CN104479354A - In situ polymerization micro-crosslinking sodium polyacrylate modified polyether sulfone microspheres as well as preparation method and application thereof - Google Patents
In situ polymerization micro-crosslinking sodium polyacrylate modified polyether sulfone microspheres as well as preparation method and application thereof Download PDFInfo
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- C08J2381/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen, or carbon only; Polysulfones; Derivatives of such polymers
- C08J2381/06—Polysulfones; Polyethersulfones
Abstract
The invention discloses in situ polymerization micro-crosslinking sodium polyacrylate modified polyether sulfone microspheres as well as a preparation method and application thereof. The preparation method is characterized by comprising the following steps: adding 10-25 parts of polyether sulfone, 90-75 parts of a solvent and 4-10 parts of water into a reaction kettle, adding sodium acrylate which accounts for 2-20% of the mass of the polyether sulfone solution after dissolution, and performing polymerization reaction at 50-95 DEG C for 2-24 hours in the presence of a crosslinking agent and an initiating agent to obtain a sodium polyacrylate modified polyether sulfone solution; placing for 'aging' to prepare a modified polyether sulfone ball dripping stock solution so as to ensure that sodium polyacrylate is directly crosslinked among polyether sulfone network chains; and preparing modified polyether sulfone microspheres by adopting a liquid-liquid phase separation method. The modified microspheres are low in elution rate and have efficient, lasting and stable adsorptive capacity. The modified microspheres can be prepared into an adsorption column which is widely used for adsorbing heavy metal ions and dyes. The prepared modified polyether sulfone microspheres can be prepared into a filtering adsorption column, the adsorption quantity to copper ions is 10-140mg/g, and the adsorption quantity to methylene blue is 60-630mg/g.
Description
Technical field
The present invention relates to a kind of in-situ polymerization micro-crosslinking sodium polyacrylate modified poly (ether-sulfone) microballoon and its production and use, the preparation field of function of dominant macromolecular material.
Background technology
Polyethersulfone (Polyethersulfone is called for short PES) material was first succeeded in developing and commercial a kind of special engineering plastics in 1972 by ICI company of Britain, and its trade mark is " Victrex PES ".PES special engineering plastics, because its second-order transition temperature is high, physicochemical stability is good, is a kind of engineering speciality polymer material of excellent performance.Microballoon prepared by polyethersulfone has the heat-resisting of excellence, resistance to oxidation and hydrolytic resistance and good mechanical property and balling property, the polyethersulfone microballoon of blending and modifying is applied to the existing a lot of reports in field such as environmental toxin absorption and water treatment, but utilize the micro-crosslinking sodium polyacrylate of in-situ polymerization to carry out modification to polyethersulfone microballoon, improve the absorption property of micro-sphere material, there is no research report and product appearance both at home and abroad so far.
Modification is carried out to polyethersulfone microballoon a lot of with the research report improving its absorption property in purifying treatment, mainly comprise two large class methods (Zhao CS et al., Progress in Materials Science, 2013,58:76): (1) this modifies (2) blend method.This is modifies be directly on polyethersulfone chain by chemical process, introduce functional group thus carry out chemical modification to it, the functional group introduced possesses the performance of adsorb harmful components.This is modifies also can produce and allow its negative effect such as chain rupture, degradation while carrying out chemical modification to polyethersulfone chain, thus limits its application.Physical blending method directly properties-correcting agent is mixed in polyethersulfone solution, is then prepared into polyethersulfone microballoon.First the people (ChemicalEngineering Journal, 2013,215-216:72) such as such as Zhang X have prepared graphene oxide (GO), then carry out blending and modifying to polyethersulfone and obtain modified poly (ether-sulfone) microballoon for sewage disposal.Comparatively convenient by the method for physical modification polyethersulfone microballoon, but when being simply blended in polyethersulfone balling-up, properties-correcting agent exists and comparatively serious washes out problem, and the consistency of properties-correcting agent and polyethersulfone is also bad, blending and modifying amount is limited.
