CN104193878A - Preparation method of NMA (N-methylol acrylamide) modified fluorinated acrylate emulsion - Google Patents
Preparation method of NMA (N-methylol acrylamide) modified fluorinated acrylate emulsion Download PDFInfo
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- CN104193878A CN104193878A CN201410349927.6A CN201410349927A CN104193878A CN 104193878 A CN104193878 A CN 104193878A CN 201410349927 A CN201410349927 A CN 201410349927A CN 104193878 A CN104193878 A CN 104193878A
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- fluorinated acrylate
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Abstract
The invention discloses a preparation method of an NMA (N-methylol acrylamide) modified fluorinated acrylate emulsion. The preparation method comprises the following steps: firstly, preparing a solution by use of an anionic emulsifier, a non-ionic emulsifier and a crosslinking agent with part of deionized water; adding the residual deionized water, a fluorinated acrylate monomer and an acrylate monomer into a polymerization kettle; introducing nitrogen for replacing; after pre-emulsifying for 30 minutes at 60 DEG C, firstly, adding a reducing agent and then simultaneously adding an oxidizing agent and a copper sulfate aqueous solution; and maintaining the temperature of a water bath at 70 DEG C and reacting for 4-7 hours. By adding a special catalyst copper sulfate into a redox initiating system and strictly controlling the reaction temperature in the polymerization process, under the condition of not adding comonomers, 40-50nm NMA modified fluorinated acrylate emulsion can be obtained within 4-7 hours by feeding at one time. The method is simple to operate and the obtained emulsion is good in stability.
Description
Technical field
The present invention relates to a kind of fluorinated acrylate emulsion, particularly relate to a kind of preparation method of NMA modified fluoride-containing acrylic ester emulsion.
Background technology
Microemulsion is a kind of isotropic, transparent or semitransparent dispersion system on stable on thermodynamics, optics, its particle diameter is less than 100nm, and miniemulsion particle diameter is 100～400nm, ordinary emulsion particle diameter generally in hundreds of nanometer to thousands of nanometers. median size increases and to be twice, and minimum film-forming temperature raises 2.8 ℃.Particle diameter is larger, and the compactness of its latex film and smoothness are also poorer.And the particle diameter of microemulsion is less than order of magnitude of ordinary emulsion, its volume is with regard to little three orders of magnitude, and this reduces the minimum film-forming temperature of microemulsion, and number of effective particles increases greatly, thereby microemulsion has better perviousness and affinity.
Micro-emulsion polymerization reaction is mostly radical polymerization, preparating mechanism be take Micellar nucleation mechanism as main, and homogeneous nucleation is also deposited, and in whole polymerization process, system inside all exists a large amount of micellas, under very high transformation efficiency, still can produce new polymer particle, show the feature of continuous nucleation.In conventional synthetic method, be not in polymerization process, to add comonomer etc., adopt exactly special surface promoting agent, cost is higher, complex operation, and also emulsion property is poor.
Fluorinated acrylate monomer has low surface energy and surface tension, and the acrylic ester monomer copolymerization of easy and structural similitude, on polyacrylic ester polymer side chain, introduce perfluoroalkyl, can obtain waterproof, antifouling, grease proofing, the fluorinated acrylate polymer with good solvent resistance.NMA modified fluoride-containing acrylic ester emulsion latex particle size is very little, there is fabulous wettability, levelling property and rheological, can with conventional emulsions physical blending, realize 2 kinds of emulsion property complementations, the surface property of modified acroleic acid esters polymer is played a very important role.By adding this NMA modified fluoride-containing acrylic ester emulsion, can significantly reduce the viscosity of blending emulsion, improve the water tolerance of glued membrane, solvent resistance, glued membrane has the high transparency, can be used as the protection varnish of metallic substance.
Summary of the invention
The object of the present invention is to provide a kind of method of the NMA of preparation modified fluoride-containing acrylic ester emulsion, in polymerization process, do not add comonomer, and reaction monomers once feeds intake, without adding, adopt [copper sulfate/Potassium Persulphate-Sulfothiorine] catalysis-redox initiation system, in 4-7 hour, just can make the NMA modified fluoride-containing acrylic ester emulsion that particle diameter is 25nm.
