CN101235124B - Fluorine silicon di-block copolymers and preparation method thereof - Google Patents
Fluorine silicon di-block copolymers and preparation method thereof Download PDFInfo
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- CN101235124B CN101235124B CN2008100704428A CN200810070442A CN101235124B CN 101235124 B CN101235124 B CN 101235124B CN 2008100704428 A CN2008100704428 A CN 2008100704428A CN 200810070442 A CN200810070442 A CN 200810070442A CN 101235124 B CN101235124 B CN 101235124B
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Abstract
A fluorine silicon diblock copolymer and a corresponding preparation method relate to a fluorine silicon low surface energy diblock copolymer. The invention provides a fluorine silicon diblock copolymer (dimethyl silicone polymer-b-polyheptafluorobutyric methacrylate ester copolymer) and a corresponding preparation method, with mild reaction conditions, definite product structure, kept skeleton structure of each block and simple operation, wherein the fluorine silicon diblock copolymer is dimethyl silicone polymer-b-polyheptafluorobutyric methacrylate ester copolymer. The preparation method comprises preparing dimethyl silicone polymer macromolecule inducer terminated by bromine atom and preparing dimethyl silicone polymer-b-polyheptafluorobutyric methacrylate ester copolymer.
Description
Technical field
The present invention relates to a kind of fluorine silicon low-surface-energy di-block copolymer, especially relating to a kind of is macromole evocating agent with the macromole polydimethylsiloxane, is that catalyzer, N-(n-propyl group)-2-pyridyl-methanamine are the preparation method who gathers seven fluorine butyl methyl acrylate under the common catalysis of catalyst ligand through the synthetic subject polymer polydimethylsiloxane-b-of atom transition free radical polymerization reaction at Cu (I) Br.
Background technology
The poly-seven fluorine butyl methyl acrylate of polydimethylsiloxane-b-are a kind of novel low surface energy fluorosilicic block copolymers, do not appear in the newspapers so far, and it has lower surface energy, is expected to be used widely in antifouling paint, surface-modifying agent field.Organosilicon polymer has some special excellent properties, and as snappiness, extremely low second-order transition temperature, low surface tension, high gas permeability, high heat-resisting and high oxidation resistance voltinism, but the mechanical property of silicone resin is relatively poor, not organic solvent-resistant or the like.Fluorocarbon resin is that surface energy is minimum and chemical stability good in all polymkeric substance, the polymkeric substance that solvent resistance and weather resisteant are all very good, but its price is expensive many than organosilicon relatively; The silicon-fluorine polymer thing has then overcome both shortcomings, integrates both advantages, and it has comprehensive performance and economic worth.The method of at present synthetic silicon-fluorine polymer thing mainly contains three kinds: arrive the fluorine carbon skeleton with the polysiloxane macromonomer grafting 1.; With the grafting of perfluoro side chain to the polysiloxane skeleton; 3. will contain siloxanes and contain two kinds of organic fluorine or above vinyl monomer carries out copolymerization.These three kinds of methods all have shortcoming separately: as finishing the side-chain structure that reacts and destroyed polysiloxane with the polysiloxane macromonomer grafting usually to the method on the polysiloxane skeleton to the method for fluorine carbon skeleton with the grafting of perfluoro side chain under the precious metal high-temperature catalytic; To contain siloxanes and to contain the skeleton that does not at all have polysiloxane in the copolymer chain that method that two kinds of organic fluorine or above vinyl monomer carry out copolymerization obtains and utilize, therefore to have lost some advantage of polysiloxane.
Summary of the invention
It is clear and definite and keep the original skeleton structure of each block and fluorine silicon di-block copolymers (polydimethylsiloxane-b-gathers seven fluorine butyl methyl acrylate copolymers) easy and simple to handle and preparation method thereof to the purpose of this invention is to provide a kind of reaction conditions gentleness, reaction product structure.
Fluorine silicon di-block copolymers of the present invention is the poly-seven fluorine butyl methyl acrylate copolymers of polydimethylsiloxane-b-, and its structural formula is:
Wherein x is the polymerization degree of polydimethylsiloxane (PDMS), and y is the polymerization degree of poly-seven fluorine butyl methyl acrylate (PHFBMA).
