CN102199261A - Polyethylene glycol (PEG)-b-polystyrene (PSt)-b-perfluorohexylethyl acrylate (PFHEA) and preparation method thereof - Google Patents
Polyethylene glycol (PEG)-b-polystyrene (PSt)-b-perfluorohexylethyl acrylate (PFHEA) and preparation method thereof Download PDFInfo
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- CN102199261A CN102199261A CN2011100916122A CN201110091612A CN102199261A CN 102199261 A CN102199261 A CN 102199261A CN 2011100916122 A CN2011100916122 A CN 2011100916122A CN 201110091612 A CN201110091612 A CN 201110091612A CN 102199261 A CN102199261 A CN 102199261A
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Abstract
The invention discloses PEG-b-PSt-b-PFHEA. The PEG-b-PSt-b-PFHEA is prepared by treating bromine-terminated PEG as a macroinitiator, obtaining a PEG-b-PSt diblock copolymer through an atom transfer radical polymerization reaction, and treating the diblock copolymer as the macroinitiator to initiate PFHEA monomer polymerization. The preparation method has the advantages of mild reaction conditions, economy, simple operation and high product yield. The product of the present invention has a clearer structure and a narrower molecular weight distribution than products prepared by common radical polymerization reactions, and has a microphase separation structure, and low interfacial energy and surface energy which allow protein adsorption to be inhibited.
Description
Technical field
The present invention relates to a kind of fluorine-containing amphipathic three block copolymer and synthetic, especially relate to poly-perfluoro hexyl ethyl propylene acid esters of a kind of polyoxyethylene glycol-b-polystyrene-b-and preparation method thereof.
Background technology
The research of environmentally friendly bionical antifouling paint causes people's extensive concern.The poly-perfluoro hexyl ethyl propylene acid esters of polyoxyethylene glycol-b-polystyrene-b-is a kind of novel fluorine-containing amphipathic three block copolymer with micro phase separation structure, does not appear in the newspapers as yet so far; Wherein the polyoxyethylene glycol block has lower interfacial energy, and poly-perfluoro hexyl ethyl propylene acid esters block has very low surface energy, and polystyrene block can provide enough bonding strengths, so it is expected to be used widely in antifouling paint, tensio-active agent field.Polyoxyethylene glycol has excellent biological compatibility and wetting ability, can form stable hydration layer at polymer surfaces with the water effect, has lower interfacial energy, but the absorption of arrestin matter; The fluorocarbon surface energy is low, and chemical stability is good, has extremely low surface energy, prevents adhering to of exotic.This fluorine-containing triblock copolymer concentrates lower interfacial energy and extremely low surface energy in one, and comprehensive performance is arranged.
The method of at present synthetic fluoropolymer mainly contains: 1, fluorochemical monomer and one or more vinyl monomer are carried out copolymerization; 2. fluoro-containing group is received on other main polymer chain; 3. other group is received on the fluoropolymer main chain.These three kinds of methods all have shortcoming separately: as fluoro-containing group is received on other main polymer chain method with other group is received way on the fluoropolymer main chain need be finished reaction usually under high temperature or katalysis and productive rate is low; Fluorochemical monomer and one or more vinyl monomer are carried out the polymkeric substance that the method for copolymerization obtains be random copolymers, no clear and definite molecular structure and composition, molecular weight distribution broad (＞1.5) and utilize.
Summary of the invention
At the deficiencies in the prior art, the purpose of this invention is to provide a kind of reaction conditions gentleness, simple to operate, product and have predetermined molecular weight and structure is clear and definite, product has micro phase separation structure poly-perfluoro hexyl ethyl propylene acid esters of fluorine-containing triblock copolymer polyoxyethylene glycol-b-polystyrene-b-and preparation method.
Polyoxyethylene glycol of the present invention-b-polystyrene-b-gathers perfluoro hexyl ethyl propylene acid esters, and its structural formula is:
Wherein: x is the polymerization degree of polyoxyethylene glycol (PEG), x=1～200; N is the polymerization degree of polystyrene (PSt), n=1～500; M is the polymerization degree of poly-perfluoro hexyl ethyl propylene acid esters (PFHEA), m=1～200.
