CN1740227A - Nanometer composite acrylic resin with high solid content and low viscosity and the prepn of its coating - Google Patents
Nanometer composite acrylic resin with high solid content and low viscosity and the prepn of its coating Download PDFInfo
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Abstract
The present invention belongs to the field of new chemical material, and is one kind of nanometer composite acrylic resin with high solid content and low viscosity and the preparation of its coating. The nanometer composite acrylic resin is prepared with nanometer oxide sol and acrolactic ester monomer or acrolactic ester resin, and through mixing, decompression distillation to eliminate alcohol or water, and in-situ polymerization or mixing. It has solid content higher than 70 wt%, viscosity lower than 2500 mPa.s, and content of nanometer oxide dispersed homogeneously in the resin system in 1-30 wt%. The nanometer composite acrylic resin may be cross-linked and cured together with isocyanate or amino resin to obtain nanometer composite acrylic resin coating, and the coating has high transparency and glossiness, high antiwear performance, high scratch resistance, high hardness, high weather resistance, etc. and may be used for automobile, plastic, metal, etc.
Description
Technical field
The present invention relates to the new chemical materials field, is about a kind of nanometer composite acrylic resin of high-solid lower-viscosity and the preparation method of coating thereof.
Background technology
The acrylate resin coating is owing to weathering resistance, solvent resistance and gloss retention etc. with high-clarity, high glossiness, high tenacity, excellence are widely used as automotive coatings, coiled material coating, plastic coating, metallic coating etc., but conventional acrylate coatings solid content is low, environment is had certain pollution, and wear resistance, scoring resistance, hardness, weathering resistance etc. still have much room for improvement.
Chinese patent ZL02111699.7 has reported a kind of preparation method of high scoring resistance nano compound polyurethane paint, by adopting nano silicon, lime carbonate etc. nanometer particle-modified, original position or blend obtain nano composite acrylic acid ester polyurethane coating, and scoring resistance can improve more than 25%; U.S. Pat 6177138 has been reported a kind of high abrasion coated material of being made up of nano silicon dioxide sol, organo-siloxane, solidifying agent; Japanese Patent JP2004323634 has reported a kind of nano modified acrylic ester composition and preparation method thereof, adopt the nano modified acrylic ester composition of inorganic nano-particle, thermoplastic acrylic resin, thermosetting acrylate resins, have high transparent, high Young's modulus etc., can be used for the internal and external ornament of automobile.
Nanoparticle wherein both can be that nano oxide powder also can be a nano-oxide colloidal sol.Even also be difficult to evenly spread to fully in the resin after the nano oxide powder particle surface modification, be difficult to more effective performance of improving coating like this, even cause the transparency of resin viscosity rising and reduction coating.Nano-oxide colloidal sol surface modification is easy, easy homodisperse in acrylic resin and in the coating, and form very strong interaction between polymer molecule, not only can significantly improve the performance of coating, and keep the transparency of coating simultaneously, but nano-oxide colloidal sol is dispersion medium (alcosol or the water-sol) with alcohol or water normally, is difficult to be introduced directly in solvent borne acrylic resin and the coating thereof.
Summary of the invention
The object of the present invention is to provide that a kind of technology is easy, practical, the preparation method of the nanometer composite acrylic resin of the high-solid lower-viscosity of excellent performance and coating thereof.
The nanometer composite acrylic resin of a kind of high-solid lower-viscosity that the present invention proposes, less than 2500mPa.s, nano-oxide accounts for nanometer composite acrylic resin 1-30wt% greater than 70wt%, viscosity for its molecular resin amount 1000-50000, hydroxyl value 50-250mgKOH/g, solid content.
The preparation method of the nanometer composite acrylic resin of a kind of high-solid lower-viscosity that the present invention proposes, adopt nano-oxide colloidal sol and hydroxy acryl acid ester monomer or hydroxy acryl acid resin blend, alcohol or the water in the colloidal sol is removed in elder generation's underpressure distillation, what situ aggregation method or blending method prepared high-solid lower-viscosity then receives composite acrylic resin, and products therefrom nano-oxide amount is 1-30wt%.
