CN108219070A - A kind of novel salt tolerant super absorbent resin and preparation method thereof - Google Patents
A kind of novel salt tolerant super absorbent resin and preparation method thereof Download PDFInfo
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- CN108219070A CN108219070A CN201711477626.1A CN201711477626A CN108219070A CN 108219070 A CN108219070 A CN 108219070A CN 201711477626 A CN201711477626 A CN 201711477626A CN 108219070 A CN108219070 A CN 108219070A
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- super absorbent
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
- C08B37/0024—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid beta-D-Glucans; (beta-1,3)-D-Glucans, e.g. paramylon, coriolan, sclerotan, pachyman, callose, scleroglucan, schizophyllan, laminaran, lentinan or curdlan; (beta-1,6)-D-Glucans, e.g. pustulan; (beta-1,4)-D-Glucans; (beta-1,3)(beta-1,4)-D-Glucans, e.g. lichenan; Derivatives thereof
- C08B37/0027—2-Acetamido-2-deoxy-beta-glucans; Derivatives thereof
- C08B37/003—Chitin, i.e. 2-acetamido-2-deoxy-(beta-1,4)-D-glucan or N-acetyl-beta-1,4-D-glucosamine; Chitosan, i.e. deacetylated product of chitin or (beta-1,4)-D-glucosamine; Derivatives thereof
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Abstract
The invention belongs to marine chemical industry engineering technology, and in particular to a kind of novel salt tolerant super absorbent resin and preparation method thereof.It is prepared by aminoethyl chitosan, acrylic acid, initiator, crosslinking agent by the polymerization of free radical initiation grafting.Have the present invention provides a kind of compared with novel chitosan base high water-absorption resin of high water absorption ability and salt resistance ability and preparation method thereof.A kind of novel aminoethyl chitosan grafting acrylic acid super absorbent resin general formula is as shown in figure I：
Description
Technical field
The invention belongs to marine chemical industry engineering technology, and in particular to a kind of novel salt tolerant super absorbent resin and its preparation
Method.
Background technology
High hydroscopic resin (Superabsorbent Polymer, abbreviation SAP) is a kind of functional high molecule material, because of it
Extensive concern is obtained with powerful water imbibition and excellent water-retaining property, at present, high hydroscopic resin is mainly used in medicine and defends
The fields such as life, farmland water conservation, control of desert.Although traditional acrylic compounds super absorbent resin with higher water absorbing capacity,
But salt resistant character is poor, not degradable in soil.There are a large amount of ions in soil, influence the water absorbing capacity of super absorbent resin
And ability is reused, Reusability causes to accumulate in soil.
Chitin (chitin) is the polysaccharide that N- acetyl-D-glucoses amine is combined into β-l, 4 keys, is crab, shrimp etc.
The cell wall constituent of the mushrooms such as the ectoskeleton of shell-fish, beetle etc. and mushroom, is widely present in nature.Chitosan
(chitosan) be chitin deacetylate product, have raw material sources extensively, it is good biocompatibility, degradable etc. excellent
Point, and the amino of chitosan 2 and the hydroxyl of 6 are more active, are easy to be chemically modified, obtain chitosan derivatives.Shell
Aminoethyl chitosan of the glycan through being chemically modified to obtain has preferable water-soluble.
After being chemically modified, super absorbent resin can be made in chitosan.Relative to traditional acrylic resin, chitosan
Class super absorbent resin has the good characteristics such as extensive raw material sources, at low cost, renewable, good biocompatibility, degradable.
Invention content：
The present invention provides a kind of novel salt tolerant high hydroscopic resin and preparation method thereof in view of the above problems.
In order to realize the above-mentioned purpose of the present invention, the present invention adopts the following technical scheme that：
A kind of novel salt tolerant super absorbent resin, resin is shown in structural formula I：
In formula, m=3-1400, n=17-8000, p=1-300, q=10-600, w=10-600.
The resin is by aminoethyl chitosan, acrylic acid, initiator, crosslinking agent according to mass ratio 1:6:0.0.05-0.3:
Resin shown in 0.05-0.3 polymerization gained formulas I.