The preparation method of the poly-perfluoro hexyl ethyl propylene acid esters of polyoxyethylene glycol of the present invention-b-polystyrene-b-, step is:
1) the end capped polyoxyethylene glycol macromole evocating agent of preparation active bromine:
Under nitrogen atmosphere protection, count in molar ratio, with the polyoxyethylene glycol monomethyl ether: 2-bromine isobutyl acylbromide: triethylamine is 1: 1.5～7.5: 2.0～10.0 to react under ice-water bath, reaction finishes after-filtration, in filtrate, add organic solvent tetrahydrofuran or methylene dichloride, use sodium hydrogen carbonate solution, deionized water, dilute hydrochloric acid and deionized water wash at least 1 time successively, separatory, organic layer siccative drying, filter, tetrahydrofuran (THF) or methylene dichloride are removed in the filtrate decompression distillation, obtained the end capped polyoxyethylene glycol macromole evocating agent of active bromine;
2) the end capped polyoxyethylene glycol of preparation bromine-b-polystyrene copolymer macromole evocating agent:
Under protection of inert gas, with the end capped polyoxyethylene glycol macromole of active bromine is initiator, with the cuprous bromide is catalyzer, with N, N, N '; N "; N "; N "-PMDETA (PMDETA) is a catalyst ligand, with vinylbenzene be initiator in molar ratio: catalyzer: catalyst ligand: vinylbenzene=1: 1: 1: 10～400 ratio, in toluene, carry out atom transition free radical polymerization reaction, reaction mixture through at least 3 times freezing-vacuumize-thaw cycles after, the reacting by heating thing, behind the reaction 4h, institute's synthetic polymkeric substance is dissolved with tetrahydrofuran (THF) or methylene dichloride, and remove catalyzer under 100 ℃～120 ℃ by the neutral alumina post, it is deposited in precipitation agent ether or the alkane again, after repeated precipitation-dissolving-precipitation at least 3 times, product is dried 24～30h in vacuum drying oven, the end capped polyoxyethylene glycol of bromine-b-polystyrene copolymer macromole evocating agent;
3) the poly-perfluoro hexyl ethyl propylene acid esters of preparation polyoxyethylene glycol-b-polystyrene-b-:
Under protection of inert gas; with the end capped polyoxyethylene glycol of bromine-b-polystyrene copolymer is macromole evocating agent; with the cuprous bromide is catalyzer; with N; N; N '; N "; N "; N "-PMDETA (PMDETA) is a catalyst ligand; with monomer perfluoro hexyl ethyl propylene acid esters be initiator in molar ratio: catalyzer: catalyst ligand: perfluoro hexyl ethyl propylene acid esters=1: 1: 1: 10～100 ratio, in toluene, carry out atom transition free radical polymerization reaction, reaction mixture through at least 3 times freezing-vacuumize-thaw cycles after; the reacting by heating thing; behind the reaction 10h, institute's synthetic polymkeric substance is dissolved with tetrahydrofuran (THF) or methylene dichloride, and remove catalyzer under 90 ℃～120 ℃ by the neutral alumina post; it is deposited in precipitation agent ether or the alkane again; after repeated precipitation-dissolving-precipitation at least 3 times, product is dried 24～30h in vacuum drying oven, the poly-perfluoro hexyl ethyl propylene acid esters of polyoxyethylene glycol-b-polystyrene-b-.
Among the preparation method of the poly-perfluoro hexyl ethyl propylene acid esters of above-mentioned polyoxyethylene glycol-b-polystyrene-b-: the purity of the described nitrogen of step 1) preferably surpasses 99.99% by quality ratio.
Among the preparation method of the poly-perfluoro hexyl ethyl propylene acid esters of above-mentioned polyoxyethylene glycol-b-polystyrene-b-: the described temperature of reaction of step 1) is preferably 25～120 ℃, and the reaction times is preferably 10～24h; Described sodium hydrogen carbonate solution is preferably saturated solution; The concentration of described dilute hydrochloric acid is preferably 0.1mol/L; Described siccative is preferably anhydrous magnesium sulfate or anhydrous sodium sulphate.
Among the preparation method of the poly-perfluoro hexyl ethyl propylene acid esters of above-mentioned polyoxyethylene glycol-b-polystyrene-b-: step 2) or 3) the preferred purity of described rare gas element surpasses 99.99% nitrogen by quality ratio.
Among the preparation method of the poly-perfluoro hexyl ethyl propylene acid esters of above-mentioned polyoxyethylene glycol-b-polystyrene-b-: step 2) or 3) described polymeric reaction temperature is preferably 25～120 ℃, the reaction times is preferably 4～20h.
Among the preparation method of the poly-perfluoro hexyl ethyl propylene acid esters of above-mentioned polyoxyethylene glycol-b-polystyrene-b-: step 2) or 3) described freezing be to adopt liquid nitrogen, be preferably under the temperature condition below-80 ℃ and carry out; Described vacuumizing is to adopt oil pump to vacuumize, and vacuum tightness is preferably 0.08～0.1MPa.
