CN101831230A - Method for preparing polyacrylate/nano-SiO2 compound coating agent by using reactive emulsifier - Google Patents
Method for preparing polyacrylate/nano-SiO2 compound coating agent by using reactive emulsifier Download PDFInfo
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- CN101831230A CN101831230A CN 201010144027 CN201010144027A CN101831230A CN 101831230 A CN101831230 A CN 101831230A CN 201010144027 CN201010144027 CN 201010144027 CN 201010144027 A CN201010144027 A CN 201010144027A CN 101831230 A CN101831230 A CN 101831230A
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Abstract
The invention relates to a method for preparing polyacrylate/nano-SiO2 compound coating agent which is suitable for bottom layer coating in clothing leathers and instep leathers, by using a reactive emulsifier. The polyacrylate has excellent optical stability, chemical resistance and favorable adhesive property and is widely used as an adhesive, a coating film-forming agent, a functional film, and a medical polymer and in the fields of water treatment and the like, but polyacrylate emulsion has the defects of embrittlement at low temperature, stickiness and strength loss at high temperature, easy after tack and the like, which restrict the application range and the use value of the polyacrylate emulsion. In the invention, the polyacrylate/nano-SiO2 compound coating agent is prepared by substituting conventional emulsifier with reactive emulsifier by utilizing the nanometer effect of an inorganic nanometer material and synchronously adopting a conventional emulsion polymerization method and a sol-gel method. The compound coating agent prepared by the invention has fine granules, excellent adhesive force, good filling capacity, strong water resistance and flexible and transparent formed film, and meanwhile, the damages to the human body and the environment, which are caused by the use of large amount of emulsifiers, are reduced.
Description
Technical field
The present invention relates to a kind of employing reactive emulsifier and prepare polyacrylic ester/nanometer SiO
2The method of composite paint, particularly a kind of method that is applicable to the composite paint that clothing leather, upper leather middle and bottom layers are covered with paint, lacquer, colour wash, etc.
Technical background
Leather finish is the important procedure during leather goods are produced, and it not only can increase the leather surface aesthetic property, improves the wearing quality of leather, can also revise the leather surface defective, enlarges leather use range and use value.Hide finishes is as the top finishing material of leather, and external impression, sanitation performance and the physical and mechanical properties of leatherware all had fundamental influence.Therefore polyacrylic ester is widely used as aspects such as tackiness agent, coating membrane-forming agent owing to have excellent light stability, chemical-resistant and good adhesive property.But polyacrylate dispersion still exists, and low temperature becomes fragile, high temperature becomes shortcomings such as strong, the easy after tack of glutinous mistake, has limited its range of application and use value.Letex polymerization is to produce one of important method of polyacrylic ester, have heat radiation easily, unique advantages such as rate of polymerization is big, molecular weight is high, inexpensive, safety, environmental protection, now be widely used.But the existence of small-molecular emulsifier also can cause certain defective to emulsion property, because the emulsifying agent molecule is unbound state in polymeric film, move to the glue-line surface easily, therefore the performance such as bonding, water-fast, heat-resisting of glued membrane has big gap with solvent borne polymer phase ratio, thereby uses emulsifying agents also can cause environmental pollution to limit the development space of polymer emulsion in a large number simultaneously.
Summary of the invention
The purpose of this invention is to provide a kind of polyacrylic ester/nanometer SiO that adopts the reactive emulsifier preparation to be applicable to clothing leather, the covering with paint of upper leather middle and bottom layers
2The method of composite paint.
The technical solution used in the present invention is:
Described reactive emulsifier prepares polyacrylic ester/nanometer SiO
2The method of composite paint is characterized in that: the raw material compositing range of nano combined finishing agent is:
Acrylic ester monomer 22wt%～28wt%;
Emulsifying agent 2wt%～5wt%;
Initiator 0.4wt%～0.8wt%;
Tetraethoxy 0.5wt%～2wt%;
Silane coupling agent 3wt%～5wt%;
All the other are deionized water;
Its preparation method is:
With there-necked flask heating in water bath to 38～43 ℃, add emulsifying agent and water, stir certain hour, after treating that emulsifying agent is uniformly dispersed, add tetraethoxy and silane coupling agent, isothermal reaction 20min, the esters of acrylic acid mix monomer of adding 1/3～1/5 is warmed up to 70～75 ℃, reaction 30min, drip residue mix monomer and initiator solution respectively, after dropwising, be warming up to 80～85 ℃, insulation reaction 2h, regulate about emulsion pH to 7 under the room temperature, promptly get nano combined finishing agent.
