CN104428327A - 含氟聚合物的制造方法 - Google Patents
含氟聚合物的制造方法 Download PDFInfo
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- CN104428327A CN104428327A CN201380035831.6A CN201380035831A CN104428327A CN 104428327 A CN104428327 A CN 104428327A CN 201380035831 A CN201380035831 A CN 201380035831A CN 104428327 A CN104428327 A CN 104428327A
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- Prior art keywords
- monomer
- polymkeric substance
- fluorine
- carbonatoms
- comonomer
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- 239000011737 fluorine Substances 0.000 title claims abstract description 62
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 238000000034 method Methods 0.000 title claims abstract description 33
- 229920000642 polymer Polymers 0.000 title abstract description 17
- 238000004519 manufacturing process Methods 0.000 title abstract description 11
- 239000000178 monomer Substances 0.000 claims abstract description 198
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- 239000000463 material Substances 0.000 claims abstract description 11
- 238000012545 processing Methods 0.000 claims abstract description 11
- 239000000126 substance Substances 0.000 claims description 100
- 125000004432 carbon atom Chemical group C* 0.000 claims description 66
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- 125000001309 chloro group Chemical group Cl* 0.000 claims description 23
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims description 17
- 125000000217 alkyl group Chemical group 0.000 claims description 15
- 125000001931 aliphatic group Chemical group 0.000 claims description 14
- 229910052801 chlorine Inorganic materials 0.000 claims description 14
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- 125000001246 bromo group Chemical group Br* 0.000 claims description 12
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- 125000005843 halogen group Chemical group 0.000 claims description 7
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Abstract
本发明提供一种赋予纤维制品等基材优异的拨水拨油性,在其加工处理中,防止聚合物附着于辊的性能优异的拨水拨油剂组合物。提供一种包含由第一单体形成的第一聚合物和由第二单体形成的第二聚合物的含氟聚合物的制法,该制法包括:(I)将第一单体聚合,获得第一聚合物的工序、和(II)在第一聚合物的存在下将第二单体投料使之聚合,由此获得第二聚合物的工序,第一单体和第二单体的至少一方含有含氟单体(a),第一单体和第二单体的双方含有卤化烯烃(b)。
Description
技术领域
本发明涉及对纤维制品(例如地毯)、纸、无纺布、石材、静电过滤器、防尘罩、燃料电池的部件赋予优异的拨水性、拨油性、防污性的含氟聚合物和含有该聚合物的处理剂组合物,特别是涉及表面处理剂组合物。
背景技术
目前已提案有各种含氟化合物。含氟化合物具有耐热性、耐氧化性、耐候性等特性优异的优点。利用含氟化合物的自由能低、即难以附着这样的特性,含氟化合物例如被用作拨水拨油剂和防污剂。例如,美国专利第5247008号说明书记载了丙烯酸或者甲基丙烯酸的全氟烷基酯、和丙烯酸或者甲基丙烯酸的烷基酯、和丙烯酸或者甲基丙烯酸的氨基烷基酯的共聚物的水性分散物,其为用于纤维制品、皮革、纸和矿物基材的精加工剂。