Among the preparation method of the poly-perfluoro hexyl ethyl propylene acid esters of above-mentioned polyoxyethylene glycol-b-polystyrene-b-: step 2) or 3) described precipitation agent preferably selects sherwood oil or normal hexane.
Among the preparation method of the poly-perfluoro hexyl ethyl propylene acid esters of above-mentioned polyoxyethylene glycol-b-polystyrene-b-: step 2) or 3) described vacuum-drying temperature is preferably 20～40 ℃; Vacuum tightness is preferably 0.08～-0.1MPa.
The preparation feedback formula of the poly-perfluoro hexyl ethyl propylene acid esters of above-mentioned polyoxyethylene glycol-b-polystyrene-b-is as follows:
Wherein x is the polymerization degree of polyoxyethylene glycol (PEG), and n is the polymerization degree of polystyrene (PSt), and m is the polymerization degree of poly-perfluoro hexyl ethyl propylene acid esters (PFHEA).
The present invention is a macromole evocating agent with the end capped polyoxyethylene glycol of bromine, through atom transition free radical polymerization reaction synthesizing polyethylene glycol-b-polystyrene di-block copolymer, be that macromole evocating agent causes the synthetic subject polymer polyoxyethylene glycol of fluorine hexyl ethyl propylene acid esters monomer polymerization-poly-perfluoro hexyl ethyl propylene acid esters of b-polystyrene-b-with this di-block copolymer again, the present invention compares with the chemical synthesis process of existing fluoropolymer, and beneficial effect is:
1. employing atom transfer radical polymerization, reaction conditions gentleness not only, the product yield height, being compared to general radical polymerization, to have the structure of the temperature of reaction of milder and reaction product distincter, and molecular weight distribution is narrower.2. than 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 and very low interfacial energy and surface energy, but the absorption of arrestin matter.
Embodiment
For being easy to further understand the present invention, the following example will the present invention is further elaborated.
Embodiment 1
1) under nitrogen (purity surpasses 99.99% by quality ratio) atmosphere protection, the umber meter reacts 1 part of polyoxyethylene glycol monomethyl ether (number-average molecular weight is 750), 1.5 parts of 2-bromine isobutyl acylbromides and 2 parts of triethylamines under ice-water bath in molar ratio.Behind reinforced the finishing, continue reaction 24h under the room temperature, reaction finishes after-filtration, adding methylene dichloride in filtrate, is 0.1mol/L hydrochloric acid and deionized water wash with saturated sodium bicarbonate solution, deionized water, concentration successively, repeated washing 3 times, separatory, the organic layer anhydrous magnesium sulfate drying refilters, and dichloromethane solvent is removed in the filtrate decompression distillation obtained the end capped polyoxyethylene glycol macromole evocating agent of lurid active bromine;
2) under nitrogen (purity surpasses 99.99% by quality ratio) atmosphere protection (the necessary strict deoxygenation of reaction system), umber meter in molar ratio, with 1 part of end capped polyoxyethylene glycol of active bromine is initiator, 1 part of cuprous bromide is a catalyzer, 1 part of N, N, N '; N "; N "; N "-PMDETA (PMDETA) is that monomer reacts down at 110 ℃ for catalyst ligand and 400 parts vinylbenzene, before heating, reaction mixture through 3 times freezing-vacuumize-thaw cycles after, behind the reacting by heating 4h, institute's synthetic polymkeric substance is dissolved with tetrahydrofuran solvent, solution after will diluting is removed catalyzer by the neutral alumina post, it is deposited in the precipitation agent sherwood oil, with product (vacuum tightness is 0.08Mpa) oven dry 24h in 30 ℃ of vacuum drying ovens, obtains the end capped polyoxyethylene glycol of bromine-b-polystyrene block copolymer after repeated precipitation-dissolving-precipitation at least 3 times;
3) under nitrogen (purity surpasses 99.99% by quality ratio) atmosphere protection (the necessary strict deoxygenation of reaction system), umber meter in molar ratio, with the 1 part of end capped polyoxyethylene glycol of bromine-b-polystyrene is initiator, 1 part cuprous bromide is a catalyzer, 1 part of N, N, N '; N "; N "; N "-PMDETA (PMDETA) is that monomer reacts down at 90 ℃ for catalyst ligand and 100 parts perfluoro hexyl ethyl propylene acid esters, before heating, reaction mixture through 3 times freezing-vacuumize-thaw cycles after, behind the reacting by heating 10h, institute's synthetic polymkeric substance is dissolved with tetrahydrofuran solvent, solution after will diluting is removed catalyzer by the neutral alumina post, it is deposited in the sherwood oil, with product (vacuum tightness is 0.08Mpa) oven dry 24h in 30 ℃ of vacuum drying ovens, obtains the fluorine-containing triblock copolymer of the poly-perfluoro hexyl ethyl propylene acid esters of polyoxyethylene glycol-b-polystyrene-b-after repeated precipitation-dissolving-precipitation at least 3 times;
Above-mentioned freezing be to adopt liquid nitrogen, under the temperature condition below-80 ℃, carry out; Described vacuumizing is to adopt oil pump to vacuumize, and vacuum tightness is 0.1MPa.
Embodiment 2
1) removing polyoxyethylene glycol monomethyl ether (number-average molecular weight is 2000) is 1 especially, and other is with the step 1) among the embodiment 1;
2) except that styrene monomer was 100 ℃ of 300 parts, temperature of reaction, other was with the step 2 among the embodiment 1);
3) be that 80 ℃, reaction times are the 8h except that temperature of reaction, other is with the step 3) among the embodiment 1;
Make the fluorine-containing triblock copolymer of the poly-perfluoro hexyl ethyl propylene acid esters of polyoxyethylene glycol-b-polystyrene-b-.
Embodiment 3
1) removing 2-bromine isobutyl acylbromide is that 3 parts, triethylamine are 4.5 especially, and other is with the step 1) among the embodiment 1;
2) except that styrene monomer was 90 ℃ of 300 parts, temperature of reaction, other was with the step 2 among the embodiment 1);
3) be that 80 ℃, reaction times are the 8h except that temperature of reaction, other is with the step 3) among the embodiment 1;
Make the fluorine-containing triblock copolymer of the poly-perfluoro hexyl ethyl propylene acid esters of polyoxyethylene glycol-b-polystyrene-b-.
Embodiment 4
1) removing 2-bromine isobutyl acylbromide is that 5 parts, triethylamine are 7.5 especially, and other is with the step 1) among the embodiment 1;
2) removing styrene monomer is 200 especially, and other is with the step 2 among the embodiment 2);
3) be the 10h except that the reaction times, other is with the step 3) among the embodiment 2;
Make the fluorine-containing triblock copolymer of the poly-perfluoro hexyl ethyl propylene acid esters of polyoxyethylene glycol-b-polystyrene-b-.
Claims (9)
1. polyoxyethylene glycol-b-polystyrene-b-gathers perfluoro hexyl ethyl propylene acid esters, and its structural formula is:
Wherein: x is the polymerization degree of polyoxyethylene glycol (PEG), x=1～200; N is the polymerization degree of polystyrene (PSt), n=1～500; M is the polymerization degree of poly-perfluoro hexyl ethyl propylene acid esters (PFHEA), m=1～200.
2. the described polyoxyethylene glycol of claim 1-b-polystyrene-b-gathers the preparation method of perfluoro hexyl ethyl propylene acid esters, and step is:
1) the end capped polyoxyethylene glycol macromole evocating agent of preparation active bromine:
Under nitrogen atmosphere protection, count in molar ratio, with the polyoxyethylene glycol monomethyl ether: 2-bromine isobutyl acylbromide: triethylamine is 1: 1.5～7.5: 2.0～10.0 to react under ice-water bath, reaction finishes after-filtration, in filtrate, add organic solvent tetrahydrofuran or methylene dichloride, use sodium hydrogen carbonate solution, deionized water, dilute hydrochloric acid and deionized water wash at least 1 time successively, separatory, organic layer siccative drying, filter, tetrahydrofuran (THF) or methylene dichloride are removed in the filtrate decompression distillation, obtained the end capped polyoxyethylene glycol macromole evocating agent of active bromine;
2) the end capped polyoxyethylene glycol of preparation bromine-b-polystyrene copolymer macromole evocating agent:
Under protection of inert gas, with the end capped polyoxyethylene glycol macromole of active bromine is initiator, with the cuprous bromide is catalyzer, with N, N, N '; N "; N "; N "-PMDETA (PMDETA) is a catalyst ligand, with vinylbenzene be initiator in molar ratio: catalyzer: catalyst ligand: vinylbenzene=1: 1: 1: 10～400 ratio, in toluene, carry out atom transition free radical polymerization reaction, reaction mixture through at least 3 times freezing-vacuumize-thaw cycles after, the reacting by heating thing, behind the reaction 4h, institute's synthetic polymkeric substance is dissolved with tetrahydrofuran (THF) or methylene dichloride, and remove catalyzer under 100 ℃～120 ℃ by the neutral alumina post, it is deposited in precipitation agent ether or the alkane again, after repeated precipitation-dissolving-precipitation at least 3 times, product is dried 24～30h in vacuum drying oven, the end capped polyoxyethylene glycol of bromine-b-polystyrene copolymer macromole evocating agent;
3) the poly-perfluoro hexyl ethyl propylene acid esters of preparation polyoxyethylene glycol-b-polystyrene-b-:
Under protection of inert gas; with the end capped polyoxyethylene glycol of bromine-b-polystyrene copolymer is macromole evocating agent; with the cuprous bromide is catalyzer; with N; N; N '; N "; N "; N "-PMDETA (PMDETA) is a catalyst ligand; with monomer perfluoro hexyl ethyl propylene acid esters be initiator in molar ratio: catalyzer: catalyst ligand: perfluoro hexyl ethyl propylene acid esters=1: 1: 1: 10～100 ratio, in toluene, carry out atom transition free radical polymerization reaction, reaction mixture through at least 3 times freezing-vacuumize-thaw cycles after; the reacting by heating thing; behind the reaction 10h, institute's synthetic polymkeric substance is dissolved with tetrahydrofuran (THF) or methylene dichloride, and remove catalyzer under 90 ℃～120 ℃ by the neutral alumina post; it is deposited in precipitation agent ether or the alkane again; after repeated precipitation-dissolving-precipitation at least 3 times, product is dried 24～30h in vacuum drying oven, the poly-perfluoro hexyl ethyl propylene acid esters of polyoxyethylene glycol-b-polystyrene-b-.
3. as the preparation method of the poly-perfluoro hexyl ethyl propylene acid esters of polyoxyethylene glycol-b-polystyrene-b-as described in the claim 2, it is characterized in that: the purity of the described nitrogen of step 1) surpasses 99.99% by quality ratio.
4. as the preparation method of the poly-perfluoro hexyl ethyl propylene acid esters of polyoxyethylene glycol-b-polystyrene-b-as described in the claim 2, it is characterized in that: the described temperature of reaction of step 1) is 25～120 ℃, and the reaction times is 10～24h; Described sodium hydrogen carbonate solution is a saturated solution; The concentration of described dilute hydrochloric acid is 0.1mol/L; Described siccative is anhydrous magnesium sulfate or anhydrous sodium sulphate.
5. as the preparation method of the poly-perfluoro hexyl ethyl propylene acid esters of polyoxyethylene glycol-b-polystyrene-b-as described in the claim 2, it is characterized in that: step 2) or 3) described rare gas element is that purity surpasses 99.99% nitrogen by quality ratio.
6. as the preparation method of the poly-perfluoro hexyl ethyl propylene acid esters of polyoxyethylene glycol-b-polystyrene-b-as described in the claim 2, it is characterized in that: step 2) or 3) described polymeric reaction temperature is 25～120 ℃, the reaction times is 4～20h.
7. as the preparation method of the poly-perfluoro hexyl ethyl propylene acid esters of polyoxyethylene glycol-b-polystyrene-b-as described in the claim 2, it is characterized in that: step 2) or 3) described freezing be to adopt liquid nitrogen, under the temperature condition below-80 ℃, carry out; Described vacuumizing is to adopt oil pump to vacuumize, and vacuum tightness is 0.08～0.1MPa.
8. as the preparation method of the poly-perfluoro hexyl ethyl propylene acid esters of polyoxyethylene glycol-b-polystyrene-b-as described in the claim 2, it is characterized in that: step 2) or 3) described precipitation agent selects sherwood oil or normal hexane.
9. as the preparation method of the poly-perfluoro hexyl ethyl propylene acid esters of polyoxyethylene glycol-b-polystyrene-b-as described in the claim 2, it is characterized in that: step 2) or 3) described vacuum-drying temperature is 20～40 ℃; Vacuum tightness is 0.08～-0.1MPa.
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| CN110354701A (en) * | 2019-03-15 | 2019-10-22 | 烟台金正环保科技有限公司 | A kind of preparation method of high anti-pollution water-oil separating ultrafiltration membrane |
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| CN110354701A (en) * | 2019-03-15 | 2019-10-22 | 烟台金正环保科技有限公司 | A kind of preparation method of high anti-pollution water-oil separating ultrafiltration membrane |
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| CN114163589A (en) * | 2021-10-27 | 2022-03-11 | 吉林省东驰新能源科技有限公司 | Block polymer and preparation method thereof, block polymer electrolyte and preparation method thereof, and polymer lithium battery |
| CN115612478A (en) * | 2022-12-19 | 2023-01-17 | 中石化西南石油工程有限公司 | Polymer thickening agent and preparation method and application thereof |
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