CN102199261B - 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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- CN102199261B CN102199261B CN201110091612A CN201110091612A CN102199261B CN 102199261 B CN102199261 B CN 102199261B CN 201110091612 A CN201110091612 A CN 201110091612A CN 201110091612 A CN201110091612 A CN 201110091612A CN 102199261 B CN102199261 B CN 102199261B
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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 a kind of polyoxyethylene glycol-b-PS-b-and gather perfluoro hexyl ethyl propylene acid esters and preparation method thereof.
Background technology
The research of environmentally friendly bionical antifouling paint causes people's extensive concern.It is a kind of novel fluorine-containing amphipathic three block copolymer with micro phase separation structure that polyoxyethylene glycol-b-PS-b-gathers perfluoro hexyl ethyl propylene acid esters, does not appear in the newspapers as yet so far; Wherein the polyoxyethylene glycol block has lower interfacial energy, gather perfluoro hexyl ethyl propylene acid esters block and have 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 chemicalstability 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 under high temperature or katalysis, accomplish usually react and productive rate 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, MWD broad (＞1.5) and utilize.
Summary of the invention
To the deficiency of prior art, the purpose of this invention is to provide fluorine-containing triblock copolymer polyoxyethylene glycol-b-PS-b-that a kind of reaction conditions is gentle, simple to operate, product has predetermined molecular weight and structure clear and definite, product has micro phase separation structure and gather perfluoro hexyl ethyl propylene acid esters and preparation method.
Polyoxyethylene glycol according to the invention-b-PS-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 PS (PSt), n=1～500; The polymerization degree of m for gathering perfluoro hexyl ethyl propylene acid esters (PFHEA), m=1～200.
Polyoxyethylene glycol according to the invention-b-PS-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, meter in molar ratio, with the polyoxyethylene glycol monomethyl ether: 2-bromine isobutyl acylbromide: triethylamine is 1: 1.5～7.5: 2.0～10.0 under ice-water bath, to react; Reaction finishes after-filtration; In filtrating, add organic solvent tetrahydrofuran or methylene dichloride, use sodium hydrogen carbonate solution, deionized water, Hydrogen chloride and deionized water wash at least 1 time successively, separatory; Organic layer is dry with siccative; Filter, THF or methylene dichloride are removed in the filtrate decompression distillation, obtain 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, be initiator with the end capped polyoxyethylene glycol macromole of active bromine, with the cuprous bromide 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 100 ℃～120 ℃ following reaction 4h, dissolves institute's synthetic polymkeric substance with THF or methylene dichloride; And remove catalyzer through the neutral alumina post, again it is deposited in precipitation agent ether or the alkane, after repeated precipitation-dissolving-deposition at least 3 times; Product is dried 24～30h in vacuum drying oven, get the end capped polyoxyethylene glycol of bromine-b-polystyrene copolymer macromole evocating agent;
3) preparation polyoxyethylene glycol-b-PS-b-gathers perfluoro hexyl ethyl propylene acid esters:
Under protection of inert gas,, with the cuprous bromide catalyzer so that the end capped polyoxyethylene glycol of bromine-the b-polystyrene copolymer is a macromole evocating agent; 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 90 ℃～120 ℃ following reaction 10h, dissolves institute's synthetic polymkeric substance with THF or methylene dichloride; And remove catalyzer through the neutral alumina post, again it is deposited in precipitation agent ether or the alkane, after repeated precipitation-dissolving-deposition at least 3 times; Product is dried 24～30h in vacuum drying oven, get polyoxyethylene glycol-b-PS-b-and gather perfluoro hexyl ethyl propylene acid esters.
Above-mentioned polyoxyethylene glycol-b-PS-b-gathers among the preparation method of perfluoro hexyl ethyl propylene acid esters: the purity of the said nitrogen of step 1) preferably surpasses 99.99% by quality ratio.
Above-mentioned polyoxyethylene glycol-b-PS-b-gathers among the preparation method of perfluoro hexyl ethyl propylene acid esters: the said temperature of reaction of step 1) is preferably 25～120 ℃, and the reaction times is preferably 10～24h; Said sodium hydrogen carbonate solution is preferably saturated solution; The concentration of said Hydrogen chloride is preferably 0.1mol/L; Said siccative is preferably anhydrous magnesium sulfate or SODIUM SULPHATE ANHYDROUS 99PCT.
Above-mentioned polyoxyethylene glycol-b-PS-b-gathers among the preparation method of perfluoro hexyl ethyl propylene acid esters: step 2) or 3) the preferred purity of said rare gas element surpasses 99.99% nitrogen by quality ratio.
