CN100554292C - A kind of fast preparation method of super absorbent resin - Google Patents
A kind of fast preparation method of super absorbent resin Download PDFInfo
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- CN100554292C CN100554292C CNB2007100430813A CN200710043081A CN100554292C CN 100554292 C CN100554292 C CN 100554292C CN B2007100430813 A CNB2007100430813 A CN B2007100430813A CN 200710043081 A CN200710043081 A CN 200710043081A CN 100554292 C CN100554292 C CN 100554292C
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Abstract
The invention discloses a kind of quick method for preparing polyacrylic acid sodium salt type super absorbent resin (SAP), it is characterized in that: be monomer with vinylformic acid, ionic membrane caustic soda is a neutralizing agent, add linking agent and redox initiator, adopt the method preparation of aqueous solution polymerization, and the SAP particle behind drying, pulverizing, the sub-sieve is carried out surface-crosslinked processing.In the present invention, after utilizing the neutralization heat of vinylformic acid and ionic membrane caustic soda or neutralizer being heated to the polyreaction initial temperature, add redox initiator, mix, at high temperature carry out polyreaction then.Whole polymerization rate is fast, and the existing high suction physiological saline rate of prepared super absorbent resin, and very fast suction physiological saline speed is arranged again, and product is applicable to hygienic articles.This technology is fit to the belt serialization and produces.
Description
Technical field
The present invention relates to a kind of fast preparation method of super absorbent resin, relate in particular to and utilize acid-base neutralisation heat, directly make the monomer solution temperature reach the polyreaction initial temperature, in polymerization process, utilize heat of polymerization that reaction is tending towards fully, thereby polyreaction can be finished at short notice.The super absorbent resin that obtains by the inventive method has the suction physiological saline rate under good normal pressure and the 2kPa pressure, and water conservation energy and low residual monomer amount can be used as hygienic articles, for example disposable paper diaper and sanitary towel etc. effectively.
Background technology
High hydrophilous resin is called for short SAP, super absorbent resin effectively utilizes its a large amount of rapidly water system liquid that absorb, as body fluid such as people's urine, blood, sweat, even under load, the feature that the liquid that has absorbed also can not discharge is widely used as paper nappy, the physiology water-retaining agent with the absorbent commodity of sanitary materials such as paper handkerchief.Present sustainable development along with China's economic is to the demand constantly rising of SAP, so super absorbent resin preparation cost competitive power has tremendous influence.But because the backwardness of present domestic production technology, show that polymerization reaction time is long, caused production efficiency low, and the SAP product performance of producing are low, make domestic SAP product to contend with, so need the SAP production technology of developing low-cost at present in a hurry with external manufacturer.
As everyone knows, cross linked polyacrylate (salt) class generally adopts production technique such as inverse suspension polymerization method, reversed emulsion polymerization, water solution polymerization process as a principal item of super absorbent resin.Comprise intermittently and continuous processing with regard to water solution polymerization process.And adopt the travelling belt production technique is a kind of method of important aqueous solution polymerization continuous production super absorbent resin.But, it is long that general aqueous solution polymerization prepares its polymerization reaction time of super absorbent resin, for example in clear 60-161409 of Japanese Patent JP and the U.S. Pat 4525527, because in the neutralization reaction process, neutralization heat is taken away, made that the starting temperature of polyreaction is low, though polyreaction can be carried out more reposefully, but the required time that reacts completely was wanted more than 4 hours.In Chinese patent CN1208352C, adopted the prepolymerized method of monomer solution, make prepolymerized monomer liquid viscosity reach 1000-8000mPa.s, though make that like this thickness of material can increase on the reactive polymeric band, and shorten the residence time of material on belt reactor, but because its polymerization initial reaction temperature lower (being lower than 40 ℃) polymerization reaction time is still more than 30min, and owing to adopt prepolymerization, monomer solution viscosity increases, make the production operation difficulty strengthen, cause material conveying pipe to stop up easily.In Chinese patent CN1690086, composite oxidation and the light initiation system of Japanese catalyst company's employing, the concentration of monomer solution when the monomer solution temperature is 90-95 ℃, is added polymerization starter greater than 45%, and polyreaction can be finished in 3min.But because reacting initial temperature is higher than the kick off temperature of oxidation initiator, shortened the inductive phase of initiated polymerization greatly, made production process be not easy control, and, cause the residual monomer content in the finished product higher because at high temperature polyreaction is violent.