Sodium polyacrylate (PSA) is a kind of polymkeric substance of water-soluble linear structure, has stronger wetting ability, Chang Zuowei additive or properties-correcting agent widespread use in the preparation of hydrophilic material.In view of the carboxyl on PSA molecular chain possesses good absorption property, it is also widely used in the absorption property modification of multiple material.But because PSA is very easily water-soluble, this makes microballoon slowly the washing out after modification along with sodium polyacrylate of preparing, and the performance of modification microballoon will weaken gradually.
Summary of the invention
The object of the invention is a kind of in-situ polymerization micro-crosslinking sodium polyacrylate modified poly (ether-sulfone) microballoon developed for the deficiencies in the prior art and its production and use, be characterized in that the micro-crosslinking sodium polyacrylate of in-situ polymerization can well be fixed between polyethersulfone lattice chain, blending modified polyether sulphone (PES) microballoon, this modification microballoon eluting rate is low, has efficient, lasting, stable adsorptive power.
Object of the present invention is realized by following technical measures: wherein said raw material number, except specified otherwise, is parts by weight.
In-situ polymerization micro-crosslinking sodium polyacrylate modified poly (ether-sulfone) microballoon is made up of following component:
1) polyethersulfone solution is made up of following component
Polyethersulfone 10 ~ 25 parts
Solvent 90 ~ 75 parts
4 ~ 10 parts, water
2) in-situ polymerization micro-crosslinking sodium polyacrylate modified polyether sulfolane solution is made up of following component
2 ~ 20% of monomeric acrylic sodium polyethersulfone solution quality
0.5 ~ 10% of crosslinkers monomers molar fraction
0.25 ~ 5% of initiator monomer molar mark
Wherein, linking agent is N, N'-methylene-bisacrylamide or glycidyl methacrylate; Initiator is dibenzoyl peroxide or Diisopropyl azodicarboxylate.
Described solvent is any one in N-Methyl pyrrolidone, DMF, N,N-dimethylacetamide or dimethyl sulfoxide (DMSO).
The preparation method of in-situ polymerization micro-crosslinking sodium polyacrylate modified poly (ether-sulfone) microballoon comprises the following steps:
1) modified poly (ether-sulfone) drips the preparation of ball solution
Polyethersulfone 10 ~ 25 parts, solvent 90 ~ 75 parts and 4 ~ 10 parts, water are added in the reactor with agitator, thermometer and well heater, stirring and dissolving completely after add monomeric acrylic sodium be polyethersulfone solution quality 2 ~ 20%, linking agent be reaction monomers molar fraction 0.5 ~ 10%, initiator is 0.25 ~ 5% of reaction monomers molar fraction, under agitation, in temperature 50 ~ 95 DEG C of polyreaction 2-24h, obtain sodium polyacrylate modified polyether sulfolane solution, through placing " slaking " obtained modified poly (ether-sulfone) stoste;
2) preparation of modified poly (ether-sulfone) microballoon
Modified poly (ether-sulfone) is dripped the press filtration of ball stoste, extrude with volume pump in syringe needle endoporus, syringe needle model is 5
#~ 16
#, it is 20 ~ 200/min that modified polyether sulfolane solution oozes speed; Nascent drop in atmosphere after 8 ~ 30cm distance in water-bath or water-solvent bath coagulation forming obtain modified poly (ether-sulfone) microballoon;
3). the aftertreatment of modified poly (ether-sulfone) microballoon
Modified poly (ether-sulfone) microballoon, at temperature 50 ~ 60 DEG C of poach 8 ~ 72h, removes residual solvent and unreacted monomer.
Polyethersulfone number-average molecular weight in described polyethersulfone microballoon is 20000 ~ 60000.
