CN103951781A - Preparation method of efficient molecular sieve desiccant with core-shell nanostructure - Google Patents
Preparation method of efficient molecular sieve desiccant with core-shell nanostructure Download PDFInfo
- Publication number
- CN103951781A CN103951781A CN201410206050.5A CN201410206050A CN103951781A CN 103951781 A CN103951781 A CN 103951781A CN 201410206050 A CN201410206050 A CN 201410206050A CN 103951781 A CN103951781 A CN 103951781A
- Authority
- CN
- China
- Prior art keywords
- molecular sieve
- core
- siccative
- efficient molecular
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Graft Or Block Polymers (AREA)
- Polymerisation Methods In General (AREA)
Abstract
The invention discloses a preparation method of an efficient molecular sieve desiccant with a core-shell nanostructure. The preparation method comprises the steps of 1, mixing montmorillonite and a first mixed monomer, stirring at constant speed, and standing to form a stable montmorillonite intercalation dispersion liquid; 2, adding a mixed emulsifying agent and a proper amount of water into the montmorillonite intercalation dispersion liquid in a stirring state, uniformly stirring, then, adding a redox initiator, and finishing polymerization to obtain an intercalation seed emulsion; 3, adding the mixed emulsifying agent, a second mixed monomer, the redox initiator and 1, 2-divinyl benzene into the intercalation seed emulsion in the step 2 at the temperature of 73-76 DEG C and at constant speed, and continuing to preserve the heat and cure after the dropwise adding operation is ended to obtain a core-shell latex particle; 4, demulsifying the core-shell latex particle, drying and crushing to obtain a final product. The efficient molecular sieve desiccant is prepared by polymerizing a low-soap emulsion, and therefore, the water absorption capacity of a nanocomposite is greatly improved on the premise of ensuring the required mechanical strength.
Description
Technical field
The invention belongs to material of construction manufacturing technology field, particularly relate to a kind of preparation method of nano core-shell structure efficient molecular sieve siccative.
Background technology
Window is the chief component in buildings exterior-protected structure, and the performance quality of window will greatly have influence on the heating air conditioning energy consumption of building, indoor acousto-optic thermal environment and air quality.Double glazing is as the core component of the exterior window of energy saving, and the functional lifetime of developed country's double glazing can reach more than 30 years, and the double glazing functional lifetime that China produces at present only had about 8 years, and what have even just lost efficacy for 2 years afterwards.Double glazing inefficacy main manifestations is that aqueous vapor enters intermediate air layer formation knot mist phenomenon by sealed structure, therefore packing technique is the key point that prevents that double glazing lost efficacy, also be the basic guarantee of coated glass validity, otherwise Low-E coated glass is oxidation deactivation rapidly, lose incubation and thermal insulation function.
China is vast in territory, and climate difference is large, and weather effect causes exterior window energy-efficient performance to reduce and lost efficacy, and has a strong impact on the actual energy-saving effect of exterior window and long-term energy-saving effect.Water is diffused on the interface of seal gum and glass and spacer bar via seal gum, causes bonding plane ageing failure.The deficiency of the aspects such as packing technique, climatope effect in addition, has aggravated the already present problem of double glazing application aspect industry, according to typical climatic characteristic, improves the energy-conservation lasting retentivity of exterior window and long-range nature, is problem in the urgent need to address at present.
Summary of the invention
The object of the invention is to propose a kind of preparation method of nano core-shell structure efficient molecular sieve siccative, to solve existing siccative, contain emulsifying agent, affect the problem of water-absorbent, water tolerance.
In order to solve the problems of the technologies described above, the present invention has adopted following technical scheme: a kind of preparation method of nano core-shell structure efficient molecular sieve siccative, comprises the following steps:
Step 1, mixes vinylformic acid, vinylbenzene, methyl methacrylate, butyl acrylate to make the first mix monomer according to the weight proportion of 5～10:25～30:40～45:20～25; 1～30 weight part polynite mixes with 30 weight part the first mix monomers, at the uniform velocity stirs and forms stable montmorillonite intercalation dispersion liquid, standing 20～30 hours; Because vinylformic acid is water-soluble monomer, both contained hydrophilic radical-COOH, contain again hydrophobic grouping-CH simultaneously
3therefore in this low soap letex polymerization, can be similar to the effect of playing emulsifying agent, vinylformic acid for 5%-10%, it had both played the effect of polymerization single polymerization monomer, wherein part propylene acid mono can be used as again emulsifying agent, and simultaneously acrylic acid second-order transition temperature is 105 degree left and right, similar to vinylbenzene, methyl methacrylate; Vinylbenzene is owing to containing phenyl ring, and its second-order transition temperature is 105 degree left and right, be vitreous state at normal temperatures, can improve the rigidity of multipolymer, and because employing DVB (1,2-Vinylstyrene) is linking agent, it is easy to make vinylbenzene and other monomer copolymerizations simultaneously; The second-order transition temperature of polymethylmethacrylate is similar to polystyrene, under the prerequisite of second-order transition temperature that does not affect multipolymer, can reduce costs; The second-order transition temperature of butyl acrylate is-56 degree left and right, is rubbery state at normal temperatures, can improve the toughness of multipolymer, prevents that multipolymer from brittle rupture in use occurring.The multipolymer obtaining according to this proportioning, known according to the calculating of fox formula, its second-order transition temperature, in 60 degree left and right, is vitreous state under normal temperature condition, can guarantee that siccative has certain rigidity and toughness.
