CN107298821A - A kind of preparation method of highly hygroscopic speed hygroscopic material - Google Patents
A kind of preparation method of highly hygroscopic speed hygroscopic material Download PDFInfo
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F120/04—Acids; Metal salts or ammonium salts thereof
- C08F120/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
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- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
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Abstract
The invention belongs to field of polymer material preparing technology, and in particular to a kind of preparation method of highly hygroscopic speed hygroscopic material.The present invention is using natural sponge as template, it is modified through silicate impregnation and pretreatment natural sponge powder is made, again by acrylic acid, with pretreatment natural sponge powder after sodium hydroxide solution and sodium alginate soln mixing, acrylamide solution etc. reacts, it is separated by filtration to obtain hygroscopic material crude product, then the plant standing that will be enriched in amino acid is mouldy, the ferment filtrate obtained rich in amino acid and microorganism is collected in fermentation, again by pepsin and hygroscopic agent crude product hybrid infusion, filter cake and ferment filtrate are banked up into reaction after being separated by filtration, reaction product is finally washed into drying, highly hygroscopic speed hygroscopic material can be obtained, gained hygroscopic material of the invention has faster suction, radial migratory pathway, absorbent capacity is larger simultaneously, it is a kind of preferable absorbent product.
Description
Technical field
The invention belongs to field of polymer material preparing technology, and in particular to a kind of preparation of highly hygroscopic speed hygroscopic material
Method.
Background technology
Humidity not only influences the living environment of people, is also directly linked to industrial and agricultural production, article warehouse, historical relic, archives
Deng preservation.Therefore, air dewetting has been common problem, with the development and growth in the living standard of production, empty
Gas dehumidifying has developed and has formed a new technology.
Hygroscopic material includes inorganic hygroscopic material and the major class of organic hygroscopic material two.Inorganic hygroscopic material such as charcoal, molecule
Sieve, discoloration silica gel etc., more in solid granular, absorbent capacity is low, and consumption is big, repeats humidity absorption and release process and is easy to crush, shadow
Ring using effect.Hygroscopic material of organic macromolecule is new functional high molecule material, it be by super absorbent resin development and
Produce, be a kind of water-base resin being modified by chemistry with physical method, with molecule with excellent moisture absorption, performance of keeping humidity
In hydrophilic radical absorb moisture.The ability of moisture is higher than general inorganic suction in hygroscopic material of organic macromolecule absorption air
Wet stock, and it is corrosion-free, pollution-free and renewable.According to difference of the adsorbent to absorption affinity between adsorbate, absorption can be divided
For physical absorption and chemisorbed.The process of macromolecule moisture absorption is broadly divided into 2 stages：First stage is circulated by gas,
Moisture in air is contacted by polymer particle surface, is referred to as outside transmittance process or external diffusion；Second stage be moisture from
Polymer particle surface is transmitted to inside pellet pores, is referred to as internal transmittance process or interior diffusion.First stage is mainly physics suction
It is attached, and second stage is mainly chemisorbed.And organic macromolecule absorption is based on chemisorbed.Chemisorption capacity it is big
The small difference with the difference that sorption chemical bonding force size is formed between adsorbed molecule and adsorbent surface atom.Chemisorbed
Need certain activation energy, under the same conditions, chemisorbed（Or desorption）Speed is slower than physical absorption.
Polyacrylics are that, using an earliest class product in hygroscopic material of organic macromolecule, its water sucting principle is profit
Water and hydroaropic substance are combined together with the mode of chemical bond, with superpower water absorbing properties, but polyacrylics
Moisture pick-up properties is simultaneously not fully up to expectations.Particular problem shows that absorbent capacity is very low, and its moisture absorption mechanism mainly passes through chemistry in addition
Absorption, compared to physical absorption, moisture absorption, radial migratory pathway are slower.Therefore, how to overcome prior art not enough, exploitation is a kind of have compared with
Big absorbent capacity and very fast suction, the hygroscopic material of radial migratory pathway, have important practical significance.
The content of the invention
, there is absorbent capacity for polyacrylic hygroscopic material traditional at present in the technical problems to be solved by the invention
It is low and inhale, there is provided a kind of preparation method of highly hygroscopic speed hygroscopic material the problem of radial migratory pathway is slow.
In order to solve the above-mentioned technical problem, the technical solution adopted in the present invention is：
（1）Take natural sponge to be crushed after drying, and cross 50 mesh sieves, collect sieving and obtain natural sponge powder, by natural sponge
Powder sodium silicate solution takes out after soaking, and dries again, obtains pre-processing natural sponge powder；
（2）Acrylic acid, sodium hydroxide solution and sodium alginate soln are mixed, reaction is stirred at room temperature, pre-polymerization liquid is obtained；
（3）Pretreatment natural sponge powder and acrylamide solution are added in pre-polymerization liquid, stirring is mixed to get mixed liquor, then
Potassium peroxydisulfate is added into mixed liquor, is heated, stirring reaction is separated by filtration and obtains filter residue, as hygroscopic material crude product, standby；
（4）By waiting mass ratio to crush soybean, Chinese yam and lotus rhizome, obtaining mixed powder is minced, and gained mixed powder is minced and is laid in
In bamboo sieve, bamboo sieve is put into greenhouse, the surface from mildewing until mixed powder minces is stood, obtains mouldy mixed powder and mince；
（5）Above-mentioned mouldy mixed powder is minced and is fitted into after being mixed with water in fermentation tank, sealing and fermenting is filtered after fermentation ends, is divided
From obtaining ferment filtrate；
（6）Dipping is vibrated after standby hygroscopic material crude product and pepsin solution are mixed, dipping is separated by filtration after terminating
It to filter cake, then will be stacked in after filter cake and the mixing of above-mentioned ferment filtrate in greenhouse, stand after the completion of reaction, question response, obtain anti-
Product is answered, is freeze-dried after being rinsed repeatedly with absolute ethyl alcohol, produces highly hygroscopic speed hygroscopic material.
Step（1）Described in natural sponge be as ear sponge, honeycomb silk floss, silk floss, grass silk floss in one kind.
Step（2）Described in acrylic acid, the volume ratio of sodium hydroxide solution and sodium alginate soln be 3:3:1, hydrogen
The mass fraction of sodium hydroxide solution is 50%, and the mass fraction of sodium alginate soln is 10%, the stirring reaction time is 20~
30min。
Step（3）Described in pretreatment natural sponge powder and acrylamide solution and pre-polymerization liquid mass ratio be 1:
1:10, the mass fraction of acrylamide solution is 10%, and the addition of potassium peroxydisulfate is the 0.5~1.0% of mixed liquor quality, heating
Temperature afterwards is 65~75 DEG C, and the stirring reaction time is 2~3h.
Step（4）Described in greenhouse in temperature be 30~40 DEG C, relative air humidity be 70~80%, time of repose is 5
~7 days.
Step（5）Described in mouldy mixed powder to mince with the mass ratio of water be 1:3, sealing and fermenting temperature is 30~40
DEG C, the sealing and fermenting time is 7~9 days.
Step（6）Described in hygroscopic material crude product and pepsin solution mass ratio be 1:10, pepsin solution
Mass fraction be 20%, vibration dip time is 5~7h, and the mass ratio of filter cake and ferment filtrate is 1:3, greenhouse temperature is 30
~50 DEG C, it is 10~15 days to stand the reaction time.
The beneficial effects of the invention are as follows：
（1）The present invention is modified through silicate impregnation using the natural biological sponge with abundant pore structure as template, makes template table
The silicone hydroxyl quantity increase in face, improves the adsorption capacity of template, then by the mixture of sodium alginate and acrylic acid in persulfuric acid
Under the initiation of potassium, the H in acrylic molecules on hydroxyl carbon atom is seized and is produced free radical, then trigger PAA and
Template generation sodium alginate/PAA/template free radical, so that chain growth polymerization is carried out with PAA, while acrylic acid
Sodium can also produce free radical, carry out the homopolymerization of PAA, finally in template surface formation one layer polypropylene acid water suction tree
Lipid layer, obtains the hygroscopic agent crude product with loose structure, and the plant that then will be enriched in amino acid stands mouldy, fermentation, Ran Houshou
Collection obtains the ferment filtrate rich in amino acid and microorganism, hygroscopic agent crude product is digested by pepsin, in crude product
Natural biological sponge template carry out initial breakdown, then with being rich in the ferment filtrate of amino acid and microorganism microorganism to preliminary
Crude product after degraded carries out secondary degraded, until natural biological sponge template degradation, makes the suction itself with loose structure completely
Hollow structure is further presented in humectant crude product, and then adds the porosity and effective moisture absorption specific surface area of hygroscopic agent, improves
The physics wettability power of hygroscopic agent, so as to improve the moisture absorption rate and radial migratory pathway of hygroscopic agent；
（2）The amino acid being rich in ferment filtrate of the present invention is degraded in the presence of microorganism generates hydrophilic amino and carboxylic
Base, is attached to hygroscopic agent surface in the presence of biological self-crosslinking, so as to add the hydrophilic amino and carboxylic on hygroscopic agent surface
Radix amount, improves the chemical hygroscopic ability of hygroscopic agent again, and the raising of chemical hygroscopic performance can hold the moisture absorption of hygroscopic agent
Amount further increase, with splendid moisture sorption effect.
Embodiment
Take natural sponge to be put into 20~30min of crushing in pulverizer after drying, and cross 50 mesh sieves, collect sieving and obtain day
Right sponge powder, soaks taking-up after 1~2h for 20% sodium silicate solution by natural sponge powder mass fraction, dries again,
Obtain pre-processing natural sponge powder, be by volume 3:3:1 by acrylic acid, mass fraction be 50% sodium hydroxide solution and
Mass fraction is that 10% sodium alginate soln is fitted into mixing in reactor, starts agitator with 100~200r/min rotating speed in room
Lower 20~the 30min of stirring reaction of temperature, obtains pre-polymerization liquid, is in mass ratio 1:1:10 will pretreatment natural sponge powder and quality point
Number is added in pre-polymerization liquid for 10% acrylamide solution, is uniformly mixed and is obtained mixed liquor, then addition is mixed into reactor
Close the potassium peroxydisulfate of liquid quality 0.5~1.0%, be heated to 65~75 DEG C, with 200~300r/min rotating speeds stirring reaction 2~
3h, is separated by filtration and obtains filter residue, as hygroscopic material crude product, by waiting mass ratio to crush soybean, Chinese yam and lotus rhizome, is mixed
Crushed material, gained mixed powder is minced and is laid in bamboo sieve, by bamboo sieve be put into temperature be 30~40 DEG C, relative air humidity be 70
In~80% greenhouse, the surface from mildewing until mixed powder minces of standing 5~7 days obtains mouldy mixed powder and minced, then will be mouldy mixed
It is 1 in mass ratio to close crushed material and water:It is fitted into after 3 mixing in fermentation tank, sealing and fermenting 7~9 days at 30~40 DEG C, fermentation knot
Filtered after beam, isolated ferment filtrate, be then that 20% pepsin solution presses quality by hygroscopic material crude product and mass fraction
Than for 1:Vibration 5~7h of dipping is placed on shaking table after 10 mixing, dipping is separated by filtration after terminating and obtains filter cake, then by filter cake and
Ferment filtrate is 1 in mass ratio:It is stacked in after 3 mixing in the greenhouse that temperature is 30~50 DEG C, stands reaction 10~15 days, treats anti-
After the completion of answering, reaction product is obtained, is rinsed after 20~30min and is freeze-dried repeatedly with absolute ethyl alcohol, highly hygroscopic speed is produced and inhales
Wet stock.Described natural sponge is as one kind in ear sponge, honeycomb silk floss, silk floss, grass silk floss.
Example 1
Take to be put into pulverizer after drying as ear sponge and crush 20min, and cross 50 mesh sieves, collect sieving and obtain as ear sponge powder
End, by as ear sponge powder mass fraction is takes out after 20% sodium silicate solution immersion 1h, dries, is pre-processed again
It is by volume 3 as ear sponge powder:3:Acrylic acid, mass fraction are 50% sodium hydroxide solution and mass fraction is by 1
10% sodium alginate soln, which is fitted into reactor, to be mixed, and starts agitator and reaction is stirred at room temperature with 100r/min rotating speed
20min, obtains pre-polymerization liquid, is in mass ratio 1:1:10 will pre-process as acryloyl that ear sponge powder and mass fraction are 10%
Amine aqueous solution is added in pre-polymerization liquid, is uniformly mixed and is obtained mixed liquor, then the mistake of addition mixed liquor quality 0.5% into reactor
Potassium sulfate, is heated to 65 DEG C, with 200r/min rotating speed stirring reaction 2h, is separated by filtration and obtains filter residue, as hygroscopic material
Crude product, by waiting mass ratio to crush soybean, Chinese yam and lotus rhizome, obtaining mixed powder is minced, and gained mixed powder is minced and is laid in bamboo
In sieve, bamboo is sieved and is put into the greenhouse that temperature is 30 DEG C, relative air humidity is 70%, the surface that stands 5 days until mixed powder minces
It is mouldy, obtain mouldy mixed powder and mince, then it is 1 in mass ratio that mouldy mixed powder, which is minced with water,:Load fermentation tank after 3 mixing
In, sealing and fermenting 7 days at 30 DEG C are filtered, isolated ferment filtrate, then by hygroscopic material crude product and matter after fermentation ends
It is that 20% pepsin solution is 1 in mass ratio to measure fraction:Vibration dipping 5h on shaking table is placed on after 10 mixing, after dipping terminates
It is separated by filtration and obtains filter cake, then by filter cake and ferment filtrate is 1 in mass ratio:The greenhouse that temperature is 30 DEG C is stacked in after 3 mixing
In, reaction 10 days are stood, after the completion of question response, reaction product are obtained, is rinsed after 20min and is freeze-dried repeatedly with absolute ethyl alcohol,
Produce highly hygroscopic speed hygroscopic material.
Example 2
Take honeycomb silk floss to be put into after drying in pulverizer and crush 25min, and cross 50 mesh sieves, collect sieving and obtain natural sponge powder
End, soaks taking-up after 1h for 20% sodium silicate solution by the continuous powder mass fraction of honeycomb, dries again, obtain pre-processing honeybee
Nest silk floss powder, is by volume 3:3:Acrylic acid, mass fraction are 50% sodium hydroxide solution and mass fraction is 10% sea by 1
Solution of sodium alginate, which is fitted into reactor, to be mixed, and starts agitator and reaction 25min is stirred at room temperature with 150r/min rotating speed, obtain
It is in mass ratio 1 to pre-polymerization liquid:1:10 will pre-process honeycomb silk floss powder and mass fraction adds for 10% acrylamide solution
Into pre-polymerization liquid, it is uniformly mixed and obtains mixed liquor, then the potassium peroxydisulfate of mixed liquor quality 0.8% is added into reactor, heats
Be warming up to 70 DEG C, with 250r/min rotating speed stirring reaction 2h, be separated by filtration and obtain filter residue, as hygroscopic material crude product, by etc. matter
Amount is than soybean, Chinese yam and lotus rhizome are crushed, and obtaining mixed powder minces, and gained mixed powder is minced and is laid in bamboo sieve, bamboo is sieved
It is put into the greenhouse that temperature is 35 DEG C, relative air humidity is 75%, the surface from mildewing that stands 6 days until mixed powder minces is sent out
Mould mixed powder minces, then it is 1 in mass ratio that mouldy mixed powder, which is minced with water,:It is fitted into after 3 mixing in fermentation tank, it is close at 35 DEG C
Seal ferment 8 days, is filtered, isolated ferment filtrate after fermentation ends, is then 20% stomach by hygroscopic material crude product and mass fraction
Protein enzyme solution is 1 in mass ratio:Vibration dipping 6h on shaking table is placed on after 10 mixing, dipping is separated by filtration after terminating and filtered
Cake, then by filter cake and ferment filtrate be 1 in mass ratio:It is stacked in after 3 mixing in the greenhouse that temperature is 40 DEG C, stands reaction 13
My god, after the completion of question response, reaction product is obtained, is rinsed after 25min and is freeze-dried repeatedly with absolute ethyl alcohol, produce highly hygroscopic speed
Hygroscopic material.
Example 3
Take silk floss to be put into after drying in pulverizer and crush 30min, and cross 50 mesh sieves, collect sieving and obtain natural sponge powder,
By silk floss powder mass fraction to be taken out after 20% sodium silicate solution immersion 2h, dry again, obtain pre-processing silk floss powder
End, is by volume 3:3:Acrylic acid, mass fraction are 50% sodium hydroxide solution and mass fraction is 10% sodium alginate by 1
Solution, which is fitted into reactor, to be mixed, and starts agitator and reaction 30min is stirred at room temperature with 200r/min rotating speed, obtain pre-polymerization
Liquid, is in mass ratio 1:1:10 will pre-process silk floss powder and mass fraction is added to pre-polymerization liquid for 10% acrylamide solution
In, it is uniformly mixed and obtains mixed liquor, then the potassium peroxydisulfate of mixed liquor quality 1.0% is added into reactor, it is heated to 75
DEG C, with 300r/min rotating speed stirring reaction 3h, it is separated by filtration and obtains filter residue, as hygroscopic material crude product, will be big by grade mass ratio
Beans, Chinese yam and lotus rhizome are crushed, and are obtained mixed powder and are minced, and gained mixed powder is minced and is laid in bamboo sieve, and bamboo sieve is put into temperature
In the greenhouse for being 80% for 40 DEG C, relative air humidity, the surface from mildewing until mixed powder minces of standing 7 days obtains mouldy mixed powder
Mince, then it is 1 in mass ratio that mouldy mixed powder, which is minced with water,:It is fitted into after 3 mixing in fermentation tank, the sealing and fermenting 9 at 40 DEG C
My god, filtered after fermentation ends, isolated ferment filtrate, be then 20% pepsin by hygroscopic material crude product and mass fraction
Solution is 1 in mass ratio:Vibration dipping 7h on shaking table is placed on after 10 mixing, dipping is separated by filtration after terminating and obtains filter cake, then
It is 1 in mass ratio by filter cake and ferment filtrate:It is stacked in after 3 mixing in the greenhouse that temperature is 50 DEG C, stands reaction 15 days, treats anti-
After the completion of answering, reaction product is obtained, is rinsed after 30min and is freeze-dried repeatedly with absolute ethyl alcohol, produce highly hygroscopic speed hygroscopic material
Material.
Comparative example：Using water solution polymerization process, using acrylic acid and acrylamide as raw material, initiator is made with potassium peroxydisulfate,
N, N'- methylene-bisacrylamide make crosslinking agent and polyacrylic acid/acrylamide high-hygroscopicity resin are made.
To highly hygroscopic speed hygroscopic material made from example 1~3 and the polyacrylic acid of comparative example/acrylamide high-hygroscopicity
Resin carries out performance detection, and its testing result is as shown in table 1：
Table 1（Test environment：25 DEG C of temperature, relative humidity 90%）
In summary, highly hygroscopic speed hygroscopic material produced by the present invention has faster suction, radial migratory pathway, while absorbent capacity
It is larger, it is a kind of preferable absorbent product.
Claims (7)
1. a kind of preparation method of highly hygroscopic speed hygroscopic material, it is characterised in that specifically preparation process is：
（1）Take natural sponge to be crushed after drying, and cross 50 mesh sieves, collect sieving and obtain natural sponge powder, by natural sponge
Powder sodium silicate solution takes out after soaking, and dries again, obtains pre-processing natural sponge powder；
（2）Acrylic acid, sodium hydroxide solution and sodium alginate soln are mixed, reaction is stirred at room temperature, pre-polymerization liquid is obtained；
（3）Pretreatment natural sponge powder and acrylamide solution are added in pre-polymerization liquid, stirring is mixed to get mixed liquor, then
Potassium peroxydisulfate is added into mixed liquor, is heated, stirring reaction is separated by filtration and obtains filter residue, as hygroscopic material crude product, standby；
（4）By waiting mass ratio to crush soybean, Chinese yam and lotus rhizome, obtaining mixed powder is minced, and gained mixed powder is minced and is laid in
In bamboo sieve, then bamboo sieve is put into greenhouse, stands the surface from mildewing until mixed powder minces, obtain mouldy mixed powder and mince；
（5）Above-mentioned mouldy mixed powder is minced and is fitted into after being mixed with water in fermentation tank, sealing and fermenting is filtered after fermentation ends, is divided
From obtaining ferment filtrate；
（6）Dipping is vibrated after standby hygroscopic material crude product and pepsin solution are mixed, dipping is separated by filtration after terminating
It to filter cake, then will be stacked in after filter cake and the mixing of above-mentioned ferment filtrate in greenhouse, stand after the completion of reaction, question response, obtain anti-
Product is answered, is freeze-dried after being rinsed repeatedly with absolute ethyl alcohol, produces highly hygroscopic speed hygroscopic material.
2. a kind of preparation method of highly hygroscopic speed hygroscopic material according to claim 1, it is characterised in that：Step（1）
Described in natural sponge be as ear sponge, honeycomb silk floss, silk floss, grass silk floss in one kind.
3. a kind of preparation method of highly hygroscopic speed hygroscopic material according to claim 1, it is characterised in that：Step（2）
Described in acrylic acid, the volume ratio of sodium hydroxide solution and sodium alginate soln be 3:3:1, the quality of sodium hydroxide solution
Fraction is 50%, and the mass fraction of sodium alginate soln is 10%, and the stirring reaction time is 20~30min.
4. a kind of preparation method of highly hygroscopic speed hygroscopic material according to claim 1, it is characterised in that：Step（3）
Described in pretreatment natural sponge powder and acrylamide solution and pre-polymerization liquid mass ratio be 1:1:10, acrylamide is molten
The mass fraction of liquid is 10%, and the addition of potassium peroxydisulfate is the 0.5~1.0% of mixed liquor quality, the temperature after heating for 65~
75 DEG C, the stirring reaction time is 2~3h.
5. a kind of preparation method of highly hygroscopic speed hygroscopic material according to claim 1, it is characterised in that：Step（4）
Described in greenhouse temperature be 30~40 DEG C, relative air humidity be 70~80%, time of repose is 5~7 days.
6. a kind of preparation method of highly hygroscopic speed hygroscopic material according to claim 1, it is characterised in that：Step（5）
Described in mouldy mixed powder to mince with the mass ratio of water be 1:3, sealing and fermenting temperature is 30~40 DEG C, and the sealing and fermenting time is
7~9 days.
7. a kind of preparation method of highly hygroscopic speed hygroscopic material according to claim 1, it is characterised in that：Step（6）
Described in hygroscopic material crude product and pepsin solution mass ratio be 1:10, the mass fraction of pepsin solution is 20%,
Vibration dip time is 5~7h, and the mass ratio of filter cake and ferment filtrate is 1:3, greenhouse temperature is 30~50 DEG C, when standing reaction
Between be 10~15 days.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108104107A (en) * | 2017-12-12 | 2018-06-01 | 周荣 | A kind of method using zeolite and Flyash liquefaction sand foundation |
| CN108585630A (en) * | 2018-05-18 | 2018-09-28 | 赵顺全 | A kind of preparation method of high intensity moisture absorption mineral wool board |
| CN109095945A (en) * | 2018-08-29 | 2018-12-28 | 佛山市森昂生物科技有限公司 | A kind of preparation method of antibacterial mould-proof-type zeolite keynote wet stock |
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Cited By (5)
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| CN108104107A (en) * | 2017-12-12 | 2018-06-01 | 周荣 | A kind of method using zeolite and Flyash liquefaction sand foundation |
| CN108104107B (en) * | 2017-12-12 | 2020-08-18 | 上海先科桥梁隧道检测加固工程技术有限公司 | Method for reinforcing liquefied sandy soil foundation by using zeolite and fly ash |
| CN108585630A (en) * | 2018-05-18 | 2018-09-28 | 赵顺全 | A kind of preparation method of high intensity moisture absorption mineral wool board |
| CN108585630B (en) * | 2018-05-18 | 2021-05-25 | 陈露 | Preparation method of high-strength moisture-absorption mineral wool board |
| CN109095945A (en) * | 2018-08-29 | 2018-12-28 | 佛山市森昂生物科技有限公司 | A kind of preparation method of antibacterial mould-proof-type zeolite keynote wet stock |
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Application publication date: 20171027 |