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Publication numberCN101020731 A
Publication typeApplication
Application numberCN 200710020567
Publication date22 Aug 2007
Filing date12 Mar 2007
Priority date12 Mar 2007
Also published asCN100497413C
Publication number200710020567.5, CN 101020731 A, CN 101020731A, CN 200710020567, CN-A-101020731, CN101020731 A, CN101020731A, CN200710020567, CN200710020567.5
Inventors刘庆安, 孟祥春, 孙艳松
Applicant安徽大学
Export CitationBiBTeX, EndNote, RefMan
External Links: SIPO, Espacenet
Process of preparing solvent type fluoric acrylate copolymer
CN 101020731 A
Abstract
The present invention is process of preparing solvent type fluoric acrylate copolymer, and features that hydroxyl radical containing acrylate monomer and at least one kind of acrylate monomer are solution polymerized to prepare acrylate copolymer with hydroxyl radical in the side chain, that equal-molar fluoric RfOH and diisocyanate OCN-Z-NCO are reacted in the presence of catalyst to prepare RfO2CNH-Z-NCO with one unreacted -NCO radical, and that the acrylate copolymer with hydroxyl radical in the side chain and RfO2CNH-Z-NCO with one unreacted -NCO radical in certain ratio are further reacted to prepare the solvent type fluoric acrylate copolymer. The solvent type fluoric acrylate copolymer may be used as waterproof and oil-proof agent for fabric, leather, etc.
Claims(2)  translated from Chinese
1.溶剂型含氟丙烯酸酯共聚物的制备方法,其特征在于:(1)以含有羟基的丙烯酸酯或丙烯酰胺单体M与一种以上的丙烯酸酯单体采用溶液聚合制备侧链含有羟基的丙烯酸酯共聚物A,结构示意为: A method for producing a fluorine-containing solvent-based acrylic copolymer, wherein: acrylate or acrylamide monomer M (1) in combination with one or more hydroxyl group-containing acrylate monomer was prepared by solution polymerization of a hydroxyl-containing side chain acrylate copolymer A, the structure illustrated as: 以及 As well as R=H,CH3R1=CH3,C2H5,C4H9,CH2CH(C2H5)C4H9,C12H25R2=CH3,C2H5,C4H9,CH2CH(C2H5)C4H9,C12H25,R1(2)在催化剂存在下,由等摩尔的含氟醇RfOH与二异氰酸酯OCN-Z-NCO反应,制备得反应物B,结构示意为:RfO2CNH-Z-NCO,反应物B保留一个未反应的-NCO基,反应示意为: R = H, CH3R1 = CH3, C2H5, C4H9, CH2CH (C2H5) C4H9, C12H25R2 = CH3, C2H5, C4H9, CH2CH (C2H5) C4H9, C12H25, R1 (2) in the presence of a catalyst, and other fluorine-containing alcohol by mole RfOH reacted with a diisocyanate OCN-Z-NCO, was prepared reactant B, the structure illustrated as: RfO2CNH-Z-NCO, a reactant B retain unreacted -NCO group, the reaction is illustrated as: ,含氟醇RfOH与二异氰酸酯OCN-Z-NCO的摩尔数均为含有羟基的丙烯酸酯或丙烯酰胺单体M摩尔数的0.8~1.2倍。 Acrylate or acrylamide monomer M, and a fluorine-containing alcohol RfOH diisocyanate OCN-Z-NCO are the number of moles of the number of moles of hydroxyl group-containing 0.8 to 1.2 times. (3)将前述制备取得的侧链含有羟基的丙烯酸酯共聚物A和反应物B两部分进行反应,制得溶剂型含氟丙烯酸酯共聚物;结构示意为: (3) the preparation of the aforementioned side chain made of acrylate copolymer containing hydroxyl reactants A and B two parts response system solvent-fluorinated acrylate copolymer; structure illustrated as: 以及 As well as R=H,CH3R1=CH3,C2H5,C4H9,CH2CH(C2H5)C4H9,C12H25R2=CH3,C2H5,C4H9,CH2CH(C2H5)C4H9,C12H25,R1。 R = H, CH3R1 = CH3, C2H5, C4H9, CH2CH (C2H5) C4H9, C12H25R2 = CH3, C2H5, C4H9, CH2CH (C2H5) C4H9, C12H25, R1.
2.根据权利要求1所述的溶剂型含氟丙烯酸酯共聚物A的制备方法,其特征在于:(1)所述侧链含有羟基的丙烯酸酯共聚物A,采用含有羟基的丙烯酸酯或丙烯酰胺单体M与一种以上丙烯酸酯单体在自由基引发剂过氧化二苯甲酰的存在下进行溶液聚合,过氧化二苯甲酰占整个聚合体系总量的0.03~1.0%,聚合温度70~100℃,时间4~8小时;聚合反应所用溶剂为甲苯、或为二甲苯、或为丁酮、或为甲基异丁基甲酮、或为醋酸乙酯、或为醋酸丁酯,溶剂用量在整个聚合反应体系总量中占33~85%;含有羟基的丙烯酸酯或丙烯酰胺单体M为丙烯酸-β-羟乙酯、或为丙烯酸-β-羟丙酯、或为N-羟甲基丙烯酰胺、或为甲基丙烯酸-β-羟乙酯、或为甲基丙烯酸-β-羟丙酯;在制备共聚物A所用共聚单体中占1~25%;所述一种以上丙烯酸酯单体为丙烯酸甲酯、或为丙烯酸乙酯、或为丙烯酸丁酯、或为丙烯酸-2-乙基己酯、或为丙烯酸月桂酯、或为甲基丙烯酸甲酯、或为甲基丙烯酸乙酯、或为甲基丙烯酸丁酯、或为甲基丙烯酸月桂酯,在制备共聚物A所用共聚单体中占75~99%。 The solvent-based process for preparing 1, wherein the fluorine-containing acrylate copolymer as claimed in claim A, characterized in that: (1) the side-chain hydroxyl-containing acrylate copolymer A, using acrylate or hydroxyl group-containing amide monomer M with one or more acrylate monomers of a radical initiator in the presence of dibenzoyl peroxide solution polymerization, dibenzoyl peroxide accounted for 0.03% to 1.0% of the total amount of the polymerization system, the polymerization temperature 70 ~ 100 ℃, time 4 to 8 hours; the polymerization solvent used is toluene, or xylene, or butanone, or methyl isobutyl ketone, or ethyl acetate, or butyl acetate, the amount of solvent accounting for 33 to 85% in the total amount of the entire polymerization reaction system; acrylate or acrylamide monomers M having hydroxyl acrylic -β- hydroxyethyl acrylate, hydroxypropyl acrylate or methacrylate -β-, or N- methylol acrylamide, methacrylic -β- or hydroxyethyl methacrylate, or hydroxypropyl methacrylate is methyl methacrylate -β-; in the preparation of the copolymer A comonomer accounts for 1 to 25% by; the one or more acrylic ester monomer is methyl acrylate, or ethyl acrylate, or butyl acrylate, or 2-ethylhexyl acrylate, or lauryl acrylate, or methyl methacrylate, or methacrylic acid ethyl or butyl methacrylate, or lauryl methacrylate, 75 to 99% as used in the preparation of the copolymer A comonomer. (2)反应物B,即所述含有一个未反应的-NCO基的化合物RfO2CNH-Z-NCO,由等摩尔的二异氰酸酯OCN-Z-NCO和含氟醇RfOH反应而成,反应是在溶剂中,催化剂存在下,反应温度50~100℃,时间2~6小时;含氟醇与二异氰酸酯的摩尔数均为含有羟基的丙烯酸酯或丙烯酰胺单体M摩尔数的0.8~1.2倍;所用溶剂为丙酮、或为丁酮、或为环己酮、或为甲基异丁基甲酮、或为三氟甲基苯、或为三氟三氯乙烷、或为三氯乙烯、或为四氯乙烯,溶剂用量占整个反应体系总量的20~80%;所述二异氰酸酯OCN-Z-NCO为2,4-甲苯二异氰酸酯(2,4-TDI),或为异佛尔酮二异氰酸酯(IPDI),或为甲苯二异氰酸酯(2,4-TDI含量约80%),或为对苯二异氰酸酯(PPDI),或为二苯基甲烷-4,4'-二异氰酸酯(MDI),1,6-己二异氰酸酯(HDI)、或为萘-1,5-二异氰酸酯(NDI)、或为二环己基甲烷-4,4'-二异氰酸酯(HMDI);所述含氟醇RfOH为全氟己基乙醇、或为全氟辛基乙醇;或为N-羟乙基全氟辛酰胺、或为N-羟乙基全氟庚酰胺;或为N-甲基-N-羟乙基全氟辛基磺酰胺、或为N-乙基-N-羟乙基全氟辛基磺酰胺、或为N-丙基-N-羟乙基全氟辛基磺酰胺;所述催化剂为二月桂酸二丁基锡、或为二醋酸二丁基锡、或为辛酸亚锡、或为三亚乙基二胺、或为N-乙基吗啡啉、或为N、N'-二甲基环己胺、或为二乙烯三胺;催化剂用量为整个反应体系总量的0.01%~2%;(3)将上述制备出的侧链含有羟基的丙烯酸酯共聚物A和反应物B两部分进行反应,制备出溶剂型含氟丙烯酸酯共聚物;缩合温度50~100℃,时间2~6小时。 (2) reactant B, i.e., the one containing unreacted -NCO group-containing compound RfO2CNH-Z-NCO, by an equimolar amount of a diisocyanate OCN-Z-NCO and a fluorine-containing alcohol RfOH reaction from the reaction in a solvent the presence of the catalyst, the reaction temperature is 50 ~ 100 ℃, for 2 to 6 hours; number of moles of the fluorine-containing alcohol with a diisocyanate are contained 0.8 to 1.2 times as acrylate or acrylamide monomer M moles of hydroxyl groups; the use of solvent is acetone, or methyl ethyl ketone, or cyclohexanone, or methyl isobutyl ketone, benzene or a trifluoromethyl group, or a trifluoromethyl trichloroethane, or trichlorethylene, or tetrachloro 20 to 80% of ethylene, the total amount of solvent used in an amount of the entire reaction system; the diisocyanate OCN-Z-NCO as 2,4-toluene diisocyanate (2,4-TDI), or isophorone diisocyanate ( IPDI), or toluene diisocyanate (2,4-TDI content of about 80%), or p-phenylene diisocyanate (PPDI), or diphenylmethane-4,4'-diisocyanate (MDI), 1, hexamethylene diisocyanate (HDI), or naphthalene-1,5-diisocyanate (NDI), or dicyclohexylmethane-4,4'-diisocyanate (HMDI); the fluorinated alcohol RfOH as perfluoro hexyl alcohol, octyl alcohol or perfluoro; or N- hydroxyethyl perfluorooctanoate amide, or N- hydroxyethyl perfluoro heptanamide; or N- methyl -N- hydroxyethyl perfluorooctanoate sulfonamide, or N- ethyl -N- hydroxyethyl perfluorooctane sulfonamide, or N- propyl -N- hydroxyethyl perfluorooctane sulfonamide; the catalyst is di-n tributyltin, or dibutyl tin diacetate, or stannous octoate or triethylene diamine, or N- ethyl morpholine, or N, N'- dimethyl-cyclohexylamine, or divinyl triamine; catalyst in an amount of from 0.01% to 2% of the total amount of the reaction system; (3) The above prepared side chains containing acrylate copolymer A and reactant B are both part of hydroxyl groups reacted to prepare solvent-containing fluoro-acrylate copolymer; condensation temperature of 50 ~ 100 ℃, for 2 to 6 hours.
Description  translated from Chinese
溶剂型含氟丙烯酸酯共聚物的制备方法 Preparation of solvent-fluorinated acrylate copolymer

技术领域 FIELD

本发明涉及溶剂型含氟丙烯酸酯共聚物的制备方法,该聚合物可作防水防油剂用于织物、皮革等。 The present invention relates to a method of solvent-based fluorinated acrylate copolymer, the polymer can be used for water and oil repellent fabric, leather.

背景技术 BACKGROUND

众所周知,含有全氟侧链的丙烯酸酯共聚物具有优异的防水、防油性能和极低的表面张力,主要是由于上述含氟共聚物在固体表面成膜后,含氟侧链规则的向外整齐排列和伸展,从而发挥出优良的防水防油效果。 It is well known acrylate copolymers containing perfluoro side chain has excellent waterproof, oil performance and low surface tension, mainly due to the above-described fluorine-containing copolymer outwardly solid surface after the film formation, a fluorine-containing side chain rule neatly arranged and stretching, and thus play an excellent water and oil repellency effect. 因此在织物、皮革等多个领域获得应用。 So get used in a number of areas of fabric, leather.

该类聚合物一般都是首先制备含有全氟烷基侧链的丙烯酸酯单体,一般有如下几种结构:(1)全氟烷基乙醇的丙烯酸酯,结构为Rf-CH2CH2O2CCH=CH2,Rf为6~8个碳原子的全氟烷基,即Rf=CnF2n+1,n=6~8。 The polymers are generally prepared first acrylate monomer containing a perfluoroalkyl side chain, the general structure of the following categories: (1) perfluoroalkyl ethanol acrylate, the structure Rf-CH2CH2O2CCH = CH2, Rf a perfluoroalkyl group having 6 to 8 carbon atoms, i.e., Rf = CnF2n + 1, n = 6 ~ 8.

(2)全氟庚酸或全氟辛酸先与乙醇胺反应形成N-羟乙基金氟庚(辛)酰胺,再与丙烯酰氯反应形成丙烯酸酯,结构为RfCONHCH2CH2O2CCH=CH2,Rf为全氟己基或全氟庚基,即Rf=CnF2n+1,n=6,7。 (2) perfluoro heptanoic acid or perfluoro-octanoic acid is formed first and ethanolamine N- hydroxyethyl gold fluoro heptyl (octyl) amide, and then formation of an acrylate acrylic acid chloride is reacted with structure RfCONHCH2CH2O2CCH = CH2, Rf is a perfluoro hexyl group or perfluoroheptanoic group, i.e., Rf = CnF2n + 1, n = 6,7.

(3)N-烷基-N-羟乙基全氟辛基磺酰胺的丙烯酸酯,结构为RfSO2N(R)CH2CH2O2CCH=CH2,Rf为全氟辛基,即Rf=C8F17。 (3) N- alkyl -N- hydroxyethyl perfluoro octyl sulfonamide acrylate, the structure RfSO2N (R) CH2CH2O2CCH = CH2, Rf is a perfluoro-octyl, i.e., Rf = C8F17. R为1~3个碳原子的烷基,即R=CnH2n+1,n=1~3。 R is an alkyl group having 1 to 3 carbon atoms, i.e., R = CnH2n + 1, n = 1 ~ 3.

(4)N-烷基-N-羟乙基全氟辛基磺酰胺先与等摩尔的2,4-TDI(或IPDI)反应,然后再与等摩尔丙烯酸羟乙酯或羟丙酯缩合,结构为:; (4) N- alkyl -N- hydroxyethyl perfluorooctane sulfonamide first with an equimolar amount of 2,4-TDI (or IPDI) and then reacting with an equimolar hydroxyethyl acrylate or hydroxypropyl acrylate condensation, structure:; Or R1为1~3个碳的烷基,R2为H,CH3。 R1 is 1 to 3 carbon alkyl group, R2 is H, CH3.

(5)N-羟乙基全氟庚(辛)酰胺先与等摩尔的2,4-TDI反应,然后再与等摩尔丙烯酸-β-羟乙酯或羟丙酯缩合,结构为: (5) N- hydroxyethyl perfluoroheptanoic (octyl) amide to react with the equimolar reaction of 2,4-TDI, and then with an equimolar acrylate, hydroxyethyl acrylate or hydroxypropyl acrylate -β- condensed structure: Rf为-C7F15,-C6F13;R2为H,CH3;R3为H,CH3。 Rf is -C7F15, -C6F13; R2 is H, CH3; R3 is H, CH3.

由于上述单体单独形成聚合物的物理性能较差,通常需要与一种或几种非氟单体形成共聚物以提高使用性能。 Because of the above monomers formed separately poor physical properties of the polymer, and usually require one or more non-fluorinated monomers to form a copolymer in order to improve performance.

含有全氟烷基侧链的聚合物具有一定防水、防油性必须使全氟烷基侧链足够长,通常全氟烷基应不少于6个碳原子,但是长侧链全氟烷基聚合物在常用溶剂中溶解性不好,特别是上述(1)~(3)类单体所形成的共聚物通常只能溶解在少数含氟或含有其它卤素的溶剂中,出于环保的考虑,目前用这几类单体制备的含氟丙烯酸酯共聚物基本上都是采用乳液聚合方法制备的,乳液聚合在制备过程中需要加入表面活性剂、助溶剂等,如果控制条件不当则发生分层现象,这对于含氟丙烯酸酯单体的乳液共聚来说尤其明显,还存在产品贮存稳定性差、成膜物理性能较差等问题。 Polymers containing perfluoroalkyl side chain has a waterproof, oil must be sufficiently long perfluoroalkyl side chain, typically a perfluoroalkyl group of not less than 6 carbon atoms, but a long perfluoroalkyl side chain polymerization was poor solubility in common solvents, especially the copolymer (1) to (3) above are formed based monomer is usually soluble only in a small number of fluorine or other halogen-containing solvent, for environmental reasons, At present, a fluorine-containing acrylate copolymers prepared using these types of monomers are basically prepared by emulsion polymerization, emulsion polymerization in the preparation process requires the addition of surfactants, co-solvents and the like, if the control condition is improper delamination occurred phenomenon, which for the emulsion copolymerization of fluorine-containing acrylate monomer is especially evident, there are still the product poor storage stability, poor film-forming properties and other physical problems. 最让人感到无奈的是产品适用面窄,通用性不好,需要针对某个具体应用对象做量身定制的产品。 Most people feel helpless narrow product applicability, versatility is bad, to do customized products for a specific application objects.

上述(1)~(3)类单体所形成的共聚物性能下降很快,即存在耐久性问题,最初人们认为是由于防水防油剂脱落所致,现在已经明白是由于该类聚合物全氟烷基侧链取向混乱所致。 (1) to (3) properties of the copolymer formed by the above-described monomer drops quickly, i.e., durability problems exist, initially thought to be due to the loss caused by water and oil repellent, now understand such polymers is due to the full perfluoroalkyl side chain orientation caused confusion. 当该类聚合物在固体表面成膜后只有含氟侧链规则向外整齐排列和伸展,才能发挥出优良的防水防油效果。 When a type of polymer film only after the solid surface fluorinated side chain rule out neatly arranged and stretching, can play an excellent water and oil repellency effect.

相比(1)~(3)类单体,(4)、(5)两类单体及由它们形成的共聚物溶解性能应该有所改善,即它们不会仅仅溶解于少数几种含氟的溶剂。 Compared to (1) to (3) based monomer, (4), (5) and two types of monomer copolymer formed by them should be improved solubility, i.e. they do not dissolve in only a few of the fluorine-containing solvents. 上述(4)、(5)两类单体由于单体分子中能形成比(1)~(3)类单体更多的氢键,可以减轻全氟烷基侧链取向混乱的情况,使全氟烷基侧链保持固定的定向排列,还可以增加共聚物与底物的结合牢度。 Above (4), (5) Since the two types of monomer in the monomer molecule can form ratio (1) to (3) more hydrogen bond based monomer, can reduce a perfluoroalkyl side chain orientation confusion, so that perfluoroalkyl side chain to maintain a fixed orientation, but also can increase fastness copolymer to substrate. 但是相比(1)~(3)类单体,(4)、(5)两类单体的竞聚率与共聚的其他单体相差更大,如果继续采用乳液聚合肯定不如采用溶液聚合效果好。 But compared to (1) to (3) monomers, (4), (5) categories monomer reactivity ratio with other monomers bigger difference, certainly not as good if you continue using the emulsion solution polymerization effect Okay. 毕竟,在本发明提出的方法中采用溶液聚合可以通过调节某种单体在反应器中的浓度以达到预期的目的。 After all, by solution polymerization in the method of the present invention can be made by adjusting a monomer concentration in the reactor to achieve the intended purpose.

除了价格因素之外,上述存在的问题阻碍了该类聚合物的广泛应用。 In addition to the price factor, the above problems hindered the widespread use of such polymers.

发明内容 SUMMARY

由于上述本领域存在的不足,本发明从性能方面的考虑并结合本发明的制备方法特点,提供了溶剂型含氟丙烯酸酯聚合物的制备方法,具体步骤如下:1、以含有羟基的丙烯酸酯或丙烯酰胺单体M与一种以上的丙烯酸酯单体采用溶液聚合制备侧链含有羟基的丙烯酸酯共聚物A,结构示意为: Because of these shortcomings exist in the art, the invention in conjunction with consideration of performance characteristics of the preparation method of the present invention, there is provided a method for preparing fluorinated solvent-based acrylic polymer, concrete steps are as follows: 1, hydroxyl-containing acrylate or acrylamide monomer M and one or more acrylate monomers by solution polymerization of an acrylate copolymer A side chain containing a hydroxyl group was prepared, the structure illustrated as: R=H,CH3R1=CH3,C2H5,C4H9,CH2CH(C2H5)C4H9,C12H25R2=CH3,C2H5,C4H9,CH2CH(C2H5)C4H9,C12H25,R12、在催化剂存在下,由等摩尔的含氟醇RfOH与二异氰酸酯OCN-X-NCO反应,制备得反应物B,结构示意为:RfO2CNH-Z-NCO,反应物B保留一个未反应的一NCO基,反应示意为: R = H, CH3R1 = CH3, C2H5, C4H9, CH2CH (C2H5) C4H9, C12H25R2 = CH3, C2H5, C4H9, CH2CH (C2H5) C4H9, C12H25, R12, in the presence of a catalyst, etc. by mole and a fluorine-containing alcohol RfOH diisocyanate OCN-X-NCO reaction, the reaction was prepared to give B, the structure illustrated as: RfO2CNH-Z-NCO, a reactant B retain an unreacted NCO groups, the reaction is illustrated as: ,含氟醇RfOH与二异氰酸酯OCN-Z-NCO的摩尔数均为含有羟基的丙烯酸酯或丙烯酰胺单体M摩尔数的0.8~1.2倍。 Acrylate or acrylamide monomer M, and a fluorine-containing alcohol RfOH diisocyanate OCN-Z-NCO are the number of moles of the number of moles of hydroxyl group-containing 0.8 to 1.2 times.

3、将前述制备取得的侧链含有羟基的丙烯酸酯共聚物A和反应物B两部分进行反应,制得溶剂型含氟丙烯酸酯共聚物;结构示意为: 3, the side chains made of the aforementioned preparation containing hydroxyl acrylate copolymer A and B reactants react in two parts, to obtain solvent-fluorinated acrylate copolymer; structure illustrated as: R=H,CH3R1=CH3,C2H5,C4H9,CH2CH(C2H5)C4H9,C12H25R2=CH3,C2H5,C4H9,CH2CH(C2H5)C4H9,C12H25,R1。 R = H, CH3R1 = CH3, C2H5, C4H9, CH2CH (C2H5) C4H9, C12H25R2 = CH3, C2H5, C4H9, CH2CH (C2H5) C4H9, C12H25, R1.

以下是对本发明所作的更加详尽的描述:一、本发明中所制备的侧链含有羟基的丙烯酸酯共聚物A:侧链含有羟基的丙烯酸酯共聚物A,是以含有羟基的丙烯酸酯(或丙烯酰胺)单体M与一种以上的丙烯酸酯单体在自由基引发剂过氧化二苯甲酰的存在下进行溶液聚合,聚合温度70~100℃,时间4~8小时。 The following is a more detailed description of the invention made: one, a side chain in the present invention was prepared containing acrylate copolymer A hydroxyl group: acrylate copolymer A containing side chain hydroxyl group, is a hydroxyl group-containing acrylate (or acrylamide) monomer M and one or more acrylate monomers of a radical initiator dibenzoyl peroxide, the presence of solution polymerization, the polymerization temperature is 70 ~ 100 ℃, time 4 to 8 hours.

引发剂过氧化二苯甲酰用量为整个聚合反应体系总量的0.03~1.0%,聚合速率与引发剂浓度平方根成正比,分子量和引发剂用量的平方根成反比,引发剂用量过大会使共聚物分子量大大降低影响产品性能,但过小则聚合速度过慢。 Dibenzoyl peroxide initiator throughout the polymerization in an amount of 0.03 to 1.0% of the total reaction system, the rate of polymerization is proportional to the square root of the initiator concentration, molecular weight, and inversely proportional to the square root of the amount of initiator, initiator amount is too large the copolymer will molecular weight greatly reduce the impact of product performance, but too small too slow polymerization.

温度对聚合反应影响较大,温度升高聚合速度加快,分子量下降,反应温度的确定还要考虑引发剂的半衰期温度,使加入的引发剂过氧化二苯甲酰在一定时间内持续有效。 Temperature effect on the polymerization reaction is large, the temperature rise speed of polymerization, the molecular weight decreases, the reaction temperature should also be considered to determine the half-life temperature of the initiator, so that the added initiator dibenzoyl peroxide within a certain time period effective.

本发明所使用的含有羟基的丙烯酸酯(或丙烯酰胺)单体M包括:丙烯酸-β-羟乙酯、丙烯酸-β-羟丙酯、N-羟甲基丙烯酰胺、甲基丙烯酸-β-羟乙酯、甲基丙烯酸-β-羟丙酯。 The present invention is used in hydroxyl group-containing acrylate (or acrylamide) monomers M comprising: -β- acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate -β-, N- methylol acrylamide, methacrylic acid -β- hydroxyethyl methacrylate, hydroxypropyl methacrylate -β-. 在制备共聚物A的丙烯酸酯单体中占1~25%。 Amount of 1 to 25% of copolymer A in the preparation of acrylate monomers.

本发明所使用的其它不饱和单体包括:丙烯酸甲酯、丙烯酸乙酯、丙烯酸丁酯、丙烯酸-2-乙基己酯、丙烯酸月桂酯、甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸丁酯、甲基丙烯酸月桂酯等;在制备共聚物A的丙烯酸酯单体中占75~99%。 Other unsaturated monomers used in the present invention include: methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, methyl butyl methacrylate, lauryl methacrylate and the like; 75% to 99% in the preparation of an acrylate copolymer A monomer.

溶剂选自:甲苯、二甲苯、丁酮、甲基异丁基甲酮、醋酸乙酯、醋酸丁酯等。 Solvent is selected from: toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate and the like. 在共聚反应体系总量中占33~85%。 Accounting for 33 to 85% in the total amount of the copolymerization reaction system.

溶剂选择主要是考虑溶解能力,对聚合反应有无影响如链转移常数是否较高。 Solvent selection mainly on account of solvency, whether the impact on the polymerization reaction such as chain transfer constant is high. 溶剂用量主要考虑对单体浓度的影响,后者对共聚物分子量有影响。 Amount of solvent primarily consider the impact on the monomer concentration, which affect the molecular weight of the copolymer.

二、本发明中所制备的反应物B,含有一个未反应的-NCO基,由等摩尔的二异氰酸酯OCN-Z-NCO与含氟醇RfOH反应而成,结构示意为:RfO2CNH-Z-NCO。 Second, the reactant B in the present invention is prepared, containing an unreacted -NCO group, by an equimolar amount of a diisocyanate OCN-Z-NCO reaction from fluorine-containing alcohol RfOH, the structure illustrated as: RfO2CNH-Z-NCO .

制备上述反应物B是在催化剂存在下,二异氰酸酯OCN-Z-NCO与等摩尔的含氟醇RfOH进行反应,反应温度50~100℃,时间2~6小时。 B is the preparation of the above reactants in the presence of a catalyst, a diisocyanate OCN-Z-NCO with an equimolar fluorine-containing alcohol RfOH, a reaction temperature of 50 ~ 100 ℃, for 2 to 6 hours. 二异氰酸酯与等摩尔含氟醇反应后的所得产物RfO2CNH-Z-NCO,即反应物B保留一个未反应的-NCO基。 Diisocyanate, and the like resulting product was a fluorine-containing alcohol moles after RfO2CNH-Z-NCO, i.e. a reactant B retain unreacted -NCO groups. 含氟醇RfOH与二异氰酸酯OCN-Z-NCO的摩尔数相等,且均为含有羟基的丙烯酸酯或丙烯酰胺单体M摩尔数的0.8~1.2倍。 And the number of moles of the fluorine-containing alcohol RfOH diisocyanate OCN-Z-NCO are equal, and are 0.8 to 1.2 times or acrylamide monomer M moles of hydroxyl group-containing acrylic acid.

二异氰酸酯OCN-Z-NCO包括:2,4-甲苯二异氰酸酯(2,4-TDI), Diisocyanate OCN-Z-NCO include: 2,4-toluene diisocyanate (2,4-TDI), 异佛尔酮二异氰酸酯(IPDI), Isophorone diisocyanate (IPDI), 甲苯二异氰酸酯(2,4-TDI含量约80%,2,6-TDI含量约80%), (About 80% 2,4-TDI content, 2,6-TDI content of about 80%) of toluene diisocyanate, 对苯二异氰酸酯(PPDI), P-phenylene diisocyanate (PPDI), 二苯基甲烷-4,4'-二异氰酸酯(MDI), Diphenylmethane-4,4'-diisocyanate (MDI), 1,6-己二异氰酸酯(HDI),OCN-(CH2)6-NCO萘-1,5-二异氰酸酯(NDI), Hexamethylene diisocyanate (HDI), OCN- (CH2) 6-NCO naphthalene-1,5-diisocyanate (NDI), 二环己基甲烷-4,4'-二异氰酸酯(HMDI), Dicyclohexylmethane-4,4'-diisocyanate (HMDI), 等。 And so on.

选择二异氰酸酯主要考虑两个-NCO的反应活性是否相差较大,活性相差越大越有利于二异氰酸酯与等摩尔含氟醇反应后保留一个未反应的-NCO基。 Select diisocyanate mainly consider two -NCO reactive whether the difference between the larger, the greater the difference the more favorable activity diisocyanate and the like after a mole of the fluorine-containing alcohol retain unreacted -NCO groups. 如果两个-NCO基活性一样则就有较多的副产物形成,即有的二异氰酸酯两个-NCO都被反应掉,形成一个二异氰酸酯连接两个氟醇,这样的话就不能与侧链含有羟基的丙烯酸酯共聚物A反应。 If two -NCO groups have more active as the by-product formation, i.e. some two -NCO diisocyanate are reacted to form a diisocyanate connecting two fluorine alcohol, so it can not contain a side chain A hydroxy acrylate copolymer reaction. 2,4-甲苯二异氰酸酯(2,4-TDI)中2个-NCO基反应活性相差较大,4-NCO活性比2-NCO高6.7倍(50℃)和4.7倍(72~74℃),但使用2,4-甲苯二异氰酸酯(2,4-TDI)涂层有变黄的倾向。 2,4-toluene diisocyanate (2,4-TDI) in two -NCO groups reactive larger difference, 4-NCO activity 6.7 times higher than the 2-NCO (50 ℃) and 4.7 times (72 ~ 74 ℃) , but using 2,4-toluene diisocyanate (2,4-TDI) coating tends to turn yellow. 对于异佛尔酮二异氰酸酯(IPDI)而言情况比较复杂,无催化剂情况下,仲-NCO基比伯-NCO基活性快5.5倍(20℃,正丁醇),如用二月桂酸二丁基锡催化,仲-NCO基比伯-NCO基活性快11.5倍(20℃,正丁醇),但如使用三亚乙基二胺催化,则伯-NCO基比仲-NCO基活性大。 For isophorone diisocyanate (IPDI) is concerned the situation is more complex, the absence of a catalyst, the secondary -NCO Ji Bibo -NCO group activity 5.5 times faster (20 ℃, n-butanol), such as the use of dibutyl tin dilaurate catalysis, Chung Ji Bibo -NCO 11.5 times faster -NCO group activity (20 ℃, n-butanol), but if the use of triethylenediamine catalysis, the primary than secondary -NCO groups -NCO groups active big. 对苯二异氰酸酯(PPDI)尽管两个-NCO基无活性差异,但一个-NCO基反应后由于形成氨基甲酸酯,相对于原来的-NCO基吸电子效应下降,使另一个未反应的-NCO基钝化,使用对苯二异氰酸酯(PPDI)涂层也有变黄的倾向。 Post-phenylene diisocyanate (PPDI) although no difference in the activity of the two -NCO groups, but due to a reaction of -NCO group to form a carbamate, with respect to the original -NCO group electron withdrawing effect decreased, so that the other unreacted - NCO group passivation, using p-phenylene diisocyanate (PPDI) coatings also have a tendency to yellowing.

二异氰酸酯分子中两个-NCO基反应活性差别越大,反应选择性越好,对于本发明制备的溶剂型含氟丙烯酸酯共聚物越有利。 Diisocyanate molecule, the greater the activity of the two -NCO groups reacted difference, the better reaction selectivity, for solvent-fluorinated acrylate copolymer of the present invention is prepared, the better. 因此对于本发明来说使用2,4-甲苯二异氰酸酯(2,4-TDI),异佛尔酮二异氰酸酯(IPDI),甲苯二异氰酸酯(2,4-TDI含量约80%),对苯二异氰酸酯(PPDI)等比使用二苯基甲烷-4,4'-二异氰酸酯(MDI),1,6-己二异氰酸酯(HDI)、萘-1,5-二异氰酸酯(NDI)、二环己基甲烷-4,4'-二异氰酸酯(HMDI)等效果好。 Thus the present invention is the use of 2,4-toluene diisocyanate (2,4-TDI), isophorone diisocyanate (IPDI), toluene diisocyanate (2,4-TDI content of about 80%), terephthalic diisocyanate (PPDI) using geometric diphenylmethane-4,4'-diisocyanate (MDI), 1,6- hexamethylene diisocyanate (HDI), naphthalene-1,5-diisocyanate (NDI), dicyclohexyl methane Good-4,4'-diisocyanate (HMDI) and other effects.

含氟醇RfOH包括:全氟己基乙醇 C6F13CH2CH2OH全氟辛基乙醇 C8F17CH2CH2OHN-羟乙基全氟辛酰胺 C7F15CONHCH2CH2OHN-羟乙基全氟庚酰胺 C6F13CONHCH2CH2OHN-甲基-N-羟乙基全氟辛基磺酰胺 Fluorine-containing alcohols RfOH comprising: perfluorohexyl ethanol C6F13CH2CH2OH perfluorooctyl ethanol C8F17CH2CH2OHN- hydroxyethyl perfluoro octanamide C7F15CONHCH2CH2OHN- hydroxyethyl perfluoro heptanamide C6F13CONHCH2CH2OHN- methyl -N- hydroxyethyl perfluorooctane sulfonamide N-乙基-N-羟乙基全氟辛基磺酰胺 N- Ethyl -N- hydroxyethyl perfluorooctane sulfonamide N-丙基-N-羟乙基全氟辛基磺酰胺 N- propyl--N- hydroxyethyl perfluorooctane sulfonamide 等。 And so on.

催化剂选自:二月桂酸二丁基锡、二醋酸二丁基锡、辛酸亚锡、三亚乙基二胺、N-乙基吗啡啉、N、N'-二甲基环己胺、二乙烯三胺。 Catalyst is selected from: dibutyl tin dilaurate, dibutyl tin diacetate, stannous octoate, triethylenediamine, N- ethyl-morpholine, N, N'- dimethyl-cyclohexylamine, diethylene triamine.

二月桂酸二丁基锡、二醋酸二丁基锡、辛酸亚锡等有机锡化合物对芳香族或脂肪族异氰酸酯与伯醇反应均有较强的催化作用,催化-NCO基与伯醇的反应能力比叔胺要强得多,有机锡化合物作为催化剂并留在产物中,有可能会在产品应用过程中,在光照射下促进聚合物降解老化。 Dibutyl tin dilaurate, dibutyl tin diacetate, stannous octoate and other organic tin compounds to aromatic or aliphatic isocyanate with a primary alcohol have a strong ability to catalytic reaction, the catalytic -NCO group with a primary alcohol is a tertiary amine much stronger, an organic tin compound as a catalyst and left in the product, there may be in the application of the product, in the polymer degradation under light irradiation to promote the aging. 使用胺类则无此担忧,叔胺对芳香族二异氰酸酯TDI有较强的催化作用,但是对脂肪族二异氰酸酯如HDI催化作用极弱。 Use amine does not have this concern, tertiary aromatic diisocyanates TDI strong catalytic effect, but the aliphatic diisocyanates such as HDI catalytic very weak. 三亚乙基二胺因其N原子无空间位阻影响催化能力较强。 Triethylenediamine its N atom without steric affect the catalytic ability.

溶剂包括:丙酮、丁酮、环己酮、甲基异丁基甲酮、三氟甲基苯、三氟三氯乙烷、三氯乙烯、四氯乙烯等。 Solvents include: acetone, methyl ethyl ketone, cyclohexanone, methyl isobutyl ketone, trifluoromethyl benzene, trifluoro-trichloroethane, trichlorethylene, tetrachlorethylene or the like.

溶剂选择主要是考虑溶解能力,对-NCO基的反应性有无影响三、溶剂型含氟丙烯酸酯聚合物的制备:将前述制备取得的侧链含有羟基的丙烯酸酯共聚物A和反应物B两部分进行反应,反应温度50~100℃,时间2~6小时。 Solvent selection is mainly on account solvency of the -NCO reactive whether the impact of the three preparation, solvent-fluorinated acrylate polymers: preparation of the side chain to achieve the aforementioned acrylate copolymer containing reactants A and B hydroxyl two parts reaction, the reaction temperature is 50 ~ 100 ℃, for 2 to 6 hours. 制得溶剂型含氟丙烯酸酯共聚物。 Prepared by solvent-fluorinated acrylate copolymer.

从以上的描述中可以看出,本发明所提出的溶剂型含氟丙烯酸酯共聚物的制备方法简单易行。 As can be seen from the above description, the method of the present invention proposed solvent-fluorinated acrylate copolymer easy. 相对于背景技术提及的(1)~(3)类单体所形成的共聚物,本发明所述的含氟丙烯酸酯共聚物分子中能形成更多的氢键,可以减轻全氟烷基侧链取向混乱的情况,使全氟烷基侧链保持固定的定向排列,从而延缓防水防油性能的下降,同时增加共聚物与底物的结合牢度,改善背景技术提及的(1)~(3)类单体所形成的共聚物产品适用面窄,通用性不好的状况。 (1) to (3) copolymers formed by monomers mentioned with respect to the background art, the fluorine-containing acrylate copolymer molecules according to the present invention can form more hydrogen bond, can reduce perfluoroalkyl case side chain orientation confusion, so that a perfluoroalkyl side chain to maintain a constant orientation, thus delaying the water and oil repellency decreases, while increasing fastness copolymer to substrate, improving BACKGROUND mentioned (1) The copolymer product ~ (3) based monomer formed narrow applicability, versatility bad condition. 另外背景技术提及的(4)~(5)类单体的竞聚率与共聚的其他单体相差较大,采用乳液聚合的方法得到的共聚物结构链节比均一性不会很理想,有可能影响共聚物的性能,而采用本发明的制备方法可以在制备共聚物A时采用不同的单体比来的解决这一问题。 In addition (4) - (5) monomer reactivity ratios BACKGROUND mentioned monomers and other large difference, obtained by the method using emulsion copolymer structure chain links are not desirable than uniformity, may affect the properties of the copolymer, and the production method of the present invention may be in the preparation of the copolymer A is different than the monomers to the solution to this problem. 乳液聚合过程中如果控制条件不当则发生分层现象,这对于含氟丙烯酸酯单体的乳液共聚来说尤其明显,产品还存在贮存稳定性差、成膜物理性能较差等问题。 Emulsion polymerization process if the control conditions are improper delamination occurs, which is particularly evident, the product there is poor storage stability, poor film-forming properties and other physical problems for the emulsion copolymerization of fluorine-containing acrylate monomer is.

具体实施方式 DETAILED DESCRIPTION

下面通过实施例更具体地对本发明作进一步地说明,但不是为了限定本发明。 The following examples of the present invention will be further described more specifically, but not intended to limit the present invention.

实施例1共聚物A的制备:在四口瓶中加入甲苯140g,通入氮气置换内部空气后,升温至85℃,搅拌下滴加由丙烯酸甲酯100.0g、丙烯酸丁酯28.4g、丙烯酸-β-羟乙酯11.6g(0.1mol)及溶解其中的过氧化二苯甲酰0.3g组成的混合液,维持反应温度83~87℃,约2小时滴完。 Example 1 Preparation of copolymer A: the 4-neck flask was added toluene 140g, after the internal air is replaced by nitrogen, warmed to 85 ℃, by methyl acrylate was added dropwise with stirring 100.0g, butyl acrylate 28.4g, acrylic acid - dibenzoyl 0.3g mixture solution β- hydroxyethyl methacrylate 11.6g (0.1mol) and dissolve the peroxide, maintaining the reaction temperature 83 ~ 87 ℃, about 2 hours drops finished. 滴完后继续反应2小时,补加溶有0.1g过氧化二苯甲酰的甲苯溶液10毫升,继续维持反应2小时,降温,向四口瓶中补甲苯至瓶内物总重700g,停止搅拌。 After the dropping, reaction was continued for 2 hours, supplemented with a solution of 0.1g of a toluene solution of dibenzoyl peroxide in 10 ml, to maintain reaction for 2 hours, cooled, four-necked flask to make up the total weight of toluene to a bottle 700g, stop stir. 制备的共聚物A浓度为20%。 Copolymer A prepared at a concentration of 20%.

反应物B的制备:在另一四口瓶中加入环己酮90g,2,4-甲苯二异氰酸酯17.4g(0.1mol)、二月桂酸二丁基锡0.1g,升温至75℃。 Preparation of reactant B is: In another four-necked flask was added cyclohexanone 90g, 2,4- toluene diisocyanate 17.4g (0.1mol), dibutyl tin dilaurate 0.1g, was heated to 75 ℃. 搅拌下滴加全氟己基乙醇36.4g(0.1mol)与环己酮125g的混合液,滴完后继续于75℃搅拌反应3小时。 Added dropwise with stirring perfluorohexyl ethanol 36.4g (0.1mol) of cyclohexanone and 125g of mixed solution was added dropwise to continue at 75 ℃ reaction was stirred for 3 hours. 降温,得反应物B的溶液,其中不挥发份浓度为20%。 Cooling, the reaction solution obtained was B, wherein the nonvolatile content of 20%.

溶剂型含氟丙烯酸酯共聚物的制备:将上述反应物B加入内有前述制备的共聚物A的四口瓶中,升温至75~80℃搅拌反应5小时,降温,停止搅拌。 Preparing a solvent-type fluorine-containing acrylate copolymer: A four neck flask copolymer A prepared above, was heated to 75 ~ 80 ℃ reaction was stirred for 5 hours, cooling, stirring was stopped in the above B was added to the reactants. 得本发明的溶剂型含氟丙烯酸酯共聚物。 Solvent was fluorinated acrylate copolymer of the present invention.

实施例2共聚物A的制备:与实施例1相同。 Example 2 Preparation of copolymer A: same as in Example 1.

反应物B的制备:在另一四口瓶中加入甲基异丁基甲酮90g,甲苯二异氰酸酯(2,4-TDI含量约80%)17.4g(0.1mol)、二醋酸二丁基锡0.1g,升温至75℃。 Preparation of reactant B is: In another four-necked flask was added methyl isobutyl ketone 90g, toluene diisocyanate (2,4-TDI content of about 80%) 17.4g (0.1mol), dibutyl tin diacetate 0.1g, heating to 75 ℃. 搅拌下滴加全氟辛基乙醇46.4g(0.1mol)与甲基异丁基甲酮165g的混合液,滴完后继续搅拌反应3小时。 Added dropwise with stirring perfluorooctyl ethanol 46.4g (0.1mol) of methyl isobutyl ketone and 165g of mixed solution was added dropwise to the reaction and stirring was continued for 3 hours. 降温,得反应物B的溶液,其中不挥发份浓度为20%。 Cooling, the reaction solution obtained was B, wherein the nonvolatile content of 20%.

溶剂型含氟丙烯酸酯共聚物的制备:将上述反应物B加入内有前述制备的共聚物A的四口瓶中,升温至75~80℃搅拌反应4小时,降温,停止搅拌。 Preparing a solvent-type fluorine-containing acrylate copolymer: A four neck flask copolymer A prepared above, was heated to 75 ~ 80 ℃ reaction was stirred for 4 hours, cooling, stirring was stopped in the above B was added to the reactants. 得本发明的溶剂型含氟丙烯酸酯共聚物。 Solvent was fluorinated acrylate copolymer of the present invention.

实施例3共聚物A的制备:与实施例1相同。 Copolymer A Production Example 3: The same as in Example 1.

反应物B的制备:在另一四口瓶中加入丙酮100g,异佛尔酮二异氰酸酯17.8g(0.08mol)、辛酸亚锡0.035g,升温至50℃。 Preparation of reactant B is: In another 4-neck flask was added acetone 100g, isophorone diisocyanate 17.8g (0.08mol), stannous octoate 0.035g, warmed to 50 ℃. 搅拌下滴加全氟辛基乙醇37.1g(0.08mol)与丙酮120g的混合液,滴完后继续搅拌反应6小时。 Added dropwise with stirring perfluorooctyl ethanol, 37.1g (0.08mol) and the mixture of 120g of acetone was added dropwise to the reaction and stirring was continued for 6 hours. 降温,得反应物B的溶液,其中不挥发份浓度为20%。 Cooling, the reaction solution obtained was B, wherein the nonvolatile content of 20%.

溶剂型含氟丙烯酸酯共聚物的制备:将上述反应物B加入内有前述制备的共聚物A的四口瓶中,维持50℃搅拌反应6小时,降温,停止搅拌。 Preparation of solvent-fluorinated acrylate copolymer: There will be four bottles prepared above copolymer A, maintaining 50 ℃ reaction is stirred 6 hours, cooling, stop stirring the above reactant B to join. 得本发明的溶剂型含氟丙烯酸酯共聚物。 Solvent was fluorinated acrylate copolymer of the present invention.

实施例4共聚物A的制备:与实施例1相同。 Example 4 Preparation of copolymer A: the same as in Example 1.

反应物B的制备:在另一四口瓶中加入三氟甲苯12.8g,对苯二异氰酸酯12.8g(0.08mol)、三亚乙基二胺1.2g,升温至70℃。 Preparation of reactant B is: In another four-necked flask was charged trifluoromethylphenyl 12.8g, p-phenylene diisocyanate 12.8g (0.08mol), triethylenediamine 1.2g, warmed to 70 ℃. 搅拌下滴加N-羟乙基全氟辛酰胺36.6g(0.08mol)与三氟甲苯36.6g的混合液,滴完后继续反应4小时。 Added dropwise with stirring N- hydroxyethyl perfluorooctanoate amide 36.6g (0.08mol) and 36.6g of a mixture of benzotrifluoride was added dropwise to the reaction was continued for 4 hours. 降温,得反应物B的溶液,其中不挥发份浓度为50%。 Cooling, the reaction solution obtained was B, wherein the nonvolatile content of 50%.

溶剂型含氟丙烯酸酯共聚物的制备:将上述反应物B先加入三氟甲苯153g稀释至不挥发份浓度约为20%,然后加入内有前述制备的共聚物A的四口瓶中,维持75℃继续搅拌反应4小时,降温,停止搅拌。 Preparation of solvent-fluorinated acrylate copolymer: The above reactant B to join trifluorotoluene 153g diluted to a nonvolatile content of about 20%, and then added to the foregoing preparation of copolymer A four-necked flask, maintain 75 ℃ stirring was continued for 4 hours, cooling, stirring was stopped. 得本发明的溶剂型含氟丙烯酸酯共聚物。 Solvent was fluorinated acrylate copolymer of the present invention.

实施例5共聚物A的制备:与实施例1相同。 Example 5 Preparation of copolymer A: the same as in Example 1.

反应物B的制备:在另一四口瓶中加入三氟三氯乙烷10.2g,二苯基甲烷-4,4'-二异氰酸酯30.0g(0.12mol)、N-乙基吗啡啉2.0g,升温至70℃。 Preparation of reactant B is: In another four-necked flask was charged trifluorotrichloroethane 10.2g, diphenylmethane-4,4'-diisocyanate 30.0g (0.12mol), N- ethyl morpholine 2.0g temperature was raised to 70 ℃. 搅拌下滴加N-羟乙基全氟庚酰胺48.9g(0.12mol)与三氟三氯乙烷10g的混合液,滴完后维持75℃继续反应4小时。 Added dropwise with stirring N- hydroxyethyl perfluoro heptanamide 48.9g (0.12mol) and the mixture of 10g of trifluorotrichloroethane was added dropwise to maintain 75 ℃ reaction was continued for 4 hours. 降温,得反应物B的溶液,其中不挥发份浓度为80%。 Cooling, the reaction solution obtained was B, wherein the nonvolatile content of 80%.

溶剂型含氟丙烯酸酯共聚物的制备:将上述反应物B先加入三氟三氯乙烷297g稀释至不挥发份浓度约为20%,然后加入内有前述制备的共聚物A的四口瓶中,维持75℃搅拌反应4小时,降温,停止搅拌。 Preparation of solvent-fluorinated acrylate copolymer: The above reactant B to join trifluorotrichloroethane 297g diluted to a nonvolatile content of about 20%, and then added to the foregoing preparation of copolymer A four-necked bottles in maintaining 75 ℃ stirred for 4 hours, cooling, stirring was stopped. 得本发明的溶剂型含氟丙烯酸酯共聚物。 Solvent was fluorinated acrylate copolymer of the present invention.

实施例6共聚物A的制备:与实施例1相同。 Example 6 Preparation of copolymer A: the same as in Example 1.

反应物B的制备:在另一四口瓶中加入三氯乙烯63g,1,6-己二异氰酸酯20.2g(0.12mol)、二乙烯三胺1.0g,升温至60℃。 Preparation of reactant B is: In another four-necked flask was added trichlorethylene 63g, 1,6- hexamethylene diisocyanate 20.2g (0.12mol), diethylene triamine 1.0g, warmed to 60 ℃. 搅拌下滴加N-甲基-N-羟乙基全氟辛基磺酰胺66.9g(0.12mol)与三氯乙烯67g的混合液,滴完后维持60℃继续反应5小时。 Added dropwise with stirring N- methyl -N- hydroxyethyl perfluorooctane sulfonamide mixture of 66.9g (0.12mol) and 67g of trichlorethylene was added dropwise to maintain the reaction was continued for 5 hours 60 ℃. 降温,得反应物B的溶液,其中不挥发份浓度为40%。 Cooling, the reaction solution obtained was B, wherein the nonvolatile content of 40%.

溶剂型含氟丙烯酸酯共聚物的制备:将上述反应物B先加入三氯乙烯218g稀释至不挥发份浓度约为20%,然后加入内有前述制备的共聚物A的四口瓶中,维持60℃搅拌反应5小时,降温,停止搅拌。 Preparation of solvent-fluorinated acrylate copolymer: The above reactant B to join trichlorethylene 218g diluted to a nonvolatile content of about 20%, followed by the addition of four bottles in the foregoing preparation of copolymer A, maintenance 60 ℃ reaction was stirred for 5 hours, cooling, stirring was stopped. 得本发明的溶剂型含氟丙烯酸酯共聚物。 Solvent was fluorinated acrylate copolymer of the present invention.

实施例7共聚物A的制备:与实施例1相同。 Example 7 Preparation of copolymer A: the same as in Example 1.

反应物B的制备:在另一四口瓶中加入四氯乙烯45g,2,4-甲苯二异氰酸酯20.9g(0.12mol)、二乙烯三胺0.5g,升温至60℃。 Preparation of reactant B is: In another four-necked flask was added tetrachlorethylene 45g, 2,4- toluene diisocyanate 20.9g (0.12mol), diethylene triamine 0.5g, warmed to 60 ℃. 搅拌下滴加N-乙基-N-羟乙基全氟辛基磺酰胺68.6g(0.12mol)与四氯乙烯164g的混合液,滴完后维持60℃继续反应5小时。 Added dropwise with stirring ethyl N- -N- hydroxyethyl perfluorooctane sulfonamide 68.6g (0.12mol) of a mixture of tetrachlorethylene 164g was added dropwise to maintain the reaction was continued for 5 hours 60 ℃. 降温,得反应物B的溶液,其中不挥发份浓度为30%。 Cooling, the reaction solution obtained was B, wherein the nonvolatile content of 30%.

溶剂型含氟丙烯酸酯共聚物的制备:将上述反应物B先加入四氯乙烯151g稀释至不挥发份浓度约为20%,然后加入内有前述制备的共聚物A的四口瓶中,维持60℃搅拌反应5小时,降温,停止搅拌。 Preparation of solvent-fluorinated acrylate copolymer: The above reactant B to join the PCE 151g diluted to a nonvolatile content of about 20%, and then added to the previous four jars prepared copolymer A, maintenance 60 ℃ reaction was stirred for 5 hours, cooling, stirring was stopped. 得本发明的溶剂型含氟丙烯酸酯共聚物。 Solvent was fluorinated acrylate copolymer of the present invention.

实施例8共聚物A的制备:与实施例1相同。 Example 8 Preparation of copolymer A: the same as in Example 1.

反应物B的制备:在另一四口瓶中加入丁酮100g,萘-1,5-二异氰酸酯25.2g(0.12mol)、N,N′-二甲基环己胺0.5g,升温至65℃。 Preparation of reactant B is: In another four-necked flask was added methyl ethyl ketone 100g, naphthalene-1,5-diisocyanate 25.2g (0.12mol), N, N'- dimethyl cyclohexylamine 0.5g, warmed to 65 ℃. 搅拌下滴加N-丙基-N-羟乙基全氟辛基磺酰胺70.2g(0.12mol)与丁酮282g的混合液,滴完后维持65℃继续搅拌反应5小时。 Added dropwise with stirring N- propyl -N- hydroxyethyl perfluorooctane sulfonamide 70.2g (0.12mol) and the mixture of 282g of methyl ethyl ketone was added dropwise to maintain 65 ℃ stirring was continued for 5 hours. 降温,得反应物B的溶液,其中不挥发份浓度约为20%。 Cooling, the reaction solution obtained was B, wherein the nonvolatile content of about 20%.

溶剂型含氟丙烯酸酯共聚物的制备:将上述反应物B加入内有前述制备的共聚物A的四口瓶中,维持65℃搅拌反应5小时,降温,停止搅拌。 Preparing a solvent-type fluorine-containing acrylate copolymer: The above reaction was added 4-neck flask B of copolymer A prepared above, maintaining 65 ℃ was stirred for 5 hours, cooling, stirring was stopped. 得本发明的溶剂型含氟丙烯酸酯共聚物。 Solvent was fluorinated acrylate copolymer of the present invention.

实施例9共聚物A的制备:与实施例1相同。 Example 9 Preparation of copolymer A: the same as in Example 1.

反应物B的制备:在另一四口瓶中加入甲基异丁基甲酮100g,二环己基甲烷-4,4'-二异氰酸酯31.5g(0.12mol)、三亚乙基二胺0.3g,升温至70℃。 Preparation of reactant B is: In another four-necked flask was added methyl isobutyl ketone 100g, dicyclohexylmethane-4,4'-diisocyanate 31.5g (0.12mol), triethylenediamine 0.3g, warmed to 70 ℃. 搅拌下滴加N-乙基-N-羟乙基全氟辛基磺酰胺68.6g(0.12mol)与甲基异丁基甲酮298g的混合液,滴完后维持100℃继续搅拌反应2小时。 Added dropwise with stirring a mixture of N- ethyl -N- hydroxyethyl perfluorooctane sulfonamide 68.6g (0.12mol) and methyl isobutyl ketone 298g is added dropwise to maintain continued 100 ℃ reaction was stirred for 2 hours. 降温,得反应物B的溶液,其中不挥发份浓度为20%。 Cooling, the reaction solution obtained was B, wherein the nonvolatile content of 20%.

溶剂型含氟丙烯酸酯的制备:将上述反应物B加入内有前述制备的共聚物A的四口瓶中,维持100℃继续搅拌反应2小时,降温,停止搅拌。 Preparing a solvent-type fluorine-containing acrylate: A four neck flask of the above prepared copolymer A B was added to the above reaction was maintained continued 100 ℃ was stirred for 2 hours, cooling, stirring was stopped. 得本发明的溶剂型含氟丙烯酸酯共聚物。 Solvent was fluorinated acrylate copolymer of the present invention.

实施例10共聚物A的制备:与实施例1相同。 Example 10 Preparation of copolymer A: the same as in Example 1.

反应物B的制备:在另一四口瓶中加入环己酮100g,异佛尔酮二异氰酸酯22.2g(0.1mol)、辛酸亚锡0.07g,升温至70℃。 Preparation of reactant B is: In another four-necked flask was added cyclohexanone 100g, isophorone diisocyanate 22.2g (0.1mol), stannous octoate 0.07g, warmed to 70 ℃. 搅拌下滴加N-甲基-N-羟乙基全氟辛基磺酰胺55.7g(0.1mol)与环己酮212g的混合液,滴完后继续搅拌反应6小时。 Added dropwise with stirring N- methyl -N- hydroxyethyl perfluorooctane sulfonamide mixture of 55.7g (0.1mol) and 212g of cyclohexanone was added dropwise to the reaction and stirring was continued for 6 hours. 降温,得反应物B的溶液,其中不挥发份浓度为20%。 Cooling, the reaction solution obtained was B, wherein the nonvolatile content of 20%.

溶剂型含氟丙烯酸酯共聚物的制备: Solvent-fluorinated acrylate copolymer prepared by:

将上述反应物B加入内有前述制备的共聚物A的四口瓶中,维持75℃搅拌反应5小时,降温,停止搅拌。 The four-necked flask B to the above reaction was added to the above prepared copolymer A, maintaining 75 ℃ was stirred for 5 hours, cooling, stirring was stopped. 得本发明的溶剂型含氟丙烯酸酯共聚物。 Solvent was fluorinated acrylate copolymer of the present invention.

实施例1~10含氟丙烯酸酯共聚物结构示意如下: 1 to 10 fluorinated acrylate copolymer structure examples indicate the following:

上述结构示意图中,-Z-和-Rf见下表: The above-described structure diagram, -Z- and -Rf table below:

实施例11共聚物A的制备:在四口瓶中加入醋酸丁酯140g和丙烯酸月桂酯6.0g,通入氮气置换内部空气后,升温至85℃,搅拌下滴加由丙烯酸甲酯115.0g、丙烯酸月桂酯6.0g、丙烯酸-β-羟丙酯13.0g(0.1mol)及溶解其中的过氧化二苯甲酰0.4g组成的混合液,维持反应温度83~87℃,约2小时滴完。 Example 11 Preparation of copolymer A: the 4-neck flask was added 140g of butyl acetate and lauryl acrylate 6.0g, after the internal air is replaced by nitrogen, warmed to 85 ℃, by methyl acrylate was added dropwise with stirring 115.0g, lauryl acrylate 6.0g, hydroxy propyl acrylate -β- 13.0g (0.1mol) and dissolved therein 0.4g of dibenzoyl peroxide mixture consisting of, maintaining the reaction temperature 83 ~ 87 ℃, about 2 hours drops finished. 滴完后继续搅拌反应2小时,补加溶有0.2g过氧化二苯甲酰的甲苯溶液10毫升,继续维持反应2小时。 After the dropping, stirring was continued for 2 hours, supplemented with a solution of 0.2g toluene solution of dibenzoyl peroxide in 10 ml, the continuation of the reaction for 2 hours. 停止搅拌向四口瓶中补醋酸丁酯至瓶内物总重700g,使制备的共聚物A浓度为20%。 4-neck flask stirring was stopped to fill the bottle was butyl acetate to the total weight of 700g, the copolymer A prepared at a concentration of 20%.

反应物B的制备:在另一四口瓶中加入丁酮100g,2,4-甲苯二异氰酸酯17.4g(0.1mol)、二月桂酸二丁基锡0.1g,升温至70℃。 Preparation of reactant B is: In another four-necked flask was added methyl ethyl ketone 100g, 2,4- toluene diisocyanate 17.4g (0.1mol), dibutyl tin dilaurate 0.1g, warmed to 70 ℃. 搅拌下滴加N-乙基-N-羟乙基全氟辛基磺酰胺57.1g(0.1mol)与丁酮198g的混合液,滴完后继续搅拌反应5小时。 Added dropwise with stirring ethyl N- -N- hydroxyethyl perfluorooctane sulfonamide 57.1g (0.1mol) and 198g of a mixture of methyl ethyl ketone was added dropwise to the reaction and stirring was continued for 5 hours. 降温,停止搅拌。 Cooling, stirring was stopped. 得反应物B的溶液,其中不挥发份浓度为20%。 The reaction solution obtained was B, wherein the nonvolatile content of 20%.

溶剂型含氟丙烯酸酯共聚物的制备:将上述反应物B加入内有前述制备的共聚物A的四口瓶中,回流下搅拌反应5小时,降温,停止搅拌。 Preparation of solvent-fluorinated acrylate copolymer: There will be four bottles prepared above copolymer A in the above reactant B, stirring for 5 hours, cooling, stop stirring under reflux. 得本发明的溶剂型含氟丙烯酸酯共聚物。 Solvent was fluorinated acrylate copolymer of the present invention. 结构示意如下: Structures indicate the following: 实施例12共聚物A的制备:在四口瓶中加入醋酸乙酯70g和丙烯酸-2-乙基己酯10.0g,通入氮气置换内部空气后,升温至75℃,搅拌下滴加由丙烯酸乙酯120.0g、丙烯酸-2-乙基己酯8.6g、N-羟甲基丙烯酰胺1.4g(13.85mmol)及溶解其中的过氧化二苯甲酰1.4g组成的混合液,维持反应温度75~77℃,约2小时滴完。 Example 12 Preparation of copolymer A: the 4-neck flask was added 70g of ethyl acetate and 2-ethylhexyl acrylate, 10.0g, after the internal air is replaced by nitrogen, heated to 75 ℃, from acrylic acid was added dropwise with stirring ethyl 120.0g, 2-ethylhexyl acrylate, 8.6g, 1.4g dibenzoyl mixture consisting of N- methylol acrylamide 1.4g (13.85mmol) and dissolve the peroxide, maintaining the reaction temperature of 75 ~ 77 ℃, about two hours drop end. 滴完后继续反应2小时,补加溶有0.7g过氧化二苯甲酰的甲苯溶液10毫升,再继续维持于75℃反应2小时。 After the dropping, reaction was continued for 2 hours, supplemented with a solution of 0.7g toluene solution of dibenzoyl peroxide in 10 ml, and then maintained at 75 ℃ continued for 2 hours. 停止搅拌向四口瓶中补醋酸乙酯至瓶内物总重700g,使制备的共聚物A浓度为20%。 4-neck flask stirring was stopped to fill the bottle with ethyl acetate to the total weight 700g, the copolymer A prepared at a concentration of 20%.

反应物B的制备:在另一四口瓶中加入丙酮8.8g,对苯二异氰酸酯2.2g(13.85mmol)、三亚乙基二胺1.0g,升温至56℃,回流,搅拌下滴加N-丙基-N-羟乙基全氟辛基磺酰胺8.1g(13.85mmol)与丙酮30g的混合液,滴完后继续回流搅拌反应6小时。 Preparation of reactant B is: In another 4-neck flask was added acetone 8.8g, p-phenylene diisocyanate, 2.2g (13.85mmol), triethylenediamine 1.0g, warmed to 56 ℃, reflux with stirring was added dropwise N- propyl -N- hydroxyethyl perfluorooctane sulfonamide mixture of 8.1g (13.85mmol) and 30g of acetone was added dropwise to the reaction mixture was stirred at reflux continued for 6 hours. 降温,得反应物B的溶液,其中不挥发份浓度约为20%。 Cooling, the reaction solution obtained was B, wherein the nonvolatile content of about 20%.

溶剂型含氟丙烯酸酯共聚物的制备:将上述反应物B加入内有前述制备的共聚物A的四口瓶中,升温至回流后搅拌反应6小时,得本发明的溶剂型含氟丙烯酸酯共聚物。 Preparation of solvent-fluorinated acrylate copolymer: four bottles will be added to the above reaction was prepared above copolymer B of A, heated to reflux and stirred for 6 hours to obtain a solvent-fluorinated acrylate present invention copolymer. 结构示意如下: Structures indicate the following: 实施例13共聚物A的制备:在四口瓶中加入二甲苯500g和甲基丙烯酸月桂酯14.0g,通入氮气置换内部空气后,升温至95~100℃,搅拌下滴加由二甲苯293g、甲基丙烯酸甲酯100.0g、甲基丙烯酸月桂酯13.0g、甲基丙烯酸-β-羟乙酯13.0g(0.1mol)及溶解其中的过氧化二苯甲酰0.2g组成的混合液,维持反应温度95~100℃,约2小时滴完。 Example 13 Preparation of copolymer A: 4-neck flask was added in 500g of xylene and lauryl methacrylate 14.0g, after the internal air is replaced by nitrogen, warmed to 95 ~ 100 ℃, added dropwise with stirring by xylene 293g , a mixture consisting of methyl methacrylate 100.0g, lauryl methacrylate 13.0g, methacrylate -β- hydroxyethyl methacrylate 13.0g (0.1mol) was dissolved therein and dibenzoyl peroxide 0.2g, maintained The reaction temperature is 95 ~ 100 ℃, for about two hours drop end. 滴完后继续反应2小时,补加溶有0.08g过氧化二苯甲酰的甲苯溶液10毫升,继续维持反应1小时。 After the dropping, reaction was continued for 2 hours, supplemented with a toluene solution of 0.08g dissolved dibenzoyl peroxide in 10 ml, to maintain the reaction for 1 hour. 停止搅拌,改反应装置为蒸馏装置,蒸出溶剂242g,使瓶内物总重700g,制备的共聚物A浓度为20%。 Stirring was stopped, the reaction apparatus was changed distillation apparatus, the solvent was evaporated 242g, so that the bottle on the total weight of 700g, the copolymer A prepared at a concentration of 20%.

反应物B的制备:与实施例10相同。 Preparation of reactant B: The same as in Example 10.

溶剂型含氟丙烯酸酯共聚物的制备:将上述反应物B加入内有前述制备的共聚物A的四口瓶中,维持75℃搅拌反应5小时,降温,停止搅拌。 Preparation of solvent-fluorinated acrylate copolymer: There will be four bottles prepared above copolymer A in the above reactant B added, maintaining the reaction was stirred for 5 hours 75 ℃, cooling, stop stirring. 得本发明的溶剂型含氟丙烯酸酯共聚物。 Solvent was fluorinated acrylate copolymer of the present invention.

实施例14共聚物A的制备:在四口瓶中加入丁酮140g,通入氮气置换内部空气后,升温至70℃,搅拌下滴加由甲基丙烯酸乙酯100.0g、甲基丙烯酸丁酯25.6g、甲基丙烯酸-β-羟丙酯14.4g(0.1mol)及溶解其中的过氧化二苯甲酰0.4g组成的混合液,维持反应温度70℃,约2小时滴完。 Example 14 Preparation of copolymer A: the 4-neck flask was added methyl ethyl ketone 140g, after the internal air is replaced by nitrogen, warmed to 70 ℃, added dropwise with stirring from ethyl methacrylate 100.0g, butyl methacrylate 25.6g, 0.4g mixture consisting of dibenzoyl -β- hydroxy propyl methacrylate 14.4g (0.1mol) and dissolve the peroxide, maintaining the reaction temperature is 70 ℃, about two hours drop end. 滴完后继续反应4小时,补加溶有0.1g过氧化二苯甲酰的甲苯溶液10毫升,继续维持反应2小时。 After the dropping, reaction was continued for 4 hours, a solution of toluene solution supplemented with 0.1g of benzoyl peroxide in 10 ml, to maintain the reaction for 2 hours. 停止搅拌向四口瓶中补丁酮至瓶内物总重700g,使制备的共聚物A浓度为20%。 The stirring was stopped to the 4-neck flask contents were patch-one to the total weight of 700g, the copolymer A prepared at a concentration of 20%.

反应物B的制备:与实施例10相同。 Preparation of reactant B: The same as in Example 10.

溶剂型含氟丙烯酸酯共聚物的制备:将上述反应物B加入内有前述制备的共聚物A的四口瓶中,维持70℃搅拌反应5小时,降温,停止搅拌。 Preparation of solvent-fluorinated acrylate copolymer: There will be four bottles prepared above copolymer A in the above reactant B added, maintaining the reaction was stirred for 5 hours 70 ℃, cooling, stop stirring. 得本发明的溶剂型含氟丙烯酸酯共聚物。 Solvent was fluorinated acrylate copolymer of the present invention.

实施例13~14含氟丙烯酸酯共聚物结构示意如下: Examples 13 to 14 fluorinated acrylate copolymer structure according to indicate the following: 上述结构示意中,实施例13:R1=CH3R2=n-C12H25R=H实施例14:R1=C2H5R2=n-C4H9R=CH3实施例15共聚物A的制备:在四口瓶中加入甲基异丁基甲酮140g,通入氮气置换内部空气后,升温至87℃,搅拌下滴加由甲基丙烯酸乙酯70.0g、丙烯酸乙酯35.0g、甲基丙烯酸-β-羟丙酯35.0g(0.243mol)及溶解其中的过氧化二苯甲酰0.3g组成的混合液,维持反应温度85~90℃,约2小时滴完。 In the above structure schematically, Example 13: R1 = CH3R2 = n-C12H25R = H Example 14: R1 = C2H5R2 = n-C4H9R = CH3 Preparation Example 15 A copolymer of: a four-neck flask was added methyl isobutyl ketone 140g, after the internal air is replaced by nitrogen, warmed to 87 ℃, added dropwise with stirring from ethyl methacrylate 70.0g, ethyl acrylate 35.0g, methacrylate -β- hydroxypropyl methacrylate 35.0g (0.243mol) and wherein the mixture is dissolved 0.3g of dibenzoyl peroxide composition, maintaining the reaction temperature 85 ~ 90 ℃, about 2 hours drops finished. 滴完后继续反应2小时,补加溶有0.1g过氧化二苯甲酰的甲苯溶液10毫升,再继续维持反应2小时。 After the dropping, reaction was continued for 2 hours, supplemented with a solution of 0.1g of a toluene solution of dibenzoyl peroxide in 10 ml, and then continue to maintain the reaction for 2 hours. 停止搅拌向四口瓶中补甲基异丁基甲酮至瓶内物总重700g,使制备的共聚物A浓度为20%。 4-neck flask stirring was stopped to fill methyl isobutyl ketone to the bottle on the total weight of 700g, the copolymer A prepared at a concentration of 20%.

反应物B的制备:在另一四口瓶中加入甲基异丁基甲酮125g,2,4-甲苯二异氰酸酯42.3g(0.24 3mol)、二月桂酸二丁基锡0.09g,升温至70℃。 Preparation of reactant B is: In another four-necked flask was added methyl isobutyl ketone 125g, 2,4- toluene diisocyanate 42.3g (0.24 3mol), dibutyl tin 0.09g, warmed to 70 ℃. 搅拌下滴加N-乙基-N-羟乙基全氟辛基磺酰胺138.8g(0.243mol)与甲基异丁基甲酮600g的混合液,滴完后继续反应5小时。 Added dropwise with stirring ethyl N- -N- hydroxyethyl perfluorooctane sulfonamide 138.8g (0.243mol) of methyl isobutyl ketone and 600g of mixed solution was added dropwise to the reaction was continued for 5 hours. 降温,得反应物B的溶液,其中不挥发份浓度为20%。 Cooling, the reaction solution obtained was B, wherein the nonvolatile content of 20%.

溶剂型含氟丙烯酸酯的制备:将上述反应物B加入内有前述制备的共聚物A的四口瓶中,维持70℃搅拌反应5小时,降温,停止搅拌。 Preparing a solvent-type fluorine-containing acrylate: A four neck flask of the above prepared copolymer A in said reactant B is added, maintaining 70 ℃ was stirred for 5 hours, cooling, stirring was stopped. 得本发明的溶剂型含氟丙烯酸酯共聚物。 Solvent was fluorinated acrylate copolymer of the present invention. 结构示意如下: Structures indicate the following:

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Classifications
International ClassificationC08F2/04, D06M101/00, D06M15/277, C08F220/56, C08F8/30, C08F220/26
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