CN118344263B - Temperature-sensitive cross-linking agent, preparation method and application thereof, water-absorbent resin and preparation method thereof - Google Patents
Temperature-sensitive cross-linking agent, preparation method and application thereof, water-absorbent resin and preparation method thereof Download PDFInfo
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- 239000003431 cross linking reagent Substances 0.000 title claims abstract description 68
- 239000011347 resin Substances 0.000 title claims abstract description 62
- 229920005989 resin Polymers 0.000 title claims abstract description 62
- 239000002250 absorbent Substances 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 77
- 238000000034 method Methods 0.000 claims abstract description 33
- VPYJNCGUESNPMV-UHFFFAOYSA-N triallylamine Chemical compound C=CCN(CC=C)CC=C VPYJNCGUESNPMV-UHFFFAOYSA-N 0.000 claims abstract description 30
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims abstract description 15
- 239000000203 mixture Substances 0.000 claims abstract description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 36
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 24
- 238000001125 extrusion Methods 0.000 claims description 19
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 18
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 18
- 238000005469 granulation Methods 0.000 claims description 15
- 230000003179 granulation Effects 0.000 claims description 15
- 230000002745 absorbent Effects 0.000 claims description 12
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- 239000000017 hydrogel Substances 0.000 claims description 6
- DIURKPUKYORPET-UHFFFAOYSA-N 2-bromo-n-prop-2-enylacetamide Chemical compound BrCC(=O)NCC=C DIURKPUKYORPET-UHFFFAOYSA-N 0.000 claims description 3
- AZOOMRDAGOXGNJ-UHFFFAOYSA-N 2-chloro-n-prop-2-enylacetamide Chemical compound ClCC(=O)NCC=C AZOOMRDAGOXGNJ-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 238000010521 absorption reaction Methods 0.000 abstract description 28
- 229920001002 functional polymer Polymers 0.000 abstract description 2
- 239000002861 polymer material Substances 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 10
- 238000007873 sieving Methods 0.000 description 9
- 238000004132 cross linking Methods 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- 239000012153 distilled water Substances 0.000 description 5
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical group C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
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- 238000001000 micrograph Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
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- 230000001105 regulatory effect Effects 0.000 description 3
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- 239000003153 chemical reaction reagent Substances 0.000 description 2
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- 230000007613 environmental effect Effects 0.000 description 2
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- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
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- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
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Abstract
The invention relates to the technical field of functional polymer materials, and discloses a temperature-sensitive cross-linking agent, a preparation method and application thereof, water-absorbent resin and a preparation method thereof. The method for preparing the temperature-sensitive cross-linking agent comprises the following steps: in the presence of water and hexadecyl trimethyl ammonium bromide, triallylamine and N-allylamide compounds are contacted and mixed with each other to obtain a mixture I; the dosage mole ratio of the triallylamine to the N-allylamide compound is 1:1-1.2. The temperature-sensitive cross-linking agent provided by the invention not only has good temperature resistance, but also can regulate and control the water absorption rate of the water-absorbent resin through temperature when being applied to the water-absorbent resin.
Description
Technical Field
The invention relates to the technical field of functional polymer materials, in particular to a temperature-sensitive cross-linking agent, a preparation method and application thereof, water-absorbent resin and a preparation method thereof.
Background
The water-absorbent resin is used as a key high-molecular functional material, has excellent liquid absorption capacity, rapid liquid absorption speed and excellent liquid retention performance, and has wide application in various fields such as sanitary articles, agriculture, forestry, gardening, buildings, adsorption and the like. However, in the field of high Wen Dulou, the use of water-absorbent resins is relatively small, mainly due to the following two reasons: firstly, the water-absorbent resin is poor in temperature resistance; secondly, the difficulty in adjusting and controlling the water absorption rate is high, and the water absorption rate is swelled to a high rate before reaching the injection target layer, so that the construction and plugging efficiency are influenced.
In the process of preparing the water-absorbent resin, the cross-linking agent plays a role in importance, and can cross-link linear macromolecules into a three-dimensional network structure, so that the water-absorbent resin has water absorption property and is insoluble in water, and certain strength can be maintained. The type and amount of the crosslinking agent have an important influence on the performance of the water absorbent resin.
The most commonly used cross-linking agent in the water-absorbent resin reported in the literature is N, N-methylene bisacrylamide, but the N, N-methylene bisacrylamide structure contains amide bonds, the bonds are easy to hydrolyze and break at high temperature, and the prepared water-absorbent resin has poor temperature resistance. In addition, N, N-methylene bisacrylamide does not have temperature-sensitive property and cannot regulate and control the water absorption rate of the water absorbent resin through temperature.
As CN103664632A discloses a water-soluble triene cross-linking agent and a synthesis method of high-temperature resistant water-absorbent resin, the invention uses water-soluble triene as cross-linking agent, solves the problem that the water-absorbent resin is not high-temperature resistant after absorbing water at present, and further widens the application range of the water-absorbent resin. However, the water-absorbent resin in the invention has no temperature-sensitive property, and the water absorption rate of the water-absorbent resin cannot be regulated and controlled by temperature.
Disclosure of Invention
The invention aims to solve the problems of poor temperature resistance and high difficulty in adjusting and controlling the water absorption rate of water-absorbent resin in the prior art.
In order to achieve the above object, a first aspect of the present invention provides a method for preparing a temperature-sensitive crosslinking agent, the method comprising:
in the presence of water and hexadecyl trimethyl ammonium bromide, triallylamine and N-allylamide compounds are contacted and mixed with each other to obtain a mixture I;
The N-allylamide compound is selected from any one of N-allyl-2-iodoacetamide, N-allyl-2-bromoacetamide, N-allyl-2-chloroacetamide, N-allyl-2-iodopropionamide, N-allyl-2-bromopropionamide, N-allyl-2-chloropropionamide, N-allyl-3-iodopropionamide, N-allyl-3-bromopropionamide and N-allyl-3-chloropropionamide;
The dosage mole ratio of the triallylamine to the N-allylamide compound is 1:1-1.2.
Preferably, the weight ratio of the amount of water to the total amount of triallylamine and N-allylamide based compounds is 0.6 to 0.9:1.
Preferably, the weight ratio of the amount of the cetyl trimethyl ammonium bromide to the total amount of the triallylamine and the N-allylamide compound is 0.005-0.015:1.
Preferably, the conditions for contacting mixture i include: the temperature is 28-38 ℃ and the time is 2-4h.
The second aspect of the invention provides a temperature-sensitive crosslinking agent prepared by the method of the first aspect.
The third aspect of the invention provides an application of the temperature-sensitive crosslinking agent in the water-absorbent resin.
A fourth aspect of the present invention provides a method of producing a water absorbent resin, the method comprising:
In the presence of water and sodium hydroxide, carrying out contact mixing I on acrylic acid, ammonium persulfate and a temperature-sensitive cross-linking agent, and extruding and granulating the obtained hydrogel;
The temperature-sensitive cross-linking agent is the temperature-sensitive cross-linking agent of the second aspect.
Preferably, the weight ratio of the acrylic acid to the ammonium persulfate to the temperature-sensitive crosslinking agent is 50-60:0.05-0.2:1.
Preferably, the sodium hydroxide is used in an amount of 0.2 to 0.6g and the water is used in an amount of 1 to 3g, relative to 1g of acrylic acid.
Preferably, the conditions for contacting the mixture II include: the temperature is 60-70 ℃ and the time is 2-5h.
Preferably, the conditions of extrusion granulation include: the temperature is 20-60 ℃ and the rotating speed is 10-100rpm.
A fifth aspect of the present invention provides a water absorbent resin produced by the method of the fourth aspect.
Compared with the prior art, the invention has at least the following advantages:
(1) According to the method for preparing the temperature-sensitive cross-linking agent, the prepared temperature-sensitive cross-linking agent has temperature-sensitive property, and the number of cross-linking chemical bonds can be regulated and controlled through temperature, so that the cross-linking density of the water-absorbent resin is changed.
(2) When the temperature-sensitive cross-linking agent provided by the invention is applied to water-absorbent resin or is used for preparing the water-absorbent resin, the temperature-sensitive cross-linking agent not only has good temperature resistance, but also can regulate the water absorption rate of the water-absorbent resin through temperature;
Preferably, the water absorption rate of the water absorption resin in distilled water at the environmental temperature of 10-80 ℃ is 20-60g/g, and the water absorption rate in distilled water at the environmental temperature of 80-300 ℃ is 200-400g/g.
(3) The method for preparing the temperature-sensitive cross-linking agent provided by the invention has the advantages of simple steps, mild reaction conditions and almost no byproducts, and belongs to green synthetic chemistry.
Drawings
FIG. 1 is a technical schematic diagram of the application of the temperature-sensitive crosslinking agent of the invention to water-absorbent resin to regulate the water absorption rate;
FIG. 2 is a scanning electron microscope image of the water-absorbent resin obtained in example 1 of the present invention after water absorption at 25 ℃;
FIG. 3 is a scanning electron microscope image of the water-absorbent resin obtained in example 1 of the present invention after absorbing water at 300 ℃.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
As previously described, a first aspect of the present invention provides a method of preparing a temperature-sensitive cross-linking agent, the method comprising:
in the presence of water and hexadecyl trimethyl ammonium bromide, triallylamine and N-allylamide compounds are contacted and mixed with each other to obtain a mixture I;
The N-allylamide compound is selected from any one of N-allyl-2-iodoacetamide, N-allyl-2-bromoacetamide, N-allyl-2-chloroacetamide, N-allyl-2-iodopropionamide, N-allyl-2-bromopropionamide, N-allyl-2-chloropropionamide, N-allyl-3-iodopropionamide, N-allyl-3-bromopropionamide and N-allyl-3-chloropropionamide;
The dosage mole ratio of the triallylamine to the N-allylamide compound is 1:1-1.2.
The inventor of the present invention found in the research process that in the presence of water and cetyl trimethyl ammonium bromide, triallylamine and specific N-allylamide compounds are used as raw materials, and other technical characteristics are matched according to specific dosage proportions, so that the temperature-sensitive crosslinking agent can be prepared. The temperature-sensitive cross-linking agent belongs to quaternary ammonium salt, is easy to dissolve in water, and has 3 allyl groups and one N-allylamide group in groups connected with a central N atom. The synthetic route of the temperature-sensitive crosslinking agent is as follows:
wherein R is 、、X is any one of Cl, br and I.
The inventor of the invention further researches and discovers that the temperature-sensitive cross-linking agent has obvious temperature-sensitive property when being applied to the water-absorbent resin, and can regulate and control the water absorption rate of the water-absorbent resin. Specifically, when the temperature is low, four carbon-carbon double bonds in the crosslinking agent can form crosslinking chemical bonds through chemical reaction, and at the moment, the crosslinking density of the water-absorbent resin is high, and the water absorption rate is low; with the rise of temperature, the crosslinking chemical bond containing the amide bond gradually generates hydrolysis bond breaking, at the moment, the crosslinking density of the water-absorbent resin gradually decreases, and the water absorption rate gradually increases; when all the crosslinking chemical bonds containing the amide bonds are hydrolyzed and broken under the condition of higher temperature, the crosslinking density of the water-absorbent resin is minimum and the water absorption rate is maximum. The technical principle of the temperature-sensitive cross-linking agent applied to the water absorption resin for regulating and controlling the water absorption rate is shown in figure 1.
Preferably, the weight ratio of the water to the total amount of the triallylamine and the N-allylamide compound is 0.6 to 0.9:1.
Preferably, the weight ratio of the amount of the cetyl trimethyl ammonium bromide to the total amount of the triallylamine and the N-allylamide compound is 0.005-0.015:1.
Preferably, the conditions for contacting mixture i include: the temperature is 28-38 ℃ and the time is 2-4h. Under the preferred condition, the water-absorbent resin with better temperature-sensitive performance can be obtained by adopting the technical scheme provided by the invention.
According to a particularly preferred embodiment of the invention, the specific operations of the method comprise: firstly, triallylamine is added to a container in the presence of water and cetyltrimethylammonium bromide, and then the N-allylamide compound is added to the container for 1-3 hours to carry out contact mixing I.
As previously described, the second aspect of the present invention provides a temperature-sensitive cross-linking agent prepared by the method of the first aspect.
As described above, the third aspect of the present invention provides the use of the temperature-sensitive crosslinking agent according to the second aspect in a water-absorbent resin.
As described above, the fourth aspect of the present invention provides a method for producing a water absorbent resin, the method comprising:
In the presence of water and sodium hydroxide, carrying out contact mixing I on acrylic acid, ammonium persulfate and a temperature-sensitive cross-linking agent, and extruding and granulating the obtained hydrogel;
The temperature-sensitive cross-linking agent is the temperature-sensitive cross-linking agent of the second aspect.
Preferably, the weight ratio of the acrylic acid to the ammonium persulfate to the temperature-sensitive crosslinking agent is 50-60:0.05-0.2:1.
The "amount of the temperature-sensitive crosslinking agent" in the present invention refers to the weight of the solute in the temperature-sensitive crosslinking agent (the solvent is not included).
Preferably, the sodium hydroxide is used in an amount of 0.2 to 0.6g and the water is used in an amount of 1 to 3g, relative to 1g of acrylic acid.
Preferably, the conditions for contacting the mixture II include: the temperature is 60-70 ℃ and the time is 2-5h.
Preferably, the conditions of extrusion granulation include: the temperature is 20-60 ℃ and the rotating speed is 10-100rpm.
The apparatus used for the extrusion granulation is not particularly limited in the present invention, and the apparatus used for the extrusion granulation is exemplified by a twin screw extrusion granulator.
According to a preferred embodiment of the invention, the method further comprises: drying, crushing and sieving the product obtained after extrusion granulation; more preferably, the drying conditions include: the temperature is 100-120 ℃ and the time is 2-6h; the sieving is sieving with 50 mesh Chinese standard sieve and taking out the sieve.
As described above, the fifth aspect of the present invention provides a water absorbent resin produced by the method of the fourth aspect.
The present invention will be described in detail by examples.
In the examples below, unless otherwise indicated, all means, reagents, materials and the like referred to are conventional and commercially available. Wherein, unless otherwise indicated, all reagents used were commercially available analytically pure products.
The following preparation examples are used to illustrate the method of preparing the temperature-sensitive crosslinking agent according to the present invention.
Preparation example 1
Firstly, adding 13.72g of triallylamine into a reaction bottle in the presence of water and hexadecyl trimethyl ammonium bromide, uniformly stirring, then dropwise adding an N-allylamide compound into the reaction bottle within 2 hours to carry out contact mixing I, and continuously stirring until the system is transparent after the dropwise adding is finished to obtain a temperature-sensitive cross-linking agent Z1 with the effective concentration of 55.0wt%; wherein,
The N-allylamide compound is N-allyl-3-chloropropionamide;
The molar ratio of the triallylamine to the N-allyl-3-chloropropionamide is 1:1, a step of;
The weight ratio of the amount of water to the total amount of triallylamine and N-allyl-3-chloropropionamide was 0.81:1, a step of;
The weight ratio of the amount of cetyltrimethylammonium bromide to the total amount of triallylamine and N-allyl-3-chloropropionamide was 0.011:1, a step of;
the conditions of contact mixture I are: the temperature was 30℃and the time was 2.5h.
Preparation example 2
Firstly, adding 27.44g of triallylamine into a reaction bottle in the presence of water and hexadecyl trimethyl ammonium bromide, uniformly stirring, then dropwise adding N-allyl-3-chloropropionamide into the reaction bottle within 2 hours for contact mixing I, and continuing stirring until the system is transparent after the dropwise adding is finished to obtain a temperature-sensitive cross-linking agent Z2 with the effective concentration of 51.6wt%; wherein,
The N-allylamide compound is N-allyl-3-chloropropionamide;
the molar ratio of the triallylamine to the N-allyl-3-chloropropionamide is 1:1.2;
The weight ratio of the amount of water to the total amount of triallylamine and N-allyl-3-chloropropionamide was 0.83:1, a step of;
The weight ratio of the amount of cetyltrimethylammonium bromide to the total amount of triallylamine and N-allyl-3-chloropropionamide was 0.008:1, a step of;
The conditions of contact mixture I are: the temperature was 28℃and the time was 3 hours.
Preparation example 3
According to the method of preparation example 1, except that the raw materials, the proportion and the reaction conditions are different, a temperature-sensitive cross-linking agent Z3 is obtained, and the effective concentration is 54.4wt%;
The specific raw materials and the proportion and the reaction conditions thereof are as follows:
the N-allylamide compound is N-allyl-2-iodoacetamide;
the molar ratio of triallylamine to N-allyl-2-iodoacetamide is 1:1.1;
the weight ratio of the amount of water to the total amount of triallylamine and N-allyl-2-iodoacetamide was 0.82:1, a step of;
the weight ratio of the amount of cetyltrimethylammonium bromide to the total amount of triallylamine and N-allyl-2-iodoacetamide was 0.01:1, a step of;
The conditions of contact mixture I are: the temperature was 38℃and the time was 2h.
Preparation example 4
According to the method of preparation example 1, except that the raw materials and the proportion thereof are different, a temperature-sensitive cross-linking agent Z4 is obtained, and the effective concentration is 59.3wt%;
The specific raw materials and the proportion thereof are as follows:
The N-allylamide compound is N-allyl-2-chloropropionamide;
the molar ratio of triallylamine to N-allyl-2-iodoacetamide is 1:1.05;
The weight ratio of the amount of water to the total amount of triallylamine and N-allyl-2-iodoacetamide was 0.62:1, a step of;
The weight ratio of the amount of cetyltrimethylammonium bromide to the total amount of triallylamine and N-allyl-2-iodoacetamide was 0.012:1.
Preparation example 5
According to the method of preparation example 1, except that the reaction conditions are different, a temperature-sensitive cross-linking agent Z5 is obtained, and the effective concentration is 40.2wt%;
the specific reaction conditions are as follows: the conditions of contact mixture I are: the temperature was 45℃and the time was 2.5h.
The following examples are presented to illustrate the method of preparing the water absorbent resin provided by the present invention.
Example 1
In the presence of water and sodium hydroxide, carrying out contact mixing II on acrylic acid, ammonium persulfate and a temperature-sensitive cross-linking agent Z1 with the weight of solute being 0.5g, putting the obtained hydrogel into a double-screw extrusion granulator for extrusion granulation, and then drying, crushing and sieving the product obtained after extrusion granulation (sieving by using a 50-mesh Chinese standard sieve and taking a screen bottom) to obtain the water-absorbent resin; wherein,
The weight ratio of the acrylic acid to the ammonium persulfate to the temperature-sensitive crosslinking agent is 57.6:0.1:1, a step of;
the amount of sodium hydroxide was 0.4g and the amount of water was 2g relative to 1g of acrylic acid;
the conditions for contact mixing II are: the temperature is 65 ℃ and the time is 3 hours;
The conditions for extrusion granulation are: the temperature is 25 ℃ and the rotating speed is 20rpm;
The drying conditions are as follows: the temperature was 105℃and the time was 4 hours.
Example 2
In the presence of water and sodium hydroxide, carrying out contact mixing II on acrylic acid, ammonium persulfate and a temperature-sensitive cross-linking agent Z1 with the weight of solute being 0.5g, putting the obtained hydrogel into a double-screw extrusion granulator for extrusion granulation, and then drying, crushing and sieving the product obtained after extrusion granulation (sieving by using a 50-mesh Chinese standard sieve and taking a screen bottom) to obtain the water-absorbent resin; wherein,
The weight ratio of the acrylic acid to the ammonium persulfate to the temperature-sensitive crosslinking agent is 50:0.05:1, a step of;
the amount of sodium hydroxide was 0.6g and the amount of water was 1g relative to 1g of acrylic acid;
the conditions for contact mixing II are: the temperature is 60 ℃ and the time is 5 hours;
The conditions for extrusion granulation are: the temperature is 60 ℃ and the rotating speed is 10rpm;
The drying conditions are as follows: the temperature was 110℃and the time was 2 hours.
Example 3
In the presence of water and sodium hydroxide, carrying out contact mixing II on acrylic acid, ammonium persulfate and a temperature-sensitive cross-linking agent Z1 with the weight of solute being 0.5g, putting the obtained hydrogel into a double-screw extrusion granulator for extrusion granulation, and then drying, crushing and sieving the product obtained after extrusion granulation (sieving by using a 50-mesh Chinese standard sieve and taking a screen bottom) to obtain the water-absorbent resin; wherein,
The weight ratio of the acrylic acid to the ammonium persulfate to the temperature-sensitive crosslinking agent is 60:0.2:1, a step of;
the amount of sodium hydroxide was 0.2g and the amount of water was 3g relative to 1g of acrylic acid;
The conditions for contact mixing II are: the temperature is 70 ℃ and the time is 2 hours;
The conditions for extrusion granulation are: the temperature is 40 ℃ and the rotating speed is 50rpm;
the drying conditions are as follows: the temperature was 120℃and the time was 6 hours.
Examples 4 to 7
Experiments were performed according to the method of example 1, replacing the temperature-sensitive crosslinking agent Z1 with temperature-sensitive crosslinking agents Z2 to Z5, respectively, each having a solute weight of 0.5 g.
Comparative example 1
An experiment was performed as in example 1, substituting 0.5g of N, N-methylenebisacrylamide with the temperature-sensitive crosslinking agent Z1.
Comparative example 2
An experiment was performed according to the method of example 1, based on an aqueous solution of a water-soluble triene crosslinking agent having an effective concentration of 50.4wt% in CN103664632A, by replacing the temperature-sensitive crosslinking agent Z1 with the above aqueous solution of a water-soluble triene crosslinking agent having a solute weight of 0.5 g.
Test case
Weighing 0.2g of the water-absorbent resin prepared in the example, placing the water-absorbent resin in a high-temperature aging-resistant tank filled with enough distilled water, sealing, placing the aging tank in a muffle furnace, setting different temperatures, taking out the water-absorbent resin after 8 hours, weighing the mass of the water-absorbent resin, and then respectively calculating the water absorption rate of the water-absorbent resin at each temperature by a natural rate method. The results are shown in Table 1.
The present invention provides an exemplary scanning electron microscope image of the water-absorbent resin obtained in example 1 after water absorption at 25℃in FIG. 2; and a scanning electron microscope image of the water absorbent resin obtained in example 1 after water absorption at 300 ℃ is exemplarily provided in fig. 3. As can be seen by comparing fig. 2 and fig. 3, the water-absorbent resin maintains similar three-dimensional porous structure after absorbing water at different temperatures, which indicates that the water-absorbent resin provided by the invention has good temperature resistance. In addition, under the same magnification, the structure of the water-absorbent resin is compact after absorbing water at 25 ℃, the pore diameter is smaller, and the structure is more loose and the pore diameter is larger after absorbing water at 300 ℃, which indirectly proves that the water-absorbent resin has small water absorption magnification at low temperature and large water absorption magnification at high temperature.
TABLE 1
The result shows that the method for preparing the temperature-sensitive cross-linking agent has obvious temperature-sensitive property and good temperature resistance. Particularly preferably, the water absorption rate of the water absorbent resin prepared by the temperature-sensitive cross-linking agent in distilled water at the environment temperature of 10-80 ℃ is 20-60g/g, and the water absorption rate of the water absorbent resin in distilled water at the environment temperature of 80-300 ℃ is 200-400g/g, but the water-soluble triene cross-linking agents in the traditional cross-linking agent N, N-methylene bisacrylamide and CN103664632A have no temperature-sensitive property.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (7)
1. A method of preparing a temperature-sensitive cross-linking agent, comprising:
in the presence of water and hexadecyl trimethyl ammonium bromide, triallylamine and N-allylamide compounds are contacted and mixed with each other to obtain a mixture I;
The N-allylamide compound is selected from any one of N-allyl-2-iodoacetamide, N-allyl-2-bromoacetamide, N-allyl-2-chloroacetamide, N-allyl-2-iodopropionamide, N-allyl-2-bromopropionamide, N-allyl-2-chloropropionamide, N-allyl-3-iodopropionamide, N-allyl-3-bromopropionamide and N-allyl-3-chloropropionamide;
the dosage mole ratio of the triallylamine to the N-allylamide compound is 1:1-1.2;
the weight ratio of the water to the total amount of the triallylamine and the N-allylamide compound is 0.6-0.9:1, a step of;
the weight ratio of the dosage of the cetyl trimethyl ammonium bromide to the total dosage of the triallylamine and the N-allylamide compound is 0.005-0.015:1, a step of;
the conditions for contacting mixture I include: the temperature is 28-38 ℃ and the time is 2-4h.
2. A temperature-sensitive cross-linking agent prepared by the method of claim 1.
3. The use of the temperature-sensitive crosslinking agent of claim 2 in water-absorbent resins.
4. A method for producing a water absorbent resin, characterized in that the method comprises:
In the presence of water and sodium hydroxide, carrying out contact mixing I on acrylic acid, ammonium persulfate and a temperature-sensitive cross-linking agent, and extruding and granulating the obtained hydrogel;
The temperature-sensitive crosslinking agent is the temperature-sensitive crosslinking agent of claim 2.
5. The method according to claim 4, wherein the acrylic acid, the ammonium persulfate and the temperature-sensitive crosslinking agent are used in an amount of 50 to 60 by weight: 0.05-0.2:1, a step of;
and/or the sodium hydroxide is used in an amount of 0.2 to 0.6g and the water is used in an amount of 1 to 3g relative to 1g of acrylic acid.
6. The method of claim 4, wherein the conditions for contacting the mixture ii comprise: the temperature is 60-70 ℃ and the time is 2-5h;
And/or, the conditions of extrusion granulation include: the temperature is 20-60 ℃ and the rotating speed is 10-100rpm.
7. A water absorbent resin produced by the method of any one of claims 4 to 6.
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| CN103664632A (en) * | 2013-12-06 | 2014-03-26 | 中国石油大学(华东) | Synthesis method of water-soluble triene cross-linking agent and high-temperature resistant water-absorbing resin |
| CN110982093A (en) * | 2019-12-25 | 2020-04-10 | 湖北理工学院 | Method for preparing quick-response temperature-sensitive hydrogel by adopting room-temperature eutectic solvent liquid front-end polymerization |
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| AU2003216593A1 (en) * | 2002-04-12 | 2003-10-27 | L'oreal | Cosmetic, esp. anti-wrinkle compositions containing water-soluble or -dispersible lcst polymers |
| CN106279494B (en) * | 2015-05-12 | 2018-06-12 | 万华化学集团股份有限公司 | A kind of acrylic absorbent resin of high rate of liquid aspiration and its preparation method and application |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103664632A (en) * | 2013-12-06 | 2014-03-26 | 中国石油大学(华东) | Synthesis method of water-soluble triene cross-linking agent and high-temperature resistant water-absorbing resin |
| CN110982093A (en) * | 2019-12-25 | 2020-04-10 | 湖北理工学院 | Method for preparing quick-response temperature-sensitive hydrogel by adopting room-temperature eutectic solvent liquid front-end polymerization |
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