The aminoethyl chitosan structure as shown in formula II,
In formula, m=3-400, n=17-2300.
The crosslinking agent is N,N methylene bis acrylamide, ethylenediamine, N hydroxymethyl acrylamide；Initiator is over cure
Sour ammonium, potassium peroxydisulfate or sodium peroxydisulfate.
A kind of preparation method of novel salt tolerant super absorbent resin, by aminoethyl chitosan, acrylic acid, initiator, friendship
Join agent according to mass ratio 1:6:0.0.05-0.3:Resin shown in 0.05-0.3 polymerization gained formulas I.
Further,
(1) aminoethyl chitosan is dissolved in the water, in N2Under protection, heating water bath is stirred to 40-80 DEG C to aminoethyl shell
Glycan is dissolved completely in water；Wherein the mass ratio of aminoethyl chitosan and water is 1:50-100；
(2) N is being kept2And under conditions of stirring, initiator is added in into above-mentioned lysate, it is anti-under the conditions of 60-80 DEG C
It answers 10-30 minutes；Wherein the mass ratio of aminoethyl chitosan and initiator is 1:0.05-0.3；
(3) N is being kept2And under conditions of stirring, acrylic monomers, acrylic monomers and chlorine are added in into above-mentioned reaction solution
The mass ratio of second ammonia chitosan is 6-10:1, then add in crosslinking agent, the mass ratio of aminoethyl chitosan and crosslinking agent is 1:
0.05-0.3；It is then warming up to 50-90 DEG C, reacts 2-5h, gained reaction solution is cooled to room temperature, then with unitary strong base solution tune PH
To neutrality to get resin shown in gained formula I.
The reaction product being adjusted to neutrality is dried to constant weight in 45-65 DEG C of baking oven to get formula institute through methanol dehydration
Obtain resin shown in formula I.
The aminoethyl chitosan structure as shown in formula II,
In formula, m=3-400, n=17-2300.
The crosslinking agent is N,N methylene bis acrylamide, ethylenediamine or N hydroxymethyl acrylamide；Initiator was
Ammonium sulfate, potassium peroxydisulfate or sodium peroxydisulfate；Unitary highly basic is sodium hydroxide or potassium hydroxide.
In the present invention, acrylic acid and the-NH on aminoethyl chitosan2It is graft-polymerized, obtains polymer, polymer warp
Infrared spectrum analysis determines structure, it was demonstrated that acrylic acid has successfully been grafted in aminoethyl chitosan structure.
Principle：Amino in chitosan is chitosan and the main graft site in acrylic acid-grafted polymerize and crosslinking position
Point.The raising of amino content can make polymerisation be more easy to occur.And amino increases, and increases the water suction in resin structure
Radical species are conducive to improve the salt tolerance of super absorbent resin.
Advantage for present invention：
1. resin of the present invention is to introduce a large amount of ethylenediamine bases in the structure of chitosan, chitosan is made to have preferably
It is water-soluble.
2. resin of the present invention increases the graft site on chitosan due to the introducing of amino, be conducive to acrylic acid and gather in shell
Grafting on sugared skeleton while water absorbing capacity is ensured, increases the salt resistance ability of resin.
Description of the drawings
Fig. 1 is the infrared spectrogram of chitosan, and infrared signature absorbs (cm-1)：1590,893.
Fig. 2 is the infrared spectrogram of aminoethyl chitosan, and infrared signature absorbs (cm-1):3255,2919,1632,
1525,1375,1316,1027,607。
Fig. 3 is the infrared spectrogram of AEMCS-AA super absorbent resins provided in an embodiment of the present invention, and infrared signature is inhaled
Receive (cm-1):3343,2929,1712,1557,1452,1400,1152,1021,613.
Specific embodiment
The invention will be further described with reference to the accompanying drawings of the specification, and protection scope of the present invention is not only limited to
Following embodiment.
