CN109942737A - The amphiphilic polymer micro-sphere material of uniform particle sizes, preparation method and application - Google Patents
The amphiphilic polymer micro-sphere material of uniform particle sizes, preparation method and application Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 65
- 239000002245 particle Substances 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 229920000642 polymer Polymers 0.000 title claims abstract description 13
- 239000004005 microsphere Substances 0.000 title claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 59
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000000178 monomer Substances 0.000 claims abstract description 20
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000000203 mixture Substances 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 26
- 239000003999 initiator Substances 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 21
- 239000004088 foaming agent Substances 0.000 claims description 20
- 239000003995 emulsifying agent Substances 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 16
- 239000002270 dispersing agent Substances 0.000 claims description 15
- 238000006116 polymerization reaction Methods 0.000 claims description 14
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 4
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 4
- 239000011347 resin Substances 0.000 claims description 4
- 229920005989 resin Polymers 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical group N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 3
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 claims description 3
- 235000019441 ethanol Nutrition 0.000 claims description 3
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 2
- 108010010803 Gelatin Proteins 0.000 claims description 2
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- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical compound OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
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- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 2
- 239000013049 sediment Substances 0.000 claims description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims 1
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- 239000011575 calcium Substances 0.000 claims 1
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- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims 1
- 125000003944 tolyl group Chemical group 0.000 claims 1
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- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
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- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
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- DCXXMTOCNZCJGO-UHFFFAOYSA-N tristearoylglycerol Chemical group CCCCCCCCCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCCCC DCXXMTOCNZCJGO-UHFFFAOYSA-N 0.000 description 2
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- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
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- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
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- OOCMUZJPDXYRFD-UHFFFAOYSA-L calcium;2-dodecylbenzenesulfonate Chemical compound [Ca+2].CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O.CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O OOCMUZJPDXYRFD-UHFFFAOYSA-L 0.000 description 1
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Landscapes
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses the amphiphilic polymer micro-sphere materials of uniform particle sizes a kind of, preparation method and application, belong to polymeric material field, solve the problems such as existing preparation method partial size is difficult to, polymer yield is low, application effect is bad.It is evenly dispersed that the present invention using N- vinylpyrrolidone and divinylbenzene as monomer, by certain way makes it form lotion in water phase；Using suitable water phase composition and ratio, reinforcing hydrophobic monomer divinylbenzene is affine with hydrophilic monomer N- vinylpyrrolidone, improves its yield；It is polymerize again by conditional regulatories such as stringent temperature and revolving speed, finally obtains the amphiphilic polymer resin material of uniform particle sizes.There is very excellent amphiphilic performance by series characterization and applicating evaluating discovery, the material, there is the concentration and separation performance of very wide spectrum to organic matter in water body, the fields such as analysis detection, engineering of water treatment and Domestic water purifying can be respectively applied to according to its particle size.
Description
Technical field
The invention belongs to high molecular material preparation method and applications fields, and in particular to a kind of uniform particle sizes' is amphipathic
Polymer microballoon material and the preparation method and application thereof.
Background technique
In recent years, problem of environmental pollution receives more and more extensive concern.Emerging organic pollutant is as in recent years
Research hotspot, although ambient concentration is low, because distribution is wide, toxicity is high and becomes problem urgently to be resolved.Absorption method is current
Main micro- Organic Pollutants minimizing technology and U.S. EPA are also to the recommended method of the micro- Organic Pollutants of many classes.However, this
A little pollutant kinds are various, and existing majority adsorbent such as active carbon is preferable to hydrophobic organic compound effect, but to many hydrophilic
Property organic matter be difficult to efficient absorption removal.For this purpose, developing a kind of with amphiphilic polymer microballoon is to solve the problems, such as this
Important directions.