The reaction formula of fluorine silicon di-block copolymers of the present invention is as follows:
Wherein x is the polymerization degree of polydimethylsiloxane (PDMS), and y is the polymerization degree of poly-seven fluorine butyl methyl acrylate (PHFBMA).
The preparation method of fluorine silicon di-block copolymers of the present invention comprises following concrete steps:
1) the end capped polydimethylsiloxane macromole evocating agent of preparation bromine atoms: under the nitrogen atmosphere protection, with single methyl alcohol terminated polydimethylsiloxane and 2-bromine isobutyl acylbromide is that starting raw material reacts at inert organic solvents, reaction finishes after-filtration, inert organic solvents is removed in the filtrate decompression distillation, again it is dissolved in the methylene dichloride, wash with sodium hydrogen carbonate solution, separatory, organic layer siccative drying, refilter, at last dichloromethane solvent is removed in the filtrate decompression distillation and obtained the end capped polydimethylsiloxane macromole evocating agent of oily xanchromatic bromine atoms; In molar ratio, single methyl alcohol terminated polydimethylsiloxane: 2-bromine isobutyl acylbromide: triethylamine is 1: (1.35～3.20): (2.52～6.04);
2) the poly-novel di-block copolymer of seven fluorine butyl methyl acrylate of preparation polydimethylsiloxane-b-: atom transfer radical polymerization is carried out under inert atmosphere protection; with the end capped polydimethylsiloxane macromole of bromine atoms is initiator; with the cuprous halide is catalyzer; to contain the pyridine ring compound or to contain a kind of in the derivative of pyridine ring compound is catalyst ligand; in inert solvent toluene, carry out atom transfer radical polymerization; in molar ratio; monomer (seven fluorine butyl methyl acrylate): catalyzer: initiator: catalyst ligand=(15～100): 1: 1: 2; then through freezing-vacuumize-thaw cycles at least 3 times after; after reacting by heating finishes; institute's synthetic polymkeric substance is diluted with inert solvents such as tetrahydrofuran (THF) or methylene dichloride; solution after will diluting is again removed catalyzer by alumina column; filtrate is removed inert solvent with Rotary Evaporators; be deposited in the precipitation agent; repeatedly after the dissolving-precipitation at least 3 times again with the product vacuum-drying that obtains; obtain poly-seven fluorine butyl methyl acrylate copolymer, the i.e. fluorine silicon di-block copolymers of polydimethylsiloxane-b-.
In step 1), used inert organic solvents is selected from tetrahydrofuran (THF) or methylene dichloride etc.; The purity of used nitrogen is more preferably greater than 99.995%; The time of stirring is 12～24h; The temperature of reaction is 0～40 ℃; Used sodium hydrogen carbonate solution is preferably saturated solution; Rotary Evaporators is preferably adopted in used distillation; Filter paper filtering is preferably adopted in used filtration; The most handy anhydrous magnesium sulfate of siccative or anhydrous sodium sulphate.
In step 2) in, described rare gas element preferably adopts high purity nitrogen, and its concentration is more preferably greater than 99.995%; Described catalyst ligand is preferably N-(n-propyl group)-2-pyridyl-methanamine; Described the most handy freezing liquid nitrogen, temperature are preferably in below-80 ℃; Described vacuumizing preferably adopted oil pump; Described alumina column preferably adopts the alkali alumina post; Rotary Evaporators is preferably adopted in used evaporation; The temperature of heating is 40～120 ℃, and the time of heating preferably is controlled at 3～10h; Described vacuum drying temperature is preferably 40～50 ℃, and vacuum tightness is preferably 0.08～-0.1MPa.Precipitation agent can be selected lower alcohol for use, particular methanol or ethanol.
Compare with the chemical synthesis process of existing silicon-fluorine polymer thing, the beneficial effect that the present invention has is:
1. employing atom transfer radical polymerization, reaction conditions gentleness not only, the product yield height is compared to general free radical method, and the structure with the temperature of reaction of milder and reaction product is more clear, and molecular weight distribution is narrower.2. be compared to anionic polymerization, have still less side reaction and gentle more reaction conditions, much lower relatively to the requirement of series reaction things such as reaction monomers, solvent.3. the final product among the present invention has micro phase separation structure.
