CN104211879A - Method for preparing high-solid-content graphene oxide grafted polyacrylate composite emulsion by using in-situ method - Google Patents
Method for preparing high-solid-content graphene oxide grafted polyacrylate composite emulsion by using in-situ method Download PDFInfo
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Abstract
The invention relates to a method for preparing a high-solid-content graphene oxide grafted polyacrylate composite emulsion by using an in-situ method. The method comprises the following steps: carrying out ultrasonic treatment on mixed graphene oxide, sulfoxide chloride and N,N-dimethyl formamide; refluxing, raising temperature, carrying out heat preservation and cooling; adding N,N-dimethyl formamide to perform rotary evaporation; adding triethylamine and hydroxyethyl acrylate, and dissolving black powder which is obtained by suction filtration and washing into distilled water; adding sodium lauryl sulfate to carry out ultrasonic treatment, thereby obtaining double-bonded graphene oxide; mixing the double-bonded graphene oxide with sodium lauryl sulfate and distilled water to perform ultrasonic treatment; raising temperature and adding ammonium persulfate and distilled water; and dropwise adding acrylic acid, methyl methacrylate, butyl acrylate and an initiator solution, carrying out heat preservation and discharging. By introducing the double-bonded graphene oxide into the preparation process of the polyacrylate emulsion, the obtained composite emulsion is high in solid content, high in film breaking strength, basically invariable in elongation at break, and high in water absorption rate.
Description
Technical field
the present invention relates to a kind of preparation method of polyacrylate dispersion, be specifically related to a kind of method that in-situ method is prepared high solids content graphene oxide grafted polyacrylic acid ester composite emulsion.
Background technology
Graphene (Graphene) be a kind of by carbon atom with sp
2hybridized orbital forms the flat film that hexangle type is honeycomb lattice, has good electricity, calorifics and mechanical property etc., thereby is widely used in the research of the aspects such as heat-resisting and fire-retardant composite in polymeric substrate, composite conductive thin film, fortifying fibre.The compound method of conventional polymkeric substance and Graphene has solution blended process, scorification and in-situ method.Solution blended process is the solution system that can dissolve polymer can make again Graphene disperse based on, and the effect by solvent makes polymkeric substance and Graphene carry out to a certain degree compound.In scorification, do not need solvent, Graphene or modified graphene directly mix under molten with polymkeric substance, and this method is widely used in the compound of thermoplastic polymer.These two kinds of methods are simple, still, due to strong Intermolecular Forces and the surface inertness of graphene film interlayer, make its dispersiveness in organic solvent not good, and also difficult and other organic substrates carry out the compound of profound level.
In-situ method refers to Graphene or modified graphene is incorporated in the preparation process of polymkeric substance, by the method, improves the interaction force between bi-material, reaches the object of preparing stability of composite materials.In-situ method need to carry out modification to Graphene, introduces functional group and makes the effect by functional group between modified graphene and polymeric matrix reach the compound object of original position, is about to Graphene and is grafted on the molecular chain of polymkeric substance.
The research of Graphene modified polyacrylate emulsion mainly concentrates on graphene oxide and restores into Graphene with after polymer emulsion blend, thereby reaches the object of preparing polyacrylic ester/Graphene composite emulsion.It is less that in-situ method is prepared the report of polyacrylic ester/Graphene composite emulsion, and the solid content of the composite emulsion of preparation is in 20% left and right.
Summary of the invention
The object of this invention is to provide a kind of in-situ method and prepare the method for high solids content graphene oxide grafted polyacrylic acid ester composite emulsion, make the composite emulsion that solid content, ultimate strength and water-intake rate are higher.