Among the present invention, situ aggregation method is with nano-oxide colloidal sol and hydroxy acryl acid ester monomer blend, the alcohol and water in the colloidal sol is removed in elder generation's underpressure distillation, adds vinyl monomer, solvent then, adopts solution polymerization process or separation of polymeric method to prepare the high-solid lower-viscosity nanometer composite acrylic resin.
Among the present invention, blending method is with nano-oxide colloidal sol and hydroxy acryl acid resin blend, and the alcohol and water in the colloidal sol is removed in underpressure distillation, directly prepares the high-solid lower-viscosity nanometer composite acrylic resin.
Among the present invention, nano-oxide colloidal sol adopts the nano-oxide alcosol or the water-sol, and nano-oxide alcosol or water-sol median size are 10-250nm.
Among the present invention, hydroxy acryl acid ester monomer is vinylformic acid hydroxyl ester or hydroxyethyl methacrylate ester, adopts 1-3 kind wherein.
Among the present invention, adopt the hydroxy acryl acid resin of hydroxyl value 50-250mgKOH/g, adopt 1-3 kind wherein.
Among the present invention, comonomer is acrylate, methacrylic ester or vinyl aromatic compounds, adopts 1-6 kind wherein.
Among the present invention, nano-oxide colloidal sol is the sol particles that silane coupling agent, titanate coupling agent or lipophilic surfactant were handled, and adopts 1-3 kind wherein.
The present invention implements as follows more specifically:
Specifically, (1) nanometer composite acrylic resin of situ aggregation method preparation is by nano-oxide colloidal sol, hydroxy acrylate monomer, comonomer, solvent composition, wherein, i contains a kind of nano-oxide colloidal sol at least, ii, at least contain a kind of hydroxy acrylate monomer, iii contains a kind of comonomer at least, iv contains a kind of solvent at least; (2) nanometer composite acrylic resin of blending method preparation is made up of nano-oxide colloidal sol, Hydroxylated acrylic resin, and wherein, i contains a kind of nano-oxide colloidal sol at least, and ii contains a kind of Hydroxylated acrylic resin at least.
The preparation method of the nanometer composite acrylic resin of the high-solid lower-viscosity that the present invention proposes, the nano-oxide colloidal sol of selecting for use is the nano-oxide alcosol or the nano-oxide alcohol water-sol, the nano-oxide median size is 10-250nm, be to select for use preferably through silane coupling agent, titanate coupling agent, the sol particles that lipophilic surfactant etc. are handled, as nano silicon dioxide sol, nano titanic oxide sol, nano-aluminium oxide colloidal sol, nanometer ferric oxide colloidal sol, nano zircite colloidal sol etc., adopt 1-3 kind wherein, the nano-oxide consumption accounts for the 1-30wt% of nanometer composite acrylic resin amount.
The preparation method of the nanometer composite acrylic resin of the high-solid lower-viscosity that the present invention proposes, the hydroxy acryl acid ester monomer of selecting for use is vinylformic acid hydroxyl ester, hydroxyethyl methacrylate ester, adopt 1-3 kind wherein, as Hydroxyethyl acrylate, Propylene glycol monoacrylate, hydroxyethyl methylacrylate, Rocryl 410 etc.
The preparation method of the nanometer composite acrylic resin of the high-solid lower-viscosity that the present invention proposes, adopting preparation acrylic resin conventional usefulness vinyl monomer such as acrylate, methacrylic ester, vinyl aromatic compounds etc. is comonomer, adopt 1-6 kind wherein, as methyl acrylate, ethyl propenoate, butyl acrylate, methyl methacrylate, butyl methacrylate, Rocryl 410, vinylbenzene, alpha-methyl styrene etc.
