CN1657581A - Preparation method of acrylic resin / nano SIQ2 composite paint - Google Patents
Preparation method of acrylic resin / nano SIQ2 composite paint Download PDFInfo
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- CN1657581A CN1657581A CN2005100416893A CN200510041689A CN1657581A CN 1657581 A CN1657581 A CN 1657581A CN 2005100416893 A CN2005100416893 A CN 2005100416893A CN 200510041689 A CN200510041689 A CN 200510041689A CN 1657581 A CN1657581 A CN 1657581A
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- nano silicon
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Abstract
A decorative composite acrylic resin/nano-SiO2 paint for leather is prepared from ethyl silicate and the mixture of absolute alcohol and ammonium octadecyltrimethyl chloride through mixing, stirring, heating to 35-45 deg.C, dropping the mixture of secondary distilled water and absolute alcohol, regulating pH=8-9, stirring to obtain nano-SiO2 sol, mixing with acrylic acid under water bath and ultrasonic treating.
Description
Technical field
The present invention relates to the preparation method of a kind of leather, particularly a kind of acrylic resin/nanometer SiO with nano combined finishing agent
2The preparation method of composite paint.
Background technology
Leather industry and human lives and development and national economy are closely bound up, are the mainstay industries in the light industry.In recent years, both production and marketing thrive for China's leather, fur and goods industry thereof, exports powerfully, and export value ranked first of the light industry every profession and trade in continuous 3 years.But still there are some problems in leather industry in fast development, mainly being that added value of product is lower (exploits comparative advantages, promote light industry (leather) industry sustainable and healthy development, two kings appraise through comparison the news briefing of ten anniversaries, Bureau of Economic Operations of National Development and Reform Commission, on February 6th, 2004, Beijing), the integral level of skin material still far lags behind developed countries such as America and Europe.
Hide finishes is as the coating and decorating material of leather, to external impression, sanitation performance and the physical and mechanical properties of leatherware all have fundamental influence (Ma Jianzhong, Lan Yunjun. process hides ornamenting materials chemistry. Beijing: the .1998 of China Light Industry Press).Acrylic resin is a big class of hide finishes, and Emulsion acrylic resin hide finishes clinging power is strong, smooth coating, light, warping strength, extensibility big, Stability Analysis of Structures and ageing-resistant, but still has the traditional drawback of " hot sticky cold crisp, not anti-solvent ".Most researchers all is conceived to adjust monomeric kind and proportioning and introduces organic molecules such as organosilicon, urethane acrylic resin is carried out modification both at home and abroad at present, though can make polymkeric substance lightly crosslinked by this modification, but be difficult to satisfy the requirement of the good use properties of finished leather, as ventilation property, permeability to water vapour, kishke feel, comfortableness.The key that overcomes the acrylic resin coating finiss shortcoming is to improve derivatized polymers and improves polymkeric substance and hide fiber bonded stability (Wei Deqing, Xie Fei, Jia Li etc. leather finish is synthesized and performance study with linking agent. Chinese leather, 2002,31 (9): 25～30; Fan Haojun, stone is green, Wang Lijun etc. the research of polysiloxane/acrylic resin latex interpenetrating(polymer)networks (IPN). and Chinese leather, 2002,31 (13): 23～25), and give finished leather good use properties, this also existing just acrylic resin coating finiss material modified can not have both.