另外,目前以提高针对洗涤或者干洗等的拨水拨油性的耐久性为目的,尝试将含有氟烷基聚合性单体与具有粘接性基团的单体共聚,掺合含有氟烷基的聚合物和被膜强度高的聚合物。在涂料(涂布剂)的领域,通过使用具有多层结构的颗粒聚合物来维持氟的特性,成功赋予加工性的新特性(例如,日本特开平06-56944号公报)。
另外,为了使其具有耐久性、低温固化等的特性,多层结构颗粒聚合物的组合物被提唱。(例如,日本特开平02-001795号公报、日本特开平07-278422号公报、日本特开平11-172126号公报、日本特开平2007-291373号公报)
另外,将现有的一般水性分散液稀释调和而成的拨水拨油剂加工浴中,由于被处理的布料进入时受到的物理冲击,使分散液变坏,乳液颗粒发生凝集、沉降,在拨辊上附着聚合物,屡次发生布料污染、辊污染等的故障。虽然提案有夹杂物的稳定性优异的方法(例如,日本特开平9-118877号公报、WO2004/069924号公报),但随着近年来的拨水拨油加工的多样性,都未达到能够提供充分满足的稳定性。另外,针对聚合物附着在辊上的问题,聚合物的粘着性越高越容易发生问题。另外,含有氟烷基的聚合物的氟烷基的碳原子数为6以下时,聚合物的熔点降低,有比碳原子数8以上的物质粘着性高的倾向。
现有技术文献
专利文献
专利文献1:美国专利第5247008号说明书
专利文献2:日本特开平06-56944号公报
专利文献3:日本特开平02-001795号公报
专利文献4:日本特开平07-278422号公报
专利文献5:日本特开平11-172126号公报
专利文献6:日本特开平2007-291373号公报
专利文献7:日本特开平9-118877号公报
专利文献8:WO2004/069924号公报
发明内容
发明所要解决的课题
本发明的目的在于,提供赋予纤维制品等基材优异的拨水拨油性,在其加工处理中,防止聚合物附着于辊的性能优异的拨水拨油剂组合物。
用于解决课题的方法
本发明人等为了解决上述问题点,以提供抑制粘着性高的聚合物部分的生成,发挥高拨水拨油性,且耐久性(特别是,拨水拨油性的洗涤耐久性)也优异的拨水拨油剂组合物为目的,进行精心研究。其结果发现,通过变更具有含有特定化学结构的聚合单元的聚合物与具有含有氟烷基的单体的聚合单元的聚合物的聚合开始时刻,能够达到上述目的,以致完成本发明。
本发明提供一种含氟聚合物,其包含由第一单体形成的第一聚合物和由第二单体形成的第二聚合物,
第二单体在第一聚合物的存在下聚合,
第一单体和第二单体的至少一方含有含氟单体(a),
第一单体和第二单体的双方含有卤化烯烃(b)。
另外,本发明提供一种包含由第一单体形成的第一聚合物和由第二单体形成的第二聚合物的含氟聚合物的制法,该制法包括:
(I)将第一单体聚合,获得第一聚合物的工序、和
(II)在第一聚合物的存在下将第二单体投料使之聚合,由此获得第二聚合物的工序,
第一单体和第二单体的至少一方含有含氟单体(a),
第一单体和第二单体的双方含有卤化烯烃(b)。
另外,本发明还提供以上述的含氟聚合物为必须成分的拨水拨油剂。
含氟聚合物具有源自含氟单体的重复单元和源自卤化烯烃等非氟单体的重复单元。
含氟聚合物能够通过分批投料制造。通过分批投料,进行单体的两步聚合。分批投料意味着,迟于一种以上的单体的投料(聚合开始),进行其他的一种以上单体的投料(聚合开始)。两步聚合意味着,在将含有一种以上的单体的第一单体聚合所获得的第一聚合物的存在下,进行含有其他的一种以上的单体的第二单体聚合。
发明的效果
根据本发明,能够获得赋予纤维制品等基材优异的拨水拨油性,在其加工处理中,防止聚合物附着于辊的性能优异的拨水拨油剂组合物。而且,拨水拨油性的耐久性高。
具体实施方式
本发明的含氟聚合物包含源自第一单体的重复单元和源自第二单体的重复单元。第一聚合物和第二聚合物可以共聚。即,第一聚合物和第二聚合物可以化学结合。或者,第一聚合物和第二聚合物不形成化学键,可以物理结合。物理结合的例子为第一聚合物形成核、第二聚合物形成壳的核/壳结构。核/壳结构中,第一聚合物和第二聚合物虽然有不化学结合的情况,但也可以化学结合。
本发明中,作为单体,使用含氟单体(a)和卤化烯烃单体(b)。根据需要可以使用非氟非交联性单体(c)和/或非氟交联性单体(d)。
第一单体和第二单体的至少一方含有含氟单体。优选第一单体含有含氟单体,第二单体不含含氟单体。
第一单体和第二单体的双方含有卤化烯烃单体。
第一单体可以含有非氟非交联性单体。优选第二单体不含非氟非交联性单体。通过使第二单体不含非氟非交联性单体,在含有含氟聚合物的处理剂的加工处理中,防止聚合物附着在辊上导致辊污染的性能优异。
第一单体和第二单体的至少一方可以含有非氟交联性单体。含氟聚合物含有非氟交联性单体时,可以是第一单体不含非氟交联性单体而第二单体含有非氟交联性单体,或者可以是第一单体含有非氟交联性单体而第二单体不含非氟交联性单体。
第一单体和第二单体中的单体的优选种类有以下方式。
[表1]
含氟单体和非氟交联性单体可以分别存在于第一单体和第二单体双方。即,能够使用除了含氟单体存在于第一单体和第二单体的双方以外与方式1~7同样的方式、除了非氟交联性单体存在于第一单体和第二单体的双方以外与方式1~7相同的方式。
(a)含氟单体
含氟单体是下式所示的含氟单体:
CH2=C(-X)-C(=O)-Y-Z-Rf
[式中,X是氢原子、一价的有机基团或卤原子,
Y是-O-或-NH-,
Z是直接键合或二价的有机基团,
Rf是碳原子数1~20的氟烷基。]
Z例如可以是碳原子数1~20的直链亚烷基或支链状亚烷基、例如式-(CH2)x-(式中,x为1~10。)所示的基团、或者式-SO2N(R1)R2-或式-CON(R1)R2所示的基团(式中,R1为碳原子数1~10的烷基,R2为碳原子数1~10的直链亚烷基或支链状亚烷基。)、或者式-CH2CH(OR3)CH2-(式中,R3表示氢原子或碳原子数1~10的酰基(例如甲酰基或乙酰基等)。)所示的基团、或者式-Ar-CH2-(式中,Ar为根据需要具有取代基的亚芳基。)所示的基团、-(CH2)m-SO2-(CH2)n-基或-(CH2)m-S-(CH2)n-基(其中,m为1~10,n为0~10)。X的具体例为H、Me(甲基)、Cl、Br、I、F、CN、CF3。
