CN104530295B - A kind of green super absorbent resin and preparation method thereof - Google Patents
A kind of green super absorbent resin and preparation method thereof Download PDFInfo
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- CN104530295B CN104530295B CN201510023308.2A CN201510023308A CN104530295B CN 104530295 B CN104530295 B CN 104530295B CN 201510023308 A CN201510023308 A CN 201510023308A CN 104530295 B CN104530295 B CN 104530295B
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Abstract
The invention discloses a kind of green super absorbent resin, acrylic acid, function monomer, cross-linking agent, other component are that 1:0.01～0.1:0.00001～0.001:0.1～1 makes according to mass ratio；Acrylic acid is added to the water and obtains acrylic acid aqueous solution, in acrylic acid aqueous solution, add unitary strong alkali aqueous solution obtain acrylic acid brine solution, function monomer, cross-linking agent and other components it is sequentially added in acrylic acid brine solution, add initiator and carry out Raolical polymerizable, obtain aqueous thick product, be dried, sieving after mechanical activation comminution obtains final products.Green monomer with double bond is carried out radical copolymerization with acrylic acid (salt) etc. by chemical reaction by the present invention, make green monomer by being covalently bound in super absorbent resin chemical constitution, solve existing green super absorbent resin and use the problem of process decolouring, use process do not have chance water " fade ", fade, the green phenomenon such as uneven.
Description
Technical field
The invention belongs to high absorbency material technical field, be specifically related to a kind of green super absorbent resin,
The invention still further relates to the preparation method of this green super absorbent resin.
Background technology
High hydrophilous resin (English Super Absorbent Polymer, be called for short SAP) is a kind of novel
Functional high molecule material, because having the strongest water absorption and excellent water-retaining property and in agricultural gardening, desert
Preventing and treating, etc. aspect have broad application prospects.The High hydrophilous resin at research initial stage is mainly acrylates
Polymer, product is white or close to colourless.Along with the continuous expansion of High hydrophilous resin application,
The super absorbent resin with different colours becomes the focus of research and development, motley High hydrophilous resin
In addition to there is practical value, also add ornamental value for it.Current main of colored super absorbent resin
Purposes has: kind of a careless crystal mud of growing flower, the substrate of soilless culture, the toy (ocean baby) of imbibition
Etc..There is the super absorbent resin of different color in use, added a color to life, one
Part enjoyment.
Current colored super absorbent resin is mainly in super absorbent resin production process or product
The dyestuff of middle addition different colours, makes super absorbent resin present different colors.Dyestuff can be according to it
Dissolubility is simply divided into water-soluble dye, lipid-soluble dye, insoluble dyes.
If the dyestuff added is water miscible, then in use, when super absorbent resin absorbs water
After, water-soluble dye will be dissolved in water, causes colored super absorbent resin " to fade ", fade.
If dyestuff is insoluble solid, then can due to dye solids and High hydrophilous resin density,
Particle diameter is different, causes dye solids to mix dispersion with super absorbent resin uneven, in use goes out
The problems such as existing dye solids is layered with super absorbent resin, separate；
So the dyestuff major part used in colored super absorbent resin production process is insoluble in the fat of water
Dissolubility organic dyestuff.Although water-fast fat-soluble organic dyestuff overcomes lacking of both the above dyestuff
Point, but himself there is also problems.
The super absorbent resin sold in the market be mainly polyacrylic acid (salt), polyacrylamide,
Polypropylene nitrile High hydrophilous resin.The synthon acrylic acid (salt) of these High hydrophilous resins, acryloyl
The initiator of amine, acrylonitrile and polyreaction, cross-linking agent are the most water miscible, its free radical
Polymerization is also many with water as medium, uses aqueous solution polymerization method to produce；Even if using inverse emulsion polymerization etc.
