CN107199025A - A kind of preparation method of the organic polymer chromatograph packing material of dopen Nano diamond - Google Patents
A kind of preparation method of the organic polymer chromatograph packing material of dopen Nano diamond Download PDFInfo
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- CN107199025A CN107199025A CN201710415061.8A CN201710415061A CN107199025A CN 107199025 A CN107199025 A CN 107199025A CN 201710415061 A CN201710415061 A CN 201710415061A CN 107199025 A CN107199025 A CN 107199025A
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Abstract
The invention discloses a kind of preparation method of the organic polymer chromatograph packing material of dopen Nano diamond, comprise the following steps：(1) monodispersed linear polystyrene seed microballoon of the particle diameter between 1~3 μm is prepared；(2) carboxylated Nano diamond is prepared；(3) mixing dibutyl phthalate with polystyrene seed microballoon activates polystyrene seed microballoon, it is subsequently added monomer styrene, crosslinking agent divinylbenzene, carboxylated Nano diamond, emulsifying agent dodecyl sodium sulfate, stabilizer polyvinyl alcohol, initiator benzoyl peroxide and pore-foaming agent toluene, it is sufficiently stirred for making polystyrene seed microspheres swell, then heating triggers monomer polymerization, fully pore-foaming agent is removed after polymerization through surname extraction, the last scrubbed organic polymer chromatograph packing material for obtaining dopen Nano diamond of the particle diameter between 6~10 μm.The chromatograph packing material that the present invention is provided improves separating effect, mechanical stability and the resistance to acids and bases of performance liquid chromatographic column stationary phase.
Description
Technical field
Present document relates to a kind of preparation method of performance liquid chromatographic column stationary phase, and in particular to organic polymer chromatograph packing material
Preparation method.
Background technology
High performance liquid chromatography be analyze subject a kind of important analysis method, it be widely used in agricultural, industry,
Food, medicine and life science etc. field.Separation is the core of chromatographic technique, influences the factor of chromatographic isolation a lot, fixed
It is mutually the most key.The conventional stationary phase matrix of high performance liquid chromatography has silica gel and organic polymer, and Silica Surface has silicone hydroxyl, easily
In progress chemical modification, and its is firm in structure, will not be swelled in organic solvent, is more satisfactory filler, but silica gel
It is only suitable for using in the range of PH=2-8, which has limited its application.On the contrary, the organic polymer PH scope of applications compare silicon
Glue is much broader, but its separative efficiency and rigidity also have certain defect.In order to improve these defects of silica gel and organic polymer, respectively
Plant Solid-phase synthesis method to arise at the historic moment, such as with polymer overmold silicon ball, carbon ball or metal oxide, but prepared by these methods
Complexity, and the stationary phase of synthesis is still not ideal enough in stability and separating effect, fortunately, the materialogy developed rapidly
To we provide more selections.Nano diamond possesses various special natures, and skill is produced in Detonation Process, impact compress method etc.
Art is reduced after its use cost, and its application field starts continuous extension, and such as aviation, shipping industry, petrochemical industry are answered
Nano diamond polymer composite body, nano diamond polishing liquid of polishing etc..Nanogold is used in current HPLC
The report of hard rock is actually rare, and two patents of CN101513607 and CN101850242A pass through organic polymer and CNT
The mode of copolymerization and doping prepares HPLC fillers, but its bar-shaped form limits its application in filler, and can influence
The separating property of filler.
The content of the invention
It is an object of the invention to provide a kind of organic polymer for the dopen Nano diamond that manufacture craft is simple, cost is low
The preparation method of thing chromatograph packing material, to improve separating effect, mechanical performance and the resistance to acids and bases of performance liquid chromatographic column stationary phase.
For achieving the above object, the present invention is adopted the following technical scheme that：
The invention provides a kind of preparation method of the organic polymer chromatograph packing material of dopen Nano diamond, including it is as follows
Step：
(1) monodispersed linear polystyrene seed microballoon of the particle diameter between 1~3 μm is prepared；
(2) carboxylated Nano diamond is prepared；
(3) mixing dibutyl phthalate with polystyrene seed microballoon activates polystyrene seed microballoon, with
Monomer styrene, crosslinking agent divinylbenzene, carboxylated Nano diamond, emulsifying agent dodecyl sodium sulfate, stabilizer are added afterwards
Polyvinyl alcohol, initiator benzoyl peroxide and pore-foaming agent toluene, are sufficiently stirred for making polystyrene seed microspheres swell, Ran Houjia
Thermal initiation monomer polymerize, and pore-foaming agent is removed through surname extraction fully after polymerization, it is last it is scrubbed obtain particle diameter 6~10 μm it
Between dopen Nano diamond organic polymer chromatograph packing material.
Further, step (1) prepares monodispersed linear polyphenyl second of the particle diameter between 1~3 μm using dispersion copolymerization method
Alkene seed microballoon, specifically implements in accordance with the following steps：Using styrene as monomer, polyvinylpyrrolidone is stabilizer, azo two
Isobutyronitrile is initiator, and monodispersed linear polystyrene seed microballoon is generated by radical polymerization in reaction medium, is planted
Seed footpath is between 1-3 μm, and uniform particle sizes are without classification；The reaction medium is molten for the mixing of absolute ethyl alcohol or second alcohol and water
Liquid.
Further, in step (1), the quality of styrene monomer is the 5~30% of reaction medium quality, is preferably
25%；The rate of charge of stabilizer polyvinylpyrrolidone and reaction medium is 0.5~4g：100mL, preferably 1.6g：100mL；
Initiator azodiisobutyronitrile consumption is the 1~5% of monomer mass, preferably 2.2%；Ethanol in the mixed solution of second alcohol and water
Volumetric concentration more than 75%, preferably 90%.
Further, in step (1), polymeric reaction temperature is 40~85 DEG C, preferably 80 DEG C；Mixing speed 100~
400 revs/min；Reaction time is 8~24 hours, preferably 24 hours.
Further, in step (2), described carboxylated Nano diamond is handled with the mixed liquor of the concentrated sulfuric acid and concentrated nitric acid
Nano diamond and obtain.
Further, in step (2), the volume ratio of the concentrated sulfuric acid and concentrated nitric acid in the mixed liquor of the concentrated sulfuric acid and concentrated nitric acid
Between 2~4, preferably 3:1.
Again further, in step (2), described carboxylated Nano diamond is prepared via a method which：In the concentrated sulfuric acid
Nano diamond is added with the mixed liquor of concentrated nitric acid, is reacted 6~12 hours under the conditions of 80~140 DEG C, that is, obtains carboxylated
Nano diamond；Preferable reaction temperature is 100 DEG C, and the reaction time is 12 hours.
Further, in step (3), the mass ratio of dibutyl phthalate and polystyrene seed microballoon 2~5 it
Between, preferably 2.The preferred room temperature of activation temperature, soak time is preferably 12~24 hours, preferably 24 hours.
Further, in step (3), monomer styrene quality be organic phase (by monomer styrene, crosslinking agent divinylbenzene,
Emulsifying agent dodecyl sodium sulfate, stabilizer polyvinyl alcohol, initiator benzoyl peroxide and pore-foaming agent toluene composition) gross mass
10~20%, the mass ratio of cross-linker divinylbenzene and styrene is between 2~3, the quality of carboxylated Nano diamond
The 0.1~2% of monomer styrene quality is accounted for, the quality of emulsifying agent dodecyl sodium sulfate accounts for the 2~4% of organic phase gross mass,
The quality of stabilizer polyvinyl alcohol accounts for the 0.5~5% of organic phase gross mass, and the quality of initiator benzoyl peroxide accounts for monomer benzene
The 0.4~6% of Ethylene mass, the quality of pore-foaming agent toluene accounts for the 20~70% of organic phase gross mass.
Further, in step (3), monomer styrene quality is the 14% of organic phase gross mass, crosslinking agent divinyl
The mass ratio of benzene and styrene is 2：1, the quality of emulsifying agent dodecyl sodium sulfate accounts for the 2.5% of organic phase gross mass, stabilization
The quality of agent polyvinyl alcohol accounts for the 1.5% of organic phase gross mass, and the quality of initiator benzoyl peroxide accounts for monomer styrene matter
The 5~6% of amount, the quality of pore-foaming agent toluene accounts for the 50% of organic phase gross mass.
Further, in step (3), the quality of carboxylated Nano diamond accounts for the 0.3~1% of monomer styrene quality.
Further, in step (3), it is swelled by the way that realization is stirred at room temperature, mixing speed is 100~300 revs/min, stirring
Time is 12~24 hours, and it is 10~70 times to make swelling ratio.
Further, in step (3), polymerization is carried out under agitation, and reaction temperature is 60~85 DEG C (preferably 80 DEG C), stirring speed
Spend for 100~300 revs/min, the reaction time is 12~48 hours (preferably 48 hours).
Further, in step (3), it is that will polymerize obtained polymer microballoon through first that described surname extraction, which removes pore-foaming agent,
Benzene surname extraction 12~48 hours, to remove pore-foaming agent.
Further, in step (3), washing reagent preferred alcohol and water.
The granularity of microballoon of the present invention is by pore-foaming agent, crosslinking agent, dispersion stabilizer solubility, swelling temperature, reaction
Temperature, the selection of initiator concentration and swelling ratio are controlled.The particle diameter model of the base ball of the polystyrene-divinylbenzene of synthesis
It is trapped among between 6-10 μm, synthesized base ball is uniformly high, without being classified and being sieved.
The organic polymer chromatograph packing material for the dopen Nano diamond that the present invention is provided, is made with polystyrene-divinylbenzene
For organic polymer matrix, adulterate carboxylated Nano diamond wherein, forms polystyrene-divinylbenzene-oxidation nanometer gold
The compound microballoon of hard rock.Wherein carboxylated Nano diamond is largely embedded into inside organic substrate, by controlling nanometer
The organic polymeric microspheres for measuring different dopings of diamond.
The organic polymer chromatograph packing material of dopen Nano diamond of the present invention can be used as consolidating for performance liquid chromatographic column
Phase is determined, when in use, using homogenate method dress post.
Compared with prior art, the beneficial effects of the present invention are：
(1) the organic polymer chromatograph packing material uniform particle sizes of dopen Nano diamond of the present invention change without classification
Learn stability good, can be used for a long time；Good mechanical property, and resistance to acids and bases is good, is applicable in the range of pH value 1~14.
(2) preparation method of the organic polymer chromatograph packing material of dopen Nano diamond of the present invention is simple, cost
It is low.
(3) the organic polymer chromatograph packing material of dopen Nano diamond of the present invention is solid as performance liquid chromatographic column
When determining phase, compared with undoped polystyrene-divinylbenzene microspheres, analysis time is not only shortened, peak type is improved,
Separating degree increases, and energy quick separating aldehydes matter, the need for being widely used in actual analysis.
Brief description of the drawings
Fig. 1 be embodiment it is 2-in-1 into doping carboxylated Nano diamond polystyrene divinyl benzene microballoon scanning electricity
Mirror (2000 times of amplification).
Fig. 2 be embodiment it is 2-in-1 into doping carboxylated Nano diamond polystyrene divinyl benzene microballoon transmission electricity
Mirror.
Fig. 3 be embodiment it is 2-in-1 into doping carboxylated Nano diamond polystyrene divinyl benzene microballoon to four kinds of phenol
The separation of class material；Wherein, 1 (Isosorbide-5-Nitrae-resorcinol), 2 (phenol), 3 (bisphenol-As), 4 (tert-butyl phenols).
Fig. 4 is the polystyrene divinyl benzene microballoon of the Nano diamond that undopes of comparative example synthesis to four kinds of aldehydes matters
Separation；Wherein, 1 (Isosorbide-5-Nitrae-resorcinol), 2 (phenol), 3 (bisphenol-As), 4 (tert-butyl phenols).
Fig. 5 is the polystyrene divinyl benzene microballoon of the Nano diamond that undopes of comparative example synthesis to different benzene homologues
Separation；Wherein, 1 (Isosorbide-5-Nitrae-hydroquinones), 2 (benzoic acid), 3 (phenol), 4 (P-hydroxybenzoic acid), 5 (benzaldehydes), 6 (first
Benzene).
Fig. 6 be embodiment it is 2-in-1 into doping carboxylated Nano diamond polystyrene divinyl benzene microballoon to different benzene
It is the separation of thing；Wherein, 1 (Isosorbide-5-Nitrae-hydroquinones), 2 (benzoic acid), 3 (phenol), 4 (P-hydroxybenzoic acid), 5 (benzaldehydes), 6
(toluene).
Fig. 7 be embodiment it is 2-in-1 into doping carboxylated Nano diamond polystyrene divinyl benzene microballoon and comparative example
The measuring mechanical property of the polystyrene divinyl benzene microballoon of the Nano diamond that undopes of synthesis.
Embodiment
Technical scheme is described further with instantiation below, but protection scope of the present invention do not limit with
This：
Comparative example：Undope Nano diamond styrene-divinylbenzene polymer filler preparation, its step is：
1st, the synthesis of monodisperse polystyrene seed：The ethanol water of addition 90%, adds stabilizer in flask
Polyvinylpyrrolidone, 80 DEG C of warming-in-water is then respectively adding styrene monomer and initiator azodiisobutyronitrile, and stirring is anti-
Answer 24 hours.Wherein the quality of monomer styrene is 25% (m/m) of ethanol water quality, stabilizer polyvinylpyrrolidone
Quality is 1.6% (m/v) of ethanol water volume, and initiator azodiisobutyronitrile quality is monomer styrene quality
2.2% (m/m), reaction medium is 90% ethanol water, and mixing speed obtains particle diameter at 300 revs/min, after filtration washing and is
2 μm of polystyrene seed.
2nd, the synthesis of polystyrene-divinylbenzene microspheres：Take the polystyrene seed and phthalic acid two in step 1
Butyl ester is mixed in flask, is stirred 24 hours at 20 DEG C, and mixing speed is 200 revs/min, wherein polystyrene seed and adjacent benzene
The mass ratio of dibutyl carboxylic acid is 2:4；It is organic phase gross mass to configure monomer styrene quality in organic phase, the organic phase
The mass ratio of 14% (m/m), cross-linker divinylbenzene and styrene is 2：1, the quality of emulsifier sodium lauryl sulfate is
2.5% (m/m) of organic phase gross mass, the quality of stabilizer polyvinyl alcohol is 1.5% (m/m) of organic phase gross mass, is triggered
The quality of agent benzoyl peroxide is 0.8% (m/m) of organic phase gross mass, and the quality of pore-foaming agent toluene is organic phase gross mass
50% (m/m), by configured it is organic be added to flask, 20 DEG C are stirred 24 hours, and mixing speed is 200 revs/min, is made molten
Swollen ratio is 55；Then heat up 80 DEG C of reactions, 250 revs/min of mixing speed, and in 48 hours reaction time, isolated polymer is micro-
Ball, pore-foaming agent was removed by polymer microballoon with toluene surname extraction 48 hours, was then cleaned with water, ethanol, obtain particle diameter 6~
10 μm of polystyrene-divinylbenzene microspheres.
3rd, with first alcohol and water (v/v=90:10) as mobile phase, flow velocity is 1mL/min, photodiode array detector
Separate a variety of benzene homologues.As a result brief description of the drawings is seen.
Embodiment 1：The preparation of the styrene-divinylbenzene polymer filler of doping carboxylated Nano diamond, its step
For：
1st, the synthesis of monodisperse polystyrene seed：The ethanol water of addition 90%, adds stabilizer in flask
Polyvinylpyrrolidone, 80 DEG C of warming-in-water is then respectively adding styrene monomer and initiator azodiisobutyronitrile, and stirring is anti-
Answer 24 hours.Wherein the quality of monomer styrene is 25% (m/m) of ethanol water quality, stabilizer polyvinylpyrrolidone
Quality is 1.6% (m/v) of ethanol water volume, and initiator azodiisobutyronitrile quality is monomer styrene quality
2.2% (m/m), reaction medium is 90% ethanol water, and mixing speed obtains particle diameter at 300 revs/min, after filtration washing and is
2 μm of polystyrene seed.
2nd, the configuration concentrated sulfuric acid and concentrated nitric acid volume ratio are 3:1 mix acid liquor, adds Nano diamond, is warming up to 100 DEG C
Reaction 12 hours, filters and is washed with deionized water only, obtain carboxylated Nano diamond.Take the polystyrene seed in step 1
Mix, stirred 24 hours at 20 DEG C in flask with dibutyl phthalate, mixing speed is 200 revs/min, wherein polyphenyl
The mass ratio of ethene seed and dibutyl phthalate is 2:4；Configuring monomer styrene quality in organic phase, the organic phase is
The mass ratio of 14% (m/m) of organic phase gross mass, cross-linker divinylbenzene and styrene is 2：1, carboxylated nanometer Buddha's warrior attendant
The quality of stone is the 0.33% of monomer and crosslinking agent gross mass, and the quality of emulsifier sodium lauryl sulfate is organic phase gross mass
2.5% (m/m), the quality of stabilizer polyvinyl alcohol is 1.5% (m/m) of organic phase gross mass, initiator benzoyl peroxide first
The quality of acyl is 0.8% (m/m) of organic phase gross mass, and the quality of pore-foaming agent toluene is 50% (m/m) of organic phase gross mass,
By configured it is organic be added to flask, 20 DEG C are stirred 24 hours, and mixing speed is 250 revs/min, and it is 55 to make swelling ratio；So
Heat up 80 DEG C of reactions, 250 revs/min of mixing speed, 48 hours reaction time, isolated polymer microballoon, by polymer afterwards
Microballoon removes pore-foaming agent in 48 hours with toluene surname extraction, is then cleaned with water, ethanol, obtains particle diameter in 6~10 μm of polyphenyl second
Alkene-divinylbenzene microspheres.
3rd, with first alcohol and water (v/v=90:10) as mobile phase, flow velocity is 1mL/min, photodiode array detector
Separate a variety of benzene homologues.As a result brief description of the drawings is seen.
Embodiment 2
1st, the step of reference implementation example 1, first passes through emulsion dispersion polymerization synthesis 2 μm of monodisperse polystyrene kinds of particle diameter
Son, the mass concentration of styrene monomer is 25%, and stabilizer polyvinylpyrrolidone feeds intake with the mixed solution of second alcohol and water
Than for 1.6% (m/v), initiator azodiisobutyronitrile quality is the 2.2% of monomer mass, using 90% ethanol water for Jie
Matter, 80 DEG C of reaction temperature, mixing speed is in 300 revs/min, 24 hours reaction time；
2nd, the configuration concentrated sulfuric acid and concentrated nitric acid volume ratio are 3:1 mix acid liquor, adds Nano diamond, is warming up to 100 DEG C
Reaction 12 hours, filters and is washed with deionized water only, obtain carboxylated Nano diamond.Take the polystyrene seed in step 1
Mix, stirred 24 hours at 20 DEG C in flask with dibutyl phthalate, mixing speed is 200 revs/min, wherein polyphenyl
The mass ratio of ethene seed and dibutyl phthalate is 2:4；Configuring monomer styrene quality in organic phase, the organic phase is
The mass ratio of 14% (m/m) of organic phase gross mass, cross-linker divinylbenzene and styrene is 2：1, carboxylated nanometer Buddha's warrior attendant
The quality of stone is the 1.0% of monomer and crosslinking agent gross mass, and the quality of emulsifier sodium lauryl sulfate is organic phase gross mass
2.5% (m/m), the quality of stabilizer polyvinyl alcohol is 1.5% (m/m) of organic phase gross mass, initiator benzoyl peroxide first
The quality of acyl is 0.8% (m/m) of organic phase gross mass, and the quality of pore-foaming agent toluene is 50% (m/m) of organic phase gross mass,
By configured it is organic be added to flask, 20 DEG C are stirred 24 hours, and mixing speed is 250 revs/min, and it is 55 to make swelling ratio；So
After be warming up to 80 DEG C of reactions, 250 revs/min of mixing speed, 48 hours reaction time, isolated polymer microballoon will polymerize
Thing microballoon removes pore-foaming agent in 48 hours with toluene surname extraction, is then cleaned with water, ethanol, obtains particle diameter in 6~10 μm of polyphenyl
Ethene-divinylbenzene microspheres.
3rd, with first alcohol and water (v/v=90:10) as mobile phase, flow velocity is 1mL/min, photodiode array detector
Separate a variety of benzene homologues.As a result brief description of the drawings is seen.
Embodiment 3：Chromatographic performance is tested
Instrument：The liquid chromatographs of Waters 1525, the photodiode array detectors of Waters 2998
Sample：Benzoic acid, 1,4- hydroquinones, benzaldehyde, phenol, toluene, P-hydroxybenzoic acid, bisphenol-A, tert-butyl benzene
Phenol (being that analysis is pure)
Mobile phase：First alcohol and water
Splitter：Self-made fill is loaded on 4 × 120mm stainless steel tube
Flow velocity：1mL/min
Wavelength：280nm
Chromatogram is referring to Fig. 3,4,5,6.
Fig. 1 is the scanning electron microscope (SEM) photograph of the polystyrene-divinylbenzene microspheres of dopen Nano diamond prepared by embodiment 2
(2000 times of amplification), by the observation to scanning electron microscope (SEM) photograph, it can be found that the grain of the base ball of the polystyrene-divinylbenzene of synthesis
Footpath is distributed very narrow and particle size range between 6-9 μm, and synthesized base ball is uniformly high, without being classified and being sieved.
Fig. 2 illustrates that diamond enters inside polymer microballoon, and a nanometer Buddha's warrior attendant is observed that by the contrast of Fig. 3,4,5,6
The doping of stone is greatly improved to separating effect, and Fig. 2 and Fig. 3 contrast can be found that four kinds of aldehydes matters in dopen Nano gold
Separating degree and the symmetry at peak are substantially better than the filler for the Nano diamond that undopes after hard rock.Fig. 6 and Fig. 5 compare it can be found that figure
6 kinds of analytes do not have conditions of streaking substantially, and the chromatographic column for being generally speaking doped with Nano diamond not only shortens analysis time,
Peak type is improved, separating degree increases, and energy quick separating aldehydes matter, the need of actual analysis can be widely used in
Will.
Embodiment 4：Chromatographic column pressure test
Instrument：The liquid chromatographs of Waters 1525
Splitter：Be respectively provided with embodiment it is 2-in-1 into doping carboxylated Nano diamond polystyrene divinyl benzene it is micro-
4 × 120mm of the polystyrene divinyl benzene microballoon of ball and the Nano diamond that undopes of comparative example synthesis stainless steel tube
Mobile phase：Water
Method of testing：Using water as mobile phase, gradually increase flow velocity and record the change of pressure, it is as a result shown in Figure 7.
Fig. 7 experimental data shows that the pressure that the polystyrene divinyl benzene microballoon for the Nano diamond that undopes is born exists
When within 3000psi, flow velocity and pressure are linear to be increased, and pressure rises suddenly more than 3000psi rear pillars pressure, illustrate filler by
Destruction, and the pressure of the polystyrene divinyl benzene microballoon for the carboxylated Nano diamond that adulterates increases with flow velocity increase is linear,
Do not occur the phenomenon (instrument bears pressure for 4000psi) that pressure rises sharply in the range of 3800psi, illustrate carboxylated of adulterating
The polystyrene divinyl benzene microballoon mechanical performance of Nano diamond is stronger.
Claims (10)
1. a kind of preparation method of the organic polymer chromatograph packing material of dopen Nano diamond, comprises the following steps：
(1) monodispersed linear polystyrene seed microballoon of the particle diameter between 1~3 μm is prepared；
(2) carboxylated Nano diamond is prepared；
(3) mixing dibutyl phthalate with polystyrene seed microballoon activates polystyrene seed microballoon, then adds
Enter monomer styrene, crosslinking agent divinylbenzene, carboxylated Nano diamond, emulsifying agent dodecyl sodium sulfate, the poly- second of stabilizer
Enol, initiator benzoyl peroxide and pore-foaming agent toluene, are sufficiently stirred for making polystyrene seed microspheres swell, and then heating is drawn
Bill body polymerize, and fully removes pore-foaming agent through surname extraction after polymerization, finally scrubbed to obtain particle diameter between 6~10 μm
The organic polymer chromatograph packing material of dopen Nano diamond.
2. preparation method as claimed in claim 1, it is characterised in that：Step (1) using dispersion copolymerization method prepare particle diameter 1~
Monodispersed linear polystyrene seed microballoon between 3 μm, specifically implements in accordance with the following steps：Using styrene as monomer, gather
Vinylpyrrolidone is stabilizer, and azodiisobutyronitrile is initiator, and single point is generated by radical polymerization in reaction medium
Scattered linear polystyrene seed microballoon, seed particle size is between 1-3 μm, and uniform particle sizes are without classification；The reaction medium is
The mixed solution of absolute ethyl alcohol or second alcohol and water；
Wherein, the quality of styrene monomer is the 5~30% of reaction medium quality, and stabilizer polyvinylpyrrolidone is situated between with reaction
The rate of charge of matter is 0.5~4g：100mL, initiator azodiisobutyronitrile consumption is the 1~5% of monomer mass, second alcohol and water
The volumetric concentration of ethanol is more than 75% in mixed solution.
3. preparation method as claimed in claim 2, it is characterised in that：In step (1), polymeric reaction temperature is 40~85 DEG C,
Mixing speed is at 100~400 revs/min, and the reaction time is 8~24 hours.
4. the preparation method as described in one of claims 1 to 3, it is characterised in that：In step (2), described carboxylated nanometer
Diamond is to handle Nano diamond with the mixed liquor of the concentrated sulfuric acid and concentrated nitric acid and obtain；The mixing of the concentrated sulfuric acid and concentrated nitric acid
The volume ratio of the concentrated sulfuric acid and concentrated nitric acid is between 2~4 in liquid.
5. preparation method as claimed in claim 4, it is characterised in that：In step (2), described carboxylated Nano diamond leads to
Following method is crossed to prepare：Nano diamond is added in the mixed liquor of the concentrated sulfuric acid and concentrated nitric acid, is reacted under the conditions of 80~140 DEG C
6~12 hours, that is, obtain carboxylated Nano diamond.
6. the preparation method as described in one of claims 1 to 3 or 5, it is characterised in that：In step (3), the fourth of phthalic acid two
The mass ratio of ester and polystyrene seed microballoon is between 2~5, and activation temperature is room temperature, and soak time is 12~24 hours.
7. the preparation method as described in one of claims 1 to 3 or 5, it is characterised in that：In step (3), monomer styrene quality
For the 10~20% of organic phase gross mass, the mass ratio of cross-linker divinylbenzene and styrene is between 2~3, and carboxylated is received
The quality of rice diamond accounts for the 0.1~2% of monomer styrene quality, and it is total that the quality of emulsifying agent dodecyl sodium sulfate accounts for organic phase
The 2~4% of quality, the quality of stabilizer polyvinyl alcohol accounts for the 0.5~5% of organic phase gross mass, initiator benzoyl peroxide
Quality account for the 0.4~6% of monomer styrene quality, the quality of pore-foaming agent toluene accounts for the 20~70% of organic phase gross mass；Institute
The organic phase stated by monomer styrene, crosslinking agent divinylbenzene, emulsifying agent dodecyl sodium sulfate, stabilizer polyvinyl alcohol, draw
Send out agent benzoyl peroxide and pore-foaming agent toluene composition.
8. preparation method as claimed in claim 7, it is characterised in that：In step (3), the quality of carboxylated Nano diamond is accounted for
The 0.3~1% of monomer styrene quality.
9. preparation method as claimed in claim 7, it is characterised in that：In step (3), it is swelled by the way that realization is stirred at room temperature, stirs
It is 100~300 revs/min to mix speed, and mixing time is 12~24 hours, and it is 10~70 times to make swelling ratio；
Polymerization is carried out under agitation, and reaction temperature is 60~85 DEG C, and mixing speed is 100~300 revs/min, and the reaction time is
12~48 hours.
10. preparation method as claimed in claim 9, it is characterised in that：In step (3), washing reagent is second alcohol and water.
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