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Process of preparing solvent type fluoric acrylate copolymer

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CN101020731A
CN101020731A CN 200710020567 CN200710020567A CN101020731A CN 101020731 A CN101020731 A CN 101020731A CN 200710020567 CN200710020567 CN 200710020567 CN 200710020567 A CN200710020567 A CN 200710020567A CN 101020731 A CN101020731 A CN 101020731A
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acrylate
copolymer
nco
fluoric
radical
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CN 200710020567
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Chinese (zh)
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CN100497413C (en )
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刘庆安
孟祥春
孙艳松
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安徽大学
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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.

Description

溶剂型含氟丙烯酸酯共聚物的制备方法 Preparing a solvent-type fluorine-containing 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 for preparing a fluorinated acrylate copolymer solvent, the polymer can be made water and oil repellent for textiles, leather and the like.

背景技术 Background technique

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 having an excellent waterproof, oil and low surface tension properties, mainly due to the outward of the fluorinated copolymer after the solid film on the surface, the fluorine-containing side chain rule alignment and stretching, thereby fulfilling excellent water and oil repellency effect. 因此在织物、皮革等多个领域获得应用。 Thereby obtaining a plurality of the field of application of textiles, leather and the like.

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。 Such polymers are generally prepared first acrylate monomer containing a perfluoroalkyl side chain, there are several general structure: (1) acrylate perfluoroalkyl ethanol, 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 to form ethanolamine and N- hydroxyethyl gold perfluoroheptanoic (octyl) amide, and then forming the acrylate acryloyl chloride with structure RfCONHCH2CH2O2CCH = CH2, Rf is a perfluoro hexyl group or perfluoro heptane 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 mole to 2,4-TDI (or IPDI) is reacted with the like, and then mol of hydroxyethyl acrylate or hydroxypropyl acrylate and the like 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- hept-hydroxyethyl perfluoro (octyl) -amide and 2,4-TDI to equimolar reaction, equimolar then -β- hydroxyethyl acrylate, hydroxypropyl acrylate or condensed with 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。 Due to the above monomers alone poor physical properties of the polymer formed is generally necessary to form a copolymer with one or more non-fluorinated monomers 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 having a certain waterproof, oil must be sufficiently long perfluoroalkyl side chain, typically a perfluoroalkyl group of not less than 6 carbon atoms, but the long side chain perfluoroalkyl polymerization It was bad solubility in common solvents, particularly a copolymer of (1) to (3) monomer is typically formed by dissolving only a few containing fluorine or other halogen in a solvent, for environmental reasons, of fluorine-containing acrylate copolymers prepared using these types of monomers are prepared using substantially the emulsion polymerization process, emulsion polymerization process need to be added in the preparation of a surfactant, co-solvent, if improperly controlled conditions delamination occurs phenomenon, which is particularly evident for the emulsion copolymerization of a fluorinated acrylate monomer, the product there is a difference in storage stability, poor film-forming properties of the 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 is a product suitable for narrow, common good, to do tailor-made product 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 in the monomer drops quickly, i.e., the problem in durability, initially thought to be due to the fall due to water and oil repellent, is now understood because such polymers Full fluoroalkyl side chain orientation due to the chaotic. 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 such polymers in the solid surface forming only a fluorinated side chain alignment and extending outwardly regular, 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。 As compared to (1) to (3) monomer, (4), (5) two kinds of monomers and copolymers formed by them should be improved solubility, i.e. they do not dissolve in only a few fluorine solvent. 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。 (4) above, (5) two kinds of monomers are monomers where in the molecule can form ratio (1) to (3) more hydrogen bonding monomer, a perfluoroalkyl side chain can reduce the alignment disorder of the a perfluoroalkyl side chain to maintain a fixed alignment, can also increase the fastness of the copolymer and the 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。 However, compared with (1) to (3) monomer, (4), (5) a monomer reactivity ratio of two monomers copolymerized with other larger difference, certainly not if continued emulsion polymerization solution polymerization results it is good. 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, in the solution polymerization method proposed by the present invention by adjusting certain 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 price factors, the above-mentioned 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: Due to the above-described deficiencies in the art, from consideration of the present invention and the performance features of the present invention is prepared by combining the method, there is provided a method of preparing a fluorine-containing solvent-based acrylate polymer, the specific steps are as follows: 1, a hydroxyl group containing acrylate M or acrylamide monomer with one or more acrylate monomer solution polymerization prepared acrylic copolymer a side chain containing a hydroxyl group, a schematic of the structure: 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, a fluorine-containing alcohol moles with RfOH a diisocyanate OCN-X-NCO reaction, the reactant B have to be prepared, a schematic structure of: RfO2CNH-Z-NCO, a reactant B retains a unreacted NCO groups, the reaction is schematically as follows: ,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。 , RfOH fluorine-containing alcohol with two moles of diisocyanate OCN-Z-NCO are hydroxyl group-containing acrylate or acrylamide monomer M 0.8 ~ 1.2 times the number of moles.

