CN102702452B - 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 polymethacrylicacid 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 aone-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 for the triblock polymer of suspended nano Zero-valent Iron.
Background technology
Nano zero valence iron has stronger reductibility, can also be very good underground water renovation agent by the heavy metal contaminants in absorption and the reductive action reparation underground water with the efficient deoxidization, degradation of hydrochloric ethers such as trieline in water.Another advantage of nano zero valence iron is that granularity is little, can inject the stratum by the original position injection method, thereby realizes the original position reparation to underground water pollutant.But, pure nano zero valence iron easy precipitation 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, and is all synthetic by atom transition free radical polymerization reaction.Concrete operational path such as Fig. 1～shown in Figure 5, step is as follows:
1. synthetic polymethyl tert-butyl acrylate (PtBMA): add acetone and methyl-phenoxide in the reactor and carry out deoxidation and handle, 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 tetrahydrofuran (THF) (THF), after then filtering with neutral alumina solvent and unreacted monomer are evaporated, again polymer P tBMA is dried to after the constant weight standby;
2. synthesize polymethyl tert-butyl acrylate-polymethylmethacrylate (PtBMA-PMMA): after the adding methyl-phenoxide carries out the deoxidation processing in reactor; add PtBMA, methyl methacrylate, 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 with neutral alumina solvent and unreacted monomer are evaporated, again polymer P tBMA-PMMA is dried to after the constant weight standby;
3. synthetic polymethyl tert-butyl acrylate-polymethylmethacrylate-polystyrene (PtBMA-PMMA-PSt): add methyl-phenoxide in the reactor and carry out after deoxidation handles, 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 with neutral alumina solvent and unreacted monomer are evaporated, again polymer P tBMA-PMMA-PSt is dried to after the constant weight standby;
4. preparation acetyl sulfate: after in container, adding chloroform and diacetyl oxide and it being cooled to 0 ℃, slowly add the vitriol oil, then reaction system is stirred behind the 10min standby;
5. the sulfonation that PtBMA-PMMA-PSt is hydrolyzed prepares PMAA-PMMA-PSS: add chloroform in container; add the PtBMA-PMMA-PSt that has prepared again; and then adding acetyl sulfate; with reaction system at 50～60 ℃ of following stirring reactions; add methyl alcohol behind reaction 10～12h and make the reaction system stopped reaction, add an amount of NaHCO then
3The pH of mixed value is transferred to neutrality, add distilled water subsequently and with organic solvent evaporation, with the evaporated liquor dialysis tubing purifying of dialysing in distilled water of packing into, the polymkeric substance drying of the purifying of will dialysing then makes final product PMAA-PMMA-PSS to constant weight.
Found through experiments, above-mentioned technology has following problem:
1. to use different catalyzer respectively (as CuCl, CuBr and CuBr in each step reaction
2), part (PMDETA and two pyridines) and solvent (acetone and methyl-phenoxide), so must remove solvent, catalyzer and the part of back clean after per step, reaction was finished, so that reaching enough pure, required polymkeric substance of per step could not influence next step reaction, complex steps, the solvent that is evaporated in addition and tetrahydrofuran (THF) consumption are all very big, cause bigger waste and contaminate environment.
2. because the reaction of per step all needs to keep oxygen-free environment, divide three-step reaction to carry out the deoxygenation operation behind the dress sample, 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 needs target product is carried out purifying after finishing, thereby also loses a large amount of target products in a large amount of solvents of loss, 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 atom radical transfer legal system that the invention provides a kind of improvement is equipped with the method for polymethyl acrylic acid-polymethylmethacrylate-polystyrolsulfon acid triblock polymer, and to solve the many defectives in the existing production technique, its process comprises the steps:
A. synthesize polymethyl tert-butyl acrylate-polymethylmethacrylate-polystyrene: with the methacrylic tert-butyl acrylate, the toluene(mono)chloride sulphonyl, CuCl, PMDETA is by 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 successively, at 40 ℃～60 ℃, under the anhydrous and oxygen-free condition, continuing logical nitrogen reacts, add methyl methacrylate and methyl-phenoxide again behind reaction 10～12h, then with reaction system at 25 ℃～35 ℃, continue to react under the logical nitrogen, add vinylbenzene and methyl-phenoxide again behind reaction 10～12h, then at 75 ℃～85 ℃, continue to react under the logical nitrogen, behind reaction 40～60h reaction mixture is diluted with tetrahydrofuran (THF), diluent after filtration, concentrate, precipitation makes polymethyl tert-butyl acrylate-polymethylmethacrylate-polystyrene, and is standby to the constant weight through lyophilize then;
B. hydrolysis sulfonation: the polymethyl tert-butyl acrylate-polymethylmethacrylate-polystyrene 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, then at 60～65 ℃, react under the reflux conditions, add the vitriol oil and diacetyl oxide mixture again behind reaction 22～25h, then with reaction system at 75 ℃～85 ℃, react under the reflux conditions, 3～4h is by evaporation in reaction, dialysis, be dried to constant weight, get final product polymethyl acrylic acid-polymethylmethacrylate-polystyrolsulfon acid triblock polymer.
The mol ratio of described methyl methacrylate and toluene(mono)chloride sulphonyl is 15～40: 1; Described methyl-phenoxide and methyl methacrylate volume ratio are 1: 1～2.
Described 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 described vitriol oil and the diacetyl oxide mixture, and described 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-polystyrene (PtBMA-PMMA-PSt), with trifluoroacetic acid polymethyl tert-butyl acrylate being hydrolyzed to polymethyl acrylic acid then, is that polystyrolsulfon acid obtains PMAA-PMMA-PSS with acetyl sulfate with the polystyrene sulfonation.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.Show the functional group that has among the PMAA-PMMA-PSS after tested, 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, reduced the probability of operation failure (by existing literature method operation, second step and the 3rd step polyreaction are difficult to successfully), (in every 1g target product, original method consumption is about 300ml as the consumption of tetrahydrofuran (THF) to have reduced simultaneously the consumption of reactant and solvent to a great extent; 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, improve among the PtBMA-PMMA-PSt percent hydrolysis and the sulphonation rate of functional group and (used 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, can not influence the chlorine atomic reaction activity on the synthetic macromole evocating agent (as PBMA-PMMA) like this, the polymerization of easier trigger monomer atom, thereby the length of increase chain.
4. owing to from start to finish all select for use CuCl as catalyzer, again because the initiator that begins most is the toluene(mono)chloride sulphonyl, for making a haloid element unanimity in the reaction system, avoided using CuBr to introduce unnecessary element.
5. the present invention replaces two pyridines as part with PMDETA, cooperates efficient to exceed ten times than two pyridines, is liquid under the PMDETA normal temperature, 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, infrared spectras, the result shows that handicraft product of the present invention has the functional group in the required target product, confirms that by the gel chromatography test sintetics PMAA-PMMA-PSS molecular weight can reach about 100,000.After tested, the particle diameter that the present invention is used for the production of Deco island, suspension Beijing gold Science and Technology Ltd. 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 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: 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 in the reactor 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 remained on 60 ℃, continue to react under the logical nitrogen.Add 1.61g methyl-phenoxide, 1.51g methyl methacrylate 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 tetrahydrofuran (THF) (THF), be to filter in the neutral alumina post of 50cm and wash alumina column with 1L THF diluent in length then, then filtered liquid be evaporated to thick liquid (the filtered liquid rotary evaporation is advisable with the sheet white precipitate that can settle out) with Rotary Evaporators in methyl alcohol.Solvent and unreacted monomer are removed, 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, get polymkeric substance polymethyl tert-butyl acrylate-polymethylmethacrylate-polystyrene (PtBMA-PMMA-PSt) 11g, standby;
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, add 46g diacetyl oxide and 45g 98% vitriol oil behind the reaction 24h, reaction system is remained on 85 ℃ then, the reflux conditions lower magnetic force stirs and reacts, adding 20g methyl alcohol behind the reaction 4h stops reaction, 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, getting final product is polymethyl acrylic acid-polymethylmethacrylate-polystyrolsulfon acid triblock polymer (PMAA-PMMA-PSS) 10g.
Embodiment 2:
A. synthetic PtBMA-PMMA-PSt: 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 in the reactor 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 remained on 50 ℃, continue to react under the logical nitrogen.Add 4.51g methyl-phenoxide, 4.01g methyl methacrylate 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 tetrahydrofuran (THF) (THF), be to filter in the neutral alumina post of 100cm and wash alumina column with 2L THF diluent in length then, then filtered liquid be evaporated to thick liquid (the filtered liquid rotary evaporation is advisable with the sheet white precipitate that can settle out) with Rotary Evaporators in methyl alcohol.Solvent and unreacted monomer are removed, 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, get polymkeric substance polymethyl tert-butyl acrylate-polymethylmethacrylate-polystyrene (PtBMA-PMMA-PSt) 21g, standby;
B. hydrolysis sulfonation: whole PtBMA-PMMA-PSt of above-mentioned preparation are dissolved into 1500g, 1, after in the 2-ethylene dichloride, add the 10.26g trifluoroacetic acid, keep 65 ℃ of system temperatures then, under refluxad magnetic agitation is reacted, add 90g diacetyl oxide and 88.2g 98% vitriol oil behind the reaction 25h, reaction system is remained on 80 ℃ then, the reflux conditions lower magnetic force stirs and reacts, adding 20g methyl alcohol behind the reaction 4h stops reaction, 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, getting final product is polymethyl acrylic acid-polymethylmethacrylate-polystyrolsulfon acid triblock polymer (PMAA-PMMA-PSS) 20g.
Embodiment 3:
A. synthetic PtBMA-PMMA-PSt: 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 in the reactor 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 remained on 40 ℃, continue to react under the logical nitrogen.Add 4.89g methyl-phenoxide, 4.01g methyl methacrylate 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 tetrahydrofuran (THF) (THF), be to filter in the neutral alumina post of 100cm and wash alumina column with 2L THF diluent in length then, then filtered liquid be evaporated to thick liquid (the filtered liquid rotary evaporation is advisable with the sheet white precipitate that can settle out) with Rotary Evaporators in methyl alcohol.Solvent and unreacted monomer are removed, 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, get polymkeric substance polymethyl tert-butyl acrylate-polymethylmethacrylate-polystyrene (PtBMA-PMMA-PSt) 27g, standby;
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, add 135g diacetyl oxide and 132.2g 98% vitriol oil behind the reaction 22h, reaction system is remained on 80 ℃ then, the reflux conditions lower magnetic force stirs and reacts, adding 20g methyl alcohol behind the reaction 4h stops reaction, 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, getting final product is 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. synthesize polymethyl tert-butyl acrylate-polymethylmethacrylate-polystyrene: with the methacrylic tert-butyl acrylate, the toluene(mono)chloride sulphonyl, CuCl, PMDETA is by 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 successively, at 40 ℃～60 ℃, under the anhydrous and oxygen-free condition, continuing logical nitrogen reacts, add methyl methacrylate and methyl-phenoxide again behind reaction 10～12h, then with reaction system at 25 ℃～35 ℃, continue to react under the logical nitrogen, add vinylbenzene and methyl-phenoxide again behind reaction 10～12h, then at 75 ℃～85 ℃, continue to react under the logical nitrogen, behind reaction 40～60h reaction mixture is diluted with tetrahydrofuran (THF), diluent after filtration, concentrate, precipitation makes polymethyl tert-butyl acrylate-polymethylmethacrylate-polystyrene, and is standby to the constant weight through lyophilize then;
B. hydrolysis sulfonation: the polymethyl tert-butyl acrylate-polymethylmethacrylate-polystyrene 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, then at 60～65 ℃, react under the reflux conditions, add the vitriol oil and diacetyl oxide mixture again behind reaction 22～25h, then with reaction system at 75 ℃～85 ℃, react under the reflux conditions, 3～4h is by evaporation in reaction, dialysis, be dried to constant weight, get final product polymethyl acrylic acid-polymethylmethacrylate-polystyrolsulfon acid triblock polymer.
2. the preparation method of the triblock polymer for the suspended nano Zero-valent Iron according to claim 1, the mol ratio that it is characterized in that described methyl methacrylate and toluene(mono)chloride sulphonyl is 15～40: 1; Described methyl-phenoxide and methyl methacrylate volume ratio are 1: 1～2.
3. the preparation method of the triblock polymer for the suspended nano Zero-valent Iron according to claim 1 is characterized in that described 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 of the triblock polymer for the 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 described vitriol oil and the diacetyl oxide mixture, and described vitriol oil concentration is 98%.
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