CN109385163B - A PEEK modified acrylic full shielding infrared and ultraviolet water-based transparent thermal insulation coating - Google Patents

Abstract

Translated fromChinese

本发明涉及一种PEEK改性丙烯酸全屏蔽红外线和紫外线水性透明隔热涂料，由PEEK改性水性丙烯酸树脂、助溶剂、底材促进剂、纳米透明隔热剂、纳米光催化剂、透明纳米色浆、助剂和水组成；所述PEEK改性水性丙烯酸树脂，由反应活性的丙烯酸改性聚醚醚酮，通过ATRP自由基聚合反应合成；本发明制得的水性透明隔热涂料，具有优异的附着力、耐腐蚀性、耐老化性、耐湿热性、耐磨性、自洁性、抗辐射性、抗静电性、自阻燃性和机械性能；其可见光透过率平均大于70％，全屏蔽紫外线和红外线，隔热性能非常显著。广泛用于各种建筑物玻璃、车用玻璃、工程塑料、钢结构及水泥表面上的隔热与保护。The invention relates to a PEEK-modified acrylic water-based transparent heat-insulating paint that fully shields infrared and ultraviolet rays. , additives and water; the PEEK-modified water-based acrylic resin is synthesized from reactive acrylic acid-modified polyether ether ketone by ATRP free radical polymerization; the water-based transparent thermal insulation coating prepared by the present invention has excellent Adhesion, corrosion resistance, aging resistance, heat and humidity resistance, abrasion resistance, self-cleaning, radiation resistance, antistatic properties, self-flammability and mechanical properties; the average visible light transmittance is greater than 70%, and the total Shields ultraviolet and infrared rays, and the thermal insulation performance is very significant. Widely used for heat insulation and protection on various building glass, vehicle glass, engineering plastics, steel structures and cement surfaces.

Description

Translated fromChinese

一种PEEK改性丙烯酸全屏蔽红外线和紫外线水性透明隔热涂料A PEEK-modified acrylic full shielding infrared and ultraviolet water-based transparent heat insulationcoating

技术领域technical field

本发明涉及一种水性隔热涂料，尤其涉及到一种PEEK改性丙烯酸全屏蔽红外线和紫外线水性透明隔热涂料，属于水性功能涂料技术领域。The invention relates to a water-based heat-insulating paint, in particular to a PEEK-modified acrylic water-based transparent heat-insulating paint that fully shields infrared and ultraviolet rays, and belongs to the technical field of water-based functional paints.

背景技术Background technique

中国有建筑近400亿平方米，95％属不节能建筑，与气候条件相近的发达国家相比，我国每平方米采暖制冷能耗约为发达国家的3倍，但舒适度远不如人，为此，国家建筑节能新标准规定，新建建筑节能必须达50％，到2020年，要使全社会建筑的总能耗能够达到65％的总目标。据资料表明，中国总量正逐年上升，目前我国建筑能耗占总能耗的40％，其中通过门窗损失的能量为46％，即每年通过玻璃窗损耗的能量约2.25亿吨标准煤，相当于21个三峡电站年发电量，所以建筑节能首先要从门窗抓起。而高性能的选择性屏蔽材料可以使玻璃对光谱具有选择性透过功能，在能透过大部分可见光而不影响采光的前提下，又能阻挡红外光、远红外光、紫外光，阻断热辐射,从而降低空调或取暖装置的能耗，达到节能的目的。China has nearly 40 billion square meters of buildings, 95% of which are non-energy-efficient buildings. Compared with developed countries with similar climatic conditions, my country's heating and cooling energy consumption per square meter is about three times that of developed countries, but the comfort level is far less than that of human beings. Therefore, the new national building energy efficiency standard stipulates that the energy efficiency of new buildings must reach 50%. According to data, the total amount in China is increasing year by year. At present, the energy consumption of buildings in my country accounts for 40% of the total energy consumption, of which 46% is lost through doors and windows, that is, the energy lost through glass windows is about 225 million tons of standard coal every year, which is equivalent to The annual power generation of 21 Three Gorges Power Stations, so building energy conservation must first start from doors and windows. The high-performance selective shielding material can make the glass selectively transmit the spectrum. On the premise that most visible light can pass through without affecting the lighting, it can also block infrared light, far-infrared light, and ultraviolet light. Heat radiation, thereby reducing the energy consumption of air conditioning or heating devices, to achieve the purpose of energy saving.

太阳到达地面的辐射波段范围大约为200～2500nm，其中200～400nm为紫外线，400～800nm为可见光，800～2500nm为近红外线，而近红外又可分为短波近红外(800～1100nm)和长波近红外(1100～2500nm)，人眼只对可见光有直接感知，所以要达到节能的目的，就需要尽可能的屏蔽红外线和紫外线屏，只让可见光透过。The radiation band range of the sun reaching the ground is about 200-2500nm, of which 200-400nm is ultraviolet, 400-800nm is visible light, 800-2500nm is near-infrared, and near-infrared can be divided into short-wave near-infrared (800-1100nm) and long-wave Near-infrared (1100-2500nm), the human eye only has direct perception of visible light, so to achieve the purpose of energy saving, it is necessary to shield infrared and ultraviolet screens as much as possible, and only allow visible light to pass through.

