CN1042541C - Process and apparatus for preparing polymer water absorbent with high water absorption - Google Patents
Process and apparatus for preparing polymer water absorbent with high water absorption Download PDFInfo
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- CN1042541C CN1042541C CN92114785A CN92114785A CN1042541C CN 1042541 C CN1042541 C CN 1042541C CN 92114785 A CN92114785 A CN 92114785A CN 92114785 A CN92114785 A CN 92114785A CN 1042541 C CN1042541 C CN 1042541C
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
- C08F20/04—Acids, Metal salts or ammonium salts thereof
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Abstract
The present invention relates to a method and a device for preparing polymer water absorbent with high water-absorbing rate, and the polymer contains unsaturated monomers of carboxyl vinyl. A thin film bag of an olefine polymer containing fluorine or polyolefin, which is filled with a water solution of unsaturated monomers, a crosslinking agent and initiator, is put in a horizontal water bath disk of a horizontal water bath reactor or in a composite card of a vertical water bath reactor of a card insertion type for reacting; a water current is forced to flow through thins film bags filled with liquor in the two reactors for taking the polyreaction heat away; therefore, the reaction is easy to control, and the product quality is improved. The present invention is suitable for the commercial production of the polymer water absorbent whose water-absorbing rate is 900 to 3000 times and absorbing rate of 0.9 wt% of salt solution is 60 to 90 times.
Description
The present invention relates to a kind of manufacture method and device of carboxylic unsaturated vinyl monomer polymeric water absorbent.
Polymeric water absorbent also claims absorbent polymer, absorbent resin, it is a kind of polymkeric substance of water-swellable, can promptly absorb the water of tens times of deadweights and even thousands of times when meeting water by hydration, even pressurization can not be extruded water, the performance of this excellence makes it obtain many application, at first is disposable hygienic material (wanting youngster's diaper, sanitary napkin, the clean bag of pet etc.), on agricultural, make soil improvement agent and water-holding agent, the civil engineering leakproof, antifogging coating, the industrial siccative etc. of doing.
Preparation polymeric water absorbent method can be by acrylate and starch-grafted, acrylate and carboxy cellulose grafting, vinylformic acid (salt) polymerization, vinylformic acid and CALCIUM ACRYLATE copolymerization.The device of realizing above-mentioned polymerization process has two roller dryers, common polymeric kettle, special-purpose casting mold framework, Flat bottom container, kneader, single cylinder screw reactor etc.Polymerisate is a kind of aqueous gel polymkeric substance, need carry out drying, and drying means has multiple again, and hot-air dry, infrared drying, low-temperature vacuum drying, two roller dryings etc. are arranged.
The method for making of relevant acrylic polymers water-retaining agent has many patents, because can produce a large amount of polymerization reaction heats during the acrylic monomer polymerization, the viscosity of polymerisate is big, is rubber-like, this product water-intake rate after roller drying or dry air is not high, is generally 400～600 times.What have takes low-temperature vacuum drying, though water-intake rate can improve, there are some masty problems in practical going up.
Japanese Patent (JP 03,115,313) adopts Flat bottom container, carries out the polymerization of vinylformic acid (salt) monomer solution and prepares absorbent resin.Thick 15 millimeters of reaction material liquid layer, the Flat bottom container bottom temp carries out polyreaction under keeping 35 ℃, afterreaction reached gelation in 20 minutes, implode occurs: centre portions reaches 105 ℃, 100 ℃ of container bottoms, and a large amount of water vapors are overflowed, the polymerisate drying is pulverized, water-intake rate is not high, is 420 times, and inhaling 0.9 weight % salt solution is 49 times.
Chinese patent (CN 85104864) is medium wayward with high density vinylformic acid (salt) or starch graft acrylic acid (salt) polyreaction for overcoming, the problem that polymerization reaction heat is difficult to get rid of adopts lower concentration monomer solution (10～20%) to react in polymeric kettle.Monomer concentration one improves slightly, just thickness very of polymerisate then, discharging difficulty.Further reduce monomer concentration, then polymerisate is low because of solid content, and energy consumption for drying is big, does not reach 600 times with common exsiccant product water-intake rate simultaneously, but some masty problems of existence are still gone up in practicality.
Japanese Patent (clear 62-100507) then adopts the single cylinder screw reactor for vinylformic acid (salt) monomer solution, carries out polyreaction under 84 ℃ and decompression, and purpose is to make aqueous solvent in time to extract out, improves monomer conversion.Yet because this reactor has determined that the residence time of material in equipment is short, only 20 minutes, the polymerisate vacuum-drying at low temperatures of still needing did not obtain the good product of performance, and it inhales 0.9 weight % salt solution is 52 times.