Other polymerization methodses, its reaction essence (in each droplet) remains water-soluble monomer water-soluble
Radical polymerization in liquid.And the dyestuff major part used in colour super absorbent resin production process is insoluble
In the fat-soluble organic dyestuff of water, these dyestuffs are during super absorbent resin generates, water insoluble,
Absorption, the mode such as be mingled with just can only be relied on to be present between super absorbent resin microparticle surfaces or microgranule；
Even if taking special producing technique, these dyestuffs are wrapped in Super Absorbent Polymer Particles with " centre of sphere " form
(or microsphere) center, but during super absorbent resin uses, need imbibition repeatedly, dehydration
Shrink, owing to dye granule is inconsistent, also with the coefficient of expansion of Super Absorbent Polymer Particles (or microsphere)
Super Absorbent Polymer Particles (or microsphere) can be caused to deform, rupture, pulverize, will originally be wrapped in center
Organic dyestuff discharge.Due to the combination between these dyestuffs and super absorbent resin (or microsphere)
Effect (adsorb, be mingled with, wrap up) is the most weak, and the two is the most heterogeneous, therefore during life-time service,
Arise that dyestuff and super absorbent resin segregation phenomenon, cause uneven color.And these dyestuffs are insoluble
Yu Shui, can flock together in water precipitation, will cause super absorbent resin color fade, and dyestuff
But flock together.After all, the adhesion between dyestuff and super absorbent resin that has its source in of problem
The most weak, both are easily separated at the non-homophase of molecular level.
Green is the symbol of life, and a lot of people have a preference for green, and green High hydrophilous resin can serve as without soil
The substrate of cultivation, is integrally forming with the green flowers and plants of cultivation, intersperses the flower of redness therebetween, can decorate
Environment；Green High hydrophilous resin is also used as the nicknack of imbibition, plays for child, such as
Make the Malachitum frog of imbibition, green locust or green plants.
Presently commercially available green High hydrophilous resin is all in High hydrophilous resin production process or in product
Adding what green colouring material realized, such green High hydrophilous resin existence there is also previously described kind
Plant drawback.
Summary of the invention
It is an object of the invention to provide a kind of green super absorbent resin, solve existing green high water suction
Property resin use process decolouring problem.
It is a further object to provide the preparation method of a kind of green super absorbent resin.
The technical solution adopted in the present invention is: a kind of green super absorbent resin, by acrylic acid, function
Monomer, cross-linking agent, other component are 1:0.01～0.1:0.00001～0.001:0.1～1 according to mass ratio
Polymerization prepares；
Function monomer is the soluble azo dyes with double bond, himself is green, after polymerization still
For green, it is by being covalently bound in super absorbent resin structure；
Other component be acrylamide, potassium acrylate, 2-acrylamide-2-methylpro panesulfonic acid, in one
Individual or multiple combinations.
The feature of the present invention also resides in,
Function monomer concrete structure formula is:
In any one.
Cross-linking agent is N, N'-methylene-bisacrylamide.
Another technical scheme of the present invention is: the preparation side of a kind of green super absorbent resin
Method, specifically includes following steps:
Step 1, is added to the water acrylic monomers and stirs, obtain acrylic acid aqueous solution；Wherein,
Acrylic monomers is 1:0.5～5 with the mass ratio of water；
Step 2, under agitation, adds unitary highly basic in the acrylic acid aqueous solution that step 1 obtains
Aqueous solution, stirring makes neutralization reaction carry out completely, obtaining the acrylic acid saline that degree of neutralization is 50%～80%
Solution；
Step 3, under the conditions of being kept stirring for, adds merit in the acrylic acid brine solution that step 2 obtains
Energy monomer, obtains mixture A after stirring；Wherein acrylic monomers with the mass ratio of function monomer is
1:0.01～0.1；Described function monomer is a kind of soluble azo dyes with double bond, concrete structure formula
For:
In any one；
Step 4, under the conditions of being kept stirring for, adds cross-linking agent in mixture A, after stirring
To mixture B；Wherein acrylic monomers is 1:0.00001～0.001 with the mass ratio of cross-linking agent；
Step 5, adds other components in mixture B, is sufficiently stirred for obtaining mixture C；Wherein third
Acrylic monomer is 1:0.1～1 with the mass ratio of other components；
Step 6, adds initiator in mixture C, after being thoroughly mixed uniformly, controls reaction temperature
Degree is 65 DEG C～80 DEG C, is kept stirring for reaction and carries out 1～5 hour, obtains aqueous thick product；Described draw
The quality sending out agent is the 0.1%～1% of acrylic monomers quality；
Step 7, aqueous thick product drying step 7 obtained, sieves after mechanical activation comminution and is finally produced
Product, i.e. green super absorbent resin.
The feature of the present invention also resides in,
In step 1, acrylic monomers is to remove polymerization inhibitor.
In step 2, unitary strong alkali aqueous solution is sodium hydroxide solution or potassium hydroxide solution.
