CN109438746A - A kind of super absorbent resin and preparation method thereof with porous three-dimensional structure - Google Patents
A kind of super absorbent resin and preparation method thereof with porous three-dimensional structure Download PDFInfo
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- CN109438746A CN109438746A CN201811197956.XA CN201811197956A CN109438746A CN 109438746 A CN109438746 A CN 109438746A CN 201811197956 A CN201811197956 A CN 201811197956A CN 109438746 A CN109438746 A CN 109438746A
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- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
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- C08F289/00—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds not provided for in groups C08F251/00 - C08F287/00
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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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Abstract
The invention discloses a kind of super absorbent resin and preparation method thereof with porous three-dimensional structure, specific steps are as follows: collagenic gel solution, crosslinking agent, initiator, P123 and nano silicon oxide are successively added into the water-soluble unsaturated monomer solution neutralized, carry out polymerization reaction, the gel of generation is handled using the low temperature rapid shaping technique of 3 D-printing later, obtains partial size in the faint yellow graininess sample of 0.20-0.71mm.Have the beneficial effect that the present invention prepares the macropore and micropore size of super absorbent resin using the low temperature rapid shaping technique of 3 D-printing；The present invention adds P123 and nano silicon oxide, acts synergistically with three-dimensional printing technology, forms interconnected more size aperture structures inside resin, overflows closed decentralized medium inside resin, eliminates the raw material smell that resin is volatilized by water absorption and swelling；Super absorbent resin produced by the present invention, infiltration rate is fast, can be used as the purposes of hygienic material.
Description
Technical field
The present invention relates to high molecular material applied technical fields, more particularly, to a kind of high suction with porous three-dimensional structure
Water-base resin and preparation method thereof.
Background technique
High-hydroscopicity functional polymer resin material can be absorbed due to having a large amount of hydrophilic radical in its molecular structure
The water that hundreds times or even thousands of times of its own quality, while its three-dimensional net structure being cross-linked to form keeps its not soluble in water but can delay
The moisture that slow release is absorbed, thus have widely in fields such as agriculture and forestry, construction material, food industry and amenities
Using wherein especially more large with paper diaper and sanitary napkin use.
When in paper diaper or sanitary napkin absorbed layer super absorbent resin or paper pulp fiber after absorption of liquid, can rapidly it is swollen
It is swollen to causing super absorbent resin to be closed with the hole in the void space or super absorbent resin in paper pulp fiber, thus
The conduction for inhibiting liquid causes later liquid that cannot penetrate the region expanded by liquid absorption again, on the one hand causes
Remaining liquid can not reach the part of deeper, so that the ability of absorbed layer storage liquid is greatly reduced, on the other hand, cause
Remaining liquid transfers to edge flowing to lead to that side leakage occurs.Moreover, containing salt in urine and blood, protein molecule etc. can subtract
The infiltration rate and uptake of weak super absorbent resin.
Protein macromolecule in blood, size between 1-100nm, micropore, it is mesoporous be all not enough to quickly absorb accommodate
Protein macromolecule group, and current macromolecule resin material is mostly using foaming agent come the micropore inside forming material, but this
The size, shape in hole and distribution slightly cannot all control well, and the connected ratio between micropore is difficult to ensure, still cannot be prevented
Only the case where obstruction, side leakage, occurs, and the three-dimensional printing-forming method based on quick forming principle is expected to realize that macropore, micropore are total
The multilevel structure deposited yet there are no report currently, the low temperature rapid shaping technique of 3 D-printing to be applied to the preparation of macromolecule resin
Road.
The super absorbent resin used as hygienic material, it is known that be situated between using crosslinking agent, initiator, modifying agent and dispersion
Matter etc. is produced by polymerization reaction, and therefore, when generating super absorbent resin, a small amount of decentralized medium can be closed in water imbibition tree
In rouge particle, it cannot be removed by the post-processing approach of heating, still, in super absorbent resin water absorption and swelling, these dispersions
Medium can but overflow to volatilize the smell of raw material components.Because these hygienic materials are worn on human body, even if smell
Slightly, also the people for dressing this hygienic material can be made not feel well, it is therefore desirable to develop odorlessness material.
The prior art such as Authorization Notice No. is the Chinese invention patent of 104958785 B of CN, is disclosed a kind of with second level
Composite bone repairing material of three-dimensional structure and preparation method thereof.This method utilizes low temperature rapid shaping technique by nano-hydroxy-apatite
Stone, fibroin and collagen blend prepare the three-dimensional plural gel with macroporous structure according to design aperture, then pass through the later period
Freeze-drying makes solvent be distilled to obtain micropore, to prepare the bone renovating bracket material with second level three-dimensional structure.But
It is the 3 D-printing method is for bone renovating material field.
Summary of the invention
That one of the objects of the present invention is to provide a kind of infiltration rates is fast, uptake is more, preparation process is simple, it is porous to have
The preparation method of the super absorbent resin of three-dimensional structure.
The second object of the present invention is to provide that a kind of infiltration rate is fast, uptake is more, the height with porous three-dimensional structure
Water-absorbing resins.
The present invention in view of the above technology in the problem of mentioning, the technical solution taken are as follows:
A kind of preparation method of the super absorbent resin with porous three-dimensional structure, including unsaturated monomer neutralizes, collagen
Gel solution preparation, polymerization reaction, 3 D-printing, crushing and screening processing, specific steps are as follows:
Unsaturated monomer neutralizes: taking the hydroxide or carbonate compound of alkali or alkaline earth metal, is added dropwise to containing acid
In the water-soluble unsaturated monomer of base, make the acidic group neutralization ratio of unsaturated monomer in the range of 40-85%, unsaturated monomer
Concentration is in the aqueous solution of 30-55wt% range；
Collagenic gel solution: using beef tendon as raw material, by degreasing, crushing, dissolve, saltout, dialysis prepares collagen, by collagen
Swelling in acetum and being prepared into mass percent is 2-5% collagenic gel solution；
Polymerization reaction: will be mixed in unsaturated monomer with solution with weight ratio 10:1-1:10 with collagenic gel solution,
Crosslinking agent, initiator, P123, nano silicon oxide is added, carries out polymerization reaction；
3 D-printing: the gel that polymerization reaction generates being fitted into the syringe of low temperature rapid forming equipment outfit, will be three-dimensional
The needle diameter of printer is set as 100-500 μm, and print speed is 4-10mm/ seconds, and syringe needle walking spacing is 200-500 μm,
The temperature setting of receiving device is -25 DEG C -5 DEG C, and gel is squeezed out and carries out low temperature rapid shaping；It is former based on discrete/stack shaping
The low temperature rapid shaping technique of reason squeezes out the gel that polymerization reaction generates by specific needle aperture, sweeping when syringe needle squeezes out
The macroporous structure that path hole forms resin is retouched, then makes solvent distil to obtain a large amount of fine holes by the freeze-drying in later period
Hole, to prepare the super absorbent resin with more size aperture structures；Large aperture inside super absorbent resin can be fast
Speed, which absorbs, accommodates protein macromolecule group in blood, and small-bore and large aperture act synergistically, and make the hole inside macromolecule resin
It is interconnected, greatly improves the infiltration rate, liquid absorption amount, gas permeability and drainage of blood, urine etc., on the one hand reduce
Macromolecule resin is because of obstruction or side leakage phenomenon caused by water suction Fast-swelling, on the other hand, the fine air permeability of porous structure
Keep macromolecule resin dry tack free salubrious, decrease even is eliminated diaper or amenities because of skin allergy caused by airtight even
Eczema phenomenon, and traditional preparation method is extremely difficult to this requirement；
Crushing and screening processing: the gel strand of low-temperature setting is crushed, and is freeze-dried, and sieving obtains partial size in 0.20-
The faint yellow graininess sample of 0.71mm.
Preferably, the additive amount of P123 used is the 0.1-10wt% of resin total amount, nano oxygen in polymerization procedure
The additive amount of SiClx is the 0.01-5wt% of resin total amount；In the polymerization, P123 and nano silicon oxide are added, high water absorption is made
Property resin inside formed it is mesoporous, it is synergistic with subsequent three-dimensional printing technology, form macropore inside super absorbent resin, be situated between
More size aperture structures of the connectivity such as hole, micropore, so that closed decentralized medium in super absorbent resin production process be made to overflow
Out, meanwhile, nano silicon oxide has nano-scale, can be contained in the aperture structure of super absorbent resin, absorption is enclosed in
The decentralized medium of remaining inside resin reaches elimination high-hydroscopicity to decrease or even eliminate the decentralized medium inside resin
Resin volatilizes the problem of raw material smell because of water absorption and swelling.
A kind of preparation method of the super absorbent resin with porous three-dimensional structure, the macropore knot of made super absorbent resin
Structure range is 50-500 μm, and the scan path hole that macropore hole is extruded by gel by syringe needle is formed, micron order hole
Structure is formed by the gel after printing by freeze-drying.
A kind of preparation method of the super absorbent resin with porous three-dimensional structure, the made height with second level three-dimensional structure
For the porosity of water-absorbing resins within the scope of 85%-99%, vortex disappearance index is not more than 25sec/g.
A kind of preparation method of the super absorbent resin with porous three-dimensional structure, the made height with second level three-dimensional structure
The amount of the residual decentralized medium of water-absorbing resins is not more than 2000ppm.
The invention also discloses a kind of preparation method systems using the above-mentioned super absorbent resin with porous three-dimensional structure
The super absorbent resin obtained, the super absorbent resin have porous three-dimensional network structure.
Compared with the prior art, the advantages of the present invention are as follows: the present invention uses the low temperature rapid shaping technique of 3 D-printing
The macropore and micropore size of super absorbent resin are prepared, infiltration rate, the liquid absorption amount, gas permeability of blood, urine etc. are improved；
The present invention adds P123 and nano silicon oxide, acts synergistically with three-dimensional printing technology, and more size aperture knots are formed inside resin
Structure makes hole be interconnected, so that closed decentralized medium inside super absorbent resin be made to overflow, and can adsorb surplus inside resin
Remaining decentralized medium, to eliminate the problem of super absorbent resin volatilizes raw material smell because of water absorption and swelling；System of the present invention
The super absorbent resin obtained, infiltration rate is fast, can be used as the purposes of hygienic material.
Specific embodiment
The present invention program is described further below by embodiment:
Embodiment 1:
A kind of preparation method of the super absorbent resin with porous three-dimensional structure, including unsaturated monomer neutralizes, collagen
Gel solution preparation, polymerization reaction, 3 D-printing, crushing and screening processing, specific steps are as follows:
1) unsaturated monomer neutralizes: taking natrium carbonicum calcinatum, is slowly added to the aqueous solution of the acrylic monomers to lasting stirring
In, in adition process, after the temperature of reaction system is maintained at 40 DEG C hereinafter, adding, the acidic group neutralization ratio of acrylic monomers is made to exist
In the range of 65%, the concentration of acrylic monomers is in the aqueous solution of 45wt% range；
The water-soluble unsaturated monomer containing acidic group is selected from acrylic acid, methacrylic acid, 2- allylamine -2- methylpropane
One of sulfonic acid, Malin's acid, fumaric acid, maleic acid, maleic anhydride, fumaric acid, fumaric acid acid anhydride or
It is several；
Carboxylic acid group's part containing acid-based monomers should be neutralized to control the pH value of finished product, be in neutrality it or subacidity, if at
Product pH value is non-to be in neutrality or when subacidity, more dangerous when with human contact, neutralizer is the hydrogen-oxygen of alkali or alkaline earth metal
Compound or carbonate compound, such as: one of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate or ammoniac compounds are more
Kind；
When carrying out Raolical polymerizable, for concentration in 30wt% or less, the hydrogel of generation is too soft and stickiness is big, no
Benefit machining, for concentration in 50wt% or more, close to saturated concentration, reaction is fierce, is difficult to control；
2) collagenic gel solution: using beef tendon as raw material, by degreasing, crushing, dissolve, saltout, dialysis prepares collagen, by glue
It is 3% collagenic gel solution that original, which swells in acetum and is prepared into mass percent,；
3) polymerization reaction: it will be mixed with solution with collagenic gel solution, be added with weight ratio 5:1 in unsaturated monomer
N, N '-methylene-bisacrylamide, persulfate, 2wt% P123,2wt% nano silicon oxide, carry out polymerization reaction；?
In polymerization reaction, P123 and nano silicon oxide are added, keeps formation inside super absorbent resin mesoporous, with subsequent 3 D-printing skill
Art is synergistic, and more size aperture structures of the connectivity such as macropore, mesoporous, micropore are formed inside super absorbent resin, thus
Closed decentralized medium in super absorbent resin production process is overflowed, meanwhile, nano silicon oxide has nano-scale, Ke Yirong
It is contained in the aperture structure of super absorbent resin, absorption is enclosed in the decentralized medium of the remaining inside resin, to reduce even
The decentralized medium inside resin is eliminated, reaches elimination super absorbent resin and volatilizes asking for raw material smell because of water absorption and swelling
Topic；
The additive amount of crosslinking agent used is 0.01-0.4wt%, on the basis of the weight of the unsaturated monomer of neutralization；Addition
Amount in 0.01wt% hereinafter, the hydrated body after polymerization reaction is too soft and have the unfavorable machining of stickiness, additive amount 0.4wt% with
On, the water imbibition of resin is too low, and performance is bad；
Crosslinking agent is N, N '-bis- (2- acrylic) amine, N, N '-methylene-bisacrylamide, N, N '-di-2-ethylhexylphosphine oxide methyl-prop
Acrylamide, acrylic acid acrylic ester, glycol diacrylate, polyethyleneglycol diacrylate, ethylene glycol dimethacrylate,
Polyethylene glycol dimethacrylate, glycerol tri-acrylate, glycerol trimethacrylate, glycerol add the three of ethylene oxide
The triacrylate or trimethyl acrylic ester of acrylate or the additional ethylene oxide of trimethyl acrylic ester, trihydroxymethyl propane,
Trihydroxymethyl propane trimethyl acrylic ester, trihydroxymethyl propane triacrylate, N, N, N- tri- (2- acrylic) amine, diacrylate second
Diol ester, three acrylic acid polyoxyethylene glycerides, three acrylic acid diethyl polyoxyethylene glycerides, two propylene triethyleneglycol esters, mountain
Pears alcohol polyglycidyl ether, polyglycerol polyglycidyl ether, ethylene glycol diglycidylether, diethylene glycol diglycidyl glycerol
One or more of ether, polyethyleneglycol diglycidylether, double glycerine polyglycidyl ethers；
The additive amount of initiator used is 0.5-2.0wt%, on the basis of the weight of the unsaturated monomer of neutralization；Addition is too
It is few, too slow, unfavorable economic benefit is reacted, is added too much, reaction too fast response heat is not easy to control and is easy to polymerize excessive and formed
Gelatinous solid.
4) 3 D-printing: the gel that polymerization reaction generates is fitted into the syringe of low temperature rapid forming equipment outfit, by three
The needle diameter of dimension printer is set as 240 μm, and print speed is 6mm/ seconds, and syringe needle walking spacing is 300 μm, receiving device
Temperature setting is -20 DEG C, and gel is squeezed out and carries out low temperature rapid shaping；Low temperature based on discrete/stack shaping principle is rapid-result fastly
Type technology squeezes out the gel that polymerization reaction generates by specific needle aperture, and scan path hole when syringe needle squeezes out is formed
Then the macroporous structure of resin makes solvent distil to obtain a large amount of fine holes, to prepare by the freeze-drying in later period
Super absorbent resin with more size aperture structures；Large aperture inside super absorbent resin can quickly absorb receiving blood
Middle protein macromolecule group, small-bore and large aperture act synergistically, and so that the hole inside macromolecule resin is interconnected, mention significantly
Infiltration rate, liquid absorption amount, gas permeability and the drainage of high blood, urine etc., on the one hand reduce macromolecule resin because
Absorb water obstruction or side leakage phenomenon caused by Fast-swelling, and on the other hand, the fine air permeability of porous structure makes macromolecule resin table
Face is dry salubrious, and decrease even is eliminated diaper or amenities because of skin allergy even eczema phenomenon caused by airtight, and passes
The preparation method of system is extremely difficult to this requirement；
5) crushing and screening is handled: the gel strand of low-temperature setting being crushed, is freeze-dried, sieving obtains partial size and exists
The faint yellow graininess sample of 0.20-0.71mm.
High-hydroscopicity tree made from a kind of preparation method using the above-mentioned super absorbent resin with porous three-dimensional structure
The macroporous structure range of rouge, the super absorbent resin is 400 μm, and porosity is in 95% range, vortex disappearance index
15.3sec/g, the absorbability of normal saline solution are 92g/g, and the amount for remaining decentralized medium is 150ppm, sense of smell test
Average value is 0.1.
Embodiment 2:
A kind of preparation method of the super absorbent resin with porous three-dimensional structure, including unsaturated monomer neutralizes, collagen
Gel solution preparation, polymerization reaction, 3 D-printing, crushing and screening processing, specific steps are as follows:
1) unsaturated monomer neutralizes: taking natrium carbonicum calcinatum, is slowly added to the aqueous solution of the acrylic monomers to lasting stirring
In, in adition process, after the temperature of reaction system is maintained at 40 DEG C hereinafter, adding, the acidic group neutralization ratio of acrylic monomers is made to exist
In the range of 40%, the concentration of acrylic monomers is in the aqueous solution of 32wt% range；
2) collagenic gel solution: using beef tendon as raw material, by degreasing, crushing, dissolve, saltout, dialysis prepares collagen, by glue
It is 2% collagenic gel solution that original, which swells in acetum and is prepared into mass percent,；
3) polymerization reaction: it will be mixed with solution with collagenic gel solution, added with weight ratio 10:1 in unsaturated monomer
Enter N, N '-methylene-bisacrylamide, persulfate, 1wt% P123,2wt% nano silicon oxide, carry out polymerization reaction；
4) 3 D-printing: the gel that polymerization reaction generates is fitted into the syringe of low temperature rapid forming equipment outfit, by three
The needle diameter of dimension printer is set as 300 μm, and print speed is 7mm/ seconds, and syringe needle walking spacing is 250 μm, receiving device
Temperature setting is -15 DEG C, and gel is squeezed out and carries out low temperature rapid shaping.
5) crushing and screening is handled: the gel strand of low-temperature setting being crushed, is freeze-dried, sieving obtains partial size and exists
The faint yellow graininess sample of 0.20-0.71mm.
High-hydroscopicity tree made from a kind of preparation method using the above-mentioned super absorbent resin with porous three-dimensional structure
The macroporous structure range of rouge, the super absorbent resin is 300 μm, and porosity is in 90% range, vortex disappearance index
16.2sec/g, the absorbability of normal saline solution are 90g/g, and the amount for remaining decentralized medium is 200ppm, sense of smell test
Average value is 0.0.
Embodiment 3:
A kind of preparation method of the super absorbent resin with porous three-dimensional structure, including unsaturated monomer neutralizes, collagen
Gel solution preparation, polymerization reaction, 3 D-printing, crushing and screening processing, specific steps are as follows:
1) unsaturated monomer neutralizes: taking natrium carbonicum calcinatum, is slowly added to the aqueous solution of the acrylic monomers to lasting stirring
In, in adition process, after the temperature of reaction system is maintained at 40 DEG C hereinafter, adding, the acidic group neutralization ratio of acrylic monomers is made to exist
In the range of 80%, the concentration of acrylic monomers is in the aqueous solution of 50wt% range.
2) collagenic gel solution: using beef tendon as raw material, by degreasing, crushing, dissolve, saltout, dialysis prepares collagen, by glue
It is 4% collagenic gel solution that original, which swells in acetum and is prepared into mass percent,.
3) polymerization reaction: it will be mixed with solution with collagenic gel solution, be added with weight ratio 1:1 in unsaturated monomer
N, N '-methylene-bisacrylamide, persulfate, 3wt% P123,0.5wt% nano silicon oxide, carry out polymerization reaction.
4) 3 D-printing: the gel that polymerization reaction generates is fitted into the syringe of low temperature rapid forming equipment outfit, by three
The needle diameter of dimension printer is set as 250 μm, and print speed is 7mm/ seconds, and syringe needle walking spacing is 300 μm, receiving device
Temperature setting is -20 DEG C, and gel is squeezed out and carries out low temperature rapid shaping.
5) crushing and screening is handled: the gel strand of low-temperature setting being crushed, is freeze-dried, sieving obtains partial size and exists
The faint yellow graininess sample of 0.20-0.71mm.
High-hydroscopicity tree made from a kind of preparation method using the above-mentioned super absorbent resin with porous three-dimensional structure
The macroporous structure range of rouge, the super absorbent resin is 300 μm, and porosity is in 92% range, vortex disappearance index
16.5sec/g, the absorbability of normal saline solution are 88g/g, and the amount for remaining decentralized medium is 180ppm, sense of smell test
Average value is 0.1.
Comparative example 1:
Without 3 D-printing step, the gel that polymerization reaction generates directly is subjected to crushing and screening processing, rest part
It is completely the same with embodiment 1.
Comparative example 2:
In polymerization procedure, it is not added with P123, rest part and embodiment 1 are completely the same.
Comparative example 3:
In polymerization procedure, it is not added with nano silica, rest part and embodiment 1 are completely the same.
Embodiment 4:
It regard embodiment 1 as test group, comparative example 1, comparative example 2, comparative example 31, control group 2, control group as a control group
3, vortex disappearance index, the absorbability of normal saline solution, residual dispersion Jie are carried out to the super absorbent resin that each group generates
The amount and sense of smell of matter are tested, and test result is shown in Table 2.
Test method:
1) whirlpool disappearance index (VI): five measurements are averaged as a result, after removal peak and minimum；100mL
Beaker in be added 0.9% sodium-chloride water solution 50mL, electromagnetic mixer stirring, revolving speed 600rpm is weighed with assay balance
2.000 ± 0.001 grams of super absorbent resins are poured into beaker and start stopwatch, the time required to record whirlpool disappears.Gained
Numerical value divided by the weight of practical super absorbent resin up to whirlpool disappearance exponential number.
2) absorbability of normal saline solution
The sodium-chloride water solution of 500g mass fraction 0.9% is added to the 500mL beaker of the magnetic stirring bar with 3cm long
In, while with magnetic stirrer solution, 2.0g water-absorbing resins (Ag) is accurately weighed, is added in beaker, so that not staying
Under be not swollen agglomerate, then with the speed stirring mixture of 600rpm 1 hour.
With diameter 20cm, 106 μm of sieve pore of JIS standard screen filters out gel, is retained in excessive contained in the gel in sieve
Moisture is substantially drained with fluorocarbon resin sheet, is then tilted the sieve and is placed 30 minutes further to drain.It will be retained in sieve
Gel quality (Bg) weighing, the absorbability of normal saline solution is calculated by following equation.
Absorbability (g/g)=B/A of normal saline solution.
3) amount of decentralized medium is remained
Remain in the amount of the petroleum hydrocarbon decentralized medium in water-absorbing resins using headspace gas chromatography measurement.
A) drafting of calibration curve
The petroleum hydrocarbon decentralized medium (hereinafter referred to as " decentralized medium ") that 0.1g is used to polymerize sample is accurately weighed to be packed into
In 50ml helical content bottle, DMF is then added thereto and is accurate to 40g, is then stirred, is marked with magnetic stirring bar
Quasi- sample solution.
In 20ml capacity bottle, the standard sample solution of 0.01g, 0.04g, 0.2g and 0.5g are accurately weighed respectively, to
DMF, which is wherein added, makes the amount of content in each bottle up to 0.75g.
In addition, 0.75g distilled water is added into each bottle, further fastening after then being clogged with rubber septum and aluminium lid.
The bottle is heated 2 hours at 110 DEG C, 1ml gas phase portion is collected, is then injected into gas chromatograph, obtains chromatogram.
Calibration curve is drawn (when mixing with petroleum hydrocarbon by the loading capacity of decentralized medium in each bottle and the peak area of chromatogram
When closing object as decentralized medium, there are multiple peak values, therefore calibration curve is drawn by gross area value and loading capacity).
B) measurement remains the amount of decentralized medium in the sample
About 2g sample to be tested is fitted into aluminium cup, is then contained with hot-air drier with adjustment within dry 2 hours at 105 DEG C
Water.
It accurately weighs the above-mentioned sample of 0.10g to be put into 20ml capacity bottle, after 0.75gDMF is added, adds 0.75g steaming
Distilled water.It after bottle is vibrated, is gently mixed, bottle is clogged with rubber septum and aluminium lid, is then fastened.
The bottle is heated 2 hours at 110 DEG C, 1ml gas phase portion is collected, is then injected into gas chromatograph, obtains chromatography
Figure.
By the calibration curve drawn according to the peak area of gained chromatogram, calculates and disperse to be situated between contained in 0.10g sample
The amount of matter is then convert into the amount [ppm] of decentralized medium contained by every 1g sample.
In the present invention, as follows for measuring the gas chromatograph condition of the amount of residual decentralized medium:
Model: GC-14A+HSS2B (HEADSPACE autosampler) is manufactured by Shimadzu Corporation
Filler: Squalane25%Shimalite (NAW) (101)
80-100 mesh
Column: 3.2mm φ × 2m
Column temperature: 80 DEG C
Inlet temperature: 180 DEG C
Detector temperature: 180 DEG C
Detector: FID
Carrier gas: N2
Bottle heating temperature: 110 DEG C
Syringe setting temperature: 110 DEG C
4) sense of smell is tested
In swelling, smell of the water-absorbing resins from decentralized medium is compared by following method.At 25 DEG C, to
It is packed into 0.9% salt water of 20.0g mass fraction in 140mL volumetric glass bottle with cover, is stirred with the magnetic stirring bar of 3cm long.
After 4.0g water-absorbing resins are added into vial, bottle is tightly sealed.According to following " 6 grades of odour intensity representations ", by 5
The personnel of group determine the smell of the decentralized medium in vial, by being evaluated after being averaged.
16 grades of odour intensity representations of table
The performance test results of 2 super absorbent resin of table
As shown in Table 2, the whirlpool disappearance index of test group is much smaller than control group 1, control group 2 and control group 3, illustrates three-dimensional
Printing, the addition of P123, nano silica all produce beneficial effect to the aperture structure of macromolecule resin, control group 1
Vortex disappearance index is greater than control group 2 and control group 3, illustrates that 3 D-printing step is greater than the pore size influences of macromolecule resin
P123 or nano silica；The absorbability of the normal saline solution of test group is greater than control group 1, control group 2 and control group
3, illustrate that the aperture structure of macromolecule resin enhances its absorbability, the absorbability of the normal saline solution of control group 1 is big
In control group 2 and control group 3, illustrate influence of the 3 D-printing step to the absorbability of the normal saline solution of macromolecule resin
Greater than P123 or nano silica；The amount of the residual decentralized medium of test group is much smaller than control group 1, control group 2 and control group
3, illustrate that more size aperture structures of macromolecule resin have decreased or even eliminated closed decentralized medium, control group 1 inside resin
The amount of residual decentralized medium be greater than control group 2 and control group 3, illustrate 3 D-printing step closed to resin inside dispersion Jie
The elimination effect of matter is greater than P123 or nano silica；The sense of smell test average value of test group is less than control group 1, control
Group 2 and control group 3 illustrate that more size aperture structures of macromolecule resin have decreased or even eliminated closed dispersion inside resin and have been situated between
Matter.
Routine operation in operating procedure of the invention is well known to those skilled in the art, herein without repeating.
Technical solution of the present invention is described in detail in embodiment described above, it should be understood that the above is only
For specific embodiments of the present invention, it is not intended to restrict the invention, all any modifications made in spirit of the invention,
Supplement or similar fashion substitution etc., should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of preparation method of the super absorbent resin with porous three-dimensional structure, including unsaturated monomer neutralizes, collagen is solidifying
Sol solution preparation, polymerization reaction, 3 D-printing, crushing and screening processing, it is characterised in that: the 3 D-printing step are as follows: by three
The temperature parameter for tieing up the reception device of printing is set as -25 DEG C -5 DEG C, and it is fast that the gel that polymerization reaction is generated squeezes out progress low temperature
Rapid-result type.
2. a kind of preparation method of super absorbent resin with porous three-dimensional structure according to claim 1, feature
It is, the unsaturated monomer neutralization procedure are as follows: take the hydroxide or carbonate compound of alkali or alkaline earth metal, be added dropwise
To in the water-soluble unsaturated monomer containing acidic group, make the acidic group neutralization ratio of unsaturated monomer in the range of 40-85%, it is unsaturated
The concentration of monomer is in the aqueous solution of 30-55wt% range.
3. a kind of preparation method of super absorbent resin with porous three-dimensional structure according to claim 1, feature
It is, the collagenic gel solution preparation step are as follows: using beef tendon as raw material, by degreasing, crushing, dissolve, saltout, preparation of dialysing
Collagen, it is 2-5% collagenic gel solution that collagen, which is swollen in acetum, and is prepared into mass percent.
4. a kind of preparation method of super absorbent resin with porous three-dimensional structure according to claim 1, feature
Be, the polymerization procedure are as follows: by unsaturated monomer and solution and collagenic gel solution with weight ratio 10:1-1:10 into
Row mixing, is added crosslinking agent, initiator, P123, nano silicon oxide, carries out polymerization reaction.
5. a kind of preparation method of super absorbent resin with porous three-dimensional structure according to claim 4, feature
It is, the additive amount of the P123 is the 0.1-10wt% of resin total amount, and the additive amount of nano silicon oxide is resin total amount
0.01-5wt%.
6. a kind of preparation method of super absorbent resin with porous three-dimensional structure according to claim 1, feature
It is, the crushing and screening processing step are as follows: the gel strand of low-temperature setting is crushed, is freeze-dried, sieving obtains partial size
In the faint yellow graininess sample of 0.20-0.71mm.
7. a kind of preparation method of super absorbent resin with porous three-dimensional structure according to claim 1, feature
It is, the macroporous structure range of the super absorbent resin is 50-500 μm, and macropore hole is extruded by gel by syringe needle
Scan path hole formed, micron order pore structure by the gel after printing by freeze-drying formed.
8. a kind of preparation method of super absorbent resin with porous three-dimensional structure according to claim 1, feature
It is, the porosity of the super absorbent resin with second level three-dimensional structure is within the scope of 85%-99%, vortex disappearance index
No more than 25sec/g.
9. a kind of preparation method of super absorbent resin with porous three-dimensional structure according to claim 1, feature
It is, the amount of the residual decentralized medium of the super absorbent resin with porous three-dimensional structure is not more than 2000ppm.
10. the described in any item preparation methods of the claim 1-9 super absorbent resin obtained with porous three-dimensional structure.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020190334A1 (en) * | 2019-03-18 | 2020-09-24 | Hewlett-Packard Development Company, L.P. | Three-dimensional printing |
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2018
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020190334A1 (en) * | 2019-03-18 | 2020-09-24 | Hewlett-Packard Development Company, L.P. | Three-dimensional printing |
| US11591494B2 (en) | 2019-03-18 | 2023-02-28 | Hewlett-Packard Development Company, L.P. | Three-dimensional printing with epoxy and amine compounds |
| US11787110B2 (en) | 2019-03-18 | 2023-10-17 | Hewlett-Packard Development Company, L.P. | Three-dimensional printing with epoxy and amine compounds |
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Application publication date: 20190308 |