The technical solution adopted in the present invention is:
In-situ method is prepared the method for high solids content graphene oxide grafted polyacrylic acid ester composite emulsion, it is characterized in that:
By following steps, realized:
Step 1: the preparation of two key graphene oxides:
In 100mL there-necked flask, add 0.2-0.5 part graphene oxide, 25-40 part sulfur oxychloride and 0.5-0.8 part DMF, supersound process 30-90min;
Add reflux logical nitrogen, from room temperature, be warmed up to 50-80 ℃, insulation 24-48h;
Be cooled to room temperature, add 20-26 part DMF, rotary evaporation 1-2h at 40-55 ℃;
Add 0.10-0.25 part triethylamine and 0.15-0.30 part Hydroxyethyl acrylate, stirring at normal temperature 6-12h, placement is spent the night, and removes supernatant liquor;
Add 500 parts of distilled water suction filtrations, use distilled water wash solid sample, the black powder obtaining is dissolved in 20-50 part distilled water, add 0.2-0.5 part sodium lauryl sulphate, supersound process 10-40min, lyophilize obtains two key graphene oxides;
Step 2: the preparation of graphene oxide graft polypropylene acid esters high solids content composite emulsion:
In 100mL there-necked flask, add two key graphene oxides of 0.01-0.04 part, the sodium lauryl sulphate of 2.0-3.5 part and distilled water 24-34 part, stir it is mixed, supersound process 15-30min;
Be warming up to after 75-80 ℃, add the mixed solution of 0.1-0.4 part ammonium persulphate and 2.3-9.0 part distilled water, stir 10min; Drip vinylformic acid 0.6-2.4 part, methyl methacrylate 4-10 part, butyl acrylate 10-18 part and initiator solution, initiator solution is formulated by the ammonium persulphate of 0.1-0.4 part and the distilled water of 2.3-9.0 part, 60-120min adds, insulation 60min, discharging.
The present invention has the following advantages:
The present invention introduces two key graphene oxides in the preparation process of polyacrylate dispersion, has prepared the composite emulsion of high solids content.This patent is for improving the interaction of polyacrylic ester molecular chain in Graphene and emulsion, graphene oxide is carried out to the modification of two keys, on its surface, introduce vinyl, it is being incorporated in the preparation process of polyacrylate dispersion by suitable technique, by the reaction between vinyl, reach the object of graphene oxide graft polypropylene acid esters, on this basis the technique of letex polymerization is designed, polymerization fully disperses two key graphene oxides by the effect of emulsifying agent in earlier stage; Add in advance part initiator, make a large amount of absorption initiators on two key graphene oxide lamellas, for later stage graft polymerization provides more reaction site, thereby prepare the composite emulsion that solid content is high.Make like this graphene oxide be grafted on polyacrylic ester molecular chain by the free radical reaction between vinyl, form stable covalent linkage between the two, utilize the good physical and mechanical properties of Graphene class material to reach the enhancement to polyacrylic ester molecular chain, and then show good mechanical property.In addition, the introducing of graphene oxide increases the space between molecular chain, is beneficial to entering of water molecules, and matrix material wettability or water absorbability are had to significant castering action.
Through evidence, preparation method of the present invention can obtain solid content at the composite emulsion of 40% left and right, and the film forming of composite emulsion is than pure-acrylic emulsion, and ultimate strength has improved 40%, and elongation at break is substantially constant, and water-intake rate has improved 100%.
Embodiment
Below in conjunction with embodiment, the present invention will be described in detail.
The present invention introduces two key graphene oxides in the preparation process of polyacrylate dispersion, has prepared the composite emulsion of high solids content.This patent is for improving the interaction of polyacrylic ester molecular chain in Graphene and emulsion, graphene oxide is carried out to the modification of two keys, on its surface, introduce vinyl, it is being incorporated in the preparation process of polyacrylate dispersion by suitable technique, by the reaction between vinyl, reach the object of preparing high solids content graphene oxide grafted polyacrylic acid ester composite emulsion.Make like this graphene oxide be grafted on polyacrylic ester molecular chain by the free radical reaction between vinyl, form stable covalent linkage between the two, utilize the good physical and mechanical properties of Graphene class material to reach the enhancement to polyacrylic ester molecular chain, and then show good mechanical property.In addition, the introducing of graphene oxide increases the space between molecular chain, is beneficial to entering of water molecules, and matrix material wettability or water absorbability are had to significant castering action.
In-situ method involved in the present invention is prepared the method for high solids content graphene oxide grafted polyacrylic acid ester composite emulsion, by following steps, realizes (consumption in following steps all refers to mass parts):
Step 1: the preparation of two key graphene oxides:
In 100mL there-necked flask, add 0.2-0.5 part graphene oxide (GO), 25-40 part sulfur oxychloride (SOCl
2) and 0.5-0.8 part DMF (DMF), supersound process 30-90min;
Add reflux logical nitrogen, from room temperature, be warmed up to 50-80 ℃, insulation 24-48h;
Be cooled to room temperature, add 20-26 part DMF (DMF), rotary evaporation 1-2h at 40-55 ℃;
Add 0.10-0.25 part triethylamine and 0.15-0.30 part Hydroxyethyl acrylate (HEA), stirring at normal temperature 6-12h, placement is spent the night, and removes supernatant liquor;
Add 500 parts of distilled water suction filtrations, use distilled water wash solid sample, the black powder obtaining is dissolved in 20-50 part distilled water, add 0.2-0.5 part sodium lauryl sulphate (SDS), supersound process 10-40min, lyophilize obtains two key graphene oxides;
Step 2: the preparation of graphene oxide graft polypropylene acid esters high solids content composite emulsion:
In 100mL there-necked flask, add two key graphene oxides of 0.01-0.04 part, the sodium lauryl sulphate (SDS) of 2.0-3.5 part and distilled water 24-34 part, stir it is mixed, supersound process 15-30min;
Be warming up to after 75-80 ℃, add the mixed solution of 0.1-0.4 part ammonium persulphate (APS) and 2.3-9.0 part distilled water, stir 10min; Drip vinylformic acid (AA) 0.6-2.4 part, methyl methacrylate (MMA) 4-10 part, butyl acrylate (BA) 10-18 part and initiator solution, initiator solution is formulated by the ammonium persulphate (APS) of 0.1-0.4 part and the distilled water of 2.3-9.0 part, 60-120min adds, insulation 60min, discharging.
Embodiment 1:
Step 1: the preparation of two key graphene oxides:
In 100mL there-necked flask, add 0.2 part of graphene oxide (GO), 25 parts of sulfur oxychloride (SOCl
2) and 0.5 part of DMF (DMF), supersound process 30min;
Add reflux logical nitrogen, from room temperature, be warmed up to 50 ℃, insulation 24h;
Be cooled to room temperature, add 20 parts of DMFs (DMF), rotary evaporation 1h at 40 ℃;
Add 0.10 part of triethylamine and 0.15 part of Hydroxyethyl acrylate (HEA), stirring at normal temperature 6h, placement is spent the night, and removes supernatant liquor;
Add 500 parts of distilled water suction filtrations, use distilled water wash solid sample, the black powder obtaining is dissolved in 20 parts of distilled water, add 0.2 part of sodium lauryl sulphate (SDS), supersound process 10min, lyophilize obtains two key graphene oxides;
Step 2: the preparation of graphene oxide graft polypropylene acid esters high solids content composite emulsion:
In 100mL there-necked flask, add 24 parts of two key graphene oxides of 0.01 part, the sodium lauryl sulphate (SDS) of 2.0 parts and distilled water, stir it is mixed, supersound process 15min;
Be warming up to after 75 ℃, add the mixed solution of 0.1 part of ammonium persulphate (APS) and 2.3 parts of distilled water, stir 10min; Drip 0.6 part, vinylformic acid (AA), 4 parts of methyl methacrylates (MMA), 10 parts of butyl acrylates (BA) and initiator solution, initiator solution is formulated by the distilled water of the ammonium persulphate (APS) of 0.1 part and 2.3 parts, 60min adds, insulation 60min, discharging.