Described emulsifying agent is one or both in 1-allyloxy-3-(4-nonylphenol)-2-propyl alcohol polyoxyethylene ether ammonium sulfate, hydroxyethyl methacrylate propanesulfonic acid sodium, 3-allyloxy-2-hydroxyl-1-propane sulfonic acid sodium, 2-acrylamido-2 methyl propane sulfonic acid sodium salt, the sodium vinyl sulfonate.
Described silane coupling agent is a kind of or its mixture in vinyltrimethoxy silane, vinyltriethoxysilane, methacryloxypropyl trimethoxy silane, vinyl silane triisopropoxide, the tetramethyl divinyl disiloxane.
Described initiator is any in ammonium persulphate, Potassium Persulphate or the Sodium Persulfate.
Described acrylic ester monomer is two or more in butyl acrylate, butyl methacrylate, methyl methacrylate, vinylbenzene, the methyl acrylate.
Described acrylic ester monomer adds in batches, and drop rate is 1.5g/min～2.0g/min, and stir speed (S.S.) is 300rpm, and solid content is 28wt%～32wt%.
Described reactive emulsifier prepares polyacrylic ester/nanometer SiO
2The method of composite paint is characterized in that:
With there-necked flask heating in water bath to 38 ℃, add emulsifying agent 1-allyloxy-3-(4-the nonylphenol)-2-propyl alcohol polyoxyethylene ether ammonium sulfate of 2wt% and the deionized water of 60wt%, rotating speed with 300rpm stirs 20min, after treating that emulsifying agent is uniformly dispersed, add the tetraethoxy of 1wt% and the silane coupling agent vinyl Trimethoxy silane of 4wt%, isothermal reaction 20min, add 1/5 butyl acrylate, the mix monomer of methyl methacrylate, mix monomer accounts for the 25wt% of system total mass, two kinds of monomeric mol ratios are 3: 2, be warmed up to 70 ℃, react 30min, drip the ammonium persulfate aqueous solution of remaining mix monomer and 0.5wt% respectively, after dropwising, be warming up to 80 ℃, insulation reaction 2h; Add sodium bicarbonate aqueous solution under the room temperature, regulate emulsion pH about 7, promptly get nano combined finishing agent.
The invention has the beneficial effects as follows:
The present invention adopts reactive emulsifier to carry out letex polymerization, because of it is the tensio-active agent that has reactive group, not only has surfactivity, and has a higher rate of polymerization, can with adsorbed matrix generation chemical reaction, for good and all being bonded to matrix surface becomes the part of matrix, so the electrical property of polymer emulsion, optical property, surface property and water tolerance etc. will be improved; When inorganic nano-particle was scattered in the polymeric matrix, the performance of mixture can obtain very big improvement, especially showed aspects such as thermotolerance, flame retardant resistance and mechanical property.Utilize the composite paint of this method preparation, particle is trickle, clinging power is good, fillibility is good, water tolerance is strong, the film forming soft and transparent; The low temperature that has overcome the existence of conventional polypropylene acid esters hide finishes becomes fragile, high temperature becomes shortcomings such as strong, the easy after tack of glutinous mistake; Reduced effectively and used the disadvantageous effect of small-molecular emulsifier to environment and film performance generation, range of application is wider, more excellent performance.
Embodiment
The present invention is described in detail below by embodiment:
(1) the raw material compositing range of nano combined finishing agent is:
Acrylic ester monomer 22wt%～28wt%;
Emulsifying agent 2wt%～5wt%;
Initiator 0.4wt%～0.8wt%;
Tetraethoxy 0.5wt%～2wt%;
Silane coupling agent 3wt%～5wt%;
All the other are deionized water.
(2) by the following examples, the present invention is further elaborated.
Embodiment 1:
With there-necked flask heating in water bath to 38 ℃, add emulsifying agent 1-allyloxy-3-(4-the nonylphenol)-2-propyl alcohol polyoxyethylene ether ammonium sulfate of 2wt% and the deionized water of 60wt%, rotating speed with 300rpm stirs 20min, after treating that emulsifying agent is uniformly dispersed, add the tetraethoxy of 1wt% and the silane coupling agent vinyl Trimethoxy silane of 4wt%, isothermal reaction 20min.(mix monomer accounts for the 25wt% of system total mass to add the mix monomer of 1/5 butyl acrylate, methyl methacrylate, two kinds of monomeric mol ratios are 3: 2), be warmed up to 70 ℃, reaction 30min, drip the ammonium persulfate aqueous solution of remaining mix monomer and 0.5wt% respectively, after dropwising, be warming up to 80 ℃, insulation reaction 2h; Add sodium bicarbonate aqueous solution under the room temperature, regulate emulsion pH about 7, promptly get nano combined finishing agent.
