CN105884944A - Preparation method of porous polymer microspheres and application of prepared porous polymer microspheres - Google Patents
Preparation method of porous polymer microspheres and application of prepared porous polymer microspheres Download PDFInfo
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Abstract
The invention belongs to the technical field of polymer materials, and in particular, relates to a preparation method of porous polymer microspheres and an application of the prepared porous polymer microspheres. The method comprises the steps: together adding a polymerization monomer and an initiator into a reaction solvent, stirring until the polymerization monomer and the initiator are completely dispersed in the reaction solvent, placing the mixed solution in a reaction kettle, and sealing; placing the reaction kettle in a drying oven, and carrying out a reaction at a certain temperature for a period of time; and after the reaction is finished, naturally cooling, filtering a reaction liquid, washing the obtained product with a non-toxic volatile solvent, drying, and thus obtaining the porous polymer microspheres. The method is simple and feasible, and can prepare the porous polymer microspheres in the low-toxic solvent in one step; contamination of other additives on the product is avoided; the reaction speed is fast; the controllability is strong, and the polymer microspheres with high specific surface area and different pore structures can be directly synthesized. The prepared polymer microspheres have good accumulation property, and micro-pores have relatively strong adsorption capacity on organic matters.
Description
Technical field
The invention belongs to technical field of polymer materials, particularly to preparation method and the made porous of a kind of porous polymer microsphere
The purposes of polymer microballoon.
Background technology
Porous polymer microsphere is the ball-type Powdered Polymer Materials of a kind of porous.Owing to having ball-type, porous, highly cross-linked etc.
Characteristic, so this material is with the combination property of the excellences such as good fluidity, porosity height, Stability Analysis of Structures, low, the easy functionalization of density,
In fields such as water process, medicine, biomedicine, catalysis, there is application widely.
At present, the preparation method of porous polymer microsphere mainly has two classes.The first kind is that the monomer under porogen participates in (includes crosslinking
Agent) copolymerization method.The method is exactly to add porogen in reaction system to carry out polyreaction, is removed by porogen after end to be polymerized again
Going, the space that porogen occupied originally is retained so that polymer microballoon has loose structure.Porogen used by this method predominantly has
Three kinds of the mixture of machine solvent, line polymer and organic solvent and line polymer.According to the difference of copolyreaction method,
Such preparation method can be divided into again suspension polymerisation, emulsion polymerization, dispersin polymerization, precipitation polymerization etc..As, Okubo etc. is with methyl
Acrylic acid methyl ester. and cinnamic copolymer, toluene are porogen, and polyvinyl alcohol is dispersion stabilizer, passes through dimethacrylate
Glycol ester (EGDMA) and the suspension polymerisation of divinylbenzene (DVB), react 24h, be prepared for porous polymer at 70 DEG C
Microsphere (Okubo M., Konishi Y., Inohara T., Minami H., J.Appl.Polym.Sci., 2002,86:1087-1091)；
Moustafa etc. are with phthalic acid diethyl alcohol ester as dispersion stabilizer, and ethanol is porogen, by acrylic acid and methacrylic acid
The dispersin polymerization of ethylene oxidic ester prepare porous polymer microsphere (Moustafa A.B., Faizalla A., J.Appl.Polym.Sci.,
1999,73:1793-1798).The particle diameter of the porous polymer microsphere that this kind of method prepares mainly is determined by the dispersion condition being polymerized, and
The size of micropore and form are then by kind and the consumption decision of porogen.Although it is many to utilize the method can prepare better performances
Pore polymer microsphere, but there is also some problems.The reaction system that this kind of method uses is typically the most complicated, need to introduce porogen,
The auxiliary agent such as dispersant or stabilizer, these auxiliary agents not only need to remove after the reaction, and the most easily pollute product in course of reaction
Thing, affects product property.It addition, such method generally requires the reaction long period when preparing, combined coefficient is relatively low.
Equations of The Second Kind prepares the rear cross-linking method that the method for porous polymer microsphere is line style or low cross-linking copolymer.The method mainly includes
Following steps.First, the linear or polymer microballoon of low crosslinking degree is prepared by dispersin polymerization or emulsion polymerization, as next
The seed of step polymerization, simultaneously works as the effect of linear polymer porogen.By cross-linking monomer and function monomer, the most also include causing
Hole agent joins in seed system, makes seed the most swelling.Then, heating up and add initiator, trigger monomer is polymerized.Finally,
By the porogen being dried and in soxhlet extraction methods removing microsphere, obtain porous polymer microsphere.This kind of method is gathered in preparation porous
During compound microsphere, main problem is that step is many, comparatively laborious.