Embodiment 2:
Step 1: the preparation of two key graphene oxides:
In 100mL there-necked flask, add 0.35 part of graphene oxide (GO), 32 parts of sulfur oxychloride (SOCl
2) and 0.65 part of DMF (DMF), supersound process 60min;
Add reflux logical nitrogen, from room temperature, be warmed up to 65 ℃, insulation 36h;
Be cooled to room temperature, add 23 parts of DMFs (DMF), rotary evaporation 1.5h at 47 ℃;
Add 0.17 part of triethylamine and 0.22 part of Hydroxyethyl acrylate (HEA), stirring at normal temperature 9h, placement is spent the night, and removes supernatant liquor;
Add 500 parts of distilled water suction filtrations, use distilled water wash solid sample, the black powder obtaining is dissolved in 35 parts of distilled water, add 0.35 part of sodium lauryl sulphate (SDS), supersound process 25min, lyophilize obtains two key graphene oxides;
Step 2: the preparation of graphene oxide graft polypropylene acid esters high solids content composite emulsion:
In 100mL there-necked flask, add 29 parts of two key graphene oxides of 0.02 part, the sodium lauryl sulphate (SDS) of 2.7 parts and distilled water, stir it is mixed, supersound process 22min;
Be warming up to after 77 ℃, add the mixed solution of 0.2 part of ammonium persulphate (APS) and 5.6 parts of distilled water, stir 10min; Drip 1.5 parts, vinylformic acid (AA), 7 parts of methyl methacrylates (MMA), 14 parts of butyl acrylates (BA) and initiator solution, initiator solution is formulated by the distilled water of the ammonium persulphate (APS) of 0.2 part and 5.6 parts, 90min adds, insulation 60min, discharging.
Embodiment 3:
Step 1: the preparation of two key graphene oxides:
In 100mL there-necked flask, add 0.5 part of graphene oxide (GO), 40 parts of sulfur oxychloride (SOCl
2) and 0.8 part of DMF (DMF), supersound process 90min;
Add reflux logical nitrogen, from room temperature, be warmed up to 80 ℃, insulation 48h;
Be cooled to room temperature, add 26 parts of DMFs (DMF), rotary evaporation 2h at 55 ℃;
Add 0.25 part of triethylamine and 0.30 part of Hydroxyethyl acrylate (HEA), stirring at normal temperature 12h, placement is spent the night, and removes supernatant liquor;
Add 500 parts of distilled water suction filtrations, use distilled water wash solid sample, the black powder obtaining is dissolved in 50 parts of distilled water, add 0.5 part of sodium lauryl sulphate (SDS), supersound process 40min, lyophilize obtains two key graphene oxides;
Step 2: the preparation of graphene oxide graft polypropylene acid esters high solids content composite emulsion:
In 100mL there-necked flask, add 34 parts of two key graphene oxides of 0.04 part, the sodium lauryl sulphate (SDS) of 3.5 parts and distilled water, stir it is mixed, supersound process 30min;
Be warming up to after 80 ℃, add the mixed solution of 0.4 part of ammonium persulphate (APS) and 9.0 parts of distilled water, stir 10min; Drip 2.4 parts, vinylformic acid (AA), 10 parts of methyl methacrylates (MMA), 18 parts of butyl acrylates (BA) and initiator solution, initiator solution is formulated by the distilled water of the ammonium persulphate (APS) of 0.4 part and 9.0 parts, 120min adds, insulation 60min, discharging.
Innovative point of the present invention focuses on in-situ method and high solids content, and the object of graphene oxide being carried out to two key modifications is in order to make it carry out chemical reaction with polyacrylic ester, forms chemical bond, but not physical blending.Generally, due to the restriction of technology, the solid content of polyacrylate dispersion and modified graphene oxide composite emulsion is lower, the composite emulsion of preparing according to the present invention, solid content can reach 40% left and right, the intensity of emulsion film forming has improved 40%, and elongation at break is substantially constant, and water-intake rate has improved 100%.
It is cited that content of the present invention is not limited to embodiment, and the conversion of any equivalence that those of ordinary skills take technical solution of the present invention by reading specification sheets of the present invention, is claim of the present invention and contains.
Claims (1)
1. in-situ method is prepared the method for high solids content graphene oxide grafted polyacrylic acid ester composite emulsion, it is characterized in that:
By following steps, realized:
Step 1: the preparation of two key graphene oxides:
In 100mL there-necked flask, add 0.2-0.5 part graphene oxide, 25-40 part sulfur oxychloride and 0.5-0.8 part DMF, supersound process 30-90min;
Add reflux logical nitrogen, from room temperature, be warmed up to 50-80 ℃, insulation 24-48h;
Be cooled to room temperature, add 20-26 part DMF, rotary evaporation 1-2h at 40-55 ℃;
Add 0.10-0.25 part triethylamine and 0.15-0.30 part Hydroxyethyl acrylate, stirring at normal temperature 6-12h, placement is spent the night, and removes supernatant liquor;
Add 500 parts of distilled water suction filtrations, use distilled water wash solid sample, the black powder obtaining is dissolved in 20-50 part distilled water, add 0.2-0.5 part sodium lauryl sulphate, supersound process 10-40min, lyophilize obtains two key graphene oxides;
Step 2: the preparation of graphene oxide graft polypropylene acid esters high solids content composite emulsion:
In 100mL there-necked flask, add two key graphene oxides of 0.01-0.04 part, the sodium lauryl sulphate of 2.0-3.5 part and distilled water 24-34 part, stir it is mixed, supersound process 15-30min;
Be warming up to after 75-80 ℃, add the mixed solution of 0.1-0.4 part ammonium persulphate and 2.3-9.0 part distilled water, stir 10min; Drip vinylformic acid 0.6-2.4 part, methyl methacrylate 4-10 part, butyl acrylate 10-18 part and initiator solution, initiator solution is formulated by the ammonium persulphate of 0.1-0.4 part and the distilled water of 2.3-9.0 part, 60-120min adds, insulation 60min, discharging.
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| CN105085835A (en) * | 2014-05-14 | 2015-11-25 | 泰山玻璃纤维有限公司 | Graphene modified polyvinyl acetate film forming agent preparation method |
| CN105879847A (en) * | 2015-01-12 | 2016-08-24 | 冯云 | Nano-composite mesoporous material |
| CN106084106A (en) * | 2016-06-15 | 2016-11-09 | 湖州超能生化有限公司 | A kind of preparation method of low molecular weight sodium polyacrylate |
| CN106832220A (en) * | 2016-12-30 | 2017-06-13 | 长沙乐远化工科技有限公司 | A kind of preparation of epoxy acrylate of Graphene graft modification and its application in photocureable coating |
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| CN105085835A (en) * | 2014-05-14 | 2015-11-25 | 泰山玻璃纤维有限公司 | Graphene modified polyvinyl acetate film forming agent preparation method |
| CN105085835B (en) * | 2014-05-14 | 2018-01-16 | 泰山玻璃纤维有限公司 | A kind of graphene modified polyvinyl acetate class film forming agent preparation method |
| CN105879847A (en) * | 2015-01-12 | 2016-08-24 | 冯云 | Nano-composite mesoporous material |
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| CN106832220A (en) * | 2016-12-30 | 2017-06-13 | 长沙乐远化工科技有限公司 | A kind of preparation of epoxy acrylate of Graphene graft modification and its application in photocureable coating |
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| CN109082056A (en) * | 2018-07-18 | 2018-12-25 | 桐城市明丽碳化硼制品有限公司 | A kind of rare earth graphene film and preparation method thereof |
| CN109486335A (en) * | 2018-11-22 | 2019-03-19 | 福州大学 | A kind of carbon-carbon double bond addition prepares graphene/phenylethylene ethylene/propenoic acid ester anticorrosive paint method |
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| CN110218284B (en) * | 2019-05-16 | 2022-09-23 | 国家纳米科学中心 | Preparation method of graphene-based polymer and preparation method of quartz crystal oscillator plate |
| CN110698944A (en) * | 2019-11-06 | 2020-01-17 | 青岛爱尔家佳新材料股份有限公司 | Graphene oxide modified water-based fireproof coating and preparation method thereof |
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