CN103788288A - Water- and oil-repellent composition - Google Patents

Water- and oil-repellent composition Download PDF

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CN103788288A
CN103788288A CN201410001414.6A CN201410001414A CN103788288A CN 103788288 A CN103788288 A CN 103788288A CN 201410001414 A CN201410001414 A CN 201410001414A CN 103788288 A CN103788288 A CN 103788288A
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acrylate
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meth
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CN103788288B (en
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榎本孝司
山本育男
宫原正弘
薄谷光宏
南里昌史
久保田浩治
坂下浩敏
南晋一
仲村尚子
武内留美
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Daikin Industries Ltd
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    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
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    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
    • D06M15/277—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof containing fluorine
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    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/285—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acid amides or imides
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    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
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    • C08F220/1806—C6-(meth)acrylate, e.g. (cyclo)hexyl (meth)acrylate or phenyl (meth)acrylate
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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Abstract

本发明涉及一种含氟聚合物，包括来源于下列的重复单元：（A）由通式CH2=C(-X)-C(=O)-Y-Z-Rf表示的含氟单体，其中X为氢原子、单价有机基团或卤原子，Y为-O-或-NH-；Z为直接键或二价有机基团；Rf为具有1-20个碳原子的氟烷基；和（B）具有环烃基的（甲基）丙烯酸酯单体，其提供赋予基材优异的拒水、拒油和防污性质的拒水和拒油剂。The present invention relates to a fluorine-containing polymer comprising repeating units derived from: (A) a fluorine-containing monomer represented by the general formula CH 2 =C(-X)-C(=O)-YZ-Rf, wherein X is a hydrogen atom, a monovalent organic group or a halogen atom, Y is -O- or -NH-; Z is a direct bond or a divalent organic group; Rf is a fluoroalkyl group having 1-20 carbon atoms; and ( B) A (meth)acrylate monomer having a cyclohydrocarbyl group, which provides a water- and oil-repellent agent that imparts excellent water-repellent, oil-repellent, and antifouling properties to a substrate.

Description

拒水和拒油组合物Water and oil repellent compositions

本申请是2009年9月11日提交的申请号为第200980136040.6号、名称为“拒水和拒油组合物”的发明专利申请的分案申请。This application is a divisional application of the invention patent application with application number 200980136040.6 and titled "Water and Oil Repellent Composition" filed on September 11, 2009.

相关申请的交叉引用Cross References to Related Applications

本申请要求于2008年9月15日提交的美国申请第61/096,927号的优先权，其公开内容引入本文以供参考。This application claims priority to US Application Serial No. 61/096,927, filed September 15, 2008, the disclosure of which is incorporated herein by reference.

技术领域technical field

本发明涉及含氟聚合物和处理组合物，特别是含有该聚合物的表面处理组合物，其赋予纺织品（例如，地毯）、纸张、无纺布、砌石、静电过滤器、防尘面具和燃料电池部件以优异的拒水、拒油和抗污性。The present invention relates to fluoropolymers and treatment compositions, particularly surface treatment compositions containing the polymers, which impart to textiles (e.g., carpets), paper, nonwovens, masonry, electrostatic filters, dust masks and Fuel cell components are characterized by excellent water repellency, oil repellency and stain resistance.

背景技术Background technique

迄今，已经提出了多种含氟化合物。含氟化合物具有有利的作用，其具有耐热性、抗氧化、耐候性等方面的优异性质。通过利用含氟化合物的低自由能性质，即难以附着的性质，含氟化合物被用作，例如，拒水和拒油剂和防污剂。例如，美国专利第5247008号公开了一种用于纺织品、皮革、纸张和矿物质的整饰化合物，该化合物包括丙烯酸或甲基丙烯酸的全氟烷基酯、丙烯酸或甲基丙烯酸的烷基酯、和丙烯酸或甲基丙烯酸的氨基烷基酯的聚合物的水分散体。Hitherto, various fluorine-containing compounds have been proposed. Fluorine-containing compounds have advantageous effects, which have excellent properties in terms of heat resistance, oxidation resistance, weather resistance, and the like. Fluorine-containing compounds are used as, for example, water- and oil-repellent agents and antifouling agents by utilizing the low free energy property of fluorine-containing compounds, that is, the property of being difficult to adhere. For example, U.S. Patent No. 5,247,008 discloses a finishing compound for textiles, leather, paper, and minerals that includes perfluoroalkyl acrylate or methacrylate, alkyl acrylate or methacrylate , and an aqueous dispersion of a polymer of an aminoalkyl acrylate or methacrylate.

可用作拒水和拒油剂的含氟化合物的实例包括具有来源于具有氟烷基的（甲基）丙烯酸酯的重复单元的含氟聚合物。近来的多个研究结果表明，在用表面处理剂对纤维的实际处理中，重要的表面性质不是静止接触角，而是动态接触角，尤其是后退接触角。即，水的前进接触角不依赖于氟烷基侧链的碳数，而在碳数为至多7的情况下水的后退接触角显著低于碳数为至少8的情况下的后退接触角。与此相对应，X-射线分析显示当侧链的碳数为至少7时侧链结晶。已知实际的拒水性与侧链的结晶度相关，并且表面活性剂分子的迁移率是显示实际性能的重要因素（例如，MAEKAWA Takashige,FINE CHEMICAL,Vol.23,No.6,12页(1994)）。由于上面提到的原因，认为在侧链中具有至多为7（尤其是至多为6）的低碳数的氟烷基的丙烯酸酯聚合物具有低结晶性，使得聚合物不能满足实际的性能（尤其是拒水性）。Examples of fluorine-containing compounds that can be used as the water- and oil-repellent agent include fluorine-containing polymers having repeating units derived from (meth)acrylates having a fluoroalkyl group. A number of recent research results show that in the actual treatment of fibers with surface treatment agents, the important surface properties are not the static contact angle, but the dynamic contact angle, especially the receding contact angle. That is, the advancing contact angle of water does not depend on the carbon number of the fluoroalkyl side chain, but the receding contact angle of water with a carbon number of up to 7 is significantly lower than that of a carbon number of at least 8. Corresponding to this, X-ray analysis shows that the side chain crystallizes when the carbon number of the side chain is at least 7. It is known that the actual water repellency is related to the crystallinity of the side chain, and the mobility of the surfactant molecule is an important factor showing the actual performance (for example, MAEKAWA Takashige, FINE CHEMICAL, Vol.23, No.6, page 12 (1994 )). For the reasons mentioned above, it is considered that the acrylate polymer having a fluoroalkyl group having a low carbon number of up to 7 (especially up to 6) in the side chain has low crystallinity, so that the polymer cannot satisfy practical properties ( especially water repellency).

近年来的研究结果（EPA Report"PRELIMINARY RISKASSESSMENT OF THE DEVELOPMENTAL TOXICITY ASSOCIATEDWITH EXPOSURE TO PERFLUOROOCTANOIC ACID AND ITSSALTS"（EPA报告“与暴露于全氟辛酸及其盐相关的发育毒性的初步风险评估”）（http://www.epa.gov/opptintr/pfoa/pfoara.pdf））等明确PFOA（全氟辛酸）不确定地具有环境载荷的潜在风险。EPA（美国环境保护局）于2003年4月14日宣布EPA加强了对PFOA的科学调查。Research results in recent years (EPA Report "PRELIMINARY RISKASSESSMENT OF THE DEVELOPMENTAL TOXICITY ASSOCIATEDWITH EXPOSURE TO PERFLUOROOCTANOIC ACID AND ITSSALTS" (EPA Report "Preliminary Risk Assessment of Developmental Toxicity Associated with Exposure to Perfluorooctanoic Acid and Its Salts") ( http://www .epa.gov/opptintr/pfoa/pfoara.pdf )) and others clearly indicate that PFOA (perfluorooctanoic acid) has potential risks of environmental loads indefinitely. EPA (US Environmental Protection Agency) announced on April 14, 2003 that EPA has strengthened its scientific investigation on PFOA.

另一方面，联邦公报（Federal Register）（FR Vol.68,No.73/2003年4月16日[FRL-7303-8]）（http://www.epa.gov/opptintr/pfoa/pfoafr.pdf）、2003年4月，星期一发行的EPA环境新闻稿"EPA INTENSIFIESSCIENTIFIC INVESTIGATION OF A CHEMICAL PROCESSING AID"（EPA加强对化学加工助剂的科学调查）（http://www.epa.gov/opptintr/pfoa/pfoaprs.pdf）、和EPA OPPT FACTSHEET（2003年4月14日）（http://www.epa.gov/opptintr/pfoa/pfoafacts.pdf）宣布“调聚物”可能会代谢或分解为PFOA。其还宣布“调聚物”用于大量的市售产品中，包括灭火泡沫、护理产品和清洁产品以及地毯、纺织品、纸张和皮革上的抗污、防污渍和抗油涂层。On the other hand, Federal Register (FR Vol. 68, No. 73/April 16, 2003 [FRL-7303-8]) ( http://www.epa.gov/opptintr/pfoa/pfoafr .pdf ), EPA Environmental Press Release "EPA INTENSIFIESSCIENTIFIC INVESTIGATION OF A CHEMICAL PROCESSING AID" issued on Monday, April 2003 (http://www.epa.gov/ opptintr/pfoa/pfoaprs.pdf), and EPA OPPT FACTSHEET (April 14, 2003) ( http://www.epa.gov/opptintr/pfoa/pfoafacts.pdf ) announced that "telomers" may metabolize or Break down into PFOA. It also announced that "telomers" are used in a number of commercially available products, including fire-fighting foams, care and cleaning products, and stain-, stain-, and oil-repellent coatings on carpet, textiles, paper, and leather.

发明内容Contents of the invention

本发明要解决的问题The problem to be solved by the present invention

本发明的目的是提供一种处理组合物，其可以赋予基材诸如纺织品以优异的拒水、拒油和防污性。An object of the present invention is to provide a treatment composition which can impart excellent water repellency, oil repellency and stain repellency to substrates such as textiles.

解决该问题的方案Solution to the problem

本发明提供一种含氟聚合物，其包括来源于下列的重复单元：The present invention provides a fluoropolymer comprising repeat units derived from:

（A）由下列通式表示的含氟单体：(A) A fluorine-containing monomer represented by the following general formula:

CH2=C(-X)-C(=O)-Y-Z-RfCH 2 =C(-X)-C(=O)-YZ-Rf

其中X为氢原子、单价有机基团或卤原子，Wherein X is a hydrogen atom, a monovalent organic group or a halogen atom,

Y为-O-或-NH-；Y is -O- or -NH-;

Z为直接键或二价有机基团；Z is a direct bond or a divalent organic group;

Rf为具有1-20个碳原子的氟烷基；和Rf is a fluoroalkyl group having 1-20 carbon atoms; and

（B）具有环烃基的（甲基）丙烯酸酯单体。(B) A (meth)acrylate monomer which has a cyclohydrocarbyl group.

发明的效果The effect of the invention

本发明提供一种处理剂组合物，其赋予基材诸如纺织品以优异的拒水、拒油和防污性。The present invention provides a treatment agent composition which imparts excellent water repellency, oil repellency and stain resistance to substrates such as textiles.

具体实施方式Detailed ways

本发明的含氟聚合物包括：Fluoropolymers of the present invention include:

（A）含氟单体，和(A) fluoromonomers, and

（B）具有环烃基的（甲基）丙烯酸酯单体。(B) A (meth)acrylate monomer which has a cyclohydrocarbyl group.

下面解释单体（A）和（B）。The monomers (A) and (B) are explained below.