The object of the invention is at the polymeric reaction condition that prepared the polymeric water absorbent existence that contains the carboxyl unsaturated monomer in the past wayward, polymerization reaction heat is difficult to get rid of, owing to the high-adhesiveness of polymerisate makes the aftertreatment difficulty, problems such as product water-intake rate and absorption salt ratio are low provide a kind of polyreaction that makes can stably be controlled at polymerization process and device under the conditions suitable.Adopt polymerization process of the present invention and device, polymerization reaction heat is easy to get rid of, and polymerisate is easy to dispose, and available normal air exsiccant method obtains the polymeric water absorbent of high water absorbing capacity and high absorption salt ratio, reduces residual monomer content.
The carboxyl unsaturated monomer that contains that the present invention is used has vinylformic acid, alkali metal salts of acrylic acids, the mixture of vinylformic acid and alkali metal salts of acrylic acids, methacrylic acid, methacrylic acid alkali metal salt, the mixture of methacrylic acid and methacrylic acid alkali metal salt, vinylformic acid and CALCIUM ACRYLATE, a kind of in vinylformic acid and the methacrylic acid is in the reactant feed liquid, with water is solvent, and monomeric concentration is 20～50% (weight).
In the applied monomer of the present invention, what often adopt is the mixture of vinylformic acid and alkali metal salts of acrylic acids, acrylic acid aqueous solution partly neutralizes with alkali-metal oxyhydroxide, and vinylformic acid is 0: 100 to 100: 0 to the mol ratio of alkali metal salts of acrylic acids, is preferably 50: 50 to 10: 90.
The linking agent that the present invention uses is a polyvalent alcohol, the amides that difunctionality unsaturated group nitrogen replaces, as N, N '-methylene bis acrylamide, the two acrylics of difunctionality unsaturated group, as methacrylate-condensed ethandiol ester, two vinylformic acid-condensed ethandiol ester etc., consumption is 0～1% of a monomer weight.
The used initiator of the present invention is the water-soluble persulphate that adopts usually, as Potassium Persulphate, ammonium persulphate etc., also can use oxidation-reducting system initiator, and as ammonium persulfate-sodium bisulfite, the consumption of initiator is 0.01～1% of a monomer weight.
The method that the present invention prepares carboxylic unsaturated vinyl monomer polymeric water absorbent is the aqueous solution that contains the carboxyl unsaturated monomer, the reaction mixture can of linking agent and catalyzer is in bag film, place the water-bath device in the form of sheets, make water force to flow through outer two sides of bag film, the feed liquid layer is below the water surface, polyreaction is carried out under the temperature of determining, polymerization reaction heat in time is forced to recirculated water and takes away, implode can not take place, reaction finishes, and bag film internal reaction thing becomes flaky hydrated gel, be easy to peel off very much, carry out hot-air dry again, pulverize, obtain polymeric water absorbent.
A kind of material of the optional multipolymer from tetrafluoroethylene, polyvinylidene difluoride (PVDF), tetrafluoroethylene and R 1216 of bag film, polyethylene, polypropylene or above-mentioned a kind of polyolefine and a kind of fluorine-containing polyolefinic blend that the present invention is used is made, and wherein fluorine-containing polyolefine is best.
The temperature of water-bath of the present invention is controlled at 30～90 ℃.
Polymeric reaction product is a sheet aqueous gel polymkeric substance, after peeling off from bag film, can adopt hot-air dry, roller drying, and perhaps chopping is placed on hot-air dry.
The horizontal water-bath device (Fig. 1) that the present invention uses is to be formed by the horizontal water-bath dish of multilayer stack combinations, and the water in the water tank is squeezed into each layer water-bath dish by recycle pump, returns water tank by overflow port then, constitutes the pump circulation of current.1. the bag film that the horizontal water-bath dish of each layer (Fig. 2) is equipped with feed liquid places metal perforated plate 2. to go up, and naturally in the form of sheets, the water of certain temperature is forced 3. to flow through the bag film outside by water distributor by pump and reached two sides up and down, is back to water tank by overflow weir, overflow port.Whole feed liquid layers are below the water surface in the bag film.Horizontal water-bath device can be arranged in parallel by a plurality of horizontal water-bath dishes and constitute, and can place a plurality of bag films that the reactant feed liquid is housed in each water-bath dish.
