CN102702452A - Preparation method of triblock polymers with suspension nanometer zero-valent irons - Google Patents
Preparation method of triblock polymers with suspension nanometer zero-valent irons Download PDFInfo
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Abstract
The invention discloses a preparation method of triblock polymers with suspension nanometer zero-valent irons. The preparation method comprises the steps of utilizing an atom transfer radical polymerization(ATRP) method to synthetize triblock polymers of poly(t-butyl methacrylate), polymethyl methacrylate and polrvinyl benzene, hydrolyzing the poly(t-butyl methacrylate) to prepare polymethacrylic acid using trifluoroacetic acid, and finally sulfonating the polrvinyl benzene to prepare polystyrolsulfon acid using sulfuric acid acetyl. The method improves the original three-step reaction into a one-step reaction in the synthetic process of the polymers, thereby reducing the operation steps, reducing the consumption of raw materials, improving reaction stability and improving the productivity of aimed compounds; and adding trifluoroacetic acid in a hydrolysis process, so that the hydrolysis process is thorough and the reactivity and the suspension property of products are improved. The experiment results show that the triblock polymers comprise functional groups in required target products, the molecular weight can reach about 100 thousand, and the stabilization time of suspension effects of nanometer zero-valent irons can reach more than two months.
Description
Technical field
The present invention relates to a kind of preparation method of polymkeric substance, relate in particular to the preparation method of the triblock polymer that is used for the suspended nano Zero-valent Iron.
Background technology
Nano zero valence iron has stronger reductibility, in water, can the efficient deoxidization, degradation of hydrochloric ethers such as trieline can also be repaired the heavy metal contaminants in the underground water through absorption and reductive action, is very good underground water renovation agent.Another advantage of nano zero valence iron is that granularity is little, can inject the stratum through the original position injection method, thereby realizes the original position reparation to underground water pollutant.But pure nano zero valence iron is prone to deposition in water, so the various countries scientist has researched and developed multiple suspension agent and realizes its stable suspersion.
In various nano zero valence iron suspension agents; Polymethyl acrylic acid-polymethylmethacrylate-polystyrolsulfon acid triblock polymer (PMAA-PMMA-PSS) has better adsorption capability to nano zero valence iron; Have more negative charge; The nano zero valence iron of suspension is not reunited owing to electrostatic repulsion, can be in electronegative soil particle surface adsorption yet.In addition, there is good avidity in its polymethyl methacrylate base group to hydrochloric ether, and the nano zero valence iron of suspension is tended at the hydrochloric ether surface aggregation, thus quick degradating chloro hydrocarbon.Therefore PMAA-PMMA-PSS is very good nano zero valence iron suspension agent.
At present, the PMAA-PMMA-PSS triblock polymer is not also realized industrial production, all is through the atom transition free radical polymerization reaction synthetic.Concrete operational path such as Fig. 1～shown in Figure 5, step is following:
1. synthetic polymethyl tert-butyl acrylate (PtBMA): in reactor drum, add acetone and methyl-phenoxide and carry out the deoxidation processing; Add toluene(mono)chloride sulphonyl, PMDETA and methacrylic tert-butyl acrylate then successively; Under nitrogen protection, add CuCl; Again reaction system is diluted reaction mixture behind reaction 3～5h down at 40 ℃～60 ℃ with THF (THF); After then filtering solvent and unreacted monomer are evaporated, be dried to after the constant weight polymer P tBMA subsequent use again with neutral alumina;
2. synthetic polymethyl tert-butyl acrylate-polymethylmethacrylate (PtBMA-PMMA): after the adding methyl-phenoxide carries out the deoxidation processing in reactor drum; Add PtBMA, TEB 3K, CuBr and the two pyridine for preparing successively, under nitrogen protection, add CuBr
2, then reaction system is being diluted reaction mixture behind reaction 2～3h down at 20 ℃～30 ℃ with THF, after then filtering solvent and unreacted monomer are evaporated with neutral alumina, be dried to after the constant weight polymer P tBMA-PMMA subsequent use again;
