CN1339510A - Method for preparing high water absorption resin by ultraviolet radiation process - Google Patents
Method for preparing high water absorption resin by ultraviolet radiation process Download PDFInfo
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- CN1339510A CN1339510A CN 01141864 CN01141864A CN1339510A CN 1339510 A CN1339510 A CN 1339510A CN 01141864 CN01141864 CN 01141864 CN 01141864 A CN01141864 A CN 01141864A CN 1339510 A CN1339510 A CN 1339510A
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Abstract
本发明涉及一种用紫外光辐射法制备高吸水性树脂的方法,该方法首先在丙烯酸中加入占其体积0.5～5倍的去离子水,用氢氧化钠部分中和,配制成丙烯酸溶液,也可再加入一定量的共聚单体,然后在该溶液中加入光敏剂;在配好的丙烯酸溶液中通氮气除氧气,取部分放在反应器底部,反应器密闭,用紫外光辐射聚合,射辐时通入氮气,反应完毕即得到高吸水性树脂。利用本发明制备的高吸水性树脂,其原料配方中可以不加交联剂,树脂靠自交联产生的网状结构吸水;与其他方法相比较,水分更容易到达树脂内部,从而吸水倍数更高,可有效降低成本。同时紫外光辐射在常温下进行,不仅操作便捷,时间短,操作过程容易控制,而且后期处理简便。The invention relates to a method for preparing superabsorbent resin by means of ultraviolet radiation. In the method, deionized water accounting for 0.5 to 5 times its volume is added to acrylic acid, partially neutralized with sodium hydroxide, and acrylic acid solution is prepared. It is also possible to add a certain amount of comonomer, and then add a photosensitizer to the solution; pass nitrogen gas to remove oxygen in the prepared acrylic acid solution, take part and put it at the bottom of the reactor, seal the reactor, and use ultraviolet light to radiate and polymerize. Nitrogen gas is introduced during the radiation, and the superabsorbent resin is obtained after the reaction is completed. The superabsorbent resin prepared by the present invention does not need to add a crosslinking agent in the raw material formula, and the resin absorbs water through the network structure produced by self-crosslinking; compared with other methods, the water can reach the inside of the resin more easily, so the water absorption ratio is higher. High, can effectively reduce costs. At the same time, the ultraviolet radiation is carried out at room temperature, which is not only convenient to operate, short in time, easy to control the operation process, but also easy to post-process.
Description
Technical Field
The invention relates to a method for preparing super absorbent resin by using radiation technology, in particular to a method for preparing super absorbent resin by using an ultraviolet radiation method.
Background
The super absorbent resin is a functional polymer material which is rapidly developed in recent years, and the water absorption capacity of the super absorbent resin can reach hundreds of times to thousands of times. Once absorbing water, the absorbed water is not easy to be pressed out by mechanical pressure, has excellent water retention performance, and has wide application in the aspects of biology, medicine, sanitary products, agriculture, forestry and gardening. Further, industrially, it is also useful as a thickener, oxygen absorbent, dehydrating agent, antistaling agent, antifogging material and the like. The traditional method generally adopts methods such as solution polymerization or reversed phase suspension polymerization, the reaction time is generally more than 1 hour, the reaction temperature is higher than the normal temperature, a cross-linking agent is required to be added, a dispersing agent is required to be added in the reversed phase suspension polymerization, and the subsequent drying and purification and other treatment are difficult, so that the methods are limited in application. For example, patent application No. CN92111822 discloses a solution polymerization synthesis method of ternary polymerization super absorbent resin, which adopts sodium acrylate, acrylamide and starch for copolymerization, and adopts a two-step polymerization process of pre-polymerizing sodium acrylate and acrylamide and then adding starch to accelerate the reaction speed, wherein the reaction time still needs 1-2 hours.
In view of the above problems, the prior art has developed a method for preparing a super absorbent resin by using radiation technology, which generally includes ultraviolet radiation, gamma ray radiation, ultrasonic radiation, and the like. Radiation polymerization is another good method for preparing super absorbent resin because of the advantages of less additives, short operation time, easy process control, simple post-treatment, low operation cost and the like. The documents "Radiation modification of water absorption of cassavastarch by acrylic acid/acrylamide, Radiation physics and Chemistry 59(2000), (413) 427" disclose that the water absorption of tapioca starch is modified by polymerizing acrylic acid and acrylamide and grafting onto the tapioca starch by gamma ray Radiation. In addition, ultraviolet radiation is often used for surface modification, heterogeneous grafting and other applications, for example, chinese patent application CN01130787 adopts an ultraviolet surface grafting method to polymerize and graft acrylic acid and the like onto the surface of polypropylene, so as to make a flexible and tough super absorbent material.
Disclosure of Invention
The invention aims to provide a method for preparing high water absorption resin by using an ultraviolet radiation method, namely, ultraviolet light is directly used for initiating polymerization at normal temperature, a cross-linking agent is not required to be added, or the dosage of the cross-linking agent is much less than that of solution polymerization, the operation is simple and convenient, and the product can be obtained in a short time and under a condition. The water absorption rate of the prepared super absorbent resin is high, and the equilibrium water absorption multiple can reach six, seven and hundred times.
The method for preparing the super absorbent resin sequentially comprises the following steps:
a. adding deionized water which accounts for 0.5-5 times of the volume of acrylic acid into the acrylic acid, partially neutralizing the acrylic acid by using sodium hydroxide to prepare an acrylic acid solution with a neutralization degree of 20-80%, then adding a comonomer into the acrylic acid solution to enable the molar ratio of the comonomer to the acrylic acid to be 0-1: 1, then adding a crosslinking agent N, N' -dimethyl bisacrylamide to enable the molar percentage of the crosslinking agent in the solution to be 0-5 per thousand, and then adding a photosensitizer into the solution to enable the molar percentage of the photosensitizer in the solution to be 0.1 per thousand to be saturated;
b. and introducing nitrogen into the prepared solution to remove oxygen, then adding a part of the solution to the bottom of the reactor, sealing the reactor, performing polymerization by ultraviolet radiation, introducing nitrogen during radiation to ensure that the nitrogen flow is 5-25L/h, adjusting the intensity and the irradiation time of the ultraviolet light according to the requirements of different water absorption rates and balanced water absorption times of the water-absorbent resin, and obtaining the super absorbent resin after the reaction is finished.
The comonomer added in the step a can adopt acrylamide or butyl acrylate; the added photosensitizer is any one of benzophenone, xanthone and N, N' -diaryl p-phenylenediamine. The ultraviolet radiation polymerization equation related by the invention is (taking a photosensitizer as an example): excitation Initiation by hydrogen abstraction
Increase in growthNote: superscript S represents singlet and superscript T represents triplet. R represents-OH, -ONa, -NH2，-OC4H9And the like.
Aromatic ketone and its derivative are excited to singlet S after absorbing ultraviolet light, then rapidly cross to triplet, when meeting hydrogen donor, the carbonyl abstracts hydrogen and is reduced to hydroxyl, and simultaneously a free radical is generated,thereby initiating chain growth. When the main chain is provided with free radicals, termination reaction can be carried out, and the main chain can also be combined with each other to be crosslinked, the reaction between the other side groups can also promote crosslinking, when a crosslinking agent is added, the two double bonds of the crosslinking agent can also cause the crosslinking reaction, and the reticular structure obtained by the crosslinking reaction enables the ultraviolet polymerization product to swell and absorb water.
The preparation method of the super absorbent resin has the advantages that:
(1) the raw material formulation of the water-absorbent resin may contain no crosslinking agent, or contain a crosslinking agent in a much smaller amount than that used in the solution polymerization, and the resin absorbs water by virtue of a network structure resulting from self-crosslinking. Compared with the case of adding the cross-linking agent, the water content can reach the inside of the resin more easily, so that the water absorption multiple is higher, and the cost of the product is reduced.
(2) Ultraviolet radiation is carried out at normal temperature, the operation is convenient and efficient, and the light intensity and the radiation time can be freely adjusted.
(3) The water absorption rate and the equilibrium water absorption capacity of the water-absorbent resin can be controlled by adjusting the intensity of ultraviolet light and the irradiation time.
Detailed Description
Example 1:
deionized water was added to acrylic acid in an amount of 1 time the volume of the solution, and the solution was partially neutralized with sodium hydroxide to prepare an acrylic acid solution having a neutralization degree of 80%. Adding a photosensitizer benzophenone into the solution until the solution is saturated, and then adding a cross-linking agent N, N '-dimethyl bisacrylamide to enable the molar percentage content of the cross-linking agent N, N' -dimethyl bisacrylamide to be 5 per mill. Introducing nitrogen into the prepared acrylic acid solution to remove oxygen, adding 4ml of the acrylic acid solution at the bottom of a reactor, sealing the reactor, introducing nitrogen, carrying out radiation polymerization for 10min by using a 1000-watt ultraviolet lamp, wherein the distance between a lamp tube and a sample is 35cm, the nitrogen flow is 5L/h, and obtaining a target product after the reaction is finished, wherein the water absorption multiple of the product is 620 times.