（A）含氟单体(A) Fluorinated monomer

含氟单体由下式表示：The fluorine-containing monomer is represented by the following formula:

CH2=C(-X)-C(=O)-Y-Z-RfCH 2 =C(-X)-C(=O)-YZ-Rf

其中in

X为氢原子、单价有机基团或卤原子；X is a hydrogen atom, a monovalent organic group or a halogen atom;

Y为-O-或-NH-；Y is -O- or -NH-;

Z为直接键或二价有机基团；Z is a direct bond or a divalent organic group;

Rf为具有1-20个碳原子的氟烷基。Rf is a fluoroalkyl group having 1 to 20 carbon atoms.

Z可以是，例如，具有1-20个碳原子的直链亚烃基或支链亚烃基，诸如由式-(CH2)x-[其中x为1-10]代表的基团或由式-SO2N(R1)R2-或式-CON(R1)R2-[其中R1为具有1-10个碳原子的烷基，且R2为具有1-10个碳原子的直链亚烃基或支链亚烃基]或由式-CH2CH(OR3)CH2-[其中R3为氢原子或具有1-10个碳原子的酰基（例如，甲酰基或乙酰基）]或由式-Ar-CH2-[其中Ar是任选地具有取代基的亚芳基]、或由式-(CH2)m-SO2-(CH2)n-基团或-(CH2)m-S-(CH2)n-基团[其中m为1-10，n为0-10]代表的基团。Z may be, for example, a linear or branched chain alkylene group having 1 to 20 carbon atoms, such as a group represented by the formula -(CH 2 ) x -[wherein x is 1 to 10] or a group represented by the formula - SO 2 N(R 1 )R 2 -or formula -CON(R 1 )R 2 -[wherein R 1 is an alkyl group having 1-10 carbon atoms, and R 2 is a straight group having 1-10 carbon atoms chain alkylene or branched chain alkylene] or by the formula -CH 2 CH (OR 3 ) CH 2 -[wherein R 3 is a hydrogen atom or an acyl group having 1-10 carbon atoms (for example, formyl or acetyl)] or by a group of the formula -Ar-CH 2 -[wherein Ar is an optionally substituted arylene group], or by a group of the formula -(CH 2 ) m -SO 2 -(CH 2 ) n - or -(CH 2 ) A group represented by an m -S-(CH 2 ) n - group [where m is 1-10 and n is 0-10].

X可以是，例如，H、Me（甲基）、Cl、Br、I、F、CN或CF3。X can be, for example, H, Me (methyl), Cl, Br, I, F, CN or CF3 .

含氟单体（A）优选是由下式代表的丙烯酸酯：The fluorine-containing monomer (A) is preferably an acrylate represented by the following formula:

CH2=C(-X)-C(=O)-Y-Z-Rf    （1）CH 2 =C(-X)-C(=O)-YZ-Rf (1)

其中in

X为氢原子、具有1-21个碳原子的直链或支链烷基、氟原子、氯原子、溴原子、碘原子、CFX1X2基团（其中X1和X2中的每一个为氢原子、氟原子、氯原子、溴原子或碘原子）、氰基、具有1-21个碳原子的直链或支链氟烷基、取代或未取代的苄基或取代或未取代的苯基；X is a hydrogen atom, a linear or branched chain alkyl group having 1-21 carbon atoms, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a CFX 1 X 2 group (each of X 1 and X 2 hydrogen atom, fluorine atom, chlorine atom, bromine atom or iodine atom), cyano group, straight chain or branched fluoroalkyl group with 1-21 carbon atoms, substituted or unsubstituted benzyl group or substituted or unsubstituted phenyl;

Y为-O-或-NH-基团；Y is -O- or -NH-group;

Z为具有1-10个碳原子的脂族基团、具有6-18个碳原子的芳族或环脂族基团、-CH2CH2N(R1)SO2-基团（其中R1为具有1-4个碳原子的烷基）、-CH2CH(OZ1)CH2-基团（其中Z1为氢原子或乙酰基)、-(CH2)m-SO2-(CH2)n-基团、或-(CH2)m-S-(CH2)n-基团（其中m为1-10且n为0-10)，Z is an aliphatic group having 1-10 carbon atoms, an aromatic or cycloaliphatic group having 6-18 carbon atoms, a -CH 2 CH 2 N(R 1 )SO 2 - group (wherein R 1 is an alkyl group with 1-4 carbon atoms), -CH 2 CH(OZ 1 )CH 2 - group (where Z 1 is a hydrogen atom or acetyl group), -(CH 2 ) m -SO 2 -( CH 2 ) n -groups, or -(CH 2 ) m -S-(CH 2 ) n -groups (wherein m is 1-10 and n is 0-10),

Rf为具有1-20个碳原子的直链或直链氟烷基。Rf is a linear or linear fluoroalkyl group having 1 to 20 carbon atoms.

含氟单体（A）可以用卤原子等在（丙烯酸酯或甲基丙烯酸酯的）α-位上取代。因此，在式（1）中，X可以是具有2-21个碳原子的直链或支链烷基、氟原子、氯原子、溴原子、碘原子、CFX1X2基团（其中X1和X2代表氢原子、氟原子、氯原子、溴原子或碘原子）、氰基、具有1-21个碳原子的直链或支链氟烷基、取代或未取代的苄基或取代或未取代的苯基。The fluorine-containing monomer (A) may be substituted with a halogen atom or the like at the α-position (of acrylate or methacrylate). Therefore, in formula (1), X can be a linear or branched chain alkyl group with 2-21 carbon atoms, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a CFX 1 X 2 group (where X 1 and X2 represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom), a cyano group, a linear or branched fluoroalkyl group having 1-21 carbon atoms, a substituted or unsubstituted benzyl group or a substituted or Unsubstituted phenyl.

在式（1）中，Rf基团优选是全氟烷基。Rf基团的数目优选为1-12，例如1-6，尤其是4-6。Rf基团的实例包括-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和-C8F17。In formula (1), the Rf group is preferably a perfluoroalkyl group. The number of Rf groups is preferably 1-12, such as 1-6, especially 4-6. Examples of Rf groups include -CF3 , -CF2CF3 , -CF2CF2CF3 , -CF ( CF3 ) 2 , -CF2CF2CF2CF3 , -CF2CF ( CF3 ) 2 , -C(CF 3 ) 3 , -(CF 2 ) 4 CF 3 , -(CF 2 ) 2 CF(CF 3 ) 2 , -CF 2 C(CF 3 ) 3 , -CF(CF 3 )CF 2 CF 2 CF 3 , -(CF 2 ) 5 CF 3 , -(CF 2 ) 3 CF(CF 3 ) 2 , -(CF 2 ) 4 CF(CF 3 ) 2 and -C 8 F 17 .

Z优选是具有1-10个碳原子的脂族基团、具有6-18个碳原子的芳族或环脂族基团、-CH2CH2N(R1)SO2-基团（其中R1为具有1-4个碳原子的烷基）或-CH2CH(OZ1)CH2-基团（其中Z1为氢原子或乙酰基）或-(CH2)m-SO2-(CH2)n-基团或-(CH2)m-S-(CH2)n-基团（其中m为1-10，n为0-10)。脂族基团优选为亚烃基（尤其是具有1-4个，例如1个或2个碳原子）。芳族基团或环脂族基团可以是取代的或未取代的。S基团或SO2基团可以直接与Rf基团键合。Z is preferably an aliphatic group having 1 to 10 carbon atoms, an aromatic or cycloaliphatic group having 6 to 18 carbon atoms, a —CH 2 CH 2 N(R 1 )SO 2 — group (where R 1 is an alkyl group with 1-4 carbon atoms) or -CH 2 CH(OZ 1 )CH 2 - group (wherein Z 1 is a hydrogen atom or acetyl group) or -(CH 2 ) m -SO 2 - (CH 2 ) n -group or -(CH 2 ) m -S-(CH 2 ) n -group (where m is 1-10, n is 0-10). Aliphatic groups are preferably hydrocarbylene groups (especially having 1 to 4, eg 1 or 2 carbon atoms). An aromatic or cycloaliphatic group may be substituted or unsubstituted. The S group or the SO2 group can be directly bonded to the Rf group.

含氟单体（A）的具体实例包括，但不限于下列各项：Specific examples of fluorine-containing monomers (A) include, but are not limited to the following:

CH2=C(-H)-C(=O)-O-(CH2)2-RfCH 2 =C(-H)-C(=O)-O-(CH 2 ) 2 -Rf

CH2=C(-H)-C(=O)-O-C6H4-RfCH 2 =C(-H)-C(=O)-OC 6 H 4 -Rf

CH2=C(-Cl)-C(=O)-O-(CH2)2-RfCH 2 =C(-Cl)-C(=O)-O-(CH 2 ) 2 -Rf

CH2=C(-H)-C(=O)-O-(CH2)2N(-CH3)SO2-RfCH 2 =C(-H)-C(=O)-O-(CH 2 ) 2 N(-CH 3 )SO 2 -Rf

CH2=C(-H)-C(=O)-O-(CH2)2N(-C2H5)SO2-RfCH 2 =C(-H)-C(=O)-O-(CH 2 ) 2 N(-C 2 H 5 )SO 2 -Rf

CH2=C(-H)-C(=O)-O-CH2CH(-OH)CH2-RfCH 2 =C(-H)-C(=O)-O-CH 2 CH(-OH)CH 2 -Rf

CH2=C(-H)-C(=O)-O-CH2CH(-OCOCH3)CH2-RfCH 2 =C(-H)-C(=O)-O-CH 2 CH(-OCOCH 3 )CH 2 -Rf

CH2=C(-H)-C(=O)-O-(CH2)2-S-RfCH 2 =C(-H)-C(=O)-O-(CH 2 ) 2 -S-Rf

CH2=C(-H)-C(=O)-O-(CH2)2-S-(CH2)2-RfCH 2 =C(-H)-C(=O)-O-(CH 2 ) 2 -S-(CH 2 ) 2 -Rf

CH2=C(-H)-C(=O)-O-(CH2)3-SO2-RfCH 2 =C(-H)-C(=O)-O-(CH 2 ) 3 -SO 2 -Rf

CH2=C(-H)-C(=O)-O-(CH2)2-SO2-(CH2)2-RfCH 2 =C(-H)-C(=O)-O-(CH 2 ) 2 -SO 2 -(CH 2 ) 2 -Rf

CH2=C(-H)-C(=O)-NH-(CH2)2-RfCH 2 =C(-H)-C(=O)-NH-(CH 2 ) 2 -Rf

CH2=C(-CH3)-C(=O)-O-(CH2)2-S-RfCH 2 =C(-CH 3 )-C(=O)-O-(CH 2 ) 2 -S-Rf

CH2=C(-CH3)-C(=O)-O-(CH2)2-S-(CH2)2-RfCH 2 =C(-CH 3 )-C(=O)-O-(CH 2 ) 2 -S-(CH 2 ) 2 -Rf

CH2=C(-CH3)-C(=O)-O-(CH2)3-SO2-RfCH 2 =C(-CH 3 )-C(=O)-O-(CH 2 ) 3 -SO 2 -Rf

CH2=C(-CH3)-C(=O)-O-(CH2)2-SO2-(CH2)2-RfCH 2 =C(-CH 3 )-C(=O)-O-(CH 2 ) 2 -SO 2 -(CH 2 ) 2 -Rf

CH2=C(-CH3)-C(=O)-NH-(CH2)2-RfCH 2 =C(-CH 3 )-C(=O)-NH-(CH 2 ) 2 -Rf

CH2=C(-F)-C(=O)-O-(CH2)2-S-RfCH 2 =C(-F)-C(=O)-O-(CH 2 ) 2 -S-Rf

CH2=C(-F)-C(=O)-O-(CH2)2-S-(CH2)2-RfCH 2 =C(-F)-C(=O)-O-(CH 2 ) 2 -S-(CH 2 ) 2 -Rf

CH2=C(-F)-C(=O)-O-(CH2)2-SO2-RfCH 2 =C(-F)-C(=O)-O-(CH 2 ) 2 -SO 2 -Rf

CH2=C(-F)-C(=O)-O-(CH2)2-SO2-(CH2)2-RfCH 2 =C(-F)-C(=O)-O-(CH 2 ) 2 -SO 2 -(CH 2 ) 2 -Rf

CH2=C(-F)-C(=O)-NH-(CH2)2-RfCH 2 =C(-F)-C(=O)-NH-(CH 2 ) 2 -Rf

CH2=C(-Cl)-C(=O)-O-(CH2)2-S-RfCH 2 =C(-Cl)-C(=O)-O-(CH 2 ) 2 -S-Rf

CH2=C(-Cl)-C(=O)-O-(CH2)2-S-(CH2)2-RfCH 2 =C(-Cl)-C(=O)-O-(CH 2 ) 2 -S-(CH 2 ) 2 -Rf

CH2=C(-Cl)-C(=O)-O-(CH2)2-SO2-RfCH 2 =C(-Cl)-C(=O)-O-(CH 2 ) 2 -SO 2 -Rf

CH2=C(-Cl)-C(=O)-O-(CH2)2-SO2-(CH2)2-RfCH 2 =C(-Cl)-C(=O)-O-(CH 2 ) 2 -SO 2 -(CH 2 ) 2 -Rf

CH2=C(-Cl)-C(=O)-NH-(CH2)2-RfCH 2 =C(-Cl)-C(=O)-NH-(CH 2 ) 2 -Rf

CH2=C(-CF3)-C(=O)-O-(CH2)2-S-RfCH 2 =C(-CF 3 )-C(=O)-O-(CH 2 ) 2 -S-Rf

CH2=C(-CF3)-C(=O)-O-(CH2)2-S-(CH2)2-RfCH 2 =C(-CF 3 )-C(=O)-O-(CH 2 ) 2 -S-(CH 2 ) 2 -Rf

CH2=C(-CF3)-C(=O)-O-(CH2)2-SO2-RfCH 2 =C(-CF 3 )-C(=O)-O-(CH 2 ) 2 -SO 2 -Rf

CH2=C(-CF3)-C(=O)-O-(CH2)2-SO2-(CH2)2-RfCH 2 =C(-CF 3 )-C(=O)-O-(CH 2 ) 2 -SO 2 -(CH 2 ) 2 -Rf

CH2=C(-CF3)-C(=O)-NH-(CH2)2-RfCH 2 =C(-CF 3 )-C(=O)-NH-(CH 2 ) 2 -Rf

CH2=C(-CF2H)-C(=O)-O-(CH2)2-S-RfCH 2 =C(-CF 2 H)-C(=O)-O-(CH 2 ) 2 -S-Rf

CH2=C(-CF2H)-C(=O)-O-(CH2)2-S-(CH2)2-RfCH 2 =C(-CF 2 H)-C(=O)-O-(CH 2 ) 2 -S-(CH 2 ) 2 -Rf

CH2=C(-CF2H)-C(=O)-O-(CH2)2-SO2-RfCH 2 =C(-CF 2 H)-C(=O)-O-(CH 2 ) 2 -SO 2 -Rf

CH2=C(-CF2H)-C(=O)-O-(CH2)2-SO2-(CH2)2-RfCH 2 =C(-CF 2 H)-C(=O)-O-(CH 2 ) 2 -SO 2 -(CH 2 ) 2 -Rf

CH2=C(-CF2H)-C(=O)-NH-(CH2)2-RfCH 2 =C(-CF 2 H)-C(=O)-NH-(CH 2 ) 2 -Rf

CH2=C(-CN)-C(=O)-O-(CH2)2-S-RfCH 2 =C(-CN)-C(=O)-O-(CH 2 ) 2 -S-Rf

CH2=C(-CN)-C(=O)-O-(CH2)2-S-(CH2)2-RfCH 2 =C(-CN)-C(=O)-O-(CH 2 ) 2 -S-(CH 2 ) 2 -Rf

CH2=C(-CN)-C(=O)-O-(CH2)2-SO2-RfCH 2 =C(-CN)-C(=O)-O-(CH 2 ) 2 -SO 2 -Rf

CH2=C(-CN)-C(=O)-O-(CH2)2-SO2-(CH2)2-RfCH 2 =C(-CN)-C(=O)-O-(CH 2 ) 2 -SO 2 -(CH 2 ) 2 -Rf

CH2=C(-CN)-C(=O)-NH-(CH2)2-RfCH 2 =C(-CN)-C(=O)-NH-(CH 2 ) 2 -Rf

CH2=C(-CF2CF3)-C(=O)-O-(CH2)2-S-RfCH 2 =C(-CF 2 CF 3 )-C(=O)-O-(CH 2 ) 2 -S-Rf

CH2=C(-CF2CF3)-C(=O)-O-(CH2)2-S-(CH2)2-RfCH 2 =C(-CF 2 CF 3 )-C(=O)-O-(CH 2 ) 2 -S-(CH 2 ) 2 -Rf

CH2=C(-CF2CF3)-C(=O)-O-(CH2)2-SO2-RfCH 2 =C(-CF 2 CF 3 )-C(=O)-O-(CH 2 ) 2 -SO 2 -Rf

CH2=C(-CF2CF3)-C(=O)-O-(CH2)2-SO2-(CH2)2-RfCH2=C(-CF2CF3)-C(=O)-NH-(CH2)2-RfCH 2 =C(-CF 2 CF 3 )-C(=O)-O-(CH 2 ) 2 -SO 2 -(CH 2 ) 2 -RfCH 2 =C(-CF 2 CF 3 )-C(= O)-NH-(CH 2 ) 2 -Rf

CH2=C(-F)-C(=O)-O-(CH2)3-S-RfCH 2 =C(-F)-C(=O)-O-(CH 2 ) 3 -S-Rf

CH2=C(-F)-C(=O)-O-(CH2)3-S-(CH2)2-RfCH 2 =C(-F)-C(=O)-O-(CH 2 ) 3 -S-(CH 2 ) 2 -Rf

CH2=C(-F)-C(=O)-O-(CH2)3-SO2-RfCH 2 =C(-F)-C(=O)-O-(CH 2 ) 3 -SO 2 -Rf

CH2=C(-F)-C(=O)-O-(CH2)3-SO2-(CH2)2-RfCH 2 =C(-F)-C(=O)-O-(CH 2 ) 3 -SO 2 -(CH 2 ) 2 -Rf

CH2=C(-F)-C(=O)-NH-(CH2)3-RfCH 2 =C(-F)-C(=O)-NH-(CH 2 ) 3 -Rf

CH2=C(-Cl)-C(=O)-O-(CH2)3-S-RfCH 2 =C(-Cl)-C(=O)-O-(CH 2 ) 3 -S-Rf

CH2=C(-Cl)-C(=O)-O-(CH2)3-S-(CH2)2-RfCH 2 =C(-Cl)-C(=O)-O-(CH 2 ) 3 -S-(CH 2 ) 2 -Rf

CH2=C(-Cl)-C(=O)-O-(CH2)3-SO2-RfCH 2 =C(-Cl)-C(=O)-O-(CH 2 ) 3 -SO 2 -Rf

CH2=C(-Cl)-C(=O)-O-(CH2)3-SO2-(CH2)2-RfCH 2 =C(-Cl)-C(=O)-O-(CH 2 ) 3 -SO 2 -(CH 2 ) 2 -Rf

CH2=C(-CF3)-C(=O)-O-(CH2)3-S-RfCH 2 =C(-CF 3 )-C(=O)-O-(CH 2 ) 3 -S-Rf

CH2=C(-CF3)-C(=O)-O-(CH2)3-S-(CH2)2-RfCH 2 =C(-CF 3 )-C(=O)-O-(CH 2 ) 3 -S-(CH 2 ) 2 -Rf

CH2=C(-CF3)-C(=O)-O-(CH2)3-SO2-RfCH 2 =C(-CF 3 )-C(=O)-O-(CH 2 ) 3 -SO 2 -Rf

CH2=C(-CF3)-C(=O)-O-(CH2)3-SO2-(CH2)2-RfCH 2 =C(-CF 3 )-C(=O)-O-(CH 2 ) 3 -SO 2 -(CH 2 ) 2 -Rf

CH2=C(-CF2H)-C(=O)-O-(CH2)3-S-RfCH 2 =C(-CF 2 H)-C(=O)-O-(CH 2 ) 3 -S-Rf

CH2=C(-CF2H)-C(=O)-O-(CH2)3-S-(CH2)2-RfCH 2 =C(-CF 2 H)-C(=O)-O-(CH 2 ) 3 -S-(CH 2 ) 2 -Rf

CH2=C(-CF2H)-C(=O)-O-(CH2)3-SO2-RfCH 2 =C(-CF 2 H)-C(=O)-O-(CH 2 ) 3 -SO 2 -Rf

CH2=C(-CF2H)-C(=O)-O-(CH2)3-SO2-(CH2)2-RfCH 2 =C(-CF 2 H)-C(=O)-O-(CH 2 ) 3 -SO 2 -(CH 2 ) 2 -Rf

CH2=C(-CN)-C(=O)-O-(CH2)3-S-RfCH 2 =C(-CN)-C(=O)-O-(CH 2 ) 3 -S-Rf

CH2=C(-CN)-C(=O)-O-(CH2)3-S-(CH2)2-RfCH 2 =C(-CN)-C(=O)-O-(CH 2 ) 3 -S-(CH 2 ) 2 -Rf

CH2=C(-CN)-C(=O)-O-(CH2)3-SO2-RfCH 2 =C(-CN)-C(=O)-O-(CH 2 ) 3 -SO 2 -Rf

CH2=C(-CN)-C(=O)-O-(CH2)3-SO2-(CH2)2-RfCH 2 =C(-CN)-C(=O)-O-(CH 2 ) 3 -SO 2 -(CH 2 ) 2 -Rf

CH2=C(-CF2CF3)-C(=O)-O-(CH2)3-S-RfCH 2 =C(-CF 2 CF 3 )-C(=O)-O-(CH 2 ) 3 -S-Rf

CH2=C(-CF2CF3)-C(=O)-O-(CH2)3-S-(CH2)2-RfCH 2 =C(-CF 2 CF 3 )-C(=O)-O-(CH 2 ) 3 -S-(CH 2 ) 2 -Rf

CH2=C(-CF2CF3)-C(=O)-O-(CH2)3-SO2-RfCH 2 =C(-CF 2 CF 3 )-C(=O)-O-(CH 2 ) 3 -SO 2 -Rf

CH2=C(-CF2CF3)-C(=O)-O-(CH2)2-SO2-(CH2)2-RfCH 2 =C(-CF 2 CF 3 )-C(=O)-O-(CH 2 ) 2 -SO 2 -(CH 2 ) 2 -Rf

其中Rf为具有1-20个碳原子的氟烷基。wherein Rf is a fluoroalkyl group having 1 to 20 carbon atoms.