Amphiphilic polymer material currently used for water process is more rare, and in environmental analysis field, Waters company
HLB Solid Phase Extraction major gene its simultaneously there is hydrophobe skeleton, can simultaneously to hydrophobe organic matter carry out concentration and separation, in ring
Consequence is occupied in the sample pre-treatments of border.But up to the present, the filler preparation process of the extraction column not yet discloses, only
Know be its skeleton be vinylpyrrolidone-divinylbenzene.Many researchers also once carry out it exploring and copy, but there are still one
Fixed problem needs overcome.Patent ZL201110230789.6 proposes a kind of N- vinylpyrrolidone-divinylbenzene microspheres
Preparation method prepares divinylbenzene microspheres by dispersin polymerization, carries out swollen-state polymerization N- vinylpyrrolidone is added.The party
Method is cumbersome, expensive, and does not confirm the success of secondary swollen-state polymerization in patent by characterizations such as infrared, elemental analyses
Rate, the application effect that microballoon is prepared to it also do not relate to.This seminar patent early period ZL201510603600.1 first passage
Two kinds of monomers successfully polymerize by suspension polymerisation, however, this method is there is also yield is unstable, it is universal lower；N content compared with
It is low, hydrophily is not strong；It is obvious to organic matter absorption property in water body in turn result in it for the problems such as microspherulite diameter size is uneven
It is worse than the filler of HLB.The lower reason of yield is hydrophilic monomer N- vinylpyrrolidone and hydrophobic monomer divinylbenzene
Compatibility is insufficient, and then the material of its output is more that divinylbenzene autohemagglutination forms, this is also the not strong reason of hydrophily.It solves
Certainly this problem needs to reinforce by suitable intermediary the two affinity.And partial size is unevenly suspension polymerisation itself
The shortcomings that, it may be considered that change synthetic operation step, adjusts the formula of water phase to overcome.
Summary of the invention
It is uneven for N- vinylpyrrolidone-divinylbenzene low yield, the partial size prepared in the prior art, absorption effect
The disadvantages of fruit is undesirable, the present invention is directed to by developing a kind of completely new lotion-micella-suspension polymerization, this method can be efficient
Uniform particle sizes' amphiphilic polymer resin material is prepared, and the material can have excellent richness to hydrophobe organic matter in water body
Collection separation and Adsorption performance.
In order to achieve the goal above, the present invention adopts the following technical scheme:
The present invention provides amphiphilic polymer micro-sphere materials of a kind of uniform particle sizes and preparation method thereof, including following step
It is rapid:
(1) it prepares the first oil mutually and the second oily phase: monomer divinylbenzene, pore-foaming agent being uniformly mixed with initiator and prepare the
Monomer N-vinyl pyrrolidones, pore-foaming agent and initiator are uniformly mixed and prepare the second oily phase, wherein monomer two by one oily phase
Volume content of the Ethenylbenzene in the first oily phase is 20%-75%；The pore in pore-foaming agent and the second oily phase in first oily phase
The volume ratio of agent is 1:1, and pore-foaming agent total volume is 10%-75% of first oil mutually with the second oily phase total volume；Monomer N- ethylene
Volume content of the base pyrrolidones in the second oily phase is 20%-80%；In initiator and the second oily phase in first oily phase
The mass ratio of initiator is 1:1；The total dosage of initiator is monomer divinylbenzene and monomer N-vinyl pyrrolidones gross mass
0.5-3%；
(2) it prepares water phase: emulsifier, dispersing agent being added in water, wherein emulsifier is water phase gross mass
0.1-5%；Dispersant dosage is the 0.05-2% of water phase gross mass；
(3) by heated aqueous to 50-65 DEG C, first oil of 50v% (volume) or more is separately added into mutually with 50v%'s or more
Second oily phase, after pre-polymerization 5-10 minutes, starts reaction 0.5-2 hours；
(4) reaction solution temperature is slowly risen to 80-100 DEG C, remaining first oil is mutually mixed uniformly with the second oil
Afterwards, be placed in reaction solution in batches, react 3-24 hours under the stirring of 100-2000rpm, after the reaction was completed by sediment into
Row filtering is then alternately cleaned with ethyl alcohol and aqueous solution, obtains resin material after dry.
