CN102311599B - Method for preparing super absorbent resin - Google Patents
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- CN102311599B CN102311599B CN201010222453.0A CN201010222453A CN102311599B CN 102311599 B CN102311599 B CN 102311599B CN 201010222453 A CN201010222453 A CN 201010222453A CN 102311599 B CN102311599 B CN 102311599B
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Abstract
The invention relates to a method for preparing a super absorbent resin with biodegradability and high water absorbability. In the method, peroxide is added in a process for producing the resin.
Description
Technical field
The present invention is about a kind of manufacture method to the good hydroscopic substance of the absorption aqueous solution, specifically, relates to a kind of manufacture method of super absorbent resin.
Background technology
The present invention is to absorbing the good hydroscopic substance of the aqueous solution about a kind of, be called super absorbent resin, this super absorbent resin has powerful moisture holding capacity, can absorb hundred times even thousand times to the water of weight own, after water suction, can maintain immobilising kenel by swelling tool, can seepage even if exert pressure also not, absorbed water can gently disengage in atmosphere.At present this super absorbent resin is applied to widely the anti-dewdrop condensing agent in water retention agent, the material of construction of agricultural or gardening aspect and is removed the material of moisture content in oil, or the waterproof outer coating in cable and sanitary product are as diaper, women sanitary articles, deserted wiping cloth etc.
Above-mentioned super absorbent resin, because meeting directly contacts with human body, so that the security of super absorbent resin becomes is very important.Generally speaking the physical properties that, super absorbent resin must possess comprises the gel force after absorbency under uptake rate, absorbing power, pressure, low monomer residue amount and absorption.Good super absorbent resin not only will meet above-mentioned physical properties, possesses good security, and the more important thing is must low pollution and province's energy.
Known super absorbent resin composition material has starch acrylonitrile (hydrolyzed starchacrylonitrile) graftomer (the Japanese Patent Publication communique clear 49 (1974)-43 of meeting water decomposition type at present, 395), Starch with Acrylic Acid graftomer (the Japanese Patent Publication communique clear 51 (1976)-125 of neutralization, 468), saponification ethene acetic acid-propylene multipolymer (Japanese Patent Publication communique clear 52 (1977)-14, 689), hydrolyzed acrylonitrile multipolymer or acrylamide copolymer (Japanese patent gazette clear 53 (1978)-15, 959), and part in and polyacrylic acid (Japanese Patent Publication announces clear 55 (1980)-84, 304) etc.The wherein raw material of starch acrylonitrile graftomer, easily cause decomposition because containing starch, so cannot preserve for a long time, moreover its manufacture method is very complicated again, so the preparation of super absorbent resin now accounts for maximum part mainly with using vinylformic acid or carrying out with acrylate the super absorbent resin that cross-linking polymerization makes, its main cause is that the raw material-vinylformic acid of acrylate multipolymer can be rapidly by industrial mass production, and the super absorbent resin making has very high water-retaining capacity, and there is cheap for manufacturing cost and tool economic benefit, more can not cause again the decomposition of putrescibility, therefore become the super absorbent resin generalizing most.
The problem that quasi-solution of the present invention is determined is, the above-mentioned super absorbent resin making with acrylate multipolymer still exists a serious problem, can long-term storage or use because of at present commercially available super absorbent resin, after use, be regarded as waste mainly with the mode processing such as burning or bury.If must, with the processing mode of additional heat energy, easily cause energy loss and waste in burning mode, with the mode such as bury process because of waste corruption consuming time permanent and institute palpus space is very huge, difficult execution; Taking environmental conservation into consideration and energy saving, can solve foregoing problems to develop the super absorbent resin that biology can decomposition type, and this problem also stimulates and cause exploration and the research that we can decomposition type super absorbent resin to exploitation manufacture.