Embodiment 1
The preparation of salt-tolerant super absorbent polymer
Chitosan and the chlorethamin hydrochloric acid solution of a concentration of 1mol/L of 75mL that 1.5g molecular weight is 1,500,000 are mixed, 65
At DEG C, stir to chitosan and be completely dissolved；The sodium hydroxide solution of a concentration of 1mol/L of 75mL is added drop-wise to above-mentioned shell dropwise again
In glycan solution, 18h is reacted under the conditions of 80 DEG C, is cooled to room temperature, product is dialysed three days with deionized water, and freeze-drying obtains ammonia
Ethyl chitosan.Aminoethyl chitosan can also prepare in a manner that following documents are recorded simultaneously：Je J Y,Kim S
K.Antimicrobial action of novel chitin derivative[J].Biochimica Et Biophysica
Acta-General Subjects,2006,1760(1):104-9.
1.0g aminoethyl chitosans are added in 100mL deionized waters, in N2Under protective condition, it is warming up in water-bath
60 DEG C, stirring is completely dissolved aminoethyl chitosan；0.1g ammonium persulfates are added in solution, and reaction after ten minutes, is slowly dripped
Add 6g acrylic acid and 5mLN, N- methylene-bisacrylamide solution (containing 0.15g), be warming up to 80 DEG C, react 3 hours.Product is cold
But it is 24 hours dry in 60 DEG C of drying boxes after methanol dehydration with 1mol/L sodium hydroxide solution tune PH to neutrality to room temperature.
Product is ground, 40 mesh and 80 mesh sieve, and obtains resin shown in formula I, wherein, m=600, n=3400, p+w+q=1200.
Infrared spectrogram shows：The infrared spectrogram (Fig. 3) of super absorbent resin position compared with chitosan infrared spectrogram
In 1590cm-1- the NH at place2Characteristic absorption peak disappears, and shows-NH3Base has occurred that reaction, while high hydroscopic resin is infrared
Spectrogram is in 1557cm-1,1452cm-1And 1400cm-1There is-COO in place-Symmetrical and asymmetric absorption peak, illustrate acrylic acid
It has been grafted on the skeleton of aminoethyl chitosan.Demonstrate the synthesis success of high hydroscopic resin.
Embodiment 2
1.0g aminoethyl chitosans are added in 100mL deionized waters, in N2Under protective condition, it is warming up in water-bath
60 DEG C, stirring is completely dissolved aminoethyl chitosan；0.05g potassium peroxydisulfates are added in solution, and reaction after ten minutes, is slowly dripped
Add 4g acrylic acid and 5mLN, N- methylene-bisacrylamide solution (containing 0.15g), be warming up to 70 DEG C, react 3 hours.Product is cold
But it is 24 hours dry in 60 DEG C of drying boxes after methanol dehydration with 1mol/L sodium hydroxide solution tune pH to neutrality to room temperature.
Product is ground, 40 mesh and 80 mesh sieve, and obtains resin shown in formula I, wherein, m=600, n=3400, p+w+q=800.
High hydroscopic resin water imbibition, the measure of salt tolerance are carried out to above-described embodiment is obtained resin shown in formula I：
Water suction (brine) multiplying power assay method of salt-tolerant super absorbent polymer is as follows：
0.05g 40-80 height of eye water-absorbing resins samples, package is in the sieve of 100 mesh, under room temperature, being totally submerged
In 500mL deionized waters, after resin complete swelling, sieve is taken out, suspension to no water droplet is dripped, and weighs the matter of sample after water suction
Amount.The water absorbent rate of super absorbent resin is calculated as follows：
Q=(m2-m1)/m1
Wherein, Q is water absorbent rate, unit g/g；m1For dry-eye disease weight, g；m2For example weight under saturation water suction state,
g。
The salt tolerance method of high hydroscopic resin is identical with water imbibition, and salting liquid is that the sodium chloride that mass fraction is 0.9% is molten
Liquid.Result of the test is as shown in table 1.It is compareed using the super absorbent resin of brightness up to Chemical Manufacture.
