CN101225132A - Method for preparing inverse suspension polymerization polymethacrylic acid moisture-absorption resin - Google Patents
Method for preparing inverse suspension polymerization polymethacrylic acid moisture-absorption resin Download PDFInfo
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Abstract
The invention discloses an inverse suspension polymerization preparation method for polymethacrylic acid highly absorbent resin, which belongs to the hygroscopic material field; the preparation method is characterized of using cyclohexane as solvent, using methacrylic acid as monomer, using potassium persulfate as initiator, using N, N'- methylene diacrylamide as cross-bonding agent, using octadecanol phosphatide as dispersing agent, and using ethylhydroxyethylcellulose as thickening agent. The polymethacrylic acid highly absorbent resin is prepared by the inverse suspension polymerization method, with a moisture absorption rate greater than or equal to 7g/g.min, under the conditions of air temperature being at 30 DEG C and relative humidity at 90%.
Description
Technical field
The invention belongs to the hygroscopic material field, be specifically related to the preparation method of inverse suspension polymerization polymethacrylic acid moisture-absorption resin.
Background technology
The high-hygroscopicity polymkeric substance has starch system, cellulose system and system of synthetic resin three major types by the raw material sources branch.Wherein synthetic resin is a kind of functional high molecule material that contains the strongly hydrophilic group and have certain degree of crosslinking, its water absorbing properties and hygroscopic property are all relatively good, develop (Zou Xinxi at home and abroad rapidly, super strength water absorbent, Beijing, Chemical Industry Press, 1991), particularly the U.S. and Japan are with fastest developing speed, have had many oleic series products to realize suitability for industrialized production.
The inverse suspension polymerization method is one of main method of producing synthetic resin high-hydroscopicity and high-hygroscopicity resin.Inverse suspension polymerization technology is to be dispersed particle with the water, and oil phase is a dispersion medium, makes the suspension of water-in-oil-type, adopt the method for water soluble starter initiated polymerization, its aftertreatment technology is easy, easily forms powdery or granular disintegration, is subject to people's attention day by day.
In using high suction of inverse suspension polymerization method production or high moisture-absorption resin process, if polymer fluid dispersion system instability will obtain gelatinous thick product.Simultaneously, also there is phenomenon such as sudden and violent poly-, the sticking wall of gel that reacts.Therefore, in the inverse suspension polymerization process, must add suitable dispersion agent and thickening material, to avoid the generation of the problems referred to above." the inverse suspension polymerization legal system is got the sodium polyacrylate super absorbent resin " [Luo Xiaofeng, Li Jingui, He Peixin, applied chemistry, 1993,10 (5): 34]; " polyacrylate High hydrophilous resin synthesising process research progress " [Gu Jintao, Peng Xianhu, Chinese tackiness agent, 2000,10 (2): 45]; " inverse suspension method prepares the salt tolerant High hydrophilous resin " [Chen Riqing etc., chemistry of forest product and industry, 2,006 26 (1): 28]; " inverse suspension polymerization synthesizing super absorbent resin " [Zhang Weidang, Taiyuan City college of education journal, 2,006 5 (2): 107]; " research of inverse suspension method synthesizing high-hydroscopicity resin " [Guo Jianwei etc., fine chemistry industry, 2,001 18 (6): 43]; Chinese patent CN1834122A.Reported the inverse suspension polymerization method of polyacrylic acid superabsorbent in the above-mentioned document, yet there are no bibliographical information and adopt the inverse suspension polymerization legal system to be equipped with polymethyl acrylic acid.