Performance test:
Modified poly (ether-sulfone) microballoon prepared above, its diameter is 1000 ~ 4000 μm, and porosity is 65 ~ 89%, and specific surface area is 6.5 ~ 12.5m
2/ g, loading capacity is 0.5 ~ 2.2mequiv/g; Modified poly (ether-sulfone) microballoon is 10 ~ 140mg/g to the adsorptive capacity of cupric ion, and modified poly (ether-sulfone) microballoon is 60 ~ 630mg/g to the adsorptive capacity of methylene blue.And the testing method of these performance index is see document: Xiang T et al., Separation Science and Technology, 2013,48:1627, and Shi ZQ et al., Ind.Eng.Chem.Res., 2014,53 (36): 14084.
In-situ polymerization provided by the invention micro-crosslinking sodium polyacrylate modified poly (ether-sulfone) microballoon can be made into Filtration Adsorption post, is widely used in Dynamic Adsorption of Heavy Metal Ions, cationic dyestuff.
Compared with prior art, tool has the following advantages in the present invention:
1, preparation method of the present invention is single stage method, and micro-crosslinking sodium polyacrylate is between direct polymerization to polyethersulfone solution lattice chain.Sodium polyacrylate modified poly (ether-sulfone) microballoon eluting rate is low, makes it to have efficient, lasting, stable adsorptive power.
2, the polyethersulfone of in-situ polymerization of the present invention micro-crosslinking sodium polyacrylate modification drips that ball solution is very homogeneous, balling-up good, makes prepared polyethersulfone sphere physical, chemical stability good, acid and alkali-resistance, corrosion-resistant.
3, the adsorptive power of modified poly (ether-sulfone) microballoon heavy metal ion of the present invention and dyestuff is comparatively strong, and being 10 ~ 140mg/g to the adsorptive capacity of cupric ion, is 60 ~ 630mg/g to the adsorptive capacity of methylene blue.
4, preparation method of the present invention is simple, and efficiently, easy to operate, cost is low, is conducive to suitability for industrialized production.
Embodiment
Below by embodiment, the present invention is specifically described; what be necessary to herein means out is that the present embodiment is only used to further illustrate the present invention; can not be interpreted as limiting the scope of the invention, the person skilled in the art in this field can make some nonessential improvement and adjustment according to the content of foregoing invention.
Embodiment 1.
By polyethersulfone 12 parts, N,N-dimethylacetamide 88 parts, 5 parts, water, puts into the reactor with agitator, thermometer and well heater, under agitation dissolves completely in temperature 50 C.Add sodium acrylate 8 parts, the add-on of N, N'-methylene-bisacrylamide is 10% of reaction monomers molar fraction, and the add-on of Diisopropyl azodicarboxylate is 1% of reaction monomers molar fraction.In temperature 80 DEG C reaction 24h after under agitation progressively adding, obtained sodium polyacrylate modified polyether sulfolane solution.Deaeration after filtration, places " slaking " obtained polyethersulfone and drips ball solution.
Modified poly (ether-sulfone) is dripped the press filtration of ball stoste, extrude with volume pump in syringe needle endoporus, syringe needle model is 7
#, it is 80/min that modified polyether sulfolane solution oozes speed; Nascent drop obtains modified poly (ether-sulfone) microballoon in the middle coagulation forming of water-N,N-dimethylacetamide mixing bath (50:50, volume fraction) in atmosphere after 15cm distance; Modified poly (ether-sulfone) microballoon, at temperature 60 C poach 48h, removes residual solvent and unreacted monomer.Prepared modified poly (ether-sulfone) microsphere diameter is 2200 μm, and porosity is 85%, and specific surface area is 8.2m
2/ g, loading capacity is 1.7mequiv/g.
Can be made into Filtration Adsorption post with modified poly (ether-sulfone) microballoon prepared by embodiment 1, being 70mg/g to the adsorptive capacity of cupric ion, is 433mg/g to the adsorptive capacity of methylene blue.
Embodiment 2.
