CN104492397B - A kind of for carboxyl Magnetic Polystyrene Microsphere composite reducing ammonia burst size in cigarette smoke and its preparation method and application - Google Patents
A kind of for carboxyl Magnetic Polystyrene Microsphere composite reducing ammonia burst size in cigarette smoke and its preparation method and application Download PDFInfo
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- CN104492397B CN104492397B CN201410766405.6A CN201410766405A CN104492397B CN 104492397 B CN104492397 B CN 104492397B CN 201410766405 A CN201410766405 A CN 201410766405A CN 104492397 B CN104492397 B CN 104492397B
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
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- B01J20/261—Synthetic macromolecular compounds obtained by reactions only involving carbon to carbon unsaturated bonds
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- A—HUMAN NECESSITIES
- A24—TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
- A24D—CIGARS; CIGARETTES; TOBACCO SMOKE FILTERS; MOUTHPIECES FOR CIGARS OR CIGARETTES; MANUFACTURE OF TOBACCO SMOKE FILTERS OR MOUTHPIECES
- A24D3/00—Tobacco smoke filters, e.g. filter-tips, filtering inserts; Filters specially adapted for simulated smoking devices; Mouthpieces for cigars or cigarettes
- A24D3/06—Use of materials for tobacco smoke filters
- A24D3/14—Use of materials for tobacco smoke filters of organic materials as additive
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- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
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- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
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Abstract
The present invention relates to a kind of carboxyl Magnetic Polystyrene Microsphere composite for reducing ammonia burst size in cigarette smoke, for the hollow ball structure of porous surface, by carboxyl polystyrene polymeric microsphere and nanometer Fe3O4Self assembly forms, described nanometer Fe3O4Self assembly is compounded in the surface of carboxyl polystyrene polymeric microsphere；Add this carboxyl polystyrene magnetic macromolecular microsphere interpolation material to cigarette filter rod, it is possible to the burst size of ammonia in selectivity reducing cigarette main flume, effective percentage is up to 23.5 more than %.
Description
Technical field
The present invention relates to a kind of carboxyl Magnetic Polystyrene Microsphere composite for reducing ammonia burst size in cigarette smoke and
Preparation method and application, belong to Harm reduction techniques and add Material Field.
Background technology
Ammonia is the precursors such as one of main nuisance in cigarette smoke, mainly protein, aminoacid, nitrate and ammonium salt
Material is produced by burning or thermal cracking mode during cigarette burning.Ammonia not only affects the sucking quality of Medicated cigarette and also can sting
Swashing vision and the respiratory system of human body, blood ammonia increases cranial nerve histologic lesion the most obvious.Therefore reduce in cigarette mainstream flue gas
The content of ammonia is to improving cigarette quality, and raising is sucked safety and had great importance.
The most less as the research of selectivity unique objects thing using reducing ammonia of main stream smoke of cigarette the most both at home and abroad.Mainly have logical
Cross the means of improvement Cigarette processing technique such as microwave treatment or electron beam/x-ray irradiation to reduce containing of ammonia in tobacco shred or Nicotiana tabacum L.
Amount, the most also has and adds the additive reductions such as active component protoporphyrin compound, cross-linked esterification rice porous starch in filter stick
Ammonia content in main flume, but these method preparation process are loaded down with trivial details, control severe reaction conditions, industrial applications difficulty
Bigger.
Magnetic macromolecular microsphere refers to internal super containing magnetic metal or metal-oxide (ferrum, cobalt, nickel and oxide thereof)
Fine powder and there is the polymer microsphere of magnetic response.It is a kind of novel functional high molecule material, not only has macromolecule
The feature of microsphere and there is magnetic response.Can reach under the effect of externally-applied magnetic field with the immobilized medicine of magnetic macromolecular microsphere
Strengthening the purpose of targeted therapy, carry out graft copolymerization by styrene and acrylic acid, the functional groups that surface has can be with spy
Fixed nuisance carries out acting on thus reduces the effect of nuisance.