Solvent-thermal method is a kind of new method preparing porous polymer material.The method is exactly by the mixed system such as monomer, initiator
It is placed under High Temperature High Pressure and carries out polyreaction.Owing to reaction temperature is higher, so response speed is fast, efficiency is high.Particularly, should
Under the conditions of solvent be in critical or supercriticality, reacting substance physics in a solvent, chemical reactivity all have the biggest change,
Present the change being different from normal temperature and pressure, it is possible to prepare the porous material with special construction.As, patent CN
100562531C announces a kind of method utilizing solvent thermal to prepare mesoporous polydivinylbenezene material, and the method is by divinylbenzene
Monomer dispersion, in organic solvent acetonitrile, adds azodiisobutyronitrile initiator, loads reactor after stirring；At 80～180 DEG C
Under the conditions of solvent thermal polymerization 12～48 hours；Vapor away organic solvent and obtain mesoporous polydivinylbenezene.But, the party's legal system
Standby utilizing acetonitrile solvent, acetonitrile self has stronger toxicity and expensive, and reaction time is longer, and prepare is
The material of the loose winding of polymeric chain with polydivinylbenezene as skeleton, shape is random, piles up ability, and apparent density is
0.070kg/L, tap density is 0.087kg/L so that it is apply limited.
Summary of the invention
Present invention aims to that length reaction time that above-mentioned prior art exists, solvent toxicity be big, complicated process of preparation,
The problems such as product morphology is irregular, it is provided that the preparation method of a kind of porous polymer microsphere, the method is simple, reaction system
In in addition to solvent, monomer, initiator, it is not necessary to add other auxiliary agents, it is to avoid the auxiliary agent such as dispersant, the stabilizer dirt to product
Dye；In the solvent that toxicity is relatively low, a step can prepare porous polymer microsphere；Response speed is fast, and generally no greater than 12 is little
Time just can prepare microspheres product；Controllability is strong, can directly be closed by the regulation and control to reaction condition and the selection to organic solvent
Become out to have polymer microballoon high-specific surface area, Different Pore Structures.The polymer microballoon good fluidity prepared, its micropore
Structure has stronger absorbability to organic solvent.
The present invention also provides for the purposes of porous polymer microsphere prepared by the method.
The purpose of the present invention is achieved through the following technical solutions:
The preparation method of the porous polymer microsphere of the present invention comprises the following steps, but is not limited to following steps:
Polymerization monomer is joined in reaction dissolvent together with initiator, stirs to being polymerized monomer, initiator is thoroughly dispersed in reaction
In solvent, it is placed in reactor, seals；Reactor is placed in baking oven, reacts a period of time at a certain temperature；Reaction knot
Shu Hou, natural cooling, filtering reacting liquid, products therefrom washs to removing through nontoxic volatile solvents such as ethanol, methanol or propanol
Dereaction solvent, be dried, obtain porous polymer microsphere.
Wherein, described polymerization monomer is divinylbenzene or divinylbenzene and styrene monomer such as styrene, methylbenzene second
The mixture of the arbitrary proportion such as alkene or t-butyl styrene (volume).The method can make divinylbenzene monomers or divinyl
Base benzene and cinnamic mixture occur precipitation one solvent thermal polymerization to react, it is thus achieved that porous polymer microsphere.It addition, be used as
Styrene monomer (methyl styrene, t-butyl styrene etc.) containing vinyl-functional and divinylbenzene list on phenyl ring
Body generation polyreaction.
Described initiator is azodiisobutyronitrile, benzoyl peroxide or persulfide (such as potassium peroxydisulfate, sodium peroxydisulfate etc.),
Preferably azodiisobutyronitrile.The quality of described initiator is the 5%～20% of polymerization monomer mass.
Described reaction dissolvent is acetic acid or acetic acid and any one mixing in ethanol, methanol, ethylene glycol and oxolane
Solution, in the mixed reaction solvent that wherein acetic acid and ethanol, methanol or ethylene glycol form, ethanol, methanol or ethylene glycol institute
The volume accounted for is less than the 15% of reaction dissolvent cumulative volume, and the specific surface area of the porous polymer microsphere that reaction prepares is with ethanol, first
The increase of alcohol or ethylene glycol proportion in reaction dissolvent and increase；In the mixed reaction solvent that acetic acid and oxolane form,
Volume shared by oxolane is less than the 30% of reaction dissolvent cumulative volume, and the porous polymer microsphere that reaction prepares is with oxolane
The increase of proportion in reaction dissolvent and increase.Therefore, form by changing solvent, porous polymer microsphere can be regulated and controled
Specific surface area size.