Summary of the invention
The preparation method's of inverse suspension polymerization polymethacrylic acid moisture-absorption resin provided by the invention condition and step are as follows:
The solvent that uses is hexanaphthene; Methacrylic acid is a monomer, and consumption is the 35-40% of weight of solvent, and with the aqueous sodium hydroxide solution neutralization of mass concentration 30%, degree of neutralization is 60-70%; Potassium Persulphate is an initiator, and consumption is 0.3～0.5% of a monomer weight; N, N '-methylene-bisacrylamide are linking agent, and consumption is 0.05～0.1% of a monomer weight; Octadecanol phosphoric ester is a dispersion agent, and consumption is 1～5% of a monomer weight; Type 3U is a thickening material, and consumption is 1～3% of a monomer weight;
The concrete operations step: 1) cyclohexane solvent and the dispersion agent of adding proportional quantity in three mouthfuls of containers, stir under the room temperature, make the dispersion agent dissolving; 2) under-3 ℃～10 ℃ refrigerative conditions, use the aqueous sodium hydroxide solution of mass concentration 30% to neutralize the methacrylic acid of proportional quantity, degree of neutralization is 60-70%, the methacrylic acid solution of becoming reconciled in obtaining; 3), the initiator with proportional quantity, linking agent water dissolution, the consumption of water be initiator and linking agent weight sum 37-61 doubly; The aqueous thickener solution that adds proportional quantity then, described aqueous thickener solution, the weight that is water are that the 54-90 water dissolution thickening material doubly of thickening material weight obtains, in the methacrylic acid solution of becoming reconciled in the adding again that stirs, stir, obtain monomer mixed solution; 4) solvent in three mouthfuls of containers of step 1) is under agitation heated up, begin to drip above-mentioned monomer mixed solution when being warming up to 55 ℃, be added dropwise to complete in 40-45 minute, at 55-75 ℃ of isothermal reaction 4-6 hour; 5) after reaction finishes, reduce to room temperature, filter, use the methanol wash product, oven dry gets the high moisture-absorption resin of inverse suspension polymerization polymethacrylic acid.
The high moisture-absorption resin of gained inverse suspension polymerization polymethacrylic acid is at 30 ℃, during relative humidity 90%, and moisture absorption speed 〉=7g/g.min.
The rate of moisture absorption testing method:
With 10g testing sample constant weight in 120 ℃.Weigh then and be accurate to 0.01g (it is fast that the speed of weighing is wanted, and reduces the airborne time that exposes as far as possible).Sample packed into hangs on that to have pneumatic blending, relative humidity be that temperature is 30 ℃ in 90% the climatic chamber in the non-woven bag, after 30 minutes, bag is taken out weigh.Be calculated as follows rate of moisture absorption:
In the formula:
N-rate of moisture absorption (g/g.min),
After the moisture absorption of Q-sample heavy (g),
Before the moisture absorption of W-sample heavy (g),
The 30-time is 30 minutes (min).
Embodiment
Embodiment 1
In there-necked flask, add 120 gram hexanaphthenes, add 1.3 gram dispersion agent octadecanol phosphoric esters, stir under the room temperature.42 gram methacrylic acids are placed beaker, under-3 ℃ of conditions, neutralize with 39.02 grams, 30% aqueous sodium hydroxide solution.With 0.17 gram Potassium Persulphate and 0.04 gram N, N '-methylene-bisacrylamide restrains water dissolution with 10; 0.6 gram Type 3U is fully dissolved with 40 gram water, add in the aqueous solution of initiator and linking agent, mix in the methacrylic acid solution of becoming reconciled in the adding of back, make monomer mixed solution.There-necked flask is warming up to 55 ℃, and the dropping monomer mixed solution dripped off in 45 minutes, reacted 6 hours down at 55 ℃, after reaction finishes, reduced to room temperature, filter, and methanol wash, 110 ℃ of oven dry get the particulate state polymethacrylic acid moisture-absorption resin.The high moisture-absorption resin of gained is at 30 ℃, and during relative humidity 90% (following examples are test with this understanding all), moisture absorption speed is 7.8g/g.min.
Embodiment 2
In there-necked flask, add 120 gram hexanaphthenes, add 0.48 gram dispersion agent octadecanol phosphoric ester, stir under the room temperature.48 gram methacrylic acids are placed beaker, under 10 ℃ of conditions, neutralize with 48.3 grams, 30% aqueous sodium hydroxide solution.With 0.19 gram Potassium Persulphate and 0.04 gram N, N '-methylene-bisacrylamide restrains water dissolution with 10; 1.4 gram Type 3Us are fully dissolved with 90 gram water, add in the aqueous solution of initiator and linking agent, mix in the methacrylic acid solution of becoming reconciled in the adding of back, make monomer mixed solution.There-necked flask is warming up to 55 ℃, drips monomer mixed solution, be warming up to 65 ℃ after dripping off in 40 minutes, react 4 hours, after reaction finishes, reduce to room temperature, filter, methanol wash, 100 ℃ of oven dry must the particulate state polymethacrylic acid moisture-absorption resin.The high moisture-absorption resin of gained is at 30 ℃, and during relative humidity 90%, moisture absorption speed is 12.9g/g.min.
