CN114605628B - 一种高疏水耐磨型涂层防污剂 - Google Patents
一种高疏水耐磨型涂层防污剂 Download PDFInfo
- Publication number
- CN114605628B CN114605628B CN202210085428.5A CN202210085428A CN114605628B CN 114605628 B CN114605628 B CN 114605628B CN 202210085428 A CN202210085428 A CN 202210085428A CN 114605628 B CN114605628 B CN 114605628B
- Authority
- CN
- China
- Prior art keywords
- compound
- coating
- modified
- allyl
- perfluoropolyether
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000011248 coating agent Substances 0.000 title claims abstract description 48
- 238000000576 coating method Methods 0.000 title claims abstract description 48
- 239000002519 antifouling agent Substances 0.000 title claims abstract description 16
- 239000010702 perfluoropolyether Substances 0.000 claims abstract description 45
- 229910000077 silane Inorganic materials 0.000 claims abstract description 16
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000002904 solvent Substances 0.000 claims abstract description 9
- 150000001875 compounds Chemical class 0.000 claims description 33
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- -1 perfluoroalkyl iodide compound Chemical class 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 238000005299 abrasion Methods 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 5
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 5
- BHELZAPQIKSEDF-UHFFFAOYSA-N allyl bromide Chemical compound BrCC=C BHELZAPQIKSEDF-UHFFFAOYSA-N 0.000 claims description 4
- 238000006459 hydrosilylation reaction Methods 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 4
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 3
- 238000006555 catalytic reaction Methods 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 238000002390 rotary evaporation Methods 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 claims description 2
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 claims description 2
- 239000004721 Polyphenylene oxide Substances 0.000 claims 3
- 229920000570 polyether Polymers 0.000 claims 3
- 150000004292 cyclic ethers Chemical class 0.000 claims 2
- 125000000217 alkyl group Chemical group 0.000 claims 1
- 230000002209 hydrophobic effect Effects 0.000 claims 1
- 238000005406 washing Methods 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 22
- 230000003373 anti-fouling effect Effects 0.000 abstract description 16
- 238000004140 cleaning Methods 0.000 abstract description 10
- 239000000047 product Substances 0.000 description 10
- 239000000203 mixture Substances 0.000 description 9
- 239000011521 glass Substances 0.000 description 8
- 239000000758 substrate Substances 0.000 description 8
- 229910000831 Steel Inorganic materials 0.000 description 7
- 239000010959 steel Substances 0.000 description 7
- 210000002268 wool Anatomy 0.000 description 7
- 230000003301 hydrolyzing effect Effects 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- XPBBUZJBQWWFFJ-UHFFFAOYSA-N fluorosilane Chemical compound [SiH3]F XPBBUZJBQWWFFJ-UHFFFAOYSA-N 0.000 description 5
- 238000005507 spraying Methods 0.000 description 5
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 150000004756 silanes Chemical class 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- 229920001774 Perfluoroether Polymers 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 229920002521 macromolecule Polymers 0.000 description 3
- 238000009832 plasma treatment Methods 0.000 description 3
- YXRKNIZYMIXSAD-UHFFFAOYSA-N 1,6-diisocyanatohexane Chemical compound O=C=NCCCCCCN=C=O.O=C=NCCCCCCN=C=O.O=C=NCCCCCCN=C=O YXRKNIZYMIXSAD-UHFFFAOYSA-N 0.000 description 2
- SFHYNDMGZXWXBU-LIMNOBDPSA-N 6-amino-2-[[(e)-(3-formylphenyl)methylideneamino]carbamoylamino]-1,3-dioxobenzo[de]isoquinoline-5,8-disulfonic acid Chemical compound O=C1C(C2=3)=CC(S(O)(=O)=O)=CC=3C(N)=C(S(O)(=O)=O)C=C2C(=O)N1NC(=O)N\N=C\C1=CC=CC(C=O)=C1 SFHYNDMGZXWXBU-LIMNOBDPSA-N 0.000 description 2
- 239000006116 anti-fingerprint coating Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 239000013638 trimer Substances 0.000 description 2
- IQSVJXQJXBCPBX-UHFFFAOYSA-N 1,1,2,2,3,3,4,4,5,5,6,6,7,7,7-pentadecafluoroheptoxy-(1,1,2,2,2-pentafluoroethyl)-bis(trifluoromethoxy)silane Chemical compound FC(F)(F)O[Si](OC(F)(F)F)(C(F)(F)C(F)(F)F)OC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F IQSVJXQJXBCPBX-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 125000000262 haloalkenyl group Chemical group 0.000 description 1
- 230000033444 hydroxylation Effects 0.000 description 1
- 238000005805 hydroxylation reaction Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 239000002335 surface treatment layer Substances 0.000 description 1
- 210000004243 sweat Anatomy 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/338—Polymers modified by chemical after-treatment with inorganic and organic compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/336—Polymers modified by chemical after-treatment with organic compounds containing silicon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/337—Polymers modified by chemical after-treatment with organic compounds containing other elements
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D171/00—Coating compositions based on polyethers obtained by reactions forming an ether link in the main chain; Coating compositions based on derivatives of such polymers
- C09D171/02—Polyalkylene oxides
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Paints Or Removers (AREA)
- Polyethers (AREA)
- Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
Abstract
本发明公开了一种高疏水耐磨型涂层防污剂,按重量份计,由75~80份氢氟醚类溶剂和20~25份可水解固化的改性全氟聚醚硅烷组成,所述的可水解固化的改性全氟聚醚硅烷的结构式为:Cf‑O‑Rf‑E。本发明的高疏水耐磨型涂层防污剂相比现有的涂层防污剂,涂层初始水接触角更高,防污性能更强,且涂层水滴滑动角低,微弱的倾斜下,水滴即可带动污垢自动滑落,实现涂层的自清洁功能,带来更好的用户体验感。
Description
技术领域
本发明属于表面与界面领域,具体涉及一种高疏水耐磨型涂层防污剂。
背景技术
涂层防污剂通常是一种改性全氟聚醚硅烷,以20wt%浓度溶解在氢氟醚、氟碳类溶剂中,通过喷涂、旋涂等成膜工艺应用于玻璃基材表面。其涂层具有防污、抗油、耐刮伤、耐磨等性能,可简单地帮助去除屏幕汗液、皮肤油脂以及化妆品等污渍,并带来良好的滑爽性,从而大幅度提升用户体验感。目前市面上的抗指纹剂厂家诸如大金、信越、巨化、松井新材、优尔新材等,其产品钢丝绒耐磨次数均能达到10000次以上,具有良好的耐磨稳定性。Z型全氟聚醚具有良好的润滑性和柔顺性,因此目前国内外厂家均采用Z型全氟聚醚作为含氟链段进行改性制备防污涂层,由于其醚键结构特性,导致涂层接触角普遍在111°~115°之间,水滴、油污在屏幕表面的滑动角较大,需通过纸巾或无尘布擦拭去除,清洁较为繁琐,长时间擦拭更是会导致屏幕刮伤现象。
如CN113454163A公开了能够对基材的表面赋予优异的拒水拒油性,并且能够形成拒水拒油性的耐摩擦性和耐候性优异的表面层的含氟醚组合物和包含该含氟醚组合物的涂布液,涂层初始接触角为114°。
又如CN106432686公开了一种新型全氟聚醚烷氧基硅烷化合物及其合成方法,其合成方法为:端羟基全氟聚醚(PFPE)、3-(2-氨基乙基)氨基丙基三甲氧基硅烷、3-(2,3-环氧丙氧)丙基三甲氧基硅烷(KH560)、HDI三聚体按摩尔比1:2:2:1反应,反应过程中采用一定量的溶剂稀释混合端羟基全氟聚醚、3-(2-氨基乙基)氨基丙基三甲氧基硅烷后再滴加入HDI三聚体,一定温度下反应6小时后,再滴加KH560,一定温度下再反应6小时后减压去除溶剂即得全氟聚醚烷氧基硅烷化合物。
又如CN105778080A公开了一种全氟聚醚改性硅烷化合物及包含其的表面处理组合物和薄膜,所述的表面处理组合物包含其总重量的0.1%-20%全氟聚醚改性硅烷化合物和80%-99.9%的溶剂,所述的薄膜是涂布所述的表面处理组合物获得的薄膜。
以上现有技术均是以全氟聚醚衍生硅氧烷作为主剂,其涂层具有一定的耐磨性能,但涂层接触角最高均不超过120°,无法实现涂层表面的自清洁功能。
发明内容
本发明针对现有技术的缺陷,提供一种具有超强的防水、防污综合性能,可实现表面的水等污染物自清洁功能的高疏水耐磨型涂层防污剂。
为解决以上技术问题,本发明采用的技术方案为:一种高疏水耐磨型涂层防污剂,按重量份计,由75~80份氢氟醚类溶剂和20~25份可水解固化的改性全氟聚醚硅烷组成,所述的可水解固化的改性全氟聚醚硅烷的结构式为:
Cf-O-Rf-E
所述的Cf的结构式为CF3-(CF2)a-,其中a为2~9;
所述的Rf的结构式为-CH2-(CF2O)n-(CF2CF2O)S-CH2-,其中n为20~30,s为20~30,且n/s的比值为0.9~1。
优选的,所述的E的结构式选自以下结构式中的一种:
-O-(CH2)3-Si(OCH3)3、-O-(CH2)3-Si(OC2H5)3、
优选的,所述的可水解固化的改性全氟聚醚硅烷选自具有以下结构的化合物中的至少一种:
CF3CF2CF2-O-CH2-(CF2O)20-(CF2CF2O)20-CH2-OCH2CH2CH2Si(OCH3)3
CF3CF2CF2CF2CF2-O-CH2-(CF2O)25-(CF2CF2O)25-CH2-OCH2CH2CH2Si(OCH3)3
CF3-(CF2)9-O-CH2-(CF2O)30-(CF2CF2O)30-CH2-OCH2CH2CH2Si(OCH2CH3)3
优选的,所述的氢氟醚类溶剂为HFE7200、HFE347、六氟丙烯三聚体和全氟环醚中的至少一种。
本发明通过对Z型全氟聚醚分子链的改性,引入刚性直链型氟硅烷短链结构,并修饰上可水解型官能团制备两嵌段兼具柔性和刚性的全氟聚醚改性硅烷。刚性氟硅烷部分,表面能较低,当处于两相环境中趋向于向空气中定向排列,导致涂层最外层形成致密的纳米级薄膜,涂层初始水接触角较高,达到125~130.5°,水滴滑动角仅为2.5~4°,微弱的倾斜即可实现涂层的自清洁功能。中间全氟聚醚部分赋予涂层良好的柔顺性,可保证持久的耐钢丝绒摩擦和耐橡皮擦摩擦性能。综上所述,该全氟聚醚改性硅烷的结构设计,其制备的涂层可进一步提升用户体验感,满足高端触摸屏、户外镜头等领域的使用。
本发明的含有可水解固化的改性全氟聚醚硅烷中的Cf的结构式为CF3-(CF2)a-,a为2~9。Cf作为短链型刚性含氟链段,-CF3的表面能位6mN/m,-CF2O-表面能则达到18.0mN/m,由于端基低表面能特性,倾向于在界面处定向排列,形成致密的含氟涂层,提高了涂层的防水防油性能。
本发明的含有可水解固化的改性全氟聚醚硅烷中的Rf的结构式为-CH2-(CF2O)n-(CF2CF2O)S-CH2-,其中n为20~30,s为20~30,且n/s的比值为0.9~1。Rf中的氟醚键结构提供了分子链较好的柔顺性,能够赋予涂层耐磨性能,且表面爽滑度较高,用户体验感好。
本发明的含有可水解固化的改性全氟聚醚硅烷中的E的结构因具有水解型固化活性基团,与空气中微量水分水解后可与玻璃基底发生固化交联,能够在具有羟基的基地表面提供长期的耐磨稳定性。
本发明的高疏水耐磨型涂层防污剂,由改性全氟聚醚大分子和稀释剂组成,制备的涂层在保留耐磨稳定性的基础上,具有超强的防水、防污综合性能,可实现表面的水等污染物自清洁功能,能够用于高端防水、防污等表界面领域,带来更好的用户体验感。
本发明中的可水解固化的改性全氟聚醚硅烷可通过下述制备方法获得:
(1)全氟烷基改性全氟聚醚化合物的制备:将全氟烷基碘化合物(CF3-(CF2)a-I),用滴液漏斗加入双端全氟聚醚醇(HO-CH2-(CF2O)n-(CF2CF2O)s-CH2-OH(用HO-Rf-OH表示),其中n为20~30,s为20~30)的氟化溶液中。随后加入KOH的乙醇溶液,一定温度下搅拌反应24h,该温度范围控制在40~70℃。反应产物通过全氟环醚与乙醇的混合溶液萃取洗涤二次,随后旋蒸得到全氟烷基改性全氟聚醚化合物待用。双端全氟聚醚醇可采用苏威FLUOROLINK(注册商标)D4000。反应机理如下:
(2)将全氟烷基改性全氟聚醚化合物与烯丙基溴等卤素烯基化合物,在四丁基溴化铵的存在下导入烯丙基双键,得到单端烯丙基封端的改性化合物,反应机理如下:
(3)将单端烯丙基封端的改性化合物通过三甲氧基硅烷类可水解性硅烷进行硅氢加成反应制备具有可水解性基团封端的改性全氟聚醚大分子,反应机理如下:
(4)进一步地将(2)中得到的单端烯丙基封端的改性化合物在K2OsO2(OH)4的催化作用下,进行双键氧化得到双羟基化合物,可制备一端含有两个羟基的改性全氟聚醚化合物,反应机理如下:
(5)进一步地将一端含有两个羟基的改性全氟聚醚化合物通过烯丙基溴等卤素烯基化合物,在四丁基溴化铵的存在下导入烯丙基双键,可制备一端含有两个烯丙基双键的化合物,反应机理如下:
(6)将(4)中得到的一端含有两个烯丙基双键的化合物与三乙氧基硅烷进行硅氢加成反应得到另一种可水解性基团封端的改性全氟聚醚大分子,反应机理如下:
与现有技术相比,本发明具有以下有益效果:
1、涂层自清洁功能好,本发明通过对Z型全氟聚醚分子链的改性,引入了刚性直链型氟硅烷短链结构,刚性氟硅烷部表面能较低,当处于两相环境中趋向于向空气中定向排列,导致涂层最外层形成致密的纳米级薄膜,涂层初始水接触角较高,本发明的高疏水耐磨型涂层防污剂形成的涂层初始水接触角在125°以上,防污性能更强,且涂层水滴滑动角低,滑动角在4.0°以下,微弱的倾斜下,水滴即可带动污垢自动滑落,实现涂层的自清洁功能;
2、耐磨稳定性高,本发明通过对Z型全氟聚醚分子链的改性,修饰上可水解型官能团制备两嵌段兼具柔性和刚性的全氟聚醚改性硅烷,全氟聚醚部分赋予涂层良好的柔顺性,可保证持久的耐钢丝绒摩擦和耐橡皮擦摩擦性能,钢丝绒摩擦14000次后水接触角仍在99.38°以上。在保留耐磨稳定性的基础上,具有超强的防水、防污综合性能。
具体实施方式
以下结合具体实施方式对本发明的内容进行详细说明,但本发明并不限于以下这些实例,在不脱离本发明上述技术思想情况下,根据本领域普通技术知识和惯用手段做出的各种替换和变更,均应包括在本发明的范围内。
实施例中可水解固化的改性全氟聚醚硅烷的结构通式如下:
化合物A1的结构通式为:
CF3CF2CF2-O-CH2-(CF2O)20-(CF2CF2O)20-CH2-OCH2CH2CH2Si(OCH3)3
化合物A2的结构通式为:
CF3CF2CF2CF2CF2-O-CH2-(CF2O)25-(CF2CF2O)25-CH2-OCH2CH2CH2Si(OCH3)3
化合物A3的结构通式为:
CF3-(CF2)9-O-CH2-(CF2O)30-(CF2CF2O)30-CH2-OCH2CH2CH2Si(OCH2CH3)3
化合物B1的结构通式为:
化合物B2的结构通式为:
化合物B3的结构通式为:
实施例1
将200g的化合物A1和800g的HFE7200在室温下物理混合得到防污剂产品。
实施例2
将210g的化合物A2和790g的HFE347在室温下物理混合得到防污剂产品。
实施例3
将220g的化合物A3和780g的六氟丙烯三聚体在室温下物理混合得到防污剂产品。
实施例4
将230g的化合物B1和770g的全氟环醚在室温下物理混合得到防污剂产品。
实施例5
将240g的化合物B2和760g的HFE7200在室温下物理混合得到防污剂产品。
实施例6
将250g的化合物B3和750g的HFE7200在室温下物理混合得到防污剂产品。
对比例1
浙江巨化技术中心有限公司生产的ZAF-0815牌号防污剂。
对比例2
浙江巨化技术中心有限公司生产的全氟己基乙基三甲氧基硅烷。
性能测试:
将玻璃基材超声波清洗后,进行等离子体处理,超声波仪介质为高纯水,处理时间10min,为了保证玻璃基材表面完成硅羟基化,一般等离子体处理2次;将等离子体处理好的玻璃基材放在镀膜机传送带上,开启镀膜机,设定好喷涂高度、走速、臊面宽幅和雾化压力等参数;将实施例1-6和对比例1-2的防污剂产品用HFE7200稀释成质量分数0.1%的溶液后装入喷涂罐,调节好喷涂流量开始喷涂;将喷涂好的玻璃基材放入真空烘箱中,烘烤30min,温度为150℃,得到抗指纹涂层,进行性能测试,结果见表1,其中:
(1)耐摩擦性能和接触角测试
使用接触角测量仪(上海方瑞仪器有限公司,JCY-2型),使用注射针在25℃将体积为4微升的水滴沉积在玻璃片上。水滴与表面之间的角被定义为“水的静态接触角”。首先,在形成玻璃表面修饰上抗指纹涂层后在尚未有任何接触状态下(即磨擦次数为零),所测得之角度为初始角。然后作为磨擦耐久性评价,实施钢丝绒磨擦耐久性评价,具体作法为使用#0000钢丝绒(尺寸5mm×2mm×2mm)与表面处理层接触,在其上施以1kgf的负载,然后在此施加负载接触状态下使钢丝绒140mm/秒的速度往复运动,每往复2000次测定水的静态接触角。当接触角的值低于或接近100°时终止评价。
(2)滑动角测试
使用马萨诸塞州比尔里卡的阿斯图产品公司(AST Products,Inc.,Billerica,MA)生产的VCA Optima XE测角计。通过缓慢倾斜测角计台以允许20μl水滴滑动,从而测量滑动角。滑动角越小,自清洁效果越好。
表1实施例1-6和对比例1-2耐摩擦性能和接触角测试结果
表2实施例1-6和对比例1-2滑动角测试结果
结合表1和表2数据可以发现,用本发明的防污剂制备的涂层初始接触角达到125°以上,且涂层耐磨稳定性好,并具有极低的滑动角,水滴在其表面在微弱的倾斜下即可滑落,可实现自清洁功效,可应用于高端触摸屏、户外镜头、交通信号摄像头等防污领域。
Claims (2)
1.一种高疏水耐磨型涂层防污剂,按重量份计,由75~80份氢氟醚类溶剂和20~25份可水解固化的改性全氟聚醚硅烷组成,其特征在于,可水解固化的改性全氟聚醚硅烷通过下述制备方法获得:
(1)全氟烷基改性全氟聚醚化合物的制备:将全氟烷基碘化合物CF3-(CF2)a-I,用滴液漏斗加入双端全氟聚醚醇的氟化溶液中,随后加入KOH的乙醇溶液,40~70℃温度下搅拌反应24h,反应产物通过全氟环醚与乙醇的混合溶液萃取洗涤二次,随后旋蒸得到全氟烷基改性全氟聚醚化合物待用,双端全氟聚醚醇为苏威FLUOROLINK D4000,其中a为2~9;
(2)将全氟烷基改性全氟聚醚化合物与烯丙基溴,在四丁基溴化铵的存在下导入烯丙基双键,得到单端烯丙基封端的改性化合物;
(3)将单端烯丙基封端的改性化合物通过三甲氧基硅烷进行硅氢加成反应制备可水解固化的改性全氟聚醚硅烷;
(4)或将(2)中得到的单端烯丙基封端的改性化合物在K2OsO2(OH)4的催化作用下,进行双键氧化得到双羟基化合物,制备一端含有两个羟基的改性全氟聚醚化合物;
(5)将一端含有两个羟基的改性全氟聚醚化合物通过烯丙基溴,在四丁基溴化铵的存在下导入烯丙基双键,制备一端含有两个烯丙基双键的化合物;
(6)将(5)中得到的一端含有两个烯丙基双键的化合物与三乙氧基硅烷进行硅氢加成反应得到可水解固化的改性全氟聚醚硅烷。
2.如权利要求1所述的高疏水耐磨型涂层防污剂,其特征在于,所述的氢氟醚类溶剂为HFE7200、HFE347和全氟环醚中的至少一种。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202210085428.5A CN114605628B (zh) | 2022-01-25 | 2022-01-25 | 一种高疏水耐磨型涂层防污剂 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202210085428.5A CN114605628B (zh) | 2022-01-25 | 2022-01-25 | 一种高疏水耐磨型涂层防污剂 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN114605628A CN114605628A (zh) | 2022-06-10 |
CN114605628B true CN114605628B (zh) | 2023-11-03 |
Family
ID=81857544
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202210085428.5A Active CN114605628B (zh) | 2022-01-25 | 2022-01-25 | 一种高疏水耐磨型涂层防污剂 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN114605628B (zh) |
Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2000191668A (ja) * | 1998-12-10 | 2000-07-11 | Toray Ind Inc | 含フッ素化合物、防汚性組成物及び防汚性物品 |
JP2002030019A (ja) * | 1999-08-03 | 2002-01-29 | Mitsubishi Chemicals Corp | 光学活性1,2−二置換−2,3−ジヒドロキシプロパン類の製造法 |
WO2010144398A2 (en) * | 2009-06-10 | 2010-12-16 | 3M Innovative Properties Company | Method for treating hydrocarbon-bearing formations with polyfluoropolyether silanes |
CN105102505A (zh) * | 2013-04-04 | 2015-11-25 | 旭硝子株式会社 | 含氟醚化合物、含氟醚组合物及涂布液,以及具有表面层的基材及其制造方法 |
CN106748670A (zh) * | 2016-12-19 | 2017-05-31 | 衢州氟硅技术研究院 | 一种含醚键氟醇及其制备方法 |
CN107001619A (zh) * | 2014-11-28 | 2017-08-01 | 大金工业株式会社 | 含氟氧亚甲基的全氟聚醚改性体 |
CN107057056A (zh) * | 2017-01-18 | 2017-08-18 | 泉州市思康新材料发展有限公司 | 一种全氟聚醚改性硅烷化合物及包含其的表面处理组合物和薄膜 |
CN107556470A (zh) * | 2017-10-16 | 2018-01-09 | 龙岩思康特种化学品有限公司 | 一种全氟聚醚改性硅烷化合物及其表面处理组合物 |
CN110724256A (zh) * | 2019-10-31 | 2020-01-24 | 中国科学院兰州化学物理研究所 | 一种疏水处理剂及其制备方法和应用、耐磨自清洁玻璃及制备方法 |
CN111662443A (zh) * | 2020-07-10 | 2020-09-15 | 中国石油化工股份有限公司 | 一种端基含有羟基的直链聚全氟醚化合物及其制备方法 |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
ITMI20030971A1 (it) * | 2003-05-15 | 2004-11-16 | Solvay Solexis Spa | Preparazione di perfluoropolieteri aventi almeno un terminale -ch2oh oppure -ch(cf3)oh. |
-
2022
- 2022-01-25 CN CN202210085428.5A patent/CN114605628B/zh active Active
Patent Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2000191668A (ja) * | 1998-12-10 | 2000-07-11 | Toray Ind Inc | 含フッ素化合物、防汚性組成物及び防汚性物品 |
JP2002030019A (ja) * | 1999-08-03 | 2002-01-29 | Mitsubishi Chemicals Corp | 光学活性1,2−二置換−2,3−ジヒドロキシプロパン類の製造法 |
WO2010144398A2 (en) * | 2009-06-10 | 2010-12-16 | 3M Innovative Properties Company | Method for treating hydrocarbon-bearing formations with polyfluoropolyether silanes |
CN105102505A (zh) * | 2013-04-04 | 2015-11-25 | 旭硝子株式会社 | 含氟醚化合物、含氟醚组合物及涂布液,以及具有表面层的基材及其制造方法 |
CN107001619A (zh) * | 2014-11-28 | 2017-08-01 | 大金工业株式会社 | 含氟氧亚甲基的全氟聚醚改性体 |
CN106748670A (zh) * | 2016-12-19 | 2017-05-31 | 衢州氟硅技术研究院 | 一种含醚键氟醇及其制备方法 |
CN107057056A (zh) * | 2017-01-18 | 2017-08-18 | 泉州市思康新材料发展有限公司 | 一种全氟聚醚改性硅烷化合物及包含其的表面处理组合物和薄膜 |
CN107556470A (zh) * | 2017-10-16 | 2018-01-09 | 龙岩思康特种化学品有限公司 | 一种全氟聚醚改性硅烷化合物及其表面处理组合物 |
CN110724256A (zh) * | 2019-10-31 | 2020-01-24 | 中国科学院兰州化学物理研究所 | 一种疏水处理剂及其制备方法和应用、耐磨自清洁玻璃及制备方法 |
CN111662443A (zh) * | 2020-07-10 | 2020-09-15 | 中国石油化工股份有限公司 | 一种端基含有羟基的直链聚全氟醚化合物及其制备方法 |
Also Published As
Publication number | Publication date |
---|---|
CN114605628A (zh) | 2022-06-10 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US9587119B2 (en) | Fluorinated ether compound, fluorinated ether composition, and coating liquid, as well as substrate having surface layer, and method for its production | |
EP3006447B1 (en) | Fluorochemical surface treating agent and article treated therewith | |
EP1444305B1 (en) | Coating composition comprising a fluorochemical polyether silane partial condensate and use thereof | |
EP2725078B1 (en) | Coating composition, surface treating material containing said composition, and article whose surface is treated with said surface treating material | |
KR101853139B1 (ko) | 플루오로옥시알킬렌기 함유 폴리머 조성물 및 상기 조성물을 포함하는 표면처리제 및 상기 표면처리제로 표면 처리된 물품 | |
TWI439489B (zh) | 含有氟氧伸烷基聚合物組成物及含有該組成物的表面處理劑及以該表面處理劑處理的物品 | |
KR101756485B1 (ko) | 플루오로옥시알킬렌기 함유 폴리머 조성물 및 상기 조성물을 포함하는 표면처리제 및 상기 표면처리제로 표면처리된 물품 | |
US11001670B2 (en) | Fluoropolyether-group-containing polymer, surface treatment agent, and article | |
US20160304665A1 (en) | Fluoropolyether-containing polymer-modified silane, surface treating agent, and treated article | |
CN105524552A (zh) | 一种高性能有机硅氟纳米涂料及其应用 | |
CN104119524B (zh) | 含有氟代氧化亚烷基的聚合物改性硅烷、与该硅烷相关的表面处理剂以及物品 | |
EP4011936A1 (en) | Fluoropolyether-group-containing polymer, surface treatment agent, and article | |
TW201817832A (zh) | 含氟醚組成物、塗佈液及物品 | |
EP4137547A1 (en) | Surface treatment agent including fluoropolyether group?containing polymer and/or partial (hydrolysis) condensate of same, and article | |
CN113788942A (zh) | 一种全氟聚醚硅氧烷产品的制备方法及其产品在超疏水型防指纹涂层中的应用 | |
JP7318735B2 (ja) | フルオロポリエーテル基含有ポリマー、表面処理剤及び物品 | |
KR20160094266A (ko) | 함불소 코팅제 및 이 코팅제로 처리된 물품 | |
US20210189174A1 (en) | Fluorine-containing coating agent composition, surface treatment agent containing said composition, and article | |
CN106700810A (zh) | 一种包含四氟乙烯衍生氢氟醚的表面防污处理组合物 | |
CN109970967B (zh) | 一种利用含氟烷基链封端双端官能团全氟聚醚制备单端官能团全氟聚醚的方法 | |
CN114605628B (zh) | 一种高疏水耐磨型涂层防污剂 | |
JP4759952B2 (ja) | 含フッ素エーテルおよびその用途 | |
TW202112894A (zh) | 含有氟聚醚基之聚合物及其製造方法 | |
CN107201167B (zh) | 一种抗污耐磨涂料及其制备方法 | |
EP4265413A1 (en) | Surface treatment agent and article treated with said surface treatment agent |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |