CN1539853A - Method for producing high absorptive resin - Google Patents
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- CN1539853A CN1539853A CNA2003101053879A CN200310105387A CN1539853A CN 1539853 A CN1539853 A CN 1539853A CN A2003101053879 A CNA2003101053879 A CN A2003101053879A CN 200310105387 A CN200310105387 A CN 200310105387A CN 1539853 A CN1539853 A CN 1539853A
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Abstract
A process for preparing high-hydroscopicitiy resin includes prepolymerization between monomers to be polymerized, trigger, system and cross-linking agent, and polymerizing to obtain gel-state solid product. Its advantages are high hydroscopicity (500-2000 g/g for deionized water), high water absorbing speed (less than 10 S) and high gel strength after the water is absorbed by it.
Description
Technical field
The present invention relates to the Polymer Synthesizing field, particularly relate to a kind of production technique of super absorbent resin, specifically, relate to the production method of monomeric homopolymer of a kind of cross-linking type water-soluble polymeric and/or multipolymer.
Background technology
Super absorbent resin is a kind of functional high molecule material that has wide range of applications, can absorb deadweight and arrive several thousand times of pure water for tens times, and under general pressure, can not dewater, has the water absorbent rate height, rate of water absorption is fast, good water-retaining property, even pressurized also is difficult for performances such as dehydration, thereby in agricultural, gardening, medicine, medical treatment, artificial organs, physiological hygiene, oil, chemical, building materials, environmental protection, food, the artificial intelligence material, sensitive material, biochemical technology, papermaking, weaving, the mine, daily necessities, aspects such as makeup have very widely to be used, the important effect of play more and more in national economy and people's life.Especially in China central and west regions, the weather arid is short of rain, and super absorbent resin has important promoter action and wide application prospect for making full use of limited water resources and desert transformation etc.
In recent years, along with the continuous expansion of super absorbent resin Application Areas and the raising of living standards of the people, people have proposed more and more higher requirement to its over-all properties, not only require water absorbent rate height, the good salt tolerance of product, and require that residual monomer content in the product is low, gel-strength is high, rate of water absorption is fast, these performances are even more important in industries such as physiology and medical and health, residual monomer in the super absorbent resin and solvend how much determining it to the health effects degree.Residual monomer is 170ppm among the Japanese kokai publication hei 4-255701, and solvend is 9%; The water-absorbing resin that Te Kaiping 4-175319 announces is 67g/g to the absorption multiplying power of the 0.9%NaCl aqueous solution; Polymerization conversion is 98.0-99.5% among U.S. Pat 4857610 and the US4893999, and residual monomer content is 0.5%-2%; Announced a kind of preparation method of water absurbing polymer among the Chinese patent CN85104864, the free monomer that reaction finishes in the polymer fluid is 4.26%, and water-soluble substance is 15-20%.The water-intake rate of water-absorbing resin after treatment is 500-1300g/g.The level of residual monomers of the water-absorbing resin of announcing in the above-mentioned document and solvend are than higher, and rate of water absorption is slower, and the gel-strength of rosin products is lower.
As everyone knows, cross linked polyacrylate (salt) type is as a principal item of super absorbent resin, the general explained hereafter such as water solution polymerization process, inverse suspension polymerization method and reversed emulsion polymerization that adopt with regard to aqueous solution polymerization technology, comprise continuous processing and batch technology again.The travelling belt production technique is a kind of important aqueous solution polymerization continuous production method, promptly carries out the technology of polyreaction on a ring-like travelling belt.Carrying out polyreaction on the plane belt of movement continuously is a kind of known technology, all disclose the technology that on the travelling belt of movement continuously polymerisation obtains polymkeric substance as U.S. Pat P 4138539, German patent DE-OS 3208369 and DE-OS 35 06534, polyreaction is by initiations such as redox initiation system, thermal decomposition initiating or uviolizings.In this technology, because travelling belt is plate shaped, and the viscosity of liquid reaction component is less, more liquid, therefore can only on travelling belt, form the skim reaction mass, reaction mass thickness has only 0.5-2cm, and the throughput of this sampling device just is restricted, and throughput, time one volume yield and economy are all lower.In order to reduce the flowability of liquid reactions material, improve its viscosity, U.S. Pat 4857610 adopts the method that adds thickening material in the liquid reactions material to improve viscosity, but the adding of thickening material has reduced the purity of product again.And, prior art is owing to adopt single initiator system in polyreaction, the polymerization reaction time that carries out on travelling belt is long, maximum temperature is higher, even reach more than 100 ℃, high temperature causes the serious volatilization of monomer mixed solution component, influenced operating environment, and polymerization conversion is not high, the residual monomer content in the product is still very high.
Summary of the invention
The production method of super absorbent resin provided by the present invention, polymerization process are steady relatively, and quality product improves.The present invention is the industrial production of serialization preferably also.
Below be respectively the description of the technical solution adopted in the present invention:
The production method of super absorbent resin, its major technique characteristics are that reaction raw materials such as polymerization single polymerization monomer, initiator system, linking agent obtain the viscous prepolymer that viscosity is 5mPa.S-20000mPa.S through prepolymerization earlier, and then further polymerization generates the gelatinous solid product, obtains the super absorbent resin product through aftertreatment.