（B）具有环烃基的（甲基）丙烯酸酯单体(B) A (meth)acrylate monomer having a cyclohydrocarbyl group

具有环烃基的（甲基）丙烯酸酯单体（B）通常为不含氟的单体。具有环烃基的（甲基）丙烯酸酯单体（B）为具有（优选单价的）环烃基和单价（甲基）丙烯酸酯基团的化合物。单价环烃基与单价（甲基）丙烯酸酯基团直接键合。环烃基的实例包括饱和或不饱和的单环基团、多环基团或桥环基团。环烃基优选为饱和的基团。环烃基优选具有4-20碳原子。环烃基的实例包括具有4-20个碳原子、尤其是5-12个碳原子的环脂族基团，具有6-20个碳原子的芳族基团，和具有7-20个碳原子的芳脂族基团。环烃基的碳数特别优选为至多15，例如至多10。环烃基中的碳原子优选与（甲基）丙烯酸酯基团中的酯基直接键合。环烃基优选为饱和的环脂族基团。环烃基的具体实例包括环己基、叔丁基环己基、异冰片基、二环戊基和二环戊烯基。（甲基）丙烯酸酯基团是丙烯酸酯基团或甲基丙烯酸酯基团，优选甲基丙烯酸酯基团。The (meth)acrylate monomer (B) which has a cyclohydrocarbyl group is usually a fluorine-free monomer. The (meth)acrylate monomer (B) having a cyclic hydrocarbon group is a compound having a (preferably monovalent) cyclic hydrocarbon group and a monovalent (meth)acrylate group. The monovalent cyclic hydrocarbon group is directly bonded to the monovalent (meth)acrylate group. Examples of the cyclic hydrocarbon group include saturated or unsaturated monocyclic groups, polycyclic groups or bridged ring groups. The cyclohydrocarbyl group is preferably a saturated group. The cyclohydrocarbyl group preferably has 4 to 20 carbon atoms. Examples of the cyclohydrocarbyl group include cycloaliphatic groups having 4 to 20 carbon atoms, especially 5 to 12 carbon atoms, aromatic groups having 6 to 20 carbon atoms, and cycloaliphatic groups having 7 to 20 carbon atoms araliphatic group. The carbon number of the cyclohydrocarbyl group is particularly preferably at most 15, for example at most 10. The carbon atoms in the cyclic hydrocarbon group are preferably directly bonded to the ester group in the (meth)acrylate group. The cyclohydrocarbyl group is preferably a saturated cycloaliphatic group. Specific examples of the cyclohydrocarbyl group include cyclohexyl, tert-butylcyclohexyl, isobornyl, dicyclopentyl and dicyclopentenyl. The (meth)acrylate group is an acrylate group or a methacrylate group, preferably a methacrylate group.

具有环烃基的单体的具体实例包括甲基丙烯酸环己酯、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、甲基丙烯酸二环戊酯、丙烯酸二环戊酯、甲基丙烯酸二环戊烯酯和丙烯酸二环戊烯酯。Specific examples of the monomer having a cyclohydrocarbyl group include cyclohexyl methacrylate, tert-butylcyclohexyl methacrylate, benzyl methacrylate, isobornyl methacrylate, isobornyl acrylate, dicyclopentanyl methacrylate , dicyclopentenyl acrylate, dicyclopentenyl methacrylate and dicyclopentenyl acrylate.

（C）其他单体(C) Other monomers

本发明的含氟聚合物可以含有来源于不同于单体（A）和（B）的其他单体（C）的重复单元。其他单体（C）优选不含有氟原子。其他单体（C）的实例包括（C-1）不可交联的单体和（C-2）可交联的单体。The fluoropolymer of the present invention may contain recurring units derived from other monomers (C) than the monomers (A) and (B). Other monomers (C) preferably do not contain a fluorine atom. Examples of other monomers (C) include (C-1) non-crosslinkable monomers and (C-2) crosslinkable monomers.

（C-1）不可交联的单体(C-1) Non-crosslinkable monomers

不象可交联的单体（C-2），不可交联的单体（C-1）不具有可交联性。不可交联的单体（C-1）优选为不含氟原子的单体，并且具有碳-碳双键。不可交联的单体（C-1）优选为不含氟原子的乙烯基单体。不可交联的单体（C-1）通常为具有碳-碳双键的化合物。不可交联的单体的优选实例包括，但不限于，乙烯、乙酸乙烯酯、乙烯基卤化物诸如氯乙烯、亚乙烯基卤化物诸如偏二氯乙烯、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。不可交联的单体（C-1）不限于上面的实例。不可交联的单体（C-1）优选为乙烯基卤化物和亚乙烯基卤化物中的至少一种。Unlike the cross-linkable monomer (C-2), the non-cross-linkable monomer (C-1) is not cross-linkable. The non-crosslinkable monomer (C-1) is preferably a monomer that does not contain a fluorine atom and has a carbon-carbon double bond. The non-crosslinkable monomer (C-1) is preferably a vinyl monomer not containing a fluorine atom. The non-crosslinkable monomer (C-1) is generally a compound having a carbon-carbon double bond. Preferred examples of non-crosslinkable monomers include, but are not limited to, ethylene, vinyl acetate, vinyl halides such as vinyl chloride, vinylidene halides such as vinylidene chloride, acrylonitrile, styrene, polyethylene glycol (meth)acrylates, polypropylene glycol (meth)acrylates, methoxypolyethylene glycol (meth)acrylates, methoxypolypropylene glycol (meth)acrylates and vinyl alkyl ethers. The non-crosslinkable monomer (C-1) is not limited to the above examples. The non-crosslinkable monomer (C-1) is preferably at least one of vinyl halides and vinylidene halides.

不可交联的单体（C-1）可以是具有烷基的（甲基）丙烯酸酯。烷基可以具有1-30个碳原子，例如6-30个，诸如10-30个碳原子。例如，不可交联的单体（C-1）可以是下面通式的丙烯酸酯：The non-crosslinkable monomer (C-1) may be (meth)acrylate having an alkyl group. The alkyl group may have 1-30 carbon atoms, for example 6-30, such as 10-30 carbon atoms. For example, the non-crosslinkable monomer (C-1) can be an acrylate of the general formula:

CH2=CA1COOA2 CH 2 =CA 1 COOA 2

其中A1为氢原子或甲基或氟原子以外的卤原子（例如，氯原子、溴原子和碘原子），且A2为由CnH2n+1（n=1-30）表示的烷基。wherein A 1 is a hydrogen atom or a halogen atom other than a methyl group or a fluorine atom (for example, a chlorine atom, a bromine atom, and an iodine atom), and A 2 is an alkane represented by C n H 2n+1 (n=1-30) base.

（C-2）可交联的单体(C-2) Cross-linkable monomer

本发明的含氟聚合物可以含有来源于可交联的单体（C-2）的重复单元。可交联的单体（C-2）可以是不含氟原子并且具有至少两个反应基团和/或碳-碳双键的化合物。可交联的单体（C）可以是具有至少两个碳-碳双键的化合物或具有至少一个碳-碳双键和至少一个反应基团的化合物。反应基团的实例包括羟基、环氧基、氯甲基、封端异氰酸酯基、氨基和羧基。The fluorine-containing polymer of the present invention may contain repeating units derived from a crosslinkable monomer (C-2). The crosslinkable monomer (C-2) may be a compound that does not contain fluorine atoms and has at least two reactive groups and/or carbon-carbon double bonds. The crosslinkable monomer (C) may be a compound having at least two carbon-carbon double bonds or a compound having at least one carbon-carbon double bond and at least one reactive group. Examples of reactive groups include hydroxyl, epoxy, chloromethyl, blocked isocyanate, amino, and carboxyl.

可交联的单体（C-2）的实例包括，但不限于，双丙酮丙烯酰胺、（甲基）丙烯酰胺、N-羟甲基丙烯酰胺、（甲基）丙烯酸羟甲酯、（甲基）丙烯酸羟乙酯、（甲基）丙烯酸3-氯-2-羟丙酯、2-乙酰乙酸基（甲基）丙烯酸乙酯、（甲基）丙烯酸N,N-二甲氨基乙酯、（甲基）丙烯酸N,N-二乙氨基乙酯、丁二烯、异戊二烯、氯丁二烯和（甲基）丙烯酸缩水甘油酯。Examples of crosslinkable monomers (C-2) include, but are not limited to, diacetone acrylamide, (meth)acrylamide, N-methylolacrylamide, (meth)methylolacrylate, (meth)acrylamide base) hydroxyethyl acrylate, 3-chloro-2-hydroxypropyl (meth)acrylate, 2-acetoacetoxy ethyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate, N,N-Diethylaminoethyl (meth)acrylate, butadiene, isoprene, chloroprene and glycidyl (meth)acrylate.

当不可交联的单体（C-1）和/或可交联的单体（C-2）共聚时，根据需要可以改进各种性质，诸如拒水和拒油性、防污性、所述性质的耐清洁性和耐洗性、溶剂中的溶解性、硬度和触感。When the non-crosslinkable monomer (C-1) and/or the crosslinkable monomer (C-2) are copolymerized, various properties such as water and oil repellency, stain resistance, the properties of cleaning and washing resistance, solubility in solvents, hardness and tactility.

在含氟聚合物中，基于100重量份的含氟单体（A），（甲基）丙烯酸酯单体（B）的量可以为0.1-300重量份，优选1-80重量份，并且其他单体（C）的量可以为至多150重量份，优选0.1-100重量份。In the fluorine-containing polymer, based on 100 parts by weight of the fluorine-containing monomer (A), the amount of (meth)acrylate monomer (B) may be 0.1-300 parts by weight, preferably 1-80 parts by weight, and other The amount of monomer (C) may be up to 150 parts by weight, preferably 0.1-100 parts by weight.

基于100重量份的含氟单体（A），不可交联的单体（C-1）的量可以为至多100重量份，例如0.1-50重量份，并且可交联的单体（C-2）的量可以为至多50重量份，例如至多20重量份，尤其是0.1-15重量份。Based on 100 parts by weight of fluorine-containing monomer (A), the amount of non-crosslinkable monomer (C-1) can be up to 100 parts by weight, such as 0.1-50 parts by weight, and the amount of crosslinkable monomer (C-1) 2) The amount can be up to 50 parts by weight, for example up to 20 parts by weight, especially 0.1-15 parts by weight.

含氟单体（A）、（甲基）丙烯酸酯单体（B）和任选使用的其他单体（C）可以被聚合。包括在单体（A）中的烯属不饱和共聚单体的实例包括烷基中具有1-30个碳原子的丙烯酸烷基酯或甲基丙烯酸烷基酯，诸如丙烯酸丁酯、丙烯酸乙酯、丙烯酸甲酯、甲基丙烯酸甲酯或甲基丙烯酸丁酯。丙烯酸烷基酯或甲基丙烯酸烷基酯可以用来调整得到的聚合产物的玻璃化转变温度（Tg）；例如，具有4-20个、尤其是8-20个碳原子的长链烷基的丙烯酸酯，诸如丙烯酸十八酯或甲基丙烯酸十八酯、丙烯酸辛酯、丙烯酸2-乙基己酯或丙烯酸十二酯或甲基丙烯酸2-乙基己酯或甲基丙烯酸十二酯，可以用来形成低Tg的较软聚合物。与丙烯酸烷基酯或甲基丙烯酸烷基酯单体的共聚物可以改善多种性质，诸如拒水和拒油性和去污性（soil releasability）、所述拒水拒油性和去污性的耐清洁性、耐洗性和耐磨性、溶剂中的溶解性、硬度和触感（手感）。Fluorine-containing monomers (A), (meth)acrylate monomers (B) and optionally used other monomers (C) can be polymerized. Examples of ethylenically unsaturated comonomers included in monomer (A) include alkyl acrylates or methacrylates having 1 to 30 carbon atoms in the alkyl group, such as butyl acrylate, ethyl acrylate, , methyl acrylate, methyl methacrylate or butyl methacrylate. Alkyl acrylates or methacrylates can be used to adjust the glass transition temperature (Tg) of the resulting polymer product; for example, long chain alkyl groups with 4-20, especially 8-20 Acrylates, such as stearyl acrylate or stearyl methacrylate, octyl acrylate, 2-ethylhexyl acrylate or lauryl acrylate or 2-ethylhexyl methacrylate or lauryl methacrylate, Can be used to form softer polymers with low Tg. Copolymers with alkyl acrylate or alkyl methacrylate monomers can improve properties such as water and oil repellency and soil releasability, resistance to said water and oil repellency and soil releasability Cleanability, washability and abrasion resistance, solubility in solvents, hardness and haptics (hand).

可以使用的其他丙烯酸酯或甲基丙烯酸酯共聚单体包括（甲基）丙烯酸异丙酯、（甲基）丙烯酸异丁酯、（甲基）丙烯酸仲丁酯、（甲基）丙烯酸叔丁酯、（甲基）丙烯酸3-甲基丁酯、（甲基）丙烯酸2-乙基-正己酯、（甲基）丙烯酸环己酯、（甲基）丙烯酸环十二酯、（甲基）丙烯酸苯酯、（甲基）丙烯酸苄酯、（甲基）丙烯酸甲苯酯、（甲基）丙烯酸二环戊酯、（甲基）丙烯酸二环戊烯酯、（甲基）丙烯酸金刚烷酯、（甲基）丙烯酸异冰片酯、聚乙二醇丙烯酸酯或聚乙二醇甲基丙烯酸酯、丙二醇丙烯酸酯或丙二醇甲基丙烯酸酯、甲氧基聚乙二醇丙烯酸酯或甲氧基聚乙二醇甲基丙烯酸酯和甲氧基聚丙二醇丙烯酸酯或甲氧基丙二醇甲基丙烯酸酯。其他可用的烯属不饱和共聚单体包括氯乙烯、偏二氯乙烯、苯乙烯、丙烯腈、甲基丙烯腈、乙烯、乙烯基烷基醚、异戊二烯、或乙烯基酯，例如，乙酸乙烯酯或丙酸乙烯酯。Other acrylate or methacrylate comonomers that can be used include isopropyl (meth)acrylate, isobutyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate , 3-methylbutyl (meth)acrylate, 2-ethyl-n-hexyl (meth)acrylate, cyclohexyl (meth)acrylate, cyclododecyl (meth)acrylate, (meth)acrylic acid Phenyl ester, benzyl (meth)acrylate, cresyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, adamantyl (meth)acrylate, ( Isobornyl methacrylate, polyethylene glycol acrylate or methacrylate, propylene glycol acrylate or methacrylate, methoxypolyethylene glycol acrylate or methoxypolyethylene glycol Alcohol Methacrylate and Methoxy Polypropylene Glycol Acrylate or Methoxy Propylene Glycol Methacrylate. Other useful ethylenically unsaturated comonomers include vinyl chloride, vinylidene chloride, styrene, acrylonitrile, methacrylonitrile, ethylene, vinyl alkyl ethers, isoprene, or vinyl esters, for example, Vinyl acetate or vinyl propionate.

可以使用具有不与胺基团反应并且可与其他有机官能团反应的官能团的烯属不饱和共聚单体，以便赋予纺织品和其他基材以增加的耐久性（耐用性）的性质。此官能团的实例包括羟基、氨基和酰胺基。含有它们的烯属不饱和共聚单体的实例为丙烯酰胺、甲基丙烯酰胺、N-羟甲基丙烯酰胺、甲基丙烯酸羟乙酯、丙烯酸羟乙酯、丙烯酸3-氯-2-羟丙酯或甲基丙烯酸3-氯-2-羟丙酯、丙烯酸N,N-二甲基氨基乙酯或甲基丙烯酸N,N-二甲基氨基乙酯和丙烯酸二乙基氨基乙酯或甲基丙烯酸二乙基氨基乙酯。Ethylenically unsaturated comonomers having functional groups that do not react with amine groups and can react with other organic functional groups can be used in order to impart the property of increased durability (durability) to textiles and other substrates. Examples of such functional groups include hydroxyl, amino and amide groups. Examples of ethylenically unsaturated comonomers containing them are acrylamide, methacrylamide, N-methylolacrylamide, hydroxyethyl methacrylate, hydroxyethyl acrylate, 3-chloro-2-hydroxypropyl acrylate ester or 3-chloro-2-hydroxypropyl methacrylate, N,N-dimethylaminoethyl acrylate or N,N-dimethylaminoethyl methacrylate and diethylaminoethyl acrylate or methyl diethylaminoethyl acrylate.

本发明的含氟聚合物可以通过任意的常规聚合方法产生，并且聚合条件可以任选地选择。聚合方法包括，例如，溶液聚合、悬液聚合和乳液聚合。The fluoropolymers of the present invention can be produced by any conventional polymerization method, and the polymerization conditions can be optionally selected. Polymerization methods include, for example, solution polymerization, suspension polymerization, and emulsion polymerization.

在溶液聚合中，可以使用如下方法：在聚合引发剂的存在下将单体溶解在有机溶剂中，用氮置换气氛，并在30℃-120℃的温度范围内加热搅拌该混合物1小时-10小时。聚合引发剂的实例包括偶氮二异丁腈、过氧化苯甲酰、二叔丁基过氧化物、月桂基过氧化物、异丙基苯过氧化氢、过氧化新戊酸叔丁酯和过氧化二碳酸二异丙酯。聚合引发剂的用量基于100重量份所有单体可以为0.01-20重量份，例如0.01-10重量份。In the solution polymerization, a method may be used in which a monomer is dissolved in an organic solvent in the presence of a polymerization initiator, the atmosphere is replaced with nitrogen, and the mixture is heated and stirred in a temperature range of 30° C. to 120° C. for 1 hour to 10 hours. Hour. Examples of the polymerization initiator include azobisisobutyronitrile, benzoyl peroxide, di-t-butyl peroxide, lauryl peroxide, cumene hydroperoxide, t-butyl peroxypivalate and Diisopropyl peroxydicarbonate. The polymerization initiator may be used in an amount of 0.01-20 parts by weight, for example, 0.01-10 parts by weight, based on 100 parts by weight of all monomers.

有机溶剂对单体是惰性的，且溶解所述单体，并且有机溶剂的实例包括丙酮、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、甲基异丁基酮、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、四氯二氟乙烷和三氯三氟乙烷。有机溶剂的用量基于100重量份所有单体可以为50-2,000重量份，例如50-1,000重量份。The organic solvent is inert to the monomer and dissolves the monomer, and examples of the organic solvent include acetone, chloroform, HCHC225, isopropanol, pentane, hexane, heptane, octane, cyclohexane, benzene, Toluene, xylene, petroleum ether, tetrahydrofuran, 1,4-dioxane, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, 1,1,2,2-tetrachloroethane alkanes, 1,1,1-trichloroethane, trichloroethylene, perchloroethylene, tetrachlorodifluoroethane and trichlorotrifluoroethane. The organic solvent may be used in an amount of 50-2,000 parts by weight, for example, 50-1,000 parts by weight, based on 100 parts by weight of all monomers.

在乳液聚合中，可以使用如下方法：在聚合引发剂和乳化剂的存在下在水中乳化单体，用氮置换气氛，和例如在50℃-80℃的温度范围内搅拌聚合1小时-10小时。作为聚合引发剂，例如，可以使用水溶性引发剂，诸如过氧化苯甲酰、过氧化月桂酰、过苯甲酸叔丁酯、1-羟基环己基过氧化氢、3-羧丙酰过氧化物、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、过硫酸钾和过硫酸铵；和油溶性引发剂，诸如偶氮二异丁腈、过氧化苯甲酰、二叔丁基过氧化物、月桂基过氧化物、异丙基苯过氧化氢、过氧化新戊酸叔丁酯和过氧化二碳酸二异丙酯。聚合引发剂的用量基于100重量份单体可以为0.01-10重量份。In emulsion polymerization, a method of emulsifying monomers in water in the presence of a polymerization initiator and an emulsifier, replacing the atmosphere with nitrogen, and stirring polymerization at a temperature range of, for example, 50° C. to 80° C. for 1 hour to 10 hours can be used. . As the polymerization initiator, for example, water-soluble initiators such as benzoyl peroxide, lauroyl peroxide, tert-butyl perbenzoate, 1-hydroxycyclohexyl hydroperoxide, 3-carboxypropionyl peroxide can be used , acetyl peroxide, azobisisobutyromidine dihydrochloride, azobisisobutyronitrile, sodium peroxide, potassium persulfate and ammonium persulfate; and oil-soluble initiators such as azobisisobutyronitrile, persulfate Benzoyl oxide, di-tert-butyl peroxide, lauryl peroxide, cumene hydroperoxide, tert-butyl peroxypivalate, and diisopropyl peroxydicarbonate. The polymerization initiator may be used in an amount of 0.01 to 10 parts by weight based on 100 parts by weight of the monomer.

为了获得在保存稳定性方面较佳的水中的聚合物分散体，理想的是通过使用能够施加强剪切能的乳化装置（例如，高压匀浆机和超声均质机）将单体分散在水中，并且然后使用油溶性聚合引发剂进行聚合。作为乳化剂，各种乳化剂诸如阴离子乳化剂、阳离子乳化剂和非离子乳化剂可以以基于100重量份单体的0.5-20重量份的量使用。当单体未完全相容时，优选将能够使它们充分相容的相容性试剂（例如，水溶性有机溶剂和低分子量单体）加入至这些单体中。通过加入相容性试剂，可以改善乳化性和可聚合性。In order to obtain a polymer dispersion in water that is superior in storage stability, it is desirable to disperse the monomer in water by using an emulsification device capable of applying strong shear energy (for example, a high-pressure homogenizer and an ultrasonic homogenizer) , and then polymerized using an oil-soluble polymerization initiator. As the emulsifier, various emulsifiers such as anionic emulsifiers, cationic emulsifiers and nonionic emulsifiers may be used in an amount of 0.5 to 20 parts by weight based on 100 parts by weight of the monomer. When the monomers are not fully compatible, it is preferable to add a compatibilizing agent capable of making them sufficiently compatible (for example, a water-soluble organic solvent and a low molecular weight monomer) to these monomers. Emulsification and polymerizability can be improved by adding compatibilizing agents.

水溶性有机溶剂的实例包括丙酮、甲基乙基酮、乙酸乙酯、丙二醇、二丙二醇一甲基醚、二丙二醇、三丙二醇和乙醇。水溶性有机溶剂的用量基于100重量份水可以为1-50重量份，例如10-40重量份。低分子量单体的实例为甲基丙烯酸甲酯、甲基丙烯酸缩水甘油酯、甲基丙烯酸2,2,2-三氟乙酯。低分子量单体的用量基于100重量份所有单体可以为1-50重量份，例如10-40重量份。Examples of water-soluble organic solvents include acetone, methyl ethyl ketone, ethyl acetate, propylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol, tripropylene glycol, and ethanol. The water-soluble organic solvent may be used in an amount of 1-50 parts by weight, such as 10-40 parts by weight, based on 100 parts by weight of water. Examples of low molecular weight monomers are methyl methacrylate, glycidyl methacrylate, 2,2,2-trifluoroethyl methacrylate. The low molecular weight monomer may be used in an amount of 1-50 parts by weight, for example, 10-40 parts by weight, based on 100 parts by weight of all monomers.