In step 4, cross-linking agent is N, N'-methylene-bisacrylamide.
In step 5, other components are acrylamide, potassium acrylate, 2-acrylamide-2-methylpro panesulfonic acid
In one or more combination.
During in step 6, initiator is Ammonium persulfate., potassium peroxydisulfate, sodium peroxydisulfate any one.
The invention has the beneficial effects as follows: the preparation method of a kind of green super absorbent resin of the present invention, pass through
Function monomer with double bond is carried out radical copolymerization with acrylic acid (salt) etc. by chemical reaction, makes merit
Energy monomer, by being covalently bound in super absorbent resin chemical constitution, solves existing green high suction
Water-base resin uses the problem of process decolouring, and binding strength is good, during use, does not haves chance water and " falls
Color ", fade, the green phenomenon such as uneven, good-looking durable, clean environment firendly, it is adaptable to support as flowers
The prasioleta mud planted, the toy of imbibition, such as the Malachitum frog of imbibition, green locust etc., tool
There is good market prospect.
Detailed description of the invention
Below in conjunction with detailed description of the invention, the present invention is described in detail.
One green super absorbent resin of the present invention, by acrylic acid, function monomer, cross-linking agent, other group
Dividing according to mass ratio is that 1:0.01～0.1:0.00001～0.001:0.1～1 polymerization prepares；
Wherein, function monomer is the soluble azo dyes with double bond, himself is green, be polymerized with
After remain as green, it is by being covalently bound in super absorbent resin structure, and concrete structure formula is:
In any one；
Cross-linking agent is N, N'-methylene-bisacrylamide；
Other component is in acrylamide, potassium acrylate, 2-acrylamide-2-methylpro panesulfonic acid
Or multiple combinations.
The preparation method of above-mentioned green super absorbent resin, specifically includes following steps:
Step 1, is added to the water the acrylic monomers removing polymerization inhibitor and stirs, obtain acrylic acid
Aqueous solution；Wherein, acrylic monomers is 1:0.5～5 with the mass ratio of water；
Step 2, under agitation, adds unitary highly basic in the acrylic acid aqueous solution that step 1 obtains
Aqueous solution, unitary strong alkali aqueous solution is sodium hydroxide solution or potassium hydroxide solution, and its mass concentration is preferred
20%～50%, stirring makes neutralization reaction carry out completely, obtaining the acrylic acid that degree of neutralization is 50%～80%
Saline solution；
Step 3, under the conditions of being kept stirring for, adds merit in the acrylic acid brine solution that step 2 obtains
Energy monomer, obtains mixture A after stirring；Wherein acrylic monomers with the mass ratio of function monomer is
1:0.01～0.1；Function monomer is a kind of soluble azo dyes with double bond, himself is green,
Polymerization remains as green, by being covalently bound in super absorbent resin structure, specifically after polymerization later
Structural formula can be in following three kinds any one, but be not limited to these three kinds:
Step 4, under the conditions of being kept stirring for, adds cross-linking agent N, N'-di-2-ethylhexylphosphine oxide in mixture A
Acrylamide, obtains mixture B after stirring；Wherein acrylic monomers with the mass ratio of cross-linking agent is
1:0.00001～0.001；
Step 5, adds other components in mixture B, is sufficiently stirred for obtaining mixture C；Wherein third
Acrylic monomer is 1:0.1～1 with the mass ratio of other components；Other components be acrylamide, potassium acrylate,
One or more combination in 2-acrylamide-2-methylpro panesulfonic acid；
Step 6, adds in initiator ammonium persulfate, potassium peroxydisulfate, sodium peroxydisulfate in mixture C and appoints
Meaning one, after being thoroughly mixed uniformly, controlling reaction temperature is 65 DEG C～80 DEG C, is kept stirring for reaction
Carry out 1～5 hour, obtain aqueous thick product；The quality of initiator be acrylic monomers quality 0.1%～
1%；
Step 7, aqueous thick product drying step 7 obtained, by 40 mesh standard sieves after mechanical activation comminution
After obtain final products, i.e. green super absorbent resin.