Embodiment 2:
With there-necked flask heating in water bath to 40 ℃, add emulsifying agent 1-allyloxy-3-(4-the nonylphenol)-2-propyl alcohol polyoxyethylene ether ammonium sulfate of 3wt% and the deionized water of 60wt%, rotating speed with 300rpm stirs 20min, after treating that emulsifying agent is uniformly dispersed, add the tetraethoxy of 0.8wt% and the silane coupling agent tetramethyl divinyl disiloxane of 4wt%, isothermal reaction 20min.(mix monomer accounts for the 26wt% of system total mass to add the mix monomer of 1/5 butyl acrylate, methyl methacrylate, two kinds of monomeric mol ratios are 2: 1), be warmed up to 72 ℃, reaction 30min, drip the persulfate aqueous solution of remaining mix monomer and 0.6wt% respectively, after dropwising, be warming up to 80 ℃, insulation reaction 2h; Add aqueous sodium carbonate under the room temperature, regulate emulsion pH about 7, promptly get nano combined finishing agent.
Embodiment 3:
With there-necked flask heating in water bath to 42 ℃, add emulsifying agent 1-allyloxy-3-(4-the nonylphenol)-2-propyl alcohol polyoxyethylene ether ammonium sulfate of 3.5wt% and the deionized water of 62wt%, rotating speed with 300rpm stirs 20min, after treating that emulsifying agent is uniformly dispersed, add the tetraethoxy of 1.5wt% and the silane coupling agent vinyl triethoxyl silane of 3.5wt%, isothermal reaction 20min.(mix monomer accounts for the 27wt% of system total mass to add the mix monomer of 1/3 butyl acrylate, methyl acrylate, two kinds of monomeric mol ratios 2: 1), be warmed up to 75 ℃, reaction 30min, drip the ammonium persulfate aqueous solution of remaining mix monomer and 0.7wt% respectively, after dropwising, be warming up to 80 ℃, insulation reaction 2h; Add sodium acetate aqueous solution under the room temperature, regulate emulsion pH about 7, promptly get nano combined finishing agent.
Embodiment 4:
With there-necked flask heating in water bath to 45 ℃, emulsifying agent 1-allyloxy-3-(4-the nonylphenol)-2-propyl alcohol polyoxyethylene ether ammonium sulfate, the HPMAS of 1wt% and the deionized water of 60wt% that add 3wt%, rotating speed with 300rpm stirs 20min, after treating that emulsifying agent is uniformly dispersed, add the tetraethoxy of 2wt% and the silane coupling agent vinyl three isopropoxy silane of 3.5wt%, isothermal reaction 20min.(mix monomer accounts for the 27wt% of system total mass to add the mix monomer of 1/3 butyl acrylate, methyl acrylate, two kinds of monomeric mol ratios are 2: 1), be warmed up to 75 ℃, reaction 30min, begin to drip respectively the sodium persulfate aqueous solution of remaining mix monomer and 0.8wt%, after dropwising, be warming up to 85 ℃, insulation reaction 2h; Add the sodium hydrogen phosphate aqueous solution under the room temperature, regulate emulsion pH about 7, promptly get nano combined finishing agent.
Embodiment 5:
With there-necked flask heating in water bath to 45 ℃, add emulsifying agent 1-allyloxy-3-(4-the nonylphenol)-2-propyl alcohol polyoxyethylene ether ammonium sulfate of 3.5wt% and the deionized water of 1.5wt%HPMAS and 58wt%, rotating speed with 300rpm stirs 20min, after treating that emulsifying agent is uniformly dispersed, add the tetraethoxy of 1wt% and the silane coupling agent methacryloxypropyl trimethoxy silane of 3wt%, isothermal reaction 20min.(mix monomer accounts for the 25wt% of system total mass to add 1/3 butyl acrylate, methyl methacrylate and cinnamic mix monomer, three kinds of monomeric mol ratios are 3: 2: 1), be warmed up to 75 ℃, reaction 30min, drip the sodium persulfate aqueous solution of remaining mix monomer and 0.8wt% respectively, after dropwising, be warming up to 85 ℃, insulation reaction 2h; Add ammonia soln under the room temperature, regulate emulsion pH about 7, promptly get nano combined finishing agent.