Embodiment
In order to be easy to further understand the present invention, the following example will the invention will be further elaborated.
Embodiment 1
1) under the nitrogen atmosphere protection, 1 part of single methyl alcohol terminated polydimethylsiloxane, 1.35 parts of 2-bromine isobutyl acylbromides and 2.52 parts of triethylamines are reacted under 0 ℃.Then with above-mentioned solution stirring reaction 24h, after reaction finishes, with its filtration, the filtrate decompression distillation except that desolvating, is dissolved in it in methylene dichloride again, for several times with the saturated sodium bicarbonate solution washing, separatory, organic layer dewaters with anhydrous magnesium sulfate drying, refilters, and at last dichloromethane solvent is removed in the filtrate decompression distillation and is obtained oily xanchromatic macromole evocating agent;
2) the necessary strict deoxygenation of reaction system, with 1 part macromole is initiator, 1 part cuprous bromide is a catalyzer, 2 parts N-(n-propyl group)-2-pyridyl-methanamine is that seven fluorine butyl methyl acrylate of catalyst ligand and 15 parts are that monomer is 40 ℃ of reactions down, before heating, reactant solution through 4 times freezing-vacuumize-thaw cycles after, heated solution, after reaction 10h finishes, institute's synthetic polymkeric substance is diluted with tetrahydrofuran solvent, solution after will diluting is again removed catalyzer by alumina column, filtrate removed with Rotary Evaporators desolvate, time the obvious retrogradation of viscosity, it is deposited in the precipitation agent, again the product that obtains is placed on after the dissolving-precipitation 4 times repeatedly that oven dry obtains the poly-seven fluorine butyl methyl acrylate copolymers of polydimethylsiloxane-b-in 40 ℃ of vacuum drying ovens (vacuum tightness is 0.08Mpa).
Embodiment 2
1) under the argon gas atmosphere protection, 1 part of single methyl alcohol terminated polydimethylsiloxane, 1.5 parts of 2-bromine isobutyl acylbromides and 3 parts of triethylamines are reacted under 5 ℃.Then with above-mentioned solution stirring reaction 20h, after reaction finishes, with its filtration, the filtrate decompression distillation except that desolvating, is dissolved in it in methylene dichloride again, uses the sodium hydrogen carbonate solution washed twice, separatory, organic layer dewaters with anhydrous magnesium sulfate drying, refilters, and at last dichloromethane solvent is removed in the filtrate decompression distillation and is obtained oily xanchromatic macromole evocating agent;
2) the necessary strict deoxygenation of reaction system, with 1 part macromole is initiator, 1 part cuprous chloride is a catalyzer, 2 parts 1,1,4,7, the 7-PMDETA is that seven fluorine butyl methyl acrylate of catalyst ligand and 20 parts are that monomer is 50 ℃ of reactions down, before heating, reactant solution through 4 times freezing-vacuumize-thaw cycles after, heated solution, after reaction 9h finishes, institute's synthetic polymkeric substance is diluted with dichloromethane solvent, and the solution after will diluting is again removed catalyzer by alumina column, filtrate is removed with Rotary Evaporators desolvate, time the obvious retrogradation of viscosity, it is deposited in the precipitation agent, again the product that obtains is placed on after the dissolving-precipitation 4 times repeatedly in 50 ℃ of vacuum drying ovens (vacuum tightness for-0.1MPa) oven dry obtains the poly-seven fluorine butyl methyl acrylate copolymers of polydimethylsiloxane-b-.
