CN105399900A - Preparation method of superabsorbent resin - Google Patents
Preparation method of superabsorbent resin Download PDFInfo
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- CN105399900A CN105399900A CN201510968750.2A CN201510968750A CN105399900A CN 105399900 A CN105399900 A CN 105399900A CN 201510968750 A CN201510968750 A CN 201510968750A CN 105399900 A CN105399900 A CN 105399900A
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- 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
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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Abstract
The present invention discloses a preparation method of a superabsorbent resin containing starch grafted acrylic acid (AA), acrylamide (AM) and 2-acrylamido-2-methyl propane sulfonic acid (AMPS). The preparation method of the superabsorbent resin is as below: adding an initiator into gelatinized starch to conduct initiation; then neutralizing the AA and AMPS solution with NaOH or KOH solution under the condition of sufficient cooling; then adding the monomer mixture of AA, AM and AMPS into the starch solution to conduct a starch graft polymerization reaction. The method uses starch as a graft monomer material, which is widely available, inexpensive, biodegradable, environmentally friendly and easy to operate and more friendly to the environment; the obtained resin has good salt resistance and high water absorption rate, and can reach imbibition equilibrium within 5 min.
Description
Technical field
The present invention relates to a kind of preparation method of High hydrophilous resin, particularly relate to the preparation method of the water-absorbing resin of starch graft acrylic acid, acrylamide and 2-acrylamide-2-methylpro panesulfonic acid.
Background technology
High hydrophilous resin is a kind of novel high polymer material that fast development is in recent decades got up, and it has good water-absorbent and water-retentivity.Therefore it applies very extensive in agricultural, forestry, environmental protection, food etc., in national economy and people's life, play very important effect.
At present, the preparation method of High hydrophilous resin mainly contains water solution polymerization process and via Inverse-Phase Suspension Polymerization etc.Because water solution polymerization process is easy and simple to handle and more friendly to environment, so industrial general use this method carrys out synthesizing super absorbent resin.In prior art, multiplex vinylformic acid prepares High hydrophilous resin, and vinylformic acid (AA) monomer is ionic comonomer, owing to having hydrophilic radical-COO
-, the water-intake rate of monomer whose High hydrophilous resin of synthesis after part neutralization is very high, but salt resistance is very poor; Not enough for overcoming this, have employed the technique means adding nonionic monomers acrylamide (AM) and AA copolymerization in prior art, this technology can solve salt tolerance problem effectively, but the water-intake rate of product reduces greatly.The product rate of water absorption of prior art is lower simultaneously.
Chinese invention patent 2012105651781 discloses a kind of Organic-inorganic composite water-absorbent material, and described composite absorbent material inorganic part is flyash; Organic moiety is base material with starch, adds vinylformic acid and 2-acrylamide-2-methyl propane sulfonic, by hydroscopic high-molecular resin that free radical polymerization obtains in water.Gelatinization time prepared by this product reaches 60min, and its product will use distilled water and absolute ethanol washing repeatedly respectively, and the water absorbent rate of its product 20min is only 745g/g.Do not provide the salt absorbing rate of its test in addition in that patent, therefore the patented product salt tolerance has no way of investigating.
Chinese invention patent application 2014103442649 discloses a kind of monkey grass graft ternary polymerization high-salt tolerance absorbent resin, prepared by the raw material of following weight content: monkey grass element powder 4-12 part, vinylformic acid 100-140 part, acrylamide 70-120 part, 2-acrylamide-2-methylpro panesulfonic acid 25-50 part, sodium hydroxide solution 230-270 part, linking agent 0.04-0.12 part, initiator 0.8-1.2 part, aqueous ethanolic solution 80-200 part.But this patent system in need to use monkey grass, therefore its apply can by the restriction in its source, simultaneously its cost is excessive.
Chinese invention patent application 2013106947513 discloses a kind of preparation method with the salt tolerant water-absorbing resin of high rate of water absorption, adopt the method for radical polymerization, take water as solvent, with ammonium persulphate and Tetramethyl Ethylene Diamine redox system for initiator, N, N '-methylene-bisacrylamide and nano silicon are the salt tolerant water-absorbing resin with high rate of water absorption that linking agent and monomeric acrylic, the copolymerization of 2-acrylamide-2-methylpro panesulfonic acid obtain.But there is the more difficult deficiency of biological degradation in resin prepared by this patent application technical scheme, and its preparation cost is relatively high.
