CN104262521A - Preparation method of styrene-divinylbenzene copolymer hydrophobic catalyst support - Google Patents
Preparation method of styrene-divinylbenzene copolymer hydrophobic catalyst support Download PDFInfo
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- CN104262521A CN104262521A CN201410449037.2A CN201410449037A CN104262521A CN 104262521 A CN104262521 A CN 104262521A CN 201410449037 A CN201410449037 A CN 201410449037A CN 104262521 A CN104262521 A CN 104262521A
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Abstract
The invention discloses a preparation method of a styrene-divinylbenzene copolymer hydrophobic catalyst support, which is characterized by comprising the following steps: adding deionized water, organic matter polyvinyl alcohol-1799, inorganic salt and sodium dodecyl benzene sulfonate into a reaction vessel, heating to 25-40 DEG C while stirring, adding a mixture of styrene, divinylbenzene, benzoperoxide, toluene, n-heptane and dichloroethane, heating to 70-90 DEG C, carrying out suspension polymerization reaction for 7-9 hours while stirring, and filtering; and washing the reaction solid with deionized water and anhydrous ethanol, extracting with acetone in a Soxhlet extractor for 12-48 hours, washing the solid with methanol and deionized water, drying, and screening to obtain the styrene-divinylbenzene copolymer hydrophobic catalyst support. The Pt/SDB hydrophobic catalyst prepared by using the product as the support has favorable use effect when being used for heavy water tritium extraction and wastewater detritiation.
Description
Technical field
The invention belongs to the preparation of organic high molecular compound, relate to the preparation method of styrene diethylene benzene copoly mer (being called for short SDB) hydrophobic catalyst carrier.Large stone (φ 2 ~ 5mm) styrene diethylene benzene copoly mer obtained with the present invention is Pt/SDB hydrophobic catalyst prepared by carrier, there is the resistance to mass transfer of minimizing bed, prevent liquid flooding, and improve the advantages such as fluid communication efficiency, be specially adapted to the through engineering approaches application of heavy water detritiation, waste water detritiation etc.
Background technology
Along with the continuous maturation of nuclear technique and developing rapidly of nuclear industry, tritium is as the nuclear matter of key, and its consumption increases day by day, and therefore, radio-protective and the safety of tritium are more and more important.The exploitation of fusion reactor, hybrid fusion-fission reactor and big area nuclear energy will be faced with the process problem containing tritium heavy water become increasingly conspicuous, greatly developing particularly due to the inland construction of nuclear power station, the solution containing HTO of greater amount (as gone up ton every year), has formed the operation of restriction inland Nuclear power plants and " bottleneck " of development.Consider from economy and secure context, all have employed hydrogen isotope catalyticing exchanging reaction, traditional inorganic hydrophilic catalyzer, as platinum/aluminium sesquioxide (Pt/Al to containing the process of tritium in HTO (heavy water)
2o
3), when being applied to hydrogen-water catalyticing exchanging reaction, run into liquid water and be easy to the problems such as poisoning, inactivation, and hydrophobic catalyst can accelerate the carrying out of hydrogen isotope catalyzed reaction ideally, thus hydrophobic catalyst has been the critical material that hydrogen-water liquid-phase catalysis exchanges.In prior art, the research of hydrophobic catalyst all concentrates on the catalyzer such as Pt/PTFE, Pt/C/PTFE and Pt/SDB.Adopt the hydrophobic catalyst that PTFE (tetrafluoroethylene) is carrier, still face catalytic stability problem.Pt/SDB has become the kind of current primary study and application, but mainly also there is following problem in the preparation method of prior art: SDB hydrophobic catalyst carrier hydrophobic stability is poor, the catalytic activity of SDB hydrophobic catalyst not enough and catalytic stability is poor, and catalyst particle size diameter is less than normal etc. not enough, through engineering approaches requirement can not be reached, be thus extremely necessary the preparation research carrying out Large stone (φ 2 ~ 5mm) SDB hydrophobic catalyst carrier.
Summary of the invention
Object of the present invention is intended to overcome deficiency of the prior art, a kind of preparation method of styrene diethylene benzene copoly mer hydrophobic catalyst carrier is provided, thus the method for provide a kind of suspension polymerization to prepare particle diameter is large, pore structure is controlled, ultimate compression strength is high, hydrophobicity is excellent styrene diethylene benzene copoly mer hydrophobic catalyst carrier.