Step 2, the blending emulsifiers of disodium 4-dodecyl-2,4 '-oxydibenzenesulfonate and allyl group polyethoxye sulfonate is made blending emulsifiers according to the mass ratio of 1:1, to inflated with nitrogen protection in described montmorillonite intercalation dispersion liquid, add 0.1～0.5 weight part blending emulsifiers and 300 weight parts waters, the post-heating that stirs is warming up to 72～76 ℃, under whipped state, add 0.05～0.2 weight part oxidation-reduction type initiator, after polymerization completes, obtain intercalation seed emulsion;
Step 3, mixes vinylformic acid, vinylbenzene, methyl methacrylate, butyl acrylate to make the second mix monomer according to the weight proportion of 10～15:30～35:40～45:10～15; By 0.02～0.1 weight part blending emulsifiers, 70 weight part the second mix monomers, 0.1～0.4 weight part oxidation-reduction type initiator, 0.2～1 weight part 1,2-Vinylstyrene joins in the intercalation seed emulsion that step 2 makes with constant speed under the temperature condition at 73～76 ℃, continues insulation slaking again and obtain core-shell latex particles after dropwising; Said ratio, according to fox formula, calculate known, simultaneously owing to there being crosslinking structure in polymeric system, the second-order transition temperature of this multipolymer can be more than 80 degree, improved the intensity of siccative shell, the structure that the siccative that makes finally to obtain is a kind of hard outside soft inside, is guaranteeing that siccative has under the condition of higher-strength, still has certain toughness.
Step 4, makes nano core-shell structure efficient molecular sieve siccative after the sub-breakdown of emulsion of core-shell latex particles, finish-drying pulverizing.
The preparation method of nano core-shell structure efficient molecular sieve siccative as above, preferred, described blending emulsifiers is that disodium 4-dodecyl-2,4 '-oxydibenzenesulfonate and allyl group polyethoxye sulfonate mix by the mass ratio of 1:1
The preparation method of nano core-shell structure efficient molecular sieve siccative as above, preferred, described oxidation-reduction type initiator is that ammonium persulphate and sodium bisulfite form by the mixed in molar ratio of 1:1.
The preparation method of nano core-shell structure efficient molecular sieve siccative as above, preferred, in step 4, the drying temperature of nucleocapsid latex particle is 110～125 ℃.
The preparation method of nano core-shell structure efficient molecular sieve siccative as above, preferred, the sub-breakdown of emulsion of core-shell latex particles, dry, cross respectively 25 orders, 40 mesh sieves after pulverizing, make the nano core-shell structure efficient molecular sieve siccative of granularity between 25～40 orders.
The preparation method of nano core-shell structure efficient molecular sieve siccative as above, preferred, the polynite granularity in step 1 is ultra-fine polynite more than 2500 orders.
The preparation method of nano core-shell structure efficient molecular sieve siccative as above, preferably, step 1, mixes vinylformic acid, vinylbenzene, methyl methacrylate, butyl acrylate to make the first mix monomer according to the weight proportion of 8～10:25～30:42～45:20～25.
The preparation method of nano core-shell structure efficient molecular sieve siccative as above, preferably, step 3, mixes vinylformic acid, vinylbenzene, methyl methacrylate, butyl acrylate to make the second mix monomer according to the weight proportion of 12～15:32～35:43～45:14～15.
Compared with prior art, beneficial effect of the present invention is: this invention is a kind of organic/inorganic composite material, its water-intake rate exceeds a lot of doubly (water-intake rate of traditional inorganic dry drying prescription is 50 times of left and right) than pure inorganic dry drying prescription, simultaneously because the toughness of the inorganic drying material of tradition is poor, in use there will be broken phenomenon, can further reduce its drying property.In siccative production process, only use a small amount of Polymerizable Emulsifier (allyl group polyethoxye sulfonate) and anionic emulsifier (disodium 4-dodecyl-2,4 '-oxydibenzenesulfonate), far below emulsifying agent threshold concentration, on the basis of improving drying property, saved the cost of product.
Accompanying drawing explanation
Fig. 1 is X-ray diffraction spectrogram of the present invention, in figure, a is the X-ray diffraction spectral curve of polynite powder, in figure, b is the X-ray diffraction spectral curve of nano core-shell structure poly-(vinylformic acid/vinylbenzene/1,2-Vinylstyrene/methyl methacrylate)/poly-(vinylformic acid/styrene/methacrylic acid methyl esters)/polynite efficient molecular sieve siccative;
Fig. 2 is that the water-retaining capacity of explanation nano core-shell structure poly-(vinylformic acid/vinylbenzene/1,2-Vinylstyrene/methyl methacrylate)/poly-(vinylformic acid/styrene/methacrylic acid methyl esters)/polynite efficient molecular sieve siccative is with the variation diagram of polynite content.
Embodiment
Below in conjunction with specific embodiment, the present invention is described in further detail, but not as a limitation of the invention.
Traditional letex polymerization all will be used emulsifying agent, so that polymerization system is stable, but emulsifying agent is brought in the finished product and is gone, even also cannot be by the complete Ex-all of emulsifying agent by washing process.Because the existence of emulsifying agent can have influence on optical property, electrical property, the compactness of filming, water tolerance, scrub resistance and the sticking power etc. of emulsion polymer, limited the range of application of product; Expensive emulsifying agent has increased again the cost of product simultaneously.In order to overcome the drawback of bringing due to emulsifying agent, developed new emulsion polymerization systems---low soap letex polymerization.This letex polymerization is the new technology growing up on conventional emulsion polymerization basis, and so-called low soap letex polymerization refers to only add the emulsion polymerization process of micro-emulsifying agent (being less than micelle-forming concentration CMC) in reaction process.