3. synthetic polymethyl tert-butyl acrylate-polymethylmethacrylate-PS (PtBMA-PMMA-PSt): after the adding methyl-phenoxide carries out the deoxidation processing in reactor drum; Add PtBMA-PMMA, vinylbenzene and the PMDETA for preparing successively; Under nitrogen protection, add CuBr; Then reaction system is diluted reaction mixture behind reaction 40～48h down at 70 ℃～80 ℃ with THF; After then filtering solvent and unreacted monomer are evaporated, be dried to after the constant weight polymer P tBMA-PMMA-PSt subsequent use again with neutral alumina;
4. preparation acetyl sulfate: after in container, adding chloroform and diacetyl oxide and it being cooled to 0 ℃, slowly add the vitriol oil, stir behind the 10min reaction system subsequent use then;
5. the PtBMA-PMMA-PSt sulfonation that is hydrolyzed is prepared PMAA-PMMA-PSS: in container, add chloroform; Add the PtBMA-PMMA-PSt that has prepared again; And then adding acetyl sulfate; Reaction system at 50～60 ℃ of following stirring reactions, is added methyl alcohol behind reaction 10～12h and makes the reaction system stopped reaction, add an amount of NaHCO then
3The pH of mixed value is transferred to neutrality, add zero(ppm) water subsequently and,, make final product PMAA-PMMA-PSS after polymkeric substance drying to the constant weight of the purifying of will dialysing then the evaporated liquor dialysis tubing purifying of in zero(ppm) water, dialysing of packing into organic solvent evaporation.
Find that through experiment above-mentioned technology has following problem:
1. to use different catalyst respectively (like CuCl, CuBr and CuBr in each step reaction
2), part (PMDETA with two pyridines) and solvent (acetone and methyl-phenoxide); So must remove solvent, catalyzer and the part of back clean after per step reaction is accomplished; So that reaching enough pure, required polymkeric substance of per step could not influence next step reaction; Complex steps, solvent that is evaporated in addition and THF consumption are all very big, cause bigger waste and contaminate environment.
2. because the reaction of per step all need keep oxygen-free environment, divide three-step reaction after dress appearance, to carry out the deoxygenation operation, step is very loaded down with trivial details, and needs to use a large amount of nitrogen, influences product cost and working efficiency.
3. per step reaction all need be carried out purifying to title product after finishing, thereby in the loss high amounts of solvents, also loses a large amount of title products, thereby causes productive rate on the low side.
4. only use acetyl sulfate to make hydrolytic reagent and can not make the abundant hydrolysis of polymkeric substance.
Summary of the invention
The method that the present invention provides a kind of atom radical transfer legal system of improvement to be equipped with polymethyl acrylic acid-polymethylmethacrylate-polystyrolsulfon acid triblock polymer, to solve the many defectives in the existing production technique, its process comprises the steps:
A. synthetic polymethyl tert-butyl acrylate-polymethylmethacrylate-PS: methacrylic tert-butyl acrylate, toluene(mono)chloride sulphonyl, CuCl, PMDETA are pressed 30～60: 1: 1.0～1.5: 2.0～3.0 mol ratio; And with methacrylic tert-butyl acrylate volume ratio be after 1～2 methyl-phenoxide adds in the reactor drum successively; Under 40 ℃～60 ℃, anhydrous and oxygen-free condition; Continuing logical nitrogen reacts; Reaction adds TEB 3K and methyl-phenoxide behind 10～12h again, then with reaction system 25 ℃～35 ℃, continue to react under the logical nitrogen, add vinylbenzene and methyl-phenoxide again behind reaction 10～12h; Then 75 ℃～85 ℃, continue to react under the logical nitrogen; Behind reaction 40～60h reaction mixture is diluted with THF, diluent makes polymethyl tert-butyl acrylate-polymethylmethacrylate-PS through filtering, concentrate, precipitating, and is subsequent use after lyophilize to constant weight then;
B. hydrolysis sulfonation: the polymethyl tert-butyl acrylate-polymethylmethacrylate-PS of above-mentioned preparation is dissolved into 1 of 10～20 times of amounts; In the 2-ethylene dichloride; Adding mole number again is the trifluoroacetic acid of 1.5～2.0 times of methacrylic tert-butyl acrylates; Under 60～65 ℃, reflux conditions, react then, add the vitriol oil and diacetyl oxide mixture again behind reaction 22～25h, then reaction system is reacted under 75 ℃～85 ℃, reflux conditions; React 3～4h after evaporate, dialyse, be dried to constant weight, get final product polymethyl acrylic acid-polymethylmethacrylate-polystyrolsulfon acid triblock polymer.
The mol ratio of said TEB 3K and toluene(mono)chloride sulphonyl is 15～40: 1; Said methyl-phenoxide and TEB 3K volume ratio are 1: 1～2.
Said vinylbenzene and toluene(mono)chloride sulphonyl mol ratio are 300～600: 1; Methyl-phenoxide is 1: 1～2 with the volume of styrene ratio.
The volume ratio of the vitriol oil and diacetyl oxide is 1: 1 in the said vitriol oil and the diacetyl oxide mixture, and said vitriol oil concentration is 98%.
The technical progress that the present invention obtains:
The present invention at first utilizes Transfer Radical Polymerization to synthesize the triblock polymer of polymethyl tert-butyl acrylate-polymethylmethacrylate-PS (PtBMA-PMMA-PSt); With trifluoroacetic acid polymethyl tert-butyl acrylate is hydrolyzed to polymethyl acrylic acid then, uses acetyl sulfate that the PS sulfonation is obtained PMAA-PMMA-PSS as polystyrolsulfon acid.The present invention changes existing three-step reaction method into the single step reaction method, has reduced the loaded down with trivial details property of operation steps, has reduced raw materials consumption, has improved the productive rate of reaction stability and target compound; In hydrolytic process, add trifluoroacetic acid, made hydrolysis more thorough, improved reactive behavior and the suspension property of PMAA-PMMA-PSS.Have the functional group among the PMAA-PMMA-PSS through test shows, molecular weight can reach about 100,000, can reach more than two months steady time the suspension effect of nano zero valence iron.
1. atom transition free radical polymerization reaction adopts continuous synthesis among the present invention; Operation stepss such as deoxidation, THF dilution, neutral alumina filtration have been simplified greatly; The probability that has reduced operation failure is (by existing literature method operation; Second step was difficult to successfully with the 3rd step polyreaction), the while has reduced the consumption of reactant and solvent to a great extent, and (in every 1g title product, original method consumption is about 300ml like the consumption of THF; The inventive method consumption is about 100ml), reduced production cost, reduced environmental pollution.
2. only use acetyl sulfate can not make the abundant hydrolysis of PtBMA-PMMA-PSt as the hydrolysis sulphonating agent; The present invention uses trifluoroacetic acid with its hydrolysis earlier; Re-use acetyl sulfate with its sulfonation; Having improved percent hydrolysis and the sulphonation rate of functional group among the PtBMA-PMMA-PSt, (use trifluoroacetic acid hydrolysis, about 90% functional group all can be hydrolyzed among the PtBMA-PMMA-PSt, and the hydrolysis sulfonation efficient of original method is only about 60%.）。
3. the present invention improves atom radical transfer method, adopts the single step reaction method, and the chlorine atomic reaction that can not influence like this on the synthetic macromole evocating agent (like PBMA-PMMA) is active, trigger monomer atom polymerization more easily, thereby the length of increase chain.
4. owing to from start to finish all select for use CuCl,,, avoided using CuBr to introduce unnecessary element for making the haloid element in the reaction system consistent again because of the initiator that begins most is the toluene(mono)chloride sulphonyl as catalyzer.
5. the present invention replaces two pyridines as part with PMDETA, cooperates efficient to exceed ten times than two pyridines, and PMDETA normal temperature is liquid down, is easier to operation.
6. the present invention adopts liquid nitrogen freezing-vacuumize-lead to the repeated deoxygenation technology of nitrogen, has ensured the anhydrous and oxygen-free environment of reaction system, has ensured the transformation efficiency of reactant.
