CN101880351B - Method for preparing microcrystalline muscovite composite sulfonic acid type high-hydroscopic resin by water-soluble polymerization process - Google Patents
Method for preparing microcrystalline muscovite composite sulfonic acid type high-hydroscopic resin by water-soluble polymerization process Download PDFInfo
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- CN101880351B CN101880351B CN2010102221941A CN201010222194A CN101880351B CN 101880351 B CN101880351 B CN 101880351B CN 2010102221941 A CN2010102221941 A CN 2010102221941A CN 201010222194 A CN201010222194 A CN 201010222194A CN 101880351 B CN101880351 B CN 101880351B
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Abstract
The invention relates to a method for preparing microcrystalline muscovite composite sulfonic acid type high-hydroscopic resin by a water-soluble polymerization process. In the method, ammonium persulfate or ammonium persulfate and sodium hydrosulfite are used as initiating agents; N,N-methylene-bisacrylamide is used as a cross-linking agent; acrylic acid, acrylamide and sodium styrenesulfonate are used as comonomers; microcrystalline muscovite is added into a copolymerization system to form a stable suspended matter; and then the microcrystalline muscovite composite sulfonic acid type high-hydroscopic resin is prepared by aqueous solution polymerization. The water absorption and the salt absorption of the prepared microcrystalline muscovite composite sulfonic acid type high-hydroscopic resin reach 780 to 1,150 times and 80 to 140 times respectively, and the temperature resistance is more than 220 DEG C; and the resin can be directly used in the industries such as agriculture, forestry and the like.
Description
One, technical field
The present invention relates to a kind of preparation method of water solution polymerization process microcrystal muscovite composite sulfonic acid type High hydrophilous resin, the microcrystal muscovite composite sulfonic acid type High hydrophilous resin of the present invention's preparation is applicable to agricultural gardening water conservation, soil improvement, afforestation, deserted mountain transformation and the desert afforestation etc. of industries such as farming, woods.
Two, technical background
Super absorbent resin (being called for short SAR) is one type of novel functional high molecule material of current domestic and international broad research exploitation.People such as Gugliemell had prepared super absorbent resin through the research to starch-grafted vinyl cyanide in 1961. and Fanta has accomplished the synthetic and performance study of partially hydrolysed starch grafted propylene lonitrile copolymer super absorbent resin in 1966 subsequently; And realized that successfully industriallization, its commodity are called SGP (Starch Graft Polymer).
At present, number of research projects has been carried out to super absorbent resin in countries in the world, has all obtained bigger progress at aspects such as its kind, method of manufacture, performance and Application Areass.Developed countries such as U.S.A, day, moral, method are on the forefront always, though the development of China SAR is started late, develop very fast.
Super absorbent resin is because of having these two distinctive character of high-hydroscopicity and high-moisture-retention, and purposes is very extensive, we can say " all there is its ample scope for abilities in every field relevant with water ".In the medical and hygiene article field; Utilize it to make absorbing material; Like sanitary towel, baby' diaper, medical absorbent cotton etc.; Its consumption accounts for more than 95% of all super absorbent resin YO: at building field, the water-resisting layer that can be used for anti-seep water and underwater pipeline in the construction work through the sealing material that mixing such as rubber, super absorbent resin and auxiliary agent are obtained is made; In the eagroforestry field; Utilize the high-moisture-retention of super absorbent resin to carry out agricultural gardening water conservation, soil improvement; In soil, add the super absorbent resin of 0.1wt%, can make soil have suff water to provide plant required in a long time, improve crop yield; In afforestation, deserted mountain transformation, desert afforestation, super absorbent resin capable of using keeps soil moisture to improve plant germination rate and surviving rate.In Application Areass such as artificial snow manufacturing, perfume slowly-releasing, food interpolation, fresh-keeping of vegetables, all can find the use of super absorbent resin in addition.
In the investigation of materials field, compoundization of material is one of trend of researchdevelopment, and super absorbent resin is no exception.In order to improve performance, reduce cost, the compound High hydrophilous resin of a series of wilkinites, kaolin, illite, sericite and zeyssatite has appearred.Microcrystal muscovite (Microcrystal muscovite) is a kind of novel white mica mineral wealth with microlitic structure (about 1 μ m of crystallographic dimension～10 μ m) of discovered in recent years.The distinctive physical and chemical performances of a series of traditional white micas such as that microcrystal muscovite not only has is heat-resisting, acid and alkali-resistance, insulation, intensity height; Also having natural superfine, be prone to mill, be prone to characteristics such as processing, whiteness height, active height, is a kind of mineral powder raw material of excellent property.The research report of relevant microcrystal muscovite composite high-water uptake property resin seldom; Up to the present unique bibliographical information is Shen Shangyue etc. with the superfine powder and the vinylformic acid of microcrystal muscovite is main raw material; Adopt solution polymerization process to prepare microcrystal muscovite/ZX-I super-strong moisture absorbing property matrix material, inhaling the zero(ppm) water multiplying power is 420g/g, and inhaling the tap water multiplying power is 220g/g; Inhaling the saline water multiplying power is 55g/g, and the research of relevant microcrystal muscovite composite sulfonic acid type High hydrophilous resin does not also appear in the newspapers.
Three, summary of the invention
In view of this; The object of the invention is exactly in the preparation method that a kind of water solution polymerization process microcrystal muscovite composite sulfonic acid type High hydrophilous resin is provided; Introduce the 3rd monomer styrene sodium sulfonate and acrylic amide, acrylic acid copolymer with further raising gel-strength, salt absorbing rate and temperature resistance, obtain water-intake rate, salt absorbing rate and temperature resistance microcrystal muscovite composite sulfonic acid type High hydrophilous resin preferably.
According to the object of the invention, a kind of method of water solution polymerization process microcrystal muscovite composite sulfonic acid type High hydrophilous resin has been proposed, its characteristic has following process step:
A) 10gNaOH is dissolved in the 200mL deionized water, in ice bath, vinylformic acid slowly is added drop-wise in the NaOH aqueous solution then, fully stir; Reaction 0.5～2h; NaOH and vinylformic acid mol ratio are 0.5～0.7: 1, add microcrystal muscovite then, and 30～50 ℃ are evenly stirred 24h; To form steady suspension, microcrystal muscovite accounts for 20～60% of Acrylic Acid Monomer quality total amount;
B) in above-mentioned suspension-s, add acrylic amide, SSS and N, N '-methylene-bisacrylamide fully stirs 30min, is warming up to 60～80 ℃, then initiator slowly is added drop-wise in the polymerization system initiated polymerization 2～4 hours; The mass ratio of vinylformic acid, acrylic amide and SSS is 3～7: 3～7: 1～3; N, N '-methylene-bisacrylamide account for 0.02～0.2% of vinylformic acid, acrylic amide and SSS monomer mass total amount; Initiator accounts for 0.1%～2.0% of vinylformic acid, acrylic amide and SSS monomer mass total amount;
C) synthetic microcrystal muscovite composite sulfonic acid type High hydrophilous resin is filtered, uses methanol wash; 70～110 ℃ of oven dry; Pulverize and promptly get particulate state, lurid microcrystal muscovite composite sulfonic acid type High hydrophilous resin; The microcrystal muscovite composite sulfonic acid type High hydrophilous resin water-intake rate that obtains and salt absorbing rate reach 780～1150 times and 80～140 times respectively, temperature resistance is greater than 220 ℃;
Initiator used in the present invention is an ammonium persulphate; Perhaps be ammonium persulphate and sodium sulfite anhy 96, the mass ratio of ammonium persulphate and sodium sulfite anhy 96 is 2～3: 1.
Advantage of the present invention and effect are:
1) reaction is directly carried out in the aqueous solution, non-environmental-pollution, and method is simple, need not nitrogen protection, therefore saved the nitrogen device, reduced the input expense of equipment;
2) introduce the 3rd monomer styrene sodium sulfonate and acrylic amide, acrylic acid copolymer, improved gel-strength, salt absorbing rate and temperature resistance;
3) compare with normally used acrylic acid-acrylamide High hydrophilous resin; Owing to added microcrystal muscovite, improved solid content, salt tolerance and gel-strength, also reduced cost; For the Sustainable development of China's agricultural, there is significant meaning aspects such as the improvement in saltings.
Water-intake rate, salt absorbing rate and the water-retentivity measuring method of water solution polymerization process microcrystal muscovite composite sulfonic acid type High hydrophilous resin of the present invention are following:
Water-intake rate is measured: the High hydrophilous resin that is cut into certain particle size that takes a morsel is put into baking oven, about 110 ℃ of baking 2h, and accurate weighing 0.5g drying prods; Put into the beaker of 1000mL; Add 1000mL zero(ppm) water then, fully suction at ambient temperature, water-absorbing resin is water white transparency shape jelly.Filter with 100 order stainless steel sifts, adopt the natural filtration method to measure, to substantially anhydrous drippage.Measure the quality of filtering back water, calculate the water absorbent rate of resin, its formula: water absorbent rate=(adding quality-superfluous water quality)/resin quality.
Salt absorbing rate is measured: take by weighing the 0.5g dried resin and put into beaker; Adding 500ml concentration is 0.9% the KCl aqueous solution; At room temperature leave standstill suction; Reach the unnecessary salt solution of saturated back filtering, and claim its quality, then the quality of absorption salt ratio=(quality of the quality-dried resin of resin behind the suction salt solution)/dried resin.
Four, embodiment
In order to understand the present invention better, further set forth content of the present invention below in conjunction with embodiment, but content of the present invention not only is confined to following embodiment.
Embodiment 1:
10gNaOH is dissolved in the 200mL deionized water, in ice bath, 25.7g vinylformic acid slowly is added drop-wise in the NaOH aqueous solution then, fully stir, reaction 2h adds the 10.3g microcrystal muscovite then, and 50 ℃ are evenly stirred 24h, to form steady suspension.In above-mentioned suspension-s, add 17.13g acrylic amide, 8.57g SSS and 0.031g N; N '-methylene-bisacrylamide; Fully stir 30min; Be warming up to 60 ℃, then 0.193g ammonium persulphate and 0.064g sodium sulfite anhy 96 slowly be added drop-wise in the polymerization system initiated polymerization 4 hours.After reaction finishes synthetic microcrystal muscovite composite sulfonic acid type High hydrophilous resin is filtered, uses methanol wash; 70～110 ℃ of oven dry; Pulverize and promptly get particulate state, lurid microcrystal muscovite composite sulfonic acid type High hydrophilous resin; The microcrystal muscovite composite sulfonic acid type High hydrophilous resin water-intake rate that obtains and salt absorbing rate reach 980 times and 123 times respectively, temperature resistance is greater than 220 ℃.
Embodiment 2:
10gNaOH is dissolved in the 200mL deionized water, in ice bath, 30g vinylformic acid slowly is added drop-wise in the NaOH aqueous solution then, fully stir, reaction 2h adds the 9g microcrystal muscovite then, and 50 ℃ are evenly stirred 24h, to form steady suspension.In above-mentioned suspension-s, add 30g acrylic amide, 9g SSS and 0.07g N; N '-methylene-bisacrylamide fully stirs 30min, is warming up to 60 ℃; Then 0.46g ammonium persulphate and 0.23g sodium sulfite anhy 96 slowly are added drop-wise in the polymerization system initiated polymerization 4 hours.After reaction finishes synthetic microcrystal muscovite composite sulfonic acid type High hydrophilous resin is filtered, uses methanol wash; 70～110 ℃ of oven dry; Pulverize and promptly get particulate state, lurid microcrystal muscovite composite sulfonic acid type High hydrophilous resin; The microcrystal muscovite composite sulfonic acid type High hydrophilous resin water-intake rate that obtains and salt absorbing rate reach 1100 times and 135 times respectively, temperature resistance is greater than 220 ℃.
Embodiment 3:
10gNaOH is dissolved in the 200mL deionized water, in ice bath, 36g vinylformic acid slowly is added drop-wise in the NaOH aqueous solution then, fully stir, reaction 2h adds the 21.6g microcrystal muscovite then, and 50 ℃ are evenly stirred 24h, to form steady suspension.In above-mentioned suspension-s, add 15.43g acrylic amide, 5.14g SSS and 0.113gN; N '-methylene-bisacrylamide fully stirs 30min, is warming up to 80 ℃; Then the 1.13g ammonium persulphate slowly is added drop-wise in the polymerization system initiated polymerization 4 hours.After reaction finishes synthetic microcrystal muscovite composite sulfonic acid type High hydrophilous resin is filtered, uses methanol wash; 70～110 ℃ of oven dry; Pulverize and promptly get particulate state, lurid microcrystal muscovite composite sulfonic acid type High hydrophilous resin; The microcrystal muscovite composite sulfonic acid type High hydrophilous resin water-intake rate that obtains and salt absorbing rate reach 785 times and 84 times respectively, temperature resistance is greater than 220 ℃.
Claims (2)
1. the preparation method of a water solution polymerization process microcrystal muscovite composite sulfonic acid type High hydrophilous resin is characterized in that having following process step:
A) 10gNaOH is dissolved in the 200mL deionized water, in ice bath, vinylformic acid slowly is added drop-wise in the NaOH aqueous solution then, fully stir; Reaction 0.5～2h; NaOH and vinylformic acid mol ratio are 0.5～0.7: 1, add microcrystal muscovite then, and 30～50 ℃ are evenly stirred 24h; To form steady suspension, microcrystal muscovite accounts for 20～60% of Acrylic Acid Monomer quality total amount;
B) in above-mentioned suspension-s, add acrylic amide, SSS and N, N '-methylene-bisacrylamide fully stirs 30min, is warming up to 60～80 ℃, then initiator slowly is added drop-wise in the polymerization system initiated polymerization 2～4 hours; The mass ratio of vinylformic acid, acrylic amide and SSS is 3～7: 3～7: 1～3; N, N '-methylene-bisacrylamide account for 0.02～0.2% of vinylformic acid, acrylic amide and SSS monomer mass total amount; Initiator accounts for 0.1%～2.0% of vinylformic acid, acrylic amide and SSS monomer mass total amount;
C) synthetic microcrystal muscovite composite sulfonic acid type High hydrophilous resin is filtered, uses methanol wash; 70～110 ℃ of oven dry; Pulverize and promptly get particulate state, lurid microcrystal muscovite composite sulfonic acid type High hydrophilous resin; The microcrystal muscovite composite sulfonic acid type High hydrophilous resin water-intake rate that obtains and salt absorbing rate reach 780～1150 times and 80～140 times respectively, temperature resistance is greater than 220 ℃.
2. the preparation method of a kind of water solution polymerization process microcrystal muscovite composite sulfonic acid type High hydrophilous resin according to claim 1 is characterized in that: described initiator is an ammonium persulphate; Perhaps be ammonium persulphate and sodium sulfite anhy 96, the mass ratio of ammonium persulphate and sodium sulfite anhy 96 is 2～3: 1.
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| CN103509199B (en) * | 2012-06-26 | 2016-03-09 | 中国石油化工股份有限公司 | Swelling particulate of polymer for drilling fluid and preparation method thereof |
| CN102875727A (en) * | 2012-10-15 | 2013-01-16 | 成都理工大学 | Preparation method for micro-crystal muscovite compounded and crylic acid-acrylamide-itaconic acid polymerized super absorbent resin |
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| CN1264932C (en) * | 2004-02-05 | 2006-07-19 | 成都理工大学 | Titanate KR-38S surface modified micro-crystal white mica active filler preparing method |
| CN101117422A (en) * | 2007-03-21 | 2008-02-06 | 成都理工大学 | Method for preparing alta-mud composite highly-absorbent resin by optical polymerization process |
| CN101289526A (en) * | 2007-04-18 | 2008-10-22 | 成都理工大学 | Method for preparing kaolin complex high hydroscopic resin through light polymerization method |
| CN101225139A (en) * | 2007-12-21 | 2008-07-23 | 中国科学院长春应用化学研究所 | Method for preparing polyacrylic acid/acrylamide moisture-absorption resin |
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