含氟聚合物可以通过任何已知的方法应用于纤维基材（诸如纺织品）从而在液体中处理纺织品。应用于纺织品的溶液中含氟聚合物的浓度可以在0.5-20重量%或1-5重量%的范围内。当纺织品为布料时，该布料可以浸泡在溶液中或溶液可以附着或喷雾至该布料上。经处理的纺织品进行干燥，优选在100℃至200℃的温度下加热，以便形成拒油性。Fluoropolymers can be applied to fibrous substrates such as textiles by any known method to treat textiles in liquids. The concentration of fluoropolymer in the solution applied to textiles may be in the range of 0.5-20% by weight or 1-5% by weight. When the textile is cloth, the cloth may be soaked in the solution or the solution may be attached or sprayed onto the cloth. The treated textile is dried, preferably heated at a temperature of 100°C to 200°C, in order to develop oil repellency.

或者，含氟聚合物可以经清洗过程应用于纺织品，诸如在洗衣应用或干洗过程中。Alternatively, fluoropolymers can be applied to textiles via a cleaning process, such as in laundry applications or dry cleaning.

被处理的纺织品一般为织物，包括编织、针织和无纺织物、衣服形式和地毯中的织物，但也可以是纤维或纱线或中间纺织产品诸如碎料或粗纱。纺织材料可以是天然纤维诸如棉花或羊毛，人造纤维诸如粘胶人造丝或莱赛尔（lyocell）或合成纤维诸如聚酯、聚酰胺或丙烯酸类纤维，或可以是纤维混合物诸如天然和合成纤维的混合物。本发明的聚合产物特别有效地使纤维素纤维诸如棉花或人造丝变得疏油和拒油。本发明的方法通常还使纺织品疏水和拒水。用本发明的聚合产物处理织物与未处理的织物相比赋予织物以拒油性同时赋予触感的改善，并且与用已知的含氟聚合物纺织品处理剂处理的织物相比也赋予了触感的改善。The textiles to be treated are typically fabrics, including woven, knitted and nonwoven fabrics, fabrics in clothing forms and carpets, but can also be fibers or yarns or intermediate textile products such as scrap or roving. Textile materials may be natural fibers such as cotton or wool, man-made fibers such as viscose rayon or lyocell or synthetic fibers such as polyester, polyamide or acrylic, or may be a blend of fibers such as natural and synthetic fibers mixture. The polymer products of the present invention are particularly effective in rendering cellulosic fibers such as cotton or rayon oleophobic and oil repellent. The methods of the present invention also generally render textiles hydrophobic and water-repellent. Treatment of fabrics with the polymeric products of the present invention imparts oil repellency to fabrics while imparting an improvement in feel when compared to untreated fabrics and also imparts an improvement in feel when compared to fabrics treated with known fluoropolymer textile treatments .

纤维基材另外可以为皮革。聚合产物可以在皮革加工的各个阶段从水溶液或乳液应用于皮革，例如在皮革湿部加工或皮革涂饰期间，从而使皮革变得疏水和疏油。The fibrous substrate can additionally be leather. Polymerization products can be applied to leather from aqueous solutions or emulsions at various stages of leather processing, for example during leather wet end processing or leather finishing, thereby rendering the leather hydrophobic and oleophobic.

纤维基材另外可以为纸。聚合产物可以应用于预成型纸或在造纸的各个阶段中应用，例如在纸的干燥期间。The fibrous substrate may additionally be paper. The polymerization product can be applied to preformed paper or at various stages of papermaking, for example during drying of the paper.

本发明的表面处理剂优选地为溶液、乳液或气溶胶的形式。表面处理剂通常包括含氟聚合物和介质（特别是液体介质，例如有机溶剂和/或水）。表面处理剂中含氟聚合物的浓度可以为，例如0.1-50重量%。The surface treatment agent of the present invention is preferably in the form of a solution, emulsion or aerosol. Surface treatments typically include fluoropolymers and media (especially liquid media such as organic solvents and/or water). The concentration of the fluoropolymer in the surface treatment agent may be, for example, 0.1 to 50% by weight.

本发明的表面处理剂优选包括含氟聚合物和水性介质。如本文所使用，术语“水性介质”是指仅由水组成的介质，以及除水以外还包含有机溶剂（基于100重量份水，有机溶剂的量为至多80重量份，例如0.1-50重量份，特别是5-30重量份）的介质。含氟聚合物优选通过乳液聚合制备含氟聚合物的分散体来产生。本发明的表面处理剂优选包括含氟聚合物颗粒在水性介质中的水分散体。分散体中的含氟聚合物颗粒优选具有0.01-200微米、例如0.1-5微米、尤其是0.05-0.2微米的平均粒度。平均粒度可以通过动态光散射装置、电子显微镜等来测量。The surface treatment agent of the present invention preferably comprises a fluoropolymer and an aqueous medium. As used herein, the term "aqueous medium" refers to a medium consisting of water only, and containing an organic solvent in addition to water (based on 100 parts by weight of water, the amount of the organic solvent is up to 80 parts by weight, such as 0.1-50 parts by weight , especially 5-30 parts by weight) medium. The fluoropolymer is preferably produced by emulsion polymerization to prepare a dispersion of the fluoropolymer. The surface treating agent of the present invention preferably comprises an aqueous dispersion of fluoropolymer particles in an aqueous medium. The fluoropolymer particles in the dispersion preferably have an average particle size of 0.01-200 microns, such as 0.1-5 microns, especially 0.05-0.2 microns. The average particle size can be measured by a dynamic light scattering device, an electron microscope, and the like.

表面处理剂可以通过已知步骤应用于待处理的基材。表面处理剂的应用可以通过浸渍、喷雾和涂敷来进行。通常，表面处理剂用有机溶剂或水稀释，通过已知步骤诸如浸渍涂布、喷涂和泡沫涂布而附着于基材的表面，并干燥。如果需要，处理液体与合适的交联剂一起应用，然后固化。也可能将防蛀剂、软化剂、抗微生物剂、阻燃剂、抗静电剂、颜料固定剂、防皱剂等加入至表面处理剂中。与基材接触的处理液体中含氟化合物的浓度基于处理液体，可以为0.01-10重量%（尤其对于浸渍涂布），例如0.05-10重量%（尤其对于喷涂）。The surface treatment agent can be applied to the substrate to be treated by known procedures. The application of the surface treatment agent can be carried out by dipping, spraying and coating. Usually, the surface treatment agent is diluted with an organic solvent or water, attached to the surface of the substrate by known procedures such as dip coating, spray coating, and foam coating, and dried. The treating fluid is applied with a suitable crosslinker, if desired, and then cured. It is also possible to add mothproofing agents, softeners, antimicrobial agents, flame retardants, antistatic agents, pigment fixing agents, anti-wrinkling agents, etc. to the surface treatment agent. The concentration of the fluorine-containing compound in the treatment liquid in contact with the substrate may be 0.01-10% by weight (especially for dip coating), for example 0.05-10% by weight (especially for spray coating), based on the treatment liquid.

要用本发明的表面处理剂（例如，拒水和拒油剂）处理的基材优选为纺织品。纺织品包括各种实例。纺织品的实例包括动物或植物来源的天然纤维诸如棉花、大麻、羊毛和蚕丝；合成纤维诸如聚酰胺、聚酯、聚乙烯醇、聚丙烯腈、聚氯乙烯和聚丙烯；半合成纤维诸如人造丝和乙酸酯；无机纤维诸如玻璃纤维、碳纤维和石棉纤维；和这些纤维的混合物。The substrate to be treated with the surface treatment agent (for example, water and oil repellent) of the present invention is preferably a textile. Textiles include various examples. Examples of textiles include natural fibers of animal or vegetable origin such as cotton, hemp, wool, and silk; synthetic fibers such as polyamide, polyester, polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride, and polypropylene; semi-synthetic fibers such as rayon and acetate; inorganic fibers such as glass fibers, carbon fibers, and asbestos fibers; and mixtures of these fibers.

纺织品可以是任何形式诸如纤维、纱线和织物。Textiles can be in any form such as fibers, yarns and fabrics.

术语“处理”是指处理剂通过浸渍、喷雾、涂敷等应用于基材。作为处理剂的活性组分的含氟聚合物通过处理可以穿透基材的内部或可以附着在基材的表面上。The term "treating" means that a treating agent is applied to a substrate by dipping, spraying, coating, or the like. The fluorine-containing polymer as an active component of the treatment agent may penetrate the inside of the substrate by the treatment or may adhere to the surface of the substrate.

实施例Example

现在通过实施例、比较例和测试例详细地说明本发明。然而，本发明不限于这些。The present invention is now explained in detail by way of Examples, Comparative Examples and Test Examples. However, the present invention is not limited to these.

在下面的实施例、比较例和测试例中，除非另外指明，份数和百分比按重量计。In the following Examples, Comparative Examples and Test Examples, parts and percentages are by weight unless otherwise specified.

测试步骤以如下方式进行。The test procedure was carried out as follows.

拒水性测试Water repellency test

处理的织物保存在温度为21℃和湿度为65%的恒温恒湿器中至少4小时。使用已经在21℃下保存的测试液体（异丙醇（IPA）、水、和其混合物，如表2中所示）。在温度为21℃和湿度为65%的空调房间内进行测试。一滴0.05ML测试液体通过微量吸管轻轻地滴在织物上。如果静置30秒后液滴保留在织物上，则测试液体测试合格。拒水性表示为与测试合格的测试液体中异丙醇（IPA）的最大含量（体积%）对应的点。拒水性评价为12个水平，为不合格、0、1、2、3、4、5、6、7、8、9和10，其顺序为较差的水平至优异的水平。加至数字的符号“+”是指结果优于该数字本身，并且加至数字的符号“-”是指结果劣于该数字本身。The treated fabrics were kept in a thermo-hygrostat at a temperature of 21°C and a humidity of 65% for at least 4 hours. Test liquids (isopropanol (IPA), water, and mixtures thereof, as indicated in Table 2) that had been stored at 21°C were used. The test was carried out in an air-conditioned room with a temperature of 21°C and a humidity of 65%. A drop of 0.05 mL of the test liquid is gently dripped onto the fabric through a micropipette. The test liquid passed the test if droplets remained on the fabric after standing for 30 seconds. Water repellency is expressed as the point corresponding to the maximum content (volume %) of isopropanol (IPA) in the test liquid that passed the test. Water repellency was evaluated on 12 levels of unacceptable, 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, and 10 in order from poor level to excellent level. A "+" sign added to a number means that the result is better than the number itself, and a "-" sign added to a number means that the result is worse than the number itself.

表1.拒水性测试液体Table 1. Water repellency test liquids

Figure BDA0000452345670000141
Figure BDA0000452345670000141

接触角Contact angle

当水滴滴至基材上时，使用自动接触角测量计DROPMASTER700（由Kyowa Interface Science Co.Ltd.制造）测量前进接触角、后退接触角和滑移角的每一个。Each of the advancing contact angle, receding contact angle, and slip angle was measured using an automatic contact angle meter DROPMASTER700 (manufactured by Kyowa Interface Science Co. Ltd.) when water droplets were dropped onto the substrate.

制备例1Preparation Example 1

在1升高压釜中，装入CF3CF2-(CF2CF2)n-CH2CH2OCOC(CH3)=CH2（n=2.0）（13FMA）（78.4g）、甲基丙烯酸异冰片酯（IBMA）（26.0g）、纯水（250g）、三丙二醇（35.1g）、聚氧乙烯油基醚（5.4g）和聚氧乙烯异十三烷基醚（5.4g）并在60℃温度下搅拌15分钟，然后用超声波乳化并分散。在用氮置换高压釜中的气氛后，通过注射装入氯乙烯（VCM）（30g）。此外，加入2,2-偶氮双-(2-脒基丙烷)二盐酸盐（0.91g）从而在60℃进行反应5小时，并且获得聚合物的水分散体。获得的聚合物中单体的组成（重量比）为13FMA/IBMA/VCM=60/20/20。In a 1-liter autoclave, charge CF 3 CF 2 -(CF 2 CF 2 ) n -CH 2 CH 2 OCOC(CH 3 )=CH 2 (n=2.0) (13FMA) (78.4 g), methacrylic acid Isobornyl ester (IBMA) (26.0g), purified water (250g), tripropylene glycol (35.1g), polyoxyethylene oleyl ether (5.4g) and polyoxyethylene isotridecyl ether (5.4g) were mixed in Stir at 60°C for 15 minutes, then ultrasonically emulsify and disperse. After replacing the atmosphere in the autoclave with nitrogen, vinyl chloride (VCM) (30 g) was charged by injection. Furthermore, 2,2-azobis-(2-amidinopropane) dihydrochloride (0.91 g) was added to perform a reaction at 60° C. for 5 hours, and an aqueous dispersion of a polymer was obtained. The composition (weight ratio) of monomers in the obtained polymer was 13FMA/IBMA/VCM=60/20/20.

制备例2Preparation example 2

在1升高压釜中，装入CF3CF2-(CF2CF2)n-CH2CH2OCOC(CH3)=CH2（n=2.0）（13FMA）（78.4g）、甲基丙烯酸环己酯（CHMA）（26.0g）、纯水（250g）、三丙二醇（35.1g）、聚氧乙烯油基醚（5.4g）和聚氧乙烯异十三烷基醚（5.4g）并在60℃温度下搅拌15分钟，然后用超声波乳化并分散。在用氮置换高压釜中的气氛后，通过注射装入氯乙烯（VCM）（30g）。此外，加入2,2-偶氮双-(2-脒基丙烷)二盐酸盐（0.91g）从而在60℃进行反应5小时，并且获得聚合物的水分散体。获得的聚合物中单体的组成（重量比）为13FMA/CHMA/VCM=60/20/20。In a 1-liter autoclave, charge CF 3 CF 2 -(CF 2 CF 2 ) n -CH 2 CH 2 OCOC(CH 3 )=CH 2 (n=2.0) (13FMA) (78.4 g), methacrylic acid Cyclohexyl ester (CHMA) (26.0g), purified water (250g), tripropylene glycol (35.1g), polyoxyethylene oleyl ether (5.4g) and polyoxyethylene isotridecyl ether (5.4g) were mixed in Stir at 60°C for 15 minutes, then ultrasonically emulsify and disperse. After replacing the atmosphere in the autoclave with nitrogen, vinyl chloride (VCM) (30 g) was charged by injection. Furthermore, 2,2-azobis-(2-amidinopropane) dihydrochloride (0.91 g) was added to perform a reaction at 60° C. for 5 hours, and an aqueous dispersion of a polymer was obtained. The composition (weight ratio) of monomers in the obtained polymer was 13FMA/CHMA/VCM=60/20/20.

制备例3Preparation example 3

在1升高压釜中，装入CF3CF2-(CF2CF2)n-CH2CH2OCOC(CH3)=CH2（n=2.0）（13FMA）（78.4g）、甲基丙烯酸异冰片酯（IBMA）（13.0g）、丙烯酸十八酯（StA）（13.0g）、纯水（250g）、三丙二醇（34.3g）、聚氧乙烯油基醚（5.4g）和聚氧乙烯异十三烷基醚（5.4g）并在60℃温度下搅拌15分钟，然后用超声波乳化并分散。在用氮置换高压釜中的气氛后，通过注射装入氯乙烯（VCM）（30g）。此外，加入2,2-偶氮双-(2-脒基丙烷)二盐酸盐（0.91g）从而在60℃进行反应5小时，并且获得聚合物的水分散体。获得的聚合物中单体的组成（重量比）为13FMA/StA/IBMA/VCM=60/10/10/20。In a 1-liter autoclave, charge CF 3 CF 2 -(CF 2 CF 2 ) n -CH 2 CH 2 OCOC(CH 3 )=CH 2 (n=2.0) (13FMA) (78.4 g), methacrylic acid Isobornyl ester (IBMA) (13.0g), stearyl acrylate (StA) (13.0g), purified water (250g), tripropylene glycol (34.3g), polyoxyethylene oleyl ether (5.4g) and polyoxyethylene Isotridecyl ether (5.4 g) was stirred at 60°C for 15 minutes, then ultrasonically emulsified and dispersed. After replacing the atmosphere in the autoclave with nitrogen, vinyl chloride (VCM) (30 g) was charged by injection. Furthermore, 2,2-azobis-(2-amidinopropane) dihydrochloride (0.91 g) was added to perform a reaction at 60° C. for 5 hours, and an aqueous dispersion of a polymer was obtained. The composition (weight ratio) of monomers in the obtained polymer was 13FMA/StA/IBMA/VCM=60/10/10/20.

比较制备例1Comparative Preparation Example 1

在1升高压釜中，装入CF3CF2-(CF2CF2)n-CH2CH2OCOC(CH3)=CH2（n=2.0）（13FMA）（78.4g）、甲基丙烯酸十八酯（StA）（26.0g）、纯水（250g）、三丙二醇（35.1g）、聚氧乙烯油基醚（5.4g）和聚氧乙烯异十三烷基醚（5.4g）并在60℃温度下搅拌15分钟，然后用超声波乳化并分散。在用氮置换高压釜中的气氛后，通过注射装入氯乙烯（VCM）（30g）。此外，加入2,2-偶氮双-(2-脒基丙烷)二盐酸盐（0.91g）从而在60℃进行反应5小时，并且获得聚合物的水分散体。获得的聚合物中单体的组成（重量比）为13FMA/StA/VCM=60/20/20。In a 1-liter autoclave, charge CF 3 CF 2 -(CF 2 CF 2 ) n -CH 2 CH 2 OCOC(CH 3 )=CH 2 (n=2.0) (13FMA) (78.4 g), methacrylic acid Stearyl ester (StA) (26.0g), purified water (250g), tripropylene glycol (35.1g), polyoxyethylene oleyl ether (5.4g) and polyoxyethylene isotridecyl ether (5.4g) were mixed in Stir at 60°C for 15 minutes, then ultrasonically emulsify and disperse. After replacing the atmosphere in the autoclave with nitrogen, vinyl chloride (VCM) (30 g) was charged by injection. Furthermore, 2,2-azobis-(2-amidinopropane) dihydrochloride (0.91 g) was added to perform a reaction at 60° C. for 5 hours, and an aqueous dispersion of a polymer was obtained. The composition (weight ratio) of monomers in the obtained polymer was 13FMA/StA/VCM=60/20/20.

实施例1Example 1

制备例1中获得的两种水性液体的每一个（各2g和4g）用纯水稀释以制备测试溶液（1000g）。将一块尼龙塔夫绸布（510mm X205mm）浸渍在测试溶液中，通过熨平机并且用针板拉幅机在160℃下处理2分钟。测试布进行拒水性测试。对于尼龙白布（510mm X205mm）、PET塔夫绸布（510mm X205mm）和PET夏令织物（510mm X205mm）重复上述步骤。结果显示在表A中。Each of the two aqueous liquids obtained in Preparation Example 1 (2 g and 4 g each) was diluted with pure water to prepare a test solution (1000 g). A piece of nylon taffeta cloth (510mm x 205mm) was dipped in the test solution, passed through the ironer and treated with a pin tenter at 160°C for 2 minutes. Test cloth for water repellency test. Repeat the above steps for nylon white cloth (510mm X205mm), PET taffeta cloth (510mm X205mm) and PET summer fabric (510mm X205mm). The results are shown in Table A.

实施例2-3和比较例1Embodiment 2-3 and comparative example 1

制备例2和3以及比较制备例1的每一个中制备的聚合物以与实施例1相同的方式用于处理，并且进行拒水性测试。结果显示在表A中。The polymers prepared in each of Preparation Examples 2 and 3 and Comparative Preparation Example 1 were treated in the same manner as in Example 1, and subjected to a water repellency test. The results are shown in Table A.

表ATable A

Figure BDA0000452345670000161
Figure BDA0000452345670000161

表A（续）Table A (continued)

Figure BDA0000452345670000162
Figure BDA0000452345670000162

Figure BDA0000452345670000171
Figure BDA0000452345670000171

制备例4Preparation Example 4

在500mL可拆式玻璃烧瓶中，装入CF3CF2-(CF2CF2)n-CH2CH2OCOC(CH3)=CH2（n=2.0）（13FMA）（36.2g）、甲基丙烯酸异冰片酯（IBMA）（24.0g）、纯水（115g）、三丙二醇（16.2g）、聚氧乙烯油基醚（2.5g）和聚氧乙烯异十三烷基醚（2.5g）并在60℃温度下搅拌15分钟，然后用超声波乳化并分散。在用氮置换烧瓶中的气氛后，加入2,2-偶氮双-(2-脒基丙烷)二盐酸盐（0.42g）从而在60℃进行反应5小时，并且获得聚合物的水分散体。获得的聚合物中单体的组成（重量比）为13FMA/IBMA=60/40。In a 500mL detachable glass flask, put CF 3 CF 2 -(CF 2 CF 2 ) n -CH 2 CH 2 OCOC(CH 3 )=CH 2 (n=2.0) (13FMA) (36.2g), formazan Isobornyl acrylate (IBMA) (24.0g), purified water (115g), tripropylene glycol (16.2g), polyoxyethylene oleyl ether (2.5g) and polyoxyethylene isotridecyl ether (2.5g) and stirred at 60°C for 15 minutes, and then ultrasonically emulsified and dispersed. After replacing the atmosphere in the flask with nitrogen, 2,2-azobis-(2-amidinopropane) dihydrochloride (0.42 g) was added to conduct a reaction at 60° C. for 5 hours, and a water dispersion of the polymer was obtained body. The composition (weight ratio) of monomers in the obtained polymer was 13FMA/IBMA=60/40.

制备例5Preparation Example 5

在500mL可拆式玻璃烧瓶中，装入CF3CF2-(CF2CF2)n-CH2CH2OCOC(CH3)=CH2（n=2.0）（13FMA）（36.2g）、甲基丙烯酸环己酯（24.0g）、纯水（115g）、三丙二醇（16.2g）、聚氧乙烯油基醚（2.5g）和聚氧乙烯异十三烷基醚（2.5g）并在60℃温度下搅拌15分钟，然后用超声波乳化并分散。在用氮置换烧瓶中的气氛后，加入2,2-偶氮双-(2-脒基丙烷)二盐酸盐（0.42g）从而在60℃进行反应5小时，并且获得聚合物的水分散体。获得的聚合物中单体的组成（重量比）为13FMA/CHMA=60/40。In a 500mL detachable glass flask, put CF 3 CF 2 -(CF 2 CF 2 ) n -CH 2 CH 2 OCOC(CH 3 )=CH 2 (n=2.0) (13FMA) (36.2g), formazan Cyclohexyl acrylate (24.0g), purified water (115g), tripropylene glycol (16.2g), polyoxyethylene oleyl ether (2.5g) and polyoxyethylene isotridecyl ether (2.5g) were mixed at 60 Stir at ℃ for 15 minutes, then ultrasonically emulsify and disperse. After replacing the atmosphere in the flask with nitrogen, 2,2-azobis-(2-amidinopropane) dihydrochloride (0.42 g) was added to conduct a reaction at 60° C. for 5 hours, and a water dispersion of the polymer was obtained body. The composition (weight ratio) of monomers in the obtained polymer was 13FMA/CHMA=60/40.