含氟单体(a)优选是下述通式(I)所示的丙烯酸酯或丙烯酰胺,
CH2=C(-X)-C(=O)-Y-Z-Rf (I)
[式中,X是氢原子、碳原子数1~21的直链状或支链状的烷基、氟原子、氯原子、溴原子、碘原子、CFX1X2基(其中,X1和X2是氢原子、氟原子、氯原子、溴原子或碘原子。)、氰基、碳原子数1~21的直链状或支链状的氟烷基、取代或非取代的苄基、取代或非取代的苯基;
Y是-O-或-NH-;
Z是碳原子数1~10的脂肪族基团、碳原子数6~18的芳香族基团或环状脂肪族基团、-CH2CH2N(R1)SO2-基(其中,R1是碳原子数1~4的烷基。)、-CH2CH(OZ1)CH2-基(其中,Z1是氢原子或乙酰基。)、-(CH2)m-SO2-(CH2)n-基或-(CH2)m-S-(CH2)n-基(其中,m为1~10,n为0~10),
Rf是碳原子数1~20的直链状或支链状的氟烷基。]
有含氟单体(a)的(丙烯酸酯或甲基丙烯酸酯的)α位取代有卤原子等的情况。因此,式(1)中,X可以是碳原子数2~21的直链状或支链状的烷基、氟原子、氯原子、溴原子、碘原子、CFX1X2基(其中,X1和X2是氢原子、氟原子、氯原子、溴原子或碘原子。)、氰基、碳原子数1~21的直链状或支链状的氟烷基、取代或非取代的苄基、取代或非取代的苯基。
上述式(1)中,Rf基优选为全氟烷基。Rf基的碳原子数优选为1~12、例如为1~6、特別为4~6。Rf基的例子为-CF3、-CF2CF3、-CF2CF2CF3、-CF(CF3)2、-CF2CF2CF2CF3、-CF2CF(CF3)2、-C(CF3)3、-(CF2)4CF3、-(CF2)2CF(CF3)2、-CF2C(CF3)3、-CF(CF3)CF2CF2CF3、-(CF2)5CF3、-(CF2)3CF(CF3)2、-(CF2)4CF(CF3)2、-C8F17等。
Z优选为碳原子数1~10的脂肪族基团、碳原子数6~18的芳香族基团或环状脂肪族基团、-CH2CH2N(R1)SO2-基(其中,R1为碳原子数1~4的烷基。)、-CH2CH(OZ1)CH2-基(其中,Z1是氢原子或乙酰基。)、-(CH2)m-SO2-(CH2)n-基或者-(CH2)m-S-(CH2)n-基(其中,m为1~10,n为0~10)。脂肪族基团优选为亚烷基(特别是,碳原子数为1~4,例如为1或2。)。芳香族基团或环状脂肪族基团可以是取代或非取代。S基或SO2基可以与Rf基直接键合。
作为含氟单体(a)的具体例,例如能够例示以下的单体,但不被这些限定。
CH2=C(-H)-C(=O)-O-(CH2)2-Rf
CH2=C(-H)-C(=O)-O-C6H4-Rf
CH2=C(-Cl)-C(=O)-O-(CH2)2-Rf
CH2=C(-H)-C(=O)-O-(CH2)2N(-CH3)SO2-Rf
CH2=C(-H)-C(=O)-O-(CH2)2N(-C2H5)SO2-Rf
CH2=C(-H)-C(=O)-O-CH2CH(-OH)CH2-Rf
CH2=C(-H)-C(=O)-O-CH2CH(-OCOCH3)CH2-Rf
CH2=C(-H)-C(=O)-O-(CH2)2-S-Rf
CH2=C(-H)-C(=O)-O-(CH2)2-S-(CH2)2-Rf
CH2=C(-H)-C(=O)-O-(CH2)3-SO2-Rf
CH2=C(-H)-C(=O)-O-(CH2)2-SO2-(CH2)2-Rf
CH2=C(-H)-C(=O)-NH-(CH2)2-Rf
CH2=C(-CH3)-C(=O)-O-(CH2)2-S-Rf
CH2=C(-CH3)-C(=O)-O-(CH2)2-S-(CH2)2-Rf
CH2=C(-CH3)-C(=O)-O-(CH2)3-SO2-Rf
CH2=C(-CH3)-C(=O)-O-(CH2)2-SO2-(CH2)2-Rf
CH2=C(-CH3)-C(=O)-NH-(CH2)2-Rf
CH2=C(-F)-C(=O)-O-(CH2)2-S-Rf
CH2=C(-F)-C(=O)-O-(CH2)2-S-(CH2)2-Rf
CH2=C(-F)-C(=O)-O-(CH2)2-SO2-Rf
CH2=C(-F)-C(=O)-O-(CH2)2-SO2-(CH2)2-Rf
CH2=C(-F)-C(=O)-NH-(CH2)2-Rf
CH2=C(-Cl)-C(=O)-O-(CH2)2-S-Rf
CH2=C(-Cl)-C(=O)-O-(CH2)2-S-(CH2)2-Rf
CH2=C(-Cl)-C(=O)-O-(CH2)2-SO2-Rf
CH2=C(-Cl)-C(=O)-O-(CH2)2-SO2-(CH2)2-Rf
CH2=C(-Cl)-C(=O)-NH-(CH2)2-Rf
CH2=C(-CF3)-C(=O)-O-(CH2)2-S-Rf
CH2=C(-CF3)-C(=O)-O-(CH2)2-S-(CH2)2-Rf
CH2=C(-CF3)-C(=O)-O-(CH2)2-SO2-Rf
CH2=C(-CF3)-C(=O)-O-(CH2)2-SO2-(CH2)2-Rf
CH2=C(-CF3)-C(=O)-NH-(CH2)2-Rf
CH2=C(-CF2H)-C(=O)-O-(CH2)2-S-Rf
CH2=C(-CF2H)-C(=O)-O-(CH2)2-S-(CH2)2-Rf
CH2=C(-CF2H)-C(=O)-O-(CH2)2-SO2-Rf
CH2=C(-CF2H)-C(=O)-O-(CH2)2-SO2-(CH2)2-Rf
CH2=C(-CF2H)-C(=O)-NH-(CH2)2-Rf
CH2=C(-CN)-C(=O)-O-(CH2)2-S-Rf
CH2=C(-CN)-C(=O)-O-(CH2)2-S-(CH2)2-Rf
CH2=C(-CN)-C(=O)-O-(CH2)2-SO2-Rf
CH2=C(-CN)-C(=O)-O-(CH2)2-SO2-(CH2)2-Rf
CH2=C(-CN)-C(=O)-NH-(CH2)2-Rf
CH2=C(-CF2CF3)-C(=O)-O-(CH2)2-S-Rf
CH2=C(-CF2CF3)-C(=O)-O-(CH2)2-S-(CH2)2-Rf
CH2=C(-CF2CF3)-C(=O)-O-(CH2)2-SO2-Rf
CH2=C(-CF2CF3)-C(=O)-O-(CH2)2-SO2-(CH2)2-Rf
CH2=C(-CF2CF3)-C(=O)-NH-(CH2)2-Rf
CH2=C(-F)-C(=O)-O-(CH2)3-S-Rf
CH2=C(-F)-C(=O)-O-(CH2)3-S-(CH2)2-Rf
CH2=C(-F)-C(=O)-O-(CH2)3-SO2-Rf
CH2=C(-F)-C(=O)-O-(CH2)3-SO2-(CH2)2-Rf
CH2=C(-F)-C(=O)-NH-(CH2)3-Rf
CH2=C(-Cl)-C(=O)-O-(CH2)3-S-Rf
CH2=C(-Cl)-C(=O)-O-(CH2)3-S-(CH2)2-Rf
CH2=C(-Cl)-C(=O)-O-(CH2)3-SO2-Rf
CH2=C(-Cl)-C(=O)-O-(CH2)3-SO2-(CH2)2-Rf
CH2=C(-CF3)-C(=O)-O-(CH2)3-S-Rf
CH2=C(-CF3)-C(=O)-O-(CH2)3-S-(CH2)2-Rf
CH2=C(-CF3)-C(=O)-O-(CH2)3-SO2-Rf
CH2=C(-CF3)-C(=O)-O-(CH2)3-SO2-(CH2)2-Rf
CH2=C(-CF2H)-C(=O)-O-(CH2)3-S-Rf
CH2=C(-CF2H)-C(=O)-O-(CH2)3-S-(CH2)2-Rf
CH2=C(-CF2H)-C(=O)-O-(CH2)3-SO2-Rf
CH2=C(-CF2H)-C(=O)-O-(CH2)3-SO2-(CH2)2-Rf
CH2=C(-CN)-C(=O)-O-(CH2)3-S-Rf
CH2=C(-CN)-C(=O)-O-(CH2)3-S-(CH2)2-Rf
CH2=C(-CN)-C(=O)-O-(CH2)3-SO2-Rf
CH2=C(-CN)-C(=O)-O-(CH2)3-SO2-(CH2)2-Rf
CH2=C(-CF2CF3)-C(=O)-O-(CH2)3-S-Rf
CH2=C(-CF2CF3)-C(=O)-O-(CH2)3-S-(CH2)2-Rf
CH2=C(-CF2CF3)-C(=O)-O-(CH2)3-SO2-Rf
CH2=C(-CF2CF3)-C(=O)-O-(CH2)2-SO2-(CH2)2-Rf
[上述式中,Rf是碳原子数1~20的氟烷基。]
(b)卤化烯烃单体
卤化烯烃单体(b)优选为取代有1~10的氯原子、溴原子或碘原子的碳原子数2~20的烯烃。卤化烯烃单体(b)优选为碳原子数2~20的氯化烯烃,特别是具有1~5的氯原子的碳原子数2~5的烯烃。卤化烯烃单体(b)的优选具体例为卤化乙烯,例如氯乙烯、溴乙烯、碘乙烯;偏卤乙烯,例如偏氯乙烯、偏溴乙烯、偏碘乙烯。由于拨水拨油性(特别是拨水拨油性的耐久性)高,所以优选氯乙烯。
(c)非氟非交联性单体
非氟非交联性单体(c)是不含氟原子的单体。非氟非交联性单体(c)不具有交联性官能团。非氟非交联性单体(c)与交联性单体(d)不同,为非交联性。非氟非交联性单体(c)优选为具有碳-碳双键的非氟单体。非氟非交联性单体(c)优选为不含氟的乙烯基单体。非氟非交联性单体(c)一般来说是具有一个碳-碳双键的化合物。
优选的非氟非交联性单体(c)可以是下式所示的化合物,
CH2=CA-T
[式中,A是氢原子、甲基或者氟原子以外的卤原子(例如,氯原子、溴原子和碘原子),
T是氢原子、碳原子数1~30(例如,1~20)的链状或环状的烃基或者具有酯键的链状或环状的碳原子数1~31(例如,1~20)的有机基团。]
碳原子数1~30的链状或环状的烃基的例子为碳原子数1~30的直链或支链的脂肪族烃基、碳原子数4~30的环状脂肪族基团、碳原子数6~30的芳香族烃基、碳原子数7~30的芳香脂肪族烃基。
具有酯键的链状或环状的碳原子数1~31的有机基团的例子为-C(=O)-O-Q和-O-C(=O)-Q(其中,Q是碳原子数1~30的直链或支链的脂肪族烃基、碳原子数4~30的环状脂肪族基团、碳原子数6~30的芳香族烃基、碳原子数7~30的芳香脂肪族烃基)。优选碳原子数12~30(特别是18~30)的直链或支链的脂肪族烃基、碳原子数4~30的环状脂肪族基团、碳原子数6~30的芳香族烃基、碳原子数7~30的芳香脂肪族烃基,进一步优选碳原子数12~30(特别是18~30)的直链或支链的脂肪族烃基、碳原子数4~30的环状脂肪族基团。
非氟非交联性单体(c)的优选例例如包括乙烯、乙酸乙烯酯、丙烯腈、苯乙烯、聚乙二醇(甲基)丙烯酸酯、聚丙二醇(甲基)丙烯酸酯、甲氧基聚乙二醇(甲基)丙烯酸酯、甲氧基聚丙二醇(甲基)丙烯酸酯和乙烯基烷基醚。非氟非交联性单体(c)不受这些例子限定。
非氟非交联性单体(c)可以是具有烷基的(甲基)丙烯酸酯。烷基的碳原子数可以是1~30,例如可以是6~30(例如10~30,特别是18~30)。例如,非氟非交联性单体(c)可以是以下通式所示的丙烯酸酯,
CH2=CA1COOA2
[式中,A1是氢原子、甲基或者氟原子以外的卤原子(例如,氯原子、溴原子和碘原子),
A2是CnH2n+1(n=1~30)所示的烷基。]
由于防止聚合物附着在辊上的性能提高,所以含氟聚合物优选具有源自A2为碳原子数12~30、特别是18~30的烷基的丙烯酸酯(CH2=CA1COOA2)的重复单元。
非氟非交联性单体(c)可以是具有环状烃基的(甲基)丙烯酸酯单体。具有环状烃基的(甲基)丙烯酸酯单体(B)是具有(优选一价的)环状烃基和一价的(甲基)丙烯酸酯基的化合物。一价的环状烃基和一价的(甲基)丙烯酸酯基直接结合。作为环状烃基可以列举饱和或不饱和的单环基、多环基、交联环基等。环状烃基优选饱和基团。环状烃基的碳原子数优选为4~20。作为环状烃基,可以列举碳原子数4~20、特别是5~12的环状脂肪族基团、碳原子数6~20的芳香族基团、碳原子数7~20的芳香脂肪族基团。环状烃基的碳原子数为15以下,例如特别优选为10以下。环状烃基的环中的碳原子优选与(甲基)丙烯酸酯基中的酯基直接结合。环状烃基优选为饱和的环状脂肪族基团。环状烃基的具体例是环己基、叔丁基环己基、异冰片基、双环戊基、双环戊烯基。(甲基)丙烯酸酯基是丙烯酸酯基或甲基丙烯酸酯基,优选甲基丙烯酸酯基。作为具有环状烃基的单体的具体例,可以举出甲基丙烯酸环己酯、甲基丙烯酸叔丁基环己酯、甲基丙烯酸苄酯、甲基丙烯酸异冰片酯、丙烯酸异冰片酯、甲基丙烯酸双环戊酯、丙烯酸双环戊酯、丙烯酸双环戊烯酯等。
(d)非氟交联性单体
本发明的含氟聚合物可以具有源自非氟交联性单体(d)的重复单元。非氟交联性单体(d)是不含氟原子的单体。非氟交联性单体(d)至少具有两个反应性基团和/或碳-碳双键,可以是不含氟的化合物。非氟交联性单体(d)可以是至少具有两个碳-碳双键化合物、或者具有至少一个碳-碳双键和至少一个反应性基团的化合物。反应性基团团的例子为羟基、环氧基、氯甲基、封端异氰酸酯基、氨基、羧基等。非氟交联性单体(d)可以是具有反应性基团的单(甲基)丙烯酸酯、(甲基)二丙烯酸酯或单(甲基)丙烯酰胺。或者,非氟交联性单体(d)可以是二(甲基)丙烯酸酯。
作为非氟交联性单体(d),例如可以二丙酮(甲基)丙烯酰胺、(甲基)丙烯酰胺、N-羟甲基(甲基)丙烯酰胺、(甲基)丙烯酸羟基甲酯、(甲基)丙烯酸羟基乙酯、3-氯-2-羟基丙基(甲基)丙烯酸酯、2-乙酰乙酰氧基乙基(甲基)丙烯酸酯、丁二烯、异戊二烯、氯丁二烯、(甲基)丙烯酸缩水甘油酯、1,6-己二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯等,但不被这些限定。
本说明书中,“(甲基)丙烯酸酯”意味着丙烯酸酯或甲基丙烯酸酯,“(甲基)丙烯酰胺”意味着丙烯酰胺或甲基丙烯酰胺。
通过将非氟非交联性单体(c)和/或非氟交联性单体(d)共聚,能够根据需要改善拨水拨油性、防污性以及这些性能的耐清洗性、耐洗涤性、对于溶剂的溶解性、硬度、触感等各种性质。
含氟聚合物中,相对于含氟单体(a)100重量份,卤化烯烃(b)的量可以是2~500重量份,例如是5~200重量份,特别是20~150重量份,非氟非交联性单体(c)的量可以是1000重量份以下,例如是0.1~300重量份,特别是1~200重量份,
非氟交联性单体(d)的量可以是50重量份以下,例如是30重量份以下,特别是0.1~20重量份。
关于卤化烯烃单体的量,第一单体中的卤化烯烃单体与第二单体中的卤化烯烃单体的重量比可以是3~97∶97~3,例如是5~50∶95~50,特别是8~40∶92~60。或者,相对于第一单体和第二单体中的卤化烯烃单体的合计,第一单体中的卤化烯烃单体的比例优选为0.1~49重量%,更优选为5~40重量%,特别优选为8~35重量%,更特別优选为15~30重量%。
卤化烯烃单体以外的同样种类的单体(例如,含氟单体)在第一单体和第二单体的双方中含有的情况下,第一单体中的同种单体和第二单体中的同种单体的重量比可以为3~97∶97~3,例如为5~95∶95~5,特别为10~90∶90~10。
本发明中的含氟聚合物可以用通常的聚合方法的任一种制造,而且聚合反应的条件也能够任意选择。作为这样的聚合方法,可以举出溶液聚合、悬浮聚合、乳液聚合。
溶液聚合中,可以采用在聚合引发剂的存在下,使单体溶解于有机溶剂,进行氮取代后,在30~120℃的范围内加热搅拌1~10小时的方法。作为聚合引发剂,例如可以列举偶氮二异丁腈、过氧化苯甲酰、二叔丁基过氧化物、月桂基过氧化物、氢过氧化枯烯、叔丁基过氧化新戊酸酯、二异丙基过氧化二碳酸酯等。相对于单体100重量份,以0.01~20重量份、例如为0.01~10重量份的范围使用聚合引发剂。
有机溶剂为对单体呈惰性并溶解这些物质的溶剂,例如为酯类(例如,碳原子数2~30的酯,具体而言,乙酸乙酯、乙酸丁酯)、酮类(例如,碳原子数2~30的酮,具体而言,甲基乙基酮、二异丁基酮)、醇(例如,碳原子数1~30的醇,具体而言,异丙醇)。作为有机溶剂的具体例子,可以举出丙酮、氯仿、HCHC225、异丙醇、戊烷、己烷、庚烷、辛烷、环己烷、苯、甲苯、二甲苯、石油醚、四氢呋喃、1,4-二噁烷、甲基乙基酮、甲基异丁酮、二异丁酮、乙酸乙酯、乙酸丁酯、1,1,2,2-四氯乙烷、1,1,1-三氯乙烷、三氯乙烯、全氯乙烯、四氯二氟乙烷、三氯三氟乙烷等。相对于单体的总计100重量份,以10~2000重量份、例如50~1000重量份的范围使用有机溶剂。
乳液聚合中,采用在聚合引发剂和乳化剂的存在下,使单体在水中乳化,进行氮取代后,在50~80℃的范围搅拌1~10小时,使其共聚的方法。聚合引发剂可以使用过氧化苯甲酰、过氧化月桂酰、叔丁基过苯甲酸酯、1-羟基环己基氢过氧化物、3-羧基丙酰基过氧化物、过氧化乙酰、偶氮二异丁脒-二盐酸盐、偶氮二异丁腈、过氧化钠、过硫酸钾、过硫酸铵等水溶性的物质或者偶氮二异丁腈、过氧化苯甲酰、二叔丁基过氧化物、月桂基过氧化物、氢过氧化枯烯、叔丁基过氧化新戊酸酯、二异丙基过氧化二碳酸酯等油溶性的物质。相对于单体100重量份,以0.01~10重量份的范围使用聚合引发剂。
为了获得放置稳定性优异的共聚物水分散液,希望使用高压均质器、超声波均质器之类的能够赋予强力破碎能量的乳化装置,将单体在水中微粒子化,使用油溶性聚合引发剂进行聚合。另外,作为乳化剂能够使用阴离子性、阳离子性或非离子性的各种乳化剂,相对于单体100重量份,以0.5~20重量份的范围使用。优选使用阴离子性和/或非离子性和/或阳离子性的乳化剂。在单体完全不相容的情况下,优选添加使这些单体充分相容的相容剂,例如,添加水溶性有机溶剂、低分子量的单体。通过添加相容剂,能够提高乳化性和共聚性。