Example 2:
deionized water was added to acrylic acid in an amount of 5 times the volume thereof, and partially neutralized with sodium hydroxide to prepare an acrylic acid solution having a neutralization degree of 40%. Adding photosensitizer xanthone to make the mole percentage content of xanthone in the solution be 0.1 ‰. Introducing nitrogen into the prepared acrylic acid solution to remove oxygen, adding 4ml of the acrylic acid solution at the bottom of a reactor, sealing the reactor, introducing nitrogen, carrying out radiation polymerization for 3min by using a 2000-watt ultraviolet lamp tube, wherein the distance between the lamp tube and a sample is 15cm, the nitrogen flow is 25L/h, and obtaining a target product after the reaction is finished, wherein the water absorption multiple of the product is 560 times.
Example 3:
deionized water in an amount of 0.5 times the volume of acrylic acid was added thereto, partially neutralized with sodium hydroxide to prepare an acrylic acid solution having a neutralization degree of 50%, and acrylamide was added in an amount such that the molar ratio of acrylamide to acrylic acid was 1: 3. Adding a photosensitizer benzophenone to saturate the benzophenone in the solution. Introducing nitrogen into the prepared mixed solution of acrylic acid and acrylamide to remove oxygen, adding 2ml of the mixed solution at the bottom of a reactor, sealing the reactor, introducing nitrogen, carrying out radiation polymerization for 1min by using a 2000-watt ultraviolet lamp tube, wherein the distance between the lamp tube and a sample is 30cm, the nitrogen flow is 25L/h, and obtaining a target product after the reaction is finished, and the water absorption multiple is 650 times.
Example 4:
adding deionized water 2 times the volume of the acrylic acid, partially neutralizing with sodium hydroxide to prepare an acrylic acid solution with a neutralization degree of 60%, and adding a certain amount of butyl acrylate to ensure that the molar ratio of the butyl acrylate to the acrylic acid is 1: 1. Adding a photosensitizer benzophenone to ensure that the molar percentage of the photosensitizer benzophenone in the solution is 5 percent. Introducing nitrogen into the prepared acrylic acid and acrylamide solution to remove oxygen, adding 4ml of the acrylic acid and acrylamide solution at the bottom of a reactor, sealing the reactor, introducing nitrogen, carrying out radiation polymerization for 3min by using a 1000-watt ultraviolet lamp tube, wherein the distance between the lamp tube and a sample is 25cm, the nitrogen flow is 20L/h, and obtaining a target product after the reaction is finished, and the water absorption multiple is 680 times.
Example 5:
deionized water 3 times the volume of the acrylic acid was added, partially neutralized with sodium hydroxide to prepare an acrylic acid solution having a neutralization degree of 65%, and acrylamide was added in an amount such that the molar ratio of acrylamide to acrylic acid was 1: 5. Addingphotosensitizer xanthone to make the mole percentage content of photosensitizer xanthone in the solution be 1%. Introducing nitrogen into the prepared acrylic acid and acrylamide solution to remove oxygen, adding 4ml of the acrylic acid and acrylamide solution at the bottom of a reactor, sealing the reactor, introducing nitrogen, carrying out radiation polymerization for 7min by using a 1000-watt ultraviolet lamp tube, wherein the distance between the lamp tube and a sample is 20cm, the nitrogen flow is 15L/h, and obtaining a target product after the reaction is finished, and the water absorption multiple is 750 times.
Example 6:
adding deionized water with the volume 4 times of that of acrylic acid, partially neutralizing with sodium hydroxide to prepare an acrylic acid solution with the neutralization degree of 70%, and adding a certain amount of acrylamide to ensure that the molar ratio of the acrylamide to the acrylic acid is 1: 7; adding photosensitizer N, N '-diaryl p-phenylenediamine to make the mole percentage content of N, N' -diaryl p-phenylenediamine in the solution be 0.5 per mill. Introducing nitrogen into the prepared acrylic acid and acrylamide solution to remove oxygen, adding 6ml of the acrylic acid and acrylamide solution at the bottom of a reactor, sealing the reactor, introducing nitrogen, carrying out radiation polymerization for 10min by using a 500-watt ultraviolet lamp tube, wherein the distance between the lamp tube and a sample is 15cm, the nitrogen flow is 10L/h, and obtaining a target product after the reaction is finished, and the water absorption multiple of the target product is 700 times.
Example 7:
deionized water 5 times the volume of the acrylic acid is added, sodium hydroxide is used for partial neutralization to prepare an acrylic acid solution with the neutralization degree of 80%, and acrylamide is added in a certain amount so that the molar ratio of the acrylamide to the acrylic acid is 1: 9. Adding photosensitizer N, N '-diaryl p-phenylenediamine to make the mole percentage content of N, N' -diaryl p-phenylenediamine in the solution be 0.2 per mill. Introducing nitrogen into the prepared acrylic acid and acrylamide solution to remove oxygen, adding 4ml of the acrylic acid and acrylamide solution at the bottom of a reactor, sealing the reactor, introducing nitrogen, carrying out radiation polymerization for 12min by using a 1000-watt ultraviolet lamp tube, wherein the distance between the lamp tube and a sample is 10cm, the nitrogen flow is 5L/h, and obtaining a target product after the reaction is finished, and the water absorption multiple is 630 times.
Measurement of Water absorption:
drying the water-absorbent resin prepared by radiation in an oven, grinding part of the water-absorbent resin into powder, grinding and sieving the powder, selecting particles in the range of 20-40 meshes, accurately weighing 0.0900-0.1000 g, soaking the particles in sufficient deionized water, starting timing, sieving the water-absorbent resin with a 200-mesh sieve at intervals of 1 minute, naturally filtering and drying the water-absorbent resin, weighing the water-absorbent resin, and measuring the water absorption times of the resin to represent the water absorption rate.
When the equilibrium water absorption capacity is measured, the water is absorbed for more than 48 hours and then weighed.
Water absorption capacity (g/g) ═ weight of resin after water absorption (g) -weight of dry resin (g)]/weight of dry resin (g)
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| CN 01141864 CN1339510A (en) | 2001-09-21 | 2001-09-21 | Method for preparing high water absorption resin by ultraviolet radiation process |
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| CN 01141864 CN1339510A (en) | 2001-09-21 | 2001-09-21 | Method for preparing high water absorption resin by ultraviolet radiation process |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100558761C (en) * | 2006-09-14 | 2009-11-11 | 台湾塑胶工业股份有限公司 | Method for producing high-performance high-water-absorptivity resin |
| CN101143912B (en) * | 2006-09-14 | 2010-09-29 | 台湾塑胶工业股份有限公司 | Method for producing high-performance high-water-absorptivity resin |
| CN102127244A (en) * | 2010-12-13 | 2011-07-20 | 上海华谊丙烯酸有限公司 | Method for preparing super absorbent resin with low residual acrylic monomer content |
| CN101550202B (en) * | 2008-03-31 | 2011-09-21 | 上海恒谊化工有限公司 | A kind of preparation method of novel inverse emulsion polymer |
| CN102617781A (en) * | 2012-03-16 | 2012-08-01 | 珠海农神生物科技有限公司 | Synthesis method for resin with high water absorbability |
| CN101168580B (en) * | 2006-10-27 | 2012-09-26 | 台湾塑胶工业股份有限公司 | A kind of production method of water-absorbent resin |
| CN104193895A (en) * | 2014-08-21 | 2014-12-10 | 湖南省核农学与航天育种研究所 | Water-absorbing resin for flower soilless culture and preparation method thereof |
| CN105801775B (en) * | 2016-03-14 | 2018-08-31 | 河北五星电力设备有限公司 | A kind of water uptake expansion bag for emergency flood fighting |
-
2001
- 2001-09-21 CN CN 01141864 patent/CN1339510A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100558761C (en) * | 2006-09-14 | 2009-11-11 | 台湾塑胶工业股份有限公司 | Method for producing high-performance high-water-absorptivity resin |
| CN101143912B (en) * | 2006-09-14 | 2010-09-29 | 台湾塑胶工业股份有限公司 | Method for producing high-performance high-water-absorptivity resin |
| CN101168580B (en) * | 2006-10-27 | 2012-09-26 | 台湾塑胶工业股份有限公司 | A kind of production method of water-absorbent resin |
| CN101550202B (en) * | 2008-03-31 | 2011-09-21 | 上海恒谊化工有限公司 | A kind of preparation method of novel inverse emulsion polymer |
| CN102127244A (en) * | 2010-12-13 | 2011-07-20 | 上海华谊丙烯酸有限公司 | Method for preparing super absorbent resin with low residual acrylic monomer content |
| CN102127244B (en) * | 2010-12-13 | 2012-11-28 | 上海华谊丙烯酸有限公司 | Method for preparing super absorbent resin with low residual acrylic monomer content |
| CN102617781A (en) * | 2012-03-16 | 2012-08-01 | 珠海农神生物科技有限公司 | Synthesis method for resin with high water absorbability |
| CN102617781B (en) * | 2012-03-16 | 2014-12-31 | 珠海农神生物科技有限公司 | Synthesis method for resin with high water absorbability |
| CN104193895A (en) * | 2014-08-21 | 2014-12-10 | 湖南省核农学与航天育种研究所 | Water-absorbing resin for flower soilless culture and preparation method thereof |
| CN105801775B (en) * | 2016-03-14 | 2018-08-31 | 河北五星电力设备有限公司 | A kind of water uptake expansion bag for emergency flood fighting |
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