CN101560278B - Methyl methacrylate-styrene copolymer containing fluoro-acrylate and preparation method thereof - Google Patents
Methyl methacrylate-styrene copolymer containing fluoro-acrylate and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a methyl methacrylate-styrene copolymer containing fluoro-acrylate and a preparation method thereof. The copolymer is prepared from the following compositions in percentage bymass: 1 percent of monomers, 0.025 to 0.09 percent of sodium dodecylsulfate, 0.025 to 0.09 percent of polyoxyethylene nonyl phenyl ether, 0.09 to 0.15 percent of tetrafluoropropanol, 0.045 to 0.075 p ercent of normal butanol, 4.0 to 7.5 percent of water and 0.005 to 0.02 percent of initiator. The copolymer solves the problems of expensive fluorine materials and poor compatibility when fluorine-containing materials are used for improving the hydrophobicity of epoxy resin, and provides the method for synthesizing the copolymer containing the fluoro-acrylate. The method is simple and pollution-free, has low cost, and is a good method for preparing the copolymer containing the fluoro-acrylate.
Description
Technical field
The invention belongs to the synthetic of fluoro-acrylate copolymer, be specially a kind of fluorinated acrylate-copolymer of methyl methacrylatestyrene and preparation method thereof.
Technical background
Resins, epoxy has the performance of numerous excellences; its body material as coating is widely used in the protection against corrosion field; but the coating curing rear surface that Resins, epoxy forms energy is higher and have a large amount of hydrophilic radicals because of behind the epoxy resin cure; cause the water regain of coating too high; very easily reduce protective value to metal substrate; therefore, the hydrophobicity of raising Resins, epoxy is most important.At this defective of Resins, epoxy hydrophobicity difference, research all selects low-surface-energy material that Resins, epoxy is carried out modification.Typical low surface energy material is silicon and fluorine.The fluorine material all is better than silicon materials at aspects such as low surface energy, heat-resisting, weather-proof, hydrophobics, it should be noted that: though 1. its unique properties, because the fluorochemical monomer price is high, this has just limited the application of some fluorine modified products; 2. even if the fluorine material has many impayable excellent properties, but it and other incompatibility of materials are very limited its application, and the consistency that therefore solves fluoropolymer also is to study a great problem of fluorine material at present; Because it is above two hang-ups, so considerably less with the application of fluorine material modification Resins, epoxy at present.
Existing fluorinated copolymer synthetic method is a solution polymerization process, and solution polymerization generally need be adopted fluorine-containing organic solvent, can bring the raising and the environmental pollution of cost thus.Become new direction of polymerization with water solution system as the letex polymerization of polymerization environment in recent years, adopting classical letex polymerization is the important method of preparation fluoropolymer emulsion.But when adopting classical emulsion polymerization to prepare fluoropolymer, the emulsion instability can and be deposited in polymerization layering takes place in the process, causes the transformation efficiency of fluorochemical monomer to reduce.
Summary of the invention
Purpose of the present invention is exactly the defective that exists in the present fluoro-acrylate copolymer technology of preparing, and the defective that exists when in epoxy resin modification, using of fluorine material, the present invention is on the basis of classical letex polymerization, by passing through methyl methacrylate (MMA), vinylbenzene (St) carries out copolymerization with fluorinated acrylate, increase the consumption of conventional emulsifier sodium lauryl sulphate (SDS) and polyoxyethylene nonylphenol ether (OP-10), when pre-emulsification, adopt simultaneously the method for high-speed stirring, need only add a spot of propyl carbinol and C3-Fluoroalcohol as solubility promoter, just can make stable emulsion, and the transformation efficiency of fluorochemical monomer is very high, and the multipolymer cost is low; Resulting polymers and epoxy resin compatibility are good, and be good to the epoxy coat hydrophobically modified.