The preparation method of the nanometer composite acrylic resin of the high-solid lower-viscosity that the present invention proposes, the solvent that adopts is preparation acrylic resin common solvent, adopt 1-3 kind wherein, consumption accounts for below the 30wt% of nanometer composite acrylic resin amount, as dimethylbenzene, solvent oil, N-BUTYL ACETATE etc.
The preparation method of the nanometer composite acrylic resin of the high-solid lower-viscosity that the present invention proposes, the Hydroxylated acrylic resin hydroxyl value of selecting for use is 50-250mgKOH/g, adopts 1-3 kind wherein.
The preparation method of the nanometer composite acrylic resin of the high-solid lower-viscosity that the present invention proposes, adopt Nano sol and hydroxy acryl acid ester monomer or hydroxy acryl acid resin blend, at 20-70 ℃ of following underpressure distillation 10-120 minute, vacuum tightness is 0.1-1.0MPa, removes alcohol or water in the nano-oxide colloidal sol.
The preparation method of the nanometer composite acrylic resin of the high-solid lower-viscosity that the present invention proposes, the concrete technology of situ aggregation method is as follows: in having the four-necked bottle of vacuum distillation apparatus, add nano-oxide colloidal sol, the hydroxy acrylate monomer, mixing the back is 0.1-1.0MPa in vacuum tightness, 20-70 ℃ following underpressure distillation 10-120 minute, after treating that solvent is removed fully, remove vacuum distillation apparatus, the comonomer commonly used that adds other preparation acrylate resin, solvent adopts the separation of polymeric method that adopts among solution polymerization process or the patent of invention ZL99119978.2 to prepare the nanometer composite acrylic resin of solid content greater than the high-solid lower-viscosity of 70wt%.
The preparation method of the nanometer composite acrylic resin of the high-solid lower-viscosity that the present invention proposes, the concrete technology of blending method is as follows: in having the four-necked bottle of vacuum distillation apparatus, add nano-oxide colloidal sol, Hydroxylated acrylic resin, mixing the back is 0.1-1.0MPa in vacuum tightness, 20-70 ℃ following underpressure distillation 10-120 minute, after treating that solvent is removed fully, directly obtain the nanometer composite acrylic resin of high-solid lower-viscosity.
The preparation method of a kind of nanometer composite acrylic resin coating that the present invention proposes, be with nanometer composite acrylic resin and polyisocyanates or aminoresin blend, be heating and curing 0.5-24 hour by self-vulcanizing or 20-250 ℃, obtain the nanometer composite acrylic resin coating, the consumption of polyisocyanates or aminoresin calculates by the coating preparation conventional amount used, can take the circumstances into consideration to add auxiliary agents such as acrylic resin coating thinner commonly used, defoamer, flow agent, mill base, catalyzer as required.
Specifically, the nanometer composite acrylic resin coating is made up of nanometer composite acrylic resin, polyisocyanates or aminoresin, auxiliary agent, wherein, (1) contains a kind of nanometer composite acrylic resin at least, (2) contain a kind of polyisocyanates or contain a kind of aminoresin at least at least, (3) contain auxiliary agent.
The preparation method of the nanometer composite acrylic resin coating that the present invention proposes, the polyisocyanate curing agent of employing is aliphatic polyisocyante, alicyclic polyisocyanates, aromatic polyisocyanate etc., adopts 1-2 kind wherein.
The preparation method of the nanometer composite acrylic resin coating that the present invention proposes, the amino resin curing agents of employing is methyl-etherified aminoresin, butyl ether aminoresin etc., adopts 1-2 kind wherein.
The nano composite acrylic acid ester resin coating of a kind of high-solid lower-viscosity of the present invention can be applied to the finish paint of automobile, coiled material, plastics, metal etc.
Resin viscosity is pressed GB/T 1723-1993 and is measured, coating gloss is pressed GB/T 1743-1991 and is measured, and coating abrasion performance is pressed GB/T 1768-1991 and measured, and the coating pencil hardness is pressed GB6739-1991 and measured, (MTS Inc. USA) measures the coating scoring resistance by Nano IndenterXP.
The nano composite acrylic acid ester resin of a kind of high-solid lower-viscosity of the present invention and the preparation method of coating thereof, have the following advantages: alcohol or the water in the colloidal sol is removed in underpressure distillation after (1) nano-oxide colloidal sol and hydroxy acrylate monomer or the Hydroxylated acrylic resin blend, nano-oxide is dispersed in monomer or the resin, adopt situ aggregation method or blending method can prepare solid content greater than 70%, viscosity is lower than the nano composite acrylic acid ester resin of 2500mPa.s; (2) preparation method who adopts the present invention to propose, coating transparent good, glossiness is high; (3) preparation method who adopts the present invention to propose, nanoparticle is evenly distributed in the acrylic resin coating with the primary particle state, interaction between particle and the acrylate copolymer is strong, can significantly improve the performance of coating, especially compare with the acrylic resin coating of no nano-particles filled, abrasion property and scoring resistance improve more than 30%, and hardness and weathering resistance also improve a lot; (4) preparation method who adopts the present invention to propose, technology is easy, practical.
Description of drawings
Fig. 1 is transmission electron microscope (TEM) figure of nano-oxide colloidal sol.
Fig. 2 is scanning electron microscope (SEM) figure that adds the nanometer composite acrylic resin coating section of 5% nano-oxide.
Embodiment
Embodiment 1:
Situ aggregation method prepares the high-solid lower-viscosity nanometer composite acrylic resin, be in having the four-necked bottle of vacuum distillation apparatus, add nano-oxide colloidal sol, the hydroxy acrylate monomer, mixing the back is 0.1-1.0MPa in vacuum tightness, 20-70 ℃ of following underpressure distillation 10-120min, after treating that solvent is removed fully, remove vacuum distillation apparatus, add methyl methacrylate, vinylbenzene, comonomers such as butyl acrylate, dimethylbenzene, N-BUTYL ACETATE, the Methyl amyl ketone equal solvent, prepare nanometer composite acrylic resin with solution polymerization process, the solid content of experiment parameter and resin, viscosity is as follows:
| Example | 1 | 2 | 3 | 4 | 5 |
| Nano oxidized species class modifier nano-oxide Yong amount (wt%) nano composite acrylic acid | Nano silicon dioxide sol, nano-aluminium oxide colloidal sol 10 70 | Nano zircite colloidal sol 2 82 | Nano oxidized ferrum collosol, nano-aluminium oxide colloidal sol 5 73 | Nano silicon dioxide sol 28 77 | Nano silicon dioxide sol, nano titanic oxide sol 16 85 |
| Resin content (wt%) nanometer composite acrylic resin viscosity (mPa.s) | 1930 | 2350 | 1990 | 2460 | 2290 |
The nanometer composite acrylic resin that obtains is mixed by a certain percentage with polyisocyanates or aminoresin, and can add acrylic resin coating defoamer commonly used, flow agent, mill base, catalyzer etc. as required, being heating and curing ambient cure or 20-250 ℃ can obtain the nanometer composite acrylic resin coating in 0.5-24 hour, and experiment parameter and coating performance are as follows:
| Example | 1 | 2 | 3 | 4 | 5 |
| Curing agent gloss (60 °) pencil hardness scoring resistance (GPa, load 1mN) wearability (weightless mg/200 Zhuan) | Zhi fat Zu polyisocyanates NCO/OH=0.9 95 3H 6.1 21 | Aromatic polyisocyanate NCO/OH=1.1 97 2H 7.5 25 | Alicyclic polyisocyanates NCO/OH=1.2 93 3H 7.2 23 | Nanometer composite acrylic resin is Yu amino resins (the Zhi amount is than=60/40) 91 5H 6.6 15 | Nanometer composite acrylic resin is Yu amino resins (the Zhi amount is than=80/20) 94 4H 6.9 19 |
Embodiment 2:
Blending method prepares the high-solid lower-viscosity nanometer composite acrylic resin, in having the four-necked bottle of vacuum distillation apparatus, add nano-oxide colloidal sol, Hydroxylated acrylic resin, mixing the back is 0.1-1.0MPa in vacuum tightness, 20-70 ℃ of following underpressure distillation 10-120min, after treating that solvent is removed fully, obtain the nanometer composite acrylic resin of solid content greater than 70wt%, solid content, the viscosity of experiment parameter and resin are as follows:
| Example | 1 | 2 | 3 | 4 | 5 |
| Nano oxidized species class nano-oxide Yong amount (wt%) nanometer composite acrylic resin content (wt%) nano composite acrylic acid | Nano silicon dioxide sol, nano-aluminium oxide colloidal sol 10 75 2160 | Nano zircite colloidal sol 2 88 1970 | Nano oxidized ferrum collosol, nano-aluminium oxide colloidal sol 5 79 2050 | Nano silicon dioxide sol 28 73 1740 | Nano silicon dioxide sol, nano titanic oxide sol 16 85 2330 |
Resin viscosity (mPa.s)
The nanometer composite acrylic resin that obtains is mixed by a certain percentage with polyisocyanates or aminoresin, and can add acrylic resin coating defoamer commonly used, flow agent, mill base, catalyzer etc. as required, being heating and curing ambient cure or 20-250 ℃ can obtain the nanometer composite acrylic resin coating in 0.5-24 hour, and experiment parameter and coating performance are as follows:
| Example | 1 | 2 | 3 | 4 | 5 |
| Curing agent gloss (60 °) pencil hardness scoring resistance (GPa, load 1mN) wearability (weightless mg/200 Zhuan) | Zhi fat Zu polyisocyanates NCO/OH=0.9 95 3H 7.3 24 | Aromatic polyisocyanate NCO/OH=1.1 97 2H 7.9 30 | Alicyclic polyisocyanates NCO/OH=1.2 93 2H 7.5 26 | Nanometer composite acrylic resin is Yu amino resins (the Zhi amount is than=60/40) 91 4H 7.1 20 | Nanometer composite acrylic resin is Yu amino resins (the Zhi amount is than=80/20) 94 3H 7.2 25 |
Claims (13)
1, a kind of nanometer composite acrylic resin of high-solid lower-viscosity, it is characterized in that molecular resin amount 1000-50000, hydroxyl value 50-250mgKOH/g, solid content greater than 70wt%, viscosity less than 2500mPa.s, nano-oxide accounts for nanometer composite acrylic resin 1-30wt%.
2, a kind of preparation method of nanometer composite acrylic resin of high-solid lower-viscosity, it is characterized in that adopting nano-oxide colloidal sol and hydroxy acryl acid ester monomer or hydroxy acryl acid resin blend, alcohol or the water in the colloidal sol is removed in elder generation's underpressure distillation, and situ aggregation method or blending method prepare the nanometer composite acrylic resin of high-solid lower-viscosity then.
3, method as claimed in claim 2, it is characterized in that situ aggregation method is with nano-oxide colloidal sol and hydroxy acryl acid ester monomer blend, the alcohol and water in the colloidal sol is removed in elder generation's underpressure distillation, add vinyl monomer, solvent then, adopt solution polymerization process or separation of polymeric method to prepare the high-solid lower-viscosity nanometer composite acrylic resin.
4, method as claimed in claim 2 is characterized in that blending method is with nano-oxide colloidal sol and hydroxy acryl acid resin blend, and the alcohol and water in the colloidal sol is removed in underpressure distillation, directly prepares the high-solid lower-viscosity nanometer composite acrylic resin.
5, method as claimed in claim 2 is characterized in that nano-oxide colloidal sol adopts the nano-oxide alcosol or the water-sol, and nano-oxide alcosol or water-sol median size are 10-250nm.
6, method as claimed in claim 2 is characterized in that hydroxy acryl acid ester monomer is vinylformic acid hydroxyl ester or hydroxyethyl methacrylate ester, adopts 1-3 kind wherein.
7, method as claimed in claim 2 is characterized in that adopting the hydroxy acryl acid resin of hydroxyl value 50-250mgKOH/g, adopts 1-3 kind wherein.
8, method as claimed in claim 2 is characterized in that comonomer is acrylate, methacrylic ester or vinyl aromatic compounds, adopts 1-6 kind wherein.
9, method as claimed in claim 2 is characterized in that nano-oxide colloidal sol is the sol particles that silane coupling agent, titanate coupling agent or lipophilic surfactant were handled, and adopts 1-3 kind wherein.
10, a kind of preparation method of nanometer composite acrylic resin coating of high-solid lower-viscosity as claimed in claim 1 or 2, it is characterized in that adopting nanometer composite acrylic resin and the polyisocyanates or the aminoresin blend of above-mentioned high-solid lower-viscosity, in ambient cure, or 20-250 ℃ be heating and curing 0.5-24 hour, can obtain the nanometer composite acrylic resin coating.
11, method as claimed in claim 10 is characterized in that polyisocyanates is aliphatic polyisocyante, alicyclic polyisocyanates or aromatic polyisocyanate, adopts 1-2 kind wherein.
12, method as claimed in claim 10 is characterized in that aminoresin is methyl-etherified aminoresin, butyl ether aminoresin, adopts 1-2 kind wherein.
13, nanometer composite acrylic resin coating as claimed in claim 10 is as the application of automotive coatings, coiled material coating, plastic coating, metallic coating.
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| CN101553510B (en) * | 2006-12-11 | 2012-11-21 | 巴斯夫欧洲公司 | Method of reducing the viscosity of aqueous polymer dispersions of water-soluble polymers |
| CN105255372A (en) * | 2014-01-09 | 2016-01-20 | 苏州斯迪克新材料科技股份有限公司 | Pressure-sensitive adhesive for electronic film sticking |
| CN104910744A (en) * | 2014-03-11 | 2015-09-16 | 董春珍 | Nano-silica/alcoholic hydroxyl containing poly(methyl)acrylate paint |
| CN106232628A (en) * | 2014-04-30 | 2016-12-14 | 阿克佐诺贝尔国际涂料股份有限公司 | The method preparing acrylic acid series powder coating resin system |
| CN106862031A (en) * | 2015-12-10 | 2017-06-20 | 富创得科技股份有限公司 | The film plating process of class diamond material |
| CN107629597A (en) * | 2017-09-26 | 2018-01-26 | 安徽喜宝高分子材料有限公司 | A kind of strong permanent seal cooling wall face sealing wax of uvioresistant |
| CN109401159A (en) * | 2018-12-13 | 2019-03-01 | 西安理工大学 | A kind of preparation method of the enhanced water resistance acrylic resin with uvioresistant performance |
| CN113402920A (en) * | 2021-06-16 | 2021-09-17 | 电子科技大学 | Preparation method of FeSiAl-based organic-inorganic double-layer core-shell structure |
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| CN100400590C (en) | 2008-07-09 |
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Assignee: Zhejiang Yutong Fada Paint Manufacture Co., Ltd. Assignor: Fudan University Contract fulfillment period: 2008.8.8 to 2013.8.7 contract change Contract record no.: 2009330000714 Denomination of invention: Nanometer composite acrylic resin with high solid content and low viscosity and the prepn of its coating Granted publication date: 20080709 License type: Exclusive license Record date: 2009.4.20 |
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