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Preparing for all-fluoroalkyl compound containing active end group and use thereof

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Publication number
CN101024743A
CN101024743A CN 200710090028 CN200710090028A CN101024743A CN 101024743 A CN101024743 A CN 101024743A CN 200710090028 CN200710090028 CN 200710090028 CN 200710090028 A CN200710090028 A CN 200710090028A CN 101024743 A CN101024743 A CN 101024743A
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group
anti
used
compound
perfluoroalkyl
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CN 200710090028
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Chinese (zh)
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CN100567233C (en )
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王贤明
杨凯
张燕
卢伟
阎永江
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海洋化工研究院
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Abstract

The invention relates to a perfluoroalkyl group compound that is compounded from perfluoroalkyl group monomer A with hydroxyl and diisocyanate B under the existing of solvent and catalyst. It could be used on the hull of ship and submarine to have anti-drag and antifouling effect, used on the engine of craft to have waterproofing and anti-icing effect, etc.

Description

含活性端基的全氟烷基化合物的制备及其应用 Preparation and application of perfluoroalkyl end groups containing an active compound of

技术领域 FIELD

本发明涉及含氟化合物或组合物,其含有至少一个含氟可重复单元和至少一个含氟端基。 The present invention relates to a fluorine-containing compounds or compositions, containing at least one fluorine-containing repeatable unit and at least one fluorine-containing terminal group. 本发明同时涉及涂料等方面,其含氟化物组合物可作为涂料组分使用或作为其他活性添加剂使用。 The present invention also relates to coatings aspect, fluoride containing compositions which can be used as a coating or as a component of other active additives. 添加或使用该氟化物组合物的制品可具有较低的表面能。 Or adding the product of the fluorochemical composition may have a lower surface energy.

背景技术 Background technique

涂料或活性添加剂主要作用于各种物体表面,起装饰或保护作用。 Major role in a variety of coating or the surface-active additive, protective or decorative effect. 由于长期暴露在外非常容易受到水、灰尘、油污等的污染。 Due to the long exposed easily contaminated water, dust, oil and the like. 减少污物在物体表面存留或使物体表面更易清洁,就需要涂层表面具有较低的表面张力,提高物体表面的自洁性。 Or to reduce the surface dirt remaining on the surface easier to clean, it is necessary coating surface has low surface tension, improve self-cleaning surface of an object.

在高分子及高分子基材上使用某些氟化物或含氟的组合物,使其具有疏水疏油性等性能,已有广泛的应用。 Use of certain fluoride or fluorine-containing polymer and a polymer base in the composition, so as to have a hydrophobic oil repellency and other properties, has been widely used. 如Banks主编的《有机氟化学品及其工业应用》中所提到的。 The editor of the Banks "organic fluorine chemicals and industrial application" mentioned. Philips,RW和Dettre,RH在1976年就已公开了氟化物片段(J.Col.and Interface Sci.,56(2),1976),根据所公开的资料显示,基本上任何含有CnF2n+1(n≥6)的聚合物、化合物和低聚物都拥有疏水疏油性能。 Philips, RW and Dettre, RH 1976 already discloses a fluoride fragment (J.Col.and Interface Sci., 56 (2), 1976), display based on the information disclosed, containing substantially no CnF2n + 1 ( n≥6) polymer compound and the hydrophobic oligomer has oleophobic properties. 但当n≥8时,某些氟化物或含氟单体呈现固体蜡状性质,较难溶解,利用困难。 But when n≥8, fluoride or fluorine-containing monomer exhibit certain waxy solid nature, less soluble, difficult to use.

发明内容 SUMMARY

本发明的目的之一是提供一种含活性端基的全氟烷基化合物,以及制备方法。 One object of the present invention is to provide a reactive end group-containing perfluoroalkyl compounds, and methods for preparing.

本发明的目的之二是提供包含所述的含活性端基的全氟烷基化合物的低表面能涂料组合物。 Another object of the present invention is to provide a comprising the two active end-containing low surface energy perfluoroalkyl compound coating composition.

本发明的含活性端基的全氟烷基化合物,是含有羟基的全氟烷基单体A与二异氰酸酯B在溶剂和催化剂存在下合成的。 Containing reactive end groups of perfluoroalkyl compound of the present invention is a perfluoroalkyl group containing hydroxyl monomers A and B diisocyanate synthesized in the presence of a solvent and a catalyst.

所述的A:是具有下面结构的含羟基的全氟烷基单体:CnF2n+1CH2CH2OH式中n=6,8,10;所述的B:是具有下面通式结构的二异氰酸酯:OCN-R-NCO式中R为脂肪、脂环或芳香族的二价基团,包括不少于两个碳的脂肪基团、脂环族基团、单环芳香族基团、稠环芳香族基团以及其他连接基团所连接的非稠环芳香族基团。 According to A: having the following structure is a hydroxyl-containing monomer is a perfluoroalkyl group: CnF2n + 1CH2CH2OH where n = 6,8,10; said B: having the following general structure diisocyanate: OCN- R-NCO wherein R is an aliphatic, alicyclic or aromatic divalent radical, including not less than two carbons aliphatic groups, cycloaliphatic groups, monocyclic aromatic groups, fused ring aromatic group groups, and non-fused cyclic aromatic groups other linking groups are attached.

所述的A和B满足:羟基与异氰酸根比为1∶4;A和B占总投料量的75~90%重量百分比。 The A and B satisfy: hydroxyl and isocyanato ratio 1:4; A and B, the total of 75 to 90 weight percent of the feeding amount.

所述的二异氰酸酯可以是单一的,也可以是由二种或多种二异氰酸酯组成的混合物。 The diisocyanate may be a single, or a mixture of two or more diisocyanates thereof.

所述的二异氰酸酯包括:己二异氰酸酯、二甲苯撑二异氰酸酯、异佛尔酮二异氰酸酯、2,2,4-三甲基己烷撑二异氰酸酯、苯二甲撑二异氰酸酯、甲苯环己撑二异氰酸酯、4,4`-双(异氰酸酯环己基)甲烷、2,4`-甲苯二异氰酸酯、4,4`-二苯甲烷二异氰酸酯、3,3`-二甲基二苯基甲烷-4,4`-二异氰酸酯、1,5-萘二异氰酸酯、多次甲基多苯基多异氰酸酯。 Said diisocyanate comprising: hexamethylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, 2,2,4-trimethyl hexane support diisocyanate, xylylene diisocyanate, toluene cyclohexylene diisocyanate, 4,4'-bis (isocyanate cyclohexyl) methane, 2,4`- tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, diphenyl dimethyl methane 3,3`- -4 , 4`- diisocyanate, 1,5-naphthalene diisocyanate, polymethine polyphenyl polyisocyanate.

所述的溶剂可以是酯类或强极性溶剂,例如乙酸乙酯、乙酸丁酯或N-甲基吡咯烷酮、N,N`-二甲基甲酰胺或N,N`-二甲基乙酰胺。 The solvent can be an ester or strongly polar solvents, such as ethyl acetate, butyl acetate or N- methylpyrrolidone, N, N'-dimethylformamide or N, N'-dimethylacetamide . 最优选是乙酸乙酯或乙酸丁酯中任选一种或两种混合组成的溶剂。 Most preferably ethyl acetate or butyl acetate, optionally, one or two kinds of mixed solvent composed. 用量是总投料量的10-25%重量百分比。 The amount of 10 to 25% by weight of the total feeding amount.

所述的催化剂是二月桂酸二丁基锡或辛酸亚锡中任选一种。 Said catalyst is dibutyl tin dilaurate or stannous octoate Choose one. 用量是总投料量的0.1-3%重量百分比。 The amount of 0.1-3% by weight of the total feeding amount.

所述的含活性端基的全氟烷基化合物按下述方法制备:在氮气或氩气保护下,将本发明所述的二异氰酸酯在搅拌下溶于有机溶剂体系中。 The reactive end groups containing perfluoroalkyl compound was prepared as follows: Under a nitrogen or argon blanket, the diisocyanates of the present invention is dissolved in an organic solvent system under stirring. 待完全溶解后,加入催化剂。 After complete dissolution, the catalyst is added. 在0~25℃下,分批加入含羟基的全氟烷基单体。 At 0 ~ 25 ℃, perfluoroalkyl added portionwise hydroxyl group-containing monomer. 反应2-8小时,最佳时间为2-6小时;再在60-80℃下,反应2-10小时,最佳时间为4-8小时。 The reaction 2-8 hours, the optimal time is 2-6 hours; then at 60-80 deg.] C, reaction was 10 hours, the optimum time is 4-8 hours. 冷却至室温,得到透明的低粘度溶液。 It cooled to room temperature to give a clear solution of low viscosity.

所述的低表面能涂料组合物包括:含活性端基的全氟烷基化合物、至少一种含羟基的丙烯酸树脂(市售产品)、适量的稀释剂、颜填料等。 The low surface energy coating composition comprising: a reactive end group-containing perfluoroalkyl compound, at least one hydroxyl group-containing acrylic resin (commercial product), an appropriate amount of diluents, fillers and the like.

所述的含活性端基的全氟烷基化合物与含羟基的丙烯酸树脂的比例是1∶5~1∶15。 Ratio of perfluoroalkyl-containing compound and the acrylic resin containing the hydroxyl group-reactive end groups is 1/5 to 1:15.

所述的稀释剂包括甲苯、二甲苯、丙酮、丁酮中任选一种或两种混合组成的溶剂。 The diluents include toluene, xylene, acetone, butanone, optionally, one or two kinds of mixed solvent composed. 用量是总投料量的10-50%重量百分比。 The amount of from 10 to 50% by weight of the total feeding amount.

所述的颜填料是金红石型钛白粉、滑石粉、云母、漂珠、重质碳酸钙、氧化铁红、氧化锌中任选一种或两种,以及两种以上混合组成。 The pigment is rutile titanium dioxide, talc, mica, floating beads, calcium carbonate, red iron oxide, zinc oxide, and optionally one or two, and of two or more components.

所述的低表面能涂料组合物制备方法:上述物质按照常规制漆方法混合配制,采用刷涂或喷涂等工艺,得到光滑平整的低表面能涂层。 The preparation of low surface energy coating composition: The above materials are mixed according to a conventional paints formulated using spraying or brushing, etc., to obtain a smooth low surface energy coating.

所得到的含活性端基的全氟烷基化合物具有下列综合性能:(1)优良的溶解性能,可溶于常见的有机溶剂和极性溶剂。 The resulting reactive end group-containing compounds having a perfluoroalkyl overall performance the following: (1) excellent solubility, soluble in common organic solvents and a polar solvent.

(2)优良的反应性能,化合物一端为全氟烷基结构,另一端为异氰酸酯结构,可保证化合物具有一个活性反应端基。 (2) excellent in reactivity, one end of an isocyanate compound structure is a perfluoroalkyl group structure, the other end, can ensure a compound having an active group reactive end.

(3)优越的低表面能,本化合物一端基为全氟链段,该产物与树脂配合后,形成微观“梳”状结构,全氟链段为“梳齿”,可提供优异的疏水性能,水接触角在100°以上。 (3) an excellent low surface energy, the present compound is a perfluorinated end group segment, the resin mixed with the product to form a microscopic "comb" like structure, perfluoro segment of "comb teeth", can provide excellent hydrophobic properties , water contact angle above 100 °.

(4)优越的持久性,该产物与树脂固化后,全氟链段以化学键形式接入树脂,形成支链,可经溶剂擦拭600次后,水接触角基本不变。 (4) excellent durability, the resin is cured and the product is, after the access segment perfluoro resin is chemically form, branched form, the wiper 600 may be a solvent-water contact angle substantially constant.

本发明得到的含活性端基的全氟烷基化合物与含羟基的丙烯酸树脂配合,可得到具有自清洁、减阻等性能涂层。 The present invention is obtained containing reactive end groups and perfluoroalkyl compounds with hydroxyl group-containing acrylic resin, to obtain self-cleaning, and other drag reduction properties of the coating. 在国防、工农业生产和日常生活中有着广泛的应用前景。 It has a wide range of applications in defense, industrial and agricultural production and daily life. 如建筑外墙涂料、减阻防污涂料、防雾防冰涂料等方面有重要的潜在应用。 Aspects such as exterior house paint, drag-reducing coatings, anti-fog anti-ice coating has important potential applications. 此技术用于室外天线上,可防止积雪沉积从而保证通信质量;用在船、潜艇的外壳上,不但减少水的阻力,提高航行速度,还能达到防污的功效;用在石油输送管道内壁能防止黏附、堵塞,减少损耗;用于航空飞行器发动机上,起到防水防冰效果;用在纺织品上,还能制成防水、防污的服装等。 This technique for outdoor antenna, the deposition can be prevented to ensure the communication quality of the snow; used in the ship's hull, submarine, not only to reduce the water resistance, increase the speed of navigation, but also to achieve the effect of the antifouling; in petroleum pipeline the inner wall can be prevented from adhesion, clogging, to reduce the loss; for aviation aircraft engines, anti-icing functions waterproof effect; used in textiles, but also made of water, pollution of clothing.

附图说明 BRIEF DESCRIPTION

图1是实施例3低表面能涂层的表面能水接触角测量效果图。 1 FIG. 3 is a surface of a low surface energy coating embodiment embodiment can effect the water contact angle measurements FIG.

图2是实施例4低表面能涂层的表面能水接触角测量效果图。 FIG 2 is capable of measuring the water contact angle of the surface renderings Example 4 low surface energy coating embodiment.

图3是实施例5低表面能涂层的表面能水接触角测量效果图。 3 embodiment is a low surface energy surface coating 5 embodiment can effect the water contact angle measurements FIG.

图4是实施例6低表面能涂层的表面能水接触角测量效果图。 FIG 4 is capable of measuring the water contact angle of the surface of FIG. 6 Effect embodiment the low surface energy coating embodiment.

具体实施方式 detailed description

下面列举的实施例对本发明进一步说明,但本发明不只限于这些实施例。 The following examples further include explanation of the invention, but the present invention is not limited to these embodiments.

实施例1:含活性端基的全氟烷基化合物的制备将60份甲苯二异氰酸脂溶解于140份的乙酸乙酯中,加入0.5份二月桂酸二丁基锡,然后加入800份全氟烷基乙醇。 Example 1: Preparation of perfluoroalkyl end groups containing an active compound of 60 parts of toluene diisocyanate were dissolved in 140 parts of ethyl acetate was added 0.5 parts of dibutyl tin dilaurate, followed by addition of 800 parts of perfluoro alkyl alcohol. 反应在0-25℃下搅拌反应4小时,再在60-80℃下搅拌8小时。 The reaction was stirred for 4 hours at 0-25 ℃, stirred at 60-80 ℃ 8 hours. 反应物冷却至室温后,得到1000份均相液体。 After the reaction was cooled to room temperature to obtain 1000 parts of a homogeneous liquid.

实施例2:含活性端基的全氟烷基化合物的制备将40份二苯甲烷二异氰酸脂溶解于200份的乙酸乙酯中,加入0.5份二月桂酸二丁基锡,然后加入700份全氟烷基乙醇。 Example 2: Preparation of perfluoroalkyl end groups containing an active compound of 40 parts of diphenylmethane diisocyanate were dissolved in 200 parts of ethyl acetate was added 0.5 parts of dibutyl tin dilaurate, followed by addition of 700 parts of perfluoroalkylethanols. 反应在0-25℃下搅拌反应2小时,再在60-80℃下搅拌6小时。 The reaction was stirred for 2 hours at 0-25 ℃, stirred at 60-80 ℃ 6 hours. 反应物冷却至室温后,得到1000份均相液体。 After the reaction was cooled to room temperature to obtain 1000 parts of a homogeneous liquid.

实施例3:低表面能涂层的制备将实施例1产物与丙烯酸树脂(牌号BS2150)配合,按下述步骤制备:A组分:将100份BS2150丙烯酸树脂、60份颜填料(30份氧化铁红、20份氧化锌和10份重质碳酸钙)和60份稀释剂(50份二甲苯和10份丙酮混合)加入到容器中,在2000rpm转速下高速分散2小时,当细度为30~50μm时,用100目滤网过滤,计量包装;B组分为实施例1的产物;将A、B组分按重量比为5∶1均匀混合后,采用喷涂工艺施工,室温固化,固化时间10小时以上,得到光滑平整的低表面能涂层。 Example 3: Preparation of low surface energy coating in Example 1 and the product of the acrylic resin (Grade BS2150) complex, prepared by the following steps: A component: 100 parts of BS2150 acrylic resin, 60 parts of pigment (30 parts by oxidation red iron oxide, zinc oxide and 20 parts of calcium carbonate 10 parts by weight) and 60 parts of diluent (50 parts of xylene and 10 parts of acetone and mixed) was added to the vessel, a high speed disperser at a speed of 2000rpm for 2 hours when a fineness of 30 when ~ 50 m, with a 100 mesh screen filter, weighing and packaging; B component of the product of Example 1 embodiment; after a, B components in a weight ratio of 5:1 uniformly mixed, spraying construction process, room temperature curing, curing more than 10 hours, to obtain a smooth low surface energy coating. 对涂层表面能水接触角测量达到109°。 Coating the surface of the water contact angle measurements can reach 109 °. 效果见图1。 The effect shown in Figure 1. 该涂料可应用于船舶减阻防污的需要,具有良好的效果。 The coating may be applied to the ship require anti-fouling drag reduction, with good results.

实施例4:低表面能涂层的制备将实施例1产物与丙烯酸树脂(牌号BS9960)配合,按下述步骤制备:A组分:将100份BS9960丙烯酸树脂、70份颜填料(金红石型钛白粉10份氧化铁红、50份漂珠和10份云母)和60份稀释剂(50份甲苯和10份丁酮混合)加入到容器中,在2000rpm转速下高速分散3小时,当细度为30~50μm时,用100目滤网过滤,计量包装;B组分为实施例1产物; Example 4: Preparation of low surface energy coating in Example 1 and the product of the acrylic resin (Grade BS9960) complex, prepared by the following steps: A component: 100 parts of BS9960 acrylic resin, 70 parts pigment (Jin Hongshi type titanium White red iron oxide 10 parts, 50 parts and 10 parts of mica floating beads) and 60 parts of diluent (50 parts toluene 10 parts methyl ethyl ketone and mixed) was added to the vessel, a high speed disperser at a speed of 2000rpm for 3 hours when the fineness when 30 to 50 m, with a 100 mesh screen filter, weighing and packaging; B component product of Example 1;

将A、B组分按重量比8∶1均匀混合后,采用喷涂工艺施工,室温固化,固化时间10小时以上,得到光滑平整的低表面能涂层,对涂层表面能水接触角测量达到107°;效果见图2。 The A, B components after 8:1 weight ratio were uniformly mixed, spraying construction process, curing temperature, curing time over 10 hours to obtain a smooth low surface energy coating, the coating surface can reach the water contact angle measurements 107 °; Figure 2 results. 该涂料可应用于航空飞行器上,起到防水防冰的效果。 The coating can be applied on aerial vehicles, play a waterproof anti-icing effect.

实施例5:低表面能涂层的制备将实施例2产物与丙烯酸树脂(牌号BS960)配合,按下述步骤制备:A组分:将100份BS960丙烯酸树脂、70份颜填料(10份金红石型钛白粉、25份滑石粉、25份云母和10份重质碳酸钙)和60份稀释剂(50份二甲苯和10份丙酮混合)加入到容器中,在2000rpm转速下高速分散3小时,当细度为30~50μm时,用100目滤网过滤,计量包装;B组分为实施例2的产物;将A、B组分按重量比11∶1均匀混合后,采用刷涂工艺施工,室温固化,固化时间12小时以上,得到光滑平整的低表面能涂层,对涂层表面能水接触角测量达到105°。 Example 5: Preparation of low surface energy coating of the product of Example 2 and the acrylic resin (Grade BS960) complex, prepared by the following steps: A component: 100 parts of BS960 acrylic resin, 70 parts of pigment (10 parts Jin Hongshi type titanium white, 25 parts of talc, 25 parts mica, calcium carbonate and 10 parts by weight) and 60 parts of diluent (50 parts of xylene and 10 parts of acetone and mixed) was added to the vessel, a high speed disperser at a speed of 2000rpm for 3 hours when the fineness of time from 30 to 50 m, with a 100 mesh screen filter, weighing and packaging; B component of the product of Example 2; and a, B component of the 11 to 1 ratio by weight were uniformly mixed, applied by brush construction process , room temperature curing, the curing time is more than 12 hours to obtain a smooth low surface energy coating, the coating surface can be measured the water contact angle reaches 105 °. 效果见图3。 The effect shown in Figure 3. 该涂料可应用于室外天线罩上,可防止积雪堆积,从而保证通信质量。 The coating may be applied to an outdoor antenna cover to prevent accumulation of snow, so as to ensure the communication quality.

实施例6:低表面能涂层的制备将实施例2的产物与丙烯酸树脂(牌号BS985)配合,按下述步骤制备: Example 6: Preparation of low surface energy coating embodiment of the product with the acrylic resin (Grade BS985) Example 2 complex was prepared by the following steps:

A组分:将100份BS985丙烯酸树脂、75份颜填料(25份滑石粉、25份云母和25份重质碳酸钙)和60份稀释剂(50份甲苯和10份丁酮混合)加入到容器中,在2000rpm转速下高速分散4小时,当细度为30~50μm时,用100目滤网过滤,计量包装;B组分:为实施例2的产物;将A、B组分按重量比10∶1均匀混合后,采用刷涂工艺施工,室温固化,固化时间24小时以上,得到光滑平整的低表面能涂层。 Component A: 100 parts of BS985 acrylic resin, 75 parts of pigment (25 parts of talc, 25 parts mica and 25 parts by weight of calcium carbonate) and 60 parts of diluent (50 parts toluene 10 parts methyl ethyl ketone and mixed) was added to vessel, a high speed disperser at a speed of 2000rpm for 4 hours when a fineness of 30 to 50 m when, with a 100 mesh screen filter, weighing and packaging; component B: the product of Example 2; and a, B components by weight after uniformly mixing ratio 10:1, by brush construction process, room temperature curing, the curing over 24 hours, to obtain a smooth low surface energy coating. 对涂层表面能水接触角测量达到100°;效果见图4。 Coating the surface of the water contact angle measurements can reach 100 °; Figure 4 results. 该涂料可应用于建筑外墙涂料上,防涂鸦、保持建筑的清洁和美观。 The coating may be applied on the building exterior coatings, anti-graffiti, kept clean and aesthetic construction.

实施例7:对实施例4、5中的涂层进行耐擦拭实验,经有机溶剂600次擦拭后,水接触角不变。 Example 7: Example of embodiment 4, the coating for scratch test, after 600 wipes the organic solvent, the water contact angle change.

Claims (9)

1.一种含活性端基的全氟烷基化合物,其特征在于,由含有羟基的全氟烷基单体A与二异氰酸酯β在溶剂和催化剂存在下合成;所述的A:是具有下面结构的含羟基的全氟烷基单体:CnF2n+1CH2CH2OH式中n=6,8,10;所述的B:是具有下面通式结构的二异氰酸酯:OCN-R-NCO式中R为脂肪、脂环或芳香族的二价基团,包括不少于两个碳的脂肪基团、脂环族基团、单环芳香族基团、稠环芳香族基团以及其他链接基团所连接的非稠环芳香族基团;所述的A和B满足:羟基与异氰酸根比为1∶4;A和B占总投料量的75~90%重量百分比。 An active compound-containing perfluoroalkyl end groups, characterized in that the hydroxyl group-containing monomer is a perfluoroalkyl group with a diisocyanate A β in the presence of a solvent and a synthesis catalyst; said A: having the following perfluoroalkyl group-containing monomer structure hydroxyl group: CnF2n + 1CH2CH2OH where n = 6,8,10; said B: having the following general structure diisocyanate: OCN-R-NCO wherein R is a fatty , alicyclic or aromatic divalent radical, including not less than two carbons aliphatic groups, cycloaliphatic groups, monocyclic aromatic groups, fused ring aromatic group and other groups are attached links non-condensed polycyclic aromatic group; a and B satisfy the: ratio of hydroxyl groups to isocyanato 1:4; a and B, the total of 75 to 90 weight percent of the feeding amount.
2.根据权利要求1的含活性端基的全氟烷基化合物,其特征在于,所述的二异氰酸酯是一种或几种组合。 The perfluoroalkyl end groups containing an active compound as claimed in claim 1, wherein said diisocyanate is one or more combinations thereof.
3.根据权利要求2的含活性端基的全氟烷基化合物,其特征在于,所述的二异氰酸酯包括:己二异氰酸酯、二甲苯撑二异氰酸酯、异佛尔酮二异氰酸酯、2,2,4-三甲基己烷撑二异氰酸酯、苯二甲撑二异氰酸酯、甲苯环己撑二异氰酸酯、4,4`-双(异氰酸酯环己基)甲烷、2,4`-甲苯二异氰酸酯、4,4`-二苯甲烷二异氰酸酯、3,3`-二甲基二苯基甲烷-4,4`-二异氰酸酯、1,5-萘二异氰酸酯、多次甲基多苯基多异氰酸酯。 3. containing reactive end groups of the perfluoroalkyl compound according to claim 2, characterized in that said diisocyanate comprising: hexamethylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, 2,2, 4- trimethyl hexane diisocyanate support, xylylene diisocyanate, cyclohexylene diisocyanate, toluene diisocyanate, 4,4'-bis (isocyanate cyclohexyl) methane, 2,4`- tolylene diisocyanate, 4,4 '- diphenylmethane diisocyanate, dimethyl 3,3`- -4,4`- diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, polymethine polyphenyl polyisocyanate.
4.根据权利要求1的含活性端基的全氟烷基化合物,其特征在于,所述的溶剂是酯类或强极性溶剂。 The perfluoroalkyl end groups containing an active compound as claimed in claim 1, wherein said solvent is an ester or strongly polar solvents.
5.根据权利要求4的含活性端基的全氟烷基化合物,其特征在于,所述的溶剂是乙酸乙酯、乙酸丁酯或N-甲基吡咯烷酮、N,N`-二甲基甲酰胺或N,N`-二甲基乙酰胺,选择其中一种或几种;用量是总投料量的10-25%重量百分比。 According to claim-containing reactive end groups of the perfluoroalkyl compound 4, wherein said solvent is ethyl acetate, butyl acetate or N- methylpyrrolidone, N, N'-dimethylformamide amide or N, N'-dimethylacetamide, wherein the selected one or more; an amount from 10 to 25% by weight of the total feeding amount.
6.根据权利要求1的含活性端基的全氟烷基化合物,其特征在于,所述的催化剂是二月桂酸二丁基锡或辛酸亚锡中任选一种,用量是总投料量的0.1-3%重量百分比。 The perfluoroalkyl end groups containing an active compound as claimed in claim 1, wherein said catalyst is dibutyl tin dilaurate or stannous octoate optionally one of the feeding amount is the total amount of 0.1 to 3% by weight.
7.根据权利要求1的含活性端基的全氟烷基化合物,其特征在于,制备方法是:在惰性气体保护下,将二异氰酸酯在搅拌下溶于有机溶剂体系中,溶解后加入催化剂,分批加入含羟基的全氟烷基单体,反应2-10小时,冷却至室温,得到透明的低粘度溶液。 7. perfluoroalkyl end groups containing an active compound according to claim 1, wherein the preparation method is: under the protection of inert gas, the diisocyanate is dissolved in an organic solvent system under stirring, the catalyst was added and dissolved, was added portionwise hydroxyl group-containing monomer is a perfluoroalkyl group, the reaction 10 hours, cooled to room temperature to give a clear solution of low viscosity.
8.一种低表面能涂料组合物,其特征在于,包括如权利要求1的含活性端基的全氟烷基化合物、至少一种含羟基的丙烯酸树脂、适量的稀释剂、颜填料。 A low surface energy coating composition comprising a perfluoroalkyl group-containing compound reactive end groups of the appropriate amount of a diluent, fillers as claimed in claim acrylic resin containing at least one hydroxyl group.
9.根据权利要求8的低表面能涂料组合物,其特征在于,所述的含活性端基的全氟烷基化合物与含羟基的丙烯酸树脂的比例是1∶5~1∶15。 According to claim 8, wherein the low surface energy coating composition, wherein the ratio of the reactive end groups containing a perfluoroalkyl compound and a hydroxyl-containing acrylic resin is 1/5 to 1:15.
CN 200710090028 2007-03-26 2007-03-26 Preparing for all-fluoroalkyl compound containing active end group and application thereof CN100567233C (en)

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CN102352558A (en) * 2011-06-10 2012-02-15 上海汇宇精细化工有限公司 Stain-resistant leather treatment agent and preparation method
CN102352558B (en) 2011-06-10 2013-06-05 上海汇宇精细化工有限公司 Stain-resistant leather treatment agent and preparation method
CN102876150A (en) * 2011-07-14 2013-01-16 上海大通高科技材料有限责任公司 High weather resistant anti-pasting and doodling-proof water-based paint and preparing method thereof
CN102676034A (en) * 2012-04-24 2012-09-19 三元控股集团有限公司 Anti-doodling coating for outdoor facility and preparation method of anti-doodling coating
CN102676034B (en) * 2012-04-24 2015-08-19 三元控股集团有限公司 Anti-graffiti coating and preparation method for outdoor facilities
US9574089B2 (en) 2012-10-04 2017-02-21 Basf Coatings Gmbh Fluorine-containing nonaqueous coating material composition, coating methods, and the use of the coating material composition
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