1 high hydroscopic resin water imbibition of table, salt tolerance test table
| Resin types | Water imbibition | Salt tolerance |
| Aminoethyl chitosan resin | 647 times | 99 times |
| Brightness reaches resin | 478 times | 65 times |
The results show that the super absorbent resin prepared, while having higher water absorption energy, salt resistant character is also more excellent
It is good.Meanwhile this resin after degrading in the soil, can play the effect of the coordinate plant growth of chitosan using chitosan as skeleton,
Therefore resin of the present invention has multi-efficiency, has good use value.
Claims (9)
1. a kind of novel salt tolerant super absorbent resin, which is characterized in that resin is shown in structural formula I：
In formula, m=3-1400, n=17-8000, p=1-300, q=10-600, w=10-600.
2. novel salt tolerant super absorbent resin as described in claim 1, which is characterized in that the resin is gathered by aminoethyl shell
Sugar, acrylic acid, initiator, crosslinking agent are according to mass ratio 1:6:0.0.05-0.3:Resin shown in 0.05-0.3 polymerization gained formulas I.
3. novel salt tolerant super absorbent resin as described in claim 2, which is characterized in that the aminoethyl chitosan structure
As shown in formula II,
In formula, m=3-400, n=17-2300.
4. novel salt tolerant super absorbent resin as described in claim 2, which is characterized in that the crosslinking agent be N, N- methylenes
Base bisacrylamide, ethylenediamine, N hydroxymethyl acrylamide；Initiator is ammonium persulfate, potassium peroxydisulfate or sodium peroxydisulfate.
5. a kind of preparation method of novel salt tolerant super absorbent resin described in claim 1, which is characterized in that by aminoethyl
Chitosan, acrylic acid, initiator, crosslinking agent are according to mass ratio 1:6:0.0.05-0.3:It is set shown in 0.05-0.3 polymerization gained formulas I
Fat.
6. the preparation method of novel salt tolerant super absorbent resin as described in claim 5, which is characterized in that
(1) aminoethyl chitosan is dissolved in the water, in N2Under protection, heating water bath is stirred to 40-80 DEG C to aminoethyl chitosan
It is dissolved completely in water；Wherein the mass ratio of aminoethyl chitosan and water is 1:50-100；
(2) N is being kept2And under conditions of stirring, initiator is added in into above-mentioned lysate, 10- is reacted under the conditions of 60-80 DEG C
30 minutes；Wherein the mass ratio of aminoethyl chitosan and initiator is 1:0.05-0.3；
(3) N is being kept2And under conditions of stirring, acrylic monomers, acrylic monomers and chloroethene ammonia are added in into above-mentioned reaction solution
The mass ratio of chitosan is 6-10:1, then add in crosslinking agent, the mass ratio of aminoethyl chitosan and crosslinking agent is 1:0.05-
0.3；50-90 DEG C is then warming up to, reacts 2-5h, gained reaction solution is cooled to room temperature, then with unitary strong base solution tune PH into
Property is to get resin shown in gained formula I.
7. the preparation method of novel salt tolerant super absorbent resin as described in claim 6, which is characterized in that it is described adjust to
Neutral reaction product is dried to constant weight in 45-65 DEG C of baking oven to get resin shown in formula obtained by formula I through methanol dehydration.
8. the preparation method of novel salt tolerant super absorbent resin as described in claim 6, which is characterized in that the aminoethyl
Chitosan structure as shown in formula II,
In formula, m=3-400n=17-2300.
9. the preparation method of novel salt tolerant super absorbent resin as described in claim 6, which is characterized in that the crosslinking agent
For N,N methylene bis acrylamide, ethylenediamine or N hydroxymethyl acrylamide；Initiator is ammonium persulfate, potassium peroxydisulfate or mistake
Sodium sulphate；Unitary highly basic is sodium hydroxide or potassium hydroxide.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112390910A (en) * | 2020-11-30 | 2021-02-23 | 池州学院 | Preparation method of super absorbent resin without chemical cross-linking agent |
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Application publication date: 20180629 |