As further improvement of the present invention, in step (1), the initiator is azodiisobutyronitrile, azo two
One or more of different heptonitrile, azo-bis-iso-dimethyl, dibenzoyl peroxide, benzoyl peroxide.
As further improvement of the present invention, in step (1), the pore-foaming agent be toluene, dimethylbenzene, isobutanol,
One or more of n-butanol, cyclohexanol.
As further improvement of the present invention, in step (1), the mass ratio of n-vinyl pyrrolidone and divinylbenzene
For 10-95:5-90.
As further improvement of the present invention, in step (2), the dispersing agent is polyvinyl alcohol, gelatin, polydiene
Or mixtures thereof one of alkyl dimethyl ammonium chloride, polyvinylpyrrolidone, hydroxyethyl cellulose；The emulsifier is tristearin
One or more of sour sodium, lauryl sodium sulfate and calcium dodecyl benzene sulfonate.
As further improvement of the present invention, the first oil is mutually and the volume ratio of the second oily phase total volume and water phase is 5-
20:80-95.
As further improvement of the present invention, the first oil is mutually and the volume ratio of the second oily phase is 1:3-3:1.
As further improvement of the present invention, in step (2), water phase is divided into two parts, be denoted as the first water phase with
Second water phase is separately added into the first oil phase and the second of 50v% or more of 50v% or more by the first heated aqueous to 50-65 DEG C
The second water phase is added in oily phase, pre-polymerization after 5-10 minutes, start reaction 0.5-2 hours, wherein the total water phase volume of the first water phase Zhan
50% or more.
As further improvement of the present invention, the material average grain diameter is 1-300 μm, specific surface area 50-950
m2/ g, N content 0.3-6.8%, contact angle are 60-110 °.
Application of the amphiphilic polymer micro-sphere material of above-mentioned uniform particle sizes as water treatment facilities or system filler.
As further improvement of the present invention, 1-5 μm of partial size of microballoon can be used for chromatographic column filler.
As further improvement of the present invention, 20-50 μm of partial size of microballoon can be used for on-line/off-line Solid Phase Extraction and fill out
Material.
As further improvement of the present invention, 100-300 μm of partial size of microballoon can be used for Domestic water purifying device assembly filler,
Remove micro murder by poisoning organic matter in water body.
As further improvement of the present invention, 100-300 μm of partial size of microballoon can be used in engineering of water treatment, and removal is difficult
Degradation of organic substances.
Compared with the prior art, the invention has the benefit that
(1) preparation method of the amphiphilic polymer micro-sphere material of uniform particle sizes of the present invention, by adjusting oily phase and water phase
Ratio and dosing method, substep temperature reaction solve described in the prior art that microballoon yield is unstable, the universal lower, N of yield
The problems such as content is lower, hydrophily is not strong and its microspherulite diameter size is uneven.
(2) preparation method of amphiphilic macromolecule adsorbent material of the invention, required low raw-material cost, preparation method letter
It is single, it is conducive to promote.
(3) amphiphilic macromolecule adsorbent material of the invention, for average grain diameter between 1-300 μm, uniform particle diameter is preferable；
Specific surface area 50-950m2/ g all has good adsorption effect to hydrophily, hydrophobic organic compound, and performance is substantially better than biography
System phenylethylene resin series and existing N- vinylpyrrolidone-divinylbenzene microspheres.
(4) amphiphilic macromolecule adsorbent material of the invention, have many advantages, such as it is environmental-friendly, reusable, in substance point
It has a extensive future from fields such as, environment measuring, purification of water quality.
Detailed description of the invention
Fig. 1 is the FT-IR map of amphiphilic macromolecule adsorbent material of the invention.
Fig. 2 is the SEM spectrum of amphiphilic macromolecule adsorbent material of the invention.
Fig. 3 is the static contact angle picture of amphiphilic macromolecule adsorbent material of the invention.
Fig. 4 is the chromatogram that amphiphilic macromolecule adsorbent material of the invention is chromatographic column filler detection organic acid.