The invention has the beneficial effects as follows: due in the function monomer chemical constitution in the present invention with double bond,
Can be with monomer, cross-linking agent N such as acrylic acid (salt), N'-methylene-bisacrylamide is copolymerized,
With the homogeneous copolymers of function monomer construction unit in generating structure.And the polymer molecule of function monomer
Manifest itself by green, make the High hydrophilous resin synthesized by the present invention naturally present green, add in fact
By value.Meanwhile, a kind of green High hydrophilous resin that the present invention provides, owing to being not high to inhale common
In water-resin, mixing adds marennin, but by chemical reaction, green polymer is embedding by chemical bond
Duan Gongju is in High hydrophilous resin chemical constitution, in use, does not haves chance water and " fades ", takes off
The phenomenons such as color, green are uneven.A kind of green High hydrophilous resin that the present invention provides, green " does not fades ",
Good-looking durable, clean environment firendly, it is adaptable to support prasioleta mud, the toy of imbibition planted as flowers,
Such as the Malachitum frog of imbibition, green locust etc., there is good market prospect.
Embodiment 1
The acrylic monomers 10g removing polymerization inhibitor is added in 50g water and stirs, obtain propylene
Aqueous acid；Under agitation, with the sodium hydroxide solution that mass concentration is 25% by aforesaid propylene acid
Aqueous solution is neutralized to 80%, obtains the acrylic acid brine solution that degree of neutralization is 80%；It is being kept stirring for condition
Under, in the acrylic acid brine solution that above-mentioned degree of neutralization is 80%, add 1g function monomer M1, and stir
Uniformly obtain mixture A；Under the conditions of being kept stirring for, in mixture A, add 0.01g cross-linking agent N,
N'-methylene-bisacrylamide, obtains mixture B after stirring；10g is added in mixture B
Acrylamide, is sufficiently stirred for obtaining mixture C；0.1g initiator persulfuric acid is added in mixture C
Ammonium, after being thoroughly mixed uniformly, controlling reaction temperature is 65 DEG C, is kept stirring for reaction and carries out 5 hours,
Obtain aqueous thick product；The aqueous thick product drying that will obtain, by 40 mesh standard sieves after mechanical activation comminution
After obtain the greeny super absorbent resin of outward appearance.
Function monomer M1 described in the present embodiment be 4-amino-4 ＇-chlorine diphenyl diimide through acrylated instead
The acrylate that should prepare, chemical entitled 4-acrylamido-4 ＇-chlorine diphenyl diimide, structural formula is as follows:
The function monomer M1 used in the present embodiment can use the conventional synthesis process of azo compound
Preparation.
The green High hydrophilous resin preparing the present embodiment is according to People's Republic of China's agricultural industry criteria
Water suction (saline) multiple assay method described in NY 886-2010 " agricultural water-retaining agent " is measured.
Recording Water absorption is 516, and inhaling saline multiple is 32.
The green High hydrophilous resin preparing the present embodiment carries out fading in aqueous solution as follows
Experiment: make tea-bag with the nylon cloth of 250 mesh, High hydrophilous resin 1g prepared by the present embodiment dress
Enter in tea-bag, after being placed in the large beaker filling 1000g water immersion 2 days, propose tea-bag and be suspended on
Above large beaker, unabsorbed moisture is made naturally to drench in large beaker.Observing water in large beaker is nothing
Color.Take in large beaker water and load sample cell, with distilled water as reference, with Agilent-8453 type ultraviolet-
Visible absorption spectra instrument mensuration sample, at the absorption spectrum of 600-760nm, does not finds that testing sample is in this district
Between have absorption, i.e. do not have and meet the water phenomenon that fades, fade.
Embodiment 2
The acrylic monomers 10g removing polymerization inhibitor is added in 5g water and stirs, obtain acrylic acid
Aqueous solution；Under agitation, with the sodium hydroxide solution that mass concentration is 20% by aforesaid propylene sour water
Solution is neutralized to 60%, obtains the acrylic acid brine solution that degree of neutralization is 60%；Under the conditions of being kept stirring for,
In the acrylic acid brine solution that above-mentioned degree of neutralization is 60%, add 0.1g function monomer M2, and stir all
Even obtain mixture A；Under the conditions of being kept stirring for, in mixture A, add 0.0001g cross-linking agent N,
N'-methylene-bisacrylamide, obtains mixture B after stirring；1g2-is added in mixture B
Acrylamide-2-methylpro panesulfonic acid, is sufficiently stirred for obtaining mixture C；0.01g is added in mixture C
Initiator sodium peroxydisulfate, after being thoroughly mixed uniformly, controlling reaction temperature is 80 DEG C, is kept stirring for anti-
Should carry out 1 hour, obtain aqueous thick product；The aqueous thick product drying that will obtain is logical after mechanical activation comminution
The greeny super absorbent resin of outward appearance is obtained after crossing 40 mesh standard sieves.
Function monomer M2 described in the present embodiment is that 4-amino-3 ＇, 5 ＇-dinitro diphenyl diimide is through third
The acrylate that alkene acylation reaction prepares, chemical entitled 4-acrylamido-3 ＇, 5 ＇-dinitro diphenyl diimide,
Structural formula is as follows:
The function monomer M2 used in the present embodiment can use the conventional synthesis process of azo compound
Preparation.
The High hydrophilous resin preparing the present embodiment is according to People's Republic of China (PRC) agricultural industry criteria NY
Water suction (saline) multiple assay method described in 886-2010 " agricultural water-retaining agent " is measured.Survey
Obtaining Water absorption is 673, and inhaling saline multiple is 45.
The High hydrophilous resin preparing the present embodiment carries out the experiment of fading in aqueous solution as follows:
Make tea-bag with the nylon cloth of 250 mesh, the High hydrophilous resin 1g preparing the present embodiment is loaded tea
In leaf bag, after being placed in the large beaker filling 1000g water immersion 2 days, propose tea-bag and be suspended on big burning
Above Bei, unabsorbed moisture is made naturally to drench in large beaker.It is colourless for observing water in large beaker.
Take water in large beaker and load sample cell, with distilled water as reference, inhale with Agilent-8453 type ultraviolet-visible
Receipts spectrophotometer sample, at the absorption spectrum of 600-760nm, does not finds that testing sample has suction in this interval
Receive, i.e. do not have and meet the phenomenon that water fades, fades.
Embodiment 3
The acrylic monomers 10g removing polymerization inhibitor is added in 25g water and stirs, obtain propylene
Aqueous acid；Under agitation, with the sodium hydroxide solution that mass concentration is 30% by aforesaid propylene acid
Aqueous solution is neutralized to 70%, obtains the acrylic acid brine solution that degree of neutralization is 70%；It is being kept stirring for condition
Under, in the acrylic acid brine solution that above-mentioned degree of neutralization is 70%, add 0.4g function monomer M3, and stir
Mix and uniformly obtain mixture A；Under the conditions of being kept stirring for, in mixture A, add 0.005g crosslinking
Agent N, N'-methylene-bisacrylamide, obtains mixture B after stirring；Add in mixture B
5g potassium acrylate, is sufficiently stirred for obtaining mixture C；0.005g initiator mistake is added in mixture C
Potassium sulfate, after being thoroughly mixed uniformly, controlling reaction temperature is 70 DEG C, is kept stirring for reaction and carries out 3
Hour, obtain aqueous thick product；The aqueous thick product drying that will obtain, by 40 mesh after mechanical activation comminution
The greeny super absorbent resin of outward appearance is obtained after standard screen.
Function monomer M3 described in the present embodiment is that 4-amino-2 ＇, 4 ＇-dinitro diphenyl diimide is through third
The acrylate that alkene acylation reaction prepares, chemical entitled 4-acrylamido-2 ＇, 4 ＇-dinitro diphenyl diimide,
Structural formula is as follows:
The function monomer M3 used in the present embodiment can use the conventional synthesis process of azo compound
Preparation.
The High hydrophilous resin preparing the present embodiment is according to People's Republic of China (PRC) agricultural industry criteria NY
Water suction (saline) multiple assay method described in 886-2010 " agricultural water-retaining agent " is measured.Survey
Obtaining Water absorption is 628, and inhaling saline multiple is 39.
The High hydrophilous resin preparing the present embodiment carries out the experiment of fading in aqueous solution as follows:
Make tea-bag with the nylon cloth of 250 mesh, the High hydrophilous resin 1g preparing the present embodiment is loaded tea
In leaf bag, after being placed in the large beaker filling 1000g water immersion 2 days, propose tea-bag and be suspended on big burning
Above Bei, unabsorbed moisture is made naturally to drench in large beaker.It is colourless for observing water in large beaker.
Take water in large beaker and load sample cell, with distilled water as reference, inhale with Agilent-8453 type ultraviolet-visible
Receipts spectrophotometer sample, at the absorption spectrum of 600-760nm, does not finds that testing sample has suction in this interval
Receive, i.e. do not have and meet the phenomenon that water fades, fades.