It is raw material that NMA modified fluoride-containing acrylic ester emulsion of the present invention be take fluorinated acrylate monomer and acrylic ester monomer, at water soluble oxidized reduction initiating system, metallic salt catalyzer, under the effect of anionic emulsifier, nonionic emulsifier, linking agent, carry out letex polymerization and form.Suitable fluorinated acrylate monomer of the present invention is that (methyl) perfluoroalkyl acrylate, (methyl) vinylformic acid are containing the fluorine-containing alkyl ester of heteroatoms, (methyl) vinylformic acid perfluoroalkyl carboxylic acid amide esters, (methyl) vinylformic acid perfluoroalkyl sulphonamide ester.Suitable acrylic ester monomer of the present invention is (methyl) alkyl-acrylates, (methyl) acrylic acid hydroxy alkyl ester, (methyl) vinylformic acid amido ethyl ester etc.Oxygenant in water soluble oxidized reduction initiating system comprises Potassium Persulphate, ammonium persulphate, reductive agent comprises Sulfothiorine, S-WAT, composite ratio (mass ratio) is 5: 4, and its total consumption is 5～9 parts (the present invention all be take total monomer consumption 100 weight parts as calculating benchmark except particularly pointing out).Suitable anionic emulsifier is alkyl-sulphate or alkylsulfonate, and conventional alkyl-sulphate has sodium lauryl sulphate, potassium octadecyl sulfate etc.; Conventional alkylsulfonate has Sodium dodecylbenzene sulfonate, sodium laurylsulfonate etc.Suitable nonionic emulsifier is poly-lauryl alcohol oxyethane, polypropylene glycol oxyethane, polyethylene oxide Sorbitol Powder mono fatty acid ester, alkylphenol polyoxyethylene.The composite ratio (mass ratio) of anionic emulsifier and nonionic emulsifying agent is 4: 1, and its consumption is 8～10 parts.It is considered herein that in emulsion polymerization systems adds appropriate metallic salt catalyzer can accelerate the generating rate of free radical, nucleation period is shortened, the polymerization initial stage, a large amount of solubilization micelles changed emulsion particle into, thereby obtain the microemulsion that particle diameter is very thin, the metallic salt catalyzer of selecting is copper sulfate, and its consumption is 0.02～0.04 part.The present invention adopts linking agent to improve the physical strength of polymeric film, available linking agent has Viscoat 295 (TMPTA), N hydroxymethyl acrylamide (NMA), Ethylene glycol dimethacrylate (EGDMA), and its consumption is 12 parts.In emulsion polymerization systems of the present invention, the consumption of deionized water is 10～15 times of total monomer consumption.First with part deionized water, various auxiliary agents are mixed with to solution, remaining deionized water and mix monomer are joined in polymeric kettle, logical nitrogen is replaced, and at 60 ℃, after pre-emulsification 30min, first adds Sulfothiorine, again Potassium Persulphate and micro-copper sulfate solution are added simultaneously, maintain bath temperature at 70 ℃, react after 4-7 hour, transformation efficiency reaches 93-98%, cooling discharge, can obtain particle diameter is the NMA modified fluoride-containing acrylic ester emulsion of 20-30nm.
The present invention is owing to having added special catalyst sulfuric acid copper in redox initiation system, and in polymerization process the strict temperature of reaction of controlling, therefore in the situation that not needing to add comonomer, adopt and once feed intake, in 4-7 hour, obtained the NMA modified fluoride-containing acrylic ester emulsion of 40-50nm, simple to operate and gained latex stability is good.
NDJ-1 type Rotary Viscosimeter is measured emulsion viscosity.Condition determination is as follows: surveying fixed time temperature is 25 ℃; Use No. 1 rotor; Rotating speed is 60r/min, sees GB/T1723-1993.
Emulsion package stability
According to GB6753.3-86, measure emulsion package stability.
Freeze-thaw stability
According to GB/T9268-1988, measure emulsion freeze-thaw stability.
Latex film after tackiness
According to GB/T1762-1989, measure paint film after tackiness.
Paint film resistance to medium
According to GB/274-1988, measure the medium-resistance of filming
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention, should understand, these embodiment are only not used in and limit the scope of the invention for the present invention is described, in addition should understand, after having read the content of the present invention's instruction, those skilled in the art can make various changes or modification to the present invention, and these equivalent form of values fall within the application's appended claims limited range equally.