作为水溶性有机溶剂,可以列举丙酮、甲基乙基酮、乙酸乙酯、丙二醇、一缩二丙二醇单甲基醚、一缩二丙二醇、二缩三丙二醇、乙醇等,相对于水100重量份,可以以1~50重量份、例如10~40重量份的范围使用。另外,作为低分子量的单体,可以列举甲基丙烯酸甲酯、甲基丙烯酸缩水甘油酯、2,2,2-三氟乙基甲基丙烯酸酯等,相对于单体的总量100重量份,可以以1~50重量份、例如10~40重量份的范围使用。
聚合中可以使用链转移剂。对应于链转移剂的使用量,可以变化共聚物的分子量。链转移剂的例子为月桂硫醇、硫代乙二醇、硫代甘油等含有巯基的化合物(特别是,(例如碳原子数1~30的)烷基硫醇)、次磷酸钠、亚硫酸氢钠等无机盐等。链转移剂的使用量相对于单体的总量100重量份,可以以0.01~10重量份、例如0.1~5重量份的范围使用。
一般来说,在含有第一单体的液体中进行聚合反应制造第一聚合物,接着在含有第一聚合物和第二单体的液体中进行聚合物反应制造第二聚合物,获得由第一聚合物和第二聚合物构成的含氟聚合物。可以在第一聚合物的聚合中开始第二聚合物的聚合,或者也可以在第一聚合物的聚合完成后开始第二聚合物的聚合。可以在第一聚合物的聚合反应(即,第一单体的聚合反应)结束了10%以上(即,10~100%),例如在40%以上(即,40~100%),特别是在70%以上(即,70~100%)之后,开始第二聚合物的聚合。聚合反应结束比例%(即,聚合反应进行比例%)意味着已反应的单体(聚合的单体)的摩尔%。例如,聚合反应结束10%时,已聚合的单体为10摩尔%,未反应(未聚合)的单体为90摩尔%。第一单体是至少两种单体的组合时,第一单体的摩尔%基于第一单体中的至少两种单体的总计摩尔数。
第一聚合物的聚合中意味着第一聚合物的聚合反应(即,第一单体的聚合反应)没有完全结束。例如,第一聚合物的聚合在结束了10%以上~不足40%、40%以上~不足70%或者70%以上~不足100%(特别是80%~99%,更特别是85%~98%)后,可以开始第二聚合物的聚合。
第一聚合物的聚合完成后意味着第一聚合物的聚合反应(即,第一单体的聚合反应)大约结束了100%。
在第一聚合物的聚合中开始第二聚合物的聚合时,第二聚合物具有源自第一单体和第二单体的重复单元。在第一聚合物的聚合完成后开始第二聚合物的聚合时,第二聚合物具有仅源自第二单体的重复单元。
第一单体的投料可以一次性(一次)进行,或者连续进行。第一单体的投料优选一次进行。
第二单体的投料可以一次性进行,或者连续进行。第二单体的连续的投料优选在第二单体的聚合中使单体气体(特别是,氯乙烯等卤化烯烃)的压力为一定而进行。
本发明的含氟聚合物中,第一聚合物与第二聚合物进行化学结合或者没有化学结合。
在开始第二单体的聚合的时刻,优选在聚合体系中实质上不存在未反应的非氟非交联性单体。实质上不存在意味着,在开始第二单体的聚合的时刻,未反应的非氟非交联性单体的量相对于投入的非氟非交联性单体,为10摩尔%以下,优选为8摩尔%以下,进一步优选为5摩尔%以下,特别是为3摩尔%以下,更特别为1摩尔%以下。通过使非氟非交联性单体实质上不存在,在含有含氟聚合物的处理剂的加工处理中,防止聚合物附着在辊上导致辊污染的性能优异。
本发明的含氟聚合物优选通过乳液聚合制造。在由第一聚合物和第二聚合物形成的水性分散体的颗粒中,第二聚合物可以将第一聚合物包围,含氟聚合物可以具有由第二聚合物的壳包围第一聚合物的核的核/壳结构。
含氟聚合物能够通过在液体中处理纤维制品而已知的方法的任一一种方法,适用于纤维状基材(例如,纤维制品等)。适用于纤维制品的溶液中的含氟聚合物的浓度例如可以是0.5重量%~20重量%,或者是1重量%~5重量%。纤维制品是布时,可以将布浸入溶液,或者,可以将溶液附着或者喷雾在布上。为了显现拨油性,可以将被处理的纤维制品干燥,优选例如在100℃~200℃下加热。
或者,含氟聚合物可以通过洗涤法适用于纤维制品,例如可以在洗涤适用或者干洗法等中适用于纤维制品。
被处理的纤维制品典型地是布,其中包括机织物、针织物和无纺布、衣料品形态的布和地毯,但也可以是纤维或纱或中间纤维制品(例如,棉条或粗纱等)。纤维制品材料可以是天然纤维(例如,棉或羊毛等)、化学纤维(例如,粘胶丝或莱赛尔(Lyocell)等)、或合成纤维(例如,聚酯、聚酰胺或丙烯酸纤维等),或者可以是纤维的混合物(例如,天然纤维和合成纤维的混合物等)。本发明的制造聚合物在将纤维素类纤维(例如,棉或人造丝等)制成疏油性和拨油性时特别有效。另外,本发明的方法一般来说将纤维制品制成疏水性和拨水性。
或者,纤维状基材可以是皮革。为了将皮革制成疏水性和疏油性,可以将制造聚合物在皮革加工的各种阶段,例如可以在皮革的湿润加工的期间中或者在皮革的精加工期间中将制造聚合物由水溶液或水性乳化物适用于皮革。
或者,纤维状基材可以是纸。可以将制造聚合物适用于预先成形的纸,或者在制纸的各个阶段例如适用于纸的干燥期间中。
本发明的表面处理剂优选溶液、乳液或气溶胶的形态。表面处理剂含有含氟聚合物(表面处理剂的活性成分)和介质(特别是液状介质,例如有机溶剂和/或水)。在表面处理剂中,含氟聚合物的浓度例如可以为0.01~50重量%。
本发明的表面处理剂优选含有含氟聚合物和水性介质。本说明书中,“水性介质”意味着仅由水构成的介质、以及除了水还含有有机溶剂(有机溶剂的量是相对于水100重量份为80重量份以下,例如为0.1~50重量份,特别为5~30重量份。)的介质。含氟聚合物优选通过乳液聚合制造含氟聚合物的分散液。表面处理剂优选含氟聚合物的颗粒分散在水性介质中的水性分散液。分散液中,含氟聚合物的平均粒径优选为0.01~200微米,例如为0.1~5微米,特别为0.05~0.2微米。平均粒径能够通过动态光散射装置、电子显微镜等测定。
本发明的表面处理剂能够通过现有已知的方法适用于被处理物。通常采用将该表面处理剂分散在有机溶剂或水中进行稀释,通过浸涂、喷涂、泡沫涂布等已知方法,使其附着在被处理物的表面并进行干燥的方法。另外,如果需要,可以与适当的交联剂同时适用并进行固化。而且,能够向本发明的表面处理剂中添加防虫剂、柔软剂、抗菌剂、阻燃剂、抗静电剂、涂料固定剂、防皱剂等进行并用。与基材接触的处理液中的含氟聚合物的浓度可以为0.01~10重量%(特别是在浸涂的情况下),例如为0.05~10重量%。