2. 1. the bag film that the vertical card insert type water-bath device (Fig. 3) that the present invention uses is equipped with feed liquid fold slabbing by the pair of metal orifice plate, the such card of many groups inserts water-bath mutually with interval, the water of certain temperature is forced 3. 4. to flow through about every group of card and two sides with metal perforated plate by water distributor by pump, and water tank is returned in overflow.In accompanying in the vertical card insert type water-bath device composite card of reaction cartridge material liquid bag film can be vertically, in level or the arbitrarily angled insertion water-bath.Whole feed liquids are below the water surface in the bag film.
The advantage of the method and apparatus of preparation polymeric water absorbent provided by the invention is to make the reaction mixture feed liquid to become sheet to carry out polyreaction, the water of certain temperature forces to flow through bag film two sides that feed liquid is housed, thereby polyreaction can be under the control condition of determining stable carrying out, polyreaction heat energy is in time got rid of, so implode can not take place.Polymerization process can proceed to the degree of requirement, reduces residual monomer content in the product.The aqueous gel sheet product of polyreaction can easily be peeled off, and is convenient to aftertreatment and disposes.The monomer concentration of reaction mixture feed liquid can improve, so the product solid content is big, and the drying treatment energy consumption reduces, and the drying of polymerisate can be carried out in common drying machinery.The manufacturing method and apparatus of polymeric water absorbent provided by the invention can be made high water absorbing capacity and the high brinish polymeric water absorbent of inhaling, and inhales 900～3000 times of distilled water, inhales 60～90 times of 0.9 weight % salt solutions.Make the polymeric water absorbent three-waste free discharge with method and apparatus provided by the invention, be suitable for suitability for industrialized production.
Embodiment 1
400 parts of the acrylic acid aqueous solutions of concentration 75 weight % carry out the part neutralization with 450 parts of the aqueous sodium hydroxide solutions of concentration 25 weight %, through N
2The displacement back adds N, N '-20 parts of (N of methylene bis acrylamide solution, 0.6 part of N '-methylene bis acrylamide) and 30 parts of (containing 0.9 part of ammonium persulphate) these reaction mixture feed liquid cans of ammonium persulfate aqueous solution in the bag film that tetrafluoroethylene and R 1216 are made, place in the water-bath dish of horizontal reactor 6 millimeters of feed liquid bed thickness.60 ℃ water forced refluence 4 hours, reaction mass become sheet aqueous gel product, peel off bag film after, pulverize behind 105～110 ℃ of hot-air dries.Measuring water-intake rate with following method is 959 times, inhales 72 times of 0.9 weight % salt solutions.
The measuring method of water-intake rate:
Taking by weighing 0.1 gram (be accurate to radix point after the 3rd) particle diameter is 60～100 purpose samples, place in 500 ml beakers, add 300 ml distilled waters, stir and made sample dispersion in water in 5 minutes, placed 25 minutes, filter with 100 order terylene mesh bags then, take by weighing the weight of mesh bag and swell gel, be calculated as follows:
Measuring method to 0.9 weight % salt solution specific absorption:
Identical with the method for measuring water-intake rate, just replace distilled water with 0.9% (weight) sodium chloride aqueous solution.
Comparative example:
The reaction mixture feed liquid is formed with embodiment 1 identical, the reaction mixture feed liquid adds flat Stainless Steel Disc, 6 millimeters of liquid level thickness, and 60 ℃ of water temperatures are kept in the Stainless Steel Disc below, other operation is identical with embodiment 1, and measuring water-intake rate after the product drying and crushing is 600 times.
Embodiment 2
It is identical with embodiment 1 that the reaction mixture feed liquid is formed, but do not add linking agent N, and N '-methylene bis acrylamide operates identically with embodiment 1, and gained water-retaining agent water-intake rate is 3085 times, and inhaling 0.9 weight % salt solution is 90 times.
Embodiment 3
600 parts of the acrylic acid aqueous solutions of concentration 50 weight %, other composition is identical with embodiment 1, operates identically with embodiment 1, and the gained water-intake rate is 1082 times.
Embodiment 4
Reaction mixture feed liquid composition is identical with embodiment 1 with operation, but the bag film that feed liquid is housed places vertical card insert type water-bath device, 6 millimeters of feed liquid bed thickness, and gained water-retaining agent water-intake rate is 1119 times.
Embodiment 5
Reaction mixture feed liquid composition and operation are identical with embodiment 1, and just bag film is made by polyethylene, and the polymeric gel product is peelable, and gained water-retaining agent water-intake rate is 930 times.