The carboxyl contained in carboxyl polystyrene magnetic macromolecular microsphere can and ammonia between there is stronger chemical action, therefore carry
The magnetic macromolecular microsphere alternative having carboxy functional group reduces the burst size of ammonia in flue gas, there is presently no about this side
The research report in face and patent.
Summary of the invention
It is an object of the invention to provide a kind of carboxyl Magnetic Polystyrene Microsphere for reducing ammonia burst size in cigarette smoke multiple
Condensation material and its preparation method and application, is obtained by the styrene emulsion self assembly of magnetic material with high molecular graft acrylic acid
To a kind of carboxyl Magnetic Polystyrene Microsphere with carboxy functional group.This materials application can be had in cigarette filter rod
Effect reduces the harmful substance ammonia in cigarette smoke, and releasing content of coke tar is basically unchanged, it is achieved thereby that selectivity reducing cigarette cigarette
The purpose of ammonia burst size in gas.
The present invention is achieved by the following technical solutions:
A kind of carboxyl Magnetic Polystyrene Microsphere composite for reducing ammonia burst size in cigarette smoke, for porous surface
Hollow ball structure, by carboxyl polystyrene polymeric microsphere and nanometer Fe3O4Self assembly forms, described nanometer Fe3O4From group
Dress is compounded in the surface of carboxyl polystyrene polymeric microsphere.
Preferably, a diameter of 50-150 μm of described carboxyl polystyrene polymeric microsphere.
The present invention further provides described for reducing the carboxyl Magnetic Polystyrene Microsphere composite wood of ammonia burst size in cigarette smoke
The preparation method of material, comprises the following steps:
Step (1): under inert atmosphere protection, in aqueous solvent, is polymerized monomer styrene and acrylic acid, dispersant and draws
Send out agent and prepare carboxyl polystyrene polymeric microsphere by suspension polymerisation；
Preferably, described styrene and acrylic acid mol ratio are 1-10:1.
Preferably, the dispersant of described suspension polymerisation is the combination of dodecylbenzene sodium sulfonate and PEG4000, the two mass ratio
For 1:1.5-4.
Preferably, described dispersant is 5-15:40-150 with the mass ratio being polymerized monomer total amount.
Preferably, the initiator of described suspension polymerisation is selected from azodiisobutyronitrile (AIBN), dibenzoyl peroxide (BPO).
Preferably, described initiator and the mass ratio 1-2:10-60 being polymerized monomer total amount.
Preferably, described aqueous solvent and the mass ratio 5-10:1 being polymerized monomer total amount.
Preferably, first the aqueous solution comprising styrene and acroleic acid polymerization monomer is heated to 60-70 DEG C, then is added dropwise over drawing
Send out agent, then heat to 70-85 DEG C and carry out suspension polymerization 8-20 hour.Because only reaching uniform temperature, cause
The addition competence exertion effect of agent.
Suspension polymerisation terminates, reaction mixture after cooling, filter, wash to remove the complete monomer of unreacted, initiator and
The materials such as dispersant obtain pure carboxyl polystyrene polymeric microsphere.
Step (2): under oxygen free condition, in aqueous solvent, ferrous salt and weak base generate hydroxide by heating reflux reaction
The blackish green precipitation of ferrum；Dropping oxidant carries out being oxidizing to blackish green precipitation and is fully converted to black precipitate the most several times, then
Continue to be heated to reflux generating nanometer Fe3O4；
Preferably, by the way of being passed through noble gas in aqueous solution, drive the oxygen dissolved in reaction system away, form anaerobic
Condition.
Preferably, described ferrous salt is selected from ferrous sulfate, Ferrous ammonium sulfate.
Preferably, described weak base is selected from carbamide and organic amine；Described organic amine can be hexamethylenetetramine.
Described carbamide and organic amine can the most slowly discharge hydroxyl, contribute to controlling ferrous ion and hydroxyl
Speed in conjunction with precipitation.
Preferably, the ratio 1-2:0.5-1 of the amount of the material of described weak base and ferrous salt.