Specific embodiment
The present invention is described further combined with specific embodiments below, following embodiment is only used to better illustrate technology
Scheme, and cannot be limited the scope of the invention with this.
Application principle
The material basic structure is shown below, according to reaction mechanism it is found that two double bonds of added monomer divinylbenzene
It may all open and carry out chain growth；The monomer radical being activated in reaction can be with N- vinylpyrrolidone, divinylbenzene shape
The free radical of Cheng Xin carries out chain growth until chain termination.
During the reaction, addition dispersing agent effectively prevent the reunion or agglomeration of microballoon, influences the particle diameter distribution of product.Add
Add pore-foaming agent, so that certain spatial position is occupied in microballoon polymerization, it is to after the reaction was completed, pore-foaming agent is molten from microballoon
Solution comes out, and forms certain aperture, influences particle size, distribution and specific surface area.Addition emulsifier makes the water of reaction system
It mutually dissolves each other with organic phase, the surface tension reduced between two-phase makes stable system, forms uniform emulsion.Initiator is added,
Decompose it with suitable speed, control reaction rate, polymer molecular weight and conversion ratio.Regulate and control each additive, makes
The amphiphilic macromolecule adsorbent material finally synthesized, microspherulite diameter is between 1-300 μm, uniform particle sizes, large specific surface area, to hydrophilic
Property, hydrophobic organic compound all have good adsorption effect.
Amphiphilic polymer micro-sphere material of the present invention can be widely used for the separation, extraction, enrichment of various compounds
And purification.In medicament slow release, the cell marking etc. of medical domain；The fixation of the enzyme of field of biotechnology, cell of different nature
Catalysis reaction etc.；Adsorbed in the performance liquid chromatographic column filler, ion exchange resin, water process of chemical field etc.；In addition
It can be also used for the fields such as coating, cosmetics, reprographic printing.
Embodiment 1
The amphiphilic macromolecule adsorbent material prepared in the present embodiment, its step are as follows:
(1) match liquefaction phase: 2gN- vinylpyrrolidone, 3g divinylbenzene are added separately to containing 0.05g AIBN's
In 15ml toluene solution, ice bath is uniformly mixed, and respectively obtains the first oil mutually and the second oily phase, toluene total volume be the first oil mutually and
The 74% of second oily phase total volume, initiator A IBN gross mass accounts for the 1% of N- vinylpyrrolidone and divinylbenzene gross mass.
(2) it configures water phase: 0.5g emulsifier SDS, 0.25g dispersing agent HEC being added in 100mL aqueous solution；Emulsifier is used
Amount is the 0.49% of water phase gross mass, and dispersant dosage is the 0.25% of water phase gross mass；
(3) water phase is divided into two parts, is denoted as the first water phase and the second water phase, the total water phase volume of the first water phase Zhan respectively
Score 50%；
(4) it synthesizes amphiphilic macromolecule adsorbent material: by the first heated aqueous to 55 DEG C, being separately added into volume fraction 70%
For first oil mutually with the second oily phase, after five minutes, the second water phase is added in pre-polymerization, and after reacting 1 hour, temperature is slowly risen to 80 DEG C, will
After the 30% the first oil of remaining volume fraction mutually mixes uniformly with the second oil, it is slowly positioned at reaction solution, in stirring for 800rpm
Mix lower reaction 24 hours.Solution after reaction is precipitated, is filtered, methanol is 12 hours dry at washing 5 times, 65 DEG C, final
To amphiphilic macromolecule adsorbent material.
To the material carry out infrared spectroscopy (FT-IR) structural characterization map as shown in Figure 1,1690cm-1Characteristic peak
For the C=O key of N- vinylpyrrolidone, 708cm-1And 795cm-1It is the characteristic peak of phenyl ring.
Scanning electron microscope (SEM) scanning spectra carry out to the material is as shown in Fig. 2, what the amphiphilic macromolecule adsorbed
For partial size integrated distribution at 50 μm, the particle diameter distribution of the material is more uniform, surveys through full-automatic specific surface area and lacunarity analysis instrument
It is fixed, specific surface area 780m2/ g obtains N element content 1.8% by elemental analysis, and static contact angle is analyzed such as Fig. 3 institute
Show, this material angle is 77 °.