By polyethersulfone 10 parts, N-Methyl pyrrolidone 90 parts, 4 parts, water, puts into the reactor with agitator, thermometer and well heater, under agitation dissolves completely in temperature 50 C.Add sodium acrylate 4 parts, the add-on of N, N'-methylene-bisacrylamide is 5% of reaction monomers molar fraction, and the add-on of Diisopropyl azodicarboxylate is 5% of reaction monomers molar fraction.In temperature 95 DEG C reaction 2h after under agitation progressively adding, obtained sodium polyacrylate modified polyether sulfolane solution.Deaeration after filtration, places " slaking " obtained polyethersulfone and drips ball solution.
Modified poly (ether-sulfone) is dripped the press filtration of ball stoste, extrude with volume pump in syringe needle endoporus, syringe needle model is 5
#, it is 200/min that modified polyether sulfolane solution oozes speed; Nascent drop in atmosphere through 30cm distance after in water-bath coagulation forming obtain modified poly (ether-sulfone) microballoon; Modified poly (ether-sulfone) microballoon, at temperature 50 C poach 8h, removes residual solvent and unreacted monomer.Prepared modified poly (ether-sulfone) microsphere diameter is 1000 μm, and porosity is 89%, and specific surface area is 6.5m
2/ g, loading capacity is 0.95mequiv/g.
Can be made into Filtration Adsorption post with modified poly (ether-sulfone) microballoon prepared by embodiment 2, being 18mg/g to the adsorptive capacity of cupric ion, is 95mg/g to the adsorptive capacity of methylene blue.
Embodiment 3.
By polyethersulfone 20 parts, N,N-dimethylacetamide 80 parts, 4 parts, water, puts into the reactor with agitator, thermometer and well heater, under agitation dissolves completely in temperature 50 C.Add sodium acrylate 2 parts, the add-on of N, N'-methylene-bisacrylamide is 3% of reaction monomers molar fraction, and the add-on of Diisopropyl azodicarboxylate is 0.25% of reaction monomers molar fraction.In temperature 50 C reaction 18h after under agitation progressively adding, obtained sodium polyacrylate modified polyether sulfolane solution.Deaeration after filtration, places " slaking " obtained polyethersulfone and drips ball solution.
Modified poly (ether-sulfone) is dripped the press filtration of ball stoste, extrude with volume pump in syringe needle endoporus, syringe needle model is 10
#, it is 100/min that modified polyether sulfolane solution oozes speed; Nascent drop in atmosphere through 20cm distance after in water-bath coagulation forming obtain modified poly (ether-sulfone) microballoon; Modified poly (ether-sulfone) microballoon, at temperature 50 C poach 36h, removes residual solvent and unreacted monomer.Prepared modified poly (ether-sulfone) microsphere diameter is 2600 μm, and porosity is 74%, and specific surface area is 9.2m
2/ g, loading capacity is 0.5mequiv/g.
Can be made into Filtration Adsorption post with modified poly (ether-sulfone) microballoon prepared by embodiment 3, being 10mg/g to the adsorptive capacity of cupric ion, is 60mg/g to the adsorptive capacity of methylene blue.
Embodiment 4.
By polyethersulfone 15 parts, DMF 85 parts, 10 parts, water, puts into the reactor with agitator, thermometer and well heater, under agitation dissolves completely in temperature 50 C.Add sodium acrylate 20 parts, the add-on of glycidyl methacrylate is 5% of reaction monomers molar fraction, and the add-on of Diisopropyl azodicarboxylate is 2% of reaction monomers molar fraction.In temperature 65 DEG C reaction 24h after under agitation progressively adding, obtained sodium polyacrylate modified polyether sulfolane solution.Deaeration after filtration, places " slaking " obtained polyethersulfone and drips ball solution.