Embodiment 3
In there-necked flask, add 120 gram hexanaphthenes, add 2.25 gram dispersion agent octadecanol phosphoric esters, stir under the room temperature.45 gram methacrylic acids are placed beaker, under-1 ℃ of condition, neutralize with 48.78 grams, 30% aqueous sodium hydroxide solution.With 0.135 gram Potassium Persulphate and 0.03 gram N, N '-methylene-bisacrylamide restrains water dissolution with 10.065; 0.9 gram Type 3U is fully dissolved with 81 gram water, add in the aqueous solution of initiator and linking agent, mix in the methacrylic acid solution of becoming reconciled in the adding of back, make monomer mixed solution.There-necked flask is warming up to 55 ℃, drips monomer mixed solution, be warming up to 75 ℃ after dripping off in 45 minutes, react 5 hours, after reaction finishes, reduce to room temperature, filter, methanol wash, 115 ℃ of oven dry must the particulate state polymethacrylic acid moisture-absorption resin.The high moisture-absorption resin of gained is at 30 ℃, and during relative humidity 90%, moisture absorption speed is 10.6g/g.min.
Embodiment 4
In there-necked flask, add 120 gram hexanaphthenes, add 0.93 gram dispersion agent octadecanol phosphoric ester, stir under the room temperature.46 gram methacrylic acids are placed beaker, under 0 ℃ of condition, neutralize with 46.68 grams, 30% aqueous sodium hydroxide solution.With 0.23 gram Potassium Persulphate and 0.04 gram N, N '-methylene-bisacrylamide restrains water dissolution with 9.99; 0.46 gram Type 3U is fully dissolved with 30 gram water, add in the aqueous solution of initiator and linking agent, mix in the methacrylic acid solution of becoming reconciled in the adding of back, make monomer mixed solution.There-necked flask is warming up to 55 ℃, and the dropping monomer mixed solution dripped off in 45 minutes, reacted 6 hours down at 60 ℃, after reaction finishes, reduced to room temperature, filter, and methanol wash, 90 ℃ of oven dry get the particulate state polymethacrylic acid moisture-absorption resin.The high moisture-absorption resin of gained is at 30 ℃, and during relative humidity 90%, moisture absorption speed is 10.7g/g.min.
Embodiment 5
In there-necked flask, add 120 gram hexanaphthenes, add 1.07 gram dispersion agent octadecanol phosphoric esters, stir under the room temperature.43 gram methacrylic acids are placed beaker, under 3 ℃ of conditions, neutralize with 42.88 grams, 30% aqueous sodium hydroxide solution.With 0.17 gram Potassium Persulphate and 0.04 gram N, N '-methylene-bisacrylamide restrains water dissolution with 10; 1.29 gram Type 3Us are fully dissolved with 90 gram water, add in the aqueous solution of initiator and linking agent, mix in the methacrylic acid solution of becoming reconciled in the adding of back, make monomer mixed solution.There-necked flask is warming up to 55 ℃, and the dropping monomer mixed solution dripped off in 43 minutes, reacted 5 hours down at 65 ℃, after reaction finishes, reduced to room temperature, filter, and methanol wash, 120 ℃ of oven dry get the particulate state polymethacrylic acid moisture-absorption resin.The high moisture-absorption resin of gained is at 30 ℃, and during relative humidity 90%, moisture absorption speed is 8.4g/g.min.
Embodiment 6
In there-necked flask, add 120 gram hexanaphthenes, add 1.32 gram dispersion agent octadecanol phosphoric esters, stir under the room temperature.44 gram methacrylic acids are placed beaker, under 5 ℃ of conditions, neutralize with 43.2 grams, 30% aqueous sodium hydroxide solution.With 0.18 gram Potassium Persulphate and 0.022 gram N, N '-methylene-bisacrylamide restrains water dissolution with 10; 1.1 gram Type 3Us are fully dissolved with 60 gram water, add in the aqueous solution of initiator and linking agent, mix in the methacrylic acid solution of becoming reconciled in the adding of back, make monomer mixed solution.There-necked flask is warming up to 55 ℃, and the dropping monomer mixed solution dripped off in 41 minutes, reacted 5 hours down at 65 ℃, after reaction finishes, reduced to room temperature, filter, and methanol wash, 110 ℃ of oven dry get the particulate state polymethacrylic acid moisture-absorption resin.The high moisture-absorption resin of gained is at 30 ℃, and during relative humidity 90%, moisture absorption speed is 9.6g/g.min.
Embodiment 7
In there-necked flask, add 120 gram hexanaphthenes, add 1.32 gram dispersion agent octadecanol phosphoric esters, stir under the room temperature.44 gram methacrylic acids are placed beaker, under 7 ℃ of conditions, neutralize with 43.2 grams, 30% aqueous sodium hydroxide solution.With 0.18 gram Potassium Persulphate and 0.044 gram N, N '-methylene-bisacrylamide restrains water dissolution with 10; 1.1 gram Type 3Us are fully dissolved with 59.4 gram water, add in the aqueous solution of initiator and linking agent, mix in the methacrylic acid solution of becoming reconciled in the adding of back, make monomer mixed solution.There-necked flask is warming up to 55 ℃, and the dropping monomer mixed solution dripped off in 42 minutes, reacted 5 hours down at 65 ℃, after reaction finishes, reduced to room temperature, filter, and methanol wash, 110 ℃ of oven dry get the particulate state polymethacrylic acid moisture-absorption resin.The high moisture-absorption resin of gained is at 30 ℃, and during relative humidity 90%, moisture absorption speed is 9.9g/g.min.
Claims (1)
1. the preparation method of inverse suspension polymerization polymethacrylic acid moisture-absorption resin is characterized in that, step and condition are:
The solvent that uses is hexanaphthene; Methacrylic acid is a monomer, and consumption is the 35-40% of weight of solvent, and with the aqueous sodium hydroxide solution neutralization of mass concentration 30%, degree of neutralization is 60-70%; Potassium Persulphate is an initiator, and consumption is 0.3～0.5% of a monomer weight; N, N '-methylene-bisacrylamide are linking agent, and consumption is 0.05～0.1% of a monomer weight; Octadecanol phosphoric ester is a dispersion agent, and consumption is 1～5% of a monomer weight; Type 3U is a thickening material, and consumption is 1～3% of a monomer weight;
1) cyclohexane solvent and the dispersion agent of adding proportional quantity in three mouthfuls of containers stir under the room temperature, make the dispersion agent dissolving; 2) under-3 ℃～10 ℃ refrigerative conditions, use the aqueous sodium hydroxide solution of mass concentration 30% to neutralize the methacrylic acid of proportional quantity, degree of neutralization is 60-70%, the methacrylic acid solution of becoming reconciled in obtaining; 3), the initiator with proportional quantity, linking agent water dissolution, the consumption of water be initiator and linking agent weight sum 37-61 doubly; The aqueous thickener solution that adds proportional quantity then, described aqueous thickener solution, the weight that is water are that the 54-90 water dissolution thickening material doubly of thickening material weight obtains, in the methacrylic acid solution of becoming reconciled in the adding again that stirs, stir, obtain monomer mixed solution; 4) solvent in three mouthfuls of containers of step 1) is under agitation heated up, begin to drip above-mentioned monomer mixed solution when being warming up to 55 ℃, be added dropwise to complete in 40-45 minute, at 55-75 ℃ of isothermal reaction 4-6 hour; 5) after reaction finishes, reduce to room temperature, filter, use the methanol wash product, oven dry gets the high moisture-absorption resin of inverse suspension polymerization polymethacrylic acid.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102408505A (en) * | 2011-10-12 | 2012-04-11 | 浙江卫星石化股份有限公司 | Method for preparing super absorbent resin by inverse suspension polymerization |
| CN104861104A (en) * | 2015-06-08 | 2015-08-26 | 广州天赐高新材料股份有限公司 | Quick-wetting carboxylic acid copolymer thickening agent and preparation method thereof |
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| JP2938920B2 (en) * | 1990-01-31 | 1999-08-25 | 住友精化株式会社 | Method for producing water absorbent resin |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102408505A (en) * | 2011-10-12 | 2012-04-11 | 浙江卫星石化股份有限公司 | Method for preparing super absorbent resin by inverse suspension polymerization |
| CN102408505B (en) * | 2011-10-12 | 2014-04-23 | 浙江卫星石化股份有限公司 | Method for preparing super absorbent resin by inverse suspension polymerization |
| CN104861104A (en) * | 2015-06-08 | 2015-08-26 | 广州天赐高新材料股份有限公司 | Quick-wetting carboxylic acid copolymer thickening agent and preparation method thereof |
| CN104861104B (en) * | 2015-06-08 | 2017-01-04 | 广州天赐高新材料股份有限公司 | A kind of fast moistening polymers of carboxylic acid thickening agent and preparation method thereof |
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