Nano material receives whole world scientist's concern with its remarkable performance in recent years, is considered to the strategy field, forward position of 21 century.Organic becomes one of the focus of field of nanometer technology research (L.Matejka, O.Dukh, J.Kolarik.Polymer, 2000,41:1449 rapidly because of its particular performances; R.Takahashi, A.Terauchi.Polymer.2001,42:5151).As far back as nineteen sixty-eight, Stober etc. prepare particle diameter at nano level SiO
220th century the eighties people use it for preparation Organic (Yang-Yen Yua one after another, Ching-Yi Chen, Wen-Chang Chen.Synthesisand characterization of organic-inorganic hybrid thin films frompoly (acrylic) and monodispersed colloidal silica.Polymer, 2003,44:593～601; Alison M.Morrow a, Norman S.Allen a, Michele Edge a, etc..Akinetic investigation into the act of stabilizers on the photo-oxidationof water based silica acrylic-based coatings.Polymer Degradation andStability, 2000,69:143～156; Costas S.Patrickios, Theoni K.Georgiou.Covalent amphiphilic polymer networks.Current Opinion in Colloid andInterface Science, 2003,8:76～85; E.Bourgeat-Lami, P.Espiard, A.Guyot, C.Gauthier, L.David, G.Vigier, Angew.Makromol.Chem.1996,242:105.).Studies show that nanometer SiO
2Particle is uniformly dispersed in polymkeric substance, can improve intensity, elasticity, wear resistance, the ageing resistance of material significantly, increases macromolecular material weathering resistance (L.M.Liu, Z.N.Qi, X.G.Zhu, J.Appl.Polym.Sci., 1999,71:1133.; H.Schmidt, B.Seiferling,, Mater.Res.Soc.Symp.Proc., 1986,73:739.; H.H.Huang, G.L.Wilkes, J.G.Carlson.Polymer, 1989,30:2001).Nanometer SiO
2Polymer composites has become the new focus of material area research.
About nanometer SiO
2The research of modification hide finishes aspect, rarely have both at home and abroad report (Ma Jianzhong, Liu Lingyun, Zhang Zhijie. the research of nano-silicon dioxide modified acrylic resin. 31), but nanometer SiO Chinese leather, 2004,33 (9):
2Aspect coating, obtained using widely.
Summary of the invention
The objective of the invention is to overcome the shortcoming of above-mentioned prior art, a kind of acrylic resin/nanometer SiO is provided
2The preparation method of composite paint, the clinging power of Zhi Bei composite paint and according to said method from the plate excellent property, film forming softness, transparent, sanitation performance is good.
For achieving the above object, the preparation method that the present invention adopts is: getting mass fraction is 15～25 parts pure tetraethyl silicate and 15～17 parts dehydrated alcohol, 1.0～2.0 parts octadecyl trimethyl ammonium chloride mixes, stirred 15～25 minutes, when system temperature reaches 35～45 ℃, in reaction system, drip mass fraction and be the mixing solutions of the dehydrated alcohol of 5～6 parts redistilled water and 15～17 parts, and regulate pH with the hydrochloric acid soln of 1mol/L and reach 8.0～9.0,35～45 ℃ of following insulated and stirred 1.2～1.8 hours, promptly get nano silicon dioxide sol; After the nano silicon dioxide sol of preparation placed 6～7 days, getting mass percent is 4～6% nano silicon dioxide sols and acrylic resin blend under 30～40 ℃ of water-baths, stirred 0.5～1.5 hour, adopting power is the ultrasonication 20～25 minutes of 750～850W, promptly gets acrylic resin/nanometer SiO
2Composite paint.
The present invention is incorporated into nanotechnology in traditional tanning industry, the adding of nanoparticle can significantly improve physical and mechanical properties, water tolerance, the solvent resistance of nano combined finishing agent film and cover with paint, lacquer, colour wash, etc. the sanitation performance of back leather sample coating, conventional acrylic resin " hot sticky cold crisp ", poor, the not solvent-proof common disadvantage of weathering resistance have been overcome, can obtain clinging power and from the plate excellent property, film forming softness, transparent, the nano combined finishing agent that sanitation performance is good.
Embodiment
Embodiment 1, pure tetraethyl silicate and 17 parts dehydrated alcohol, 1.0 parts the octadecyl trimethyl ammonium chloride of getting mass fraction and be 15 parts mix, stirred 15 minutes, when system temperature reaches 35 ℃, in reaction system, drip mass fraction and be the mixing solutions of the dehydrated alcohol of 5 parts redistilled water and 15 parts, and regulate pH with the hydrochloric acid soln of 1mol/L and reach 9.0,35 ℃ of following insulated and stirred 1.2 hours, promptly get nano silicon dioxide sol; After the nano silicon dioxide sol of preparation placed 6～7 days, getting mass percent is 4% nano silicon dioxide sol and acrylic resin blend under 30 ℃ of water-baths, stirred 0.5 hour, adopting power is the ultrasonication 20 minutes of 750W, promptly gets acrylic resin/nanometer SiO
2Composite paint.