Technical scheme of the present invention is:
A kind of fluorinated acrylate-copolymer of methyl methacrylatestyrene, this multipolymer are according to following composition and proportioning preparation:
The constituent mass proportioning
Monomer 1
Sodium lauryl sulphate (SDS) 0.025～0.09
Polyoxyethylene nonylphenol ether (OP-10) 0.025～0.09
C3-Fluoroalcohol 0.09～0.15
Propyl carbinol 0.045～0.075
Water 4.0～7.5
Initiator 0.005～0.02
Wherein monomer is made up of fluorinated acrylate, methyl methacrylate (MMA) and vinylbenzene (St), and constituent mass per-cent is in the monomer: fluorinated acrylate 2%～46%, methyl methacrylate 27%～50%, vinylbenzene (St) 27%～50%;
Described fluorinated acrylate is perfluor alkyl ethide acrylate, dodecafluorhe-ptylacrylate, methacrylic acid ten difluoro heptyl esters or vinylformic acid hexafluoro butyl ester ester;
Described initiator is Diisopropyl azodicarboxylate (AIBN) or Potassium Persulphate-sodium bisulfite (KPS-NaHSO
3).
Above the preparation method of described fluorinated acrylate-copolymer of methyl methacrylatestyrene, comprise the steps:
(1) in reactor, adds sodium lauryl sulphate (SDS) and polyoxyethylene nonylphenol ether (OP-10), C3-Fluoroalcohol, propyl carbinol, fluorinated acrylate, methyl methacrylate (MMA), vinylbenzene (St) and water respectively, stirred 30～60 minutes down at 30～45 ℃ then, obtain pre-emulsion;
(2) 2/3 of the pre-emulsion that the last step is obtained shift out standbyly, then reactor is kept under the nitrogen atmosphere, system is warming up to 70 ℃～85 ℃, adds initiator A IBN or KPS-NaHSO
3Its consumption is to be 0.5%～2% of monomer mass, reacted 1.5 hours, again the pre-emulsion that shifts out was all dripped in 2～3 hours, reacted again after dropwising 3～6 hours, with ethanol or salt solution breakdown of emulsion, filtration, washing, oven dry obtained fluorinated acrylate-copolymer of methyl methacrylatestyrene at last after reaction finished.
Above stirring in the step (1) among the described preparation method be high-speed stirring, stirring velocity is 1500 rev/mins～4500 rev/mins.
Beneficial effect of the present invention is:
(1) at the high shortcoming of fluorochemical monomer price, we carry out copolymerization by methyl methacrylate (MMA), vinylbenzene (St) with fluorinated acrylate, contain the character that a spot of fluorinated acrylate monomer just can demonstrate fully fluorine monomer in the multipolymer that generates, so just can under the good prerequisite of maintenance multipolymer overall performance, reduce cost;
(2) at the problem of fluorine material and epoxy resin compatibility difference, we carry out copolymerization by methyl methacrylate (MMA), vinylbenzene (St) with fluorinated acrylate, in the multipolymer that generates owing to contain the methyl methacrylate good (MMA), vinylbenzene (St) with epoxy resin compatibility, thereby have good consistency with Resins, epoxy, fluoro-acrylate copolymer can not separated out from Resins, epoxy; Thereby the modified epoxy coating has been reached more than 130 ° the contact angle of water, given the epoxy coat excellent hydrophobicity;
(3) traditional fluorinated copolymer synthetic method is a solution polymerization process, and solution polymerization generally need be adopted fluorine-containing organic solvent, can bring the raising and the environmental pollution of cost thus.Become new direction of polymerization with water solution system as the letex polymerization of polymerization environment in recent years, adopting classical letex polymerization is the important method of preparation fluoropolymer emulsion.But when adopting classical emulsion polymerization to prepare fluoropolymer, the emulsion instability can and be deposited in polymerization layering takes place in the process, causes the transformation efficiency of fluorochemical monomer to reduce.At the defective that exists in the present fluoro-acrylate copolymer technology of preparing, the present invention is on the basis of classical letex polymerization, by increasing the consumption of conventional emulsifier sodium lauryl sulphate (SDS) and polyoxyethylene nonylphenol ether (OP-10), when pre-emulsification, adopt simultaneously the method for high-speed stirring, need only add a spot of propyl carbinol and C3-Fluoroalcohol as solubility promoter, just can make stable emulsion, and the transformation efficiency of fluorochemical monomer is very high.