Through testing method testing authentications such as nucleus magnetic resonance, ir spectras, the result shows that handicraft product of the present invention has the functional group in the required target product, confirms that through the gel chromatography test sintetics PMAA-PMMA-PSS molecular weight can reach about 100,000.Through test, the present invention's particle diameter that Deco island, Beijing gold Science and Technology Ltd. produces that is used to suspend is the nano zero valence iron of 20～50nm, and its suspension effect is highly stable, and can reach more than two months steady time.
Description of drawings
Fig. 1～Fig. 5 is the prior art processes schematic flow sheet.
Fig. 6 is a process flow diagram of the present invention.
Embodiment
Embodiment 1: as shown in Figure 6, the preparation method of polymethyl acrylic acid-polymethylmethacrylate-polystyrolsulfon acid triblock polymer (PMAA-PMMA-PSS) may further comprise the steps:
A. synthetic PtBMA-PMMA-PSt: in reactor drum, add stirring and dissolving behind 4.88g methyl-phenoxide, 0.19g toluene(mono)chloride sulphonyl, 0.35g PMDETA and the 4.26g methacrylic tert-butyl acrylate successively; Then respectively with liquid nitrogen freezing, vacuumize, logical nitrogen carries out deoxygenation (triplicate); Under nitrogen protection, add 0.11g CuCl subsequently, then reaction system is remained on 60 ℃, continues to react under the logical nitrogen.Add 1.61g methyl-phenoxide, 1.51g TEB 3K behind the reaction 12h, reaction system is remained on 30 ℃, continues to react under the logical nitrogen.Add 34.21g methyl-phenoxide, 31.25g vinylbenzene again behind the reaction 12h, reaction system is remained on 80 ℃, continues to react under the logical nitrogen.Behind the reaction 48h reaction mixture is diluted with 500ml THF (THF); Be to filter in the neutral alumina post of 50cm and wash alumina column diluent in length then, then filtered liq be evaporated to thick liquid (the filtered liq rotary evaporation is advisable with the sheet white precipitate that can in methyl alcohol, settle out) with Rotary Evaporators with 1L THF.Remove solvent and unreacted monomer; The thick liquid of evaporation under agitation dropwise is added drop-wise in the 600ml methyl alcohol and precipitates; Throw out is used the methanol extraction triplicate again with the THF dissolving, and (consumption of the used THF of second, third time can be advisable resolution of precipitate with firm, and the consumption of THF is about 150ml in every 1g polymkeric substance; The consumption of methyl alcohol is about 200ml in every 1g polymkeric substance), subsequently with the throw out lyophilize to constant weight, polymkeric substance polymethyl tert-butyl acrylate-polymethylmethacrylate-PS (PtBMA-PMMA-PSt) 11g, subsequent use;
B. hydrolysis sulfonation: whole PtBMA-PMMA-PSt of above-mentioned preparation are dissolved into 450g 1; After in the 2-ethylene dichloride; Add the 5.13g trifluoroacetic acid, keep 62 ℃ of system temperatures then, under refluxad magnetic agitation is reacted, and adds the 46g diacetyl oxide and 45g 98% vitriol oil behind the reaction 24h; Then reaction system being remained on 85 ℃, reflux conditions lower magnetic force stirs and reacts; Add 20g methyl alcohol behind the reaction 4h reaction is stopped, adding the 100g deionized water then and organic solvent evaporation is fallen, the dialysis tubing of packing into the purifying of in deionized water, dialysing; Then through lyophilize to constant weight, final product be polymethyl acrylic acid-polymethylmethacrylate-polystyrolsulfon acid triblock polymer (PMAA-PMMA-PSS) 10g.
