CN110734553A - Preparation method of degradable super absorbent resins - Google Patents
Preparation method of degradable super absorbent resins Download PDFInfo
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- CN110734553A CN110734553A CN201910958567.2A CN201910958567A CN110734553A CN 110734553 A CN110734553 A CN 110734553A CN 201910958567 A CN201910958567 A CN 201910958567A CN 110734553 A CN110734553 A CN 110734553A
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- super absorbent
- polylactic acid
- absorbent resins
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- acid prepolymer
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
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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
- C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
- C08G63/08—Lactones or lactides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
- C08J3/245—Differential crosslinking of one polymer with one crosslinking type, e.g. surface crosslinking
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2303/00—Characterised by the use of starch, amylose or amylopectin or of their derivatives or degradation products
- C08J2303/02—Starch; Degradation products thereof, e.g. dextrin
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/05—Alcohols; Metal alcoholates
- C08K5/053—Polyhydroxylic alcohols
Abstract
preparation methods of degradable super absorbent resin, which is characterized by comprising the following steps of (1) adding lactide and stannous octoate into a reaction kettle according to a proportion, carrying out polymerization reaction under the protection of nitrogen to obtain polylactic acid prepolymer, (2) adding hydroxyethyl methacrylate, starch, glycerol, water, an initiator and the polylactic acid prepolymer into the reaction kettle according to a proportion, carrying out graft modification at constant temperature, drying and crushing the product after the reaction is finished, and obtaining degradable super absorbent resin.
Description
Technical Field
The invention belongs to the field of functional polymers, and particularly relates to water-absorbent resins, and more particularly relates to a preparation method of degradable super-absorbent resins.
Background
The super absorbent resin is functional polymer materials with special performance, and has the capacity of absorbing water with the weight of hundreds of times or even thousands of times of the self-quality, is widely applied to the fields of medical treatment and health, agriculture, forestry and building industry and the like.
The invention patent of application No. 201910086976.8 discloses a preparation method of degradable high-performance water-absorbent resins, which adopts sodium acrylate graft modified poly butylene succinate to prepare the degradable water-absorbent resins, and the water-absorbent resins have degradability, but have long degradation period and weak salt resistance, and adopt petroleum-based monomers as raw materials, and have high price.
Disclosure of Invention
The invention mainly aims to provide a preparation method of degradable super absorbent resins, which solves the problems of slow degradation speed, weak salt resistance and high cost of the existing super absorbent resins.
In order to achieve the technical effects, the invention adopts the following technical scheme that degradable super absorbent resins are prepared by a method comprising (1) adding lactide and stannous octoate into a reaction kettle in proportion, and carrying out polymerization reaction under the protection of nitrogen to obtain polylactic acid prepolymer.
(2) Adding hydroxyethyl methacrylate, starch, glycerol, water, an initiator and a polylactic acid prepolymer into a reaction kettle in proportion, carrying out graft modification at constant temperature, and drying and crushing a product after the reaction is finished to obtain degradable super absorbent resins.
Wherein the adding amount of the stannous octoate in the step (1) is 0.1-0.5 percent of the amount of the lactide substance, the reaction temperature is 125-135 ℃, and the average molecular weight of the prepolymer is 1500-2000.
In the step (2), the hydroxyethyl methacrylate, the starch, the glycerol, the water, the initiator and the polylactic acid prepolymer are respectively in parts by weight: 3.6-5.8: 30-40: 3-7: 33-40: 0.2-0.4: 16-21, and the reaction temperature is 80 ℃.
The initiator is of azodiisobutyronitrile and benzoyl peroxide.
The hydroxyethyl methacrylate and the glycerol are used as cross-linking agents and generate cross-linking with starch to form a three-dimensional structure.
The polylactic acid prepolymer is grafted to the starch, so that the rigidity of a starch molecular chain is improved, the gel strength can be improved, and the biological biodegradability of the polylactic acid can improve the degradation speed of the discarded material.
The invention has the beneficial effects that:
(1) the degradable super absorbent resin does not contain post-acrylate, has low toxicity and is more suitable for application in the aspect of human body contact.
(2) The degradable super absorbent resin has high gel strength after absorbing water, and avoids poor water retention effect caused by collapse.
(3) The functional group in the structure is nonionic, and the salt resistance is strong.
(4) The low molecular polylactic acid is introduced into the starch material, so that the biodegradability of the resin can be improved; compared with petroleum-based resin, the cost is low.
Detailed Description
For further understanding of the present invention , the following embodiments are provided to illustrate the technical solutions of the present invention, and the scope of the present invention is not limited by the following embodiments.
Example 1
kinds of degradable high-hydroscopicity resin is prepared through the process including (1) proportionally adding lactide and stannous octoate into reactor, and nitrogen protection for polymerizing reaction to obtain polylactic acid prepolymer.