Chinese invention patent application 201510134574.2 discloses a kind of high Baidu vinylformic acid High hydrophilous resin and preparation method thereof, vinylformic acid (through rectification process removing stopper) is added drop-wise in aqueous sodium hydroxide solution, obtain the neutralization solution of vinylformic acid and sodium salt thereof, toughner, tensio-active agent, linking agent and initiator is added successively in neutralization solution, stir, polyreaction obtains hydrogel and obtains Primary product, after finally obtain water-absorbing resin through a series of aftertreatment.The preparation method of this patent is water solution polymerization process, but its preparation process is complicated, especially acrylic acid rectification process is carried out, the pick up finally obtained is at about 62g/g, pre-treatment and aftertreatment all very very complicated in its patent preparation process, make its preparation cost very high, and pick up neither be very desirable.
" cotton straws graft acrylic acid prepares super absorbent resin " (wears merit, Zhang Na, Su Kuo is big. chemical engineering and equipment [J]. and Xinjiang, 2012. to 10 phases) disclosed technology is after cotton stalk powder is carried out soda boiling, Potassium Persulphate (KSB) is adopted to be initiator, N, N '-methylene-bisacrylamide (MBAM) is linking agent, make itself and acrylic graft copolymer synthesizing super absorbent resin, finally determine that top condition is by Experimental Comparison: soda boiling cotton stalk powder and acrylic acid massfraction are 1: 8, Potassium Persulphate consumption is 0.025 of monomer mass, linking agent N, N '-methylene-bisacrylamide (MBAM) consumption is 0.083% of monomer mass, vinylformic acid degree of neutralization is 70%, reaction times is 4h, bake out temperature is 90 DEG C.The test of water absorbent rate is carried out to the resin prepared under top condition, has absorbed distilled water and reach 207 times.But the technology of this file still needs to carry out pre-treatment to remove stopper to vinylformic acid, and products therefrom water-intake rate is very low, and preparation cost is higher.
Chinese invention patent application 2015106106409 discloses a kind of preparation method of High hydrophilous resin, the standby water-absorbing resin forming a kind of " dual network structure " of this patent system, being used for Detection job mark is the salt absorbing rate of 0.9%NaCl solution, and its salt absorbing rate is only at about 40 times.
Have bibliographical information, along with the concentration of sodium chloride solution increases, the pick up of water-absorbing resin declines, and after saltiness reaches massfraction 3%, pick up no longer declines along with the increase of concentration.Therefore the NaCl solution Smoking indexes that mass metering mark is 3% merits attention.But water-absorbing resin of the prior art to saltiness be 3% solution pick up all undesirable.
In addition, when preparing High hydrophilous resin in prior art, generally vinylformic acid need carried out rectification process removing stopper in advance.
Summary of the invention
The invention provides one overcome prior art deficiency, be easy to biological degradation, cheap, have higher rate of water absorption and high Smoking indexes, the salt solution being particularly 3% to saltiness massfraction has the preparation method of the High hydrophilous resin of high rate of liquid aspiration and water absorbent rate.
The preparation method of a kind of High hydrophilous resin of the present invention is: in reaction vessel, add the starch of monomer total mass 3% and the water of 25ml-30ml, then 80-85 DEG C of temperature gelatinization 30 minutes, make it be cooled to temperature of reaction 30-50 DEG C and add initiator under nitrogen protection and cause passing into, by vinylformic acid (AA) and 2-acrylamide-2-methylpro panesulfonic acid (AMPS) solution, under abundant cooling conditions, direct 7.5mol/LNaOH or KOH solution are neutralized to mole degree of neutralization is respectively 65mol%-85mol%, then under abundant cooling conditions by vinylformic acid, acrylamide (AM) and 2-acrylamide-2-methylpro panesulfonic acid mix with mol ratio 1:1:0.5-1:2:1, its above-mentioned mix monomer is joined in aforesaid starch solution the mixing solutions forming concentration range (g/ml) 36-47%, the 0.02-0.035% linking agent of monomer total mass is added again in reaction system, starch-grafted polyreaction is carried out in well-beaten condition, drying treatment is carried out after reaction terminates, and shatter and obtain water-absorbing resin.Initiator used is Potassium Persulphate, ammonium persulphate or Potassium Persulphate one sodium bisulfite, and linking agent used is two vinylformic acid glycol ester, vinylformic acid trimethyl-tryptophane three fat, tetraallyloxyethane or N, N '-methylene-bisacrylamides.