Embodiment 2:
A. synthetic PtBMA-PMMA-PSt: in reactor drum, add stirring and dissolving behind 9.51g methyl-phenoxide, 0.19g toluene(mono)chloride sulphonyl, 0.51g PMDETA and the 8.53g methacrylic tert-butyl acrylate successively; Then respectively with liquid nitrogen freezing, vacuumize, logical nitrogen carries out deoxygenation (triplicate); Under nitrogen protection, add 0.15g CuCl subsequently, then reaction system is remained on 50 ℃, continues to react under the logical nitrogen.Add 4.51g methyl-phenoxide, 4.01g TEB 3K behind the reaction 10h, reaction system is remained on 250 ℃, continues to react under the logical nitrogen.Add 65.51g methyl-phenoxide, 62.49g vinylbenzene again behind the reaction 10h, reaction system is remained on 85 ℃, continues to react under the logical nitrogen.Behind the reaction 60h reaction mixture is diluted with 1L THF (THF); Be to filter in the neutral alumina post of 100cm and wash alumina column diluent in length then, then filtered liq be evaporated to thick liquid (the filtered liq rotary evaporation is advisable with the sheet white precipitate that can in methyl alcohol, settle out) with Rotary Evaporators with 2L THF.Remove solvent and unreacted monomer; The thick liquid of evaporation under agitation dropwise is added drop-wise in the 600ml methyl alcohol and precipitates; Throw out is used methanol extraction triplicate (consumption of the used THF of second, third time can be advisable resolution of precipitate with firm) again with the THF dissolving; Subsequently with the throw out lyophilize to constant weight, polymkeric substance polymethyl tert-butyl acrylate-polymethylmethacrylate-PS (PtBMA-PMMA-PSt) 21g, subsequent use;
B. hydrolysis sulfonation: whole PtBMA-PMMA-PSt of above-mentioned preparation are dissolved into 1500g; 1, in the 2-ethylene dichloride after, add the 10.26g trifluoroacetic acid; Keep 65 ℃ of system temperatures then, under refluxad magnetic agitation is reacted; Add the 90g diacetyl oxide and 88.2g 98% vitriol oil behind the reaction 25h, then reaction system is remained on 80 ℃, reflux conditions lower magnetic force and stir and react, add 20g methyl alcohol behind the reaction 4h and make to react and stop; Add the 100g deionized water then and organic solvent evaporation is fallen; The dialysis tubing of packing into the purifying of in deionized water, dialysing, then through lyophilize to constant weight, final product be polymethyl acrylic acid-polymethylmethacrylate-polystyrolsulfon acid triblock polymer (PMAA-PMMA-PSS) 20g.
Embodiment 3:
A. synthetic PtBMA-PMMA-PSt: in reactor drum, add stirring and dissolving behind 13.89g methyl-phenoxide, 0.38g toluene(mono)chloride sulphonyl, 1.04g PMDETA and the 12.79g methacrylic tert-butyl acrylate successively; Then respectively with liquid nitrogen freezing, vacuumize, logical nitrogen carries out deoxygenation (triplicate); Under nitrogen protection, add 0.29g CuCl subsequently, then reaction system is remained on 40 ℃, continues to react under the logical nitrogen.Add 4.89g methyl-phenoxide, 4.01g TEB 3K behind the reaction 11h, reaction system is remained on 35 ℃, continues to react under the logical nitrogen.Add 98.88g methyl-phenoxide, 93.74g vinylbenzene again behind the reaction 11h, reaction system is remained on 75 ℃, continues to react under the logical nitrogen.Behind the reaction 40h reaction mixture is diluted with 1.5L THF (THF); Be to filter in the neutral alumina post of 100cm and wash alumina column diluent in length then, then filtered liq be evaporated to thick liquid (the filtered liq rotary evaporation is advisable with the sheet white precipitate that can in methyl alcohol, settle out) with Rotary Evaporators with 2L THF.Remove solvent and unreacted monomer; The thick liquid of evaporation under agitation dropwise is added drop-wise in the 600ml methyl alcohol and precipitates; Throw out is used methanol extraction triplicate (consumption of the used THF of second, third time can be advisable resolution of precipitate with firm) again with the THF dissolving; Subsequently with the throw out lyophilize to constant weight, polymkeric substance polymethyl tert-butyl acrylate-polymethylmethacrylate-PS (PtBMA-PMMA-PSt) 27g, subsequent use;
B. hydrolysis sulfonation: whole PtBMA-PMMA-PSt of above-mentioned preparation are dissolved into 2000g 1; After in the 2-ethylene dichloride; Add the 16.39g trifluoroacetic acid, keep 60 ℃ of system temperatures then, under refluxad magnetic agitation is reacted, and adds the 135g diacetyl oxide and 132.2g 98% vitriol oil behind the reaction 22h; Then reaction system being remained on 80 ℃, reflux conditions lower magnetic force stirs and reacts; Add 20g methyl alcohol behind the reaction 4h reaction is stopped, adding the 100g deionized water then and organic solvent evaporation is fallen, the dialysis tubing of packing into the purifying of in deionized water, dialysing; Then through lyophilize to constant weight, final product be polymethyl acrylic acid-polymethylmethacrylate-polystyrolsulfon acid triblock polymer (PMAA-PMMA-PSS) 25g.