The present invention has overcome the deficiency in the above-mentioned technology, reasonably utilized acid-base neutralisation heat, make the temperature of monomer solution in the neutralization reaction process, just reach the starting temperature of polyreaction, and adopted redox initiator system, even make polyreaction under than higher temperature of reaction, still can carry out to quick and stable, and polyreaction is complete.Super absorbent resin by the inventive method preparation has good absorbent and rate of liquid aspiration and low remaining acrylic acid content.
Summary of the invention
The invention provides a kind of quick method for preparing super absorbent resin, realized that in the present invention polyreaction carries out apace.In preparation process, effectively utilized acid-base neutralisation heat, thereby directly the temperature of monomer solution is increased to the starting temperature of polyreaction, with this understanding, in monomer solution, add the oxidation initiator, after mixing, add the reduction initiator solution again, after in induction period in polymerization, initiator and monomer solution being mixed, the reaction tray of injecting comparatively high temps is carried out polyreaction rapidly, thereby make polyreaction finish at short notice, and the super absorbent resin that obtains thus has excellent absorbent and pick up faster, and the residual acrylic acid content in the product is also lower.By method of the present invention, can realize the large-scale production of super absorbent resin product, effectively improve the space-time production capacity of product, thereby can reduce production cost of products.
The present invention realizes by the following technical solutions: a kind of quick method for preparing super absorbent resin, it is to be monomer by ice crystal type vinylformic acid, mass concentration is that 32% ionic membrane caustic soda is that neutralizing agent carries out neutralization reaction, after neutralization reaction finishes, when the temperature of monomer solution rises to starting temperature 50-80 ℃ of polyreaction, under whipped state, the acrylic acid solution that adds linking agent, then add the aqueous solution of oxidation initiator, after mixing, add the reduction initiator solution again, in induction period in polymerization, mixing of materials is evenly also injected the reaction tray of handling through insulation and carry out polyreaction, polyreaction was finished in 2～15 minutes, obtained cavernous high water absorbent resin gel.The polymeric gel of gained is carried out slitting, and broken granulation, drying, pulverizing, sub-sieve are conciliate in stripping and slicing, carry out the surface-crosslinked processing of particulate at last.Wherein, institute's acid-base neutralisation degree is 65-85%, the acid-base neutralisation temperature of reaction is controlled at 50-80 ℃, the mass concentration of monomer solution is 15～45%, described linking agent quality is the 0.1-0.6% of monomer mass, described initiator quality is the 0.1-0.6% of monomer mass, and polymeric reaction temperature is between 60-110 ℃, and the temperature difference in the polymerization process between initial reaction temperature and the maximum temperature is no more than 40 ℃.
In the technique scheme, described linking agent is selected from N, N-dimethylene bisacrylamide, and polyethyleneglycol diacrylate, Viscoat 295, at least a in the Phthalic acid, diallyl ester.Described redox initiator is selected from a kind of in ferrous of Potassium Persulphate/sodium bisulfite, ammonium persulphate/S-WAT, Sodium Persulfate/xitix, benzoyl peroxide/xitix, hydrogen peroxide/sulfuric acid.
In technique scheme, the consumption and the kind of described linking agent are most important.When dosage of crosslinking agent was very few, then cross-linking density was little, failed to form three-dimensional net structure, and solvability increases in water, and suction physiological saline multiplying power is not high; Along with the increase of dosage of crosslinking agent, polymkeric substance forms network structure gradually, and the pick up of resin improves.But when dosage of crosslinking agent was too big, cross-linking set increased in the polymer ions network structure, and cross-linking density is excessive, cause that micropore diminishes in the network structure, pick up also can descend, so dosage of crosslinking agent should be selected according to practical situation, is advisable with scope of disclosure in the technical scheme.
Described initiator amount is also very important, and initiator amount affects the molecular weight of polymerization rate and polymerization reactant, causes polymer network structure to change to some extent, finally influences the pick up of resin.
In technical scheme, utilize acid-base neutralisation heat that the temperature of monomer solution is raise, the temperature that neutralization back monomer solution is reached is as the initial temperature of polyreaction, and it is not less than 50 ℃, is not higher than 80 ℃.Too low initial reaction temperature can prolong polymerization reaction time, reduces polymeric productivity, and destroys the absorbent of resin.Too high polymerization initiation temperature makes induction period in polymerization shorten, and is difficult to control in operating process, cause easily when initiator and mixing of monomer liquid are incomplete, with regard to polymerization reaction take place, cause polyreaction not carry out effectively, have influence on the performance of the finished product.
In technical scheme, the temperature difference between polymeric initial temperature and the top temperature in polymerization process is no more than 40 ℃, and the less temperature difference can make polyreaction carry out more reposefully, and makes the performance of prepared absorbent resin that better improvement be arranged.