Described polymerization monomer is 0.001～0.05 with the volume ratio of reaction dissolvent.
Described reaction temperature controls at 80～160 DEG C.
The described response time controlled at 2～48 hours.
Described reactor is the common stainless steel water thermal synthesis reactor containing polytetrafluoroethylliner liner.
The porous polymer microsphere that the present invention prepares, granularity is micron order, and mean diameter is 1～4 μm；Specific surface area is
200～810m2/g；Aperture is 2～4nm；Apparent density is 0.25～0.28kg/L, and tap density is 0.36～0.39kg/L,
Dispersibility and sphericity are the best.
The porous polymer microsphere that the present invention prepares can serve as organic solvent adsorbent, and can be recycled for multiple times.
Compared with the prior art the present invention has the advantage that
1, course of reaction is simple, and reaction system is in addition to reaction dissolvent, polymerization monomer, initiator, it is not necessary to add other auxiliary agents,
Avoiding the pollution to product of the auxiliary agent such as dispersant, stabilizer, a step can prepare porous polymer microsphere.
2, the present invention mainly uses nontoxic, acetic acid at a low price as the solvent of solvent thermal reaction.
3, response speed is fast, within generally less than 12 hours, just can prepare porous polymer microsphere product.
4, reaction controllability is strong, product good sphericity, the pore structure of easily dimmable porous polymer microsphere, the microsphere hole prepared
Footpath is at about 2nm, by reaction condition, the selection of organic solvent, and can be 200～810m2Regulation product microsphere in/g range
Specific surface area.
5, the porous polymer microsphere specific surface area prepared is big, has certain absorbability to Organic substance.
6, the porous polymer microsphere apparent density that prepared by the present invention is 0.25～0.28kg/L, tap density is 0.36～0.39kg/L,
Prepare 0.087kg/L, 0.070kg/L of product apparently higher than patent CN 100562531C, the porous that the present invention prepares is described
Polymer microballoon bulk property is better than product prepared by patent CN 100562531C.Porous polymer microsphere prepared by the present invention
Tap density is about 1.45 with the ratio of apparent density, higher than the 1.27 of patent CN 100562531C product, the present invention is described
The regularity of product is better than patent CN 100562531C, the most totally can improve the filling capacity of porous polymer microsphere.
Accompanying drawing explanation
The scanning electron microscope (SEM) photograph of the polymer microballoon of Fig. 1: embodiment 1.
The scanning electron microscope (SEM) photograph of the polymer microballoon of Fig. 2: embodiment 2.
The scanning electron microscope (SEM) photograph of the polymer microballoon of Fig. 3: embodiment 3.
The scanning electron microscope (SEM) photograph of the polymer microballoon of Fig. 4: embodiment 4.
The scanning electron microscope (SEM) photograph of the polymer microballoon of Fig. 5: embodiment 5.
The scanning electron microscope (SEM) photograph of the polymer microballoon of Fig. 6: embodiment 6.
The scanning electron microscope (SEM) photograph of the polymer microballoon of Fig. 7: embodiment 7.
The scanning electron microscope (SEM) photograph of the polymer microballoon of Fig. 8: embodiment 8.
The scanning electron microscope (SEM) photograph of the polymer microballoon of Fig. 9: embodiment 9.
The scanning electron microscope (SEM) photograph of the polymer microballoon of Figure 10: embodiment 10.
The scanning electron microscope (SEM) photograph of the polymer microballoon of Figure 11: embodiment 11.
The scanning electron microscope (SEM) photograph of the polymer microballoon of Figure 12: embodiment 12.
The scanning electron microscope (SEM) photograph of the polymer microballoon of Figure 13: embodiment 13.
Detailed description of the invention
Below in conjunction with embodiment and accompanying drawing, the present invention will be further described, but is not limited to this.The divinyl used in embodiment
Benzene monomer is divinylbenzene 80 (trade name represents that divinyl benzene content is 80%), and initiator all carries out recrystallization, residue
Medicine is analytical pure.