Embodiment 2, pure tetraethyl silicate and 16 parts dehydrated alcohol, 1.6 parts the octadecyl trimethyl ammonium chloride of getting mass fraction and be 20 parts mix, stirred 20 minutes, when system temperature reaches 42 ℃, in reaction system, drip mass fraction and be the mixing solutions of the dehydrated alcohol of 6 parts redistilled water and 17 parts, and regulate pH with the hydrochloric acid soln of 1mol/L and reach 8.5,42 ℃ of following insulated and stirred 1.5 hours, promptly get nano silicon dioxide sol; After the nano silicon dioxide sol of preparation placed 6～7 days, getting mass percent is 6% nano silicon dioxide sol and acrylic resin blend under 40 ℃ of water-baths, stirred 1.0 hours, adopting power is the ultrasonication 23 minutes of 850W, promptly gets acrylic resin/nanometer SiO
2Composite paint.
Embodiment 3, pure tetraethyl silicate and 15 parts dehydrated alcohol, 1.3 parts the octadecyl trimethyl ammonium chloride of getting mass fraction and be 18 parts mix, stirred 23 minutes, when system temperature reaches 37 ℃, in reaction system, drip mass fraction and be the mixing solutions of the dehydrated alcohol of 5.2 parts redistilled water and 16 parts, and regulate pH with the hydrochloric acid soln of 1mol/L and reach 8.3,37 ℃ of following insulated and stirred 1.8 hours, promptly get nano silicon dioxide sol; After the nano silicon dioxide sol of preparation placed 6～7 days, getting mass percent is 5% nano silicon dioxide sol and acrylic resin blend under 38 ℃ of water-baths, stirred 1.5 hours, adopting power is the ultrasonication 21 minutes of 800W, promptly gets acrylic resin/nanometer SiO
2Composite paint.
Embodiment 4, pure tetraethyl silicate and 17 parts dehydrated alcohol, 1.8 parts the octadecyl trimethyl ammonium chloride of getting mass fraction and be 23 parts mix, stirred 18 minutes, when system temperature reaches 45 ℃, in reaction system, drip mass fraction and be the mixing solutions of the dehydrated alcohol of 5.8 parts redistilled water and 15.6 parts, and regulate pH with the hydrochloric acid soln of 1mol/L and reach 8.8,45 ℃ of following insulated and stirred 1.4 hours, promptly get nano silicon dioxide sol; After the nano silicon dioxide sol of preparation placed 6～7 days, getting mass percent is 4.5% nano silicon dioxide sol and acrylic resin blend under 35 ℃ of water-baths, stirred 0.8 hour, adopting power is the ultrasonication 25 minutes of 780W, promptly gets acrylic resin/nanometer SiO
2Composite paint.
Embodiment 5, pure tetraethyl silicate and 15 parts dehydrated alcohol, 2.0 parts the octadecyl trimethyl ammonium chloride of getting mass fraction and be 25 parts mix, stirred 22 minutes, when system temperature reaches 39 ℃, in reaction system, drip mass fraction and be the mixing solutions of the dehydrated alcohol of 5.5 parts redistilled water and 16.8 parts, and regulate pH with the hydrochloric acid soln of 1mol/L and reach 8.0,39 ℃ of following insulated and stirred 1.3 hours, promptly get nano silicon dioxide sol; After the nano silicon dioxide sol of preparation placed 6～7 days, getting mass percent is 5.3% nano silicon dioxide sol and acrylic resin blend under 33 ℃ of water-baths, stirred 1.6 hours, adopting power is the ultrasonication 22 minutes of 760W, promptly gets acrylic resin/nanometer SiO
2Composite paint.
Embodiment 6, pure tetraethyl silicate and 16 parts dehydrated alcohol, 1.5 parts the octadecyl trimethyl ammonium chloride of getting mass fraction and be 21 parts mix, stirred 25 minutes, when system temperature reaches 43 ℃, in reaction system, drip mass fraction and be the mixing solutions of the dehydrated alcohol of the redistilled water of 5..6 part and 15 parts, and regulate pH with the hydrochloric acid soln of 1mol/L and reach 8.9,43 ℃ of following insulated and stirred 1.7 hours, promptly get nano silicon dioxide sol; After the nano silicon dioxide sol of preparation placed 6～7 days, getting mass percent is 4.9% nano silicon dioxide sol and acrylic resin blend under 31 ℃ of water-baths, stirred 1.3 hours, adopting power is the ultrasonication 24 minutes of 820W, promptly gets acrylic resin/nanometer SiO
2Composite paint.
Composite paint according to preparation method's preparation of the present invention is compared with the acrylic resin coating finiss film, and physical and mechanical properties has improved 48.66%, and water resisting property raising 60.49%, solvent resistance improve 60.56%, nanometer SiO
2Adding reached the toughness reinforcing effect of synchronous enhancing, overcome the not solvent-proof shortcoming of acrylic resin; Leather sample after composite paint is covered with paint, lacquer, colour wash, etc. back leather sample and acrylic resin is covered with paint, lacquer, colour wash, etc. is compared, and ventilation property has improved 15.4%, and permeability to water vapour has improved 11.5%.Composite paint is coated with the dressing leather sample after standing 100,000 jackknifing, and coating is not seen damage.Nanometer SiO
2The FTIR of colloidal sol, tem observation result show: SiO is arranged in the colloidal sol
2Structure generates; And be uniformly dispersed no agglomeration.
Claims (7)
1, acrylic resin/nanometer SiO
2The preparation method of composite paint is characterized in that:
1) nanometer SiO
2The preparation of colloidal sol
Pure tetraethyl silicate and 15～17 parts dehydrated alcohol, 1.0～2.0 parts the octadecyl trimethyl ammonium chloride of getting mass fraction and be 15～25 parts mix, stirred 15～25 minutes, when system temperature reaches 35～45 ℃, in reaction system, drip mass fraction and be the mixing solutions of the dehydrated alcohol of 5～6 parts redistilled water and 15～17 parts, and regulate pH with the hydrochloric acid soln of 1mol/L and reach 8.0～9.0,35～45 ℃ of following insulated and stirred 1.2～1.8 hours, promptly get nano silicon dioxide sol;
2) acrylic resin/nanometer SiO
2The preparation of composite paint
After the nano silicon dioxide sol of preparation placed 6～7 days, getting mass percent is 4～6% nano silicon dioxide sols and acrylic resin blend under 30～40 ℃ of water-baths, stirred 0.5～1.5 hour, adopting power is the ultrasonication 20～25 minutes of 750～850W, promptly gets acrylic resin/nanometer SiO
2Composite paint.
2, acrylic resin according to claim 1/nanometer SiO
2The preparation method of composite paint, it is characterized in that: pure tetraethyl silicate and 17 parts dehydrated alcohol, 1.0 parts the octadecyl trimethyl ammonium chloride of getting mass fraction and be 15 parts mix, stirred 15 minutes, when system temperature reaches 35 ℃, in reaction system, drip mass fraction and be the mixing solutions of the dehydrated alcohol of 5 parts redistilled water and 15 parts, and regulate pH with the hydrochloric acid soln of 1mol/L and reach 9.0,35 ℃ of following insulated and stirred 1.2 hours, promptly get nano silicon dioxide sol; After the nano silicon dioxide sol of preparation placed 6～7 days, getting mass percent is 4% nano silicon dioxide sol and acrylic resin blend under 30 ℃ of water-baths, stirred 0.5 hour, adopting power is the ultrasonication 20 minutes of 750W, promptly gets acrylic resin/nanometer SiO
2Composite paint.
3, acrylic resin according to claim 1/nanometer SiO
2The preparation method of composite paint, it is characterized in that: pure tetraethyl silicate and 16 parts dehydrated alcohol, 1.6 parts the octadecyl trimethyl ammonium chloride of getting mass fraction and be 20 parts mix, stirred 20 minutes, when system temperature reaches 42 ℃, in reaction system, drip mass fraction and be the mixing solutions of the dehydrated alcohol of 6 parts redistilled water and 17 parts, and regulate pH with the hydrochloric acid soln of 1mol/L and reach 8.5,42 ℃ of following insulated and stirred 1.5 hours, promptly get nano silicon dioxide sol; After the nano silicon dioxide sol of preparation placed 6～7 days, getting mass percent is 6% nano silicon dioxide sol and acrylic resin blend under 40 ℃ of water-baths, stirred 1.0 hours, adopting power is the ultrasonication 23 minutes of 850W, promptly gets acrylic resin/nanometer SiO
2Composite paint.
4, acrylic resin according to claim 1/nanometer SiO
2The preparation method of composite paint, it is characterized in that: pure tetraethyl silicate and 15 parts dehydrated alcohol, 1.3 parts the octadecyl trimethyl ammonium chloride of getting mass fraction and be 18 parts mix, stirred 23 minutes, when system temperature reaches 37 ℃, in reaction system, drip mass fraction and be the mixing solutions of the dehydrated alcohol of 5.2 parts redistilled water and 16 parts, and regulate pH with the hydrochloric acid soln of 1mol/L and reach 8.3,37 ℃ of following insulated and stirred 1.8 hours, promptly get nano silicon dioxide sol; After the nano silicon dioxide sol of preparation placed 6～7 days, getting mass percent is 5% nano silicon dioxide sol and acrylic resin blend under 38 ℃ of water-baths, stirred 1.5 hours, adopting power is the ultrasonication 21 minutes of 800W, promptly gets acrylic resin/nanometer SiO
2Composite paint.
5, acrylic resin according to claim 1/nanometer SiO
2The preparation method of composite paint, it is characterized in that: pure tetraethyl silicate and 17 parts dehydrated alcohol, 1.8 parts the octadecyl trimethyl ammonium chloride of getting mass fraction and be 23 parts mix, stirred 18 minutes, when system temperature reaches 45 ℃, in reaction system, drip mass fraction and be the mixing solutions of the dehydrated alcohol of 5.8 parts redistilled water and 15.6 parts, and regulate pH with the hydrochloric acid soln of 1mol/L and reach 8.8,45 ℃ of following insulated and stirred 1.4 hours, promptly get nano silicon dioxide sol; After the nano silicon dioxide sol of preparation placed 6～7 days, getting mass percent is 4.5% nano silicon dioxide sol and acrylic resin blend under 35 ℃ of water-baths, stirred 0.8 hour, adopting power is the ultrasonication 25 minutes of 780W, promptly gets acrylic resin/nanometer SiO
2Composite paint.
6, acrylic resin according to claim 1/nanometer SiO
2The preparation method of composite paint, it is characterized in that: pure tetraethyl silicate and 15 parts dehydrated alcohol, 2.0 parts the octadecyl trimethyl ammonium chloride of getting mass fraction and be 25 parts mix, stirred 22 minutes, when system temperature reaches 39 ℃, in reaction system, drip mass fraction and be the mixing solutions of the dehydrated alcohol of 5.5 parts redistilled water and 16.8 parts, and regulate pH with the hydrochloric acid soln of 1mol/L and reach 8.0,39 ℃ of following insulated and stirred 1.3 hours, promptly get nano silicon dioxide sol; After the nano silicon dioxide sol of preparation placed 6～7 days, getting mass percent is 5.3% nano silicon dioxide sol and acrylic resin blend under 33 ℃ of water-baths, stirred 1.6 hours, adopting power is the ultrasonication 22 minutes of 760W, promptly gets acrylic resin/nanometer SiO
2Composite paint.
