CN105339398A - 含氟共聚物的水性分散液 - Google Patents
含氟共聚物的水性分散液 Download PDFInfo
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Abstract
一种含氟共聚物的水性分散液,其以(A)?[CH2=CHRCOO(NH)rR1NR2R3R4]+?Y-所示的(甲基)丙烯酸酯;(B)CmF2m+1CpH2p(NR’SO2)qOCOCR=CH2所示的(甲基)丙烯酸全氟烷基烷基酯或(甲基)丙烯酸多氟烷基烷基酯,或者CnF2n+1(CH2CF2)a(CF2CF2)b(CH2CH2)cOCOCR=CH2所示的(甲基)丙烯酸多氟烷基酯;(C)(甲基)丙烯酸苄基酯;(D)所述(A)、(C)成分以外的非氟类聚合性单体;以及(E)含交联性基团的聚合性单体作为共聚单元。该水性分散液作为以含氟共聚物为有效成分的拒水拒油剂使用时,可改善拒水拒油剂水性分散液的分散稳定性。
Description
技术领域
本发明涉及含氟共聚物的水性分散液。更具体地说,涉及化学稳定性优异、可有效用作拒水拒油剂水性分散液等的含氟共聚物的水性分散液。
背景技术
利用含氟聚合物的拒水拒油性的表现起因于氟原子的低表面能,通常大多使用含氟(甲基)丙烯酸酯类聚合物作为拒水拒油剂的有效成分。
为了表现作为拒水拒油剂的性能,加工液中的拒水拒油剂颗粒均匀地吸附于纤维表面是很重要的。一般来说,与天然纤维或合成纤维的种类无关,纤维表面的ζ(zeta)电位通常具有负(阴离子)电位。因此拒水拒油剂颗粒的电位必须是适度的正(阳离子)电位,由此在纤维表面进行稳定的吸附,表现稳定的性能。
而拒水拒油剂颗粒的正电位过大时,可见在具有负电位的纤维表面一次选择性吸附较多的拒水拒油剂颗粒,从而性能不稳定的现象;或者由于排斥,拒水拒油剂颗粒的均匀吸附受到抑制,因而性能降低的情况等。因此在供纤维等的加工的拒水拒油剂中,从获得稳定的加工性的方面考虑,控制拒水拒油剂颗粒的表面电位是很重要的一点。
为了使颗粒表面具有正(阳离子)电位,有人提出使用阳离子性乳化剂。例如专利文献1中提出:在包含季铵盐的阳离子性表面活性剂和聚丙二醇类化合物的存在下,对含多氟烷基的(甲基)丙烯酸酯和不含氟原子的聚合性单体进行乳化处理,然后在聚合引发剂的存在下进行共聚反应,从而制造水性分散液的方法。
但是,在纤维等的连续加工中,染色等的前工序中使用的染料、试剂等成为杂质,它们被混入加工浴中并蓄积。这些杂质大多是亲水性的阴离子性物质,因此与阳离子性乳化剂反应,引起拒水拒油剂的聚集沉降所导致的问题或拒水拒油性降低。
并且根据纤维等的加工目的或加工对象而并用各种试剂的情形在近年来非常多,基于这种实际情况,人们强烈要求拒水拒油剂与其它并用试剂的相容性,换言之即化学稳定性。
专利文献2中记载了将拒水拒油剂与去污剂并用,经拒水、拒油、去污加工的纤维制品,这里所使用的去污剂是含有氟类单体和含亲水性基团的单体的含氟共聚物,作为含亲水性基团的单体,可示出具有离子性基团(即阳离子性基团或阴离子性基团)以及不饱和键的单体,例如2-甲基丙烯酰氧基乙基三甲基氯化铵、N,N,N-三甲基-N-(2-羟基-3-甲基丙烯酰氧基丙基)氯化铵。
所述去污剂用含氟共聚物中,含亲水性基团的单体的量相对于其与氟类单体的合计量为10-80重量%,优选15-60重量%,例如20-50重量%,在示出去污剂的合成例的合成例2中,使用
丙烯酸全氟辛基乙基酯 60g(60重量%)
甲基丙烯酸甲氧基聚乙二醇酯 30g(30重量%)
甲基丙烯酸2-羟基乙酯 8g(8重量%)
2-甲基丙烯酰氧基乙基三甲基氯化铵 2g(2重量%),
且描述了所得共聚物组成与所加入的单体组成大致一致。
现有技术文献
专利文献
专利文献1:日本特开2004-262954号公报
专利文献2:日本特开2007-270378号公报
专利文献3:WO2007/105633。
发明内容
发明所要解决的课题
本发明的目的在于提供:在作为以含氟共聚物为有效成分的拒水拒油剂使用时,可改善拒水拒油剂水性分散液的分散稳定性的含氟共聚物的水性分散液。
解决课题的方案
所述本发明的目的通过一种含氟共聚物的水性分散液实现,该含氟共聚物以如下成分作为共聚单元:
(A)通式[1]所示的(甲基)丙烯酸酯,
[CH2=CHRCOO(NH)rR1NR2R3R4]+Y- [I]
(这里,R为氢原子或甲基,R1为碳原子数1-30的直链状、分支状或脂环式的亚烷基或亚苯基,R2、R3、R4分别为相同或彼此不同的碳原子数1-30的直链状、分支状或脂环式的烷基或芳烷基,r为0或1,Y-为阴离子基团);
(B)通式[IIa]所示的(甲基)丙烯酸全氟烷基烷基酯或其全氟烷基的一部分氟原子被氢原子置换的(甲基)丙烯酸多氟烷基烷基酯,
CmF2m+1CpH2p(NR’SO2)qOCOCR=CH2 [IIa]
(这里,R为氢原子或甲基,R’为碳原子数1-5的烷基,m为4-14的整数,p为1-4的整数,q为0或1)
或者通式[IIb]所示的(甲基)丙烯酸多氟烷基酯,
CnF2n+1(CH2CF2)a(CF2CF2)b(CH2CH2)cOCOCR=CH2 [IIb]
(这里,R为氢原子或甲基,n为1-6的整数,a为1-4的整数,b为1-3的整数,c为1-3的整数);
(C)(甲基)丙烯酸苄基酯;
(D)所述(A)、(C)成分以外的非氟类聚合性单体;以及
(E)含交联性基团的聚合性单体。
这里,(甲基)丙烯酸酯是指丙烯酸酯或甲基丙烯酸酯。
发明效果
形成乳液的水性分散液的分散稳定性通过控制分散颗粒表面的荷电量进行,从对纤维等的吸附性考虑,通常使用阳离子性表面活性剂。但是由于在水性分散液中有杂质混入,可见表面活性剂从分散液颗粒的表面脱落,发生水性分散液分散不良的情况。
为解决这样的问题,本发明中使用(A)成分即末端具有季铵基的(甲基)丙烯酸酯作为荷电性的聚合性单体,进一步在含氟共聚物中使(甲基)丙烯酸苄基酯共聚,由此可以将作为(A)成分的荷电性聚合性单体的使用比例抑制为较低,具体来说,发现通过使该使用量的有效范围为共聚物中0.1-1.0重量%,即使比所述专利文献2所述的2重量%低,拒水拒油性能也可保持较高。
这样,可有效地改善形成以含氟共聚物为有效成分的拒水拒油剂的水性分散液的分散稳定性。
具体实施方式
上述通式[I]所示的具有末端季铵基的(甲基)丙烯酸酯单体可例示以下所述单体,如果有市售商品则可直接使用。这里,阴离子基团Y-表示Cl-、Br-、I-、RSO4 -、H2PO4 -、RCOO-、ROSO2 -、RSO-、ROPO4H-、CO3 -、RSO3 -(这里,R为氢原子、烷基或芳基)等。
甲基丙烯酰氧基乙基三甲基氯化铵
甲基丙烯酰氧基氨基丙基三甲基氯化铵
甲基丙烯酰氧基乙基二甲基乙基氯化铵
甲基丙烯酰氧基乙基二甲基正戊基氯化铵
甲基丙烯酰氧基乙基二甲基苄基氯化铵
甲基丙烯酰氧基氨基丙基二甲基苄基氯化铵
甲基丙烯酰氧基乙基三甲基硫酸甲酯铵
甲基丙烯酰氧基氨基丙基三甲基硫酸甲酯铵
甲基丙烯酰氧基乙基二甲基乙基硫酸乙酯铵
甲基丙烯酰氧基氨基丙基二甲基乙基硫酸乙酯铵
甲基丙烯酰氧基乙基三甲基铵对甲苯磺酸盐
甲基丙烯酰氧基氨基丙基三甲基铵对甲苯磺酸盐
这些(A)成分单体在含氟共聚物中以达到约0.1-1.0重量%、优选约0.2-0.7重量%的比例共聚。共聚比例比这低,则不仅粒径分布、ζ电位变差,而且保存稳定性也完全不足。而以比这多的比例使用时也有同样问题。
作为上述通式[IIa]所示的(甲基)丙烯酸全氟烷基烷基酯或(甲基)丙烯酸多氟烷基烷基酯,例如示出以下所述的(甲基)丙烯酸酯化合物。这里,m为4-14的整数。
CH2=CHCOOCH2CmF2mH
CH2=C(CH3)COOCH2CmF2mH
CH2=CHCOOCH2CmF2m+1
CH2=C(CH3)COOCH2CmF2m+1
CH2=CHCOOC2H4CmF2m+1
CH2=C(CH3)COOC2H4CmF2m+1
CH2=CHCOOC3H6CmF2m+1
CH2=C(CH3)COOC3H6CmF2m+1
CH2=CHCOOC4H8CmF2m+1
CH2=C(CH3)COOC4H8CmF2m+1
CH2=CHCOOC2H4N(CH3)SO2CmF2m+1
CH2=C(CH3)COOC2H4N(CH3)SO2CmF2m+1
CH2=CHCOOC2H4N(C2H5)SO2CmF2m+1
CH2=C(CH3)COOC2H4N(C2H5)SO2CmF2m+1
CH2=CHCOOC2H4N(C3H7)SO2CmF2m+1
CH2=C(CH3)COOC2H4N(C3H7)SO2CmF2m+1
CH2=CHCOOC2H4Cm-3F2m-6CF(CF3)2
CH2=C(CH3)COOC2H4Cm-3F2m-6CF(CF3)2
而且,所述通式[IIb]所示的(甲基)丙烯酸多氟烷基酯记载于专利文献3中,例如可举出以下的化合物。
C2F5(CH2CF2)(CF2CF2)(CH2CH2)OCOCR=CH2
C2F5(CH2CF2)(CF2CF2)2(CH2CH2)OCOCR=CH2
C2F5(CH2CF2)2(CF2CF2)(CH2CH2)OCOCR=CH2
C2F5(CH2CF2)2(CF2CF2)2(CH2CH2)OCOCR=CH2
C4F9(CH2CF2)(CF2CF2)(CH2CH2)OCOCR=CH2
C4F9(CH2CF2)2(CF2CF2)(CH2CH2)OCOCR=CH2
C4F9(CH2CF2)(CF2CF2)2(CH2CH2)OCOCR=CH2
C4F9(CH2CF2)2(CF2CF2)2(CH2CH2)OCOCR=CH2
作为(B)成分的这些(甲基)丙烯酸全氟烷基烷基酯[IIa]或(甲基)丙烯酸多氟烷基烷基酯、或者(甲基)丙烯酸多氟烷基酯[IIb]是以在含氟共聚物中占约10-80重量%、优选约25-80重量%的比例共聚的。共聚比例比这低,则无法发挥必要的拒水拒油性,而以比这高的比例使用,则其它共聚成分的共聚比例相对降低,无法获得来源于它们的所需的性质。
(C)成分的(甲基)丙烯酸苄基酯、优选甲基丙烯酸苄基酯是以在含氟共聚物中占约5-80重量%、优选约5-50重量%的比例共聚的。未共聚(甲基)丙烯酸苄基酯,则无法降低(A)成分即具有末端季铵基的(甲基)丙烯酸酯的共聚比例。
作为(D)成分,即(A)、(C)成分以外的非氟类单体,从拒水拒油性的平衡上,例如优选使用如下的至少一种:甲基、乙基、丙基、异丙基、正丁基、正己基、2-乙基己基、正辛基、月桂基、硬脂基等碳原子数1-18的直链状或分支状烷基,环己基等环烷基,苄基等芳烷基,甲氧基甲基、2-甲氧基乙基、2-乙氧基乙基、2-丁氧基乙基、3-乙氧基丙基等碳原子数2-6的烷氧基烷基进行酯化所得的丙烯酸酯或甲基丙烯酸酯,富马酸或马来酸的二甲基、二乙基、二丙基、二丁基、二辛基等碳原子数1-8的烷基的二烷基酯,乙酸乙烯基酯、辛酸乙烯基酯等乙烯基酯,例如苯乙烯、乙烯基甲苯、α-甲基苯乙烯、乙烯基萘、丙烯腈、甲基丙烯腈、氯乙烯、偏二氯乙烯等可其它可共聚的乙烯基化合物。
这些非氟类单体中,优选使用偏二氯乙烯。通过使这些非氟类单体共聚,可以改良与纤维等基材的密合性,成膜性、皮膜强度也得到改善,可赋予优异的拒水拒油性。非氟类单体的共聚比例是在含氟共聚物中约1-30重量%,优选约5-25重量%。
(E)成分即含交联性基团的聚合性单体例如可使用多元醇的单或多(甲基)丙烯酸酯,具有碳原子数1-4的烷基的含羟基烷基的(甲基)丙烯酸酯或含乙烯基醚,含酰胺基的(甲基)丙烯酸酯,含环氧基的(甲基)丙烯酸酯、乙烯基醚或烯丙基醚,含卤素基团的(甲基)丙烯酸酯或乙烯基醚,含N-羟甲基的(甲基)丙烯酸酯,含氮丙啶基的(甲基)丙烯酸酯,含羧基的聚合性单体、二烯类单体等,优选使用聚亚烷基二醇单(甲基)丙烯酸酯、(甲基)丙烯酸羟基烷基酯或含羟甲基的(甲基)丙烯酰胺。
多元醇的单或多(甲基)丙烯酸酯例如可举出:乙二醇单(甲基)丙烯酸酯、丙二醇单(甲基)丙烯酸酯、1,4-丁烷二醇单(甲基)丙烯酸酯、1,6-己烷二醇单(甲基)丙烯酸酯、1,9-壬烷二醇单(甲基)丙烯酸酯、新戊二醇单(甲基)丙烯酸酯、四甘醇单(甲基)丙烯酸酯、聚乙二醇单(甲基)丙烯酸酯、三丙二醇单(甲基)丙烯酸酯、聚丙二醇单(甲基)丙烯酸酯、二羟甲基三环癸烷单丙烯酸酯、甘油甲基丙烯酸酯丙烯酸酯、3-丙烯酰氧基甘油单甲基丙烯酸酯等,这些聚亚烷基二醇(甲基)丙烯酸酯中,为多(甲基)丙烯酸酯时,优选并非所有的多元醇基团被酯化,必须是至少1个羟基以交联性基团的形式存在。
含羟基烷基的(甲基)丙烯酸酯或乙烯基醚例如可举出:(甲基)丙烯酸2-羟基乙酯、丙烯酸2-羟基丙酯、丙烯酸4-羟基丁酯、(甲基)丙烯酸2-羟基-3-氯丙基酯、2-羟基乙基乙烯基醚、羟基丁基乙烯基醚等。
含酰胺基的(甲基)丙烯酸酯例如可举出:丙烯酰胺、甲基丙烯酰胺、N-甲基(甲基)丙烯酰胺、N-羟甲基(甲基)丙烯酰胺、N-甲氧基甲基丙烯酰胺、N-丁氧基甲基丙烯酰胺、双丙酮丙烯酰胺等。
含环氧基的(甲基)丙烯酸酯、乙烯基醚或烯丙基醚例如可举出:(甲基)丙烯酸缩水甘油基酯、缩水甘油基乙烯基醚、烯丙基缩水甘油基醚等。
含卤素基团的(甲基)丙烯酸酯或乙烯基醚除上述的(甲基)丙烯酸2-羟基-3-氯丙基酯之外,例如还可举出氯乙基乙烯基醚等。
含N-羟甲基的(甲基)丙烯酸酯除上述的N-羟甲基(甲基)丙烯酰胺之外,例如还可举出N-丁氧基羟甲基(甲基)丙烯酰胺等。
含氮丙啶基的(甲基)丙烯酸酯例如可举出(甲基)丙烯酸氮丙啶基乙酯等。
含羧基的聚合性单体例如可举出:富马酸或马来酸的单甲基、单乙基、单丙基、单丁基、单辛基等碳原子数1-8的烷基的单烷基酯等。
另外,二烯类单体可举出:丁二烯、戊二烯、异戊二烯、氯丁二烯等。
以上所例示的含交联性基团的单体优选使用含亲水性交联性基团的聚合性单体,除此之外也可以使用含有异氰酸酯基、封端异氰酸酯基、烷氧基甲硅烷基、氨基、烷氧基甲基酰胺基、硅烷醇基、铵基、噁唑啉基、链烯基、磺酸基等的聚合性单体。
这些含交联性基团的单体以在含氟共聚物中占约0.3-30重量%、优选约1-20重量%的比例共聚。将这些含交联性基团的聚合性单体作为拒水拒油性含氟共聚物的有效成分进一步共聚,则对纤维等基材的附着性牢固,可见拒水拒油剂的耐久性、耐洗涤性、耐干洗性等提高的效果。
这些各聚合性单体的共聚反应可在非离子类表面活性剂、优选聚氧化乙烯类非离子表面活性剂的存在下,通过乳液聚合法进行。聚氧化乙烯类非离子性表面活性剂可使用:聚氧化乙烯与己基苯酚、辛基苯酚、壬基苯酚、多环苯基醚、十六烷醇、油酸、C12-C18的烷基胺、去水山梨糖醇单脂肪酸酯等的缩合反应产物,优选使用聚氧化乙烯与多环苯基醚的缩合反应产物。非离子类表面活性剂相对于含水的乳液聚合反应体系总量,以约1-20重量%的比例使用。
使用这些乳化剂进行的含氟单体的共聚反应可在无机过氧化物、偶氮化合物、有机过氧化物等的存在下,优选以过硫酸铵、过硫酸钠、过硫酸钾等水溶性无机过氧化物或者它们与亚硫酸氢钠、焦亚硫酸钠等的亚硫酸氢盐、硫代硫酸盐、肼、偶氮二甲酸酯等还原剂的氧化还原类作为催化剂进行,为了调节此时聚合体系内的pH值,可以添加磷酸盐(Na2HPO4、NaH2PO4、KH2PO4等)或硼酸盐(Na2B2O7等)具有缓冲能力的电解质物质或NaOH等使用。
共聚反应时,可使用丙二酸乙酯、乙酸乙酯等酯类,二甲醚、甲基叔丁基醚等醚类,甲醇、乙醇、异丙醇等醇类,丙酮、甲基乙基酮、甲基异丁基酮等酮类,C1-C5的链烷类,氯仿、四氯化碳、二氯乙烷等卤代烃类等作为链转移剂。
共聚反应中,相对于应生成的含氟聚合物,使用约为0.1-10重量%、优选约0.5-7重量%、进一步优选约0.5-5重量%的聚合引发剂,在约0-100℃、优选约50-80℃下,在约0.1-10MPa、优选约0.2-5MPa的加压条件下进行约1-48小时左右。聚合引发剂可根据需要在聚合反应中途再次追加使用。共聚反应的结果是,其中形成了固体成分浓度约15-35重量%的水性分散液(水性乳液)。
这样得到的作为原液的水性分散液,可以将其固体成分浓度用水、优选离子交换水稀释为约0.1-10重量%左右,然后在由纤维、布、织造布、纸、膜、毯或长丝、纱、纤维等制作的布帛制品等中作为拒水拒油剂有效应用。应用方法可以采用涂布、浸渍、喷涂、浸染(padding)、辊涂或这些的组合方法,例如使浴的固体成分浓度为约0.1-10重量%,由此可作为浸染浴使用。在该浸染浴中将被处理材料浸染,接着通过挤压辊除去过量的液体,干燥,相对于被处理材料,以所附着的含氟类共聚物量为约0.01-10重量%的比例使其附着。然后,根据被处理材料的种类,但通常在约80-120℃的温度下进行约1分钟至约2小时左右的干燥,接着在约150-180℃下进行约1-3分钟、优选在约150-170℃下进行约1-3分钟的固化,完成拒水拒油处理。
共聚反应几乎都是定量进行,因此各加入的聚合性单体的重量比例几乎为所得含氟共聚物的共聚比例。所得各氟共聚物具有约2,000-20,000,000的重均分子量Mw。
实施例
下面,通过实施例说明本发明。
实施例1
甲基丙烯酸2-(正-全氟己基)乙酯 87.2g(63.9%)
[FAMAC-6]
甲基丙烯酸苄基酯[BZMA] 22.4g(16.4%)
甲基丙烯酸2-羟基乙酯[2HEA] 5.6g(3.8%)
聚乙二醇(n:4)单甲基丙烯酸酯 4.2g(3.1%)
[PE-200](日本油脂制品PE-200)
甲基丙烯酰氧基乙基三甲基氯化铵 0.3g(0.2%)
[DMACMA]
月桂基硫醇(链转移剂)[n-BMC] 0.5g
聚氧乙烯多环苯基醚(表面活性剂) 7.0g
[N-740](日本乳化剂制品Newcol-740)
己二醇(溶剂)[HG] 25.0g
离子交换水 258.5g
将以上各成分加入内容量1L的玻璃制反应器中混合,进一步使用高压均质器乳化混合。
将反应器内用氮气置换30分钟,然后将反应器内温度缓慢升高,达到40℃后,加入(包含318.2g离子交换水总量的合计量为500.0g):
偏二氯乙烯[VDC] 11.2g(8.2%)
N-羟甲基丙烯酰胺[NMAM] 5.6g(4.1%)
(为溶解于29.3g离子交换水的溶液形式)
2,2’-偶氮二(2-脒基丙烷)·2盐酸盐 2.8g
(聚合引发剂)[NC-32P](为溶解于30.4g离子交换水的溶液形式)
,进一步使内温缓慢升高至70℃,在保持该温度的同时反应4小时。
反应终止后冷却,得到490g固体成分浓度为24.8重量%的水性分散液。对于该水性分散液进行颗粒直径、平均ζ电位的测定和40℃下经时的保存稳定性的评价。
粒径:使用粒度分布计MICROTRACUPA150,分别测定自粒径小的一侧累计频率为10%、50%、100%时的粒径(50%粒径表示平均粒径)
平均ζ电位测定:测定器使用日机装制造的ZetaPLAS,在测定温度25℃、测定pH1-7、测定浓度1mg/ml的条件下测定5次,求出其平均值
经时的保存稳定性评价:在内容量110ml的螺纹管(浅圆锥状管)内装入50g水性分散液,将其开放端部用PTEE膜密封,然后在保持40度的烘箱中放置1周、2周、3周、4周和6个月,经过规定时间后将离心管倾斜,按照以下基准目视评价底面的沉淀发生状况
等级A:沉淀几乎为零
等级B:沉淀微量析出于底面的一部分
等级C:沉淀薄薄析出于几乎整个底面,但可自底面可见到液体的整个表面
等级D:沉淀析出于整个底面,自底面无法见到液体的整个表面
等级E:沉淀大量析出,分层。
实施例2-4、比较例1-3
在实施例1中,将(A)-(D)共聚成分的种类和使用量进行各种变更。
DTFAC-103:3,3,4,4,5,5,6,6,7,7,9,9,10,10,11,11,12,12,12-十九氟癸醇丙烯酸酯
C4F9(CH2CF2)(CF2CF2)2(CH2CH2)OCOCH=CH2
FAAC-Mix:甲基丙烯酸2-(全氟烷基)乙酯
全氟烷基量是C66%、C852%、C1024%、C127%和C142%(合计91%)的混合基团,平均碳原子数为8.8
STAC:丙烯酸硬脂基酯
共聚成分量(g以及括号内的重量%)和测定结果示于下表。链转移剂(n-DMC)、表面活性剂(N-740)、聚合引发剂(NC-32P)、有机溶剂(HG)的种类和使用量、聚合时间(4小时)、聚合温度(70℃)分别与实施例1相同。离子交换水用于以使包含水的加入全部成分合计量为500g的方式调节其量。
Claims (6)
1.含氟共聚物的水性分散液,该含氟共聚物以如下成分作为共聚单元:
(A)通式[1]所示的(甲基)丙烯酸酯:
[CH2=CHRCOO(NH)rR1NR2R3R4]+Y- [I]
这里,R为氢原子或甲基,R1为碳原子数1-30的直链状、分支状或脂环式的亚烷基或亚苯基,R2、R3、R4分别为相同或彼此不同的碳原子数1-30的直链状、分支状或脂环式的烷基或芳烷基,r为0或1,Y-为阴离子基团;
(B)通式[IIa]所示的(甲基)丙烯酸全氟烷基烷基酯或其全氟烷基的一部分氟原子被氢原子置换的(甲基)丙烯酸多氟烷基烷基酯,或者通式[IIb]所示的(甲基)丙烯酸多氟烷基酯:
CmF2m+1CpH2p(NR’SO2)qOCOCR=CH2 [IIa]
这里,R为氢原子或甲基,R’为碳原子数1-5的烷基,m为4-14的整数,p为1-4的整数,q为0或1,
CnF2n+1(CH2CF2)a(CF2CF2)b(CH2CH2)cOCOCR=CH2 [IIb]
这里,R为氢原子或甲基,n为1-6的整数,a为1-4的整数,b为1-3的整数,c为1-3的整数;
(C)(甲基)丙烯酸苄基酯;
(D)所述(A)、(C)成分以外的非氟类聚合性单体;以及
(E)含交联性基团的聚合性单体。
2.权利要求1所述的含氟共聚物的水性分散液,其中,以含氟共聚物中的(A)成分为0.1-1.0重量%、(B)成分为10-80重量%、(C)成分为5-80重量%、(D)成分为1-30重量%、(E)成分为0.3-30重量%的比例共聚。
3.权利要求1所述的含氟共聚物的水性分散液,其中,含氟共聚物中为(D)成分的非氟类聚合性单体是偏二氯乙烯。
4.权利要求1所述的含氟共聚物的水性分散液,其中,含氟共聚物中为(E)成分的含交联性基团的聚合性单体是聚亚烷基二醇单(甲基)丙烯酸酯、(甲基)丙烯酸羟基烷基酯或含羟甲基的(甲基)丙烯酰胺。
5.拒水拒油剂,该拒水拒油剂是将权利要求1、2、3或4所述的含氟共聚物的水性分散液进一步用水系介质稀释,将固体成分浓度调节为0.1-10重量%而得的。
6.含氟共聚物,该含氟共聚物以如下成分作为共聚单元:
(A)通式[1]所示的(甲基)丙烯酸酯:
[CH2=CHRCOO(NH)rR1NR2R3R4]+Y- [I]
这里,R为氢原子或甲基,R1为碳原子数1-30的直链状、分支状或脂环式的亚烷基或亚苯基,R2、R3、R4分别为相同或彼此不同的碳原子数1-30的直链状、分支状或脂环式的烷基或芳烷基,r为0或1,Y-为阴离子基团;
(B)通式[IIa]所示的(甲基)丙烯酸全氟烷基烷基酯或其全氟烷基的一部分氟原子被氢原子置换的(甲基)丙烯酸多氟烷基烷基酯,或者通式[IIb]所示的(甲基)丙烯酸多氟烷基酯:
CmF2m+1CpH2p(NR’SO2)qOCOCR=CH2 [IIa]
这里,R为氢原子或甲基,R’为碳原子数1-5的烷基,m为4-14的整数,p为1-4的整数,q为0或1,
CnF2n+1(CH2CF2)a(CF2CF2)b(CH2CH2)cOCOCR=CH2 [IIb]
这里,R为氢原子或甲基,n为1-6的整数,a为1-4的整数,b为1-3的整数,c为1-3的整数;
(C)(甲基)丙烯酸苄基酯;
(D)所述(A)、(C)成分以外的非氟类聚合性单体;以及
(E)含交联性基团的聚合性单体;
其中,以(A)成分为0.1-1.0重量%、(B)成分为10-80重量%、(C)成分为5-80重量%、(D)成分为1-30重量%、(E)成分为0.3-30重量%的比例共聚。
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CN110485160A (zh) * | 2017-10-24 | 2019-11-22 | 广东德美精细化工集团股份有限公司 | 包含遥爪聚合物的高效防水防油剂的制备方法 |
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EP3015481B1 (en) * | 2013-06-25 | 2018-08-22 | Unimatec Co., Ltd. | Aqueous dispersion of fluorinated copolymer |
JP6871526B2 (ja) * | 2015-02-04 | 2021-05-12 | 日産化学株式会社 | 親水性含フッ素高分岐ポリマー及びそれを含む重合性組成物 |
CA2989690A1 (en) | 2015-06-17 | 2016-12-22 | Clariant International Ltd | Water-soluble or water-swellable polymers as water loss reducers in cement slurries |
US11384186B2 (en) | 2016-12-12 | 2022-07-12 | Clariant International Ltd | Polymer comprising certain level of bio-based carbon |
CN110300573B (zh) | 2016-12-12 | 2023-07-25 | 科莱恩国际有限公司 | 生物基聚合物在化妆、皮肤病学或药物学组合物中的用途 |
WO2018108664A1 (en) | 2016-12-15 | 2018-06-21 | Clariant International Ltd | Water-soluble and/or water-swellable hybrid polymer |
US11542343B2 (en) | 2016-12-15 | 2023-01-03 | Clariant International Ltd | Water-soluble and/or water-swellable hybrid polymer |
WO2018108667A1 (en) | 2016-12-15 | 2018-06-21 | Clariant International Ltd | Water-soluble and/or water-swellable hybrid polymer |
WO2018108663A1 (en) | 2016-12-15 | 2018-06-21 | Clariant International Ltd | Water-soluble and/or water-swellable hybrid polymer |
JP2019081884A (ja) * | 2017-10-31 | 2019-05-30 | 株式会社イーテック | 組成物 |
JPWO2021235540A1 (zh) * | 2020-05-22 | 2021-11-25 |
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JPWO2014208338A1 (ja) | 2017-02-23 |
CN105339398B (zh) | 2017-06-20 |
EP3015481A4 (en) | 2017-01-18 |
EP3015481B1 (en) | 2018-08-22 |
US20160185948A1 (en) | 2016-06-30 |
JP5950043B2 (ja) | 2016-07-13 |
KR20160022858A (ko) | 2016-03-02 |
KR101819978B1 (ko) | 2018-01-19 |
EP3015481A1 (en) | 2016-05-04 |
WO2014208338A1 (ja) | 2014-12-31 |
US10023733B2 (en) | 2018-07-17 |
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