Content of the present invention is: the preparation method of styrene diethylene benzene copoly mer hydrophobic catalyst carrier, it is characterized in that step is:
A, batching: get each component raw material by the mass ratio of deionized water 100 ~ 200 mass parts, organism 0.1 ~ 0.5 mass parts, inorganic salt 0.1 ~ 0.5 mass parts, Sodium dodecylbenzene sulfonate 0.01 ~ 0.06 mass parts, vinylbenzene 2 ~ 10 mass parts, Vinylstyrene 2 ~ 13 mass parts, benzoyl peroxide 0.02 ~ 0.6 mass parts, toluene 8 ~ 16 mass parts, normal heptane 6 ~ 13 mass parts and ethylene dichloride 5 ~ 12 mass parts;
Described organism can be any one in polyvinyl alcohol-1799, polyvinyl alcohol-2099, polyvinyl alcohol-2499, polyvinyl alcohol-2699, Natvosol, gelatin and Xylo-Mucine;
Described inorganic salt can be any one in calcium phosphate, magnesiumcarbonate, sodium-chlor and calcium phosphate powder;
B, prepare the crude product of styrene diethylene benzene copoly mer: by deionized water, organism, inorganic salt and Sodium dodecylbenzene sulfonate (being called for short SDBS) join in reaction vessel (such as: there-necked flask), 25 ~ 40 DEG C are heated under stirring, after solids (all) dissolves, the vinylbenzene will mixed again, Vinylstyrene, benzoyl peroxide, toluene, the mixture of normal heptane and ethylene dichloride joins in reaction vessel, being heated to temperature is 70 ~ 90 DEG C, suspension polymerization is carried out under stirring, (to sclerosis after reaction times 7 ~ 9h, after aging), filter, solids is the crude product of styrene diethylene benzene copoly mer,
C, prepare styrene diethylene benzene copoly mer hydrophobic catalyst carrier: the solids (i.e. the crude product of styrene diethylene benzene copoly mer) obtained after reaction is used deionized water, absolute ethanol washing, in turn to remove responseless vinylbenzene and the impurity such as divinylbenzene monomers and organism solubility dispersion agent; Use the acetone of solids quality 3 ~ 8 times of quality again by solids in apparatus,Soxhlet's (industrial adopt the existing equipment with identical function effect) after extracting 12 ~ 48h, filter, to remove the organic impuritys such as first benzene and heptane mixing pore-creating agent and ethylene dichloride, form pore structure, then solids is used methyl alcohol, deionized water wash in turn, pore structure is fixed; (the porous small ball shape after purification) solids is dry, screening again, i.e. obtained (Large stone of white) styrene diethylene benzene copoly mer (being called for short SDB) hydrophobic catalyst carrier.
In content of the present invention: the consumption mass ratio of organism described in step a and inorganic salt mass parts is preferably 1:1.
In content of the present invention: the consumption mass ratio of vinylbenzene described in step a and Vinylstyrene mass parts is preferably 1:1.3
In content of the present invention: the mass parts consumption of (initiator) described in step a benzoyl peroxide is preferably 0.1 ~ 0.6 mass parts.
In content of the present invention: under stirring described in step b, to carry out suspension polymerization be agitator speed is carry out suspension polymerization under the condition of 10 ~ 300rpm/min; Being preferably agitator speed is carry out suspension polymerization under the condition of 85 ~ 125rpm/min.
In content of the present invention: being heated to temperature described in step b is 70 ~ 90 DEG C; Being preferably and being heated to temperature is 80 ~ 85 DEG C.
In content of the present invention: solids described in step c is that solids uses deionized water, absolute ethanol washing 2 ~ 4 times in turn respectively with deionized water, absolute ethanol washing in turn, and the quality of each washing deionized water, dehydrated alcohol is 3 ~ 8 times of solids quality.
In content of the present invention: solids described in step c is that solids uses methyl alcohol, deionized water wash 2 ~ 4 times in turn respectively with methyl alcohol, deionized water wash in turn, and the quality of each washing deionized water, dehydrated alcohol is 3 ~ 8 times of solids quality.
In content of the present invention: dry described in step c, screening be by solids temperature be 50 ~ 60 DEG C, pressure dry 12 ~ 36h under being the condition of 0.1MPa, sieve again (crossing 2 ~ 5mm sieve), i.e. the Large stone styrene diethylene benzene copoly mer hydrophobic catalyst carrier of obtained white, particle diameter φ 2 ~ 5mm; The ratio of described Large stone can reach 35% ~ 40%.
In content of the present invention: described each component raw material of use first can carry out refinement treatment: the commercial styrene of purchase is carried out distillation before the use and refined, step is as follows: 1. join in the separating funnel of 1000mL by the vinylbenzene of 500mL (being called for short St) monomer, with the NaOH solution washing three times of 150mL5%; 2. repeatedly wash with deionized water until neutral (pH is 7 ~ 8), put into a little anhydrous MgSO
4namely dry to liquid clarification; 3. the vinylbenzene rectification under vacuum after above-mentioned drying, the cut after distillation is collected, for subsequent use.The still-process of Vinylstyrene (being called for short DVB) monomer is the same with styrene monomer.Benzoyl peroxide (being called for short BPO) adopts chloroform to be solvent, CH
3oH makes precipitation agent, utilizes recrystallizing and refining process etc.
Adopt the present invention, the specific surface area of obtained styrene diethylene benzene copoly mer hydrophobic catalyst carrier and pore volume (i.e. pore structure) see the following form with the relation of DVB (Vinylstyrene) consumption:
From in table, the consumption of the specific surface area of catalyzer and pore volume and DVB is proportionate, and mean pore size and DVB consumption are negative correlation; The increase of DVB concentration, be easier to obtain less micelle, their tight agglomeration are grown up, combining more densely causes the space of generation less, little hole number increases gradually, and thus make the SDB bead mean pore size finally obtained reduce, specific surface area and pore volume increase.In table, the mean pore size of SDB is distributed between 5.5 ~ 8.9nm, and PtCl
6 2-ionic radius r
pt4+(6) be 0.063nm; Thus the Pt that this ligancy is 6 is conducive to
4+enter in duct, and easily reach a few nano-scale subsequently through the Pt of reduction deposition.
Compared with prior art, the present invention has features and beneficial effect:
(1) the present invention is adopted, take vinylbenzene as monomer, Vinylstyrene is comonomer, linking agent, benzoyl peroxide is initiator, toluene+normal heptane is mixing pore-creating agent, and ethylene dichloride is binding agent, and organism polyvinyl alcohol-1799 grade is macromolecule dispersing agent, Sodium dodecylbenzene sulfonate is tensio-active agent, dispersion aids, and inorganic salt are inorganic dispersant; The synergy that the present invention utilizes inorganic salt and water-soluble polymers to make composite dispersing agent and anion surfactant to do between dispersion aids, prepare Large stone (φ 2 ~ 5mm) the porous SDB hydrophobic catalyst carrier of different crosslinking structure, Large stone ratio can reach 35% ~ 40%, that is adopt composite dispersing agent to be conducive to controlledly synthesis Large stone (φ 2 ~ 5mm) SDB hydrophobic catalyst carrier, and there is the ability of expanding production;
(2) adopt the present invention, adopt suspension polymerization (i.e. suspension crosslinking copolymerization) legal system for Large stone (φ 2 ~ 5mm) styrene diethylene benzene copoly mer hydrophobic catalyst carrier; Suspension polymerization is the effective ways preparing styrene-divinylbenzene bead.Monomer and pore-creating agent are mixed into uniform oil phase, initiator is added in oil phase, make it dissolve, finally oil phase is joined and dissolved in the aqueous phase of composite dispersing agent.Under stirring and composite dispersing agent effect, drop by constantly dispersion and combination, thus obtains relatively uniform bead.In reaction process, be constantly cross-linked with each other between molecular chain, the final multipolymer forming three-dimensional space net structure, this cross-linking copolymer molecular chain can not dissolve in oil phase, progressively separates out, is separated.Now, polymkeric substance is solid phase, and unreacted monomer and mixing pore-creating agent are liquid phase.After reaction terminates, obtain sphere polymers.Because mixing pore-creating agent remains among spheroid, during method removing pore-creating agent with solvent wash or extracting, just can form mutually through hole, make polymkeric substance have larger specific surface area and pore volume.
(3) suspension polymerization of the present invention's employing, there is simple and easy to do feature, especially composite dispersing agent and Sodium dodecylbenzene sulfonate is adopted to have better dispersion effect than single dispersion agent, be easy to obtain Large stone SDB, achieve the controlledly synthesis such as the specific surface area to carrier, aperture, ultimate compression strength; From in infrared spectrum, containing a large amount of suspended double bond in carrier, this suspended double bond is to the performance of SDB hydrophobic catalyst carrier, and the catalytic activity of Pt/SDB catalyzer and stability have important impact;
(4) adopt the present invention, the specific surface area of obtained styrene diethylene benzene copoly mer hydrophobic catalyst carrier is at 300 ~ 500m
2/ g, aperture 2 ~ 10nm, contact angle are greater than 100 °, ultimate compression strength 10 ~ 30N/ grain, heatproof be greater than 350 DEG C, the small ball's diameter 2 ~ 5mm; The Pt/SDB hydrophobic catalyst that the styrene diethylene benzene copoly mer obtained with the present invention is prepared for carrier, there is the resistance to mass transfer of minimizing bed, prevent liquid flooding, and improve the advantages such as fluid communication efficiency, for through engineering approaches application such as heavy water detritiation, waste water detritiations, catalytic efficiency is high, hydrophobic stability is excellent, can use by normal temperature, result of use is good;
(5) product preparation process of the present invention is simple, and operation is easy, easily operates, practical.
Accompanying drawing explanation
Fig. 1 is the FT-IR spectrogram of SDB (styrene diethylene benzene copoly mer) under different DVB (Vinylstyrene) consumption; As seen from the figure, 1640cm
-1the absorption peak at place corresponds to the stretching vibration of C=C key, 989cm
-1the absorption peak at place corresponds to the=outer formation vibration in the face of C-H key, and not this two characteristic peaks appearance in pure PS, and along with the increase of DVB and St mol ratio, the intensity of absorption peak obviously strengthens.Illustrate that Vinylstyrene does not have full entry polyreaction, cause the unreacted suspended double bond of part left behind, suspended double bond reserved and DVB consumption are proportionate;
Fig. 2 be under different DVB (Vinylstyrene) consumption SDB (styrene diethylene benzene copoly mer) room temperature to thermogravimetric (TG) curve of 800 DEG C; As seen from the figure, all samples before 300 DEG C all without mass loss; There is obvious weightlessness in pure PS, namely its molecular backbone chain starts to decompose fracture from 300 DEG C; Along with DVB consumption increase, the thermally-stabilised of SDB raises gradually, when DVB and St mol ratio is 1:5 ~ 1:1, SDB before 345 ~ 375 DEG C almost without weightlessness; Show that DVB consumption increases, degree of crosslinking is improved, the initial decomposition temperature of sample improves, and the resistance toheat of SDB obtains improvement in various degree;
Fig. 3 is the influence curve of DVB (Vinylstyrene) consumption to SDB (styrene diethylene benzene copoly mer) ultimate compression strength; Each sample is chosen 50 SDB beads respectively and is carried out intensity test, and get its mean value as final ultimate compression strength, result is shown in Fig. 3; As shown in Figure 3, along with the increase of DVB consumption, ultimate compression strength also increases thereupon, illustrates that in SDB molecular structure, cross-linking set number increases, the rigidity reinforced of bead; As n (DVB): n (St)=1:1, ultimate compression strength reaches 27N/ grain, shows that its mechanical mechanics property is excellent; The SDB mechanical mechanics property of this experiment synthesis is excellent, the impact of resistance to deuterium-oxide, has good stability;
Fig. 4 (a) and Fig. 4 (b) are respectively the SDB carrier photo under 200 DEG C of conditions before and after supporting Pt, Fig. 4 (c) and Fig. 4 (d) be respectively SDB before and after supporting Pt in water, soak 30d after dispersion photo;
By the SDB carrier shown in Fig. 4 (a) He Fig. 4 (b), under 200 DEG C of conditions, before and after supporting Pt, photo is known, and after load, the color of SDB becomes grey black from white, and this is because Pt load is relevant at carrier surface; After Pt metal load, because the mechanical mechanics property of SDB is excellent, in loading process, its shape does not change; Fig. 4 (c) and Fig. 4 (d) soak the dispersion photo after 30d for SDB before and after load in water, can find, all Large stone SDB and Pt/SDB swim on the water surface owing to having good hydrophobicity, there is not sinking, after load is described, SDB still has excellent hydrophobicity, can be used as the hydrophobic catalyst of LPCE reaction.
Embodiment
The invention will be further described for embodiment plan given below; but can not be interpreted as it is limiting the scope of the invention; some nonessential improvement and adjustment that person skilled in art makes the present invention according to the content of the invention described above, still belong to protection scope of the present invention.
Embodiment 1:
The preparation method of styrene diethylene benzene copoly mer hydrophobic catalyst carrier, step is:
200g deionized water is added in there-necked flask, 0.5g polyvinyl alcohol-1799, 0.5g calcium phosphate, the Sodium dodecylbenzene sulfonate of 0.06g, be made into uniform aqueous phase, stir, be heated to 30 DEG C, after all dissolving, the 10gSt (i.e. vinylbenzene) will mixed again, 13gDVB (i.e. Vinylstyrene), 0.2gBPO (i.e. benzoyl peroxide), 15.8g toluene, 12.4g normal heptane and 11.6g ethylene dichloride join in there-necked flask, the required rotating speed of adjustment is 100rpm/min, be heated to 85 DEG C, suspension polymerization is carried out under stirring, after reaction times 8h, filter, solids is the crude product of styrene diethylene benzene copoly mer, solids is used deionized water, absolute ethanol washing in turn, again with the acetone of solids quality 5 times of quality by solids in apparatus,Soxhlet's after extracting 30h, filter, then solids is used methyl alcohol, deionized water wash in turn, solids is dry, screening again, i.e. obtained styrene diethylene benzene copoly mer hydrophobic catalyst carrier.
Utilize the chemical composition by determination of infrared spectroscopy SDB hydrophobic catalyst carrier, its infrared spectra as shown in Figure 1.As seen from the figure, Vinylstyrene does not have full entry polyreaction, and cause the unreacted suspended double bond of part left behind, suspended double bond reserved and DVB consumption are proportionate.
Embodiment 2:
The preparation method of styrene diethylene benzene copoly mer hydrophobic catalyst carrier, step is:
200g deionized water is added in there-necked flask, 0.35g polyvinyl alcohol-2099, 0.5g calcium phosphate, the Sodium dodecylbenzene sulfonate of 0.06g, be made into uniform aqueous phase, stir, be heated to 30 DEG C, after all dissolving, the 10gSt will mixed again, 13gDVB, 0.2gBPO, 15.8g toluene, 12.4g normal heptane and 11.6g ethylene dichloride join in there-necked flask, the required rotating speed of adjustment is 100rpm/min, be heated to 85 DEG C, suspension polymerization is carried out under stirring, after reaction times 7h, filter, solids is the crude product of styrene diethylene benzene copoly mer, solids is used deionized water, absolute ethanol washing in turn, again with the acetone of solids quality 3 times of quality by solids in apparatus,Soxhlet's after extracting 48h, filter, then solids is used methyl alcohol, deionized water wash in turn, solids is dry, screening again, i.e. obtained styrene diethylene benzene copoly mer hydrophobic catalyst carrier.
From Fig. 2 thermogravimetric curve, all samples before 300 DEG C all without mass loss.There is obvious weightlessness in pure PS, namely its molecular backbone chain starts to decompose fracture from 300 DEG C.Show that DVB consumption increases, degree of crosslinking is improved, the initial decomposition temperature of sample improves, and the resistance toheat of SDB obtains improvement in various degree.As shown in Figure 3, along with the increase of DVB consumption, ultimate compression strength also increases thereupon, illustrates that in SDB molecular structure, cross-linking set number increases, the rigidity reinforced of bead.As n (DVB): n (St)=1:1, ultimate compression strength reaches 27N/ grain, shows that its mechanical mechanics property is excellent.As shown in Table 1, the consumption of the specific surface area of catalyzer and pore volume and DVB is proportionate, and mean pore size and DVB consumption are negative correlation.The increase of DVB concentration, be easier to obtain less micelle, their tight agglomeration are grown up, combining more densely causes the space of generation less, little hole number increases gradually, and thus make the SDB bead mean pore size finally obtained reduce, specific surface area and pore volume increase.From Fig. 4 (a) and Fig. 4 (b), after load, the color of SDB becomes grey black from white, and this is because Pt load is relevant at carrier surface.Fig. 4 (c) and Fig. 4 (d) is known, all Large stone SDB and Pt/SDB swim on the water surface owing to having good hydrophobicity, do not have sinking, after load is described, SDB still has excellent hydrophobicity, can be used as the hydrophobic catalyst of LPCE reaction.
Embodiment 3:
The preparation method of styrene diethylene benzene copoly mer hydrophobic catalyst carrier, step is:
200g deionized water is added in there-necked flask, 0.2g polyvinyl alcohol-2499, 0.5g calcium phosphate, the Sodium dodecylbenzene sulfonate of 0.06g, be made into uniform aqueous phase, stir, be heated to 30 DEG C, after all dissolving, the 10gSt will mixed again, 13gDVB, 0.2gBPO, 15.8g toluene, 12.4g normal heptane and 11.6g ethylene dichloride join in there-necked flask, the required rotating speed of adjustment is 100rpm/min, be heated to 85 DEG C, suspension polymerization is carried out under stirring, after reaction times 9h, filter, solids is the crude product of styrene diethylene benzene copoly mer, solids is used deionized water, absolute ethanol washing in turn, again with the acetone of solids quality 8 times of quality by solids in apparatus,Soxhlet's after extracting 12h, filter, then solids is used methyl alcohol, deionized water wash in turn, solids is dry, screening again, i.e. obtained styrene diethylene benzene copoly mer hydrophobic catalyst carrier.
Embodiment 4:
The preparation method of styrene diethylene benzene copoly mer hydrophobic catalyst carrier, step is:
200g deionized water is added in there-necked flask, 0.1g polyvinyl alcohol-2699, 0.5g calcium phosphate, the Sodium dodecylbenzene sulfonate of 0.06g, be made into uniform aqueous phase, stir, be heated to 30 DEG C, after all dissolving, the 10gSt will mixed again, 13gDVB, 0.2gBPO, 15.8g toluene, 12.4g normal heptane and 11.6g ethylene dichloride join in there-necked flask, the required rotating speed of adjustment is 100rpm/min, be heated to 85 DEG C, suspension polymerization is carried out under stirring, after reaction times 8h, filter, solids is the crude product of styrene diethylene benzene copoly mer, solids is used deionized water, absolute ethanol washing in turn, again with the acetone of solids quality 6 times of quality by solids in apparatus,Soxhlet's after extracting 40h, filter, then solids is used methyl alcohol, deionized water wash in turn, solids is dry, screening again, i.e. obtained styrene diethylene benzene copoly mer hydrophobic catalyst carrier.
Embodiment 5 ~ 7:
Organism is Natvosol, gelatin, Xylo-Mucine respectively, and the corresponding respectively consumption of each kind is 0.5g, 0.2g, 0.1g; Inorganic salt are magnesiumcarbonate, sodium-chlor, calcium phosphate powder respectively, and consumption is 0.5g; Other component raw material and consumption, reaction conditions are all identical with embodiment 1, omit.
Embodiment 8 ~ 13:
Stirring velocity is respectively 10rpm/min, 50rpm/min, 85rpm/min, 125rpm/min, 165rpm/min, 300rpm/min; Other is all identical with embodiment 1, omits.
Embodiment 14 ~ 17:
Initiator B PO (i.e. benzoyl peroxide) consumption is respectively 0.1g, 0.16g, 0.2g, 0.6g; Other component raw material and consumption, reaction conditions are all identical with embodiment 1, omit.
Embodiment 18 ~ 20:
Be heated to suspension polymerization temperature and be respectively 70 ~ 75 DEG C, 75 ~ 80 DEG C, 85 ~ 90 DEG C; Other is all identical with embodiment 1, omits.
Embodiment 21 ~ 24:
Vinylstyrene consumption is respectively 10.4g, 7.8g, 5.2g, 2.6g; Other component raw material and consumption, reaction conditions are all identical with embodiment 1, omit.
Embodiment 25:
The preparation method of styrene diethylene benzene copoly mer hydrophobic catalyst carrier, step is:
A, batching: get each component raw material by the mass ratio of deionized water 150 mass parts, organism 0.3 mass parts, inorganic salt 0.3 mass parts, Sodium dodecylbenzene sulfonate 0.03 mass parts, vinylbenzene 6 mass parts, Vinylstyrene 7.8, benzoyl peroxide 0.3 mass parts, toluene 12 mass parts, normal heptane 9 mass parts and ethylene dichloride 8 mass parts;
Described organism can be any one in polyvinyl alcohol-1799, polyvinyl alcohol-2099, polyvinyl alcohol-2499, polyvinyl alcohol-2699, Natvosol, gelatin and Xylo-Mucine;
Described inorganic salt can be any one in calcium phosphate, magnesiumcarbonate, sodium-chlor and calcium phosphate powder;
B, prepare the crude product of styrene diethylene benzene copoly mer: by deionized water, organism, inorganic salt and Sodium dodecylbenzene sulfonate (being called for short SDBS) join in reaction vessel (such as: there-necked flask), 32 DEG C are heated under stirring, after solids (all) dissolves, the vinylbenzene will mixed again, Vinylstyrene, benzoyl peroxide, toluene, the mixture of normal heptane and ethylene dichloride joins in reaction vessel, being heated to temperature is 80 DEG C, suspension polymerization is carried out under stirring, (to sclerosis after reaction times 8h, after aging), filter, solids is the crude product of styrene diethylene benzene copoly mer,
C, prepare styrene diethylene benzene copoly mer hydrophobic catalyst carrier: the solids (i.e. the crude product of styrene diethylene benzene copoly mer) obtained after reaction is used deionized water, absolute ethanol washing, in turn to remove responseless vinylbenzene and the impurity such as divinylbenzene monomers and organism solubility dispersion agent; Use again the acetone of solids quality 6 times of quality by solids in apparatus,Soxhlet's (industrial adopt the existing equipment with identical function effect) after extracting 30h, filter, to remove the organic impuritys such as first benzene and heptane mixing pore-creating agent and ethylene dichloride, form pore structure, then solids is used methyl alcohol, deionized water wash in turn, pore structure is fixed; (the porous small ball shape after purification) solids is dry, screening again, i.e. obtained (white) styrene diethylene benzene copoly mer (being called for short SDB) hydrophobic catalyst carrier.
Embodiment 26:
The preparation method of styrene diethylene benzene copoly mer hydrophobic catalyst carrier, step is:
A, batching: get each component raw material by the mass ratio of deionized water 100 mass parts, organism 0.1 mass parts, inorganic salt 0.1 mass parts, Sodium dodecylbenzene sulfonate 0.01 mass parts, vinylbenzene 2 mass parts, Vinylstyrene 2.6 parts, benzoyl peroxide 0.02 mass parts, toluene 8 mass parts, normal heptane 6 mass parts and ethylene dichloride 5 mass parts;
Described organism can be any one in polyvinyl alcohol-1799, polyvinyl alcohol-2099, polyvinyl alcohol-2499, polyvinyl alcohol-2699, Natvosol, gelatin and Xylo-Mucine;
Described inorganic salt can be any one in calcium phosphate, magnesiumcarbonate, sodium-chlor and calcium phosphate powder;
B, prepare the crude product of styrene diethylene benzene copoly mer: by deionized water, organism, inorganic salt and Sodium dodecylbenzene sulfonate (being called for short SDBS) join in reaction vessel (such as: there-necked flask), 25 DEG C are heated under stirring, after solids (all) dissolves, the vinylbenzene will mixed again, Vinylstyrene, benzoyl peroxide, toluene, the mixture of normal heptane and ethylene dichloride joins in reaction vessel, being heated to temperature is 70 DEG C, suspension polymerization is carried out under stirring, (to sclerosis after reaction times 9h, after aging), filter, solids is the crude product of styrene diethylene benzene copoly mer,
C, prepare styrene diethylene benzene copoly mer hydrophobic catalyst carrier: the solids (i.e. the crude product of styrene diethylene benzene copoly mer) obtained after reaction is used deionized water, absolute ethanol washing, in turn to remove responseless vinylbenzene and the impurity such as divinylbenzene monomers and organism solubility dispersion agent; Use again the acetone of solids quality 3 times of quality by solids in apparatus,Soxhlet's (industrial adopt the existing equipment with identical function effect) after extracting 48h, filter, to remove the organic impuritys such as first benzene and heptane mixing pore-creating agent and ethylene dichloride, form pore structure, then solids is used methyl alcohol, deionized water wash in turn, pore structure is fixed; (the porous small ball shape after purification) solids is dry, screening again, i.e. obtained (white) styrene diethylene benzene copoly mer (being called for short SDB) hydrophobic catalyst carrier.
Embodiment 27:
The preparation method of styrene diethylene benzene copoly mer hydrophobic catalyst carrier, step is:
A, batching: get each component raw material by the mass ratio of deionized water 200 mass parts, organism 0.5 mass parts, inorganic salt 0.5 mass parts, Sodium dodecylbenzene sulfonate 0.06 mass parts, vinylbenzene 10 mass parts, Vinylstyrene 13 amount part, benzoyl peroxide 0.6 mass parts, toluene 16 mass parts, normal heptane 13 mass parts and ethylene dichloride 12 mass parts;
Described organism can be any one in polyvinyl alcohol-1799, polyvinyl alcohol-2099, polyvinyl alcohol-2499, polyvinyl alcohol-2699, Natvosol, gelatin and Xylo-Mucine;
Described inorganic salt can be any one in calcium phosphate, magnesiumcarbonate, sodium-chlor and calcium phosphate powder;
B, prepare the crude product of styrene diethylene benzene copoly mer: by deionized water, organism, inorganic salt and Sodium dodecylbenzene sulfonate (being called for short SDBS) join in reaction vessel (such as: there-necked flask), 40 DEG C are heated under stirring, after solids (all) dissolves, the vinylbenzene will mixed again, Vinylstyrene, benzoyl peroxide, toluene, the mixture of normal heptane and ethylene dichloride joins in reaction vessel, being heated to temperature is 90 DEG C, suspension polymerization is carried out under stirring, (to sclerosis after reaction times 7h, after aging), filter, solids is the crude product of styrene diethylene benzene copoly mer,
C, prepare styrene diethylene benzene copoly mer hydrophobic catalyst carrier: the solids (i.e. the crude product of styrene diethylene benzene copoly mer) obtained after reaction is used deionized water, absolute ethanol washing, in turn to remove responseless vinylbenzene and the impurity such as divinylbenzene monomers and organism solubility dispersion agent; Use the acetone of solids quality 8 times of quality again by solids in apparatus,Soxhlet's (industrial adopt the existing equipment with identical function effect) after extracting 12h, filter, to remove the organic impuritys such as first benzene and heptane mixing pore-creating agent and ethylene dichloride, form pore structure, then solids is used methyl alcohol, deionized water wash in turn, pore structure is fixed; (the porous small ball shape after purification) solids is dry, screening again, i.e. obtained (white) styrene diethylene benzene copoly mer (being called for short SDB) hydrophobic catalyst carrier.
Embodiment 28 ~ 34:
The preparation method of styrene diethylene benzene copoly mer hydrophobic catalyst carrier, step is:
A, batching: get each component raw material by the mass ratio of deionized water 100 ~ 200 mass parts, organism 0.1 ~ 0.5 mass parts, inorganic salt 0.1 ~ 0.5 mass parts, Sodium dodecylbenzene sulfonate 0.01 ~ 0.06 mass parts, vinylbenzene 2 ~ 10 mass parts, Vinylstyrene 2 ~ 13 mass parts, benzoyl peroxide 0.02 ~ 0.6 mass parts, toluene 8 ~ 16 mass parts, normal heptane 6 ~ 13 mass parts and ethylene dichloride 5 ~ 12 mass parts;
Described organism can be any one in polyvinyl alcohol-1799, polyvinyl alcohol-2099, polyvinyl alcohol-2499, polyvinyl alcohol-2699, Natvosol, gelatin and Xylo-Mucine;
Described inorganic salt can be any one in calcium phosphate, magnesiumcarbonate, sodium-chlor and calcium phosphate powder;
In each embodiment, the concrete mass parts consumption of each component raw material sees the following form:
B, prepare the crude product of styrene diethylene benzene copoly mer: by deionized water, organism, inorganic salt and Sodium dodecylbenzene sulfonate (being called for short SDBS) join in reaction vessel (such as: there-necked flask), 25 ~ 40 DEG C are heated under stirring, after solids (all) dissolves, the vinylbenzene will mixed again, Vinylstyrene, benzoyl peroxide, toluene, the mixture of normal heptane and ethylene dichloride joins in reaction vessel, being heated to temperature is 70 ~ 90 DEG C, suspension polymerization is carried out under stirring, (to sclerosis after reaction times 7 ~ 9h, after aging), filter, solids is the crude product of styrene diethylene benzene copoly mer,
C, prepare styrene diethylene benzene copoly mer hydrophobic catalyst carrier: the solids (i.e. the crude product of styrene diethylene benzene copoly mer) obtained after reaction is used deionized water, absolute ethanol washing, in turn to remove responseless vinylbenzene and the impurity such as divinylbenzene monomers and organism solubility dispersion agent; Use again the acetone of solids quality 3 ~ 8 times of quality by solids in apparatus,Soxhlet's (industrial adopt the existing equipment with identical function effect) after extracting 12 ~ 48h, filter, to remove the organic impuritys such as first benzene and heptane mixing pore-creating agent and ethylene dichloride, form pore structure, then solids is used methyl alcohol, deionized water wash in turn, pore structure is fixed; (the porous small ball shape after purification) solids is dry, screening again, i.e. obtained (white) styrene diethylene benzene copoly mer (being called for short SDB) hydrophobic catalyst carrier.
In above-described embodiment 25 ~ 34: under stirring described in step b, to carry out suspension polymerization be agitator speed is carry out under the condition of 10 ~ 300rpm/min that suspension polymerization, preferably agitator speed are 85 ~ 125rpm/min, best agitator speed is 100rpm/min.
In above-described embodiment 28 ~ 34: be heated to temperature described in step b and be 70 ~ 90 DEG C and be preferably and replace with that to be heated to temperature be 80 ~ 85 DEG C.
In above-described embodiment: (in step c) described solids is that solids uses deionized water, absolute ethanol washing 2 ~ 4 times in turn respectively with deionized water, absolute ethanol washing in turn, and the quality of each washing deionized water, dehydrated alcohol is 3 ~ 8 times of solids quality.
In above-described embodiment: (in step c) described solids is that solids uses methyl alcohol, deionized water wash 2 ~ 4 times in turn respectively with methyl alcohol, deionized water wash in turn, and the quality of each washing deionized water, dehydrated alcohol is 3 ~ 8 times of solids quality.
In above-described embodiment: (in step c) described drying, screening be by solids temperature be 50 ~ 60 DEG C, pressure dry 12 ~ 36h under being the condition of 0.1MPa, sieve again (crossing 2 ~ 5mm sieve), i.e. the Large stone styrene diethylene benzene copoly mer hydrophobic catalyst carrier of obtained white, particle diameter φ 2 ~ 5mm.The ratio of described Large stone can reach 35% ~ 40%.
In above-described embodiment: described each component raw material of use first can carry out refinement treatment: the commercial styrene of purchase is carried out distillation before the use and refined, step is as follows: 1. join in the separating funnel of 1000mL by the vinylbenzene of 500mL (being called for short St) monomer, with the NaOH solution washing three times of 150mL5%; 2. repeatedly wash with deionized water until neutral (pH is 7 ~ 8), put into a little anhydrous MgSO
4namely dry to liquid clarification; 3. the vinylbenzene rectification under vacuum after above-mentioned drying, the cut after distillation is collected, for subsequent use.The still-process of Vinylstyrene (being called for short DVB) monomer is the same with styrene monomer.Benzoyl peroxide (being called for short BPO) adopts chloroform to be solvent, CH
3oH makes precipitation agent, utilizes recrystallizing and refining process etc.
In above-described embodiment: each raw material adopted is commercially available prod.
In above-described embodiment: in the percentage adopted, do not indicate especially, be quality (weight) percentage or well known to a person skilled in the art percentage; Described quality (weight) part can be all gram.
In above-described embodiment: the processing parameter (temperature, time etc.) in each step and each amounts of components numerical value etc. are scope, and any point is all applicable.
The concrete same prior art of technology contents described in content of the present invention and above-described embodiment.
The invention is not restricted to above-described embodiment, all can implement described in content of the present invention and there is described good result.
Claims (10)
1. the preparation method of styrene diethylene benzene copoly mer hydrophobic catalyst carrier, is characterized in that step is:
A, batching: get each component raw material by the mass ratio of deionized water 100 ~ 200 mass parts, organism 0.1 ~ 0.5 mass parts, inorganic salt 0.1 ~ 0.5 mass parts, Sodium dodecylbenzene sulfonate 0.01 ~ 0.06 mass parts, vinylbenzene 2 ~ 10 mass parts, Vinylstyrene 2 ~ 13 mass parts, benzoyl peroxide 0.02 ~ 0.6 mass parts, toluene 8 ~ 16 mass parts, normal heptane 6 ~ 13 mass parts and ethylene dichloride 5 ~ 12 mass parts;
Described organism can be any one in polyvinyl alcohol-1799, polyvinyl alcohol-2099, polyvinyl alcohol-2499, polyvinyl alcohol-2699, Natvosol, gelatin and Xylo-Mucine;
Described inorganic salt can be any one in calcium phosphate, magnesiumcarbonate, sodium-chlor and calcium phosphate powder;
B, prepare the crude product of styrene diethylene benzene copoly mer: join in reaction vessel by deionized water, organism, inorganic salt and Sodium dodecylbenzene sulfonate, being heated to temperature under stirring is 25 ~ 40 DEG C, again the mixture of the vinylbenzene mixed, Vinylstyrene, benzoyl peroxide, toluene, normal heptane and ethylene dichloride is joined in reaction vessel, being heated to temperature is 70 ~ 90 DEG C, suspension polymerization is carried out under stirring, after reaction times 7 ~ 9h, filter, solids is the crude product of styrene diethylene benzene copoly mer;
C, prepare styrene diethylene benzene copoly mer hydrophobic catalyst carrier: the solids obtained after reaction is used deionized water, absolute ethanol washing in turn, use the acetone of solids quality 3 ~ 8 times of quality again by solids in apparatus,Soxhlet's after extracting 12 ~ 48h, filter, then solids is used methyl alcohol, deionized water wash in turn, solids is dry, screening again, i.e. obtained styrene diethylene benzene copoly mer hydrophobic catalyst carrier.
2., by the preparation method of styrene diethylene benzene copoly mer hydrophobic catalyst carrier described in claim 1, it is characterized in that: the consumption mass ratio of organism described in step a and inorganic salt mass parts is 1:1.
3., by the preparation method of styrene diethylene benzene copoly mer hydrophobic catalyst carrier described in claim 1, it is characterized in that: the consumption mass ratio of vinylbenzene described in step a and Vinylstyrene mass parts is 1:1.3.
4., by the preparation method of styrene diethylene benzene copoly mer hydrophobic catalyst carrier described in claim 1, it is characterized in that: the mass parts consumption of benzoyl peroxide described in step a is 0.1 ~ 0.6 mass parts.
5. by the preparation method of styrene diethylene benzene copoly mer hydrophobic catalyst carrier described in claim 1, it is characterized in that: to carry out suspension polymerization under stirring described in step b be agitator speed is the suspension polymerization carried out under 10 ~ 300rpm/min condition.
6. by the preparation method of styrene diethylene benzene copoly mer hydrophobic catalyst carrier described in claim 1, it is characterized in that: to carry out suspension polymerization under stirring described in step b be agitator speed is carry out suspension polymerization under the condition of 85 ~ 125rpm/min.
7. by the preparation method of styrene diethylene benzene copoly mer hydrophobic catalyst carrier described in claim 1, it is characterized in that: be heated to temperature described in step b and be 70 ~ 90 DEG C and replace with that to be heated to temperature be 80 ~ 85 DEG C.
8. by the preparation method of styrene diethylene benzene copoly mer hydrophobic catalyst carrier described in claim 1, it is characterized in that: solids described in step c is that solids uses deionized water, absolute ethanol washing 2 ~ 4 times in turn respectively with deionized water, absolute ethanol washing in turn, and the quality of each washing deionized water, dehydrated alcohol is 3 ~ 8 times of solids quality.
9. by the preparation method of styrene diethylene benzene copoly mer hydrophobic catalyst carrier described in claim 1, it is characterized in that: solids described in step c is that solids uses methyl alcohol, deionized water wash 2 ~ 4 times in turn respectively with methyl alcohol, deionized water wash in turn, and the quality of each washing deionized water, dehydrated alcohol is 3 ~ 8 times of solids quality.
10. by the preparation method of styrene diethylene benzene copoly mer hydrophobic catalyst carrier described in claim 1, it is characterized in that: dry described in step c, screening be by solids temperature be 50 ~ 60 DEG C, pressure dry 12 ~ 36h under being the condition of 0.1MPa, then to sieve.
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| CN105504566A (en) * | 2016-01-26 | 2016-04-20 | 西南科技大学 | Preparation method of columnar styrene and divinyl benzene copolymer hydrophobic catalyst carrier |
| CN107973872A (en) * | 2017-12-11 | 2018-05-01 | 西南科技大学 | Nano ferriferrous oxide adulterates the preparation method of styrene diethylene benzene copoly mer hydrophobic catalyst carrier |
| CN107973873A (en) * | 2017-12-11 | 2018-05-01 | 西南科技大学 | A kind of preparation method of super-hydrophobic high resistance to compression styrene diethylene benzene copoly mer catalyst carrier |
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| CN113019464A (en) * | 2021-03-11 | 2021-06-25 | 哈尔滨工程大学 | Preparation method of spherical SDB hydrophobic carrier with controllable size and Pt/SDB hydrophobic catalyst |
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| CN105504566A (en) * | 2016-01-26 | 2016-04-20 | 西南科技大学 | Preparation method of columnar styrene and divinyl benzene copolymer hydrophobic catalyst carrier |
| CN105504566B (en) * | 2016-01-26 | 2018-01-16 | 西南科技大学 | A kind of preparation method of column styrene divinylbenzene copolymer hydrophobic catalyst carrier |
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| CN107973873B (en) * | 2017-12-11 | 2020-06-19 | 西南科技大学 | Preparation method of super-hydrophobic high-compression-resistance styrene-divinylbenzene copolymer catalyst carrier |
| CN111993713A (en) * | 2020-08-31 | 2020-11-27 | 安徽扬子地板股份有限公司 | High-toughness waterproof board and preparation method thereof |
| CN113019464A (en) * | 2021-03-11 | 2021-06-25 | 哈尔滨工程大学 | Preparation method of spherical SDB hydrophobic carrier with controllable size and Pt/SDB hydrophobic catalyst |
| CN113234187A (en) * | 2021-05-17 | 2021-08-10 | 西南科技大学 | Preparation method of nano-silica hybrid modified styrene-divinylbenzene copolymer hydrophobic catalyst carrier material |
| CN115672409A (en) * | 2022-11-10 | 2023-02-03 | 广州启轩新材料科技有限公司 | Method for preparing Pt/SDB hydrophobic catalyst by hydrazine hydrate reduction |
| CN115888820A (en) * | 2022-11-10 | 2023-04-04 | 广州启轩新材料科技有限公司 | Method for preparing Pt/SDB hydrophobic catalyst by sodium borohydride reduction |
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