(2) Adding hydroxyethyl methacrylate, starch, glycerol, water, azodiisobutyronitrile and polylactic acid prepolymer into a reaction kettle in proportion, carrying out graft modification at constant temperature, and drying and crushing products after the reaction is finished to obtain degradable super absorbent resins.
Wherein the adding amount of the stannous octoate in the step (1) is 0.1 percent of the amount of the lactide substance, the reaction temperature is 1255 ℃, and the average molecular weight of the prepolymer is 1500.
In the step (2), the hydroxyethyl methacrylate, the starch, the glycerol, the water, the initiator and the polylactic acid prepolymer are respectively in parts by weight: 3.6:40:7:33:0.4:16, the reaction temperature is 80 ℃.
Example 2
kinds of degradable high-hydroscopicity resin is prepared through the process including (1) proportionally adding lactide and stannous octoate into reactor, and nitrogen protection for polymerizing reaction to obtain polylactic acid prepolymer.
(2) Adding hydroxyethyl methacrylate, starch, glycerol, water, an initiator and a polylactic acid prepolymer into a reaction kettle in proportion, carrying out graft modification at constant temperature, and drying and crushing a product after the reaction is finished to obtain degradable super absorbent resins.
Wherein the adding amount of the stannous octoate in the step (1) is 0.5 percent of the amount of the lactide substance, the reaction temperature is 135 ℃, and the average molecular weight of the prepolymer is 1500.
In the step (2), the hydroxyethyl methacrylate, the starch, the glycerol, the water, the benzoyl peroxide and the polylactic acid prepolymer are respectively in parts by weight: 5.8:30:3:40:0.2:21, the reaction temperature is 80 ℃.
Example 3
kinds of degradable high-hydroscopicity resin is prepared through the process including (1) proportionally adding lactide and stannous octoate into reactor, and nitrogen protection for polymerizing reaction to obtain polylactic acid prepolymer.
(2) Hydroxyethyl methacrylate, a silane coupling agent, starch, glycerol, water, an initiator and a polylactic acid prepolymer are added into a reaction kettle in proportion, grafting modification is carried out at constant temperature, and after the reaction is finished, products are dried and crushed to obtain degradable super absorbent resins.
Wherein the adding amount of the stannous octoate in the step (1) is 0.1-0.5 percent of the amount of the lactide substance, the reaction temperature is 125-135 ℃, and the average molecular weight of the prepolymer is 1500-2000.
In the step (2), the hydroxyethyl methacrylate, the starch, the glycerol, the water, the initiator and the polylactic acid prepolymer are respectively in parts by weight: 4.7:35:6:34:0.3:20, the reaction temperature is 80 ℃.
The initiator is azobisisobutyronitrile.
Comparative example 1
degradable super absorbent resins are prepared by the following method that (1) hydroxyethyl methacrylate, starch, glycerol, water and azodiisobutyronitrile are added into a reaction kettle according to a proportion, grafting modification is carried out at constant temperature, and after the reaction is finished, products are dried and crushed to obtain degradable super absorbent resins.
Wherein the adding amount of the stannous octoate in the step (1) is 0.1 percent of the amount of the lactide substance, the reaction temperature is 1255 ℃, and the average molecular weight of the prepolymer is 1500.
In the step (2), the hydroxyethyl methacrylate, the starch, the glycerol, the water, the azobisisobutyronitrile and the polylactic acid prepolymer are respectively in parts by weight: 3.6:40:7:49:0.4, the reaction temperature is 80 ℃.
Comparative example 2
kinds of degradable high-hydroscopicity resin is prepared through the process including (1) proportionally adding lactide and stannous octoate into reactor, and nitrogen protection for polymerizing reaction to obtain polylactic acid prepolymer.
(2) Adding sodium acrylate, starch, water, azodiisobutyronitrile and polylactic acid prepolymer into a reaction kettle in proportion, carrying out graft modification at constant temperature, drying and crushing products after the reaction is finished, and obtaining degradable super absorbent resins.
Wherein the adding amount of the stannous octoate in the step (1) is 0.1 percent of the amount of the lactide substance, the reaction temperature is 1255 ℃, and the average molecular weight of the prepolymer is 1500.
In the step (2), the hydroxyethyl methacrylate, the starch, the glycerol, the water, the initiator and the polylactic acid prepolymer are respectively in parts by weight: 10.6:40: 33:0.4:16, the reaction temperature is 80 ℃.
The materials obtained in examples and comparative examples were subjected to a performance test, and the results are shown in table 1.
TABLE 1
As can be seen from table 1, examples 1 to 3 have good absorption effects on pure water, physiological saline and artificial urine, and have good water retention effects; in comparative example 1, polylactic acid was not added, resulting in a decrease in water retention and degradation properties; in comparative example 2, the effect of absorbing normal saline and artificial urine was remarkably reduced by replacing the crosslinking agent with sodium acrylate.
The foregoing illustrates and describes the principles, general features, and advantages of the present invention. It should be understood by those skilled in the art that the above embodiments do not limit the scope of the present invention in any way, and all technical solutions obtained by using equivalent substitution methods fall within the scope of the present invention.
Claims (4)
- The preparation method of degradable super absorbent resins is characterized by comprising the following steps of (1) adding lactide and stannous octoate into a reaction kettle in proportion, and carrying out polymerization reaction under the protection of nitrogen to obtain polylactic acid prepolymer;(2) adding hydroxyethyl methacrylate, starch, glycerol, water, an initiator and a polylactic acid prepolymer into a reaction kettle in proportion, carrying out graft modification at constant temperature, and drying and crushing a product after the reaction is finished to obtain degradable super absorbent resins.
- 2. The method for preparing kinds of degradable super absorbent resins according to claim 1, wherein the amount of stannous octoate added in step (1) is 0.1-0.5% of the amount of lactide material, the reaction temperature is 125-135 ℃, and the average molecular weight of the polylactic acid prepolymer is 1500-2000.
- 3. The preparation method of kinds of degradable super absorbent resins according to claim 1, wherein the weight parts of hydroxyethyl methacrylate, starch, glycerol, water, initiator and polylactic acid prepolymer in step (2) are respectively 3.6-5.8: 30-40: 3-7: 33-40: 0.2-0.4: 16-21, and the reaction temperature is 80 ℃.
- 4. The method for preparing kinds of degradable super absorbent resins of claim 3, wherein the initiator is kinds selected from azobisisobutyronitrile and benzoyl peroxide.
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| CN201910958567.2A CN110734553A (en) | 2019-10-10 | 2019-10-10 | Preparation method of degradable super absorbent resins |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113603836A (en) * | 2021-08-02 | 2021-11-05 | 徐州莫大新材料科技有限公司 | Reaction method and device for high-molecular polymer solid water degradable cross-linking agent |
| CN115232628A (en) * | 2022-06-23 | 2022-10-25 | 北京晋荣农业科技有限公司 | Soil conditioner, preparation method thereof and soil conditioning method |
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| CN87100437A (en) * | 1986-01-24 | 1987-09-09 | 制铁化学工业株式会社 | Produce a kind of method of water-absorbing resin |
| CN1554684A (en) * | 2003-12-22 | 2004-12-15 | 中国农业科学院农业气象研究所 | Process for preparng simply dextrinized starch as powerful water absorbing and preserving agent |
| CN101134807A (en) * | 2007-10-25 | 2008-03-05 | 上海同杰良生物材料有限公司 | Polylactic acid radical biological degradable material and method for preparing same |
| CN101914213A (en) * | 2010-08-24 | 2010-12-15 | 北京希涛技术开发有限公司 | Synthetic method of anti-compression and anti-bacterial super absorbent polymer for physiology |
| AU2010200315A1 (en) * | 2010-01-28 | 2011-08-11 | Green Chemical Co., Ltd | Biodegradable resin composition, method for production thereof and biodegradable film therefrom |
| CN102226001A (en) * | 2011-04-26 | 2011-10-26 | 东北师范大学 | Fully biodegradable nano-starch graft polylactic acid |
| CN103145931A (en) * | 2013-03-25 | 2013-06-12 | 山东汇盈新材料科技有限公司 | Biodegradable agricultural water retaining material and preparation method thereof |
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- 2019-10-10 CN CN201910958567.2A patent/CN110734553A/en not_active Withdrawn
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN87100437A (en) * | 1986-01-24 | 1987-09-09 | 制铁化学工业株式会社 | Produce a kind of method of water-absorbing resin |
| CN1554684A (en) * | 2003-12-22 | 2004-12-15 | 中国农业科学院农业气象研究所 | Process for preparng simply dextrinized starch as powerful water absorbing and preserving agent |
| CN101134807A (en) * | 2007-10-25 | 2008-03-05 | 上海同杰良生物材料有限公司 | Polylactic acid radical biological degradable material and method for preparing same |
| AU2010200315A1 (en) * | 2010-01-28 | 2011-08-11 | Green Chemical Co., Ltd | Biodegradable resin composition, method for production thereof and biodegradable film therefrom |
| CN101914213A (en) * | 2010-08-24 | 2010-12-15 | 北京希涛技术开发有限公司 | Synthetic method of anti-compression and anti-bacterial super absorbent polymer for physiology |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113603836A (en) * | 2021-08-02 | 2021-11-05 | 徐州莫大新材料科技有限公司 | Reaction method and device for high-molecular polymer solid water degradable cross-linking agent |
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| CN115232628A (en) * | 2022-06-23 | 2022-10-25 | 北京晋荣农业科技有限公司 | Soil conditioner, preparation method thereof and soil conditioning method |
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