Claims (4)
1. preparation method who is used for the triblock polymer of suspended nano Zero-valent Iron is characterized in that it may further comprise the steps:
A. synthetic polymethyl tert-butyl acrylate-polymethylmethacrylate-PS: methacrylic tert-butyl acrylate, toluene(mono)chloride sulphonyl, CuCl, PMDETA are pressed 30～60: 1: 1.0～1.5: 2.0～3.0 mol ratio; And with methacrylic tert-butyl acrylate volume ratio be after 1～2 methyl-phenoxide adds in the reactor drum successively; Under 40 ℃～60 ℃, anhydrous and oxygen-free condition; Continuing logical nitrogen reacts; Reaction adds TEB 3K and methyl-phenoxide behind 10～12h again, then with reaction system 25 ℃～35 ℃, continue to react under the logical nitrogen, add vinylbenzene and methyl-phenoxide again behind reaction 10～12h; Then 75 ℃～85 ℃, continue to react under the logical nitrogen; Behind reaction 40～60h reaction mixture is diluted with THF, diluent makes polymethyl tert-butyl acrylate-polymethylmethacrylate-PS through filtering, concentrate, precipitating, and is subsequent use after lyophilize to constant weight then;
B. hydrolysis sulfonation: the polymethyl tert-butyl acrylate-polymethylmethacrylate-PS of above-mentioned preparation is dissolved into 1 of 10～20 times of amounts; In the 2-ethylene dichloride; Adding mole number again is the trifluoroacetic acid of 1.5～2.0 times of methacrylic tert-butyl acrylates; Under 60～65 ℃, reflux conditions, react then, add the vitriol oil and diacetyl oxide mixture again behind reaction 22～25h, then reaction system is reacted under 75 ℃～85 ℃, reflux conditions; React 3～4h after evaporate, dialyse, be dried to constant weight, get final product polymethyl acrylic acid-polymethylmethacrylate-polystyrolsulfon acid triblock polymer.
2. the preparation method who is used for the triblock polymer of suspended nano Zero-valent Iron according to claim 1, the mol ratio that it is characterized in that said TEB 3K and toluene(mono)chloride sulphonyl is 15～40: 1; Said methyl-phenoxide and TEB 3K volume ratio are 1: 1～2.
3. the preparation method who is used for the triblock polymer of suspended nano Zero-valent Iron according to claim 1 is characterized in that said vinylbenzene and toluene(mono)chloride sulphonyl mol ratio are 300～600: 1; Methyl-phenoxide is 1: 1～2 with the volume of styrene ratio.
4. the preparation method who is used for the triblock polymer of suspended nano Zero-valent Iron according to claim 1 is characterized in that the volume ratio of the vitriol oil and diacetyl oxide is 1: 1 in the said vitriol oil and the diacetyl oxide mixture, and said vitriol oil concentration is 98%.
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| EP1650282A1 (en) * | 2004-10-19 | 2006-04-26 | National Starch and Chemical Investment Holding Corporation | Reactive hot melt adhesive with block acryclic copolymer |
| CN101104653A (en) * | 2006-07-14 | 2008-01-16 | 同济大学 | Process for preparing polymer modified carbon nano-tube |
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| CN101104653A (en) * | 2006-07-14 | 2008-01-16 | 同济大学 | Process for preparing polymer modified carbon nano-tube |
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