CN115007122A - Drying agent and preparation method thereof - Google Patents

Drying agent and preparation method thereof Download PDF

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CN115007122A
CN115007122A CN202210771176.1A CN202210771176A CN115007122A CN 115007122 A CN115007122 A CN 115007122A CN 202210771176 A CN202210771176 A CN 202210771176A CN 115007122 A CN115007122 A CN 115007122A
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desiccant
moisture absorption
moisture
water
parts
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CN115007122B (en
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戴增添
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Dongguan Dingxing Industry Co ltd
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/26Synthetic macromolecular compounds
    • B01J20/265Synthetic macromolecular compounds modified or post-treated polymers
    • B01J20/267Cross-linked polymers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/26Drying gases or vapours
    • B01D53/261Drying gases or vapours by adsorption
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/26Drying gases or vapours
    • B01D53/28Selection of materials for use as drying agents
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00Processes of polymerisation
    • C08F2/46Polymerisation initiated by wave energy or particle radiation
    • C08F2/48Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F261/00Macromolecular compounds obtained by polymerising monomers on to polymers of oxygen-containing monomers as defined in group C08F16/00
    • C08F261/02Macromolecular compounds obtained by polymerising monomers on to polymers of oxygen-containing monomers as defined in group C08F16/00 on to polymers of unsaturated alcohols
    • C08F261/04Macromolecular compounds obtained by polymerising monomers on to polymers of oxygen-containing monomers as defined in group C08F16/00 on to polymers of unsaturated alcohols on to polymers of vinyl alcohol
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06Polymers provided for in subclass C08G
    • C08F290/062Polyethers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00Chemical modification by after-treatment
    • C08F8/12Hydrolysis

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  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Abstract

The invention relates to the technical field of drying agents, in particular to a drying agent and a preparation method thereof, wherein the drying agent comprises a drying agent bag and a drying agent body accommodated in the drying agent bag, and the drying agent body comprises moisture absorption type resin and a plurality of silica gels attached to the surface of the moisture absorption type resin; the moisture absorption resin is prepared from the following raw materials: acrylic acid, acrylamide, polyvinyl alcohol, a crosslinking agent, a photoinitiator, water and sodium hydroxide solution. The surface of the moisture absorption type resin is adhered with a plurality of silica gels, the silica gels absorb moisture of air, the silica gels absorb water and are condensed into liquid water, and the liquid water directly contacts the moisture absorption type resin, so that the moisture absorption type resin can absorb the liquid water in the silica gels, the water absorption efficiency is improved, the integral water absorption capacity of the drying agent is increased, the saturated water absorption rate of the drying agent is increased, an unexpected effect is obtained in the actual application process, and the drying agent is applied to transportation environments such as sea transportation, freight transportation and the like, so that the cost is obviously saved.

Description

Drying agent and preparation method thereof
Technical Field
The invention relates to the technical field of drying agents, in particular to a drying agent and a preparation method thereof.
Background
Desiccants refer to substances that remove moisture from moist substances and are often classified into two categories: chemical desiccants, such as calcium sulfate and calcium chloride, dry by combining with water to form hydrates; physical desiccants, such as silica gel, activated alumina, and the like, dry by physically adsorbing water. Moisture management is closely related to the yield of the product. In the case of food products, at the proper temperature and humidity, bacteria and mold in the food can multiply at an alarming rate, spoil the food, and cause moisture and color change. Electronic products also suffer from metal oxidation due to excessive humidity, resulting in defective products. The desiccant is used to avoid the generation of defective products caused by excessive moisture.
Although the traditional chemical drying agent and physical drying agent can absorb water from the air to achieve the effects of drying and moisture prevention, the water absorption amount is low and the traditional chemical drying agent and physical drying agent are easy to saturate, so that the using amount of the drying agent needs to be increased to obtain more effective adsorption, the occupied space is larger, the weight is heavier, and the traditional chemical drying agent and physical drying agent are not beneficial to saving the cost when being applied to transportation environments such as maritime transportation, freight transportation and the like.
Disclosure of Invention
In order to overcome the disadvantages and shortcomings of the prior art, an object of the present invention is to provide a desiccant, wherein a plurality of silica gels are attached to the surface of a moisture-absorbing resin, and the silica gels are used for absorbing moisture of air, so that the silica gels absorb water and are condensed into liquid water, which is more beneficial for the moisture-absorbing resin to absorb the liquid water in the silica gels, thereby increasing the overall water absorption capacity of the desiccant and increasing the saturated water absorption rate of the desiccant.
The second purpose of the invention is to provide a preparation method of the drying agent, which has the advantages of simple operation, convenient control, high production efficiency and low production cost and can be used for large-scale production.
One of the purposes of the invention is realized by the following technical scheme: a desiccant comprises a desiccant material bag and a desiccant body accommodated in the desiccant material bag, wherein the desiccant body comprises moisture absorption type resin and a plurality of silica gels attached to the surface of the moisture absorption type resin;
the moisture-absorbing resin is prepared from the following raw materials in parts by weight:
Figure BDA0003724046690000021
the desiccant provided by the invention adopts the desiccant bag as a carrier, the moisture absorption type resin with a plurality of silica gels attached to the surface is filled, the desiccant bag protects the moisture absorption type resin, the silica gels are attached to the surface of the moisture absorption type resin, the silica gels absorb moisture of air, the silica gels absorb water and are condensed into liquid water, and the liquid water directly contacts the moisture absorption type resin, so that the moisture absorption type resin can absorb the liquid water in the silica gels, the water absorption efficiency is improved, the integral water absorption capacity of the desiccant is increased, the saturated water absorption rate of the desiccant is increased, an unexpected effect is obtained in the actual application process, and the desiccant is applied to transportation environments such as sea transportation, freight transportation and the like, and the cost is remarkably saved.
In addition, the moisture-absorbing resin takes acrylic acid as a main body, and acrylamide, polyvinyl alcohol, a cross-linking agent, a photoinitiator, water and a sodium hydroxide solution are added, namely, the monomer residue obtained by photo-initiated polymerization is low, and the water and saline absorption effects are better under the weak acid or weak alkaline condition.
Preferably, the preparation method of each part of the cross-linking agent comprises the following steps:
a1, uniformly mixing 100 parts by weight of polyethylene glycol and 0.15-0.20 part by weight of polymerization inhibitor, adding 3-4 parts by weight of acrylic acid, 0.4-0.5 part by weight of esterification catalyst, 100 parts by weight of organic solvent and 150 parts by weight of cyclohexane, stirring, heating to 85-95 ℃, and preserving heat for 5-7 hours to obtain a crosslinked semi-finished product;
a2, adding a sodium carbonate solution into the crosslinking semi-finished product to adjust the pH value to 6.5-7.5, washing, extracting, and drying under vacuum and reduced pressure for 24 hours to obtain the crosslinking agent.
By adopting the technical scheme, the preparation method of the cross-linking agent is characterized in that esterification catalysis is carried out under the action of an esterification catalyst, a polymerization inhibitor and cyclohexane, and the prepared cross-linking agent is particularly suitable for preparing the moisture-absorption resin disclosed by the invention, so that the moisture-absorption resin has a specific cross-linking degree, the moisture-absorption resin can form a porous network structure, and the water absorption rate is improved.
Preferably, the polymerization inhibitor is methyl hydroquinone or 2-tertiary butyl hydroquinone; the organic solvent is toluene, and the esterification catalyst is at least one of dicyclohexylcarbodiimide, N' -diisopropylcarbodiimide and 4-dimethylaminopyridine.
By adopting the technical scheme, the acrylic acid is prevented from self-polymerization, and the esterification rate of the cross-linking agent is improved, so that the moisture absorption resin with a specific cross-linking degree can be formed under the ultraviolet radiation, and the moisture absorption rate is improved.
Preferably, the photoinitiator is alpha, alpha-dimethoxy-alpha-phenylacetophenone and 2, 4-dihydroxybenzophenone in a weight ratio of 3: 1-5, mixing; the concentration of the sodium hydroxide solution is 50-60 wt%.
By adopting the technical scheme, the alpha, alpha-dimethoxy-alpha-phenylacetophenone and the 2, 4-dihydroxy benzophenone are synergistic, the polymerization initiating efficiency under ultraviolet radiation is higher, the moisture absorption resin is promoted to obtain higher molecular weight, the water absorption rate is improved, and the monomer residue is reduced. The concentration of the sodium hydroxide solution is 50-60 wt%, the neutralization degree of acrylic acid can be conveniently adjusted to 75-88% after the sodium hydroxide solution is added, and resin saponification is carried out, so that an unexpected effect is achieved on the water absorption and salt absorption rate of the moisture absorption resin under a weak acid or weak alkaline condition, and the monomer residue is reduced.
Preferably, the silica gel is fine-pore silica gel and/or coarse-pore silica gel; the particle size distribution of the silica gel is 230-460 meshes; the weight ratio of the moisture-absorbing resin to the silica gel is 100: 5-20.
Adopt above-mentioned technical scheme, silica gel is a gel, microporous structure has, consequently, stronger adsorptivity has, pore silica gel and coarse pore silica gel belong to high active adsorption material, coarse pore silica gel has higher adsorption capacity under the high condition of relative humidity, pore silica gel then adsorption capacity is higher than coarse pore silica gel under the lower condition of relative humidity, utilize the moisture content of silica gel adsorption air, silica gel water absorption is congealed into liquid water, liquid water direct contact moisture absorption type resin, more be favorable to the liquid water in the moisture absorption type resin absorption silica gel, improve water absorption efficiency. The weight ratio of the moisture absorption resin to the silica gel is 100:5-20, so that the water absorption efficiency is effectively improved, and the phenomenon that the combination of the moisture absorption resin and the silica gel is influenced due to mutual extrusion when the silica gel expands due to excessive use is avoided. More preferably, the silica gel is formed by mixing fine-pore silica gel and coarse-pore silica gel in a weight ratio of 1: 1-2.
The second purpose of the invention is realized by the following technical scheme: the preparation method of the drying agent comprises the following steps:
s, prefabricating a moisture-absorbing resin semi-finished product:
s1, taking acrylic acid, acrylamide, polyvinyl alcohol, a cross-linking agent, a photoinitiator, water and a plurality of sodium hydroxide solutions according to parts by weight;
s2, adding acrylic acid into water according to parts by weight, then adding a sodium hydroxide solution to adjust the neutralization degree of the acrylic acid to be 75-88%, and then adding polyvinyl alcohol, acrylamide, a cross-linking agent and a photoinitiator to mix uniformly to obtain a mixed solution;
s3, fully reacting the mixed solution at the temperature of 20-35 ℃ under stirring and ultraviolet radiation to obtain a reactant;
s4, adding a sodium hydroxide solution into the reactant, carrying out saponification reaction for 1-3h at 70-90 ℃, filtering, and dehydrating with 95% ethanol to obtain a semi-finished product of the moisture absorption resin;
r, preparing moisture absorption type resin particles with a plurality of silica gels attached to the surfaces;
p, packaging: and filling the moisture absorption type resin particles into a desiccant bag, and sealing and storing to obtain the desiccant.
By adopting the technical scheme, in the step S of prefabricating the semi-finished product of the moisture-absorption type resin, sodium hydroxide is adopted to adjust the neutralization degree of acrylic acid to 75-88%, then polyvinyl alcohol, acrylamide, a special cross-linking agent and a special photoinitiator are added and mixed, then the UV radiation is adopted to promote full reaction under the stirring of 20-35 ℃, then sodium hydroxide solution is adopted to saponify the semi-finished product, then filtration and 95% ethanol dehydration are carried out, and the obtained semi-finished product of the moisture-absorption type resin has the characteristics of low monomer residue and better water absorption and saline absorption effects under the weak acidic or weak alkaline condition. The method is characterized in that the neutralization degree of acrylic acid, the dosage of a cross-linking agent and the dosage of a photoinitiator are controlled, the three components have synergistic effects to ensure that the moisture-absorbing resin has an excellent water absorption effect, and the combined action of polyvinyl alcohol and acrylamide and saponification reaction of reactants are combined to play an unexpected effect on the water absorption and water absorption rate of the moisture-absorbing resin under weak acid or weak alkaline conditions and reduce monomer residues. And step R, preparing moisture absorption resin particles with a plurality of silica gels attached to the surfaces by using the moisture absorption resin semi-finished product so as to form a granular structure in the preparation process of the moisture absorption resin semi-finished product, and the moisture absorption effect is better. Further, in the step S4, the sodium hydroxide solution is added in an amount of 20 to 30 parts by weight and at a concentration of 50 to 60 wt%.
Preferably, the irradiance of the ultraviolet radiation is 0.8-1.4W/m 2 @340nm, and the irradiation time is 30-60 min; in the step S3, the rotation speed of stirring is 100-200 r/min.
By adopting the technical scheme, the wavelength is 340nm, and the irradiance is 0.8-1.4W/m 2 The ultraviolet radiation initiates polymerization, the product purity is higher, the synthesis time is short, the cost is lower, the polymerization temperature is easier to control by combining the environment of 20-35 ℃, and the influence on the overall water absorption effect of the moisture absorption resin caused by imploding caused by local overheating can be prevented; the stirring speed is 100-200r/min, so that the molecular weight of the polymerization product is promoted to be uniform, and the partial moisture absorption resin is prevented from being excessively crosslinked to reduce the water absorption.
Preferably, the method for preparing the moisture-absorption resin particles with a plurality of silica gels attached to the surfaces thereof comprises the following steps:
r1, taking 100 parts of moisture-absorbing resin semi-finished product, 1-5 parts of micron-sized zeolite powder with the particle size of 30-60 mu m, 5-20 parts of silica gel and a plurality of polyoxyethylene-water solutions with the concentration of 1-3 wt% for later use;
r2, adding a polyoxyethylene-water solution into the semi-finished product of the hygroscopic resin dropwise to make the water content of the semi-finished product reach 32-50 wt%, then adding micron-sized zeolite powder, and mixing uniformly to obtain pre-formed particles;
r3, adding silica gel to the pre-granulated material, and drying the resultant with a drum dryer to obtain moisture-absorbent resin particles having a plurality of silica gels attached to the surface thereof.
By adopting the technical scheme, a plurality of silica gel moisture absorption resin particles are attached to the surface of the method, wherein the polyoxyethylene-water solution is dropwise added in the step R2 to ensure that the moisture content of the moisture absorption resin semi-finished product reaches 32-50 wt%, which is beneficial to granulation of the moisture absorption resin, and has equivalent particle size, improved strength and improved water absorption capacity; the micron-sized zeolite powder is added to facilitate granulation and dispersion of the moisture-absorbing resin, and the micron-sized zeolite powder has a porous adsorption structure and is more beneficial to water absorption; step R3 silica gel was added and dried by a drum dryer to adhere some silica gel to the surface of the moisture-absorbent resin particles and dried.
Further, the concentration of the polyoxyethylene-water solution is 1-3 wt%; the particle size of the micron-sized zeolite powder is 30-60 mu m.
The invention has the beneficial effects that: the desiccant provided by the invention adopts the desiccant bag as a carrier, the moisture absorption type resin with a plurality of silica gels attached to the surface is filled, the desiccant bag protects the moisture absorption type resin, the silica gels are attached to the surface of the moisture absorption type resin, the silica gels absorb moisture of air, the silica gels absorb water and are condensed into liquid water, and the liquid water directly contacts the moisture absorption type resin, so that the moisture absorption type resin can absorb the liquid water in the silica gels, the water absorption efficiency is improved, the integral water absorption capacity of the desiccant is increased, the saturated water absorption rate of the desiccant is increased, an unexpected effect is obtained in the actual application process, and the desiccant is applied to transportation environments such as sea transportation, freight transportation and the like, and the cost is remarkably saved.
In addition, the moisture-absorbing resin takes acrylic acid as a main body, and acrylamide, polyvinyl alcohol, a cross-linking agent, a photoinitiator, water and a sodium hydroxide solution are added, namely, the monomer residue obtained by photo-initiated polymerization is low, and the water and saline absorption effects are better under the weak acid or weak alkaline condition.
The preparation method disclosed by the invention is simple to operate, convenient to control, high in production efficiency and low in production cost, and can be used for large-scale production.
Detailed Description
The present invention will be further described with reference to the following examples for facilitating understanding of those skilled in the art, and the description of the embodiments is not intended to limit the present invention.
Example 1
A desiccant comprises a desiccant material bag and a desiccant body accommodated in the desiccant material bag, wherein the desiccant body comprises moisture absorption type resin and a plurality of silica gels attached to the surface of the moisture absorption type resin;
the moisture-absorbing resin is prepared from the following raw materials in parts by weight:
Figure BDA0003724046690000061
Figure BDA0003724046690000071
the preparation method of each part of the cross-linking agent comprises the following steps:
a1, mixing 100 parts by weight of polyethylene glycol and 0.18 part by weight of polymerization inhibitor uniformly, adding 3.5 parts by weight of acrylic acid, 0.45 part by weight of esterification catalyst, 200 parts by weight of organic solvent and 200 parts by weight of cyclohexane, stirring, heating to 90 ℃, and keeping the temperature for 6 hours to obtain a cross-linked semi-finished product;
a2, adding a sodium carbonate solution into the crosslinking semi-finished product to adjust the pH value to 7.0, washing, extracting, and drying under vacuum and reduced pressure for 24 hours to obtain the crosslinking agent.
The polymerization inhibitor is methyl hydroquinone; the organic solvent is toluene.
The esterification catalyst is dicyclohexylcarbodiimide.
The photoinitiator is alpha, alpha-dimethoxy-alpha-phenylacetophenone and 2, 4-dihydroxy benzophenone in a weight ratio of 3: 3, and mixing.
The silica gel is formed by mixing fine-pore silica gel and coarse-pore silica gel according to a weight ratio of 1: 1.5; the particle size distribution of the silica gel is 325 meshes.
The preparation method of the drying agent comprises the following steps:
s, prefabricating a moisture-absorbing resin semi-finished product:
s1, taking acrylic acid, acrylamide, polyvinyl alcohol, a cross-linking agent, a photoinitiator, water and a plurality of sodium hydroxide solutions according to parts by weight;
s2, adding acrylic acid into water according to parts by weight, then adding a sodium hydroxide solution with the concentration of 55 wt% to adjust the neutralization degree of the acrylic acid to be 80%, and then adding polyvinyl alcohol, acrylamide, a cross-linking agent and a photoinitiator to be uniformly mixed to obtain a mixed solution;
s3, fully reacting the mixed solution at 30 ℃ under stirring and ultraviolet radiation to obtain a reactant;
s4, adding 25 parts of 55 wt% sodium hydroxide solution into the reactant, performing saponification reaction for 2 hours at 80 ℃, filtering, and dehydrating with 95% ethanol to obtain a semi-finished product of the moisture absorption resin;
r, preparing moisture absorption resin particles with a plurality of silica gels attached to the surfaces:
r1, taking 100 parts of semi-finished product of hygroscopic resin, 3 parts of micron-sized zeolite powder with the particle size of 50 mu m, 15 parts of silica gel and a plurality of polyoxyethylene-water solutions with the concentration of 2 wt% for later use;
r2, adding a polyoxyethylene-water solution into the semi-finished product of the moisture absorption resin dropwise to make the water content of the semi-finished product reach 40 wt%, then adding micron-sized zeolite powder, and mixing uniformly to obtain a pre-formed granule;
r3, adding silica gel into the pre-granulated substance, and drying by adopting a drum dryer to obtain moisture absorption type resin particles with a plurality of silica gels attached to the surfaces;
p, packaging: and filling the moisture absorption type resin particles into a desiccant bag, and sealing and storing to obtain the desiccant.
The irradiance of the ultraviolet radiation is 1W/m 2 @340nm, and the irradiation time is 40 min; in the step S3, the stirring speed is 150 r/min.
Example 2
A desiccant comprises a desiccant material bag and a desiccant body accommodated in the desiccant material bag, wherein the desiccant body comprises moisture absorption type resin and a plurality of silica gels attached to the surface of the moisture absorption type resin;
the moisture-absorbing resin is prepared from the following raw materials in parts by weight:
Figure BDA0003724046690000081
the preparation method of each part of the cross-linking agent comprises the following steps:
a1, uniformly mixing 100 parts of polyethylene glycol and 0.15 part of polymerization inhibitor according to parts by weight, adding 3 parts of acrylic acid, 0.4 part of esterification catalyst, 100 parts of organic solvent and 150 parts of cyclohexane, stirring, heating to 85 ℃, and preserving heat for 5 hours to obtain a cross-linked semi-finished product;
a2, adding a sodium carbonate solution into the cross-linking semi-finished product to adjust the pH value to 6.5, washing, extracting, and drying under reduced pressure for 24 hours to obtain the cross-linking agent.
The polymerization inhibitor is 2-tert-butyl hydroquinone; the organic solvent is toluene.
The esterification catalyst is N, N' -diisopropylcarbodiimide.
The photoinitiator is alpha, alpha-dimethoxy-alpha-phenylacetophenone and 2, 4-dihydroxy benzophenone in a weight ratio of 3: 1 are mixed.
The silica gel is formed by mixing fine-pore silica gel and coarse-pore silica gel according to the weight ratio of 1: 1; the particle size distribution of the silica gel is 230 meshes.
The preparation method of the drying agent comprises the following steps:
s, prefabricating a moisture-absorbing resin semi-finished product:
s1, taking acrylic acid, acrylamide, polyvinyl alcohol, a cross-linking agent, a photoinitiator, water and a plurality of sodium hydroxide solutions according to parts by weight;
s2, adding acrylic acid into water according to parts by weight, then adding a sodium hydroxide solution with the concentration of 50 wt% to adjust the neutralization degree of the acrylic acid to be 75%, and then adding polyvinyl alcohol, acrylamide, a cross-linking agent and a photoinitiator to be uniformly mixed to obtain a mixed solution;
s3, fully reacting the mixed solution at 20 ℃ under stirring and ultraviolet radiation to obtain a reactant;
s4, adding 20 parts of 50 wt% sodium hydroxide solution into the reactant, performing saponification reaction for 1h at 70 ℃, filtering, and dehydrating with 95% ethanol to obtain a semi-finished product of the moisture absorption resin;
r, preparing moisture absorption resin particles with a plurality of silica gels attached to the surfaces:
r1, taking 100 parts of semi-finished product of hygroscopic resin, 1 part of micron-sized zeolite powder with the particle size of 30 mu m, 5 parts of silica gel and a plurality of polyoxyethylene-water solutions with the concentration of 1 wt% for later use;
r2, adding polyoxyethylene-water solution into the semi-finished product of the hygroscopic resin dropwise until the water content reaches 32 wt%, and then adding micron-sized zeolite powder to mix uniformly to obtain pre-formed particles;
r3, adding silica gel into the pre-granulated substance, and drying by adopting a drum dryer to obtain moisture absorption type resin particles with a plurality of silica gels attached to the surfaces;
p, packaging: and filling the moisture absorption type resin particles into a desiccant bag, and sealing and storing to obtain the desiccant.
The irradiance of the ultraviolet radiation is 0.8W/m 2 @340nm, and the irradiation time is 30 min; in the step S3, the rotation speed of stirring is 100 r/min.
Example 3
A desiccant comprises a desiccant material bag and a desiccant body accommodated in the desiccant material bag, wherein the desiccant body comprises moisture absorption type resin and a plurality of silica gels attached to the surface of the moisture absorption type resin;
the moisture-absorbing resin is prepared from the following raw materials in parts by weight:
Figure BDA0003724046690000101
the preparation method of each part of the cross-linking agent comprises the following steps:
a1, uniformly mixing 100 parts of polyethylene glycol and 0.20 part of polymerization inhibitor according to parts by weight, adding 4 parts of acrylic acid, 0.5 part of esterification catalyst, 300 parts of organic solvent and 300 parts of cyclohexane, stirring, heating to 95 ℃, and preserving heat for 7 hours to obtain a cross-linked semi-finished product;
a2, adding a sodium carbonate solution into the crosslinking semi-finished product to adjust the pH value to 7.5, washing, extracting, and drying under vacuum and reduced pressure for 24 hours to obtain the crosslinking agent.
The polymerization inhibitor is methyl hydroquinone; the organic solvent is toluene.
The esterification catalyst is 4-dimethylamino pyridine.
The photoinitiator is alpha, alpha-dimethoxy-alpha-phenylacetophenone and 2, 4-dihydroxy benzophenone in a weight ratio of 3: 5, mixing the components.
The silica gel is formed by mixing fine-pore silica gel and coarse-pore silica gel according to a weight ratio of 1: 2; the particle size distribution of the silica gel is 460 meshes.
The preparation method of the drying agent comprises the following steps:
s, prefabricating a moisture-absorbing resin semi-finished product:
s1, taking acrylic acid, acrylamide, polyvinyl alcohol, a cross-linking agent, a photoinitiator, water and a plurality of sodium hydroxide solutions according to parts by weight;
s2, adding acrylic acid into water according to parts by weight, then adding a sodium hydroxide solution with the concentration of 60 wt% to adjust the neutralization degree of the acrylic acid to 88%, and then adding polyvinyl alcohol, acrylamide, a cross-linking agent and a photoinitiator to be uniformly mixed to obtain a mixed solution;
s3, fully reacting the mixed solution at 35 ℃ under stirring and ultraviolet radiation to obtain a reactant;
s4, adding 30 parts of 60 wt% sodium hydroxide solution into the reactant, performing saponification reaction for 3 hours at 90 ℃, filtering, and dehydrating with 95% ethanol to obtain a semi-finished product of the moisture absorption resin;
r, preparing moisture absorption resin particles with a plurality of silica gels attached to the surfaces:
r1, taking 100 parts of semi-finished product of hygroscopic resin, 5 parts of micron-sized zeolite powder with the particle size of 60 mu m, 20 parts of silica gel and a plurality of polyoxyethylene-water solutions with the concentration of 3 wt% for later use;
r2, adding a polyoxyethylene-water solution into the semi-finished product of the moisture absorption resin dropwise to enable the water content to reach 50 wt%, adding micron-sized zeolite powder, and mixing uniformly to obtain a pre-formed particle;
r3, adding silica gel into the pre-granulated substance, and drying by adopting a drum dryer to obtain moisture absorption type resin particles with a plurality of silica gels attached to the surfaces;
p, packaging: and filling the moisture absorption type resin particles into a desiccant bag, and sealing and storing to obtain the desiccant.
The irradiance of the ultraviolet radiation is 1.4W/m 2 @340nm, and the irradiation time is 60 min; in the step S3, the stirring speed is 200 r/min.
Example 4
A desiccant comprises a desiccant material bag and a desiccant body accommodated in the desiccant material bag, wherein the desiccant body comprises moisture absorption type resin and a plurality of silica gels attached to the surface of the moisture absorption type resin;
the moisture-absorbing resin is prepared from the following raw materials in parts by weight:
Figure BDA0003724046690000121
the preparation method of each part of the cross-linking agent comprises the following steps:
a1, uniformly mixing 100 parts of polyethylene glycol and 0.18 part of polymerization inhibitor according to parts by weight, adding 3.6 parts of acrylic acid, 0.42 part of esterification catalyst, 150 parts of organic solvent and 230 parts of cyclohexane, stirring, heating to 88 ℃, and preserving heat for 5.8 hours to obtain a cross-linked semi-finished product;
a2, adding a sodium carbonate solution into the crosslinking semi-finished product to adjust the pH value to 7.0, washing, extracting, and drying under vacuum and reduced pressure for 24 hours to obtain the crosslinking agent.
The polymerization inhibitor is 2-tert-butyl hydroquinone; the organic solvent is toluene.
The esterification catalyst is 4-dimethylamino pyridine.
The photoinitiator is alpha, alpha-dimethoxy-alpha-phenylacetophenone and 2, 4-dihydroxy benzophenone in a weight ratio of 3: 4, and mixing.
The silica gel is formed by mixing fine-pore silica gel and coarse-pore silica gel according to a weight ratio of 1: 1.8; the particle size distribution of the silica gel is 270 meshes.
The preparation method of the drying agent comprises the following steps:
s, prefabricating a moisture-absorbing resin semi-finished product:
s1, taking acrylic acid, acrylamide, polyvinyl alcohol, a cross-linking agent, a photoinitiator, water and a plurality of sodium hydroxide solutions according to parts by weight;
s2, adding acrylic acid into water according to parts by weight, then adding a sodium hydroxide solution with the concentration of 57 wt% to adjust the neutralization degree of the acrylic acid to 78%, and then adding polyvinyl alcohol, acrylamide, a cross-linking agent and a photoinitiator to be uniformly mixed to obtain a mixed solution;
s3, fully reacting the mixed solution at 28 ℃ under stirring and ultraviolet radiation to obtain a reactant;
s4, adding 27 parts of 57 wt% sodium hydroxide solution into the reactant, performing saponification reaction at 85 ℃ for 1.5h, filtering, and dehydrating with 95% ethanol to obtain a semi-finished product of the moisture absorption resin;
r, preparing moisture absorption resin particles with a plurality of silica gels attached to the surfaces:
r1, taking 100 parts of semi-finished product of hygroscopic resin, 3 parts of micron-sized zeolite powder with the particle size of 50 mu m, 15 parts of silica gel and a plurality of polyoxyethylene-water solutions with the concentration of 1.5 wt% for later use;
r2, adding a polyoxyethylene-water solution into the semi-finished product of the moisture absorption resin dropwise to make the water content reach 43 wt%, then adding micron-sized zeolite powder, and mixing uniformly to obtain pre-formed particles;
r3, adding silica gel into the pre-granulated substance, and drying by adopting a drum dryer to obtain moisture absorption type resin particles with a plurality of silica gels attached to the surfaces;
p, packaging: and filling the moisture absorption type resin particles into a desiccant bag, and sealing and storing to obtain the desiccant.
The irradiance of the ultraviolet radiation is 1.2W/m 2 @340nm, and the irradiation time is 45 min; in the step S3, the stirring speed is 180 r/min.
Comparative example 1
This comparative example differs from example 1 in that:
silica gel is not attached to the surface of the moisture-absorbing resin, and the moisture-absorbing resin and the silica gel are dispersed and filled into a desiccant bag;
in the preparation method of the drying agent, the steps R and P are changed into the following steps:
step R, infrared drying and crushing are carried out on the semi-finished product of the moisture-absorbing resin to obtain moisture-absorbing resin powder; namely, it is not necessary to prepare moisture-absorbent resin particles having a plurality of silica gels attached to the surface thereof;
step P, packaging: and mixing the moisture-absorbing resin powder and the silica gel according to the weight part ratio of 100:10, filling the mixture into a desiccant bag, and sealing and storing to obtain the desiccant.
Comparative example 2
This comparative example differs from example 1 in that:
silica gel is not attached to the surface of the moisture-absorbing resin, and the moisture-absorbing resin and the silica gel are dispersed and filled into a desiccant bag;
in the preparation method of the drying agent, the steps R3 and P are changed into:
step R3, adding no silica gel, and directly drying the pre-granulated substance by a drum dryer to obtain hygroscopic resin particles;
step P, packaging: and mixing the moisture absorption resin particles and silica gel according to the weight ratio of 100:10, filling the mixture into a desiccant bag, and sealing and storing to obtain the desiccant.
Comparative example 3
This comparative example differs from example 1 in that:
the cross-linking agent adopts N' N-methylene bisacrylamide which is commercially available.
Comparative example 4
This comparative example differs from example 1 in that:
and (3) the step S4 is not subjected to saponification reaction, namely the reactant of the step S3 is directly filtered and dehydrated by 95% ethanol to obtain a semi-finished product of the moisture absorption type resin.
Comparative example 5
This comparative example differs from example 1 in that:
the desiccant body is of moisture-absorbing resin, i.e., the desiccant body does not contain silica gel.
In the step R3, the pre-granulated product is dried directly by a drum dryer without adding silica gel, to obtain the moisture absorbent resin particles with a plurality of silica gels attached to the surface.
Comparative example 6
This comparative example differs from example 1 in that:
the desiccant body is silica gel, namely the desiccant body does not contain moisture-absorption resin; the silica gel is formed by mixing fine-pore silica gel and coarse-pore silica gel according to a weight ratio of 1: 1.5.
Performance testing
Taking the drier bodies of the examples 1-4 and the comparative examples 1-6, respectively taking 0.3g of the dosage, and respectively testing the saturated moisture absorption rate and the moisture absorption rate; the test method is as follows:
saturated moisture absorption rate: testing at 25 ℃ and RH being 100 percent until the desiccant body is continuously weighed for 1h twice and does not exceed 1mg, and calculating by referring to GB T6284-2006 Standard of drying and reducing method for general method of water determination in chemical products;
moisture absorption rate: testing by referring to a static adsorption method 3.7.1 of GB T34709-2017 silica gel general test method, and testing under the conditions of RH being 20%, RH being 50% and RH being 90% respectively;
the test results are shown in table 1 below:
TABLE 1
Figure BDA0003724046690000151
Figure BDA0003724046690000161
As can be seen from table 1 above, in the desiccant of the present invention, the desiccant body is adopted to adhere a plurality of silica gels on the surface of the moisture-absorbing resin, and the silica gels are used to absorb moisture of air, so that the silica gels absorb water and condense into liquid water, which is more beneficial for the moisture-absorbing resin to absorb the liquid water in the silica gels, thereby increasing the overall water absorption capacity of the desiccant and increasing the saturated water absorption of the desiccant. Compared with the comparative examples 1-2, the surface of the moisture-absorbent resin of example 1 is adhered with silica gel, and the moisture-absorbent resin is granulated, so that the moisture absorption rate is remarkably increased; compared with the comparative example 3, the special cross-linking agent of the example 1 is more beneficial to promoting the moisture absorption effect of the moisture absorption type resin combined with the silica gel; compared with the comparative example 4, the moisture absorption rate of the whole desiccant body is obviously improved by the saponification reaction of the moisture absorption resin step S4 in the example 1; compared with the comparative example 5, the moisture absorption effect is more obvious when the moisture absorption type resin with a plurality of silica gels attached to the surface is adopted in the example 1, and the high-efficiency moisture absorption effect is difficult to be exerted because the moisture absorption capacity of the moisture absorption type resin is lower if the moisture absorption type resin is only adopted; compared with the example 1, the desiccant body prepared by only mixing the fine-pore silica gel and the coarse-pore silica gel in the comparative example 6 has obviously insufficient moisture absorption rate and is easy to saturate, and the cost is not saved in transportation environments such as sea transportation, freight transportation and the like.
The above-described embodiments are preferred implementations of the present invention, and the present invention may be implemented in other ways without departing from the spirit of the present invention.

Claims (10)

1. A desiccant, characterized by: the desiccant comprises a desiccant material bag and a desiccant body accommodated in the desiccant material bag, wherein the desiccant body comprises moisture absorption type resin and a plurality of silica gels attached to the surface of the moisture absorption type resin;
the moisture-absorbing resin is prepared from the following raw materials in parts by weight:
Figure FDA0003724046680000011
2. the desiccant according to claim 1, wherein each portion of said cross-linking agent is prepared by a process comprising the steps of:
a1, uniformly mixing 100 parts by weight of polyethylene glycol and 0.15-0.20 part by weight of polymerization inhibitor, adding 3-4 parts by weight of acrylic acid, 0.4-0.5 part by weight of esterification catalyst, 100 parts by weight of organic solvent and 150 parts by weight of cyclohexane, stirring, heating to 85-95 ℃, and preserving heat for 5-7 hours to obtain a crosslinked semi-finished product;
a2, adding a sodium carbonate solution into the crosslinking semi-finished product to adjust the pH value to 6.5-7.5, washing, extracting, and drying under vacuum and reduced pressure for 24 hours to obtain the crosslinking agent.
3. A desiccant as claimed in claim 2, wherein: the polymerization inhibitor is methyl hydroquinone or 2-tert-butyl hydroquinone; the organic solvent is toluene.
4. A desiccant as claimed in claim 2, wherein: the esterification catalyst is at least one of dicyclohexylcarbodiimide, N' -diisopropylcarbodiimide and 4-dimethylaminopyridine.
5. A desiccant as claimed in claim 1, wherein: the photoinitiator is alpha, alpha-dimethoxy-alpha-phenylacetophenone and 2, 4-dihydroxy benzophenone in a weight ratio of 3: 1-5, mixing; the concentration of the sodium hydroxide solution is 50-60 wt%.
6. A desiccant as claimed in claim 1, wherein: the silica gel is fine-pore silica gel and/or coarse-pore silica gel; the particle size distribution of the silica gel is 230-460 meshes; the weight ratio of the moisture-absorbing resin to the silica gel is 100: 5-20.
7. A process for the preparation of a desiccant as claimed in any one of claims 1 to 6, characterized in that it comprises the following steps:
s, prefabricating a moisture absorption type resin semi-finished product:
s1, taking acrylic acid, acrylamide, polyvinyl alcohol, a cross-linking agent, a photoinitiator, water and a plurality of sodium hydroxide solutions according to parts by weight;
s2, adding acrylic acid into water according to parts by weight, then adding a sodium hydroxide solution to adjust the neutralization degree of the acrylic acid to be 75-88%, and then adding polyvinyl alcohol, acrylamide, a cross-linking agent and a photoinitiator to be uniformly mixed to obtain a mixed solution;
s3, fully reacting the mixed solution at the temperature of 20-35 ℃ under stirring and ultraviolet radiation to obtain a reactant;
s4, adding a sodium hydroxide solution into the reactant, performing saponification reaction for 1-3h at 70-90 ℃, filtering, and dehydrating with 95% ethanol to obtain a semi-finished product of the moisture absorption resin;
r, preparing moisture absorption type resin particles with a plurality of silica gels attached to the surfaces;
p, packaging: and filling the moisture absorption resin particles into a desiccant bag, and sealing and storing to obtain the desiccant.
8. The method of claim 7, wherein the desiccant is selected from the group consisting of: the irradiance of the ultraviolet radiation is 0.8-1.4W/m 2 @340nm, and the irradiation time is 30-60 min; in the step S3, the rotation speed of stirring is 100-200 r/min.
9. The method of claim 7, wherein the desiccant is selected from the group consisting of: the preparation method of the moisture absorption type resin particles with a plurality of silica gels attached to the surfaces comprises the following steps:
r1, taking 100 parts of moisture-absorbing resin semi-finished product, 1-5 parts of micron-sized zeolite powder with the particle size of 30-60 mu m, 5-20 parts of silica gel and a plurality of polyoxyethylene-water solutions with the concentration of 1-3 wt% for later use;
r2, adding a polyoxyethylene-water solution into the semi-finished product of the hygroscopic resin dropwise to make the water content of the semi-finished product reach 32-50 wt%, then adding micron-sized zeolite powder, and mixing uniformly to obtain pre-formed particles;
r3, adding silica gel to the pre-granulated material, and drying the resultant with a drum dryer to obtain moisture-absorbent resin particles having a plurality of silica gels attached to the surface thereof.
10. A process for the preparation of a desiccant as claimed in claim 9 in which: the concentration of the polyoxyethylene-water solution is 1-3 wt%; the particle size of the micron-sized zeolite powder is 30-60 mu m.
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