现在透明隔热涂料都采用纳米稀土材料作为屏蔽隔热材料，几乎所有的水性树脂都可以作为成膜树脂，但涂层的耐水性、耐老化、自洁性、耐腐蚀性等性能还不是很理想，存在涂料寿命短、粘污性差，因而提高涂膜的耐大气腐蚀性、耐沾污性、耐湿热性、自洁性是非常必要的。Now transparent thermal insulation coatings all use nano-rare earth materials as shielding and thermal insulation materials, and almost all water-based resins can be used as film-forming resins, but the water resistance, aging resistance, self-cleaning, corrosion resistance and other properties of the coating are not very good. Ideally, there are coatings with short life and poor fouling properties, so it is very necessary to improve the atmospheric corrosion resistance, fouling resistance, humidity and heat resistance, and self-cleaning properties of the coating film.

发明内容SUMMARY OF THE INVENTION

本发明采用由纳米稀土、金属氧化物组成的纳米复合材料如ZnO、ITO、ATO、IAO、LaB₆、WO₃、TiO₂作为透明隔热材料；纳米ITO、ATO在1300nm～2500nm(长波近红外线)间有较好的屏蔽作用；纳米LaB₆、CeO₂在200nm～400nm(紫外线)及800nm～1300nm(短波近红外线)有非常好的屏蔽作用，却不会吸收太多的可见光；纳米WO₃对人体有危害的波长在200nm～400nm、介于紫外线和γ射线间的电磁辐射X射线有很好的屏蔽作用，同时氧化钨对长波、短波近红外线均有一定屏蔽作用，可见光透过率高；纳米TiO₂、ZnO、CeO₂、SiO₂具有光催化作用和自洁去污功能；因此，本发明既能屏蔽所有的紫外线和近红外线，又能满足高的可见光透过率。The invention adopts nanometer composite materials composed of nanometer rare earth and metal oxides, such as ZnO, ITO, ATO, IAO,_LaB6 , WO3,_TiO2 , as the transparent heat insulation material_; ) has good shielding effect; nano-LaB₆ and CeO₂ have very good shielding effect at 200nm-400nm (ultraviolet) and 800-1300nm (short-wave near-infrared), but they will not absorb too much visible light; nano-WO₃ The electromagnetic radiation X-rays with wavelengths between 200nm and 400nm, which are harmful to the human body, between ultraviolet rays and gamma rays have a good shielding effect. At the same time, tungsten oxide has a certain shielding effect on long-wave and short-wave near-infrared rays, and the visible light transmittance is high. ; Nano TiO₂ , ZnO, CeO₂ , SiO₂ have photocatalysis and self-cleaning decontamination functions; therefore, the present invention can shield all ultraviolet rays and near-infrared rays, and can meet high visible light transmittance.

本发明采用PEEK改性的水性丙烯酸树脂，在丙烯酸树脂分子骨架中含有一个酮键和两个醚键的重复单元，PEEK结构具有抗α、β、γ、X射线作用，是所有工程材料中性能全面、抗辐射性最好的，因此，PEEK改性的水性醇酸树脂能有效地提高涂膜的附着力、耐腐蚀性、耐高温性、耐水蒸汽性、耐老化性、耐湿热性、耐磨性、抗辐射性、抗静电性、自阻燃性和机械性能。The present invention adopts PEEK-modified water-based acrylic resin, which contains repeating units of one ketone bond and two ether bonds in the molecular skeleton of the acrylic resin. The PEEK structure has the effect of resisting α, β, γ and X-rays, and is the best among all engineering materials. It has the best comprehensive and radiation resistance. Therefore, PEEK-modified water-based alkyd resin can effectively improve the adhesion, corrosion resistance, high temperature resistance, water vapor resistance, aging resistance, humidity and heat resistance of the coating film. Abrasion resistance, radiation resistance, antistatic properties, self-flammability and mechanical properties.

为了解决上面所述的技术问题，本发明采取以下技术方案：本发明涉及一种PEEK改性丙烯酸全屏蔽红外线和紫外线水性透明隔热涂料，其组成为：PEEK改性丙烯酸水性树脂30.0～70.0％、纳米透明隔热剂15.0～40.0％、纳米光催化剂5.0～15.0％、透明纳米色浆0～10.0％、助溶剂2.0～10.0％、底材促进剂0.5～3.0％、助剂2.0～10.0％、去离子水至100％。In order to solve the above-mentioned technical problems, the present invention adopts the following technical solutions: The present invention relates to a PEEK-modified acrylic water-based transparent heat-insulating paint that fully shields infrared and ultraviolet rays, which is composed of: PEEK-modified acrylic water-based resin 30.0-70.0% , Nano transparent heat insulating agent 15.0-40.0%, nano-photocatalyst 5.0-15.0%, transparent nano-color paste 0-10.0%, cosolvent 2.0-10.0%, substrate accelerator 0.5-3.0%, auxiliary 2.0-10.0% , deionized water to 100%.