Embodiment 1
0.1ml is polymerized monomer divinylbenzene and 0.0046mg initiator azodiisobutyronitrile joins 100ml reaction dissolvent
In acetic acid, (polymerization monomer divinylbenzene is 0.001 with the volume ratio of reaction dissolvent acetic acid, the matter of initiator azodiisobutyronitrile
Amount is the 5% of polymerization monomer divinylbenzene quality), stirring is complete to polymerization monomer divinylbenzene, initiator azodiisobutyronitrile
Entirely it is dispersed in reaction dissolvent acetic acid, is placed in reactor, seal；Being placed in baking oven by reactor, arranging oven temperature is 120 DEG C,
12 hours response time.After reaction terminates, natural cooling, filtering reacting liquid, products therefrom is molten to removing reaction through washing with alcohol
Agent acetic acid, be dried, obtain porous polydivinylbenezene microsphere.The mean diameter of porous polydivinylbenezene microsphere is 2.8475 μm,
Specific surface area is 540m2/ g, mean pore size is 2.165nm, and tap density is 0.36kg/L, and apparent density is 0.25kg/L,
Saturated extent of adsorption to organic solvent-normal hexane is 1.2451g/g.The scanning electron microscope of product porous polydivinylbenezene microsphere such as figure
1.The good sphericity of product porous polydivinylbenezene microsphere, tap density is 1.44 with the ratio of apparent density, and regularity is good.
Organic solvent is had certain absorbability.
Embodiment 2
5.0ml is polymerized monomer divinylbenzene and 919mg initiator azodiisobutyronitrile joins 100ml reaction dissolvent acetic acid
In (volume ratio of polymerization monomer divinylbenzene and reaction dissolvent acetic acid is 0.05, and the quality of initiator azodiisobutyronitrile is poly-
Close the 20% of monomer divinylbenzene quality), stirring is completely dispersed to polymerization monomer divinylbenzene, initiator azodiisobutyronitrile
In reaction dissolvent acetic acid, it is placed in reactor, seals；Being placed in baking oven by reactor, arranging oven temperature is 120 DEG C,
12 hours response time.After reaction terminates, natural cooling, filtering reacting liquid, products therefrom is molten to removing reaction through washing with alcohol
Agent acetic acid, be dried, obtain porous polydivinylbenezene microsphere.The mean diameter of porous polydivinylbenezene ball is 1.8512 μm,
Specific surface area is 570m2/ g, mean pore size is 2.285nm, and tap density is 0.37kg/L, and apparent density is 0.25kg/L,
Saturated extent of adsorption to organic solvent-normal hexane is 1.2564g/g.The scanning electron microscope of product porous polydivinylbenezene microsphere such as figure
2.The good sphericity of product porous polydivinylbenezene microsphere, tap density is 1.48 with the ratio of apparent density, to organic solvent
There is certain absorbability.
Embodiment 3
2.5ml is polymerized monomer divinylbenzene and 229.75mg initiator benzoyl peroxide joins 100ml reaction dissolvent second
In acid, (polymerization monomer divinylbenzene is 0.025 with the volume ratio of reaction dissolvent acetic acid, the quality of initiator benzoyl peroxide
For being polymerized the 10% of monomer divinylbenzene quality), stirring is complete to polymerization monomer divinylbenzene, initiator benzoyl peroxide
It is dispersed in reaction dissolvent acetic acid, is placed in reactor, seal；Being placed in baking oven by reactor, arranging oven temperature is 120 DEG C,
12 hours response time.After reaction terminates, natural cooling, filtering reacting liquid, products therefrom is molten to removing reaction through washing with alcohol
Agent acetic acid, be dried, obtain porous polydivinylbenezene microsphere.The mean diameter of porous polydivinylbenezene ball is 2.6512 μm,
Specific surface area is 438m2/ g, mean pore size is 2.288nm, and tap density is 0.37kg/L, and apparent density is 0.25kg/L,
Saturated extent of adsorption to organic solvent-normal hexane is 1.0842g/g.The scanning electron microscope of product porous polydivinylbenezene microsphere such as figure
3。
Embodiment 4
2.5ml is polymerized monomer divinylbenzene and 229.75mg initiator potassium persulfate joins in 100ml reaction dissolvent acetic acid
(polymerization monomer divinylbenzene is 0.025 with the volume ratio of reaction dissolvent acetic acid, and the quality of initiator potassium persulfate is single for polymerization
The 10% of body divinylbenzene quality), stirring to polymerization monomer divinylbenzene, initiator potassium persulfate are thoroughly dispersed in reacts molten
In agent acetic acid, it is placed in reactor, seals；Being placed in baking oven by reactor, arranging oven temperature is 80 DEG C, the response time 12
Hour.After reaction terminates, natural cooling, filtering reacting liquid, products therefrom extremely removes reaction dissolvent acetic acid through washing with alcohol, does
Dry, obtain porous polydivinylbenezene microsphere.The mean diameter of porous polydivinylbenezene microsphere is 1.021 μm, specific surface area
For 418m2/ g, mean pore size is 2.108nm, and tap density is 0.37kg/L, and apparent density is 0.27kg/L, to having
The saturated extent of adsorption of machine solvent hexane is 1.0214g/g.Scanning electron microscope such as Fig. 4 of product porous polydivinylbenezene microsphere.
Embodiment 5
Polymerization monomer 1.0ml divinylbenzene, 1.5ml styrene and 229.75mg initiator azodiisobutyronitrile are joined
In 100ml reaction dissolvent acetic acid, (polymerization monomer divinylbenzene, styrene are 0.025 with the volume ratio of reaction dissolvent acetic acid, draw
Send out agent azodiisobutyronitrile quality be polymerization monomer divinylbenzene, the 10% of styrene quality), stirring to polymerization monomer diethyl
Alkenyl benzene, styrene and initiator azodiisobutyronitrile are thoroughly dispersed in reaction dissolvent acetic acid, are placed in reactor, seal；
Being placed in baking oven by reactor, arranging oven temperature is 160 DEG C, 12 hours response time.After reaction terminates, natural cooling,
Filtering reacting liquid, products therefrom to removing reaction dissolvent acetic acid, being dried, obtains porous polydivinylbenezene-benzene through washing with alcohol
Ethylene complex microsphere.The mean diameter of porous polydivinylbenezene-styrene complex microsphere is 2.1285 μm, and specific surface area is
200m2/ g, mean pore size is 1.511nm, and tap density is 0.39kg/L, and apparent density is 0.28kg/L, to organic
The saturated extent of adsorption of solvent hexane is 0.5716g/g.The scanning electricity of product porous polydivinylbenezene-styrene complex microsphere
Mirror such as Fig. 5.
Embodiment 6
Monomer 1.0ml divinylbenzene, 1.5ml methyl styrene and 229.75mg initiator azodiisobutyronitrile will be polymerized add
In 100ml reaction dissolvent acetic acid, (polymerization monomer divinylbenzene, methyl styrene with the volume ratio of reaction dissolvent acetic acid are
0.025, the quality of initiator azodiisobutyronitrile be polymerization monomer divinylbenzene, the 10% of methyl styrene quality), stirring
It is thoroughly dispersed in reaction dissolvent acetic acid to polymerization monomer divinylbenzene, methyl styrene and initiator azodiisobutyronitrile, puts
In reactor, seal；Being placed in baking oven by reactor, arranging oven temperature is 160 DEG C, 12 hours response time.Reaction
After end, natural cooling, filtering reacting liquid, products therefrom to removing reaction dissolvent acetic acid, being dried, obtains many through washing with alcohol
Hole polydivinylbenezene-methyl styrene complex microsphere.The average particle of porous polydivinylbenezene-methyl styrene complex microsphere
Footpath is 2.2328 μm, and specific surface area is 242m2/ g, mean pore size is 1.724nm, and tap density is 0.42kg/L, pine
Dress density is 0.31kg/L, and the saturated extent of adsorption to organic solvent-normal hexane is 0.6542g/g.Product porous polydivinylbenezene
The scanning electron microscope of-methyl styrene complex microsphere such as Fig. 6.
Embodiment 7
Polymerization monomer 1.0ml divinylbenzene, 1.5ml t-butyl styrene and 229.75mg initiator azodiisobutyronitrile are added
Enter in 100ml reaction dissolvent acetic acid (polymerization monomer divinylbenzene, t-butyl styrene and the volume ratio of reaction dissolvent acetic acid
Be 0.025, the quality of initiator azodiisobutyronitrile be polymerization monomer divinylbenzene, the 10% of t-butyl styrene quality),
Stirring is thoroughly dispersed in reaction dissolvent acetic acid to polymerization monomer divinylbenzene, t-butyl styrene and initiator azodiisobutyronitrile
In, it is placed in reactor, seals；Being placed in baking oven by reactor, arranging oven temperature is 160 DEG C, 12 hours response time.
After reaction terminates, natural cooling, filtering reacting liquid, products therefrom, obtains to removing reaction dissolvent acetic acid, being dried through washing with alcohol
To porous polydivinylbenezene-t-butyl styrene complex microsphere.Porous polydivinylbenezene-t-butyl styrene complex microsphere
Mean diameter be 2.2856 μm, specific surface area is 252m2/ g, mean pore size is 1.711nm, and tap density is
0.49kg/L, apparent density is 0.38kg/L, and the saturated extent of adsorption to organic solvent-normal hexane is 0.5921g/g.Product porous
Scanning electron microscope such as Fig. 7 of polydivinylbenezene-t-butyl styrene complex microsphere.
Embodiment 8
2.5ml is polymerized monomer divinylbenzene and 229.75mg initiator azodiisobutyronitrile joins 100ml reaction dissolvent second
In acid, (polymerization monomer divinylbenzene is 0.025 with the volume ratio of reaction dissolvent acetic acid, the quality of initiator azodiisobutyronitrile
For being polymerized the 10% of monomer mass), stirring is thoroughly dispersed in reaction to polymerization monomer divinylbenzene, initiator azodiisobutyronitrile
In solvent acetic acid, it is placed in reactor, seals；Being placed in baking oven by reactor, arranging oven temperature is 120 DEG C, during reaction
Between 2 hours.Reaction terminate after, natural cooling, filtering reacting liquid, products therefrom through washing with alcohol to remove reaction dissolvent acetic acid,
It is dried, obtains porous polydivinylbenezene microsphere.The mean diameter of porous polydivinylbenezene microsphere is 2.7548 μm, specific surface
Amass as 232m2/ g, mean pore size is 2.035nm, and tap density is 0.37kg/L, and apparent density is 0.25kg/L, right
The saturated extent of adsorption of organic solvent-normal hexane is 0.5841g/g.Scanning electron microscope such as Fig. 8 of product porous polydivinylbenezene microsphere.
Embodiment 9
2.0ml is polymerized monomer divinylbenzene, 0.5ml styrene and 229.75mg initiator azodiisobutyronitrile join
In 100ml reaction dissolvent acetic acid, (polymerization monomer divinylbenzene, styrene are 0.025 with the volume ratio of reaction dissolvent acetic acid, draw
Send out agent azodiisobutyronitrile quality be polymerization monomer divinylbenzene, the 10% of styrene quality), stirring to exhausted monomer divinyl
Base benzene, styrene and initiator azodiisobutyronitrile are thoroughly dispersed in reaction dissolvent acetic acid, are placed in reactor, seal；Will
Reactor is placed in baking oven, and arranging oven temperature is 120 DEG C, 48 hours response time.After reaction terminates, natural cooling, mistake
Filter reactant liquor, products therefrom to removing reaction dissolvent acetic acid, being dried, obtains porous polydivinylbenezene-benzene second through washing with alcohol
Alkene complex microsphere.The mean diameter of porous polydivinylbenezene-styrene complex microsphere is 3.1547 μm, and specific surface area is
261m2/ g, mean pore size is 2.152nm, and tap density is 0.38kg/L, and apparent density is 0.26kg/L, to organic
The saturated extent of adsorption of solvent hexane is 0.5926g/g.The scanning electricity of product porous polydivinylbenezene-styrene complex microsphere
Mirror such as Fig. 9.
Embodiment 10
2.5ml is polymerized monomer divinylbenzene and 229.75mg initiator azodiisobutyronitrile joins 85ml acetic acid and 15ml
In ethanol mixed reaction solution (polymerization monomer divinylbenzene is 0.025 with acetic acid, the volume ratio of ethanol mixed reaction solution,
The quality of initiator azodiisobutyronitrile is the 10% of polymerization monomer divinylbenzene quality, and etoh solvent accounts for acetic acid, ethanol mixing
The 15% of reaction solution cumulative volume), stirring is extremely polymerized monomer divinylbenzene, initiator azodiisobutyronitrile is thoroughly dispersed in acetic acid,
In ethanol mixed reaction solution, it is placed in reactor, seals；Being placed in baking oven by reactor, arranging oven temperature is 120 DEG C,
6 hours response time.After reaction terminates, natural cooling, filtering reacting liquid, products therefrom is molten to removing reaction through washing with alcohol
Agent acetic acid, be dried, obtain porous polydivinylbenezene microsphere.The mean diameter of porous polydivinylbenezene microsphere is 3.6852 μm,
Specific surface area is 673m2/ g, mean pore size is 2.382nm, and tap density is 0.37kg/L, and apparent density is 0.28kg/L,
Saturated extent of adsorption to organic solvent-normal hexane is 1.3841g/g.The scanning electron microscope of product porous polydivinylbenezene microsphere such as figure
10。
Embodiment 11
2.5ml is polymerized monomer divinylbenzene and 229.75mg initiator azodiisobutyronitrile joins 85ml acetic acid and 15ml methanol
In mixed reaction solution, (polymerization monomer divinylbenzene is 0.025 with acetic acid, the volume ratio of methanol mixed reaction solution, causes
The quality of agent azodiisobutyronitrile is the 10% of polymerization monomer divinylbenzene quality, and solvent methanol accounts for acetic acid, methanol mixed reaction
The 30% of overall solution volume), stirring is thoroughly dispersed in acetic acid, first to polymerization monomer divinylbenzene, initiator azodiisobutyronitrile
In alcohol mixed reaction solution, it is placed in reactor, seals；Being placed in baking oven by reactor, arranging oven temperature is 120 DEG C,
12 hours response time.After reaction terminates, natural cooling, filtering reacting liquid, products therefrom is molten to removing reaction through washing with alcohol
Agent acetic acid, is dried, obtains porous polydivinylbenezene microsphere.The mean diameter of porous polydivinylbenezene microsphere is 3.8682 μm,
Specific surface area is 630m2/ g, mean pore size is 2.405nm, and tap density is 0.37kg/L, and apparent density is 0.27kg/L,
Saturated extent of adsorption to organic solvent-normal hexane is 1.3250g/g.The scanning electron microscope of product porous polydivinylbenezene microsphere such as figure
11。
Embodiment 12
2.5ml is polymerized monomer divinylbenzene and 229.75mg initiator azodiisobutyronitrile joins 70ml acetic acid and 30ml
In oxolane mixed reaction solution, (polymerization monomer divinylbenzene with the volume ratio of acetic acid, oxolane mixed reaction solution is
0.025, the quality of initiator azodiisobutyronitrile be polymerization monomer divinylbenzene quality 10%, solvents tetrahydrofurane account for acetic acid,
The 30% of oxolane mixed reaction solution cumulative volume), stirring is complete to polymerization monomer divinylbenzene, initiator azodiisobutyronitrile
Entirely it is dispersed in acetic acid, oxolane mixed reaction solution, is placed in reactor, seal；Reactor is placed in baking oven, if
Putting oven temperature is 120 DEG C, 12 hours response time.After reaction terminates, natural cooling, filtering reacting liquid, products therefrom warp
Washing with alcohol, to removing reaction dissolvent acetic acid and oxolane, being dried, obtains porous polydivinylbenezene microsphere.The poly-diethyl of porous
The mean diameter of alkenyl benzene microsphere is 3.1842 μm, and specific surface area is 810m2/ g, mean pore size is 2.862nm, jolt ramming
Density is 0.39kg/L, and apparent density is 0.28kg/L, and the saturated extent of adsorption to organic solvent-normal hexane is 1.5958g/g.Produce
Scanning electron microscope such as Figure 12 of thing porous polydivinylbenezene microsphere.
Embodiment 13
2.5ml is polymerized monomer divinylbenzene and 229.75mg initiator azodiisobutyronitrile joins 85ml acetic acid and 15ml
In ethylene glycol mixed reaction solution (polymerization monomer divinylbenzene is 0.025 with acetic acid, the volume ratio of ethylene glycol mixed reaction solution,
The quality of initiator azodiisobutyronitrile is the 10% of polymerization monomer divinylbenzene quality, and solvent diethanol accounts for acetic acid, ethylene glycol
The 15% of mixed reaction solution cumulative volume), stirring is thoroughly dispersed in polymerization monomer divinylbenzene, initiator azodiisobutyronitrile
In acetic acid, ethylene glycol mixed reaction solution, it is placed in reactor, seals；Reactor is placed in baking oven, oven temperature is set
It is 120 DEG C, 12 hours response time.After reaction terminates, natural cooling, filtering reacting liquid, products therefrom is through washing with alcohol extremely
Remove reaction dissolvent acetic acid and ethylene glycol, be dried, obtain porous polydivinylbenezene microsphere.Porous polydivinylbenezene microsphere
Mean diameter is 4.01821 μm, and specific surface area is 712m2/ g, mean pore size is 2.574nm, and tap density is 0.37kg/L,
Apparent density is 0.26kg/L, and the saturated extent of adsorption to organic solvent-normal hexane is 1.4108g/g.The poly-divinyl of product porous
The scanning electron microscope of benzene microsphere such as Figure 13.
Embodiment 14
As a example by the porous polydivinylbenezene microsphere prepared in embodiment 2, organic solvent is being circulated by test polymer microsphere
The performance of absorption use.Concrete operation step is as follows:
(1) 50ml deionized water and 10ml normal hexane are joined in 100ml beaker, stratification.
(2) polyalcohol stephanoporate microballoons of load weighted certain mass (m1) is added, owing to porous polydivinylbenezene microsphere has super thin
Aqueous, only can adsorb upper strata organic solvent-normal hexane.
(3) after the absorption of porous polydivinylbenezene microsphere is saturated, solution is all poured in sand core funnel known to quality (m2),
Filter until dripless is dripped bottom sand core funnel.
(4) sand core funnel quality (m3) after filtration is weighed.
(5) by three above different quality, the saturated extent of adsorption ((m3-m2-m1) of porous polydivinylbenezene microsphere can be calculated
/m1)。
(6) the porous polydivinylbenezene microsphere of absorption normal hexane is placed in 80 DEG C of baking ovens, 1h.
(7) dried porous polydivinylbenezene microsphere is carried out second adsorption experiment, circulation step (1) (6).
(8) dried porous polydivinylbenezene microsphere is carried out three adsorption experiments, circulation step (1) (5).
Experimental result shows: adsorbance is 1.0564g/g for the first time, and saturated extent of adsorption is 1.0483g/g for the second time, for the third time
Adsorbance is 1.0455g/g.Illustrate that this porous polydivinylbenezene microsphere has the spy of recycling in terms of Adsorption of Organic
Property.
Claims (10)
1. the preparation method of a porous polymer microsphere, it is characterised in that comprise the following steps: will polymerization monomer and initiator one
Rising joins in reaction dissolvent, stirs to being polymerized monomer, initiator is thoroughly dispersed in reaction dissolvent, is placed in reactor, close
Envelope；Reactor is placed in baking oven, reacts a period of time at a certain temperature；After reaction terminates, natural cooling, filters reaction
Liquid, products therefrom to removing reaction dissolvent, being dried, obtains many through nontoxic volatile solvent washings such as ethanol, methanol or propanol
Pore polymer microsphere.
The preparation method of porous polymer microsphere the most according to claim 1, it is characterised in that described polymerization monomer is diethyl
The mixture of alkenyl benzene or divinylbenzene and styrene monomer arbitrary volume ratio.
The preparation method of porous polymer microsphere the most according to claim 1, it is characterised in that described styrene monomer is
Styrene, methyl styrene or t-butyl styrene.
The preparation method of porous polymer microsphere the most according to claim 1, it is characterised in that described initiator is azo
Bis-isobutyronitrile, benzoyl peroxide or persulfide；The quality of described initiator is the 5%～20% of polymerization monomer mass.
5. according to the preparation method of the porous polymer microsphere described in claim 1 or 3, it is characterised in that described initiator is
Azodiisobutyronitrile.
The preparation method of porous polymer microsphere the most according to claim 1, it is characterised in that described reaction dissolvent is second
Any one mixed solution in acid or acetic acid and ethanol, methanol, ethylene glycol and oxolane；Acetic acid and ethanol, methanol
Or in the mixed reaction solvent of ethylene glycol composition, ethanol, methanol or the volume shared by ethylene glycol are overall less than reaction dissolvent
Long-pending 15%；Acetic acid is with the mixed reaction solvent of oxolane composition, and the volume shared by oxolane is total less than reaction dissolvent
The 30% of volume.
The preparation method of porous polymer microsphere the most according to claim 1, it is characterised in that described polymerization monomer is with anti-
The volume ratio answering solvent is 0.001～0.05.
The preparation method of porous polymer microsphere the most according to claim 1, it is characterised in that described reaction temperature controls
At 80～160 DEG C；The described response time controlled at 2～48 hours.
The porous polymer microsphere that the preparation method of porous polymer microsphere the most according to claim 1 prepares, its feature exists
It is 1～4 μm in mean diameter；Specific surface area is 200～810m2/g；Aperture is 2～4nm；Apparent density is 0.25～0.28kg/L,
Tap density is 0.36～0.39kg/L.
The porous polymer microsphere that the preparation method of porous polymer microsphere the most according to claim 1 prepares is as organic
The application of solvent adsorption agent.
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