Beneficial effect (1), (2) have solved with fluorine material improves the problem that the hydrophobic the biggest problem of Resins, epoxy is fluorine material price costliness and consistency difference; Beneficial effect (3) provides a kind of method of synthetic fluoro-acrylate copolymer, and method is simple, and cost is low, and is pollution-free, is the good method of preparation fluoro-acrylate copolymer.
Description of drawings
Fig. 1 is the infrared spectrum of multipolymer among the embodiment 1.
Embodiment
Embodiment 1
The sodium lauryl sulphate (SDS) that in the four-hole bottle of 250ml, adds 0.25 gram, 0.25 gram polyoxyethylene nonylphenol ether (OP-10), 0.8 gram C3-Fluoroalcohol, 0.4 gram propyl carbinol, 1.0 gram perfluor alkyl ethide acrylate (FA), 2.4 gram methyl methacrylate (MMA), 2.4 gram vinylbenzene (St), 43 gram distilled water, in 40 ℃, pre-emulsification is 30 minutes under 2500 rev/mins the stirring velocity, obtain pre-emulsion, then 2/3 pre-emulsion is poured in the constant pressure funnel, again four-hole bottle is filled the nitrogen deoxygenation after 30 minutes (following reaction process keeps under the nitrogen atmosphere), be warming up to 80 ℃, in the remaining pre-emulsion of four-hole bottle, add 0.06 gram Potassium Persulphate (KPS), 0.03 gram sodium bisulfite (NaHSO
3), reacted 1.5 hours, in four-hole bottle, dripped the whole pre-emulsions that before shifted out in the constant pressure funnel with 2 hours then, dropwise the back system and react 3 hours again, and keep reacting under 80 ℃ always.Reaction finishes back with ethanol or salt solution breakdown of emulsion.Product suction filtration, washing, 50 ℃ of oven dry obtain perfluor alkyl ethide acrylate-copolymer of methyl methacrylatestyrene.
The sign of multipolymer:
Multipolymer carries out Infrared Characterization, 1151cm
-1There are the O-C key characteristic peak of MMA, 1603cm in the place
-1, 1584cm
-1, 1494cm
-1, 1454cm
-1The skeletal vibration peak that phenyl ring is arranged is except that the characteristic peak of above-mentioned copolymer, at 1244cm
-1Obvious absorption peaks has also appearred in the place, and this is the characteristic peak of F-C key, and at 760cm
-1, 700cm
-1The place has also occurred-CF
2CF
3Absorption peak, have the feature of terpolymer; Fig. 1 is the infrared spectrum of multipolymer:
Multipolymer carries out nuclear-magnetism and characterizes, and has at 3.5～3.7ppm place in the methyl methacrylate (MMA)-OCH
3The chemical shift of last hydrogen, there is the chemical shift of hydrogen on the phenyl ring at the 7.2ppm place, and has at 4.0～4.4ppm place in the perfluor alkyl ethide acrylate (FA)-OCH
2The chemical shift of last hydrogen has the feature of terpolymer;
More than analyze as can be known, we have successfully synthesized novel substance perfluor alkyl ethide acrylate-copolymer of methyl methacrylatestyrene, and in the polymerization process of the present invention, about the Transformation efficiency is up to 90 % of fluorochemical monomer.