The amphiphilic resin for taking this embodiment of 500mg to synthesize, is inserted in the solid phase extraction column of 6ml.Configure single concentration point
Not Wei 1ppb 32 kinds of each 1L of antibiotic contamination solution, Solid Phase Extraction experiment is carried out with the flow velocity of 10ml/min；32 kinds anti-
The raw element pollutant rate of recovery is specifically shown in Table 1 between 92-102%.
1 antibiotics organic substance determination of recovery rates of table
Embodiment 2
Other conditions examine influence of the different pore-foaming agent dosages to material property with embodiment 1, and experimental result is shown in Table 2.
The different pore-foaming agent dosages of table 2 generate the performance of material
As shown in Table 2, pore-foaming agent dosage is within the scope of the 10%-75% of oily phase total volume, with the increasing of pore-foaming agent dosage
Add, partial size gradually becomes smaller, and generated material property is in claimed range.But pore-foaming agent dosage is too low, polymeric material partial size mistake
Greatly.Pore-foaming agent dosage is excessively high, and solution easily at paste, can not aggregate into microballoon, pore-foaming agent dosage is too high or too low all to be influenced to gather
Close object material property.
Embodiment 3
Other conditions examine influence of the different initiator amounts to material property with embodiment 1, and experimental result is shown in Table 3.
The performance of material produced by the different initiator amounts of table 3
As shown in Table 3, initiator amount influences less particle size within the scope of the 0.5%-3% of monomer total amount, right
Yield has a certain impact, and with the reduction of initiator content, yield is reduced.But initiator amount is too low, can not initiation reaction,
Initiator amount is excessively high to cause implode, and polymer is made to reunite together.
Embodiment 4
Other conditions examine influence of the different emulsifiers dosage to material property with embodiment 1, and experimental result is shown in Table 4.
The performance of material produced by 4 different emulsifiers dosage of table
As shown in Table 4, emulsifier is within the scope of the 0.1%-5% of water phase total amount, with the increase of emulsifier,
Partial size reduces, but emulsifier is too low, will lead to that partial size is excessive, and emulsifier is excessively high to generate excessive foam, and grain
The too small solution of diameter can not be post-processed at thick.
Embodiment 5
Other conditions examine influence of the different dispersant dosages to material property with embodiment 1, and experimental result is shown in Table 5.
The performance of material produced by the different dispersant dosages of table 5
As shown in Table 5, dispersant dosage is within the scope of the 0.05%-2% of water phase total amount, with the increasing of dispersant dosage
Add, change of size is little.But dispersant dosage is too low, and partial size can be too big, and dispersant dosage is excessively high, keeps solution excessively sticky, nothing
Method post-processing.
Embodiment 6
Other conditions are warming up to influence of the different temperatures to material property with embodiment 1, inspection, and experimental result is shown in Table 6.
Table 6 is warming up to the performance of material produced by different temperatures
As shown in Table 6,80 DEG C of -100 DEG C of temperature ranges are warming up to, the influence to partial size is little, and temperature is too low, initiator without
Method causes polymerization, and solution is sticky, can not be post-processed.Temperature is excessively high, and initiator meeting fast decoupled is also easy to produce security risk.
Embodiment 7
Other conditions examine influence of the different speeds of agitator to material property with embodiment 1, and experimental result is shown in Table 7.
The performance of material produced by 7 different emulsifiers dosage of table
As shown in Table 7, in a certain range, with the reduction of revolving speed, partial size can become larger revolving speed.Revolving speed is too low, will lead to
Partial size is excessive, but revolving speed is excessive, and partial size not necessarily can be smaller and smaller.And after revolving speed reaches certain value, foam easily overflows, and turns
It is fast to will appear experimental provision shaking greatly, there is security risk.