Modified poly (ether-sulfone) is dripped the press filtration of ball stoste, extrude with volume pump in syringe needle endoporus, syringe needle model is 16
#, it is 20/min that modified polyether sulfolane solution oozes speed; Nascent drop obtains modified poly (ether-sulfone) microballoon in the middle coagulation forming of water-DMF mixing bath (50:50, volume fraction) in atmosphere after 8cm distance; Modified poly (ether-sulfone) microballoon, at temperature 60 C poach 72h, removes residual solvent and unreacted monomer.Prepared modified poly (ether-sulfone) microsphere diameter is 4000 μm, and porosity is 82%, and specific surface area is 10.5m
2/ g, loading capacity is 2.2mequiv/g.
Can be made into Filtration Adsorption post with modified poly (ether-sulfone) microballoon prepared by embodiment 4, being 140mg/g to the adsorptive capacity of cupric ion, is 630mg/g to the adsorptive capacity of methylene blue.
Embodiment 5.
By polyethersulfone 25 parts, N,N-dimethylacetamide 75 parts, 6 parts, water, puts into the reactor with agitator, thermometer and well heater, under agitation dissolves completely in temperature 50 C.Add sodium acrylate 14 parts, the add-on of N, N'-methylene-bisacrylamide is 6% of reaction monomers molar fraction, and the add-on of dibenzoyl peroxide is 2% of reaction monomers molar fraction.In temperature 70 C reaction 20h after under agitation progressively adding, obtained sodium polyacrylate modified polyether sulfolane solution.Deaeration after filtration, places " slaking " obtained polyethersulfone and drips ball solution.
Modified poly (ether-sulfone) is dripped the press filtration of ball stoste, extrude with volume pump in syringe needle endoporus, syringe needle model is 10
#, it is 90/min that modified polyether sulfolane solution oozes speed; Nascent drop obtains modified poly (ether-sulfone) microballoon in the middle coagulation forming of water-N,N-dimethylacetamide mixing bath (50:50, volume fraction) in atmosphere after 15cm distance; Modified poly (ether-sulfone) microballoon, at temperature 50 C poach 72h, removes residual solvent and unreacted monomer.Prepared modified poly (ether-sulfone) microsphere diameter is 2800 μm, and porosity is 65%, and specific surface area is 12.5m
2/ g, loading capacity is 1.9mequiv/g.
Can be made into Filtration Adsorption post with modified poly (ether-sulfone) microballoon prepared by embodiment 5, being 110mg/g to the adsorptive capacity of cupric ion, is 520mg/g to the adsorptive capacity of methylene blue.
Embodiment 6.
By polyethersulfone 18 parts, dimethyl sulfoxide (DMSO) 82 parts, 5 parts, water, puts into the reactor with agitator, thermometer and well heater, under agitation dissolves completely in temperature 50 C.Add sodium acrylate 10 parts, the add-on of N, N'-methylene-bisacrylamide is 0.5% of reaction monomers molar fraction, and the add-on of Diisopropyl azodicarboxylate is 3% of reaction monomers molar fraction.In temperature 90 DEG C reaction 15h after under agitation progressively adding, obtained sodium polyacrylate modified polyether sulfolane solution.Deaeration after filtration, places " slaking " obtained polyethersulfone and drips ball solution.
Modified poly (ether-sulfone) is dripped the press filtration of ball stoste, extrude with volume pump in syringe needle endoporus, syringe needle model is 9
#, it is 120/min that modified polyether sulfolane solution oozes speed; Nascent drop in atmosphere through 12cm distance after in water-bath coagulation forming obtain modified poly (ether-sulfone) microballoon; Modified poly (ether-sulfone) microballoon, at temperature 55 DEG C of poach 24h, removes residual solvent and unreacted monomer.Prepared modified poly (ether-sulfone) microsphere diameter is 2450 μm, and porosity is 78%, and specific surface area is 11.2m
2/ g, loading capacity is 1.8mequiv/g.
Can be made into Filtration Adsorption post with modified poly (ether-sulfone) microballoon prepared by embodiment 6, being 98mg/g to the adsorptive capacity of cupric ion, is 490mg/g to the adsorptive capacity of methylene blue.
Claims (5)
1. in-situ polymerization micro-crosslinking sodium polyacrylate modified poly (ether-sulfone) microballoon, is characterized in that:
1) polyethersulfone solution is made up of following component, is by weight:
Polyethersulfone 10 ~ 25 parts
Solvent 90 ~ 75 parts
4 ~ 10 parts, water
2) the micro-crosslinking sodium polyacrylate of in-situ polymerization is made up of following component:
2 ~ 20% of monomeric acrylic sodium polyethersulfone solution quality
0.5 ~ 10% of crosslinkers monomers molar fraction
0.25 ~ 5% of initiator monomer molar mark
Wherein, linking agent is N, N'-methylene-bisacrylamide or glycidyl methacrylate; Initiator is dibenzoyl peroxide or Diisopropyl azodicarboxylate.
2. in-situ polymerization micro-crosslinking sodium polyacrylate modified poly (ether-sulfone) microballoon according to claim 1, is characterized in that solvent is any one in N-Methyl pyrrolidone, DMF, N,N-dimethylacetamide or dimethyl sulfoxide (DMSO).
3. the preparation method of in-situ polymerization micro-crosslinking sodium polyacrylate modified poly (ether-sulfone) microballoon according to claim 1 or 2, is characterized in that the method comprises the following steps:
1) modified poly (ether-sulfone) drips the preparation of ball stoste
Polyethersulfone 10 ~ 25 parts, solvent 90 ~ 75 parts and 4 ~ 10 parts, water are added in the reactor with agitator, thermometer and well heater, after stirring and dissolving is complete, add monomeric acrylic sodium be polyethersulfone solution quality 2 ~ 20%, linking agent be reaction monomers molar fraction 0.5 ~ 10%, initiator is 0.25 ~ 5% of reaction monomers molar fraction, under agitation, in temperature 50 ~ 95 DEG C of polyreaction 2-24h, obtaining sodium polyacrylate modified polyether sulfolane solution, dripping ball stoste through placing " slaking " obtained modified poly (ether-sulfone);
2) preparation of modified poly (ether-sulfone) microballoon
Extrude in syringe needle endoporus with volume pump, syringe needle model is 5
#~ 16
#, it is 20 ~ 200/min that modified polyether sulfolane solution oozes speed; Nascent drop in atmosphere after 8 ~ 30cm distance in water-bath or water-solvent bath coagulation forming obtain modified poly (ether-sulfone) microballoon;
3). the aftertreatment of modified poly (ether-sulfone) microballoon
Modified poly (ether-sulfone) microballoon, at temperature 50 ~ 60 DEG C of poach 8 ~ 72h, removes residual solvent and unreacted monomer.
4. the preparation method of in-situ polymerization micro-crosslinking sodium polyacrylate modified poly (ether-sulfone) microballoon according to claim 3, is characterized in that the polyethersulfone number-average molecular weight in hollow-fibre membrane is 20000 ~ 60000.
5. the purposes of in-situ polymerization micro-crosslinking sodium polyacrylate modified poly (ether-sulfone) microballoon according to claim 1, is characterized in that adsorption column made by this modified poly (ether-sulfone) microballoon, is widely used in Adsorption of Heavy Metal Ions and dyestuff.
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| CN109331750B (en) * | 2018-11-05 | 2021-03-12 | 四川大学 | Heparinoid gel microsphere and preparation method and application thereof |
| CN110844971A (en) * | 2019-12-13 | 2020-02-28 | 南京林业大学 | Method for standard-reaching treatment of heavy metal in ammonia-phosphorus double-complex electroplating wastewater |
| CN115487784A (en) * | 2021-06-17 | 2022-12-20 | 中国科学院大连化学物理研究所 | Enrichment material and preparation method thereof and enrichment method of extracellular vesicles in biological sample solution |
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