Use:
First component: take by weighing above-mentioned perfluor alkyl ethide acrylate-copolymer of methyl methacrylatestyrene 0.05 gram, (Yangzhou U.S.A is coated with scholar Nanjing speciality coating limited liability company to the epoxy colored paint, the H06-7 corrosion-resistant epoxy paint) 1.0 restrains to reactor 1, in reactor 1, add mixed solvent 0.8 gram, wherein mixed solvent is formulated by following mass ratio by dimethylbenzene, propyl carbinol, acetone: dimethylbenzene: propyl carbinol: acetone=1: 0.43: 1, stir, obtain uniform solution, illustrate that multipolymer, epoxy colored paint are fine in the solvability of mixed solvent;
Second component: take by weighing solidifying agent ethylene glycol bis trimellitic acid 1,2-anhydride ester (TMEG) 0.3 and restrain in reactor 2, in reactor 2, add mixed solvent (the same) 0.8 gram, stir, TMEG dissolves fully up to solidifying agent, obtain the solution of clear, illustrate that the solvability of multipolymer in mixed solvent is fine.Obtain the second component;
First and second liang of components are mixed, and the mixing solutions homogeneous illustrates that the consistency of each component such as multipolymer, epoxy colored paint, solidifying agent in selected mixed solvent is good;
At last the whole first and second liang of components of gained are mixed, be coated in body surface, be placed on 90 ℃ and solidified 3 hours down, solidified 2 hours down in 120 ℃, gained modified epoxy coating is 132 ° to the contact angle of water, and the epoxy coat hydrophobicity is greatly improved.
Contact angle is measured (following examples together)
About 25 ℃ of room temperatures, adopt sessile drop method to measure the contact angle of coating and water, that is: the position of control syringe needle is in the appropriate position of screen, regulate microsyringe, after suction, the de-bubble, extract about 5 μ L water droplets and be added drop-wise on the coating sample, take the shape synoptic diagram of water droplet on coating behind the 20s, calculate contact angle by computer software.Each sample is got 3 different positions arbitrarily and is surveyed its contact angle, gets its mean value.
Embodiment 2
SDS, the 0.5 gram OP-10,0.9 gram C3-Fluoroalcohol, 0.3 gram propyl carbinol, 1.5 gram perfluor alkyl ethide acrylate (FA), 2.4 gram methyl methacrylates (MMA), 2.4 gram vinylbenzene (St), the 43 gram distilled water that in the four-hole bottle of 250ml, add 0.25 gram, in 35 ℃, pre-emulsification is 30 minutes under 3000 rev/mins the stirring velocity, then 2/3 pre-emulsion is poured in the constant pressure funnel.Filled the nitrogen deoxygenation 30 minutes (following reaction process keeps under the nitrogen atmosphere) to system, system is warming up to 78 ℃, adds 0.05 gram KPS, 0.025 gram NaHSO in the remaining pre-emulsion of four-hole bottle
3, reacted 1.5 hours, in four-hole bottle, drip the mixed solution 3 hours in the constant pressure funnel then, reacted again after dropwising 4 hours, and keep reacting under 78 ℃ always.Reaction finishes back with ethanol or salt solution breakdown of emulsion.Suction filtration, washing, oven dry obtains the finished product.
First component: take by weighing above-mentioned perfluor alkyl ethide acrylate-copolymer of methyl methacrylatestyrene 0.05 gram, epoxy colored paint (with embodiment 1) 1.0 restrains to reactor 1, in reactor 1, add mixed solvent (with embodiment 1) 0.8 gram, stir, obtain uniform solution, illustrate that multipolymer, epoxy colored paint are fine in the solvability of mixed solvent;
Second component: take by weighing solidifying agent ethylene glycol bis trimellitic acid 1,2-anhydride ester (TMEG) 0.3 gram,, obtain clear solution, illustrate that solidifying agent is fine in the solvability of mixed solvent with 0.7 gram mixed solvent (with embodiment 1) dissolving;
First and second liang of components are mixed, and the mixing solutions homogeneous illustrates that the consistency of each component such as multipolymer, epoxy colored paint, solidifying agent in selected mixed solvent is good.
Embodiment 3
SDS, the 0.45 gram OP-10,0.8 gram C3-Fluoroalcohol, 0.4 gram propyl carbinol, 2.0 gram perfluor alkyl ethide acrylate (FA), 2.4 gram methyl methacrylates (MMA), 2.4 gram vinylbenzene (St), the 43 gram distilled water that in the four-hole bottle of 250ml, add 0.3 gram, in 45 ℃, pre-emulsification is 30 minutes under 2500 rev/mins the stirring velocity, then 2/3 pre-emulsion is poured in the constant pressure funnel.Fill the nitrogen deoxygenation 30 minutes (following reaction process keeps under the nitrogen atmosphere) to system, system is warming up to 70 ℃, adds 0.1 gram AIBN in the remaining pre-emulsion of four-hole bottle, reacts 1.5 hours, drip the mixed solution 5 hours in the constant pressure funnel then, and keep reacting under 70 ℃ always.Reaction finishes back with ethanol or salt solution breakdown of emulsion.Suction filtration, washing, oven dry obtains the finished product;
The first component: take by weighing above-mentioned multipolymer 0.05 gram, epoxy colored paint (with embodiment 1) 1.0 grams with 0.8 gram mixed solvent (with embodiment 1) dissolving, illustrate that multipolymer is fine in the solvability of mixed solvent;
Second component: take by weighing solidifying agent ethylene glycol bis trimellitic acid 1,2-anhydride ester (TMEG) 0.3 and restrain in reactor 2, in reactor 2, add mixed solvent (with embodiment 1) 0.8 gram, stir, TMEG dissolves fully up to solidifying agent, obtain the solution of clear, illustrate that the solvability of solidifying agent in mixed solvent is fine;
First and second liang of components are mixed, and the mixing solutions homogeneous illustrates that the consistency of each component such as multipolymer, epoxy colored paint, solidifying agent in selected mixed solvent is good.
Embodiment 4
SDS, the 0.25 gram OP-10,0.8 gram C3-Fluoroalcohol, 0.4 gram propyl carbinol, 2.5 gram perfluor alkyl ethide acrylate (FA), 2.4 gram methyl methacrylates (MMA), 2.4 gram vinylbenzene (St), the 43 gram distilled water that in the four-hole bottle of 250ml, add 0.25 gram, in 40 ℃, pre-emulsification is 30 minutes under 2800 rev/mins the stirring velocity, then 2/3 pre-emulsion is poured in the constant pressure funnel.Filled the nitrogen deoxygenation 30 minutes (following reaction process keeps under the nitrogen atmosphere) to system, system is warming up to 82 ℃, adds 0.04 gram KPS, 0.02 gram NaHSO in the remaining pre-emulsion of four-hole bottle
3, reacted 1.5 hours, in four-hole bottle, drip the mixed solution 2 hours in the constant pressure funnel then, reacted again after dropwising 5 hours, and keep reacting under 82 ℃ always.Reaction finishes back with ethanol or salt solution breakdown of emulsion.Suction filtration, washing, oven dry obtains the finished product;
The first component: take by weighing above-mentioned multipolymer 0.04 gram, epoxy colored paint (with embodiment 1) 1.0 grams with 0.7 gram mixed solvent (with embodiment 1) dissolving, illustrate that multipolymer is fine in the solvability of mixed solvent;
Second component: take by weighing solidifying agent ethylene glycol bis trimellitic acid 1,2-anhydride ester (TMEG) 0.3 and restrain in reactor 2, in reactor 2, add mixed solvent (with embodiment 1) 0.8 gram, stir, TMEG dissolves fully up to solidifying agent, obtain the solution of clear, illustrate that the solvability of solidifying agent in mixed solvent is fine;
First and second liang of components are mixed, and the mixing solutions homogeneous illustrates that the consistency of each component such as multipolymer, epoxy colored paint, solidifying agent in selected mixed solvent is good.
Embodiment 5
SDS, the 0.25 gram OP-10,0.9 gram C3-Fluoroalcohol, 0.5 gram propyl carbinol, 3.0 gram perfluor alkyl ethide acrylate (FA), 2.4 gram methyl methacrylates (MMA), 2.4 gram vinylbenzene (St), the 43 gram distilled water that in the four-hole bottle of 250ml, add 0.3 gram, in 40 ℃, pre-emulsification is 30 minutes under 2500 rev/mins the stirring velocity, then 2/3 pre-emulsion is poured in the constant pressure funnel.Filled the nitrogen deoxygenation 30 minutes (following reaction process keeps under the nitrogen atmosphere) to system, system is warming up to 85 ℃, adds 0.06 gram KPS, 0.03 gram NaHSO in the remaining pre-emulsion of four-hole bottle
3, reacted 1.5 hours, in four-hole bottle, drip the mixed solution 3 hours in the constant pressure funnel then, reacted again after dropwising 4 hours, and keep reacting under 85 ℃ always.Reaction finishes back with ethanol or salt solution breakdown of emulsion.Suction filtration, washing, oven dry obtains the finished product.
The first component: take by weighing above-mentioned multipolymer 0.03 gram, epoxy colored paint (with embodiment 1) 1.0 grams with 0.6 gram mixed solvent (with embodiment 1) dissolving, illustrate that multipolymer is fine in the solvability of mixed solvent;
Second component: take by weighing solidifying agent ethylene glycol bis trimellitic acid 1,2-anhydride ester (TMEG) 0.3 and restrain in reactor 2, in reactor 2, add mixed solvent (with embodiment 1) 0.9 gram, stir, TMEG dissolves fully up to solidifying agent, obtain the solution of clear, illustrate that the solvability of solidifying agent in mixed solvent is fine;
First and second liang of components are mixed, and the mixing solutions homogeneous illustrates that the consistency of each component such as multipolymer, epoxy colored paint, solidifying agent in selected mixed solvent is good.
Embodiment 6
SDS, the 0.3 gram OP-10,0.9 gram C3-Fluoroalcohol, 0.4 gram propyl carbinol, 3.5 gram perfluor alkyl ethide acrylate (FA), 2.4 gram methyl methacrylates (MMA), 2.4 gram vinylbenzene (St), the 43 gram distilled water that in the four-hole bottle of 250ml, add 0.3 gram, in 40 ℃, pre-emulsification is 30 minutes under 3000 rev/mins the stirring velocity, then 2/3 pre-emulsion is poured in the constant pressure funnel.Filled the nitrogen deoxygenation 30 minutes (following reaction process keeps under the nitrogen atmosphere) to system, system is warming up to 84 ℃, adds 0.06 gram KPS, 0.03 gram NaHSO in the remaining pre-emulsion of four-hole bottle
3, reacted 1.5 hours, in four-hole bottle, drip the mixed solution 3 hours in the constant pressure funnel then, reacted again after dropwising 5 hours, and keep reacting under 84 ℃ always.Reaction finishes back with ethanol or salt solution breakdown of emulsion.Suction filtration, washing, oven dry obtains the finished product.
The first component: take by weighing above-mentioned multipolymer 0.02 gram, epoxy colored paint (with embodiment 1) 1.0 grams with 0.7 gram mixed solvent (with embodiment 1) dissolving, illustrate that multipolymer is fine in the solvability of mixed solvent;
Second component: take by weighing solidifying agent ethylene glycol bis trimellitic acid 1,2-anhydride ester (TMEG) 0.3 and restrain in reactor 2, in reactor 2, add mixed solvent (with embodiment 1) 0.8 gram, stir, TMEG dissolves fully up to solidifying agent, obtain the solution of clear, illustrate that the solvability of solidifying agent in mixed solvent is fine;
First and second liang of components are mixed, and the mixing solutions homogeneous illustrates that the consistency of each component such as multipolymer, epoxy colored paint, solidifying agent in selected mixed solvent is good.
Embodiment 7
SDS, the 0.3 gram OP-10,0.9 gram C3-Fluoroalcohol, 0.5 gram propyl carbinol, 4.0 gram perfluor alkyl ethide acrylate (FA), 2.3 gram methyl methacrylates (MMA), 2.5 gram vinylbenzene (St), the 43 gram distilled water that in the four-hole bottle of 250ml, add 0.3 gram, in 42 ℃, pre-emulsification is 30 minutes under 3000 rev/mins the stirring velocity, then 2/3 pre-emulsion is poured in the constant pressure funnel.Filled the nitrogen deoxygenation 30 minutes (following reaction process keeps under the nitrogen atmosphere) to system, system is warming up to 80 ℃, adds 0.06 gram KPS, 0.03 gram NaHSO in the remaining pre-emulsion of four-hole bottle
3, reacted 1.5 hours, in four-hole bottle, drip the mixed solution 2 hours in the constant pressure funnel then, reacted again after dropwising 6 hours, and keep reacting under 80 ℃ always.Reaction finishes back with ethanol or salt solution breakdown of emulsion.Suction filtration, washing, oven dry obtains the finished product.
The first component: take by weighing above-mentioned multipolymer 0.05 gram, epoxy colored paint (with embodiment 1) 1.0 grams with 0.9 gram mixed solvent (with embodiment 1) dissolving, illustrate that multipolymer is fine in the solvability of mixed solvent;
Second component: take by weighing solidifying agent ethylene glycol bis trimellitic acid 1,2-anhydride ester (TMEG) 0.3 and restrain in reactor 2, in reactor 2, add mixed solvent (with embodiment 1) 0.8 gram, stir, TMEG dissolves fully up to solidifying agent, obtain the solution of clear, illustrate that the solvability of solidifying agent in mixed solvent is fine;
First and second liang of components are mixed, and the mixing solutions homogeneous illustrates that the consistency of each component such as multipolymer, epoxy colored paint, solidifying agent in selected mixed solvent is good.
Embodiment 8
SDS, the 0.4 gram OP-10,0.8 gram C3-Fluoroalcohol, 0.4 gram propyl carbinol, 4.0 gram perfluor alkyl ethide acrylate (FA), 2.4 gram methyl methacrylates (MMA), 2.4 gram vinylbenzene (St), the 43 gram distilled water that in the four-hole bottle of 250ml, add 0.3 gram, in 39 ℃, pre-emulsification is 30 minutes under 2500 rev/mins the stirring velocity, then 2/3 pre-emulsion is poured in the constant pressure funnel.Fill the nitrogen deoxygenation 30 minutes (following reaction process keeps under the nitrogen atmosphere) to system, system is warming up to 70 ℃, adds 0.12 gram AIBN in the remaining pre-emulsion of four-hole bottle, reacts 1.5 hours, drip the mixed solution 4 hours in the constant pressure funnel then, and keep reacting under 70 ℃ always.Reaction finishes back with ethanol or salt solution breakdown of emulsion.Suction filtration, washing, oven dry obtains the finished product.
The first component: take by weighing above-mentioned multipolymer 0.05 gram, epoxy colored paint (with embodiment 1) 1.0 grams with 0.8 gram mixed solvent (with embodiment 1) dissolving, illustrate that multipolymer is fine in the solvability of mixed solvent;
Second component: take by weighing solidifying agent ethylene glycol bis trimellitic acid 1,2-anhydride ester (TMEG) 0.3 and restrain in reactor 2, in reactor 2, add mixed solvent (with embodiment 1) 0.8 gram, stir, TMEG dissolves fully up to solidifying agent, obtain the solution of clear, illustrate that the solvability of solidifying agent in mixed solvent is fine;
First and second liang of components are mixed, and the mixing solutions homogeneous illustrates that the consistency of each component such as multipolymer, epoxy colored paint, solidifying agent in selected mixed solvent is good.