In embodiment 7, number 6 is tested, and is chemically and physically characterized, material specific surface area synthesized by the embodiment reaches
950m2/ g, partial size 5um or so；N element content is 1.5%；Static contact angle is 83 °.Use the material chromatography column, inspection
8 kinds of small molecular organic acids (oxalic acid, tartaric acid, formic acid, malic acid, malonic acid, lactic acid, acetic acid, citric acid) is surveyed.Mobile phase is
0.1% phosphate aqueous solution and acetonitrile (90:10), Detection wavelength 210nm；It is detected under 30 DEG C, the flow velocity of 1ml/min,
Gained spectrogram is shown in Fig. 4.The results show that microballoon of the partial size in 1-5um can be used for chromatographic column filler.
Embodiment 8
Other conditions are examined after the first oily phase, the second oily phase is added, the differential responses time is to material property with embodiment 1
Influence, experimental result is shown in Table 8.
The performance of material produced by the 8 differential responses time of table
As shown in Table 8, after the first oily phase, the second oily phase is added, the reaction time is in 3-24 hours ranges to particle size
It influences less, but has certain influence to the degree of polymerization, because the reaction time is too short, the degree of polymerization is low, and particle is relatively soft.Reaction time
Too long, little to grain diameter influence, the increase reaction time, which is equal to, increases its degree of polymerization, but during the experiment, will appear once in a while
Reaction time is too long, reunion serious situation, so the reaction time is unsuitable too long.
Embodiment 9
Other conditions change the step the ratio of addition the first oil phase and the second oily phase in (4) with embodiment 1, specifically: it will
First heated aqueous mutually divides with the second oily phase, pre-polymerization 5 to after 55 DEG C, being separately added into the first oil of different volumes ratio (being shown in Table 9)
Zhong Hou is added the second water phase and temperature is slowly risen to 80 DEG C, by the first oil Xiang Yu of residual volume score after reaction 1 hour
After two oil mix uniformly, it is slowly positioned at reaction solution, is reacted 24 hours under the stirring of 800rpm.Will reaction after solution into
Row precipitating, filtering, methanol is 12 hours dry at washing 5 times, 65 DEG C, finally obtains amphiphilic macromolecule adsorbent material.
The performance of material produced by the first oily phase of different proportion, the second oily phase is added in table 9
As shown in Table 9, the first oily phase is added, the different proportion of the second oily phase in the appropriate range influences polymerization reaction
Less, but if the first of addition the oily phase, the amount of the second oily phase are too low for the first time, it will affect partial size, partial size has becoming of becoming larger
Gesture.
Embodiment 10
Other conditions examine influence of the first water phase that different proportion is added to material property, experimental result with embodiment 1
It is shown in Table 10.
The performance of material produced by 10 the first water phase of different proportion of table
As shown in Table 10, the amount of the first water phase is added within the scope of 50%-100%, change of size is little, but the first water phase
Additive amount it is too low, entire grease system can be made uneven, dispersion is uneven, and partial size becomes larger.
Embodiment 11
Other conditions examine the first oil mutually and the second oil mutually compare material property with water phase different volumes with embodiment 1
It influences, experimental result is shown in Table 11.
The performance of 11 first oil phase of table and the second oil phase with water phase different volumes than produced material
As shown in Table 11, first oil mutually and second oil phase with water phase volume ratio in a certain range, it is little to grain diameter influence,
But volume ratio is too small or excessive, has broken water and oil balance, is difficult to react.
Embodiment 12
Other conditions examine the first oil mutually to compare the influence of material property with the second oily phase different volumes with embodiment 1, real
It tests and the results are shown in Table 12.
Performance of the 12 first oil phase of table with the second oily phase different volumes than produced material
As shown in Table 12, the first oil mutually with the volume ratio of the second oily phase in a certain range, with the reduction of the first oily phase,
Partial size is to increase, and the first oil is mutually very few, because divinylbenzene easily reacts, partial size can be made relatively large；First oil is mutually excessive, reaction
It is not easy to carry out.
