合物；颜料润湿剂和分散剂；提供表面效果的添加剂，如用于得到诸如锤纹漆或桔皮织物的添加剂；防泡剂；基体润湿剂；表面流平剂；粘合促进剂；脱模剂；其他与本发明的有机聚合物不同的有机聚合物；表面活性剂，疏水助剂；非自由基聚合硅树脂。
有机硅共聚物(O)可以纯净形式或作为诸如用于多种基体的涂层、粘合剂和保护涂层的水性或有机结合的组分被应用，特别是任何种类的织物和纤维，例如纤维素纤维、棉纤维和纸纤维，以及聚合物纤维，包括但不限于聚酯、聚酰胺或聚氨酯纤维。
包含具有可后交联羟甲基基团的不饱和单体A1)的有机硅共聚物(O)可用于涂布成形制品和能够与羟甲基官能发生化学反应的表面，例如木材或木基材料，以及涂覆纸基体和成形制品。
上述基体用有机硅共聚物(O)处理，赋予处理的基体以改善的机械性能，特别是干和湿拉伸强度。另外，给定适当的硅氧烷含量，典型的硅氧烷性质同时被提供，包括基体的可调疏水性。
上述通式的所有上述符号各自具有其独立的意义。硅原子在通式中为四价。
下述实施例用于详述本发明。下述实施例中的量和百分数除非另外特别陈述，全部以重量计。
实施例
实施例1(本发明的聚合物分散体的制备)：
反应组分：
27份甲基丙烯酸甲酯
27份丙烯酸正丁酯
7.7份单甲基丙烯酰-PDMS(Mn约3200g/mol)
7.5份N-羟甲基丙烯酰胺(50％水溶液)
2份衣康酸
0.15份过氧二硫酸铵
1.5份十二烷基硫酸钠
292份水
0.5份十六烷
全部反应物被称入反应罐中，在室温下搅拌五分钟。而后，混合物在约750bar的压力下用购自Avestin Europe GmbH，慕尼黑，德国的EmulsiFlex C5高压均化器均化。形成的微乳液被转移至搅拌罐中，在75℃氮气下聚合6小时，得到水性聚合物分散体，固含量19％。
实施例2(本发明的聚合物分散体的制备)：
反应组分：
27份甲基丙烯酸甲酯
27份丙烯酸正丁酯
7.7份聚甲基丙烯酰硅树脂，含59％SiO4/2、37％ Me3SiO1/2和4％甲基丙烯酰甲基二甲基甲硅烷基单元
7.5份N-羟甲基丙烯酰胺(50％水溶液)
2份衣康酸
0.15份过氧二硫酸铵
1.5份十二烷基硫酸钠
292份水
0.5份十六烷
重复实施例1的过程。
固含量：18％
实施例3(本发明的聚合物分散体的制备)：
反应组分：
27份甲基丙烯酸甲酯
27份丙烯酸正丁酯
7.7份单甲基丙烯酰-PDMS(Mn约6000g/mol)
7.5份N-羟甲基丙烯酰胺(50％水溶液)
4份甲基丙烯酸N，N-二乙基氨基乙酯
0.15份过氧二硫酸铵
1.5份十二烷基硫酸钠
292份水
0.5份十六烷
重复实施例1的过程。
固含量：18％
实施例4(本发明的聚合物分散体的制备)：
反应组分：
27份甲基丙烯酸甲酯
27份丙烯酸正丁酯
7.7份单甲基丙烯酰-PDMS(Mn约6000g/mol)
7.5份N-羟甲基丙烯酰胺(50％水溶液)
4份甲基丙烯酸N，N-二乙基氨基乙酯
2份衣康酸
0.15份过氧二硫酸铵
1.5份十二烷基硫酸钠
292份水
0.5份十六烷
重复实施例1的过程。
固含量：19％
实施例5(本发明的聚合物分散体的制备)：
反应组分：
27份甲基丙烯酸甲酯
27份丙烯酸正丁酯
7.7份聚甲基丙烯酰硅树脂，含59％SiO4/2、37％ Me3SiO1/2和4％甲基丙烯酰甲基二甲基甲硅烷基单元
7.5份N-羟甲基丙烯酰胺(50％水溶液)
4份甲基丙烯酸N，N-二乙基氨基乙酯
0.15份过氧二硫酸铵
1.5份十二烷基硫酸钠
292份水
0.5份十六烷
重复实施例1的过程。
固含量：24％
实施例6(本发明的聚合物分散体的制备)：
反应组分：
27份甲基丙烯酸甲酯
27份丙烯酸正丁酯
7.7份α，ω-双甲基丙烯酰-PDMS(Mn约1000)
7.5份N-羟甲基丙烯酰胺(50％水溶液)
2份甲基丙烯酸N，N-二乙基氨基乙酯
2份衣康酸
0.15份过氧二硫酸铵
1.5份十二烷基硫酸钠
292份水
0.5份十六烷
重复实施例1的过程。
固含量：19％
实施例7(本发明的聚合物分散体的制备)：
反应组分：
27份甲基丙烯酸甲酯
27份丙烯酸正丁酯
7.7份聚甲基丙烯酰硅树脂，含59％SiO4/2、37％ Me3SiO1/2和4％甲基丙烯酰甲基二甲基甲硅烷基单元
7.5份N-羟甲基丙烯酰胺(50％水溶液)
2份甲基丙烯酸N，N-二乙基氨基乙酯
6份衣康酸
0.15份过氧二硫酸铵
1.5份十二烷基硫酸钠
292份水
0.5份十六烷
重复实施例1的过程。
固含量：19％
实施例8(本发明的聚合物分散体的制备)：
反应组分：
27份甲基丙烯酸甲酯
27份丙烯酸正丁酯
7.7份聚甲基丙烯酰硅树脂，含59％SiO4/2、37％ Me3SiO1/2和4％甲基丙烯酰甲基二甲基甲硅烷基单元
7.5份N-羟甲基丙烯酰胺(50％水溶液)
2份甲基丙烯酸N，N-二乙基氨基乙酯
0.15份过氧二硫酸铵
7份聚乙烯醇，水解度88％，粘度4mPas
292份水
0.5份十六烷
重复实施例1的过程。
固含量：18％
性能测试
在实施例1-7中得到的聚合物分散体用水稀释成5％的活性含量，并用喷枪(
Figure A200780020193D00161
 2000 Dekor)喷雾在非织造布上。当在室温下干燥和在140℃下储存5分钟后，进行各种测试：
液滴测试：液滴润湿纤维所用的时间。
应力应变测量：测量在152mm×25mm的干燥和湿润的织物样品上用1446型
Figure A200780020193D00162
装置上进行，速度为12.7mm/min。大量测量：F-max[N]、F-max[g-force]、拉伸F-max[％]、运行直到断裂，TEA[J]。
Figure A200780020193D00171

Claims (8)

1.一种有机硅共聚物(O)，其通过在水性介质中自由基聚合以下组分得到：
A1)选自以下的烯键式不饱和单体：N-羟甲基丙烯酰胺(NMA)、N-羟甲基甲基丙烯酰胺、N-羟甲基烯丙基氨基甲酸酯、以及N-羟甲基丙烯酰胺、N-羟甲基甲基丙烯酰胺、N-羟甲基烯丙基氨基甲酸酯的烷基醚或酯，与
A2)选自乙烯酯、(甲基)丙烯酸酯、乙烯基芳族化合物、烯烃、1，3-二烯、乙烯醚和乙烯卤化物的烯键式不饱和单体，和
A3)任意地辅助单体，和
B)单或多烯键式不饱和聚有机硅氧烷。
2.依据权利要求1的有机硅共聚物(O)，其中所述烯键式不饱和单体A2)包括具有1-15个碳原子的羧酸的乙烯酯。
3.依据权利要求1或2的有机硅共聚物(O)，其中所述辅助单体A3)选自烯键式不饱和一元和二元羧酸、烯键式不饱和羧酸酰胺和腈、富马酸和马来酸的单和二酯、烯键式不饱和磺酸及其盐、环氧官能化烯键式不饱和共聚单体、具有羟基或CO基团的烯键式不饱和单体和烯键式不饱和硅烷。
4.依据权利要求1-3之一的有机硅共聚物(O)，其中所述烯键式不饱和聚有机硅氧烷B)具有通式[1]：
(SiO4/2)k(R1SiO3/2)m(R1 2SiO2/2)p(R1 3SiO1/2)q
[O1/2SiR3 2-L-X]s[O1/2H]t         [1]
其中
L表示二价的任选取代的芳基、杂芳基或脂族基(CR4 2)b，
R1、R3、R4表示氢原子或单价C1-C20烃基或C1-C20烃氧基，其任选被-CN、-NCO、-NR2 2、-COOH、-COOR2、-PO(OR2)2、卤素、丙烯酰、环氧、-SH、-OH或-CONR2 2取代，并且在每个中的一种或多种相互不相邻的亚甲基单元可以被基团-O-、-CO-、-COO-、-OCO-、或-OCOO-、-S-、或-NR2-替代，以及在每个中的一种或多种相互不相邻的次甲基单元可以被基团-N＝、-N＝N-、或-P＝替代，
X表示烯键式不饱和基，
R2表示氢或单价的任选取代的烃基，
b代表至少为1的整数值，
s代表至少为1的整数值，
t代表0或整数值，
k+m+p+q代表至少为2的整数值。
5.依据权利要求1-4之一的有机硅共聚物(O)，其中所述自由基聚合在乳液或微乳液中发生。
6.通过干燥权利要求1-5之一的有机硅共聚物(O)的水分散体得到的再分散聚合物粉末。
7.一种制备有机硅共聚物(O)的方法，其包括：
A1)选自以下的烯键式不饱和单体：N-羟甲基丙烯酰胺(NMA)、N-羟甲基甲基丙烯酰胺、N-羟甲基烯丙基氨基甲酸酯、以及N-羟甲基丙烯酰胺、N-羟甲基甲基丙烯酰胺、N-羟甲基烯丙基氨基甲酸酯的烷基醚或酯，与
A2)选自乙烯酯、(甲基)丙烯酸酯、乙烯基芳族化合物、烯烃、1，3-二烯、乙烯醚和乙烯卤化物的烯键式不饱和单体，和
A3)任选地辅助单体，和
B)单或多烯键式不饱和聚有机硅氧烷
在水性介质中自由基聚合。
8.依据权利要求1-6之一的有机硅共聚物(O)作为涂料、粘合剂和保护涂层的用途。
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