Further in the technical scheme, after polymerization finishes, gel is carried out broken granulation, drying, pulverizing, sub-sieve, then particulate resins is carried out surface-crosslinked processing, described surface crosslinking agent is selected from least a in propylene glycol, butyleneglycol, glycol ether, diglycidyl ether of ethylene glycol, the glycerol etc.
Because the utilization of technique scheme, the present invention compared with prior art has following advantage:
1) the present invention has utilized the neutralization heat of vinylformic acid and ionic membrane caustic soda, add redox initiator after in the neutralization reaction process, making reaction monomers solution directly reach the initial temperature of polyreaction, then monomer liquid is at high temperature carried out polyreaction, the heat of polymerization that discharges in the reaction process is used for improving the gel solids content effectively and is kept temperature of reaction, shorten polymerization reaction time, improved polyreaction efficient.
2) initiator of polyreaction adopts redox system among the present invention, makes polyreaction can carry out more reposefully under initial reaction temperature, and avoided since at high temperature induction period in polymerization lack the trouble of bringing in the operating process.
3) superabsorbent gels prepared in accordance with the present invention is carried out fragmentation, drying, pulverizing, sub-sieve and surface-crosslinked processing, prepared thus final absorbent resin product has good pick up, water conservation energy, rate of liquid aspiration and low residual monomer amount.
4) the simple control easily of the preparation technology of absorbent resin provided by the invention.
Embodiment
The invention will be further described below in conjunction with embodiment, but the present invention is not limited to embodiment.
Performance test in embodiment and the comparative example is as follows:
Normal pressure is inhaled the physiological saline rate: get 0.2g SAP sample and place a tea-bag, this tea-bag is immersed in 0.9% the sodium chloride aqueous solution, treat that resin absorption is saturated after, take out, drop goes excess liquid, the calculating of weighing obtains the suction physiological saline rate of resin.
SAP sample normal pressure pick up
In the formula: m
1---sample saturated absorption physiological saline after draining with the tea-bag total mass;
m
0---absorb the tea-bag quality of physiological saline after draining.
Water conservation energy: take by weighing super absorbent resin about 0.2g and pack in ready-made 2.5 * 3 inches tea-bag, seal this tealeaves sack, and the SAP sample is evenly distributed in the tea-bag, this tea-bag flatly is placed between two blocks of glasscloths then, and place it in the Stainless Steel Disc that contains 0.9wt%NaCl solution, make sample all be immersed in the liquid, kept submerged state 30 minutes, then tea-bag is taken out, dewatered 3 minutes with 250 * 9.81m/s2 (250G) with whizzer, carry out weighing then, compare test with a blank tea-bag simultaneously.
The centrifugal guarantor's liquid of SAP sample rate
In the formula: m
1---sample and the tea-bag saturated absorption physiological saline total mass after centrifugal;
m
0---absorb the tea-bag quality of physiological saline after centrifugal.
2kPa inhales the physiological saline rate down: with the 0.2g particle diameter is that 300-600 μ m SAP toner is dispersed on the nylon wire of a cylinder equably, place at an upper portion thereof and can not hinder cylinder lid and the load that moves up and down, its charge capacity is 2kPa, this device is placed and can evenly absorb on the equipment of the 0.9%NaCl aqueous solution, make the SAP resin in the cylinder can absorb 0.9% the NaCl aqueous solution equably.Behind the 30min, device is weighed, calculate, obtain inhaling under the resin 2kPa pressure physiological saline rate.
The SAP load is the pick up of (2kPa) down
In the formula: m
1---the total mass of sample and tool lid cylinder after the imbibition dehydration;
m
0---the clean quality of tool lid cylinder.
The test of residual monomer content: in being placed with the 250ml beaker of magnetic agitation rotor, add 0.9wt% sodium chloride aqueous solution 100g, the super absorbent resin that accurately takes by weighing the 0.5g drying is designated as W1, after starting magnetic agitation, the sample that takes by weighing is added in this solution, cover beaker with film, stir to take out after 1 hour and filter, collect filtrate and weighing, be designated as W2, filtrate is carried out liquid-phase chromatographic analysis.
Obtain residual acrylic acid content in the super absorbent resin according to the filtrate quality.The content of residual acrylic acid (ppm)=X * W2/W1 in the super absorbent resin
X---liquid-phase chromatographic analysis acrylic acid content, ppm.
Embodiment 1
Get 32wt% ionic membrane caustic soda 694g, 700g dilutes with deionized water, ice crystal type vinylformic acid with 460g in 10 minutes at normal temperatures adds in the alkali lye, the acrylic acid solution 40g that adds the polyethyleneglycol diacrylate (molecular weight 400) of 4wt% then, this moment, the monomer solution temperature rose to 50 ℃.