Since the material has absorption and control release performance to many kinds of substance, it can be used for point of different material
From.
Schematically the present invention and embodiments thereof are described above, description is not limiting, institute in attached drawing
What is shown is also one of embodiments of the present invention, and actual process is not limited thereto.So if the common skill of this field
Art personnel are enlightened by it, without departing from the spirit of the invention, are not inventively designed and the technical solution
Similar frame mode and embodiment, are within the scope of protection of the invention.
Claims (10)
1. the preparation method of the amphiphilic polymer micro-sphere material of uniform particle sizes, which comprises the following steps:
(1) the first oil phase and the second oily phase are prepared: monomer divinylbenzene, pore-foaming agent are uniformly mixed to the first oil of preparation with initiator
Monomer N-vinyl pyrrolidones, pore-foaming agent and initiator are uniformly mixed and prepare the second oily phase, wherein monomer divinyl by phase
Volume content of the benzene in the first oily phase is 20%-75%；Pore-foaming agent total volume is the first oil phase and the second oily phase total volume
10%-75%；Volume content of the monomer N-vinyl pyrrolidones in the second oily phase is 20%-80%；The total dosage of initiator is single
The 0.5-3% of body divinylbenzene and monomer N-vinyl pyrrolidones gross mass；
(2) it prepares water phase: emulsifier, dispersing agent being added in water, wherein emulsifier is the 0.1-5% of water phase gross mass；
Dispersant dosage is the 0.05-2% of water phase gross mass；
(3) by heated aqueous to 50-65 DEG C, it is separately added into the first oil phase of 50v% or more and the second oily phase of 50 v% or more, in advance
After 5-10 minutes poly-, start reaction 0.5-2 hours；
(4) reaction solution temperature is slowly risen to 80-100 DEG C, after remaining first oil is mutually mixed uniformly with the second oil, point
It criticizes and is placed in reaction solution, react 3-24 hours under the stirring of 100-2000 rpm, after the reaction was completed carried out sediment
Filter is then alternately cleaned with ethyl alcohol and aqueous solution, obtains resin material after dry.
2. the method as described in claim 1, which is characterized in that initiator is azodiisobutyronitrile, azobisisoheptonitrile, azo
One or more of two isobutyl dimethyl phthalates, dibenzoyl peroxide, benzoyl peroxide.
3. the method as described in claim 1, which is characterized in that pore-foaming agent is toluene, dimethylbenzene, isobutanol, n-butanol, hexamethylene
One or more of alcohol.
4. the method as described in claim 1, which is characterized in that in step (1), n-vinyl pyrrolidone and divinylbenzene
Mass ratio be 10-95:5-90.
5. the method as described in claim 1, which is characterized in that pore-foaming agent and the second oil in step (1), in the first oily phase
The volume ratio of pore-foaming agent in phase is 1:1；The mass ratio of initiator in first oily phase and the initiator in the second oily phase is 1:
1。
6. the method as described in claim 1, which is characterized in that in step (1), the volume ratio of the first oil phase and the second oily phase
For 1:3-3:1.
7. the method as described in claim 1, which is characterized in that dispersing agent is polyvinyl alcohol, gelatin, polydiallyldimethyl chlorination
Or mixtures thereof one of ammonium, polyvinylpyrrolidone, hydroxyethyl cellulose.
8. the method as described in claim 1, which is characterized in that emulsifier is odium stearate, lauryl sodium sulfate and 12
One or more of alkyl benzene calcium sulfonate.
9. the method as described in claim 1, which is characterized in that the volume ratio of the first oil phase and the second oily phase total volume and water phase
For 5-20:80-95.
10. the method as described in claim 1, which is characterized in that in step (2), water phase is divided into two parts, is denoted as
One water phase and the second water phase, by the first heated aqueous to 50-65 DEG C, be separately added into the first oil of 50v% or more mutually with 50 v% with
On the second oily phase, pre-polymerization is added the second water phase, starts to react 0.5-2 hours, wherein the first total water of water phase Zhan after 5-10 minute
50% or more of phase volume.
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