Openly manufacture and have that biology can decompose or the easy super absorbent resin of self degraded through looking into current existing several sections of patent documentations, as the starch acrylonitrile of water decomposition type (hydrolyzedstarchacrylonitrile) graftomer (Japanese Patent Publication communique clear 49 (1974)-43, 395), Starch with Acrylic Acid graftomer (the Japanese Patent Publication communique clear 51 (1976)-125 of neutralization, 468), via poly-gamma-glutamic acid and polyepoxides, (Japanese Patent is opened flat 11-343339, Unexamined Patent 7-224163, Unexamined Patent 7-300563 etc.) reaction produce water-absorbent resin, or polysaccharide water gel (United States Patent (USP) 650716), use the crude substance linking agent such as Rhizoma amorphophalli powder (the open CN1410463A of China's Mainland patent), yacon (the open CN1846544A of China's Mainland patent).Though the above linking agent contributes to the cleaning of absorbent resin waste, but Polysaccharides compound treatment process complexity wherein, the super absorbent resin performance making is low, cannot reach sanitary product required function now, the super absorbent resin of manufacturing with poly-gamma-glutamic acid must use the refining essence nutrient solution via radioactive rays processing, also must remove in process of production thalline, not only increase production cost, technique is also very complicated.Therefore find the disclosed method of aforementioned patent publication all exist make super absorbent resin be difficult for preserving, lower to water receptivity, or weak etc. the shortcoming of intensity.These problems are all with to manufacture the raw material of super absorbent resin relevant, all can face the problems referred to above taking article such as starch, cereal, chitin, carbohydrates as raw material.
The super absorbent resin of industrial volume production is crosslinked and obtain mainly with vinylformic acid raw material now, resin entirety is high to the receptivity of the liquid such as water, urine, be easy to preserve and intensity good, be difficult for decomposing the problem of degenerating but remain.
Summary of the invention
The object of the present invention is to provide a kind of manufacture method of super absorbent resin, to overcome the defect existing in known technology.
For achieving the above object, the manufacture method of super absorbent resin provided by the invention, the method comprises:
(a) formed by the Raolical polymerizable of acidic group monomer solution, there is internal crosslinking structure and in the Super Absorbent Polymer Particles of surface-crosslinked processing;
(b) add again the superoxide that accounts for resin total amount 0.5～5% and carry out the manufacture method that surface treatment is feature.
The manufacture method of described super absorbent resin, wherein superoxide is to be selected from hydrogen peroxide, tert-butyl hydroperoxide, SPC-D, sodium perchlorate, sodium periodate, Sodium Persulfate, Potassium Persulphate, ammonium persulphate or Sodium peroxoborate.
The making method of described super absorbent resin system, the super absorbent resin of wherein making, the YI value of placing the xanthochromia test gained of a week under 50 degree Celsius and 60%RH is not less than 70.
The manufacture method of described super absorbent resin, the super absorbent resin of wherein making, the normal saline solution that adds L-AA makes its colloid intensity after swelling 3 hours be not more than 200g; After 24 hours lower than 50g.
According to the super absorbent resin of manufacture of the present invention and remain with superior absorption performance and the intensity with acrylic acid series super absorbent resin, also show good Biodegradable, be expected to promote the synthesis technique of super absorbent resin with this, and reduce the impact of super absorbent resin to environmental influence.
Embodiment
The present invention finds to carry out super absorbent resin after surface treatment while carrying out surface treatment with the aqueous solution that contains a superoxide again, can make one and have high strength, high absorbent capacity and be easy to the super absorbent resin that corruption is decomposed, its corruption degree of decomposition also can be verified assessment fast via science mode.
The hydrophilic resin that contains that represents acrylate copolymer, on its resinous polymer chain, having wetting ability official can roll into a ball as acidic group, amide group, amino and sulfonic group etc. by machine more.Hydrophilic resin of the present invention is to comprise: polyacrylic acid or the vinylformic acid salt after neutralization, this salt includes the salt of the alkali metal cations such as lithium, sodium, potassium or ammonium salt and aforementioned both polymkeric substance, and the vinylformic acid degree of neutralization after its neutralization is 30～70mol%.In addition also can be formed by aforementioned both and water-soluble or water-insoluble monomer copolymerization containing hydrophilic resin, described monomer can be methacrylic acid, toxilic acid, fumaric acid, β-crotonic acid, methylene-succinic acid, vinyl sulfonic acid, 2-(first) acrylamide amino-2-methyl propane sulfonic acid, (methyl) acryloxy paraffinic hydrocarbons sulfonic acid and alkali metal cation salt or ammonium salt etc. that they are all, in addition still there are the monomers such as N-vinyl acetamide, (methyl) acrylamide, N,N-DMAA.
In the time that the present invention uses the monomer beyond aforementioned vinylformic acid, its consumption can be all acrylic acid 50% or less amount, and preferably usage quantity is below 30%, and best usage quantity is to be no more than 10% of Acrylic Acid Monomer.This improves absorbent resin monomer, one or both that are mainly vinylformic acid or its esters form, but consideration based in function and physical properties, its acrylic acid neutralization can before polymerization or after polymerization be, neutralization ratio is preferably 50～95mol%, and optimum range is between 60～80mol%; The salt that forms Acrylates, this salt can be an alkali metal salt or amine salt etc., is preferably wherein lithium or sodium salt.
Prepare absorbent resin, convention is all carrying out before Raolical polymerizable before, first add Raolical polymerizable linking agent in unreacted monomer solution, this Raolical polymerizable linking agent is to be selected from the compound with two or more unsaturated double-bonds, as: N, N '-bis-(2-propenyl) amine, N, N '-methyne bisacrylamide, N, the two Methacrylamides of N '-methyne, vinylformic acid propylene, glycol diacrylate, polyethyleneglycol diacrylate, ethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, glycerol tri-acrylate, glycerine trimethacrylate, triacrylate or the trimethacrylate of glycerine additional ring oxidative ethane, triacrylate or the trimethacrylate of trihydroxymethyl propane additional ring oxidative ethane, trihydroxymethyl propane trimethacrylate, trihydroxymethyl propane triacrylate, N, N, N-tri-(2-propenyl) amine, ethylene glycol diacrylate, three vinylformic acid polyoxyethylene glycerides, three vinylformic acid diethyl polyoxyethylene glycerides, two propylene triethyleneglycol ester etc., also optional use has the compound of two or more epoxy group(ing), as sorbyl alcohol polyglycidyl ether, polyglycerol polyglycidyl ether, ethylene glycol diglycidylether, Diethylene Glycol diglycidylether, polyethyleneglycol diglycidylether, two glycerol polyglycidyl ethers etc.After carrying out free radical reaction, just can make super absorbent resin there is suitable degree of crosslinking, and make super absorbent resin colloid have suitable processibility.
Above-mentioned Raolical polymerizable linking agent can be used alone or two or more mixing is used, suitable additive amount is (taking the total solid of reactant as benchmark) between weight percent 0.001wt% to 5wt%, and more suitable consumption is weight percentage between 0.01wt% to 3wt%.Additive capacity below weight percent 0.001wt% after polymerization hydrated body too soft and have the unfavorable mechanical workout of stickiness, additive capacity is too low in the above water-absorbent of weight percent 5wt%, reduces the performance of super absorbent resin.
Polyreaction is to produce free radical by the decomposition of Raolical polymerizable initial (or initiation) agent to start.Free radical starting agent can be selected thermolysis type initiator, applicable thermolysis type initiator has superoxide, as: hydrogen peroxide, two-tributyl superoxide, peroxidation acid amides or persulphate (ammonium salt, an alkali metal salt) etc., and two (N, N-bis-stretches methyl NSC 18620) dihydrochlorides of azo-compound (2-amidine propane) dihydrochloride, 2.2 '-azo-groups as two in: 2.2 '-azo-group; Also can use reductive agent to become oxidation-reduction type initiator, as: acid accumulator sulfite, thiosulphate, xitix or ferrous salt; Or oxidation-reduction type initiator and thermolysis type initiator are merged to use.
First react and produce free radical with oxidation-reduction type initiator, when its radical transfer is the carrying out of initiated polymerization to monomer, while carrying out due to polyreaction, can discharge a large amount of heats elevates the temperature, when temperature arrives the decomposition temperature of thermolysis type initiator, can cause again the decomposition of second segment thermolysis type initiator, and whole polyreaction is more attained in completely.The suitable consumption of general Raolical polymerizable initiator be weight percentage for 0.001wt% to 10wt% (taking in and acrylate weight as benchmark), more suitable consumption is between 0.1wt% to 5wt%, when operating weight per-cent 0.001wt% is following, react too slow unfavorable economic benefit, when operating weight per-cent 10wt% is above, react that too fast response heat is wayward.
Above-mentioned polyreaction can be in conventional batch reaction vessel, or reacts on conveyer belt type reactor.The super absorbent resin of reaction gained, first utilizes pulverizer to be cut into volume 10mm
3below little gelinite, then screen.The gelinite diameter of the fixing particle diameter of screening is advisable below with 2.00mm, with better between 0.05mm to 1.50mm, gelinite below particle diameter 0.05mm is dried, pulverization process, easily improve and produce finished product fine powder amount, gelinite more than particle diameter 2.00mm, easily, because thermal conduction effect is not good, cause the remaining monomer of finished product higher, the shortcoming that physical property is performed poor.The particle size dispersion of acrylate gelinite is more concentrated, not only can make the physical property performance of gelinite after oven dry reach optimum regime, and more be conducive to control time and the temperature of drying.Therefore particle diameter is greater than 2.00mm and is less than that gelinite below 0.05mm is sent reactor back to again, pulverizer is regenerated.
Bake out temperature is dried and is advisable with 100 DEG C to 180 DEG C Celsius, if bake out temperature is lower than below 100 DEG C, drying time is not had economic benefit too for a long time: bake out temperature is higher than more than 180 DEG C, to make linking agent carry out ahead of time crosslinking reaction, make follow-up drying process, cannot effectively remove remaining monomer because degree of crosslinking is too high, reach the effect that reduces remaining monomer.
Super absorbent resin is a kind of hydrophilic polymer that is not dissolved in water, resin inside has inhomogeneity bridging structure, generally for improve quality as: improve uptake rate, improve colloid intensity, improve anti-caking effect or hydraulic permeability etc., all can remake on the surface of this resin further bridge formation processing.This surface-crosslinked processing utilizes has and can apply with the multiple functional radical linking agent of acid-base reaction, existing many patent publications before the present invention, as: disperse super absorbent resin and linking agent in organic solvent, to carry out surface-crosslinked processing (Japanese Patent JP-A-56-131608, JP-A-57-44627, JP-A-58-42602, JP-A58-117222), use inorganic powder directly linking agent and cross-linking agent solution to be sneaked into super absorbent resin processing (Japanese Patent JP-A60-163956, JP-A-60-255814), add after linking agent with vapour cure (Japanese Patent JP-A-1-113406), with an organic solvent, water and polyvalent alcohol carry out surface treatment (Japanese Patent JP-A-1-292004, No. 6346569, United States Patent (USP)) use organic solution, water, ether (ether) compound (Japanese Patent JP-A-2-153903) though etc. disclosed surface treatment method can improve uptake rate and improve water absorbent rate under pressure, but will cause the confining force too much adverse consequences that declines, reduce the performance of practical application.
According to the present invention, in the time of surface treatment, can react the linking agent using for polyvalent alcohol is as glycerol, ethylene glycol, Diethylene Glycol, triethylene glycol, polyoxyethylene glycol, propylene glycol, Isosorbide-5-Nitrae butyleneglycol, three shin ylmethyl propane, sorbyl alcohol etc. simultaneously; Maybe can use polyamine as quadrol, two quadrols, Triethylene Diamine, polyethyene diamine; Maybe can use the compound with two or more epoxy group(ing) as sorbyl alcohol polyglycidyl ether, polyglycerol polyglycidyl ether, ethylene glycol diglycidylether, Diethylene Glycol diglycidylether, polyethyleneglycol diglycidylether, two glycerol polyglycidyl ethers etc.; Also can use alkylene carbonate as ethylene carbonate, 4-methyl isophthalic acid, 3-dioxolane-2-ketone, 4,5-dimethyl-1,3-dioxolane-2-ketone, 4,4-dimethyl-1,3-dioxolane-2-ketone, 4-ethyl-1,3-dioxolane-2-ketone, 1,3-dioxane-2-ketone, 4,6-dimethyl-1,3-dioxane-2-ketone or 1,3-Dioxepane-2-ketone etc.
The usage of above-mentioned linking agent can be used alone or two or more mixing is used.Suitable additives amount is (taking the total solid of reactant as benchmark) between weight percent 0.001wt% to 10wt%, more suitable consumption is between 0.005wt% to 5wt%, linking agent additive capacity cannot show effect below weight percent 0.001wt% time, in the time that weight percent 10wt% is above, water-absorbent is too low, reduces resin property.
After super absorbent resin carries out surface crosslinking agent coating processing, heat-treat with the temperature in 90 DEG C to 230 DEG C temperature ranges again, make surface crosslinking agent can evenly and fast carry out crosslinking reaction, also make internal crosslinking agent carry out crosslinking reaction and reach the desired result of invention simultaneously.
Thermal treatment temp is below 90 DEG C, and cross-linking reaction time is not had economic benefit too for a long time, the easy deteriorated quality that affects of the more than 230 DEG C resin of thermal treatment temp.For wish obtains good surface treatment effect, the present invention can do heat treated temperature adjustment according to need, and thermal treatment temp height heat treatment time is short; The low heat treatment time of thermal treatment temp is long, therefore its heat treatment time was advisable with 30 minutes to 150 minutes.Being applicable to thermal treatment unit of the present invention comprises: tunnel like mixing drier, rotary drum dryer, desk-top moisture eliminator, fluidized bed dryer, pneumatic dryer and infrared dryer etc.
According to the present invention, it is the super absorbent resin made from known different method for makings later carrying out surface-crosslinked processing, carry out surface treatment with an aqueous solution that contains superoxide again, can obtain having the super absorbent resin of Biodegradable and good absorption performance, described in this, superoxide can be hydrogen peroxide, tert-butyl hydroperoxide, SPC-D, sodium perchlorate, sodium periodate, Sodium Persulfate, Potassium Persulphate, ammonium persulphate, Sodium peroxoborate etc., be the 0.05wt%～10wt% of resin total amount and these peroxide aqueous solutions make an addition to the amount of super absorbent resin, optimum addition is 0.5～5wt%, if being less than 0.05wt%, addition is not easy to cause xanthochromia and the decomposition of super absorbent resin, and addition while being greater than 5wt% because of the enough initiation reactions of its amount of peroxides, therefore being greater than this addition easily causes the wasting of resources and is not inconsistent economic benefit.Addition manner is that water-soluble superoxide direct sprinkling is made an addition to super absorbent resin, super absorbent resin after interpolation can be assessed by the method for the assessment super absorbent resin xanthochromia degree described in Chinese patent CN 1137159C the speed of its xanthochromia, super absorbent resin is placed in to 50 DEG C, in the climatic chamber of 60%RH, simulation super absorbent resin is in discarded environment of burying process, placing the xanthochromia of observing super absorbent resin for 2 weeks produces and starts the degraded process of addling and assess xanthochromia speed and whether palliating degradation degree has Biodegradable, and palliating degradation degree can be put respectively 3 hours/24 hours after super absorbent resin slowly being added 0.9wt% physiological saline and L-AA stir, carry out again the strength test of water-absorbing resin colloid.The assessment mode that Japanese Patent JP-A05-247221, JP-A-07-059813, JP-A-08-337726 etc. chat is assessed.
For showing water absorbent rate under the pressure of super absorbent resin of the present invention, the present invention utilizes pressurized to absorb heavy (pressure load: 20g/cm
2and 49g/cm
2) mode measures, pressurized absorbed dose is to measure according to the method described in the 7th page, European patent 0339461A specification sheets; The super absorbent resin of initial weight is placed in the right cylinder of sieve shading portion, in addition 20g/cm of powder
2and 49g/cm
2pressure, then this right cylinder is placed on absorptivity demand tstr, allow this super absorbent resin absorb 0.9% sodium chloride aqueous solution one hour, then will survey the weight of water suction weight institute value divided by super absorbent resin, obtain pressurized and absorb tuple value.
Confining force of the present invention is to utilize tea bag test method determination, and with five measurements, removes after maximum and Schwellenwert, averages; The super absorbent resin of 0.2g is contained in tea bag, and is soaked in 0.9% the NaCl aqueous solution 20 minutes, the tea bag after then this being soaked is placed in whizzer centrifugal (diameter 23cm, rotating speed 1400rpm) weighing after three minutes.The numerical value of gained first deducts the not blank group tea bag heavy (with same steps operation) of filling super absorbent resin and heavily obtains confining force numerical value divided by polymkeric substance again.
The method of assessment super absorbent resin yellowing is to chat mutually roughly the same with Chinese patent CN 1137159C, its colourity detecting instrument is SZ-∑ 80COLORMEASURING SYSTEM (Nippon Denshoku Kogyo Co., Ltd), controlled thermohygrostat is that glad thousand auspicious companies manufacture, model is AJH-80, but test conditions is under 50 DEG C and 60%RH Celsius, to place after one week, to analyze its colourity again and change.
Colloid strength detection of the present invention, 1.000 ± 0.001g super absorbent resin slowly to be added to the beaker that fills 30ml 0.9% physiological saline and 0.005wt%L-xitix according to described methods such as Japanese Patent JP-A05-247221, be placed on electromagnetic mixer and stir 1 minute, leave standstill after 3 hours/24 hours, beaker is placed on STEVENS colloid intensity determinator platform again, makes its centre just to suspention column jecket.Digit on STEVENS colloid intensity determinator panel makes zero, and the speed of fall of setting suspention column jecket is 1.0mm/sec, falls distance for 25mm mensuration.
Describe the present invention in detail with reference example and preferred embodiment below; But the interest field of the present patent application is not limited by these embodiment.
Reference example
1) in 100c.c Conical flask, add the water of 30g vinylformic acid (production of wooden land AE factory of Tai Su company) and 32.4g; In 100c.c Conical flask, take in addition 48% aqueous sodium hydroxide solution 24.3g, lower aqueous sodium hydroxide solution is slowly added in acrylic acid aqueous solution and neutralized in ice-cold; Now obtaining monomer solution concentration is 42wt%, and the molar percentage that the neutralization of vinylformic acid part is sodium acrylate is 70mol%.
2) add again the glycerol polyoxyethylene glycol triglycidyl ether (n=7) of 0.046g in the acrylic acid solution of acrylate moiety neutralization, and holding temperature is in 20 DEG C of left and right.
3) add 0.016g L-AA, two (2-amidine propane) dihydrochlorides of 2.2-azo-group of 0.2g Sodium Persulfate and 0.2g are with initial action.
4) after reaction, utilize cut pulverizer to be cut into the gelinite below 2mm diameter this high hydroscopicity resin hydrogel body.
5) be dried 2 hours with 130 DEG C of temperature; Utilize the fixing particle diameter of screen cloth screening 0.1mm～0.85mm, obtain powdery super absorbent resin.
6) weigh the obtained super absorbent resin 10g in step 1～5, add ethylene carbonate/water=1/1 (weight ratio) solution 0.4g, carry out solid-liquid mixing with mixing machine, then with 215 DEG C of temperature heat treated 30 minutes.
7), after cooling, obtain confining force 32.0g/g and 20g/cm
2water absorbent rate 30.5g/g under pressure, 49g/cm
2the super absorbent resin of water absorbent rate 22.9g/g (a) under pressure.
8) assess yellowing and the colloid intensity of super absorbent resin (a), its result is as shown in table 1.
Embodiment mono-
Weigh the super absorbent resin (a) that accounts for 100 % by weight reference examples, add account for 5 % by weight containing 10% aqueous hydrogen peroxide solution, after mixing super absorbent resin (b), record its confining force and be 32.1g/g and at 20g/cm
2water absorbent rate under pressure is 30.2g/g, 49g/cm
2water absorbent rate under pressure is 22.8g/g, then assesses yellowing and the colloid intensity of super absorbent resin, and its result is as shown in table 1.
Embodiment bis-
Weigh the super absorbent resin (a) that accounts for 100 % by weight reference examples, add account for 16.67 % by weight containing 30% aqueous hydrogen peroxide solution, after mixing super absorbent resin (c), record its confining force and be 32.0g/g and at 20g/cm
2water absorbent rate under pressure is 30.3g/g, 49g/cm
2water absorbent rate under pressure is 22.6g/g, then assesses yellowing and the colloid intensity of super absorbent resin, and its result is as shown in table 1.
Embodiment tri-
Weigh the super absorbent resin (a) that accounts for 100 % by weight reference examples, add account for 5 % by weight containing the 10% Sodium peroxoborate aqueous solution, after mixing super absorbent resin (d), record its confining force and be 32.2g/g and at 20g/cm
2water absorbent rate under pressure is 30.1g/g, 49g/cm
2water absorbent rate under pressure is 22.5g/g, then assesses yellowing and the colloid intensity of super absorbent resin, and its result is as shown in table 1.
Embodiment tetra-
Weigh the super absorbent resin (a) that accounts for 100 % by weight reference examples, add account for 12.5 weight fraction containing 40% the Sodium peroxoborate aqueous solution, after mixing super absorbent resin (e), record its confining force and be 32.3g/g and at 20g/cm
2water absorbent rate under pressure is 30.4g/g, 49g/cm
2water absorbent rate under pressure is 22.8g/g, then assesses yellowing and the colloid intensity of super absorbent resin, and its result is as shown in table 1.