其中，所述纳米光催化剂为纳米TiO₂、ZnO、CeO₂、SiO₂中的至少一种；所述纳米光催化剂其粒径为D₅₀≤40nm、D₉₀≤70nm、固含量为5.0～15.0％的纳米水性分散体。Wherein, the nano-photocatalyst is at least one of nano-TiO₂ , ZnO, CeO₂ and SiO₂ ; the particle size of the nano-photocatalyst is D₅₀ ≤ 40nm, D₉₀ ≤ 70nm, and the solid content is 5.0-15.0 % of the nano-aqueous dispersion.

所述助溶剂为醇类、醇酯类、醇醚类溶剂中的至少一种。The auxiliary solvent is at least one of alcohols, alcohol esters and alcohol ethers.

所述助剂至少包括分散剂、增稠剂、消泡剂、流平剂、成膜助剂、基材润湿剂、pH调节剂中的一种或几种的组合。The auxiliary agent includes at least one or a combination of a dispersing agent, a thickening agent, a defoaming agent, a leveling agent, a film-forming auxiliary agent, a substrate wetting agent, and a pH adjusting agent.

所述PEEK改性丙烯酸水性树脂，基于申请的发明专利“一种ATRP合成的聚醚醚酮改性丙烯酸水性树脂”中所述，按重量份数计，其成分为：10.0～20.0份丙烯酸改性改性聚醚醚酮、30.0～60.0份软单体、6.0～12.0份硬单体、0.2～2.0份乳化剂、0.6～1.5份配体、1.0～2.0份催化剂、0.5～1.5份引发剂、去离子水50.0～80.0份。The PEEK-modified acrylic water-based resin is based on the description in the applied invention patent "A polyether ether ketone modified acrylic water-based resin synthesized by ATRP", and its components in parts by weight are: 10.0-20.0 parts of acrylic acid modified modified polyether ether ketone, 30.0-60.0 parts of soft monomer, 6.0-12.0 parts of hard monomer, 0.2-2.0 parts of emulsifier, 0.6-1.5 parts of ligand, 1.0-2.0 parts of catalyst, 0.5-1.5 parts of initiator , 50.0 to 80.0 parts of deionized water.

所述PEEK改性丙烯酸水性树脂，采用ATRP自由基聚合反应制备，步骤如下：The PEEK-modified acrylic water-based resin is prepared by ATRP radical polymerization, and the steps are as follows:

将引发剂溶于去离子水中，配制成5％～10％的引发剂溶液；按配方重量比，依次将丙烯酸改性聚醚醚酮、催化剂、软单体、硬单体、乳化剂、配体、余下的去离子水加入到反应器中，通氮气0.5～1h，高速搅拌10～30min至乳化均匀，然后升温至60～110℃，滴加引发剂水溶液，在0.5～1h内滴加完毕，保持恒温继续反应6～12h，得所述的PEEK改性丙烯酸水性树脂。Dissolve the initiator in deionized water to prepare a 5% to 10% initiator solution; according to the formula weight ratio, sequentially mix the acrylic modified polyether ether ketone, catalyst, soft monomer, hard monomer, emulsifier, formula The body and the remaining deionized water are added to the reactor, nitrogen is passed through for 0.5-1h, high-speed stirring for 10-30min until the emulsification is uniform, then the temperature is raised to 60-110 ℃, and the initiator aqueous solution is added dropwise, and the addition is completed within 0.5-1h , keep the constant temperature and continue the reaction for 6 to 12 hours to obtain the PEEK modified acrylic water-based resin.

所述软单体为丙烯酸甲酯、丙烯酸乙酯、丙烯酸正丙酯、丙烯酸正丁酯、丙烯酸异丁酯、丙烯酸叔丁酯、丙烯酸异辛酯、甲基丙烯酸正丁酯、甲基丙烯酸异丁酯、甲基丙烯酸叔丁酯、丙烯酸月桂酯、甲基丙烯酸月桂酯、甲基丙烯酸异辛酯中的至少一种。The soft monomers are methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, isooctyl acrylate, n-butyl methacrylate, isobutyl methacrylate At least one of butyl ester, tert-butyl methacrylate, lauryl acrylate, lauryl methacrylate, and isooctyl methacrylate.

所述硬单体为苯乙烯、甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸异冰片酯中的至少一种。The hard monomer is at least one of styrene, methyl methacrylate, ethyl methacrylate and isobornyl methacrylate.