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 chain hydroxyl group-containing preparation obtained acrylate copolymer A and part B two reactants to react, to obtain a fluorine-containing solvent-acrylate copolymers; is a schematic structure: 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, in the side chain of the present invention is prepared comprising the hydroxy acrylic copolymer A: acrylate copolymer A containing pendant hydroxyl group is a hydroxyl group-containing acrylate (or acrylamide) monomer M with one or more acrylate monomers the presence of a free radical initiator dibenzoyl peroxide by solution polymerization, the polymerization temperature is 70 ~ 100 ℃, for 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 total reaction system, polymerization rate and the square root of initiator concentration, molecular weight, and inversely proportional to the square root of the amount of initiator, the initiator used is too large the copolymer will Effect of the molecular weight significantly reduce performance, but too small, the polymerization rate is too slow.

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。 Effect of temperature on the polymerization reaction is large, the polymerization temperature rises faster, the molecular weight decreases, the reaction temperature should also be considered to determine the half-life temperature of the initiator, an initiator of dibenzoyl peroxide was added continuously effective over time.

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。 Used in the present invention, 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%。 In the amount of 1 to 25% of acrylate monomer in the copolymer A prepared.

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% of acrylate monomer in the copolymer a prepared.

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% of 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 the solubility of the polymerization reaction chain transfer constant, such as whether the impact of whether higher. 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。 The amount of solvent primarily consider the impact on the monomer concentration, which affect the molecular weight 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 reaction product B of the present invention is prepared, containing one unreacted -NCO group, the reaction of equimolar amount of a diisocyanate OCN-Z-NCO with a fluorine-containing alcohol from RfOH, a schematic structure of: 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。 Preparation of the reaction product B in the presence of a catalyst, a diisocyanate OCN-Z-NCO to react with an equimolar amount of fluorine-containing alcohol RfOH, the reaction temperature is 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 and the resulting product after the reaction of the fluorine-containing alcohol moles RfO2CNH-Z-NCO, i.e., reactant B a retention 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。 Equal to the number of moles of fluorine-containing alcohol RfOH with a diisocyanate OCN-Z-NCO, and are 0.8 to 1.2 times or acrylamide monomers M number of 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), A 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%), Toluene diisocyanate (2,4-TDI content of about 80%, 2,6-TDI content of about 80%), 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。 Wait.