Claims (4)
1. reactive emulsifier prepares polyacrylic ester/nanometer SiO
2The method of composite paint is characterized in that:
The raw material compositing range of nano combined finishing agent is:
Acrylic ester monomer 22wt%～28wt%;
Emulsifying agent 2wt%～5wt%;
Initiator 0.4wt%～0.8wt%;
Tetraethoxy 0.5wt%～2wt%;
Silane coupling agent 3wt%～5wt%;
All the other are deionized water;
Its preparation method is:
With there-necked flask heating in water bath to 38～43 ℃, add emulsifying agent and water, stir certain hour, after treating that emulsifying agent is uniformly dispersed, add tetraethoxy and silane coupling agent, isothermal reaction 20min, the esters of acrylic acid mix monomer of adding 1/3～1/5 is warmed up to 70～75 ℃, reaction 30min, drip residue mix monomer and initiator solution respectively, after dropwising, be warming up to 80～85 ℃, insulation reaction 2h, regulate about emulsion pH to 7 under the room temperature, promptly get nano combined finishing agent;
Described emulsifying agent is one or both in 1-allyloxy-3-(4-nonylphenol)-2-propyl alcohol polyoxyethylene ether ammonium sulfate, hydroxyethyl methacrylate propanesulfonic acid sodium, 3-allyloxy-2-hydroxyl-1-propane sulfonic acid sodium, 2-acrylamido-2 methyl propane sulfonic acid sodium salt, the sodium vinyl sulfonate;
Described silane coupling agent is a kind of or its mixture in vinyltrimethoxy silane, vinyltriethoxysilane, methacryloxypropyl trimethoxy silane, vinyl silane triisopropoxide, the tetramethyl divinyl disiloxane;
Described initiator is any in ammonium persulphate, Potassium Persulphate or the Sodium Persulfate.
2. reactive emulsifier according to claim 1 prepares polyacrylic ester/nanometer SiO
2The method of composite paint is characterized in that: described acrylic ester monomer is two or more in butyl acrylate, butyl methacrylate, methyl methacrylate, vinylbenzene, the methyl acrylate.
3. reactive emulsifier according to claim 1 prepares polyacrylic ester/nanometer SiO
2The method of composite paint is characterized in that: described acrylic ester monomer adds in batches, and drop rate is 1.5g/min～2.0g/min, and stir speed (S.S.) is 300rpm, and solid content is 28wt%～32wt%.
4. prepare polyacrylic ester/nanometer SiO according to claim 1,2 or 3 described reactive emulsifiers
2The method of composite paint is characterized in that:
With there-necked flask heating in water bath to 38 ℃, add emulsifying agent 1-allyloxy-3-(4-the nonylphenol)-2-propyl alcohol polyoxyethylene ether ammonium sulfate of 2wt% and the deionized water of 60wt%, rotating speed with 300rpm stirs 20min, after treating that emulsifying agent is uniformly dispersed, add the tetraethoxy of 1wt% and the silane coupling agent vinyl Trimethoxy silane of 4wt%, isothermal reaction 20min, add 1/5 butyl acrylate, the mix monomer of methyl methacrylate, mix monomer accounts for the 25wt% of system total mass, and two kinds of monomeric mol ratios are 3: 2, is warmed up to 70 ℃, reaction 30min, drip the ammonium persulfate aqueous solution of remaining mix monomer and 0.5wt% respectively, after dropwising, be warming up to 80 ℃, insulation reaction 2h, add sodium bicarbonate aqueous solution under the room temperature, regulate emulsion pH about 7, promptly get nano combined finishing agent.
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| CN 201010144027 CN101831230A (en) | 2010-04-09 | 2010-04-09 | Method for preparing polyacrylate/nano-SiO2 compound coating agent by using reactive emulsifier |
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| CN 201010144027 CN101831230A (en) | 2010-04-09 | 2010-04-09 | Method for preparing polyacrylate/nano-SiO2 compound coating agent by using reactive emulsifier |
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| CN102020817A (en) * | 2010-11-11 | 2011-04-20 | 陕西科技大学 | Method for preparing nano silicon oxide modified silicone acrylate emulsifier-free emulsion |
| CN102140217A (en) * | 2011-03-31 | 2011-08-03 | 广东工业大学 | Preparation method and use of polyacrylate/silica solution composite material |
| CN102304316A (en) * | 2011-07-22 | 2012-01-04 | 陕西科技大学 | Polyacrylate/nanometer ZnO composite finishing agent and preparation method thereof |
| CN103059188A (en) * | 2012-12-18 | 2013-04-24 | 华中科技大学 | Preparing method of composite styrene-acrylic emulsion containing silicon dioxide |
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| WO2013078778A1 (en) * | 2011-12-02 | 2013-06-06 | Ma Jianzhong | Method for preparing casein-base nanometer silicon dioxide composite leather coating agent by using bi-in situ method |
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Application publication date: 20100915 |