Prepolymerization among the present invention reaction can be carried out in a batch mixing pre-polymerization reactor, and the batch mixing pre-polymerization reactor has and the polyreaction raw material mixed and carries out prepolymerized effect.The batch mixing pre-polymerization reactor can adopt a kind of horizontal cylindrical container, the stirring rake that can guarantee the material one-way movement is installed at the center, this stirring rake comprises multilayer propelling oar, multilayer turbine oar or has the screw shaped stirring rake of spirane structure, can guarantee unidirectional the travelling forward of reaction mass like this and air-teturning mixed phenomenon not occur, thus avoided the polyreaction material in the batch mixing pre-polymerization reactor overstand and further polymerization generate polymer gel.Also can adopt two batch mixing stills arranged side by side as the batch mixing pre-polymerization reactor, two stills hocket batch mixing, prepolymerization and to travelling belt discharge liquid prepolymer, use two stills just to eliminate single still shortcoming of the caused excessive polymerization generation gel of overstand of appearance easily, certainly, other can guarantee that the polyreaction material mixes and the equipment of one-way movement also can adopt.Chuck is equipped with in batch mixing pre-polymerization reactor outside, is used for feeding heat-eliminating medium (as water coolant) and guarantees that to remove reaction heat prepolymerization reacts basic constant temperature and steadily carry out, and nitrogen inlet is equipped with in inside, can blast the air in the nitrogen replacement material continuously.The temperature of prepolymerization reaction is generally 5 ℃-40 ℃, preferred 10 ℃-30 ℃.The residence time of polyreaction material in batch mixing prepolymerization reactor was generally 0.5 minute-15 minutes, and preferred 2 minutes-12 minutes, most preferably 3 minutes-9 minutes.Prepolymer is a thick liquid, and viscosity (employing rotary viscosity design determining) is 5mPa.S-20000mPa.S, preferred 100mPa.S-8000mPa.S, and 1000mPa.S-5000mPa.S most preferably, the solids weight content in the prepolymer is 10-80%, preferred 25-50%.
The present invention adopts the first prepolymerization reaction mode of further polyreaction again with whole polyreaction, the prepolymerization product obviously improves with respect to the viscosity of liquid reactions material, the mobile reduction, the serialization production of easier and following travelling belt is complementary, and make whole polyreaction steady relatively, exothermic phase is to disperseing, the highest polymerization temperature reduces, improve operating environment, bring out the best in each other more with the employing composite initiation system of the following stated of the present invention, improve the quality of products greatly, show rate of water absorption, water absorbent rate, gel-strength, the content of residual monomer and solvend, reaction times, aspects such as maximum temperature.
Polyreaction of the present invention can adopt single common initiator system, but the advantage of employing composite initiation system will be very obvious.The composite initiation system that adopts comprises low temperature initiator system and high temperature initiator system.The low temperature initiator system is meant that kick off temperature is lower than 40 ℃, preferred 30 ℃ initiator system, consumption is the 0.156-1.05% of total polymerization monomer weight, preferred 0.256-0.85%, can adopt redox initiation system, redox system comprises oxidant constituents and reductive agent component, and the former adopts organo-peroxides such as dicumyl peroxide, its consumption is generally the 0.15-0.75% of total polymerization monomer weight, preferred 0.25%-0.55%; The latter adopts reductive agents such as ferrous salt such as ferrous sulfate, and its consumption is generally the 2%-6% of oxygenant, is equivalent to the 0.006%-0.3% of total polymerization monomer weight.In order to guarantee the steady of polymerization process, generally in initiator system, add sodium ethylene diamine tetracetate (EDTA) complexing agent the ferrous ion complexing, form water soluble chelate compound, make it progressively to discharge, also add second-stage reduction agent sodium formaldehyde sulphoxylate simultaneously, can restore into ferrous ion to the ferric ion that oxidation of divalent iron ion generates, reduce coloured ferric ion concentration, this initiator system is minimum can be near 0 ℃ of initiated polymerization.Certainly, other low temperature initiator system also can adopt, comprise that redox systems such as Potassium Persulphate (ammonium)/sulfurous acid (hydrogen) sodium, Potassium Persulphate (ammonium)/ferrous sulfate, dibenzoyl peroxide/benzhydrylamine and low temperature azo-initiator are as 2,2 '-azo two (2-amidine propane) dihydrochlorides etc., these initiator systems can cause 10 ℃ of-30 ℃ of temperature ranges.The main effect of low temperature initiator system is to cause the prepolymerization reaction, and kick off temperature is generally 5 ℃-40 ℃, preferred 10-30 ℃.The high temperature initiator system that adopts is that kick off temperature is higher than 40 ℃, preferred 45 ℃ water soluble starter, comprise peralcohol class initiator and azo-initiator etc., the former is as Potassium Persulphate, ammonium persulphate, hydrogen peroxide, dibenzoyl peroxide, di-t-butyl peroxide, peroxidation trimethylacetic acid tertiary butyl ester etc., the latter such as Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile) etc., the kick off temperature of these initiators is generally more than 40 ℃, just cause at low temperature initiators and begin to cause after decomposition is finished substantially, effect be prevent when temperature of reaction is higher low temperature initiators concentration low excessively cause speed of reaction to reduce and reaction not exclusively, can improve speed of reaction and polymerization conversion.The consumption of high-temperature initiator is generally the 0.01-5.0% of total polymerization monomer weight, preferred 0.10-1.5%.