For low soap letex polymerization, owing to only there being micro-emulsifying agent in system, under the cooperation of part hydrophilic monomer (as vinylformic acid, methacrylic acid etc.), can form monomer solubilization micelle, thereby control the size distribution of latex particle, obtain size distribution narrower, the latex particle that particle diameter is less, also greatly reduces conventional emulsion polymerization simultaneously and introduces the disadvantageous effect of emulsifying agent to system.
Initiator is integral part important in letex polymerization, directly affects the transformation efficiency of polymerization rate, monomer, size of final particle etc.Due to the reaction activity (40～50kJ/mol) of the redox initiation system reaction activity (being greater than 120kJ/mol) much smaller than thermal initiation system, can lower the kick off temperature of system, to a certain degree can reduce energy consumption of reaction, can avoid partial function monomer hydrolysis reaction at high temperature simultaneously.We take ammonium persulphate/sodium bisulfite as redox initiator, when initiator amount is less than 0.05 part (amount of monomer is 30 parts), and monomer conversion lower (being less than 75%); Along with the increase of initiator amount, the number that causes solubilization micelle formation latex particle increases gradually, and under the certain condition of amount of monomer, in system, the particle diameter of latex particle will reduce gradually, and monomer conversion increases gradually; But when initiator amount is greater than 0.2 part (amount of monomer is 30 parts), the particle diameter of particle, monomer conversion just do not have too large variation substantially, but size distribution changes greatly.This is mainly because emulsifier in system is certain, the number that makes to cause front formed solubilization micelle is also constant, because the concentration of free radical is excessive, when solubilization micelle in system is all caused, again can be by the monomer droplet initiated polymerization in emulsion system, thereby form new latex particle, this has just increased source (monomer droplet nucleation) and ratio thereof that non-Micellar nucleation forms latex particle, make finally to obtain the size inequality of latex particle, quantity is not etc., but because the number of solubilization micelle is after all than large several orders of magnitude of the number of monomer droplet, therefore on average get off, the median size of latex particle changes little, but it is very wide to distribute, particle diameter is larger.
Embodiment 1
Accurate weighing 0.1kg granularity is 2500 object polynites, dispersed with stirring (mass ratio of vinylformic acid/styrene/methacrylic acid methyl esters/butyl acrylate is 5:30:45:20) in 3kg the first mix monomer at the uniform velocity, within standing 24 hours, polynite is fully infiltrated, obtain montmorillonite intercalation dispersion liquid.The blending emulsifiers that adds 30kg water, 0.02kg disodium 4-dodecyl-2,4 '-oxydibenzenesulfonate and allyl group polyethoxye sulfonate to make according to the mass ratio of 1:1; stir; in nitrogen protection, 250rpm rotating speed, stir, to montmorillonite intercalation dispersion liquid, add 0.007kg oxidation-reduction type initiator (mixture that ammonium persulphate/sodium bisulfite forms with mol ratio 1:1) polyase 13 0 minute under the condition of water bath heating of 75 ± 2 ℃, obtain intercalation seed emulsion.Again the blending emulsifiers of 0.005kg disodium 4-dodecyl-2,4 '-oxydibenzenesulfonate and allyl group polyethoxye sulfonate is made to blending emulsifiers according to the mass ratio of 1:1, 7kg the second mix monomer (mass ratio of vinylformic acid/styrene/methacrylic acid methyl esters/butyl acrylate is 10:30:40:15), 0.015kg oxidation-reduction type initiator (mixture that ammonium persulphate/sodium bisulfite forms with mol ratio 1:1) and 0.05kg linking agent 1, 2-Vinylstyrene joins in above-mentioned intercalation seed emulsion with constant speed, at 75 ± 2 ℃, continue again insulation slaking 2 hours after dropwising, core-shell latex particles obtaining is through breakdown of emulsion, dry, after pulverizing, cross respectively 25 orders, 40 mesh sieves, make the nano core-shell structure efficient molecular sieve siccative of granularity between 25～40 orders.
As shown in Figure 1, from curve a and curve b, the characteristic diffraction peak completely dissolve of the montmorillonite layered crystal in nano core-shell structure efficient molecular sieve siccative Central Plains, i.e. the laminated structure of polynite is peeled off substantially, obtains exfoliated nano-composite.
Embodiment 2
Accurate weighing 0.5kg granularity is 2500 object polynites, dispersed with stirring (mass ratio of vinylformic acid/styrene/methacrylic acid methyl esters/butyl acrylate is 5:30:45:20) in 3kg the first mix monomer at the uniform velocity, within standing 24 hours, polynite is fully infiltrated, obtain montmorillonite intercalation dispersion liquid.The blending emulsifiers that adds 30kg water, 0.02kg disodium 4-dodecyl-2,4 '-oxydibenzenesulfonate and allyl group polyethoxye sulfonate to make according to the mass ratio of 1:1; stir; in nitrogen protection, 250rpm rotating speed, stir, to montmorillonite intercalation dispersion liquid, add 0.007kg oxidation-reduction type initiator (mixture that ammonium persulphate/sodium bisulfite forms with mol ratio 1:1) polyase 13 0 minute under the condition of water bath heating of 75 ± 2 ℃, obtain intercalation seed emulsion.Again the blending emulsifiers of 0.005kg disodium 4-dodecyl-2,4 '-oxydibenzenesulfonate and allyl group polyethoxye sulfonate is made to blending emulsifiers according to the mass ratio of 1:1, 7kg the second mix monomer (mass ratio of vinylformic acid/styrene/methacrylic acid methyl esters/butyl acrylate is 10:30:40:15), 0.015kg oxidation-reduction type initiator (mixture that ammonium persulphate/sodium bisulfite forms with mol ratio 1:1) and 0.05kg linking agent 1, 2-Vinylstyrene joins in above-mentioned intercalation seed emulsion with constant speed, at 75 ± 2 ℃, continue again insulation slaking 2 hours after dropwising, core-shell latex particles obtaining is through breakdown of emulsion, dry, after pulverizing, cross respectively 25 orders, 40 mesh sieves, make the nano core-shell structure efficient molecular sieve siccative of granularity between 25～40 orders.