Embodiment 4
The acrylic monomers 10g removing polymerization inhibitor is added in 40g water and stirs, obtain propylene
Aqueous acid；Under agitation, with the potassium hydroxide solution that mass concentration is 50% by aforesaid propylene acid
Aqueous solution is neutralized to 50%, obtains the acrylic acid brine solution that degree of neutralization is 50%；It is being kept stirring for condition
Under, in the acrylic acid brine solution that above-mentioned degree of neutralization is 50%, add 0.8g function monomer M1, and stir
Mix and uniformly obtain mixture A；Under the conditions of being kept stirring for, in mixture A, add 0.001g crosslinking
Agent N, N'-methylene-bisacrylamide, obtains mixture B after stirring；Add in mixture B
7g acrylamide and the mixture of 2-acrylamide-2-methylpro panesulfonic acid, be sufficiently stirred for obtaining mixture
C；In mixture C, add 0.07g initiator potassium persulfate, after being thoroughly mixed uniformly, control
Reaction temperature is 75 DEG C, is kept stirring for reaction and carries out 2 hours, obtains aqueous thick product；By containing of obtaining
The thick product drying of water, obtains the greeny high-hydroscopicity of outward appearance by after 40 mesh standard sieves after mechanical activation comminution
Resin.
Function monomer M1 structural formula described in the present embodiment is as follows:
The function monomer M1 used in the present embodiment can use the conventional synthesis process of azo compound
Preparation.
The High hydrophilous resin preparing the present embodiment is according to People's Republic of China (PRC) agricultural industry criteria NY
Water suction (saline) multiple assay method described in 886-2010 " agricultural water-retaining agent " is measured.Survey
Obtaining Water absorption is 548, and inhaling saline multiple is 37.
The High hydrophilous resin preparing the present embodiment carries out the experiment of fading in aqueous solution as follows:
Make tea-bag with the nylon cloth of 250 mesh, the High hydrophilous resin 1g preparing the present embodiment is loaded tea
In leaf bag, after being placed in the large beaker filling 1000g water immersion 2 days, propose tea-bag and be suspended on big burning
Above Bei, unabsorbed moisture is made naturally to drench in large beaker.It is colourless for observing water in large beaker.
Take water in large beaker and load sample cell, with distilled water as reference, inhale with Agilent-8453 type ultraviolet-visible
Receipts spectrophotometer sample, at the absorption spectrum of 600-760nm, does not finds that testing sample has suction in this interval
Receive, i.e. do not have and meet the phenomenon that water fades, fades.
Claims (8)
1. a green super absorbent resin, it is characterised in that by acrylic acid, function monomer, cross-linking agent,
Other component is that 1:0.01～0.1:0.00001～0.001:0.1～1 polymerization prepares according to mass ratio；
Described function monomer is the soluble azo dyes with double bond, himself is green, after polymerization
Remaining as green, it is by being covalently bound in super absorbent resin structure, function monomer concrete structure
Formula is:
In any one；
Other component described be acrylamide, potassium acrylate, 2-acrylamide-2-methylpro panesulfonic acid, in
One or more combination；
The polymerization preparation process of green super absorbent resin is as follows:
Step 1, is added to the water acrylic monomers and stirs, obtain acrylic acid aqueous solution；Wherein,
Acrylic monomers is 1:0.5～5 with the mass ratio of water；
Step 2, under agitation, adds unitary highly basic in the acrylic acid aqueous solution that step 1 obtains
Aqueous solution, stirring makes neutralization reaction carry out completely, obtaining the acrylic acid saline that degree of neutralization is 50%～80%
Solution；
Step 3, under the conditions of being kept stirring for, adds merit in the acrylic acid brine solution that step 2 obtains
Energy monomer, obtains mixture A after stirring；Wherein acrylic monomers with the mass ratio of function monomer is
1:0.01～0.1；
Step 4, under the conditions of being kept stirring for, adds cross-linking agent in mixture A, after stirring
To mixture B；Wherein acrylic monomers is 1:0.00001～0.001 with the mass ratio of cross-linking agent；
Step 5, adds other components in mixture B, is sufficiently stirred for obtaining mixture C；Wherein third
Acrylic monomer is 1:0.1～1 with the mass ratio of other components；
Step 6, adds initiator in mixture C, after being thoroughly mixed uniformly, controls reaction temperature
Degree is 65 DEG C～80 DEG C, is kept stirring for reaction and carries out 1～5 hour, obtains aqueous thick product；Described draw
The quality sending out agent is the 0.1%～1% of acrylic monomers quality；
Step 7, aqueous thick product drying step 6 obtained, sieves after mechanical activation comminution and is finally produced
Product, i.e. green super absorbent resin.
2. a kind of green super absorbent resin as claimed in claim 1, it is characterised in that described crosslinking
Agent is N, N'-methylene-bisacrylamide.
3. the preparation method of a green super absorbent resin, it is characterised in that specifically include following steps:
Step 1, is added to the water acrylic monomers and stirs, obtain acrylic acid aqueous solution；Wherein,
Acrylic monomers is 1:0.5～5 with the mass ratio of water；
Step 2, under agitation, adds unitary highly basic in the acrylic acid aqueous solution that step 1 obtains
Aqueous solution, stirring makes neutralization reaction carry out completely, obtaining the acrylic acid saline that degree of neutralization is 50%～80%
Solution；
Step 3, under the conditions of being kept stirring for, adds merit in the acrylic acid brine solution that step 2 obtains
Energy monomer, obtains mixture A after stirring；Wherein acrylic monomers with the mass ratio of function monomer is
1:0.01～0.1；Described function monomer is a kind of soluble azo dyes with double bond, concrete structure formula
For:
In any one；
Step 4, under the conditions of being kept stirring for, adds cross-linking agent in mixture A, after stirring
To mixture B；Wherein acrylic monomers is 1:0.00001～0.001 with the mass ratio of cross-linking agent；
Step 5, adds other components in mixture B, is sufficiently stirred for obtaining mixture C；Wherein third
Acrylic monomer is 1:0.1～1 with the mass ratio of other components；
Step 6, adds initiator in mixture C, after being thoroughly mixed uniformly, controls reaction temperature
Degree is 65 DEG C～80 DEG C, is kept stirring for reaction and carries out 1～5 hour, obtains aqueous thick product；Described draw
The quality sending out agent is the 0.1%～1% of acrylic monomers quality；
Step 7, aqueous thick product drying step 6 obtained, sieves after mechanical activation comminution and is finally produced
Product, i.e. green super absorbent resin.
The preparation method of a kind of green super absorbent resin the most as claimed in claim 3, it is characterised in that
In described step 1, acrylic monomers is to remove polymerization inhibitor.
The preparation method of a kind of green super absorbent resin the most as claimed in claim 3, it is characterised in that
In described step 2, unitary strong alkali aqueous solution is sodium hydroxide solution or potassium hydroxide solution.
The preparation method of a kind of green super absorbent resin the most as claimed in claim 3, it is characterised in that
In described step 4, cross-linking agent is N, N'-methylene-bisacrylamide.
The preparation method of a kind of green super absorbent resin the most as claimed in claim 3, it is characterised in that
In described step 5, other components are acrylamide, potassium acrylate, 2-acrylamide-2-methylpro panesulfonic acid
In one or more combination.
The preparation method of a kind of green super absorbent resin the most as claimed in claim 3, it is characterised in that
During in described step 6, initiator is Ammonium persulfate., potassium peroxydisulfate, sodium peroxydisulfate any one.
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| CN201510023308.2A CN104530295B (en) | 2015-01-16 | 2015-01-16 | A kind of green super absorbent resin and preparation method thereof |
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| CN110079060A (en) * | 2019-03-29 | 2019-08-02 | 桐乡珠力高分子材料科技有限公司 | Improve level-dyeing property Masterbatch and preparation method thereof |
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| DE19805121A1 (en) * | 1998-02-09 | 1999-08-12 | Basf Ag | Process for the preparation of dye-containing, aqueous polymer dispersions |
| CN1232550C (en) * | 2000-04-13 | 2005-12-21 | 三洋化成工业株式会社 | Crosslinked polymer, process for producing same, absorbent structure and absorbent article |
| US6749646B2 (en) * | 2001-11-07 | 2004-06-15 | Bayer Polymers Llc | Dip-dyeable polycarbonate process |
| EP1462485A1 (en) * | 2003-03-26 | 2004-09-29 | Rolic AG | Polymerizable dichroic azo dyes |
| CN101210058B (en) * | 2006-12-27 | 2010-07-21 | 中国科学院大连化学物理研究所 | Molecular engram polymer with selectivity to genistein and daidzein |
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