In formula, trifluoroethyl methacrylate can also be the vinylformic acid perfluoroalkyl analog derivatives such as Hexafluorobutyl mathacrylate, dodecafluoroheptyl methacrylate, and methyl methacrylate can also be the acrylic acid alkyl ester derivatives such as butyl acrylate.
According to above formula, water is joined in withstand voltage polymeric kettle, add monomer trifluoroethyl methacrylate and methyl methacrylate, compound emulsifying agent.With nitrogen, replace three times, open and stir, temperature is risen to 60 ℃, after pre-emulsification 30min, first add Sulfothiorine, then Potassium Persulphate and copper sulfate solution are added simultaneously.System moment is become translucent light blue from oyster white, and temperature rises rapidly, maintains bath temperature at 70 ℃, calculates a monomer conversion every two hours.After polyreaction 7 hours, transformation efficiency reaches 97%, cooling discharge, and just can obtain particle diameter is the NMA modified fluoride-containing acrylic ester emulsion of 42.7nm.
Table 1 emulsion and film performance
Table 1 is perfluoroalkyl methacrylate, and alkyl methacrylate mass ratio is gained emulsion and film performance after copolymerization in 1: 4.As can be seen from Table 1, poly-fluorine-containing acrylic ester microemulsion has good water resistance and solvent resistance, and emulsion viscosity is lower, and after tackiness reaches 1 grade, and elongation at break is very low, latex film hardening.Filming of being prepared by this microemulsion has good physicals and lower surface energy, can be used for providing the top coat with outstanding waterproof/antifouling property.
Claims (1)
1. a preparation method for NMA modified fluoride-containing acrylic ester emulsion, is characterized in that, step is as follows:
Take fluorinated acrylate monomer and acrylic ester monomer as raw material, at water soluble oxidized reduction initiating system, metallic salt catalyst sulfuric acid copper, under the effect of anionic emulsifier, nonionic emulsifier and linking agent, carry out letex polymerization;
Described fluorinated acrylate monomer is trifluoroethyl methacrylate or Hexafluorobutyl mathacrylate; Described acrylic ester monomer is methyl methacrylate or butyl acrylate;
Oxygenant in water soluble oxidized reduction initiating system is Potassium Persulphate or ammonium persulphate, reductive agent is Sulfothiorine or S-WAT, oxygenant and reductive agent mass ratio are 5: 4, take total consumption 100 mass parts of fluorinated acrylate monomer and acrylic ester monomer as calculating benchmark, below mentioning consumption is all as benchmark, and the total consumption of water soluble oxidized reduction initiating system is 5～9 parts; Described anionic emulsifier is alkyl-sulphate or alkylsulfonate, and described nonionic emulsifier is poly-lauryl alcohol oxyethane, polypropylene glycol oxyethane, polyethylene oxide Sorbitol Powder mono fatty acid ester, alkylphenol polyoxyethylene; The mass ratio of anionic emulsifier and nonionic emulsifying agent is 4: 1, and total consumption of ionic emulsifying agent and nonionic emulsifying agent is 8～10 parts; Copper sulfate consumption is 0.02～0.04 part; Linking agent has Viscoat 295, N hydroxymethyl acrylamide or Ethylene glycol dimethacrylate, and dosage of crosslinking agent is 12 parts; The consumption of deionized water is fluorinated acrylate monomer and acrylic ester monomer consumption 10～15 times;
First with part deionized water, anionic emulsifier, nonionic emulsifier and linking agent are mixed with to solution, remaining deionized water, fluorinated acrylate and acrylic ester monomer are joined in polymeric kettle, logical nitrogen is replaced, after 60 ℃ of pre-emulsification 30min, first add reductive agent, again oxygenant and copper sulfate solution are added simultaneously, maintain bath temperature at 70 ℃, reaction 4-7 hour.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106220777A (en) * | 2016-08-22 | 2016-12-14 | 王利萍 | A kind of preparation method with lasting super-hydrophobic material |
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| CN1772777A (en) * | 2005-11-16 | 2006-05-17 | 广州市化学工业研究所 | Fluorosilicone modified acrylic emulsion for weather resistant antifouling paint |
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| CN106220777A (en) * | 2016-08-22 | 2016-12-14 | 王利萍 | A kind of preparation method with lasting super-hydrophobic material |
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Application publication date: 20141210 |