The operation that the present invention can intermittently change, the industrial production of serialization preferably, a kind of continuous production technology step is:
1, earlier various liquid reactions materials is blasted nitrogen replacement air wherein, add the batch mixing pre-polymerization reactor through the metering back then, reaction mass mixes in the batch mixing pre-polymerization reactor and carries out prepolymerization and react the liquid prepolymer that obtains having certain viscosity.
2, the heavy-gravity liquid prepolymer adds on the travelling belt of circular flow continuously, further aggregates into the gelatinous solid product.
3, the gelatinous solid product with carry out post-processing steps such as drying, pulverizing after travelling belt separates, obtain the super absorbent resin product.
Travelling belt of the present invention in certain operation area local be preferably formed as groove shape container with certain depth and in this zone beyond revert to flat structure, so just can obtain the polyreaction material coating with the suitable thickness of container depth, thereby can reach high conversion and high productive capacity simultaneously.Formation with groove shape container of certain depth, can be by the side board that in certain operation area of conveyer belt system, installs and fixes with certain altitude, the common groove shape container with certain depth of forming of the baffle plate of both sides and intermediary travelling belt abbreviates the Flapper type travelling belt as; Or other structure formation miscellaneous, all can as long as can reach this purpose.With regard to the Flapper type travelling belt, the adhesive that has owing to polymer gel has difficulties itself and baffle plate and separating of travelling belt surface, therefore general employing plastics film is as spacer medium, plastics film generally just covered the travelling belt surface before groove shape container forms, in general, should satisfy following relation: D 〉=d+2h between the width D of film and travelling belt width d and the height of baffle plate h, this has just prevented that liquid material from adhesion phenomenon occurring with direct contact of baffle surface.The length of side board (being the length of groove shape container) is generally 50cm-300cm, preferred 100-250cm.
The making material of travelling belt must have good tensile and snappiness, has good fatigue resistance under the repeated flex stress, has good deformation behavior and the corrosive of anti-reaction reagent performance under polymeric reaction condition.In general, single-material can't meet the demands, travelling belt will be made by multilayer material, for example metallic substance travelling belt, interpolation synthon or the Rubber Conveyor Belt Scrap of glass fibre and the mechanical property requirement that the steel core string rubber can satisfy travelling belt, coat plastics or Resins, epoxy such as layer of polyethylene, polypropylene, polyvinyl chloride, polystyrene, polyisobutene on its surface again, can satisfy the chemical resistance of travelling belt.
The width of travelling belt is generally 20cm-200cm, and the degree of depth of groove shape container is generally 7-30cm, and the material bed thickness of formation is preferably greater than 2cm at least greater than 1cm.The solution polymerization that carries out on travelling belt was generally finished at 5 minutes-60 minutes, preferred 10-30 minute, can reach very high time one volume yield like this.The polymer gel of production shifts from travelling belt with the semi-solid block continuously of a kind of softish, further processes then as dry and pulverizing or the like.
The reaction raw materials of the formed super absorbent resin of the present invention is identical with prior art, for the monomeric homopolymer of water-soluble polymeric or/and multipolymer.Mainly comprise water-soluble polymeric main monomer, comonomer, initiator system, alkaline neutraliser, linking agent etc.
The polymerization main monomer generally comprises vinylformic acid (salt) and acrylamide.The consumption of main monomer is generally 50%-100% (the total polymerization monomer weight of forming with main monomer and comonomer is a radix), preferred 75%-95%.
Comonomer comprises methacrylic acid (salt), Methacrylamide, vinyl cyanide, methacrylonitrile, vinyl pyridine, vinyl acetate, toxilic acid, fumaric acid, methylene-succinic acid, vinyl sulfonic acid, acrylamide propane sulfonic acid etc., also comprise the hydroxy ester compounds, particularly vinylformic acid of polymerizable acid and the hydroxy methacrylate and the hydroxy propyl ester of methacrylic acid.Can adopt wherein one or more as comonomer, the consumption of comonomer is generally 0-50% (is radix with the total polymerization monomer weight), preferred 5%-25%.
The mass concentration of total polymerization monomer in whole water solution system that main monomer and comonomer are formed is generally 10%-60%, preferred 25%-45%.
Alkaline neutraliser generally comprises sodium hydroxide, potassium hydroxide, sodium bicarbonate, yellow soda ash, saleratus, salt of wormwood, volatile salt, bicarbonate of ammonia and ammoniacal liquor etc.The consumption of alkaline neutraliser generally is to make acrylic acid degree of neutralization reach 5%-50%, preferred 15%-35%.Can not add alkaline neutraliser when adopting acrylamide as polymerization single polymerization monomer yet.
Linking agent is a kind of bifunctional or multi-functional comonomer of containing, generally comprise: Vinylstyrene, N, a N ' methylene-bis acrylic amine, glycol methacrylate, ethylene glycol diacrylate, contract glycol ether double methyl methacrylate, contract diethylene glycol acrylate, polyoxyethylene glycol double methyl methacrylate, polyoxyethylene glycol double methacrylate, pentaerythritol triacrylate, glycerol diacrylate and vinylformic acid allyl ester compounds.The consumption of linking agent is generally the 0-15% of total polymerization amount of monomer, preferred 0.02%-2.5%.
Also can add the gel-strength toughener in the reaction raw materials, the gel-strength toughener is an inorganic, metal oxide, as aluminum oxide (Al
2O
3), silicon oxide (SiO
2), zinc oxide (ZnO) and titanium oxide (TiO
2) etc., do not require white as fruit product, also can add kaolin, diatomite and wilkinite etc.One or more that can adopt above-claimed cpd (or mixture) are as the gel-strength toughener, and its consumption is the 1%-50% of total polymerization monomer weight, is preferably 2%-20%.
Advantage of the present invention:
1, adopts a kind of composite initiation system that all has high efficiency of initiation at low temperature and high temperature, the polyreaction that can guarantee the low temperature initiator system can cause (minimum can near 0 ℃) in lower temperature, thereby guarantee that the polymkeric substance that obtains has higher linear molecule amount (being noncrosslinking linear high molecular molecular weight), this is highly beneficial for the water absorbent rate, rate of water absorption and the gel-strength that improve product; The high temperature initiator system can so that polymerization reaction late stage can not decompose and cause rate of polymerization to reduce rapidly because of the major part of low temperature initiators, can keep higher rate of polymerization, thereby make whole polyreaction more steady, polymerisation conversion improves greatly, effectively reduces the residual monomer content of product.
2, before adding travelling belt, adopts the liquid reactions material prepolymerized method, the low temperature initiator system works in the prepolymerization reaction, the prepolymerization product obviously improves with respect to the viscosity of liquid reactions material, the mobile reduction, easier and operation travelling belt is complementary, and forms thicker material coating, and composite initiation system also makes whole polymerization process relative steady with prepolymerized acting in conjunction, exothermic phase is to dispersion, and the highest polymerization temperature obviously reduces, and has improved operating environment.
3, in the polyreaction material, add the gel-strength toughener, to improve the gel-strength after rosin products absorbs water.
4, can form serialization travelling belt production method than thick polymer material coating, high productive capacity and time-space yield.
5, Zhi Bei super absorbent resin product is white or flaxen powder or particle, and also further processing treatment obtains the product of needs.The water absorbent rate of resin (deionized water) 500～2000g/g inhales physiological saline (the 0.9%NaCl aqueous solution) 50～150g/g, and rate of water absorption was less than 10 seconds, and the hydrogel that resin suction back forms has higher gel-strength.The performance of described super absorbent resin is measured according to following side.
The mensuration of water absorbent rate and suction salt solution multiplying power: the super absorbent resin water absorbent rate is meant the weight of 1 gram deionized water that super absorbent resin absorbs among the present invention, inhales the weight that the physiological saline multiple generally is meant the 1 gram 0.9%NaCl aqueous solution that super absorbent resin absorbed.Measuring method adopts filtration method, at room temperature accurately weighing 0.100g super absorbent resin adds in the beaker, add weighing 500ml deionized water (perhaps 0.9%NaCl aqueous solution 30ml) then, stir with glass stick, placed 1 hour, slowly add in 100 purpose Φ, 150 * 150 round shape stainless (steel) wires then hydrogel, normal pressure filters out unabsorbed free water, left standstill after the filtration 5 minutes, weighing absorbs the quality of surplus water (physiological saline), calculates water absorbent rate (inhaling the physiological saline multiple).
Solubles content: take by weighing the there-necked flask that toner 0.500g places 1500-2000ml, add the deionized water of 1000ml, stir 12 hours after-filtration down, measure the solids component in the filtrate in 80-120rpm.Solubles content=(solid weight/weight resin in the filtrate) * 100%
Residual monomer content: take by weighing the there-necked flask that toner 0.500g places 1500-2000ml, add the deionized water of 1000ml, stir 12 hours after-filtration down in 80-120rpm, residual monomer content is measured with high performance liquid chromatography (HPLC) in the filtrate.Residual monomer content=(the residual monomer weight/weight resin in the filtrate) * 10
6Ppm.
Rate of water absorption: on the constant temperature magnetic stirrer, in the 100ml beaker, add iron core glass stirrer and the 50ml deionized water of a heavy 1.25g, homo(io)thermism is in 25 ℃.Start stirring, rotating speed 100 ± 20rpm can see the whirlpool in the deionized water, pours into＞80 purpose super absorbent resin 1.000g, picks up counting the time of record till stirrer can not rotate simultaneously.
Embodiment
Embodiment 1
In the container of crossing with nitrogen replacement, 100.0kg vinylformic acid is dissolved in the 150.0kg deionized water, add solution, 1.0kg 10%N that 13.9kgNaOH and 50.0kg deionized water are formed then, the N '-methylene-bisacrylamide aqueous solution fed nitrogen replacement air wherein about 30 minutes.Aforesaid liquid mixture, initiator system and 10.0kgSi0
2Fine powder (Φ≤100 μ m) mixes and the prepolymerization reaction with the continuous batch mixing pre-polymerization reactor that adds horizontal tubular of certain flow together, and the prepolymerization product further aggregates into gelatinous solid with the groove shape container of the flow adding Flapper type travelling belt formation of 2.0kg/min.Initiator system comprises low temperature initiated oxidation reduction system and the 0.15kg Diisopropyl azodicarboxylate high-temperature initiator that 0.4kg dicumyl peroxide, 0.017kg ferrous sulfate, 0.34kgEDTA and 0.102kg sodium formaldehyde sulphoxylate are formed.The prepolymerization temperature of reaction is 20 ℃, the prepolymerization reaction times is 5 minutes, and the travelling speed of prepolymerization product viscosity 3000mPa.S travelling belt is 10cm/min, and the polymerization reaction time on travelling belt is 20 minutes, 75 ℃ of maximum temperature, the polymer gel thickness of generation is 7cm.Gel-strength after the suction of super absorbent resin product is higher, and water absorbent rate 1500g/g inhales salt solution multiplying power 100g/g, rate of water absorption 6.5s, solubles content 2.7%, residual monomer content 46ppm.
Comparative Examples 1
Working method is with embodiment 1, difference is that reaction mass does not carry out the direct groove shape container that adds on the travelling belt of prepolymerization reaction, and liquid reactions material viscosity is 5mPa.S, and the polymerization time on travelling belt is 26 minutes, 92 ℃ of maximum temperature, the polymer gel thickness of generation is 7cm.Gel-strength after the suction of super absorbent resin product is higher, and water absorbent rate 1450g/g inhales salt solution multiplying power 96g/g, solubles content 3.1%, residual monomer content 59ppm.
Comparative Examples 2
Working method is with embodiment 1, and difference is that initiator system only adopts Diisopropyl azodicarboxylate, and consumption is 0.25kg.The liquid material viscosity of coming out from the batch mixing pre-polymerization reactor is 5mPa.S, and the polymerization time on travelling belt is 86 minutes, 102 ℃ of maximum temperature, and the polymer gel thickness of generation is 6cm.Gel-strength after the suction of super absorbent resin product is poorer slightly than embodiment 1, and water absorbent rate 1250g/g inhales salt solution multiplying power 88g/g, solubles content 7.1%, and residual monomer content is greater than 10000ppm.
Embodiment 2-6
Working method is with embodiment 1, and difference is to add comonomer acrylamide, vinylbenzene, vinyl cyanide, vinyl-acetic ester, Rocryl 410 respectively, and consumption is 10.0kg.
Embodiment 7-11
Working method is with embodiment 1, and difference is that the alkaline neutraliser that adds is respectively yellow soda ash, sodium bicarbonate, potassium hydroxide, salt of wormwood and bicarbonate of ammonia.
Embodiment 12-14
Working method is with embodiment 1, and difference is that the low temperature initiator system that adopts is respectively Potassium Persulphate/S-WAT (0.05kg/0.05kg), ammonium persulphate/sodium bisulfite (0.05kg/0.05kg) and VA-044 (0.05kg).
Embodiment 15-18
Working method is with embodiment 1, and difference is that the high temperature initiator system that adopts is respectively 2,2'-Azobis(2,4-dimethylvaleronitrile), dibenzoyl peroxide, peroxidation carbonic acid diisopropyl ester and Potassium Persulphate.
Embodiment 19-22
Working method is with embodiment 1, and difference is linking agent 10%N, and N '-methylene-bisacrylamide amount of aqueous solution used is respectively 0.3kg, 0.6kg, 3.0kg and 6.0kg.
Embodiment 23-29
Working method is with embodiment 1, and difference is that the linking agent that adds is respectively Vinylstyrene, ethylene glycol diacrylate, glycol methacrylate, contract diethylene glycol acrylate, polyoxyethylene glycol double methyl methacrylate, pentaerythritol triacrylate and vinylformic acid allyl ester.
Embodiment 30-33
Working method is with embodiment 1, and difference is SiO
2The consumption of powder is respectively 5kg, 15kg, 20kg and 35kg.
Embodiment 34-39
Working method is with embodiment 1, and difference is that the gel-strength toughener is respectively Al
2O
3Powder, ZnO powder, TiO
2Powder, kaolin, diatomite and wilkinite.
Embodiment 40-42
Working method is with embodiment 1, and difference is that the prepolymerization reaction times was respectively 2 minutes, 8 minutes and 13 minutes, and resulting prepolymerization product viscosity is respectively 1000mPa.S, 5000mPa.S and 8500mPa.S.
Embodiment 43-46
Working method is with embodiment 1, and difference is that the prepolymerization temperature of reaction is respectively 5 ℃, 15 ℃, 25 ℃ and 35 ℃, and resulting prepolymerization product viscosity is respectively 200,1350mPa.S, 5000mPa.S and 9000mPa.S.
Embodiment 47-49
Working method is with embodiment 1, and difference is that the travelling belt belt speed is respectively 6cm/min, 9cm/min and 15cm/min.
Embodiment 50-53
Working method is with embodiment 1, and difference is that prepolymerization product flow is respectively 1.0kg/min, 1.5kg/min, 2.5kg/min and 4kg/min.
Embodiment 54
Working method is with embodiment 1, and difference is to adopt crimping type travelling belt.
Embodiment 55
Working method is with embodiment 1, and difference is that the batch mixing pre-polymerization reactor is that two stills arranged side by side replace batch mixing.
The test-results of embodiment 2-29 sees Table one, and the test-results of embodiment 30-55 sees Table two.
Aforesaid method only provides as an example, and the present invention is not limited to these examples, and the present invention can also be used for the synthetic method or the equipment preparation of other similar or relevant polymkeric substance, but does not all exceed essence of the present invention and protection domain.
Table one
| The embodiment numbering | The highest polymerization temperature/℃ | Travelling belt polymerization time/min | Material thickness/cm | Water absorbent rate g/g | Inhale salt solution multiplying power g/g | Rate of water absorption/s | Residual monomer content/% | Solubles content/% |
| ??2 | ?76 | ?21 | ?7 | ?1400 | ?90 | ?6 | ?48 | ?2.8 |
| ??3 | ?77 | ?20 | ?6.5 | ?1550 | ?105 | ?6 | ?39 | ?2.7 |
| ??4 | ?74 | ?22 | ?7 | ?1600 | ?103 | ?7 | ?43 | ?2.6 |
| ??5 | ?72 | ?25 | ?7 | ?1650 | ?113 | ?7 | ?41 | ?2.7 |
| ??6 | ?76 | ?20 | ?6.5 | ?1700 | ?110 | ?6.5 | ?44 | ?2.8 |
| ??7 | ?75 | ?20 | ?7 | ?1500 | ?98 | ?6 | ?46 | ?2.8 |
| ??8 | ?75 | ?21 | ?7 | ?1450 | ?96 | ?6 | ?46 | ?2.7 |
| ??9 | ?74 | ?21 | ?7 | ?1430 | ?90 | ?7 | ?41 | ?2.6 |
| ??10 | ?72 | ?22 | ?7 | ?1500 | ?99 | ?7 | ?39 | ?2.7 |
| ??11 | ?76 | ?20 | ?7 | ?1560 | ?103 | ?7 | ?40 | ?2.8 |
| ??12 | ?79 | ?25 | ?6.5 | ?1500 | ?98 | ?7 | ?41 | ?2.7 |
| ??13 | ?78 | ?26 | ?6.5 | ?1500 | ?96 | ?6.5 | ?44 | ?2.8 |
| ??14 | ?79 | ?26 | ?7 | ?1450 | ?90 | ?6 | ?46 | ?2.8 |
| ??15 | ?80 | ?22 | ?7 | ?1430 | ?99 | ?6 | ?46 | ?2.7 |
| ??16 | ?76 | ?21 | ?7 | ?1500 | ?103 | ?7 | ?41 | ?2.6 |
| ??17 | ?77 | ?23 | ?6.5 | ?1560 | ?103 | ?7 | ?39 | ?2.7 |
| ??18 | ?76 | ?22 | ?6.5 | ?1500 | ?99 | ?7 | ?40 | ?2.8 |
| ??19 | ?76 | ?21 | ?7 | ?2000 | ?130 | ?7 | ?41 | ?3.4 |
| ??20 | ?77 | ?20 | ?6.5 | ?1850 | ?120 | ?6.5 | ?45 | ?3.2 |
| ??21 | ?74 | ?22 | ?7 | ?1000 | ?78 | ?6 | ?35 | ?2.3 |
| ??22 | ?72 | ?25 | ?7 | ?650 | ?67 | ?5.5 | ?32 | ?0.9 |
| ??23 | ?76 | ?21 | ?7 | ?1400 | ?90 | ?6.5 | ?47 | ?2.8 |
| ??24 | ?77 | ?20 | ?6.5 | ?1550 | ?105 | ?6 | ?39 | ?2.7 |
| ??25 | ?74 | ?22 | ?7 | ?1600 | ?102 | ?7 | ?44 | ?2.6 |
| ??26 | ?72 | ?25 | ?7 | ?1650 | ?114 | ?7 | ?42 | ?2.7 |
| ??27 | ?76 | ?20 | ?6.5 | ?1700 | ?110 | ?6.5 | ?43 | ?2.8 |
| ??28 | ?75 | ?20 | ?7 | ?1500 | ?97 | ?6 | ?45 | ?2.8 |
| ??29 | ?75 | ?21 | ?7 | ?1450 | ?95 | ?6.5 | ?46 | ?2.7 |
Table two
| The embodiment numbering | The highest polymerization temperature/℃ | Travelling belt polymerization time/min | Material thickness/cm | Water absorbent rate g/g | Inhale salt solution multiplying power g/g | Rate of water absorption/s | Residual monomer content/% | Solubles content/% |
| ??30 | ?76 | ?21 | ?7 | ?1650 | ?110 | ?6 | ?48 | ?2.8 |
| ??31 | ?77 | ?20 | ?6.5 | ?1350 | ?95 | ?7 | ?39 | ?2.3 |
| ??32 | ?74 | ?22 | ?7 | ?1150 | ?89 | ?8 | ?43 | ?2.1 |
| ??33 | ?72 | ?25 | ?7 | ?830 | ?79 | ?8 | ?41 | ?1.4 |
| ??34 | ?76 | ?20 | ?6.5 | ?1700 | ?110 | ?6.5 | ?44 | ?2.8 |
| ??35 | ?75 | ?20 | ?7 | ?1500 | ?98 | ?6 | ?46 | ?2.8 |
| ??36 | ?75 | ?21 | ?7 | ?1450 | ?96 | ?6 | ?46 | ?2.7 |
| ??37 | ?74 | ?21 | ?7 | ?1430 | ?90 | ?7 | ?41 | ?2.6 |
| ??38 | ?72 | ?22 | ?7 | ?1500 | ?99 | ?7 | ?39 | ?2.7 |
| ??39 | ?76 | ?20 | ?7 | ?1260 | ?88 | ?6 | ?40 | ?2.8 |
| ??40 | ?79 | ?26 | ?6.5 | ?1500 | ?98 | ?7 | ?41 | ?2.7 |
| ??41 | ?73 | ?19 | ?6.5 | ?1500 | ?96 | ?6.5 | ?44 | ?2.8 |
| ??42 | ?65 | ?16 | ?7 | ?1450 | ?90 | ?6 | ?46 | ?2.8 |
| ??43 | ?82 | ?28 | ?7 | ?1430 | ?99 | ?6 | ?46 | ?2.7 |
| ??44 | ?76 | ?24 | ?7 | ?1500 | ?103 | ?7 | ?41 | ?2.6 |
| ??45 | ?72 | ?18 | ?6.5 | ?1560 | ?103 | ?7 | ?39 | ?2.7 |
| ??46 | ?66 | ?15 | ?6.5 | ?1500 | ?99 | ?7 | ?40 | ?2.8 |
| ??47 | ?80 | ?25 | ?14 | ?1500 | ?100 | ?7 | ?41 | ?3.4 |
| ??48 | ?77 | ?22 | ?9 | ?1450 | ?97 | ?6.5 | ?45 | ?3.2 |
| ??49 | ?72 | ?19 | ?5 | ?1500 | ?98 | ?6 | ?46 | ?2.7 |
| ??50 | ?72 | ?20 | ?3.5 | ?1650 | ?107 | ?5.5 | ?32 | ?2.9 |
| ??51 | ?74 | ?21 | ?5 | ?1400 | ?90 | ?6.5 | ?47 | ?2.8 |
| ??52 | ?78 | ?23 | ?9 | ?1550 | ?105 | ?6 | ?39 | ?2.7 |
| ??53 | ?81 | ?26 | ?14 | ?1600 | ?102 | ?7 | ?44 | ?2.6 |
| ??54 | ?72 | ?25 | ?7 | ?1550 | ?110 | ?7 | ?42 | ?2.7 |
| ??55 | ?76 | ?20 | ?6.5 | ?1600 | ?106 | ?6.5 | ?43 | ?2.8 |
Claims (15)
1, the production method of super absorbent resin, it is characterized in that reaction raw materials such as polymerization single polymerization monomer, initiator system, linking agent obtain the viscous prepolymer that viscosity is 5mPa.S-20000mPa.S through prepolymerization earlier, and then further polymerization generates the gelatinous solid product, obtains the super absorbent resin product through aftertreatment.
2, production method according to claim 1, the viscosity that it is characterized in that described viscous prepolymer is 100mPa.S-8000mPa.S, preferred 1000mPa.S-5000mPa.S.
3, production method according to claim 1 is characterized in that the solids weight content in the prepolymer is 10-80%, preferred 25-50%.
4, production method according to claim 1 is characterized in that the temperature of prepolymerization reaction is 5 ℃-40 ℃, preferred 10 ℃-30 ℃.
5, production method according to claim 1 is characterized in that the prepolymerization reaction times is 0.5-15 minute.
6, production method according to claim 1 is characterized in that prepolymerization reaction employing kick off temperature is lower than 40 ℃ low temperature initiator system.
7, production method according to claim 1 is characterized in that prepolymer adds the enterprising one-step polymerization reaction of travelling belt of circular flow continuously.
8, production method according to claim 7, it is characterized in that in the operation area of travelling belt local form have the groove shape container of certain depth and in this zone beyond revert to flat structure.
9, production method according to claim 7 is characterized in that polyreaction on travelling belt generally at 5-60 minute, finishes in preferred 10-30 minute.
10, production method according to claim 1 is characterized in that described initiator system is a kind of composite initiation system, comprises that kick off temperature is lower than 40 ℃, and preferred 30 ℃ low temperature initiator system and kick off temperature are higher than 40 ℃ preferred 45 ℃ high temperature initiator system.
11, production method according to claim 10, it is characterized in that described low temperature initiator system is redox system or low temperature azo-initiator, consumption is the 0.156-1.05% of total polymerization monomer weight, preferred 0.256-0.85%, the high temperature initiator system is peralcohol class initiator or azo-initiator, consumption is the 0.01-5.0% of total polymerization monomer weight, preferred 0.10-1.5%.