比较制备例2Comparative Preparation Example 2

在500mL可拆式玻璃烧瓶中，装入CF3CF2-(CF2CF2)n-CH2CH2OCOC(CH3)=CH2（n=2.0）（13FMA）（40.20g）、纯水（75g）、三丙二醇（10.8g）、聚氧乙烯油基醚（1.65g）和聚氧乙烯异十三烷基醚（1.65g）并在60℃温度下搅拌15分钟，然后用超声波乳化并分散。在用氮置换烧瓶中的气氛后，加入2,2-偶氮双-(2-脒基丙烷)二盐酸盐（0.28g）从而在60℃进行反应5小时，并且获得聚合物的水分散体。获得的聚合物中单体的组成（重量比）为13FMA=100。In a 500mL detachable glass flask, put CF 3 CF 2 -(CF 2 CF 2 ) n -CH 2 CH 2 OCOC(CH 3 )=CH 2 (n=2.0) (13FMA) (40.20g), pure Water (75g), tripropylene glycol (10.8g), polyoxyethylene oleyl ether (1.65g) and polyoxyethylene isotridecyl ether (1.65g) were stirred at 60°C for 15 minutes and then ultrasonically emulsified And scatter. After replacing the atmosphere in the flask with nitrogen, 2,2-azobis-(2-amidinopropane) dihydrochloride (0.28 g) was added to conduct a reaction at 60° C. for 5 hours, and a water dispersion of the polymer was obtained body. The composition (weight ratio) of monomers in the obtained polymer was 13FMA=100.

比较制备例3Comparative Preparation Example 3

在500mL可拆式玻璃烧瓶中，装入CF3CF2-(CF2CF2)n-CH2CH2OCOC(CH3)=CH2（n=2.0）（13FMA）（36.2g）、丙烯酸十八酯（StA）（24.0g）、纯水（115g）、三丙二醇（16.2g）、聚氧乙烯油基醚（2.5g）和聚氧乙烯异十三烷基醚（2.5g）并在60℃温度下搅拌15分钟，然后用超声波乳化并分散。在用氮置换烧瓶中的气氛后，加入2,2-偶氮双-(2-脒基丙烷)二盐酸盐（0.42g）从而在60℃进行反应5小时，并且获得聚合物的水分散体。获得的聚合物中单体的组成（重量比）为13FMA/StA=60/40。In a 500mL detachable glass flask, fill CF 3 CF 2 -(CF 2 CF 2 ) n -CH 2 CH 2 OCOC(CH 3 )=CH 2 (n=2.0) (13FMA) (36.2g), acrylic acid Stearyl ester (StA) (24.0g), purified water (115g), tripropylene glycol (16.2g), polyoxyethylene oleyl ether (2.5g) and polyoxyethylene isotridecyl ether (2.5g) were mixed in Stir at 60°C for 15 minutes, then ultrasonically emulsify and disperse. After replacing the atmosphere in the flask with nitrogen, 2,2-azobis-(2-amidinopropane) dihydrochloride (0.42 g) was added to conduct a reaction at 60° C. for 5 hours, and a water dispersion of the polymer was obtained body. The composition (weight ratio) of monomers in the obtained polymer was 13FMA/StA=60/40.

测试例1test case 1

使用获自制备例4和5以及比较例2和3中的每一个的含氟聚合物，通过浇铸在聚酯膜上形成聚合物膜并测量膜上的接触角。结果显示在表B中。Using the fluoropolymer obtained in each of Preparation Examples 4 and 5 and Comparative Examples 2 and 3, a polymer film was formed on a polyester film by casting and the contact angle on the film was measured. The results are shown in Table B.

表BForm B

Figure BDA0000452345670000181
Figure BDA0000452345670000181

表B（续）Form B (continued)

Figure BDA0000452345670000182
Figure BDA0000452345670000182

Claims (17)

1.一种含氟聚合物，包括来源于下列的重复单元：1. A fluoropolymer comprising repeat units derived from: （A）由下列通式表示的含氟单体：(A) A fluorine-containing monomer represented by the following general formula: CH2=C(-X)-C(=O)-Y-Z-RfCH 2 =C(-X)-C(=O)-YZ-Rf 其中in X为氢原子、单价有机基团或卤原子，X is a hydrogen atom, a monovalent organic group or a halogen atom, Y为-O-或-NH-；Y is -O- or -NH-; Z为直接键或二价有机基团；Z is a direct bond or a divalent organic group; Rf为具有1-20个碳原子的氟烷基；和Rf is a fluoroalkyl group having 1-20 carbon atoms; and （B）具有环烃基的（甲基）丙烯酸酯单体。(B) A (meth)acrylate monomer which has a cyclohydrocarbyl group. 2.根据权利要求1所述的含氟聚合物，其中所述含氟单体（A）由下式表示：2. The fluoropolymer according to claim 1, wherein the fluoromonomer (A) is represented by the following formula: CH2=C(-X)-C(=O)-Y-Z-RfCH 2 =C(-X)-C(=O)-YZ-Rf 其中in X为氢原子；具有1-21个碳原子的直链或支链烷基；氟原子；氯原子；溴原子；碘原子；CFX1X2基团，其中X1和X2中的每一个为氢原子、氟原子、氯原子、溴原子或碘原子；氰基；具有1-21个碳原子的直链或支链氟烷基；取代或未取代的苄基；或取代或未取代的苯基； X is a hydrogen atom; a linear or branched alkyl group having 1-21 carbon atoms; a fluorine atom; a chlorine atom; a bromine atom; an iodine atom ; is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom; a cyano group; a straight-chain or branched fluoroalkyl group with 1-21 carbon atoms; a substituted or unsubstituted benzyl group; or a substituted or unsubstituted phenyl; Y为-O-或-NH-基团；Y is -O- or -NH-group; Z为具有1-10个碳原子的脂族基团；具有6-18个碳原子的芳族或环脂族基团；-CH2CH2N(R1)SO2-基团，其中R1为具有1-4个碳原子的烷基；-CH2CH(OZ1)CH2-基团，其中Z1为氢原子或乙酰基；-(CH2)m-SO2-(CH2)n-基团、或-(CH2)m-S-(CH2)n-基团，其中m为1-10且n为0-10；Z is an aliphatic group having 1-10 carbon atoms; an aromatic or cycloaliphatic group having 6-18 carbon atoms; a -CH 2 CH 2 N(R 1 )SO 2 - group, wherein R 1 is an alkyl group with 1-4 carbon atoms; -CH 2 CH(OZ 1 )CH 2 -group, wherein Z 1 is a hydrogen atom or an acetyl group; -(CH 2 ) m -SO 2 -(CH 2 ) n -group, or -(CH 2 ) m -S-(CH 2 ) n -group, wherein m is 1-10 and n is 0-10; Rf为具有1-20个碳原子的直链或支链氟烷基。Rf is a linear or branched fluoroalkyl group having 1 to 20 carbon atoms. 3.根据权利要求1所述的含氟聚合物，其中所述（甲基）丙烯酸酯单体（B）为具有饱和的环烃基的单体。3. The fluorine-containing polymer according to claim 1, wherein the (meth)acrylate monomer (B) is a monomer having a saturated cyclic hydrocarbon group. 4.根据权利要求1所述的含氟聚合物，其中所述（甲基）丙烯酸酯单体（B）中的环烃基具有4-20个碳原子。4. The fluoropolymer according to claim 1, wherein the cyclohydrocarbyl group in the (meth)acrylate monomer (B) has 4 to 20 carbon atoms. 5.根据权利要求1所述的含氟聚合物，其中在所述（甲基）丙烯酸酯单体（B）中，所述环烃基中的碳原子直接与所述（甲基）丙烯酸酯基团中的酯基键合。5. The fluoropolymer according to claim 1, wherein in the (meth)acrylate monomer (B), the carbon atoms in the cyclic hydrocarbon group are directly connected to the (meth)acrylate group Ester linkages in the group. 6.根据权利要求1所述的含氟聚合物，其中所述（甲基）丙烯酸酯单体（B）中的环烃基为选自环己基、叔丁基环己基、异冰片基、二环戊基和二环戊烯基中的至少一种。6. The fluoropolymer according to claim 1, wherein the cyclohydrocarbyl group in the (meth)acrylate monomer (B) is selected from cyclohexyl, tert-butylcyclohexyl, isobornyl, dicyclopentyl and at least one of dicyclopentenyl. 7.根据权利要求1所述的含氟聚合物，其中所述（甲基）丙烯酸酯单体（B）为选自甲基丙烯酸环己酯、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、甲基丙烯酸二环戊酯、丙烯酸二环戊酯、甲基丙烯酸二环戊烯酯和丙烯酸二环戊烯酯中的至少一种。7. The fluoropolymer according to claim 1, wherein the (meth)acrylate monomer (B) is selected from cyclohexyl methacrylate, tert-butylcyclohexyl methacrylate, benzyl methacrylate At least one of ester, isobornyl methacrylate, isobornyl acrylate, dicyclopentanyl methacrylate, dicyclopentanyl acrylate, dicyclopentenyl methacrylate and dicyclopentenyl acrylate. 8.根据权利要求1所述的含氟聚合物，其中所述含氟聚合物还包括单体（A）和（B）以外的其他单体（C）。8. The fluoropolymer according to claim 1, wherein the fluoropolymer further comprises monomers (C) other than monomers (A) and (B). 9.根据权利要求8所述的含氟（单体）聚合物，其中所述其他单体（C）不含氟原子。9. The fluorine-containing (monomer) polymer according to claim 8, wherein the other monomer (C) does not contain fluorine atoms. 10.根据权利要求8所述的含氟聚合物，其中所述其他单体（C）为选自乙烯基卤化物和亚乙烯基卤化物中的至少一种。10. The fluorine-containing polymer according to claim 8, wherein the other monomer (C) is at least one selected from vinyl halides and vinylidene halides. 11.根据权利要求1所述的含氟聚合物，其中所述含氟聚合物以下单体组成：11. The fluoropolymer of claim 1, wherein the fluoropolymer is composed of the following monomers: 单体（A），Monomer (A), 单体（B），和monomer (B), and 其他单体（C），所述单体（C）是（C-1）不可交联的单体与（C-2）可交联的单体的组合。Other monomers (C) which are combinations of (C-1) non-crosslinkable monomers and (C-2) crosslinkable monomers. 12.根据权利要求11所述的含氟聚合物，其中所述其他单体（C-1）为选自乙烯基卤化物和亚乙烯基卤化物中的至少一种。12. The fluorine-containing polymer according to claim 11, wherein the other monomer (C-1) is at least one selected from vinyl halides and vinylidene halides. 13.一种拒水和拒油剂，包括根据权利要求1-12中任一项所述的含氟聚合物。13. A water- and oil-repellent agent comprising the fluoropolymer according to any one of claims 1-12. 14.根据权利要求13所述的拒水和拒油剂，其还含有水介质。14. The water and oil repellent agent according to claim 13, further comprising an aqueous medium. 15.根据权利要求13所述的拒水和拒油剂，其为水分散体。15. The water and oil repellent agent according to claim 13, which is an aqueous dispersion. 16.一种处理基材的方法，包括用根据权利要求13-15中任一项所述的拒水和拒油剂处理所述基材。16. A method of treating a substrate comprising treating the substrate with the water- and oil-repellent agent according to any one of claims 13-15. 17.一种用根据权利要求13-15中任一项所述的拒水和拒油剂处理的纺织品。17. A textile treated with the water and oil repellent according to any one of claims 13-15.
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