Above-mentioned polyoxyethylene glycol-b-PS-b-gathers among the preparation method of perfluoro hexyl ethyl propylene acid esters: step 2) or 3) said polymeric reaction temperature is preferably 25～120 ℃, the reaction times is preferably 4～20h.
Above-mentioned polyoxyethylene glycol-b-PS-b-gathers among the preparation method of perfluoro hexyl ethyl propylene acid esters: step 2) or 3) said freezing be to adopt liquid nitrogen, be preferably under the temperature condition below-80 ℃ and carry out; Said vacuumizing is to adopt oil pump to vacuumize, and vacuum tightness is preferably 0.08～0.1MPa.
Above-mentioned polyoxyethylene glycol-b-PS-b-gathers among the preparation method of perfluoro hexyl ethyl propylene acid esters: step 2) or 3) said precipitation agent preferably selects sherwood oil or normal hexane.
Above-mentioned polyoxyethylene glycol-b-PS-b-gathers among the preparation method of perfluoro hexyl ethyl propylene acid esters: step 2) or 3) said vacuum-drying temperature is preferably 20～40 ℃; Vacuum tightness is preferably 0.08～-0.1MPa.
The preparation feedback formula that above-mentioned polyoxyethylene glycol-b-PS-b-gathers perfluoro hexyl ethyl propylene acid esters is following:
Wherein x is the polymerization degree of polyoxyethylene glycol (PEG), and n is the polymerization degree of PS (PSt), the polymerization degree of m for gathering 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-PS di-block copolymer; Be that the synthetic subject polymer polyoxyethylene glycol of macromole evocating agent initiation fluorine hexyl ethyl propylene acid esters monomer polymerization-b-PS-b-gathers perfluoro hexyl ethyl propylene acid esters with this di-block copolymer again; The present invention compares with the chemical synthesis process of existing fluoropolymer, and beneficial effect is:
1. employing ATRP, not only reaction conditions is gentle, and product yield is high, and being compared to general radical polymerization, to have the structure of temperature of reaction and reaction product of milder distincter, and MWD 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 be done further elaboration to the present invention.
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; In filtrating, add methylene dichloride, use saturated sodium bicarbonate solution, deionized water, concentration to be 0.1mol/L hydrochloric acid and deionized water wash, repeated washing 3 times successively; Separatory; Organic layer is used 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), the umber meter is that initiator, 1 part of cuprous bromide are catalyzer, 1 part of N with 1 part of end capped polyoxyethylene glycol of active bromine in molar ratio; 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, and the solution after will diluting is removed catalyzer through the neutral alumina post, and 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, obtain the end capped polyoxyethylene glycol of bromine-b-polystyrene block copolymer after repeated precipitation-dissolving-deposition at least 3 times;
3) in the protection of nitrogen (purity by quality ratio surpass 99.99%) atmosphere (the necessary strict deoxygenation of reaction system) down, umber meter in molar ratio is that initiator, 1 part cuprous bromide are catalyzer, 1 part of N with the 1 part of end capped polyoxyethylene glycol of bromine-b-PS; 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, and the solution after will diluting is removed catalyzer through the neutral alumina post, and it is deposited in the sherwood oil; With product (vacuum tightness is 0.08Mpa) oven dry 24h in 30 ℃ of vacuum drying ovens, obtain the fluorine-containing triblock copolymer that polyoxyethylene glycol-b-PS-b-gathers perfluoro hexyl ethyl propylene acid esters after repeated precipitation-dissolving-deposition at least 3 times;
Above-mentioned freezing be to adopt liquid nitrogen, under the temperature condition below-80 ℃, carry out; Said 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 that polyoxyethylene glycol-b-PS-b-gathers perfluoro hexyl ethyl propylene acid esters.
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 that polyoxyethylene glycol-b-PS-b-gathers perfluoro hexyl ethyl propylene acid esters.
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 that polyoxyethylene glycol-b-PS-b-gathers perfluoro hexyl ethyl propylene acid esters.