12, production method according to claim 11, it is characterized in that the redox system in the described low temperature initiator system is selected from dicumyl peroxide/ferrous sulfate, Potassium Persulphate (ammonium)/sulfurous acid (hydrogen) sodium, Potassium Persulphate (ammonium)/ferrous sulfate, dibenzoyl peroxide/benzhydrylamine, wherein oxidation component is the 0.15-0.75% of total polymerization monomer weight, reduction components is the 0.006%-0.3% of total polymerization monomer weight, the low temperature azo-initiator can be 2,2 '-azo two (2-amidine propane) dihydrochloride, peralcohol class initiator in the high temperature initiator system is selected from Potassium Persulphate, ammonium persulphate, hydrogen peroxide, dibenzoyl peroxide, di-t-butyl peroxide, peroxidation trimethylacetic acid tertiary butyl ester, the high temperature azo-initiator is selected from Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile).
13, production method according to claim 1, it is characterized in that adding in the reaction raw materials inorganic, metal oxide gellike intensity reinforcing agent, its consumption is the 1%-50% of total polymerization monomer weight, and the gel-strength toughener can be one or more in aluminum oxide, silicon oxide, zinc oxide, titanium oxide, kaolin, diatomite, the wilkinite.
14, production method according to claim 1 is characterized in that described super absorbent resin is that the monomeric homopolymer of water-soluble polymeric is or/and multipolymer.
15, production method according to claim 14, it is characterized in that water-soluble monomer comprises the water-soluble polymeric main monomer or/and comonomer, the consumption of polymerization main monomer is 50%-100%, comonomer is the 0-50% of total polymerization monomer weight, the consumption of linking agent is the 0-15% of total polymerization amount of monomer, preferred 0.02%-2.5%.
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| CN101143912B (en) * | 2006-09-14 | 2010-09-29 | 台湾塑胶工业股份有限公司 | Method for producing high-performance high water absorption resin |
| CN101173016B (en) * | 2006-11-01 | 2011-02-02 | 台湾塑胶工业股份有限公司 | Method for producing high-performance high absorbent resin |
| CN101168580B (en) * | 2006-10-27 | 2012-09-26 | 台湾塑胶工业股份有限公司 | Method for producing high water absorption resin |
| CN106893030A (en) * | 2015-12-18 | 2017-06-27 | 中国石油化工股份有限公司 | A kind of compound salt tolerant water-absorbing resin and preparation method thereof |
| CN108084365A (en) * | 2018-01-03 | 2018-05-29 | 中国化学赛鼎宁波工程有限公司 | The preparation method and its preparation facilities of a kind of super absorbent resin |
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| CN112341565A (en) * | 2020-12-01 | 2021-02-09 | 四川省农业科学院生物技术核技术研究所 | Acrylic acid water-retaining layer of coated fertilizer and preparation method and device thereof |
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- 2003-11-01 CN CN 200310105387 patent/CN1208352C/en not_active Expired - Fee Related
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| CN101143912B (en) * | 2006-09-14 | 2010-09-29 | 台湾塑胶工业股份有限公司 | Method for producing high-performance high water absorption resin |
| CN101168580B (en) * | 2006-10-27 | 2012-09-26 | 台湾塑胶工业股份有限公司 | Method for producing high water absorption resin |
| CN101173016B (en) * | 2006-11-01 | 2011-02-02 | 台湾塑胶工业股份有限公司 | Method for producing high-performance high absorbent resin |
| CN106893030A (en) * | 2015-12-18 | 2017-06-27 | 中国石油化工股份有限公司 | A kind of compound salt tolerant water-absorbing resin and preparation method thereof |
| CN108084365B (en) * | 2018-01-03 | 2024-10-01 | 中国化学赛鼎宁波工程有限公司 | Preparation method and preparation device of super absorbent resin |
| CN108084365A (en) * | 2018-01-03 | 2018-05-29 | 中国化学赛鼎宁波工程有限公司 | The preparation method and its preparation facilities of a kind of super absorbent resin |
| CN110103557A (en) * | 2019-05-21 | 2019-08-09 | 远程电缆股份有限公司 | A kind of resistance seawater, acid-base solution, industrial wastewater and sanitary sewage cable are blocked water composite band material and preparation method thereof with fire resisting |
| CN111116817A (en) * | 2019-12-14 | 2020-05-08 | 浙江卫星新材料科技有限公司 | Preparation method of high-absorptivity resin with low residual monomer |
| CN111303354B (en) * | 2020-02-27 | 2023-05-26 | 河北工程大学 | Gradient initiation method for preparing composite super absorbent resin |
| CN111303354A (en) * | 2020-02-27 | 2020-06-19 | 河北工程大学 | Gradient initiation method for preparing composite super absorbent resin |
| CN112341565A (en) * | 2020-12-01 | 2021-02-09 | 四川省农业科学院生物技术核技术研究所 | Acrylic acid water-retaining layer of coated fertilizer and preparation method and device thereof |
| CN114380956A (en) * | 2022-01-19 | 2022-04-22 | 浙江三赢新材料有限公司 | Preparation method of asymmetric water-absorbent resin and liquid drop former used for preparation |
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