Embodiment 3
Accurate weighing 1kg granularity is 2500 object polynites, dispersed with stirring (mass ratio of vinylformic acid/styrene/methacrylic acid methyl esters/butyl acrylate is 5:30:45:20) in 3kg the first mix monomer at the uniform velocity, within standing 24 hours, polynite is fully infiltrated, obtain montmorillonite intercalation dispersion liquid.The blending emulsifiers that adds 30kg water, 0.02kg disodium 4-dodecyl-2,4 '-oxydibenzenesulfonate and allyl group polyethoxye sulfonate to make according to the mass ratio of 1:1; stir; in nitrogen protection, 250rpm rotating speed, stir, to montmorillonite intercalation dispersion liquid, add 0.007kg oxidation-reduction type initiator (mixture that ammonium persulphate/sodium bisulfite forms with mol ratio 1:1) polyase 13 0 minute under the condition of water bath heating of 75 ± 2 ℃, obtain intercalation seed emulsion.Again the blending emulsifiers of 0.005kg disodium 4-dodecyl-2,4 '-oxydibenzenesulfonate and allyl group polyethoxye sulfonate is made to blending emulsifiers according to the mass ratio of 1:1, 7kg the second mix monomer (mass ratio of vinylformic acid/styrene/methacrylic acid methyl esters/butyl acrylate is 10:30:40:15), 0.015kg oxidation-reduction type initiator (mixture that ammonium persulphate/sodium bisulfite forms with mol ratio 1:1) and 0.05kg linking agent 1, 2-Vinylstyrene joins in above-mentioned intercalation seed emulsion with constant speed, at 75 ± 2 ℃, continue again insulation slaking 2 hours after dropwising, core-shell latex particles obtaining is through breakdown of emulsion, dry, after pulverizing, cross respectively 25 orders, 40 mesh sieves, make the nano core-shell structure efficient molecular sieve siccative of granularity between 25～40 orders.
Embodiment 4
Accurate weighing 1.5kg granularity is 2500 object polynites, dispersed with stirring (mass ratio of vinylformic acid/styrene/methacrylic acid methyl esters/butyl acrylate is 5:30:45:20) in 3kg the first mix monomer at the uniform velocity, within standing 24 hours, polynite is fully infiltrated, obtain montmorillonite intercalation dispersion liquid.The blending emulsifiers that adds 30kg water, 0.02kg disodium 4-dodecyl-2,4 '-oxydibenzenesulfonate and allyl group polyethoxye sulfonate to make according to the mass ratio of 1:1; stir; in nitrogen protection, 250rpm rotating speed, stir, to montmorillonite intercalation dispersion liquid, add 0.007kg oxidation-reduction type initiator (mixture that ammonium persulphate/sodium bisulfite forms with mol ratio 1:1) polyase 13 0 minute under the condition of water bath heating of 75 ± 2 ℃, obtain intercalation seed emulsion.Again the blending emulsifiers of 0.005kg disodium 4-dodecyl-2,4 '-oxydibenzenesulfonate and allyl group polyethoxye sulfonate is made to blending emulsifiers according to the mass ratio of 1:1, 7kg the second mix monomer (mass ratio of vinylformic acid/styrene/methacrylic acid methyl esters/butyl acrylate is 10:30:40:15), 0.015kg oxidation-reduction type initiator (mixture that ammonium persulphate/sodium bisulfite forms with mol ratio 1:1) and 0.05kg linking agent 1, 2-Vinylstyrene joins in above-mentioned intercalation seed emulsion with constant speed, at 75 ± 2 ℃, continue again insulation slaking 2 hours after dropwising, core-shell latex particles obtaining is through breakdown of emulsion, dry, after pulverizing, cross respectively 25 orders, 40 mesh sieves, make the nano core-shell structure efficient molecular sieve siccative of granularity between 25～40 orders.
Embodiment 5
Accurate weighing 0.5kg granularity is 2500 object polynites, dispersed with stirring (mass ratio of vinylformic acid/styrene/methacrylic acid methyl esters/butyl acrylate is 5:30:45:20) in 3kg the first mix monomer at the uniform velocity, within standing 24 hours, polynite is fully infiltrated, obtain montmorillonite intercalation dispersion liquid.The blending emulsifiers that adds 30kg water, 0.02kg disodium 4-dodecyl-2,4 '-oxydibenzenesulfonate and allyl group polyethoxye sulfonate to make according to the mass ratio of 1:1; stir; in nitrogen protection, 250rpm rotating speed, stir, to montmorillonite intercalation dispersion liquid, add 0.01kg oxidation-reduction type initiator (mixture that ammonium persulphate/sodium bisulfite forms with mol ratio 1:1) polyase 13 0 minute under the condition of water bath heating of 75 ± 2 ℃, obtain intercalation seed emulsion.Again the blending emulsifiers of 0.01kg disodium 4-dodecyl-2,4 '-oxydibenzenesulfonate and allyl group polyethoxye sulfonate is made to blending emulsifiers according to the mass ratio of 1:1, 7kg the second mix monomer (mass ratio of vinylformic acid/styrene/methacrylic acid methyl esters/butyl acrylate is 12:34:42:15), 0.025kg oxidation-reduction type initiator (mixture that ammonium persulphate/sodium bisulfite forms with mol ratio 1:1) and 0.05kg linking agent 1, 2-Vinylstyrene joins in above-mentioned intercalation seed emulsion with constant speed, at 75 ± 2 ℃, continue again insulation slaking 2 hours after dropwising, core-shell latex particles obtaining is through breakdown of emulsion, dry, after pulverizing, cross respectively 25 orders, 40 mesh sieves, make the nano core-shell structure efficient molecular sieve siccative of granularity between 25～40 orders.