所述乳化剂为十二烷基硫酸钠、十二烷基苯磺酸钠、油酸钾、油酸钠、琥珀酸酯磺酸钠、甘油硬脂酸酯、甘油油酸酯、月桂醇聚氧乙烯醚、月桂酸聚氧乙烯酯、双十二烷基苯基醚二磺酸钠、月桂酸钠、OP-10、苯乙基酚聚氧乙烯醚、吐温中的至少一种。The emulsifier is sodium lauryl sulfate, sodium dodecylbenzenesulfonate, potassium oleate, sodium oleate, sodium succinate sulfonate, glyceryl stearate, glycerol oleate, lauryl alcohol At least one of oxyethylene ether, polyoxyethylene laurate, sodium didodecyl phenyl ether disulfonate, sodium laurate, OP-10, phenethyl phenol polyoxyethylene ether, and Tween.

所述配体为N,N,N’,N’-四甲基乙二胺、N,N,N’,N’,N”-五甲基丙烯酸甲酯基二乙烯基三胺、N,N,N’,N’,N”,N”-六甲基丙烯酸正丁酯基三乙烯基四胺、2,2’-联吡啶、N,N,N’,N’,N”-五甲基二乙烯基三胺、N,N,N’,N’,N”,N”-六甲基丙烯酸甲酯基三乙烯基四胺中的至少一种。The ligands are N,N,N',N'-tetramethylethylenediamine, N,N,N',N',N"-pentamethacrylate methyl divinyltriamine, N, N,N',N',N",N"-N-butyl trivinyltetramine hexamethacrylate, 2,2'-bipyridine, N,N,N',N',N"-penta At least one of methyldivinyltriamine and N,N,N',N',N",N"-hexamethacrylate methyltrivinyltetramine.

所述催化剂为溴化亚铜、氯化亚铜、溴化铜中的至少一种。The catalyst is at least one of cuprous bromide, cuprous chloride and cupric bromide.

所述引发剂为4-[2-(2-溴-2-甲基丙酰氧基)乙氧基]-4-氧代-2-磺酸基丁酸二钠、4-[10-(2-溴-2-甲基丙酰氧基)癸氧基]-4-氧代-2-磺酸基丁酸二钠、4-[6-(2-溴-2-甲基丙酰氧基)己氧基]-4-氧代-2-磺酸基丁酸二钠、4-[10-(2-溴-2-甲基丙酰氧基)辛氧基]-4-氧代-2-磺酸基丁酸二钠、2-氯丙酰胺、2-溴丙酰胺、2-碘代丙烯酸甲酯、2-氯代丙腈、2-溴丙烯酸乙酯、2-溴丙烯酸甲酯、二溴丙烯酸乙酯、1-溴代乙腈、2-甲基-2-溴代丙烯酸乙酯、2-溴代异丁酸乙酯、2-溴丙烯酸乙酯、N,N-二乙基-2-溴代丙烯酰胺中的至少一种。The initiator is 4-[2-(2-bromo-2-methylpropionyloxy) ethoxy]-4-oxo-2-sulfobutyric acid disodium, 4-[10-( 2-Bromo-2-methylpropionyloxy)decyloxy]-4-oxo-2-sulfobutyric acid disodium, 4-[6-(2-bromo-2-methylpropionyloxy] base)hexyloxy]-4-oxo-2-sulfobutyric acid disodium, 4-[10-(2-bromo-2-methylpropionyloxy)octyloxy]-4-oxo -Disodium 2-sulfobutyrate, 2-chloropropionamide, 2-bromopropionamide, methyl 2-iodoacrylate, 2-chloropropionitrile, ethyl 2-bromoacrylate, methyl 2-bromoacrylate ester, ethyl dibromoacrylate, 1-bromoacetonitrile, 2-methyl-2-bromoethyl acrylate, 2-bromoisobutyric acid ethyl ester, 2-bromoethyl acrylate, N,N-diethyl at least one of yl-2-bromoacrylamides.

所述纳米透明隔热剂为ITO、ATO、IAO、LaB₆、WO₃中的至少两种以上；所述纳米透明隔热剂其粒径为D₅₀≤70nm、D₉₀≤100nm、固含量为15.0～25.0％的纳米水性分散体。The nano transparent heat insulating agent is at least two kinds of ITO, ATO, IAO, LaB₆ , and WO₃ ; the particle size of the nano transparent heat insulating agent is D₅₀ ≤ 70 nm, D₉₀ ≤ 100 nm, and the solid content is 15.0 to 25.0% of the nano-aqueous dispersion.

所述纳米透明隔热剂，其组成为：纳米透明隔热剂15.0～25.0％、硅烷偶联剂1.0～5.0％、乙醇5.0～20.0％、高分子润湿分散剂5.0～20.0％、消泡剂0.1～0.5％、pH调节剂0.1～0.5％、增稠剂0.1～0.5％、去离子水至100％。The nano transparent heat insulating agent is composed of: nano transparent heat insulating agent 15.0-25.0%, silane coupling agent 1.0-5.0%, ethanol 5.0-20.0%, polymer wetting and dispersing agent 5.0-20.0%, defoaming agent 0.1-0.5% of pH regulator, 0.1-0.5% of pH adjuster, 0.1-0.5% of thickener, and deionized water to 100%.

所述高分子润湿分散剂为含有下述分子结构The polymer wetting and dispersing agent contains the following molecular structure

中的至少一种。

at least one of them.

所述纳米透明隔热剂，其制备步骤如下：Described nano transparent heat insulating agent, its preparation step is as follows:

a)将纳米透明隔热剂粉体放入烘箱，在40～50℃条件下干燥5h，将干燥好的纳米粉料加入溶有硅烷偶联剂的乙醇溶液中，超声波分散1h，制得预分散液；a) Put the nano transparent heat insulating agent powder into an oven, dry it at 40-50 ℃ for 5 hours, add the dried nano powder material to the ethanol solution dissolved with silane coupling agent, and ultrasonically disperse it for 1 hour to prepare a Dispersions;

b)将预分散液加入带有回流冷凝器和搅拌器的反应器中，升温至80～90℃，搅拌，回流反应24h，过滤出料，在70～80℃下真空干燥，得改性纳米粉体；b) Add the pre-dispersed liquid to a reactor with a reflux condenser and a stirrer, raise the temperature to 80-90 °C, stir, reflux for 24 h, filter the material, and vacuum dry at 70-80 °C to obtain the modified nanometer powder;

c)在高速分散机中加入去离子水、高分子润湿分散剂，搅拌均匀，加入改性纳米粉体，高速分散30min，调pH值为7.5～8.0，移至纳米砂磨机循环研磨8～10h，经激光粒度仪检测，当分散体的粒径为D₅₀≤70nm、D₉₀≤100nm、为合格，调粘消泡，得固含量为15.0～25.0％的所述纳米透明隔热剂。c) Add deionized water and polymer wetting and dispersing agent to the high-speed disperser, stir evenly, add the modified nano-powder, disperse at high speed for 30 minutes, adjust the pH value to 7.5-8.0, move to the nano-sand mill for circular grinding 8 ~10h, tested by a laser particle size analyzer, when the particle size of the dispersion is D₅₀ ≤ 70nm, D₉₀ ≤ 100nm, it is qualified, and the viscosity is adjusted and defoamed, and the nano transparent heat insulating agent with a solid content of 15.0-25.0% is obtained. .

本发明提出一种PEEK改性丙烯酸全屏蔽红外线和紫外线水性透明隔热涂料的制备方法，步骤如下：按配方重量比计把去离子水、助溶剂、底材促进剂或基材润湿剂加入到容器中，然后加入PEEK改性水性丙烯酸树脂，低速搅拌下缓慢加入纳米透明隔热剂、纳米光催化剂、透明纳米色浆，搅拌至均匀，再按配方要求加入消泡剂、成膜助剂、增稠剂、pH调节剂，搅拌，过滤，得所述的一种PEEK改性丙烯酸全屏蔽红外线和紫外线水性透明隔热涂料。The invention provides a preparation method of PEEK-modified acrylic acid fully shielding infrared and ultraviolet water-based transparent heat-insulating paint. The steps are as follows: adding deionized water, cosolvent, substrate accelerator or substrate wetting agent according to the formula weight ratio Into the container, then add PEEK modified water-based acrylic resin, slowly add nano transparent heat insulation agent, nano photocatalyst, transparent nano color paste under low speed stirring, stir until uniform, and then add defoamer and film forming aid according to the formula requirements , thickener, pH regulator, stirring and filtering to obtain the PEEK-modified acrylic water-based transparent heat-insulating paint with full shielding of infrared and ultraviolet rays.

本发明制得的一种PEEK改性丙烯酸全屏蔽红外线和紫外线水性透明隔热涂料，涂层具有优异的附着力、耐腐蚀性、耐水蒸汽性、耐老化性、耐湿热性、耐磨性、自洁性、抗辐射性、抗静电性、自阻燃性和机械性能；其可见光透过率大于70％，全屏蔽紫外线和红外线，隔热性能非常显著。广泛用于各种建筑物玻璃、车用玻璃、工程塑料、钢结构及水泥表面上的隔热与保护。The PEEK modified acrylic acid fully shielded infrared and ultraviolet water-based transparent heat-insulating paint prepared by the invention has excellent adhesion, corrosion resistance, water vapor resistance, aging resistance, damp heat resistance, abrasion resistance, Self-cleaning, anti-radiation, anti-static, self-flammability and mechanical properties; its visible light transmittance is greater than 70%, fully shielding ultraviolet and infrared rays, and its thermal insulation performance is very significant. Widely used for heat insulation and protection on various building glass, vehicle glass, engineering plastics, steel structures and cement surfaces.

具体实施方式Detailed ways

下面结合实施例对本发明的一种PEEK改性丙烯酸全屏蔽红外线和紫外线水性透明隔热涂料做进一步的描述。可以理解的是，此处所描述的具体实施例仅仅用于解释相关发明，而非对该发明的限定。A kind of PEEK-modified acrylic full-shielding infrared and ultraviolet water-based transparent thermal insulation coating of the present invention will be further described below in conjunction with the examples. It should be understood that the specific embodiments described herein are only used to explain the related invention, but not to limit the invention.

实施例1Example 1

一种PEEK改性丙烯酸全屏蔽红外线和紫外线水性透明隔热涂料，按重量份计，其组成为：PEEK改性水性丙烯酸树脂A 45.0份、丙二醇甲醚2.5份、硅烷偶联剂1.0份、20％纳米ATO分散体20.0份、20％纳米WO₃分散体10.0份、20％纳米LaB₆分散体5.0份、10％纳米TiO₂分散体8.0份、流平剂0.1份、消泡剂0.1份、增稠剂0.3份、pH调节剂0.2份、去离子水7.8份；A PEEK-modified acrylic water-based transparent heat-insulating coating that fully shields infrared and ultraviolet rays, in parts by weight, comprising: 45.0 parts of PEEK-modified water-based acrylic resin A, 2.5 parts of propylene glycol methyl ether, 1.0 parts of a silane coupling agent, 20 parts of 20.0 parts of % nano ATO dispersion, 10.0 parts of 20% nano WO₃ dispersion, 5.0 parts of 20% nano LaB₆ dispersion, 8.0 parts of 10% nano TiO₂ dispersion, 0.1 part of leveling agent, 0.1 part of defoamer, 0.3 part of thickener, 0.2 part of pH adjuster, 7.8 part of deionized water;

其中，所述PEEK改性水性丙烯酸树脂A为发明专利“一种ATRP合成的聚醚醚酮改性丙烯酸水性树脂”中的实施例4所述。Wherein, the PEEK-modified water-based acrylic resin A is described in Example 4 of the invention patent "A polyether ether ketone modified acrylic water-based resin synthesized by ATRP".

实施例2Example 2

一种PEEK改性丙烯酸全屏蔽红外线和紫外线水性透明隔热涂料，按重量份计，其组成为：PEEK改性水性丙烯酸树脂B 42.0份、二丙二醇丁醚2.0份、硅烷偶联剂1.0份、20％纳米ITO分散体20.0份、20％纳米WO₃分散体15.0份、10％纳米CeO₂分散体6.0份、35％透明氧化铁红色浆4.0份、流平剂0.1份、消泡剂0.1份、增稠剂0.3份、pH调节剂0.2份、去离子水9.3份；A PEEK-modified acrylic water-based transparent heat-insulating coating that fully shields infrared and ultraviolet rays, in parts by weight, comprising: 42.0 parts of PEEK-modified water-based acrylic resin B, 2.0 parts of dipropylene glycol butyl ether, 1.0 parts of a silane coupling agent, 20.0 parts of 20% nano ITO dispersion, 15.0 parts of 20% nano WO₃ dispersion, 6.0 parts of 10% nano CeO₂ dispersion, 4.0 parts of 35% transparent iron oxide red paste, 0.1 part of leveling agent, 0.1 part of defoamer , 0.3 part of thickener, 0.2 part of pH regulator, 9.3 part of deionized water;

其中，所述PEEK改性水性丙烯酸树脂B为发明专利“一种ATRP合成的聚醚醚酮改性丙烯酸水性树脂”中的实施例5所述。Wherein, the PEEK-modified water-based acrylic resin B is described in Example 5 of the invention patent "A polyether ether ketone modified acrylic water-based resin synthesized by ATRP".

实施例3Example 3

一种PEEK改性丙烯酸全屏蔽红外线和紫外线水性透明隔热涂料，按重量份计，其组成为：PEEK改性水性丙烯酸树脂C 46.0份、二丙二醇甲醚3.0份、硅烷偶联剂1.0份、25％纳米ATO分散体12.0份、25％纳米LaB₆分散体6.0份、25％纳米WO₃分散体10.0份、15％纳米ZnO分散体8.0份、流平剂0.1份、消泡剂0.1份、增稠剂0.3份、pH调节剂0.2份、去离子水13.3份；A PEEK-modified acrylic water-based transparent heat-insulating coating that fully shields infrared and ultraviolet rays, in parts by weight, comprising: 46.0 parts of PEEK-modified water-based acrylic resin C, 3.0 parts of dipropylene glycol methyl ether, 1.0 parts of a silane coupling agent, 12.0 parts of 25% nano ATO dispersion, 6.0 parts of 25% nano LaB₆ dispersion, 10.0 parts of 25% nano WO₃ dispersion, 8.0 parts of 15% nano ZnO dispersion, 0.1 part of leveling agent, 0.1 part of defoamer, 0.3 part of thickener, 0.2 part of pH adjuster, 13.3 part of deionized water;

其中，所述PEEK改性水性丙烯酸树脂C为发明专利“一种ATRP合成的聚醚醚酮改性丙烯酸水性树脂”中的实施例6所述。Wherein, the PEEK-modified water-based acrylic resin C is described in Example 6 of the invention patent "A polyether ether ketone modified acrylic water-based resin synthesized by ATRP".

按照相关标准，对本发明实施例中的PEEK改性丙烯酸全屏蔽红外线和紫外线水性透明隔热涂料进行检测，其性能指标如表1所示。According to relevant standards, the PEEK-modified acrylic water-based transparent thermal insulation coating with full shielding infrared and ultraviolet rays in the embodiment of the present invention is tested, and its performance index is shown in Table 1.

表1：全屏蔽红外线和紫外线水性透明隔热涂料性能技术指标Table 1: Performance and technical indicators of fully shielded infrared and ultraviolet water-based transparent thermal insulation coatings

本发明的纳米透明隔热涂料采用纳米透明隔热剂复合体系作为隔热材料，比市面上单独采用ATO、ITO、LaB₆、WO₃的纳米透明隔热涂料的涂层在紫外-可见光-红外透过光谱对比，本发明的可见光平均透过率大于70％；在320～380nm处的透过率为1％，在700～900nm处的透过率为1％，在1000～2000nm处的透过率小于3％；也就是说，本发明的涂料涂层完全屏蔽紫外线和红外线，只有可见光能透过，且隔热效果非常显著。The nano-transparent heat-insulating paint of the present invention adopts the nano-transparent heat-insulating agent composite system as the heat-insulating material, which is more efficient in ultraviolet-visible-infrared than the coating of the nano-transparent heat-insulating paint which uses ATO, ITO, LaB₆ and WO₃ alone on the market. Through spectrum comparison, the average transmittance of visible light of the present invention is greater than 70%; the transmittance at 320-380nm is 1%, the transmittance at 700-900nm is 1%, and the transmittance at 1000-2000nm is 1%. The pass rate is less than 3%; that is, the paint coating of the present invention completely shields ultraviolet rays and infrared rays, only visible light can pass through, and the heat insulation effect is very significant.

尽管本发明已作了详细说明并引证了实施例，但对于本领域的普通技术人员，显然可以按照上述说明而做出的各种方案、修改和改动，都应该包括在权利要求的范围之内。Although the present invention has been described in detail and cited the embodiments, for those of ordinary skill in the art, it is obvious that various schemes, modifications and changes that can be made according to the above description should be included within the scope of the claims. .

Claims (8)

1. The PEEK modified acrylic acid water-based transparent heat-insulating coating capable of fully shielding infrared rays and ultraviolet rays is characterized in that: the water-based transparent heat insulation coating comprises the following components in percentage by weight: 30.0-70.0% of PEEK modified acrylic acid water-based resin, 15.0-40.0% of nano transparent heat insulating agent, 5.0-15.0% of nano photocatalyst, 0-10.0% of transparent nano color paste, 2.0-10.0% of cosolvent, 0.5-3.0% of substrate accelerator, 2.0-10.0% of auxiliary agent and 100% of deionized water;

the PEEK modified acrylic acid water-based resin comprises the following components in parts by weight: 10.0-20.0 parts of acrylic modified polyether ether ketone, 30.0-60.0 parts of soft monomer, 6.0-12.0 parts of hard monomer, 0.2-2.0 parts of emulsifier, 0.6-1.5 parts of ligand, 1.0-2.0 parts of catalyst, 0.5-1.5 parts of initiator and 50.0-80.0 parts of deionized water;

the ligand is at least one of N, N, N ', N ' -tetramethylethylenediamine, N, N, N ', N ' -pentamethyl methacrylate divinyl triamine, N, N, N ', N ', N ' -N-butyl hexamethylacrylate trivinyl tetramine, 2 ' -bipyridine, N, N, N ', N ' -pentamethyl divinyl triamine, N, N, N ', N ', N ' -methyl hexamethylacrylate trivinyl tetramine; the catalyst is at least one of cuprous bromide and cuprous chloride; the initiator is 4- [2- (2-bromo-2-methylpropionyloxy) ethoxy ] -4-oxo-2-sulfobutyric acid disodium, 4- [10- (2-bromo-2-methylpropionyloxy) decyloxy ] -4-oxo-2-sulfobutyric acid disodium, 4- [6- (2-bromo-2-methylpropionyloxy) hexyloxy ] -4-oxo-2-sulfobutyric acid disodium, 4- [10- (2-bromo-2-methylpropionyloxy) octyloxy ] -4-oxo-2-sulfobutyric acid disodium, 2-chloropropionamide, 2-bromopropionamide, 2-iodoacrylic acid methyl ester, methyl acetate, ethyl acetate, At least one of 2-chloropropionitrile, 2-ethyl bromoacrylate, 2-methyl bromoacrylate, ethyl dibromoacrylate, 1-bromoacetonitrile, ethyl 2-bromoisobutyrate and N, N-diethyl-2-bromoacrylamide;

the nano transparent heat insulating agent is ITO, ATO, IAO or LaB₆、WO₃At least two or more of (1); the particle diameter of the nano transparent heat insulating agent is D₅₀≤70nm、D₉₀A nano aqueous dispersion with the solid content of 15.0-25.0% and the particle size of less than or equal to 100 nm;

the nanometer transparent heat insulating agent comprises the following components: 15.0-25.0% of nano transparent heat insulating agent, 1.0-5.0% of silane coupling agent, 5.0-20.0% of ethanol, 5.0-20.0% of polymer wetting dispersant, 0.1-0.5% of defoaming agent, 0.1-0.5% of pH regulator, 0.1-0.5% of thickening agent and 100% of deionized water;

the macromolecular wetting dispersant has the following molecular structure

、

、

、

At least one of;

the auxiliary agent at least comprises one or a combination of a plurality of dispersing agents, thickening agents, defoaming agents, flatting agents, film forming auxiliary agents, base material wetting agents and pH adjusting agents.

2. The PEEK modified acrylic acid water-based transparent heat insulation coating of claim 1, which is characterized in that: the cosolvent is at least one of alcohol solvents, alcohol esters and alcohol ether solvents.

3. The PEEK modified acrylic acid water-based transparent heat insulation coating of claim 1, which is characterized in that: the nano photocatalyst is nano TiO₂、ZnO、CeO₂At least one of; the nano photocatalystHaving a particle diameter of D₅₀≤40nm、D₉₀The nano water-based dispersion is less than or equal to 70nm and has a solid content of 5.0-15.0%.

4. The PEEK modified acrylic acid water-based transparent heat insulation coating of claim 1, which is characterized in that: the soft monomer is at least one of methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, isooctyl acrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, lauryl acrylate, lauryl methacrylate and isooctyl methacrylate; the hard monomer is at least one of styrene, methyl methacrylate, ethyl methacrylate and isobornyl methacrylate.

5. The PEEK modified acrylic acid water-based transparent heat insulation coating of claim 1, which is characterized in that: the emulsifier is at least one of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, potassium oleate, sodium succinate sulfonate, glyceryl stearate, glyceryl oleate, polyoxyethylene lauryl ether, polyoxyethylene laurate, sodium didodecyl phenyl ether disulfonate, sodium laurate, OP-10, polyoxyethylene phenethyl phenol ether and Tween.

6. The PEEK modified acrylic acid water-based transparent heat insulation coating of claim 1, which is characterized in that: the PEEK modified acrylic acid water-based resin is prepared by ATRP free radical polymerization reaction, and the steps are as follows: dissolving an initiator in deionized water to prepare an initiator solution with the concentration of 5-10 percent; according to the weight ratio of the formula, sequentially adding the acrylic acid modified polyether-ether-ketone, the catalyst, the soft monomer, the hard monomer, the emulsifier, the ligand and the rest deionized water into a reactor, introducing nitrogen for 0.5-1 h, stirring at a high speed for 10-30 min until emulsification is uniform, then heating to 60-110 ℃, dropwise adding an initiator aqueous solution, keeping constant temperature and continuing to react for 6-12 h after the dropwise adding is finished within 0.5-1 h, thereby obtaining the PEEK modified acrylic acid aqueous resin.

7. The PEEK modified acrylic acid water-based transparent heat insulation coating of claim 1, which is characterized in that: the preparation method of the nano transparent heat insulating agent comprises the following steps:

a) putting the nano transparent heat insulating agent into an oven, drying for 5 hours at 40-50 ℃, adding the dried nano powder into an ethanol solution dissolved with a silane coupling agent, and performing ultrasonic dispersion for 1 hour to prepare a pre-dispersion liquid;

b) adding the pre-dispersion liquid into a reactor with a reflux condenser and a stirrer, heating to 80-90 ℃, stirring, carrying out reflux reaction for 24 hours, filtering and discharging, and carrying out vacuum drying at 70-80 ℃ to obtain modified nano powder;

c) adding deionized water and a polymer wetting dispersant into a high-speed dispersion machine, uniformly stirring, adding modified nano powder, dispersing at a high speed for 30min, adjusting the pH value to 7.5-8.0, transferring to a nano sand mill, circularly grinding for 8-10 h, and detecting by a laser particle size analyzer until the particle size of the dispersion is D₅₀≤70nm、D₉₀And (3) adjusting the viscosity and defoaming to obtain the nano transparent heat insulating agent with the solid content of 15.0-25.0% when the nano transparent heat insulating agent is qualified and is not more than 100 nm.

8. The preparation method of the PEEK modified acrylic acid full-shielding infrared and ultraviolet water-based transparent heat insulation coating as claimed in claim 1, characterized in that: the preparation method comprises the following steps:

adding deionized water, cosolvent and substrate promoter into a container according to the weight percentage, then adding PEEK modified waterborne acrylic resin, slowly adding a nano transparent heat insulating agent, a nano photocatalyst and transparent nano color paste under low-speed stirring, stirring until the mixture is uniform, then adding an auxiliary agent according to the formula requirement, stirring and filtering to obtain the PEEK modified acrylic full-shielding infrared and ultraviolet waterborne transparent heat insulating coating.