Course of reaction, the addition of aqueous solvent there is no the biggest impact, therefore, can add according to the size of real reaction container
Appropriate water, and ensure that reacting substance therein is completely dissolved.
Preferably, described ferrous salt and weak base, in the presence of Complexing/Dispersing Agent, generate hydroxide by heating reflux reaction
Ferrous blackish green precipitation.
Preferably, described Complexing/Dispersing Agent is selected from ethylene glycol, polyethylene glycol 200, dodecylbenzene sodium sulfonate.
The existence effect of described Complexing/Dispersing Agent is the concentration controlling to be hydrated ferrous ion in solution, slows down and reacts with hydroxyl
Speed；Strict demand be there is no for addition.
Preferably, described oxidant is selected from hydrogen peroxide, sodium hypochlorite etc..
Preferably, the addition of described oxidant determines according to making blackish green precipitation be fully converted to black precipitate standard.
Preferably, heat by the way of slowly intensification, the reaction system comprising ferrous salt and weak base be heated to 85-90 DEG C,
Reflux and within 1-1.5 hour, form the blackish green precipitation of ferrous hydroxide.
Preferably, after adding oxidant, then the nanometer Fe being heated to reflux described in generation in 3-4 hour at 85-90 DEG C3O4。
Generate nanometer Fe3O4Reaction terminate after, reaction mixture is cooled to room temperature, then filter and be washed with deionized to
Neutrality, seals up for safekeeping in water standby then.
Step (3): under inert atmosphere conditions, carboxyl polystyrene polymeric microsphere step (1) prepared is uniform with water
It is mixed to form the aqueous solution of carboxyl polystyrene polymeric microsphere, is slowly added into the nanometer Fe that step (2) prepares3O4With water
Mixed liquor in, stand after stirring and i.e. obtain black carboxyl polystyrene magnetic macromolecular microsphere.
Preferably, in the aqueous solution of described carboxyl polystyrene polymeric microsphere, the content of carboxyl polystyrene polymeric microsphere
For 1-5wt%.
Preferably, nanometer Fe3O4With nanometer Fe in the mixed liquor of water3O4Content be 0.1-0.5wt%.
Preferably, described nanometer Fe3O4It is 1～6 with the pH of the mixed liquor of water.
Preferably, described carboxyl polystyrene polymeric microsphere and nanometer Fe3O4Mass ratio be 5-10:0.5-2.
Preferably, described stirring is for be first stirred vigorously 10-60 minute, and then the speed of stirring 150～500rpm stirs 1-2 hour,
Stand 5-10 hour the most again and both obtain described black carboxyl polystyrene magnetic macromolecular microsphere.The effect of described stirring
It is to make both mix homogeneously so that it is be easy to be fully contacted, beneficially being smoothed out of self assembly.
The present invention open reduction ammonia of main stream smoke of cigarette that is used as by described carboxyl polystyrene magnetic macromolecular microsphere further is released
The application adding material high-volume, described carboxyl polystyrene magnetic macromolecular microsphere adds material and can add in cigarette filter rod
Use.The addition of magnetic macromolecular microsphere material is interpolation 3-5mg in every filter tip filter stick.
Further, described cigarette filter rod is the binary compound filter candle being composited by two sections of common cellulose acetate filter rods；Described
Carboxyl polystyrene magnetic macromolecular microsphere is dispersed on the cross section of two sections of filter sticks and ensures through flue gas and add filling of material
Tap is touched, it is possible to the burst size of ammonia in selectivity reducing cigarette main flume, effective percentage is up to more than 23.5%.
Technique effect and the advantage of the present invention are:
1. the carboxyl polystyrene magnetic macromolecular microsphere of the present invention is not medicine ball but the hollow ball of porous surface, energy completely
Material surface and inside is enough made to be fully contacted with flue gas, beneficially flue gas quick transmission in the material.
2., containing specific functional group carboxyl in invention material, with the harmful substance ammonia in flue gas, strong change can directly occur
Effect thus improve adsorption efficiency to ammonia.
Accompanying drawing explanation
Fig. 1 is the FT-IR figure of the carboxyl polystyrene magnetic macromolecular microsphere that embodiment 1 prepares, and uses Brooker company of Germany
VERTEX 7 type characterizes the characteristic group of material；
Fig. 2 is the scanning electron microscope (SEM) photograph of the carboxyl polystyrene magnetic macromolecular microsphere that embodiment 1 prepares, and uses Holland to fly to receive desk-top sweeping
Retouch Electronic Speculum Phenom prox type and observe the pattern of material.
Detailed description of the invention
Below by way of specific instantiation, technical scheme is described.Should be understood that one or more sides that the present invention mentions
Method step do not repel there is also before and after described combination step additive method step or between these steps specifically mentioned also
May be inserted into additive method step；Should also be understood that these embodiments are merely to illustrate the present invention rather than limit the model of the present invention
Enclose.And, except as otherwise noted, the numbering of various method steps is only the convenient tool differentiating various method steps, rather than for limit
The ordering of various method steps or the restriction enforceable scope of the present invention, being altered or modified of its relativeness, becoming without essence
In the case of more technology contents, when being also considered as the enforceable category of the present invention.
Embodiment 1
Nanometer Fe3O4Synthesis: weighing 139.01g green vitriol, 60.06g carbamide is dissolved in 500ml deionized water
In, stirring is to being completely dissolved formation clear transparent solutions, then adds 50ml ethylene glycol under agitation in system, mixed
Close uniformly, in system, be passed through high pure nitrogen drive the oxygen dissolved in solution away.The most slowly heat up, it is seen that the color of solution
Ultimately produced blackish green precipitation by light green gradually becoming cloudy, reflux 1 hour under the conditions of 90 DEG C, now drip several times in system
Add 30% hydrogen peroxide to blackish green precipitation and be fully converted to black precipitate, be then further continued for refluxing 3 hours.Reacted system
It is cooled to room temperature, filters with deionized water afterwards and be washed to neutrality, transfer to be marked with sealing in the beaker of deionized water and preserve standby
With.
The synthesis of carboxyl polystyrene magnetic macromolecular microsphere: in the case of logical nitrogen is protected, depend in 500mL three-necked bottle
Aqueous solution (including PEG 4000 about 1g), 70ml water and the 0.3g dodecane of the PEG 4000 of secondary addition 10ml 10wt%
Base benzene sulfonic acid sodium salt, high-speed stirred is also heated to 65 DEG C, is added dropwise over 10ml styrene, 2ml acrylic acid and 1.0g mistake
The mixed liquor of oxidation dibenzoyl, continues to be warmed up to 85 DEG C, constant 8 hours, cooled and filtered, washing, the most anti-to remove
The things such as the monomer answered, initiator.
The synthesis of carboxyl polystyrene magnetic macromolecular microsphere: by the dilute hydrochloric acid regulation nanometer Fe of 1:43O4Mixed liquor with water
PH is the acid-base value regulating solution in the range of 1～6.Take aforementioned prepared carboxyl polystyrene polymeric microsphere 2g again to add water
It is diluted to 50mL, under logical nitrogen is protected, is slowly added into 130g nanometer Fe3O4Mixed liquor (nanometer Fe with water3O4Content
In 0.3wt%), first it is stirred vigorously 20 minutes, then stirs 1 hour with the speed of stirring of 150～500rpm, then stand 7 hours
Obtain atrous product (diameter 50-150 μm).
Fig. 1 is the infrared spectrogram of carboxyl polystyrene magnetic macromolecular microsphere, 1450cm in figure-1、1491cm-1、
1601cm-1、3024cm-1、754cm-1And 697cm-1Absworption peak should belong to cinnamic feature stretching vibration absorb
Peak.1728cm-1For the strong absworption peak of C=O stretching vibration, 906cm-1For C-O stretching vibration absworption peak, this high score is described
Sub-microsphere contains carboxyl, shows that acrylic acid is by own combined in polymer microsphere with styrene copolymerized.
Fig. 2 is the scanning electron microscope (SEM) photograph of gained carboxyl polystyrene magnetic macromolecular microsphere, it can be seen that magnetic Nano
Fe3O4Granule and carboxyl polystyrene microsphere define Fe by electrostatic self-assembled effect3O4The microsphere of cladding, these little magnetic
Property microsphere aggregation body is assembled into the hollow ball of surface 50-150 with holes μm further.
Electronegative owing to the polystyrene polymeric microsphere surface of preparation contains hydrophilic group carboxyl, then with at persalt
The nanometer Fe of reason positively charged nanometer3O4Mixing, both electrostatic interaction self assemblies are Fe3O4The complex microsphere of cladding.Institute
Actually become by a lot of composite magnetic microsphere aggregation with this microsphere seen from figure.
Carboxyl Magnetic Polystyrene Microsphere embodiment 1 prepared props up with 3mg/ and adds to by two sections of common cellulose acetate filter rods again
In the binary compound filter candle filter tip closed, microsphere is dispersed on the cross section of two sections of filter sticks, and on online smoking machine, suction (is taken out
Inhale capacity 35ml/ minute), measure the ammonia burst size in cigarette mainstream flue gas according to YC/T245-2008, and be not added with material
The Medicated cigarette of material compares, and the results are shown in Table 1.
Table 1 magnetic macromolecular microsphere reduces the result of flue gas ammonia burst size
The above results shows, material of the present invention may be used for the production of composite filter tip Medicated cigarette, and carboxyl Magnetic Polystyrene Microsphere exists
Interpolation in filter tip does not make the tar generation significant change of Medicated cigarette, and this filter tip adds material to smoking property of cigarette quality without bad shadow
Ringing, this material shows selectivity in reducing cigarette smoke and reduces the burst size of ammonia in main flume in the evaluation of nuisance
20.92%.
Embodiment 2
Nanometer Fe3O4Synthesis: weigh 13.90g green vitriol and be dissolved in 250ml deionized water, in system
It is passed through high pure nitrogen and drives the oxygen dissolved in solution away, be subsequently adding the aqueous solution 100ml containing 28g hexamethylenetetramine, molten
Liquid immediately becomes bottle green, then is added thereto to 2g polyethylene glycol 200, and stirring slowly heated up after half an hour, it is seen that solution
Color gradually becomes cloudy and ultimately produces blackish green precipitation, refluxes 1.5 hours, then drip several times in system under the conditions of 85 DEG C
Aqueous sodium hypochlorite solution to blackish green precipitation is fully converted to black precipitate, is then further continued for refluxing 4 hours.It is cooled to room temperature,
Afterwards with deionized water filtration washing to neutral, transfer to be marked with sealing in the beaker of deionized water and save backup.
The synthesis of carboxyl polystyrene magnetic macromolecular microsphere: in the case of logical nitrogen is protected toward in 250ml three-necked bottle successively
Add aqueous solution (including PEG 4000 about 0.5g), 25ml water and the 0.3g dodecyl of 5ml 10wt%PEG 4000
Benzene sulfonic acid sodium salt, high-speed stirred also heats, and when being warming up to 65 DEG C, is added dropwise over mixed liquor (the benzene second of monomer, water and initiator
Alkene 7ml, acrylic acid 2ml, 0.3g dibenzoyl peroxide and 25ml water also stir), continue to be warmed up to 85 DEG C,
After constant 20 hours, natural cooling, prepare carboxyl polystyrene polymeric microsphere.
The synthesis of carboxyl polystyrene magnetic macromolecular microsphere: by the dilute hydrochloric acid regulation nanometer Fe of 1:43O4Mixed liquor, at pH
Value is the acid-base value regulating solution in the range of 1～6.Take aforementioned prepared carboxyl polystyrene polymeric microsphere 2g again and add water dilute
It is interpreted into 50mL, under logical nitrogen is protected, is slowly added into 20g nanometer Fe3O4Mixed liquor (nanometer Fe with water3O4Content 0.5wt%)
In, first it is stirred vigorously 30 minutes, then stirs 2 hours with the speed of stirring of 150～500rpm, then stand 7 hours and obtain atrous
Product (diameter 50-150 μm).
Carboxyl Magnetic Polystyrene Microsphere embodiment 2 prepared props up with 3mg/ and adds to by two sections of common cellulose acetate filter rods again
In the binary compound filter candle filter tip closed, microsphere is dispersed on the cross section of two sections of filter sticks, and on online smoking machine, suction (is taken out
Inhale capacity 35ml/ minute), measure the ammonia burst size in cigarette mainstream flue gas according to YC/T245-2008, and be not added with material
The Medicated cigarette of material compares, and the results are shown in Table 2.
Table 2 magnetic macromolecular microsphere reduces the result of flue gas ammonia burst size
The above results shows, material of the present invention may be used for the production of composite filter tip Medicated cigarette, and carboxyl Magnetic Polystyrene Microsphere exists
Interpolation in filter tip does not make the tar generation significant change of Medicated cigarette, and this filter tip adds material to smoking property of cigarette quality without bad shadow
Ringing, this material shows selectivity in reducing cigarette smoke and reduces the burst size of ammonia in main flume in the evaluation of nuisance
23.50%.
Claims (14)
1., for reducing a preparation method for the carboxyl Magnetic Polystyrene Microsphere composite of ammonia burst size in cigarette smoke, described composite is the hollow ball structure of porous surface, by carboxyl polystyrene polymeric microsphere and nanometer Fe3O4Self assembly forms, described nanometer Fe3O4Self assembly is compounded in the surface of carboxyl polystyrene polymeric microsphere, comprises the following steps:
Step (1): under inert atmosphere protection, in aqueous solvent, polymerization monomer styrene and acrylic acid, dispersant and initiator prepare carboxyl polystyrene polymeric microsphere by suspension polymerisation；Described styrene and acrylic acid mol ratio are 1-10:1, described dispersant is 5-15:40-150 with the mass ratio being polymerized monomer total amount, described initiator and the mass ratio 1-2:10-60 being polymerized monomer total amount, described aqueous solvent and the mass ratio 5-10:1 being polymerized monomer total amount；
Step (2): under oxygen free condition, in aqueous solvent, ferrous salt and weak base generate the blackish green precipitation of ferrous hydroxide by heating reflux reaction；Dropping oxidant carries out being oxidizing to blackish green precipitation and is fully converted to black precipitate the most several times, is further continued for being heated to reflux generating nanometer Fe3O4；
Step (3): under inert atmosphere conditions, carboxyl polystyrene polymeric microsphere step (1) prepared and water are uniformly mixed to form the aqueous solution of carboxyl polystyrene polymeric microsphere, are slowly added into the nanometer Fe that step (2) prepares3O4With in the mixed liquor of water, described nanometer Fe3O4It is 1～6 with the pH of the mixed liquor of water, stands after stirring and i.e. obtain black carboxyl polystyrene magnetic macromolecular microsphere, a diameter of 50-150 μm of described carboxyl polystyrene magnetic macromolecular microsphere.
2. preparation method as claimed in claim 1, it is characterised in that the dispersant of described suspension polymerisation is the combination of dodecylbenzene sodium sulfonate and PEG4000, and the two mass ratio is 1:1.5-4.
3. preparation method as claimed in claim 2, it is characterised in that the initiator of described suspension polymerisation is selected from azodiisobutyronitrile and dibenzoyl peroxide.
4. preparation method as claimed in claim 1, it is characterised in that step (1) also includes following characteristics:
First the aqueous solution comprising styrene and acroleic acid polymerization monomer is heated to 60-70 DEG C, then is added dropwise over initiator, then heat to 70-85 DEG C and carry out 8-20 hour prepared described carboxyl polystyrene polymeric microsphere of suspension polymerization.
5. preparation method as claimed in claim 1, it is characterized in that, step (1) described suspension polymerisation terminates, and reaction mixture is cooled, and the monomer, initiator and the dispersant material that then filter, wash removing unreacted complete obtain pure carboxyl polystyrene polymeric microsphere.
6. preparation method as claimed in claim 1, it is characterised in that in step (2), also includes any one in following characteristics or multinomial:
A () described ferrous salt is selected from ferrous sulfate and Ferrous ammonium sulfate；
B () described weak base is selected from organic amine；
C () described oxidant is selected from hydrogen peroxide and sodium hypochlorite；
D () drives the oxygen dissolved in reaction system by the way of being passed through noble gas in aqueous solution away, form oxygen free condition.
7. preparation method as claimed in claim 1, it is characterised in that in step (2), described ferrous salt and weak base, in the presence of Complexing/Dispersing Agent, generated the blackish green precipitation of ferrous hydroxide by heating reflux reaction.
8. preparation method as claimed in claim 7, it is characterised in that described Complexing/Dispersing Agent is selected from ethylene glycol, polyethylene glycol 200 and dodecylbenzene sodium sulfonate.
9. preparation method as claimed in claim 1, it is characterised in that in step (2), the mol ratio of described weak base and ferrous salt is 1-2:0.5-1.
10. preparation method as claimed in claim 1, it is characterized in that, in step (2), heat by the way of slowly intensification, the reaction system comprising ferrous salt and weak base is heated to 85-90 DEG C, refluxes and within 1-1.5 hour, form the blackish green precipitation of ferrous hydroxide；After adding oxidant, then the nanometer Fe being heated to reflux described in generation in 3-4 hour at 85-90 DEG C3O4。
11. preparation methoies as claimed in claim 1, it is characterised in that in step (2), generate nanometer Fe3O4After reaction terminates, reaction mixture is cooled to room temperature, then filters and is washed with deionized to neutrality, then sealing up for safekeeping in water standby.
12. preparation methoies as claimed in claim 1, it is characterised in that in step (3), also include any one in following characteristics or multinomial:
A, in the aqueous solution of () described carboxyl polystyrene polymeric microsphere, the content of carboxyl polystyrene polymeric microsphere is 1-5wt%；
(b) nanometer Fe3O4With nanometer Fe in the mixed liquor of water3O4Content be 0.1-0.5wt%；
(c) described nanometer Fe3O4It is 1～6 with the pH of the mixed liquor of water；
(d) described carboxyl polystyrene polymeric microsphere and nanometer Fe3O4Mass ratio be 5-10:0.5-2；
E () described stirring is for be first stirred vigorously 10-60 minute, then the speed of stirring 150～500rpm stirs 1-2 hour, stands and within 5-10 hour, i.e. obtains described black carboxyl polystyrene magnetic macromolecular microsphere.
Carboxyl Magnetic Polystyrene Microsphere composite prepared by 13. preparation methoies as claimed in claim 1 is for reducing the purposes of ammonia burst size in cigarette smoke.
14. purposes as claimed in claim 13, it is characterised in that described carboxyl Magnetic Polystyrene Microsphere composite is added on the cross section of two sections of filter sticks of acetate fiber binary compound filter candle；Every filter tip filter stick adds 3-5mg.
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| CN201410766405.6A CN104492397B (en) | 2014-12-11 | 2014-12-11 | A kind of for carboxyl Magnetic Polystyrene Microsphere composite reducing ammonia burst size in cigarette smoke and its preparation method and application |
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| CN112266770B (en) * | 2020-11-25 | 2022-02-01 | 甘肃烟草工业有限责任公司 | Beeswax/polystyrene composite phase change energy storage material and preparation method and application thereof |
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| CN102987559B (en) * | 2012-12-27 | 2014-05-14 | 安徽中烟工业有限责任公司 | Composite filter stick capable of selectively reducing releasing amount of harmful phenol in main stream smoke of cigarettes |
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