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 diisocyanates two -NCO reactive primary consideration whether different, the difference of activity more conducive diisocyanate -NCO group and the like retained after a reaction of fluorine-containing alcohol moles unreacted. 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 the two -NCO groups have activity as more byproducts are formed, i.e. some two -NCO diisocyanate are reacted to form a diisocyanate connecting two fluoroalcohol, so would not contain side chains with acrylate copolymer a reaction of a hydroxyl group. 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 quite different reactive groups -NCO, 6.7-fold and 4.7-fold higher activity of 4-NCO (50 ℃) (72 ~ 74 ℃) ratio of 2-NCO , but using 2,4-toluene diisocyanate (2,4-TDI) the 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) situation is more complex, without a catalyst, the secondary -NCO reactive groups -NCO Ji Bibo 5.5 times faster (20 ℃, n-butanol), using as dibutyl tin dilaurate catalysis, secondary -NCO reactive groups -NCO Ji Bibo 11.5 times faster (20 ℃, n-butanol), but using triethylenediamine as catalyst, the large primary than secondary -NCO group -NCO reactive groups. 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。 After phenylene diisocyanate (PPDI) two -NCO groups although no difference in activity, but due to the formation of a urethane reaction of -NCO group, an -NCO group with respect to the original electron withdrawing effect decreased, so that the other unreacted - NCO groups passivated using p-phenylene diisocyanate (PPDI) the coating tends to be 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。 Diisocyanates two -NCO groups in the molecule the greater the reaction activity difference, the better the selectivity of the reaction, the solvent is advantageous for the preparation of fluorinated acrylate copolymers of the present invention. 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 for 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%), terephthaloyl diisocyanate (PPDI) using geometric diphenylmethane-4,4'-diisocyanate (MDI), 1,6- hexamethylene diisocyanate (HDI), naphthalene-1,5-diisocyanate (NDI), dicyclohexylmethane 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 alcohol RfOH comprising: C6F13CH2CH2OH perfluorohexyl ethanol perfluorooctyl ethanol C8F17CH2CH2OHN--hydroxyethyl perfluoro-hydroxyethyl perfluoro octanamide C7F15CONHCH2CH2OHN- enantholactam C6F13CONHCH2CH2OHN- -N- methyl-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- -N- propyl-hydroxyethyl perfluorooctane sulfonamide 等。 Wait.

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, organotin compounds of aromatic or aliphatic isocyanate with a primary alcohol have a strong ability to catalytic reaction, the catalytic -NCO group and primary alcohol is a tertiary amine much stronger, an organic tin compound as a catalyst and left in the product, there may be the application of the product, to promote polymer degradation under light irradiation 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 of this concern no amines, tertiary amines have a strong catalytic effect on the aromatic diisocyanates TDI, but the aliphatic diisocyanates such as HDI catalysis 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 N atoms because no bit strong steric influence catalytic performance.

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-phenyl, trifluoromethyl-trichloroethane, trichlorethylene, tetrachlorethylene and 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 mainly on account of the solubility, reactivity to whether the impact was prepared -NCO group three, the solvent of the fluorine-containing acrylate polymers: Preparation of the side chain of the obtained hydroxyl group-containing acrylate copolymer A and reactant B 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。 Fluorine-containing solvent to prepare an 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 for preparing a fluorine-containing solvent-acrylate copolymer of the proposed invention is simple. 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。 With respect to the copolymers formed by monomers mentioned background art (1) to (3), fluorine-containing acrylate copolymer molecules according to the present invention can form more hydrogen bond, perfluoroalkyl group can be reduced side chain orientation confusion, so that a perfluoroalkyl side chain to maintain a fixed alignment, thereby delaying the drop water and oil properties, while increasing fastness copolymer with the substrate, to improve the background art mentioned (1) ~ (3) monomer copolymer product is formed narrow applicability, universality poor 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。 Further (4) to (5) monomer reactivity ratio of the background art mentioned other monomers copolymerizable with large difference, obtained by emulsion polymerization method copolymer structure over the link ratio is not uniformity, It may affect the properties of the copolymer, but prepared using the method of the present invention may be employed to solve this problem different monomer ratio in the preparation of the copolymer a. 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。 The emulsion polymerization process if improperly controlled conditions delamination occurs, which is particularly evident, the product there is also a difference in storage stability, poor film-forming properties and other physical problems for the emulsion copolymerization of a fluorinated 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 further illustrate the present invention more specifically by way of examples, 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: 4-neck flask was added 140 g of toluene, after the inside air replaced with nitrogen gas, temperature was raised to 85 ℃, added dropwise with stirring 100.0 g of a methyl acrylate, 28.4 g butyl acrylate, acrylic acid - β- hydroxyethyl 11.6g (0.1mol) and dissolved therein 0.3g of dibenzoyl peroxide mixture solution, maintaining the reaction temperature 83 ~ 87 ℃, dropwise for about 2 hours. 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 dibenzoyl peroxide in 10 ml of toluene, continue to maintain the reaction for 2 hours, cooled, four-necked flask of toluene up to a total weight of 700 g of the bottle was, stops stir. 制备的共聚物A浓度为20%。 A copolymer was 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: In another flask four cyclohexanone 90g, 2,4- toluene diisocyanate 17.4g (0.1mol), dibutyl tin dilaurate 0.1g, warmed 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) and 125g of cyclohexanone, the mixture was added dropwise to the reaction continued at 75 deg.] C 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 to obtain composition B, wherein the nonvolatile concentration 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。 Solvent Preparation of Fluorinated Acrylate Copolymer: The reaction was added to the above four neck flask B copolymer A prepared in the foregoing, the reaction was stirred to warm to 75 ~ 80 ℃ 5 h, cooled, stirring was stopped. 得本发明的溶剂型含氟丙烯酸酯共聚物。 Fluorine-containing solvent to give acrylate copolymers 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: In another methyl isobutyl ketone 4-neck flask 90g, toluene diisocyanate (2,4-TDI content of about 80%) 17.4g (0.1mol), two dibutyltin 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) and methyl isobutyl ketone 165g of the mixture, stirring was continued for 3 hours after dropping. 降温,得反应物B的溶液,其中不挥发份浓度为20%。 Cooling the reaction solution to obtain composition B, wherein the nonvolatile concentration 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。 Solvent Preparation of Fluorinated Acrylate Copolymer: The reaction was added to the above four neck flask B copolymer A prepared in the foregoing, the reaction was stirred to warm to 75 ~ 80 ℃ 4 h, cooled, stirring was stopped. 得本发明的溶剂型含氟丙烯酸酯共聚物。 Fluorine-containing solvent to give acrylate copolymers of the present invention.

实施例3共聚物A的制备:与实施例1相同。 Example 3 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: In another 4-neck flask of acetone was added 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) of acetone and 120g of a mixture, stirring was continued for 6 hours After finishing the dropping. 降温,得反应物B的溶液,其中不挥发份浓度为20%。 Cooling the reaction solution to obtain composition B, wherein the nonvolatile concentration 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。 Solvent Preparation of Fluorinated Acrylate Copolymer: The reaction was added to the above four neck flask copolymer B prepared in the preceding A, maintaining the reaction was stirred for 50 ℃ 6 hours, and cooling, stirring was stopped. 得本发明的溶剂型含氟丙烯酸酯共聚物。 Fluorine-containing solvent to give acrylate copolymers 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: 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: In another trifluoromethylbenzene 4-neck flask was added 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 perfluoro octanamide 36.6g (0.08 mol) 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 to obtain composition 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。 Solvent Preparation of Fluorinated Acrylate Copolymer: The reaction was added to B-trifluoromethylphenyl 153g nonvolatile content was diluted to about 20%, and then there are added to the preparation of copolymer A 4-neck flask, maintained stirring was continued for 75 deg.] C for 4 hours, cooled, stirring was stopped. 得本发明的溶剂型含氟丙烯酸酯共聚物。 Fluorine-containing solvent to give acrylate copolymers 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: 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: In another flask four trifluorotrichloroethane 10.2g, diphenylmethane-4,4'-diisocyanate 30.0g (0.12mol), N- ethyl morpholine 2.0g heated 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 heptanamide N- perfluoro-hydroxyethyl 48.9g (0.12mol) of a mixture of 10g of trifluorotrichloroethane was added dropwise to maintain the reaction was continued for 75 ℃ 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 to obtain composition 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。 Solvent Preparation of Fluorinated Acrylate Copolymer: The reaction was added to B trifluorotrichloroethane 297g diluted to a nonvolatile content of about 20%, and then there are added the prepared copolymer A four-necked flask in maintaining the reaction was stirred 75 ℃ 4 h, cooled, stirring was stopped. 得本发明的溶剂型含氟丙烯酸酯共聚物。 Fluorine-containing solvent to give acrylate copolymers 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: 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: In another flask four trichlorethylene 63g, 1,6- hexamethylene diisocyanate 20.2g (0.12mol), diethylenetriamine 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 a mixture of N- methyl -N--hydroxyethyl perfluorooctane sulfonamide 66.9g (0.12mol) and 67g of trichlorethylene was added dropwise to maintain a 60 deg.] C 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40%。 Cooling the reaction solution to obtain composition 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。 Solvent Preparation of Fluorinated Acrylate Copolymer: The reaction was diluted with B added to 218g trichlorethylene to a nonvolatile content of about 20%, and then there are added 4-neck flask of preparing the copolymer A, maintained 60 deg.] C was stirred for 5 hours, cooled, stirring was stopped. 得本发明的溶剂型含氟丙烯酸酯共聚物。 Fluorine-containing solvent to give acrylate copolymers 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: 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: In another flask four tetrachlorethylene 45g, 2,4- toluene diisocyanate 20.9g (0.12mol), diethylenetriamine 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 164g of tetrachlorethylene was added dropwise to maintain a 60 deg.] C 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30%。 Cooling the reaction solution to obtain composition 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。 Solvent Preparation of Fluorinated Acrylate Copolymer: The reaction was diluted with B added to 151g of tetrachlorethylene to a nonvolatile content of about 20%, and then there are added 4-neck flask copolymer A prepared in the foregoing, is maintained 60 deg.] C was stirred for 5 hours, cooled, stirring was stopped. 得本发明的溶剂型含氟丙烯酸酯共聚物。 Fluorine-containing solvent to give acrylate copolymers 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: 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: In another flask four-butanone 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) of a mixture of 282g of methyl ethyl ketone was added dropwise to maintain the stirring was continued for 65 deg.] C 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 to obtain composition 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。 Solvent Preparation of Fluorinated Acrylate Copolymer: A was added to the above reaction flask B four of the prepared copolymer A, 65 deg.] C to maintain the reaction stirred for 5 hours, cooled, stirring was stopped. 得本发明的溶剂型含氟丙烯酸酯共聚物。 Fluorine-containing solvent to give acrylate copolymers 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: 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: In a separate four-neck 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 ethyl N- -N--hydroxyethyl perfluorooctane sulfonamide 68.6g (0.12mol) and methyl isobutyl ketone 298g of the mixture was added dropwise to maintain the reaction was continued stirring for 100 ℃ 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 to obtain composition B, wherein the nonvolatile concentration 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 copolymer A prepared in the above was added to the reaction B, the reaction was continued to maintain the 100 deg.] C for 2 hours, cooled, stirring was stopped. 得本发明的溶剂型含氟丙烯酸酯共聚物。 Fluorine-containing solvent to give acrylate copolymers 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: 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: In another flask four 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 55.7g (0.1mol) and 212g of cyclohexanone, stirring was continued for 6 hours After finishing the dropping. 降温,得反应物B的溶液,其中不挥发份浓度为20%。 Cooling the reaction solution to obtain composition B, wherein the nonvolatile concentration of 20%.

溶剂型含氟丙烯酸酯共聚物的制备: Preparing a solvent-type fluorine-containing acrylate copolymer:

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。 4-necked flask was added the above reaction B was prepared in the copolymer A, 75 deg.] C is maintained with stirring for 5 hours, cooled, stirring was stopped. 得本发明的溶剂型含氟丙烯酸酯共聚物。 Fluorine-containing solvent to give acrylate copolymers 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 ~ 10 fluorinated acrylate copolymer a schematic configuration example of the embodiment is as follows:

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

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: four-necked flask was added 140g of butyl acetate and 6.0 g of lauryl acrylate, the inside air replaced with nitrogen gas, temperature was raised to 85 ℃, added dropwise with stirring 115.0 g of methyl acrylate, 6.0 g of lauryl acrylate, propyl acrylate, hydroxypropyl -β- 13.0g (0.1mol) was dissolved therein and dibenzoyl peroxide mixture consisting of 0.4g, maintaining the reaction temperature 83 ~ 87 ℃, dropwise for about 2 hours. 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, reaction was continued for 2 hours, additional solution of 0.2g toluene solution of dibenzoyl peroxide in 10 ml, maintaining the reaction was continued 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%。 The stirring was stopped to fill the bottle to a total butyl acetate contents were four 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: In another flask four-butanone 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 in a mixture of 198g methyl ethyl ketone, stirring was continued after dropwise 57.1g (0.1mol) for 5 hours. 降温,停止搅拌。 Cool, stirring was stopped. 得反应物B的溶液,其中不挥发份浓度为20%。 Reactant B to give a solution, wherein a 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。 Solvent Preparation of Fluorinated Acrylate Copolymer: A four neck flask of the copolymer A prepared in the above reaction was added to B, stirred under reflux for 5 hours, cooled, stirring was stopped. 得本发明的溶剂型含氟丙烯酸酯共聚物。 Fluorine-containing solvent to give acrylate copolymers of the present invention. 结构示意如下: Structure schematically as follows: 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: 70g of ethyl acetate was added and 2-ethylhexyl acrylate, 10.0g four-neck flask, after the inside air replaced with nitrogen gas, temperature was raised to 75 ℃, from acrylic acid was added dropwise with stirring under 120.0 g ethyl acrylate, 2-ethylhexyl acrylate, 8.6g, N- methylol acrylamide, 1.4g (13.85 mmol) was dissolved therein and dibenzoyl peroxide mixture consisting of 1.4g, maintaining the reaction temperature 75 ~ 77 ℃, dropwise for about 2 hours. 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, additional solution of 0.7g toluene solution of dibenzoyl peroxide in 10 ml, maintained at 75 deg.] C was 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%。 The stirring was stopped four-neck flask ethyl acetate up to a total weight of the bottle was 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: In another 4-neck flask was added 8.8 g of acetone, p-phenylene diisocyanate 2.2g (13.85mmol), triethylenediamine 1.0g, warmed to 56 ℃, reflux with stirring was added dropwise N- mixture -N- propyl-hydroxyethyl perfluorooctane sulfonamide 8.1g (13.85mmol) and 30g of acetone was added dropwise to stirred refluxing was 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 to obtain composition 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。 The four reaction flask was added the above reaction B of the copolymer A prepared, warmed to reflux for 6 hours, to obtain a solvent type fluorine-containing acrylate according to the present invention: preparing a solvent-type fluorine-containing acrylate copolymer copolymer. 结构示意如下: Structure schematically as follows: 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: four-necked flask was added 500g of xylene and 14.0 g of lauryl methacrylate, the inside air replaced with nitrogen gas, temperature was raised to 95 ~ 100 ℃, 293g of xylene was added dropwise with stirring , 100.0 g of methyl methacrylate, 13.0 g of lauryl methacrylate, hydroxyethyl methacrylate, -β- 13.0g (0.1mol) and dissolved therein 0.2g of dibenzoyl peroxide mixture solution, maintained The reaction temperature is 95 ~ 100 ℃, dropwise for about 2 hours. 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 solution of 0.08g of dibenzoyl peroxide in 10 ml toluene, maintaining the reaction continued 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 is a distillation apparatus to change, 242g solvent was distilled off, 700 g of the total weight of composition in the bottle, 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: same as 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。 Solvent Preparation of Fluorinated Acrylate Copolymer: A four neck flask of the copolymer A prepared in the above B was added to the reaction, maintaining 75 deg.] C was stirred for 5 hours, cooled, stirring was stopped. 得本发明的溶剂型含氟丙烯酸酯共聚物。 Fluorine-containing solvent to give acrylate copolymers 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: In a four-neck flask 140 g of methyl ethyl ketone, the inside air replaced with nitrogen gas, temperature was raised to 70 ℃, added dropwise with stirring by the 100.0 g of ethyl methacrylate, butyl methacrylate 25.6 g of, -β- methacrylate, hydroxypropyl methacrylate 14.4g (0.1mol) and dissolved therein 0.4g of dibenzoyl peroxide mixture solution, maintaining the reaction temperature 70 ℃, dropwise for about 2 hours. 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 supplemented with 0.1g dissolved dibenzoyl peroxide in 10 ml toluene, maintaining the reaction was continued 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%。 One to four stirring was stopped flask contents were patch to a 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: same as 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。 Solvent Preparation of Fluorinated Acrylate Copolymer: A four neck flask of the copolymer A prepared in the above reaction was added to B, stirred 70 deg.] C maintained for 5 hours, cooled, stirring was stopped. 得本发明的溶剂型含氟丙烯酸酯共聚物。 Fluorine-containing solvent to give acrylate copolymers of the present invention.

实施例13~14含氟丙烯酸酯共聚物结构示意如下: 14 fluorinated acrylate copolymer Examples 13 to a schematic structure of 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-described illustrative configuration, Example 13: R1 = CH3R2 = n-C12H25R = H Example 14: = C2H5R2 = n-C4H9R R1 = CH3 Preparation of copolymer A of Example 15: 4-neck flask was added methyl isobutyl 140 g of ketone, after the inside air replaced with nitrogen gas, temperature was raised to 87 deg.] C, added dropwise with stirring 70.0 g of the ethyl methacrylate, 35.0 g ethyl acrylate, propyl methacrylate, hydroxypropyl -β- 35.0g (0.243mol) and wherein the mixture is dissolved 0.3g of dibenzoyl peroxide composition, maintaining the reaction temperature 85 ~ 90 ℃, dropwise for about 2 hours. 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, additional solution of 0.1g toluene solution of dibenzoyl peroxide in 10 ml, maintaining the reaction was continued 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 a total weight of 700g bottle was 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: In a separate four-neck flask was added methyl isobutyl ketone 125g, 2,4- toluene diisocyanate 42.3g (0.24 3mol), dibutyl tin dilaurate 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 the mixture 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 to obtain composition B, wherein the nonvolatile concentration 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 copolymer A prepared in the above reaction was added to B, stirred 70 deg.] C maintained for 5 hours, cooled, stirring was stopped. 得本发明的溶剂型含氟丙烯酸酯共聚物。 Fluorine-containing solvent to give acrylate copolymers of the present invention. 结构示意如下: Structure schematically as follows:

Claims (2)

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-acrylate copolymer, wherein: (1) a hydroxyl group containing acrylate or acrylamide monomer M with one or more acrylate monomers prepared by solution polymerization of a hydroxyl-containing side chain acrylate copolymer a, a schematic structure of: 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, a fluorine-containing alcohol equimolar RfOH reacted with a diisocyanate OCN-Z-NCO, reactant B have to be prepared, a schematic structure of: RfO2CNH-Z-NCO, a reactant B retained unreacted -NCO group, the reaction is schematically as follows: ,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。 , RfOH fluorine-containing alcohol with two moles of diisocyanate OCN-Z-NCO are hydroxyl group-containing acrylate or acrylamide monomer M 0.8 ~ 1.2 times the number of moles. (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) Preparation of the side chain of the obtained hydroxyl group-containing acrylate copolymers A and B the reactants react in two parts, to obtain a fluorine-containing solvent-acrylate copolymers; is a schematic structure: 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 The fluorine-containing solvent according to a method of preparing an acrylate copolymer as claimed in claim A, wherein: (1) the side-chain hydroxyl-containing acrylate copolymer A, using acrylate or a hydroxyl-containing amide monomer M with one or more acrylate monomers in a radical polymerization initiator solution was carried out in the presence of dibenzoyl peroxide, dibenzoyl peroxide accounted for 0.03 to 1.0% of the total amount of the polymerization system, the polymerization temperature 70 ~ 100 ℃, for 4 to 8 hours; the polymerization solvent used is toluene or xylene, or butanone, or methyl isobutyl ketone, or from ethyl acetate, butyl acetate, or is, the amount of solvent accounting for 33 to 85% of the total amount of the entire polymerization reaction system; hydroxyl group-containing acrylate or acrylamide monomer is acrylic M -β- hydroxyethyl acrylate, hydroxypropyl acrylate, or an acrylic -β-, or-methylol is N- 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; one or more of the acrylic ester monomers are methyl acrylate, or ethyl acrylate, or a propionyl 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%。 Butyl, 2-ethylhexyl acrylate, or is, or lauryl acrylate, or methyl methacrylate, or methyl acrylate, butyl acrylate, or methyl methacrylate, or methacrylic acid lauryl methacrylate, 75 to 99% comonomer in copolymer A used in the preparation. (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 (2) the reaction product B, which is a -NCO group containing unreacted compound RfO2CNH-Z-NCO, in equimolar diisocyanate OCN-Z-NCO and a fluorine-containing alcohol obtained by reacting RfOH, the reaction in a solvent the presence of a catalyst, the reaction temperature is 50 ~ 100 ℃, for 2 to 6 hours; the number of moles of fluorine-containing alcohol and a diisocyanate are contained 0.8 to 1.2 times acrylate or acrylamide monomer M of the number of moles of hydroxyl groups; used the solvent is acetone, or butanone, or cyclohexanone, or methyl isobutyl ketone, benzene or a trifluoromethyl group, or a trifluoromethyl trichloroethane, or trichlorethylene, or from tetrachloro 20 to 80% of ethylene, the total amount of the entire reaction system with a solvent; the diisocyanate OCN-Z-NCO is 2,4-toluene diisocyanate (2,4-TDI), or isophorone diisocyanate ( IPDI), or toluene diisocyanate (2,4-TDI content of about 80%), or from p-phenylene diisocyanate (PPDI), or from diphenylmethane-4,4'-diisocyanate (MDI), 1, 1,6-diisocyanate (HDI), or from naphthalene-1,5-diisocyanate (NDI), or from dicyclohexylmethane-4,4'-diisocyanate (of HMDI); the fluorine-containing 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。 RfOH as perfluorohexyl alcohol, perfluorooctyl alcohol or from; or perfluorooctanoate is N- hydroxyethyl acrylamide, N- hydroxyethyl or from perfluoro heptanoic acid amide; or as N- methyl -N- isethionic perfluorooctyl sulfonamide group, or is N- ethyl -N--hydroxyethyl perfluorooctane sulfonamide, or is N- -N- propyl-hydroxyethyl perfluorooctane sulfonamide; the catalyst is dibutyl tin dilaurate, or dibutyl tin diacetate as, or stannous octoate, triethylenediamine, or is, or is N- ethyl morpholine, or of N, N'- dimethyl-cyclohexylamine, or as diethylene triamine; catalyst in an amount of from 0.01% to 2% of the entire reaction system; (3) the above-prepared side chain contains an acrylate copolymer a and reactant B composed of two hydroxyl groups reacting prepared the solvent fluorinated acrylate copolymer; condensation temperature of 50 ~ 100 ℃, for 2 to 6 hours.
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