Claims (8)
1. polyoxyethylene glycol-b-PS-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, meter in molar ratio, with the polyoxyethylene glycol monomethyl ether: 2-bromine isobutyl acylbromide: triethylamine is that react under ice-water bath 1:1.5～7.5:2.0～10.0; Reaction finishes after-filtration; In filtrating, add organic solvent tetrahydrofuran or methylene dichloride, use sodium hydrogen carbonate solution, deionized water, Hydrogen chloride and deionized water wash at least 1 time successively, separatory; Organic layer is dry with siccative; Filter, THF or methylene dichloride are removed in the filtrate decompression distillation, obtain 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, be initiator with the end capped polyoxyethylene glycol macromole of active bromine, with the cuprous bromide catalyzer; With N, N, N '; N ", N ", N "-PMDETA (PMDETA) is a catalyst ligand; With vinylbenzene be initiator in molar ratio: the ratio of catalyzer: catalyst ligand: vinylbenzene=1:1:1:10～400, 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 100 ℃～120 ℃ following reaction 4h, dissolves institute's synthetic polymkeric substance with THF or methylene dichloride; And remove catalyzer through the neutral alumina post, again it is deposited in precipitation agent ether or the alkane, after repeated precipitation-dissolving-deposition at least 3 times; Product is dried 24～30h in vacuum drying oven, get the end capped polyoxyethylene glycol of bromine-b-polystyrene copolymer macromole evocating agent;
3) preparation polyoxyethylene glycol-b-PS-b-gathers perfluoro hexyl ethyl propylene acid esters:
Under protection of inert gas,, with the cuprous bromide catalyzer so that the end capped polyoxyethylene glycol of bromine-the b-polystyrene copolymer is a macromole evocating agent; 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: the ratio of perfluoro hexyl ethyl propylene acid esters=1:1:1:10～100, 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 90 ℃～120 ℃ following reaction 10h, dissolves institute's synthetic polymkeric substance with THF or methylene dichloride; And remove catalyzer through the neutral alumina post, again it is deposited in precipitation agent ether or the alkane, after repeated precipitation-dissolving-deposition at least 3 times; Product is dried 24～30h in vacuum drying oven, get polyoxyethylene glycol-b-PS-b-and gather perfluoro hexyl ethyl propylene acid esters.
2. polyoxyethylene glycol-b-PS-b-gathers the preparation method of perfluoro hexyl ethyl propylene acid esters, it is characterized in that according to claim 1: the purity of the said nitrogen of step 1) surpasses 99.99% by quality ratio.
3. polyoxyethylene glycol-b-PS-b-gathers the preparation method of perfluoro hexyl ethyl propylene acid esters, it is characterized in that according to claim 1: the said temperature of reaction of step 1) is 25～120 ℃, and the reaction times is 10～24h; Said sodium hydrogen carbonate solution is a saturated solution; The concentration of said Hydrogen chloride is 0.1mol/L; Said siccative is anhydrous magnesium sulfate or SODIUM SULPHATE ANHYDROUS 99PCT.
4. polyoxyethylene glycol-b-PS-b-gathers the preparation method of perfluoro hexyl ethyl propylene acid esters, it is characterized in that: step 2 according to claim 1) or 3) said rare gas element is that purity surpasses 99.99% nitrogen by quality ratio.
5. polyoxyethylene glycol-b-PS-b-gathers the preparation method of perfluoro hexyl ethyl propylene acid esters, it is characterized in that: step 2 according to claim 1) or 3) said polymeric reaction temperature is 25～120 ℃, the reaction times is 4～20h.
6. polyoxyethylene glycol-b-PS-b-gathers the preparation method of perfluoro hexyl ethyl propylene acid esters, it is characterized in that: step 2 according to claim 1) or 3) said freezing be to adopt liquid nitrogen, under the temperature condition below-80 ℃, carry out; Said vacuumizing is to adopt oil pump to vacuumize, and vacuum tightness is 0.08～0.1MPa.
7. polyoxyethylene glycol-b-PS-b-gathers the preparation method of perfluoro hexyl ethyl propylene acid esters, it is characterized in that: step 2 according to claim 1) or 3) said precipitation agent selects sherwood oil or normal hexane.
8. polyoxyethylene glycol-b-PS-b-gathers the preparation method of perfluoro hexyl ethyl propylene acid esters, it is characterized in that: step 2 according to claim 1) or 3) said vacuum-drying temperature is 20～40 ℃; Vacuum tightness is 0.08～-0.1MPa.
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| CN107686542B (en) * | 2016-08-30 | 2021-06-18 | 复旦大学 | Highly-ordered fluorine-containing polymer material |
| CN108641052B (en) * | 2018-05-16 | 2020-12-11 | 东北师范大学 | Halogenated polymer, polymer film, preparation method and application thereof |
| CN110354701B (en) * | 2019-03-15 | 2021-12-14 | 烟台金正环保科技有限公司 | Preparation method of high pollution-resistant oil-water separation ultrafiltration membrane |
| CN114163589B (en) * | 2021-10-27 | 2023-03-28 | 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 |
| CN115612478B (en) * | 2022-12-19 | 2023-04-18 | 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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