In the preparation method of a kind of High hydrophilous resin of the present invention, the linking agent preferably used is N, N '-methylene-bisacrylamide, dosage of crosslinking agent is the 0.023%-0.025% of monomer total mass; Initiator used is Potassium Persulphate.
Further, in preparation method of the present invention, mole degree of neutralization of vinylformic acid (AA) and 2-acrylamide-2-methylpro panesulfonic acid (AMPS) solution and NaOH or KOH solution neutralization reaction is 75%, i.e. pH=6.4, and polymeric reaction temperature is 30-50 DEG C.
The polymeric reaction temperature of the preferred preparation method of High hydrophilous resin of the present invention is 50 DEG C, when reacting at this temperature, and its rate of polymerization is the most suitable, can reduce the reaction times simultaneously, cost-saving, and can avoid implode.
In the preferred preparation method of a kind of High hydrophilous resin of the present invention, linking agent N used, the consumption of N '-methylene-bisacrylamide is 0.023% of monomer total mass, the consumption of initiator potassium persulfate is 0.15% of monomer total mass, the consumption of starch is 3% of monomer total mass, 2-acrylamide-2-methylpro panesulfonic acid used: vinylformic acid: the mol ratio of acrylamide is 1:2:0.5.
The present invention directly uses vinylformic acid containing stopper as monomer, and need not carry out prior rectification process again, directly synthesizes quaternary resin, not only can obtain imbibition, particularly inhale the resin of high density salt solution, and can reduce the cost of manufacture.
Present invention employs starch material, starch is a kind of biomass material of abundance, due to the reactable of hydroxyl in starch molecule, its new performance can be given by the method for grafting, copolymerization and modification, again because of its have cheap, abundance, can biodegradable characteristic.Rarely have with the quaternary High hydrophilous resin of monomer Starch synthesis and wish to become a kind of novel functional material.
Advantage of the present invention is:
(1) the present invention take starch as grafted monomer raw material, and wide material sources, cheap, biological degradability good, environmental friendliness.
(2) synthesize water-absorbing resin with vinylformic acid, generally need carry out underpressure distillation process removing stopper to vinylformic acid.And the present invention directly uses the vinylformic acid containing stopper to carry out polyreaction, reduce reaction cost.
(3) the present invention adopts water solution polymerization process synthesizing super absorbent resin, and because its equipment is simple, consume energy low, efficiency is high, and cost is low, environmentally friendly.
(4) the good salt resistance of water-absorbing resin tool prepared of the present invention and have very high water-intake rate, the resin obtained can reach imbibition balance in 5 minutes.Simultaneously to inhale salt solution higher for resin of the present invention, detects through reality, its multiplying power absorbing high salt-containing liquid of resin of the present invention all higher than prior art, as being NaCl and 3%Na of 3% to massfraction
2sO
4solution salt absorbing rate, at about 50 times, reaches desirable effect.
Embodiment
The specific examples affecting High hydrophilous resin pick up factor below in conjunction with High hydrophilous resin preparation method of the present invention and pick up testing method and assessment explains orally in detail to the present invention.
One, embodiment is prepared
Embodiment 1 monomer ratio is on the impact of resin pick up
The degree of neutralization of fixing ω (NMBA)=0.022%, ω (KPS)=0.15%, AA and AMPS is 75%, and different monomers mol ratio is on the impact of resin water absorbent rate in table 1, and table 1 is level of factor.Drawn by table 2, optimum molar combination is: A
2b
2c
1d
1, i.e., during monomer ratio: n (AMPS): n (AA): n (AM)=1:2:0.5, ω (starch)=3%, the liquid absorbency rate of water-absorbing resin reaches maximum value.Major cause is the increase along with AA and AM ratio in the middle of solution, hydrophilic radical-COO
-increase, pick up raises, and when its ratio is too high, during copolymerization, self-crosslinking occurs, and during imbibition, polymer network expansion is limited, and its liquid absorbency rate is declined; When AMPS consumption increases, the SO in solution
3 -increased number, electric density is comparatively large, and polymkeric substance is comparatively stretched, and water absorbent rate increases, and when AMPS consumption is excessive, the soluble part in resin increases, and water absorbent rate declines.
Embodiment 2 dosage of crosslinking agent is on the impact of High hydrophilous resin liquid absorbency rate
Fixing ω (KPS)=0.15%(take total mass as benchmark), the degree of neutralization of AA and AMPS is 75%, n (AMPS): n (AA): n (AM)=1:2:0.5, ω (starch)=3%.The consumption of linking agent on the impact of High hydrophilous resin liquid absorbency rate in table 3.As shown in Table 3, along with the increase of dosage of crosslinking agent, resin liquid absorbency rate first raises rear decline, and when dosage of crosslinking agent is 0.023% of total mass, the liquid absorbency rate of resin is the highest.Major cause be dosage of crosslinking agent lower time, crosslinking reaction is incomplete, and crosslinking degree is more weak, and the spacial framework of formation is not obvious, thus the water absorbent rate of resin is reduced; When dosage of crosslinking agent is excessive, degree of crosslinking is higher, and in the three-dimensional space network of formation, cross-linking set is many, and cross-linking density is comparatively large, causes certain difficulty, cause the liquid absorbency rate of resin to decline to entering of water molecules.
Embodiment 3 initiator amount is on the impact of resin liquid absorbency rate
Fixing ω (NMBA)=0.023%(take total mass as benchmark), the degree of neutralization of AA and AMPS is 75%, n (AMPS): n (AA): n (AM)=1:2:0.5, ω (starch)=3%.The consumption of initiator on the impact of High hydrophilous resin liquid absorbency rate in table 4.As shown in Table 4, initiator amount very little time, speed of response is slow, and in reaction system, reactive behavior point is less, and resin can not effectively form three-dimensional space network structure, thus liquid absorbency rate is lower; When initiator amount is higher, rate of polymerization is too fast, and resin formation has the three-dimensional network space compared with higly branched chain, therefore pick up reduces.So the liquid absorbency rate of resin is the highest when initiator amount is 0.15%.
Embodiment 4 monomer concentration is on the impact of resin liquid absorbency rate
Fixing ω (NMBA)=0.023% (taking total mass as benchmark), ω (KPS)=0.15% take total mass as benchmark), the degree of neutralization of AA and AMPS is 75%, n (AMPS): n (AA): n (AM)=1:2:0.5, ω (starch)=3%.As known from Table 5, along with the reduction of monomer concentration, the liquid absorbency rate of resin first increases rear reduction, and when monomer concentration is 41%, the liquid absorbency rate of resin is the highest.This is because when monomer concentration is too high, the activated monomer quantity in unit volume is more, and reaction is violent, and reaction heat is difficult to remove, and easily self-crosslinking occurs, therefore pick up declines; When monomer concentration is too low, in unit volume, reactive behavior point is few, and resin can not form effective three-dimensional network space structure, thus the imbibition ability of resin declines.
Embodiment 5 temperature is on the impact of resin liquid absorbency rate
Fixing ω (NMBA)=0.023% (taking total mass as benchmark), ω (KPS)=0.15% take total mass as benchmark), n (AMPS): n (AA): n (AM)=1:2:0.5, ω (starch)=3%, monomer concentration is 41%.As known from Table 6, the optimum temps of this experiment is 50 DEG C, because the too low decomposition being unfavorable for initiator of temperature, the living radical of generation is less, is unfavorable for grafting, and in the unit time, the amount of monomer of grafting is less, and the pick up of resin is declined; When temperature is too high, activated monomer quantity is many, and rate of polymerization is accelerated, and heat is difficult to get rid of, and causes reaction too violent, easily causes monomer implode, and the chain termination of high temperature aggravation simultaneously, makes its imbibition ability reduce.
Embodiment 6 degree of neutralization is to the liquid absorbency rate of resin
Fixing ω (NMBA)=0.023% (taking total mass as benchmark), ω (KPS)=0.15%(take total mass as benchmark), n (AMPS): n (AA): n (AM)=1:2:0.5, ω (starch)=3%, monomer concentration is 41%, and temperature is 50 DEG C.The consumption of degree of neutralization on the impact of High hydrophilous resin liquid absorbency rate in table 7.As shown in Table 7, degree of neutralization is 75% is best.This is because in right lower time, in solution, acidity is higher, and polymerization velocity is very fast, and reaction is difficult to control, and easily forms high crosslinked polymkeric substance, makes pick up decline simultaneously; When degree of neutralization increases, monomer reaction activity is low.Speed of response declines, and the carboxylic acid potassium group of strong absorptive increases simultaneously, and osmotic pressure inside cross-linked network is increased, and pick up improves; But degree of neutralization is too high, also cause the water-soluble increase of gained resin, pick up declines.
