CN102924649A - Preparation method of high-hydrophobicity leather coating agent - Google Patents
Preparation method of high-hydrophobicity leather coating agent Download PDFInfo
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Abstract
The invention relates to a preparation method of a high-hydrophobicity leather coating agent. The acrylate leather coating agent has excellent film-forming property, light stability, weather resistance and binding property, but has some defects, such as poor water resistance, poor solvent resistance, lack of functionality and the like, due to the linear structure of the acrylate resin. In order to overcome the defects above, the invention provides a semicontinuous seed emulsion polymerization method for preparing the core-shell acrylate resin: the shell is properly cross-linked, so that the acrylate resin is converted into a reticular structure from the linear structure, thereby enhancing the water resistance and solvent resistance of the acrylate resin; and besides, organic fluorine is introduced into the shell, so that the acrylate resin has high hydrophobicity. After the high-hydrophobicity leather coating agent forms a film, the contact angle with water is up to 124 degrees, and the film feels smooth and not sticky; the 24-hour water absorptivity is less than 10%; and after being soaked in methylbenzene for 48 hours, the film only swells, but is not dissolved.
Description
Technical field
The present invention relates to a kind of preparation method of hide finishes, particularly a kind of method that adopts semi-continuous seed emulsion polymerization to prepare high hydrophobic type hide finishes.
Background technology
The leather finish operation has considerable effect in the course of processing of leather, on the one hand coating and decorating material forms the gorgeous film of one deck light at leather surface, makes that leather surface is smooth, color even is consistent.Can improve on the other hand the use value of finished leather.
In numerous hide finishess, the Acrylic Resin Leather Finishing Agent clinging power is strong, smooth coating is bright, warping strength, Stability Analysis of Structures and ageing-resistant, and have inexpensive, safe, do not fire, nontoxic, the advantage such as environmental pollution is little, be a class filmogen that is most widely used in the coating material for leather.But acrylic resin is the linear polymeric polymkeric substance, exists some defectives, such as water-fast, poor solvent resistance etc., and functional outstanding, limited to a certain extent its range of application.
In recent years, the consumers demand of day by day increasing for satisfying the human consumer, improve finished product leather class and development of new market, a lot of research staff are gathered in the hide finishes aspect with property with sight, such as ultraviolet ray-resistance type, antimicrobial form, high hydrophobic type hide finishes etc.
The high hydrophobicity of high hydrophobic type hide finishes is main relevant with its surperficial chemical composition and structure.High hydrophobic surface refers to and the contact angle of the water film coated surface greater than 120 °.Prepare at present high hydrophobic method of filming and mainly contain chemical Vapor deposition process (Xinhua Chen, Guangbin Yang, Linghao Kong, et al..Direct Growth of Hydroxy Cupric Phosphate Heptahydrate Monocrystal with Honeycomb-Like Porous Structures on Copper Surface Mimicking Lotus Leaf[J] .Crystal Growth﹠amp; Design, 2009,9 (6): 2656-2661), etching method, template, self-assembly method (electrostatic self-assembled and covalency self-assembly) (Javier Bravo layer by layer, Lei Zhai, Robert E.Cohen, et al..Transparent Superhydrophobic Films Based on Silica Nanoparticles [J] .Langmuir, 2007,23 (13): 7293-7298), chemical precipitation method and pickling process etc.Adopt the preparation of these methods high hydrophobic film higher to equipment requirements, be difficult to reach under the usual terms, and temperature requirement is generally more than 150 ℃, and the condition of this high temperature is only applicable to rigidity or soft abiotic material surface, and is unpractical for leather.Existing hide finishes with high hydrophobicity energy mainly is to obtain (Yuanyuan Hu by fluorine-containing latex and polyacrylate dispersion blend, Chaocan Zhang.Preparation and structure of fluorinated/non-fluorinated polyacrylate gradient emulsion blend film[J] .Materials Letters, 2010,64:2091-2093) or be fluorine-contaninig polyacrylate emulsion (the Ruiqin Bai of low-solid content, Teng Qiu.Synthesis and characterization of core-shell polysilsesquioxane-poly (styrene-butyl acrylate-fluorinated acrylate) hybrid latex particles[J] .Colloids and Surfaces A:Physicochem.Eng.Aspects, 2012,396:251-257) or be solvent-borne type, such not environmental protection of material and be difficult to satisfy the demand of producing.
Summary of the invention
The object of the invention is to overcome that Acrylic Resin Leather Finishing Agent is water-fast, the defective of poor solvent resistance, a kind of method of the high hydrophobic type hide finishes of hud typed fluorine-contaninig polyacrylate class of the standby high solids content of employing semi-continuous seed emulsion polymerization legal system that can give the high hydrophobic property of hide finishes is provided.
For achieving the above object, the technical solution used in the present invention is:
1) at first with there-necked flask heating in water bath to 45 ℃～50 ℃, then in there-necked flask, add 22 parts of deionized water solutions that are dissolved with 0.6 part of emulsifying agent and 0.1 part ~ 0.14 part of sodium bicarbonate by mass fraction, after emulsification evenly, add again 5 parts of mix monomer A, stir 20min, add again 3.5 parts of deionized water solutions that are dissolved with 0.06 part ~ 0.09 part of initiator, stir 30min, be warming up to 75 ℃ ~ 80 ℃, reaction 30min obtains seed emulsion;
2) drip simultaneously the stratum nucleare pre-emulsion that is formed by 0.1 part of emulsifying agent, 2.5 parts of deionized waters, 5.5 parts of mix monomer A and 3 parts of deionized waters that are dissolved with 0.024 part ~ 0.036 part of initiator in the seed emulsion with constant pressure funnel, 2h ~ 2.5h drips off, formation stratum nucleare emulsion after isothermal reaction is finished;
3) in the stratum nucleare emulsion, drip by 0.5 part of emulsifying agent, 12.5 parts of deionized waters and 24.5 parts of shell pre-emulsions that mix monomer B forms simultaneously by constant pressure funnel again, be dissolved with 13.5 parts of deionized water solutions of 0.116 part ~ 0.174 part of initiator, 3h ~ 4h drips off, after isothermal reaction is finished, be warming up to 85 ℃ and react again 2h, be cooled to 40 ℃ and namely get high hydrophobic type hide finishes;
The described mix monomer A mixture that to be methyl methacrylate mix by the mass ratio of 1:1 ~ 6 with butyl acrylate;
The described emulsifying agent mixture that to be polyoxyethylene nonylphenol ether-2-sulfonic group monomester succinate disodium salt and sodium lauryl sulphate form by the mass ratio of 8:2;
Described mix monomer B is vinylbenzene: methyl methacrylate: butyl acrylate: vinyltriethoxysilane: methacrylic acid: organic fluorine is pressed 1:(2.2 ~ 3.32): (3.68 ~ 4.8): (0.24 ~ 0.5): (0 ~ 0.2): the mixture of (1 ~ 2) mass ratio.
Described initiator is the ammonium persulphate Potassium Persulphate.
Described organic fluorine is vinylformic acid hexafluoro butyl ester, dodecafluorhe-ptylacrylate, methacrylic acid 2,2,2-trifluoro ethyl ester, Hexafluorobutyl mathacrylate, dodecafluoroheptyl methacrylate, ten difluoro heptyl propyl group methyl dimethoxysilanes, ten difluoro heptyl propyl trimethoxy silicanes or ten trifluoro octyl group Trimethoxy silanes.
The present invention is by the standby high solid content core-shell type acrylate containing fluorine hide finishes of semi-continuous seed emulsion polymerization legal system, the suitable crosslinked and introducing organic fluorine to shell, can improve that Acrylic Resin Leather Finishing Agent is water-fast, the defective of poor solvent resistance, and have high hydrophobic characteristics.The fluorine-containing side chain alkyl carbon atoms of the organic fluorine number that the present invention adopts is less than 8, degradable, and there is not the hidden danger of welding, harm humans health in the lifeless matter cumulative bad.Utilize the prepared high hydrophobic type hide finishes of the present invention to have following characteristics: emulsion solid content can reach 35%, contact angle with water after the film forming can reach 124 °, and feel is smooth, without sticking sense, the 24h water-intake rate is less than 10%, in toluene, soak the 48h film only swelling do not dissolve.
Embodiment
Embodiment 1:
1) at first with there-necked flask heating in water bath to 45 ℃, then in there-necked flask, add 22 parts of deionized water solutions that are dissolved with 0.6 part of emulsifying agent and 0.1 part of sodium bicarbonate by mass fraction, after emulsification evenly, add again 5 parts of mix monomer A, stir 20min, add again 3.5 parts of deionized water solutions that are dissolved with 0.06 part of ammonium persulphate, stir 30min, be warming up to 75 ℃, reaction 30min obtains seed emulsion;
2) drip simultaneously the stratum nucleare pre-emulsion that is formed by 0.1 part of emulsifying agent, 2.5 parts of deionized waters, 5.5 parts of mix monomer A and 3 parts of deionized waters that are dissolved with 0.024 part of initiator ammonium persulfate in the seed emulsion with constant pressure funnel, 2h drips off, formation stratum nucleare emulsion after isothermal reaction is finished;
3) in the stratum nucleare emulsion, drip by 0.5 part of emulsifying agent, 12.5 parts of deionized waters and 24.5 parts of shell pre-emulsions that mix monomer B forms simultaneously by constant pressure funnel again, be dissolved with 13.5 parts of deionized water solutions of 0.116 part of initiator ammonium persulfate, 4h drips off, after isothermal reaction is finished, be warming up to 85 ℃ and react again 2h, be cooled to 40 ℃ and namely get high hydrophobic type hide finishes;
The described mix monomer A mixture that to be methyl methacrylate mix by the mass ratio of 1:2 with butyl acrylate;
The described emulsifying agent mixture that to be polyoxyethylene nonylphenol ether-2-sulfonic group monomester succinate disodium salt and sodium lauryl sulphate form by the mass ratio of 8:2;
Described mix monomer B is vinylbenzene: methyl methacrylate: butyl acrylate: vinyltriethoxysilane: dodecafluoroheptyl methacrylate is pressed the mixture of 1:2.2:3.68:0.3:1 mass ratio.
Embodiment 2:
1) at first with there-necked flask heating in water bath to 47 ℃, then in there-necked flask, add 22 parts of deionized water solutions that are dissolved with 0.6 part of emulsifying agent and 0.12 part of sodium bicarbonate by mass fraction, after emulsification evenly, add again 5 parts of mix monomer A, stir 20min, add again 3.5 parts of deionized water solutions that are dissolved with 0.08 part of Potassium Persulphate, stir 30min, be warming up to 77 ℃, reaction 30min obtains seed emulsion;
2) drip simultaneously the stratum nucleare pre-emulsion that is formed by 0.1 part of emulsifying agent, 2.5 parts of deionized waters, 5.5 parts of mix monomer A and 3 parts of deionized waters that are dissolved with 0.030 part of initiator potassium persulfate in the seed emulsion with constant pressure funnel, 2.5h drip off formation stratum nucleare emulsion after isothermal reaction is finished;
3) in the stratum nucleare emulsion, drip by 0.5 part of emulsifying agent, 12.5 parts of deionized waters and 24.5 parts of shell pre-emulsions that mix monomer B forms simultaneously by constant pressure funnel again, be dissolved with 13.5 parts of deionized water solutions of 0.120 part of initiator potassium persulfate, 3h drips off, after isothermal reaction is finished, be warming up to 85 ℃ and react again 2h, be cooled to 40 ℃ and namely get high hydrophobic type hide finishes;
The described mix monomer A mixture that to be methyl methacrylate mix by the mass ratio of 1:3 with butyl acrylate;
The described emulsifying agent mixture that to be polyoxyethylene nonylphenol ether-2-sulfonic group monomester succinate disodium salt and sodium lauryl sulphate form by the mass ratio of 8:2;
Described mix monomer B is vinylbenzene: methyl methacrylate: butyl acrylate: vinyltriethoxysilane: methacrylic acid: vinylformic acid hexafluoro butyl ester is pressed the mixture of 1:3.0:4.0:0.24:0.1:1.5 mass ratio.
Embodiment 3:
1) at first with there-necked flask heating in water bath to 50 ℃, then in there-necked flask, add 22 parts of deionized water solutions that are dissolved with 0.6 part of emulsifying agent and 0.14 part of sodium bicarbonate by mass fraction, after emulsification evenly, add again 5 parts of mix monomer A, stir 20min, add again 3.5 parts of deionized water solutions that are dissolved with 0.07 part of ammonium persulphate, stir 30min, be warming up to 79 ℃, reaction 30min obtains seed emulsion;
2) drip simultaneously the stratum nucleare pre-emulsion that is formed by 0.1 part of emulsifying agent, 2.5 parts of deionized waters, 5.5 parts of mix monomer A and 3 parts of deionized waters that are dissolved with 0.028 part of initiator ammonium persulfate in the seed emulsion with constant pressure funnel, 2h drips off, formation stratum nucleare emulsion after isothermal reaction is finished;
3) in the stratum nucleare emulsion, drip by 0.5 part of emulsifying agent, 12.5 parts of deionized waters and 24.5 parts of shell pre-emulsions that mix monomer B forms simultaneously by constant pressure funnel again, be dissolved with 13.5 parts of deionized water solutions of 0.150 part of initiator ammonium persulfate, 3.5h drip off, after isothermal reaction is finished, be warming up to 85 ℃ and react again 2h, be cooled to 40 ℃ and namely get high hydrophobic type hide finishes;
The described mix monomer A mixture that to be methyl methacrylate mix by the mass ratio of 1:5 with butyl acrylate;
The described emulsifying agent mixture that to be polyoxyethylene nonylphenol ether-2-sulfonic group monomester succinate disodium salt and sodium lauryl sulphate form by the mass ratio of 8:2;
Described mix monomer B is vinylbenzene: methyl methacrylate: butyl acrylate: vinyltriethoxysilane: methacrylic acid: dodecafluorhe-ptylacrylate is pressed the mixture of 1:2.6:4.3:0.4:0.2:2 mass ratio.
Embodiment 4:
1) at first with there-necked flask heating in water bath to 46 ℃, then in there-necked flask, add 22 parts of deionized water solutions that are dissolved with 0.6 part of emulsifying agent and 0.13 part of sodium bicarbonate by mass fraction, after emulsification evenly, add again 5 parts of mix monomer A, stir 20min, add again 3.5 parts of deionized water solutions that are dissolved with 0.09 part of Potassium Persulphate, stir 30min, be warming up to 76 ℃, reaction 30min obtains seed emulsion;
2) drip simultaneously the stratum nucleare pre-emulsion that is formed by 0.1 part of emulsifying agent, 2.5 parts of deionized waters, 5.5 parts of mix monomer A and 3 parts of deionized waters that are dissolved with 0.028 part of initiator potassium persulfate in the seed emulsion with constant pressure funnel, 2h drips off, formation stratum nucleare emulsion after isothermal reaction is finished;
3) in the stratum nucleare emulsion, drip by 0.5 part of emulsifying agent, 12.5 parts of deionized waters and 24.5 parts of shell pre-emulsions that mix monomer B forms simultaneously by constant pressure funnel again, be dissolved with 13.5 parts of deionized water solutions of 0.174 part of initiator potassium persulfate, 3h drips off, after isothermal reaction is finished, be warming up to 85 ℃ and react again 2h, be cooled to 40 ℃ and namely get high hydrophobic type hide finishes;
The described mix monomer A mixture that to be methyl methacrylate mix by the mass ratio of 1:4 with butyl acrylate;
The described emulsifying agent mixture that to be polyoxyethylene nonylphenol ether-2-sulfonic group monomester succinate disodium salt and sodium lauryl sulphate form by the mass ratio of 8:2;
Described mix monomer B is vinylbenzene: methyl methacrylate: butyl acrylate: vinyltriethoxysilane: methacrylic acid: methacrylic acid 2,2, the 2-trifluoro ethyl ester is pressed the mixture of 1:3.32:4.5:0.45:0.15:1.3 mass ratio.
Embodiment 5:
1) at first with there-necked flask heating in water bath to 48 ℃, then in there-necked flask, add 22 parts of deionized water solutions that are dissolved with 0.6 part of emulsifying agent and 0.11 part of sodium bicarbonate by mass fraction, after emulsification evenly, add again 5 parts of mix monomer A, stir 20min, add again 3.5 parts of deionized water solutions that are dissolved with 0.06 part of ammonium persulphate, stir 30min, be warming up to 80 ℃, reaction 30min obtains seed emulsion;
2) drip simultaneously the stratum nucleare pre-emulsion that is formed by 0.1 part of emulsifying agent, 2.5 parts of deionized waters, 5.5 parts of mix monomer A and 3 parts of deionized waters that are dissolved with 0.33 part of initiator ammonium persulfate in the seed emulsion with constant pressure funnel, 2.5h drip off formation stratum nucleare emulsion after isothermal reaction is finished;
3) in the stratum nucleare emulsion, drip by 0.5 part of emulsifying agent, 12.5 parts of deionized waters and 24.5 parts of shell pre-emulsions that mix monomer B forms simultaneously by constant pressure funnel again, be dissolved with 13.5 parts of deionized water solutions of 0.160 part of initiator ammonium persulfate, 4h drips off, after isothermal reaction is finished, be warming up to 85 ℃ and react again 2h, be cooled to 40 ℃ and namely get high hydrophobic type hide finishes;
The described mix monomer A mixture that to be methyl methacrylate mix by the mass ratio of 1:6 with butyl acrylate;
The described emulsifying agent mixture that to be polyoxyethylene nonylphenol ether-2-sulfonic group monomester succinate disodium salt and sodium lauryl sulphate form by the mass ratio of 8:2;
Described mix monomer B is vinylbenzene: methyl methacrylate: butyl acrylate: vinyltriethoxysilane: methacrylic acid: ten trifluoro octyl group Trimethoxy silanes are pressed the mixture of 1:3.2:4.8:0.5:0.05:1.8 mass ratio.
According to the high hydrophobic type hide finishes excellent property of the present invention preparation, to film and compare with pure third, the contact angle that high hydrophobic type hide finishes is filmed with water has improved 46 °, has filmed the 24h water absorption decreased 49.74%.The properties of filming sees Table 1.
Table 1 properties of filming
Claims (3)
1. the preparation method of a high hydrophobic type hide finishes is characterized in that:
1) at first with there-necked flask heating in water bath to 45 ℃～50 ℃, then in there-necked flask, add 22 parts of deionized water solutions that are dissolved with 0.6 part of emulsifying agent and 0.1 part ~ 0.14 part of sodium bicarbonate by mass fraction, after emulsification evenly, add again 5 parts of mix monomer A, stir 20min, add again 3.5 parts of deionized water solutions that are dissolved with 0.06 part ~ 0.09 part of initiator, stir 30min, be warming up to 75 ℃ ~ 80 ℃, reaction 30min obtains seed emulsion;
2) drip simultaneously the stratum nucleare pre-emulsion that is formed by 0.1 part of emulsifying agent, 2.5 parts of deionized waters, 5.5 parts of mix monomer A and 3 parts of deionized waters that are dissolved with 0.024 part ~ 0.036 part of initiator in the seed emulsion with constant pressure funnel, 2h ~ 2.5h drips off, formation stratum nucleare emulsion after isothermal reaction is finished;
3) in the stratum nucleare emulsion, drip by 0.5 part of emulsifying agent, 12.5 parts of deionized waters and 24.5 parts of shell pre-emulsions that mix monomer B forms simultaneously by constant pressure funnel again, be dissolved with 13.5 parts of deionized water solutions of 0.116 part ~ 0.174 part of initiator, 3h ~ 4h drips off, after isothermal reaction is finished, be warming up to 85 ℃ and react again 2h, be cooled to 40 ℃ and namely get high hydrophobic type hide finishes;
The described mix monomer A mixture that to be methyl methacrylate mix by the mass ratio of 1:1 ~ 6 with butyl acrylate;
The described emulsifying agent mixture that to be polyoxyethylene nonylphenol ether-2-sulfonic group monomester succinate disodium salt and sodium lauryl sulphate form by the mass ratio of 8:2;
Described mix monomer B is vinylbenzene: methyl methacrylate: butyl acrylate: vinyltriethoxysilane: methacrylic acid: organic fluorine is pressed 1:(2.2 ~ 3.32): (3.68 ~ 4.8): (0.24 ~ 0.5): (0 ~ 0.2): the mixture of (1 ~ 2) mass ratio.
2. the preparation method of high hydrophobic type hide finishes according to claim 1, it is characterized in that: described initiator is the ammonium persulphate Potassium Persulphate.
3. the preparation method of high hydrophobic type hide finishes according to claim 1, it is characterized in that: described organic fluorine is vinylformic acid hexafluoro butyl ester, dodecafluorhe-ptylacrylate, methacrylic acid 2,2,2-trifluoro ethyl ester, Hexafluorobutyl mathacrylate, dodecafluoroheptyl methacrylate, ten difluoro heptyl propyl group methyl dimethoxysilanes, ten difluoro heptyl propyl trimethoxy silicanes or ten trifluoro octyl group Trimethoxy silanes.
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| CN103937357A (en) * | 2014-03-28 | 2014-07-23 | 陕西科技大学 | Preparation method of water-repellent hybrid fluorine-containing resin coating |
| CN104987458A (en) * | 2015-07-22 | 2015-10-21 | 陕西科技大学 | Non-ionic fluorine-containing emulsion and preparation method therefor |
| CN105256578A (en) * | 2015-11-09 | 2016-01-20 | 广州大学 | Waterborne three-proofing leather finishing agent and using method thereof |
| CN107541127A (en) * | 2016-06-27 | 2018-01-05 | 威县双赢化工有限公司 | A kind of high-strength waterproof emulsion and preparation method thereof |
| CN108484834A (en) * | 2018-03-13 | 2018-09-04 | 广州立邦涂料有限公司 | A kind of core-shell emulsion and the environment-friendly interior wall coating containing the lotion |
| CN109182622A (en) * | 2018-08-09 | 2019-01-11 | 广州市迪孚卡乐进出口贸易有限公司 | A kind of corium nursing waterproof film forming agent and preparation method thereof |
| CN109651558A (en) * | 2018-11-06 | 2019-04-19 | 广州集泰化工股份有限公司 | A kind of water soluble acrylic acid dispersion of self-crosslinking core-shell structure and its preparation method and application |
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| CN103937357A (en) * | 2014-03-28 | 2014-07-23 | 陕西科技大学 | Preparation method of water-repellent hybrid fluorine-containing resin coating |
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| CN104987458A (en) * | 2015-07-22 | 2015-10-21 | 陕西科技大学 | Non-ionic fluorine-containing emulsion and preparation method therefor |
| CN104987458B (en) * | 2015-07-22 | 2017-03-15 | 陕西科技大学 | A kind of non-ionic fluorine-containing latex and preparation method thereof |
| CN105256578A (en) * | 2015-11-09 | 2016-01-20 | 广州大学 | Waterborne three-proofing leather finishing agent and using method thereof |
| CN105256578B (en) * | 2015-11-09 | 2019-02-12 | 广州大学 | A kind of aqueous three proofings leather finishing agent and its application method |
| CN107541127A (en) * | 2016-06-27 | 2018-01-05 | 威县双赢化工有限公司 | A kind of high-strength waterproof emulsion and preparation method thereof |
| CN107541127B (en) * | 2016-06-27 | 2020-09-04 | 威县双赢化工有限公司 | High-strength waterproof emulsion and preparation method thereof |
| CN108484834A (en) * | 2018-03-13 | 2018-09-04 | 广州立邦涂料有限公司 | A kind of core-shell emulsion and the environment-friendly interior wall coating containing the lotion |
| CN109182622A (en) * | 2018-08-09 | 2019-01-11 | 广州市迪孚卡乐进出口贸易有限公司 | A kind of corium nursing waterproof film forming agent and preparation method thereof |
| CN109182622B (en) * | 2018-08-09 | 2021-02-26 | 广州市迪孚卡乐进出口贸易有限公司 | Leather care waterproof film forming agent and preparation method thereof |
| CN109651558A (en) * | 2018-11-06 | 2019-04-19 | 广州集泰化工股份有限公司 | A kind of water soluble acrylic acid dispersion of self-crosslinking core-shell structure and its preparation method and application |
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