Embodiment 3
1) under the nitrogen atmosphere protection, 1 part of single methyl alcohol terminated polydimethylsiloxane, 1.8 parts of 2-bromine isobutyl acylbromides and 3 parts of triethylamines are reacted under 15 ℃.Then with above-mentioned solution stirring reaction 18h, after reaction finishes, with its filtration, the filtrate decompression distillation except that desolvating, is dissolved in it in methylene dichloride again, uses the saturated sodium bicarbonate solution washed twice, separatory, organic layer dewaters with anhydrous magnesium sulfate drying, refilters, and at last dichloromethane solvent is removed in the filtrate decompression distillation and is obtained oily xanchromatic macromole evocating agent;
2) the necessary strict deoxygenation of reaction system, with 1 part macromole is initiator, 1 part cuprous bromide is a catalyzer, 2 parts 1,1,4,7, the 7-PMDETA is that seven fluorine butyl methyl acrylate of catalyst ligand and 20 parts are that monomer is 60 ℃ of reactions down, before heating, reactant solution through 4 times freezing-vacuumize-thaw cycles after, heated solution, after reaction 8h finishes, institute's synthetic polymkeric substance is diluted with tetrahydrofuran (THF), and the solution after will diluting is again removed catalyzer by the alkali alumina post, filtrate is removed with Rotary Evaporators desolvate, time the obvious retrogradation of viscosity, it is deposited in the precipitation agent, again the product that obtains is placed on after the dissolving-precipitation 4 times repeatedly that (vacuum tightness is 0.09MPa) oven dry obtains the poly-seven fluorine butyl methyl acrylate copolymers of polydimethylsiloxane-b-in 45 ℃ of vacuum drying ovens.
Embodiment 4
1) under the nitrogen atmosphere protection, 1 part of single methyl alcohol terminated polydimethylsiloxane, 1.8 parts of 2-bromine isobutyl acylbromides and 3 parts of triethylamines are reacted under 20 ℃.Then with above-mentioned solution stirring reaction 15h, after reaction finishes, with its filtration, the filtrate decompression distillation except that desolvating, is dissolved in it in methylene dichloride again, uses the saturated sodium bicarbonate solution washed twice, separatory, organic layer dewaters with anhydrous magnesium sulfate drying, refilters, and at last dichloromethane solvent is removed in the filtrate decompression distillation and is obtained oily xanchromatic macromole evocating agent;
2) the necessary strict deoxygenation of reaction system, with 1 part macromole is initiator, 1 part cuprous bromide is a catalyzer, 2 parts N-(n-propyl group)-2-pyridyl-methanamine is that seven fluorine butyl methyl acrylate of catalyst ligand and 30 parts are that monomer is 60 ℃ of reactions down, before heating, reactant solution through 4 times freezing-vacuumize-thaw cycles after, heated solution, after reaction 6h finishes, institute's synthetic polymkeric substance is diluted with tetrahydrofuran (THF), solution after will diluting is again removed catalyzer by the alkali alumina post, filtrate removed with Rotary Evaporators desolvate, time the obvious retrogradation of viscosity, it is deposited in the precipitation agent, again the product that obtains is placed on after the dissolving-precipitation 4 times repeatedly that (vacuum tightness is 0.09MPa) oven dry obtains the poly-seven fluorine butyl methyl acrylate copolymers of polydimethylsiloxane-b-in 40 ℃ of vacuum drying ovens.
Embodiment 5
1) be the 17h except the reaction times, other is with the step 1) among the embodiment 4;
2) the necessary strict deoxygenation of reaction system, with 1 part macromole is initiator, 1 part cuprous chloride is a catalyzer, 2 parts N-(n-propyl group)-2-pyridyl-methanamine is that seven fluorine butyl methyl acrylate of catalyst ligand and 35 parts are that monomer is 120 ℃ of reactions down, before heating, reactant solution through 4 times freezing-vacuumize-thaw cycles after, heated solution, after reaction 3h finishes, institute's synthetic polymkeric substance is diluted with tetrahydrofuran (THF), solution after will diluting is again removed catalyzer by the alkali alumina post, filtrate removed with Rotary Evaporators desolvate, time the obvious retrogradation of viscosity, it is deposited in the precipitation agent, again the product that obtains is placed on after the dissolving-precipitation 4 times repeatedly that (vacuum tightness is 0.09MPa) oven dry obtains the poly-seven fluorine butyl methyl acrylate copolymers of polydimethylsiloxane-b-in 40 ℃ of vacuum drying ovens.
Embodiment 6
1) under the nitrogen atmosphere protection, 1 part of single methyl alcohol terminated polydimethylsiloxane, 2 parts of 2-bromine isobutyl acylbromides and 3.2 parts of triethylamines are reacted under 25 ℃.Then with above-mentioned solution stirring reaction 14h, after reaction finishes, with its filtration, the filtrate decompression distillation except that desolvating, is dissolved in it in methylene dichloride again, uses the saturated sodium bicarbonate solution washed twice, separatory, organic layer dewaters with anhydrous magnesium sulfate drying, refilters, and at last dichloromethane solvent is removed in the filtrate decompression distillation and is obtained oily xanchromatic macromole evocating agent;
2) change 1,1,4,7 into except part, outside the 7-PMDETA, other is with the step 2 among the embodiment 5).
Embodiment 7
1) under the nitrogen atmosphere protection, 1 part of single methyl alcohol terminated polydimethylsiloxane, 3.2 parts of 2-bromine isobutyl acylbromides and 3.5 parts of triethylamines are reacted under 25 ℃.Then with above-mentioned solution stirring reaction 16h, after reaction finishes, with its filtration, the filtrate decompression distillation except that desolvating, is dissolved in it in methylene dichloride again, uses the saturated sodium bicarbonate solution washed twice, separatory, organic layer dewaters with anhydrous magnesium sulfate drying, refilters, and at last dichloromethane solvent is removed in the filtrate decompression distillation and is obtained oily xanchromatic macromole evocating agent;
2) the necessary strict deoxygenation of reaction system, with 1 part macromole is initiator, 1 part cuprous chloride is a catalyzer, 2 parts N-(n-propyl group)-2-pyridyl-methanamine is that seven fluorine butyl methyl acrylate of catalyst ligand and 40 parts are that monomer is 75 ℃ of reactions down, before heating, reactant solution through 4 times freezing-vacuumize-thaw cycles after, heated solution, after reaction 7h finishes, institute's synthetic polymkeric substance is diluted with tetrahydrofuran (THF), solution after will diluting is again removed catalyzer by the alkali alumina post, filtrate removed with Rotary Evaporators desolvate, time the obvious retrogradation of viscosity, it is deposited in the precipitation agent, again the product that obtains is placed on after the dissolving-precipitation 4 times repeatedly that (vacuum tightness is 0.08MPa) oven dry obtains the poly-seven fluorine butyl methyl acrylate copolymers of polydimethylsiloxane-b-in 45 ℃ of vacuum drying ovens.
Embodiment 8
1) be 30 ℃ except that temperature of reaction, all the other are with the step 1) among the embodiment 7;
2) the necessary strict deoxygenation of reaction system, with 1 part macromole is initiator, 1 part cuprous bromide is a catalyzer, 2 parts 1,1,4,7, the 7-PMDETA is that seven fluorine butyl methyl acrylate of catalyst ligand and 45 parts are that monomer is 70 ℃ of reactions down, before heating, reactant solution through 4 times freezing-vacuumize-thaw cycles after, heated solution, after reaction 6h finishes, institute's synthetic polymkeric substance is diluted with tetrahydrofuran (THF), solution after will diluting is again removed catalyzer by the alkali alumina post, filtrate removed with Rotary Evaporators desolvate, time the obvious retrogradation of viscosity, it is deposited in the precipitation agent, again the product that obtains is placed on after the dissolving-precipitation 4 times repeatedly that (vacuum tightness is 0.09MPa) oven dry obtains the poly-seven fluorine butyl methyl acrylate copolymers of polydimethylsiloxane-b-in 40 ℃ of vacuum drying ovens.
Embodiment 9
1) be 35 ℃ except that temperature of reaction, all the other are with the step 1) among the embodiment 7;
2) the necessary strict deoxygenation of reaction system, with 1 part macromole is initiator, 1 part cuprous bromide is a catalyzer, 2 parts 1,1,4,7, the 7-PMDETA is that seven fluorine butyl methyl acrylate of catalyst ligand and 50 parts are that monomer is 80 ℃ of reactions down, before heating, reactant solution through 4 times freezing-vacuumize-thaw cycles after, heated solution, after reaction 5h finishes, institute's synthetic polymkeric substance is diluted with tetrahydrofuran (THF), and the solution after will diluting is again removed catalyzer by the alkali alumina post, filtrate is removed with Rotary Evaporators desolvate, time the obvious retrogradation of viscosity, it is deposited in the precipitation agent, again the product that obtains is placed on after the dissolving-precipitation 4 times repeatedly that (vacuum tightness is 0.08MPa) oven dry obtains the poly-seven fluorine butyl methyl acrylate copolymers of polydimethylsiloxane-b-in 40 ℃ of vacuum drying ovens.
Embodiment 10
1) removing temperature of reaction is 40 ℃, and the reaction times is outside the 14h, and all the other are with the step 1) among the embodiment 7;
2) the necessary strict deoxygenation of reaction system, with 1 part macromole is initiator, 1 part cuprous bromide is a catalyzer, 2 parts N-(n-propyl group)-2-pyridyl-methanamine is that catalyst ligand is that seven fluorine butyl methyl acrylate of catalyst ligand and 50 parts are that monomer is 90 ℃ of reactions down, before heating, reactant solution through 4 times freezing-vacuumize-thaw cycles after, heated solution, after reaction 5h finishes, institute's synthetic polymkeric substance is diluted with tetrahydrofuran (THF), solution after will diluting is again removed catalyzer by the alkali alumina post, filtrate removed with Rotary Evaporators desolvate, time the obvious retrogradation of viscosity, it is deposited in the precipitation agent, again the product that obtains is placed on after the dissolving-precipitation 4 times repeatedly that (vacuum tightness is 0.09MPa) oven dry obtains the poly-seven fluorine butyl methyl acrylate copolymers of polydimethylsiloxane-b-in 45 ℃ of vacuum drying ovens.
Embodiment 11
1) removing temperature of reaction is 35 ℃, and the reaction times is outside the 24h, and all the other are with the step 1) among the embodiment 7;
2) the necessary strict deoxygenation of reaction system, with 1 part macromole is initiator, 1 part cuprous chloride is a catalyzer, 2 parts N-(n-propyl group)-2-pyridyl-methanamine is that catalyst ligand is that seven fluorine butyl methyl acrylate of catalyst ligand and 70 parts are that monomer is 120 ℃ of reactions down, before heating, reactant solution through 4 times freezing-vacuumize-thaw cycles after, heated solution, after reaction 3.5h finishes, institute's synthetic polymkeric substance is diluted with tetrahydrofuran (THF), solution after will diluting is again removed catalyzer by the alkali alumina post, filtrate removed with Rotary Evaporators desolvate, time the obvious retrogradation of viscosity, it is deposited in the precipitation agent, again the product that obtains is placed on after the dissolving-precipitation 4 times repeatedly that (vacuum tightness is 0.08MPa) oven dry obtains the poly-seven fluorine butyl methyl acrylate copolymers of polydimethylsiloxane-b-in 40 ℃ of vacuum drying ovens.
Embodiment 12
1) be 40 ℃ except that temperature of reaction, all the other are with the step 1) among the embodiment 11;
2) demonomerization is that 100 parts, catalyst ligand are 1,1,4,7, and 7-PMDETA, Heating temperature are outside 100 ℃, and all the other are with the step 2 among the embodiment 11).
Claims (10)
1. a fluorine silicon di-block copolymers is characterized in that the poly-seven fluorine butyl methyl acrylate copolymers for polydimethylsiloxane-b-, and its structural formula is:
Wherein x is the polymerization degree of polydimethylsiloxane, and y is the polymerization degree of poly-seven fluorine butyl methyl acrylate.
2. the preparation method of a kind of fluorine silicon di-block copolymers as claimed in claim 1 is characterized in that its reaction formula is:
Wherein x is the polymerization degree of polydimethylsiloxane, and y is the polymerization degree of poly-seven fluorine butyl methyl acrylate.
3. the preparation method of a kind of fluorine silicon di-block copolymers as claimed in claim 1 is characterized in that comprising following concrete steps:
1) the end capped polydimethylsiloxane macromole evocating agent of preparation bromine atoms: under the nitrogen atmosphere protection, with single methyl alcohol terminated polydimethylsiloxane, 2-bromine isobutyl acylbromide and triethylamine are that starting raw material reacts at inert organic solvents, reaction finishes after-filtration, inert organic solvents is removed in the filtrate decompression distillation, again it is dissolved in the methylene dichloride, wash with sodium hydrogen carbonate solution, separatory, organic layer siccative drying, refilter, at last dichloromethane solvent is removed in the filtrate decompression distillation and obtained the end capped polydimethylsiloxane macromole evocating agent of oily xanchromatic bromine atoms; In molar ratio, single methyl alcohol terminated polydimethylsiloxane: 2-bromine isobutyl acylbromide: triethylamine is 1: 1.35～3.20: 2.52～6.04;
2) the poly-seven fluorine butyl methyl acrylate di-block copolymers of preparation polydimethylsiloxane-b-: atom transfer radical polymerization is carried out under inert atmosphere protection; with the end capped polydimethylsiloxane macromole of bromine atoms is initiator; with the cuprous halide is catalyzer; to contain the pyridine ring compound or to contain a kind of in the derivative of pyridine ring compound is catalyst ligand; in inert solvent toluene, carry out atom transfer radical polymerization; in molar ratio; seven fluorine butyl methyl acrylate: catalyzer: initiator: catalyst ligand=15～100: 1: 1: 2; then through freezing-vacuumize-thaw cycles at least 3 times after; after reacting by heating finishes; institute's synthetic polymkeric substance is diluted with inert solvent tetrahydrofuran (THF) or methylene dichloride; solution after will diluting is again removed catalyzer by alumina column; filtrate is removed inert solvent with Rotary Evaporators; be deposited in the precipitation agent; repeatedly after the dissolving-precipitation at least 3 times again with the product vacuum-drying that obtains; obtain poly-seven fluorine butyl methyl acrylate copolymer, the i.e. fluorine silicon di-block copolymers of polydimethylsiloxane-b-.
4. the preparation method of a kind of fluorine silicon di-block copolymers as claimed in claim 3 is characterized in that in step 1), and used inert organic solvents is selected from tetrahydrofuran (THF) or methylene dichloride; The purity of used nitrogen is greater than 99.995%.
5. the preparation method of a kind of fluorine silicon di-block copolymers as claimed in claim 3 is characterized in that in step 1), and used sodium hydrogen carbonate solution is a saturated solution; Rotary Evaporators is adopted in used distillation; Filter paper filtering is adopted in used filtration; Siccative is with anhydrous magnesium sulfate or anhydrous sodium sulphate.
6. the preparation method of a kind of fluorine silicon di-block copolymers as claimed in claim 3 is characterized in that in step 2) in, described rare gas element adopts high purity nitrogen, and its concentration is greater than 99.995%.
7. the preparation method of a kind of fluorine silicon di-block copolymers as claimed in claim 3 is characterized in that in step 2) in, described catalyst ligand is N-(n-propyl group)-2-pyridyl-methanamine.
8. the preparation method of a kind of fluorine silicon di-block copolymers as claimed in claim 3 is characterized in that in step 2) in, the described freezing liquid nitrogen of using, temperature is below-80 ℃; The described employing oil pump that vacuumizes; Described alumina column adopts the alkali alumina post.
9. the preparation method of a kind of fluorine silicon di-block copolymers as claimed in claim 3 is characterized in that in step 2) in, the temperature of heating is 40～120 ℃, the time of heating is controlled at 3～10h.
10. the preparation method of a kind of fluorine silicon di-block copolymers as claimed in claim 3 is characterized in that in step 2) in, precipitation agent is a lower alcohol.
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| CN104193923A (en) * | 2014-10-13 | 2014-12-10 | 陕西省石油化工研究设计院 | Hydrophobic/oleophobic fluorosilicone triblock polymer and preparation method thereof |
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| CN105061770B (en) * | 2015-08-10 | 2017-08-04 | 广东博兴新材料科技有限公司 | A kind of organic fluorinated silicone light-cured resin and its preparation method and application |
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| CN1220276A (en) * | 1997-12-16 | 1999-06-23 | 华东理工大学 | Method for preparation of fluorosilicic block copolymer |
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| CN1220276A (en) * | 1997-12-16 | 1999-06-23 | 华东理工大学 | Method for preparation of fluorosilicic block copolymer |
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| CN104193923A (en) * | 2014-10-13 | 2014-12-10 | 陕西省石油化工研究设计院 | Hydrophobic/oleophobic fluorosilicone triblock polymer and preparation method thereof |
| CN104193923B (en) * | 2014-10-13 | 2017-01-18 | 陕西省石油化工研究设计院 | Hydrophobic/oleophobic fluorosilicone triblock polymer and preparation method thereof |
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