7, acrylic resin according to claim 1/nanometer SiO
2The preparation method of composite paint, it is characterized in that: pure tetraethyl silicate and 16 parts dehydrated alcohol, 1.5 parts the octadecyl trimethyl ammonium chloride of getting mass fraction and be 21 parts mix, stirred 25 minutes, when system temperature reaches 43 ℃, in reaction system, drip mass fraction and be the mixing solutions of the dehydrated alcohol of the redistilled water of 5..6 part and 15 parts, and regulate pH with the hydrochloric acid soln of 1mol/L and reach 8.9,43 ℃ of following insulated and stirred 1.7 hours, promptly get nano silicon dioxide sol; After the nano silicon dioxide sol of preparation placed 6～7 days, getting mass percent is 4.9% nano silicon dioxide sol and acrylic resin blend under 31 ℃ of water-baths, stirred 1.3 hours, adopting power is the ultrasonication 24 minutes of 820W, promptly gets acrylic resin/nanometer SiO
2Composite paint.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1318459C (en) * | 2005-11-30 | 2007-05-30 | 中国林业科学研究院林产化学工业研究所 | Method for preparing nano silicon dioxide-acrylate polymeric microball material |
| CN100500938C (en) * | 2007-09-28 | 2009-06-17 | 钢铁研究总院 | Nano modified acrylic resin emulsion used for zinc coating plate and preparation method thereof |
| CN102603958A (en) * | 2012-01-13 | 2012-07-25 | 陕西科技大学 | Preparation method of acrylic resin/graphene oxide nanometer composite leather finishing agent |
| CN106883708A (en) * | 2017-03-23 | 2017-06-23 | 曹昕原 | A kind of electrical equipment high moisture three-proofing coating and preparation method thereof |
| CN107384081A (en) * | 2017-08-29 | 2017-11-24 | 安徽乐踏鞋业有限公司 | A kind of finishing agent for improving the low temperature resistant dry environment of leather |
| CN110862737A (en) * | 2018-08-28 | 2020-03-06 | 郑州珊瑚纳米科技有限公司 | Polyacrylate super-hydrophobic leather brightener containing organic silicon long side chains and preparation method of coating thereof |
| CN112574621A (en) * | 2020-12-08 | 2021-03-30 | 兴业皮革科技股份有限公司 | Preparation method and application of carboxylated graphene/chitosan composite coating agent |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1554704A (en) * | 2003-12-27 | 2004-12-15 | 同济大学 | Nano modified leather polyurethane material and its preparing method |
| CN1224718C (en) * | 2004-01-12 | 2005-10-26 | 陕西科技大学 | Preparation technology of ving/polymer/modified montmorillonoid nano composite tanoing agent |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1318459C (en) * | 2005-11-30 | 2007-05-30 | 中国林业科学研究院林产化学工业研究所 | Method for preparing nano silicon dioxide-acrylate polymeric microball material |
| CN100500938C (en) * | 2007-09-28 | 2009-06-17 | 钢铁研究总院 | Nano modified acrylic resin emulsion used for zinc coating plate and preparation method thereof |
| CN102603958A (en) * | 2012-01-13 | 2012-07-25 | 陕西科技大学 | Preparation method of acrylic resin/graphene oxide nanometer composite leather finishing agent |
| CN106883708A (en) * | 2017-03-23 | 2017-06-23 | 曹昕原 | A kind of electrical equipment high moisture three-proofing coating and preparation method thereof |
| CN106883708B (en) * | 2017-03-23 | 2019-02-15 | 曹昕原 | A kind of electrical equipment high moisture three-proofing coating and preparation method thereof |
| CN107384081A (en) * | 2017-08-29 | 2017-11-24 | 安徽乐踏鞋业有限公司 | A kind of finishing agent for improving the low temperature resistant dry environment of leather |
| CN110862737A (en) * | 2018-08-28 | 2020-03-06 | 郑州珊瑚纳米科技有限公司 | Polyacrylate super-hydrophobic leather brightener containing organic silicon long side chains and preparation method of coating thereof |
| CN112574621A (en) * | 2020-12-08 | 2021-03-30 | 兴业皮革科技股份有限公司 | Preparation method and application of carboxylated graphene/chitosan composite coating agent |
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Assignee: Zhejiang Donghua Industrial Co., Ltd. Assignor: Shaanxi University of Science and Technology Contract fulfillment period: 2008.12.16 to 2016.12.15 contract change Contract record no.: 2009330000193 Denomination of invention: Preparation method of acrylic resin / nano SIQ2 composite paint Granted publication date: 20070214 License type: Exclusive license Record date: 2009.1.23 |
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