Claims (1)
1. fluorinated acrylate-copolymer of methyl methacrylatestyrene is characterized by this raw material of substance and the quality proportioning that feeds intake is:
The constituent mass proportioning
Monomer 1
Sodium lauryl sulphate 0.025～0.09
Polyoxyethylene nonylphenol ether 0.025～0.09
C3-Fluoroalcohol 0.09～0.15
Propyl carbinol 0.045～0.075
Water 4.5～7.5
Initiator 0.005～0.02
Described monomer is made up of fluorinated acrylate, methyl methacrylate and vinylbenzene, and constituent mass per-cent is in the monomer: fluorinated acrylate 2%～46%, methyl methacrylate 27%～50%, vinylbenzene 27%～50%;
Described fluorinated acrylate is perfluor alkyl ethide acrylate, dodecafluorhe-ptylacrylate, methacrylic acid ten difluoro heptyl esters or vinylformic acid hexafluoro butyl ester;
Described initiator is Diisopropyl azodicarboxylate or Potassium Persulphate-sodium bisulfite;
Wherein, this polymkeric substance is made by following steps:
(1) in reactor, adds sodium lauryl sulphate and polyoxyethylene nonylphenol ether, C3-Fluoroalcohol, propyl carbinol, fluorinated acrylate, methyl methacrylate, vinylbenzene and the water of described proportioning respectively, stirred 30～60 minutes down at 30～45 ℃ then, obtain pre-emulsion;
(2) 2/3 of the pre-emulsion that the last step is obtained shift out standby, then reactor is kept under the nitrogen atmosphere, system is warming up to 70 ℃～85 ℃, add initiator Diisopropyl azodicarboxylate or Potassium Persulphate-sodium bisulfite, its consumption is to be 0.5%～2% of monomer mass, reacted 1.5 hours, again the pre-emulsion that shifts out was all dripped in 2～3 hours, reacted again after dropwising 3～6 hours, reaction finishes back with ethanol or salt solution breakdown of emulsion, filter, wash, dry, obtain fluorinated acrylate-copolymer of methyl methacrylatestyrene at last;
Stirring in the described step (1) is a high-speed stirring, and stirring velocity is 1500 rev/mins～4500 rev/mins.
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| CN101705040B (en) * | 2009-11-05 | 2012-09-05 | 中国科学院宁波材料技术与工程研究所 | Fluorine-modified methacrylic acid epoxy powder paint and preparation method thereof |
| CN102174143B (en) * | 2011-01-29 | 2013-01-09 | 锦州惠发天合化学有限公司 | Method for preparing fluorine-containing acrylate emulsion |
| CN102199241B (en) * | 2011-03-31 | 2013-01-30 | 广东工业大学 | Preparation method and application of water-based fluorine-containing acrylate emulsion |
| CN102250279B (en) * | 2011-05-20 | 2013-05-08 | 锦州惠发天合化学有限公司 | Self-crosslinked fluorosilicate acrylic resin and preparation method thereof |
| CN104194430A (en) * | 2014-07-24 | 2014-12-10 | 蚌埠市鸿安精密机械有限公司 | High hydrophobic and oleophobic powder coating |
| CN106674416B (en) * | 2015-11-05 | 2019-08-06 | 中昊晨光化工研究院有限公司 | A kind of Fluorine-Containing Copolymer Emulsion and its synthetic method, application |
| CN109265892A (en) * | 2018-08-16 | 2019-01-25 | 天长市瑞慈有机玻璃有限公司 | Anti- method X-ray radiation organic glass masterbatch and prepare perspex bar of oil rub resistance |
| CN116285407B (en) * | 2022-12-26 | 2024-10-15 | 韩山师范学院 | High-fluidity tea residue/polypropylene composite material and preparation method thereof |
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2009
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