Get above-mentioned monomer solution 400g (50 ℃), adding initiator is that concentration is the persulfate aqueous solution 10g of 0.2wt%, concentration is the aqueous solution of sodium bisulfite 10g of 0.1wt%, the mixing time of initiator and monomer solution is no more than 30s, (200 * 280mm) carry out polyreaction just this monomer solution to be inserted in 90 ℃ of baking ovens the Teflon dish, its thickness is 7mm, reaction arrives 102 ℃ of top temperatures in the time of 6 minutes, continued insulation reaction 4 minutes, taking-up reacts completely, the polymer gel 380g that has a large amount of trickle bubbles, gel thicknesses is 6mm.
Adopt mincer to carry out the gel granulation resulting gel, gel particle obtained the dried particle that water content is 5wt% in dry 4 hours in 140 ℃ baking oven, with this dried particle pulverize, sub-sieve, obtaining most of granularity is 32～100 purpose resins.
Get above-mentioned granularity resin 100g, water, glycerine, alcoholic acid blending surface crosslinked fluid 5g mix with it, react 30 minutes down at 190～210 ℃ then, obtain the super absorbent resin through surface-crosslinked processing, and its The performance test results sees Table 1.
Embodiment 2-3
Adopt the preparation technology identical with embodiment 1, the degree of neutralization of change vinylformic acid and alkali is respectively 75wt% and 70wt%, and prepared super absorbent resin The performance test results sees Table 1.
Comparative example 1
Get 32wt% ionic membrane caustic soda 694g, 700g dilutes with deionized water, ice crystal type vinylformic acid with 460g under the cooling situation adds in the alkali lye, about 20 ℃ of control neutral temperatures, the acrylic acid solution 40g that adds the polyethyleneglycol diacrylate (molecular weight 400) of 0.5wt% after neutralization finishes then, this moment, the monomer solution temperature was 20 ℃.
Get above-mentioned monomer solution 400g (20 ℃), adding initiator is that concentration is the persulfate aqueous solution 10g of 0.2wt%, concentration is the aqueous solution of sodium bisulfite 10g of 0.1wt%, after mixing, just this monomer solution is inserted 70 ℃ Teflon (200 * 280mm) dish in carry out polyreaction, its thickness is 7mm, afterreaction arrived 92 ℃ of top temperatures in 70 minutes, continued insulation reaction 30 minutes, and took out polymer gel 400g, gel thicknesses is 6.5mm.
Adopt mincer to carry out the gel granulation resulting gel, gel particle obtained the dried particle that water content is 5wt% in dry 4 hours in 140 ℃ baking oven, with this dried particle pulverize, sub-sieve, obtaining most of granularity is 32～100 order resins.
Get the resin 100g of above-mentioned granularity, water, propylene glycol, glycol ether mixed solution 5g mix above-mentioned particulate resin, react 30 minutes down at 190～210 ℃, obtain the super absorbent resin through surface-crosslinked processing, and its The performance test results sees Table 1.
Comparative example 2
Adopt the preparation technology identical with embodiment 1, the change monomer concentration is 40wt%, makes the super absorbent resin The performance test results and sees Table 1.
Comparative example 3
Adopt the preparation technology identical with embodiment 1, but do not adopt oxidation-reduction trigger system, initiator is the persulfate aqueous solution 10g of 0.3wt%.The performance test results sees Table 1.
Table 1
Embodiment 4-6
Adopt the preparation technology identical with embodiment 1, control the acid-base neutralisation temperature, make the polymerization initial reaction temperature be respectively 60,70 and 80 ℃, make the super absorbent resin under the different polymerization reaction times, their The performance test results sees Table 2.
Embodiment 7
Adopt the preparation technology identical, the linking agent in the monomer solution is changed into Viscoat 295 and N with embodiment 1, the composite cross-linking system of N-dimethyl bisacrylamide, the polymerization initial temperature is 80 ℃.Prepared super absorbent resin The performance test results sees Table 2.
Table 2
Claims (4)
1, a kind of fast preparation method of super absorbent resin, it is characterized in that with ice crystal type vinylformic acid be monomer, with mass concentration is that 32% aqueous solution ionic membrane caustic soda is a neutralizing agent, in an encloses container, carry out neutralization reaction, utilize acid-base neutralisation reaction heat that the Acrylic Acid Sodium Acrylate monomer solution is heated up, after temperature rises to the initial temperature of polyreaction, linking agent and oxidation-reduction initiator are added in the monomer solution, mix and inject the reaction tray of handling through insulation and carry out polyreaction, polyreaction was finished in 2～15 minutes;
The degree of neutralization of vinylformic acid and sodium hydroxide is 65～85%, and the mass concentration of monomer solution is 15-45%, in the neutralization reaction process, utilizes neutralization reaction heat directly to make monomer solution be raised to 50-80 ℃ of polymerization initial reaction temperature from room temperature;
When in monomer solution, adding oxidation-reduction initiator, be to add the oxidation initiator solution earlier, after mixing, add the reductive agent initiator solution again, mix with monomer solution in second at 5-20, implantation temperature is to carry out polyreaction in 60-90 ℃ the reaction tray.
2, method according to claim 1 is characterized in that the maximum temperature of polyreaction is no more than 110 ℃, and the temperature difference in the polymerization process between initial reaction temperature and the maximum temperature is no more than 40 ℃.
3, method according to claim 1 is characterized in that used linking agent is selected from N, N-dimethylene bisacrylamide, polyethyleneglycol diacrylate, Viscoat 295, at least a in the Phthalic acid, diallyl ester; Used oxidation-reduction initiator is selected from a kind of in ferrous of Potassium Persulphate/sodium bisulfite, ammonium persulphate/S-WAT, Sodium Persulfate/xitix, benzoyl peroxide/xitix or hydrogen peroxide/sulfuric acid.
4, method according to claim 1 is characterized in that used dosage of crosslinking agent is the 0.1-0.6% of monomer mass, and used oxidation-reduction initiator amount is the 0.1-0.6% of monomer mass.
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Families Citing this family (16)
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| CN101977940B (en) * | 2008-03-31 | 2013-03-13 | 株式会社日本触媒 | Method for producing particulate water absorbing agent containing water absorbent resin as main component |
| CN101434667B (en) * | 2008-12-15 | 2010-10-13 | 中国科学院长春应用化学研究所 | Method for preparing organic polymer absorbent material using post treatment |
| CN101475660B (en) * | 2009-01-12 | 2011-05-11 | 上海华谊丙烯酸有限公司 | Continuous preparation of high hydroscopicity resin polymerization monomer solution |
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| CN102516454A (en) * | 2011-11-30 | 2012-06-27 | 沈阳工业大学 | Synthesis method for super-absorbent resin containing sulfonic acid group |
| CN102936300A (en) * | 2012-10-29 | 2013-02-20 | 天津大学 | Quick and controllable method for preparing aquagel |
| CN103113508B (en) * | 2013-01-23 | 2015-05-20 | 江苏苏博特新材料股份有限公司 | Super absorbent resin with lower liquid absorbing rate, and preparation method and application thereof |
| CN103450387A (en) * | 2013-09-05 | 2013-12-18 | 鞍钢集团矿业公司 | Super water absorbent capable of using water treated by tourmaline as solvent, and preparation method of super water absorbent |
| CN104387514A (en) * | 2014-11-08 | 2015-03-04 | 邦丽达(福建)新材料股份有限公司 | Alkali-based preparation method of polyacrylic acid |
| CN104341545A (en) * | 2014-11-08 | 2015-02-11 | 邦丽达(福建)新材料股份有限公司 | Method for preparing cross-linked polyelectrolyte |
| KR101596622B1 (en) * | 2015-01-30 | 2016-02-22 | 에스케이이노베이션 주식회사 | Absorbent polymer and method of preparing the same |
| CN105884959A (en) * | 2016-05-10 | 2016-08-24 | 中山大学 | Preparation method of polyacrylic acid super absorbent resin through room-temperature solution polymerization |
| CN108276514B (en) * | 2018-01-03 | 2020-03-24 | 中国化学赛鼎宁波工程有限公司 | Preparation method of super absorbent resin |
| CN110041449B (en) * | 2019-04-24 | 2023-09-26 | 山东昊月新材料股份有限公司 | High-absorption resin continuous polymerization equipment and application method thereof |
| CN111393684A (en) * | 2020-04-21 | 2020-07-10 | 万华化学集团股份有限公司 | Super water-absorbing polymer and preparation method thereof |
| CN115536773B (en) * | 2022-11-01 | 2023-08-04 | 江苏派克斯特纤维素有限公司 | Production method of high-temperature-resistant sodium polyacrylate |
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Effective date of registration: 20170208 Address after: 201424 Fengxian District Cang Road, lane, Lane 357, room 100, room 295 Patentee after: Shanghai Hua Yi new material Co., Ltd Address before: 200137 Pudong North Road, Shanghai, No. 2031, No. Patentee before: Shanghai Huayi Acrylic Acid Co., Ltd. |