Comparative example one
With JIS standard sieve, the super absorbent resin of embodiment bis-(c) is carried out to classification, be the super absorbent resin (f) of particle diameter 850-600um by Resin sieving selection, then assess super absorbent resin and (record confining force and be 31.8g/g and at 20g/cm
2water absorbent rate 32.3g/g under pressure, 49g/cm
2water absorbent rate under pressure is 25.5g/g) yellowing and colloid intensity, its result is as shown in table 1.
Comparative example two
With JIS standard sieve, the super absorbent resin of embodiment mono-(c) being carried out to classification, is the super absorbent resin (g) of particle diameter 300-150um by Resin sieving selection, records its confining force and be 32.2g/g and at 20g/cm
2water absorbent rate under pressure is 28.3g/g, 49g/cm
2water absorbent rate under pressure is 20.5g/g, then assesses yellowing and the colloid intensity of super absorbent resin, and its result is as shown in table 1.
Comparative example three
Weigh the super absorbent resin (a) of 100 % by weight, add 5 % by weight containing 10% 2,2 '-azo two [2-(N-phenyl amidino groups) propane] aqueous solution, after mixing super absorbent resin (h), record its confining force and be 32.1g/g and at 20g/cm
2water absorbent rate under pressure is 30.2g/g, 49g/cm
2water absorbent rate under pressure is 22.7g/g, then assesses yellowing and the colloid intensity of super absorbent resin, and its result is as shown in table 1.
Comparative example four
According to the manufacturing process in the open CN1410463A example three of Chinese patent, 4.5 parts of Rhizoma amorphophalli powders are incorporated in to 100 parts of water at 40 DEG C after gelatinization (solid content 4.5%), add taking the vinylformic acid (neutralization ratio is as 85mol%) of sodium hydroxide neutralization, Rhizoma amorphophalli powder and vinylformic acid mass ratio are 1: 50.Add again ammonium persulfate initiator, the 0.7Wt% linking agent N of vinylformic acid 0.8Wt%, N '-methylene-bisacrylamide, initiation grafting copolymerization at 60 DEG C of temperature after nitrogen gas stirring deoxygenation, and follow reaction solution to spray and enter in temperature as the helix tube type turbulent flow reactor of 90 DEG C taking nitrogen and carry out graft copolymerization 240 seconds, so send into drum-type film forming moisture eliminator with spiral squeezing and be dried 2 minutes with 150 DEG C of temperature, be crushed into after 120 object particles, assess super absorbent resin yellowing and colloid intensity, its result is as shown in table 1 again.
Can find with manufacture method of the present invention via the result of table 1, can make a super absorbent resin with good absorption performance and Biodegradable, although the mechanism of its tool Biodegradable is not bright, comply with the mode of production of the present invention and remain with superior absorption performance and the intensity with acrylic acid series super absorbent resin, also show good Biodegradable, believe the synthesis technique that is expected to promote super absorbent resin with this, and reduce the impact of super absorbent resin to environmental influence.
Table 1.
Claims (4)
1. a manufacture method for super absorbent resin, the method comprises:
(a) formed by the Raolical polymerizable of acidic group monomer solution, there is internal crosslinking structure and in the Super Absorbent Polymer Particles of surface-crosslinked processing;
(b) after Super Absorbent Polymer Particles manufacture, add again the superoxide that accounts for resin total amount 0.5～5% and carry out the manufacture method that surface treatment is feature.
2. the manufacture method of super absorbent resin according to claim 1, wherein, superoxide is to be selected from hydrogen peroxide, tert-butyl hydroperoxide, SPC-D, sodium perchlorate, sodium periodate, Sodium Persulfate, Potassium Persulphate, ammonium persulphate or Sodium peroxoborate.
3. the making method of super absorbent resin system according to claim 1, wherein, the super absorbent resin of making, the YI value of placing the xanthochromia test gained of a week under 50 degree Celsius and 60%RH is not less than 70.
4. the manufacture method of super absorbent resin according to claim 1, wherein, the super absorbent resin of making, the normal saline solution that adds L-AA makes its colloid intensity after swelling 3 hours be not more than 200g; After 24 hours lower than 50g.
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