作为用本发明的表面处理剂(例如,拨水拨油剂)处理过的被处理物,优选纤维制品。作为纤维制品能够列举各种例子。例如可以列举棉、麻、羊毛、丝等动植物性天然纤维;聚酰胺、聚酯、聚乙烯醇、聚丙烯腈、聚氯乙烯、聚丙烯等合成纤维;人造丝、乙酸酯等半合成纤维;玻璃纤维、碳纤维、石棉纤维等无机纤维;或者这些的混合纤维。
纤维制品可以是纤维、纱、布等的形态中的任意形态。
“处理”意味着通过浸渍、喷雾、涂布等将处理剂适用于被处理物。通过处理,作为处理剂的有效成分的含氟聚合物渗透到被处理物的内部和/或附着在被处理物的表面。
实施例
接着,列举实施例、比较例和试验例对本发明进行具体说明。但是,这些说明不对本发明构成限定。
以下说明中,份或%在没有特别说明的情况下,表示重量份或重量%。
特性如下进行测定。
聚合物分散液的稳定性
聚合物分散液的稳定性通过目视对聚合后附着在高压釜内的反应垢进行观察,进行了如下评价。
◎:无反应垢
○:有微量反应垢附着
△:有少量反应垢附着
×:有大量反应垢附着
聚合物的粘着性
将聚合物的水性分散液10g分散在甲醇20g中,将得到的物质利用离心分离器以60分钟10000rpm分离聚合物和乳化剂,获得测定用样品聚合物。该聚合物的粘着性通过粘性试验机TAC-2((株)RHESCA社制)进行测定。将样品聚合物0.1g,在测定温度40℃、负载500gf条件下对粘着性进行测定。
拨水性
将聚合物的水性分散液加水稀释成固态成分浓度为1重量%,从而调整处理液。将尼龙布浸渍在处理液中,使用碾压机在4kg/cm2、4m/分钟的条件下拧干,在170℃热处理1分钟后,对处理布的拨水性进行评价。
拨水性是在洗涤前(HL0)和使用AATCC88B(1)(III)进行5次或者10次重复洗涤后(HL5或者HL10)(拨水性的耐久性)进行评价。拨水性依照JIS-L-1092的喷雾法对拨水性NO.(参照下记表I)进行表示。
[表2]
表I
实施例1
向1L的高压釜中加入C6F13CH2CH2OCOC(CH3)=CH2(C6SFMA)179g、丙烯酸硬脂酯(StA)25g、二缩三丙二醇75.8g、纯水446g、聚氧化乙烯月桂基醚10.2g、聚氧化乙烯油醚2.47g、聚氧化乙烯异十三烷基醚7.6g,在60℃加温后,使用高压均质器使其乳化分散。乳化分散后,加压填充氯乙烯6g。再添加2,2-偶氮二(2-脒基丙烷)二盐酸盐1.72g,在61℃反应1小时后(聚合反应中C6SFMA结束99%,StA结束97%),将氯乙烯54g在保持高压釜的内压为0.3MPa的条件下不断地压入,再在61℃反应4小时,获得聚合物的水性分散液。用纯水浓度调整成其固态成分浓度为30重量%,测定得到的水性分散液的特性。结果示于表A。
实施例2
在乳化后,加压填充氯乙烯15g,在61℃反应1小时后(聚合反应中C6SFMA结束99%,StA结束98%),将氯乙烯45g在保持高压釜的内压为0.3MPa的条件下不断地压入,再在61℃反应4小时,除此以外,利用与实施例1同样的方法,获得聚合物的分散液。
实施例3
在乳化后,加压填充氯乙烯15g,在61℃反应1小时后(聚合反应中C6SFMA结束99%,StA 97%结束),将氯乙烯60g在保持高压釜的内压为0.3MPa的条件下不断地压入,再在61℃反应5小时,除此以外,利用与实施例1同样的方法,获得聚合物的分散液。
实施例4
在乳化后,加压填充氯乙烯15g,在61℃反应1小时后(聚合反应中C6SFMA结束99%,StA结束96%),将氯乙烯75g在保持高压釜的内压为0.3MPa的条件下不断地压入,再在61℃反应6小时,除此以外,利用与实施例1同样的方法,获得聚合物的分散液。
实施例5
在乳化后,加压填充氯乙烯15g,在61℃反应1小时后(聚合反应中C6SFMA结束99%,StA结束95%),压入辛基硫醇0.075g,将氯乙烯45g在保持高压釜的内压为0.3MPa的条件下不断地压入,再在61℃反应4.5小时,除此以外,利用与实施例1同样的方法,获得聚合物的分散液。
比较例1
向1L的高压釜中加入C6F13CH2CH2OCOC(CH3)=CH2179g、丙烯酸硬脂酯25g、二缩三丙二醇75.8g、纯水446g、聚氧化乙烯月桂醚10.2g、聚氧化乙烯油醚2.47g、聚氧化乙烯异十三烷基醚7.6g,在60℃加温后,使用高压均质器使其乳化分散。乳化分散后,添加2,2-偶氮二(2-脒基丙烷)二盐酸盐1.72g,在60℃反应1小时后(聚合反应中C6SFMA结束99%,StA结束95%),加压填充氯乙烯60g,再反应2小时,获得聚合物的水性分散液。用纯水浓度调整成其固态成分浓度为30重量%,对得到的水性分散液的特性进行测定。结果示于表A。
比较例2
向1L的高压釜中加入C6F13CH2CH2OCOC(CH3)=CH2179g、丙烯酸硬脂酯25g、二缩三丙二醇75.8g、纯水446g、聚氧化乙烯月桂醚10.2g、聚氧化乙烯油醚2.47g、聚氧化乙烯异十三烷基醚7.6g,在60℃加温后,使用高压均质器使其乳化分散。乳化分散后,加压填充氯乙烯60g。再添加2,2-偶氮二(2-脒基丙烷)二盐酸盐1.72g,在60℃反应3小时,获得聚合物的水性分散液。用纯水浓度调整成固态成分浓度为30重量%,对得到的水性分散液的特性进行测定。结果示于表A。
将各例的特性示于表A。
产业上的可利用性
本发明的含有含氟聚合物的处理剂组合物能够作为对纤维制品(例如地毯)、纸、无纺布、石材、静电过滤器、防尘罩、燃料电池的部件赋予优异的拨水性、拨油性、防污性的拨水拨油剂以及防污剂等使用。
Claims (34)
1.一种含氟聚合物,其特征在于:
包含由第一单体形成的第一聚合物和由第二单体形成的第二聚合物,
第二单体在第一聚合物的存在下聚合,
第一单体和第二单体的至少一方含有含氟单体(a),
第一单体和第二单体的双方含有卤化烯烃(b)。
2.如权利要求1所述的含氟聚合物,其特征在于:
通过将第二单体连续投料制成。
3.如权利要求1或2所述的含氟聚合物,其特征在于:
相对于第一单体和第二单体中的卤化烯烃单体的合计,第一单体中的卤化烯烃单体的比例为0.1~49重量%。
4.如权利要求1~3中任一项所述的含氟聚合物,其特征在于:
第一单体含有含氟单体(a)。
5.如权利要求1~4中任一项所述的含氟聚合物,其特征在于:
第二单体含有含氟单体(a)。
6.如权利要求1~5中任一项所述的含氟聚合物,其特征在于:
第二单体不含非氟非交联性单体(c)。
7.如权利要求1~5中任一项所述的含氟聚合物,其特征在于:
第一单体含有非氟非交联性单体(c)。
8.如权利要求1~7中任一项所述的含氟聚合物,其特征在于:
第二单体含有非氟交联性单体(d)。
9.如权利要求1~8中任一项所述的含氟聚合物,其特征在于:
第一聚合物除了含有含氟单体(a)以外,还含有非氟非交联性单体(c)和根据需要存在的非氟交联性单体(d)。
10.如权利要求1~9中任一项所述的含氟聚合物,其特征在于:
第二聚合物仅由卤化烯烃构成。
11.如权利要求1~10中任一项所述的含氟聚合物,其特征在于:
第二聚合物除了含有卤化烯烃以外,还含有含氟单体(a)和/或非氟交联性单体(d)的至少一方。
12.如权利要求1~11中任一项所述的含氟聚合物,其特征在于:
含氟单体(a)是下式所示的单体,
CH2=C(-X)-C(=O)-Y-Z-Rf
式中,X是氢原子、一价的有机基团或卤原子,
Y是-O-或-NH-,
Z是直接键合或二价的有机基团,
Rf是碳原子数1~20的氟烷基。
13.如权利要求1~12中任一项所述的含氟聚合物,其特征在于:
含氟单体(a)是下式所示的单体,
CH2=C(-X)-C(=O)-Y-Z-Rf (Ⅰ)
式中,X是氢原子、碳原子数1~21的直链状或者支链状的烷基、氟原子、氯原子、溴原子、碘原子、CFX1X2基、氰基、碳原子数1~21的直链状或者支链状的氟烷基、取代或者非取代的苄基、取代或者非取代的苯基,其中,X1和X2是氢原子、氟原子、氯原子、溴原子或碘原子;
Y是-O-或-NH-;
Z是碳原子数1~10的脂肪族基团、碳原子数6~18的芳香族基团或者环状脂肪族基团、-CH2CH2N(R1)SO2-基、-CH2CH(OZ1)CH2-基、-(CH2)m-SO2-(CH2)n-基或者-(CH2)m-S-(CH2)n-基,其中,R1是碳原子数1~4的烷基,Z1是氢原子或乙酰基,m为1~10,n为0~10;
Rf是碳原子数1~20的直链状或支链状的氟烷基。
14.如权利要求12或13所述的含氟聚合物,其特征在于:
含氟单体的氟烷基的碳原子数为6以下。
15.如权利要求1~14中任一项所述的含氟聚合物,其特征在于:
卤化烯烃(b)是取代有氯原子、溴原子或碘原子的碳原子数2~20的烯烃。
16.如权利要求1~15中任一项所述的含氟聚合物,其特征在于:
卤化烯烃(b)是氯乙烯、溴乙烯、碘乙烯、偏氯乙烯、偏溴乙烯或者偏碘乙烯。
17.如权利要求1~16中任一项所述的含氟聚合物,其特征在于:
卤化烯烃(b)是氯乙烯。
18.如权利要求5~17中任一项所述的含氟聚合物,其特征在于:
非氟非交联性单体(c)是不含氟原子、不具有交联性官能团、具有一个碳-碳双键的单体。
19.如权利要求5~18中任一项所述的含氟聚合物,其特征在于:
非氟非交联性单体(c)是下式所示的单体,
CH2=CA-T
式中,A是氢原子、甲基或氟原子以外的卤原子(例如氯原子、溴原子和碘原子),
T是氢原子、碳原子数1~30的链状或环状的烃基、或者具有酯键的链状或环状的碳原子数1~31的有机基团。
20.如权利要求19所述的含氟聚合物,其特征在于:
非氟非交联性单体(c)中,T是碳原子数12~30的长链的烃基和饱和的环状烃基。
21.如权利要求5~18中任一项所述的含氟聚合物,其特征在于:
非氟非交联性单体(c)是以下通式所示的丙烯酸酯,
CH2=CA1COOA2
式中,A1是氢原子、甲基或氟原子以外的卤原子(例如氯原子、溴原子和碘原子),
A2是CnH2n+1所表示的烷基,其中,n=1~30。
22.如权利要求21所述的含氟聚合物,其特征在于:
A2是碳原子数12~30的烷基。
23.如权利要求8~22中任一项所述的含氟聚合物,其特征在于:
非氟交联性单体(d)是至少具有两个反应性基团和/或碳-碳双键且不含氟的化合物。
24.一种含氟聚合物的制法,该含氟聚合物包含由第一单体形成的第一聚合物和由第二单体形成的第二聚合物,该制法的特征在于,包括:
(Ⅰ)将第一单体聚合,获得第一聚合物的工序、和
(Ⅱ)在第一聚合物的存在下将第二单体投料使之聚合,由此获得第二聚合物的工序,
第一单体和第二单体的至少一方含有含氟单体(a),
第一单体和第二单体的双方含有卤化烯烃(b)。
25.如权利要求24所述的制法,其特征在于:
将第二单体连续投料。
26.如权利要求24或25所述的制法,其特征在于:
第一单体中的卤化烯烃(b)和第二单体中的卤化烯烃(b)的重量比为3~97︰97~3。
27.如权利要求24~26中任一项所述的制法,其特征在于:
在第一聚合物的聚合中开始第二聚合物的聚合。
28.如权利要求24~27中任一项所述的制法,其特征在于:
在第一聚合物的聚合完成后开始第二聚合物的聚合。
29.如权利要求24~28中任一项所述的制法,其特征在于:
第一单体的聚合反应结束10%以上,例如结束40%以上,特别是结束70%以上之后,开始第二聚合物的聚合。
30.一种拨水拨油剂,其特征在于:
以权利要求1~23中任一项所述的含氟聚合物作为必须成分。
31.如权利要求30所述的拨水拨油剂,其特征在于:
还含有水性介质。
32.如权利要求30所述的拨水拨油剂,其特征在于:
是水性分散液。
33.一种处理基材的方法,其特征在于:
包括使用权利要求30~32中任一项所述的拨水拨油剂进行处理的步骤。
34.一种纤维制品,其特征在于:
其为利用权利要求30~32中任一项所述的拨水拨油剂处理过的纤维制品。
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