By the research of above-mentioned example, the present invention adopts water solution polymerization process to prepare starch-grafted AA/AM/AMPS High hydrophilous resin, and has investigated monomer ratio, monomer concentration, dosage of crosslinking agent, initiator amount, the degree of neutralization of AA and AMPS monomer and temperature to resin at distilled water, 3%NaCl, 3%Na
2sO
4the impact of solution liquid absorbency rate, and from these data, obtain the preferred process condition of synthesizing quaternary water-absorbing resin, that is: ω (NMBA)=0.023% (taking total mass as benchmark), ω (KPS)=0.15% (taking total mass as benchmark), n (AMPS): n (AA): n (AM)=1:2:0.5, monomer concentration is 41%, ω (starch)=3%, and polymerization temperature is 50 DEG C.
Two, testing example
Testing method of the present invention is: be broken into Powdered by dried resin-oatmeal, precise 0.2g puts into beaker, adds distilled water or ω (NaCl)=3% solution, after 3 minutes, with 100 object screen filtration until do not have water droplet to fall, by formula Q=(W
1-W
0)/W
0calculate the liquid absorbency rate of resin, W in formula
0for weight before imbibition, W
1for weight after imbibition.
Detected as stated above by the product that preferred process condition by aforementioned synthesis quaternary water-absorbing resin is prepared, gained height water suction data measured is as follows:
Resin inhaled distilled water, 3%NaCl and 3%Na in 3 minutes
2sO
4solution liquid absorbency rate is respectively 676g/g, 47g/g and 53g/g.
Claims (6)
1. a preparation method for High hydrophilous resin, is characterized in that: add by total monomer in reaction vessel
wt.the water of 3% starch and 25ml-30ml, then 80-85 DEG C of temperature gelatinization 30 minutes, makes it be cooled to temperature of reaction 30-50 DEG C and adds initiator under nitrogen protection and cause passing into, by AA and AMPS solution, under abundant cooling conditions, direct NaOH or KOH solution are neutralized to mole degree of neutralization is respectively 65mol%-85mol%, then under abundant cooling conditions by AA, AM, AMPS mixes with mol ratio 1:1:0.5-1:2:1, its above-mentioned mix monomer is joined in aforesaid starch solution the mixing solutions forming concentration range (g/ml) 36-47%, the 0.02-0.035% linking agent of monomer total mass is added again in reaction system, starch-grafted polyreaction is carried out in well-beaten condition, drying treatment is carried out after reaction terminates, and shatter and obtain water-absorbing resin, initiator used is Potassium Persulphate, ammonium persulphate or Potassium Persulphate one sodium bisulfite, linking agent used is two vinylformic acid glycol esters, vinylformic acid trimethyl-tryptophane three fat, tetraallyloxyethane or N, N '-methylene-bisacrylamide.
2. the preparation method of a kind of High hydrophilous resin according to claim 1, is characterized in that: linking agent used is N, N '-methylene-bisacrylamide, dosage of crosslinking agent is the 0.023%-0.025% of monomer total mass; Initiator used is Potassium Persulphate.
3. the preparation method of a kind of High hydrophilous resin according to claim 2, it is characterized in that mole degree of neutralization of vinylformic acid and 2-acrylamide-2-methylpro panesulfonic acid solution and NaOH or KOH solution neutralization reaction is 75%, i.e. pH=6.4, polymeric reaction temperature is 30-50 DEG C.
4. the preparation method of a kind of High hydrophilous resin according to claim 3, is characterized in that polymeric reaction temperature is 50 DEG C.
5. the preparation method of a kind of High hydrophilous resin according to claim 4, it is characterized in that linking agent N, the consumption of N '-methylene-bisacrylamide is 0.023% of monomer total mass, the consumption of initiator potassium persulfate is 0.15% of monomer total mass, the consumption of starch is 3% of monomer total mass, 2-acrylamide-2-methylpro panesulfonic acid used: vinylformic acid: the mol ratio of acrylamide is 1:2:0.5.
6. High hydrophilous resin prepared by the either method described in claim 1 to 5.
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| CN107938341A (en) * | 2017-12-04 | 2018-04-20 | 宜宾惠美纤维新材料股份有限公司 | A kind of preparation method of deodorization fiber cellulose fiber |
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Application publication date: 20160316 |