Claims (9)
1. manufacture method that contains the polymer water absorbent with high water absorption of carboxy vinyl unsaturated monomer, this manufacture method comprises:
(1) aqueous solution that contains the carboxy vinyl unsaturated monomer partly neutralizes with alkali metal hydroxide, and degree of neutralization is 50～90%,
(2) concentration of aqueous solution that contains the carboxy vinyl unsaturated monomer is 20～50 weight %,
(3) be linking agent with bifunctional compound, its consumption is 0～1% of a monomer weight,
(4) be initiator with water-soluble peroxide or redox system, the initiator add-on is 0.01～1% of a monomer weight,
(5) temperature of reaction is 30～90 ℃, it is characterized in that the can of reaction mixture feed liquid in fluorine-containing polyolefine or polyolefin film bag, and bag film places horizontal water-bath device or vertical card insert type water-bath device, and feed liquid is carried out polyreaction in the form of sheets.
2. by the manufacture method of the described polymer water absorbent with high water absorption of claim 1, it is characterized in that bag film is by fluorine-containing polyolefine, perhaps polyolefine, perhaps polyolefine and fluorine-containing polyolefinic blend make
3. press the manufacture method of the described polymer water absorbent with high water absorption of claim 1, it is characterized in that the bag film that the reactant feed liquid is housed places in the horizontal water-bath dish, the mechanism that horizontal water-bath dish has outside upper and lower and two sides of the bag film that makes water force to flow through feed liquid is housed forms horizontal water-bath device.
4. press the manufacture method of the described polymer water absorbent with high water absorption of claim 1, the bag film that it is characterized in that being equipped with the reactant feed liquid is folded by paired metal perforated plate and is combined into card, insert in the water-bath with interval mutually, this water-bath has makes water force to flow through the mechanism of the composite card that feed liquid is housed, and forms vertical card insert type water-bath device.
5. by the manufacture method of the described polymer water absorbent with high water absorption of claim 3, it is characterized in that horizontal water-bath device is to be arranged in a combination by more than one horizontal water-bath dish.
6. by the manufacture method of the described polymer water absorbent with high water absorption of claim 3, it is characterized in that horizontal water-bath device is to be formed by more than one horizontal water-bath dish stack combinations.
7. by the manufacture method of the described polymer water absorbent with high water absorption of claim 3, it is characterized in that each horizontal water-bath dish can be placed the more than one bag film that the reactant feed liquid is housed in the horizontal water-bath device
8. press the manufacture method of the described polymer water absorbent with high water absorption of claim 4, the composite card that it is characterized in that the bag film of the interior reaction cartridge feed liquid that metal perforated plate folds in the vertical card insert type water-bath device can be vertical, and level or any angle angle are inserted in the water-bath.
9. by the manufacture method of the described polymer water absorbent with high water absorption of claim 4, it is characterized in that vertical card insert type water-bath device contains more than one composite card.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN92114785A CN1042541C (en) | 1992-12-26 | 1992-12-26 | Process and apparatus for preparing polymer water absorbent with high water absorption |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN92114785A CN1042541C (en) | 1992-12-26 | 1992-12-26 | Process and apparatus for preparing polymer water absorbent with high water absorption |
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| Publication Number | Publication Date |
|---|---|
| CN1088941A CN1088941A (en) | 1994-07-06 |
| CN1042541C true CN1042541C (en) | 1999-03-17 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN92114785A Expired - Fee Related CN1042541C (en) | 1992-12-26 | 1992-12-26 | Process and apparatus for preparing polymer water absorbent with high water absorption |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110229256A (en) * | 2019-06-11 | 2019-09-13 | 安徽富瑞雪化工科技股份有限公司 | A kind of production method of super absorbent resin |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62310A (en) * | 1985-06-25 | 1987-01-06 | 祝原 伸一 | Quiet sleep device preventing kicking of futon |
| JPH01121308A (en) * | 1987-11-06 | 1989-05-15 | Mitsubishi Petrochem Co Ltd | Production of water absorbing complex |
| JPH03115313A (en) * | 1989-09-28 | 1991-05-16 | Kazuo Saotome | Production of water-absorptive resin |
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1992
- 1992-12-26 CN CN92114785A patent/CN1042541C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62310A (en) * | 1985-06-25 | 1987-01-06 | 祝原 伸一 | Quiet sleep device preventing kicking of futon |
| JPH01121308A (en) * | 1987-11-06 | 1989-05-15 | Mitsubishi Petrochem Co Ltd | Production of water absorbing complex |
| JPH03115313A (en) * | 1989-09-28 | 1991-05-16 | Kazuo Saotome | Production of water-absorptive resin |
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| CN1088941A (en) | 1994-07-06 |
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