Embodiment 6
Accurate weighing 0.5kg granularity is 2500 object polynites, dispersed with stirring (mass ratio of vinylformic acid/styrene/methacrylic acid methyl esters/butyl acrylate is 5:30:45:20) in 3kg the first mix monomer at the uniform velocity, within standing 24 hours, polynite is fully infiltrated, obtain montmorillonite intercalation dispersion liquid.The blending emulsifiers that adds 30kg water, 0.03kg disodium 4-dodecyl-2,4 '-oxydibenzenesulfonate and allyl group polyethoxye sulfonate to make according to the mass ratio of 1:1; stir; in nitrogen protection, 250rpm rotating speed, stir, to montmorillonite intercalation dispersion liquid, add 0.005kg oxidation-reduction type initiator (mixture that ammonium persulphate/sodium bisulfite forms with mol ratio 1:1) polyase 13 0 minute under the condition of water bath heating of 75 ± 2 ℃, obtain intercalation seed emulsion.Again the blending emulsifiers of 0.002kg disodium 4-dodecyl-2,4 '-oxydibenzenesulfonate and allyl group polyethoxye sulfonate is made to blending emulsifiers according to the mass ratio of 1:1, 7kg the second mix monomer (mass ratio of vinylformic acid/styrene/methacrylic acid methyl esters/butyl acrylate is 15:30:45:13), 0.015kg oxidation-reduction type initiator (mixture that ammonium persulphate/sodium bisulfite forms with mol ratio 1:1) and 0.1kg linking agent 1, 2-Vinylstyrene joins in above-mentioned intercalation seed emulsion with constant speed, at 75 ± 2 ℃, continue again insulation slaking 2 hours after dropwising, core-shell latex particles obtaining is through breakdown of emulsion, dry, after pulverizing, cross respectively 25 orders, 40 mesh sieves, make the nano core-shell structure efficient molecular sieve siccative of granularity between 25～40 orders.
Embodiment 7
Accurate weighing 0.5kg granularity is 2500 object polynites, dispersed with stirring (mass ratio of vinylformic acid/styrene/methacrylic acid methyl esters/butyl acrylate is 5:30:45:20) in 3kg the first mix monomer at the uniform velocity, within standing 24 hours, polynite is fully infiltrated, obtain montmorillonite intercalation dispersion liquid.The blending emulsifiers that adds 30kg water, 0.05kg disodium 4-dodecyl-2,4 '-oxydibenzenesulfonate and allyl group polyethoxye sulfonate to make according to the mass ratio of 1:1; stir; in nitrogen protection, 250rpm rotating speed, stir, to montmorillonite intercalation dispersion liquid, add 0.02kg oxidation-reduction type initiator (mixture that ammonium persulphate/sodium bisulfite forms with mol ratio 1:1) polyase 13 0 minute under the condition of water bath heating of 75 ± 2 ℃, obtain intercalation seed emulsion.Again the blending emulsifiers of 0.01kg disodium 4-dodecyl-2,4 '-oxydibenzenesulfonate and allyl group polyethoxye sulfonate is made to blending emulsifiers according to the mass ratio of 1:1, 7kg the second mix monomer (mass ratio of vinylformic acid/styrene/methacrylic acid methyl esters/butyl acrylate is 10:35:43:11), 0.04kg oxidation-reduction type initiator (mixture that ammonium persulphate/sodium bisulfite forms with mol ratio 1:1) and 0.02kg linking agent 1, 2-Vinylstyrene joins in above-mentioned intercalation seed emulsion with constant speed, at 75 ± 2 ℃, continue again insulation slaking 2 hours after dropwising, core-shell latex particles obtaining is through breakdown of emulsion, dry, after pulverizing, cross respectively 25 orders, 40 mesh sieves, make the nano core-shell structure efficient molecular sieve siccative of granularity between 25～40 orders.
Embodiment 8
Accurate weighing 0.5kg granularity is 2500 object polynites, dispersed with stirring (mass ratio of vinylformic acid/styrene/methacrylic acid methyl esters/butyl acrylate is 5:30:45:20) in 3kg the first mix monomer at the uniform velocity, within standing 24 hours, polynite is fully infiltrated, obtain montmorillonite intercalation dispersion liquid.The blending emulsifiers that adds 30kg water, 0.02kg disodium 4-dodecyl-2,4 '-oxydibenzenesulfonate and allyl group polyethoxye sulfonate to make according to the mass ratio of 1:1; stir; in nitrogen protection, 250rpm rotating speed, stir, to montmorillonite intercalation dispersion liquid, add 0.007kg oxidation-reduction type initiator (mixture that ammonium persulphate/sodium bisulfite forms with mol ratio 1:1) polyase 13 0 minute under the condition of water bath heating of 75 ± 2 ℃, obtain intercalation seed emulsion.Again the blending emulsifiers of 0.005kg disodium 4-dodecyl-2,4 '-oxydibenzenesulfonate and allyl group polyethoxye sulfonate is made to blending emulsifiers according to the mass ratio of 1:1, 7kg the second mix monomer (mass ratio of vinylformic acid/styrene/methacrylic acid methyl esters/butyl acrylate is 10:30:40:15), 0.015kg oxidation-reduction type initiator (mixture that ammonium persulphate/sodium bisulfite forms with mol ratio 1:1) joins in above-mentioned intercalation seed emulsion with constant speed, at 75 ± 2 ℃, continue again insulation slaking 2 hours after dropwising, core-shell latex particles obtaining is through breakdown of emulsion, dry, after pulverizing, cross respectively 25 orders, 40 mesh sieves, make the nano core-shell structure efficient molecular sieve siccative of granularity between 25～40 orders.
Embodiment 9
Accurate weighing 0.5kg granularity is 2500 object polynites, dispersed with stirring (mass ratio of vinylformic acid/styrene/methacrylic acid methyl esters/butyl acrylate is 5:30:45:20) in 3kg the first mix monomer at the uniform velocity, within standing 24 hours, polynite is fully infiltrated, obtain montmorillonite intercalation dispersion liquid.The blending emulsifiers that adds 30kg water, 0.02kg disodium 4-dodecyl-2,4 '-oxydibenzenesulfonate and allyl group polyethoxye sulfonate to make according to the mass ratio of 1:1; stir; in nitrogen protection, 250rpm rotating speed, stir, to montmorillonite intercalation dispersion liquid, add 0.007kg oxidation-reduction type initiator (mixture that ammonium persulphate/sodium bisulfite forms with mol ratio 1:1) polyase 13 0 minute under the condition of water bath heating of 75 ± 2 ℃, obtain intercalation seed emulsion.Again the blending emulsifiers of 0.005kg disodium 4-dodecyl-2,4 '-oxydibenzenesulfonate and allyl group polyethoxye sulfonate is made to blending emulsifiers according to the mass ratio of 1:1, 7kg the second mix monomer (mass ratio of vinylformic acid/styrene/methacrylic acid methyl esters/butyl acrylate is 10:30:40:14), 0.015kg oxidation-reduction type initiator (mixture that ammonium persulphate/sodium bisulfite forms with mol ratio 1:1) and 0.025kg linking agent 1, 2-Vinylstyrene joins in above-mentioned intercalation seed emulsion with constant speed, at 75 ± 2 ℃, continue again insulation slaking 2 hours after dropwising, core-shell latex particles obtaining is through breakdown of emulsion, dry, after pulverizing, cross respectively 25 orders, 40 mesh sieves, make the nano core-shell structure efficient molecular sieve siccative of granularity between 25～40 orders.
Effect embodiment 1
Fig. 2 is that the water absorbing properties of explanation nano core-shell structure efficient molecular sieve siccative is with the variation of content of crosslinking agent.Test is the mensuration of nano core-shell structure efficient molecular sieve siccative water-intake rate, accurately take respectively the nano core-shell structure efficient molecular sieve siccative sample that 0.1g polynite and 0.1g embodiment 1-4 make and put into 250ml beaker, the 100ml deionized water that adds 20 ℃, be immersed in the water and soak 24 hours, with 100 order mesh screens, the free water elimination of sample is refunded to beaker, and on mesh screen after standing 15min, with graduated cylinder, measure the volume V that remains water in beaker, water-intake rate Q (ml/g) is calculated as follows:
Q＝(100－V)/0.1
Get 4 of parallel samples, the mean value that fetches data is as experimental result.From accompanying drawing 2, in the present invention, polynite content is in the time of 5～10 parts, and the water absorbing properties of nano core-shell structure efficient molecular sieve siccative is best.
Effect embodiment 2
Siccative is prepared in the pure polynite of comparative example 1 use.
Siccative (not montmorillonoid-containing) prepared by comparative example 2 use straight polymers: preparation method is identical with embodiment 1.
The performance perameter of the siccative that embodiment 1-9 and comparative example 1 and 2 provide refers to table 1:
The performance perameter table of the siccative that table 1 embodiment 1-9 and comparative example 1 and 2 provide
As shown in Table 1, the efficient molecular sieve siccative that the embodiment of the present invention provides, the 4-8 that its water-intake rate is existing inorganic materials is doubly.
1,2-Vinylstyrene is linking agent, and when linking agent massfraction is very little time, the soluble fractions of matrix material increases, water absorption decreased.Therefore nano composite material is along with the increase of linking agent massfraction, and cross-linking set increases, and its reticulated structure stability increases, and water absorbent rate also increases thereupon.And the polynite of high dispersing reacts at its interlayer and Acrylic Acid Monomer, in polymerization process, the laminated structure of polynite is stripped from into monolithic layer structure substantially, most polynite exists with nanoscale in nano composite material, greatly increase its outer surface area, make polynite there is larger specific surface area, the nano effect producing is very obvious, formation be take monolithic layer nano imvite as auxiliary space cross-linking set, promote the crosslinked of matrix material, obtain crosslinked appropriate polymkeric substance; But when linking agent massfraction is too much, the cross-linking set in matrix material is overstocked, the segment molecular-weight average between network cross-linked point diminishes, and network shrinks, and then affects the water absorbing properties of matrix material, reduces its water-intake rate.For embodiment 4, due to the add-on of initiator, very little time, monomer conversion is lower, and in the product obtaining, effectively tridimensional network is less, makes the water absorption decreased of matrix material.
Above embodiment is only exemplary embodiment of the present invention, is not used in restriction the present invention, and protection scope of the present invention is defined by the claims.Those skilled in the art can make various modifications or be equal to replacement the present invention in essence of the present invention and protection domain, this modification or be equal to replacement and also should be considered as dropping in protection scope of the present invention.
Claims (8)
1. a preparation method for nano core-shell structure efficient molecular sieve siccative, is characterized in that, said method comprising the steps of:
Step 1, mixes vinylformic acid, vinylbenzene, methyl methacrylate, butyl acrylate to make the first mix monomer according to the weight proportion of 5～10:25～30:40～45:20～25; 1～30 weight part polynite mixes with 30 weight part the first mix monomers, at the uniform velocity stirs and forms stable montmorillonite intercalation dispersion liquid, standing 20～30 hours;
Step 2, the blending emulsifiers of disodium 4-dodecyl-2,4 '-oxydibenzenesulfonate and allyl group polyethoxye sulfonate is made blending emulsifiers according to the mass ratio of 1:1, to inflated with nitrogen protection in described montmorillonite intercalation dispersion liquid, add 0.1～0.5 weight part blending emulsifiers and 300 weight parts waters, the post-heating that stirs is warming up to 72～76 ℃, under whipped state, add 0.05～0.2 weight part oxidation-reduction type initiator, after polymerization completes, obtain intercalation seed emulsion;
Step 3, mixes vinylformic acid, vinylbenzene, methyl methacrylate, butyl acrylate to make the second mix monomer according to the weight proportion of 10～15:30～35:40～45:10～15; By 0.02～0.1 weight part blending emulsifiers, 70 weight part the second mix monomers, 0.1～0.4 weight part oxidation-reduction type initiator, 0.2～1 weight part 1,2-Vinylstyrene joins in the intercalation seed emulsion that step 2 makes with constant speed under the temperature condition at 73～76 ℃, continues insulation slaking again and obtain core-shell latex particles after dropwising;
Step 4, makes nano core-shell structure efficient molecular sieve siccative after the sub-breakdown of emulsion of core-shell latex particles, finish-drying pulverizing.
2. the preparation method of nano core-shell structure efficient molecular sieve siccative according to claim 1, is characterized in that, described emulsifying agent is that disodium 4-dodecyl-2,4 '-oxydibenzenesulfonate and allyl group polyethoxye sulfonate form by the mixed in molar ratio of 1:1.
3. the preparation method of nano core-shell structure efficient molecular sieve siccative according to claim 1, is characterized in that, described oxidation-reduction type initiator is that ammonium persulphate and sodium bisulfite form by the mixed in molar ratio of 1:1.
4. the preparation method of nano core-shell structure efficient molecular sieve siccative according to claim 1, is characterized in that, in step 4, the drying temperature of nucleocapsid latex particle is 110～125 ℃.
5. the preparation method of nano core-shell structure efficient molecular sieve siccative according to claim 1, it is characterized in that, the sub-breakdown of emulsion of core-shell latex particles, dry, cross respectively 25 orders, 40 mesh sieves after pulverizing, make the nano core-shell structure efficient molecular sieve siccative of granularity between 25～40 orders.
6. the preparation method of nano core-shell structure efficient molecular sieve siccative according to claim 1, is characterized in that, the polynite granularity in step 1 is ultra-fine polynite more than 2500 orders.
7. the preparation method of nano core-shell structure efficient molecular sieve siccative according to claim 1, it is characterized in that, step 1, mixes vinylformic acid, vinylbenzene, methyl methacrylate, butyl acrylate to make the first mix monomer according to the weight proportion of 8～10:25～30:42～45:20～25.
8. the preparation method of nano core-shell structure efficient molecular sieve siccative according to claim 1, it is characterized in that, step 3, mixes vinylformic acid, vinylbenzene, methyl methacrylate, butyl acrylate to make the second mix monomer according to the weight proportion of 12～15:32～35:43～45:14～15.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410206050.5A CN103951781B (en) | 2014-05-15 | 2014-05-15 | A kind of preparation method of nano core-shell structure efficient molecular sieve drier |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410206050.5A CN103951781B (en) | 2014-05-15 | 2014-05-15 | A kind of preparation method of nano core-shell structure efficient molecular sieve drier |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103951781A true CN103951781A (en) | 2014-07-30 |
| CN103951781B CN103951781B (en) | 2016-05-25 |
Family
ID=51329150
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410206050.5A Active CN103951781B (en) | 2014-05-15 | 2014-05-15 | A kind of preparation method of nano core-shell structure efficient molecular sieve drier |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103951781B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105131873A (en) * | 2015-09-07 | 2015-12-09 | 中国建筑材料科学研究总院 | Fireproof liquid of composite fireproof glass and preparation method thereof and composite fireproof glass |
| CN105131868A (en) * | 2015-09-07 | 2015-12-09 | 中国建筑材料科学研究总院 | Fireproof liquid of composite fireproof glass and preparation method thereof and composite fireproof glass |
| CN107051135A (en) * | 2017-06-04 | 2017-08-18 | 曾双 | A kind of high water absorption hygroscopic agent preparation method |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002121224A (en) * | 2000-10-13 | 2002-04-23 | Chuo Rika Kogyo Corp | Aqueous emulsion and two-pack curing type emulsion- based adhesive using the same |
| CN101659735A (en) * | 2009-09-24 | 2010-03-03 | 中国海洋石油总公司 | Polyester modified core shell self crosslinking styrene-acrylate emulsion and preparation method thereof and anticorrosion coating therewith |
| CN101838368A (en) * | 2009-04-10 | 2010-09-22 | 兰州理工大学 | Method for preparing acrylic acid/montmorillonite nano composite material |
| CN102702419A (en) * | 2012-05-29 | 2012-10-03 | 中科院广州化学有限公司 | Preparation method of montmorillonite-modified crosslinked acrylate-hybridized core-shell emulsion |
| CN102924668A (en) * | 2012-11-09 | 2013-02-13 | 常州大学 | Preparation method of corncob, acrylic acid polymer and montmorillonite composite super absorbent resin |
-
2014
- 2014-05-15 CN CN201410206050.5A patent/CN103951781B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002121224A (en) * | 2000-10-13 | 2002-04-23 | Chuo Rika Kogyo Corp | Aqueous emulsion and two-pack curing type emulsion- based adhesive using the same |
| CN101838368A (en) * | 2009-04-10 | 2010-09-22 | 兰州理工大学 | Method for preparing acrylic acid/montmorillonite nano composite material |
| CN101659735A (en) * | 2009-09-24 | 2010-03-03 | 中国海洋石油总公司 | Polyester modified core shell self crosslinking styrene-acrylate emulsion and preparation method thereof and anticorrosion coating therewith |
| CN102702419A (en) * | 2012-05-29 | 2012-10-03 | 中科院广州化学有限公司 | Preparation method of montmorillonite-modified crosslinked acrylate-hybridized core-shell emulsion |
| CN102924668A (en) * | 2012-11-09 | 2013-02-13 | 常州大学 | Preparation method of corncob, acrylic acid polymer and montmorillonite composite super absorbent resin |
Non-Patent Citations (2)
| Title |
|---|
| 张海龙等: ""P(BA-g-MMA)/纳米蒙脱土复合粒子的制备及其增韧PVC的研究"", 《中国塑料》, vol. 28, no. 7, 26 July 2014 (2014-07-26), pages 17 - 21 * |
| 王艺峰等: ""反应型乳化剂作用下的丙烯酸酯共聚物乳液"", 《武汉理工大学学报》, vol. 33, no. 1, 30 January 2011 (2011-01-30) * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105131873A (en) * | 2015-09-07 | 2015-12-09 | 中国建筑材料科学研究总院 | Fireproof liquid of composite fireproof glass and preparation method thereof and composite fireproof glass |
| CN105131868A (en) * | 2015-09-07 | 2015-12-09 | 中国建筑材料科学研究总院 | Fireproof liquid of composite fireproof glass and preparation method thereof and composite fireproof glass |
| CN105131868B (en) * | 2015-09-07 | 2016-11-30 | 中国建筑材料科学研究总院 | Fire-resistant fluid of composite fireproof glass and preparation method thereof and composite fireproof glass |
| CN107051135A (en) * | 2017-06-04 | 2017-08-18 | 曾双 | A kind of high water absorption hygroscopic agent preparation method |
| CN107051135B (en) * | 2017-06-04 | 2020-01-17 | 吉林大学第一医院 | Preparation method of high-water-absorption moisture absorbent |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103951781B (en) | 2016-05-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| AU2020227037B2 (en) | Graphene oxide-tetraethyl orthosilicate/silane composite gel material, and preparation method and use thereof | |
| CN103102876B (en) | Preparation method for inorganic-organic composite type profile control agent | |
| US10759987B1 (en) | Composite temperature resistance gel plugging agent, preparation method thereof and use thereof in profile control and water plugging of ultra-deepth reservoir | |
| CN102020817B (en) | Method for preparing nano silicon oxide modified silicone acrylate emulsifier-free emulsion | |
| CN110317512B (en) | Tunnel engineering spray film waterproof material and preparation method thereof | |
| CN104725971A (en) | Multifunctional thermal insulation coating containing titanium dioxide/attapulgite nanocomposite material and preparation method thereof | |
| CN101304958A (en) | Use of polymer microparticles in building material mixtures | |
| CN104671706B (en) | A kind of flexible compound silicate heat-protective coatings and preparation method | |
| CN103253886B (en) | A kind of Polycarboxylate superplasticizer synergist and preparation method thereof | |
| CN106883357A (en) | A kind of pre-crosslinked gel delays swollen microballoon profile control agent and its production and use | |
| CN101575191A (en) | Expanded and vitrified microsphere insulating material for construction wall and production process | |
| CN106827753A (en) | A kind of roof greening waterproof roll and preparation method | |
| CN103803844B (en) | Cracking resistance reinforcing agent of inorganic coating material for building and a preparation method of cracking resistance reinforcing agent | |
| CN103951781A (en) | Preparation method of efficient molecular sieve desiccant with core-shell nanostructure | |
| WO2024007755A1 (en) | High impermeability and low thermal conductivity inorganic lightweight foam concrete and preparation method therefor | |
| CN107311693B (en) | Protective cement concrete curing agent and preparation method and application thereof | |
| CN103864341A (en) | Concrete hardening agent and preparation method thereof | |
| CN102911674A (en) | Stable multilayer-film structural foaming agent and preparation method thereof | |
| CN103497290B (en) | Redispersible polymer latex powder and preparation method thereof | |
| CN103241977B (en) | Novel water retention agent for architectural dry powder mortar, and preparation method and application thereof | |
| CN103980412B (en) | A kind of preparation method of nano core-shell structure efficient molecular sieve drier | |
| CN105130314A (en) | Modified cement slurry for rapidly repairing concrete | |
| CN102603961B (en) | Preparation method of styrene-acrylate soap-free emulsion | |
| CN111484269B (en) | Viscosity regulator for cement-based grouting material and preparation method thereof | |
| CN103819991B (en) | Protection material suitable for dinosaur fossil and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |