CN1624008A - Colour composite high water absorbing resin and its preparation process - Google Patents
Colour composite high water absorbing resin and its preparation process Download PDFInfo
- Publication number
- CN1624008A CN1624008A CN 200410046870 CN200410046870A CN1624008A CN 1624008 A CN1624008 A CN 1624008A CN 200410046870 CN200410046870 CN 200410046870 CN 200410046870 A CN200410046870 A CN 200410046870A CN 1624008 A CN1624008 A CN 1624008A
- Authority
- CN
- China
- Prior art keywords
- parts
- water
- resin
- add
- absorbent resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Abstract
A high-hydroscopicity composite color resin is proportionally prepared from water, sodium hydroxide, kaolin, acrylic acid, trigger, cross-linking agent, and metallic oxide pigment through low-pressure polymerizing at 65-80 deg.C for 1-2 hr, cutting, drying and pulverizing.
Description
Technical field:
The present invention relates to a kind of colored composite highly-absorbent resin and preparation method thereof.
Background technology:
High hydrophilous resin (being called for short SAP) has been widely used in industries such as agricultural, individual's protection articles for use, coating, sealing material, material water-proof material in recent years.High hydrophilous resin commonly used has the hydrolysate, starch-acrylate graft copolymer, acrylamide and acrylic acid copolymer, polyacrylate of starch-acrylonitrile grafting polymkeric substance etc.The industrial chemicals price that the continuous rise of oil price causes being correlated with sharp rises, and the cost of High hydrophilous resin rises significantly, has seriously restricted the application of High hydrophilous resin in all trades and professions.For reducing cost, improve performance, the synthetic method of High hydrophilous resin constantly is improved.Chinese patent ZL98110033.3 adopts acrylamide, vinylformic acid to add the wilkinite copolymerization, adopt the redox system initiated polymerization, when being 1: 1 left and right sides, filler and monomer ratio obtain the about 480 times resin of water absorbent rate adding, this method adopts acrylamide, the two monomer copolymerizations of vinylformic acid, weak point is polymerization system monomer concentration low [(monomer+wilkinite): water=1: 2], be not easy to the control and the adjustment of resin crosslinks density, the product adaptation scope is restricted; And the low energy consumption for drying of resin in the subsequent handling that will make of monomer concentration increases, thereby increases cost.Chinese patent CN 15211196A adopts acrylamide, vinylformic acid to add the wilkinite copolymerization, adopt the redox system initiated polymerization, adding filler and monomer ratio is that to obtain water absorbent rate between 1: 2 to 1: 6 be 200～300 times resin, this method adopts acrylamide, the two monomer copolymerizations of vinylformic acid, desired initiator system complexity, the process time is long; And it is main stuffing that this method adopts wilkinite, specific surface area is big, and the oxygen of filler particles surface adsorption is obvious to the poly-effect of the resistance of polyreaction, and specific surface area causes wilkinite-OH too high levels greatly simultaneously, cross-linking density is excessive during with resin compounded, and gained compound resin water absorbent rate is on the low side.Chinese patent ZL99126336.7, ZL99126337.5 adopt starch-vinylformic acid to add to account for 5% wilkinite polymerization under the room temperature and the condition of heating respectively of monomer total amount, obtain water absorbent rate and be 460～800 times resin, the amount that this method adds filler seldom, the amplitude that reduces cost is limited.Chinese patent ZL01143497.X adopts acrylamide, vinylformic acid to add wilkinite, kaolinic mixture initiated polymerization under redox system, obtain about 200～400 times resin of water absorbent rate, this scheme is desirable from reducing the material cost aspect, but this scheme is owing to the interface inhibition of the oxygen that need overcome wilkinite absorption has adopted the redox system initiator, make that the sudden and violent poly-problem in the polymerization process is restive, be unfavorable for the control of resin crosslinks density, increased the difficulty of quality control in the process of producing product; Specific surface area causes wilkinite-OH too high levels greatly simultaneously, the excessive and difficult adjusting of cross-linking density during with resin compounded, and gained compound resin water absorbent rate is on the low side (200～400 times).Chinese patent CN 14382565A adopts vinylformic acid to add attapulgite initiated polymerization under ceric ammonium nitrate or ammonium persulphate initiator system, is adding filler: the monomer ratio is to obtain the about 600 times resin of water absorbent rate at 1: 2 o'clock.This scheme weak point is polymerization system monomer concentration low [(filler+monomer): water=1: 4], be not easy to the control and the adjustment of resin crosslinks density, make that the subject range of product is limited to, and the low energy consumption for drying increase that will make resin in the subsequent handling of monomer concentration, thereby cost increased.
Summary of the invention:
The purpose of this invention is to provide a kind of new high filler content of all respects such as agricultural, individual protection articles for use, coating, sealing material, material water-proof material, high water absorbent rate, technological process is simple, comprehensive cost is low, cost performance is high colored composite highly-absorbent resin and preparation method thereof of being widely used in.
The technical solution used in the present invention is: add wide material sources, the cheap kaolin main stuffing as colored composite highly-absorbent resin in the Acrylic Acid Monomer aqueous solution, add initiator and linking agent, obtaining the colored composite highly-absorbent resin of kaolin-polyacrylate through graft copolymerization, drying, pulverizing.
Colored composite highly-absorbent resin involved in the present invention, the mass fraction that it is characterized in that its composition is: 100～250 parts in water, 20～50 parts in sodium hydroxide, 50～150 parts of kaolin, 50～100 parts in vinylformic acid, 0.02～0.5 part of initiator, linking agent N, 0.05～0.2 part of N-methylene-bisacrylamide, 0.05～0.5 part of metal oxide pigment.
Initiator of the present invention is ammonium persulphate or Potassium Persulphate.
Linking agent of the present invention is a N,N methylene bis acrylamide.
The present invention adds the metal oxide pigment of about 0.05～0.5 part of red iron oxide, iron oxide blue, iron oxide yellow or safety non-toxics such as oxidation cadmium yellow, chromoxide green as tinting material, can prepare the colored composite highly-absorbent resin of shades of colour, color stable.
The present invention has adopted a kind of low-pressure polymerization technology: promptly before polymerization to slurry be evacuated to-0.02MPa～0.095Mpa kept 1～10 minute, stop then vacuumizing, polymerization tank is in react in 65 ℃～80 ℃ the low pressure enclosed system and finished polymerization in 1～2 hour.The present invention has saved present the most frequently used logical N
2The technological process of deoxygenation can shorten inductive phase, effectively solves oxygen to the poly-problem of the resistance of polymerization system.
The preparation method of colored composite highly-absorbent resin:
In reactor, add 100～250 parts of water of mass fraction and add 50～100 parts of sodium hydroxide again, fully 50～100 parts of vinylformic acid of adding slow neutralization in dissolving back stirs, add 50～150 parts of kaolin then, 0.05～0.5 part of metal oxide pigment, 0.02～0.5 part of ammonium persulphate, 0.05～0.2 part of N, the N-methylene-bisacrylamide mixes into uniform slurry, divide in the polymerization tank of packing into then, put into vacuum drying oven, suction keeps to-0.02Mpa to-0.095Mpa stopping to vacuumize after 1～10 minute, the case that keeps dry is airtight to be warming up to 65 ℃～80 ℃ polymerizations, react after 1～2 hour and take out, through rotary-cut, oven dry, pulverize, sieving and obtaining water absorbent rate [water absorbent rate=preceding weight of (weight before suction back weight-suction)/suction] is 450～900 times colored composite highly-absorbent resin.
The filler kaolin that the present invention adopts is a kind of hydrous alumino silicates, and chemical formula is 2SiO
2.AlO
3.2H
2O, water wherein exists with-OH form.At occurring in nature, kaolin exists with flakey, and the scale length and width are 0.2～5 μ m usually, and thickness is 0.05～2 μ m.Kaolinic this structure makes that its surface-OH group content is moderate, easily obtains the graftomer of stable uniform and can not produce excessively crosslinked again with polyacrylic acid chain generation chemical graft in the polyacrylic acid salt system.Intensity, water absorbent rate, the salt tolerance of colored composite water absorbing resin also are improved simultaneously.
Compared with prior art, the present invention has the following advantages:
A, compare with documents (Chinese patent ZL01143497.X), difference of the present invention has:
1) the monomer difference of Cai Yonging, what documents adopted is acrylamide and vinylformic acid, the present invention adopts vinylformic acid.
2) initiator system difference, documents adopts redox system, and the present invention adopts oxidation system.
3) used filler difference, it is main mixing portion kaolin that documents adopts wilkinite, the present invention adopts kaolin.
By comparison, the outstanding advantage of following points of the present invention:
1) the desired initiator system complexity of monomer (acrylamide+vinylformic acid) that adopts than file causes complex manufacturing, and the control difficulty is big, and polymerization time is longer about 1 times than the present invention.
2) be wilkinite than the filler main component that file adopted, its specific surface area is excessive thereby surperficial-and OH content height makes that the cross-linking density of compound resin is excessive, have a strong impact on the water-retaining capacity of resin, under the identical prerequisite of the ratio of adding filler, synthetic High hydrophilous resin water absorbent rate (200～400 times) has only of the present invention about 1/2 in the documents.
3) the present invention has adopted and has vacuumized airtight polymerization technique, has solved the poly-difficult problem of resistance on the one hand effectively, has accelerated polymerization velocity simultaneously, has reduced the production technique cost.
B, compare with documents (Chinese patent CN 14382565A), difference of the present invention has:
1) used filler difference, documents adopts attapulgite, and the present invention adopts kaolin.
2) the monomer concentration difference of Cai Yonging, in the documents, (monomer+filler): the ratio of water is 1: 4, and monomer concentration is low; (monomer+filler) that the present invention adopts: the ratio of water can be adjusted between 1: 1 to 1: 4 as required.
3) the present invention has adopted and has vacuumized airtight polymerization technique.
By comparison, the present invention has following outstanding advantage:
1) under the bigger situation of add-on, needs to add a large amount of water to form the suitable slurry of viscosity than used attapulgite in the file, make that the polymerization system monomer concentration is low, be not easy to the control and the adjustment of resin crosslinks density, the product adaptation scope is very restricted; The used monomer concentration of the present invention can be regulated about 1: 1 to 1: 4 in [(monomer+filler): water] ratio as required easily, be convenient to the control and the adjustment of resin crosslinks density, obtain water absorbent rate height, wide adaptability, colored composite water absorbing resin that cost performance is high.
2) than the low monomer concentration that is adopted in the file drying process of resin in the subsequent handling is extended, energy consumption increases, thereby increases the production technique cost; The present invention can finely address this problem, and the production technique cost of colored compound resin is reduced.
C, can see that from the contrast of above the present invention and prior art the present invention has significant advantage at aspects such as technical scheme and synthesis techniques:
The present invention is owing to adopt Acrylic Acid Monomer and the airtight polymerization after vacuumizing under the initiation of ammonium persulphate or Potassium Persulphate of kaolin filler, the water absorbent rate of the colored High hydrophilous resin that obtains reaches 450～900 times, the High hydrophilous resin that can prepare various uses very easily, the product adaptation scope is wide, can be widely used in all respects such as agricultural, individual's protection articles for use, coating, sealing material, material water-proof material; Compare with common sodium polyacrylate High hydrophilous resin, material cost has reduced by 30%～70%, and product has very high cost performance.
The preparation technology that the present invention adopts has significant advantage: the used monomer concentration of the present invention can be regulated about 1: 1 to 1: 4 in [(monomer+filler): water] ratio as required easily, the resin crosslinks adjustable density is strong, induction period in polymerization is short, polymerization process is mild, it is sudden and violent poly-to be easy to control, process time is short, the efficient height.
The present invention can add various metal oxide pigments easily to prepare lovely luster, stable colored High hydrophilous resin.
Embodiment:
Embodiment 1:
A kind of colored composite highly-absorbent resin and preparation method thereof, its method is that 9 kilograms of sodium hydroxide are added in 30 kg of water, fully add 20 kilograms of slow neutralization reactions of vinylformic acid then after the dissolving and stir, add 25 kilograms of kaolin then, 0.2 the kilogram mass percent concentration is 10% ammonium persulfate aqueous solution, 1.8 the kilogram mass percent concentration is 1% N, N-methylene-bisacrylamide aqueous solution becomes uniform slurry, divide in the polymerization tank of packing into, putting into the vacuum drying oven suction keeps stopping to vacuumize after 3 minutes to-0.02Mpa, the case that keeps dry is airtight to be warming up to 65 ℃ of polyreactions and to take out after 2 hours, through rotary-cut, oven dry, pulverizing obtains white composite highly-absorbent resin, and water absorbent rate is 450 times.
Embodiment 2:
A kind of colored composite highly-absorbent resin and preparation method thereof, its method is that 9 kilograms of sodium hydroxide are added in 25 kg of water, fully the dissolving back adds 20 kilograms of slow neutralization reactions of vinylformic acid and stirs, add 7.5 kilograms of kaolin then, red iron oxide 100 grams, 0.3 the kilogram mass percent concentration is 10% ammonium persulfate aqueous solution, 1.2 the kilogram mass percent concentration is 1% N, N-methylene-bisacrylamide aqueous solution becomes uniform slurry, divide in the polymerization tank of packing into, putting into the vacuum drying oven suction keeps stopping to vacuumize after 1 minute to-0.095Mpa, the case that keeps dry is airtight to be warming up to 65 ℃ of polyreactions and to take out after 1 hour, through rotary-cut, oven dry, pulverizing obtains red composite highly-absorbent resin, and water absorbent rate is 900 times.
Embodiment 3:
A kind of colored composite highly-absorbent resin and preparation method thereof, its method is that 9 kilograms of sodium hydroxide are added in 28 kg of water, fully the dissolving back adds 20 kilograms of slow neutralization reactions of vinylformic acid and stirs, add 10 kilograms of kaolin then, chromium sesquioxide 50 grams, 0.3 the kilogram mass percent concentration is 10% ammonium persulfate aqueous solution, 1.2 the kilogram mass percent concentration is 1% N, N-methylene-bisacrylamide aqueous solution becomes uniform slurry, divide in the polymerization tank of packing into, putting into the vacuum drying oven suction keeps stopping to vacuumize after 3 minutes to-0.02Mpa, the case that keeps dry is airtight to be warming up to 70 ℃ of polyreactions and to take out after 1 hour, through rotary-cut, oven dry, pulverizing obtains green composite highly-absorbent resin, and water absorbent rate is 680 times.
Embodiment 4:
A kind of colored composite highly-absorbent resin and preparation method thereof, its method is that 8 kilograms of sodium hydroxide are added in 20 kg of water, fully the dissolving back adds 20 kilograms of slow neutralization reactions of vinylformic acid and stirs, add 15 kilograms of kaolin then, 0.3 the kilogram mass percent concentration is 10% persulfate aqueous solution, 1.6 the kilogram mass percent concentration is 1% N, N-methylene-bisacrylamide aqueous solution becomes uniform slurry, divide in the polymerization tank of packing into, putting into the vacuum drying oven suction keeps stopping to vacuumize after 2 minutes to-0.05Mpa, the case that keeps dry is airtight to be warming up to 65 ℃ of polyreactions and to take out after 2 hours, through rotary-cut, oven dry, pulverizing obtains white composite highly-absorbent resin, and water absorbent rate is 560 times.
Claims (3)
1, a kind of colored composite highly-absorbent resin, the mass fraction that it is characterized in that its composition is: 0～0.5 part of 100～250 parts in water, 20～50 parts in sodium hydroxide, 50～150 parts of kaolin, 50～100 parts in vinylformic acid, initiator ammonium persulfate or 0.02～0.5 part of Potassium Persulphate, 0.05～0.2 part of linking agent N,N methylene bis acrylamide and metal oxide pigment.
2, a kind of colored composite highly-absorbent resin as claimed in claim 1 is characterized in that metal oxide pigment is made up of red iron oxide or iron oxide blue or iron oxide yellow or oxidation cadmium yellow or chromoxide green.
3, a kind of preparation method of colored composite highly-absorbent resin as claimed in claim 1, it is characterized in that concrete steps are to add 100～250 parts of water of mass fraction to add 50～100 parts of sodium hydroxide again in reactor, fully 50～100 parts of vinylformic acid of adding slow neutralization in dissolving back stirs, add 50～150 parts of kaolin then, 0～0.5 part of metal oxide pigment, 0.02～0.5 part of ammonium persulphate or Potassium Persulphate, 0.05～0.2 part of N, the N-methylene-bisacrylamide mixes into uniform slurry, divide in the polymerization tank of packing into then, put into vacuum drying oven, suction keeps to-0.02Mpa to-0.095Mpa stopping to vacuumize after 1～10 minute, the case that keeps dry is airtight to be warming up to 65 ℃～80 ℃ polymerizations, react after 1～2 hour and take out, through rotary-cut, oven dry, pulverize, sieving and obtaining water absorbent rate [water absorbent rate=preceding weight of (weight before suction back weight-suction)/suction] is 450～900 times colored composite highly-absorbent resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410046870 CN1624008A (en) | 2004-10-28 | 2004-10-28 | Colour composite high water absorbing resin and its preparation process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410046870 CN1624008A (en) | 2004-10-28 | 2004-10-28 | Colour composite high water absorbing resin and its preparation process |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1624008A true CN1624008A (en) | 2005-06-08 |
Family
ID=34763875
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200410046870 Pending CN1624008A (en) | 2004-10-28 | 2004-10-28 | Colour composite high water absorbing resin and its preparation process |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1624008A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102516443A (en) * | 2011-12-15 | 2012-06-27 | 东营市诺尔化工有限责任公司 | Method for preparing super absorbent resin |
| CN104525154A (en) * | 2014-12-23 | 2015-04-22 | 四川大学 | Method for preparing Cr(III) absorbent material by taking waste chrome-containing leather meal as raw material |
| CN104788604A (en) * | 2014-01-22 | 2015-07-22 | 亿利资源集团有限公司 | Ecological moisture-retention water-storage composite material, and preparation method thereof |
| CN113023741A (en) * | 2021-02-26 | 2021-06-25 | 温州大学 | Formula and preparation method of salt-resistant polymerized bentonite for waterproof blanket interlayer |
| CN113053578A (en) * | 2021-03-24 | 2021-06-29 | 上海上力特种电缆有限公司 | Water-blocking powder for waterproof cable, preparation method of water-blocking powder and waterproof cable |
-
2004
- 2004-10-28 CN CN 200410046870 patent/CN1624008A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102516443A (en) * | 2011-12-15 | 2012-06-27 | 东营市诺尔化工有限责任公司 | Method for preparing super absorbent resin |
| CN102516443B (en) * | 2011-12-15 | 2014-01-01 | 东营市诺尔化工有限责任公司 | Method for preparing super absorbent resin |
| CN104788604A (en) * | 2014-01-22 | 2015-07-22 | 亿利资源集团有限公司 | Ecological moisture-retention water-storage composite material, and preparation method thereof |
| CN104788604B (en) * | 2014-01-22 | 2017-01-25 | 亿利资源集团有限公司 | Ecological moisture-retention water-storage composite material, and preparation method thereof |
| CN104525154A (en) * | 2014-12-23 | 2015-04-22 | 四川大学 | Method for preparing Cr(III) absorbent material by taking waste chrome-containing leather meal as raw material |
| CN104525154B (en) * | 2014-12-23 | 2016-06-15 | 四川大学 | A kind of method preparing Cr (III) adsorbing material for raw material with discarded chrome leather scrap |
| CN113023741A (en) * | 2021-02-26 | 2021-06-25 | 温州大学 | Formula and preparation method of salt-resistant polymerized bentonite for waterproof blanket interlayer |
| CN113053578A (en) * | 2021-03-24 | 2021-06-29 | 上海上力特种电缆有限公司 | Water-blocking powder for waterproof cable, preparation method of water-blocking powder and waterproof cable |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA2095738A1 (en) | Coated inorganic particles | |
| CA2015193A1 (en) | Thickened aqueous compositions | |
| WO2017186155A1 (en) | Superabsorbent thermochromic resin and preparation method therefor | |
| EP1807457A4 (en) | Vinyl chloride resin composition and method for preparation thereof | |
| CN104231152A (en) | Preparation method of concrete thickener | |
| KR100345911B1 (en) | Method of Making Acrylic Polymers | |
| US3519594A (en) | Coated asbestos and method of making and using same | |
| CN1624008A (en) | Colour composite high water absorbing resin and its preparation process | |
| CN102167876B (en) | Butyl acrylate-styrene-acrylonitrile copolymer/titanium dioxide composite film and preparation method thereof | |
| Ulku et al. | Homogenous photopolymerization of acrylic monomers initiated with ZnO-methacrylate in non-aqueous medium and production of luminescent nanocomposites | |
| CN111333783A (en) | Preparation method of hydroxyl acrylate emulsion for water-based wood paint | |
| CN111576086B (en) | Surface sizing agent, raw material composition, preparation method and application thereof | |
| CN102060950A (en) | Method for preparing homopolymer and copolymer of dimethyl diallyl ammonium chloride | |
| Blumstein et al. | Polymerization of monolayers. VI. Influence of the nature of the exchangeable ion on the tacticity of insertion poly (methyl methacrylate) | |
| CN105601783B (en) | A kind of preparation method of compound polycarboxylate water-reducer resistance mud agent | |
| CN102728326B (en) | Method for preparing hemicellulose base heavy metal ion adsorbent through ultraviolet photocatalysis | |
| CN109851965B (en) | Nano composite high water absorption material and preparation method thereof | |
| JP2002155168A (en) | Polychloroprene latex composition and aqueous adhesive | |
| CN106883662A (en) | A kind of coating polymolecularity TiO2Filler and preparation method thereof | |
| JP2003082011A (en) | Method for producing peelable type polymer/silicate nanocomposite | |
| CN1660717A (en) | Method for fabricatng compound microsphere of macromolecule/inorganic matter | |
| CN114316631B (en) | Functionalized nano calcium carbonate for hard PVC | |
| CN1063187C (en) | Process for preparing core-shell particle toughened polystyrene material | |
| SU1052528A1 (en) | Coating composition | |
| CN1063193C (en) | Transparent core-shell particle toughened polystyrene material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |